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PHYSICAL METALLURGY OF TITANIUM

1. I. Kmilau. Ed&

in Chief

SM'me B~b&lbiagH w c , H w , ipcI4.

WATIOWAL AEROHAUTICS AND SPACE ADMlHlSTRAflOH * WASHiH6TOU, I). f.

NOVEMBER 1965

NASA T T F-338

PHYSICAL METALLURGY OF TITANIUM

I. I. Kornilov, Editor i n Chief

Works of the Fifth Conference on Metallurgy, Physical Metallurgy,

and Application of Titanium and Its Alloys
M a r c h 1963
A. A. Baykov Institute of Metallurgy

Izdatell s t v o Nauka
Moscow, 1964

NATIONAL AERONAUTICS AND SPACE ADMINISTRATION

For sale

by

the Clearinghouse for Federal Scientific and Technical Information

Price$7.00
Springfield, Virginia 22151

TABLE OF CONTENTS
Page
PREFACE

vi

PART I. METAL CHEMISTHY OF T1TAIVIU.M ALGOYS

Prospects for the Development of Investigations of the
Heat Resistance of Titanium Alloys

1
1

Phase Diagram of the System Ti-O2 and Some Properties

of the Alloys of This System
Equilibrium Diagram of the Quarternary System Ti-Al-Mo-V

29

Phase Structure of Alloys of the System Ti-Al-Fe-Cr-Siwith

a Constant Content of Aluminum and Silicon

35

Study of the Alloys of the Ternary System Ti-Al-Zr

46

Phase Equilibrium of Alloys of the Section Ti3Al-Zr of

the Ternary System Ti-Al-Zr

53

Study of the Phase Structure of the Alloys of the System

Ti-Al-Zr Along the Section Ti3Al-Zr

58

Relationship of Structures Formed on Quenching Titanium

Alloys to Equilibrium Phase Diagrams

67

Stability of 3!, Alloys of the System Ti-Mo-Cr-Fe-Al

Metastable Polymorphism of Alloys Based on Elements of
Group IV of the Periodic System

90

Dilatometric Study of Transformations in Titanium Alloys

99

Dislocation Theory of the Hydrogen Brittleness of Titanium

Alloys

110

Effect of Alloying on the Physicochemical Properties of

Titanium
Determination of the Characteristics of the Interdiffusion
of Titanium and Molybdenum From the Attenuation of y
Radiation

137

Page
PART 11. INTERACTION OF TITANIUM WITH GASES AND TRE CORROSION
PROPERTIES OF ALLOYS
On t h e R e d i s t r i b u t i o n of I m p u r i t i e s i n Titanium and I t s
Alloys During Oxidation
E f f e c t of Oxygen on t h e Mechanical P r o p e r t i e s o f HeatTreated Alloys AT3 and AT^
C h a r a c t e r i s t i c s of t h e Oxidation of C e r t a i n Titanium
Alloys During Heating P r i o r t o P l a s t i c Deformation
N i t r i d i n g o f Titanium Alloys a t High P r e s s u r e s
Corrosion of Titanium Alloys of S e r i e s VT and AT i n Solut i o n s of S u l f u r i c Acid Containing Nickel S u l f a t e
Chemical S t a b i l i t y of Titanium i n C e r t a i n Aggressive Media
and Scope of I t s Use i n Chemical I n d u s t r i a l Equipment
Chemical S t a b i l i t y of Titanium i n Hydrohalic Acids and
Halogens
E f f e c t of Sodium N i t r i t e on t h e Corrosion of Titanium by
Hydrochloric and S u l f u r i c Acid
Study of t h e Use of Titanium Alloys i n t h e Construction
of Food Machines
PART 111. MECmICAL

AND TECRNOLOGICAL PROPERTIES OF TITANIUM ALLOYS

Basic P r e r e q u i s i t e s f o r Developing High-Strength Titanium

Alloys With an a + @-Structure by Means of Alloying and
Heat T r e a t i n g
S t r e n g t h of I n t e r a t o m i c Bonding of Single-Phase Alloys i n
t h e System Ti-Nb-Cr
Study of t h e Creep of Alloys i n t h e System Ti-V-Nb-Mo
C h a r a c t e r i s t i c s of t h e Cold B r i t t l e n e s s of Titanium
Creep of Alloy -4T3 a t 350'
Study of t h e Creep and Thermal S t a b i l i t y of Alloy AT& a t 500
Determination of t h e Relaxa$ion Resistance of Alloy AT3
Creep of Alloys of t h e Quaternary System Ti-Zr-Al-Sn a t 750'

Study of t h e Mechanical P r o p e r t i e s of Titanium Alloys AT3,

AT^, AT^ and AT^ i n R e l a t i o n t o t h e Testing Temperature

276

Study of t h e Comparative Heat Resistance of Titanium Alloys

Sheet and I t s Weld J o i n t s a t 450, 550, 650 and 700

282

High-Temperature Strength of Alloys of t h e Quaternary

System Ti-Al-Mo-V

283

Heat Resistance of Titanium Alloy

Tests

AT^ i n Short-Time
28 9

Thermal S t a b i l i t y of Alloys AT3 a t Temperatures of 350

and 400'

290

E f f e c t of Conditions of P l a s t i c Deformation and Subsequent

Treatment on t h e P r o p e r t i e s of C e r t a i n Titanium Alloys

297

Study of t h e Basic Parameters of Hot and Medium Temperature

Rolling of Some Titanium Alloys Under S p e c i a l Conditions
of Stress

304

Some S t u d i e s of t h e S t r u c t u r e and P r o p e r t i e s of Alloy VT5-1

During Heating f o r Stamping

305

Some C h a r a c t e r i s t i c s of t h e Heat Treatment of Alloy AT3

With a Low Content of Alloying Elements

3x1

Some Problems of Fusion Welding of Titanium and I t s Alloys

318

Submerged Double-Arc Welding of Medium and Large Thickness

Semifinished Products of Titanium Alloys

319

Study of t h e Mutual Diffusion of Titanium With Copper and

Other Metals S u i t a b l e f o r Brazing

320

Use of O p t i c a l Emission Microanalysis i n t h e Study of

Titanium Alloys

321

Defect I n c l u s i o n s i n Titanium I n g o t s

33 2

Metastable Phases of Titanium Alloys and Conditions of

T h e i r Formation

340

PREFACE
The holding of annual scientific and technical conferences on the problem
of titanium has become an established tradition. At such conferences, the results of research done by many scientific institutions and enterprises on various aspects of this problem during the preceding year are presented, and plans
are drawn up for the further development of research and experimental industrial
work on titanium and its alloys.
The present collection includes the works of the Fifth Scientific Conference, held in Moscow in March, 1963.
The section "Metal Chemistry of Titanium Alloys" offers the results of
a further development in research on the chemical interaction between titanium
and the major elements of the periodic system in simple and multicomponent systems, and presents phase diagrams with titanium as the main component that are
of great scientific and practical interest.
Of particular importance are the results of research on the interaction of
titanium and its alloys with gaseous admixtures, particularly oxygen, nitrogen,
and hydrogen, and on the influence of these admixtures on the physical and mechanical properties of the alloys described in the second section of the collection. This section also provides data on the chemical stability and corrosion
resistance of titanium and some of its alloys in various corrosive
The physical and mechanical properties of the alloys, the results of studies of the creep and relaxation resistance and comparative high-temperature
strength of experimental industrial and mass produced alloys are comprehensively
discussed in the third section of the collection.
The present collection constitutes evidence of the further progress made
in the research on processes and phenomena taking place in titanium alloys
under various conditions of industrial production and application, and directs
the scientific and engineering thought toward the establishment of new goals in
the problem of titanium and its alloys.
It is hoped that the publication of the present collection will be met
with interest by the scientists, engineers, and technicians of the country and
will foster further progress in the scientific investigation, production and
extensive introduction of titanium and its alloys into various branches of
modern technology.
I. I. Kornilov

PART I.

METAL CIiEMTSTRY OF TITANIUM ALLOYS

PROSPECTS FOR TRE DEVELOPMEXI' OF INVESTIGATIONS OF THE REAT

IIESISTANCE OF TITANIUM ALLOYS

I. I. Kornilov

The problem of development of i n v e s t i g a t i o n s i n t o t h e h e a t r e s i s t a n c e of

t i t a n i u m a l l o y s has not been e x t e n s i v e l y t r e a t e d i n t h e l i t e r a t u r e . The s t a t e ments of c e r t a i n authors t o t h e e f f e c t t h a t on t h e b a s i s of c a l c u l a t i o n s of t h e
d i f f u s i o n a l m o b i l i t y of t i t a n i u m atoms it i s d i f f i c u l t t o expect a r i s e i n t h e
t e p e r a t u r e l i m i t of t h e high-temperature s t r e n g t h of t i t a n i u m a l l o y s above
4&-450 a r e i n c o r r e c t and have not been confirmed i n p r a c t i c e . I n i t s pure
fdrm, t i t a n i u m d i s p l a y s creep even a t room temperature, and t h i s creep i n c r e a s e s
w i t h r i s i n g temperature.
There a r e some r e a l p o s s i b i l i t i e s of s u b s t a n t i a l l y i n c r e a s i n g t h e high r e s i s t a n c e of titanium. They p e r t a i n t o t h e physicochemical f a c t o r s of t h e hardening of metals. By i n c r e a s i n g t h e s t r e n g t h of t h e chemical bond obtained by
forming s o l i d s o l u t i o n s and compounds of titanium, one can r a i s e t h e temperat u r e l e v e l of t h e s t r e n g t h of t i t a n i u m . These b a s i c f a c t o r s involved i n r a i s i n g t h e high-temperature s t r e n g t h of metals a r e discussed i n r e f e r e n c e s 1-4.
From t h e standpoint of t h e physicochemical theory of h e a t r e s i s t a n c e of
metal a l l o y s which we formulated and developed ( r e f . 3 ) , high-temperature hardening i s determined by t h e n a t u r e of t h e chemical i n t e r a c t i o n of t h e components,
t h e n a t u r e of t h e phases formed i n t h e system, t h e i r s t a t e , which depends on
equilibrium f a c t o r s , and transformations i n t h e s o l i d s t a t e . An i n c r e a s e i n
high-temperature s t r e n g t h i s achieved p r i m a r i l y a s a r e s u l t of t h e a c t i o n of
t h e s o l u t i o n and d i s p e r s i o n mechanisms of hardening of metal a l l o y s ( r e f . 3).
For t h i s reason, an important a s p e c t of t h e high-temperature s t r e n g t h of titanium a l l o y s i s t h e i n t e r a c t i o n of t i t a n i u m w i t h o t h e r elements.
On t h e b a s i s of t h e chemical p r o p e r t i e s of t i t a n i u m ( r e f s . 4 and 5 ) ) we
divided a i l t h e elements of t h e p e r i o d i c system i n t o t h r e e main groups i n r e l a t i o n t o titanium; t h e s e elements form w i t h t h e l a t t e r :
( 1 ) continuous s o l i d s o l u t i o n s ;
( 2 ) l i m i t e d s o l i d s o l u t i o n s w i t h metal compounds, and
( 3 ) i o n i c compounds.

Of all the elements of the periodic system, those which are the most important
for alloying titanium and hardening its alloys at high temperatures are
those which we classified in the first and second group. There are over 50
such elements.
According to the classification which we adopted (ref. 4)) the elements of
these two groups are characterized by the following types of equilibrium diagrams :

1. Continuous solid solutions with a- and @-modifications of titanium,

with.$ Z a-transformations; these include systems of titanium with its close
analogues Zr and Hf.
2. Continuous solid solutions with @-Ti, very.limited solid solutions
with a-Ti, and the two-phase @ + a region; these include systems of titanium
with metals of transition groups located close to titanium; V, Nb, Ta, Mo and

u.
3. Limited solid solutions of a- and $-Ti with a peritectoid reaction and
formation of compounds; these include systems with Al, Ge, Sn, Pb, La, Ce, B,
C, .O, E, etc.

4, Limited solid solutions of a- and @-Ti with a eutectoid reaction and

the formation of compounds; these include systems with Cr, Mn, Fe, Co, Ni, Cu,
Si, and many otbers.
All these types of interaction are reflected in the phase diagrams of
these systems (ref. 6). We represented them in reference 5 in the form of generalized equilibrium diagrams according to the types of interaction.
In addition to these equilibrium diagrams of binary systems, one can also
distinguish, in the corresponding ternaryand more complex systems, quasi-binary
and quasi-ternary systems which include systems made up of two, three or more
metallic compounds of titanium. Among them, one can distinguish systems composed of iso~orphouscompounds such as Ti AL-T~Sn, Ti U - T i In, Ti Sn-Ti In,

Tier2-TiFe2, TiCr2-ZrCr2, Ti Al-Ti Sn-Ti In, and many others. When certain

conditions are maintained, all these systems of metallic compounds are capable
of producing solid metallic solutions or ternary compounds.
The physicochemical theory of high-temperature strength (ref. 3) and the
equilibrium diagrams of the systems make it possible to determine the dependence of the high-temperature strength on the composition and structure of the
alloys, and to use the derived relationships for the establishment of the scientific principles to be used in the development of new heat-resistant titanium
alloys.
Let us examine some experimental data on the high-temperature strength of
titanium systems. As was shown in references 7 and 8 in the Ti-Zr system at
relatively low temperatures (300-400~),the high-temperature strength in the

region of continuous solid solutions based on a-Ti changes with the composition
by passing through a smooth maximum; as the temperature of the cu 2 $ transformation (8600) is approached, the high-temperature strength is affected by the
activated state of the atoms in the solid solution, which causes an increase in
the rate of creep of the alloys. The same type of change in high-temperature
strength should be expected in the Ti-Hf system.
In systems with continuous $ solid solutions limited by cu solid solutions
of titanium and an intermediate two-phase cu + $ region, the high-temperature
strength not only increases in the region of cu solid solutions, reaching a small
maximum near the boundary of the two-phase cu + $ region; in the two-phase region,
the high-temperature strength decreases considerably, and as one moves into the
region of $ solid solutions and of increasing concentration of elements, the
high-temperature strength increases again. We illustrated this with examples of
the high-temperature strength of Ti-V and Ti-Nb systems (ref. 9). "Compositionhigh-temperature strength" diagrams of the systems Ti-Mo and Ti-Ta, which have
not been studied experimentally, should be similar in character. Thus, in systems with continuous $ solid solutions and limited cu solid solutions, the
"composition-high-temperaturestrength" diagrams show only one maximum near the
boundary of the a 2 8 transformation, a minimum in the region of a + 8 phases,
and an increase in high-temperature strength in the region of 8 solid solutions.
Elements forming limited solid solutions with a peritectoid reaction have an
appreciable effect on the increase in the high-temperature strength of titanium.
Most effective in this respect were found to be alloys of the Ti-Al system in
the region of a limited solid solutions. Here a major part is apparently played
by Kurnakov-type compounds, which form in this system owing to the ordering of
the structure of a solid solutions. Without considering the results of studies
(refs. 5, 6, 10 and 11) on the refinement of the equilibrium diagram of the
system to be definitive, one can tell that from the a solid solutions of this
system are formed the compounds Ti6Al and Ti Al (ref. 11) and, according to

literature data (ref. 6), the compound Tim, which crystallizes from the peritectic reaction. The presence of these compounds is particularly manifested in
the variation of the mechanical properties (ref. 12) and high-temperature
strength (ref'. 13) of alloys of this system. The Ti-Sn is interesting in this
respect. It also has a region of limited a solid solutions with a peritectoid
reaction, and the compound Ti Sn, having a hexagonal lattice, is formed therein
3
(ref. 14). The high-temperature strength of the alloys of this system with
limited a solid solutions is characterized by a maximum near the limit of maximum solubility, a maximum vaiue of the high-temperature strength of the 6 phase
based on the compound Ti Sn, and a minimum of high-temperature strengt:~in the

two-phase Q: + 6 region. "Composition-high-temperaturestrength" diagrams of

this type should apply to the following analogous systems with limited solid
solutions: Ti-&, Ti-Ge, Ti-In, Ti-Ga, Ti-Pb, Ti-Ce, etc.
The above-enumerated systems of limited a solid solutions of titanium and
peritectoid reactions are the most promising for the development of heatresistant titanium alloys. The high-temperature strength of systems with a low
solubility of the components in a-Ti and a eutectoid reaction has been studied
to a lesser extent. These systems (fig. 1) are characterized by low temperatures of the eutectoid transformation. The lowest temperature of the eutectoid

Content of element, at.percent

Figure 1. Phase diagrams of titanium systems
with a eutectoid transformation. 1, Ti-Cr;
2, Ti-Mn; 3, Ti-Pe; 4, Ti-Co; 5, Ti-Ni.
transformation is found in the system Ti-Mn; the temperature of the eutectoid
transformation rises as the elements of the 4th period become farther removed
from Ti. On this basis, elements of the 4th period can be arranged in a series
characterized by a gradual rise in the temperature of the eutectoid transformation, as follows: Mn Fe Cr Co Ni Cu. A certain deviation of Mn and
Fe from the sequence of this series has thus far remained unexplained. The
solubility of these metals in a-Ti (fig. 1) amounts to tenths of one percent,
with the exception of copper, in which it attains 2 atomic (at.) percent. The
very limited solubility of these metals in a-Ti and the eutectoid transformation
determine the high-temperature strength of the alloys of similar binary systems.
A low strength can be expected in the systems Ti-Mn and Ti-Fe with low temperatures of the eutectoid transformation and a gradual rise in this strength can be
expected as one passes to the systems Ti-Cr, Ti-Co and Ti-Ni, since in the latter a gradual rise in the temperatures of the eutectoid transformation is observed. The highest values of the high-temperature strength can be assumed to
prevail in alloys of the system Ti-Cu, both because of the high concentration of
solid solutions of copper in a-Ti, and because of the maximum value of the temperature of the eutectoid transformation of this system. An additional hardening in these systems also can be caused by dispersed precipitates of the excess
phase from supersaturated a solid solutions of titanium. However, no experimental data are available on the high-temperature strength of such binary systems, and the latter must be investigated independently.
+

-t

Systems composed of titanium compounds with other metals are promising for
increasing the high-temperature strength of titanium. One of such interesting

systems is a quasi-binary section of the ternary system Ti-Al-Sn (refs. 15 and

16) passing through the compositions of two compounds: Ti Al and Ti Sn. An
3
3
experimental study of this system showed that on the polythermal section of the
alloys of these two compounds at high temperatures (fig. 2, upper part), the
system is not quasi-binary and the alloys crystallize in the eutectic type. At
low temperatures, below the temperature of formation of the compound Ti Al from

the a solid solution, the system becomes a quasi-binary one composed of two intermetallic compounds, Ti3A1-Ti Sn, Ti A l being formed from the a solid solu3
3
tion, and Ti Sn being formed during crystalfization. These two compounds with

an isomorphous hexagonal lattice form continuous solid solutions, as was shown

in reference 16.

A study of the high-temperature strength of the alloys of this section as

a function of Ti Sn content (by the flexural method) has shown that the strength

changes in accordance with the "composition-high-temperature strength" diagram

of the first type. As is evident from the series of curves in the lower part of

percent
J
Phase
diagrams
and
composition
versus
Figure 2.
high-temperature strength of alloys of the ternary
system Ti-Al-Sn along the section Ti Al-Ti Sn.

f i g u r e 2, t h e time necessary f o r t h e bending d e f l e c t i o n t o reach 2, 3, 4, 5 and

7 mm passes through a smooth maximum i n t h e region of a l l o y s containing 40-60
p e r c e n t T i Sn. The s e l e c t e d temperatures were 700-750~, and t h e s t r e s s e s ,

13-25 kg/mm2. We obtained s i m i l a r r e s u l t s on t h e s e c t i o n corresponding t o comp o s i t i o n s of t h e compounds Ti6M-Ti Sn.

Taking a s t h e b a s i s t h e compositions of t h e compounds Ti6M and Ti3=,

by

a d d i t i o n a l a l l o y i n g w i t h hardening elements, t h e a u t h o r i n c o l l a b o r a t i o n w i t h
T. T. Nartova developed new h e a t - r e s i s t a n t t i t a n i u m a l l o y s based on T i 6 u compounds w i t h a working temperature up t o 700, and a l l o y s based on Ti3M w i t h a
working temperature up t o 800'

(refs.

17 and 18).

I n a study of t h e s t r e s s - r u p t u r e s t r e n g t h of a l l o y s based on t h e compound

Ti6& a t 700 ( f i g . 3) by t h e standard extension method, we e s t a b l i s h e d t h e dependence of t h e time of f a i l u r e of t h e specimens on t h e given s t r e s s ( r e f . 18).
Although d a t a on t h e high-temperature s t r e n g t h and many o t h e r p r o p e r t i e s
of a l l o y s based on t h e compounds Ti6& and T i A l have t h u s f a r been i n s u f f i 3
c i e n t , it i s n e v e r t h e l e s s p o s s i b l e t o assume t h a t c e r t a i n compositions of a l l o y s based on t h e s e compounds make it p o s s i b l e t o a t t a i n working temperatures
of 600-800~, i.e . approximately t h o s e which correspond t o t h e temperatures of
a p p l i c a t i o n of s t a i n l e s s a u s t e n i t i c s t e e l s and c e r t a i n h e a t - r e s i s t a n t n i c k e l
a l l o y s . It should be emphasized t h a t t h e s p e c i f i c g r a v i t y of t i t a n i u m a l l o y s
based on t h e compounds T i 6 a and T i Al i s almost one-half O f t h a t of s t e e l and

n i c k e l a l l o y s . However, it should be kept i n mind t h a t t h e p l a s t i c p r o p e r t i e s

of t i t a n i u m a l l o y s based on t h e s e compounds w i l l be considerably lower t h a n
those of a u s t e n i t i c s t e e l s and n i c k e l a l l o y s .
The l i t e r a t u r e contains evidence on t h e development of h i g h l y heatr e s i s t a n t t i t a n i u m a l l o y s whose base i s t h e compound TiAl ( r e f . 1 9 ) ) a s we had
a l s o pointed o u t i n our work ( r e f . 20). Of s p e c i a l s i g n i f i c a n c e i s t h e group

log ~ / h r
Figure 3. S t r e s s - r u p t u r e s t r e n g t h of t i t a n i u m a l l o y based
on t h e compounds Ti6A.l and of a u s t e n i t i c s t e e l s a t TOO0.

of alloys based on intermetallic compounds that are heat-resistant casting

titanium alloys. Real prospects for the development of new heat-resisthnt titanium alloys are opening up thanks to studies of multicomponent systems. This
was pointed out in connection with the development of heat-resistant titanium
alloys based on a solid solutions of the system Ti-Al-Cr-Fe-Si-B (ref. 21). O f
great interest in this respect are ternary, quaternary and more complex systems
based on titanium. In these systems, one can distinguish alloy compositions
corresponding to the region of solid solutions of a- and @-Ti, and to quasibinary and quasi-ternary sections of intermetallic systems.
Among promising heat-resistant alloys based on the a-structure one should
also distinguish such important ternary systems as Ti-Al-Sn, Ti-Al-Zr, Ti-Al-Cu,
Ti-Al-Mo and many others. Among quaternary systems of this series, the following may be considered important: Ti-Al-Sn-Zr, Ti-Al-Zr-Cu, Ti-Al-Zr-Cr,
Ti-A1-V-Mo,etc.1
Let us examine the three-dimensional diagram of a part of the quaternary
system Ti-IU-V-Mo (fig. 4). A wide region of a solid solutions which is adjacent to the edge of the tetrahedron is visible in this figure. In addition, in
the portion of the system under study, there is a region of quaternary @ solid
solutions which is of interest in a study of heat-resistant alloys based on the
stable B-structure.

An example of titanium alloys with a wide region of the stable p-struct;re

is the ternary system Ti-Cr-Mo, studied in reference 22. One of the isotherms
(at 600) of the system (fig. 5) shows the principal phase regions in this

Figure 4. Three-dimensional diagram of a

part of the quaternary system Ti-K7-Mo-V.

The system Ti-Al-V-Mowas studied in detail by Ye. N. Pylayeva and KO Chih-ming

(see this collection, pp. 26-29).

Cr

Mo, w t percent

440 340 ZZD I40

T i , w t percent
Figure 5. Isothermal s e c t i o n of t h e
t e r n a r y system Ti- Cr-Mo a t 600'.

90 80

70 GO 50

system, including the wide region of @-ternary s o l i d s o l u t i o n s . This system

and o t h e r s i m i l a r ones make it possible t o develop new h e a t - r e s i s t a n t titanium
a l l o y s based on t h e s t a b l e f3-structure.
Using t h e d a t a of Ye. N. Pylayeva and KO Chih-ming, we present a
"composition-high-temperature strength" diagram of t h e a l l o y s of t h e quaternary
system Ti-A1-Mo-V ( f i g . 6 ) . The a l l o y s correspond t o a r a d i a l s e c t i o n with 20
percent Al and a variable content of t h e sum V + Mo = 1:l. The same f i g u r e
shows curves characterizing t h e time necessary f o r a bending d e f l e c t i o n of 2, 5
and 10 mm a s a function of t h e v a r i a b l e content of t h e sum V + Mo (from 0 t o 5
percent).
The t e s t s were c a r r i e d out a t 700-800' and a t a constant s t r e s s of

15 kg/mm 2

The curves show t h a t t h e a l l o y s of t h i s system have maximum values

of high-temperature s t r e n g t h a t 700-800 i n t h e v i c i n i t y of t h e s a t u r a t i o n l i m i t
of t h e a s o l i d solution.

Considering the p o s s i b i l i t i e s of obtaining working temperatures of 600-800'

f o r c e r t a i n h e a t - r e s i s t a n t titanium alloys, one can compare t h e r a t e s of increase i n t h e temperature l e v e l of t h e high-temperature s t r e n g t h of titanium a l loys with those of nickel a l l o y s . The curves representing t h e r i s e i n t h e temperature l e v e l of high-temperature s t r e n g t h with t h e years f o r titanium a l l o y s
( f i g . 7, lower curve) and n i c k e l a l l o y s ( f i g . 7, upper curve) show t h a t i n
approximately t e n years (1952-1962) t h e temperature l e v e l of t h e s t r e n g t h of
titanium a l l o y s rose from 200 t o 800, i . e . , by 600, while t h e temperature
l e v e l of nickel a l l o y s increased i n t e n years (1949-1959) from 700 t o 950,
i . e . , by 250'.
This i s explained by t h e f a c t t h a t i n titanium a l l o y s t h e r e a r e unexp l o i t e d p o s s i b i l i t i e s of hardening and r a i s i n g t h e temperature l e v e l of t h e
high-temperature strength. Studies i n t h i s d i r e c t i o n were begun only 5-6 years

Mo

V, w t p e r c e n t

Figure 6. "Composition-high-temperature s t r e n g t h " diagram a t

700-8000 of a l l o y s of t h e system Ti-Al-Mo-V; s e c t i o n w i t h 20
p e r c e n t Al a t a v a r i a b l e content V:Mo = 1:l.

-.

7lUU

Gll
4ffO
1352

If54

1356

1358

years
Figure 7. Rise i n t h e temperature l e v e l of t h e s t r e n g t h
of n i c k e l (1) and t i t a n i u m (2) a l l o y s i n 1 0 years.
ago, whereas t h e high-temperature s t r e n g t h of n i c k e l a l l o y s has now been studi e d f o r over 15 y e a r s , and t h e b a s i c f a c t o r s a f f e c t i n g t h e i r hardening have now
been almost exhausted. The p r o s p e c t s f o r a f u r t h e r i n c r e a s e i n t h e temperature
l e v e l of t h e highltemperature s t r e n g t h of t i t a n i u m a l l o y s have not y e t been exhausted, and f u r t h e r systematic. i n v e s t i g a t i o n s w i l l make it p o s s i b l e t o r a i s e
it s t i l l f u r t h e r .
Summary

1. The a r t i c l e has e s t a b l i s h e d c e r t a i n r e l a t i o n s h i p s governing t h e dependence of t h e high-temperature s t r e n g t h of t i t a n i u m a l l o y s on t h e n a t u r e of

t h e i n t e r a c t i o n of t h e components w i t h titanium, types of equilibrium diagrams
of t h e systems, and s t r u c t u r e of t h e a l l o y s .

2.
grams of
sible to
titanium

Experimentally obtained "composition-high-temperature strength" diacertain simple and multicomponent titanium systems will make it posuse these relationships for the development of new heat-resistant
alloys having optimum properties.

3. An important role in the creation of new heat-resistant titanium alloys is played by the stable structures of a and @ solid solutions and also by
metallic compounds of titanium and alloys based on these compounds.

4. Promising in this respect are multicomponent a and @ solid solutions

of systems based on titanium and the titanium compounds Ti6& and Ti3Al, which
are formed from a solid solutions of the system Ti-A1.

5. Alloys made from the phases enumerated above can have working temperatures up to 600-800~.

1. Bochvar, A. A. Physical Metallurgy (~etallovedeniye). Metallurgizdat,

(State Scientific and Technical Publishing House for Literature on
Ferrous and Nonferrous ~etallurgy), pp. 287-297,1956.
2. Osipov, K. A. Problems of the Theory and High-Temperature Strength of
Metals and Alloys (voprosy teorii zharoprochnosti metallov i splavov)
IZ~-voAN SSSR, 1960.

3. Kornilov, I. I. Physicochemical Principles of the Aigh-Temperature

Strength of Alloys (Fiziko-khimicheskiye osnovy zharoprochnosti splavov)

IZ~-voAN ,SSSR,1961.

4. --- Izv, &4! SSSR, OKhN, Mo. 4, p. 395, 1957.

5.

--p.

Coll. '%tanium and Its Alloys" (Sb. "Titan i y e p ~~lax&"), No.

NO. 10, p. 10, 1963.'
5,

7,

Hansen, M. and Anderko, K. Structures of Binary Alloys (~trukturydvoynykh

splavov) Metallurgizdat, 1962.

Glazova, V. V, and Kurnakov, N. N.

Toplivo, No. 3, p. 67, 1961.

Izv. AN SSSR, OTN, Metallurgiya i

Grigorovich, V. K. and Safonov, Yu. S.

Toplivo, No. 5 , p. 38, 1960.

Izv. AN SSSR, OTN, Metallurgiya i

Kornilov, I. I. and Vlasov, V. S. Izv. AN SSSR, OTN, Metallurgiya i

Toplivo, No. 4, p. 31, 1958.

10.

Ence, E. and Anderko, K.

Trans. AIME, Vol. El, No. 1, p.

151, 1961.

11. Grum-Grzhimaylo, N. V., Kornilov, I. I., Pylayeva, Ye. N. and Volkova, M.A.
~ o k l .AN SSSR, Vol. 137, No. 3, p. 599, 1961.

Metallovedeniye i termieheskaya obrabotka metallov, No.

12.

Moiseyev, V. N.
p. 30, 1960.

13.

Kornilov, I. I . , Pylayeva, Ye. N. and Volkova, M. A.

No. 7, P. 771, 1956.

14. Kornilov, I .
NO.

I. and Nartova, T. T.
3, p . 662, 1960.

~ o k l .AN SSSR,

---

~ o k l . AN SSSR, ~ o l .140,

---

Izv. AN SSSR, OTN, Metallurgiya 5. Toplivo, No.

---

DO~X.

AN SSSR,

V O ~ . 131, NO.

VO~.

1-48)

NO.

NO.

I z v . AN SSSR, O W ,

Zhurnal neorganicheskoy khimii, Vol.

---

6,

5,

4, p. 837, 1960.

4, p. 829, 1961.
6, p. 142, 1962.

3, p. 644, 1963.

Andrew, J. and Kessler, H. J. Metals, Vol. 8, No. 10, 1956.

Kornilov, I. I.
1960.

Izv. AU SSSR, OTN, Metallurgiya i Toplivo, No.

6, p. 130,

Kornilov, I. I., Mikheyev, V. S., Chernova, T. S. and Markovich, K. P.

Sb. "Titan i yego splavy, " Izd-vo
SSSR, NO. 7, p. 141,. 1962.
Grum-Grzhimaylo, N. V. and Gromova, V. G.
Coll. "Titanium and I t s Alloys"
(Sb. "Titan i yego splavy"). Izd-vo AN SSSR, NO. 7, p. -36, 1962.

PHASE DIAGRAM OF THE SYSTEM Ti-O2 AND SOME PROPERPIES

OF THE ALLOYS OF THIS SYSTESI

I. I, Kornilov and V. V. Glazova

The character of t h e i n t e r a c t i o n between titanium and oxygen and t h e equilibrium diagram of t h i s system heretofore have been based on t h e concept of t h e
existence of a wide region of a s o l i d s o l u t i o n s of titanium with oxygen and on
t h e existence of t h e compounds TiO, Ti203 and Ti02 i n t h i s system ( f i g . 1 ) .
The v a r i a t i o n i n t h e physicochemical, mechanical and o t h e r p r o p e r t i e s of
t h e a l l o y s of t h e system Ti-O2 has been a l s o represented u n t i l now on t h e b a s i s
of a wide region of i n t e r s t i t i a l - t y p e a s o l i d s o l u t i o n s , up t o 32 a t . p e r c e n t
O2 ( r e f s . 1-7). The l i t e r a t u r e contains only l i m i t e d d a t a on d e t a i l e d s t u d i e s
of t h e behavior of oxygen i n t h e region of a s o l i d s o l u t i o n s and on t h e i n f l u ence of c e r t a i n p o s s i b l e r e a c t i o n s i n t h e a l l o y s i n t h e s o l i d s t a t e on t h e
YS
p r o p e r t i e s of

I n the l a s t few years, evidence has accumulated i n some s t u d i e s on t h e

p o s s i b i l i t y of t h e formation of an ordered s t r u c t u r e i n t h e region of t h e a
s o l i d s o l u t i o n of titanium with oxygen. I n v e s t i g a t i o n s of a l l o y s of t i t a n i u m
with oxygen by methods of x-ray s t r u c t u r a l a n a l y s i s ( r e f s . 8 and 9) and by t h e
e l e c t r i c a l r e s i s t a n c e method ( r e f . 1 0 ) revealed an anomalous v a r i a t i o n i n prope r t i e s when t h e a l l o y contained about 25 a t percent 02.
It was noted t h a t t h e ordered s t a t e of a l l o y s of t h i s system i s s t a b l e a t
temperatures up t o 400 ( r e f . 8).
Ye. S. Makarov ( r e f . 11) used t h e x-ray
method t o reaffirm t h e continuous nature of t h e v a r i a t i o n i n t h e c r y s t a l s t r u c t u r e of t h e chemical compound of v a r i a b l e composition of a-phase-type i n t h e
system Ti-02; i n t h e view of t h e authors of t h i s a r t i c l e , t h i s i s associated
with t h e continuous r e a c t i o n of a d d i t i o n T i

xO = TiOx

Q, where x can change

continuously from zero t o a value corresponding t o t h e boundary of phase inhomogeneity. This purely physical i n t e r p r e t a t i o n of t h e behavior of oxygen i n a
s o l i d s o l u t i o n s based on titanium has not accounted f o r t h e chemical r o l e of
t h i s metalloid i n t h e formation of various types of compounds i n a medium of
m e t a l l i c s o l i d solutions.

DL, at. p e r c e n t
SU

40

0000000000

75

20
O2,

W
30
w t percent

Figure 1. Equilibrium phase diagram of a l l o y s of t h e

system Ti-O2 (according t o t h e d a t a of r e f e r e n c e 5).
1, one phase; 2, mixture of phases; 3, s t a r t of fusion;
4, p a r t i a l fusion; 7, complete f u s i o n .
A n a n a l y s i s of t h e d a t a on t h e i n t e r a c t i o n of metals of group I V of t h e
p e r i o d i c system w i t h oxygen has enabled one of t h e authors ( r e f . 1 2 ) t o postul a t e a p o s s i b l e formation of t h e compound T i 0 i n t h i s system. This i s con-

firmed i n p a r t i c u l a r by a smooth maximum on t h e c o n s t i t u t i o n diagram of t h e

system Ti-O2 corresponding t o t h e region of 25 at. p e r c e n t O2 ( f i g . 1). The
expressed arguments concerning p o s s i b l e suboxide compounds of t i t a n i u m w i t h a
m e t a l l i c bond c h a r a c t e r follow from an a n a l y s i s of t h e chemical p r o p e r t i e s of
t i t a n i u m and i t s tendency t o form i n t e r m e t a l l i c compounds w i t h e l e c t r o n e g a t i v e
elements ( r e f s . 1 2 and 13).
Considering t h e pronounced a c t i v i t y of oxygen atoms i n i n t e r s t i t i a l s o l i d
s o l u t i o n s , one could assume t h e formation of s i m i l a r compounds from t h e a s o l i d
s o l u t i o n i n t h e system Ti-O2 on slow cooling o r prolonged exposure t o low temp e r a t u r e conditions.
L a t e r , on t h e b a s i s of t h e very incomplete i n v e s t i g a t i o n s of Hurlin ( r e f .
1 4 ) i n t o t h e s t r u c t u r e of t h e s c a l e and i n v e s t i g a t i o n s i n t o t h e dependence of
t h e e l e c t r i c a l r e s i s t a n c e of c a s t a l l o y s on t h e composition c a r r i e d o u t by

Wasilewsky ( r e f . 15)) hypotheses were a l s o advanced concerning t h e p o s s i b l e exi s t e n c e of t h e compounds Ti60 and Ti30.
A l l of t h e above l e a d s t o t h e conclusion t h a t t h e n a t u r e of t h e chemical
i n t e r a c t i o n between t i t a n i u m and oxygen i s f a r from being a s simple a s would
follow from t h e phase diagram ( f i g 1) given i n Ransen ' s handbook ( r e f . 5 ) .

A t t r i b u t i n g a major t h e o r e t i c a l and p r a c t i c a l importance t o t h e problem

of t h e i n t e r a c t i o n of t i t a n i u m w i t h oxygen and t o t h e e l u c i d a t i o n of t h e chemi c a l n a t u r e of t h e a l l o y s of t h i s system, we c a r r i e d o u t a d e t a i l e d s t u d y of
t h e system Ti-O2 and t h e range of concentrations from zero t o 35 a t - p e r c e n t 02,
The a l l o y s were prepared by f u s i o n i n an a r c furnace w i t h a nonconsumable
e l e c t r o d e i n an argon atmosphere.
The s t a r t i n g m a t e r i a l f o r t h e p r e p a r a t i o n of t h e a l l o y s was i o d i d e titanium (99.9 p e r c e n t TL) w i t h t h e following main i m p u r i t i e s : M g ( 0 . 0 1 perc e n t ) , S i (0.03 p e r c e n t ) , Al (0.01 p e r c e n t ) , Fe and N i (< 0.01 p e r c e n t ) ,
C r (0.01 ~ e r c e n t ) ,O2 (0.01 ~ e r c e n t ) , and N2 (0.01 p e r c e n t ) .
Oxygen was introduced i n t o t h e a l l o y s i n t h e form of a Ti-O2 master a l l o y
containing 15.8 w t p e r c e n t . The master a l l o y was prepared by melting b a r s
pressed from t-jctanium and t i t a n i u m d i m i d e of 99.93 p e r c e n t p u r i t y i n an a r c
firnace

The above method was used t o prepare a l l o y s containing 0, 1, 3,

35 at. p e r c e n t . .

5 , 7, e t c .

a-tx p e r c e n t oxygen up t o

Alloys of 10 compositions were subjected t o chemical a n a l y s i s by u s i n g t h e

vacuum f u s i o n method. R e s u l t s of t h e a n a l y s i s showed t h a t t h e oxygen c o n t e n t
of t h e i n i t i a l mixture was i n good agreement w i t h t h e d a t a of t h e chemical
analysis.
800'

The c a s t a l l o y s were subjected t o homogenizing annealing i n vacuum a t

f o r 1000 hours.

A f t e r t h e homogenizing annealing a t 800') t h e a l l o y s were annealed a t 400,

600, 800, 850, 1000 and 1 4 0 0 ~f o r 600, -400, 1000, 100, 100 and 2 h r s , respect i v e l y , and quenched i n i c e water.
I n t h e study of t h e a l l o y s , u s e was made of methods of physicochemical
a n a l y s i s developed by N. S. Kurnakov, which involved t h e p l o t t i n g of
"composition-property" phase diagrams ( r e f s . 16.and 1 7 ) .
Such methods included microscopic and x-ray s t r u c t u r a l analyses, measurement of microhardness, e l e c t r i c a l r e s i s t a n c e , and temf.
The microhardness w a s measured w i t h a PMT-3 instrument under a load of
200 g using t h e method described i n r e f e r e n c e 18.

The
made up o
The
s i n c e all
be subjec
casting t
measured

The a l l o y w i t h 25 a t - p e r c e n t O2 i s c h a r a c t e r i z e d by t h e presence of s l i p l i n e s
i n t h e s t r u c t u r e ( f i g . 213). The same s t r u c t u r e was observed i n a l l o y s w i t h a
h i g h e r oxygen content, up t o 30 a t . p e r c e n t ( f i g . 2e). The m i c r o s t r u c t u r e of
t h e a l l o y w i t h 35 p e r c e n t oxygen i s shown i n f i g u r e 2 f .
13,

Microscopic a n a l y s i s of a l l o y s quenched from 800 showed t h a t t h o s e with

O2 were two-phase a l l o y s , and t h a t t h e s t r u c t u r e of

1 4 and 16 a t p e r c e n t

t h e remaining ones was polyhedral. It should be noted t h a t a l l specimens of

a l l o y s contaiaing more t h a n 10 a t . p e r c e n t O2 were covered w i t h cracks and
pores whose q u a n t i t y increased w i t h r i s i n g oxygen content.

Figure 2.

Microstructures of a l l o y s of t h e system Ti-O2 with t h e

following content:

a, 5 percent 02, quenching a f t e r annealing a t

600, x 500; b, 1 0 percent 02, quenching a f t e r annealing a t 600,

x 500; c, 16 percent 02, quenching a f t e r annealing a t 6000, x 500;

d, 25 percent 02, quenching a f t e r annealing a t

6000, x 200; e , 30

percent 02, quenching a f t e r annealing a t 800, x 200; f , 35 percent 02, c a s t s t a t e , x 200.

Alloys quenched from 850' had a polyhedral s t r u c t u r e , with t h e exception

of t h e a l l o y with 25 a t . p e r c e n t 02, which retained t h e s l i p l i n e s a t a l l quenching temperatures.
I n t h e analysis of t h e microhardness of a l l o y s of t h e Ti-O2 system
quenched from 400 and 6000, t h e "microhardness- composition" curves displayed
two singular minima corresponding t o compositions with 14.5 and 25 at.percent
o2 ( f i g . 3a).
The isotherm a t 800O has a noticeable i n f l e c t i o n on t h e curve a t
percent 02, and a marked minimum a t 25 a t . percent 02.

14.5 at.

Isotherms a t 1000 and 1400 of t h e "microhardness-composition" curves disp l a y singular minima f o r t h e composition with 25 percent 02.

It should be emphasized t h a t one group of a l l o y s i n t h e c a s t s t a t e exh i b i t e d a microhardness maximum i n t h e a l l o y with 25 a t . p e r c e n t 02, which f o l lowing heat treatment a t 800'

changed i n t o a minimum.

Figure 3b shows t h e dependence of t h e e l e c t r i c a l r e s i s t a n c e on t h e compos i t i o n of a l l o y s quenched a f t e r holding a t 800, 1000 and 1 4 0 0 ~ .

On quenching from 800') t h e e l e c t r i c a l resistance r i s e s abruptly from 45.8
mohm/cm f o r pure titanium t o 158 mohm/cm f o r t h e a l l o y with 10 at. percent 02.
I n t h e a l l o y with 15 a t . p e r c e n t 02, t h e e l e c t r i c a l r e s i s t a n c e r i s e s sharply,
reaching 466 mohm/cm; t h i s i s followed by a r i s e t o TOO mohm/cm f o r t h e alloy
with 22 a t . p e r c e n t 02, then by a sharp decline i n e l e c t r i c a l r e s i s t a n c e .
The a l l o y with 25 at.percent O2 has a r e s i s t a n c e of 150 mohm/cm.

As t h e

oxygen content increases, t h e e l e c t r i c a l r e s i s t a n c e r i s e s t o 639 mohm/cm.

An analysis of t h e curve representing t h e e l e c t r i c a l r e s i s t a n c e of alloys

quenched from 1000 and 1 4 0 0 ~versus composition shows t h e presence of a singul a r minimum a t 25 a t . p e r c e n t 02. It should be noted t h a t i n many cases a t 25
a t . p e r c e n t 02, t h e c a s t specimens display a maximum which a f t e r a prolonged annealing of t h e specimens changes i n t o a minimum.
Let us examine t h e dependence of t h e temf of a l l o y s of t h e Ti-O2 system
on the oxygen content, i n a couple with copper a f t e r quenching from 800, 1000
and 1 4 0 0 ~( f i g . 3c)
On quenching from 800, t h e temf decreases sharply from pure titanium (30
mv/deg) t o a composition with 1 4 at.percent O2 (-78 m~/deg). It should be

17

noted that at a content of

5 at.percent

02, the temf changes sign, indicating

a change in the type of conduction from hole to electron conduction.

loy with 25 percent 0 the value of temf is at a minimum.
2'

In the al-

On the isotherms at 1000 and 1400~)a singular minimum is preserved only

in the composition with 25 at.percent 02.

f.2

I8

24

JJ

36

02, wt percent
Figure 3. Dependence of the microhardness (a), electrical
resistance (b) and temf (c) on the composition of alloys of
the system Ti-O2 after quenching from various temperatures.

Preliminary d a t a of x - r a y s t r u c t u r a l a n a l y s i s show t h a t t h e a l l o y w i t h 25
a t . p e r c e n t O2 a t temperatures up t o 1 4 0 0 ~has one s u p e r s t r u c t u r e l i n e , while no
s u p e r s t r u c t u r e l i n e s h a v e t h u s f a r b e e n observed i n t h e a l l o y w i t h
cent 0 under t h e s e conditions of h e a t treatment.
2

14.5 a t . per-

Thus, based on t h e r e s u l t s of m i c r o s t r u c t u r a l a n a l y s i s and on t h e

ftcomposition-property" diagrams i n t h e concentration range studied,one can assume t h a t i n t h e Ti-O2 system t h e r e a r e two new compounds: Ti60 and Ti30.
The n a t u r e of t h e "composition-property" chemical diagrams a t 800' and
a l s o d a t a of t h e microscopic a n a l y s i s l e a d t o t h e conclusion t h a t t h e compound
T i 0 i s s t a b l e up t o 820-830'.
6
The compound T i 0 w i t h an ordered s t r u c t u r e i s a p p a r e n t l y s t a b l e above
3
1400, s i n c e t h e s i n g u l a r c h a r a c t e r of t h e "composition-propertytt diagrams a t
t h i s temperature remains unchanged.
A study of t h e s t a t e of t h i s compound a t h i g h e r temperatures up t o t h e
melting p o i n t ( 1 9 0 0 ~ )r e q u i r e s a s p e c i a l i n v e s t i g a t i o n .

The r e s u l t s of t h e p r e s e n t study have produced a new e q u i l i b r i u m phase

diagram of t h e a l l o y s of t h e Ti-O2 system f o r compositions containing l e s s t h a n
35 a t . p e r c e n t 02.

It follows from t h i s diagram t h a t t h e compounds Ti60 and

and T i 0 a r e formed i n t h e Ti-O2 system.

3
The s i m i l a r i t y between t i t a n i u m and zirconium and t h e n a t u r e of t h e i r i n t e r a c t i o n w i t h oxygen l e a d s t o t h e assumption t h a t t h e compound Zr60 and Z r 0
3
may e x i s t i n t h e system Zr-02.
The new compounds Ti60 and T i 0 e s t a b l i s h e d i n t h e p r e s e n t work, and t h e
3
regions of t h e i r e x i s t e n c e on t h e phase diagram of t h e Ti-O2 system a r e of
major importance i n t h e metal chemistry and p h y s i c a l metallurgy of t i t a n i u m
a l l o y s . These new compounds should s e r v e a s a b a s i s f o r t h e study of e q u i l i b r i a i n complex t i t a n i u m systems w i t h oxygen, and f o r t h e e l u c i d a t i o n of t h e
i n f l u e n c e of oxygen on t h e physicochemical and mechanical p r o p e r t i e s of t i t a nium and i t s a l l o y s ( r e f . 1 9 ) .
I n t h e l i g h t of what was s t a t e d above, it appears v e r y i n t e r e s t i n g t o
study t h e i n f l u e n c e of oxygen on t h e c h a r a c t e r i s t i c s of t h e s t a b i l i t y of t h e
chemical bond, s i n c e it i s t h e s e c h a r a c t e r i s t i c s which, i n t h e f i n a l a n a l y s i s ,
determine t h e degree of s t a b i l i t y of t h e a l l o y s i n a p p l i c a t i o n s a t high
temperatures.

02, a t . p e r c e n t
Figure 4. Phase diagram of a l l o y s of t h e system
Ti-O2 (based on t h e d a t a of t h e p r e s e n t work).
o, s t r u c t u r e of t h e a s o l i d s o l u t i o n ; @ ,
phase;^, a + 6 phase.
The p e r t i n e n t d a t a f o r t h e Ti-0

a+

system which a r e a v a i l a b l e i n t h e l i t e r a -

t u r e a r e s c a r c e and p e r t a i n t o a concentration range of not more t h a n 20 a t .

p e r c e n t 02.
To solve t h i s problem, we undertook d e t a i l e d i n v e s t i g a t i o n s of t h e thermal
expansion of t h e a l l o y s of t h e Ti-O2 system i n t h e concentration range from
zero t o 32 a t - p e r c e n t O2 a t temperatures up t o 800'.

This study was made with

an i n d i c a t o r d i l a t o m e t e r ( r e f . 20), using specimens quenched from 800'

soaking f o r 1000 h r s .
The heating was c a r r i e d o u t a t t h e r a t e of

4 deg/min.

after

I n o r d e r t o compare t h e Ti-O2 system w i t h t h e e q u i l i b r i u m phase diagram

111 on

( f i g . ?a), w e show t h e dependence of t h e r a t i o A

a l l o y a t 100, 200, 300, 400, 500, 600, 700 and 800'

t h e composition of t h e
( f i g . 5b).

It follows from t h i s f i g u r e t h a t a l l t h e isotherms a r e q u a l i t a t i v e l y s i m i l a r i n c h a r a c t e r . A t f i r s t , when t i t a n i u m i s alloyed w i t h oxygen, t h e thermal

expansion a t every given temperature shows a c e r t a i n decrease. A r e l a t i v e l y
s l i g h t minimum corresponds t o t h e composition Ti6O. A f u r t h e r r i s e i n oxygen
content causes an i n c r e a s e i n thermal expansion up t o 23 a t . p e r c e n t 0
t h i s i s followed by a p r e c i p i t o u s d e c l i n e .
sponds t o t h e composition T i 0.

A marked s i n g u l a r minimum c o r r e -

10

75

2' and

ZLI

25 3 U

35

02, a t . percent
Figure 5. Comparison w i t h t h e equilibrium phase
diagram ( a ) of t h e dependence of t h e thermal expansion ( b ) and i t s c o e f f i c i e n t ( c ) on t h e comp o s i t i o n of a l l o y s of t h e system Ti-02.

From t h e s e d a t a , values of t h e c o e f f i c i e n t of thermal expansion a a s a

f u n c t i o n of t h e composition f o r t h e temperature range of 20-loo0 were c a l c u l a t e d
(fig.
5 c ) . It follows from t h i s f i g u r e t h a t t h e concentration dependence a i s
q u a l i t a t i v e l y s i m i l a r i n c h a r a c t e r t o t h e dependence of A 1/1 on t h e composition
( f i g . 5b).
The d a t a obtained on t h e thermal expansion of a l l o y s o f t h e Ti-O2 system
over a wide concentration range l e a d t o t h e conclusion t h a t when t i t a n i u m i s
alloyed w i t h oxygen, t h e s t a b i l i t y of t h e chemical bond i n t h e a l l o y s i n c r e a s e s
up t o 14.5 a t . p e r c e n t 02. The c h a r a c t e r o f t h e concentration dependence of
t h i s c h a r a c t e r i s t i c i s d i s t i n g u i s h e d by t h e presence of s p e c i f i c p o i n t s eorresponding t o t h e compounds Ti60 and T i 0.

It should be noted t h a t t h e compound T i 0 i s p a r t i c u l a r l y c h a r a c t e r i z e d by

sharp s i n g u l a r extrema of t h e "composition-property'' curves; t h i s f e a t u r e s e t s

it a p a r t a s a chemical s p e c i e s whose i n t e r a t o m i c bonds i n t h e c r y s t a l l a t t i c e

a r e very s t r o n g .
I n connection w i t h t h e i n v e s t i g a t e d novel c h a r a c t e r of t h e chemical i n t e r a c t i o n and phase equilibrium i n t h e Ti-O2 system, t h e s t u d y of t h e i n f l u e n c e of
oxygen on t h e creep of t i t a n i u m a t various temperatures appeared of g r e a t i n t e r e s t . I n c o n t r a s t t o t h e s t u d i e s of o t h e r authors ( r e f s . 1-4)) t h i s p r o p e r t y
was s t u d i e d over a wide range of oxygen concentrations (up t o 18 a t . p e r c e n t ) .
3,

To t h i s end, a l l o y s were prepared containing 0.02, 0.39, 0.75,

Alloys containing more t h a n

4, 8, l o , 15 and 18 a t , p e r c e n t 02.

O2 were prepared by t h e powder method a t a s i n t e r i n g temperature of

Alloys of a l l compositions were annealed a t 800'

cooled from t h i s temperature.

1.25, 1.66,
4 at.percent

1500~.

f o r 200 h r and were slowly

T e s t s f o r h o t hardness were made w i t h a VIM-1 u n i t a t p r e s s u r e s of 10-3-

mm Hg.
mond pyramid
The d u r a t i o n
measurements

The hardness was determined by indenting t h e specimen w i t h a d i a The load on t h e i n d e n t e r was 1 kg.
having a l e a p angle of 136'.
of deformation a t each temperature was 0.5, 5 and 50 min. The
were made a t 300, 400, 500, 600 and 700 ( t a b l e 1).

The r e s u l t s of t h e measurements were t r e a t e d g r a p h i c a l l y by p l o t t i n g t h e

diagonal of t h e i n d e n t a t i o n versus l o g time f o r various temperatures. It was
thus e s t a b l i s h e d t h a t t h e time dependence of t h e s i z e of t h e diagonal of t h e
i n d e n t a t i o n a t each temperature i s described f a i r l y r i g o r o u s l y by t h e equation

where a and b a r e parameters dependent on t h e n a t u r e of t h e a l l o y , t h e t e s t i n g

temperature and t h e l o a d on t h e i n d e n t e r ; T i s t h e t e s t i n g time.
Parameters a and b were determined ( t a b l e 2 ) from t h e working graphs f o r
t h e dependence of t h e logarithm of t h e holding time under load.
On t h e b a s i s of t h e s e d a t a and from t h e equation

proposed i n r e f e r e n c e s 22 and 23, a c a l c u l a t i o n was made of t h e r a t e of creep

a t t h e i n s t a n t when a given value of t h e i n d e n t a t i o n diameter was reached.
I n r e f e r e n c e s 2 1 and 22 it was shown t h a t t h e concentration dependence of
t h e l o g of t h e r a t e of creep f o r a s e r i e s of a l l o y s was i n q u a l i t a t i v e agreement w i t h t h e concentration dependence of t h e r a t e of creep obtained during
extension.
Values o f l o g Vd of a l l o y s of t h e Ti-O2 system f o r d = 0.12 mm ( a t 300,
400 and 500') and d = 0.18 mm ( a t 600 and 700),
a r e shown i n Table 2.

c a l c u l a t e d from e q u a t i o n ( 2 )

We s h a l l compare t h e concentration dependence of t h e l o g of t h e r a t e of

creep, l o g Vd ( f i g s . 6b and c ) , w i t h t h e equilibrium phase diagram of t h e system ~ i - (0f i~g . 6 a ) .
The concentration dependences of l o g V shown on t h e graph give a c l e a r
d

r e p r e s e n t a t i o n o f t h e behavior of t h e a l l o y s of t h e Ti-O2 system a t h i g h temp e r a t u r e s under load. It should be noted t h a t i n an a n a l y s i s of t h e s e r e s u l t s ,

t h e h i g h e s t s t a b i l i t y of t h e a l l o y s under load corresponds t o t h e lowest negat i v e values of l o g Vd.
A t 300, t h e isotherm of l o g Vd i s c h a r a c t e r i z e d by an a p p r e c i a b l e drop i n

t h e concentration range from zero t o 2 a t . p e r c e n t , where oxygen has p r a c t i c a l l y

no i n f l u e n c e on t h e change i n l o g Vd, and hence, on t h e s t a b i l i t y of t h e a l l o y s
under load.
A f u r t h e r i n c r e a s e i n oxygen content causes a sharp drop on t h e curve
representing t h e concentration dependence of l o g Vd; t h i s corresponds t o an

i n c r e a s e i n t h e s t a b i l i t y of t h e a l l o y s under load, and l o g V

becomes

4 times

smaller than i n pure titanium. A comparison of t h i s curve w i t h t h e e q u i l i b r i u m

ddodooooooo

"
"
"
"
"
"
"
0
0
0
0
-

m w ~ n ~ ~ n + m o w ~ m
0W*~?nlNwW~-bb

"

12

15
.

18

02, a t , p e r c e n t
Figure 6. Comparison of t h e equilibrium phase
diagram w i t h t h e dependence of t h e creep r a t e on
t h e composition of t h e a l l o y s of t h e system Ti-02.
phase diagram of t h e Ti-O2 system shows t h a t a sharp i n c r e a s e i n t h e r e s i s t a n c e
t o p l a s t i c deformation, according t o t h e physicochemical t h e o r y of hightemperature s t r e n g t h ( r e f . 23)) i s a s s o c i a t e d w i t h a s h i f t t o t h e two-phase
region (a + y ) , i n which t h e second ( y ) phase i s a s o l i d s o l u t i o n based on t h e
compound Ti60 and belonging t o t h e c l a s s of Kurnakovls compounds.
The isotherms of l o g Vd a t 400, 500 and 6000 a r e completely s i m i l a r i n
c h a r a c t e r , and i n t h e concentration range of 2-8 a t . p e r c e n t 0 t h e r e i s even
2
observed a tendency toward an i n c r e a s e i n l o g V

o r a decrease i n t h e r e s i s t -

ance t o t h e p l a s t i c deformation of t h e a l l o y s a t t h e s e temperatures.

The isotherm of l o g Vd a t 7000 f o r t h e a l l o y w i t h 10 a t . p e r c e n t (3.58 w t
p e r c e n t ) O2 does not show any i n c r e a s e i n t h e r e s i s t a n c e t o p l a s t i c deformation,

a s i n t h e case of o t h e r temperatures, and t h i s again corresponds t o t h e e s t a b l i s h e d phase diagram of t h e Ti-O2 system, s i n c e a t 700' t h e a l l o y w i t h 10 a t .
percent O2 remains a single-phase a l l o y .
Thus, a complete c o r r e l a t i o n i s observed between t h e n a t u r e of t h e chemic a l i n t e r a c t i o n i n t h e Ti-O2 system, t h e type of "composition-creeptt diagram
a t various temperatures, and t h e c h a r a c t e r of t h e atomic i n t e r a c t i o n i n t h i s
system.

Summary
1. Methods of m i c r o s t r u c t u r a l and x - r a y s t r u c t u r a l a n a l y s i s a s w e l l a s
measurements of microhardness, e l e c t r i c a l r e s i s t a n c e , and temf were used t o
study t h e a l l o y s of t h e Ti-O2 system quenched a f t e r annealing a t v a r i o u s tem-

p e r a t u r e s i n t h e concentration range of zero t o 35 a t e p e r c e n t 02.

2. Results of t h e s e i n v e s t i g a t i o n s and t h e "composition-propertyt' d i a grams obtained made it p o s s i b l e t o e s t a b l i s h t h e e x i s t e n c e of t h e new compounds
Ti60 and T i 0.
3
3. The c o n c e n t r a t i o n and temperature l i m i t s of t h e e x i s t e n c e of t h e s e
compounds were determined, and a new e q u i l i b r i u m diagram of t h e Ti-O2 system
was proposed.

The compound Ti60 i s s t a b l e up t o 820-830, while t h e compound

T i 0 i s thought t o be s t a b l e above 1 4 0 0 ~ . The compositions of t h e compounds

3
should be c h a r a c t e r i z e d by a maximum degree of ordering of oxygen atoms i n t h e
l a t t i c e of t h e a s o l i d s o l u t i o n .

4.

The thermal expansion of t h e a l l o y s of t h e Ti-O2 system was s t u d i e d

over a wide temperature and concentration range. On t h e b a s i s of t h e d a t a obtained, t h e dependence of t h e c o e f f i c i e n t of thermal expansion on t h e composit i o n of t h e a l l o y s of t h e Ti-O2 system w a s e s t a b l i s h e d . Analysis of t h e conc e n t r a t i o n dependence of t h i s p r o p e r t y l e d t o t h e conclusion t h a t t h e s t a b i l i t y
of t h e chemical bond between t h e atoms of t i t a n i u m and oxygen i n c r e a s e s i n t h e
c r y s t a l l a t t i c e of a l l o y s and compounds T i 0 and T i 0.
6
3

5 . The h o t hardness of t h e a l l o y s of t h e Ti-O2 system were s t u d i e d i n t h e

concentration range of zero t o 18 a t - p e r c e n t and i n t h e temperature range of
300-700 f o r various holding times under load a t each temperature. From t h e
d a t a obtained, t h e r a t e s of p l a s t i c flow of t h e a l l o y s of t h i s system a t t h e
i n s t a n t when a given value of t h e i n d e n t a t i o n s i z e was reached were c a l c u l a t e d .

6. The general nature of the influence of oxygen on the behavior of titanium under load at various temperatures was established, and a correlation between this dependence and the new equilibrium phase diagram of the Ti-O2 system
was noted.
Finally, the authors express their thanks to T. F. Zhuchkova, who was of
great assistance in the execution of this work.
REFERENCES
1. Borisova, A. A.
p. 23, 1960.

Coll. "TitanSum and Its Alloys," Izd-vo AH SSSR, No. 3,

2. Jehknis, A. and Worher, H. J. Inst. Metals, Vol. 80, No.

4, p. 157, 1951.

3. Yakimova, A. Ya. Influence of Hydrogen and Oxygen on the Properties and

Structure of Titanium Alloys. Author's abstract of candidate's dissertation (~li~aniye
vodoroda i kisloroda na svoystva i struktum
Institut metallurgii imeni
titanovykh splavov. Avtoref kand diss )
A. A. Baykova (A. A. Baykov Institute of ~etallurgy),Moscow, 1959.

..

4. Suiter, J. J. Inst. Metals, Vol. 83, part 10, p. 460, June 1955.
5. Hansen, M. and Anderko, K. Structure of Binary Alloys (Struktura dvoynykh
splavov). Metallurgizdat, Vol. 2, 1962.
6.. E;hrlich, P.

P, z. Anorg. Chem., Val.

247, p. 53, 1941.

7. Bamps, E., Kessler, H. and Hansen, M. TASM, Vol. 45, p. 1008, 1953.
8. Anderson, S., Collen, B.,.Kuylenstierna, U. and Magnelli, A. Acta Chem.
&.and., Vol. 7, No. 10; p. 1641, 1957.
9. Nowgtny, H. and Dimakopoulu, E. Monatshf. f. Chem., Vol. 90, No. 5,
P. 620, 1959.
10. Wasilewsky, R. Trans. IUHE, p.

3, November 1957.

11. Makarov, Ye. S. and Kuznetsov, L. M.

NO. 2, p. 170, 1960.

Zhurnal Strukturnoy Khimii, Vol. 1,

Kornilov, I. I. Trudy Komissii po analiticheskoy khimii AN SSSR (~ransactions of the Commission on Analytical Chemistry of the Academy of
Sciences of the USSR), Izd-vo AN SSSR, Vol. 10, p. 18, 1960.

13.

---

Izv. AN SSSR, OTN, Metallurgiya i Gornoye Delo, No. 1, p. 152, 1963.

14. Hurlen, T. J. Inst. Metals, Vol. 89, No. 4, 1960.

5 . Wasilewsky, R. J. Trans.

A m , No.

4, p. 8, 1962.

Kurnakov, N. S. Introduction to Physicochemical Analysis (~vedeniyev

Izd-vo AN SSSR, 1938.
fiziko-khimicheskiy analiz)

Pogodin, S. A. and Anosov, V. A.

Izd-vo AH SSSR, 1947.

Fundamentals of Physicochemical Analysis.

Glazov, V. M. and Vigdorovich, V. N. Microhardness of Metals (~ikrotverdostl

metallov ) Metallurgizdat, 1960.

Kornilov, I. I. and Glazova, V. V.

P. 313, 1963.

Doklady AN SSSR, Vol. 150, No. 2,

Mints, R. S. Zav. lab., No. 12, p. 1526, 1958.

Osipov, K. A. and T'ien Te-chfeng. Izv. AH SSSR, Metallurgiya i Toplivo,
No. 4, P. 77, 1959.
Osipov, K. A. Problems of the Theory and High-Temperature Strength of
Metals and Alloys (Voprosy teorii zharoprochnosti metallov i splavov).
Izd-vo AN SSSR, 1960.
Kornilov, I. I. Physiochemical Principles of High-Temperature Strength
(~iziko-khirnicheskiye
osnovy zharoprochnosti)
Izd-vo f
W SSSR, 1961.

EQUILIBRIUM DIAGRAM OF TEIE: QUATERNARY SYSTESI Ti-Al-Mo-V

E. N. Pylayeva and KO Chih-ming

The study of the phase equilibrium of alloys of the quaternary system

Ti-Al-Mo-V adjacent to 'the titanium vertex of the tetrahedron (fig. 1) is of
theoretical and practical importance, since this system can be used as the
basic multicomponent system for the development of new high-strength and heatresistant alloys of low density.
In its chemical properties, aluminum differs substantially from titanium
and forms limited solid solutions and a series of metallic compounds with its
a and @ modifications (refs. 1-3).
Vanadium and molybdenum are located in the fifth and sixth groups of the
periodic system, close the titanium group,and are close to the latter in atomic
radii, electronegativity and other properties. They are capable of forming
continuous binary and ternary solid solutions with @-Ti and limited solid solutions with a-Ti (refs. 1 and 4). Vanadium and molybdenum are important alloying elements for high-strength titanium alloys having a @ structure.
The position of vanadium and molybdenum in the periodic system in relation
to titanium and their similar chemical properties also account for their similar
behavior in titanium alloys. Thus, for example, the binary systems Ti-Mo and
Ti-V have the same type of phase diagram (ref. 1).
In the ternary system Ti-Mo-V, there is observed a continuous shift of the
@ solid solutions and of the two-phase a + @ region from the system Ti-Mo
to the system Ti-V. This is clearly indicated by the isothermal section of the
ternary system Ti-Mo-V at 600' (fig. 2).

a and

The phase regions a, a + @ and 8 shift from the side of Ti-Mo toward that
of Ti-V, the region of the a solid solution expanding continuously from the
side of Ti-Mo (up to 0.8percent MO) to the side of Ti-V (2 percent V)
The
boundary between the a + @ and @ region passes through the points of 28 percent
Mo in the Ti-Mo system, 31 percent (MO + V) in the Ti- (MO:V = 1:1) system, and
22 percent V in the Ti-V system.

The similarity in the chemical properties of molybdenum and vanadium in relation to titanium explains the possibility of formation of similar phase

diagrams not only in the binary systems Ti-Mo and Ti-V but also in ternary systems in the portion rich in titanium, for example, in the systems Ti-Al-Mo and
Ti-AL-V (refs. 5 and 6).
In order to study the phase equilibrium in the quaternary system Ti-AlMo-V, we investigated the ternary system Ti-A.1-Moand the system Ti-Al- (MO:V =
1:1), which is the section of the concentration tetrahedron of the quaternary
system originating at the edge of the binary system Ti-Al with a constant ratio
of the weight concentration Mo:V = 1:1. The position of these two systems in
the tetrahedron is shown in figure 1 and their investigated portions are shaded.

Figure 1. Concentration tetrahedron of the

quaternary system Ti-A1-Mo-V.

V, wt percent

Mo, wt percent

M o V=7:7

Figure 2. Isothermal section of the

ternary system Ti-Mo-V at 600.

Let us examine (figs. 3 and 4) the isothermal sections at 600' of the systems Ti-Al-Mo and ~i-Al-(MO:V = 1:l). A comparison of the isothermal sections
of these systems at 6000 with the system Ti-Al-V (ref. 6) leads to the conclusion that in these three systems in the portion rich in titanium, the same phase
regions are in equilibrium, namely:
a.

Solid solutions based on a-Ti with a hexagonal close-packed structure;

b.

Solid solutions based on @-Ti with a cubic body-centered structure;

c. Limited y solid solutions based on the compound TiAl with an ordered

face-centered tetragonal structure;

Al, wt percent

Mo, wt

50

Figure 3. Isothermal section of a part of the

ternary system Ti-Al-Mo at 600.

Ti

Al, wt percent

Figure 4. Isothermal section of a part of the

system ~i-Al(MO:V = 1:l) a* 600~.

a + f3, a + y, and f3 + y regions;

d.

Two-phase

e.

Three-phase

a + f3 + y region.

The performed i n v e s t i g a t i o n shows t h a t i n t h e phase-equilibrium tetrahedron

of t h e quaternary system Ti-Al-Mo-V, t h e above-indicated phase regions s h i f t
s t e a d i l y from t h e system Ti-Al-Mo v i a t h e intermediate system Ti-Al- (MO:V = 1:l)
For t h e sake of a c l e a r treatment of t h e process of
toward t h e system Ti-Al-V.
t h i s s h i f t , we s h a l l consider f i v e s e c t i o n s of t h e phase-equilibrium t e t r a h e d r o n
of t h e quaternary system Ti-Al-Mo-V a t 600' with a constant titanium concentrat i o n of 90, 80, 70, 60 and 50 w t percent ( f i g . 5 ) .
The s e c t i o n s w i t h 90 and 80 percent Ti c u t through t h e a and a + f3 phase
regions. I n t h e s h i f t from t h e Ti-Al-Mo system t o t h e Ti-Al-V system, t h e f i e l d
of t h e a s o l i d s o l u t i o n expands continuously from 1 percent Mo t o 2.5 percent V
on t h e s e c t i o n w i t h 90 percent T i and from 1 percent Mo, 3 percent (MO-V)t o 4
percent V on t h e s e c t i o n with 80 percent Ti. The overwhelming majority of t h e s e
sections belong t o t h e a + f3 region.
The s e c t i o n with 70 percent T i shows a + y, a + f3 + y, a + f3 and f3 phase
regions. I n t h e s h i f t from t h e Ti-AX-Mo t o t h e Ti-Al-V system, t h e a + y region
expands, and t h e a + f3 + y region narrows down. Awide f i e l d of t h e a + f3 region i s found i n t h e middle p o r t i o n of t h i s section.
The regions of @ s o l i d s o l u t i o n s , which extend from t h e systems Ti-Al-Mo
and Ti-Al-V, become joined t o g e t h e r on t h i s s e c t i o n .
TL -3L'RL

XL
TL-IgV

YQ%TL

Ti-Zff AL

T~-lOtlo
TL-ZffV 80%Tt Tb-2ff NO TL-3UV ~L'%TL

T~-3ffMO

Figure 5. P a r a l l e l s e c t i o n s of t h e tetrahedron of t h e phase

equilibrium of t h e quaternary system Ti-Al-Mo-V a t 600 a t a
constant titanium concentration of 90, 80, 70, 60 and 50 w t
percent.

The s e c t i o n w i t h 60 p e r c e n t T i i s d i s t i n g u i s h e d by t h e f a c t t h a t it d i s p l a y s simultaneously t h e processes of gradual s h i f t of y, a + y, a + ,6 + y,

a + f3, and (3 regions i n t h e tetrahedron, I n t h e course of t h e s h i f t from t h e
Ti-Al-Mo system t o t h e Ti-Al-V system, t h e region of t h e p phase narrows down
smoothly a t f i r s t , t h e n expands, p a s s i n g through t h e system Ti-Al- (MO:V = 1:1).
A new phase region (p + y region) which s h i f t s s t e a d i l y from t h e Ti-Al-Mo
system t o t h e Ti-A1-V system arlpears on t h e s e c t i o n w i t h 50 p e r c e n t TL. On t h i s
s e c t i o n , i n t h e p o r t i o n adjacent t o t h e s i d e of t h e Ti-Al system of t h e t e t r a hedron, t h e complete s h i f t of t h e i n d i v i d u a l phase regions i s impaired under t h e
influence of a complex i n t e r a c t i o n o f t h e phases a t t h e aluminum v e r t e x of t h e
tetrahedron.

On t h e b a s i s of t h e above i n v e s t i g a t i o n , we p l o t t e d a diagram of t h e phase

equilibrium of t h e quaternary system Ti-Al-V-Mo i n t h e region of a l l o y s r i c h i n
t i t a n i u m a t 600' ( f i g . 6 )

I n t h e phase-equilibrium tetrahedron, t h e volume of t h e a s o l i d s o l u t i o n

i s a d j a c e n t t o t h e s i d e of t h e b i n a r y system Ti-& from zero t o 25 p e r c e n t Al.
The quaternary f3 s o l i d s o l u t i o n i s adjacent t o t h e f a c e of t h e t e r n a r y system
Ti-Mo-V when t h e t o t a l content of aluminum, molybdenum and vanadium i s over 22
p e r c e n t . The quaternary y s o l i d s o l u t i o n based on TiAl extends from t h e binary
system Ti-Al toward t h e i n t e r i o r of t h e tetrahedron. The c e n t r a l p o r t i o n of t h e
t e t r a h e d r o n i s occupied by a two-phase a + p volume. The three-phase a + p + y
volume borders on t h e two-phase a + f3, a + y, and f3 + y volumes and t r a v e r s e s
t h e t e t r a h e d r o n from t h e f a c e of t h e t e r n a r y system Ti-Al-Mo t o t h e f a c e of t h e
t e r n a r y system Ti-Al-V.
Thus, a geometrical r e p r e s e n t a t i o n of t h e studied p o r t i o n of t h e phase equil i b r i u m t e t r a h e d r o n a t 6000 r e v e a l s t h e c h a r a c t e r of t h e i n t e r a c t i o n between t h e
components and c l e a r l y shows t h e expansion of t h e phase regions i n t h e quaterna r y system Ti-Al-Mo-V.

Figure 6. Phase equilibrium diagram of t h e quaternary system

Ti-A1-Mo-V i n t h e region of a l l o y s r i c h i n t i t a n i u m a t 6 0 0 ~ .

REFERENCES
Kornilov, I. I. and Budberg, P. B. Phase Diagrams of Binary and Ternary
Titanium Systems (~iagrammysostoyaniya dvoynykh i troynykh sistem titana).
Publ. Acad. Sci. USSR, p. 22, 1961.
Grum-Grzhimaylo, N. V., Kornilov, I. I., Pylayeva, Ye. N. and Volkova, M. A.
Dokl. AN SSSR, Vol. 137, No. 3, p. 599, 1961.

3. Kornilov, I, I. Metallovedeniye i termicheskaya obrabotka metallov, No. 2,

p. 7, 1963.

4. Kornilov, I. I. and Polyakova, R. S. Izv. AN SSSR, OTN, Metallurgiya i

Toplivo, No. 1, p. 85, 1960.

5. Kornilov, I. I., Pylayeva, Ye. N. and KO Chih-ming. Zh. Neorg. Khim.,

VO~.8, NO. 2, p. 366, 1963.
6. Kornilov, I. I., Pylayeva, Ye. N. and Volkova, M. A, Sb. "Titan i yego
splavy," Publ. Acad. Sci. USSR, No. 7, p. 89, 1962.

PHASE STRUCTURF: OF ALLOYS OF THE SYSTEM Ti-Al-Fe-Cr-Si

A CONSTANT CONTENT OF ALUMINUM AND SILICON

WITH

V. S. Mikheyev and K. P. Myasnikova

I n d u s t r i a l a l l o y s of t h e AT s e r i e s ( r e f . 1) a r e high-strength a l l o y s based
on a-Ti alloyed w i t h aluminum, chromium, i r o n , s i l i c o n and boron. This multicomponent system has been studied i n s e v e r a l works ( r e f s . 2 and 3 ) . I n ref erence 2, a s t u d y was made of t h e system Ti-Al-Cr-Fe-Si-B w i t h a v a r i a b l e cont e n t of aluminum (from zero t o 7.5 w t ~ e r c e n t )and a constant content of
chromium, i r o n and s i l i c o n (0.5 w t p e r c e n t of each a l l o y i n g element). I n
r e f e r e n c e 3 , p h a s e transformations i n t h e system Ti-Al-Cr-Fe-Si w i t h a c o n s t a n t
content of aluminum (6.0 w t ~ e r c e n t )and s i l i c o n (0.3 w t p e r c e n t ) and a
v a r i a b l e content of i r o n and chromium were s t u d i e d .
The o b j e c t of t h e p r e s e n t i n v e s t i g a t i o n was a study of t h e phase e q u i l i b rium i n a l l o y s of t h e s e c t i o n of t h e t e t r a h e d r o n Ti(+0.3 percent Si)-Al-Fe-Cr a t
a constant aluminum content (7.5 w t p e r c e n t ) . I r o n and chromium were introduced
i n t h e p r o p o r t i o n of 3:1, 1:l and 1:3, t h e t o t a l being up t o 30 percent. Hencef o r t h , t h e corresponding r a d i a l s e c t i o n s w i l l be termed s e c t i o n s I, I1 and 111.
The b a s i s f o r t h e p l o t t i n g of t h e equilibrium diagram of t h e a l l o y s of t h e
s e l e c t e d s e c t i o n of t h e five-component system was a method of s p a t i a l representat i o n of p a r t i a l multicomponent systems f o r any given number of components ent e r i n g i n t o t h e composition of t h e s o l i d s o l u t i o n of t h e s o l v e n t ( r e f . 4).
One of t h e v e r t i c e s of t h e concentration t r i a n g l e which we studied was
made up of t h e a s o l i d s o l u t i o n w i t h 7.5 w t p e r c e n t Al an; 0.3 w t p e r c e n t S i ,
and t h e o t h e r two were i r o n and chromium.
The chemical i n t e r a c t i o n of t i t a n i u m w i t h aluminum, chromium, i r o n and
s i l i c o n i n b i n a r y systems and a l s o t h e s t r u c t u r e of t e r n a r y t i t a n i u m a l l o y s a r e
described i n monographs ( r e f s . 5-7).
With t h e above-indicated elements, t i t a n i u m forms a wide region of
solid
s o l u t i o n and a narrow region of a s o l i d s o l u t i o n . As t h e temperature i s lowered,
t h e s o l i d s o l u t i o n based on @-Ti undergoes a e u t e c t o i d transformation w i t h t h e
p r e c i p i t a t i o n of t h e a s o l i d s o l u t i o n and of t h e corresponding i n t e r m e t a l l i c
compounds: T i S i i n t h e system Ti-Si, TiFe i n t h e system Ti-Fe, and TiCr2 i n

5 3

t h e system Ti-Cr.

The s o l u b i l i t y of each of t h e enumerated elements i n a-Ti i s 0.3-0.5 percent a t t h e temperature of t h e eutectoid transformation ( r e f s . 8-10).
Aluminum r a i s e s t h e temperature of t h e polymorphic transformation of titanium and forms a wide region of s o l i d s o l u t i o n s based on a-Ti.

An i n v e s t i g a t i o n of t h e p r o p e r t i e s of a s o l i d s o l u t i o n s i n t h e Ti-A1 system revealed t h e presence of chemical compounds corresponding t o t h e composit i o n s ~ i ~ i lTli ,~l and Ti2Al ( r e f . 11).

I n t h e three-component system Ti-Fe-Cr, t h e Q s o l i d s o l u t i o n i s s t a b l e

over a wide temperature range. I r o n and chromium lower t h e temperature of t h e
p o l p o r p h i c transformation of titanium. The e u t e c t o i d decomposition of t h e
Q phase i s associated w i t h t h e formation of t h e a phase, TiFe and TiCr2 ( r e f .

12).
I n t h e o t h e r t e r n a r y systems Ti-Al-Fe and Ti-Al-Cr, on t h e polythermal
sections a t a constant aluminum content of 7.5 percent, phases based on a- and
@-Ti a r e i n equilibrium with i n t e r m e t a l l i c compounds corresponding t o t h e comp o s i t i o n TiFe i n t h e f i r s t system and T i e r 2 i n t h e second ( r e f s . 1 3 and 14).
S t a r t i n g Materials and Method of Preparation of t h e Alloys
The compositions of t h e investigated a l l o y s a r e shown i n t h e t a b l e . The
s t a r t i n g materials f o r t h e preparation of t h e samples were: TGOO titanium
sponge, e l e c t r o l y t i c chromium, KKL s i l i c o n , A00 aluminum, and i r o n (0.03 percent C; 0.01 percent Mn; 0.008 percent P; t r a c e s of s).
CITENICAIL COMPOSITION OF TIEE AS;LOYS STUDIED (IN w t PERCENT)

-- -.- --

I _ _

Section
I11
I

0,05
0,125
0,25
0,625
1,25
1,875
2,50
3,75
5,O
795

0,05
0,125
0,25
0,625
1,25
1,875
2,50
3,75
5,O
715

Note: A l l a l l o y s contain 0.3 w t p e r c e n t S i

and 7.5 w t percent Al.
Note: A l l commas represesent decimal p o i n t s .

Samples of t h e a l l o y s weighing 20 g were prepared by a r c f u s i o n i n argon.

The weight l o s s was no more than 0 . 3 p e r c e n t . The c a s t samples were forged i n
a i r i n t o rods 7 mm i n diameter a f t e r being heated a t 1 2 0 0 ~ .
The h e a t treatment was c a r r i e d o u t i n s e a
To prevent t h e t i t a n i u m a l l o y s from r e a c t i n g w
i n a tube made of t h i n molybdenum s h e e t .

es.
aced

The h e a t treatment consisted i n annealing

800 and 500 w i t h a holding time of 10, 15, 30

A f t e r annealing a t 1100, 1000 and 800,
quenched i n water, and t h e o t h e r was furnaceThe study of t h e p a r t i a l system was c a r r

u ra1

RKD camera.
Results
annealed s t a t e

on &Ti. The s
phase, w i t h t h
s e c t i o n I, whe
A t 1100~
i n t h e range of concentrations of Fe -t C
c e n t of s e c t i o n s I and I11 and up t o 30 w t percent of
have t h e s t r u c t u r e of t h e ,3 s o l i d s o l u t i o n . Quenching
causes a ,3 a f m a r t e n s i t e transformation ( f i g . l b ) i n
5 w t percent (Fe + ~ r ) I n higher a l l o y s , t h e p phase
+

r from zero t o 20 w t pers e c t i o n 11, t h e a l l o y s

from t h i s temperature
a l l o y s containing up t o
becomes f i x e d ( f i g l c )

I n a l l o y s w i t h 30 w t percent (Fe -t C r ) of s e c t i o n s I and 111, t h e p r e c i p i t a t i o n of a second phase i s observed along t h e boundaries and t h e f i e l d of B
g r a i n s ( f i g . I d and e ) . X-ray d i f f r a c t i o n a n a l y s i s e s t a b l i s h e d t h a t t h e secondary phase p r e c i p i t a t i n g from t h e ,3 s o l i d s o l u t i o n i s t h e i n t e r m e t a l Z i c compound' TiFe ( 6 phase) i n a l l o y s of s e c t i o n I, and i n a l l o y s of s e c t i o n 111, t h e
i n t e r m e t a l l i c compound TiCr2 of hexagonal modification (y phase).

Figure 1. Microstructure of t h e a l l o y s a f t e r various heat treatments,

x 340. a, a l l o y of s e c t i o n I with 30 percent (Fe + c r ) , c a s t ; b , a l l o y
of s e c t i o n I1 with 5 percent (Fe + cr), quenching from l l O O O ; c, a l l o y
of s e c t i o n I with 7.5 percent ( ~ +e cr) a t 1 1 0 0 ~ ;d, a l l o y of s e c t i o n I
with 30 percent (Fe + c r ) , quenching from 1 1 0 0 ~ ;e , a l l o y of s e c t i o n I11
with 30 percent (Fe + c r ) , quenching from 1 1 0 0 ~ ;f , a l l o y of s e c t i o n I
with 2.5 percent (Fe + c r ) , quenching from 10000; g, a l l o y of s e c t i o n I
with 0.2 percent (Fe + Cr), quenching from 800; h, a l l o y of s e c t i o n I1
with 7.5 percent (Fe + C r ) , quenching from 800; i, a l l o y of s e c t i o n I1
with 20 percent ( ~ +e C r ) , quenching from 800'; j, a l l o y of s e c t i o n I11
with 7.5 percent (Fe + C r ) annealing a t 6000.

Figure 1.

(Concluded)

Figure 2a shows an isothermal s e c t i o n of t h e t e t r a h e d r o n T i (+0.3 p e r c e n t

~ i ) - A l - ~ e -w~i trh a constant aluminum content (7.5 w t p e r c e n t ) a t 1 1 0 0 ~ . The
main p o r t i o n of t h e concentration t r i a n g l e i s occupied by t h e five-component f3
s o l i d s o l u t i o n . The boundaries of t h e two-phase regions B + 6 and f3 + y were
n o t a c c u r a t e l y determined, and they a r e t h e r e f o r e represented by broken l i n e s .
The compositions of t h e a l l o y s on t h e isothermal s e c t i o n a t 1100 which
undergo a m a r t e n s i t e transformation a r e marked w i t h crosses.
On quenching from 100oO, t h e a l l o y s containing i r o n and chromium (up t o 2.5
w t p e r c e n t ) t o g e t h e r w i t h t h e /3 and a t phases contain t h e e q u i l i b r i u m a phase
formed a s a r e s u l t of t h e polymorphic f3
a transformation ( f i g l f ) The amount
of t h e a s o l i d s o l u t i o n i n t h e a l l o y s decreases a s t h e sum of i r o n and chromium
increases.

The pure @ s o l i d s o l u t i o n becomes f i x e d i n a l l o y s containing 7-20 w t percent ( ~ +e ~ r of) s e c t i o n I. I n t h e microstructure of a l l o y s w i t h 5 w t pereent

of t h e a l l o y i n g components i n s e c t i o n s I1 and 111, m a r t e n s i t e needles a r e observed; t h e i r h i g h e s t q u a n t i t y i s found i n t h e a l l o y of s e c t i o n 11, a t t h e r a t i o
Fe:Cr = 1:l. An i n c r e a s e i n t h e content of i r o n and chromium i n t h e a l l o y s of
t h e s e s e c t i o n s causes a s t a b i l i z a t i o n of t h e /3 phase. A t 1000, t h e region of
e x i s t e n c e of t h e @ s o l i d s o l u t i o n narrows down considerably owing t o t h e appearance of t h e two-phase a + B region and t h e expansion of both t h e @ + 6 and
f3 + y regions as a r e s u l t of a decrease i n t h e s o l u b i l i t y of t h e i n t e r m e t a l l i c
compounds i n p-Ti w i t h increasing temperature ( f i g 2b).

Fe

Cr

Fe

Cr

Figure 2. Isothermal s e c t i o n s of t h e t e t r a h e d r o n :
a, a t 1 , 1 0 0 ~ b,
; a t 1 0 0 0 ~ ;c, a t 8 0 0 ~ ; d, a t 5000.
A f t e r annealing a t 800 and quenching from t h i s temperature, t h e a l l o y s
r i c h i n t i t a n i u m and containing up t o 0 . 2 w t p e r c e n t ( ~ +e ~ r have
)
t h e polyI
n
t
h
e
concentration
h e d r a l s t r u c t u r e of t h e a s o l i d s o l u t i o n ( f i g . l g ) .
range of i r o n and chromium of 0.5-15 w t percent, a l l t h e a l l o y s c o n s i s t of two
phases ( a + 8 ) .
It should be noted t h a t t h e microstructure of a l l o y s w i t h 7.5 w t
( ~ +e ~ r r)e f l e c t s t h e p e r i t e c t o i d c h a r a c t e r of t h e i n t e r a c t i o n of t h e
components ( f i g . l h )
This may be a confirmation of t h e phase diagram
proposed by Zwicker e t a l . ( r e f . 1 5 ) , w i t h a p e r i t e c t o i d n a t u r e of t h e
t i o n of t h e a phase by t h e r e a c t i o n 8 + a2 + a.

percent
phase
of Ti-A1
forma-

However, t h e a v a i l a b l e d a t a p e r t a i n i n g t o t h i s problem a r e i n s u f f i c i e n t t o
allow any d e f i n i t i v e conclusions. A f u r t h e r s t u d y of t h e phase transformations
i n t h e a s o l i d s o l u t i o n of t i t a n i u m i n binary, t e r n a r y and multicomponent systems w i t h aluminum i s necessary.
Alloys w i t h a high t o t a l content of i r o n and chromium (20-30 w t p e r c e n t )
have a two-phase s t r u c t u r e 8 + 6 ( a l l o y s of s e c t i o n I) o r 8 + y ( a l l o y s of

s e c t i o n 111) o r a three-phase s t r u c t u r e f3 + 6 + y ( a l l o y s of s e c t i o n 11). A

c h a r a c t e r i s t i c s t r u c t u r e of t h e three-phase s t a t e i s shown i n f i g u r e li.
I n t h e s t u d y of t h e microstructure of a l l o y s quenched from 800, no s i n g l e phase s t r u c t u r e of t h e f3 s o l i d s o l u t i o n was observed, probably because we d i d
n o t i n v e s t i g a t e t h e compositions of a l l o y s w i t h 13-20 w t percent ( ~ +e C r ) .
On t h e b a s i s of t h e s t u d i e s made i n r e f e r e n c e 3 and d a t a of m i c r o s t r u c t u r a l
and x-ray s t r u c t u r a l a n a l y s i s on t h e phase e q u i l i b r i u m i n a l l o y s w i t h h i g h e r o r
lower content of i r o n o r chromium, it i s p o s s i b l e t o p o s t u l a t e t h e e x i s t e n c e of
a narrow region of a single-phase f3 s o l i d s o l u t i o n on t h e isothermal s e c t i o n a t
800.

Figure 2c shows a phase diagram of t h e s e c t i o n of t h e t e t r a h e d r o n T i (c0.3

percent ~ i ) - A l - C r - ~ a
e t 800'.
The five-component @ s o l i d s o l u t i o n a t t h i s temperature i s i n a two-phase
and three-phase e q u i l i b r i u m w i t h t h e a + y and 6 phases. The maximum s o l u b i l i t y of t h e sum of i r o n and chromium a t 800' i n t h e five-component a s o l i d s o l u t i o n amounts t o no more than 0.4 w t percent.
Long annealing f o r 750 h r a t 500' l e a d s t o a complete e u t e c t o i d decomposit i o n of t h e @ s o l i d s o l u t i o n ( f i g . 1 3 ) . According t o t h e x-ray s t r u c t u r a l analy s i s , a l l t h e a l l o y s a t 500 have a three-phase s t r u c t u r e a + S + y.
A phase diagram a t 500 i s shown i n f i g u r e 2d.

Thus, t h e i n v e s t i g a t i o n of t h e five-component system Ti-Al-Fe-Cr-Si cont a i n i n g up t o 30 p e r c e n t ( ~ +e ~ r a)t 1100, 1000, 800 and 500 has shown t h a t
a and f3 s o l i d s o l u t i o n s and i n t e r m e t a l l i c phases TiFe and TiCr2 a r e formed i n
t h i s system. However, a more complex c h a r a c t e r of i n t e r a c t i o n can be p o s t u l a t e d
i n t h i s system. I n p a r t i c u l a r , a s was i n d i c a t e d above, t h e formation of t h e
chemical compound T i Al (a2phase) i s p o s s i b l e . Because t h e n a t u r e of t h e i n -

t e r a c t i o n i n t h e b i n a r y system Ti-Al i n t h e region of t h e a s o l i d s o l u t i o n has

n o t been d e f i n i t e l y e s t a b l i s h e d , and t h e i n f l u e n c e of i r o n o r chromium i n t h e
three-component systems Ti-Al-Fe and Ti-Al-Cr has not been elucidated, i n p l o t t i n g t h e isothermal s e c t i o n s we d i d not t a k e i n t o account t h e regions of phase
e q u i l i b r i a w i t h t h e a2 phase.
The i n v e s t i g a t i o n which was c a r r i e d o u t makes it p o s s i b l e t o draw some
conclusions w i t h regard t o t h e i n f l u e n c e of aluminum on t h e chemical i n t e r a c t i o n of t i t a n i u m w i t h chromium and i r o n . Aluminum r a i s e s t h e temperature of
t h e polymorphic transformation, a s i n d i c a t e d by t h e phase e q u i l i b r i a on t h e
isothermal s e c t i o n s a t 1000 and 8 0 0 ~ . Furthermore, aluminum decreases t h e solub i l i t y of t h e i n t e r m e t a l l i c phases i n @-Ti, and a s a r e s u l t , the boundaries of
t h e two-phase (3 + S and f3 + y regions w i t h t h e single-phase region of t h e p
phase s h i f t toward a lower t o t a l content of i r o n and chromium a s t h e c o n t e n t of
aluminum i n t h e a l l o y s i n c r e a s e s ( r e f s . 3 and 1 2 ) .

Hardness of the Alloys

The hardness of the alloys was measured on samples quenched from 1000 and

800' and annealed at 500.

The hardness of the alloys versus their composition is shown graphically in
figure 3.
The maximum hardness is exhibited by alloys containing 2.5 wt percent (Fe -t
~ r )of sections I and I11 and 5 wt percent (Fe + Cr) of section 11.
The most pronounced
martensite decomposition of (3 grains is observed in
these alloys, and this is what causes such an increase in hardness.
The hardest alloy was found to be the one containing 5 wt percent (Fe +
Cr) of section 11. It is interesting to note that in the ternary system
Ti-Fe-Cr, the maximum hardness in the quenched state is also displayed by alloys
e Cr) (ref.
with the ratio Fe :Cr = 1:1 at a content of about 5 wt percent ( ~ t12).
The minimum on the curves representing the dependence of the hardness on
in the
the composition corresponds to a content of 7.5 wt percent (Fe + ~ r )
alloys. These alloys have the structure of a fixed (3 solid solution. A further
increase in the content of alloying components in the /3 phase promotes an increase in hardness.
At 800, the change in the hardness of the alloys as a function of composition follows the phase transformations in the system.
In the region of the a solid solution, the hardness rises with the sum of
iron and chromium, reaching maximum values at the limit of maximum solubility
of the alloying elements in a-Ti.

Fe

Cr, wt percent

Figure 3. Hardness of the alloys versus composition and temperature:

a, section I, Fe:Cr = 3:l; b, section 11, Fe:Cr = 1:l; c, section 111,
Fe:Cr = 1:3; 1, alloys quenched from 1000~;2, alloys quenched from
800';
3, alloys annealed at 500~.

The appearance of t h e @ phase and i n c r e a s e i n i t s q u a n t i t y cause a decrease

i n t h e hardness of t h e a l l o y s . However, i n a l l o y s containing from 7.5 w t p e r cent (Fe +- ~ r ()a s w e l l a s on t h e llcomposition-hardnessl'
curve a t 1 0 0 0 ~ )t h~e
hardness i n c r e a s e s , s i n c e t h e @ p h a s e i s hardened by t h e alloying.
The curve
composition a t
800'.
This i s
r e s u l t i n g from
a l l o y s a t 500
800.

r e p r e s e n t i n g t h e dependence of t h e hardness of t h e a l l o y on i t s
500' l i e s above an analogous curve f o r a l l o y s quenched from
explained by t h e presence i n t h e a l l o y s of i n t e r m e t a l l i c phases
t h e e u t e c t o i d decomposition of t h e @ phase. The hardness of t h e
i n t h e region of a s o l i d s o l u t i o n v a r i e s as does t h e hardness a t

I n t h e three-phase region, because of t h e i n c r e a s e i n t h e content of t h e

i n t e r m e t a l l i c compounds TiFe and TiCr2 i n t h e a l l o y s , t h e hardness should i n crease. No such r e g u l a r change i n hardness i s observed on curve 3 ( f i g . 3 ) .
)
The a l l o y s of a l l t h e s e c t i o n s containing about 1 0 w t percent (Fe + ~ r have
minimum values of t h e hardness. This anomalous c h a r a c t e r of t h e dependence of
t h e hardness on t h e composition can be a t t r i b u t e d e i t h e r t o an incomplete eut e c t o i d decomposition of t h e p phase o r t o t h e formation of t h e phase T i Al.

Electrical Resistivity
The e l e c t r i c a l r e s i s t i v i t y was s t u d i e d on samples 5 mrn i n diameter quenched
from 1000 and 800 and annealed f o r a long time a t 500.
Results of t h e measurements a r e shown g r a p h i c a l l y i n f i g u r e

4,

The phase transformations i n t h e a l l o y s a t 1 0 0 0 ~a r e r e f l e c t e d by t h e

curve r e p r e s e n t i n g t h e e l e c t r i c a l r e s i s t i v i t y versus t h e composition.

Figure 4. E l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s versus composition and

temperature: a , s e c t i o n I, Fe:Cr = 3 : l ; b, s e c t i o n 11, Fe:Cr = 1:l;
c , s e c t i o n 111, Fe: C r = 1:3; 1, a l l o y s quenched from 1 0 0 0 ~ ;2, a l l o y s
quenched from 8 0 0 ~ ;3 a l l o y s a n n e d e d a t 500'.

I n t h e two-phase a + f3 region, t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s
changes i n s i g n i f i c a n t l y when they a r e alloyed with i r o n o r chromium (up t o 2.5
w t percent). The s h i f t t o t h e single-phase f3 region i s associated w i t h an
abrupt increase i n t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s , probably due t o a
maximum s t r e s s condition of t h e f3 grains during t h e formation of t h e a' phase.
A f u r t h e r increase i n t h e content of i r o n and chromium has l i t t l e e f f e c t on
t h e change i n t h e e l e c t r i c a l r e s i s t i v i t y of t h e alloys.
A t 8000, the curve of composition versus e l e c t r i c a l r e s i s t i v i t y r i s e s
monotonically up t o a content of 7.5 w t percent ( ~ +e ~ r ) ,then descends. This
p a t t e r n of change i n t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s a t 800 may be
due t o t h e transformations discussed above.

The eutectoid decomposition of t h e f3 phase a t 500 has a n e g l i g i b l e i n fluence on t h e dependence of t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s on t h e

composition.
Thus, t h e g r e a t e s t influence on t h e dependence of t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s on t h e composition i s exerted by t h e s t r u c t u r a l s t r e s s condit i o n of t h e g r a i n s of t h e f3 s o l i d s o l u t i o n during quenching a s a r e s u l t of t h e
formation of metastable phases.
FEF%RENCES

I.

Kornilov, I. I., Mikheyev, V. S., Chernova, T. S. and Markovich, K. P.

Coll. "Titanium and I t s Alloys," Izd-vo AN SSSR, No. 7, p. 140,
1962.

2.

Kornilov, I. I., Mikheyev, V. S. and Chernova, T. S.

Metallurgiya i Toplivo, No. 3, p. 70, 1960.

3.

Kornilov, I. I. and Boriskina, N. G. Coll. "Titanium and I t s Alloys,"

Izd-vo AN SSSR, No. 10, p. 86, 1963.

4.

Kornilov, I. I.

5. McQuillen, A.

Izv. AN SSSR, E N ,

Dokl. AlT SSSR, Vol. 81, No. 2, p. 191, 1951.

D, and McQuillen, M. K.

Titanium i it an)

, Metallurgizdat,

1958

6. Yeremenko, V. N.

Titanium and I t s Alloys

AN UkSSR, Kiev, 1960.

7.

i it an

i yego splavy).

Izd-vo

Kornilov, I. I. and Budberg, P. B. Phase Diagrams of Binary and Ternary

Titanium Systems ( ~ i a g r a m ysostoyaniya dvoynykh i troynykh sistem
t i t a n a ) . VINITI (All-union I n s t i t u t e of S c i e n t i f i c and Technical Information), MOSCOW, 1960.

8. Boriskina, N. G. and Myasnikova, K. P.

AN SSSR, No. 7, p. 61, 1962.

Coll. "Titan i yego splavy," Izd-vo

Mikheyev, V. S. and Chernova, T. S.

AN SSSR, No. 7, p. 68, 1962.

Coll. "Titan i yego splavy," Izd-vo

Pylayeva, Ye. N. and Volkova, M. A.

AN SSSR, NO. 7, p. 74, 1962.

Coll. "Titan i yego splavy," Izd-vo

Grum-Grzhimaylo, N. V., Kornilov, I. I., Pylayeva, Ye. N, and Volkova, M. A.

Dokl. AN SSSR, Vol. 137, No. 3) p. 599, 1961.
Van Thyne, Kessler, H. and Hansen, M.

J. Metals, Vol.

5, p. 1209, 1953.

Kornilov, I. I., Pylayeva, Ye. N. and Volkova, M. A.

cheskoy Khimii, Vol. 2, No. 6, p. 1391, 1958.

Zhurnal Neorgani-

Kornilov, I. I., Mikheyev, V. S. and Chernova, T. S.

V O ~ . 3, NO. 3, p. 786, 1958.

Zh. neorg. khim.,

Schulz, E, and Zwicker, U.

Zs. Metallkunde, Vol.

47, p. 529,

STUDY OF THE ALLOYS OF THE TERNARY SYSTEM Ti-Al-Zr

Ye. N. Pylayeva and M. A. Volkova

The study of the phase diagram of the ternary system Ti-Al-Zr is of great
practical interest because this system should contain a wide region of solid
solutions which may serve as the basis for the development of alloys operating
at high temperatures. Literature data pertaining to phase diagrams of this system are lacking. In reference 1, a study was made of the mechanical properties
of ternary alloys of titanium with aluminum and zirconium, and it was found that
alloying of a-Ti with aluminum and zirconium (up to 8-18percent Al + ~ r )
raises
the high-temperature strength of the alloys of the system at temperatures of
20-650~. We have studied the alloys of the ternary system Ti-Al-Zr along the
section originating from the vertex of pure zirconium and extending to the composition of the alloy of the binary system Ti-Al, containing 9 percent A l and
91 percent Ti (the alloy has the hexagonal structure of a-~i). In composition,
(8.7perthis alloy corresponds approximately to the proposed compound
cent Al; 91.3 percent ~i). The possibility of the existence of the compound
Ti6A1 was demonstrated by results of measurements of the Hall constant for al"

loys of the system Ti-Al (ref. 2). The problem of the existence of this compound has not been definitively solved.
The system Ti-& is characterized by a complex chemical interaction of the
components, which form a series of metallic compounds, and the literature contains contradictory views concerning the stoichiometric composition of these
compounds ( ~ i ~ A(ref.
1
2), Ti Al (refs. 2-4), Ti Al (ref. 5)) Ti2& (refs. 4
3
3 2

Titanium and zirconium (a and f3 modifications) form a continuous series of

solid solutions with a minimum (fig. 1).
Zirconium and aluminum form a phase diagram with a limited solubility and
several metallic compounds: Zrgil13, Zr2Al, Zr3Al, etc. (ref. 6).
In this work, use was made of methods of thermal and microstructural analysis, and the electrical resistivity and hardness of the alloys were determined.

Figure 1. Concentration t r i a n g l e of a
p a r t of t h e t e r n a r y system Ti-A1-Zr.
The s t a r t i n g m a t e r i a l s were:
AVO00 aluminum.

iodide zirconium, TGOO titanium sponge, and

The compositions of t h e a l l o y s studied were a s follows:

COMPOSITION OF U O Y S (IN TRE INITIAS, MLXTW)

(IN w t

PERCENT),

I n order t o study t h e microstructure and hardness, t h e a l l o y s were melted

i n an a r c furnace i n argon; t o study t h e e l e c t r i c a l r e s i s t i v i t y , t h e a l l o y s
were prepared by f l o a t i n g zone-melting i n helium. The d i f f e r e n c e i n t h e weight
of t h e samples before and a f t e r t h e f u s i o n did not exceed 0.5 percent, and f o r
t h i s reason t h e a l l o y s were not analyzed chemically.
The heat treatment of t h e a l l o y s was a s follows: 1200, 6 hr; l l O o O , 50
h r ; 100oO, 100 hr; 850, 200 hr; 800, 300 hr; Too0, 300 hr; 600, 400 hr; 500,
750 h r . The a l l o y s were quenched from 1100, 850, 700 and 5 0 0 ~ .

I n order t o determine t h e c r i t i c a l p o i n t of t h e a l l o y s i n t h e s o l i d s t a t e ,
a d i f f e r e n t i a l recording of t h e heating and cooling curves was c a r r i e d o u t with
a Kurnakov pyrometer using samples annealed a s indicated above. The recording
was c a r r i e d o u t i n a i r ( f o r a l l o y s of a l l compositions) and simultaneously i n a
vacuum, i n evacuated and sealed Stepanov quartz v e s s e l s ( f o r c e r t a i n a l l o y
compositions).
For a l l o y s with 70-90 percent Zr, t h e d i f f e r e n c e i n t h e temperatures obtained i n both cases was -30, and f o r a l l o y s with a lower zirconium content,
no more than 20'.
The thermograms displayed thermal e f f e c t s corresponding t o t h e following
phase transformations: on heating, a -' a + @ and on cooling, @ + a + @.The
c r i t i c a l p o i n t s i n t h e s o l i d s t a t e a r e shown on t h e graph of f i g u r e 2.

a + @ transformaAs can be seen from f i g u r e 2, t h e temperature of t h e a

t i o n decreases a s t h e content of zirconium i n t h e a l l o y s r i s e s from zero t o -65
percent, and passes through a minimum a t 460'.
+

The microstructure of t h e a l l o y s was studied on c a s t samples and a f t e r

quenching from 1100, 800 and 500, and i n c e r t a i n a l l o y s a l s o a f t e r quenching
from 850 and 700. The c a s t a l l o y s and t h e majority of t h e a l l o y s quenched from
1 2 0 0 ~have t h e s t r u c t u r e of t h e transformed @ phase. A c h a r a c t e r i s t i c appearance of such a microstructure i s shown i n f i g u r e 3a. A f t e r quenching from 1100,
t h e a l l o y s containing from zero t o 3 percent Z r had an a + a a c i c u l a r s t r u c t u r e
( f i g . 3b), where t h e a c i c u l a r s t r u c t u r e of t h e decomposed a phase i s v i s i b l e between the l i g h t g r a i n s o f t h e @ phase, i.e., a t 1100~
these alloys are i n the
a + @ region.
8, "z78ffff
76Jff

IZflfJ

7Jffff
8ffff
Effff

Z r , w t percent

Figure 2. Polythermal s e c t i o n of t h e t e r n a r y system Ti-Al-Zr:

I , single-phase alloys; 2, two-phase alloys; 3, d a t a of thermal
a n a l y s i s conducted i n a vacuum; 4, d a t a of thermal a n a l y s i s
conducted i n a i r .

After quenching from 800, depending on t h e i r content of zirconium, t h e

a l l o y s d i s p l a y t h e polyhedral s t r u c t u r e of t h e a s o l i d s o l u t i o n ( f i g 3c ) , t h e
s t r u c t u r e of t h e a c i c u l a r a phase ( s i m i l a r t o t h e s t r u c t u r e shown i n f i g u r e 3 a ) ,
and a l s o a mixed s t r u c t u r e of t h e polyhedra of t h e a s o l i d s o l u t i o n and of t h e
a c i c u l a r f3 phase (analogous t o t h e s t r u c t u r e shown i n f i g u r e 3b). The phase comp o s i t i o n of t h e a l l o y s studied by t h e microscopic method i s shown i n f i g u r e 2.

Microstructure of a l l o y s of t h e t e r n a r y system Ti-Al-Zr,

+ 10 percent Z r + 7.8 percent Al;
quenching from 1 1 0 0 ~ ;transformed f3 phase; b, a l l o y of 91 percent
T i + 9 percent A l ; quenching from llOoO, a + transform f3 phase: c,
a l l o y of 82.2 percent T i + 10 percent Z r + 7.8 percent Al; quenching
from 800, a phase; d , a l l o y of 86.8 percent T i + 5 percent Z r + 8.2
percent Al; quenching from 300, a + a2; e, a l l o y of 91 percent T i +
Figure 3.

x 200: a, a l l o y of 82.2 percent T i

9 percent Al; quenching from 800, a + a*.

The m a j o r i t y of t h e a l l o y s quenched from 500' have t h e s t r u c t u r e of t h e a

s o l i d s o l u t i o n . However, i n a l l o y s w i t h 3, 5 and 7 percent Z r , a second phase
p r e c i p i t a t e s . The s t r u c t u r e of t h e a l l o y i n t h i s region i s shown i n f i g u r e 3d.
This phase i s marked a* phase on t h e polythermal s e c t i o n and i s probably based
on t h e m e t a l l i c compound Ti3A1 ( r e f s . 2 and 3 ) .
structure w i

from zero t
smoothly.
The hardness of t h e a l l o y s was measure
w i t h a diamond pyramid a t a load of 1 0 kg.
hardness changes along a curve arched upwar
values of t h e hardness can obviously be ex
phases on quenching from t h e region of t h e
The curve r e p r e s e n t i n g t h e hardness o
curve 2) a l s o shows a hardness maximum whi
went a martensite transformation during t h
/3 s o l i d s o l u t i o n .
s changes along a curve
nce of a continuous
ed s e c t i o n . The t r e n d
of a second phase i n

After quenching from

arched upward ( f i g . 5, curv
s e r i e s of s o l i d s o l u t i o n s i
of t h e curves d i d not show
t h e a l l o y s containing from

Zff

4~7

80

706'

Z r , w t percent

Figure 4. E l e c t r i c a l r e s i s t i v i t y of a l l o y s of the t e r n a r y system

Ti-Al-Zr versus zirconium content: 1, quenching from 1 1 0 0 ~ ;2,
quenching from 800'; 3, quenching from 500.

20

40

BU

701

Z r , w t percent
Figure 5. Dependence of t h e hardness of a l l o y s
of the t e r n a r y system: 1, quenching from 11000;
2, quenching from 800'; 3, quenching from 500.

Summary
1. A study of t h e a l l o y s of t h e t e r n a r y system Ti-Al-Zr along a r a d i a l
s e c t i o n a t a r a t i o Al:Ti = 9:91 by methods of m i c r o s t r u c t u r a l and thermal
a n a l y s i s and determination of t h e e l e c t r i c a l r e s i s t i v i t y and hardness shows
the existence of a continuous s e r i e s of s o l i d s o l u t i o n s , with t h e exception of
t h e a + a2 region adjacent t o t h e a l l o y with 9 percent Al and 91 percent T i
(500, zirconium content ranging from zero t o 10 percent; see f i g u r e 2 ) .

2. A l l t h e a l l o y s of t h i s s e c t i o n undergo a polymorphic transformation

analogous t o t h e transformation i n pure titanium and zirconium and i n t h e system Ti-Zr, t h e change i n t h e temperatures of t h e polymorphic transformation
occurring along curves with a minimum (660') -65 percent ~ r ) .
3. The e l e c t r i c a l r e s i s t i v i t y and hardness of t h e a l l o y s a f t e r quenching
from 1100, 800 and 500' changes along curves protruding upward; t h e maximum
values of t h e hardness correspond t o a l l o y s quenched from t h e region of t h e
s o l i d solution.
REFERlENCES
1. Mikheyev, V. S. and Markovich, K. P. Coll. "Titanium and I t s Alloys,"
Izd-vo AN SSSR, No. 7, p. 114, 1962.

2.

Grum-Grzhimaylo, N. V . , Kornilov, I . I., Pylayeva, Ye. N. and Volkova, M. A.

Dokl. AN SSSR, Vol. 137, No. 3, p. 339, 1961.

3.

Anderko, K , ,
1-957.

4.

Ence, E. and Margolin, H.

Sagel, K. and Zwicker, U.

Zs. Metallkunde, Vol. 48, p.

Trans. AIME, Vol. 221, p. 151, 1961.

57,

5. Sato, T., Huong, Y. C. and Kondo, Y. Sumitomo Light Metal Technical Reports.
Japan, No. 1, 30-35, 1960.
6. McPherson, D, and Hansen, M. Metallography and Binary Systems of Zirconium

(~etallograf
iya i dvoynyye sistemy tsirkoniya) Part 11, Collection of
translated articles, Foreign Literature Publishing House (IL), p. 84,

1955

PHASE EQUILIBRIUM OF ALLOYS OF T m SECTION Ti3Al-Zr

OF THE TERNARY SYSTESI Ti-Al-Zr

I. I. Kornilov, T. T. Nartova and M. M. Savellyeva

The study of the phase diagram of Ti-Al-Zr is of great practical interest

because it can serve as a basis for the development of highly heat-resistant
titanium alloys.
Data on the phase diagram of this system are lacking in the literature.
The binary phase diagrams Ti-Al, Ti-Zr and Zr-Al have been studied by many
authors (ref. 1).
The Ti-Zr phase diagram is characterized by unlimited solubility between
the a and f3 modifications of titaniurn and zirconium (ref. 2).
According to the data of recent investigations, a series of metallic compounds are formed in the system Ti-Al in the region of the a solid solution,
the presence of the compound Ti3Al being the most probable (refs. 3 and 4).
The purpose df the present work was to study the phase equilibrium and
certain properties of the alloys of the system Ti-Zr-Al along a radial section
extending from the zirconium vertex to the side of Ti-Al to an alloy composition corresponding to the compound Ti Al (16 wt percent Al).
3
The indic~tedsection and the compositions of the investigated alloys are
shown on the concentration triangle of a portion of the Ti-Zr-Al system (fig.
1)
The samples were prepared by induction melting in the floating state (ref.

5). The starting materials were iodide titanium (99.87percent purity), iodide

zirconium (99.9 percent purity), and AVO00 aluminum. The chemical composition
of the alloys was checked by weighing the samples before and after fusion. The
loss did not exceed 1 percent.
The samples were subjected to homogenizing annealing in vacuum for 6 hrs
at 1200 and 50 hrs at 1100~.

percent
T L ~ LA

Figure 1. Concentration triangle of a part

of the ternary system Ti-Zr-A1.
The quenching of the homogenized samples in water was carried out under
the following conditions:
OC . .1200
..... 6

Quenching temperature,
Holding time, hours

1100 1000 900 850

50 100 150 O

750 700 500

400 500 750

At the same time, samples of alloys of the same compositions were forged
and subjected to prolonged annealing for 2500 hrs at 800' and for 3000 hrs at
500.
In order to study the alloys of the Ti3Al-Zr section, thermal, microstructural, and x-ray analyses were performed, the temperature of the start of
the fusion was determined, and the dependence of the density, hardness, mlcrohardness and electrical resistance at room temperature on the composition of the
alloys was studied by commonly used techniques. In order to develop the microstructure of the alloys, an etchant of the following composition was employed:
8 pts. glycerin, 1 pt. hydrofluoric acid, 112 pt. nitric acid, and 3-4pts.
water.
We shall examine the characteristic microstructures of the alloys of this
section from various phase regions (fig. 2) and the phase equilibrium diagram
of the section Ti Al-Zr (fig. 3).

In plotting the line of the solids of the Ti Al-Zr section, we used data

obtained from the determination of the temperatures of the start of fusion of

Figure 2. Microstructure of a l l o y containing 20 p e r c e n t Z r , x 200:

a, a l l o y quenched from 1200'; b, a l l o y quenched from 1 1 0 0 ~ ;c, a l l o y
quenched from 500.

I850

10 217 30 40 5I7 60 717 80 30 108

Z r , w t percent

Figure 3. Phase diagram of t h e s e c t i o n T i A l - Z r : 0 , a l l o y

compositions; A, d a t a of thermal a n a l y s i s method due t o
N.S. ~ u r n a k o v ) ;x , d a t a of thermal a n a l y s i s ( o p t i c a l method).

t h e a l l o y s by t h e "drop method." This method involves t h e determination of t h e

temperature of t h e s t a r t of f u s i o n of t h e a l l o y s i n a vacuum by means of an
OP-48 o p t i c a l pyrometer on samples of round c r o s s s e c t i o n having a h o l e 0.8-1
mrn i n diameter and 3-4 mm deep. The o p t i c a l pyrometer recorded t h e time when
t h e hole i n t h e sample was f i l l e d w i t h molten metal. Data obtained from t h e determination of t h e temperatures a t t h e s t a r t of f u s i o n and a microscopic analys i s of t h e c a s t s t r u c t u r e s showed t h a t a l l o y s of t h i s s e c t i o n c r y s t a l l i z e d w i t h
t h e formation of a continuous s e r i e s of f3 s o l i d s o l u t i o n s and t i t a n i u m and z i r conium. Micros t r u c t u r a l a n a l y s i s of a l l o y s quenched from 1200' shows t h a t t h e y
r e t a i n t h e single-phase @-transformed s t r u c t u r e of m a r t e n s i t e type ( f i g . 2a).
The phase transformation temperatures i n the s o l i d s t a t e of t h e a l l o y s of
a 1 analysis using a
t h e T i A l - Z r s e c t i o n were d
3
Kurnakov pyrometer, and s
Thermal a n a l y s i s shows t h
t u r e of t h e polymorphic t
and passes through a mini
firmed by d a t a on t h e mic
temperatures. Two-phase a
( i n t h e range of z
a t 1100~
(20-30 p e r c e n t ) , a t 900' (4

e a l i n g were employed.
a s e s , t h e temperai s s e c t i o n decreases
r. This i s a l s o conuenched from various
served i n t h e a l l o y s

a s e polyhedral s t r u c Alloys quenched f r o

t u r e of t h e a s o l i d s o l u t i o n over t h e e n t i r e s e c t i o n ( f i g . 2c).
X-ray a n a l y s i s confirms t h a t a t low temperatures, t h e a l l o y s of t h e T i Al-

Z r s e c t i o n have t h e single-phase hexagonal s t r u c t u r e of a-Ti o r a - Z r .

The presence of a continuous s e r i e s of s o l i d s o l u t i o n s a t low temperatures

i s a l s o conf inned by t h e "composition-property" diagrams ( f i g 4 ) . The hardness
of t h e a l l o y s changes along a curve w i t h a smooth maximum i n t h e region corresponding t o 60-70 percent Z r . The e l e c t r i c a l r e s i s t a n c e o f t h e same a l l o y s

'a
g E
E

-,

8 -h4- 400
M

---.
?

F -l5 - 300

2-

4 -&7-zoo

2 0.5. 700

20

46'

60

80

76'0

Zr, w t percent

Figure 4. P r o p e r t i e s of a l l o y s of t h e s e c t i o n
T i Al-Zr versus zirconium content.
3

changes in similar fashion as a function of the composition and is characterized

by a smooth change in this property. The density of the alloys of the investigated section changes linearly, rising with increasing zirconium content.
As was shown by the investigations, the chemical interaction of the alloys
of the Ti Al-Zr section is similar to the interaction of titanium and zirconium
3
in the binary system Ti-Zr and is characterized by the presence of a continuous
series of solid solutions based on a- and @-Ti(Zr)

1. Mikheyev, V. S, and Markovich, K. P. Coll. "Titanium and Its Alloys,"

IZ~-voAN SSSR, NO. 7, p. 114, 1962.
2. Hansen, M. Structure of Binary Alloys (~trukturabinarnykh splavov).
Metallurgizdat, Part 1, p. 160, 1941.

3.

Hayes, E. T., Roberson, A. H. and Paasche, 0. S. Rep. Inv. US Bur. Min.,

No. 826, 1951.

4. Duwes, P. J. Inst. Metals., No. 80, p. 525, 1951-1952.

5. Grum-Grzhimaylo, N. V., Kornilov, I. I., Pylayeva, Ye. N. and Volkova, M. A.
~ o k l .AN SSSR, Vol. 137, No. 3, p. 599, 1961.
6. Ense, E. and Margolin, R. Trans.

AIME, Vol. 221, No. 1, p. 151,

1961.

7. Clark, D and Terry, J. C. Bull. Inst. Metals, Vol. 3, p. 116, 1956.

8. Anderko, K., Sagel, K. and Zwicker, U. Zs. Metallkunde, Vol. 48, p. 57,
1957.
9. Fogel (,A. A. Izv. AN SSSR,
1959.

OTN, Metallurgiya i Toplivo, No. 2, p. 24,

10. Kurnakov, N. S Introduction to Physicochemical Analysis (~vedeniyev

fiziko-khimicheskiy analiz). Izd-vo AN SSSR, 1941.

STUDY OF THE PHASE STRUCTURF OF THE U O Y S OF TFE SYSTEM

Ti-Al-Zr K O N G TRE SECTION Ti3Al-Zr

I. I. Kornilov and N. G. Boriskina

Aluminum and zirconium have a d e s i r a b l e i n f l u e n c e on c e r t a i n mechanical

p r o p e r t i e s of t e r n a r y a l l o y s based on a - T i a t room temperature and high temperat u r e s ( r e f . 1). However, t h e l i t e r a t u r e l a c k s d a t a on t h e phase s t r u c t u r e of
t h e a l l o y s of t h e system Ti-Al-Zr, as a r e s u l t of which a more e x t e n s i v e development of a l l o y s of optimum compositions based on t h i s system i s hindered.
Binary phase diagrams Ti-Zr, Zr-Al. and Ti-A1 have now been s t u d i e d i n d e t a i l .
The Ti-Zr system i s characterized by t h e formation of a continuous s e r i e s of
s o l i d s o l u t i o n s based on @-Ti and (3-Zr a t high temperatures and on a - T i and
a - Z r a t low temperatures ( r e f . 2).
Zirconium and aluminum form a complex phase diagram w i t h a l i m i t e d solub i l i t y of aluminum i n (3- and a - Z r and of zirconium and aluminum. These elements
form e i g h t m e t a l l i c compounds ( r e f . 3 ) of which those r i c h e s t i n zirconium correspond t o t h e composition Z r Al, Zr2Al and Z r Al
3
5 3'
The TI-Al system i s characterized by t h e formation of a s e r i e s of m e t a l l i c
compounds : T i m 3 , TiAl and Ti3Al ( r e f s 4 and 5). The authors of r e f e r e n c e s

6 and

7 have e s t a b l i s h e d t h e formation of t h e compound T i 2Al i n t h e system

Ti-&.
C e r t a i n anomalies i n t h e change of t h e Hall e f f e c t of t h e a l l o y s of t h i s
system have enabled t h e authors of r e f e r e n c e 8 t o propose t h e e x i s t e n c e of t h e
compound Ti6&.

To c o n t r i b u t e t o t h e study of t h e a l l o y s of t h e system Ti-Al-Zr ( s e e pp,

46-57) we i n v e s t i g a t e d t h e a l l o y s of t h e s e c t i o n Ti$-Zr.
According t o t h e
d a t a of reference
@-Ti + Ti3A12

7, t h e compound Ti2Al forms by t h e p e r i t e c t o i d r e a c t i o n

Ti$

occurring a t a temperature of approximately 1300-1400~.

The compositions of t h e i n v e s t i g a t e d a l l o y s of t h e s e c t i o n T i A l - Z r a r e
2
shown i n t h e t a b l e . The s t a r t i n g m a t e r i a l s used were iodide zirconium and titanium sponge TGOO, i n which t h e t o t a l i m p u r i t i e s amounted r e s p e c t i v e l y t o 0.3
and 0.18 p e r c e n t , and AVO00 aluminum.

ELE23TRICA.L RFSISTIVITY AID DENSITY VERSUS COMPOSITION

OF TITrnIUM ALLOYS.
Content, w t p e r c e n t
T1

78,O
77,20
75,70
74,10
72,60
70,20
GG,30
(i,40
58,50
54,60
46,80
42,90
39,40
31,20
23,40
15,60
11,70
T,80
3,90
l,Y5

A1

22,O
21,80
21,30
20,OO
20,40
19,80
18,70
17,60
16,50
15,40
13,20
12,lO
41,GO
8,80
6,60
4,40
3,30
2,20
1,10
0,55

Zr

1,00
3,OO
5,OO
7,00
10,OO
15,00
20,OO
25,OO
30,OO
40,00
45,OO
50,OO
00,OO
70,00
80,00
85,OO
90,00
95,OO
97,5

Electrical resistivi t y , ohm.m/mm 2

Density,
g/cm3
ilOO"

800

500

2,1323
2,0745
2,0735
2,0957
2,0522
2,0142
1,546
1,8691
1,8124
1,5260
1,6138
1,2736
1,4534
1,7514
1,2256
1,6063
1,9805
1,5139
1,2165

2,1223
2,0754
2,0705
2,0938
2,0537
1,9983
1,4265

2,1033
2,0634
2,0554
2,0817
2,0456
1,9918
1,3520

1,6834
1,5285
1,5733
1,6952
1,4641
1,7787
1,2603
1,3026
1,4424
1,4547
1,1660

4,0815
4,0998
4,1288
4,1831
4,2154
4,2924
4,3158
4,4585
1,6603 4,5547
1,5283 4,5782
1,5079 4,7660
1,6533 4,7789
1,3947 4,9823
1,6813 5,2389
1,2232 5,3706
1,2613 5,6961
1,4375 5,7739
1,3734 5,9588
1,1369 6,0835

The a l l o y s were prepared by a r c f u s i o n w i t h a nonconsumable e l e c t r o d e i n

argon.
Samples of t h e a l l o y s , sealed i n double q u a r t z ampules under vacuum, were
subjected t o t h e following h e a t treatment: homogenizing annealing a t 1 1 0 0 ~
f o r 1 0 h r s , furnace cooling, and holding under t h e following conditions: 100oO,
A c e r t a i n change i n t h e
25 h r s ; 800, 300 h r s ; 6000, 400 h r s ; 500, 750 h r s
conditions of t h e h e a t treatment of t h e a l l o y s of t h e Ti2Al-Zr s e c t i o n a s com-

pared t o t h e conditions of t h e h e a t treatment of a l l o y s of t h e s e c t i o n s TiGAl-Zr

and T i A l - Z r i s due t o t h e h i g h e r v o l a t i l i t y i n vacuum of t h e components of t h e

a l l o y s of t h e i n v e s t i g a t e d s e c t i o n a t 1200-1100~.
The a l l o y s were s t u d i e d by m i c r o s t m c t u r a l and p a r t l y by x-ray and thermal
analyses. I n a d d i t i o n , t h e e l e c t r i c a l r e s i s t i v i t y and macro- and microhardness
of t h e a l l o y s were measured. Alloys i n t h e c a s t s t a t e and a f t e r quenching ( i n
water w i t h i c e ) from 1100, 800 and 500 were subjected t o t h e m i c r o s t r u c t u r a l
analysis.

M i c r o s t r u c t u r a l a n a l y s i s of a l l o y s of t h e s e c t i o n Ti,A1-Zr

i n the cast

s t a t e showed t h a t a s i n t h e case of a l l o y s of t h e s e c t i o n s Ti6&-Zr

and T i Al-Zr,

s o l i d s o l u t i o n s based on @-Ti and @-Zr c r y s t a l l i z e from t h e l i q u i d over t h e ent i r e concentration range of t h e components a t high temperatures. I n c a s t a l l o y s
of t h e composition Ti2& and i n a l l o y s w i t h 1 and 3 p e r c e n t Zr, a coarse-grained
polyhedral s t r u c t u r e (of a - T i type, f i g . l a ) i s observed. The @ s o l i d s o l u t i o n
of a l l o y s containing 3-30 and 80-97 p e r c e n t Z r undergoes a m a r t e n s i t e transformat i o n i n t h e course of t h e cooling, whereas c a s t a l l o y s w i t h 40-70 p e r c e n t Z r r e t a i n t h e s t r u c t u r e of t h e @ s o l i d s o l u t i o n .
A f t e r quenching from l l O o O , t h e polyhedral s t r u c t u r e of t h e a l l o y of t h e
composition Ti2A1 i s r e t a i n e d i n a l l o y s containing up t o 7 percent Zr. I n t h e
range of concentrations of 10-30 p e r c e n t Z r , t h e a l l o y s have t h e s t r u c t u r e of
The amount of t h e @ s o l i d s o l u t i o n i n c r e a s e s
-t- @ s o l i d s o l u t i o n s ( f i g . l b ) .
w i t h i n c r e a s i n g zirconium content of t h e a l l o y s . The a l l o y w i t h 40 p e r c e n t Z r
5s a pure @ s o l i d s o l u t i o n . A t l l O o O , t h e s o l i d s o l u t i o n of t h e a l l o y w i t h
45.0 p e r c e n t Z r undergoes a decomposition w i t h t h e formation of f i n e l y d i s p e r s e d
p r e c i p i t a t e s of a second phase. The microhardness of t h i s phase i s considerably
higher t h a t t h a t of t h e @ s o l i d s o l u t i o n , and it can t h e r e f o r e be assumed t h a t
t h i s phase i s a chemical compound.

The m i c r o s t r u c t u r e of a l l o y s w i t h 50-70 p e r c e n t Z r i s s i m i l a r t o t h e micros t r u c t u r e shown i n f i g u r e l c , although t h e p r e c i p i t a t e s of t h e second phase a r e

s t i l l more f i n e l y dispersed. I n a l l o y s containing over 70 p e r c e n t Z r , a mart e n s i t e decomposition of t h e f3 s o l i d s o l u t i o n i s observed. It should be noted
t h a t t h e e t c h a n t used i n t h i s work (I p t . HI?, 1 p t . HNO3 and 1 p t . g l y c e r i n )
s a t i s f a c t o r i l y r e v e a l s t h e phase components of t h e a l l o y s of t h e i n v e s t i g a t e d
s e c t i o n , which c o n t a i n up t o 50-60 p e r c e n t Z r . A t a higher zirconium content,
even on high d i l u t i o n w i t h g l y c e r i n and water, t h i s e t c h a n t causes a marked
etzhing of t h e s u r f a c e of t h e polished s e c t i o n s , and t h i s h i n d e r s t h e a n a l y s i s
of t h e a l l o y s .
A t 800, t h e s t r u c t u r e of t h e s o l i d s o l u t i o n of t h e a l l o y of t h e composit i o n Ti& i s preserved i n a l l o y s containing up t o 5-6 p e r c e n t Zr. I n t h e a l l o y

with 7 percent Z r , t h e r e i s observed a thickening of t h e g r a i n boundaries; t h i s

i s obviously due t o t h e p r e c i p i t a t i o n of t h e second phase. I n the concentrat i o n range of 10-70 p e r c e n t Z r , t h e @ s o l i d s o l u t i o n of t h e a l l o y s undergoes a
transformation which ends i n a e u t e c t o i d decomposition. I n t h e course of cooling from 1100 t o 800, t h e @ s o l i d s o l u t i o n of a l l o y s containing r e s p e c t i v e l y
20 and 50 p e r c e n t Z r decomposes w i t h t h e formation of an a d d i t i o n a l q u a n t i t y of
t h e a phase. Grains of t h e @ s o l i d s o l u t i o n which d i d not decompose during t h e
polymorphic transformation subsequently undergo a decomposition according t o
the r e a c t i o n @
a -t- m e t a l l i c compound ( f i g . I d and e ) . A t a h i g h e r zirconium
content, t h e r e i s observed a s e p a r a t i o n of coarse g r a i n s of a phase ( f i g . l f )
whose microhardness HB = 500 (whereas t h e microhardness of t h e a phase HB = 312)
+

Figure 1. Microstructure of a l l o y s a f t e r various h e a t treatments, x 315:

a, c a s t T i e a l l o y ; b, a l l o y w i t h 30 p e r c e n t Z r , quenching from 1 1 0 0 ~ ;
c , a l l o y w i t h 45 p e r c e n t Z r quenching from 1 1 0 0 ~ ;d , a l l o y w i t h 20 percent Z r , quenching from 800b ; e , a l l o y w i t h 50 p e r c e n t Z r , quenching from
8000; f , a l l o y w i t h 70 p e r c e n t Z r , quenching from 800'; g, a l l o y w i t h 30
percent Z r , quenching from 500';
h, a l l o y with 50 percent Z r , quenching
from 5 0 0 ~ ; i, a l l o y w i t h 60 p e r c e n t Z r , quenching from 500.

This phase h
t i o n of t h e B s o l i d s o l u t i o n i n a l l o y s with 45-50 percent Z r , and it may be a s
sumed t h a t t h e y both c o n s i s t of t h e same m e t a l l i c compound.
Prolonged annealing of t h e a l l o y s of t
caused a decrease i n t h e s o l u b i l i t y of z i r c o
on t h e a l l o y corresponding t o t h e compositio
by t h e photomicrographs ( f i g . l g , h and i ) ,
crease i n t h e q u a n t i t y of t h e m e t a l l i c compo
t h e a phase; t h i s i s i n agreement w i t h t h e v
t h e s o l i d s o l u t i o n based on a-Zr a t t h i s t e

of

Some a l l o y s w i t h a c h a r a c t e r i s t i c micros
annealed a t 500' were subjected t o x-ray a n a l
RKU-86camera by t h e powder method, w i t h copp
metal f i l t e r .
The a l l o y powders were a d d i t i o n a l l y annealed i n quartz ampules a t 800 f o r
f o r 100 h r s .

'jO h r s and a t 700'

The x-ray powder p a t t e r n s of t h e i n v e s t i g a t e d a l l o y s quenched from 800

( f i g . 2) show t h a t the main phase c o n s t i t u t i n g t h e a l l o y s containing up t o 50
p e r c e n t Zr i s a s o l i d s o l u t i o n based on a - T i and a-Zr.
According t o t h e d a t a of t h e x-ray a n a l y s i s , t h e a l l o y s w i t h 60 p e r c e n t Z r
have a three-phase s t r u c t u r e c o n s i s t i n g of a + @ + Zr3Al.
The presence of
very f a i n t i n d i v i d u a l r e f l e c t i o n l i n e s which may be a t t r i b u t e d t o t h e compound
Z r A l ( 6 phase) i n d i c a t e s t h e formation of t h e compound Z r Al (y phase); t h i s

5 3

presence i s j u s t a s e v i d e n t a s i n t h e binary system Z r - A l .

I n a l l o y s w i t h 20, 50 and 85 p e r c e n t Z r , t h e m e t a l l i c compound formed a l s o
corresponds t o t h e composition Zr A l . I n t h e a l l o y w i t h 85 percent Zr, t h e main

phase component i s a s o l i d s o l u t i o n based on t h e f3 modification of t i t a n i u m and

zirconium.
X-ray a n a l y s i s of a l l o y s w i t h 45, 50 and 90 p e r c e n t Z r annealed a t 500'
showed t h a t the f3 s o l i d s o l u t i o n of t h e s e a l l o y s decomposed w i t h t h e formation
of t h e a phase and of t h e compound Zr3Al.

41

Figure 2.

az

a3

44

45

46

47

49

to

Sin 8

X-ray powder p a t t e r n s of a l l o y s of t h e s e c t i o n Ti2&-Zr

a f t e r quenching from 800':

a, a l l o y Ti$;

b, a l l o y w i t h 20 p e r c e n t

Z r ; c, a l l o y w i t h 50 p e r c e n t Z r ; d, a l l o y w i t h 60 p e r c e n t Z r ; e , a l l o y
w i t h 85 percent Z r ; 1, a phase; 2, y phase; 3, f3 phase.

The diffuseness of t h e r e f l e c t i o n l i n e s on t h e x-ray p a t t e r n s of t h e s e

a l l o y s i n d i c a t e s a c e r t a i n l a c k of equilibrium i n t h i s s t a t e , although t h e x-ray
p a t t e r n s do not show t h e r e f l e c t i o n l i n e s of t h e p s o l i d s o l u t i o n . X-ray analheretofore has not
y s i s of a l l o y s w i t h 45-60 percent Z r quenched from 1100~
permitted any d e f i n i t e conclusion t o be drawn concerning t h e composition of t h e
compound formed by t h e decomposition of t h e p phase i n t h e temperature range of
1000-llOOO. For t h i s reason, and a l s o because of t h e i n s u f f i c i e n t l y complete
secd a t a of t h e thermal a n a l y s i s , t h e polythermal cross s e c t i o n of t h e Ti$-Zr
t i o n p l o t t e d on t h e b a s i s of t h e d a t a of m i c r o s t r u c t u r a l and x-ray analyses ( f i g .
3) i s only t e n t a t i v e . The transformations observed i n t h e a l l o y s of t h i s sect i o n i n d i c a t e t h e presence of a region of a three-phase equilibrium of a + @ +
Z r Al; t h e existence of t h i s region i s confirmed by t h e r e s u l t s of t h e thermal
3
analysis performed on a l l o y s containing 10-70 percent Z r . The thermal analys i s was c a r r i e d out by d i f f e r e n t i a l recording of heating curves with t h e
Kurnakov pyrometer. The a l l o y s were heated i n a i r up t o 1100-1150~. A s i s
evident from f i g u r e 3, t h e temperature of t h e e u t e c t o i d transformation of t h e
p phase decreases from 975 t o 780 a s t h e zirconium content of t h e a l l o y s i n creases from 10-70 percent.

It was impossible t o obtain d a t a on t h e temperatures of t h e phase t r a n s formations of t h e component a l l o y s containing over 70 percent Z r because of t h e
high r a t e of t h e i r oxidation.
Thermograms of t h e investigated a l l o y s show t h a t i n t h e range of 15-45
percent Z r , t h e highest oxidation r a t e begins a t temperatures of 950-920'.
In
t h e a l l o y containing 50 percent Z r , it begins a t 7 5 5 O , and i n t h e a l l o y with
90 percent Z r , t h i s temperature drops t o 600.
Let us examine t h e "composition-hardness" diagrams of t h e a l l o y s of t h e
Ti2&-Zr s e c t i o n a t t h e t h r e e temperatures of t h e h e a t treatment ( f i g . 4 ) . The

Z r , w t percent

l
s e c t i o n of t h e
Figure 3. ~ o l ~ t h e r m $cross
s e c t i o n Ti&-Zr:
1, d a t a of thermal
a n a l y s i s ; 2, compositions of a l l o y s studied.

64

200 1

70

20

J'U

40

50

60

70 80

YQ IL'O

Zr, w t percent

Figure 4. Hardness versus composition of a l l o y s

a f t e r quenching: 1, a t 11000; 2, a t 800; 3, a t 500.
hardness of t h e s e a l l o y s changes along curves having a maximum corresponding t o
30 p e r c e n t Z r a t a hardening temperature of 1100~
and 30-40 p e r c e n t Zr a t 800
I n t h e concentration range of 17-90 percent Zr, t h e a l l o y s quenched
and 500'.
from 1100~
have hardness values t h a t a r e 50-100 u n i t s h i g h e r t h a n t h o s e of t h e
a l l o y s quenched from 800 and 500'; t h i s i s explained by t h e formation of mart e n s i t e l i k e s t r u c t u r e s of t h e m e t a l l i c compound i n t h e course of quenching
from 1 1 0 0 ~ . The appearance of a s u b s t a n t i a l q u a n t i t y of equilibrium g r a i n s of
the a phase a t 800 and 500' i s a s s o c i a t e d with a decrease i n t h e hardness of
t h e s e a l l o y s . The hardness values of a l l o y s of t h i s s e c t i o n a t temperatures of
800 and 500 l i e approximately w i t h i n t h e same l i m i t s , and t h e hardness i n c r e a s e s s l i g h t l y i n t h e region of c e r t a i n a l l o y s owing t o t h e formation of an
a d d i t i o n a l q u a n t i t y of t h e m e t a l l i c compound. Measurements made on t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s of t h e Ti2Al-Zr s e c t i o n , t h e r e s u l t s of which
a r e shown i n t h e t a b l e , do not permit one t o r e l a t e t h i s p r o p e r t y t o t h e
microstructure. However, t h e d a t a i n d i c a t e t h a t t h e maximum values of t h e
e l e c t r i c a l r e s i s t i v i t y a r e displayed by t h e a l l o y of t h e composition T i , $ . ,
which i s r i c h e s t i n aluminum. The i n t r o d u c t i o n of up t o 1 0 p e r c e n t Zr s l i g h t l y
decreases t h e e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s . A f u r t h e r i n c r e a s e i n t h e
zirconium content of t h e a l l o y s causes a drop i n r e s i s t i v i t y , which reaches
minimum values i n t h e a l l o y w i t h 90 percent Z r . Values of t h e s p e c i f i c g r a v i t y
of t h e a l l o y s o f t h e Ti$-Zr
s e c t i o n a r e a l s o given i n t h e t a b l e .
The above i n v e s t i g a t i o n has shown t h a t t h e chemical i n t e r a c t i o n of t i t a nium, aluminum and zirconium i n t h e a l l o y s of t h e Ti2&-Zr s e c t i o n has a more
complex course t h a n i n t h e a l l o y s of t h e s e c t i o n s Ti6Al-Zr and T i Al-Zr, i n

which it remains analogous t o t h e i n t e r a c t i o n of t i t a n i u m w i t h zirconium.

An i n c r e a s e i n t h e aluminum content of t h e a l l o y s of t h e Ti$-Zr

system

l e a d s t o t h e appearance of phase components c h a r a c t e r i s t i c of t h e b i n a r y system Z r - A l .

1. Mikheyev, V. S. and Markovich, K. P. Coll. Titanium and I t s Alloys

i yego splavy). ~ z d - v oAN SSSR, NO. 7, p. 111, 1962.

i it an

Rec. Trav. Chim. Pays-Bas, Vol. 58, p. 973, 1939.

2.

F a s t , I. D.

3.

McPherson, D. 3. and Hansen, M.

4.

McQuillen, A. D. and McQuillen, M. A.

Trans. .ASM, Vol.

5. Yeremenko, V. N.

Titanium.

Titanium and I t s Alloys

AN UkSSR, Kiev, 1960.

i it an

46, p. 354, 1954.

Metallurgizdat, 1956.
i yego splavy).

Izd-vo

6.

Ence, E. and Margolin, H.

7.

Sato, T., Huang, Y . C, and Kondo, Y.

No. 81, p. 456, 1959.

8.

Grum-Grzhimaylo, N. V., Kornilov, I. I., Pylayeva, Ye. N, and Volkova, M. A.

~ o k l .AN SSSR, Vol. 137, No. 3, p . 599, 1961.

Trans. AIME, Vol. 209, p. 484, 1957.

J. Japan I n s t . Metals, Vol. 23,

RELATIONSHIP OF STRUCTURFS FORMED ON QUENCHING TITANIUM ALLOYS

TO EQUILIBRIUM PRASE DIAGRAMS

B. A. Kolachev and V. A. Livano

Recently, a number of published s t u d i e s ( r e f s . 1-4) have shown metastable

phase diagrams of t i t a n i u m a l l o y s i l l u s t r a t i n g s t r u c t u r e s a r i s i n g i n t h e a l l o y s
a f t e r quenching. These diagrams a r e p l o t t e d i n t h e coordinates temperature of
heating f o r quenching versus concentration of a l l o y i n g elements. I n p r i n c i p l e ,
metastable phase composition diagrams of t i t a n i u m a l l o y s can be e a s i l y r e l a t e d
t o t h e i r e q u i l i b r i u m phase diagrams i f t h e metastable p r o p e r t i e s of t h e f3 phase
a r e a l r e a d y known.
As an example, we s h a l l examine t h e phase diagram of t i t a n i u m w i t h a @
s t a b i l i z e r represented by a t r a n s i t i o n element ( f i g I ) . I n t h e problem under
consideration, t o a f i r s t approximation, it i s not important whether o r n o t
t h e r e i s a e u t e c t o i d transformation i n t h e system under study, s i n c e i n t i t a n i u m
systems w i t h t r a n s i t i o n elements, e u t e c t o i d transformations occur extremely
slowly and do not have any appreciable e f f e c t on t h e s t r u c t u r e s obtained on
quenching.

W e s h a l l assume f u r t h e r t h a t i n a l l o y s having a concentration of a l l o y i n g

elements i n t h e f3 phase lower than t h e c r i t i c a l concentration (c*), t h e r e t a k e s

p l a c e during quenching a m a r t e n s i t e transformation s t a r t i n g a t some temperature

Ti

CI

c
2

f3- s t a b i l i z e r , percent

Figure 1. Schematic phase diagram of a l l o y s

of t i t a n i u m w i t h a t r a n s i t i o n element.

Ms which decreases w i t h i n c r e a s i n g content of t h e a l l o y i n g element ( f i g . 1). I n

keeping w i t h t h e g e n e r a l p r i n c i p l e s of such transformations, one can assume t h a t
t h e m a r t e n s i t e transformations i n t i t a n i u m a l l o y s end a t a c e r t a i n temperature
Me which a l s o decreases w i t h i n c r e a s i n g content of t h e @ s t a b i l i z e r , and which
a t a c e r t a i n concentration C1 reaches t h e room temperature value ( r e f .

5).

I n t h i s case, on quenching from t h e @ region i n a l l o y s w i t h a concentration

of t h e a l l o y i n g element l e s s t h a n C1, t h e m a r t e n s i t e transformation w i l l go t o
completion, and t h e s t r u c t u r e of such a l l o y s i n t h e quenched s t a t e should be
represented only by t h e m a r t e n s i t i c a' phase. A t a concentration of t h e a l l o y i n g elements from C1to C2, t h e martensite transformation does n o t go t o comp l e t i o n , and t h e s t r u c t u r e of a l l o y s w i t h such a concentration'of t h e @ s t a b i l i z e r a f t e r quenching from t h e @ region w i l l be represented by two phases:
a f and @. F i n a l l y , i f t h e concentration of t h e f3 s t a b i l i z e r exceeds t h e
c r i t i c a l value C2, only t h e @ phase w i l l be f i x e d on quenching from t h e @ region.
I n t h e two-phase a

@ region a t temperatures below T1,

t h e concentration

of t h e @ s t a b i l i z e r i r ! t h e f3 phase i s g r e a t e r t h a n t h e c r i t i c a l value, and f o r

t h i s reason i t w i l l n o t undergo a m a r t e n s i t e transformation on quenching. The
s t r u c t u r e of a l l o y s a f t e r cooling from temperatures corresponding t o t h i s region
of t h e phase diagram w i l l be represented by a and @ phases. I n t h e temperature
range from TI t o T2, t h e concentration of t h e
s t a b i l i z e r i n t h e @ phase i n
t h e two-phase a + f3 region i s below c r i t i c a l , and t h e r e f o r e t h e @ phase changes
i n t o a phase of m a r t e n s i t e type during quenching. Since t h e m a r t e n s i t e t r a n s formation i n t h e @ phase w i t h a concentration of t h e @ s t a b i l i z e r from C1 t o C 2
does not go t o completion, t h e f i n a l s t r u c t u r e of t h e quenched a l l o y s w i l l be
represented by a, a f and (3 phases. During h e a t i n g f o r quenching up t o t h e twophase a + f3 region above temperature T2, t h e concentration of t h e @ s t a b i l i z e r
i n t h e @ phase i s l e s s t h a n C1,

and t h e r e f o r e t h e @

a f transformation goes t o

completion, a s a r e s u l t of which t h e f i n a l s t r u c t u r e w i l l be represented by t h e

a and a' phases. Naturally, when low a l l o y s a r e heated f o r quenching up t o
temperatures corresponding t o t h e a region, t h e s t r u c t u r e of t h e s e a l l o y s a f t e r
quenching w i l l be represented only by t h e a phase.
As was shown by t h e work of N. V. Ageyev ( r e f . 1-4), it may be considered
a f i r m l y e s t a b l i s h e d f a c t t h a t i n t h e m a j o r i t y of binary a l l o y s of t i t a n i u m with
t r a n s i t i o n elements, Lf t h e temperature of t h e heating f o r quenching i s high
enough, t h e w phase s e p a r a t e s on quenching from t h e @ phase. The metastable
diagram of t h e phase composition of t h e t i t a n i u m a l l o y s a f t e r quenching can t h e n
be represented by t h e diagram shown i n f i g u r e 2.

Cl

c2

@-stabilizer, percent
Figure 2. Schematic metastable diagram of t h e phase
composition of high-purity t i t a n i u m a l l o y s .
I n a l l o y s of technical-grade p u r i t y , owing f o t h e presence of i m p u r i t i e s ,
t h e l i n e s of t h e phase diagram which bound t h e two-phase region do n o t converge a t one p o i n t , and t h e metastable diagrams of t h e phase composition of
t i t a n i u m a l l o y s can t h e n be described by t h e diagram shown i n f i g u r e 3a. The
region of decomposition of t h e @ phase w i t h t h e p r e c i p i t a t i o n of t h e w phase
can be wedged i n t o t h e a + at+ @ region o r even i n t o t h e a + (3 region of t h e
metastable diagram, and t h e l a t t e r t h e n assumes t h e form i l l u s t r a t e d i n f i g u r e s
3b and c, r e s p e c t i v e l y .

It i s i n t e r e s t i n g t o note t h a t i n t h e i l l u s t r a t e d metastable diagram of

t i t a n i u m a l l o y s , regions which d i f f e r i n phase composition by o n l y one phase
border on one another d i r e c t l y . The o n l y exception i s t h e boundary between t h e
a and a t+ a + @ regions, which s e p a r a t e s regions d i f f e r i n g by two phases. This
exception i s obviously due t o t h e f a c t t h a t t h e a region of f i g u r e 2 and 3 i s
e s s e n t i a l l y a region of a n equilibrium phase diagram and not a metastable region.
Apparently, t h e law of a d j a c e n t s t a t e spaces operating i n equilibrium systems, by which "only s t a t e spaces which SLffer by one phase" ( r e f . 6 , p . 39 )
border d i r e c t l y on one another i n t h e sysrs:::, can be extended t o metastable d i a grams a s w e l l . However, t h i s law should :lot be applied t o metastable diagrams
without c e r t a i n q u a l i f i c a t i o n s . Thus, f o r example, t h e law of adjacent s t a t e
spaces w i l l not be obeyed i f any high-temperature phase changes i n t o two metasta b l e phases on quenching.
I n o r d e r t o compare t h e diagrams proposed above w i t h t h e published metasta b l e phase-composition diagrams p l o t t e d experimentally, metastable diagrams f o r
a l l o y s of t h e system Ti-Fe ( f i g . 4) and Ti-Ni ( f i g . 5 ) , p l o t t e d from t h e d a t a
of references 2 and 3, a r e i l l u s t r a t e d . These experimentally p l o t t e d metastable
diagrams unquestionably confirm t h e proposed diagrams. A t t h e same time, t h e
t h e o r e t i c a l diagrams permit a more accurate i n t e r p r e t a t i o n of t h e experimental
d a t a . Thus, f o r example, t h e l i n e s e p a r a t i n g t h e a + a' and at+ a -t- @ regions
from t h e a t and a! + @ regions ( f i g . 4) should be somewhat i n c l i n e d toward t h e

Figure 3. Schematic metastable diagram of t h e phase composition

of t i t a n i u m a l l o y s of technical-grade p u r i t y .

Fe, w t p e r c e n t
Figure 4. Metastable diagram of t h e
phase composition of a l l o y s of t h e
system Ti-Fe.

6 7 8 9

N i , w t percent
Figure 5. Metastable diagram of t h e
phase composition of a l l o y s of t h e
system Ti-Ni.

a x i s of a b s c i s s a s , while t h e l i n e s e p a r a t i n g t h e a t + f3 region from t h e

p + a region ( f i g . 5 ) should be drawn a s shown by t h e broken l i n e .

a'

-t

Not a l l of t h e published metastable diagrams of t i t a n i u m a l l o y s agree s o

w e l l with t h e proposed diagrams a s those shown i n f i g u r e s 4 and 5. These d i s crepancies may be caused by t h e following:
1. Some phase region of t h e metastable diagram may be s o small t h a t a t
the chosen concentrations of t h e a l l o y i n g elements and temperatures it could n o t
be d e t e c t e d .

2. The holding time during h e a t i n g f o r quenching was i n s u f f i c i e n t f o r t h e

establishment of t h e phase e q u i l i b r i u m corresponding t o t h e s e l e c t e d temperature
of t h e h e a t i n g f o r quenching.
3. I n any s p e c i f i c system, t h e behavior of t h e p phase on quenching may
d i f f e r from t h e behavior taken a s t h e b a s i s f o r t h e proposed diagrams, and
t h e l a t t e r should then be r e v i s e d i n accordance w i t h t h e a l t e r e d b a s i c assumpt ions.
Summary
1. On t h e b a s i s of t h e e q u i l i b r i u m phase diagrams of a l l o y s of t i t a n i u m
w i t h t r a n s i t i o n elements and transformations occurring i n t h e s e a l l o y s on
quenching, schematic metastable phase composition diagrams have been p l o t t e d .

2. The proposed sketches of metastable diagrams a r e i n s a t i s f a c t o r y

agreement w i t h t h e published experimentally p l o t t e d diagrams.

3. The t h e o r e t i c a l metastable diagrams permit a more a c c u r a t e i n t e r p r e t a t i o n of t h e experimental data.

rnERl3NCES
1. Ageyev, N. V. and Petrova, L. A. C o l l . Titanium and I t s Alloys i it
Metallurgy and Metallography, Izd-vo AN SSSR, pp.
yego splavy).

an

3-16,

1958
2.

Ageyev, N. V. and Smirnova, Z. M. Coll. Titanium and I t s Alloys i it an i

yego s p l a v ~ ) . Metallurgy and Metallography, Izd-vo AN SSSR, pp. 17-24,
1958.

3.

Ageyev, N. V. and Petrova, L. A.

4.

---

Zh. neorg. khim., Vol.

Zh. neorg. khim., Vol.

4, No. 8, 1959,

4, No. 5, 1959.

5 . J a f f y , R. I. Advances i n Metal Physics ( ~ s p e k h if i z i k i metallov)

M e t a l l u r g i z d a t , Vol. 4, pp. 77-192, 1961,

6.

Volovik, B. Y e , and Zakharov, M. V.

( ~ r o y n y y ei chetvernyye sistemy)

Ternary and Quaternary Systems

Metallurgizdat, p. 39, 1948.

STABILITY OF f3 ALLOYS OF THE SYSTEM Ti-Mo-Cr-Fe-Al

N. V. Ageyev, S. G. Glazunov, L. A. Petrova,

G. N. Tarasenko and L. P. Grankova

A study of t h e s t a b i l i t y of heating of t h e metastable f3 s o l i d s o l u t i o n of

titanium a l l o y s with a r e l a t i v e l y constant c r i t i c a l content of t h e alloying
agent (6-9 percent) has shown t h a t t h e most s t a b l e binary f3 a l l o y s a r e a l l o y s
of titanium with rhenium, nickel, molybdenum and tungsten ( r e f . 1 ) . I f an a l l o y
i s taken containing 6 a t . percent Fe, i . e . , with an i r o n content exceeding t h e
c r i t i c a l value necessary f o r t h e s t a b i l i t y of t h e f3 phase i n t h e Ti-Fe a l l o y ,
the s t a b i l i t y of t h e f3 s o l i d s o l u t i o n of t h i s a l l o y w i l l be equivalent t o t h a t
of the f3 s o l i d solution of t h e a l l o y of titanium with t h e c r i t i c a l content of
nickel (6.3 at. percent N i )

These d a t a as well a s d a t a on other titanium a l l o y s ( r e f . 1 ) have l e d t o

the conclusion t h a t an increase i n t h e concentration of t h e alloying agent
causes an increase i n s t a b i l i t y which i s g r e a t e r t h e higher t h e content of t h e
alloying agent. It should be borne i n mind, however, t h a t an increase i n the
content of t h e alloying agent a f f e c t s t h e increase i n s t a b i l i t y up t o a c e r t a i n
l i m i t above which the s t a b i l i t y remains t h e same a s i n a l l o y s with a lower
content of t h e alloying agent.
I f the increase i n t h e concentration of t h e alloying agents promoted not
only an increase i n s t a b i l i t y but a l s o an improvement i n mechanical characteri s t i c s , it would be possible t o develop a l l o y s with a high content of alloying
elements d e s p i t e t h e r i s e i n t h e density of t h e alloy. It i s known, however,
t h a t over t h e e n t i r e range of possible concentrations of t h e alloying elements,
binary titanium alloys do not e x h i b i t high mechanical c h a r a c t e r i s t i c s , with
the exception of the system Ti-Mo, i n which it i s possible t o obtain ob = 91.7
2

kg/mm a t 6 = 1 6 percent, but whose density i s 20 percent higher than t h a t of

pure titanium ( r e f . 2).
A t t h e present time, major a t t e n t i o n i s concentrated i n t h e development of
new titanium alloy3 on multicomponent a l l o y s with a metastable f3 s t r u c t u r e which
combine a high technological p l a s t i c i t y i n t h e hardened s t a t e , necessary f o r t h e
manufacture of intricate-shape p a r t s , with a high s t r e n g t h a f t e r aging ( r e f . 3 ) .

On t h e b a s i s of what was s t a t e d above concerning the e f f e c t of alloying

elements on t h e s t a b i l i t y of titanium a l l o y s , and a l s o on t h e b a s i s of

l i t e r a t u r e d a t a on t h e i n f l u e n c e of t h e s e elements on t h e various p r o p e r t i e s of
t h e a l l o y s , which w i l l be discussed below, we s e l e c t e d t h e system Ti-Mo-Fe-Cr-Al
f o r our i n v e s t i g a t i o n .
The purpose of t h e work, on t h e one hand, was a study of t h e s t a b i l i t y on
h e a t i n g of t h e metastable @ phase and, on t h e o t h e r hand, a s t u d y of t h e decomp o s i t i o n and t h e s e l e c t i o n of a l l o y s f o r a more d e t a i l e d i n v e s t i g a t i o n .
It i s known t h a t molybdenum n o t o n l y improves t h e mechanical p r o p e r t i e s of
t i t a n i u m a l l o y s , b u t has a d e s i r a b l e e f f e c t on t h e s t a b i l i t y of t h e @ phase, and
hence on t h e thermal s t a b i l i t y . I r o n i n c r e a s e s t h e s t r e n g t h of t i t a n i u m a l l o y s ,
but decreases t h e thermal s t a b i l i t y somewhat. Chromium i n c r e a s e s t h e s t r e n g t h
and h e a t r e s i s t a n c e of t i t a n i u m a l l o y s ( r e f . 4), i n c r e a s e s t h e c a l c i n a b i l i t y
(ref. 3 ) , and owing t o t h e high r a t e of decomposition of t h e p phase ( t h e a l l o y
of t i t a n i u m w i t h t h e c r i t i c a l content of 8.48 a t . p e r c e n t chromium decomposes
a t room temperature i n 50 days ( r e f . l)),makes it p o s s i b l e t o o b t a i n t h e d e s i r e d
p r o p e r t i e s w i t h a s h o r t e r holding t i m e during aging, a f e a t u r e important i n
p r a c t i c e . Although aluminum i s an a s t a b i l i z e r , when p r e s e n t i n s m a l l amounts
(1.5-4 w t , p e r c e n t ) i n t i t a n i u m a l l o y s , it a c t s l i k e @ s t a b i l i z e r s and decreases
t h e c r i t i c a l concentration of elements which i s required f o r t h e s t a b i l i z a t i o n
of t h e p s o l i d s o l u t i o n . By depressing t h e formation of metastable phases duri n g t h e h e a t treatment, aluminum i n c r e a s e s t h e thermal s t a b i l i t y and d e c r e a s e s
t h e b r i t t l e n e s s of t h e a l l o y . The combined presence of aluminum and chromium
has a d e s i r a b l e e f f e c t on t h e h e a t r e s i s t a n c e of t i t a n i u m a l l o y s and on t h e i n crease i n thermal s t a b i l i t y .

Since t h e p phase can be obtained i n t h e metastable s t a t e i n t i t a n i u m a l l o y s

a t an e l e c t r o n concentration of 4.20 el/atom ( r e f . 5 ) , t h e compositions of t h e
a l l o y s of t h e system Ti-Mo-Cr-Fe-Al were chosen ( t a b l e 1 ) s o t h a t t h e y would be
quenched i n t o a p s o l i d s o l u t i o n .
The a l l o y s were prepared from sponge TG00 (0.05 percent Fe; 0.03 p e r c e n t
2
S i ; 0.05 p e r c e n t C; 0.028 percent N; EN = 122 kg/rnm ; ob = 37.9 kg/mm2;

S =

47.8 p e r c e n t , cJy = 80.5 p e r c e n t ) from t h e master a l l o y Al-Mo (29.8 p e r c e n t Al;

70.6 p e r c e n t Mo; 0.05 p e r c e n t Si; 0.08 p e r c e n t ~ e ) ;AVO00 aluminum, KhO chromium,
and armco i r o n i n an a r c furnace by t h e double remelting method. A f t e r t h e r e melting, i n g o t s weighing 400 g were turned on a l a t h e and forged i n t o rods 15
mm i n diameter and squares 15 x 15 mm. The i n g o t s were heated f o r f o r g i n g i n
an e l e c t r i c furnace a t 1000-1100~f o r 15 min w i t h subsequent i n t e r m e d i a t e heati n g f o r 2-3 min.
A f t e r f o r g i n g , t h e i n g o t s were turned on a m i l l i n g machine and c u t i n t o
specimens f o r studying t h e microstructure, x-ray photographing of t h e polished
s e c t i o n s , and hardness measurements, and i n t o microspecimens f o r t e n s i l e t e s t i n g ( l e n g t h 1 = 25 mm; diameter of t h e working g a r t d = 1.5 mm; s i z e of head

5 x 5mm2 ), and impact

(1 = 40 mm; a =

5mm).

TABLF, 1. COMPOSITION OF ALLOYS OF TRE SYSTEM Ti-Mo-Cr-Fe-Al

(IN w t PERCENT).

6
'2

'&Il?eI

1
2
3
4

2
2
2
2

A1

--

--

Charne

TL

- .
.

-- . -- -.

- -.

Chemical a n a l y s i s
&I0

Fe

CI'

A1

1 1 1
H

First series

9
8
5
4

3
4
7
8

3
3
3
3

83
83
83
83

2,13
2,16
2,2
2,2

6
4,5
5
3,5

3
4
5
5
6
6

3
3
3
3
3
3

83
83
83
82,5
83
82,5

3,O
3,15
2,83
3,17
3,O
3,24

9,07
6,2
5,2
3,76

2,8
4,O
G,G8
7,35

2,7
3,l
2,81
3,15

0,086

0,025
0,0061

0,024
0,076

0,036 0,05
0,025

Second s e r i e s
7
8

3
5

10
9

53

8,80
7,23
5,22
3,lO
5,O
3,5

2,90
3,14
2,95
3,000
3,O
2,89

2,80
4,20
5,lO
5,20
6,O
8,5

0,082/0,01

0,042

0,0045 0,047

0,025

0,0070 0,057

3,13
2.95
3,01
2,95

0,036
0,036
0,042
0,236

0,039
0,033
0,026
0,076

2,96
3,OO
3,13
2,6
3,Ol

0,025

3.01
3,20
3,18

0,034

Third s e r i e s
11

7,5
5,s
4,5
3,5

3
5
6
7

3
3
3
3

82,5
82.5
82,5
82,5

4,20
4.20
4,20
4,06

3,05
5,15
5,90
7,Ol

5,90
6,90
4,65
5,22

Fourth s e r i e s
15
16
17
18
19

5
5
6
7
6

6,5
5,5
4,O
5,5
5

3
4
5
3
4

3
3
3
3
3

82,5
82,5
82
81,5
82

4,80
4,88
5,lO
5,80
6,lO

9,40
5,65
4,08
5,35
3,69

I 3,O't
,

5,02
4,90
3,29
4,05

Fifth series

22

3
3
3

81.5
81,5
81,O

7.15
7,20
7,80

4.6
3,55
4,10

4,O
4,83
3,94

'

0,077
0,042 0,093
0,127 0,0054
0.038
0,025 0,097

0,031
O, 10g~0,0087~

The a l l o y s were studied by metallographic and x-ray analyses. The hardness

was measured with a Vickers instrument with a 10 kg load. The mechanical prope r t i e s (ob, 6 and a=) were determined a t room temperature. The x-ray p a t t e r n s
were taken from a polished s e c t i o n i n CuK a r a d i a t i o n with a nickel f i l t e r i n
an RKU evacuated camera, and t h e heat treatment of t h e a l l o y s was c a r r i e d out
i n sealed quartz and molybdenum ampules preevacuated t o
t h e a l l o y s , t h e ampules were crushed d i r e c t l y i n water.

mm Hg.

To quench

I n order t o determine t h e quenching temperature from which t h e metastable f3

phase i s frozen, t h e a l l o y specimens (d = 10 mm, h = 5 mm and abh = 10.10-5 mm)

were quenched from 750, 800 and 850' i n water. Alloys with a high content of
a l l o y i n g agents were quenched from 800, but f o r t h e most p a r t t h e a l l o y s were
quenched from 8500. To compare t h e behavior of t h e a l l o y s during aging, they
were quenched from t h e same temperature a t 850.
The hypothesis t h a t t h e s e l e c t e d a l l o y s w i t h an e l e c t r o n concentration of
4.20 el/atom should have a metastable @ phase on cooling i n water was confirmed
by metallographical and x-ray phase a n a l y s i s which showed t h a t t h e a l l o y s of
t h e compositions i n d i c a t e d i n t a b l e 1 had a metastable @ s t r u c t u r e a f t e r quenching from 850. Their s t r u c t u r e d i f f e r e d i n g r a i n s i z e only ( f i g . l a and b,).
A l l t h e a l l o y s with t h e metastable @ s t r u c t u r e were tempered a t 100, 209,
300, 350, 400, 450 and 500 f o r 1-100 h r s , and i n some cases f o r up t o 169 hrs.
The dependence of t h e hardness of t h e a l l o y s on t h e aging temperature and on
t h e holding time i s i l l u s t r a t e d g r a p h i c a l l y ( f i g s . 2-6).
For convenience, t h e s e a l l o y s were divided i n t o f i v e s e r i e s depending upon
t h e molybdenum content. The aluminum content i n a l l t h e a l l o y s was 3 percent.
I n t h e a l l o y s of t h e f i r s t s e r i e s (with 2 percent M O ) , t h e amount of i r o n
increased from 2.8 t o 7.35 percent and t h e amount of chromium decreased from
9.07 t o 3.76 percent from a l l o y 1 t o a l l o y 4.
The hardness of a l l o y s 2, 3 and 4 does not change during heating t o 200
i n t h e course of 100 h r , whereas i n a l l o y 1 it i n c r e a s e s a f t e r 9 h r s . The cons t a n t hardness of a l l o y s 2, 3 and 4 i n d i c a t e s t h e s t a b i l i t y of t h e @ s o l i d
s o l u t i o n a t t h i s temperature. A proof of t h e s t a b i l i t y of t h e @ s o l i d s o l u t i o n
i n t h i s case i s t h e presence of only t h e l i n e s of t h e f3 s o l i d s o l u t i o n on t h e
x-ray p a t t e r n s of t h e s e a l l o y s . The x-ray p a t t e r n of a l l o y 1, tempered f o r

Figure 1. Microstructure of a l l o y s
of t h e system Ti-Mo-Cr-Fe-Al quenched
i n water from 850, x 120: a, a l l o y
15; b, a l l o y 18.

r-i

%
A
i

9-100 h r s a t 200, shows t h e w phase, which i s responsible f o r t h e i n c r e a s e

i n t h e hardness of a l l o y 1 under t h e same aging
An i n s p e c t i o n of t h e curves of t h e hardness of t h e a l l o y s s u b j e c t e d t o
aging a t h i g h e r temperatures l e a d s t o t h e conclusion t h a t t h e h i g h e r t h e chromium content and t h e lower t h e i r o n content of t h e a l l o y , t h e f a s t e r i s t h e
decomposition of t h e @ s o l i d s o l u t i o n and t h e i n c r e a s e i n hardness ( s e e f i g . 2a,
b, c and d ) . I n t h e case of aging a t 350-500, t h e f3 s o l i d s o l u t i o n of a l l o y s
1 and 2, containing up t o 4 p e r c e n t Fe, decomposes a t once, and t h a t of a l l o y s
3 and 4 (-7 p e r c e n t ~ e ) a, f t e r some time, s o t h a t t h e hardness curves of t h e s e
a l l o y s a r e a l s o s h i f t e d t o t h e r i g h t . I n a l l a l l o y s except a l l o y 1 aged a t
350-400, and i n a l l a l l o y s aged a t 400-500~, a g r a d u a l decomposition of t h e
C
,3 s o l i d s o l u t i o n and hence a gradual i n c r e a s e i n hardness a r e observed.
The
hardness of a l l o y 1 decreases during aging f o r 1-9 h r s , and i n c r e a s e s again a s
t h e aging time i s r a i s e d t o 49 h r s . This shape of t h e hardness curves i s explained by t h e f a c t t h a t on aging i n t h e temperature range of 350-400 f o r 1
h r , a l l o y 1 decomposes not w i t h t h e s e p a r a t i o n of t h e a phase, as i n t h e case
of a l l t h e a l l o y s , b u t w phase, which, a s t h e d u r a t i o n of t h e aging i n c r e a s e s ,
changes i n t o t h e a phase, a s a r e s u l t of which t h e hardness of t h e a l l o y i n c r e a s e s again a f t e r 16 h r s .
The high i r o n content of a l l o y 4 a s compared t o a l l o y s 1, 2 and 3 promotes
an i n c r e a s e i n t h e s t a b i l i t y of t h i s a l l o y on aging. Alloy 4, which c o n t a i n s
twice a s much i r o n (7.35 p e r c e n t ) a s chromium (3.76 p e r c e n t ) , decomposes a t an
aging temperature of 350-400 a f t e r 25 h r s , and a t an aging temperature of 450500 a f t e r 1 h r .
The decreased hardness of t h i s a l l o y a t an agfng temperature of 350-boo0
and even 4500 i n t h e course of 100 h r s a s compared t o i t s hardness a t an aging
temperature of 5000 f o r t h e same period of time i s probably a r e s u l t of t h e
slower decomposition of t h e @ s o l i d s o l u t i o n of t h e a l l o y a t an aging temperat u r e of 350-450 t h a n a t 500. I n o r d e r t o reach t h e hardness obtained a t an
aging temperature of 500 o r even a h i g h e r value, a longer holding time t h a n
100 h r s i s necessary during aging a t 350-450.
From an a n a l y s i s of t h e hardness curves of t h e a l l o y s of t h e first s e r i e s
(containing 2 p e r c e n t MO) it f o l l o w s t h a t a l l a l l o y s w i t h t h e exception of a l l o y
4 p r a c t i c a l l y reached a s t a b l e value of t h e hardness a f t e r 36 h r s of holding
time. Of t h e a l l o y s i n t h i s s e r i e s , t h e one deserving most a t t e n t i o n i s a l l o y
3, which has t h e lowest s c a t t e r of s t a b l e hardness.
Let us examine t h e change i n t h e hardness of a l l o y s of t h e second s e r i e s ,
containing 3 p e r c e n t Mo and various q u a n t i t i e s of i r o n and chromium. The
amount of i r o n i n c r e a s e s from 2.8 t o 8.5 p e r c e n t from a l l o y 5 t o a l l o y 10, and
t h e amount of chromium decreases from 8.8 t o 3.5 percent. The hardness of a l l
t h e i n v e s t i g a t e d a l l o y s during aging a t 200 f o r 100 h r s remains p r a c t i c a l l y
unchanged ( s e e f i g . 3a, b, c, d and e ) , i n d i c a t i n g t h e s t a b i l i t y of t h e a l l o y s
under t h e s e conditions. The d a t a on t h e hardness a r e supported by microstruct u r a l and x - r a y analyses, which i n d i c a t e t h e presence of t h e ,C3 s o l i d s o l u t i o n
alone. On heating t o higher temperatures (300 and h i g h e r ) , t h e @ s o l i d s o l u t i o n of t h e a l l o y s decomposes, and hence t h e hardness increases.

II
ZaQ/o
42.5

2
7ffL7

1;

3
7gQg

1%.t,
min
7 g f J ' min

76 Zf36 ,64 ,A!Q 736

f(l7
425

log a
min
/l7fl76' min

Il717ff
I< 2; 36' 6 4 ,I f f f f I96

holding time, h r
holding time, h r
Figure 3. Hardness of a l l o y s of t h e second series- versus
aging temperature and holding time: a, a l l o y 5; b , a l l o y
6; c, a l l o y 7 ; d, a l l o y 8; e , a l l o y 9; f , a l l o y 10.

An i n c r e a s e i n t h e content of i r o n and a decrease i n t h e content of chromium i n t h e a l l o y s of t h i s s e r i e s a s w e l l a s i n t h e a l l o y s of t h e preceding

s e r i e s r a i s e s t h e s t a b i l i t y of t h e f3 s o l i d s o l u t i o n somewhat. I n a l l o y s 10,
8 and 9, t h e hardness a t an aging temperature of 300-350 remains p r a c t i c a l l y
unchanged a t holding times of 4, 9 and 16 h r s , r e s p e c t i v e l y , i n c o n t r a s t t o
a l l o y s 5 , 6 and 7, i n which t h e change i n hardness becomes i n s i g n i f i c a n t 1 h r
a f t e r heating. An i n c r e a s e i n t h e i r o n content and decrease i n t h e chromium
content of t h e a l l o y s a l s o promote a g r e a t maximum hardness on aging. Thus, i n

M
a, d
k .ri
3 a

Mri

.ri 0

Fr sf

t h e range of 500-350,
t h a t of a l l o y

7,

t h e hardness of a l l o y

5 is

equal t o 450-500 kg/mm2,

490 and 530 kg/m2 a t 500 and 450, r e s p e c t i v e l y .

and

A t 350 and

400, t h e hardness of a>loy 7, having reached -520 kg/tnm2, continues t o i n c r e a s e .

However, a l l o y 8, whicli contains t h e same amount of i r o n a s a l l o y 7 b u t 2.12
percent l e s s chromium, and a l l o y 10, which contains t h e l a r g e s t amount of i r o n
of a l l t h e a l l o y s i n t h e second s e r i e s , do not d i f f e r i n maximum hardness from
a l l o y 5, which has t h e lowest i r o n content (2.8 p e r c e n t ) . Furthermore, i n a l l o y s
8 and 10, on heating t o 500, t h e hardness, having reached a maximum value up t o
9 hours, does not remain c o n s t a n t a s i n t h e case of a l l o y s 5, 6 , 7 and 9, and
decreases.
The d a t a obtained l e a d t o t h e assumption t h a t i n a l l o y s w i t h 3 p e r c e n t Mo,
f r o n does not have a d e s i r a b l e e f f e c t i f i t s amount exceeds -5 p e r c e n t . I n
a l l o y s containing 3-4 p e r c e n t Fe, t h e r e should be 1.5-2 times a s much chromium,
and i n a l l o y s with 5 p e r c e n t Fe, t h e chromium content should be no less than 5
p e r c e n t , s i n c e t h i s has an adverse e f f e c t on t h e s t a b i l i t y of t h e p r o p e r t i e s
( f i g . 3d and f ) . The hardness of a l l o y s 7 and 9, which c o n t a i n approximately
5 percent Fe and C r each and a r e aged a t 500, i s s t a b l e , whereas it decreases
i n a l l o y 8.
The decomposition of t h e f3 s o l i d s o l u t i o n of a l l o y s 5 , 6 and 7 during aging
a t 350-500, of a l l o y 8 a t 400-500~, and of a l l o y s 9 and 1 0 a t 450-500 begins
immediately a f t e r a holding time of one hour and proceeds with t h e p r e c i p i t a t i o n
of t h e a phase without t h e formation of t h e intermediate w phase. The a phase
which p r e c i p i t a t e s i n t h e course of t h e aging process, even a t a r e l a t i v e l y
high temperature and a long holding time, was observed i n t h e form of v e r y
f i n e l y dispersed p a r t i c l e s ( f i g . 7). X-ray phase a n a l y s i s of t h e s e a l l o y s confirmed t h e presence of t h e a phase ( f i g . 8a). On heating t o 300, a l l o y s 8, 9
and 1 0 decompose w i t h t h e p r e c i p i t a t i o n of t h e w phase, which e x i s t s f o r ano t h e r 100 hours ( f i g 8 b ) .

Analyzing t h e d a t a on a l l o y s 7-10, one can assume t h a t a l l o y 5 w i t h an

equal content of molybdenyn, i r o n and aluminum (-3 p e r c e n t ) and w i t h t h e h i g h e s t
content of chromium (-9 p e r c e n t ) i s of g r e a t e s t i n t e r e s t f o r a d e t a i l e d i n v e s t i gation, owing t o t h e h i g h e s t r a t e of decomposition of t h e f3 s o l i d s o l u t i o n , and
t o t h e establishment of a s t a b l e hardness a t a l l aging temperatures i n 36 hours.
Let u s examine t h e curves representing t h e v a r i a t i o n i n t h e hardness of t h e
a l l o y s of t h e t h i r d s e r i e s , containing 4 percent Mo and various q u a n t i t i e s of
i r o n and chromium ( s e e f i g . ha, b, c, d and e ) . Alloy 11 (5.9 p e r c e n t C r and
3.05 p e r c e n t ~ e decomposes
)
p r a c t i c a l l y a t once a t a l l aging temperatures except 200, a t which it i s s t a b l e f o r 16 hours. Alloy 1 3 (4.65 p e r c e n t C r and
5.9 percent ~ e i)s s t a b l e a t temperatures of 200 and 300 f o r 100 hours and a t
temperatures of 400 and 5 0 0 ~f o r 4 hours.
An i n c r e a s e i n t h e hardness of a l l o y 1 3 a t an aging temperature of 300 i n
9 hours i s probably due t o a c e r t a i n enrichment of t h e f3 s o l i d s o l u t i o n w i t h
t h e a l l o y i n g elements during t h e period preceding t h e s e p a r a t i o n of t h e decomp o s i t i o n products.

If

4,25

<

740

log

T,

3
4 min
74%'
7OqOffmin
1f.!?5jlsl@,l44,,{~

holding time, h r

holding time, h r

holding time, h r

holding time, h r

Z
/flO

8 25

f.

?.

3
4 l o g T, min
I
IOU0
IqDDD min
@2+36,<4,IPO,If6

holding time, h r
Figure 5. Hardness of a l l o y s of t h e f o u r t h s e r i e s versus aging temperature
and holding time: a, a l l o y 15; b, a l l o y 16; c, a l l o y 17; d, a l l o y 18; e,
a l l o y 19.
When a l l o y s 11, 1 3 and 1 4 a r e aged from 500 a f t e r t h e hardness maximum
has been reached, a d e c l i n e i n hardness i s observed; i n a l l o y 11 (with t h e
smallest i r o n content), t h e hardness decreases i n 9 hours, and i n a l l o y 13,
containing 2.85 percent more i r o n , i n 16 hours. The d e c l i n e i n hardness i n
a l l o y s 11 and 13 a t 500 i s apparently r e l a t e d t o an i n s u f f i c i e n t q u a n t i t y of
chromium. Like a l l o y s 5 and 7, a l l o y s 11 and 13, which contain approximately
t h e same amount of i r o n , have a s t a b l e hardness on heating a t 500' i f no l e s s
than 7 and 5 percent chromium i s present i n t h e a l l o y s .

2
11111

4,ZS

$ log

T,

min

IDPOD min
Y62536,6?,7t4,{Y6

/Up

'

holding time, h r

2
IF

zuoIO

425

3
4 log T, min
IqUO
IO(76; min
9 lfZ;36G$,ltG'(96

holding time, h r

1'

?
71;7

6$2'.5

3
41og T , min
luff0
7oqoD min
76Z,S~6,F~,f~~7,~~6'

holding time, h r
Figure 6. Hardness of a l l o y s of the f i f t h s e r i e s
versus aging temperature and holding time: a, a l l o y
20; b, a l l o y 21; c, a l l o y 22.
Alloy 1 2 (6.9 percent C r and 1.15 percent ~ e i)s s t a b l e a t 200 f o r 100
hrs, but decomposes i n L,h r when heated a t 450 and 500, i n 4 h r s a t 400, and
i n 9 h r s a t 300, i n c o n t r a s t t o a l l o y 13, which contains a l a r g e r amount of
i r o n but i s l e s s s t a b l e .
Alloy 1 4 (5.22 percent C r and 7.01 percent Fe) i s somewhat more s t a b l e
than a l l o y 11, but l e s s s t a b l e than a l l o y 13. On heating a t 300-450~, a l l o y 1 2
decomposes e s s e n t i a l l y l i k e a l l o y 14, but t h e l a t t e r on heating a t 300 decomposes with t h e p r e c i p i t a t i o n of t h e intermediate a phase, which i s s t a b l e f o r

Figure 7. Microstructure of a l l o y s of t h e second s e r i e s quenched from 850

1 hour i n water and aged under t h e following conditions: a, a l l o y 5, 350,
1 h r , x 340; b, a l l o y 5, 450, 1 h r , x 1350; c , a l l o y 5, 400, 100 h r s , x
1350; d, a l l o y 7 400, 100 h r s , x 1350; e , a l l o y 10, 400, 100 h r s , x 1350;
f, a l l o y 10, 4506 100 h r s , x 1350.

s of s e r i e s 11, quenched from

Figure 8
850' f o r 1 h r i n water and aged under t h e following conditions:
a, a l l o y 7, 350, 100 h r s , p-+ a phase; b, a l l o y 10, 300, 100
h r s , p + w phase.
another 100 h r s ( f i g . 9 ) ) b u t not with t h e p r e c i p i t a t i o n of t h e
I n contrast t o
maximum hardne s

UI

phase.

t h e o t h e r of

which c o n t a i n approximately t h e same amount of chromium and i r o n as does a l l o y

17, but which d i f f e r from t h e l a t t e r i n t h a t t h e y contain approximately 1 percent more molybdenum.
A s was a l r e a d y noted i n t h e case of a l l o y 3 (8.8 p e r c e n t C r and 2.8 percent Fe), a l l o y 15 (9.4 p e r c e n t C r and 3.04 p e r c e n t F e ) , which contains t h e
g r e a t e s t amount of chromium and t h e s m a l l e s t amount of i r o n i n t h e s e r i e s of

a110
300'
iron
17 i
this
for
300'
t h e samedecomposition mechanism. On heating a t 300, a l l o y s 15 and 16 decompose with t h e p r e c i p i t a t i o n of t h e w phase i n 1 and 4 h r s , r e s p e c t i v e l y . On
heating a t 350, t h e p r e c i p i t a t i o n of t h e u, phase i n a l l o y 15 takes p l a c e i n
15 min. This phase, which e x i s t s i n a l l o y 15 a t 300' f o r 121 h r s and a t 350
f o r 81 h r s , changes i n t o t h e a phase i n 144 and 100 h r s , r e s p e c t i v e l y . During
aging a t 400 and 450, a l l o y s 15 and 16 decompose a t once with t h e p r e c i p i t a t i o n
of t h e a phase.
Alloy 17, which contains approximately t h e same amount of molybdenum and
i r o n a s a l l o y 16 but 1.5 percent l e s s chromium, has a s t i l l g r e a t e r s t a b i l i t y
during aging than a l l o y 16, i.e., a l l o y 17 p r a c t i c a l l y does not decompose f o r
4 brs.
A comparison of a l l o y 16 (4.88 percent MO + 5.65 percent C r + 5.02 percent
~ e and
)
7 (2.83 percent Mo + 5.22 percent C r + 5.10 percent ~ e shows
)
t h a t molybdenum i n c r e a s e s the s t a b i l i t y of t h e a l l o y somewhat a t t h e s t a r t of t h e
aging. A 1 percent increase i n t h e molybdenum content of a l l o y 1 9 a s compared
t o a l l o y 17, t h e content of t h e o t h e r alloying elements being t h e same, a l s o
increases t h e s t a b i l i t y of t h e f3 a l l o y s . During heating a t 400, 450 and 5000,
a l l o y 1 9 i s a s s t a ~ l ea s a l l o y 17 f o r approximately 4 h r s , but on heating a t
300, a l l o y 17 i n c o n t r a s t t o a l l o y 19, which i s s t a b l e a t t h i s temperature f o r

Figure 10.
r u c t u r e of a l l o y s of
from 850' f o r 1 h r i n w a t e r and aged a t
12, i n p o l a r i z e d l i g h t , x 340; b, a l l o y
340; c, a l l o y 12, x 1350; d, a l l o y 13, x

t
e r i e s quenched
500 f o r 100 h r s : a , a l l o y
13, i n p o l a r i z e d l i g h t , x
1350.

100 h r s , decomposes a f t e r t h e same period of time w i t h t h e p r e c i p i t a t i o n of t h e

w phase. The p o s i t i v e i n f l u e n c e of molybdenum i s manifested n o t o n l y i n an i n crease of t h e s t a b i l i t y of t h e a l l o y s on heating, but a l s o i n t h e p r e s e r v a t i o n
of t h e maximum value of t h e hardness obtained i n t h e course of decomposition of
t h e a l l o y a t an aging temperature of 500, independently of t h e i r o n and chromium content of t h e a l l o y .
Alloy 18, which contains t h e same amount of molybdenum a s a l l o y 19, but
l e s s i r o n and more chromium, decomposes a t once when heated a t 350, 400 and
A t aging temperatures of 300 and 350,
450, and i n 4 h r s when he&-Led a t 300'.
a l l o y 18 decomposes w i t h t h e p r e c i p i t a t i o n of t h e w phase, t h e e x i s t e n c e of
which i s observed up t o 144 and 121 h r s , r e s p e c t i v e l y . On aging a t 400 and
450, a l l o y 18 decomposes immediately w i t h t h e s e p a r a t i o n of t h e a phase.

From an a n a l y s i s of t h e hardness curves of t h e a l l o y s of t h e f o u r t h s e r i e s ,

it follows t h a t t h e most i n t e r e s t i n g a l l o y s a r e 18 and 19, which reach a s t a b l e

hardness most r a p i d l y and t h e lowest d i f f e r e n c e i n t h e value of t h e maximum
Since t h e composition of a l l o y s
hardness during aging i n t h e range of 500-400'.
18 and 1 9 i s almost t h e same, an a l l o y w i t h an average composition i n i r o n and
chromium and w i t h 6 p e r c e n t Mo was s e l e c t e d f o r a f u r t h e r i n v e s t i g a t i o n .
Let u s examine a l l o y s 20 and 21 ( s e e f i g . 6%and b ) containing 7 p e r c e n t
Mo each and d i f f e r e n t amounts of i r o n and chromium ( a l l o y 21 contains approximately 1 p e r c e n t l e s s chromium and 0.8 p e r c e n t more i r o n t h a n a l l o y 2 0 ) . The
presence of l a r g e amounts of i r o n i n a l l o y 21 causes a more s l u g g i s h decomposit i o n of t h i s a l l o y on heating, a s a r e s u l t of which t h e hardness reaches i t s
maximum value and becomes s t a b l e a f t e r l o n g e r holding times. By comparing a l l o y s 20 and 21 w i t h a l l o y 22 ( f i g . 6 c ) , which d i f f e r from t h e f i r s t two i n
t h e i r molybdenum content, it can be seen t h a t a f u r t h e r i n c r e a s e i n t h e molybdenum content of t h e a l l o y slows down t h e decomposition process even more.
Despite t h e d i f f e r e n t decomposition r a t e s a t t h e s t a r t of t h e aging a t
300-500, a l l o y s 20-22 decompose according t o t h e same p a t t e r n , i . e . , w i t h t h e
p r e c i p i t a t i o n of a f i n e l y dispersed a phase whose s i z e and c h a r a c t e r of d i s t r i bution a r e analogous t o those observed i n t h e a l l o y s considered e a r l i e r (see
f i g . 7).
Analyzing a l l o y s 17-22 (with 5-8 p e r c e n t M O ) , one can conclude t h a t a 1-2
p e r c e n t i n c r e a s e i n t h e molybdenum content of a l l o y s 18-22 a s compared t o i t s
content of a l l o y s 15-17 s l i g h t l y i n c r e a s e s t h e s t a b i l i t y of t h e B a l l o y , and
t h a t a slow decomposition process i s even undesirable i n t h e s e a l l o y s . Among
a l l o y s containing over 7 percent Mo, a l l o y 21, whose hardness s c a t t e r was lowe s t , was chosen f o r a f u r t h e r i n v e s t i g a t i o n .
The curves r e p r e s e n t i n g t h e dependence of t h e hardness of a l l t h e i n v e s t i gated a l l o y s on t h e temperature and d u r a t i o n of aging show %hat i n a l l o y s with
2 p e r c e n t Mo (3.76 p e r c e n t C r + 7.35 p e r c e n t Fe + 3.15 percent AX and 5 . 2 percent C r + 6.68 p e r c e n t Fe + 2.81 p e r c e n t &), a t an aging temperature of 5000,
t h e hardness, having reached i t s maximum value, does not change a s t h e holding
time i n c r e a s e s t o 100 h r s , and t h a t i n a l l o y s w i t h 3 and 4 p e r c e n t Mo and
approximately t h e same content of chromium, i r o n and aluminum ( r e s p e c t i v e l y
3.5 p e r c e n t C r + 8.5 p e r c e n t Pe + 2.89 p e r c e n t Al and 5.22 p e r c e n t C r + 7.01
p e r c e n t Fe + 2.9 p e r c e n t Al), t h e hardness d e c l i n e s . I n our view, a t an aging
temperature of 500, t h e hardness should drop more r a p i d l y i n a l l o y s w i t h 2
percent Mo, and not i n a l l o y s w i t h a h i g h e r content of molybdenum (3-4 perc e n t ) , which promotes an i n c r e a s e i n s t a b i l i t y . The s t a b l e hardness i n a l l o y s
with 2 p e r c e n t Mo i s apparently explained by t h e f a c t t h a t i n a l l o y s w i t h a
small amount of molybdenum, t h e l a t t e r manifests i t s e l f more e f f e c t i v e l y t h a n
i n a l l o y s w i t h 3-4 p e r c e n t Mo, and a c t s a s i n a l l o y s w i t h 5 p e r c e n t Mo.
Since t h e mechanical p r o p e r t i e s of t h e a l l o y s of t h e system Ti-Mo-Cr-Fe-

Al quenched from 850' f o r 1 h r i n water ( t a b l e 2) were obtained by t e s t i n g

microspecimens s e n s i t i v e t o a l l t y p e s of notches and microcracks, t h e d a t a of
t h i s t a b l e should be regarded w i t h some r e s e r v a t i o n s . However, t h e s e d a t a

TABLE 2.

MECWCAL PROPERTIES OF ALLOYS OF THE: SYSTEM Ti-Mo-Cr-Fe-Al.

Alloy number

Ob,
kg/mm2

1
2
3

4
5
6
7
8

9
10
11
12
13

14
15
16
17
18

19
20
21
22

105
103

115
112

98
102
102

86
106
97
93
113

os (00.2),

6, percent

kgm/m2

kg/mm2
104
102
111

108
97
101

85
77

an

8
9
10
head unchanged

13
8
14
14

2.3
2.4
3
1
2.4
not t e s t e d
not t e s t e d
not t e s t e d
not t e s t e d
not t e s t e d

102
95

94
94
92
111
101
91

98

96

107

91

103
91.

14
5
8
4
7

98

97

5-13

7
14

bent
2.12
2.60
2.9

100
103
100

73

98
101
99
70

7
3
10

12
11

1.4
3.33

1.81
2.05
2.28

1.47
3.36
bent

1.63

confirm t h e correctness of t h e s e l e c t i o n of a l l o y s 3, 5, 12, 17, 18, 1 9 and 21

f o r a more d e t a i l e d i n v e s t i g a t i o n , since these a l l o y s have shown t h e h i g h e s t
mechanical c h a r a c t e r i s t i c s .
Summary
1. All t h e i n v e s t i g a t e d a l l o y s of t h e system Ti-Mo-Cr-Fe-Al with t h e
exception of a l l o y 1 a r e s t a b l e f o r 100 h r s a t 200. Alloy 1 i s s t a b l e f o r 9
h r s a t 200'.
Only a l l o y s 1 3 and 1 9 a r e s t a b l e f o r 100 h r s a t 300.
All t h e
remaining a l l o y s decompose; a l l o y s 10, 14, 16 and 17 decompose with t h e prec i p i t a t i o n with t h e UI phase, which e x i s t s f o r another 100 h r s , and a l l t h e
o t h e r a l l o y s decompose w i t h t h e p r e c i p i t a t i o n of t h e a phase.

2. I n a l l o y s containing 2 and 5 percent Mo, t h e s t a b i l i t y of t h e prope r t i e s i s independent of t h e r a t i o of chromium t o i r o n w i t h i n t h e i n v e s t i g a t e d

l i m i t s . The chromium content i n a l l o y s with 2 percent Mo decreased from 9.07
t o 3.76 percent, and t h e i r o n content increased from 2.8 t o 7.3 percent; t h e
chromium content i n a l l o y s with 5 percent Mo decreased from 9.40 t o 4.08 percent, while t h e i r o n content increased from 3.04 t o 5 percent.

3. For a l l o y s containing 3-5 percent Mo, not more than 5 percent Fe should
be used, since a higher i r o n content has an adverse e f f e c t on t h e s t a b i l i t y of
t h e p r o p e r t i e s . I n a l l o y s with 3-4 percent Fe, t h e amount of chromium should be
1.5-2 times g r e a t e r , and i n a l l o y s with 5 percent Fe, t h e chromium content should
not be l e s s than 5 percent.

4. I n a l l o y s containing up t o 5 percent C r and up t o 5 percent Fe, not

more than 5 percent Mo should be taken. A 1 - 2 percent increase i n t h e amount
of molybdenum s l i g h t l y increases t h e s t a b i l i t y of t h e f3 a l l o y s , and a slow decomposition process i s undesirable because of t h e presence of t h i s amount of
molybdenum.

1. Ageyev, N. V.and Petrova, L. A. Coll. Titanium and I t s Alloys

yego splavy), Izd-vo AN SSSR, No. 7, p. 26, 1962.

Titanium.

i it an

2.

McQuillen, A. D. and McQuillen, M. K.

1958

Metallurgizdat, p. 372,

3.

Tarasenko, G. N. and Glazunov, S. G. Metallovedeniye i Termicheskaya

Obrabotka Metallov, No. 2, p. 41, 1963.

4.

P u l f t s i n , N. M. Titanium Alloys and Their Use i n Machine Building

Mashgiz
( ~ i t a n o v y y esplavy i i k h primeneniye v mashinostroyenii)
( s t a t e S c i e n t i f i c and Technical Publishing House of L i t e r a t u r e on
~ a c h i n e r ' y ) ,p . 73, 1962.

5 , Ageyev, N. V. and Petrova, L. A.

1961..

Dokl. AN SSSR, Vol. 138, No. 2, p.

359,

METASTfBLE POLYMORPHISM OF ALLOYS BASED ON ELJDE1\PTS OF GROUP IV

OF THE PERIODIC SYSTEM
N. I?.

Lashko

It is a well-known fact that in titanium-base alloys, four types of metastable polymorphic transformations have been established during quenching from
temperatures of the f3 region: 1, f3 at; 2, f3 + a"; 3 , B 4 f 3 + w ; 4, Bstab +
+

In zirconium-base alloys, three types of

betastab.
established: 1, f3 'a'; 2, f3 'f3

w; 3,

pstab

transformations have been

hetaStab.
In hafnium alloys,

none of these reactions has been reliably established thus far.

A number of studies have defended the thesis that the transformations

f3

a", f3

f3 -c cu, pstab

pmetastab are determined by the concentration of the

outer electrons of transition metals in these alloys (refs. 1-4). The conditions of the metastable polymorphic transfornations may be written as follows:

where ai is the constant of the i-th transformation; x is the concentration of

the alloying element in at. percent; y is the number of its outer electrons
minus four.
Two conclusions result:
1. The metastable polymorphic transformations should occur with a decreasing concentration of the alloying element, increasing number of the group of
the periodic system, and increasing number of outer electrons;
2. The transformation in alloys containing alloying elements of one group
of the periodic system should occur at the same electron concentration, i.e.,
when the number of outer electrons per atom is the same.

Neither conclusion has been confirmed experimentally. This i s p a r t i c u l a r l y

apparent from t h e most complete d a t a on t h e conditions of t h e f i x a t i o n of t h e
metastable phase during quenching, when @stab hetastab
( t a b l e 1 ) . The con-+

c e n t r a t i o n of t h e a l l o y i n g elements,which f i x t h e @ phase during t h e quenching

of b i n a r y t i t a n i u m a l l o y s and i n t h e s t a t e of e q u i l i b r i u m form a e u t e c t o i d react i o n , d e c r e a s e s a t f i r s t a s t h e number of t h e group of t h e p e r i o d i c system i n creases (up t o group VIII),
and t h e n t h e concentration i n c r e a s e s . Nor i s t h i s
concentration c o n s t a n t i n a l l o y s w i t h a l l o y i n g elements of t h e same group ( f o r
example, i n a l l o y s w i t h elements of group V I ) .
The f i x i n g of t h e metastable @ phase on quenching should be determined by
t h e r e l a t i v e s t a b i l i t y of t h i s phase on cooling. This phase i s n a t u r a l l y l e s s
s t a b l e i n a l l o y s w i t h a p e r i t e c t o i d transformation and more s t a b l e i n b i n a r y
a l l o y s w i t h a e u t e c t o i d transformation o r i n a l l o y s forming continuous @ and
l i m i t e d a s o l i d s o l u t i o n s . The degree of s t a b i l i t y of t h e w phase i n a l l o y s of
t h e l a t t e r type should be determined by t h e change i n t h e temperature of t h e
equilibrium @ + a + (3 and a + @ " a r e l a t i v e t o t h e concentration of t h e a l l o y ing elements. To a f i r s t approximation, i n a l l o y s w i t h a e u t e c t o i d transformat i o n , t h i s q u a n t i t y should be c h a r a c t e r i z e d by t h e temperature of t h e e u t e c t o i d
transformation. Indeed, a s t h e number of t h e group of t h e a l l o y i n g element i n creases w i t h i n t h e confines of t h e same period, t h e change i n i t s c o n c e n t r a t i o n ,
which causes t h e f i x i n g of t h e metastable w phase i n t h e a l l o y , i s symbatic w i t h
t h e change i n t h e e u t e c t o i d temperature.
This a l s o a p p l i e s t o a l l o y s w i t h a l l o y i n g elements of t h e same group ( f o r
example, t o t h e a l l o y s Ti-Cr and ~i-W) .
The f i x i n g o f t h e metastable @ phase i n b i n a r y t i t a n i u m a l l o y s , which
form a continuous s e r i e s of @ s o l i d s o l u t i o n s and a l i m i t e d s e r i e s of a s o l i d
s o l u t i o n s , t a k e s p l a c e a t a lower concentration of t h e a l l o y i n g elements t h e
more pronounced i s t h e decrease i n t h e temperature of t h e s t a b l e transformation
@ -+ a + @ and a -t. p -'a.
I n o r d e r of decreasing s t a b i l i t y of t h e @ phase, such
a l l o y s can be arranged i n t h e following sequence: Ti-Mo, Ti-V, Ti-Ta, Ti-Nb.
A s an a r b i t r a r y c h a r a c t e r i s t i c of t h e degree of s t a b i l i t y of t h e @ phase during
t h e c o o l i r g of t h e s e a l l o y s , one can t a k e t h e concentration of t h e a l l o y i n g
elements which g i v e rise t o t h e equilibrium @
B + a transformation a t 600
(table 2).
-+

This c r i t e r i o n of t h e r e l a t i v e m e t a s t a b i l i t y of t h e @ phase i n zirconium

a l l o y s cannot be v e r i f i e d because of i n s u f f i c i e n t d a t a . It i s j u s t i f i e d i n
judging t h e conditions of formation of t h e w phase during t h e quenching of c e r tain alloys (table 3).

TABLE 1. CONDITIONS OF FIXATION OF THE METASTABLE (3 PHASE DURING QUENCHING

OF TITANIUM ALLOYS (REFS. 1 AND 2)

Minimum concentration of
Group
Electron
Number of
Eutectoid
of t h e
at which the meta- concentration
outer
temperature
Element
periodic
s t a b l e phase i s fixed,
electrons
el/atom
OC
a t . percent
system

V
V1

Cr

VI:

MO

VI
VII
VIII
VIII
VIII

Mn
Fe
Co
Ni

4.184
4.17

18.4

5
6
6
6
7
8

8.4

5.0
4.5-4.9
4.9

9
10

650-717

4.12

5 8
8.7

5.8-6.3

4.17
4.15

715

4.18-4.20
4.20
4.35-4.38

685

550
590
770

TABLE 2. CONDITIONS OF FIXATION OF THE METASTABLE (3 PHASE

DURING QUENCHING OF TITANIUM AL;LOYS FORMING A COPJTINUOUS
SERIES OF (3 SOLID SOLUTIONS AND A LIMITED SERIES OF a SOLID
SOLUTIONS (REFS. 1 AND 2).
Concentration of alloying elements ( i n a t .
percent ) providing f o r
Alloy
system

equilibrium
transformation

f i x i n g of t h e
metastable (3 phase
during quenching

@"a+@

TABLE 3. CONDITIONS OF FONTION OF THE METASTABLE w PHASE I N ZIRCONIUM

ALLOYS WITH A EUTECTOID TRAHSFORMATION ( ~ F S3 AND 4).

Alloy
systern
Zr-Cr
Zr-Mo
Zr-W

Content of alloying element a t

which the w phase i s formed,
a t . percent

4.5

Electron concentration
ellatom
4.09

4.0

4.08

7- 13

4.13

Eute ctoid
temperat u r e , OC

835
780

860

When t h e temperature of t h e e u t e c t o i d transformation approaches t h e temp e r a t u r e of t h e polymorphic transformation f3 " a i n pure metals, c o n d i t i o n s a r e
created which depress t h e metastable polymorphic transformations. On cooling
i n a i r , t h e e u t e c t o i d r e a c t i o n c l o s e t o t h e e q u i l i b r i u m r e a c t i o n occurs only
i n a l l o y s w i t h high e u t e c t o i d transformation temperature, when a l l main metas t a b l e polymorphic transformations (f3 -+ a ' , f3
a", f3 f3 + w, pstab + @metast a d
+

We observed t h e equilibrium product of t h e e u t e c t o i d transformaa r e depressed.

t i o n , f o r example, on cooling i n a i r (from temperatures of t h e f3 r e g i o n ) a l l o y s
of t h e system Ti-Cu w i t h a e u t e c t o i d temperature of 798' ( t h e e u t e c t o i d a +
T ~ ~ C U ) .A r e s i d u a l f3 phase was not observed i n t h i s case. It can be r e l i a b l y
s t a t e d t h a t polymorphic metastable transformations should not t a k e p l a c e i n
a l l o y s of t h e system Ti-& and Ti-Au, t h e e u t e c t o i d temperatures of which a r e
higher t h a n i n t h e a l l o y s of t h e system Ti-Cu, and equal r e s p e c t i v e l y t o 855
and 832'.
We can a l s o s t a t e t h a t i n t h e a l l o y s of t h e system Bf-Fe, t h e e u t e c t o i d
temperature of which i s high and, according t o r e f e r e n c e 5 , equal t o 1235O, t h e r e
should be no metastable polymorphic transformations on quenching from 1 2 6 0 ~ . As
i n d i c a t e d by an a n a l y s i s of t h e i r d a t a (recording and c a l c u l a t i o n of x - r a y d i f f r a c t i o n g a t t e r n s of an a l l o y of hafnium w i t h 3.5 p e r c e n t Fe a f t e r quenching
from 1260 ), t h e conclusions of t h e a u t h o r s of r e f e r e n c e 5 concerning t h e p r e s ence of f3
f3 + w transformations i n t h e s e a l l o y s a r e i n c o r r e c t . According t o
t h e i r d a t a , t h e product of t h e e u t e c t o i d reaction--the phase Hf2Fe-- i s ob+

served i n t h e quenched a l l o y . The x-ray p a t t e r n which they c i t e and i t s c a l c u l a t i o n i n d i c a t e beyond any doubt t h e presence of t h e a-Hf phase on quenching, not
t h e presence of t h e f3 + w phase, a s i n d i c a t e d by t h e authors of r e f e r e n c e 5 , who
proceeded from t h e assumption t h a t t h e w phase should be formed i n t h i s a l l o y
with an o u t e r - e l e c t r o n concentration of 4.14 el/atom. Hence, when t h i s a l l o y
i s quenched i n water from 1260, t h e transformation t a k i n g p l a c e i s f3
a+
This example c l e a r l y shows t h e advantage of t h e above-indicated c r i W$e.
+

t e r i o n f o r t h e degree of i n s t a b i l i t y of t h e f3 phase over t h e q u a n t i t a t i v e c r i t e r i o n r e l a t e d t o t h e e l e c t r o n concentration.

Metastable polymorphism i n a l l o y s based on t i t a n i u m and zirconium w i t h a

e u t e c t o i d transformation i s a l s o manifested by t h e formation of a r e s i d u a l f3
phase during quenching. I t s amount and r e s i s t a n c e t o decomposition on aging
a l s o depend on t h e e u t e c t o i d temperature. I n t i t a n i u m a l l o y s w i t h a h i g h temp e r a t u r e of t h e e u t e c t o i d transformation, no r e s i d u a l f3 phase i s formed. As
was indicated above, i n a l l o y s of t h e system Ti-Cu, t h e f3 phase i s converted
i n t o t h e products of t h e e u t e c t o i d r e a c t i o n during quenching. It i s u s u a l l y
s t a t e d t h a t no r e s i d u a l f3 phase i s formed i n t h e system Ti-Si w i t h a e u t e c t o i d
I n our e a r l i e r work ( r e f . 6 ) ) it was shown t h a t i n
temperature of 860.

t e c h n i c a l a l l o y s of the system Ti-Si, two phases were observed,

a + Ti Si
5 3'

a f t e r a r e l a t i v e l y s h o r t heating f o r quenching followed by quenching. However,

an i n v e s t i g a t i o n of t h i s system of a l l o y s , which were f i r s t homogenized a t 920
f o r 145 h r s , then furnace-cooled t o 100-200 and aged a t 600-840, revealed t h e
presence of a r e s i d u a l j3 phase ( t a b l e 4). I n t e r n a r y a l l o y s of t h e system ~ i - 6
percent Al-Si, which were subjected t o t h e same homogenizing treatment, no
residual j
3 phase was observed, but t h e phase T i S i was detected. The phases

5 3

f3

and T i S i

5 3

were found i n t h e course of an x-ray s t r u c t u r a l a n a l y s i s of anodic

d e p o s i t s i s o l a t e d from t h e a l l o y s i n e l e c t r o l y t e s of t h e following compositions:

1. Three g of potassium thiocyanate, 10 g of c i t r i c acid, 1000 m l of
methanol;

2. Three g of l i t h i u m chloride, 1 0 g of c i t r i c acid, 25 m l of g l y c e r i n ,

1000 m l of methanol

.'

TABLE 4. RESULTS OF X - M Y STRUCTURAL AXALYSIS OF MONOLITHlC

ALLOYS AND ANODIC DEPOSITS ISOLATED FROM ALLOYS OF THE! SYSTEMS Ti-Si Al!lD TF-6 PERCENT Al-Si.
-.

--

-Alloy

.,-Isla, sa,7 /Temper

0,2
0,'~
0 ,G

0,8

j,1
1,T,
0,2
0,4
/i,l

1,s
O,2
0,4
O,G
j,i
1,s

svsterc ~i -6% &-si

-

of the system

GO0
600
GOO
GOO
GOO
GOO
700
700
700
700
840
840
8/10
840
540

Dura-

100
100
100
100
100
75
75
75
50
50
50
50
50

Phase
composition
u

0,2

a+-@
u

P
o?

tl ;9

u -:-

1,s

500
500
500
GOO
GOO
700
700
700
850
850
850
850

125
125
125
125
125
125
100
100
100
50
50
50
50

+ l'ijSi3
a+l'i~Si3

+ Tir,Sia

a f l'isSin
a 4 Ti~Sis
a 4- TisSi3
a + TijSi3
a+ Ti~Si3
f Ti~Si3
a Ti~Si3
a 4 Ti6Si3

+
a+

l ~ h work
e
was c a r r i e d o u t i n cooperation with Ye. A. Vinogradova and
A. I. Glazova.
94

It i s p o s s i b l e t h a t t h e decomposition of t h e f3 phase and of t h e a l l o y s of

t h e system T i - S i i n v e s t i g a t e d e a r l i e r i s promoted by i m p u r i t i e s and a segregat i o n a l s t r u c t u r e . It i s known t h a t t h e maximum concentration of a l l o y i n g e l e ments i n t i t a n i u m a l l o y s which causes t h e f i x a t i o n of t h e f3 phase on quenching
depends on t h e p u r i t y of t h e a l l o y s . The homogenizing of t h e a l l o y s of t h e system Ti-Si promotes an i n c r e a s e i n t h e s t a b i l i t y of t h e f3 phase. Alioying of
t h e s e a l l o y s w i t h aluminum a c c e l e r a t e s t h e decomposition of t h e B phase.

IV
The metastable polymorphic transformation f3+ @ + w t a k i n g p l a c e i n t i t a n i u m
and zirconium a l l o y s during quenching o r aging i s a t t r i b u t e d t o m a r t e n s i t e t r a n s formations of a s p e c i a l type ( r e f . 7). A c h a r a c t e r i s t i c f e a t u r e of t h i s mart e n s i t e transformation i s t h e mandatory e x i s t e n c e of t h e w phase, which i s coh e r e n t l y bound t o t h e f3 phase. Apparently, i n c o n t r a s t t o t h e o t h e r m a r t e n s i t e
phases, t h e w phase does not e x i s t independently. Wben it i s formed, t h e
volume of t h e a l l o y decreases. The s e l f - c o h e r e n t bond of t h e two phases !3 t- w
i s a s i n g l e phase. The l i k e l i h o o d of such an assumption i s r e i n f o r c e d i f t h r e e
known f a c t s a r e r e c a l l e d :
1. There i s no r e l i e f on t h e s u r f a c e of t h e quenched a l l o y during t h e
formation of t h e w phase;

2. The main p l a n e s of r e f l e c t i o n .of x-rays from t h e !3 and w phases

coincide;

3 . The w phase cannot be d i s t i n g u i s h e d m e t a l l o g r a p h i c a l l y a s a s e p a r a t e

component d i f f e r e n t from t h e matrix,
The statement made i n reference 8 t h a t some very small p a r t i c l e s observed
by means of t h e e l e c t r o n microscope c o n s t i t u t e t h e w phase i s debatable. These
authors observed t h e same kind of p a r t i c l e s i n t h e a l l o y Hf-3.5 p e r c e n t Fe,
where, a s was shown above, t h e r e i s no w phase.

It i s known t h a t t h e w phase i s formed i n medium t i t a n i u m and zirconium

a l l o y s d i r e c t l y on quenching, whereas i n higher a l l o y s , it I s formed w i t h t h e
p a r t i c i p a t i o n of d i f f u s i o n processes a s a r e s u l t of t h e heating of t h e metastable j
3 phase f i x e d on quenching. I n a d d i t i o n t o t h e i n d i c a t e d c h a r a c t e r i s t i c s
of t h e f3 phase, one should note t h e independence of t h e temperature of t h e
m a r t e n s i t e transformation from t h e cooling r a t e , and a l s o identical. o r s i m i l a r
parameters of t h e c r y s t a l s t r u c t u r e of t h e w phase i n t i t a n i u m a l l o y s of d i f f e r e n t compositions ( r e f . 9). Hence, we conclude t h a t d i f f u s i o n l e s s m a r t e n s i t e
transformations have a common f e a t u r e . They occur when, a s a r e s u l t of some
processes, t h e s p e c i f i c volume of a high-temperature phase i s prepared f o r a
d i f f u s i o n l e s s transformation i n t o a low-temperature metastable phase. This may
take p l a c e a s a r e s u l t of a volume change on cooling of t h e high-temperature
phase o r a s a r e s u l t of i t s d i f f u s i o n a l change during aging.
The f i r s t condition of t h e p r e p a r a t i o n of a phase f o r a metastable polymorphic transformation was pointed out by t h e authors ( r e f . 1 0 ) and a l s o by
M. V. Yakutovich and V. D. Sadovskiy ( r e f . 1 1 ) .

The d i f f u s i o n a l p r e p a r a t i o n of a high-temperature phase f o r a subsequent

d i f f u s i o n l e s s transformation may occur i n two ways: @ ' f-3,- + x o r @ -'
+ p2,
where B i s t h e i n i t i a l phase of t h e changed composition (depleted of a l l o y i n g
elements); x i s t h e equilibrium phase;
i s t h e phase enriched w i t h a l l o y i n g
@2
elements. The f i r s t case i s r e a l i z e d i n t h e b a i n i t e transformation, when during
the isothermal treatment a u s t e n i t e p a r t i a l l y decomposes w i t h t h e p r e c i p i t a t i o n
of cementite, and t h e a u s t e n i t e depleted of carbon changes i n t o m a r t e n s i t e .
The r e a l i z a t i o n of t h e second type of transformation i n t i t a n i u m a l l o y s
was described i n a r e p o r t of R. M. Lerinman and T. V. Shchegoleva ( r e f . 1 2 ) .
They showed t h a t when t h e metastable @ phase of t i t a n i u m a l l o y s c o n t a i n i n g
chromium and manganese ages, a demixing of t h e @ phase and t h e formation of
t h e w phase t a k e place.
We have observed various cases of formation of t h e w phase i n a l l o y s of t h e
system Zr-Nb. As we know, i n t h e region of t h e e x i s t e n c e of t h e @ phase, z i r conium and niobium form a continuous s e r i e s of s o l i d s o l u t i o n s and a l i m i t e d
region of s o l u b i l i t y of niobium i n a - Z r .
The high-temperature @ phase decomposes
under equilibrium conditions i n accordance w i t h t h e e u t e c t o i d r e a c t i o n @ + a - Z r +
Nb a t 6 1 0 ~ . Four a l l o y s were taken which d i f f e r e d i n t h e type of decomposition
of t h e B phase on cooling i n water and subsequent aging.
The r e s u l t s of t h e i n v e s t i g a t i o n a r e shown i n t a b l e

5.

TAEiLE 5 . l?ESULTS OF X-RAY STRUCTURAL ANALYSIS OF fiLOYS

OF TRE SYSTEM Zr-Nb AFTER QUENCHING I N WATER AKD AGING.
M

Aging
conditions
s@ k
content, 0 PI5Temper- Dura- Phase
C E ~ - P
p e r c e n t @ @ mature, t i o n , compositions
hrs
OC

. A h @

g*

G
G

880
850
880

S
8
8

880
880
880

2
O,5
50

15

20
20
20

750
730
750

400
530

a4-P

F +- w

-4 00
430
550
4 00
550

2
50

400
550

800
800
800

15
15

Parameter of
g phase, A

2
50

2
50

?+a

P+-0

3,5G

3,553
3,545
3,545

3,510
9
fi1+Sa+wi31=3,54j

P2=3,497

CI

P
?J
u-Zl'tY l )

3,512
3,512

A f t e r quenching, i n t h e a l l o y containing 6 p e r c e n t Nb t h e r e i s formed a

r e s i d u a l f3 phase which i s r e l a t i v e l y s t a b l e on h e a t i n g f o r 2 h r s a t 400 and
which decomposes a t 5 5 0 ~ . It i s p o s s i b l e t h a t a small amount of a s t a b l e f3
phase which has not been d e t e c t e d by x-ray s t r u c t u r a l a n a l y s i s i s formed a t t h e
same time .
On quenching of t h e a l l o y containing 8 p e r c e n t Nb, t h e r e i s formed a r e l a t i v e l y s t a b l e UI phase which does not decompose f o r 2 h r s a t 400 and f o r 0.5 h r
a t 430, b u t decomposes a t 550'.
t h e r e i s formed a metaOn quenching of t h e a l l o y containing 15 p e r c e n t,%!I
s t a b l e f3 phase decomposing i n 2 h r s a t 400 i n t o a B1 phase enriched w i t h niobium and i n t o a w(f3

w) phase depleted of niobium.

Aging a t 550'

leads t o the

decomposition of t h e metastable phases and t o t h e formation of t h e a phase.

I n t h e a l l o y containing 20 percent Nb, t h e r e i s formed a r e l a t i v e l y s t a b l e
f3 phase which does n o t decompose f o r 2 h r s a t 400 b u t does decompose a t 550.

REFErnNCES
Dokl. AN SSSR, Vol.

Bagaryatskiy, Yu. A., Nosova, G. I.and Tagunova, T. V.

122, NO. 4, p. 593, 1958.
Ageyev, N. V. and Petrova, L. A.
1961.

Dokl. A% SSSR, Vol. 138, No. 2, p. 359,

Bychkov, Yu. F., Maskalets, V. I. and Rozanov, A. N.

zhurnal, Vol. 3, No. 4, p . 95, 1960.
Gridnev, V. N. and T r e f i l o v , V. I.
niya, Izd-vo AN SSSR, No. 14, p.

Inzhenerno-fizicheskiy

Voprosy f i z i k i metallov i rnetallovede-

5, 1962.

Gridnev, V. N., Rafalovskiy, V. A. and T r e f i l o v , V. I. Voprosy f i z i k i

metallov i metallovedeniya, Izd-vo AN SSSR, No. 14, p. 188, 1962.
Yelagina, L. A. and Lashko, N. F. Titanium i n I n d u s t r y
n o s t i ) . Oborongiz, p. 79, 1962.

i it an

v promyshlen-

Bagaryatskiy, Yu. A. , Nosova, G. I. and Tagunova, T. V. Problemy metallovedeniya i f i z i k i metallov, Metallurgizdat, No. 7, p. 307, 1962.
Gridnev, V. N., Petxov, Yu. N., Rafalovskiy, V. A. and T r e f i l o v , V. I.
Voprosy f i z i k i metallov i metallovedeniya, Izd-vo AN SSSR, No. 11, p. 82,
1960.
Bagaryatskiy, Yu. A., Tagunova, T. V, and Nosova, G. I. Voprosy f i z i k i
Izd-vo AN SSSR, No. 5, p. 210, 1958.
metallov i metallovede~~r'ya,

Lashko, N. F.

Zh. tekhn. f i z . ,

No.

7, p . 986, 1948.

Sadovskiy, V. D. and Yakutovich, M. V.

P. 369, 1947.

Dokl. AN SSSR, Vol.

57, go. 4,

Lerinman, R. M. and Shchegoleva, T. G. Abstracts of r e p o r t s given a t t h e

7 t h S c i e n t i f i c and Technical Conference on t h e Application of X-Rays t o
t h e Study of M a t e r i a l s ( ~ e z i s ydokladov V I I nauchno-tekhnicheskogo
soveshchaniya po primeneniyu rentgenovskikh luchey k issledovaniyu
m a t e r i a l o v ) , Izd-vo AN SSSR, Leningrad, p. 87, 1961.

DILATOMETRIC STUDY OF TRCWSFORMATIONS I N TITAKCUM ALLOYS

L. P. Luzhnikov, V. M. Novikova and A. P. Mareyev

The p r e s e n t study i s a p a r t of a more extensive i n v e s t i g a t i o n d e a l i n g w i t h

transformations during t h e h e a t treatment of t i t a n i u m a l l o y s . I n a d d i t i o n t o
t h e d i l a t o m e t r i c method, we a l s o use t h e determination of mechanical p r o p e r t i e s ,
t h e end-quench method, m i c r o s t r u c t u r a l a n a l y s i s , and o t h e r methods.
The d i l a t o m e t r i c method was used t o study t h e transformations i n t h e i n d u s t r i a l a l l o y s VT3-1, V T ~ ,V T ~ ,VT9 and VT14 ( t a b l e l ) , and w a s a l s o applied t o
a l l o y s of t h e following binary and t e r n a r y systems: Ti-Cr (2, 4, 6, 1 0 percent
~ r )Ti-Mo
,
(3, 6 , 1 0 p e r c e n t MO), Ti-Al-Cr, Ti-Al-Mo.
The t e r n a r y a l l o y s contained 4 p e r c e n t Al and t h e same amount of p s t a b i l i z e r a s t h e corresponding binary a l l o y s . The a l l o y s were prepared by double
f u s i o n i n vacuum a r c furnaces followed by hot f o r g i n g of i n g o t s and were
anium (ob = 41 kg/tnm5; 0.08 percent
s t u d i e d i n t h e forged s t a t e . Tec
O2

the preparation

oys.

The a l l o y s contained an average

of 0.12-0.13 p e r c e n t 02.
The change i n l e n g t h was recorded w i t h a Bollenrath d i l a t o m e t e r (made by
t h e L e i t z company) w i t h a programmed temperature r e g u l a t o r and a vacuum furnace.'
The d i i a t o m e t e r provided a 194-fold magnification.
I n t h e i n d i c a t e d s e r i e s of experiments, t h e change i7l t h e l e n g t h of t h e
specimens (1= 50 mm) was recorded w i t h t h e change i n temperature. The heating
was c a r r i e d o u t a t t h e r a t e of 4.5-5 deg/min. I n many cases, t h e d i l a t o m e t r i c
curves were recorded f o r t h e same a l l o y on two o r more specimens. The cilrves
i n d i c a t e d a complete r e p r o d u c i b i l i t y of t h e d a t a obtained. I n one of t h e a l l o y s
( ~+ i1 0 p e r c e n t C r ) , t h e influence of t h e heating r a t e (3 and 6 deg/min) on t h e
n a t u r e of t h e d i l a t o m e t r i c curves was s t u d i e d . It was found t h a t w i t h i n t h e s e
l i m i t s , t h e change i n t h e r a t e was not r e f l e c t e d i n t h e magnitude and p o s i t i o n
of t h e d i l a t o m e t r i c e f f e c t s on t h e temperature s c a l e .

'vacuum (6 x l o m 2mm Hg) was used i n c e r t a i n cases; a n e u t r a l atmosphere was

employed (pure argon) , I n a l l cases, no s i g n of oxidation of t h e specimens was
observed a f t e r t h e i r removal,

T m L E 1. CHEMICAL COMPOSITION OF

INDUSTRIAL ALLOYS (IN PERCENT).

Note:

Residual Ti

For reference purposes, dilatometric curves were recorded for iodide and
technical titanium (fig. 1). These curves are illustrated together with the
curves for the industrial alloys.
The temperature of the a 'f3 transformation for iodide titanium was found
to be 880, and for technical titanium, 8620, For iodide titanium, this is in
good a~reementwith McQuillen s data (882.5O) (ref. 1). The decrease in the
temperature of the polymorphic transformation in technical titanium is probably
due to the predominant action of f3 stabilizing impurities (chiefly iron and
silicon).
Before the dilatometric testing, the specimens of industrial alloys were
quenched in water from the temperature chosen for each alloy. Blanks (rods
12-13 mm in diameter) from which the specimens were made were subjected to heating for quenching, and other heat treatments of the alloys were carried out in
ordinary laboratory electric furnaces in an atmosphere of air. Specimens with
diameters of 4 mm (dilatometry) and 5 mm (mechanical tests) were turned from
these blanks. The gas-saturated layer was thus satisfactorily removed.
The dilatometric curves of most of the industrial alloys ( ~ 6 V,T ~ ,VT9,
~ ~ 1 did
4 ) not show any noticeable effects (fig. 1); this is apparently due to
the slight development of transformations in these alloys, and also to the
small difference in the dilatometric characteristics of the phases participating
in these transformations. This is confirmed by a relatively slight tendency of
the alloys under consideration to harden on aging (aging effect, 10-15percent).
It is also possible that the slight effects were not detected by the dilatometer
because the increase was too small.
Alloy VT3-1 (fig. 1) displays a distinct negative effect in the temperature
range of 286-400' (contraction), followed by a positive effect (expan~ion),~
which takes place at 450-4.70'.

ere

and subsequently the magnitude and position of the effects on the curves
are measured by using a photographic plate 18 x 24 cm on which the dilatometric
curves were recorded.

+'C
hD

I4

G
.li

a,

i3
e
g *c

Figure 1. Dilatometric curves of industrial alloys: 1, alloy VT14

(temperature of heating for quenching 8800); 2, alloy VT14 (8200);
3, alloy VT9 (950~); 4, alloy VT9 (900');
5 , alloy V T ~
(950');
6,
alloy V T ~(goo0); 7, alloy V T ~(950~); 8, alloy V T (
~
847');
9, alloy
VT3-1 (845O); lo, technical titanium (910') ; 11, iodide titanium.
This dilatometric effect indicates the formation of the w phase during the
decomposition of the f3 solid solution, fixed by quen
This is a new and important fact in the case of VT3Until now, almost all the investigators of this alloy have completely discounted the possibility that the w phase could form in this alloy (ref. 2).
Certain investigators groundlessly attribute the positive effect on the
dilatometric curves to the presence of the w phase (ref. 3).
We shall discuss this question below in more detail.
At the same time, the dilatometric curves of the other alloys show that
the formation of the w phase in the latter is impossible. In any event, this
fact is indisputable for the investigated temperatures of heating for guenching of these alloys. For the sake of a more correct and deeper understanding
of the dilatometric effects observed in complex multicomponent alloys, a study
was made of the dilatometric characteristics of a series of binary and ternary
alloys.
It should be noted that all the data published up to the present time
(refs. 4, 5, 6, etc.) indicate that the formation of the w phase during the decomposition of the f3 solid solution is associated with a negative effect of

change i n length (contraction). The disappearance of t h e w phase on f u r t h e r

heating i s due t o a p o s i t i v e e f f e c t (expansion).
The q u a n t i t i e s and composition of t h e coexisting phases i n multicomponent
alloys depend, i n addition t o t h e chemical and phase composition of t h e a l l o y ,
on t h e temperature and the length of time during which they a r e exposed t o it.
A l l of t h e above and t h e difference i n t h e dilatometric c h a r a c t e r i s t i c s of
t h e various phases i n d i c a t e t h a t a m u l t i p l i c i t y of f a c t o r s determine t h e t o t a l
( r e s u l t a n t ) c h a r a c t e r i s t i c s of a given a l l o y . This sometimes complicates t h e
i n t e r p r e t a t i o n of t h e dilatometric d a t a and causes c e r t a i n discrepancies i n t h e
l i t e r a t u r e data.

The binary and t e r n a r y alloys which we studied were quenched i n water a f t e r

being heated i n t h e f3 region.
Let us examine t h e dilatometric curves recorded f o r quenched specimens of
alloys T i - C r (2, 4, 6 and 10 percent ~ r beginning
)
with the upper curve corresponding t o t h e a l l o y T i + 1 0 percent C r ( f i g . 2 ) . I n t h e quenched s t a t e , t h i s
a l l o y c o n s i s t s of a fixed f3 phase which i s preserved i n t h e metastable s t a t e
approximately up t o 180'; a t t h i s temperature, a negative e f f e c t ( c o n t r a c t i o n )
due t o t h e formation of t h e w phase appears. A t a temperature of approximately
280-300, t h e formation of t h e w phase ceases, and t h i s phase begins t o dissolve
i n t h e f3 s o l i d solution, while a t t h e same time t h e dispersed a phase precipi t a t e s from t h e s o l u t i o n (up t o 4 0 0 ~ ) . Above 400' and up t o 530') t h e amount
of t h e a phase continues t o increase, and t h e l a t t e r coagulates, The subsequent
course of t h e dilatometric curve (above 530') corresponds t o a change i n t h e
composition and r e l a t i v e amounts of the a and f3 phase i n t h e two-phase system.
No eutectoid temperature i s observed on t h i s and t h e other curves. The next
curve p e r t a i n s t o t h e a l l o y T i + 6 percent C r , Since t h i s a l l o y i n t h e quenched
s t a t e had a f3 + w s t r u c t u r e , i t s curve begins with a negative e f f e c t . The twoBetween
phase f3 + w s t r u c t u r e i s preserved on heating up t o about 350-400'.
400 and 500, t h e amount of t h e w phase decreases, owing t o i t s d i s s o l u t i o n , and

Figure 2, Dilatometric curves of alloys of t h e system T i - C r :

1, a l l o y T i + 10 percent C r ; 2; a l l o y T i + 6 percent C r ; 3,
a l l o y T i + 4 percent C r ; 4, a l l o y T i + 2 percent C r .

t h e amount of t h e a phase which p r e c i p i t a t e s from t h e s o l i d s o l u t i o n i n c r e a s e s .

Above 500-530~, t h e a and f3 phases apparently e x i s t , but t h e i r composition and
r e l a t i v e amounts change.
The above explanation of t h e e f f e c t s shown by t h e d i l a t o m e t r i c curves i s
based on d a t a f o r t h e dependence of t h e hardness on t h e aging temperature and
a l s o on s t u d i e s (by t h e x - r a y s t r u c t u r a l method) of transformations i n analogous
a l l o y s described i n r e f e r e n c e s 4 and 7.
The curve f o r t h e a l l o y T i + 4 p e r c e n t C r i s g e n e r a l l y s i m i l a r t o t h e
preceding one, but a s should be expected, t h e d i l a t o m e t r i c e f f e c t s a r e very
weakly expressed i n t h i s c a s e .
F i n a l l y , t h e l a s t curve ( f o r t h e a l l o y T i + 2 p e r c e n t ~ r i)s c h a r a c t e r i s t i c
of quenched a l l o y s w i t h a m a r t e n s i t e s t r u c t u r e . It i s a n e a r l y s t r a i g h t l i n e ,
i n d i c a t i n g very s l i g h t transformations i n t h e s e a l l o y s during h e a t i n g . This
explanation of t h e course of t h e curves i s a l s o supported by t h e d a t a on t h e
end-quenching of t h e same a l l o y s ( f i g . 3).
This mechanism makes i t p o s s i b l e t o superimpose t h e d i l a t o m e t r i c curves
The a l l o y
(on t h e r i g h t ) onto t h e curves of t h e end-quenching (on t h e l e f t ) . '
quenched t o t h e B phase (curve 1 ) has a h a r d e n a b i l i t y curve w i t h a minimum
hardness a t t h e cooled end ( p o i n t on t h e o r d i n a t e ) .

Figure 3. Curves of end-quenching ( l e f t ) and d i l a t o m e t r i c

curves ( r i g h t ) : 1, a l l o y s quenched t o t h e @ s o l i d s o l u t i o n ;
2, a l l o y s quenched t o t h e f3 + w s t r u c t u r e ; 3, a l l o y s quenched
t o martensite; a , b and c--hardness values corresponding t o
t h e o r d i n a t e (maximum cooling r a t e on quenching).

ma he

curves of t h e end-quenching (GOST 5657-51) show t h e dependence of t h e hardness ( a x i s of o r d i n a t e s ) on t h e d i s t a n c e t o t h e end of t h e specimen cooled
w i t h w a t e r ( a x i s of a b s c i s s a s ) . As t h e d i s t a n c e from t h e end i n c r e a s e s , t h e
cooling r a t e decreases.

The a l l o y hardened t o t h e two-phase B + w s t r u c t u r e (curve 2) has a maximum hardness a t the cooled end and a t an appreciable distance from t h e l a t t e r .
F i n a l l y , t h e a l l o y quenched t o martensite (curve 3 ) has a maximum hardness
a t the cooled end; a s t h e distance from t h e l a t t e r increases, t h e hardness decreases. The maximum hardness of t h e most abruptly quenched a l l o y (ordinate on
t h e curves on t h e l e f t ) corresponds t o t h e p + w s t r u c t u r e , which i s followed by
a martensite s t r u c t u r e , and t h e minimum hardness corresponds t o t h e f i x e d p
phase ( a < c < b)

The dilatometric curves corresponding t o each of t h e a l l o y s considered a r e

shown i n t h e same f i g u r e on t h e r i g h t .
A d e f i n i t e confirmation of t h e s e d a t a i s provided by r e s u l t s of mechanical
t e s t s of t h e a l l o y s following various modes of aging. Let us examine t h e d i latometric curves of t h e t e r n a r y alloys Ti-Al-Cr containing 4 percent Al ( f i g .
4). It i s known from t h e l i t e r a t u r e t h a t t h e decomposition of t h e f3 s o l i d solut i o n with t h e formation of t h e w phase i s accelerated i f t h e a l l o y s contain
i n t e r s t i t i a l elements (oxygen, nitrogen, carbon); t h i s applies p a r t i c u l a r l y t o
t h e action of oxygen. Aluminum r e t a r d s t h i s transformation. It apparently
s h i f t s t h e transformation p -' w i n t o a region of higher temperatures. This is
p a r t i c u l a r l y apparent i n t h e a l l o y T i + 4 percent Al -t 10 percent C r .

The negative e f f e c t associated with t h e formation of t h e w phase ( f i g . 4)

decreased markedly and s h i f t e d i n t o t h e region of higher temperatures (250-350')
a s compared t o the a l l o y T i a 10 percent C r (180-300~). I n t h e region of 350480, t h e f3 + w + a phases apparently e x i s t i n t h i s alloy; t h e amount of t h e w
phase between 350-480' decreases, while t h e amount of t h e a phase increases.
Above 480-5000, t h e a l l o y has a two-phase s t r u c t u r e (a + @I. It should be noted
t h a t f o u r dilatometric curves were recorded f o r t h i s a l l o y on specimens which
were d i f f e r e n t but which were t r e a t e d i n t h e same manner. All t h e curves were
completely i d e n t i c a l . Alloying with aluminum introduced a subs-t;antial change

Figure 4. Dilatometric curves of a l l o y s of t h e system Ti-Al-Cr:

I, a l l o y T i + 4 percent Al + 10 percent C r ; 2, a l l o y T i + 4 percent Al + 6 percent C r ; 3, a l l o y T i + 4 percent Al + 4 percent
C r ; 4, a l l o y T i + 4 percent Al + 2 percent C r .

i n t o t h e course of t h e curve of t h e a l l o y T i + 6 percent C r ; i n t h i s a l l o y ,

aluminum s u b s t a n t i a l l y depressed t h e tendency t o form t h e w phase during quenching. The influence of aluminum on t h e a l l o y s T i + 4 percent C r and T i + 2 percent C r i s s l i g h t .
The curves of Ti-Cr a l l o y s with aluminum ( f i g .
p e r a t u r e (about 700) f a i r l y d i s t i n c t l y .
(fig.

4) show t h e e u t e c t o i d tem-

Let us examine t h e d i l a t o m e t r i c curves f o r t h e a l l o y s of t h e systems Ti-Mo

5) and Ti-Al-Mo ( f i g . 6).

The a l l o y Ti + 1 0 percent Mo i s apparently quenched t o t h e p s o l i d s o l u t i o n

w i t h a small amount of t h e w phase, since i t s curve begins w i t h a negative e f f e c t ; i n t h e temperature range of 500-590, a p o s i t i v e e f f e c t i s observed.
Ti

Both of t h e s e e f f e c t s s h i f t i n t o t h e range o
Al + 1 0 percent Mo ( f i g . 6).

+ 4 percent

Figure 5. Dilatometric curves of a l l o y s of t h e system Ti-Mo: 1, a l l o y T i + 10 percent Mo; 2, a l l o y

T i + 6 percent Mo; 3, a l l o y Ti + 3 percent Mo.

5
hD
5

i-4

F:

*d
e,

8
??

zo zoo

4ffo 6

1UUJ t,2'

Figure 6. Dilatometric curves of a l l o y s of t h e system

Ti-Al-Mo: 1, a l l o y T i + 4 percent Al + 10 percent Me;
2, a l l o y T i + 4 percent Al + 6 percent Mo; 3, a l l o y
Ti + 4 percent Al + 3 percent Mo.

The curves of t h e a l l o y s T i + 6 percent Mo and T i + 3 percent Mo do not

d i s p l a y any appreciable e f f e c t s . The a d d i t i o n of aluminum does n o t cause any
s u b s t a n t i a l change i n t h e c h a r a c t e r of t h e curves.
A s e r i e s of a d d i t i o n a l experiments was c a r r i e d out with t h e a l l o y VT3-1 f o r
t h e purpose of confirming t h e p o s s i b i l i t y of t h e formation of t h e w phase i n
t h i s alloy.

F i r s t , a d i l a t o m e t r i c curve was recorded f o r t h e a l l o y VT3-1 quenched from

t h e p region ( 1 0 5 0 ~ ) . It shows t h e absence of any e f f e c t s ( f i g . 7, curve 1 ) .
This i s i n agreement with t h e f a c t t h a t i n t h i s case t h e a l l o y was quenched t o
t h e a t phase (martensite).
A curve was recorded f o r t h e a l l o y VT3-1 quenched from 800'.
It i s n o t
i l l u s t r a t e d here because i t s shape i s t h e same a s t h a t of t h e curve which we
have i l l u s t r a t e d f o r t h e a l l o y quenched from 845O (see f i g . 1).

Figure 7 a l s o shows curve 2 f o r a l l o y VT3-1, recorded w i t h a specimen a f t e r

quenching from 845' and aging a t 350' f o r 1 0 h r s . The curve does not show a nega t i v e e f f e c t , s i n c e aging a t 350' had caused a p r a c t i c a l l y complete f3
w transformation p r i o r t o t h e recording of t h e d i l a t o m e t r i c curve.
+

Let us examine t h e aging e f f e c t s i n a l l o y s VT3-1 ( f i g . 8, curve 2) ,Ti + 10

percent Z r ( f i g . 8, curve 3) and T i + 4 percent Al + 10 p e r c e n t C r ( f i g . 8,
curve 1).
The aging e f f e c t i s characterized by an increase i n a given property a s a
r e s u l t of aging, i . e . , by a d i f f e r e n c e between t h e values of t h e property ( i n
t h i s case t h e Rockwell hardness) a f t e r aging and a f t e r quenching.
This increase of hardness (aging e f f e c t ) i n each a l l o y i s expressed i n percent r e l a t i v e t o t h e hardness i n t h e quenched s t a t e , The d u r a t i o n of aging a t
a l l temperatures was 1 0 hrs.
Quenching ( i n water) of t h e a l l o y s T i + 10 percent C r and T i + 10 p e r c e n t
C r + 4 percent Al was c a r r i e d out a f t e r they were heated i n t h e p region. The
a l l o y VT3-1 was quenched from t h e a + p region from 8 4 5 O , t h e standard temperat u r e of t h e heating f o r quenching of t h i s alloy.
As i s evident from f i g u r e 8, t h e nature of t h e change i n t h e hardening e f f e c t during aging of t h e two p a l l o y s i s s i m i l a r t o t h e nature of t h e change i n
t h i s e f f e c t i n a l l o y VT3-1, or, more exactly, i n t h e f3 s o l i d s o l u t i o n of t h i s
two-phase a l l o y . The s i m i l a r i t y of t h e curves c h a r a c t e r i z i n g t h e aging e f f e c t
i n a l l o y s VT3-1 and T i + 10 p e r c e n t C r i s p a r t i c u l a r l y pronounced. I n t h e region
of t h e maximum ( 3 0 0 - 4 0 0 ~ )t~h e i r aging e f f e c t s a r e even c l o s e r i n magnitude.

This s i m i l a r i t y i n t h e c h a r a c t e r of t h e change and i n t h e magnitude of t h e

aging e f f e c t s makes it p o s s i b l e t o assume a s i m i l a r i t y i n t h e n a t u r e of t h e
p w transformation as well.
+

Figure 7. Dilatometric curves of t h e a l l o y VT3-1:

1, quenching i n w a t e r from 1 0 5 0 ~30~ min; 2, quenching i n water from 8 4 5 O f o r 1 h r and aging a t 350
f o r 10 h r s .

Figure 8. Aging e f f e c t of t i t a n i u m a l l o y s f o r an
aging time of 10 h r s : 1, a l l o y T i + 1 0 p e r c e n t
C r + 4 p e r c e n t AX (quenched i n t h e @ region); 2,
a l l o y VT3-1 (quenched i n w a t e r from 845') ; 3, a l l o y T i 1- 1 0 p e r c e n t C r (quenched i n t h e @ region).
F i n a l l y , we s h a l l c i t e t h e dependence of c e r t a i n mechanical c h a r a c t e r i s t i c s
o f t h e a l l o y VT3-1 on t h e d u r a t i o n of aging a f t e r quenching from 845' ( t a b l e 2 ) .
A f t e r aging a t 350' ( t h e temperature of r a p i d formation of t h e w phase f o r
t h i s a l l o y ) f o r various p e r i o d s of time, t h e p l a s t i c i t y , p a r t i c u l a r l y as chara c t e r i z e d by elongation, decreased a t f i r s t , reaching a minimum i n 3 h r s , t h e n
increased again s u b s t a n t i a l l y a f t e r aging f o r 24 h r s . Apparently, t h e p l a s t i c i t y minimum corresponds t o t h e f u l l e s t @
w transformation, and t h e i n c r e a s e
i n t h e d u r a t i o n of aging t o 24 h r s , upon f u r t h e r decomposition of t h e f3 s o l i d
s o l u t i o n , l e a d s t o t h e appearance of t h e a phase, a decrease i n t h e amount of
t h e w phase, and an i n c r e a s e i n p l a s t i c i t y . Aging f o r 6 h r s a t 550 l e a d s t o
+

TABLE 2. DEPENDENCE OF THE MECHANICAL CHARACTERISTICS

ON THE AGING TIME OF ALLOY W3-1 AFTER QUENCRING FROM

843'.
Aging mode
Ob

t,

OC

T, hours

--

--

350
350
350
350
550

0.5
1

3
24

kg/mm2

115
141

144
147
154
128

6
percent

15
8
5.5
4.5

k'

percent

41
25
20

16
9

12

39

an appreciable i n c r e a s e i n d u c t i l i t y and a decrease i n s t r e n g t h . This corresponds t o a change i n t h e p r o p e r t i e s of t h e a l l o y r e s u l t i n g from t h e decomposit i o n of t h e p s o l i d s o l u t i o n w i t h t h e p r e c i p i t a t i o n of t h e a phase.

Thus, t h e above m a t e r i a l d e f i n i t e l y i n d i c a t e s t h e p o s s i b i l i t y of t h e format i o n of t h e w phase i n t h e a l l o y VT3-1 following t h e h e a t treatment of t h i s
a l l o y under c e r t a i n c o n d i t i o n s . These c o n d i t i o n s involve i t s quenching from t h e
two-phase a! + f3 region ( 8 4 5 O ) , when t h e (3 phase containing chromium and molybdenum above t h e c r i t i c a l concentration becomes f i x e d , and t o aging a t temperat u r e s i n t h e range of 286-460'.
The pronounced aging e f f e c t a s s o c i a t e d w i t h t h e formation of t h e w phase
t o 50 p e r c e n t ) makes it p o s s i b l e t o a s s e r t t h a t t h e maximum amount of t h e @
phase (5-8 p e r c e n t ) determined f o r t h e a l l o y VT3-1 i n r e f e r e n c e 2 i s q u i t e e r roneous. I n our view, t h e amount of t h e (3 phase i n t h i s a l l o y can reach 30-40
percent.
(.lp

Summary
1. A s t u d y was made of t h e transformations a s s o c i a t e d w i t h t h e h e a t
treatment of i n d u s t r i a l t i t a n j u m a l l o y s VT3-1, V T ~ ,~ 8 VT9
, and VT14, and a l s o
a l l o y s of t h e systems Ti-Cr, Ti-Mo, Ti-Al-Cr and Ti-Al-Mo by t h e d i l a t o m e t r i c
and o t h e r methods.

2. These i n d u s t r i a l a l l o y s i n t h e quenched s t a t e do not show any appreciab l e d i l a t o m e t r i c e f f e c t s during heating. An exception i s t h e a l l o y VT3-1, which
has a negative e f f e c t i n t h e temperature range of 286-400' a f t e r quenching from
t h e two-phase region (845').

3. The d i l a t o m e t r i c c h a r a c t e r i s t i c s of a s e r i e s of b i n a r y and t e r n a r y (with

aluminum) a l l o y s were studied; t h i s f a c i l i t a t e d t h e i n t e r p r e t a t i o n of t h e experimental d a t a f o r t h e a l l o y VT3-1.

4. The dilatometric i n v e s t i g a t i o n , t h e study of aging, and t h e use of t h e

end-quench method make it possible t o a s s e r t t h a t a f t e r quenching of t h e a l l o y
VT3-1 from 8 4 f ~ O , a f3 s o l i d s o l u t i o n of s u p e r c r i t i c a l concentration i s f i x e d together with t h e a phase. The w phase i s formed a s a r e s u l t of t h e aging (part i c u l a r l y i n t h e range of 350-500~) The amount of t h e fixed f3 phase can
apparently reach 30-40 percent. This explains t h e r e l a t i v e l y pronounced aging
e f f e c t of t h e a l l o y VT3-1 (up t o 50 ~ e r c e n t )

1. McQuillen, A. D. and McQuillen, M. K.

MOSCOW, 1958.
2.

Titanium itan an)

Metallurgizdat,

Vinogradova, Ye. A., Kohkhova, G. M. and Lashko, N. F. T i t a n v promyshhnn o s t i , Oborongiz ( s t a t e Publishing

e Defense Industry)
p. 121, 1961.

3. Verigina, Z. S.

Study of Phase Transformations i n I n d u s t r i a l Titanium

Alloys VT3 and VT3-1 (Issledovaniye f azovykh prevrashcheniy v promyshlennykh titanovykh splavakh VT3 i V T ~ - 1 ) . Author1s a b s t r a c t of Ca
's
Dissertation, Moscow, 1962.

4.

Bagaryatskiy, Yu. A., Tagunova, T. V. and Nosova, G. I. Problemy metallovedeniya i f i z i k i metallov, Metallurgizdat, Moscow, No. 5, 1958.

5. Brotzen, F. R., Harmon, E. L. and Troiano,

P* 4x3, 1955.

A.

, Vol.

203,

6 . Gridnev, V. N., Rafalovskiy, V.

A., Trefilov, V. I. and Chernenko, N. F.

Voprosy f i z i k i metallov i metallovedeniya, Izd-vo AN SSSR, No. 10,
P. 77, 1959.

7. Nosova,

G . I. X-Ray D i f f r a c t i n Study of Phase Transformations i n TitaniumBase Alloys (~entgenograficheskoyeissledovaniye fazovykh prevrashcheniy

v splavakh na osnove t i t a n a )
Author I s a b s t r a c t of Candidate s Dissertat i o n , TsNIIChM (Central S c i e n t i f i c Research I n s t i t u t e of Ferrous
~ e t a l l u r g y ) ,1961.

DISLOC~IONTFlEOIiY OF THl3 HYDROGEN BRITTLENESS OF TITANIUM ALLOYS

B. A. Kolachev, V. A. Livanov and A. A. Bukhanova

Numerous studies made by both Soviet and foreign investigators have shown
that there are two kinds of hydrogen brittleness of titanium and its alloys.
Brittleness of the first kind manifests itself at high deformation rates
and is associated with the appearance, in the structure of titanium and its
alloys, of hydride-phase precipitates which essentially act as internal cuts in
the metal. The explanation of the nature of this kind of brittleness presents
no difficulties.
Hydrogen brittleness of the second kind is manifested at low deformation
rates. It develops primarily in quenched alloys in which the hydrogen content
exceeds the solubility limit at the temperature of the tests. In this case,
solid solutions supersaturated with hydrogen are fixed on quenching which decompose on prolonged exposure to applied stresses with the formation of finely
dispersed hydride precipitates, causing a certain hardening of the alloys and
a sharp decrease in plasticity.
Hydrogen brittleness caused by decomposition which develops in the course
of deformation is the term applied to irreversible brittleness of the second
kind in the sense that if after a prolonged exposure to stresses the load is
removed, the plasticity of the alloys is not restored, and brittle failure is
observed in subsequent tests conducted at a high rate after any period of time
following the removal of the load. The explanation of brittleness of this type
does not present any particular difficulties either.
The most complex nature of hydrogen brittleness is that which develops in
titanium alloys at low deformation rates when the hydrogen content is below the
solubility limit at the temperature of the tests, and the development of brittleness is not accompanied by the appearance of hydride-phase precipitates. In its
most characteristic form, this brittleness develops in typical a -I- f3 alloys. It
may be termed reversible brittleness of the second kind. If an a + f3 titanium
alloy saturated with hydrogen is subjected to the prolonged action of stresses,
sources of hydrogen brittleness will arise in it, and if mechanical tests are
performed at a high rate immediately after the stresses are relieved, the alloys
will display a low plasticity. However, after the a + f3 alloy is aged following
the relief of previously applied stresses, its plasticity will be almost completely restored. Thus, after the relieving of preliminary stresses, the sources
of hydrogen brittleness are partially destroyed and their embrittling effect is
eliminated.
110

The following r u l e s govern r e v e r s i b l e hydrogen b r i t t l e n e s s of t h e second

kind ( r e f . 1 ) .
1. B r i t t l e n e s s of t h e second kind i s manifested over a d e f i n i t e temperat u r e range which depends on t h e deformation r a t e , n a t u r e of t h e a l l o y s (a, a: + @
o r @ a l l o y ) and t h e i r chemical composition.
2. A s t h e deformation r a t e i n c r e a s e s , t h e temperature range over which
t h e p l a s t i c i t y decreases i s reduced, t h e p l a s t i c c h a r a c t e r i s t i c s i n c r e a s e , and
if t h e deformation r a t e exceeds a c e r t a i n l i m i t , b r i t t l e n e s s is no l o n g e r
observed.

3. The temperature of t h e t r a n s i t i o n from viscous f a i l u r e t o b r i t t l e f a i l u r e r i s e s w i t h a decreasing deformation r a t e and i n c r e a s i n g hydrogen content.

4. F a i l u r e a t a low deformation r a t e t a k e s p l a c e along t h e g r a i n

boundaries.
S e v e r a l t h e o r i e s of t h e hydrogen b r i t t l e n e s s of a + @ a l l o y s have been
proposed. However, a s was shown i n r e f e r e n c e 2, t h e s e t h e o r i e s cannot account
f o r a l l t h e d e t a i l s of t h i s phenomenon. I n t h e p r e s e n t work, an attempt i s
made t o e x p l a i n t h e b a s i c r e g u l a r i t i e s of r e v e r s i b l e hydrogen b r i t t l e n e s s of
t h e second kind from t h e standpoint of t h e d i s l o c a t i o n theory.
It i s p o s t u l a t e d t h a t a t a temperature below some c r i t i c a l temperature To,
hydregen i s formed on t h e d i s l o c a t i o n s of t h e C o t t r e l l atmosphere. If t h e deformation r a t e i s low and t h e temperature i s not t o o high, s o t h a t t h e m o b i l i t y
of t h e hydrogen atoms i s comparable t o t h e r a t e of displacement of t h e d i s l o c a t i o n s , t h e atmospheres w i l l accompany t h e d i s l o c a t i o n s , lagging a c e r t a i n
d i s t a n c e behind them. Since t h e d i s l o c a t i o n i s t h e n acted upon by a f o r c e
which r e p e l s it back t o t h e i n i t i a l p o s i t i o n a t t h e c e n t e r of t h e atmosphere,
t h e r e s i s t a n c e t o p l a s t i c deformation i s somewhat increased. P l a s t i c deformat i o n i s created n o t only by t h e movement of t h e d i s l o c a t i o n s p r e s e n t i n t h e
c r y s t a l , but a l s o by t h e generation of new d i s l o c a t i o n s by any source under t h e
i n f l u e n c e of applied s t r e s s e s and t h e i r displacement along t h e g l i d e p l a n e .
Under t h e i n d i c a t e d conditions, newly formed d i s l o c a t i o n s w i l l become surrounded
by hydrogen atmospheres, and t h e i r behavior should not be s u b s t a n t i a l l y d i f f e r e n t from t h a t of "old" d i s l o c a t i o n s . The d i s l o c a t i o n s t o g e t h e r w i t h t h e hydrogen atmospheres, moving under t h e i n f l u e n c e of t h e applied s t r e s s e s , reach
t h e g r a i n boundary and may e i t h e r vanish a t t h e l a t t e r , producing a s h e a r s t e p
( i n t h i s case t h e hydrogen atmospheres a r e f r e e d ) , o r form a p i l e u p a t t h i s
boundary. I n e i t h e r of t h e s e cases, hydrogen accumulates a t t h e g r a i n boundary.
Since up t o 100 and more d i s l o c a t i o n s can move along a s i n g l e a c t i n g g l i d e plane,
and t h e p i l e u p may c o n s i s t of t h e same number of d i s l o c a t i o n s , a considerable
segregation of hydrogen a t t h e g r a i n boundaries should be expected. If t h e act u a l s t r e s s e s a r e high enough, a crack i s generated a t t h e g r a i n boundary on t h e
s t e p o r a t t h e top of t h e p i l e u p , and hydrogen apparently f a c i l i t a t e s n o t only
t h e g e n e r a t i o n of t h e crack but a l s o i t s f u r t h e r propagation.

The r e v e r s i b l e n a t u r e of t h i s b r i t t l e n e s s may be explained by t h e f a c t

t h a t i f t h e load i s removed p r i o r t o t h e appearance of cracks, thermal d i f f u s i o n w i l l g r a d u a l l y e q u a l i z e t h e hydrogen concentration over t h e volume of t h e
metal and w i l l a t l e a s t p a r t i a l l y e l i m i n a t e t h e s e g r e g a t i o n of hydrogen a t t h e
g r a i n boundary.

It should be noted t h a t i n p r i n c i p l e , d i s l o c a t i o n p i l e u p s may a r i s e n o t

only a t t h e boundary of t h e g r a i n b u t a l s o w i t h i n t h e l a t t e r . However, t h e s e
p i l e u p s apparently do not p l a y a d e c i s i v e p a r t i n t h e development of hydrogen
b r i t t l e n e s s . Before t h e conditions of t h e p i l e u p i n s i d e t h e g r a i n become
conducive t o t h e formation of a crack, t h e crack i s generated and begins t o
propagate a t t h e g r a i n boundary because of t h e h i g h e r degree o f s e g r e g a t i o n of
hydrogen and a l e s s e r r e g u l a r i t y i n t h e arrangement of t h e atoms. Thus, a
v i t a l concept i n t h e p o s t u l a t e d t h e o r y of hydrogen b r i t t l e n e s s i s t h e hypothesis
t h a t under c e r t a i n conditions, t h e d i s l o c a t i o n s move toward t h e g r a i n boundaries
t o g e t h e r w i t h t h e hydrogen atmospheres surrounding them, and t h e p r o g r e s s i n g
segregation of hydrogen causes a premature f a i l u r e .
The n a t u r e of t h e i n t e r a c t i o n of hydrogen atoms w i t h moving d i s l o c a t i o n s
depends s u b s t a n t i a l l y on t h e deformation temperature. If t h i s temperature i s
too low, t h e m o b i l i t y of t h e hydrogen atoms w i i l ' b e , . g o s l i g h t t h a t even a t a
r e l a t i v e l y low deformation r a t e v ( f i g . l ) , t h e d i s l o c a t i o n s w i l l not e n t r a i n
1
t h e hydrogen atmospheres, but escape o u t of them and move f r e e l y through t h e
metal. I n t h i s case, t h e extension curve shows a y i e l d dent, s o t h a t t h e y i e l d
p o i n t r i s e s , b u t t h e p l a s t i c i t y remains high f o r two reasons:
a.

The motion of t h e d i s l o c a t i o n s i s not r e t a r d e d by hydrogen clouds;

b.

The d i s l o c a t i o n s do not supply hydr

As t h e temperature r i s e s , t h e m o b i l i t y of t h e hydrogen atoms i n c r e

a t a c e r t a i n temperature Tn becomes comparable t o t h e v e l o c i t y of t h e d i s l o c a -

t i o n s a t t h e same deformation r a t e vl.

S t a r t i n g a t t h i s temperature, t h e

Temperature
Figure 1. Diagram of t h e influence of t e s t i n g
temperature and deformation r a t e on t h e t r a n s verse c o n t r a c t i o n of t i t a n i u m a l l o y s s a t u r a t e d
with hydrogen.

d i s l o c a t i o n s begin t o p a r t i a l l y e n t r a i n t h e hydrogen atmospheres, and t h i s

causes a decrease i n p l a s t i c i t y . A t some temperature T S n , t h e hydrogen atmospheres a r e completely e n t r a i n e d by t h e d i s l o c a t i o n s .
If t h e deformation r a t e remains unchanged a t v

1'

any f u r t h e r r i s e i n tem-

p e r a t u r e should n o t a f f e c t t h e p l a s t i c i t y appreciably.
Actually, from t h e equation r e l a t i n g t h e deformation r a t e v t o t h e v e l o c i t y
t h e d i s l o c a t i o n d e n s i t y p, and t h e minimum i n t e r a t o m i c
of t h e d i s l o c a t i o n s v
d'
d i s t a n c e b ( r e f . 3),
v = vdpb

(1)

it follows t h a t under t h e i n d i c a t e d conditions (v = c o n s t ) t h e q u a n t i t y of d i s l o c a t i o n s reaching t h e boundary p e r u n i t time remains unchanged t o a f i r s t

approximation. Although t h e r e s i s t a n c e of t h e accompanying atmosphere t o t h e
motion of d i s l o c a t i o n s should decrease t o some e x t e n t a s t h e temperature r i s e s ,
t h e amount of hydrogen supplied by t h e d i s l o c a t i o n s t o t h e g r a i n boundary w i l l
b e t h e same a s a t temperature TIn. Consequently, t h e specimens a t temperatures
above TIn w i l l e x h i b i t f a i l u r e almost a s b r i t t l e a s a t temperature Tn.
F i n a l l y , temperature To becomes s o high t h a t t h e C o t t r e l l atmospheres s t a r t
being broken down by t h e thermal motion. The d e n s i t y of t h e hydrogen atmospheres decreases, and t h e i r r e s i s t a n c e t o t h e motion of t h e d i s l o c a t i o n s dec r e a s e s . I n a d d i t i o n , each d i s l o c a t i o n b r i n g s fewer hydrogen atoms t o t h e g r a i n
boundary than i n t h e case of lower temperatures.
I n summary, beginning a t temperature To, t h e p l a s t i c i t y r i s e s sharply, and
when t h e C o t t r e l l atmospheres a r e completely broken down, hydrogen b r i t t l e n e s s
disappears.
If t h e deformation r a t e i s g r e a t e r than vl,

such a s , v2, t h e decrease i n

p l a s t i c i t y begins a t a higher temperature, s i n c e t h e m o b i l i t y of t h e hydrogen

atoms should be g r e a t e r a t a g r e a t e r v e l o c i t y of t h e d i s l o c a t i o n s , s o t h a t t h e s e
atoms can i n t e r a c t w i t h a moving d i s l o c a t i o n and accompany it. F i n a l l y , a t a
c e r t a i n deformation r a t e v
t h e temperature TIn, a t which t h e C o t t r e l l atmo-

3'

spheres begin t o be completely entrained by t h e moving d i s l o c a t i o n s , coincides

w i t h temperature To, above which t h e C o t t r e l l atmospheres a r e unstable, and a
sharp minimum then appears on t h e " p l a s t i c i t y - t e m p e r a t u r e " curve.

The temperature of t h e complete r e s t o r a t i o n of p l a s t i c i t y , TI0, apparently

depends
on t h e deformation r a t e . As was i n d i c a t e d e a r l i e r , above temperature
To, t h e C o t t r e l l . atmospheres become unstable and a r e gradually broken down by
t h e thermal motion. I f it i s considered t h a t t h e moving d i s l o c a t i o n s c a t t e r s
i t s energy along t h e p a t h of i t s motion and t h a t f o r t h i s reason, i n a d d i t i o n
t o t h e thermal energy, t h e adjacent atoms acquire energy of s c a t t e r i n g which
increases w i t h r i s i n g v e l o c i t y of t h e d i s l o c a t i o n , then one should expect t h e
temperature of t h e complete r e s t o r a t i o n of p l a s t i c i t y t o decrease w i t h an i n creasing deformation r a t e .
A t s u f f i c i e n t l y high deformation r a t e s of t h e order of v4, t h e d i s l o c a t i o n s

escape from t h e surrounding hydrogen atmospheres over t h e e n t i r e temperature

i n t e r v a l of e x i s t e n c e of t h e s e atmospheres.
L e t us now t u r n t o a mathematical a n a l y s i s of t h e p i c t u r e drawn above.
The c r i t i c a l v e l o c i t y v a t which t h e atmospheres begin t o be e n t r a i n e d by t h e
C

moving d i s l o c a t i o n s i s given according t o C o t t r e l l ( r e f . 3) by t h e equation

4~
vc = 1
where D i s t h e d i f f u s i o n c o e f f i c i e n t of t h e impurity; 1 i s t h e c h a r a c t e r i s t i c
length.
The c h a r a c t e r i s t i c l e n g t h 1may be found from t h e equation

h-l'

= 4t1bsr2
h-T '

(2)

where p i s t h e shear modulus; s a r e t h e s t r e s s e s caused by t h e dissolved atoms;

r i s the r a d i u s of t h e impurity atom; k i s Boltzmannfs constant; T i s t h e
absolute temperature.
On t h e b a s i s of equation ( 1 ) ) t h e c r i t i c a l deformation r a t e may t h e n be
expressed by t h e equation

-3'

Assuming t h a t D = Doe kT, where Q i s t h e a c t i v a t i o n energy of t h e d i f f u s i o n of

hydrogen i n titanium, we f i n d t h a t

Thus, i n keeping w i t h t h e g e n e r a l assumptions made above, t h e c r i t i c a l deformation r a t e a t which t h e d i s l o c a t i o n s begin t o e n t r a i n t h e hydrogen atmospheres i n c r e a s e s w i t h r i s i n g temperature. It i s important t o note, however,
t h a t t h i s r a t e i s independent of t h e hydrogen content of t h e a l l o y .
On t h e c o n t r a r y , t h e temperature a t which t h e p l a s t i c i t y begins t o be r e s t o r e d , To, and t h e r e l a t e d temperature TI0 depend s t r o n g l y on t h e average hydrogen concentration Co ( r e f . 31, s o t h a t

where
r

y,,

i s t h e maximum bond energy of t h e hydrogen atom, equal t o

A
--r0 4- d'

being t h e minimum d i s t a n c e of t h e impurity atom from t h e d i s l o c a t i o n c e n t e r

and d being t h e e f f e c t i v e d i s l o c a t i o n width.

The dependence of TI0 on t h e hydrogen content i s shown g r a p h i c a l l y ( f i g . 2 ) .
The same f i g u r e shows t h e temperatures TI, T2, T

and T4 given by e q u a t i o n ( 3 ) ,

below which t h e hydrogen b r i t t l e n e s s does n o t develop when t h e t e s t s a r e c a r r i e d

o u t a t t h e r a t e s vl, v2, v3 and vj+, s i n c e t h e v e l o c i t y of t h e d i s l o c a t i o n s cons i d e r a b l y exceeds t h e m o b i l i t y of t h e atoms.

Thus, t h e temperature range i n

Figure 2. Dependence of t h e temperature

range of hydrogen b r i t t l e n e s s of titanium
a l l o y s on t h e hydrogen content.

which the hydrogen brittleness can develop is limited at the top by the temperaand at the bottom by the
ture of the breakdown of the Cottrell atmospheres T
0'

temperature Tn below which the dislocations escape from the Cottrell atmospheres.
The point of intersection characterizing these temperatures determines the maximum permissible hydrogen concentration up to which the hydrogen brittleness is
not manifested at a given deformation rate. Thus, for example, at a deformation
rate vl, hydrogen brittleness is not displayed over the entire temperature interval if the hydrogen content is less than C

1'
If the hydrogen concentration is greater than C the temperature range of
1'
hydrogen brittleness increases with rising hydrogen content. As the deformation rate increases, the hydrogen concentration at which hydrogen brittleness
begins to be observed rises, and the brittleness temperature range becomes
smaller.
Such are the basic assumptions of the dislocation theory of hydrogen brittleness. The following question arises: How closely do they agree with the experimental data? We illustrate (fig. 3) the dependence of the transverse contraction of the alloy Ti 140A (2 percent Fe; 2 percent Cr; 2 percent MO) on the
temperature of the tests for various displacement rates of the cross-bars of
the rupture-test machine (ref. 4). The qualitative agreement of the behavior
of hydrogen-saturated titanium alloys predicted by the theory with the experimental data is unquestionable.
The same data make it possible to carry out an approximate but quantitative
verification of the proposed theory. If it is assumed in accordance with Haynes
(ref. 5) that p =

4.10~~
dynes/cm 2, r

= 1.5*10m8cm, b = 3.10-8 cm, and e =

Temperature,

OC

Figure 3. Dependence of the transverse contraction

of Ti 140A on the testing temperature at various
deformation rates: 1, 25.4 mm/min; 2, 12.7 mm/min;
3, 6.35 mrn/min; 4, 2.54 mm/min; 5 , 1.gmm/min;
6, 0.64 mm;min; 7, 0.13 mm/min.

0.04,

then A = 6.5.1~-21 e r g cm.

The d i s l o c a t i o n d e n s i t y p i n annealed metals i s of

8
t h e order of 10 emm2. Thus, t h e only remaining unknown q u a n t i t i e s i n equation
(3) a r e Do and Q. From reference 5 it follows t h a t t h e a c t i v a t i o n energy of
hydrogen d i f f u s i o n i n t h e f3 phase of t h e a l l o y T i 140A i n t h e temperature range
of -120 t o e50 i s approximately 3000 cal/mole. Assuming t h e d i f f u s i o n c o e f f i c i e n t of hydrogen i n t h e f3 phase of t h e a l l o y T i 140A a t room temperature t o be
t h e same a s i n t h e a l l o y ~ i - 4
percent Al-4 percent Mn, namely 1 . 9 * 1 0 - ~cm2/see,
we f i n d Do, and f o r t h e c r i t i c a l r a t e of r e l a t i v e deformation we o b t a i n t h e
formula

8
8
8
2
For d i s l o c a t i o n d e n s i t i e s of O . 5 * l O , 0.75-10 and 10 cm"
t h i s equation
i s represented g r a p h i c a l l y ( f i g . 4). The same graph shows t h e temperatures a t
which t h e p l a s t i c i t y of t h e a l l o y T i 140A begins t o decrease a t various deformation rates.

Further, i f it i s assumed t h a t r
maximum bond energy um,turns

= 1.5*10-8 cm and b = 3*10-8 cm, t h e

out t o be 0.093 eV.

assumes t h e form shown g r a p h i c a l l y i n f i g u r e

5.

I n t h i s case, equation

The same graph shows t h e

calculated curves
experimental curve

Figure 4. Temperature of t h e s t a r t of decrease i n

p l a s t i c i t y Tn versus deformation r a t e vd f o r a l l o y

3, p

8 em-*;

= 10

0 , experimental p o i n t s .

(4)

H2, w t p e r c e n t
Figure 5. Temperature of t h e s t a r t of
r e s t o r a t i o n of p l a s t i c i t y To versus hydrogen content f o r t h e a l l o y T i 1 4 0 ~ :
1, um, = 0 . 1 eV; 2,
= 0.09 eV;

urn,

3, %ax-- 0.08 eV; 4, experimental curve.

expected curves f o r bond e n e r g i e s from 0.08 t o 0 . 1 eV, and g i v e s temperatures
corresponding t o t h e sharp minimum on t h e "cross s e c t i o n - t e s t i n g temperature"
curves f o r t h e a l l o y T i 140A w i t h various hydrogen contents.
Since t h e a r t i c l e g i v e s a very approximate c a l c u l a t i o n which i n c l u d e s a
number of s i m p l i f i c a t i o n s , due p a r t i c u l a r l y t o t h e f a c t t h a t not a l l t h e physic a l q u a n t i t i e s a r e known i n t h e temperature i n t e r v a l of i n t e r e s t , it should be
recognized t h a t t h e agreement between t h e proposed mechanism of r e v e r s i b l e hydrogen b r i t t l e n e s s of t h e second kind and t h e experimental d a t a i s f u l l y s a t i s f a c t o r y . It may be assumed t h a t a f u r t h e r development and refinement of t h e
d i s l o c a t i o n t h e o r y of hydrogen b r i t t l e n e s s w i l l permit a more rigorous quantit a t i v e i n t e r p r e t a t i o n of t h e observed experimental f a c t s .
Summary
1. A d i s l o c a t i o n t h e o r y of hydrogen b r i t t l e n e s s developing a t low deformat i o n r a t e s i s proposed, based on t h e assumption t h a t on t h e d i s l o c a t i o n s , hydrogen forms C o t t r e l l atimspheres which a r e e n t r a i n e d by t h e d i s l o c a t i o n s over
a c e r t a i n temperature range. The d i s l o c a t i o n s t r a n s p o r t t h e hydrogen toward
t h e g r a i n boundaries, causing t h e appearance of hydrogen segregations which
f a c i l i t a t e t h e g e n e r a t i o n and propagation of cracks.
2. This t h e o r y makes it p o s s i b l e t o account f o r t h e b a s i c r e g u l a r i t i e s
involved i n t h e hydrogen b r i t t l e n e s s of a + /3 a l l o y s :

a. Increase i n t h e i r tendency toward hydrogen b r i t t l e n e s s with an increase

i n hydrogen content, decrease i n temperature, and decrease i n t h e deformation
rate;
b.

I n t e r c r y s t a l l i n e character of t h e f a i l u r e ;

c. Increase i n t h e temperature of t h e t r a n s i t i o n from vjscous f a i l u r e t o

b r i t t l e f a i l u r e with increasing hydrogen content.

3. The r e l a t i o n s h i p s predicted by t h e d i s l o c a t i o n theory of hydrogen

b r i t t l e n e s s a r e i n s a t i s f a c t o r y agreement with t h e experimental d a t a f o r t h e
a l l o y T i 140A.

1. Livanov, V. A.,

Bukhanova, A. A. and Kolachev, B. A.

( ~ o d o r o dv t i t a n e ) . Metallurgizdat, 1962.

2. Livanov, V. A., Bukhanova, A. A.,

Titanium and I t s Alloys
P. 207, 1963.

C o t t r e l l , A. H.
1958

i it an

Kolachev, B. A, and Guselfnikov, N. N.

i yego s ~ l a v y ) . Izd-vo A;N SSSR, No. 10,

Dislocations and P l a s t i c Flow i n Crystals, Metallurgizdat,

4.

W i l l i a m s , D. N., Schwarzberg, F. K. and J a f f e e , R. I.

p. 802-804, 1959.

5.

Haynes, R.

J. 1

Hydrogen i n Titanium

, vol.

88,

NO.

Trans. ASM, Vol. 60,

12, p. 509-512, 1960.

EFFECT OF ALLOYING ON THE PHYSICOCFJEMICAL PROPERTIES OF TITANIUM

S. F. Kovtun and R. A. Ulfyanov

Because of t h e i r h i g h s t r e n g t h , low d e n s i t y , and high c o r r o s i o n r e s i s t ance, t i t a n i u m and i t s a l l o y s a r e f i n d i n g i n c r e a s i n g l y wider a p p l i c a t i o n s i n

technology.
I n a d d i t i o n t o t h e s t u d y of t h e mechanical p r o p e r t i e s of titanium-base
a l l o y s , t h e i n v e s t i g a t i o n of t h e p h y s i c a l p r o p e r t i e s of t h e s e a l l o y s , p a r t i c u l a r l y t h e e l e c t r i c a l r e s i s t i v i t y and c o e f f i c i e n t of l i n e a r expansion, a r e of
s c i e n t i f i c and p r a c t i c a l i n t e r e s t .
I n t h e p r e s e n t work, a study was made of t h e i n f l u e n c e of a s e r i e s of
a d d i t i o n s on t h e v a r i a t i o n i n t h e e 1 e c t r i c a . X r e s i s t i v i t y and c o e f f i c i e n t of
l i n e a r expansion of t i t a n i u m and a l s o i t s o x i d i z a b i l i t y . The a d d i t i o n s used
were elements contained i n mass-produced Soviet a l l o y s (aluminum, chromium,
molybdenum) a s w e l l a s elements which thus f a r have not been used f o r a l l o y i n g
but which can be employed t o r a i s e t h e high-temperature s t r e n g t h (rhenium,
tantalum, i r i d i u m ) , t h e chemical s t a b i l i t y (palladium, beryllium) and t o i m prove t h e t e c h n o l o g i c a l p r o p e r t i e s (lanthanum). The a l l o y s were prepared by
melting i n an a r c furnace w i t h a nonconsumable e l e c t r o d e i n an atmosphere of
argon which was f i r s t p u r i f i e d by being passed through molten l i t h i u m ( r e f .
1).
The s t a r t i n g m a t e r i a l s used were t i t a n i u m sponge TGO, aluminum AOO,
e l e c t r o l y t i c chromium, 99.9 p e r c e n t pure rhenium, and o t h e r elements of high
purity.
I n o r d e r t o achieve a uniform d i s t r i b u t i o n of t h e a l l o y i n g elements i n
t h e i n g o t s , t h e a l l o y s were remelted a t l e a s t 5 times. To avoid t h e evaporat i o n of v o l a t i l e components during melting (chromium, lanthanum, e t c . ), t h e
argon p r e s s u r e i n t h e a r c furnace was r a i s e d t o t h e atmospheric value and
higher. After t h e melting, t h e a l l o y s were r o l l e d i n t o rods on a vacuum r o l l ing m i l l ; t h i s caused an a d d i t i o n a l degassing of t h e metals and prevented
t h e i r oxidation (ref. 2). P r i o r t o t h e investigation., t h e specimens prepared
from t h e rods were vacuum-annealed f o r 40 hours a t 1200'.

E l e c t r i c a l R e s i s t i v i t y of t h e Alloys
The e l e c t r i c a l r e s i s t i v i t y of t h e a l l o y s was s t u d i e d i n t h e temperature
range of -195 t o 1250. The r e s i s t i v i t y was measured by t h e compensation method
i n a vacuum u n i t w i t h a r e s i d u a l p r e s s u r e i n t h e working chamber no h i g h e r than
1-10-~
mm Bg. The measurements e s t a b l i s h e d t h a t a s t h e temperature r i s e s from
-195O t o about 350-boo0, t h e change i n t h e r e s i s t i v i t y of both i o d i d e and techn i c a l t i t a n i u m ( f i g . 1) was l i n e a r .

A s t h e heating increased f u r t h e r , t h e temperature c o e f f i c i e n t of t h e e l e c t r i c a l r e s i s t i v i t y , while remaining p o s i t i v e , decreased i n magnitude a s t h e

temperature rose. This may be explained by t h e f a c t t h a t i n t r a n s i t i o n metals,
which include titanium, t h e number of s e l e c t r o n s passing i n t o t h e d o r b i t a l dec r e a s e s w i t h r i s i n g temperature, and t h e r e l a t i o n p = f ( t ) d e v i a t e s from l i n e a r i t y (ref. 3).
I n both t e c h n i c a l and i o d i d e titanium, t h e e l e c t r i c a l r e s i s t i v i t y dec r e a s e s s h a q l y a t 882' due t o a polymorphic transformation. I n i o d i d e titanium,
t h e temperature range of t h e transformation i s no g r e a t e r t h a n 6 t o lo0, and i n
t e c h n l c a l t i t a n i u m it widens t o 20' owing t o t h e presence of i m p u r i t i e s .
As t h e temperature i s r a i s e d f u r t h e r , t h e r e s i s t i v i t y of both i o d i d e and
t e c h n i c a l t i t a n i u m i n c r e a s e s , but t h e temperature c o e f f i c i e n t of t h e r e s i s t i v i t y
of @-Ti i s considerably s m a l l e r t h a n t h a t of a-Ti.

The value of t h e r e s i s t i v i t y of i o d i d e and t e c h n i c a l t i t a n i u m and t h e

c h a r a c t e r of t h e i r temperature dependence a r e i n agreement w i t h t h e d a t a of
reference 4.
The i n v e s t i g a t i o n s showed t h a t t h e e f f e c t i v e n e s s of t h e i n f l u e n c e of a l loying elements on t h e hardness and e l e c t r i c a l r e s i s t i v i t y of t i t a n i u m ( f i g . 2)
follow t h e same p a t t e r n a s i n t h e case of metals of t h e cubic system. A t t h e
same atomic concentration, a g r e a t e r i n c r e a s e i n hardness and r e s i s t i v i t y i s
produced by a l l o y i n g elements whose atomic diameters d i f f e r more s t r o n g l y from
t h e atomic diameter of t i t a n i u m , independently of t h e type of t h e c r y s t a l
l a t t i c e . The only exception i s lanthanum,which causes a l e s s pronounced i n c r e a s e
i n hardness and r e s i s t i v i t y ; t h i s may be due t o i t s deoxidizing e f f e c t . Lanthanum,
which has a g r e a t a f f i n i t y f o r oxygen, r i d s t i t a n i u m of a c e r t a i n amount of i t s
impurities.

It follows from t h e graphs of f i g u r e s 3 and 4 t h a t t h e a l l o y i n g of t i t a n i u m

causes an i n c r e a s e i n t h e e l e c t r i c a l r e s i s t i v i t y and changes t h e temperature and
range of t h e a
f3 transformation. Among t h e i n v e s t i g a t e d metals a t equal conc e n t r a t i o n s , t h e g r e a t e s t i n c r e a s e i n r e s i s t i v i t y i s produced by aluminum, rhenium, and chromium. The l e s s e r i n c r e a s e i n r e s i s t i v i t y upon a l l o y i n g w i t h
molybdenum may be due t o t h e presence of t h e @ phase. The graphs a l s o show
t h a t both i n t h e a l l o y s and i n pure titanium, t h e temperature c o e f f i c i e n t of
e l e c t r i c a l r e s i s t i v i t y decreases w i t h t h e temperature, and t h i s decrease i s more
pronounced t h e h i g h e r t h e content of t h e a l l o y i n g element.
+

Figure 1. Temperature dependence of e l e c t r i c a l

r e s i s t i v i t y : 1, iodfde titanium; 2, t e c h n i c a l
titanium.

A t temperatures from -196 t o 200') t h e h i g h e r t h e content of chromium i n

t h e a l l o y , t h e more it r a i s e s t h e e l e c t r i c a l r e s i s t i v i t y of titanium. A t higher
temperatures, t h e r e s i s t i v i t y of t h e a l l o y w i t h 4 w t p e r c e n t C r (3.6 a t . p e r c e n t )
i s found t o be smaller t h a n i n t h e a l l o y w i t h 2 w t p e r c e n t C r , which may be due
t o t h e presence of a e u t e c t o i d i n t h e a l l o y , o r more probably of t h e chemical
compound TiCr2, which e n t e r s i n t o the e u t e c t o i d .

I n t h e region of t h e @ phase, t h e i n c r e a s e of r e s i s t i v T t y i n a l l o y s with

2 p e r c e n t C r , and p a r t i c u l a r l y i n t h e a l l o y w i t h 4 p e r c e n t C r , i s considerably

Figure 3. Temperature dependence of t h e e l e c t r i c a l r e s i s t i v i t y of a l loys of titanium with aluminum, molybdenum, and chromium: a, a l l o y T i Al (1, 6 percent Al; 2, VT5; 3, 4 percent Al; 4, 2 percent Al; 3, TGO);
b , a l l o y Ti-Mo (1, 4 percent Mo; 2, 2 percent Mo; 3, TGO); c, a l l o y
Ti-Cr (1, 4 percent C r ; 2, 2 percent C r ; 3, TGO); d, a l l o y of t h e system Ti-Al-Mo-Cr (1, 5 percent A l + 2 percent Mo + 2 percent C r ; 2, 2
percent Al + 2 percent Mo + 2 percent C r ; 3, TGO).
l e s s than i n t h e region of t h e a phase. Molybdenum and chromium lower t h e
f3 transformation, while aluminum r a i s e s it. Apparently,
temperature of t h e a
f3 region upon a l l o y i n g with aluminum which we observed
the widening of t h e a
i s due t o t h e influence of oxygen and nitrogen, which a r e present i n t e c h n i c a l
titanium i n l a r g e r q u a n t i t i e s than i n t h e iodide titanium used t o p l o t t h e
Ti-Al phase diagram i n reference 5.
Complex a l l o y i n g l e a d s t o an i n c r e a s e i n r e s i s t i v i t y over t h e e n t i r e range
The r e s i s t i v i t y of t h e a l l o y s of t h e system T i - Al-Mo-Cr i s
of -196 t o 1250'.

Figure 4. Temperature dependence of t h e e l e c t r i c a l r e s i s t i v i t y

of e l e c t r o l y t i c a l l o y s of titanium with rhenium, tantalum,
palladium and lanthanum: a, a l l o y Ti-Re (1, 3 percent Re; 2, 1
percent Re; 3, 0 . 7 percent Re; 4, 0.4 percent ~ e ) ;b, a l l o y
Ti-Ta (1, 13 percent Ta; 2, 6.5 percent Ta; 3, 1.7 percent Ta;
4, TGO) ; c, a l l o y Ti-Pd (1, 2 percent Pd; 2, 0.8 percent Pd;
3, 0.2 percent Pd; 4, TGO) ; d, a l l o y Ti-La (1, 2.2 p e r c e n t La;
2, 1.8 percent La; 3, 1 percent La; 4, 0.4 percent ~ a )

higher than i n binary a l l o y s , p a r t i c u l a r l y a t room temperatures and negative

p transformation i n comtemperatures. The temperature of t h e s t a r t of t h e a
plex a l l o y s decreases, and t h e transformation range expands t o 200-300' instead
of t h e 20' f o r t e c h n i c a l titanium. When up t o 1 w t percent rhenium i s added,
it r a i s e s t h e r e s i s t i v i t y over t h e e n t i r e temperature range. It s t a b i l i z e s t h e
p phase by decreasing t h e temperature of t h e a B transformation and extending
t h e a + p region, a s was found e a r l i e r by o t h e r methods of i n v e s t i g a t i o n ( r e f .
6). A t 3 w t percent Re, t h e r e s i s t i v i t y of t h e a l l o y a l s o i n c r e a s e s w i t h t h e
-+

-+

temperature, but l e s s than i n pure titanium and i n a l l o y s with a low rhenium

content. For t h i s reason, a t temperatures above 350, owing t o t h e presence of
t h e f3 phase, t h e r e s i s t i v i t y i s l e s s than i n a l l o y s with a rhenium concentrat i o n up t o 1 w t percent and even l e s s than i n pure titanium.
When titanium i s alloyed with tantalum (up t o 10 w t percent), t h e r e s i s t i v i t y changes i n s i g n i f i c a n t l y over t h e e n t i r e temperature range. A t temperatures
above 600, t h e a l l o y s of t h e system Ti-Ta have a lower r e s i s t i v i t y than techn i c a l titanium. Tantalum lowers t h e temperature of t h e a -+ f3 transformation
appreciably.
I n a l l o y s of titanium with palladium, t h e r e s i s t i v i t y increases over t h e
e n t i r e temperature range a s t h e palladium content r i s e s . Palladium lowers t h e
f3 transformation by s t a b i l i z i n g t h e f3 phase.1 Lanthanum
temperature of t h e a
s l i g h t l y increases t h e r e s i s t i v i t y of t h e a l l o y s over t h e e n t i r e temperature
range. Lanthanum a l s o s l i g h t l y increases t h e temperature of the polymorphic
transformation of titanium, a s was established e a r l i e r by other methods of
investigation.

Thermal Expansion
The c o e f f i c i e n t of l i n e a r expansion of t h e a l l o y s was measured by means of
a vacuum dilatometer having a reading s c a l e with a p r e c i s i o n of 0.002 mm. The
vacuum was maintained a t 1*10-~
mm Hg a t a l l temperatures. Graphs of t h e elongat i o n per u n i t length were p l o t t e d by taking i n t o account t h e expansion of the
quartz of t h e dilatometer.
Results of t h e measurements showed t h a t t h e dilatometric curves of iodide
and t e c h n i c a l titanium ( f i g . 5) coincide up t o 800'.
A t t h e temperature of t h e phase transformation t h e r e i s observed a d i s t i n c t
i n f l e c t i o n i n d i c a t i n g a change i n the c o e f f i c i e n t of l i n e a r expansion associated
with t h e transformation t o the f3 phase.

I n accordance with t h e graph, t h e temperature dependence of t h e l i n e a r expansion i n t h e range from zero t o 700 i s expressed by t h e formula

where at = 8.0-10- 6

, f3 =

2 . 7 * 1 0 - ~ , and t i s t h e temperature i n

OC.

I n t h e indicated temperature range, the c o e f f i c i e n t of l i n e a r expansion

' ~ ta content of 0.4 w t percent Pd, t h e r e s i s t i v i t y of t h e a l l o y increases

i r r e g u l a r l y over the e n t i r e temperature range.

According t o ~ G n e i s e n ' sequation, t h e breakdown of t h e c r y s t a l l a t t i c e

( f u s i o n ) of pure metals occurs at temperatures a t which t h e volume i n c r e a s e s by
6 p e r c e n t over t h e volume a t a b s o l u t e zero. Hence, t h e lower t h e melting p o i n t
of t h e metal, t h e higher t h e c o e f f i c i e n t of l i n e a r expansion, s i n c e i n t h i s
case a 6 p e r c e n t i n c r e a s e i n volume t a k e s p l a c e over a narrower temperature
range, from a b s o l u t e zero t o t h e melting p o i n t .
When t i t a n i u m i s alloyed, t h e change i n t h e average c o e f f i c i e n t of l i n e a r
expansion depends p r i m a r i l y on t h e content of t h e a l l o y i n g elements ( f i g 6).
The higher t h e concentration of t h e a l l o y i n g element, t h e g r e a t e r i s t h e change
i n t h e c o e f f i c i e n t of l i n e a r expansion.

On a l l o y i n g w i t h chromium, aluminum, lanthanum and palladium, t h e c o e f f i c i e n t of l i n e a r expansion of t h e a l l o y s i n c r e a s e s , while tantalum, molybdenum,

and p a r t i c u l a r l y rhenium decrease t h i s coef f i c i e n t
Rhenium, tantalum, chromium

Figure 3. Dilatometric curves of i o d i d e (1) and

t e c h n i c a l ( 2 ) t i t a n i u m and temperature dependence
of t h e medium ( 0 - 4 0 0 ~ )c o e f f i c i e n t of l i n e a r expansion of titanium.

Content of a l l o y i n g element, w t p e r c e n t
Figure 6. E f f e c t of a l l o y i n g elements on t h e medium c o e f f i c i e n t
of thermal expansion of t i t a n i u m i n t h e range of 0-boo0.

and molybdenum have a lower c o e f f i c i e n t of l i n e a r expansion than t i t a n i u m ,

while i n palladium and aluminum, t h i s c o e f f i c i e n t i s h i g h e r than i n t i t a n i u m .
The change i n t h e c o e f f i c i e n t of l i n e a r expansion upon a l l o y i n g i s c h i e f l y
determined by t h e r e l a t i o n of t h e c o e f f i c i e n t s of l i n e a r expansion of t h e base
of t h e a l l o y t o t h a t of t h e a l l o y i n g elements. This i s probably what causes t h e
i n c r e a s e i n t h e c o e f f i c i e n t of l i n e a r expansion of t i t a n i u m on a l l o y i n g w i t h
chromium, whose c o e f f i c i e n t i s s m a l l e r t h a n t h a t of t i t a n i u m . I n a d d i t i o n , t h e
average c o e f f i c i e n t of l i n e a r expansion i s a f f e c t e d by t h e phase composition of
t h e a l l o y s ( a t t h e concentrations studied, t h e a l l o y s w i t h chromium may c o n t a i n
t h e chemical compound ~ i ~ r * ) .
I n a s t u d y of t h e e f f e c t of a l l o y i n g on t h e c o e f f i c i e n t of l i n e a r expansion, it was noted t h a t when t h e a l l o y s were heated t o temperatures above t h o s e
of t h e phase transformations and subsequently cooled, a r e s i d u a l change i n t h e
l e n g t h of t h e specimens took p l a c e (at thermal c y c l e s below t h e temperature of
phase transformations p r a c t i c a l l y no change i n t h e l e n g t h of t h e specimens w a s
observed. Since no d a t a on t i t a n i u m a r e given i n works devoted t o t h e i n f l u ence of thermal c y c l e s on metals and a l l o y s ( r e f s . 8 and g), it appeared i n t e r e s t i n g t o carry out these investigations.
The measurements showed t h a t t h e most e f f e c t i v e change i n l e n g t h w a s d i s played by specimens of a l l o y s of t i t a n i u m w i t h molybdenum, although s m a l l
changes were noted i n specimens of pure t i t a n i u m and i t s a l l o y s w i t h chromium,
aluminum, palladium, tantalum and o t h e r metals. The specimens were heated and
cooled i n a vacuum. The heating r a t e was 1 deg/min, and t h e cooling r a t e , 18
deg/min

The h e a t i n g curves of all t h e cycles a t t h e phase transformation temperat u r e (about 880') c l e a r l y show an i n f l e c t i o n i n d i c a t i n g a decrease i n t h e co
e f f i c i e n t of l i n e a r expansion of t h e @ phase ( f i g . 7). When t h e a l l o y i s
cooled from 1 0 0 0 ~t o t h e phase transformation temperature, t h e cooling curve
coincides w i t h t h e heating curve. A t t h e temperature of t h e phase @ -+at r a n s formation, t h e cooling curve shows an abrupt c o n t r a c t i o n i n t h e l e n g t h of t h e
specimen (0.02-0.03 p e r c e n t ) , due t o a decrease i n volume as a r e s u l t of t h e
s h i f t i n t o t h e region of t h e a phase. The heating and cooling r a t e s employed
give r i s e t o a c e r t a i n temperature g r a d i e n t along t h e c r o s s s e c t i o n of t h e
f3 and @ - + atransformations encompass successive l a y e r s
samples, and t h e a
of t h e m a t e r i a l , moving from t h e edge t o t h e c e n t e r .
-+

The d i f f e r e n c e i n t h e atomic volume of t h e a and f3 phases i n t h e specimen

gives r i s e t o s t r e s s e s which r e l a x following p l a s t i c flow, and t h i s accounts
f o r t h e deformation.
Since t h e atomic volume of t h e a phase i s less t h a n t h a t of t h e f3 phase,
then during heating, t h e upper l a y e r s by changing i n t o t h e B phase have a
g r e a t e r volume and tend t o expand t h e p a r t of t h e specimen i n t h e a phase.
On cooling, t h e upper l a y e r s , which assume t h e s t r u c t u r e of t h e a phase,
c o n t r a c t t h e i n n e r p o r t i o n of t h e specimen i n t h e f3 phase. Since t h e temperat u r e g r a d l e n t along t h e c r o s s s e c t i o n of t h e specimen i s g r e a t e r during cooling
than during h e a t i n g ( t h e cooling r a t e i s h i g h e r t h a n t h e heating r a t e ) , t h e n

40

49
48

47

46
45

44

43
42
47
D

-47
-42
-43

-4

-4 5

200

40ff

6Uff 80ff t. "C

Figure 7. S e r i e s of d i l a t o m e t r i c curves
of t h e a l l o y Ti-Mo (2 w t p e r c e n t MO).
even i f one assumes t h e same y i e l d p o i n t of t h e a and @ phases a t t h e t r a n s formation temperature, t h e c o n t r a c t i n g s t r e s s e s on cooling w i l l be g r e a t e r t h a n
t h e expanding s t r e s s e s on heating. For t h i s reason, t h e l e n g t h of t h e t i t a n i u m
a l l o y decreases i r r e v e r s i b l y on slow heating and f a s t cooling ( f i g . 7). Another
cause of t h e deformation of t i t a n i u m and i t s a l l o y s may be t h e phase transformat i o n s which t&e p l a c e i n t h e metastable @ s o l i d s o l u t i o n s i n t h e i n v e s t i g a t e d
a l l o y s during cooling (from t h e formation of a' and w phases t o e q u i l i b r i u m
s t r u c t u r e s ) . The i n c r e a s e i n t h e s t a b i l i t y of t h e @ phase during cooling i s
obviously t h e reason f o r t h e g r e a t e r ( f i v e - f o l d ) deformation of specimens of
a l l o y s of t h e system Ti-Mo as compared t o t h e deformation of specimens of techn i c a l t i t a n i u m ( f i g . 8). A magnitude of t h e same o r d e r as i n t h e a l l o y of t h e
system Ti-Mo i s observed i n specimens of pure zirconium and i r o n ,
O x i d i z a b i l i t y of Alloys a t High Temperatures
I n a d d i t i o n t o studying t h e p h y s i c a l p r o p e r t i e s of t h e a l l o y s , it appeared
i n t e r e s t i n g t o Lnvestigate t h e i n f l u e n c e of t h e a l l o y i n g elements on t h e oxidiza b i l i t y of t i t a n i u m and depth of d i f f u s i o n a l s a t u r a t i o n of t h e metal by gases
i n t h e course of t h e oxidation. The o x i d i z a b i l i t y of t h e a l l o y s was s t u d i e d
p r i m a r i l y by determining t h e i n c r e a s e i n weight following i n t e r m i t t e n t exposures
t o t h e t e s t i n g temperature.
When t i t a n i u m i s alloyed w i t h aluminum, t h e o x i d i z a b i l i t y of t h e a l l o y s at
800' i n c r e a s e s w i t h r i s i n g aluminum concentration ( f i g . 9). A t 900, t h e oxid a t i o n r a t e of t h e a l l o y s decreases w i t h r i s i n g aluminum content, b u t remains
above t h e o x i d a t i o n r a t e of titanium. Obviously, t h e decrease i n t h e oxidat i o n r a t e i s caused i n t h i s case by a change i n t h e composition of t h e oxide

Figure 8. Dependence of t h e dimensions of metal

specimens on t h e number of cycles ( f o r titanium
and t h e a l l o y Ti-Mo, a tenrperature range of 100020, and f o r zirconium and iron, 1000-250') :
1, titanium TGO; 2, a l l o y Ti-Mo; 3, iodide z i r conium; 4, "armco" iron.

time

, hours

time, hours

Figure 9. Oxidizability of a l l o y s of titanium with aluminum,

a, t = 800 (1, 4
chromium, and molybdenum a t 800 and 900:
percent C r ; 2, 2 percent C r ; 3, 6 percent ~ l 4,; 2 percent MO;
5, 4 percent A l ; 6, T i ; 7, 2 percent MO); b, t = 9000 (1, 4 percent C r ; 2, 2 percent C r ; 3, 6 percent m; 4, 4 percent Al;
5, 4 percent Mo; 6, T i ; 7, 2 percent MO).
film and i t s s i n t e r i n g . The change i n t h e chemical composition of t h e oxide
film i s indicated by d a t a of the chemical analysis of the scale on a titaniumaluminum a l l o y ( r e f . 1 0 ) and a l s o by an appreciable increase i n t h e s t a b i l i t y
t o oxidation of an a l l o y with 15 percent Al a t 700 ( r e f . 11).

The o x i d a t i o n r a t e of a l l o y s of t h e system Ti-Mo a t 800 and 900' i s c l o s e

t o t h e o x i d a t i o n r a t e of t e c h n i c a l titanium. The i n f l u e n c e of molybdenum addit i o n s on t h e o x i d i z a b i l i t y of t i t a n i u m d i d not show any d e f i n i t e r e g u l a r i t y .
Alloying w i t h chromium causes an appreciable i n c r e a s e i n t h e o x i d a t i o n r a t e
The oxidation r a t e i n c r e a s e s w i t h r i s i n g chroof t h e a l l o y s a t 800 and 900'.
m i u m concentration. Experimental d a t a on t h e i n f l u e n c e of chromium, aluminum
and molybdenum on t h e o x i d i z a b i l i t y of t i t a n i u m a r e i n agreement w i t h t h e d a t a
of r e f e r e n c e s 1 0 and 11.

The a l l o y i n g of t i t a n i u m w i t h tantalum and p a r t i c u l a r l y lanthanum ( f i g

10) causes a r i s e i n t h e o x i d a t i o n r a t e a t 800, which i n c r e a s e s w i t h r i s i n g
concentration of t h e s e elements.

Alloying of t i t a n i u m w i t h palladium and rhenium has a f a v o r a b l e i n f l u e n c e

on t h e p r o t e c t i v e p r o p e r t i e s of t h e oxide f i l m . The o x i d a t i o n r a t e of a l l o y s
of t i t a n i u m w i t h palladium during t h e i n i t i a l s t a g e of o x i d a t i o n i s somewhat
g r e a t e r t h a n t h a t of pure t i t a n i u m , b u t l a t e r , owing t o t h e b e t t e r p r o t e c t i v e
p r o p e r t i e s of t h e oxide f i l m , it decreases, The o x i d a t i o n r a t e of a l l o y s cont a i n i n g 0.4 w t p e r c e n t Pd remains less t h a n t h a t of t i t a n i u m over t h e course
of t h e e n t i r e period of oxidation. A t low rhenium concentrations, t h e o x i d i z a b i l i t y of t h e a l l o y s i s somewhat g r e a t e r t h a n t h a t of pure titanium. However,
a t concentrations a s low a s 3 w t p e r c e n t Re, t h e o x i d a t i o n r a t e becomes app r e c i a b l y lower than t h a t of pure titanium. From an a n a l y s i s of k i n e t i c oxidat i o n curves p l o t t e d f o r pure t i t a n i u m and an a l l o y of t i t a n i u m w i t h 3 w t percent Re it follows t h a t , i n c o n t r a s t t o t h e curve f o r t h e o x i d a t i o n of pure
t i t a n i u m ( f i g . l l ) , t h e o x i d a t i o n curve of t h e a l l o y does not show any apprec i a b l e s c a t t e r of t h e experimental p o i n t s , i n d i c a t i n g a more uniform o x i d a t i o n
process. The main weight i n c r e a s e occurs during t h e f i r s t hour (0.2 tng/cm2).
hours, t h e weight i n c r e a s e i s o n l y 0.05 mg/cm2,
During t h e n
I n c o n t r a s t t o titanium, on which t h e r e i s formed a yellowish f i l m which
p e e l s off r e a d i l y , t h e a l l o y of t i t a n i u m w i t h 3 w t percent Re becomes coated
wTth a steel-colored f i l m which adheres f a i r l y w e l l t o t h e metal. The change
i n t h e c o l o r of t h e oxide f i l m i n d i c a t e s an appreciable degree of p e n e t r a t i o n
of rhenium i n t o t h e s c a l e . The f i l m d i d not p e e l o f f a f t e r t h e samples were
exposed t o 800' f o r 72 hrs.
According t o Wagner's theory, t h e o x i d a t i o n r a t e during a l l o y i n g may be
reduced by decreasing t h e nmnber of d e f e c t s i n t h e l a t t i c e of t h e s c a l e .
Titanium dioxide i s an a n i o n - d e f i c i e n t oxide, and t i t a n i u m i s oxidized owing
t o t h e d i f f u s i o n of oxygen through t h e oxide l a y e r ; t h e f r o n t of t h e r e a c t i o n
i s l o c a t e d a t t h e oxide-metal phase boundary ( r e f . 1 2 ) . I n t h i s case, t h e
i n t r o d u c t i o n of i o n s w i t h a h i g h e r valence (above f o u r ) should decrease t h e
concentration of t h e oxygen vacancies and t h e oxidation r a t e , while on t h e cont r a r y , t h e a d d i t i o n of i o n s of lower valence should i n c r e a s e t h e concentration
of oxygen vacancies and t h e o x i d a t i o n r a t e . The i n c r e a s e i n t h e o x i d a t i o n r a t e
upon a l l o y i n g w i t h chromium, aluminum, and lanthanum, and decrease i n t h e oxid a t i o n r a t e on a l l o y i n g w i t h rhenium a r e i n accord w i t h Wagner's theory, b u t
t h e l a t t e r i s contradicted i n t h e case of a l l o y i n g w i t h tantalum and

t i t a n i u m and t h e a l l o y T i

+ 3 percent

Re.

molybdenum. The disagreement w i t h Wagner's theory i n t h e case of a l l o y i n g

w i t h tantalum and molybdenum i s a p p a r e n t l y due t o a s l i g h t p e n e t r a t i o n of t h e s e
elements i n t o t h e s c a l e .
Alloys of t i t a n i u m and rhenium deserve p a r t i c u l a r a t t e n t i o n . Rbenium i s
a s t a b i l i z e r of t h e f3 phase ( r e f . 1 3 ) ) r a i s e s t h e hardness and s t r e n g t h of t h e
a l l o y s considerably, a s w e l l as t h e r e c r y s t a l l i z a t i o n temperature ( r e f . 14).
We have e s t a b l i s h e d t h a t rhenium i s very e f f e c t i v e i n preventing t h e
growth of g r a i n s when t h e metal i s heated ( f i g . 1 2 ) and slows down t h e d i f f u s i o n

of oxygen and nitrogen i n t o t h e metal during heating.

vestigated a l l o y s containing up t o 5 w t percent Re a r e
and s t r i p s and a r e s a t i s f a c t o r i l y machined by c u t t i n g .
assumption t h a t alloying with rhenium, p a r t i c u l a r l y i n
p o s i t i o n , may t u r n out t o be very e f f e c t i v e i n r a i s i n g
s t r e n g t h of the a l l o y s .

I n addition, t h e ine a s i l y r o l l e d i n t o bars

A l l t h i s leads t o the
a l l o y s of complex comt h e high-temperature

When t i t a n i u m i s oxidized, i n a d d i t i o n t o t h e formation of t h e oxide f i l m ,

t h e surface l a y e r of t h e metal becomes s a t u r a t e d w i t h oxygen and nitrogen, and
t h i s causes an a p p r e c i a b l e i n c r e a s e i n t h e hardness of t h e metal and a decrease
i n its plasticity.
For t h i s reason, it was i n t e r e s t i n g t o study t h e i n f l u e n c e of a l l o y i n g
elements on t h e d i f f u s i o n of atmospheric gases i n t o t h e metal.
The study w a s c a r r i e d o u t by measuring t h e microhardness ( a t a load of

50 g ) along t h e d i r e c t i o n from t h e s u r f a c e t o t h e c e n t e r of t h e samples f o l lowing oxidation a t 800'

f o r 72 hrs.

It was found t h a t i n a l l o y i n g w i t h tantalum and lanthanum, t h e depth of

oxygen d i f f u s i o n i n t o t h e metal i n c r e a s e s as t h e concentration of t h e a l l o y i n g
element r i s e s ( f i g . 13). Palladium has l i t t l e e f f e c t on t h e depth of oxygen
d i f f u s i o n . It i s c h a r a c t e r i s t i c t h a t t h e a l l o y w i t h 0.4 w t percent Pd i s d i s tinguished by a g r e a t hardness. E a r l i e r , an abnormally high e l e c t r i c a l r e s i s t i v i t y and a high o x i d a t i o n r e s i s t a n c e were observed i n an a l l o y of t h i s
composition. The m i c r o s t r u c t u r e of t h e a l l o y has a c h a r a c t e r i s t i c "basketlike"
structure.

Distance from s u r f a c e , mm
Figure 13. V a r i a t i o n i n microhardness (measured w i t h a
PMT-3 instrument a t a load of 50 g ) i n t h e a l l o y s : a, Ti-Ta
(1, 1 0 p e r c e n t Ta; 2, 5 percent Ta; 3, 1 percent Ta; 4, 0 perc e n t ~ a ) b,
; Ti-Pd (1, 0.4 percent Pd; 2, 3 percent Pd; 3, 1
percent Pd; 4, 0.1 percent ~ d ) ;c, Ti-Re (1, 3 percent Re;
2, 1 p e r c e n t Re; 3, 0.5 percent Re; 4, 0.2 percent ~ e ) ;d,
Ti-La (1, 3 p e r c e n t La; 2, 0.5 p e r c e n t La; 3, 0 . 1 percent ~ a )

A more pronounced decrease i n t h e depth of d i f f u s i o n of g a s e s i n t o t h e

metal i s observed when t i t a n i u m i s alloyed w i t h rhenium. It i s apparent from t h e
graph t h a t t h e depth of t h e d i f f u s i o n l a y e r decreases w i t h r i s i n g concentration,
and i s l e s s t h a n 0.1 mm a t a content of 3 w t p e r c e n t Re ( f o r i o d i d e titanium,
-0.4 mm) Since it i s somewhat d i f f i c u l t t o i n s u r e a s u f f i c i e n t high-temperature
oxidation r e s i s t a n c e of t h e a l l o y s during t h e a l l o y i n g , we i n v e s t i g a t e d t h e poss i b i l i t i e s of obtaining p r o t e c t i v e coatings on t i t a n i u m and i t s a l l o y s by cladding, p a r t i c u l a r l y s i n c e e l e c t r o l y t i c coatings and coatings obtained by
d i f f u s i o n a l s a t u r a t i o n have not produced s a t i s f a c t o r y r e s u l t s t h u s f a r ( r e f s .
15-18). Such coatings could g i v e p r o t e c t i o n not only a g a i n s t o x i d a t i o n but
a l s o a g a i n s t t h e a c t i o n of oxygen-containing media ( r e f s . 19, 20).

The cladding process was c a r r i e d out i n a vacuum; t h i s n o t o n l y excluded

t h e formation o f oxides and n i t r i d e s on t h e c o n t a c t s u r f a c e s , b u t a l s o promoted
t h e removal of gases "trapped" by t h e cladding metal and desorbed a t a high
temperature. Thus, when t h e j o i n t deformation o f t h e metal and coating i s suff i c i e n t l y high, f o r c e s of atomic i n t e r a c t i o n a r i s e between t h e metal and t h e
coating, and high temperatures promote d i f f u s i o n processes w i t h t h e formation
of a zone of i n t e r d i f f u s i o n . The i n v e s t i g a t i o n s showed t h a t i n t h e j o i n i n g of
metals w i t h t h e same o r a d i f f e r e n t base but a s u f f i c i e n t s o l u b i l i t y i n t h e
s o l i d s t a t e , d i f f u s i o n welding t a k e s p l a c e when t h e t o t a l r e d u c t i o n of a r e a i s
only 15 percent ( r e f . 22). This i s i l l u s t r a t e d by t h e dependence of t h e s t r e n g t h
of copper and zirconium coatings on t i t a n i u m ( f i g . 14), i.e., c o a t i n g s of metals
which i n t h e i r chemical nature and melting p o i n t s d i f f e r s h a r p l y from titanium.
Zirconium forms continuous s o l i d s o l u t i o n s w i t h titanium, whereas t h e mutual
s o l u b i l i t y of copper and t i t a n i u m i s very low. The bonding s t r e n g t h of both
coatings i n c r e a s e s w i t h i n c r e a s i n g reduction i n area. The f i n a l bonding s t r e n g t h
i s determined by t h e s t r u c t u r e of t h e intermediate l a y e r . However, t h e i n v e s t i g a t i o n s showed t h a t even when i n t e r m e t a l l i c phases a r e formed i n t h e c o n t a c t zone
( p a r t i c u l a r l y , i n t h e Cu-Ti system), because of t h e small t h i c k n e s s of t h e cont a c t zone and t h e simultaneous presence of a s o l i d s o l u t i o n i n t h i s zone, t h e
bonding i s s u f f i c i e n t l y strong, s i n c e it permits deformation and m u l t i p l e bends
without peeling.

25
'7

4h'

60

shrinkage, p e r c e n t
Figure 14. Adhesive s t r e n g t h of c e r t a i n coatings
on t i t a n i u m versus shrinkage: a , Ti-Zr, r o l l i n g
temperature, 880'; b, Ti-Cu, r o l l i n g temperature,

7800

Summary
1. When titanium i s alloyed i n t h e region of s o l i d s o l u t i o n s , t h e change
i n hardness and e l e c t r i c a l r e s i s t i v i t y a t temperatures from -196O t o t h e temp e r a t u r e s of phase transformations i s determined by t h e r e l a t i v e atomic diame t e r s and chemical n a t u r e of t h e alloying elements. Elements w i t h a g r e a t e r
d i f f e r e n c e i n atomic diameters and chemical p r o p e r t i e s a t the same concentrat i o n s cause a g r e a t e r increase i n hardness and e l e c t r i c a l r e s i s t i v i t y .

2
As t h e temperature i s r a i s e d , t h e temperature c o e f f i c i e n t of t h e
e l e c t r i c a l r e s i s t i v i t y of t i t a n i u m and i t s a l l o y s i n c r e a s e s i n magnitude while
remaining p o s i t i v e . The decrease i n t h e c o e f f i c i e n t of l i n e a r expansion of
t h e a l l o y s i s more pronounced t h e higher t h e concentration of t h e d l o y i n g
elements.
3. Alloying elements i n concentrations s o l u b l e i n t h e a phase w i t h a
c o e f f i c i e n t of thermal expansion smaller than t h a t of t i t a n i u m decrease t h e
c o e f f i c i e n t of thermal expansion of t h e a l l o y s , while a l l o y i n g elements w i t h
a c o e f f i c i e n t g r e a t e r t h a n t h a t of titanium i n c r e a s e t h i s c o e f f i c i e n t .

4. A t thermal cycles encompassing t h e region of phase transformations, an

i r r e v e r s i b l e change i n shape t a k e s p l a c e i n titanium and i t s a l l o y s a s a r e s u l t
of t h e r e l a x a t i o n of t h e s t r e s s e s a r i s i n g during t h e phase transformation.
5. Chromium, tantalum and lanthanum markedly i n c r e a s e t h e o x i d a t i o n r a t e
of titanium a t 800. Palladium i n s m a l l concentrations and rhenium have a favorable e f f e c t on t h e p r o t e c t i v e p r o p e r t i e s of t h e oxide f i l m a t t h i s temperat u r e . Rhenium s u b s t a n t i a l l y decreases t h e oxidation and depth of d i f f u s i o n of
t h e gases i n t o t h e metal.

1. m f y a n o v , R. A.,

Nechiporenko, Ye. P. and Tarsov, N. D.

metallovedeniye, Vol. 11, No. 3, pp. 461-465, 1961.

Fizika metallov i

2.

Ivanov, V. Ye., Kovtun, S. F., Tarasov, N. D. and Ulfyanov, R. A.

Tsvetnyye metally, No. 11, pp. 85-89, 1962.

3.

P o t t e r , H. H. Proc. Phys. Soc., Vol. 53, No. 300, p. 695, 1941.

4. Wyatt, J. L.

J. Metals, Vol.

5, No. 7, P. 903, 1953.

5 . Ogden, H. R., Maykuth, D. I., Finlay,

W. Z. and J a f f e e , R. I .

J. Metals,

Vol. 3, No. 12, p. 1150, 1951.

6.

Savitskiy, Ye. M., Tylkina, M. A. and Zottyev, Yu. A.

Vol. 4, No. 3, pp. 702-704, 1959.

Zh. neorg. khim.,

Savitskiy, Ye. M. and Burkhanov, G. S.

P. 1609, 1957.

Zh. neorg. khim.,

Vol. 3, No. 11,

Davidenkov, N. N. and Likhachev, V. V. I r r e v e r s i b l e Deformation of Metals

Subjected t o Cyclic Thermal E f f e c t s (~eobratimoyeformoizmeneniye metall o v p r i tsiklicheskom teplovom vozdeystvii). Mashgiz ( s t a t e S c i e n t i f i c
and Technical Publishing House of L i t e r a t u r e on ~ a c h i n e r y ) , 1962.
Akimov, L. M. and Sklyarov, N. M. Eeat Resistance of Alloys ( ~ e r m o s t o ~ k o1 s t
Coll. of Papers e d i t e d by N. M. Sklyarov, GNTI ( s t a t e Publishsplavov)
ing House of Science and ~ e c h n o l o g y ) ,1962.

Revyakin, A. V. Titanium and I t s Alloys i it an i yego splavy)

AN SSSR, No. 8, pp. 175-189, 191-205, 1962.

Izd-vo

Kornilov, I. I.
1958.
Jenkis, A. E.

Khimicheskaya nauka i promyshlennostl, Vol. 3, No. 8, p . 6,

J. I n s t . Metals, Vol. 82, No.

5 , p. 213-221, 1954.

Zh. neorg. khim., Vol. 3, No. 3, p.

Savitskiy, Ye. M, and Tylkina, M. A.

820, 1958.

S a v i t s k i y , Ye. M., Tylkina, M. A, and Tsiganova, I. A.

No. 3, P. 96, 1958.

Izv. AN SSSR, OTN,

Leyner; V. I. E l e c t r o p l a t i n g of Light Alloys ( ~ al vanicheskiye

l
pokrytiya
Metallurgizdat 1959.
legkikh splavov)

Smolenskaya, G. N., Kudryavtsev, N. T. and Karantayev, V. M. Metallovedeniye i termicheskaya obrabotka metallov, No. 11, p. 42, 1960.
Anitov, I. S. and Maksimova, A. G.
1960.

Zh. p r i k l . khim., No. 12, p. 2724,

Stroyev, A. S, and Novikova, Ye. N. Titanium and I t s Alloys

splavy). Izd-vo
SSSR, pp. 107-113, 1958.

i it an

i yego

Borisova, Ye. A. and Bogdanov, K. V. Metallovedeniye i termicheskaya

obrabotka metallov, No. 2, pp. 37-40, 1963.
I. B. Rittenhouse.

Trans. ASM, Vol. 51, NO. 871-895, 1959-

Kovtun, S. F, and Tarasov, N. D.

Avt. svid. SSSR, No. 111925, 5 August 1957.

UllyanovJ R. A , , Tarasov, N. D. and Kovtun, S. F.

PP. 74-76, 1953.

Tsvetnyye metally, No. 3,

DETEENINATION OF TRE CHARACTERISTICS OF THE INTERDIFFUSION OF TITANIUM

AND MOLYBDENUM FROM THE AFCEl!TUATION OF y RADIATION

A. Ya. Shinyayev, V. 0. Akopyan, L. F. Sokiryanskiy

and I. V. Bogolyubova

The s t u d y of t h e i n t e r d i f f u s i o n of t i t a n i u m and molybdenum i s of g r e a t

t h e o r e t i c a l i n t e r e s t , s i n c e t h e s e metals d i f f e r s t r o n g l y i n p h y s i c a l p r o p e r t i e s ,
and t h i s may s u b s t a n t i a l l y a f f e c t t h e d i f f u s i o n process. Furthermore, t h e
study of t h i s problem i s of g r e a t p r a c t i c a l i n t e r e s t . I n r e f e r e n c e 1 it was
shown t h a t i n o r d e r t o o b t a i n a good adhesion between a molybdenum coating and
t i t a n i u m and i t s a l l o y s , t h e formation of d i f f u s i o n l a y e r s i s necessary between
t h e base metal and t h e coating, and t h e bonding s t r e n g t h i s d i r e c t l y r e l a t e d
t o t h e t h i c k n e s s and s t r u c t u r e of t h e s e l a y e r s . For t h i s reason, a r a t i o n a l
s e l e c t i o n of t h e temperature conditions f o r applying t h e coating ( t h i s i n s u r e s
t h e c r e a t i o n of a d i f f u s i o n zone of d e f i n i t e t h i c k n e s s ) and t h e knowledge of
the c h a r a c t e r i s t i c s of t h e s t r u c t u r e of t h e d i f f u s i o n zone made it necessary t o
study t h e r a t e of i n t e r d i f f u s i o n between t i t a n i u m and molybdenum. The m a t e r i a l
used t o prepare t h e samples was t i t a n i u m obtained from t i t a n i u m sponge TGOO by
double f u s i o n i n a vacuum e l e c t r i c a r c furnace w i t h t h e u s e of a consumable
e l e c t r o d e and c a s t molybdenum. A f t e r p r e l i m i n a r y s t r i p p i n g , t i t a n i u m rods 18
m i n diameter were subjected t o homogenizing annealing f o r 6 h r s a t 1250'. The
annealed rods were used t o prepare samples i n t h e shape of beakers; a molybdenum plug 8 mm i n diameter and 1 2 mm long was pressed i n t o t h e opening of t h e s e
samples. P r i o r t o t h e p r e s s i n g , t h e samples were degreased i n benzene o r
carbon t e t r a c h l o r i d e . The homogenizing of t h e samples w a s c a r r i e d o u t i n a
vacuum a t temperatures of 905, 1005, 1100, 1111 and 1 2 1 0 ~w i t h a holding t i m e
of 7-240 h r s .
A t t h e f i r s t s t a g e of t h e experiments, i n o r d e r t o s t u d y t h e i n t e r d i f f u s i o n
between t i t a n i u m and molybdenum, t h e microhardness was measured and t h e micros t r u c t u r e of t h e d i f f u s i o n l a y e r s w a s examined. However, t h e s e methods d i d n o t
permit t h e determination of t h e e x t e n t of t h e d i f f u s i o n zone. The values o f
t h e microhardness a s s o c i a t e d w i t h a change i n t h e concentration of t h e t i t a n i u m
and molybdenum components d i f f e r o n l y s l i g h t l y , s o t h a t p r a c t i c a l l y no d i f f u s i o n zone i s observed. The d i f f u s i o n zone of Ti-Mo does not show up i n t h e
microstructural analysis e i t h e r .

I n t h e p r e s e n t work, i n o r d e r t o determine t h e concentration of t i t a n i u m

and molybdenum i n t h e d i f f u s i o n zone, u s e w a s made of a new method based on t h e
p r i n c i p l e of a t t e n u a t i o n of t h e i n t e n s i t y of a narrow beam (10-15 p wide) of y

r a d i a t i o n passing through various microsections of t h e zone. D e t a i l s of t h i s

method and c e r t a i n f e a t u r e s of t h e apparatus used t o perform t h e a n a l y s i s of t h e
d i f f u s i o n zone a r e described i n r e f e r e n c e 2.
I n o r d e r t o s t u d y t h e d i f f u s i o n l a y e r s by t h i s method, p l a t e s 1.5-2.0 mm
t h i c k were c u t from t h e annealed specimens and reduced t o a t h i c k n e s s of 75-150
p by p l a n e - p a r a l l e l grinding. The specimen was mounted on a s p e c i a l base connected t o a s e r i e s of micrometer screws p a r a l l e l t o t h e working s l i t e m i t t i n g a
beam of r a d i o a c t i v e r a d i a t i o n . The device was used t o determine t h e curves of
t h e a t t e n u a t i o n of y r a y i n t e n s i t y i n passing from molybdenum t o t i t a n i u m over
t h e e n t i r e d i f f u s i o n zone every 5 p. Let u s examine a t y p i c a l curve f o r a
f o r 40 h r s ( f i g . 1 ) . It i s apparent from t h e f i g u r e
specimen annealed a t 1100~
t h a t i n passing from t i t a n i u m t o molybdenum, t h e r a d i a t i o n i n t e n s i t y changes by
a f a c t o r of no l e s s than 15. This makes it p o s s i b l e t o c a r r y o u t t h e a n a l y s i s
f o r t h e content of t i t a n i u m and molybdenum i n each segment of t h e zone w i t h
g r e a t precision.
The r e l a t i o n between t h e degree of absorption of y r a d i a t i o n , given by t h e
r a t i o of t h e i n t e n s i t y of y r a d i a t i o n which has t r a v e r s e d t h e s e c t i o n of t h e
specimen under c o n s i d e r a t i o n t o t h e o r i g i n a l i n t e n s i t y of t h e i n c i d e n t r a d i a t i o n , and t h e concentrations of t h e components of t h e b i n a r y system may be der i v e d from t h e following system of equations:

1
I(2)
- 111 2,
11 '

p (x)= p1el (9)= 200

+PI P(4I ("1 '

where p i s t h e l i n e a r absorption c o e f f i c i e n t , em-';

p i s t h e weight f r a c t i o n of t h e conrponent; c i s t h e
ponent, a t . percent; I i s t h e counting r a t e , cpm; b
specimen, cm; x i s t h e p o s i t i o n of t h e microsection
t h e d i f f u s i o n zone.

p i s t h e d e n s i t y , g/cm3;
concentration of t h e comi s t h e t h i c k n e s s of t h e
being analyzed r e l a t i v e t o

S u b s c r i p t s 1 and 2 p e r t a i n t o pure t i t a n i u m and molybdenum, r e s p e c t i v e l y .

By solving system (1) w i t h r e s p e c t t o t h e concentration cl(x) a f t e r subs t i t u t i n g t h e values of t h e absorption c o e f f i c i e n t s p and d e n s i t y of t h e components p (pTi = 94 em-';

%o

= 355 cm- 1; pTi

= 4.505 ~ ' c m 3 ; p~~

= 10.22 ~ / c m 3 )

we o b t a i n t h e following equation f o r determining t h e t i t a n i u m c o n c e n t r a t i o n a s

38

4,Z

4.4

4,4

48
Z, MU

Figure 1. Change i n t h e i n t e n s i t y of
y r a d i a t i o n passing through t h e d i f f u s i o n zone from t i t a n i u m t o molybdenum.
a f u n c t i o n of t h e i n t e n s i t y of t h e r a d i a t i o n passing through each segment of
t h e specimen whose p o s i t i o n i s given by t h e coordinate x:

A nomogram ( f i g . 2) f o r use i n t h e c a l c u l a t i o n s was constructed on t h e

b a s i s of t h i s equation.

The r e s u l t s of t h e measurement of t h e t i t a n i u m concentration ( t h e molybdenum concentration was t h e balance adding up t o 100 p e r c e n t ) i n a l l t h e i n v e s t i g a t e d specimens were expressed a s t h e g r a p h i c a l dependence of t h i s concent r a t i o n on t h e d i s t a n c e i n t h e d i f f u s i o n zone. As an example, a curve of t h i s
type i s i l l u s t r a t e d f o r a specimen annealed f o r 40 h r s a t 1100 ( f i g . 3).
From t h e d a t a obtained f o r t h e d i s t r i b u t i o n of t h e d i f f u s i n g elements, one
can c a l c u l a t e t h e c o e f f i c i e n t s of i n t e r d i f f u s i o n from t h e f a m i l i a r Boltzmann
formula

The Matano g r a p h i c a l method u s u a l l y employed i n such c a l c u l a t i o n s i s very

cumbersome and has some important disadvantages. This method i s a p p l i c a b l e only

C T ~ ,a t . p e r c e n t

Figure 2. Nomograph f o r determining t h e c o n c e n t r a t i o n

of t h e components from t h e absorption of y r a d i a t i o n .

t.
nri

Figure 3. D i s t r i b u t i o n of t h e
c o n c e n t r a t i o n of t h e component
and t h e d i f f u s i o n zone.
t o t h e complete curve of c o n c e n t r a t i o n versus depth of p e n e t r a t i o n of t h e
components. The p l o t t i n g of such a curve involves considerable experimental
d i f f i c u l t i e s . Thus, a t a specimen t h i c k n e s s of over 100 p, t h e y r a d i a t i o n i s
a t t e n u a t e d very s t r o n g l y i n t h e molybdenum p o r t i o n of t h e specimen, r e s u l t i n g
i n a sharp decrease i n t h e s e n s i t i v i t y of t h e method, while a t a specimen t h i c k ness of approximately 140 p, t h e y r a d i a t i o n i s almost completely absorbed by
t h e specimens. A t t h e same time, specimens 100-150 p t h i c k a r e f u l l y adequate
f o r t h e establishment of a d i s t r i b u t i o n of t h e components i n t h e t i t a n i u m port i o n of t h e d i f f u s i o n zone. However,. it does not seem p o s s i b l e t o c a l c u l a t e
g r a p h i c a l l y t h e values of t h e d i f f u s i o n c o n s t a n t s i n t h e t i t a n i u m region alone
i n t h i s case. Furthermore, t h e g r a p h i c a l method has another s e r i o u s drawback:
i t s p r e c i s i o n a t t h e end segments of t h e d i f f u s i o n zone on both s i d e s decreases
s h a r p l y owing t o a l a r g e e r r o r i n t h e g r a p h i c a l d i f f e r e n t i a t i o n .

I n o r d e r t o avoid t h e s e drawbacks i n t h e c a l c u l a t i o n of t h e d i f f u s i o n cons t a n t s , use i s made i n t h e p r e s e n t work of an a n a l y t i c a l method of c a l c u l a t i o n

based on a l i n e a r i z a t i o n of t h e experimental concentration curve i n a p r o b a b i l i t y g r i d ( r e f . 4). The concentration curve taken from f i g u r e 3 i s shown i n t h i s
g r i d ( f i g . 4)

The concentration s c a l e corresponds t o t h e equation

Along t h e v e r t i c a l on t h e r i g h t s i d e of f i g u r e 4 i s given t h e s c a l e of
arguments of thc p r o b a b i l i t y i n t e g r a l u. The d i s t a n c e from t h e c r o s s s e c t i o n
under c o n s i d e r a t i o n t o t h e i n i t i a l boundary of Ti-Mo i s p l o t t e d along t h e abs c i s s a . The i n i t i a l p o s i t i o n of t h e phase boundary was determined from experiments w i t h i n e r t marks and c o n t r o l l e d by observing t h e changes i n t h e t h i c k n e s s
of t h e molybdenum coating i n t h e course of t h e homogenizing. For a l l t h e experiments considered, t h e concentration dependences i n t h e p r o b a b i l i t y g r i d
consisted of segments of s t r a i g h t l i n e s having a common i n i t i a l o r d i n a t e k and
slopes hl and he r e s p e c t i v e l y f o r t h e t i t a n i u m [cl(x) > 50 p e r c e n t ] and molybdenum [cg(x) < 50 p e r c e n t ] s e c t i o n s of t h e d i f f u s i o n zone.

Using equation ( 4 )

and t h e l i n e a r i z a t i o n condition of t h e segments of t h e component d i s t r i b u t i o n

curve, which can be w r i t t e n i n t h e form of t h e equation

one can r e a d i l y o b t a i n , from expression ( 3 ) , a formula f o r t h e c a l c u l a t i o n of

the interdiffusion coefficients:

where

The f u n c t i o n cp ( c ) t a k e s i n t o account t h e dependence of t h e i n t e r d i f f u s i o n

c o e f f i c i e n t on t h e concentration of t h e components ( f i g . 3 ) .

Results of c a l c u l a t i o n s of i n t e r d i f f u s i o n coeff i c i e n t s l ( f i g 6) showed

t h a t a t concentrations of 50-90 a t . p e r c e n t Ti, t h e i n t e r d i f f u s i o n c o e f f i c i e n t
'L.

G. Maksimova took p a r t i n t h e c a l c u l a t i o n s .

141

Concentration of
Ti, at. p e r c e n t

-5 -4 -3 -2 - 7

Distance from lane of o r i g i n ,

x.10 , cm

Concentration of
Ti, a t . p e r c e n t

Figure 4. D i s t r i b u t i o n of t h e
concentration of t h e components
i n the probability grid.

Figure 5. Function cp ( c ) versus

concentration: a, molybdenum
region; b, t i t a n i u m region.

CiL,at. p e r c e n t
Figure 6. C o e f f i c i e n t of i n t e r d i f f u s i o n versus
concentration of components f o r t h e t i t a n i u m
region: 1, a t 905O; 2, a t 1 1 0 0 ~ ;3, a t 1 2 1 0 ~ .
Dinter

remains p r a c t i c a l l y constant f o r t h e given temperature.

Only a t con-

c e n t r a t i o n s of 90-98 a t . p e r c e n t T i i s an appreciable i n c r e a s e observed i n

Dinter*
I n t h e molybdenum region(100-150 p e r c e n t
pendent of t h e molybdenum concentration.

MO),

t h e value of Dint,,

i s inde-

Results of a determination of Dinter

values and of t h e width of t h e d i f f u s i o n zone f o r t h e annealing modes i n v e s t i gated a r e shown i n t h e t a b l e .

I n c a l c u l a t i n g t h e values of Dinter

by t h e a n a l y t i c a l method one should

keep i n mind t h a t i n t h e v i c i n i t y of 50 percent t h e value of Dint,,

shows a d i s -

c o n t i n u i t y because t h e curve r e p r e s e n t i n g t h e d i s t r i b u t i o n of elements i n t h e

d i f f u s i o n zone i s approximated by two segments of s t r a i g h t l i n e s i n t h e probab i l i t y g r i d . That i s why t h e a n a l y t i c a l method i n t h e v i c i n i t y of 50 p e r c e n t
g i v e s a l e s s a c c u r a t e r e s u l t than t h e Matano method. However, t h e a n a l y t i c a l
method g i v e s a c c u r a t e values of D i n t e r a t t h e ends of t h e d i f f u s i o n zone, where
t h e Matano method i s p r a c t i c a l l y impossible t o apply. Therefore, i n a more det a i l e d study of i n t e r d i f f u s i o n , t h e use of both methods i s recommended, s i n c e
t h e y supplement each o t h e r .
A s was i n d i c a t e d above, t h e energy of t h e y r a d i a t i o n which we 'used made
i n the titanium

it p o s s i b l e t o determine f a i r l y a c c u r a t e l y t h e values of Dint,,

region.

Here t h e accuracy of t h e measurement of Dinter

was 20-30 percent.

The

parameters of t h e d i f f u s i o n p r o c e s s i n t h e Arrhenius equation--activation

energy Einter and value of t h e preexponential factor--were determined from t h e

~ / T
s l o p e of t h e s t r a i g h t l i n e i n t h e coordinates I n D ~ ~ ~ ~ (~f i g- . - 7).
The value of Einter

obtained was found t o be

41 kcal/mole, Do

F;:

5.6*10-~

DIFFUSION CHARACTERISTICS UNDER VARIOUS K!DIEALING CONDITIONS

FOR THE SYSTEM Ti-Mo.
Temperature
OC

Time,

hr

T o t a l depth of
d i f f u s i o n zone,

C o e f f i c i e n t of i n t e r d i f f u s i o n ,
cm2/sec
Titanium region

Molybdenum region

12ffff7/10

1ff1P

900 t,"C

Figure 7. C o e f f i c i e n t s of i n t e r d i f f u s i o n versus temperature f o r

t h e t i t a n i u m region.
From t h e s e c h a r a c t e r i s t i c s , using t h e equation of t h e temperature depend-

--

7
.

I3

ence of t h e d i f f u s i o n c o e f f i c i e n t Dinter
Of

Dinter

= Doe RT, one can determine t h e value

f o r any temperature i n t h e @ region.

I n t h e molybdenum region, t h e d e n s i t y of t h e r a d i a t i o n passing through t h e

specimen decreased sharply, making it d i f f i c u l t t o o b t a i n t h e necessary l i g h t
in this
s t a t i s t i c s . For t h i s reason, t h e accuracy of t h e measurement of Dint,,
region was considerably lower. It was found t h a t i n t h e molybdenum region, t h e
a c t i v a t i o n energy was considerably g r e a t e r t h a n i n t h e t i t a n i u m region. A more
a c c u r a t e a n a l y s i s of t h i s p a r t of t h e d i f f u s i o n zone r e q u i r e s y r a d i a t i o n of
0.1-0.3 MeV energy. ~owev&r,i n t h i s case t h e s e n s i t i v i t y of t h e a n a l y s i s of
t h e t i t a n i u m region decreases.
The
trations
which we
the data

i n t e r d i f f u s i o n between t i t a n i u m and molybdenum a t molybdenum concenup t o 8 a t . percent was s t u d i e d e a r l i e r i n reference 5. The r e s u l t s

obtained a t low molybdenum concentrations a r e i n good agreement w i t h
of t h i s work.

I n conclusion, t h e authors express t h e i r a p p r e c i a t i o n t o P r o f . S. S.

Mozhayev f o r h i s cooperation i n t h e execution of t h e computational p a r t of t h i s
work.

REFErnNCES
1. Tour, S., Styka, A. and Fischer, G.

J. Metals, Vol.

7, No.

2, p. 291,

1955.

2. Shinyayen, A. Ya., Bondarev, V. V. and Sergeyeva, Ye. V. This Collection,

p. 320. J.P.R.S. Translation No. 28,176; ~~:65-30080,
pp. 63-69.

3. Matano, C. Japan J. Phys., Vol. 8, p. 109, 1933.

4. Roll, L. D. 3. Chem. Phys., Vol. 21, p. 87, 1953.

5. Goold,

B.

J. Inst. Metals, Vol. 88, p.444, 1960.

PART 11. INTERACTION OF TITANIUM WITH GASES AI\ID

THE CORROSION PROPERTIES OF ALLOYS

ON THE FSDISTRIBUTION OF IMPURITIES IN TITANIUM

AND ITS ALLOYS DURING OXIDATION

N.V.Korolev, S. A. Gorbunov, A. S.Bogdanov and. G.P. Nadutenko

In addition to alloying elements, titanium alloys contain impurity elements

whose quantity depends on the method of preparation and grade of the titanium
sponge. The purest semifinished product used for melting titanium alloys sponge TGOO obtained by the magnesiothermic method - contains about 0.50$ of impurity elements.
Harmful elements which markedly reduce the mechanical characteristics of
alloys are oxygen, nitrogen, and carbon. These elements form interstitial solid
solutions with titanium and, even when present in extremely small amounts (hundredths and thousandths of one percent) have a harmful effect on a plastic metal,
changing it into a brittle substance. In addition to the indicated elements,
undesirable impurities also include silicon, iron and hydrogen.
The alloys are strongly oxidized in various metallurgical processes (rolling, forging, heat treatment, etc ).

The oxidized surface of the specimen is covered with a scale under which
there is formed a so-called gas-saturated layer which is basically a solid solution of oxygen in titanium.
On the basis of thermodynamic calculations made in order to establish the
possibility of formation of oxides of impurity elements and titanium, one could
expect carbon, nitrogen and iron to accumulate in the surface layer of the metal
as the oxidation time increased.
The present work was devoted to verifying the possibility of redistributing
the impurity elements between the surface layers of the bulk of the titanium
specimen in the course of oxidation in air.
Materials and Method
The study was carried out on specimens (20 x 20 x 20 mm) of technically
pure titanium VTland some titanium alloys melted with TGO sponge.
According to T s W (Tekhnicheskiye uslovtya tsvetnoy metallurgii - Specifications for nonferrous metallurgy) 4732-56, the chemical composition of the VT1

alloy should be as follows : base, Ti; 0.3% Fe; 0.15% Si; 0.1% C; 0.15% 02;

0.015% H2; 0.05% N2; 0.06% C1.

In addition to these elements, a certain amount of calcium and magnesium
(of the order of 0.01-0.02%) and up to 0.30-0.40%Al were observed in the alloy
VT1.

The samples to be tested were oxidized in undried laboratory air in a periodic weighing unit at temperatures of 800-1200~. The temperature was controlled
After oxidation followed by cooling in air, the scale was removed
within
from the specimens, and the latter were used to prepare transverse polished sections for the purpose of studying the distribution of microhardness over the
depth of the gas-saturated layer. The microhardness was measured with a PMT-3
instrument (at a load of 50 g)

so.

The emission spectral. analysis and in some cases local analysis of the
specimens were carried out with an instrument described in ref. 1. The analysis
was performed in a straight pulsed spark with the following parameters of the
unit: capacity of the working condenser 0.01 pF; charge current of the working
condenser 8.0 mA; auxiliary gap 1.50 mm; analytical gap 0.75 mm. In the determination of nitrogen, use was made of a spark burning in a stream of pure argon
No. 1 (0.o& 02; 0.17$ Np; 0.01$ ~ 0 2 ) To this end, a chamber was prepared
which was mounted on the rim of the objective of the microscope and which made
it possible to blow a uniform stream of argon onto the section under analysis.
Microelectrodes 0.20 rnm thick were made out of electrolytic copper MO. The duration of the exposure for the determination of iron, silicon, carbon and magnesium
was 1 min, and for the determination of aluminum, calcium and nitrogen, 5 see.
The following line? were selected for th? analytical tests : iron 2755.737 11 A,
silicon 2881.5781 A, aluminum 3961.5271 A, calcium 3968.468II i, carbon 2296.89
I11 1, magnesium 2795.53 II 1, nitrogen 3994.995I1 1.

The standards used for the quantitative comparison were specimens of the
original alloys subjected to oxidation, titanium nitride and carbide, alloy with
0.2% C, and alloys of titanium with 1.5% Fe, Si and f3.l.. The content of the elements in the standards was checked by chemical analysis.
After a photometric analysis of the plates, the relative intensity of the
spectral lines of the impurity element was determined with respect to the lines
of titanium by means of the formulas

where Ix and 1T-i are the line intensities of the element being analyzed and of
titanium; ASx-@ and ASTi-$ is the difference in blackening between the lines of
the impurity element or titanium and the background.

The quantitative content of the elements was calculated from the formula

is the ratio of the amount of the impurity element

where cx/cTi and

to the amount of titanium in the alloy and standard, respectively; Ix/ITi and

( I ~ / I is
~ the
~ ) ratio
~ ~ of the intensities of the element being determined to
the line of titanium in the alloy and in the standard, respectively.
In the calculations of the amount of nitrogen, account was also taken of
the nitrogen present in technical argon. When no standards were available for
certain elements, the change in the amount of the impurity on the surface of
the specimen as compared to the readings for the unoxidized surface at the center of the transverse polished section was estimated from the difference in the
ratio of the intensities of the element being determined to the titanium on the
oxidized surface and at the center of the section.
Results
The results of spectral analysis for impurity elements on the outside surface of gas-saturated layers in specimens oxidized at 800-1200~are shown in
the table below. The depth of the investigated layer was 10-15 p. According to
the data of the table, the surface gas-saturated layer on specimens oxidized at
I

Testing
temperature
OC

1200
1200
1200
1200
1200
1200
1100
1100
1100
1000
1000

900
900

Duration
of tests,
hr

Chemical composition, %

Al

Fe

0.05

0.0

0.04

0.10
0.20
0.50
1

0.5

0.02

0.7

---

---

0.04

3.6
3.3

0.12

0.65

---

--

--

Si

--

---

-1.64

0.50
0.71

0.20

0.65

0.66

0.35

0.40

0.04
0.06
0.05
0.06

0.30
0.52
0.36
0.26

0.20
0.12
0.12
0.04
0.02

0.12

0.3

0.50
0.50

0.06

0.16

4
4

1.7
3.5

1.16
--

8
16
8
16
8
16
8
96

1.7
3.5
0.0
0.0
0.0

--

0.12
0.16
0.18

0.02
800
0.1
0.50
0.16
800
0.14 0.30
0.04 0.02
Note. Sensitivity of determination: nitrogen, 0.$; carbon and
iron, 0.03%; aluminum, 0.1%; silicon, 0.05%.
0.0
0.0
0.0

0.10
0.30

1100-1200 has a high nitrogen content (up t o 3%) and carbon content (up t o 1%).
It i s c h a r a c t e r i s t i c t h a t t h e highest quantity of nitrogen was observed during
t h e i n i t i a l period of t h e oxidation.
F i g . 1 shows t h e temperature dependence of t h e f r e e energy of formation of
oxides of t h e impurity elements and of titanium, t i t a n i u m n i t r i d e , and t i t a n i u m
carbide, c a l c u l a t e d from l i t e r a t u r e d a t a ( r e f s . 2, 3). The values of t h e thermodynamic c h a r a c t e r i s t i c s l e a d one t o expect an accumulation of nitrogen and c a r bon i n t h e s u r f a c e l a y e r because t h e change AFO f o r titanium oxides has a much

Figure 1. Free energy of formation of some compounds of

t i t a n i u m and impurity elements versus temperature (based on
1 g/mole 0 2 ) .

more negative value than f o r titanium n i t r i d e and carbide. The t h i c k e r t h e oxi d e film, t h e more of t h e s e elements should be present i n t h e external. l a y e r of
t h e metal, s i n c e they should not p e n e t r a t e i n t o t h e s c a l e . However, t h e calcul a t e d amount of nitrogen was much l e s s than t h e experimental value. To elucidate

this question, special experiments were set up for the simultaneous oxidation
of a titanium specimen at temperatures of 1000-1200. During the initial period
of oxidation (from 3 min to 1 hr) it was found that during the same testing
time, the oxide layer at the spot where the temperature was 1200' had a smaller
thickness than at 1000~.
The corresponding calculations of the possibility of accumulation of nitrogen during this testing time and the obtained experimental. data lead to the conclusion that the principal cause of enrichment with nitrogen is the reaction of
titanium with the nitrogen of air, which takes place largely during the initial
period of the oxidation.
The high carbon content in the surface layer of the metal is due not only
to the thermodynamically possible accumulation, but probably also to the reaction of titanium with the carbon dioxide present in air.
Measurement of microhardness on transverse and oblique polished sections
prepared from specimens oxidized at 1100-1200 gave very high values (17002350 kg/mm2) in the metal layer adjacent to the scale. A comparison of these
values with the microhardness of a-Ti having the maximum oxygen content of
12.8 wt $ 02 (1250-2350 kg/mm2) and with the microhardness of titanium carbide
(2850 kg/rnrn2) and titanium nitride (1782 kg/mm2) confirms the presence of nitrogen and carbon in the solid solution of a-Ti. The depth of the layer with the
high micsohardness did not exceed 10-15 p in specimens oxidized for 4 hours at
1100-12000.
Let us examine the pattern of distribution of the microhardness in specimens of technically pure titanium oxidized at 1100-1200 (fig. 2).

zfl

3n
Distance from meter scale
interface, rnrn
l ff

Figure 2. Diagram of the distribution of microhardness in

samples of alloy VT1 oxidized at 1100-1200'.
1--Carbonitride layer saturated with oxygen; 2--a-Ti;
3--transformed (3-Ti.

The gas-saturated layer formed is made up of three parts. The first part
consists of an oxygen-saturated carbonitride layer with a hardness of 1350-2350
kg/mm2, the second part of a-Ti with a microhardness up to 400-300kg/mm2, and
in the third part, the structure is that of transformed @-Ti with a maximum hardwhich corresponds to the maximum solubility of oxygen in
ness of 400-500kg/&,
p-Ti (4.0-5.0wt % 02)l.

In 1952, on the basis of precise x-ray diffraction analyses of titanium

scale obtained in air, V. I. Arkhanov and G. P. Luchkin postulated that the defect structure of titanium dioxide arises because trivalent nitrogen ions
participate in the process of its formation. A consequence of the defect stmcture of the scale was a greater oxidizability of titanium at temperatures above
1100~in air than in oxygen. The investigation performed is the first experimental confirmation of this hypothesis concerning the participation of nitrogen
in the process of oxidation of titanium in air, since the high quantity of
nitrogen in the metal proves the penetration of nitrogen through the scale and
the possibility of the creation of an anomaly in the structure of rutile.
After the oxidation, aluminum and iron accumulate in the surface layer at
1100-1200~~
whereas an increase in the silicon content was noted only at 1200.
The amount of aluminum and silicon at temperatures of 800-1000~
is approximately
the same as in the initial alloy; the content of iron at 900-1000 changes somewhat. The accumulation of iron and silicon at high temperatures may be explained
by the drastic conditions of formation of the corresponding oxides, and an
important part is probably played by kinetic factors in the process of enrichment of the metal surface with aluminum. Calcium and magnesium can reduce all
the titanium oxides (see fig. 1) and hence, should be the first to penetrate
into the scale. This is confirmed by spectral analysis. At 900-1200, no increase in the content of calcium and magnesium was observed on the surface of
the metal. After testing at 800, the content of these elements on the titanium
surface was 2-3 times their amount in the alloy prior to the oxidation. Apparently, at 800 there takes place an appreciable diffusion of magnesium and
calcium ions toward the metal-scale boundary, and their per,etrationinto the
scale is difficult. At higher temperatures, this barrier is removed as a result
of the greater mobility of the atoms.
Thus, the surface layer on specimens oxidized at 1100-1200~is a interstitial solid solution of oxygen, nitrogen, and carbon, also enriched with aluminum
and iron, and at 1200' with silicon. In addition to oxygen, the presence in the
surface layer of other elements, primarily nitrogen and carbon, does not permit
us to estimate the amount of oxygen from the change in the parameter c of the
hexagonal lattice, since these elements also change the lattice parameters.
Thus, data on the change in parameter c with the quantity of oxygen present in
titanium, obtained in ref. 5, cannot be used under equilibrium annealing conditions to determine the amount of oxygen absorbed by the titanium from parameter

lThe problem of gas-saturated layers is discussed in more detail in an article

by S. A. Gorbunov and I. S. Anitov in the collection "Titanium and Its Alloys,"
No. 10, Izd-vo AN SSSR, 1963, p. 100.

c, not only for the oxidation of the specimens in air, but also for the oxidation in oxygen because of the redistribution of the impurity elements. In the
various operations of thermal treatment and welding of titanium and its alloys,
it is necessary to take into account the possibility of redistribution of the
elements both on heating in air and in vacuum, where the vaporization of different elements takes place at different rates.
The results obtained for the redistribution of the impurity elements were
also confirmed by studying certain titanium alloys.

An interesting feature encountered in the work was the nonuniformity of

the distribution of the impurity elements not only in different melts but also
in a single melt from one specimen to another. Thus, for example, the amount
of calcium and magnesium in certain specimens was 5-6 times the average content.
In some melts of technically pure titanium V ' I l , aluminum was detected in amounts
obshchesoyuznyy
of 0.3-0.4$, although according to the GOST (~osudarstvenn~~
standart - All-Union State standard) no aluminum whatever should be present in
this alloy. The nonuniformity in the content of the impurity elements in titanium and its alloys may be the cause of the great scatter in the mechanical
properties.
In the course of the investigation, the contamination of certain alloys
with alloying elements not listed in the certificate of the alloy was established. For example, a small amount of tin or chromium was detected in certain

Figure 3. Temperature dependence of free energy of formation for oxides of alloying elements and titanium (based on
1 g/mole 02).

specimens of alloy VT1. When alloying elements are present in an alloy, their
redistribution is possible, just as in the case of the impurity elements.
Let us examine the temperature dependence of the free energy of formation
of oxides of a series of alloying elements and titanium (fig. 3). Molybdenum,
vanadium, chromium, iron, manganese, tin, silicon, nickel, and copper, which
have more positive values of the change in free energy of formation of the corresponding oxides than titanium oxides, can accumulate in the surface layer at
the metal-scale boundary. However, an important part in the oxidation process
should be played by kinetic factors as well (for example, the vaporization of
Results of spectral analysis following oxidation in
volatile oxides, etc )
air of the binary alloys Ti - Mo, Ti - V, Ti - Cr, Ti - Mn, Ti - Sn, Ti - Cu,
containing up to 10% of alloying elements have shown that the surface layer of
the metal becomes enriched with these elements. For example, at certain temperatures, the amount of molybdenum, vanadium, and chromium on the surface of
the metal exceeds the initial content by a factor of 2-3, and nearly pure tin
and copper are formed on the surface of the alloys with tin and copper.

..

Summary

1. The article examined the problems of redistribution of carbon, nitrogen,

iron, aluminum, silicon, calcium, and magnesium between the surface layers and
bulk of titanium specimens after heating in air at 800-1200~.
2. Spectral analysis and microhardness measurements established that the
gas-saturated layer on specimens of titanium oxidized in air at 1100-1200~consists of an interstitial solid solution of not only oxygen but also carbon (up
to 1.0%) and nitrogen (up to 3.0%); in addition, the surface layer becomes
saturated to some extent with iron, chromium, and aluminum.

3. The study showed that at 1100-1200' the increase in the content of

nitrogen in the surface layers is due mainly to a reaction of titanium with the
nitrogen of air.

4. Thermodynamic calculations of the temperature dependence of the free

energy of formation of oxides of impurity and alloying elements confirmed the
possibility of redistribution of these elements in the course of the oxidation.
5. It was established that the gas-saturated layer becomes enriched with
the alloying elements following oxidation in air of the following binary alloys:
Ti - Mo, Ti - V, Ti - Cr, Ti - Mn, Ti - Sn, Ti - Cu.
REFERENCES

1. Genkin, A. D. and Korolev, N. V. Geologiya Rudnykh Mestorozhdeniy, No. 5,

p.

64, 1961.

2. Yesin, 0. A. and Gel d, P. V.. Physical Chemistry of Pyrometallurgical

khimiya pirometallurgicheskikh protsessov), Pt 1,
Processes (~izicheska~a
Metallurgizdat, 1962.

3. Kubaschewski, 0. and Evans, E. Thermochemistry in Metallurgy. IL, 1933.

4. Arkharov, V. I. and Luchkin, G. P. Dokl. AN SSSR, Vol. 83, No. 6, p. 837,

1932

5. Bumps. E. S., Kessler, H. A., and Hausen, M. Trans. ASM, Vol. 45, p. 1008,
1953.

6. Yeremenko, V. N. In: "Titanium and Its Alloys" (Titan

Izd-vo AN USSR, Kiev, 1960.

i yego splavy),

7. Gerasimov, Ya. I., Kystovnikov, A. N., and Shakhov, A. S. Chemical Thermodynamics in Nonferrous Metallurgy ( Khimicheskaya termodinamika v tsvetnoy
metdlurgii). Metdlurgizdat, Vol. 1, 1960; Vol. 2, 1961; Vol. 3, 1963.

EFFECT OF OXYGEN ON THE MECHANICAL PROPERTIES OF

EIEAT-TREATED ALLOYS AT3 AND AT^
B. K. V u l ' f and S. A. Yudina

( ~ r eiminar
l

~ e ~ o) r t

According t o t h e diagram of Ti-0 ( r e f . 1))oxygen r a i s e s t h e temperatures

f3 phase transformation, p a r t i c u l a r l y t h e c r i t i c a l p o i n t s of t h e t r a n of t h e a
s i t i o n i n t o t h e f3 region ( f i g . 1 ) and hence, i s an a s t a b i l i z e r . By forming
i n t e r s t i t i a l s o l i d s o l u t i o n s with titanium, oxygen increases t h e l a t t i c e cons t a n t c of t h e cr solution, having p r a c t i c a l l y no e f f e c t on constant a. As a
r e s u l t of t h e r e s u l t i n g complication of t h e l a t t i c e s t r u c t u r e , t h e s t r e s s e s
causing p l a s t i c deformation of t h e a s o l u t i o n a r e increased, and t h i s may exp l a i n t h e observed hardening e f f e c t .
02, a t . percent

02, a t . percent
2

4 5

B 7 1 I2

I4 76

02, w t percent

Figure 1. E f f e c t of
oxygen on t h e polymorphic transformation
of titanium ( r e f . 1 ) .

02, w t percent

Figure 2. E f f e c t of oxygen
on t h e mechanical characteri s t i c s of titanium.
1--data of r e f . 2;
2- -data of r e f . 3.

The effect of oxygen on the mechanical properties of titanium and its

alloys has been studied by several authors. Thus, it was shown in ref. 1 that
a rise in oxygen content from 0.2 to 13 w t % increases the hardness of titanium
from IN = 170 kg/mm2 to HV = 950-1100kg/mm2.
A diagram showing the effect of oxygen on the mechanical properties of
titanium, plotted on the basis of the data given in refs. 2 and 3, shows that
as the oxygen content rises, the strength of the specimens increases, while the
elongation decreases somewhat (fig. 2).
It has been pointed out in many papers that oxygen increases the sensitivity of titanium to notching and appreciably decreases its impact strength.
Oxygen has a similar effect on titanium alloys.
Thus, in the case of alloy VT8 belonging to the system Ti-Al-Mo, it was shown
(ref. 4) that as the oxygen content rises from 0.1 to 0.$, "hydrogen embrittlement" is strongly manifested, i.e., there 'is a decrease in the impact strength
under the influence of hydrogen. According to the view of the authors of ref.$
this is due to a decrease in the solubility of hydrogen and oxygen in titanium
when both are present.
In ref. 5, the effect of oxygen on the mechanical characteristics of certain alloys of the system Ti-Al-0 was studied; in an alloy with 7.2 wt % Al,
corresponding in aluminum content to the alloy AT8, a rise in oxygen content
from 0.18 to 0.46 wt % causes an increase in the ultimate strength from 80 to
120 kg/rnm2, and a decrease in elongation from 23 to 4%.
As the temperature rises to 600, the ultimate strength decreases, and the
elongation undergoes little change approximately up to 5007 after which it
00'.
increases sharply at 6
The dependence of the properties of alloy AT4 on the content of oxygen and
hydrogen was studied by A. M. Yakimova (refs. 6-8)and other investigators. It
should be noted that alloy AT4 was studied after cooling in air from 800. In
these studies it was shown that oxygen substantially strengthens alloy AT4 (an
average of 10 kg/m$ for every 0.1 wt $ 02). The values of the elongation and
transverse contraction underwent little change, but the impact strength an decreased more abruptly than under the influence of hydrogen. The effect of
oxygen on the mechanical properties of alloy AT4 (at a content of 0.005 w t $ H ~ )
is shown in fig. 3.
Certain data indicate a positive influence of oxygen on the high-temperature strength of titanium alloys.
It has been noted that oxygen increases the creep resistance (ref. 6). The
author explains this phenomenon by the stabilization of the cr phase as a result
of the retardation of the diffusion processes in the presence of oxygen.
The data cited indicate that under the influence of oxygen which they contain, pure titanium and some of its alloys change their mechanical characteris-

02, wt percent

Figure 3. Effect of oxygen on the mechanical characteristics

of alloy AT4 (data of ref. 7).
tics substantially; in many cases, the tensile strength values increase without
any substantial decrease in plasticity. Consequently, some authors did not
include oxygen in the category of absolutely harmful impurities, and in some
cases, its introduction as an alloying element for increasing the strength and
high-temperature strength of titanium alloys has even been recommended.
In this connection, it seems interesting to examine in more detail the
effect of oxygen on the structure, properties and thermal stability of titanium
alloys now being widely used in industrial applications.
In the present study, the effect of oxygen content on the mechanical properties of alloys of type AT has been investigated; alloys with the lowest AT^)
and highest AT^) aluminum content were selected.
Alloys AT3 and AT^ were melted in arc furnaces with a consumable electrode
by the method of double fusion. Electrodes weighing 5 kg were pressed out of
prepared mixtures; aluminum, chromium, iron, and silicon were introduced in
pure form during the preparation of the charge, while boron was introduced in
the form of a 10% Cr-B master alloy. Oxygen was introduced in the Torm of
powdered Ti02.
In order to obtain alloys with a minimum oxygen content, use was made of
titanium TG1113 with ob = 32.8 kg/mm2, and titanium TGOO with ub = 37.3 kg/mm2
was used to prepare the remaining alloys.
The alloys obtained contained an average of 0.7% Cr,
0.01@ B; the amount of aluminum was 3.0% in alloy AT3 and

0.4% Fe, 0.4% Si and

7.0% in alloy AT^.

The content of the oxygen introduced, based on the charge, was:

0.13, 0.23, 0.28, 0.33 and 0.43 wt 4.

0.10,

Check analyses f o r t h e content of oxygen performed on some of t h e specimens

showed a s a t i s f a c t o r y agreement with t h e c a l c u l a t e d d a t a .
After c a s t i n g , turning, and f a c i n g i n o r d e r t o remove t h e c a v i t i e s , t h e
ingots were forged i n t o rods of round and square cross s e c t i o n s 1 2 mm t h i c k .
The forging was open and was c a r r i e d out with a pneumatic hammer. P r i o r t o
forging, t h e i n g o t s were heated i n an e l e c t r i c furnace.
For t h e AT3 a l l o y , t h e temperatures of t h e s t a r t and end of t h e forging
were 1000 and 800, and f o r t h e AT8 d l o y , 1150 and goo0, r e s p e c t i v e l y .
After t h e forging, some of t h e rods were subjected t o a h e a t treatment cons i s t i n g i n quenching i n a i r from 850' f o r a l l o y AT3 and from 950' f o r a l l o y AT^
(holding a t t h e quenching temperature f o r l e s s than 45 min).
Gagarin-type specimens were cut from t h e rods f o r t e n s i l e t e s t s , and specimens with a Menager-type notch were prepared t o determine t h e impact s t r e n g t h .

02, a t . percent
Figure 4. E f f e c t of oxygen on t h e mechanical p r o p e r t i e s of
a l l o y s AT3 and AT^.
1 - - a l l o y AT3 i n i n i t i a l s t a t e ; 2--alloy AT3 a f t e r quenching
from 850 and cooling i n a i r ; 3--alloy AT^ i n i n i t i a l s t a t e ;
& - a l l o y AT8 a f t e r quenching from 950 and cooling i n a i r .

The mechanical t e s t s showed ( f i g . 4 and t a b l e ) t h a t i n d l o y s AT3 and AT^

t e s t e d i n t h e o r i g i n a l s t a t e , a r i s e i n oxygen content from 0.10 t o 0.43% l e a d s
t o an i n c r e a s e i n s t r e n g t h , b u t decreases t h e p l a s t i c i t y and impact s t r e n g t h .

MECEIANICAL PROPERTIES OF ALLOYS AT3 AIlD

@

-I-'

cua,

cua,

G w

Flw

$ +,

'o'
X~.~I.IIZ

6,9b

IP,?/O

'n*

E3

o+

2g

Alloy AT3 i n i n i t i a l s t a t e s

Alloy

80.3
1 0
105.3
11'1.6
118.0

13.2
1.i.7
3.4
13,5
14.

50.6
43.4
51.4
42.3
50.1

9.0
6.15
5.2
4.45
4.4

0.10
0,13
0.23
0.28
0.33
0.43

0 . .I 0
0.13
0.33
0.28
0.33
0 3

Alloy AT3 a f t e r
i n a i r from
0.10
0.13
0.23
0.28
0.33
0.43

AT^.

80
83.6
98.3
08.0
DS,1
011.5

13.9
14.7
13.5
8.6
14.3
14.3

8uenching
30
51
53.3
47.2
44.0
42.0
42.0

12.6
8.7
5.85
4.3
3.45
3.7

ig,.,/

AT^

I> 6

ill,

<[n,

9d

cg,,,,c.,

i n initial states

116.5
136.1
12i.6
127.2
136.3

0
12.5
10.9
12.3
1.45

38.3
36.4
37.0
38.3
4.8

5.7
3.3
4.6
4.0
1,1

Alloy AT^ a f t e r quenching

.
i n a i r from .950
0:10
0.13
0.23
0.38
0:33
0.43

110.4
113.9
7
108.7
109.6
122.2

16.0
6
11.1

42.4
36.2
32.8

6.2

12.0
0.0

26.9
5.5

'

5.8
5.1
4,2
3.35
2.6
0.G

I n a l l o y s AT3 and AT^ s u b j e c t e d t o t h e h e a t treatment, a r i s e i n oxygen

content l e a d s t o a s i m i l a r change i n p r o p e r t i e s , b u t t h i s e f f e c t i s manifested
t o a l e s s e r extent.
I n a l l o y AT^ containing an r e l a t i v e l y l a r g e amount of aluminum, t h e p l a s t i c i t y c h a r a c t e r i s t i c s ( 6 and $) decrease more a b r u p t l y t h a n i n a l l o y AT3; on
t h e c o n t r a r y , i n a l l o y AT3, a r i s e i n t h e oxygen content up t o 0.3% causes a
more a p p r e c i a b l e decrease i n impact s t r e n g t h a,, but p r a c t i c a l l y does n o t a f f e c t
t h e change i n 6 and $.
Summary

1. A r i s e i n oxygen content i n a l l o y s AT3 and AT^ from 0.10 t o 0.43% i n creases t h e i r s t r e n g t h but decreases t h e i r p l a s t i c i t y .

2. Alloy AT3 i s l e s s s e n s i t i v e t o a change i n t h e mechanical p r o p e r t i e s

t h a n a l l o y AT8 when t h e oxygen content r i s e s .
3. I n t h e case of a l l o y AT3, a s t h e oxygen content r i s e s , t h e r e i s observed an abrupt decrease i n impact s t r e n g t h , whereas i n t h e case of a l l o y AT8,
t h e most s e n s i t i v e c h a r a c t e r i s t i c i n t h i s r e s p e c t i s t h e t r a n s v e r s e c o n t r a c t i o n .

Bumps, E.,

Kessler, H.,

J a f f e , R. e t a l .

and Hansen, M.

J. Metals, Vol. 2, p. 1261, 1950.

Finlay, W. and Snyder, J .

J . Metals, Vol. 2, p. 277, 1950.

Kornilov, I. I., Glazunov, S. G., and Yakimova, A. M.

Metallovedeniye, Vol. 8, No. 3, p . 370, 1959.
Suiter, J .

45, p. 1008, 1953.

Trans. ASM, Vol.

J . I n s t . Metals, Vol.

84, No. 4,

p. 81,

F i z i k a Metallov i

1955.

Yakimova, A. M. Author's a b s t r a c t of Candidate's D i s s e r t a t i o n , A. A. Baykov

I n s t i t u t e of Metallurgy (IMEZC), 1960.

--- F i z i k a Metallov

--NO.

i Metallovedeniye, Vol. 12, No.

Coll. Titanium and I t s Alloys

7, p. 166, 1962.

i it an

6,

p. 891, 1961.

i yego s p l a v ~ ) . Izd-vo AN SSSR,

CKARACTl3RISTICS OF THE OXIDATION OF CERTAIN TITANIUM ALLOYS

DURING HEATING PRIOR TO PLASTIC DEFORMATION

I. M. Pavlov, A. Ye. Shelest, and Ye. G. Konstantinov

In the primary treatment, ingots and large blanks of titanium and its
alloys are heated to high temperatures at which the processes of scaling oxidation and gas saturation develop simultaneously on the surface of the metal.
These physicochemical processes are determined by the composition of the gaseous
medium and of the alloys being heated, the temperature, and the duration of the
heating. The magnitude of scaling oxidation and gas saturation depends on the
rate of the chemical reactions at the boundary between the solid and gaseous
phase and on the rate of diffusion of the interstitial elements into the solid
phase.
The problem of scaling oxidation must be studied in order to determine the
fundamental regularities of the distribution of gases between the scale and the
metal, to establish the high-temperature oxidation resistance of titanium alloys
in existence and under development, to select correctly the temperature and time
conditions of heating of these alloys, and to account for the influence of the
oxides on the boundary conditions (metal-instrument) under plastic deformation
of titanium alloys. Many studies of foreign and Soviet authors have been devoted to these problems. It is sufficient to mention the work of V. I. Arkharov,
A. V. Revyakin and others (refs. 1-5).
A comprehensive study of the conditions of plastic deformation of titanium
alloys is being conducted at the laboratory of plastic deformation of metals
and alloys at the A. A. Baykov Institute of Metallurgy. The present work
offers the results of a study of the oxidation kinetics of certain titanium
alloys.
There are several methods of studying the oxidation kinetics of metals, the
most accurate being the method of continuous weighing of the specimens. However,
when this method is used, it is impossible to draw intermediate samples in order
to determine the thickness of the gas-saturated layer. Therefore, for each testing temperature we prepared a set of specimens which were then removed from the
furnace in batches after a certain heating time had elapsed. The specimens were
in the shape of cubes 10-16mm on one side, all the faces of which were planed.
They were placed in porcelain crucible,^ which had been ignited to constant
weight, and air had free access to all the faces of the specimens. The specimens were heated in %n electric furnace to 800-1200' (every loo0), and the
heating lasted 15, 30, 60, 120 and 240 min. Before and after the heating, specimens with and without the crucibles and specimens with the scale removed were

weighed on ADV-200 analytical balances, and the change in weight was divided by
the surface area of the specimen prior to the oxidation. This technique was
,14 and VTl5. In
used to study the oxidation of alloys VT1, OT4-1, OT4, ~ 6 VT
such experiments, particular care should be taken to make sure that the preparation of the surface of all the specimens is identical, since it strongly
affects the oxidation at short holding times and, in particular, the strength
of adhesion of the scale to the base metal. For example, the rougher the treatment of the surface of the plane, the more effective is the surface of oxidation,
and the stronger is the adhesion between the scale and the metal. Thus, the
scale is not completely removed.

holding time, hr

.,75
G
.
6

\,

holding time, hr
d

60

.?

holding time, hr

holding time, hr

Figure 1. Oxidation of titanium alloys versus temperature

and heating time.

After the heating, every specimen was inspected, and the color, macrostructure, thickness and strength of the scale were thoroughly described. All
the quantities characterizing the oxidation kinetics were found directly by
weighing or by simple calculations. The weighing was used to determine: Ago-the increase in the weight of the specimen as a result of oxidation and gas
saturation per unit surface, mg/cm2; Ag4--the change in the'weight of the specimen after removal of the scde per unit surface, mg/cm2.

The unknown q u a n t i t i e s were : weight of gases i n t h e s c a l e ggs; weight of

g a s e s d i s s o l v e d i n t h e metal, gm; weight of metal which had passed i n t o t h e
s c a l e , gms.
These q u a n t i t i e s a r e r e l a t e d by t h e equations

It should be kept i n mind t h a t i n most t i t a n i u m a l l o y s t h e s c a l e c o n s i s t s

of r u t i l e Ti02, s i n c e t i t a n i u m has a g r e a t a f f i n i t y f o r oxygen, whose chemical
a c t i v i t y i s considerably lower than t h a t of t h e o t h e r metals e n t e r i n g i n t o t h e
composition of t h e a l l o y s .
Let u s examine t h e k i n e t i c o x i d a t i o n curves of t h e i n v e s t i g a t e d t i t a n i u m
a l l o y s ( f i g . 1). They a l l show t h a t d u r i n g t h e f i r s t s t a g e , t h e o x i d a t i o n f o l lows a p a r a b o l i c law, which, a s t h e d u r a t i o n of t h e oxidation i n c r e a s e s , changes
i n t o a l i n e a r law.
Our experiments confirmed t h e hypothesis t h a t t h e oxidation r a t e i s governed by t h e concentration g r a d i e n t of oxygen i n t h e s u r f a c e l a y e r s of t h e metal.
The r e a c t i o n of formation of t i t a n i u m oxides t a k e s p l a c e a t f i r s t a t t h e metals c a l e phase boundary, and then s h i f t s t o t h e boundary between t h e s o l i d and
gaseous phase. T h i s was demonstrated by means of i n e r t g r a p h i t e marks made on
t h e s u r f a c e of t h e gas-saturated specimens p r i o r t o t h e i r h e a t i n g .
We s h a l l agree t o r e f e r t o t h e l i n e a r oxidation r a t e a s t h e c h a r a c t e r i s t i c
r a t e . I t s value can be r e a d i l y determined by g r a p h i c a l d i f f e r e n t i a t i o n of t h e
k i n e t i c c u r v e s f o r longer o x i d a t i o n p e r i o d s . I n g e n e r a l , however, t h e oxidation
r a t e changes with time, d e c r e a s i n g and approaching some constant value which we
s h a l l c a l l t h e c h a r a c t e r i s t i c r a t e . The determination of t h e c h a r a c t e r i s t i c
r a t e of each a l l o y makes it p o s s i b l e t o e v a l u a t e t h e degree of i t s oxidation a t
a given temperature. The d a t a obtained i n t h e p r e s e n t work on t h e c h a r a c t e r i s t i c o x i d a t i o n r a t e of t h e i n v e s t i g a t e d a l l o y s a r e compiled i n t h e t a b l e belo~c.

CHARACTERISTIC OXIDATION RATE OF TITANIUM ALLOY DURING HEATING

FOR 4 KR I N AIR I N AN ELECTRIC FURNACE
( i n mg/cm2 h r )
'
Temp., C

VTl

0~4-1

OT4

V T ~

VT14

VT15

It is notable that in the cu + f3 and f3 alloys V T ~ , VT14 and VTl5, the oxidation rate increases monotonically with rising temperature, whereas in VT1 and
OT4-1, which have an allotropic transition range, a sharp increase in the oxidation rate is observed in this range. This is explained by a weakening of the
interatomic bonding forces in the metal lattice and by an increase in the mobility of the atoms in the temperature range of the allotropic transition.
The change in the weight of the specimens following the removal of the
scale, Agt, should be considered separately. The sign of this quantity indicates the relative quantities of the metal which penetrated into the scale and
of the gases which dissolved in the metal. The corresponding curves for each
of the temperatures are shown infigure 2. Thus, the kinetic oxidation curve and
curves representing the change in Agt clearly describe the condition of the
processes of scaling oxidation of titanium alloys and gas saturation in the
surface layers of the metal.

In. practice, the conditions of the heating may differ from those under
which the present work was carried out. Other quantitative characteristics of
the oxidation can also be obtained, but the qualitative picture'remains the
same. The magnitude of scaling oxidation and gas saturation is strongly affected by the atmosphere of the furnace and the total thermal flux. A characteristic feature of oxidation under plastic deformation is the breakdown of the

holding time, hr

holding time, hr

';;;-3"

holding time, hr

Figure 2. Change in weight of specimens of titanium alloys

after removal of scale versus temperature and heating time.

primary scale, the renovation of the metal surface as a result of the emergence
of deeper layers, and secondary oxidation which develops in the course of the
treatment.
The data obtained in the present work can be used for a comparative characterization of the high-temperature oxidation resistance of titanium alloys and
for estimating the effect of alloying elements on this important technological
property of metals.
REFERENCES

1. Arkharov, V. I. and Blankova, Ye. B. Fizika Metallov i Metallovedeniye,

V O ~ .10, NO. 1, 1960.
2. Revyakin, A. V.

Izv. AN SSSR, OTN, Metallurgiya i Toplivo, No.

5, pp. 113-

116, 1961.
3. Layner, D. I. and Tsypin, M. I. Metallovedeniye i Obrabotka Tsvetnykh
Metallov, State Scientific Design and Planning Research Institute for
Working of Nonferrous Metals (~iprotsmo)
, Metallurgizdat, No. 20, pp

42-64,1961.

4. Mozhayev, S. S., Sokiryanskiy, L. F., and Anitov, I. S. Fizika Metallov i

Metallovedeniye, Vol. 14, No. 4, pp. 637-638,1962.
5. $lesareva, Ye. N. Metallovedeniye i Obrabotka Tsvetnykh Metallov, Giprotsmo,
Metallurgizdat, No. 20, pp. 63-80,1961.

NITRIDING OF TITANIUM ALLOYS AT HIGH PFESSURES

Ye. N. Novikova

I n s t u d i e s conducted e a r l i e r on t h e n i t r i d i n g of t i t a n i u m a l l o y s i n pure
nitrogen ( r e f s . 1, 2) it was found t h a t t h e d i f f u s i o n l a y e r on t i t a n i u m i s
formed a t temperatures above 800' i n t h e course of chemical and thermal t r e a t ment of t h e l a t t e r i n an atmosphere of pure n i t r o g e n a t normal p r e s s u r e . !The
d i f f u s i o n l a y e r i s made up of two zones, The upper zone c o n s i s t s of a t h i n
n i t r i d e l a y e r , and t h e lower, t h i c k e r zone c o n s i s t s of a l a y e r of a s o l i d solut i o n of n i t r o g e n i n a-Ti.
A s t h e s a t u r a t e d temperature r i s e s , t h e depth of both l a y e r s and t h e i r
nitrogen concentration i n c r e a s e , causing an i n c r e a s e i n hardness. A t tempera-t u r e s above 950, t h e d i f f u s i o n l a y e r becomes very b r i t t l e , and t h e s t r e n g t h
and p l a s t i c i t y c h a r a c t e r i s t i c s of t h e core of t h e specimen decrease substant i a l l y ; f o r t h i s reason, t h e temperature of 950 was taken a s t h e maximum perm i s s i b l e temperature f o r t h e n i t r i d i n g of a r t i c l e s made of t i t a n i u m a l l o y s .

It was a l s o found t h a t t h e absorption of n i t r o g e n

follows t h e p a r a b o l i c law, i . e . , t h e r a t e of d i f f u s i o n
with time. Thus, f o r each temperature it was p o s s i b l e
which t h e t h i c k n e s s of t h e l a y e r p r a c t i c a l l y ceased t o
t h i s period of time i s equal t o 25-30 h r .

by t i t a n i u m a t 800-12000
of n i t r o g e n decreases
t o determine t h e time a t
i n c r e a s e . Thus, a t 950,

The decrease i n t h e r a t e of t h e growth of t h e d i f f u s i o n l a y e r with time i s

due t o t h e formation and growth on t h e t i t a n i u m s u r f a c e of a n i t r i d e phase i n
which t h e d i f f u s i o n c o e f f i c i e n t of n i t r o g e n i s considerably smaller (by more
than one order of magnitude) t h a n i n cu- and @-Ti, and decreases with r i s i n g
n i t r o g e n concentration ( r e f . 3). A s t h e depth of t h e n i t r i d e zone i n t h e l a y e r
increases, t h e amount of n i t r o g e n d i f f u s i n g through it g r a d u a l l y decreases, and
f r e s h amounts of n i t r o g e n a r e c h i e f l y consumed i n t h e enrichment of t h e n i t r i d e
zone alone, which h i n d e r s t h e p e n e t r a t i o n of n i t r o g e n i n t o t h e metal s t i l l more.
Thus, t h e most s a t u r a t e d and hence m o s t . b r i t t l e p a r t of t h e l a y e r i s t h e nitride
zone.
The a l l o y i n g of t i t a n i u m has a marked influence on t h e depth and hardness
of t h e d i f f u s i o n l a y e r . Table 1 gives t h e depth of t h e l a y e r and t h e hardness
a t t h e s u r f a c e of specimens of various a l l o y s n i t r i d e d f o r 30 h r a t 950' a t a
nitrogen supply r a t e of 0.2-0.3 l/min.
The f i r s t t e c h n o l o g i c a l samplings of n i t r i d e d a r t i c l e s made of t i t a n i u m
a l l o y s showed'that i n many cases t h e l a y e r depth a t t a i n e d was i n s u f f i c i e n t .

TABLE 1

T o t a l depth of l a y e r ,
mm

-Alloy
Technical t i t a n i u m VT1

VT~-1
VT5
VT4
V T ~
VTl 0

0.06-0.08
0.04-0.05
0.08-0 .lo
0.10-0.12
0.12-0.14
0.10-0.12

4 o .14-o -16

Hardness ( p = 5 kg)
on s u r f a c e HV,
kg/mm2

750-850
700-750

750-800
800 -900
7CQ - 750
700 - 750
750-850

Warpage of t h e p a r t s i s unavoidable i n a high-temperature process. When t h e

p a r t s a r e reduced t o t h e required dimensions, it i s necessary t o remove most of
t h e d i f f u s i o n l a y e r and sometimes t h e e n t i r e l a y e r . Furthermore, t h e b r i t t l e ness of t h e n i t r i d e zone, whose depth i n c e r t a i n a l l o y s reaches 15-20 p, causes
t h e chipping of sharp edges, which i s completely unacceptable f o r many p a r t s .
Thus, a more s u c c e s s f u l i n t r o d u c t i o n of t h e n i t r i d i n g processes i n t o t h e
i n d u s t r y r e q u i r e s t h e f i n d i n g of methods of i n c r e a s i n g t h e depth of t h e l a y e r
and e l i m i n a t i n g t h e b r i t t l e n i t r i d e zone which h i n d e r s t h e p e n e t r a t i o n of n i t r o gen i n t o t i t a n i u m .
The achievement of a l e s s b r i t t l e and deeper l a y e r w i l l i n t u r n make it
p o s s i b l e t o lower t h e temperature of t h e process, t h i s being very d e s i r a b l e f o r
preserving t h e mechanical p r o p e r t i e s of t h e c o r e of t h e p a r t and decreasing
t h e i r warpage.
It i s c l e a r from t h e above t h a t i n o r d e r t o o b t a i n a deeper d i f f u s i o n l a y e r
on titanium, one must change t h e n i t r i d i n g conditions i n such a way t h a t t h e
s a t u r a t i o n w i l l proceed only with t h e formation of a s o l i d s o l u t i o n of n i t r o g e n
i n a - T i and t h a t no conditions w i l l be c r e a t e d f o r t h e formation of t h e n i t r i d e
zone. It was p o s t u l a t e d t h a t t h e formation of t h e n i t r i d e zone could be r e t a r d e d by n i t r i d i n g i n a mixture of n i t r o g e n and an i n e r t gas ( a t a low p a r t i a l
pressure of n i t r o g e n ) o r i n r a r e f i e d n i t r o g e n .
Further s t u d i e s i n t h i s d i r e c t i o n have confirmed our hypothesis.
The n i t r i d i n g of titaniunl i n a mixture of nitrogen and argon ( r e f s . -4, 5)
a t a p a r t i a l n i t r o g e n pressure of 0.005-0.04 atm ( t h e amount of n i t r o g e n was
0.4-4 p e r c e n t of t h a t of argon) produced an i n c r e a s e i n t h e depth of p e n e t r a t i o n
of n i t r o g e n i n t o titanium, and t h e n i t r i d e zone was absent from t h e n i t r i d e d
layer.

The p o s i t i v e e f f e c t of r a r e f y i n g t h e ga,s during t h e s a t u r a t i o n of t i t a n i u m

with argon i s a l s o i n d i c a t e d by t h e r e s u l t s of references 6 and 7; t h e s e s t u d i e s
were conducted f o r t h e purpose of determining t h e degree of contamination of

t i t a n i u m with gases. It was shown i n t h e s e s t u d i e s t h a t a decrease i n pressure

frqm 76 t o 0.076 cm Hg a t 850' increased t h e weight gain of t h e specimen per
u n i t surface. After 2 h r of heating, t h e weight gain increased by a f a c t o r of
almost 2. The depth and s t r u c t u r e of t h e l a y e r were not determined.
The e f f e c t of decreasing t h e pressure during n i t r i d i n g on t h e depth of pene t r a t i o n of nitrogen and on t h e s t r u c t u r e of t h e l a y e r was s t u d i e d i n t h e present
work.
The investigati-on was c a r r i e d out on specimens of t e c h n i c a l t i t a n i u m VT1,
i n d u s t r i a l a l l o y s VT3-1, VT4, VT5, and experimental a l l o y s Ti-Al-Mo, Ti-Al-Sn,
and Ti-Al-Cu. The content of a l l o y i n g elements i n t h e s e a l l o y s was as follows:
a l l o y VT5, 5.05 percent Al; a l l o y VT4, 4.8 percent Al and 0.9 percent Mn; a l l o y
VT3-1, 5.2 percent, 1 . 9 percent C r , 1.5 percent Mo and 0.4 percent Fe; a l l o y TiAl.-Mo, 4.1 percent Al and 1.25 percent Mo; a l l o y Ti-Al-Sn, 4.98 percent Al and
0.70 percent Sn; a l l o y Ti-Al-Cu, 4.93 percent Al. and 1.15 percent Cu.
C y l i n d r i c a l specimens 1 0 mm i n diameter and 1 0 mm high were c u t from forged
rods

1 4 mm i n diameter.

The process of n i t r i d i n g a t low p r e s s u r e s i s b a s i c a l l y s i m i l a r t o n i t r i d i n g

a t normal p r e s s u r e : nitrogen from a cylinder i s successively passed through
v e s s e l s with substances absorbing moisture, a r e t o r t with heated t i t a n i u m sponge
( g e t t e r f o r removing oxygen) and t h e chamber of t h e n i t r i d i n g furnace. However,
i n order t o c r e a t e a r a r e f i e d atmosphere of nitrogen i n t h e heating zone a s well,
a l l t h e v e s s e l s and furnaces with t h e g e t t e r and specimens were placed i n a
vacuum chamber.
A l l t h e p a r t s of t h e system were connected by means of vacuum tubing. A
v e s s e l with s i l i c a g e l was connected t o t h e aircock of t h e chamber through which
nitrogen from t h e cylinder was introduced. The gases were evacuated from t h e
chamber by means of a VN-1 preliminary vacuum pump and an M-20 d i f f u s i o n pump
( f i g . 1).

The n i t r i d i n g process consisted of t h e following operations:

(1)

Charging of t h e specimens and t i t a n i u m sponge i n t o t h e furnace;

(2)

Evacuation of a i r from t h e chamber;

(3)

F i l l i n g of t h e chamber with nitrogen;

(4) Evacuation of nitrogen from t h e chamber (operations 3 and 4 were

repeated twice) ;
( 5 ) Heating of t h e furnaces;
( 6) Introduction of nitrogen and establishment of t h e s e l e c t e d
pressure i n t h e chamber;

(7) Soaking a t a continuous flow of nitrogen and a t t h e s e l e c t e d

temperature and pressure;

(8)

Cooling of t h e specimens i n t h e stream of nitrogen;

Emptying of t h e chamber.

Figure 1. Diagram of t h e process of n i t r i d i n g a t low pressures:

1, n i t r o g e n f l a s k ; 2, gas reducing valve; 3, container with s i l i c a
g e l ; 4, container with P205; 5, furnace f o r g e t t e r ; 6, furnace
f o r n i t r i d i n g ; 7, titanium turnings; 8, specimens; 9, c y l i n d r i c a l
vacuum furnace; 10, stopcock f o r evacuating and introducing t h e
gas; 11, preliminary vacuum pump; 12, d i f f u s i o n pump;
place
f o r measuring t h e pressure.
The specimens were n i t r i d e d a t 950'
100, 1, 1 0 - I and 3 x

and p a r t l y a t 870 a t pressures of 760,

mm Hg.

The consumption of nitrogen was s e t a t -- 0 . 3 l/min. A t a pressure of 10-1

mm Hg, two more processes were c a r r i e d o u t with a lower consumption of n i t r o g e n :
0 -09 and 0.03 l/min ( t h e nitrogen consumption was measured by t h e change of t h e
gas pressure i n t h e c y l i n d e r ) . Basically, t h e process l a s t e d 8 h r . A 20-hr
process was conducted a t 950' and a t t h e optimum p r e s s u r e ,
The pressure i n t h e chamber (100 and 1 mm ~ g was
) measured with a V-shaped
manometer, and smaller pressures were measured with a thermal manometer.
Let us examine t h e conditions and r e s u l t s of n i t r i d i n g of c e r t a i n a l l o y s
(table 2).
As i s apparent from t h e t a b l e s , a t a n i t r i d i n g temperature of 950 and a
nitr,,gen consumption of 0.3 l/min, t h e decrease i n pressure from atmospheric t o
1 mrn Hg l e a d s t o a s i g n i f i c a n t increase i n t h e depth of t h e e n t i r e l a y e r and t o
a very appreciable ( s e v e r a l f o l d ) increase i n t h e depth of t h e n i t r i d e zone.
Thus, f o r exitmple, i n specimens of a l l o y s VT5, Ti-Al-Sn and Ti-Al-Cu, t h e depth

TABLE 2. CONDITIONS ANI? RESULTS OF NITIUDING OF CERTAIN ALGOYS

Hardness a t a load of 50 g,
N i t r i d i n g conditions
Depth of kg/mm2, a t a d i s t a n c e from
layer,mm
c 3
ro
t h e s u r f a c e , mm
h

TIN

yz&

0,02

0,04

0.06

Technical t i t a n i u m VT1

Alloy VT3-1

lo-'
lo-'

0.3
0.09
3*10-2 0.09
760
0.3
lo-' 0.2
$0'
0.09

2.1
2.0
1.3
1.33
1.83
1.5

0.004 0,036
0.001 0.05
0.001 10.02
0.008 0.04
0.006 0.07
0.0025 0.028

Alloy VT4

1525
1144
1313
1413
1649
1313

1413
1072
508
1144
1144
412

"'

412
447
1005
412

0.08

0.10

0,15

Tm: E 2 ( ~ o , , t::leg
i

N i t r i d i n g conditions
i=

3
rn

>

Hardness a t a load of 50 f3,

Depth of kg/mm2, a t a d i s t a n c e from
layer,mm
t h e surface, mrn

T i

&
?:

0,02

0.04

0,OG

0.08

0,iO

1/
-

2.5;

0.15

A1 lo:,

'i'i

- .\I - Xlo

Alloy 'I'i - A1 - Sil

7:)s
1223
1144
il44

itii'i

as.,
!

35:i
841

8811 7131
S 9 i ' 7.151
1072
9i(i
iiu S!ii

I1

412
BSI 1.412
14GG l 3 S I
4t7
4t2
7
,412
4 2
351

555

713

st1
412

447
Gift
,381

of t h e l a y e r increased 2.5-fold, while t h e n i t r i d e zone decreased from 4-7 t o

- 2 . The weight g a i n of t h e specimens p e r u n i t s u r f a c e increased by a f a c t o r
of almost 3.
!The s m a l l e s t i n c r e a s e i n t h e depth of t h e n i t r i d e d l a y e r a t 1 mm Hg was
obtained with specimens of t e c h n i c a l t i t a n i u m and of t h e aL1oy VT3-1.
A t a p r e s s u r e of lon1 mrn Hg and a n i t r o g e n consumption of 0 . 3 l/min (temp e r a t u r e , 950) t h e depth of t h e n i t r i d e d l a y e r obtained was somewhat l e s s than
a t 1 mm Hg. However, a decrease i n n i t r o g e n consumption t o 0.03-0.09 l/min
a t t h i s p r e s s u r e promoted an i n c r e a s e i n t h e depth of t h e l a y e r and a decrease
i n t h e depth of t h e n i t r i d e zone. On specimens of technical. t i t a n i u m and a l l o y s
VT3-1, VT4 and Ti-Al-No a,t a p r e s s u r e of lo-' rnm Hg and a t a n i t r o g e n consumpt i o n of 0.09 l/min, t h e depth of t h e l a y e r obtained was g r e a t e r t h a n 1 mm Hg
Hence, it follows t h a t t h e maximum depth of t h e l a y e r i n each
and 0 . 3 l/min.
a l l o y i s obtained a t a c e r t a i n d e f i n i t e p r e s s u r e and n i t r o g e n consumption.
A f u r t h e r decrease i n pressure t o 3 x
mm Hg l e d t o a sharp decrease
i n t h e depth of t h e n i t r i d e d l a y e r and t o a decrease i n hardness, d e s p i t e t h e

f a c t t h a t t h e n i t r i d e zone was minimum ( l e s s than 1 p ) . Obviously, an increase

i n t h e nitrogen consumption was required a t t h i s pressure.
. After n i t r i d i n g f o r 20 h r a t 950, a p r e s s u r e of 10-1 mm Hg and a nitrogen
supply r a t e of 0.27 l/min, t h e depth of t h e n i t r i d e d l a y e r was found t o be 1.5
times g r e a t e r than a f t e r n i t r i d i n g f o r 30 hours a t normal pressure with t h e
o t h e r conditions being t h e same, although f o r t h e majority of t h e a l l o y s t h e
pressure of 10-I mm Hg and nitrogen supply r a t e of 0.27 l/min were not t h e
optimum values.

Photomicrographs ( f i g . 2) show t h e n i t r i d e d l a y e r obtained on a l l o y VT5

a f t e r s a t u r a t i o n a t normal pressure ( f i g . 2a) and a t a pressure of 10-1 mm Hg
(fig. 2b).

Figure 2. Microstructure of n i t r i d e d l a y e r on a l l o y Vl'5,x5OO,

obtained: a, a f t e r 30 h r , a t 950 and normal pressure; b, af'ter
20 h r a t 950' and a pressure of 0.1 mm Hg.
I n a l l t h e a l l o y s , t h e depth of t h e l a y e r following an 8-hr n i t r i d i n g a t
870 and 1 and 10-1 mm Hg was g r e a t e r than a f t e r n i t r i d i n g a t normal pressure.
These r e s u l t s i n d i c a t e t h e p o s s i b i l i t y of lowering t h e temperature when
t h e n i t r i d i n g process i s c a r r i e d out i n r a r e f i e d nitrogen.
Specimens of a l l o y s VTl and VT5 n i t r i d e d f o r 8 h r a t 950, 1 mm Hg and a
nitrogen consumption of 0.3 l/min, were subjected t o wear-resistance t e s t s on
an Arnsler machine i n a couple with n i t r i d e d s t e e l r o l l s .

The t e s t s were c a r r i e d out under t h e following conditions: load 25 kg/mm2;

s l i p r a t e of r o l l , 0 . 4 m/sec; t e s t i n g time, 2 h r ; medium, kerosene.
The t e s t s showed a high wear r e s i s t a n c e of t h e s u r f a c e of specimens n i t r i d e d
i n r a r e f i e d nitrogen. The magnitude of t h e wear ( a few t e n t h s of one milligram)
and c o e f f i c i e n t of f r i c t i o n (0.14-0.15) was t h e same a s i n specimens n i t r i d e d a t
normal. pressure.

TABLE 3
MECHANICAL CHARACTERISTICS OF SPECIMENS OF ALLOY VT4

Number of
specimens

cb

xgl~tnt~

6 , s

a n , k i ~ / c m2

Before n i t r i d i n g

85 -5

14.8

34.5

4.9

N i t r i d i n g a t 1 mm Hg

88.1

11.0

25.8

5.3

N i t r i d i n g a t normal pressure
and 950' f o r 30 h r

82.6

11.2

34.3

4.9

The mechanical c h a r a c t e r i s t i c s of t h e core of t h e specimens of a l l o y VT4

were determined a f t e r n i t r i d i n g i n r a r e f i e d nitrogen under t h e following condit i o n s : temperature, 950'; time, 20 hr; pressure, 1 mm Hg; nitrogen consumption,
0.36 l/min.
Results of t h e t e s t s a r e given i n t a b l e 3.
These d a t a i n d i c a t e t h a t t h e mechanical c h a r a c t e r i s t i c s of t h e specimens of
a l l o y VT4 a f t e r n i t r i d i n g i n r a r e f i e d nitrogen undergo l i t t l e change and a r e suff i c i e n t l y high f o r p a r t s operating under f r i c t i o n .

Summary
1. During n i t r i d i n g of titanium a l l o y s , a decrease of t h e pressure i n t h e
chamber from 760 t o 1 - 0 . 1 mm Hg l e a d s t o a 1.5-2.0-fold increase i n t h e depth
of t h e n i t r i d e d l a y e r , while t h e thickness of t h e b r i t t l e n i t r i d e zone i s r e duced severalf old.
2. It was e s t a b l i s h e d t h a t f o r each titanium a l l o y a t t h e same temperature
and n i t r i d i n g time t h e r e should e x i s t c e r t a i n pressures and a c e r t a i n nitrogen
consumption a t which a maximum depth of t h e l a y e r can be obtained.

3. The l a y e r obtained i n r a r e f i e d nitrogen r e s i s t s wear s a t i s f a c t o r i l y ,

and i t s wear r e s i s t a n c e i s a s high a s t h a t of t h e l a y e r obtained by n i t r i d i n g
a t normal pressure.

4. The mechanical ckraracteris,tics,ofthe core of the specimen of alloy VT4

following nitriding in rarefied nitrogen differ very little from the characteristics obtained in specimens nitrided at normal pressure (the ultimate and impact
strength are somewhat increased; the elongation per unit length and contraction
remain practically the same).
REFERENCES

1. Stroyev, A. S. Coll. Titanium and Its Alloys i it an i yego s~lavy). Metallurgy and Metallography, Izd-vo AN SSSR, pp. 107-114,1958.
2. Novikova, Ye. N. Coll. Titanium and Its Alloys (Titan i yego splavy). Izdvo AN SSSR, No. 3, pp. 35-40, 1960.

3.

Wasilewski, R. Y, and Kehl, G. L. J. Inst. Metals, Vol. 83, No. 3, p.

94,

1954.

4.

Smirnov, A. V. and Nachinkov, A. D. Trudy Len. in-ta aviatsionnogo priboro

stroyeniya, No. 30, pp. 3-18,1959.

5. Nachinkov, A. D. Nitriding of Titanium and Its Alloys at Reduced Nitrogen

titana i yego splavov pri ponizhennom partsial 'nom
Pressure ( ~zotirovani~e
davlenii azota) Author 's abstract of cand. dissert , Len. Institute of
Aviation Instrument Manufacture, 1961.

6. Carpenter, L. G , and Reavell, F. R.

Metallurgia, Vol. 39, (230), p. 63,

1948.

7.

Gulbransen, E. A. and Andrew, K.

Trans. AIME, Vol. 185, p.

741, 1949.

CORROSION OF T I T A N m ALLOYS OF SERIES VT AND AT IN SOLUTIONS

OF SULFURIC ACID CONTAINING N I C m SULFATE

S. A. Nikolayeva and V. A. Zinov'yev

Sulfate solutions resulting from nickel production always contain excess

sulfuric acid. Since at the present time titanium is finding increasingly wider
applications as a structural material in the nickel industry, it appeared of
interest to study the influence of nickel sulfate additions on the corrosion
properties of titanium in sulfuric acid. In order to have a wider choice of
structural material, the corrosion behavior of titanium alloys of series VT and
AT was also investigated.
Our industry produces technical titanium VTl of different types. We studied
the corrosion resistance of sheet, rod, and forged titanium. Rod titanium was
found to have the highest resistance to corrosion. It showed a tendency toward
passivation at room temperature even in sulfuric acid with a concentration of
300 g/l. Sheet and forged titanium showed approximately the same rate of corrosion of sulfuric acid with a concentration of 164 g/l, so that subsequently, the
average corrosion rate of specimens of forged and sheet titanium was taken as
the value of the corrosion rate of alloy VT1 at room temperature. The corrosion
rate was measured by the weight loss of the specimens and calculated in g/m2 hr.
Prior to the experiment, the specimens were turned on an emery wheel, then
washed with water containing soda, dried, washed in carbon tetrachloride, and
weighed.
The experiments were carried out in glass flasks with reflux condensers at
room temperature and at loo0; nickel salts were added in the form of sulfates,
and the concentration was calculated in terms of the metal in g/l.
As a rule, the corrosion rate of the investigated specimens at room temperature was not established immediately: at the start of the experiment, an
induction period was ~bservedduring >?hich the corrosion rate grcdually increased.
These experiments lasted a long time (up to 1500 hr). At loo0, the corrosion
rate was very high, and for this reason the experiments could not be long and
lasted 10 hr. Otherwise, the con~positionof the solution could have ch,anged
substantially, and the specimens could have dissolved. The corrosion rate of
titanium was studied in sulfuric acid of various concentrations. Solne of the
solutions of sulfuric acid contained nickel sulfate additions, others did not.
The values which we obtained for the corrosion rates in the investigated sulfuric acid solutions are collected in the table.

CORROSION RATE OF ALLOYS OF SERIES VT AND AT IN SULFURIC

ACID COl!QAINING ADDITIONS OF SALTS (IN g/m2 HR)

Sulfuric acid concentration, g/l

20
G

0
.

Alloy

+'
;;I
a
(d

0
G

164

83
i

ew
0
0
d

+'

;;I
(d

0
0

4 1 "

a
w
0

"

i2

i2

"

a
0
0

0
0
0

3
u
d

CU

v
2
l

O C U
0

o
.ti

.rt

8 Za dZ
\
M

a \

(dw

0 0

C U G "

Temperature 20'

From the data of the table one can conclude that such alloy components as
molybdenum and vanadium promote an increased passivation of titanium (alloys
VTI5 and ~ 6; vanadium
)
promotes passivation to a lesser extent than molybdenum
(alloy VT7). Zirconium also promotes passivation to a lesser extent than molybdenum, otherwise the corrosion rate of alloy V?g-1 would have been smaller. The
presence of aluminum, tin (alloy VT5-1)) manganese (alloy OT~), and iron (alloy
VT7) increases the corrosion rate of titanium somewhat. Passivation is promoted
by chromium, since the corrosion rate of alloys AT6 and AT^ is less than that
of VT7, OT4 and VT5-1.
An increase in the concentration of sulfuric acid leads to an increase in
the corrosion rate. It should be noted, however, that in sulfuric acid with a
concentration of 83 g/l at room temperature, the corrosion rate is practically
nil; in sulfuric acid with a concentration of 164 g/1, the corrosion rate increases by a factor of approximately 150-300 times, i.e., in the preceding case
a clear-cut passivation of the specimens was observed.
Addition of nickel sulfate to sulfuric acid of various concentrations has
a very special influence on the corrosion rate.

Let us examine the curves representing the corrosion rate versus sulfuric

. acid concentration (fig. 1) in the presence and absence of nickel sulfate (100
g/l ~i). In sulfuric acid with a concentration of 20 g/l, this phenomenon is
difficult to observe because of the low corrosion rate; in sulfuric acid with a
concentration of 83 g/l, the addition of nickel sulfate increases the corrosion
rate by a factor of almost 200. In sulfuric acid with a concentration of 164
g/l, this phenomenon is practically absent. Thus, in certain cases, nickel sulfate activates the corrosion of titanium alloys, and in other cases, this activation is lacking.
The
0
0
'
.
The influence of nickel sulfate was more clearly observed at 1
addition of nickel sulfate in the amount of 10 g/l Ni to acid with a concentration of 164 g/l decreased the corrosion rate somewhat in all cases. Let us
examine the corrosion rate of alloy V T l versus the nickel concentration in the
solution of sulfuric acid with a concentration of 164 g/l (fig. 2). It is evident from this figure that small amounts of nickel present in the solution
activate the corrosion of titanium, and that a further rise in the nickel concentration causes a decrease in the corrosion rate. For comparison, a series
of experiments was carried out in order to determine the influence of nickel
sulfate additions. The sodium sulfate concentrations were chosen so that the
sulfate ion content would correspond exactly to the concentration of this ion
produced by the addition of nickel sulfate. From the figure, it is apparent
that the sulfate ion very definitely decreases the corrosion rate of titanium.
This is in accord with the data of V. V. Andreyeva and V. I. Kazarin (ref. l),
who also observed a maximum corrosion of titanium in 40 percent sulfuric acid
at 4
0
'
.
The activation of the corrosion of titanium and its alloys by
nickel ions is apparently due to the cementation of nickel on the dissolving
surface.
We occasionally observed the presence of nickel on the titanium surface by
inspecting the specimens under the microscope and analyzing the surface formations. However, the cementation of nickel was not always detected; nor did the
corrosion rate always increase in the presence of nickel ions. In particular,
in sulfuric acid with a concentration of 164 g/l, the influence of nickel was
lacking not only when it was added up to a concentration of 100 g/l, which
markedly increased the sulfate ion concentration, but also when nickel was added
in concentrations of 0.1 and 10 g/l, when the sulfate ion concentration remained
practically unchanged. This leads to the hypothesis that complexes of nickel
with excess sulfate ions are formed, thus substantially decreasing the free concentration of nickel ions (ref. 6). At high temperatures, such complexes break
down, and the influence of nickel sulfate additions is clearly manifested.
The value of the steady state potential of dissolving titanium is very interesting.
In all cases where the specimens are in the passivated state, the value of
the steady state potential is between -0.25 and +0.02 V (relative to the standard hydrogen electrode). This is in agreement with the data of refs. 2 and 3.
The dissolution of titanium specimens at a rate of 0.1 g/rn2 hr and higher
begins at a potential of -0.3 V and at higher negative potentials.

Figure 1. Corrosion r a t e versus s u l f u r i c a c i d concentration

f o r various titanium a l l o y s i n t h e presence ( ~ u r v e s1, 3, 5,
7,9, 1 1 ) and absence (curves 2, 4, 6, 8, 10, 12) of n i c k e l
1 and 2, a l l o y VT5-1; 3 and 4, a l l o y s AT40,
s u l f a t e a t 20':
VT10, VT7, OT1; 5 and 6, a l l o y s V?g, AT3, AT^, AT^; 7 and 8,
a l l o y s V T ~ , VT3-1, vr6; 9 and 10, a l l o y s VT14, AT2-2, AT2-3;
11 and 12, a l l o y VT15.
Dissolution a t t h e r a t e of 1 g/m 2 h r and higher i s characterized by a
steady s t a t e p o t e n t i a l of -0.4 V.

It should be noted t h a t t h e s e values of steady s t a t e p o t e n t i a l s a l s o part i a l l y correspond t o a passivated titanium surface. I n 2 N.H2S04, t o which up
t o 1 N. NaF was added, i .e., i n t h e case of an a c t i v e titanium s u r f a c e ( r e f s . 4,
5)) t h e steady s t a t e p o t e n t i a l of specimens of a l l o y s VTL and VT8 was respect i v e l y -0.622 and 0.582 V.
F i n a l l y , a s e r i e s of experiments devoted t o t h e study of t h e influence of
copper s u l f a t e e d i t i o n s was c a r r i e d o u t .
I n most cases, copper i s present a s an impurity i n t h e e l e c t r o l y t e s of
n i c k e l production, and f o r t h i s reason i t s influence appeared of g r e a t i n t e r e s t .
The amount of copper s u l f a t e added t o s u l f u r i c a c i d with a concentration of 164
g / l was r e s p e c t i v e l y equal t o 0.002, 0.02 and 2 g / l ( i n terms of copper).

Figure 2. Corrosion rate of titanium VT1 versus concentration of nickel sulfate and sodium sulfate added to sulfuric
0
'
.
acid (164 g/l) at 9
By cementing on the surface of titanium,
potential toward the positive side. Titanium
passivation, so that, as can be seen from the
tically drops off to zero even when copper is
concentration of 0.02 g/l.

copper shifts its steady state

thus falls into the region of
table, its corrosion rate prac-.
added to the solution up to a

Let us examine the dependence of the steady state potential of titanium on

time for various amounts of sulfate added to the solution of sulfuric acid with a
concentration of 164 g/l (fig. 3). These experiments were carried out with rod
titanium VT1; at 20, the tendency of titanium toward passivation is apparent
from the graph. The points corresponding to the steady state potentials of
0' are located a little higher. In this case, copper shifts the
titanium at 9
steady state potential to the positive side only slightly, so that titanium
does not fall into the region of passivation, and this leads to a,n increase in
the corrosion rate from 44 to 51 g/m2 hr (0.002 g/l CU) and to 56 g/m2 hr
(0.02 g/l cu).
Thus, it may be stated in summary that the regularities corresponding to
alloy VTl are also characteristic of the other titanium alloys. The absolute
values of the corrosion rates of titanium alloys are different from those of
alloy VT1.
The alloys VTl5, VT14, AT2-1, AT2-2, and AT2-3 displayed a good corrosion
resistance in strong sulfuric acid solutions of nickel.
The other investigated alloys showed either a slightly higher or even a
lower corrosion resistance than did alloy VT1. The study of the influence of
the ions on the corrosion resistance of titanium alloys has led to the conclusion that the sulfate ion promotes the passivation of these alloys. Nickel
ions basically activate the corrosion of titanium alloys, and copper ions act
in a similar manner, but shift the steady state potential only slightly;'if,
however, the value of the steady state potential shifts into the passivation
region, the corrosion is practically reduced to zero.

ZLJ.4'

400

6JU

Ki7.4'

/J&'

time, br
Figure 3. Change in the steady state potential of titanium
VT1 in time with sulfuric acid containing additions of copper sulfate: 1, 164 g/l; 2, 164 E/I H2S04 + 0.002 g/l Cu;
3, 164 g/l H SO4 + 0.02 g/l Cu; 4, 164 g/l H2S04 + 0.2 g/l
CU; 5, 164 grl H2S04 + 2.0 g/l cu.
REFERENCES
1. Andreyeva, V. V. and Kazarin, V. I. Dokl. AN SSSR, Vol. 121, No. 5, p.873,

1958.
2. Tomashov, N. D., Al'tovskiy, R. M., and Arakelov, A. G.
V O ~ .121, NO. 5, p. 885, 1958.

3.

Stern, M. and Wissenberg, H.

Dokl. AN SSSR,

J. Electrochem. Soc., Vol. 106, p. 755, 1959.

4. Straumanis, M. E. and Chen, P. C. J. Electrochem. Soc., Vol. 98, p. 234,

1951..

5. Straumanis, M. E. and Jill, C. B. J. Electrochem. Soc., Vol. 101, p. 10,

1954

6. Yatsimirskiy, K. B. and Vasil'yev, V. P. Instability Constants of Complex

Compounds o
SSSR, 1959.

on st ant^ nestoykosti kompleksnykh soyedineniy).

Izd-vo AN

CHEMICAL STABILITY OF TITANIUM IN CERTAIN AGGRESSIVE MEDIA AND

SCOPE OF ITS USE IN CmMICAL IXDUSTRIAL EQUIPMENT
S. M. Babitskaya, V. A. Strunkin,
T. P. Zal'tsman, and Yu. I. Sorokin
Effect of Chlorine on the Corrosion of Titanium in Sulfuric Acid
Chlorine inhibits the corrosion of titanium in 50 and 87 percent sulfuric
acid at room temperature (ref. 1). It appeared interesting to study this phenomenon over a wider range of temperatures and sulfuric acid concentrations.
As is evident from the graph, the dependence of the solubility of titanium on the concentration of sulfuric acid is much more complex than on the
concentration of hydrochloric acid: there are two maxima at concentrations
of 40 and 80 percent and a minimum at 60 percent (independent of temperature). These data are in good agreement with those of Golden et al. (ref. 2).
At room temperature, titanium is stable toward sulfuric acid continuously
saturated with chlorine and having concentrations of 10-80percent. In 95
percent sulfuric acid, the corrosion rate of titanium does not exceed 0.1
mm/year during the first 50 hr, after 100 hr reaches 0.3 mm/year, and after
It should be noted that in the vapor over sul200 hr, about 0.8 -/year.
furic acid saturated with chlorine and having concentrations of 80 and 95
percent, titanium specimens ignited after 34 and 7 hr, respectively.
At 60, the protective action of chlorine is distinctly manifested only
up to a 40 percent sulfuric acid concentration, above which it practically
drops off to zero.
As the temperature rises to go0, the protective action of chlorine
is preserved up to a 40 percent concentration of sulfuric acid, the same as
at 600, but the corrosion rate is no less than 0.3 mm/year in 10 percent
sulfuric acid, and in 40 percent sulfuric acid the corrosion rate reaches
1 &year.
It is interesting to note that in 60 and 95 percent sulfuric acid,
chlorine increases the corrosion rate of titanium somewhat.

0' (the testing

No ignition of specimens in the vapor was observed at 9
lasted 200 hr)

concentration of H2S04, percent

Figure 1. Effect of clilorine on the corrosion of titaanium by sulfuric acid. 1--at 20, without chlorine;
~
chlorine; 3--at 90 without chlorine;
2--at 6 0 without
4--at 20 with chlorine; 5--at 600 with chlorine; 6-at 900 with chlorine.
Chemical Stability of Titanium in Organic Acids
Organic acids are much weaker than mineral ones, as indicated by their
dissociation constants (refs. 3, 4). For example, the dissociation constant
of a 0.1 N solution of acetic acid is approximately 100 times smaller than
the dissociation constant of a 0.1 N solution of hyd-t-ochloricacid.
No direct dependence of the corrosion rate of the metal on the dissociation constant is observed (ref. 5). C1ertain organic acids corrode metals
considerably (refs. 5-10), differing very little in this respect from strong
mineral acids. This is explained by their peculiar characteristics: high
solubility of the salts formed, ability to form water-soluble complexes with
metals, oxidation-reduction properties, and other properties. Thus, one
should not state in advance that because of their weak dissociation organic
acids are not very corrosive: it all depends on the surrounding conditions.
Such slightly dissociated organic acids as acetic, formic, oxalic, maleic,
phenoxyacetic, and certain other acids substantially corrode cast iron, steel
and other metals. Still m ~ r ecorrosive are certain substituted organic acids
whose dissociation constant; are considerably higher. For example, trichloroacetic acid is comparable in strength to mineral acids.
The literature contains only sparse indications concerning the corrosion
resistance of titanium in organic acids (refs. 9, 10).

Experiments which we carried out at 100' and with stirring have shown (see
table) that in many organic acids titanium is characterized by a good corrosion
resistance (the corrosion rate did not exceed 0.O1 mm/year). However, in
oxalic acid, titanium is strongly attacked (corrosion rate, about 100 mmlYear,
i.e., it is approximately the same as in 20 percent hydrochloric acid). An unsatisfactory stability of titanium was also observed in formic, tartaric, and
citric acid, and also in a mixture of glacial acetic acid and acetic anhydride.
It is interesting to note that in 50 percent formic acid there is observed
an unexplained scatter of data: one specimen was strongly attacked (corrosion
whereas the corrosion rates of the other two did not
rate, about 3.5 mm/yr),
exceed 0.08 mm/year. The presence of the aldehyde group makes it possible to
use this acid as a reductant. The strong acid properties of formic acid (its
dissociation constant is 12 times that of acetic acid) and its aldehyde character promote the corrosion of metals whose chemical stability is based on the
formation of an inert oxide film (titanium, stainless steels, aluminum).
The marked corrosion of titanium in hot solutions of oxalic and tartaric
acid and the higher corrosiveness of citric acid are apparently due to the
formation of complexes readily soluble in water.
In all cases, the corrosion was uniform, and in 50 percent citric acid
pitting corrosion was observed.
New Areas of Application of Titanium in Industrial Chemical Apparatus
The studywhich was carried out has revealed new prospects for the use of
titanium equipment in processes involving hydrochloric, hydrobromic, hydriodic
and sulfuric acid containing free halogens.
Titanium is recommended as a structural material for apparatus designed
for use in chlorination processes in a mediu111of hydrochloric acid.
At one plant, successful use has been made for more than a year of titanium
tips of thermocouple sleeves operating under conditions of chlorination of the
organic product in a medium of 18 percent hydrochloric. acid at 60-65O. In order
to provide for mechanical strength, the sleeve is made of two parts: the top
from a thick-walled steel tube, and the bottom (the working surface of the sleeve)
from titanium. The connection between the two parts is threaded. The steel and
the contact area of the metals are rubberized. It is interesting to note that
under these conditions the thermometer sleeve had once been used as an auxiliary
electrode for a level gage. It was then supplied with an alternating current
of industrial frequency. After a short time, corrosion was observed on the
titanium, holes were formed through the entire thickness of the part, and the
operation of the latter failed.
Laboratory experiments confirmed the harmful effect of alternating current
on titanium; the same effect had been observed under industrial conditions. Indeed, specimens of titanium VTI in a medium of 20 percent hydrochloric acid continuously saturated with gaseous chlorine at 6
0' displayed a pronounced pitting

TABLE.

CORROSION OF TITANIUM VT1 I N O E A N I C ACIDS AT 100'

WITH STIRRING.
Acid

Anthranilic
ll
II

Azelaic
11
11

Concen- Duration
Corrosion r a t e , m / y r
tratiorjof tests,in
in
A t interpercen-t;
hr
vapor
face
0,4
0,4

25
50
100

0,000
0,003
0,000

0,000
0,009
0,014

20
20
20

25
50
100

0,000
0,000
0,000

0,009
0,000
0,000

O,/t

0,001

0,000
t

AdLpic
11

I1

Tartaric
11
It

11
11
11

Citric
11
11

I1
11
11

Malelc
11
11
--

Monochloroacetic
(molten)
11
If

Formic
11
11

50

100

0,798

0,000

25
25
25

25
50
100

0,019
0,019
0,007

0,000
0,000
0,000

50
50
50

25
50
100

0,162
0,304
0,241

0,000
0,000
0,002

45
45
45

25
50
100

0,000
0,000
0,000

0,000
0,000
0,000

25

0,000

0,009

50
100

0,009
0,002

0,000
0,000

50
50
50

25
50
100

0,076
3,467
0,007

0,734

0,004

0,302

--

0,000

0,003

--

0,000
0,005
0,000

1,886

--,

p- aminobenzoic
11
11

0,4

25

0,000

0,000

094
Of4

50

0,000

200

0,OOO
0,000

0 , ~ )

0,m;

TABLE (continued)
Acid

Concen- Duration Corrosion rate, rnm/~r

tration,of tests,i;~
At inter!iquid in
vapor face
percent
hr
-.

Salicylic
11
tt

Stearic (molten)
It
It

Trichloroacetic
(molten)
It
11

Acetic (&acial) plus

acetic anhydride

25
50
100

0.17
0.17
0.17

25

0.000

0.000

50
100

0.000
0.002

0.000
0.000

50
100

0,000
0.000

0.000
0,000

0,003

1 :1

25

1, 667
1.640
1.063

0,000
0.000
0,000

0.800

0,000
0.009
0.000

0.085
0,000
0.000

It

I1

Phenoxyacetic
(molken)
I*

11

Oxalic
11
11
11
11
II

MalLc

Succinic
11
It

100
25
50
100
25
50
100

9
9
9

0.000
0.000
0.000

0.000
0.000
0.000

20
20
20

25
50
100

0.000
0.005
0.000

0,000
0,005
0.000

25

0,000

0.000

50
100

0.000
0.003

0.000
0.000

35.568
43.098
30.981
00.856
28.442

0.236
0.194
0,269
10,343
0.261
3,009

0.000
0.005
0.003

0.000
0.000
0,000

0,000
0.000
0.000

0.000
0.000
0.70

25

10
10
10
20
20
20
50

11
ft

11

0.000

0,000

11

Phenoxyacetic

0.000

Fumaric

It

0.001

25

1:i

11

1 :1

Phthalic

0.000
0.000
0,003

0.000
0,000
0.002

50
6.5
6.5
6.5

50
100
25
50
100

25

I,T:
25
50
100

0,000

0.000~

0.001

22.866

25,405

0.001)

-0,000

corrosion after only 42 hr under the influence of alternating current of industrial frequency (current density, 3.5 ~/dm2). A surface 0.06 dm2 in area
had about 35 pits, each 1 mm deep.

A titanium bubbler for feeding gaseous chlorine operated successfully for over 600 hr in the course of chlorination of an organic product in
hydrochloric acid at 50. Before being introduced into the reactor, the
chlorine from the cylinder is deliberately humidified, since dry gaseous
chlorine ignites titanium even at room temperature.
It has been recommended that titanium equipment be used in the process of
bromination of organic products in aqueous media at temperatures from zero to
'3 ( p =~ 1). The bromination of the product is rapid (a few minutes), so that
the possibility of separation of the bromine in a separate phase is excluded.
Otherwise, the use of titanium equipment would be inadmissible because of the
danger of pronounced local corrosion and even ignition of the metal.
In boiling aqueous solutions of maleic acid (particularly in the presence
of organic solvents), the following metals corrode : carbon steel, stainless
steels 1Kh18N9T and lKh18N12M3TY copper, nickel, aluminum, and lead.
In our laboratory it was shown that titanium VT1 is quite stable under
these conditions. Titanium sleeves for thermocouples (wall thickness 1.5 mm)
which have already been in operation for several thousand hours are being
used by one plant in the dehydration of maleic acid.

An experimental laboratory column of a dehydrator of maleic acid was

made of titanium VT1 and consists of 5 tube drums each 250 mm and 1.5-2mm
thick. The column operated for 200 hr without corrosion damage.
Summary

1. Titanium is distinguished by a good chemical stability in a series

of organic acids. In addition, it was noted that in a mixture of glacial
acetic acid and acetic anhydride, and in tartaric, formic, and particularly
acetic acid, titanium is strongly attacked.
2. Free chlorine substantially inhibits the corrosion of titanium by
sulfuric acid.
3. The study revealed new areas of application of titanium equipment in
the chemical industry.

REFERENCES

1. Gleelonan, L. W.

Corrosion, Vol.

14, No. 9, p.

2. Golden, L. B., Lane, I. R. and Acherman, W. L.

P. 1930, 1952.

21. 1958.
Ind. Eng. Chem., Vol.

44,

3. Fieser, L. and Fieser, M. Organic Chemistry IL, 1949.

4. Karrer, P. Textbook of Organic Chemistry (~ursOrganicheskoy khimii).

Goskhimizdat, 1960.
5. Tomashov, N. D. Theory of the Corrosion and Protection of Metals
( ~ e o r i ~korrozii
a
i zashchity metallov)

6. Teeple, H.

0. Corrosion, Vol.

Izd-vo AE SSSR, 1959.

8, No. 1, p. 14, 1952.

7. Rabald, E. Werkstoffe und Korrosion, Leipzig, Vol. 1, 1931.

8. Klinov, I. Ya. Corrosion of Chemical Apparatus and Corrosion-Resistant
Materials (Korroziya khimicheskoy apparatury i korrozionno-stoykiye
materialy) Mashingiz, 1960.

9. Labutin, A. L.

Corrosion and Methods of Protecting Equipment in the

i
Production of Organic Acids and Their Derivatives (~orrozi~a
sposob zashchity oborudovaniya v proizvodstve organicheskikh kislot i
ikh proizvodnykh) . Goskhimizdat, 1959.

10. Macleary, D.

z.

Corrosion, Vol. 18, No. 2, p.

67, 1962.

CREMICAL STABILITY OF TITANIUM I N HYDROHALIC ACIDS AND IZALWENS

Kh. L. T s e y t l i n , L. L. Fayngol'd and V. A. S t r u n k i n

E f f e c t of Halogens on t h e Corrosion of Titanium by

Hydrohalic Acids
I n i n d u s t r y , t h e choice of m a t e r i a l s f o r t h e equipment used i n processes
involving hydrohalic a c i d s i s a s s o c i a t e d w i t h c e r t a i n d i f f i c u l t i e s . A s a r u l e ,
halogens enhance t h e corrosion of metals by hydrohalic a c i d s . Thus, i n t h e
presence of f r e e c h l o r i n e , t h e r a t e of d i s s o l u t i o n of i r o n , copper, n i c k e l , lead
and c e r t a i n o t h e r metals i n hydrochloric acid i n c r e a s e s r a p i d l y ( r e f . 1). A
s a t i s f a c t o r y s t a b i l i t y under t h e s e conditions i s displayed o n l y by tantalum, a
scarce and expensive metal (ref. 2 ) .
A t room temperature, t i t a n i u m i s s t a b l e i n hydrochloric acid o n l y up t o a
concentration of 5 p e r c e n t . I n 20 percent hydrochloric acid, t h e corrosion r a t e
of t i t a n i u m i s 0.5 wnlyr, and i n 36 p e r c e n t HC1, it a t t a i n s 41 mm/yr ( r e f . 3).
Only general d a t a a r e a v a i l a b l e concerning t h e chemical s t a b i l i t y of t i t a n i u m
i n hydrobromic and hydriodic a c i d s ( r e f s . 4 and 5).

It was i n t e r e s t i n g t o determine t h e influence of halogens on t h e chemical

s t a b i l i t y of t i t a n i u m i n hydrohalic acid.
Unkil r e c e n t l y , no such d a t a were a v a i l a b l e i n t h e l i t e r a t u r e . Only i n
1959-1960 were s t u d i e s published which described t h e e f f e c t of c h l o r i n e on t h e
corrosion of t i t a n i u m by hydrochloric a c i d . Titanium was recommended a s a
s t r u c t u r a l m a t e r i a l f o r c h l o r i n a t i n g apparatus i n aqueous media ( r e f . 6).
The corrosion r a t e of t i t a n i u m i n 6 N s o l u t i o n s of hydrohalic a c i d s a t room
temperature i s i n s i g n i f i c a n t , l e s s than 0.6 mm/yr ( f i g . 1). Titanium p r a c t i c a l l y
does not corrode i n t h e vapors of t h e acids.
When t h e temperature i s r a i s e d t o 60')
c r e a s e s almost 100 times.

t h e corrosion r a t e of t i t a n i u m i n -

Titanium corrodes more s t r o n g l y i n hydrochloric than i n hydrobromic a c i d .

I n t h e vapors of t h e s e acids, t h e corrosion i n c r e a s e s markedly and reaches cons i d e r a b l e proportions.
A t 90, t h e corrosion r a t e of t i t a n i u m a t t a i n s huge p r o p o r t i o n s (about 400

mmIyr i n

hydrochloric acid and 72 mm/yr i n hydrobromic a c i d ) . I n t h e vapors of

t h e s e a c i d s , t h e corrosion i s considerably weaker, but s t i l l very s u b s t a n t i a l .

Figure 1. E f f e c t of temperature on t h e r a t e
of corrosion of t i t a n i u m by 6 N s o l u t i o n s of
hydrohalic a c i d s f o r a t e s t i n g time of 1 0 hrs.
An exception among hydrohalic a c i d s i s hydriodic a c i d . Experiments have
shown t h a t t i t a n i u m i s f a i r l y s t a b l e i n hydriodic acid containing f r e e i o d i n e up
It should be noted t h a t
t o 90' ( t h e corrosion r a t e did not exceed 0.15 m m l y r ) .
a t t h e conclusion of t h e t e s t s ( a f t e r 1300 h r s ) , a s a r e s u l t of t h e pronounced
o x i d i z a b i l i t y of hydriodic a c i d , t h e concentration of f r e e iodine i n t h e a c i d
I n o r d e r t o t i e up t h e
increased t o 0.9 g-eq/l a t 60 and t o 3 g-eq/l a t 90'.
f r e e iodine i n t o hydriodic acid, 1 p e r c e n t of red phosphorus was added. Hyd r i o d i c acid was t h u s r i d of f r e e iodine, but was contaminated w i t h a small
I n such a system a t 600, t h e c o r r o s i o n r a t e
amount of phosphorous acid H PO
3 3'
of t i t a n i u m d i d not exceed 0.04 mmlyr a f t e r 200 h r s , but was a l r e a d y 1.3 mrnIyr
a f t e r 500 h r s ,
3 mm/yr a f t e r 1000 h r s .

I n a l l cases, t h e a d d i t i o n of t h e halogen t o hydrochloric and hydrobromic

acid i n h i b i t s t h e corrosion r a t e of t i t a n i u m ( f i g s . 2 and 3 ) , and t h e e f f e c t of
p r o t e c t i v e a c t i o n decreases w i t h r i s i n g temPerature.l A t 20, about 0.001
g-eq/l of f r e e halogen i s already s u f f i c i e n t f o r a complete c e s s a t i o n of t h e
corrosion of t i t a n i u m by 6 3 HC1 a f t e r 50 h r s of t e s t i n g . A t 60') t h e e f f e c t
of p r o t e c t i v e a c t i o n reaches 250 a t t h e maximum concentration of t h e halogen
( t h e s o l u t i o n i s i n i t i a l l y s a t u r a t e d ) , and a t 90, t h e p r o t e c t i v e a c t i o n of t h e
halogen (with a s i n g l e - s t a g e s a t u r a t i o n of t h e acid by t h e halogen) i s observed
only i n t h e course of t h e f i r s t 5 h r s , a f t e r which it disappears completely.
As t h e i n i t i a l halogen concentration r i s e s , t h e d i s s o l u t i o n r a t e o f
titanium decreases ( f i g . 3 ) .

An i n c r e a s e i n t h e t e s t i n g time decreases t h e e f f e c t i v e n e s s of t h e p r o t e c t i v e a c t i o n of t h e halogen.

l ~ h e f f e c t of p r o t e c t i v e a c t i o n i s equal t o t h e r a t i o of t h e corrosion r a t e
i n t h e pure a c i d t o t h e corrosion r a t e i n t h e halogen-containing a c i d .

Concentration, g-eq/l x 10-3

Figure 2. Influence of halogen concentration i n
6 N HC1 s o l u t i o n on t h e e f f e c t of p r o t e c t i v e act i o n during t h e corrosion of t i t a n i u m f o r a t e s t i n g time of 50 h r s .
k

(d

$
a,

'd

35
3.
25
20

(d

75

16'

r:

.rl

k
k

0
U

*t

/(1

/Z

LO 40

Concentration, g - e q / l x 10-3
Figure 3. Influence of halogen concentration on
t h e corrosion of t i t a n i u m i n 6 I$ s o l u t i o n s of
hydrochloric and hydrobromic a c i d s a t 60' f o r t h e
following t e s t i n g times: 1, 1 0 h r s , HBr + Br2;
2, 25 h r s , E
3
B
r
h r s , BBr

Br2;

3, 50 h r s , HBr

+ Br2;

4, 100

Br2;

5 , 1 0 h r s , HC1 + c12(Br2, 12); 6,

12); 7, 50 h r s , HC1

25 h r s , H C l

c12(Br2,

( ~ r12);
~ , 8, 100 h r s , HC1

C12

C L ~ ( B ~12).
~ ,

Chlorine, bromine and i o d i n e i n h i b i t t h e corrosion r a t e of t;tanium by

HC1 t o t h e same e x t e n t .

6N

I n 6 N HBr, t h e a d d i t i o n of bromine a l s o s u b s t a n t i a l l y i n h i b i t s t h e corros i o n r a t e of titanium, but t h e p r o t e c t i v e a c t i o n of bromine i n t h i s case i s

longer and i s manifested a t higher temperatures (up t o 90) t h a n i n t h e case
of hydrochloric a c i d .

Chlorine was used a s an example t o show t h e e f f e c t of hydrochloric a c i d

concentration on t h e r a t e of corrosion of t i t a n i u m by t h e pure a c i d and acid i n
t h e presence of t h e halogen ( f i g . 4). A t room temperature, t i t a n i u m i s s t a b l e
a t any concentrations of hydrochloric a c i d being continuously s a t u r a t e d w i t h
gaseous c h l o r i n e , a t 60 it i s s t a b l e up t o an HC1 concentration of 20 p e r c e n t ,
and a t 90, it i s s t a b l e only up t o an HCl concentration of 5 p e r c e n t . I n 30
percent and 36 p e r c e n t HC1 a t 90, t h e p r o t e c t i v e a c t i o n of c h l o r i n e i s almost
nil.
A s shown by t h e course of t h e curves r e p r e s e n t i n g t h e e l e c t r o d e p o t e n t i a l
of t i t a n i u m versus time ( f i g . 5 ) ) t h e a d d i t i o n of c h l o r i n e s h i f t s t h e p o t e n t i a l
toward more p o s i t i v e values; t h i s e f f e c t i s more pronounced t h e h i g h e r t h e i n i t i a l concentration of f r e e c h l o r i n e i n t h e s o l u t i o n . With time, t h e p o t e n t i a l
r e t u r n s t o l e s s noble values.
A s t h e temperature r i s e s , t h e p o t e n t i a l s h i f t s i n t o t h e region of negative
values. Thus, t h e electrochemical d a t a e s s e n t i a l l y confirm t h e d a t a of t h e
gravimetric method of determining t h e corrosion of titanium.

I n t h e view of many r e s e a r c h e r s , t h e d i s s o l u t i o n r a t e i s determined by t h e

e l e c t r o d e p o t e n t i a l and i s independent of t h e manner i n which a given value of
t h e p o t e n t i a l i s maintained, whether by p o l a r i z i n g t h e m e t a l l i c sample by an
e x t e r n a l anodic c u r r e n t o r by introducing an oxidant i n t o t h e s o l u t i o n (refs.
7-11). Wben c h l o r i n e i s introduced i n t o hydrochloric acid, t h e t i t a n i u m potent i a l assumes values from +0.3 t o +l.lV, which corresponds t o t h e region of
passivated t i t a n i u m on t h e p o t e n t i o s t a t i c curve recorded under t h e same
conditions.
A higher s t a b i l i t y of t i t a n i u m ( r i s e i n t h e upper temperature l i m i t of
s t a b i l i t y t o 90, l o n g e r - l a s t i n g p r o t e c t i v e a c t i o n of t h e halogen i n hydrobromic

/ff

75

2U 2.5 <?U 35

HC1 concentration,

'?f

Figure 4. Influence of c h l o r i n e on t h e corrosion

of t i t a n i u m by hydrochloric acid: 1, a t 20 w i t h
c h l o r i n e ; 2, a t 60 w i t h c h l o r i n e ; 3, a t 90 w i t h
c h l o r i n e ; 4, a t 20' without chlorine; 5 , a t 600
without chlorine; 6, a t 90 without chlorine.

Figure 5. I n f l u e n c e of c h l o r i n e concentration on
t h e e l e c t r o d e p o t e n t i a l of t i t a n i u m i n 6 N HC1:
1, without c h l o r i n e a t 25';
2, 0.01 g-eq/l C 1 2 a t

C 1 2 a t 25';

5, without c h l o r i n e a t 60';

6, 0.002

and hydriodic acid w i t h a d d i t i o n s of f r e e bromine o r i o d i n e , r e s p e c t i v e l y , than

i n hydrochloric a c i d containing f r e e c h l o r i n e ) i s explained by t h e g r e a t e r
s t a b i l i t y of t h e complex RBr and H I a s compared t o HC1 ( t h e e q u i l i b r i u m

X2

X'

where X i s t h e halogen, i s almost completely d i s p l a c e d t o t h e

)

l e f t f o r HC1).
I n t h e view of N. D. Tomashov and R. M. A l ' t o v s k i y ( r e f . 1 2 ) ) t h e p a s s i v a t i o n of t i t a n i u m i n t h i s case i s due t o t h e adsorption of t h e X1 i o n on i t s s u r -

f a c e ; a f i l m i s t h u s formed which c o n s i s t s of an adsorbed and p o s s i b l y a chemical

phase compound of t i t a n i u m w i t h bromine o r i o d i n e . This f i l m r a i s e s t h e overvoltage of hydrogen, a s a r e s u l t of which t h e c o r r o s i o n r a t e of t i t a n i u m decreases.

Chemical S t a b i l i t y of Titanium toward Chlorine,

Bromine and I o d i n e
The first mention of t h e s t a b i l i t y of t i t a n i u m toward halogens d a t e s back
t o 1850, when Wohler wrote t h a t m e t a l l i c t i t a n i u m burns e f f e c t i v e l y i n gaseous
chlorine, b u t does n o t r e a c t w i t h it a t room temperature ( r e f . 1 3 ) . Titanium
was obtained i n t h e form of a dark-gray powder by reducing potassium f l u o t i t a n a t e
with m e t a l l i c potassium. The chemical composition of c h l o r i n e and t i t a n i u m was
was not given.
I n 1895, Moissan found t h a t a m a t e r i a l containing 95-97 p e r c e n t T i and 2-4
0
percent C r e a c t s w i t h c h l o r i n e a t 325 , thereby becoming incandescent, and r e a c t s
w i t h bromine a t 360 and w i t h i o d i n e a t higher temperatures without any apprec i a b l e incandescence. This m a t e r i a l was obtained by heating a mixture of t i t a n i c
acid w i t h carbon i n an e l e c t r i c furnace. This was an amorphous substance which
could be r e a d i l y crushed i n an a g a t e mortar and had a s p e c i f i c g r a v i t y of 4.87
( r e f s . 1 4 and 15).
From t h e n on, t h e i n c o r r e c t view t h a t t i t a n i u m r e a c t s with c h l o r i n e , bromine
and iodine only a t high temperatures (325' and h i g h e r ) has spread i n t h e l i t e r a t u r e and p r e v a i l s u n t i l today ( r e f s . 16-26). However, t h e r e a r e a l s o i n d i c a t i o n s
i n t h e l i t e r a t u r e t h a t pulverized t i t a n i u m i g n i t e s i n gaseous c h l o r i n e and l i q u i d
bromine a t room temperature, and i n i o d i n e on moderate heating ( r e f s . 27 and 28).
Recently, s e v e r a l s t u d i e s have been published i n which it i s s t a t e d , among
o t h e r t h i n g s , t h a t t i t a n i u m r e a c t s vigorously w i t h c h l o r i n e a t room temperature
and even a t - 1 8 O ( r e f s . 4, 6 and 29). However, no d i r e c t proof of t h e inflammat i o n of t i t a n i u m i n gaseous c h l o r i n e i s given.
Our experiments have shown t h a t s h e e t t i t a n i u m VT1 i g n i t e s i n gaseous
c h l o r i n e (from a c y l i n d e r i n which c h l o r i n e contains no more than 0.03 p e r c e n t
of moisture) a t room temperature i n 24 hrs; i f however, t h e gaseous c h l o r i n e i s
a d d i t i o n a l l y d r i e d by being passed through concentrated s u l f u r i c a c i d , t h e i g n i t i o n of t h e metal t a k e s p l a c e i n 1 4 h r s . I n r e a c t i v e l i q u i d bromine, t i t a n i u m
a l s o i g n i t e s a t room temperature i n only 1 0 min, and i n d r y c r y s t a l l i n e i o d i n e ,
A pronounced corrosion of t i t a n i u m i n i o d i n e i s observed
i n 15 min only a t 100'.
even a t 60, but a t room temperature t i t a n i u m d i d not corrode f o r 500 h r s ;
longer t e s t s were not c a r r i e d out ( t a b l e 1).

It seemed of i n t e r e s t a l s o t o determine t h e influence of water on t h e

r e a c t i o n of t i t a n i u m w i t h halogens. This can be done most conveniently w i t h
l i q u i d bromine, p a r t i c u l a r l y s i n c e t h e l i t e r a t u r e contains only g e n e r a l informat i o n on t h e s t a b i l i t y of t i t a n i u m toward wet bromine, t h e s e d a t a being q u i t e
c o n t r a d i c t o r y . For example, one of t h e sources a s s e r t s t h a t wet c h l o r i n e and
bromine do not a t t a c k t i t a n i u m ( r e f . 5 ) ) while another s t a t e s t h a t l i q u i d , d r y
and moist bromine a t t a c k s t i t a n i u m very r a p i d l y ( r e f . 4 ) . We d i d n o t f i n d any
more s p e c i f i c d a t a .
Our experiments showed ( t a b l e 2) t h a t t i t a n i u m r e a c t s vigorously n o t o n l y
w i t h d r y l i q u i d bromine b u t a l s o w i t h wet bromine. Water r e t a r d s t h e r e a c t i o n ,
but even i n t h e presence of considerable amounts of water t i t a n i u m undergoes
a pronounced l o c a l i z e d corrosion i n t h e bromine phase.

TABLE 1. EFFECT OF TEMPERATURE ON THE CHEMTCAL STABILITY OF TITAHIUM I N IODIBl3.

Temperature of
experiment, OC

Testing
time, h r

Average corrosion
rate,

mrnIyr

Remarks
e x t e r n a l appearance of specimen d i d
n o t change
p i t t i n g corrosion
l o c a l i z e d corrosion, s t r o n g l y corroded
edges
l o c a l i z e d corrosion, s t r o n g l y corroded
edges
i n t e n s e heating-up, s ~ e c k m e n si g n i t e d
i n t e n s e heating-up, specimens i g n i t e d

TABLE 2. EFFECT OF WATER ON TlE CHENICAL STABILITY OF TITAHIUM If3\BROMIBE AT

ROOM TWERATURF
Remarks

a f t e r 45 min, t h e s o l u t i o n began
t o b o i l , t h e specimen brightened,
t h e n i g n i t e d w i t h a b r i g h t flame.
It burned f o r 3 min. Deep p i t s
were formed on t h e s u r f a c e of t h e
t h e specimen i g n i t e d a f t e r 1 h r .
Deep p i t s formed on i t s s u r f a c e
t h e specimen i g n i t e d a f t e r 2 h r s .
Deep p i t s were formed on i t s

500

-400

a f t e r 200 h r s of t e s t i n g , t h e
specimen r e t a i n e d i t s o r i g i n a l
appearance, and a f t e r 1000 h r s ,
deep p i t s (up t o 2 . 5 mrn) formed
on some p a r t s of t h e s u r f a c e
a f t e r 200 h r s of t e s t i n g , t h e s p e c i men r e t a i n e d i t s o r i g i n a l appearance, and a f t e r 500 h r s , deep p i t s
(up t o 3 mrn) were formed on some
p a r t s of t h e s u r f ace, and whole
p i e c e s were e a t e n away

Together w i t h untouched s e c t i o n s of l u s t r o u s s u r f a c e , deeply p i t t e d a r e a s

were observed; whole p i e c e s of t h e specimen were corroded away, p a r t i c u l a r l y at
t h e edges ( f i g . 6). The s t r o n g l o c a l i z e d a t t a c k of t i t a n i u m can be explained by
t h e inhomogeneity of t h e media ( t h e s o l u b i l i t y of water i n bromine i s 0.05 p e r c e n t , and t h a t o f bromine i n water, 3 p e r c e n t ) .
I n t h i s connection, it should be noted t h a t t h e l i t e r a t u r e gives t h e i n c o r r e c t impression t h a t t i t a n i u m i s not s u b j e c t t o l o c a l i z e d a t t a c k .
I n aqueous s o l u t i o n s of bromine ( s a t u r a t e d s o l u t i o n ) t i t a n i u m i s s t a b l e up
t o 90 (no experiments were c a r r i e d o u t a t higher temperatures).
The following q u a l i t a t i v e explanation of t h e h i g h r e a c t i v i t y of t i t a n i u m
toward halogens may be accepted. I n o r d e r f o r t h e r e a c t i o n t o t a k e p l a c e i n t h e
form of combustion, t h e following conditions must be met ( r e f . 30):
1. The r e a c t i o n should be h i g h l y exothermic;

2. The r e a c t i o n should t a k e p l a c e a t a high r a t e , which i n t u r n depends on

t h e a c t i v a t i o n energy of t h e molecules of t h e r e a c t i n g substances;
3.

The products of t h e r e a c t i o n should be p a r t l y o r completely gaseous;

4. The r e a c t i o n should be s e l f - s u s t a i n i n g , which, s t r i c t l y speaking,

follows from t h e f i r s t condition, s i n c e t h e r e a c t i o n r a t e i n c r e a s e s w i t h r i s i n g
temperature.
The h e a t s of formation of TiC14, TTBr4 and T i 1

a r e r e s p e c t i v e l y equal t o

179.3, 155 and 102 kcal/mole ( r e f . 31), i . e . , t h e r e a c t i o n s of t i t a n i u m w i t h

c h l o r i n e , bromine and i o d i n e a r e s t r o n g l y exothermic. The melting p o i n t s of.
t h e h a l i d e s a r e r e s p e c t i v e l y -23, +39, +150, and t h e b o i l i n g p o i n t s a r e 136,

Figure 6. Localized corrosion of t i t a n i u m i n

bromine containing 60 percent water a t room
temperature (specimen placed i n bromine phase) :
a , c o n t r o l specimen; b, specimen a f t e r t e s t i n g
(500 h r s )

230 and 377O ( r e f . 32).

This means t h a t t h e c o r r o s i o n products ( T ~ x ~

where
,
X

i s t h e halogen) do not adhere w e l l t o t h e metal, run o f f t h e s u r f a c e , o r evapor a t e when s u f f i c i e n t l y heated by t h e h e a t of r e a c t i o n . Fresh p o r t i o n s of t i t a n i um, which had a l r e a d y been heated, immediately e n t e r i n t o t h e r e a c t i o n . There
f i n a l l y comes a moment when t h e outflow of h e a t ( l o s s t o t h e surrounding medium)
becomes l e s s than i t s inflow caused by t h e h e a t of r e a c t i o n , and i g n i t i o n t a k e s
place.

The a c t i v a t i o n energy of t h e r e a c t i o n s of t i t a n i u m w i t h c h l o r i n e and\bromine

i s apparently of t h e o r d e r of s e v e r a l u n i t s (up t o 1 0 kcal/mole). Only under
those conditions can t h e r e a c t i o n proceed r a p i d l y and i n t h e form of combustion
a t room temperature. The a c t i v a t i o n energy of t h e r e a c t i o n of t i t a n i u m w i t h
iodine i s considerably l e s s (a few t e n t h s of a kcal/mole), and f o r t h i s reason
i g n i t i o n occurs only on heating t o 100'.
The r e a c t i o n of t i t a n i u m w i t h halogens would proceed much f a s t e r (part i c u l a r l y i n t h e case of t h e r e a c t i o n w i t h gaseous c h l o r i n e ) i f it were not f o r
t h e tendency of t i t a n i u m ( l i k e t h a t of aluminum) t o p a s s i v a t e q u i c k l y i n t h e
presence of moisture o r a i r . Indeed, a s was shown by e l e c t r o n d i f f r a c t i o n
measurements ( r e f . 3 3 ) ) when t i t a n i u m i s l e f t standing i n a i r , a f i l m i s formed
which c o n s i s t s of two l a y e r s : t h e oxide l a y e r a s such, which i s
very
chemically bound t o t h e base metal, and a polymolecular l a y e r of p h y s i c a l l y
adsorbed gas o r a mixture of t h e gas w i t h water. This f i l m , f r e q u e n t l y i n v i s i b l e even t o t h e aided eye, i s compact and has good adhesive p r o p e r t i e s . Diffus i o n through such a f i l m i s slow, and t h i s e x p l a i n s t h e extremely low i n i t i a l
r a t e of r e a c t i o n of t i t a n i u m w i t h gaseous chlorine. It should be noted t h a t
broken-up p a r t i c l e s of a white f i l m of t i t a n i u m dioxide were found a t t h e end
of t h e r e a c t i o n of t i t a n i u m w i t h halogens. Hence, Tiox, which makes up t h e
n a t u r a l f i l m on titanium, does not r e a c t w i t h halogens when exposed f o r a s h o r t
time even t o high temperatures. This i n t u r n means t h a t t h e f i l m on t i t a n i u m
formed i n a i r contains pores and t h a t t h e r e a c t i o n of t i t a n i u m w i t h halogens
proceeds through t h e s e pores.
I n our case, t h e r
more quickly (10 min) t
t o t h e f a c t t h a t a cons
and moisture from t h e r
t h e r e a c t i o n i s made mo
renewed p o r t i o n s of gase

romine proceeds much

This i s due
24 h r s )
t i n removing t h e a i r
i s passed; i n a d d i t i o n
1 of heat by c o n s t a n t l y

E f f e c t of Aromatic N i t r o
of Titanium by Hydrochlo
I n r e f e r e n c e s 34 an
n i t r o compounds most
o f t e n enhance t h e corrosion of i r o n , copper, l e a d , aluminum and t b e i r a l l o y s by
e l e c t r o l y t e s . An exception was a-nitronaphthalene, which i n many c a s e s d i d not
a f f e c t t h e corrosion process.

The authors account f o r t h e enhanced corrosion by an e f f e c t i v e d e p o l a r i z i n g

i n f l u e n c e of o x i d i z i n g n i t r o compounds on t h e cathodic process. A s h o r t time
l a t e r , a mechanism of t h i s phenomenon was proposed by I. V. Oknin ( r e f . 36)) b u t
i t was experimental and based on electrochemical measurements.
No such d a t a a r e a v a i l a b l e on titanium.
Our experiments ( t a b l e 3 ) showed t h a t up t o 60' almost a l l of t h e i n v e s t i gated aromatic n i t r o compounds (10 itmes) markedly (100 times o r more) i n h i b i t .
t h e r a t e of corrosion of t i t a n i u m by a g i t a t e d hydrochloric acid i n t h e l i q u i d ,
i n t h e vapor, and a t t h e i n t e r f a c e .

It i s i n t e r e s t i n g t o note t h a t i n t h e presence of p - n i t r o a n i l i n e ( a t 60),

of two samples i n t h e l i q u i d phase, one was h i g h l y corroded (about 1.3 tnm/~r),
while t h e corrosion r a t e of t h e o t h e r sample d i d not exceed 0.13 mm/yr. No
explanation was found f o r t h i s phenomenon.

The above-described o r d e r l y p a t t e r n of t h e i n h i b i t i n g i n f l u e n c e of n i t r o
A pronounced p r o t e c t i v e
compounds on t h e corrosion of t i t a n i u m i s u p s e t a t 80'.
a c t i o n was observed only i n t h e presence of o-nitrotoluene, o-nitrophenol,
m-dinitrobenzene and 1,2,4-dinitrochlorobenzene. I n a l l t h e remaining cases,
t h e p r o t e c t i v e e f f e c t was i n s u f f i c i e n t and a s t i l l - u n e x p l a i n e d s c a t t e r o f t h e
d a t a was observed (pronounced i n h i b i t i o n of t h e corrosion r a t e i n t h e l i q u i d
phase and considerable corrosion i n t h e vapor and a t t h e i n t e r f a c e ) .
Experiments i n s t a t i o n a r y 6 N HC1 showed t h a t under t h e s e conditions a t
temperatures up t o 60, nitrobenzene, o- and m-dinitrobenzene and 1,2,4dinitrochlorobenzene e f f e c t i v e l y i n h i b i t t h e corrosion of titanium. The r e maining seven of t h e eleven n i t r o compounds considered e i t h e r have.no.appreciab l e e f f e c t on t h e corrosion process o r cause a s c a t t e r of t h e d a t a .
A t 80, a l l t h e n i t r o compounds s t u d i e d have no appreciable e f f e c t on t h e
corrosion r a t e .

The concentration of t h e n i t r o compound i n a g i t a t e d 6 N EC1 has a subs t a n t i a l i n f l u e n c e on t h e corrosion of t i t a n i u m a t 60.

A decrease i n t h e amount of t h e n i t r o compound added from 0.5 t o 0.005
p e r c e n t s h a r p l y decreases t h e e f f e c t of p r o t e c t i v e a c t i o n .

Summary
1. Free halogens markedly i n h i b i t t h e corrosion of t i t a n i u m by hydroc h l o r i c , hydrobromic and hydriodic acid.

2. Titanium i g n i t e s a t room temperature i n d r y gaseous c h l o r i n e (from a

c y l i n d e r ) i n 24 h r s , i n l i q u i d bromine i n 1 0 min, and i n d r y c r y s t a l l i n e iodine
a t 100' i n I 5 min. Water i n h i b i t s t h e r e a c t i o n of t i t a n i u m w i t h l i q u i d bromine,
but does not exclude a s t r o n g l o c a l i z e d a t t a c k and even t h e inflammation of
titanium. The use of t i t a n i u m equipment i s inadmissible i n c a s e s where t h e
s e p a r a t i o n of bromine a s a s e p a r a t e phase i s p o s s i b l e .

EFFECT OF AROMATIC NITRO COMPOUNDS (CONCENTRATION.

0.5 P E R C ~ )
TBLE 3
ON THE RATE OF TITANIUM CORROSION I N 20 PERCENT RYDROCHLORIC ACID AT A
STIRRING RATE OF 300 RPM AJiJD A TESTING TIME OF 1 0 HRS

Titanium corrosion r a t e . mm/yr

Additive

i n liquid

i n vapor

at interface

0.05
0.02
0.05
0.02
0.03
0.05
0.03
0.03
0.05
0.01
0.09
0.01

2.73
0.01
0.01
0.01
0.03
0.03
0.09
0.01
0.02
0.03
0.01
0.09

3.89

7.08
0.03
0.05
0.01
0.10
0.07

Temperature ko0

..

4.94

.........
........
........
........

0.09
0.20
0.07
0.07
0.02
0.07
0.06
0.07
0.09
0.09
0.04

nitrobenzene
o-nitrotoulene
p-nitrotoulene
o-nitrophenol
p-nitrochlorobenzene
p-nitroaniline
o-dinitrobenzene
m-dinitrobenzene
1,2, 4-dinitrochlorobenzene
p i c r i c acid
a-nitronaphthalene

.....
........
.......
.......

..
..........
......

Temperature

--

60'

12.68
0.01
0.01
0.01
0.07
0.23
1.34. 0.13
0.05
0.20
0.12
0.02
0.19

.........
........
........
........
.....
........
.......
.......
..
..........
......

nitrobenzene
o-nitrotoulene
p-nitrotoulene
o-nitrophenol
p-nitrochlorobenzene
p-nitroaniline
o-dinitrobenzene
m-dinitrobenzene
1,2, 4-dinitrochlorobenzene
p i c r i c acid
a-nitronaphthalene

0.01
0.01
0.01
0.03
0.10
0.04
0.01
0.10
0.03
0.01
0.01

6.45
-

0.09
0.19
0.12
0.13
0.08

Temperature 80'

..

.......
......

nitrobenzene
o-nitrotoulene
p-nitrotoulene
o-nitrophenol
p-nitrochlorobenzene
p-nitroaniline
o-dinitrobenzene
m-dinitrobenzene
1.2. 4.dinitrochlorobenzene
p i c r i c acid
a-nitronaphthalene

......
......

...
......
.....
.....

........

Hote:

....

The column "in l i q u i d " gives t h e average values of t h e corrosion

r a t e s of two specimens; both values were recorded i f t h e y d i f f e r e d
sharply from each o t h e r
I n a l l cases. t h e nature of t h e corrosion was uniform

3. The retarding effect of aromatic nitro compounds on the corrosion of

titanium by hydrochloric acid was established.

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NO. 1, p. 163, 1960.

2. Romanushkina, A. Ye. and Polyakova, K. K. Khimicheskaya Promyshlennostf,

No. 6, P. 535, 1959.

3. Golden, L. B., Lane, I. R, and Acheman, W. L. Ind. Eng. Chem., Vol. 44,
P o 1930, 1952.

4. Cotton, I. B. and Bradley, H. Chem, a. Ind., Vol. 22, p. 640, 1958.

5

Rtidiger, 0.) Fischer, W. R. and Knorr, W.

Zs. Metallkunde, Vol.

47, p. 8,

1956

6. Avt. svid. SSSR No. 126873, Byull. izobr., No. 6, p. 18, 1960; Tseytlin,
Kh. L. and Strunkin, V. A. Zh. Prikl. Khim., Vol. 33, No. 12, p. 2796,

1960.

7. Uhlig, H. H. and King, P. F. J. Electrochem. Soc., Vol. 106, p. 1, 1954.

8. Kolotyrkin, Ya. M. and Knyazheva, V. M. Zhurnal Fizicheskoy Khimii, Vol.
30, No. 9, P. 1990, 1956.

9. Bune, N. Ya. and Kolotyrkin, Ya. M. Doklady AN SSSR, Vol. 111, No. 5,
p. 1050, 1956.
10. Kolotyrkin, Ya. M.

Probl. Fiz. Khim., No. 1, pp. 81-93, 1958.

11. Bune, N. Ya. and Kolotyrkin, Ya. M.

p. 1543, 1961.

12. Tomashov, N. D. and Alftovskiy, R. M.

p. 610, 1959.
13. ~b'hler,F.

Zh. Fiz. Khim., Val.

35, No. 7,

Zh. Fiz. Khim., Vol. 33, No. 3,

Lieb. Ann., Vol. 73, p. 34, 1850.

14. Moisson, H. C. r., Vol. 120, p. 290, 1895.

5 . Weiss, L. and Kaiser, H. Zs. anorg. Chem., Vol. 65, p. 345, 1910.
16. 'Jllman, F. Enzyklopgdie der technischen Chemie, Berlin, Vol. 11, p. 176,
1922.

17. Technical Encyclopedia (~ekhnicheska~a

entsiklopediya), Vol. 23, p. 434,
1934.

a
metallov)
Morozov, 0. N. Chemistry of Rare Metals ( ~ h i m i ~redkikh
GONTI ?XKTP State United Publishing House of Science and Technology,
People's Commissariat of the Textile Industry, 1938.
Luchinskiy, G. P. Titanium Chemistry (~himiyatitana)

1941.

Gmelins Handbuch der anorganische Chemie, Syst -Numm,

Goskhimizdat,

41, 1951.

Nekrasov, V. V. Textbook of General Chemistry (~ursobshchey khimii)

Goskhimizdat, 1961.

Metal Corrosion (~orrozi~a

metallov), Vol. I, A handbook, edited by H. H.
Uhlig, transl. ed. V. V. Skorchelletti, Goskhimizdat, 1952.
Filyand, M. A. and Semenova, Ye. I. Properties of Rare Elements (~voystva
redkikh elementov) A handbook, GONTI, 1953.

Kornilov, I. I. Khimicheskaya Nauka i Promyshlennostl , Vol. 3, No.

Ps 803, 1958-

---

Uspekhi Khimii, Vol. 23, NO. 5, P. 529,

Yeremenko, V. N. Titanium and Its Alloys

AN SSSR, Kiev, 1960.

6,

1954.

i it an

i yego splavy).

Izd-vo

Klemrn, W. and Grimm, L. Zs. anorg. Chem., Vol. 249, p. 198, 1942.
Hutschinson, G. E. and Permar, P. R.

Corrosion, Vol.

5, No.

10, p.

319,

1949.
Macleary, D. Z. and Kuhn, M. E.

Chem. Proc., Vol. 20, No.

7, p. 67, 1957.

Andreyev, K. K. Thermal Decomposition and Combustion of Explosives

(~ermicheskoyerazlozheniye i goreniye vzryvchatykh veshchestv)
Gosenergoizdat, 1957.

Latimer, V. Oxidation States of Elements and Their Potentials in Aqueous

Solutions. IL , 1954.

Britske, E. V., Kapustinskiy, A. F., Veselovskiy, B. K., Shamovskiy, L. M.,

Chentsova, A. G. and Anvayer, B. I. Thermal Constants of Inorganic
konstanty neorganicheskikh veshchestv)
Substances (~ermicheski~e
Izd-vo AN SSSR, 1949.

Andreyeva, V. V. Trudy instituta fizicheskoy khimii, Izd-vo AN SSSR, Vol.

2, No. 4, P o 79, 1957
Pershke, V. K. and Vinogradova, A. S. Promyshlennostl Organicheskoy Khimii,
vol. 2, NO. 20, p. 419, 1936.

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Pershke, V. K. and Voroshilova, M. A.

P. 562, 1938.

36.

Oknin, I. V.

Prom. Org. Khim., Vol. 5 , No. 8-9,

Zh. Fiz. Khim., Val. 13, No. 3, P O 631, 1939.

EFFECT OF SODIUM NITRITE ON THE CORROSION OF TITANIUM BY

HYDROCHLORIC AND SULFURIC ACID

Yu. I. Sorokin and Kh. L. T s e y t l i n

The corrosion of t i t a n i u m by hydrochloric and s u l f u r i c acid i s i n h i b i t e d

i n t h e presence of oxidizing agents and anodic p o l a r i z a t i o n ( r e f s . 1-6). The
presence of n i t r i c acid i n hydrochloric and s u l f u r i c acid p a s s i v a t e s t h e
t i t a n i u m considerably, a s confirmed by t h e s l i g h t corrosion of t i t a n i u m i n cold
aqua r e g i a ( r e f s . 7 and 8 ) . A v i r t u a l l y complete p a s s i v a t i o n of t i t a n i u m i s
observed i n 20 p e r c e n t hydrochloric acid a t room temperature i n t h e presence of
1.3 percent n i t r i c acid ( r e f . 9 ) . Etching hydrochloric acid s o l u t i o n s containing hydrofluorides become l e s s a c t i v e toward t i t a n i u m when they have accumulated
ions ( r e f . 1 0 ) . Among t h e oxidants depressing t h e
a c e r t a i n q u a n t i t y of ~ i + 4
corrosion of t i t a n i u m i n acids, l i t t l e a t t e n t i o n has been given t o t h e s a l t s of
n i t r o u s acid, which a r e widely used i n i n d u s t r y and have strong o x i d i z i n g
p r o p e r t i e s . There i s evidence t o i n d i c a t e t h a t t h e a d d i t i o n of sodium n i t r i t e
i n h i b i t s t h e d i s s o l u t i o n of t i t a n i u m by hydrochloric a c i d even a t 50' ( r e f .
11). For t h i s reason, heat-exchange elements made of t i t a n i u m should be used
i n t h e processes of d i a z o t i z a t i o n of a n i l i n e , methanilic acid and p-chloro-oaminophenol, which t a k e p l a c e w i t h t h e p a r t i c i p a t i o n of hydrochloric a c i d and
sodium n i t r i t e ( r e f . 1 2 ) . It appeared of i n t e r e s t t o study i n somewhat g r e a t e r
d e t a i l t h e influence of sodium n i t r i t e on t h e corrosion of t i t a n i u m by hydroc h l o r i c and s u l f u r i c a c i d .

Exprlinental Section

Sheet titaniumVT1-lwas used i n t h e i n v e s t i g a t i o n . The experiments were

c a r r i e d o u t i n a six-compartment g l y c e r i n thermostat, using t h e technique described i n reference 13. Polished specimens of t i t a n i u m (50 x 10 x 3 wn)
suspended on hooks of g l a s s s t i r r e r s were t e s t e d i n three-neck g l a s s f l a s k s .
The samples were continuously r o t a t e d a t t h e r a t e of 100 rpm. For comparison,
experiments were c a r r i e d out' without s t i r r i n g . The corrosive media used were
pure 20 p e r c e n t hydrochloric and s u l f u r i c acid i n t h e amount of 600 m l , t o which
sodium n i t r i t e ( a n a l y t i c a l l y pure) had been added. The g l a s s f l a s k s were provided w i t h r e f l u x condensers t o which a i r had f r e e access. There was 100 m l
of acid f o r every 1 0 cm2 of s u r f a c e of t h e sample. A f t e r 10, 50, 100 and 200
h r s of t e s t i n g , t h e samples were removed from t h e corrosive medium, washed with
water, d r i e d and weighed. The corrosive l i q u i d was not renewed a f t e r each
weighing. I n o r d e r t o p l o t t h e curves, use was made of t h e d a t a of t e s t s of
two p a r a l l e l t i t a n i u m samples.

The experiments s h o ~ ~ et dh a t t i t a n i u m has a s a t i s f a c t o r y s t a b i l i t y i n 20

p e r c e n t hydrochloric and s u l f u r i c acid a t 0 and lo0 ( a f t e r a 200-hr t e s t , t h e
Under t h e s e c o n d i t i o n s , t h e a d d i t i o n
corrosion r a t e d i d not exceed 0 . 1 mm/yr).
of n i t r i t e has p r a c t i c a l l y no e f f e c t on t h e corrosion r a t e of t i t a n i u m . I n
quiescent 20 percent hydrochloric acid a t 20, t i t a n i u m depassivates quickly and
i s attacked a t t h e r a t e of approximately 0.5 mm/yr ( f i g . 1). With s t i r r i n g , t h e
access of atmospheric oxygen t o t h e s u r f a c e of t i t a n i u m i s a c c e l e r a t e d , a f f e c t i n g
t h e decrease i n t h e corrosion r a t e during t h e i n i t i a l period of t h e t e s t . When
t h e acid has acted f o r a long time, t h e d i s s o l u t i o n r a t e s of t i t a n i u m i n s t a t i o n a r y and a g i t a t e d media become s i m i l a r . The a d d i t i o n of 0.001 p e r c e n t NaN02
decreases t h e corrosion r a t e of t i t a n i u m i n quiescent and a g i t a t e d hydrochloric
acid t o 0.02 mm/yr only i n t h e course of t h e 100-hr t e s t i n g period. The addit i o n of 0.01 percent NaNO provides f o r a high s t a b i l i t y of t i t a n i u m i n t h e
2
course of t h e e n t i r e t e s t i n g period.
A r i s e i n temperature t o 60' s h a r p l y i n c r e a s e s t h e corrosion r a t e of
and s t i r r i n g a t t h i s
t i t a n i u m i n 20 p e r c e n t hydrochloric acid (up t o 300
temperature has v i r t u a l l y no e f f e c t ( f i g . 2 ) . The a d d i t i o n of n i t r i t e r e t a r d s
t h e d i s s o l u t i o n of t i t a n i u m a t 60' as w e l l , b u t i n t h i s case t h e concentration
of t h e oxidant must be r a i s e d t o 0 . 1 p e r c e n t i n o r d e r t o decrease t h e corrosion
r a t e t o 0.1 d y r .

mmIyr),

I n t h e presence of 0.01 percent NaN02, a marked i n h i b i t i o n of t h e r e a c t i o n

i s observed f o r only about 10 h r s .

A t loo0, t h e r a t e of corrosion of t i t a n i u m by hydrochloric acid i n c r e a s e s
( f i g . 3 ) and a g i t a t i o n a l s o has v i r t u a l l y no e f f e c t on t h e r e a c t i o n
t o 200
A
considerable
decrease i n t h e corrosion r a t e of t i t a n i u m ( t o 0.6-2.0
rate.
i s observed a t an i n i t i a l n i t r i t e concentration of 1 p e r c e n t .

mmIyr

mmIyr)

I n unagitated 20 p e r c e n t hydrochloric a c i d a t 20') t i t a n i u m has a negative

e l e c t r o d e p o t e n t i a l (about - 0 . 4 V ) which undergoes l i t t l e change w i t h time
( f i g . 4). The a d d i t i o n of 0.001 p e r c e n t NaN02 s h i f t s t h e p o t e n t i a l i n t o t h e
passive region (above +0.4 V ) but only during t h e i n i t i a l period of t h e t e s t i n g
(about 20 h r s ) . A s t h e d u r a t i o n of t h e t e s t i n g i n c r e a s e s , t h i s concentration
becomes i n s u f f i c i e n t t o preserve t h e s t a b l e p a s s i v e s t a t e of t i t a n i u m charact e r i z e d by the region of p o s i t i v e p o t e n t i a l values of +0.4 V and higher ( r e f .
6 ) . I n t h e presence of 0.01 percent NaN02, t h e p o s i t i v e p o t e n t i a l (about +0. 7
V ) i s preserved during t h e e n t i r e t e s t i n g p e r i o d . A t 60, t h e e l e c t r o d e potent i a l of t i t a n i u m s h i f t s i n t o t h e p a s s i v e region i f t h e i n i t i a l n i t r i t e concent r a t i o n i s 0.1 p e r c e n t o r higher. The a d d i t i o n of 1 percentNaN02ensures t h e

p r e s e r v a t i o n of t h e p o s i t i v e p o t e n t i a l i n t h e course of t h e e n t i r e period of
t e s t i n g , but i n t h i s case t h e r e i s observed an appreciable tendency of a c t i v a t i o n of t h e t i t a n i u m s u r f a c e w i t h time.

Testing time

, hr

Figure 1. E f f e c t of sodium n i t r i t e on t h e corrosion of t i t a n i u m

i n 20 p e r c e n t hydrochloric acid a t 20 percent: 1, 20 p e r c e n t HC1
without s t i r r i n g ; 2, 20 percent HC1 + 0.001 p e r c e n t NaN02 without
s t i r r i n g ; 3, 20 p e r c e n t HC1 + 0.01 p e r c e n t NaNO2 without s t i r r i n g ;
4, 20 p e r c e n t HC1 w i t h s t i r r i n g ; 5, 20 p e r c e n t RC1 + 0.001 p e r c e n t
NaN02 w i t h s t i r r i n g ; 6, 20 p e r c e n t HC1 + 0.01 p e r c e n t NaN02 w i t h
stirring.

Testing time, h r
Figure 2. E f f e c t of sodium n i t r i t e on t h e corrosion of t i t a n i u m
by 20 p e r c e n t hydrochloric acid a t 600: 1, 20 p e r c e n t HC1 without s t i r r i n g ; 2, 20 percent HC1 + 0.01 p e r c e n t NaNO2 without
s t i r r i n g ; 3, 20 p e r c e n t HC1 + 0.1 p e r c e n t NaN02 without s t i r r i n g ;
4, 20 p e r c e n t HC1 w i t h s t i r r i n g ; 5, 20 p e r c e n t HC1 + 0.01 p e r c e n t
NaN02 w i t h s t i r r i n g ; 6, 20 p e r c e n t H C l + 0.1 p e r c e n t NaN02 w i t h
stirring

zoo
fL7U

t,

(d

k k

(d

gg

ffl

-ri \

m G

Rk "

0
U

108

zoo

Testing time, h r
Figure 3. E f f e c t of sodium n i t r i t e on t h e corrosion of t i t a n i u m
by 20 percent hydrochloric acid a t 100: 1, 20 p e r c e n t H C l without
s t i r r i n g ; 2, 20 p e r c e n t HC1 + 0 . 1 percent NaN02 without s t i r r i n g ;
3, 20 pe-rccent HC1 + 1 . 0 p e r c e n t NaN02 without s t i r r i n g ; 4, 20 percent HC1 w i t h s t i r r i n g ; 5 , 20 percent HC1 + 0 . 1 p e r c e n t NaJ!J02 w i t h
s t i r r i n g ; 6, 20 percent H C l + 1 . 0 p e r c e n t N W 2 w i t h s t i r r i n g .

Testing time, h r
Figure 4. E f f e c t of sodium n i t r i t e on t h e e l e c t r o d e p o t e n t i a l of
t i t a n i u m i n 20 percent hydrochloric acid: 1, 20 percent HC1, a t
20; 2, 20 p e r c e n t HC1 + 0.001 percent NaN02 a t 20; 3, 20 p e r c e n t
HC1 + 0.01 percent NaN02, a t 20; 4, 20 percent. HC1, a t 60; 5 , 20
percent HC1 + 0.01 percent NaN02, a t 600; 6, 20 percent H C l + 0 . 1
percent NaN02, a t 60; 7, 20 p e r c e n t H C l + 1.0 p e r c e n t NaN02 a t 600.
As i n hydrochloric acid, i n quiescent 20 p e r c e n t s u l f u r i c a c i d a t 20') titanium quickly depassivates and corrodes a t t h e r a t e of about 0.6 mm/yr.
Agitat i o n decreases t h e corrosion r a t e of t i t a n i u m o n l y during t h e i n i t i a l t e s t i n g
period. I n prolonged t e s t i n g , t h e d i s s o l u t i o n r a t e s of t i t a n i u m i n quiescent
and a g i t a t e d s u l f u r i c acid become s i m i l a r , a s was t h e case i n hydrochloric acid.
The a d d i t i o n of 0.001 percent NaNO i s s u f f i c i e n t f o r t h e p a s s i v a t i o n of t i t a nium i n quiescent and a g i t a t e d s u l ? u r i c acid during t h e e n t i r e t e s t i n g p e r i o d .

A r i s e i n temperature from 60 t o 100' s h a r p l y i n c r e a s e s t h e c o r r o s i o n r a t e

of t i t a n i u m i n 20 p e r c e n t s u l f u r i c a c i d , and s t i r r i n g has p r a c t i c a l l y no e f f e c t
on t h i s r a t e i n s u l f u r i c a c i d of such c o n c e n t r a t i o n ( f i g s . 5 and 6). Sodium
n i t r i t e has b a s i c a l l y t h e same e f f e c t on t h e i n h i b i t i o n of t h e r e a c t i o n a s hydroc h l o r i c a c i d . The a d d i t i o n of 0 . 1 p e r c e n t NaN02 a t 60' decreases t h e c o r r o s i o n

mmIyr
mmIyr)

r a t e of t i t a n i u m by 20 percent s u l f u r i c a c i d t o 0 . 1
and i s i n s u f f i c i e n t
f o r a s i g n i f i c a n t and l a s t i n g decrease i n t h e c o r r o s i o n r a t e a t 100. A sharp
i s observed i n 20
decrease i n t h e c o r r o s i o n r a t e a t 100' ( t o 0.6-0.8
percent s u l f u r i c a c i d o n l y i n t h e presence of 1 p e r c e n t NaNO
2
I n 20 p e r c e n t s u l f u r i c a c i d a t 20 and 60, sodium n i t r i t e s h i f t s t h e e l e c t r o d e p o t e n t i a l s of t i t a n i u m t o t h e p o s i t i v e s i d e i n e s s e n t i a l l y t h e same way
a s i n hydrochloric a c i d .
Sodium n i t r i t e q u i c k l y decomposes i n i t s r e a c t i o n w i t h a c i d s t o form
n i t r o g e n oxides:

Nitrous acid can e x i s t only i n d i l u t e aqueous s o l u t i o n s a t low temperature.

A t room temperature, n i t r o u s a c i d q u i c k l y o x i d i z e s :

It may be assumed t h a t n i t r i c acid, being t h e end product of t h e r e a c t i o n

of n i t r i t e w i t h a c i d s , can be t h e main oxidant which p a s s i v a t e s t i t a n i u m .
A comparison of t h e d a t a which we obtained ( s e e t a b l e ) shows t h a t t h e
a d d i t i o n of low c o n c e n t r a t i o n s of n i t r i t e p a s s i v a t e s t i t a n i u m i n hydrochloric
and s u l f u r i c acid more e f f e c t i v e l y than t h e a d d i t i o n of e q u i v a l e n t q u a n t i t i e s
of n i t r i c a c i d . Apparently, t h e chief reason f o r t h e g r e a t e r p a s s i v a t i n g
e f f e c t of n i t r i t e i n t h i s case i s t h e formation of n i t r o g e n oxide upon t h e
decomposition of t h e s a l t . It should be noted t h a t t h e a d d i t i o n of 0.02 percent NaNO a l s o p r o t e c t s chromium-nickel-molybdenum s t e e l a g a i n s t c o r r o s i o n i n
2

28 p e r c e n t s u l f u r i c acid a t 70'

( r e f . 16).

There i s no fundamental d i f f e r e n c e between t h e chemical p a s s i v a t i o n of a

metal i n s o l u t i o n s of oxidants and i t s anodic p a s s i v a t i o n ( r e f . 17). I n both
cases, i n o r d e r t o convert t h e metal i n t o t h e p a s s i v e s t a t e , it i s necessary t o
reach a c e r t a i n e l e c t r o d e p o t e n t i a l above which ( i n t h e p o s i t i v e d i r e c t i o n ) t h e
d i s s o l u t i o n r a t e of t h e metal i s determined o n l y by t h e value o f t h e p o t e n t i a l
and i s independent of t h e manner i n which t h e p o t e n t i a l i s maintained, whether
by an e x t e r n a l c u r r e n t o r by t h e a d d i t i o n of oxidants t o t h e s o l u t i o n .

Testing time, h r
Figure 5 . E f f e c t of sodium n i t r i t e on t h e corrosion of t i t a n i u m
by 20 p e r c e n t s u l f u r i c a c i d a t 600: 1, 20 p e r c e n t H2S04, without
s t i r r i n g ; 2, 20 p e r c e n t H2SO4 + 0.01 percent NaN02, without stirr i n g ; 3, 20 percent H g O 4 + 0 . 1 percent NaN02, without s t i r r i n g ;
4, 20 p e r c e n t H2SO4, w i t h s t i r r i n g ; 5 , 20 percent H2SO4 + 0.01
percent NaNO2, w i t h s t i r r i n g ; 6, 20 p e r c e n t H2S04 + 0 . 1 p e r c e n t
NaN02, w i t h s t i r r i n g .
4

200

; ;
a,
+=
Ld
C

0 a,
.d h

g-3
0
k s

fU

7::

J
m
n

L?f

'

Ifl

:*
6
50

I00

200

Testing time, h r
Figure 6. E f f e c t of sodium n i t r i t e on t h e corrosion of t i t a n i u m
by 20 p e r c e n t s u l f u r i c acid a t 1000: 1, 20 p e r c e n t H2SO4, without
s t i r r i n g ; 2, 20 percent H2SO4 + 0 . 1 percent NaNO2, without stirr i n g ; 3, 20 percent H2SO4 + 1 p e r c e n t NaNO2, without s t i r r i n g ;
4, 20 percent H2SO4, w i t h s t i r r i n g ; 5 , 20 percent H2SO4 + 0 . 1 percent NaN02, with s t i r r i n g ; 6, 20 percent H2SO4 + 1 p e r c e n t NaN02,
with s t i r r i n g .
Our experiments showed t h a t a d d i t i o n s of sodium n i t r i t e p a s s l v a t e t i t a n i u m
i n 20 percent hydrochloric and s u l f u r i c acid a t 20 and 600, and markedly decrease t h e corrosion a t loo0. The s h i f t of t h e e l e c t r o d e p o t e n t i a l s of t i t a n i u m
toward t h e p o s i t i v e s i d e i n t h e presence of n i t r i t e was a s s o c i a t e d w i t h a chemi c a l p a s s i v a t i o n of t h e metal.
Oxidants maintain t h e p o s i t i v e value of t h e e l e c t r o d e p o t e n t i a l of t i t a n i u m
i n 20 p e r c e n t hydrochloric acid i f t h e y a r e adsorbed and subsequently chemisorbed;
t h e y harden and preserve t h e p r o t e c t i v e s u r f a c e f i l m ( r e f . 18).

EFFECT OF NATURE OF OXIDANT ON TI33 CORROSION RATE AND ELECTRODE POTENTIAL OF

TITANIUM I N HYDROCRLORIC AND SULFURIC ACID FOR A TESTING TIME OF 100 HRS.

Oxidant

Additive,
percent

20 p e r c e n t HC1
Potential
Corrosion
(relative t o
r a t e , mm/yr
%HE), V

20 p e r c e n t H2S04
Potential
Corrosion
(relative t o
r a t e , mm/yr
NEE)? V
-

Temperature 20'

--

--

NaN02

0.01
0.01
0.1

m03
HN03

0.55
0.02
0.66
0.14

-0.4

+0.7
-0.3
+0.6

Temperature

--

--

NaN02

0.1
0.1
1

HN03
HNO
3

20.15
0.12
18.60
0.20

0.68
0.02
0.80
0.40

-0.4
+0.4
-0.3
-0.3

15 90

-0.4
+0.1
-0.4
+0.5

60'

-0.5
+0.3
-0.2
+0.7

0.10
20.94
0.10

We showed t h a t , l i k e o t h e r oxidants ( r e f s . 1 and 9 ) , sodium n i t r i t e

p a s s i v a t e s t i t a n i u m i n a c i d s f o r only a c e r t a i n period of time which depends on
t h e concentration of t h e oxidant and temperature of t h e experiment. During
t h i s period of time, t h e concentration of n i t r i t e becomes s u f f i c i e n t t o harden
and preserve t h e p r o t e c t i v e s u r f a c e f i l m on titanium. I n our experiments, f o l lowing exposure t o a c i d s containing sodium n i t r i t e i n a q u a n t i t y s u f f i c i e n t f o r
p a s s i v a t i o n , t h e s u r f a c e of the t i t a n i u m samples was gold i n c o l o r , which l e d
t o t h e assumption t h a t a l a y e r of t i t a n i u m dioxide was formed ( r e f . 2 ) .
A comparison of t h e corrosion values which we obtained i n 20 p e r c e n t
s o l u t i o n s of hydrochloric and s u l f u r i c acid a t 20 and 100' w i t h t h e d i s s o l u t i o n
r a t e s c a l c u l a t e d from t h e c u r r e n t d e n s i t i e s of t h e p o t e n t i o s t a t i c curves ( r e f s .
6 and 18) showed t h a t t h e e f f e c t i v e n e s s of t h e chemical p a s s i v a t i o n of t i t a n i u m
i n t h e presence of sodium n i t r i t e may be e s s e n t i a l l y of t h e same o r d e r a s i n
t h e anodic p a s s i v a t i o n without an oxidant.

It should be noted only t h a t our experiments were conducted on one-piece

unstressed t i t a n i u m samples. It i s p o s s i b l e t h a t i n t h e s t r e s s condition, t h e
massive metal, t h e weld and t h e heat-affected zone behave d i f f e r e n t l y under
conditions of chemical and anodic p a s s i v a t i o n . The process of corrosion of t h e
metal under conditions of chemical and anodic p a s s i v a t i o n may a l s o have a d i f f e r e n t course i n narrow gaps, where, p a r t i c u l a r l y i n t h e presence of a small
concentration of oxidant, various f a c t o r s a r e o p e r a t i v e which r e g u l a t e t h e
access of t h e reagent t o t h e s u r f a c e of t h e metal and t h e removal of t h e corrosion products ( r e f . 1 9 ) .
Our experiments have shown t h a t electrochemical measurements make it p o s s i b l e t o e s t a b l i s h t h e d i r e c t i o n of t h e corrosion process ( e i t h e r toward a c t i v a t i o n o r p a s s i v a t i o n ) i n a s h o r t e r time than when t h e gravimetric method i s used.

Summary
1. TitaniumVTl-ldisplays a satisfactory stability in 20 percent hydro0
' and corrodes substantially
chloric and sulfuric acid at temperatures up to 1
at temperatures above 20.

2. Additions of certain sodium nitrite concentrations to hydrochloric and

sulfuric acid impart a positive electrode potential sufficient for chemical passivation to the surface of titanium.

3. Sodium nitrite markedly dgcreases the corrosion of titanium by acids

only under certain testing conditions. In order to provide for a satisfactory
stability of titanium in 20 percent hydrochloric and sulfuric acid, it is
necessary to add 0.01 percent NaN02 at 20 and 0.1 percent NaN02 at 600. A
pronounced inhibition of titanium corrosion in the presence of nitrite was also
observed at loo0, but the weight loss of the metal at this temperature was
nevertheless considerable.

4. Equipment with working surfaces made of titanium VT1-1 can be used at

0' under conditions involving the use of hydrochlolic and
temperatures up to 6
sulfuric acid containing the optimum nitrite concentration.

Tseytlin, Kh. L. and Strunkin, V. A.

NO. 12, p. 2796, 1960.

Zhurnal Prikladnoy Khimii, Vol. 33,

Andreyeva, V. V. and Kazarin, V. I. New Corrosion-Resistant Structural

Materials (~ovyyekorrozionnostoykiye konstruktsionnyye materialy).
Goskhimizdat, 1961.

---

Doklady AN SSSR, Vol. 121, No.

5, p. 873, 1958.

Tomashov, N. D., Alltovskiy,R. M. and Arakelov, A. G. Dokl. AN SSSR,

V O ~ .121, NO. 5, p. 885, 1958.
Gleekman, L. W.
Otsuka, R.

Corrosion, Vol.

14, p. 401, 1958.

Sci. papers Inst. Phys. a. Chem. Res.,. Vol.

54, No.

1, p.

97,

1960.
Moroz, L. S., Chechulin, V. V., Polin, I. V., Butalov, L. V., Shulfkin,S. M.
and Goryachev, A. P. Coll. Titanium and Its Alloys i it an i yego splavy).
Sudpromgiz (state All-Union Publishing House of the.Shipbuilding ~ndustry)
,
Leningrad, Vol. I, p. 150, 1960.
Cotton, Y. B. and Bradley, H. Chem. a. Ind., No. 22, p.

640, 1958.

Zwicker, U. Chem. Ing. Techn., Vol. 29, No. 2, p. 107, 1957.

Andreyeva, V. V. and Kazarin, V. I. Dokl. AN SSSR, Vol. 123, No. 6, p.

1048, 1958.
Klinov, I. Ya. Trudy MIKhM (~ransactionsof the Moscow Institute of
Vol. 22, p. 75, 1960.
Chemical ~achiner~),
Vashin, G. Z. and Klimov, I. Ya. Vestnik Tekhnicheskoy i Ekonomicheskoy
Informatsii (NIITEK~IM),No. 2, p. 46, 1962.
Babitskaya, S. M. and Tseytlin, Kh. L. In: Corrosion of Stainless Steels
(~orroziyanerzhaveyushchykh staley) Izd-vo AN SSSR, p. 69, 1956.

Babko, A. K. and Pyatnitskiy, I. V. Qualitative Analysis (~olichestvennyy

analiz) Goskhimizdat, p 572, 1956.

Ullman ~nz~klopadie
der technischen Chemie, Berlin, Aufl. 2, Vol. 9 , p.
726, 1932.
French Patent No. 1012443 dated 9/7/1952; C. A., 11231, 1957.
Bune, N. Ya. and Kolotyrkin, Ya. M.

Zhurnal Fizicheskoy Khimii, Vol. 35,

NO. 7, p. 1543, 1961.

Andreyeva, V. V. and Glukhova, A. I. J. Appl. Chem., Vol. 11, p. 390, 1961.
Sorokin, Yu. I. and Tseytlin, Iih. L. Zhurnal Prikladnoy Khimii, Vol. 35,

NO. 4, p. 573, 1962.

STUDY OF TRE USE OF TITANIUM ALLOYS I N TRE CONSTRUCTION OF FOOD MACHINES

F. N. Tavadze and T. A. Lashkhi

The purpose of t h e p r e s e n t work was t o continue ( r e f . 1) t h e i n v e s t i g a t i o n

and t o e s t a b l i s h t h e p o s s i b i l i t y of t h e a p p l i c a t i o n of t i t a n i u m a l l o y s of t h e
ATn s e r i e s t o t h e c o n s t r u c t i o n of food machinery.
Since t h i s branch of t h e i n d u s t r y r e q u i r e s a l a r g e number of s c a r c e n i c k e l s t a i n l e s s s t e e l s , nonferrous metals and a l l o y s , t h e s e a r c h f o r t h e i r s u b s t i t u t e s
has assumed g r e a t importance i n t h e n a t i o n a l economy.
Titanium a l l o y s a r e new s t r u c t u r a l m a t e r i a l s which, because of numerous
valuable p r o p e r t i e s (high s t r e n g t h , low d e n s i t y , c o r r o s i o n r e s i s t a n c e i n various
media, e t c . ) can be s u c c e s s f u l l y used i n various branches of i n d u s t r y . Despite
t h e high c o s t of t i t a n i u m a l l o y s , t h e i r use i s growing every y e a r i n various
branches of t h e n a t i o n a l economy.
Another advantage of t i t a n i u m a l l o y s over s t e e l s i s t h e l e n g t h of t h e l i f e
of t h e equipment because of i t s high r e s i s t a n c e t o corrosion and wear.
Experiments c a r r i e d o u t e a r l i e r ( r e f . 1) showed a high corrosion r e s i s t a n c e
of t h e t i t a n i u m a l l o y s ATn i n a number of t e c h n o l o g i c a l and food media. Because weld j o i n t s a r e u s u a l l y employed i n t h e manufacture of apparatus and equipment, t h e experiments were c a r r i e d o u t on weld j o i n t s of a l l o y s AT3 and AT^. The
specimens t o be t e s t e d , welded by argon a r c welding, were obtained from t h e welding
l a b o r a t o r y of t h e A. A. Baykov I n s t i t u t e of Metallurgy.
The t e s t s were conducted i n a s e r i e s of organic a c i d s and t e c h n o l o g i c a l
s o l u t i o n s K 1 and V 1 corresponding t o aggressive media employed i n t h e canning
and wine-making i n d u s t r y ( t a b l e 1 ) )both a t room temperature and b o i l i n g temp e r a t u r e , and a l s o i n n a t u r a l cherry plum j u i c e , t h e most aggressive food medium
( t o t a l a c i d i t y 2 percent, p~ = 2.8).
~ 9 ~
some e x p e r i I n a d d i t i o n t o t i t a n i u m a l l o y s , s t a i n l e s s s t e e l 1 ~ h 1 8 and
mental chromium-maganese s t e e l s were t e s t e d a t t h e same time.
The technique of t h e corrosion and electrochemical t e s t s consisted i n
studying t h e samples and t h e r e a c t i o n medium: t h e weight l o s s and t h e q u a n t i t y
of hydrogen evolved during t h e corrosion of t h e a l l o y s were determined; t h e
values of t h e e l e c t r o d e p o t e n t i a l s were measured; p o l a r i z a t i o n curves were
p l o t t e d ; t h e r e a c t i o n medium was analyzed chemically a f t e r t h e t e s t , and t h e
pH was determined a f t e r t h e corrosion t e s t s of t h e samples. The a l l o y samples

TABLE 1. CHEMICAL COMPOSITION OF TECHNOLOGICAL SOLUTIONS K l AND V 1 .

were observed v i s u a l l y and were subjected t o metallographic a n a l y s i s before and

a f t e r t h e i r corrosion t e s t s .
The r e s u l t s of 3000-hr corrosion t e s t s of t h e weld j o i n t s of a l l o y s AT3 and
From t h i s t a b l e it i s e v i dent t h a t on t h e c o r r o s i o n r e s i s t a n c e s c a l e , t h e a l l o y s a r e i n t h e region of
corrosion r e s i s t a n t values (ll < 0.13 mrn/yr) i n t h e case of o x a l i c and t a r t a r i c
a c i d . I n o l e i c , t a r t a r i c , a c e t i c and l a c t i c a c i d t h e corrosion of t h e a l l o y s i s
equal t o zero.

AT^ i n various organic a c i d s a r e shown i n t a b l e 2.

The r e s u l t s of corrosion t e s t s of welded t i t a n i u m samples i n t e c h n o l o g i c a l

s o l u t i o n s K1 and V 1 ( t a b l e 3) and t h e k i n e t i c curves of t h e corrosion process
( f i g . 1) show t h a t t h e samples i n t h e t e c h n o l o g i c a l s o l u t i o n K 1 a r e subjected
t o a r e l a t i v e l y high corrosion. This d i f f e r e n c e i s p a r t i c u l a r l y n o t i c e a b l e
during t h e i n i t i a l period of t h e test.
The e l e c t r o d e p o t e n t i a l s of t h e i n v e s t i g a t e d t i t a n i u m a l l o y s AT^ g r a d u a l l y
s h i f t toward t h e p o s i t i v e region ( f i g . 2 ) , which i s i n agreement w i t h t h e r e s u l t s
of t h e corrosion t e s t s .
I n order t o e s t a b l i s h t h e i n f l u e n c e of atmospheric oxygen on t h e hardening
of t h e p r o t e c t i v e f i l m , t h e e l e c t r o d e p o t e n t i a l s of t h e a l l o y s were measured
both i n t h e s t i r r e d and u n s t i r r e d s o l u t i o n . I n t h e s t i r r e d s o l u t i o n , t h e value
of t h e p o t e n t i a l i s l o c a t e d i n a more p o s i t i v e region ( f i g . 2, curve 2 ) . This
i n d i c a t e s an i n c r e a s e i n t h e p r o t e c t i v e p r o p e r t i e s of t h e s u r f a c e f i l m of
a l l o y AT^.
The presence of a p r o t e c t i v e f i l m on t i t a n i u m a l l o y s i s a l s o i n d i c a t e d by
t h e values and course of t h e p o l a r i z a t i o n curves obtained f o r a l l o y AT3 i n t h e
technological s o l u t i o n Kl. ( f i g . 3). An a n a l y s i s of t h e curves shows t h a t an
appreciable i n h i b i t i o n of anodic r e a c t i o n s t a k e s p l a c e i n t h i s case (anodic
p a s s i v i t y ) , which r e a f f i r m s what was s t a t e d above.
A s expected, t h e experiments c a r r i e d o u t on t h e welds of a l l o y s A723 and
showed t h a t i n t h i s case hydrogen i s evolved i n i n s i g n i f i c a n t amounts.
A chemical a n a l y s i s of t h e media i s shown i n t a b l e

4.

AT^

TABLE 2. RESULTS OF CORROSION TESTS I N VAFiIOUS OFGANIC ACIDS

(FOR A CORROSION RESISTANCE INDEX OF 1).
~ o r r o s i o n ,g/ m

Alloy

Medium

AT3

oxalic acid
o x a l i c acid
a c e t i c acid

AT^
AT^

hr

P e n e t r a b i l i t y of
corrosion, mm/yr

0.0115

0.0061
0.009l
0.0075

0.0172
0.0142

TABLE 3. RESULTS OF CORROSION TESTS OF WELDED PARALLE SPECIMENS OF

TITAEIUM ALLOYS AT3 AND AT^ (FOR A RESISTANCE INDEX OF 1).
PenetrabilPenetrabilCorrosion i t y of corCorrosion i t y of cor- SoluAlloy
Alloy
rosion,
tion
g/mm2, h r
g/mm2, h r
rosion,
mm/yr
mm/yr
AT3
AT3
AT3

0.0001
0.0004
0.0001

0.0002

TABLE

4.

0
0
0
0
0

00019
00076
00019
00015
00019
00038

Vl
Vl
Vl
K1
K1
~1

AT^
AT^
AT^
AT^
AT^
AT^

0.0003
0.0004
0.0009
0.0003
0.0002
0.0002

0
0
0
0
0

Solution

00057
00076
00017
00057
00038
00038

V1
V1
V1
Kl

K1
~1

RESULTS OF CRES1ICAL ANALYSIS OF TRE REACTION MEDIA.

Content of element, mg/l
Medium

Alloy
Fe

AT^

45.0

Al

not
observed
AT3 and AT^
12.40
93.80
-Chromium-manganese 893.4
AT3 and

Ti
not
observed

---

Cr

Mn

--

---

-242.5

248.0

s o l u t i o n of V 1
s o l u t i o n of Kl
s o l u t i o n of K1

The d a t a of t a b l e 4 i n d i c a t e t h a t titanium ions do not pass i n t o s o l u t i o n ,

and t h a t t h e s o l u t i o n i s enriched only w i t h aluminum and i r o n i o n s . A s should
have been expected, i n t h e technological s o l u t i o n KL i n which t h e samples underwent an i n t e n s i v e corrosion, t h e q u a n t i t y of i r o n and aluminum i o n s which had
passed i n t o s o l u t i o n was g r e a t e r than i n t h e t e c h n o l c g i c a l s o l u t i o n V l .
In
KL,
t
h
e
corrosion
of
t
h
e
chromium-manganese
a
l
l
o
y
i
s
s
e
v
e
r
a
l
times
solution
g r e a t e r t h a n t h a t of a l l o y s AT3 and AT8.

Figure 1. Corrosion r e s i s t a n c e of welded specimens

of a l l o y s AT3 and AT^: 1, AT3 i n s o l u t i o n K1; 2,
AT3 i n s o l u t i o n V1; 3, AT^ i n s o l u t i o n V1; 4, AT^ i n
s o l u t i o n K1.
V, v o l t s

Min

Hr

Log

Figure 2. Change i n t h e e l e c t r o d e p o t e n t i a l of a l l o y
AT^ i n s o l u t i o n K1: 1, without s t i r r i n g of t h e s o l u t i o n ; 2, w i t h s t i r r i n g of t h e s o l u t i o n .
The r e s u l t s of t e s t s i n n a t u r a l c h e r r y plum j u i c e a r e shown i n t a b l e

5.

The t e s t e d a l l o y s were found t o be h i g h l y s t a b l e i n c h e r r y plum j u i c e .

P a r t i c u l a r mention should be made of samples of a l l o y AT^ alloyed w i t h a l a r g e
q u a n t i t y of aluminum. A study of t h e corrosion r e s i s t a n c e of specimens of
welds of a l l o y s AT3 and AT^ was c a r r i e d o u t a t t h e b o i l i n g p o i n t i n t h e techn o l o g i c a l s o l u t i o n I(1 i n o r d e r t o determine t h e p o s s i b i l i t y of t h e i r u s e i n
t h e canning i n d u s t r y . The corrosion of t h e samples was s t u d i e d while t h e a l l o y s
were immersed i n t h e s o l u t i o n a s w e l l a s i n t h e vapor.
The r e s u l t s of t h e t e s t s ( t a b l e 6) showed t h a t t h e t e s t e d a l l o y s were not
s t a b l e under t h e s e c o n d i t i o n s (high weight l o s s ) . A metallographic a n a l y s i s o f
t h e samples was performed before and a f t e r t h e i r t e s t i n g .
A s can be seen from t h e photomicrographs of t h e polished s e c t i o n s before
t h e t e s t i n g ( f i g . 4), t h e weld-metal zone i s c h a r a c t e r i z e d by a coarse-grained
s t r u c t u r e , t h e zone b e f o r e t h e weld has a l e s s coarse-grained s t r u c t u r e , and
t h e end of t h e zone has a fine-grained s t r u c t u r e .

Figure 3. Polarization curves

for alloys AT3 in solution K1.

Figure 4. Microstructure of welded joint of alloy AT3, x 150: a, seam;

b, beginning of heat-affected zone; c, end of heat-affected zone.

TABLE 5. RESULTS OF CORROSION TESTS OF PARAUEL SPECIMENS OF TITANIUM

ALLOYS I N N A T W CHERRY PLUM JUICE.
Specimen Corrosion,
g/m2 h r
number

of corrosion,
mm/yr

Specimen Corrosion,
number
g/m2 h r
Alloy

Alloy AT3

1
2

0.0013
0.0013
0.0029
0. o u 7

0.0007
0.0007
0.0015
0.009

1
2
3

3
4

AT3
AT3

0.00003
0.00007

o.oooo4

o.oooo7

0.00013

0.00024

AT^
AT^

OF TITANlUM ALLOYS

Corrosion, P e n e t r a b i l i t y , Corrosion
corrosion, mm/yr r e s i s t a n c e
g/m2 h r
0. :?li

0.53-1
o ,817
0.041

I
I

AT^

0.00002
0.00004

TABU 6. RESULTS 0
AT THE BOILING POINT
Alloy

Penetrability
of c o r r o s i o n ,
mm/yr

0.566
0.562
0.898
0.045

Remarks
specimens
specimens
specimens
specimens

unstable
unstable
unstable
stable
I

immersed
i n vapor
immersed
i n vapor

in
of
in
of

solution
solution
solution
solution

On t h e photomicrograph of a l l o y AT3, taken a f t e r t e s t i n g f o r 250 h r s a t

t h e b o i l i n g p o i n t w i t h complete immersion of t h e samples ( f i g . 5 ) , an i n t e r c r y s t a l l i n e c h a r a c t e r of t h e corrosive a t t a c k i s observed i n t h e weld-metal
zone. Areas of i n t e n s e corrosion a r e l o c a t e d along t h e g r a i n boundaries ( f i g .
5 a ) . A t t h e o r i g i n of t h e heat-affected zone, t h e s t r u c t u r e of t h e a l l o y was
more fine-grained, had t h e appearance of an "erosion g r i d , " and an i n t e r c r y s t a l l i n e f a i l u r e of t h e a l l o y was observed ( f i g . 5 b ) . A t t h e end of the !?eata f f e c t e d zone (zone immediately ad joining t h e base m e t a l ) , l e s s i n t e r c r y s t a l l i n e
a t t a c k was observed ( f i g . 5 c ) . Results of t e s t i n g of t h e same samples i n t h e
vapor of t h e s o l u t i o n showed t h a t t h e i r corrosive a t t a c k t a k e s place t o a
l e s s e r extent than i n t h e solution.
Under t h e conditions i n v e s t i g a t e d , a l l o y AT^ was found t o be l e s s r e s i s t a n t
t o corrosion than a l l o y AT3. This i s a l s o supported by an a n a l y s i s of photomicrographs of t h e polished s e c t i o n s ( f i g . 6). Samples of a l l o y AT^ ( f i g . 6a)
show both i n t e r c r y s t a l l i n e and considerable p i t t i n g corrosion of t h e a l l o y .
This i s a l s o c h a r a c t e r i s t i c of a l l t h r e e weld zones considered. Tests of a l l o y
AT^ i n t h e vapor showed l e s s corrosive a t t a c k t h a n i n t h e case of immersion,
but t h e damage t o a l l o y AT^ was g r e a t e r t h a n t o a l l o y AT3.
After t h e corrosion t e s t s , a chemical a n a l y s i s of t h e r e a c t i o n medium was
performed ( t a b l e 7 ) .
216

Figure 5. M i c r o s t r u c t u r e of welded j o i n t of a l l o y AT3

w i t h complete immersion of specimens, x 150: a, seam;
b y beginning of t h e h e a t - a f f e c t e d zone; c, end of t h e
h e a t - a f f e c t e d zone.

The a n a l y s i s showed t h a t t h e g r e a t e s t q u a n t i t y of t i t a n i u m i o n s had passed

i n t o t h e medium from a l l o y AT^.
During t h e corrosion t e s t i n g of t i t a n i u m a l l o y s i n s o l u t i o n K1, we observed
t h a t during t h e i n i t i a l p e r i o d ( t h e f i r s t 2 h r s ) t h e s o l u t i o n turned yellow,
darkened g r a d u a l l y , then turned dark-brown i n 4 h r s . To e l u c i d a t e t h e cause of
t h e change i n t h e c o l o r of t h e r e a c t i o n medium, we conducted t h r e e p a r a l l e l experiments. I n t h e f i r s t , s o l u t i o n K1 was boiled without immersing t h e samples.

Figure 6. Microstructure of welded joint of alloy AT^

with complete immersion of specimens, x 150: a, seam;
b, beginning of heat-affected zone; c, end of heataffected zone.
The experiment showed that the color of the solution remained practically unchanged. In the second experiment, pure metallic titanium was immersed into
K1, while in the third, pure metallic aluminum was -immersed.
Experiments with metallic aluminum also showed that the color of the solution did not change. Tests with metallic titanium showed a change in the color
of the solution similar to the one described above. Consequently, the change
in the color of the reaction mixture was caused by titanium ions which had
passed into solution K1 as a result of the corrosion of the alloys. Measurements

TABU 7. RESULTS OF C H E M I C a ANALYSIS OF SOLUTION K 1 AFTER

CORROSION TESTS (250 HRS OF BOILING).
-

--

Quantity of ions, g/l

Material
Ti

.......
AT^. . . . . . . . .
titanium . . . . . .
aluminum . . . . . .

AT3..

...

steel 1 ~ 2 1 8 ~ 9
chromium-mang ane s e
m 2 ~ 1 5 . .

....

Al

1.94 0.35
2.48
0.79
none

---

0.23
0.21
5.04

--

--

Cr

Mn

Fe

Ni

--

-----

----

--

------

1.30

0.203

20.80

1.50

5.36

--

--

---

--

of t h e pH of t h e s o l u t i o n before and a f t e r t h e t e s t s showed t h a t whereas p r i o r

t o t h e t e s t t h e pH of t h e s o l u t i o n was 0.9, a f t e r t h e corrosion of a l l o y AT3
t h e pH became 1.1, and a f t e r t h e corrosion of a l l o y AT^, rose t o 2. It i s
obvious t h a t t h e more t i t a n i u m i o n s pass i n t o t h e s o l u t i o n , t h e h i g h e r i s t h e
pH. This i s i n good agreement w i t h t h e r e s u l t s obtained.
Also t e s t e d were multicomponent high a l l o y s of type AT2 i n 1 0 p e r c e n t
formic a c i d both with and without s t i r r i n g of t h e s o l u t i o n .
Results of t h e corrosion t e s t s showed an a b s o l u t e s t a b i l i t y of t h e s e a l l o y s
under t h e t e s t i n g conditions. It should be noted only t h a t t h e corrosion r e s i s t ance of t h e s e a l l o y s i s most f a v o r a b l y a f f e c t e d by complex a l l o y i n g w i t h molybdenum and vanadium, t h e n w i t h zirconium and vanadium, and t h a t a l e s s favorable
e f f e c t i s t h a t of complex a l l o y i n g w i t h zirconium and molybdenum.
Let u s examine t h e r e s u l t s of electrochemical i n v e s t i g a t i o n s ( f i g s . 7 and
8 ) . The curve r e p r e s e n t i n g t h e v a r i a t i o n i n t h e e l e c t r o d e p o t e n t i a l w i t h time
i s located i n t h e p o s i t i v e region of p o t e n t i a l s and remains n e a r l y unchanged
w i t h time (fig.
7). The p o l a r i z a t i o n curves i n d i c a t e a marked i n h i b i t i o n of t h e
anodic and cathodic r e a c t i o n s ( f i g . 8 ) . The nature of t h e v a r i a t i o n i n p o t e n t i a l
and of t h e p o l a r i z a t i o n curves i s i n good agreement w i t h t h e r e s u l t s of t h e
corrosion t e s t s of t h e s e a l l o y s .

Summary
1. The absolute corrosion r e s i s t a n c e was e s t a b l i s h e d f o r weld j o i n t s of
t i t a n i u m a l l o y s AT3 and AT^ a t room temperature i n o l e i c , o x a l i c , t a r t a r i c ,
a c e t i c , and l a c t i c a c i d , n a t u r a l c h e r r y plum j u i c e , and i n t h e t e c h n o l o g i c a l
s o l u t i o n s K 1 and V1.
2. Chemical a n a l y s i s of t h e r e a c t i o n medium e s t a b l i s h e d t h a t during t h e
corrosion of t i t a n i u m a l l o y s a t room temperature, no t r a n s f e r of t i t a n i u m i o n s
i n t o t h i s medium t a k e s p l a c e .

P
45
D

minutes
-Vd,A--(

47'F

hours

45

'

70

- --

3;

-.,

5 IU z55fl75?uulog,

45

42

z,o

431

+ YB

+Y8

Figure 7. Change i n t h e e l e c t r o d e
p o t e n t i a l of a l l o y ATa.

3.

40

Figure 8. P o l a r i z a t i o n
curves of a l l o y AT2n.

Electrochemical i n v e s t i g a t i o n s confirmed t h e r e s u l t s of t h e c o r r o s i o n

tests:
(a) The values of t h e e l e c t r o d e p o t e n t i a l s s h i f t toward t h e p o s i t i v e
region w i t h time;

( b ) The n a t u r e of t h e p o l a r i z a t i o n curves i n d i c a t e s a considerable

i n h i b i t i o n of t h e anodic r e a c t i o n s (anodic p a s s i v i t y ) .

4. R e s u l t s of t e s t s w i t h s t i r r i n g of t h e s o l u t i o n s showed t h a t
t e c t i v e f i l m on t i t a n i u m a l l o y s becomes denser w i t h time.
5. A t t h e b o i l i n g p o i n t , a considerable corrosion of t h e t i t a n i u m a l l o y s
was observed i n s o l u t i o n K1.

6. A metallographic i n v e s t i g a t i o n e s t a b l i s h e d t h e presence of i n t e r c r y s t a l l i n e and p i t t i n g corrosion of t h e weld j o i n t s of titanium.

7. Titanium a l l o y s AT2n were found t o be a b s o l u t e l y s t a b l e i n a s o l u t i o n
of 1 0 p e r c e n t formic acid i n t e s t s w i t h and without s t i r r i n g of t h e s o l u t i o n s .
REFErnNCES
1. Tavadze, I?. N. and Lashkhi, T. A. Coll. Titanium and Its Alloys
Izd-vo AN SSSR, No. 10, p. 154, 1963.
yego splavy)

i it an

i it an

2.

Yeremenko, N. V. C o l l . Titanium and I t s Alloys

vo AN SSSR, Kiev, 1955.

3.

Tomashev, N. D. Theory of Corrosion and Metal P r o t e c t i o n ( ~ e o r i y ak o r r o z i i

i zashchita metallov). Izd-vo AN SSSR, 1959.

i yego splavy)

Izd-

4. Corrosion and Chemical Stability of Materials (~orrozi~a

i khimicheskaya
stoykostfmaterialov).

A handbook, Mashgiz, 1954.

Tables of the Corrosion Resistance of Titanium and Its Alloys in Various

Corrosive Media (~ablitsykorrozionnoy stoykosti titana i yego splavov v
razlichnykh agressivnykh sredakh) Moscow, Informatsionno-izdatel* skiy
otdel, 1961.

PART 111. M E C W C A L AND TECRNOLWICAL PROPERTIES

OF TITANIUM ALLOYS

BASIC PRlBG3QTJISITES FOR DEVELOPING HIGH-STRFNGTR TITANIUM

ALLOYS WITH AN a + @-STRUCTURE BY MEANS OF ALLOYING
AID HEAT TRFATING

V. N. M o i s e y e v

pp. 177-183 o f o r i g i n a l d o c u m e n t appears i n

J.P.R.S. T r a n s l a t i o n No. 28,176; TT:~?-30080
pp. 1-10

STRENGTH OF INTERATOMIC BONDING OF SINGLE-PHASE

ALLOYS IN TKE SYSTEM Ti - Nb - Cr
K. I. Shakhova and P. B. Budberg
The strength of the interatomic bonding of the crystal lattice of metals
and alloys may be characterized by various quantities: heat of sublimation,
heat of melting, heat of solution, elastic constant, root mean square displacement of atoms at the lattice points and other parameters (ref. 1).

A relationship was established between the modulus of normal elasticity

E and shear modulus G of pure metals and metallic compounds, on the one hand,
and the characteristic temperature eK on the other (ref. 2). It was shown
that the dependence between the elastic properties and the characteristic
temperature also extends to single-phase alloys with Poisson's ratio p =
0.25-0.45 (ref. 3).
In the present work, an estimate of the interatomic bond in single-phase
alloys of the ternary system Ti - T(ro - Cr was made.
The elastic constants of $ and y alloys were determined by an electronic
method with the "Elastomat" unit1 which made it possible to obtain the
elastic characteristics within 1-1.5%. The specimens used were cylindrical
rods 80-100mm long and 6-8mm in diameter melted in an arc furnace and cast
in a vacuum.
The phase diagram of the system Ti - Nb - Cr at temperatures of 1000-600
was studied by the authors of the present article (ref. 4), who established
that the compounds TiCr2 and NbCr in the temperature interval studied form
2
a continuous series of solid solutions with a crystal lattice of MgCu2 type,
i.e., the y phase. The isothermal section of the system at 1000' is shown
in figure 1.
The study of the elastic constants of the alloys was made after quenching from 1000~the sections wi2;h ratio Ti : Nb = 4:l; 3 :2; 2 :3; 1 :4.The
results obtained are shown in table 1. It follows from this table that in
passing from the single-phase region of @ alloys to the two-phase $ + y
region, the constants E and G increase considerably.

he determination of the elastic constants was carried out in cooperation with

S. G. Fedotov.

Ti, wt percent
Figure 1. Isothermal section of the diagram of the
system Ti - Nb - Cr at 1000~.
In alloys of all the sections with a content of 50 percent Cr in which the
y phase becomes predominant (fig. l), the modulus of normal elasticity attains

values of (16-21) x 103 kg/mm2. It follows that the modulus of normal elasticity
of solid solutions of metallic compounds is considerably higher than that of
solid solutions of the pure components of the f3 phase. The values obtained
for the elastic constants of the alloys made it possible to calculate the
characteristic temperatures 8 and the root-mean-square displacements of the
atoms from the equilibrium position in the crystal lattice for solid solutions of metals and metallic compounds at K'O

I/$

and 29jK

1/g3.

The characteristic temperature was calculated from the following relations :

where E is the modulus of normal elasticity, kg/cm2 x lo6; A is the average

atomic weight; d is the density, g/cm3;

where

h = 6,62377.10-271 erg sec is Planck's constant; k

16
1.380257 x 10

erg/deg is Boltzmann's constant; NA is Avogadro's number; c is the average

propagation rate of vibrations, given by the expression

with

The root-mean-square displacements of the atoms were determined from the

Debye-Weller relation, which has the following form:

where ma

1.6724.1~-24is the mass of the hydrogen atom.

IG'

20

If

Cr, wt percent

K . d

2G' 3

40

50

60

7L7

2G'

80

Nb, wt percent

45

C4

I5

70

Cr, wt percent

Zll

30

440

5U

6U

7G'

I%,
Figure 2. Dependence of

~
80

wt percent

i/q and flg3

on the compositi(

of the $ solid solutions of the system Ti

Nb

- Cr.

TABLE 1. CHANGE IN THE ELASTIC CONSTANTS OF ALLOYS

OF THE SYSTEM Ti - Nb - Cr ALONG SECTIONSElastic constants

Composition

The values of the function

reference I.

(-)0

were taken from the table given in

0
'1'

The values of 8 as a function of the alloy composition, calculated from

formulas (1) and (2), were in practically complete agreement. T1-eyare shown
in table 2. The same table gives values of

vg

and

l/&

for single-phase

alloys of the system, determined by means of formula (3).

The data of table 2 were used to plot the curves of the dependence of

1/> and 1/g3

on the composition of the alloys (fig. 2). As the chromium content
226

TABU 2. VALUES OF 8 1/?,

vz,

FOR $ SOLID SOLUTIONS OF THE

SOLUTIONS OF THE SYSTEM Ti - Nb

ING TWEXATlTRE AT 1000~.

Composition
Section NO.~r,wt$

IT1 (Ti:Nb= 2:3)

1V (Ti:Nb =1:4)

- Cr ALONG SECTIONS AT QUENCH-

0.0.

V ~ , AV x 3 , ~

5
10

277
290

0.0728
0.077162

278

0.06870

in the $ solid solution increased, both

1I

l/z, and l/%,

0.1508
0.1441
0.1411

decreased, indicating

the influence of chromium on the increase in the interatomic bonding forces

in the solid solution. As the limit of saturation of the solid solution was
approached, values of

~ f 2and l/g-reach their minimum

(fig. 2, top).

Niobium has a much weaker effect on the interatomic forces than chromium.
The role of chromium in increasing the strength of the interatomic bond with
rising temperature is particularly apparent, since the qua!.tity
creases more rapidly than

Jg

l / de-

as a function of composition (fig. 2, bottom).

It was of interest to evaluate the strength of the bonding in solid solutions of the metallic compounds TiCr and NbCr2, i.e., the y phase.
2

This could be done only by extrapolating the values of the elastic constants to the composition of alloys corresponding to single-phase @ solid
solutiyns. The extrapolation was necessary because of the high brittleness of
the solid solutions of the compounds and the impossibility of preparing samples
from them.

The calculated values of 9,

v-2 and viz for single-phase alloys of the

section TiCr -NbCr2 as a function of composition are shown in table 3.

2
T A B U 3.

VALUES OF

1/%, I/s3'OF ALLOYS

OF THE SECTION

TiCr2-NbCrp AT QUENCHING TE24PERA.TURE OF 1000~.

From the table it follows that an increase in the content of niobium in

the y solid solution leads to a rise in the characteristic temperature and a
decrease in the values of

vz

and

a3,
,

i.e., to an increase in the bonding

forces in the lattice of the y phase as its content of niobium increases.

In the alloys of the section TiCr2-NbCr2, no estimate can be made of the
influence of chromium on the change in the interatomic bonding forces, since
the chromium content is practically constant in all of the alloys studied.
From the regularities in the change of 9,

I/z,-I/z3
in the

solid solutions

of metals and compounds of the $ and y phases of the system Ti - Nb - Cr

(table 2 and 3)) it follows that the strength of the bonding in the solid solution of metals is less than in the metallic compounds. The weakening of the
bonding forces in the solid solutions of metals with rising temperature is
also more significant than in the solid solution of metallic compounds; this
follows from a comparison of the ratios

J&

e,

which are equal to

2.02-2.04 for the $ phase and 1.88-1.93for the y phase.

The conclusions drawn with regard to the influence of chromium and niobium on the strength of the bond in @ and y solid solutions is confirmed when
the hot hardness of the alloys is investigated.

Figure 3. Change in the hardness of alloys of

the system Ti-Nb-Cr with temperature: a, section I; b, section IV.
The determination of the hot hardness is one of the methods of estimating
the strength of alloys at high temperatures. Alloys of section I containing 5,
10 and 20 percent Cr practically preserve their hardness up to 400, above
which a monotonic decrease in hardness begins up to 1000~. The alloys with
55 percent Cr, whose structure consists of a y solid solution with a certain
amount of the B phase, retains a high strength (250 kg/mm2) up to 1000~. It
should be noted that a softening of this alloy begins at a temperature above
700. Up to this temperature, the decrease in the hardness of the alloy is
approximately 16 percent (fig 3a)

Alloys of section I1 with 5, 10 and 15 percent Cr begin to soften considerably at temperaturesabove 5

0
0
'
)
while alloys with 50 and 60 percent Cr do
0
0
'
.
so above 8
From the standpoint of the nature of the change in hardness with temperature, the alloys of section I11 are analogous to the alloys of section 11.
Only the alloy of section I11 with 60 percent Cr deserves some comment. Structurally, this alloy is a y phase containing a very small amount of the $ phase,
and it retains a high value of the hardness (650-510 kg/mm2) over the entire
temperature range studied.
Among the alloys of section IV, the alloy with 5 percent Cr retains its
initial hardness up to 400-500~,
above which softening takes place (fig. 3b).
The alloy with 50 percent Cr is characterized by minimum softening: its
hardness changes from 800 to 600 kg/mm2 during heating to 1000.
Analyzing the data on the change in the hot hardness of the alloys, one
can see that the single-phase @ solid solutions soften to a greater extent than

the y phase on heating. Chromium (in $ alloys) and niobium (in y alloys) have
a favorable effect on the increase in hot hardness.
The results obtained confirm the conclusion reached earlier from the analysis of the root-mean-square displacements of the atoms at 0 and 293OK concerning the greater interatomic bonding strength of solid solutions of metallic
compounds and their lesser softening tendency with rising temperature.
Summary
1. Elastic constants of the alloys after quenching from 1000~were determined.
2. Values of the characteristic temperature and root-mean-square displacements of atoms at 0 and 293' K for single-phase $ and y solid solutions were
calculated.

3 . The predominant role of chromium in hardening the $ solid solutions

and of niobium in hardening the y phase was demonstrated.

4. The established regularities were confirmed by studying the hot hardness of the alloys.
REFERENCES
1. Frantsevich, I. N. Problems of Powder Metallurgy and Strength of Materials
(~oprosyporoshkovoy metallurgii i prochnosti materialov). Izd-vo A3 SSSR
NO. 3, p. 14, 1956.

Z. Metallkunde, Vol. 39, p. 135, 1948.

2. Koster, W.

. .

3. Livshits, B G
metallov).

Physical Properties of Metals (~izicheski~e

svoystva
Metallurgizdat, 1960.

4. Shakhova, K. I. and Budberg, P. B. A3 SSSR, Izvestiya, Otdel Tekhnicheskikh

Nauk, Metallurgiya i Toplivo, No. 6, p. 137, 1962.

STUDY OF THE3 CREEP OF ALLOYS I N THE

SYSTEM T i -V-Nb-Mo

I. I. Kornilov, 0 . K. Belousov and V. S. Mikheyev

Vanadium, niobium and molybdenum a r e important a l l o y i n g elements of titanium

a l l o y s . The i n t r o d u c t i o n of t h e s e elements i n t o t i t a n i u m i n amounts n o t exceedi n g t h e s o l u b i l i t y l i m i t of a - T i causes an i n c r e a s e i n u l t i m a t e s t r e n g t h and
preserves t h e high i n d i c e s of elongation, reduction of area, and impact s t r e n g t h
( r e f s . 1-4). I n a d d i t i o n , one can expect a s u b s t a n t i a l increase i n t h e hightemperature s t r e n g t h i n t h e region of single-phase P s o l i d s o l u t i o n s of t i t a n i u m
with t h e s e elements ( r e f s . 5-9).
One of t h e l i n e s of i n v e s t i g a t i o n i n t h e study of problems of high-temperat u r e s t r e n g t h i s t h e a n a l y s i s of t h e dependence of creep and s t r e s s - r u p t u r e
s t r e n g t h on t h e c h a r a c t e r of t h e chemical i n t e r a c t i o n between metals and o t h e r
elements of t h e p e r i o d i c system, on t h e equilibrium f a c t o r s i n t h e systems, t h e
phase and s t r u c t u r a l s t a t e , and crystal-chemical r e a c t i o n s .
The quaternary system Ti-V-Nb-Mo was s t u d i e d i n r e f . 10. It i s c h a r a c t e r i z e d by t h e presence of a volume of a l i m i t e d a 4 s o l i d s o l u t i o n , a wide r e g i o n
of
+ $4 phases, and a wide region of B4 solid s o l u t i o n s ( f i g . 1).

Tc

MO

NB

Figure 1. Phase diagram of a l l o y s of

t h e system Ti,-V-Nb-Mo a t 600'.

A study of t h e high-temperature s t r e n g t h of t h i s system was c a r r i e d out by

t h e c e n t r i f u g a l method ( r e f . 11). The t e s t i n g f o r high-temperature s t r e n g t h
was done i n t h r e e s t a g e s . I n t h e f i r s t s t a g e , t h e specimens were t e s t e d a t 500

and an i n i t i a l s t r e s s of

15 kg/mm2 f o r 100 hrs; i n t h e second stage, t h e t r a n s -

2
verse s t r e s s was increased t o 20 kg/mm and t h e t e s t i n g was continued f o r
another 100 h r s . I n t h e t h i r d s t a g e of t h e t e s t i n g , t h e temperature was r a i s e d
t o 600 a t a constant s t r e s s of 20 kg/mm2, and t h e t e s t i n g was continued f o r
another 100 h r s . Thus, t h e t o t a l t e s t i n g time was 300 h r s a t a s t r e s s of 13-20
This complex mode of t e s t i n g was
kg/mm2 and temperatures of 500 and 600'.
adopted, i n t h e f i r s t place, f o r t h e purpose of a comparison with t h e r e s u l t s
of references 5, 6 and 9 p e r t a i n i n g t o t h e high-temperature s t r e n g t h of binary
and t e r n a r y systems of t i t a n i u m with vanadium, niobium, and molybdenum, and i n
t h e second p l a c e , because of t h e g r e a t d i f f e r e n c e between t h e high-temperature
s t r e n g t h of titanium a l l o y s based on l i m i t e d a4 s o l i d s o l u t i o n s and t h e s t r e n g t h
of

p4 s o l i d s o l u t i o n s w i t h a high content of a l l o y i n g elements.

The a l l o y specimens were prepared along f o u r r a d i a l s e c t i o n s ( f i g . 1) with

the following r a t i o s of alloying elements i n each of them: V:Nb:Mo = 1:1:1
( s e c t i o n I ) ; Mo:C (v, Nb) = 2 : l ( s e c t i o n 11); Nb:C (v, MO)= 2 : l ( s e c t i o n 111;
V:C (Nb, MO) = 2 : l ( s e c t i o n IV), up t o a t o t a l content of alloying elements of
50 w t percent.
The following m a t e r i a l s were used t o prepare t h e a l l o y s : titanium sponge
TGOO of 99.8 percent p u r i t y , carbothermic vanadium of 99.82 percent p u r i t y ,
niobium of 99.4 percent p u r i t y , and molybdenum of 99.9 percent p u r i t y . The
a l l o y s were melted i n an a r c furnace i n an argon atmosphere and c a s t i n copper
ingot molds 8 mm i n diameter, then forged t o a diameter of 6 mm from 900. The
a l l o y s were vacuum-annealed f o r 20 h r s a t 750') 50 h r s a t 7000, and 150 h r s a t
600'; furnace cooling t o 200' l a s t e d 24 h r s .
An a n a l y s i s of t h e dependence of t h e bending d e f l e c t i o n 6 on the d u r a t i o n
of t h e deformation under t h e same t e s t i n g conditions of t h e a l l o y s ( f i g . 2)
makes it p o s s i b l e t o s t a t e t h a t t h e a l l o y s of t h e s e s e c t i o n s behave d i f f e r e n t l y .
The highest creep r a t e w i l l be t h a t of pure titanium, which under t h e s e l e c t e d
conditions reaches a bending d e f l e c t i o n of 5 mm i n t h e f i r s t few minutes of t h e
t e s t ( f i g . 2a).

I n t h e f i r s t few hours of t h e t e s t , a rapid increase i s observed i n t h e

creep r a t e of a l l o y s containing small amounts of t h e alloying elements, corresponding i n composition t o d i l u t e a&s o l i d s o l u t i o n s of titanium. A higher
r e s i s t a n c e t o p l a s t i c deformation i s displayed by a l l o y s located near t h e
l i m i t of s a t u r a t e d a s o l i d s o l u t i o n s a t t h i s temperature, but i n both cases a

12

$
'a'

1.50

2017

2.50

300
T, h r

50

c
Figure 2.

Z5I7

%
6
3'
T,

hr

Curves of t h e creep of titanium and titanium a l l o y s

of t h e system Ti-V-Nb-Mo.

o = 15 kg/mm2; I

Testing s t a g e s :

I, t = 500,

t = 500, o = 20 kg/mm2; 111, t = 600,

l 2.

a, s e c t i o n I, content C(V, Nb, M O ) : 1, 2.4 pero = 20 kg mm

cent; 2,
.2 percent; 3, 20.1 percent; 4, 33.0 percent; 5, 50.1
percent; b, s e c t i o n 11, content C(V, Nb, MO): 1, 1 . 5 percent;
2, 2.4 percent; 3, 8.1 percent; 4, 20.1 percent; 5, 30 percent;
c, s e c t i o n 111, content C(V, Nb, MO): 1, 3 percent; 2, 4.2 p e r cent; 3, 1 5 percent; 4, 26 percent; 5, 40.2 percent; 6, 50.1
percent; d, s e c t i o n I V , content C(V, Nb, Mo) : 1, 2 . 1 percent;
2, 8.1 percent; 3, 40.2 percent; 4, 50.1 percent.
pronounced softening of t h e a l l o y s t a k e s place during t h e second s t a g e of t h e
2
The highest r e s i s t a n c e t o p l a s t i c deformat e s t i n g (o = 20 kg/mm and t = 500').
t i o n was exhibited by a l l o y s from t h e region of fI4 s o l i d s o l u t i o n s . The creep
r a t e of t h e s e a l l o y s a t 500'

and o = 15-20 kg/mm2 i n 200 h r of t e s t i n g i n t h e

second p o r t i o n of t n e creep curve i s c l o s e t o zero, but a t 600'

t h e s e a l l o y s increases abruptly.

t h e creep of

On t h e b a s i s of d a t a obtained by studying t h e creep of a l l o y s of t h e

high-temperature s t r e n g t h " diagrams were
quaternary system, "composition
p l o t t e d i n d i c a t i n g t h e dependence of t h e time necessary f o r reaching a given
bending d e f l e c t i o n of 3, 5 and 10 mm ( f i g . 3 ) on t h e composition under c e r t a i n
given conditions. The graph a l s o shows polythermal s e c t i o n s i n t h e region of

polymorphic transformations. The shaded p o r t i o n of t h e diagrams i n d i c a t e s t h e

regions i n which e i t h e r t h e s o l u t i o n of t h e f3 phase (a " a + f3 boundary) o r i t s
f3 boundary) i s p o s s i b l e a t TOO0. Such an e x t r a p o l a t i o n of
p r e c i p i t a t i o n (a + f3
t h e curves of t h e polymorphic transformation i n t o t h e region where t h e d i f f u s i o n
processes occur very slowly i s p o s s i b l e , a s was shown i n t h e study of t h e phase
diagrams of t h e binary systems of t i t a n i u m with molybdenum and niobium ( r e f . 1 2 ) .
I n t h e l i m i t e d region of t h e CX4 s o l i d s o l u t i o n , t h e high-temperature s t r e n g t h
i n c r e a s e s with r i s i n g t o t a l content of t h e a l l o y i n g elements. The e l e v a t e d hightemperature s t r e n g t h under t h e s e l e c t e d t e s t i n g conditions corresponds approximately t o t h e s o l u b i l i t y l i m i t of t h e a s o l i d s o l u t i o n . The most pronounced

increase i n high-temperature s t r e n g t h i n t h e a
s e c t i o n I1 (with a higher molybdenum c o n t e n t ) .
more d i f f e r e n t from t i t a n i u m than a r e vanadium
g r e a t e r e x t e n t . The high-temperature s t r e n g t h
This i s most pronounc
while t h e g r e a t e s t s t
s e c t i o n 11. As i s ev
i n t h e a region a r e r
stage, and only i n t h e

region i s observed i n a l l o y s of
This element, which i s chemically
and niobium, hardens a-Ti t o a
decreases i n t h e two-phase region.
of 3, 5 and 10 mm
ng t h e f i r s t t e s t i n g
ssary t o raise the

s t r e s s t o 20 kg/mm 2 a
a l l o y s of s e c t i o n I a
s t r e n g t h i n t h e cx r e g
(with a higher molybd
content of vanadium a
which, a s was shown i
temperature s t r e n g t h

t i o n of 1 0 mm.

The

Deformation of t h
r a d i a l s e c t i o n I begin

strength.

Alloys of t h i s region, based on $ s o l i d s o l u t i o n s , d i s p l a y a high

I n a l l o y s corresponding t o compositions l o c a t e d i n t h e shaded a r e a on

= 20 kg/mm

t h e diagrams, a t 600, t h e second phase

( a phase)

which p r e c i p i t a t e d during t h e

slow furnace-cooling of t h e a l l o y s a f t e r annealing a t 600'

and t e s t i n g a t 500,

and which was not able t o d i s s o l v e completely during t h e t e s t s a t 600, i s s t i l l

p r e s e n t . This a l l o y ( f i g . 4) s t i l l contains a s i g n i f i c a n t amount of t h e f i n e l y
dispersed a phase. Alloys of t h e single-phase @ region show a f u r t h e r increase
i n high temperature s t r e n g t h a s compared t o t h e two-phase a l l o y s ; t h i s i s p a r t i c u l a r l y apparent from t h e example of a l l o y s of s e c t i o n I V . Alloys of s e c t i o n I1
(with 36 percent of t o t a l a l l o y i n g elements) were r e l a t i v e l y b r i t t l e and d i d not
withstand t h e given bending s t r e s s .

A s shown i n t h e f i g u r e s , t h e "composition
high-temperature s t r e n g t h " d i a grams agree s a t i s f a c t o r i l y with t h e change i n t h e phase equilibrium along t h e

sections of the system. The formation of a solid solution causes an increase

in high-temperature strength. In the two-phase region, as the coagulation of
the f3 phase proceeds, the high-temperature strength declines. Mloys in which
the phase boundary is extensive are the most unstable. Even in alloys with a
high total content (20 and 30 percent) of alloying elements, the high-temperature strength is lower than in single-phase a and $ alloys. This may be
attributed to the strong influence of the decrease in the temperature of the
f3 on the high-temperature strength. As was
polymorphic transformation a + f3
shown in refs. 5-6 and 13-14, the polymorphism has an appreciable effect on
the increase in plasticity upon the conversion from the hexagonal to the cubic
structure with a higher lattice symmetry. The coagulation of the a phase
along the boundaries and grain of the f3 phase and the lower temperature of its
transformation into the f3 phase make the lattice of the a phase unstable and
weaken the interaction at the phase boundary. In the finely dispersed state,
the a phase hardens the alloy somewhat, but the alloys of the equilibrium f3
phase display the greatest high-temperature strength under the given testing
conditions.
-)

Figure

4.

Microstructure of alloy with 40.2 percent

C(V, ~ b ,MO)

section I after testing at

o = 20 kg/mm2 x

600' and

1350.

In absolute values of the time.necessary for reaching a given bending deflection (5 and 10 mm), our data are somewhat lower than those cited in refs. 5
and 6, obtained by studying binary and ternary systems of titanium with vanadium and niobium. Thits'may be explained by the fact that the specimens prepared in refs. 5 and 6 by the powder-metallurgical method contained a considerable amount of dissolved gases, particularly oxygen, which substantially
hardens titanium. Thus, for example, in order to reach a 10 mm bending deflection in pure titanium, it is reported in ref. 5 that about 20 hr were required
at 500 and o = 20 kg/mm2, whereas in our case titanium TGOO softened as early

as the first few minutes of testing under the same conditions. Furthermore, in
refs. 5 and 6, use was made of vanadium containing 1.2 percent Al and a significant amount of dissolved gases.
The data obtained for the dependence of the high-temperature strength on
the composition and phase structure make it possible to conclude that all the
alloys of the a region of the quaternary system Ti-V-Nb-Mo soften rapidly at
500' and o = 15 kg/mm2 and cannot be used as heat-resistant alloys for long
periods of operation under the selected conditions.

Molybdenum, introduced within the limits of its solubility in a-Ti, is the

most useful additive for increasing the high-temperature strength of such
alloys. Alloys from the region of $4 solid solutions can be used as heatresistant alloys.
The data obtained confirm the results of ref. 8 on the nature of the
change in high-temperature strength in systems with limited solubility in the
solid state and polymorphism in one of the components.

1. Craighead, C., Simmons, O., and Eastwood, L. J. Metals, No. 3, p.

1950

485,

2. Belousov, 0. K., Kornilov, I. I., and Mikheyev, V. S. Dokl. AN SSSR, Vol.

1-47,NO. 5, p-.1102, 1962.

3.

- - -

4.

Luzhnikov, L. P. and Moiseyev, V. N. Metallovedeniye i termicheskaya

obrabotka metallov, No. 7, p. 23, 1961.

In : "~itaniwnand Its Alloys, " Izd-vo AN SSSR, No.

7, pp. 120-126,

1962.

5. Vlasov, V. S. and Kornilov, I. I. Izv. AN SSSR, OTN, Metallurgiya i

toplivo, No. 4, p. 31, 1958.
6. - - - Izv. AN SSSR, OTN, Metallurgiya i toplivo, No. 7, p. 136, 1958.
7. Rostoker, U. Metallurgy of Vanadium (~ussiantranslation). Metallurgizdat, 1959.
8. Kornilov, I. I. Physicochemical Principles of the High-Temperature

Strength of Alloys (~iziko-khimicheskiyeosnovy zharoprochnosti s~lavov)

IZ~-VOAN SSSR, 1962.

9. Kornilov, I. I. and Polyakova, R. S. Izv.

toplivo, No. 1, p. 85, 1960.

AN SSSR, OmJ, Metallurgiya i

10. Belousov, 0. K., Kornilov, I. I., and Mikheyev, V. S. In: "~itaniumand

Its Alloys," Izd-vo AN SSSR, No. 10, pp. 27-36, 1963.

11. Kornilov, I. I. Izv. S F W , Vol. 18, p.

72, 1949.

12. Hansen, M., Kamen, E., Kessler, H., and McPherson, D.

p. 881, 1951.

J. Metals, NO. 3,

Osipov, K. A. Some Activated Processes in Solid Metals and Alloys

(Nekotoryye aktiviruyemyye protsessy v tverdykh metallakh i splavakh)
1zd-vo AN SSSR, pp. 110-118, 1962.

14. Grigorovich, V. K. and Safonov, Yu. S. Izv. AN SSSR, OTN, Metallurgi~ai

toplivo, No. 5, p. 38.

CHARACTERISTICS OF TEE COLD BRITTLENESS OF TITANIUM

B. B. Chechulin and M. B. Bodunova

Introduction
The appearance of t h e cold b r i t t l e n e s s of metals i s one of t h e most
dangerous phenomena i n p r a c t i c a l a p p l i c a t i o n s . Many s t u d i e s have been devoted
t o t h e n a t u r e of cold b r i t t l e n e s s and impact b r i t t l e n e s s of metals, p a r t i c u l a r l y
s t e e l s . Nevertheless, t h e p u r e l y p h y s i c a l f a c t o r s causing some metals t o be
cold s h o r t but not o t h e r s have n o t been e s t a b l i s h e d a s y e t ( r e f . 1 ) . It should
be noted t h a t t h e cold b r i t t l e n e s s of iron-base a l l o y s has been s t u d i e d f a i r l y
thoroughly. The i n f l u e n c e of various f a c t o r s on cold b r i t t l e n e s s has been determined, and s e v e r a l formal mechanisms have even been proposed t o e x p l a i n t h e cond i t i o n s of t h e appearance of b r i t t l e n e s s i n s t e e l . On t h e o t h e r hand, t h e cold
b r i t t l e n e s s of o t h e r metals has been s t u d i e d very i n s u f f i c i e n t l y . It i s our
view t h a t t h e nature of t h e cold b r i t t l e n e s s of metals can be determined only
from extensive experimental m a t e r i a l obtained f o r t h e most d i v e r s e metals.
S t u d i e s have shown t h a t t h e cold b r i t t l e n e s s i s character is ti.^ of metals
having a body-centered cubic ( i r o n , chromium, e t c .) o r hexagonal ( z i n c , titanium, e t c ) c r y s t a l l a t t i c e . However, t h e r e g u l a r i t i e s of cold b r i t t l e n e s s
a s such have been studied only i n i r o n a l l o y s , whereas f o r many o t h e r metals
only t h e f a c t of t h e appearance of b r i t t l e n e s s under c e r t a i n c o n d i t i o n s has
been mainly e s t a b l i s h e d .

The p r e s e n t work d i s c u s s e s c e r t a i n f e a t u r e s of t h e transformation of

t e c h n i c a l l y pure t i t a n i u m i n t o a cold s h o r t s t a t e and analyzes t h e dependence
of t h e appearance of b r i t t l e n e s s i n t i t a n i u m on various external. f a c t o r s : ext e n t of t h e s t r e s s condition, deformation r a t e , and s i z e of specimens.
M a t e r i a l Used and Experimental Technique
The i n v e s t i g a t i o n was c a r r i e d out on t e c h n i c a l l y pure t i t a n i u m obtained
by remelting magnesiothermic t i t a n i u m sponge i n vacuum a r c f u r n a c e s . Three
melts of t i t a n i u m were used which a f t e r t h e p r e p a r a t i o n of t h e i n g o t s were
forged i n t o b a r s of round (14 mm i n diameter) o r square (14 mm on one s i d e )
c r o s s s e c t i o n s w h i c h were machined w i t h a wheel u n t i l t h e i r t r a n s v e r s e dimens i o n was 1 0 mm. The machined specimen blanks were subjected t o prolonged
vacuum annealing a t 750' i n o r d e r t o achieve a well-annealed e q u i l i b r i u m s t r u c t u r e and t h e maximum p o s s i b l e e l i m i n a t i o n of v o l a t i l e gaseous i m p u r i t i e s

( c h i e f l y hydrogen) from t h e metal. The chemical composition and mechanical

c h a r a c t e r i s t i c s of t h e metal employed a r e shown i n t a b l e 1.
The cold b r i t t l e n e s s of t i t a n i u m i s c h i e f l y due t o t h e so-called hydrogen
b r i t t l e n e s s ( r e f . 2). For t h i s reason, t h e specimen blanks were enriched w i t h
hydrogen i n s e p a r a t e batches t o various degrees i n a s p e c i a l u n i t a t 700'.
The hydrogen content of t h e specimens was r a i s e d i n s t e p s from 0.002 t o
0.06 w t p e r c e n t .
The main experiments involving t h e determination of t h e temperature t h r e s h o l d of b r i t t l e n e s s of t i t a n i u m and t h e dependence of t h e temperature t h r e s h o l d
on t h e sharpness of t h e notch were conducted on c y l i n d r i c a l specimens. The
smooth specimens were 7 mm i n diameter and 55 mm long. The notched specimens
(having a round notch) had an o u t e r diameter of 10 mm and a diameter i n t h e
notch of 7 mm. The i n f l u e n c e of t h e deformation r a t e on t h e c r i t i c a l temperat u r e of b r i t t l e n e s s was s t u d i e d on p r i s m a t i c Menager specimens, and t h e s c a l e
e f f e c t was studied on p r i s m a t i c specimens g e o m e t r i c a l l y s i m i l a r t o Charpy
specimens. The t e s t i n g of t h e specimens w a s c a r r i e d out by bending impact on
Charpy impact machines and by s t a t i c bending i n s p e c i a l attachments a t a punch
displacement r a t e of 0 . 1 mm/sec. The impact s t r e n g t h was determined i n t e s t s
of c y l i n d r i c a l specimens, and i n t e s t i n g Menager and Charpy specimens, i n add i t i o n t o measuring t h e energy t o f r a c t u r e , t h e S t r i b e c k deformation c h a r a c t e r i s t i c , i . e . , t h e degree of d i s t o r t i o n of t h e working c r o s s s e c t i o n of t h e
specimen a t t h e s i t e of t h e f r a c t u r e was measured.
Tensile and r u p t u r e t e s t s were c a r r i e d o u t on c y l i n d r i c a l specimens w i t h
a thinning of t h e middle p o r t i o n i n o r d e r t o exclude breaks a t t h e t i p s of t h e
specimens ( a t a high hydrogen content). The t h i n n i n g was made by means of a
c i r c u l a r r e c e s s having a r a d i u s of curvature of 90 mm; t h e minimum diameter of
t h e specimens was 5 mm. T e s t s a t high temperatures were conducted i n w a t e r (up
t o 90') o r i n a s p e c i a l furnace i n a i r ( 1 0 0 - 3 5 0 ~ ) . LOW-temperature (-I-96O)
t e s t s were made w i t h precooling i n a mixture of benzine and l i q u i d n i t r o g e n o r
i n l i q u i d nitrogen. Checking t e s t s e s t a b l i s h e d t h a t t h e t e s t i n g temperature
was recorded w i t h i n +5O.
TABU 1. CHEMICAL COMPOSITION AXD MECmICAL CEVLRACTERISTICS
OF INVESTIGATED TITANIUM

+'a

Impurity content not more

than, w t percent

Mechanical c h a r a c t e r i s t i c s
a t room temperature

R e s u l t s and Discussion
Let us consider t h e dependence of t h e impact s t r e n g t h , determined on c y l i n d r i c a l specimens, on t h e t e s t i n g temperature f o r vacuum-annealed t i t a n i u m
The impact s t r e n g t h of t i t a n i u m worked i n a vacuum does not d e c l i n e
(fig l a )
This confirms t h e a l r e a d y e s t a b l i s h e d
w i t h decreasing temperature down t o -196O.
f a c t t h a t n a t u r a l cold b r i t t l e n e s s i s lacking i n titanium. An i n c r e a s e i n t h e
sharpness of t h e notch i n t h e specimens causes a c e r t a i n decrease i n t h e impact
s t r e n g t h of t h e m a t e r i a l ( a s a r e s u l t of a g r e a t e r l o c a l i z a t i o n of p l a s t i c deformation); t h i s i s manifested t o a g r e a t e r e x t e n t t h e lower t h e t e s t i n g temperat u r e . The use of c i r c u l a r notches 1.5 mm deep w i t h a bottom r a d i u s of curvature
of 5, 2 and 0.5 mm d i d not r e v e a l any regions of abrupt decrease i n impact
s t r e n g t h , w i t h t h e exception of an unexplained minor d e c l i n e a t a temperature
below -lOOO.

"

2- 7

7dff 2QQ 3Qfl

6,"C
Figure 1. Dependence of impact s t r e n g t h of t i t a n i u m on t e s t i n g
temperature f o r various r a d i i i n t h e bottom of t h e notch of s p e c i mens: a , t i t a n i u m a f t e r annealing; b, t i t a n i u m w i t h 0.015 w t perc e n t H2; c, t i t a n i u m w i t h 0.035 w t percent H2; 1, smooth specimens
2,3,4, notched specimens (notch radius: 2-5 mm; 3-2 mm; 4-0.7 mm)

ff

The i n t r o d u c t i o n of even a small amount (0.015 p e r c e n t ) of hydrogen ( f i g .

l b ) changes appreciably t h e dependence of t h e impact s t r e n g t h on t h e t e s t i n g
temperature. While t e s t s of smooth specimens and specimens w i t h r e l a t i v e l y
" s o f t " notches (bottom r a d i u s of curvature of 5 and 2 mrn) d i d not r e v e a l any
v i s i b l e b r i t t l e n e s s t h r e s h o l d , i . e . , any sharp drop i n impact s t r e n g t h over a
narrow temperature range, t e s t s of notched specimens w i t h a bottom r a d i u s of
curvature of 0.5 mm revealed a sharp drop i n impact s t r e n g t h a t a temperature
below 100'.

An i n c r e a s e i n hydrogen content t o 0.035 percent l e d t o t h e appearance of

a cold b r i t t l e n e s s t h r e s h o l d even i n specimens without notches ( f i g . 1 ~ ) . It i s
c h a r a c t e r i s t i c t h a t t h e temperature range of appearance of b r i t t l e f r a c t u r e s , o r
c r i t i c a l b r i t t l e n e s s temperature, was found t o vary i n a r e g u l a r f a s h i o n w i t h
t h e sharpness of t h e notch: t h e lowest temperature (600) was observed i n smooth
specimens, a h i g h e r value ( 1 6 0 ~ ) - - i nspecimens w i t h a 5 mrn r a d i u s of curvature
of t h e notch bottom, and t h e h i g h e s t (200)--in specimens w i t h a 2 mm r a d i u s of
curvature of t h e notch bottom. Thus, t h e r e g u l a r i t y of t h e dependence of t h e
c r i t i c a l b r i t t l e n e s s temperature on t h e sharpness of t h e notch q u a l i t a t i v e l y
agrees very w e l l w i t h t h e r e s u l t s of a study of t h e cold b r i t t l e n e s s of s t e e l
( s e e , f o r example, r e f . 3 ) . Furthermore, t h e n a t u r e of t h e change i n impact
s t r e n g t h w i t h i n t h e temperature range of appearance of b r i t t l e n e s s i s t h e same
a s i n s t e e l : smooth specimens give t h e most abrupt d e c l i n e i n impact r e s i s t ance, while notched specimens show a smoother decrease i n impact r e s i s t a n c e .
Of g r e a t i n t e r e s t i s t h e m i c r o s t r u c t u r a l p a t t e r n of b r i t t l e and d u c t i l e
f r a c t u r e of t i t a n i u m ( f i g . 2 ) . It i s e a s i l y observed t h a t t h e b r i t t l e flaws
a r e d i r e c t r e s u l t s by l a y e r s of t h e s e p a r a t i o n of t i t a n i u m hydrides, whose
g r a i n s have t h e form of needles ( r e f . 4). The given m i c r o s t r u c t u r a l p a t t e r n
of t h e b r i t t l e and d u c t i l e f r a c t u r e i s q u i t e similar t o t h e b r i t t l e f r a c t u r e
of s t e e l along t h e twinning planes ( r e f . 5 ) . The d u c t i l e f r a c t u r e of t i t a n i u m
i s not r e l a t e d t o any o r i e n t a t i o n s w i t h i n t h e g r a i n .
L e t us now examine t h e i n f l u e n c e of t h e deformation r a t e on t h e cold
b r i t t l e n e s s of t i t a n i u m . The r e s u l t s obtained w i t h notched Menager specimens
a t various temperatures a r e shown g r a p h i c a l l y ( f i g . 3 ) . I n t h e s e t e s t s , t h e
c r i t e r i o n of d u c t i l i t y used was t h e deformation c h a r a c t e r i s t i c , i . e . , t h e deg r e e of d i s t o r t i o n of t h e working c r o s s s e c t i o n of t h e specimen a t t h e s i t e
of t h e break, a s proposed by S t r i b e c k ( r e f . 6). As can be seen from f i g u r e 3,
vacuum-annealed t i t a n i u m r e t a i n s i t s d u c t i l i t y a t a high l e v e l a s t h e t e s t i n g
temperature i s lowered t o -196') both i n impact t e s t s and i n t e s t s under s t a t i c
conditions. The h i g h e r p l a s t i c i t y i n t h e low-temperature region i n impact t e s t s
i s d i f f i c u l t t o e q l a i n i f we confine ourselves t o t h e r e s u l t s of our experiments, but it may be assumed t h a t it r e s u l t s from a l o c a l r i s e i n t h e temperat u r e of t h e metal i n t h e volume t r a v e r s e d by p l a s t i c deformation, owing t o
t h e low thermal conductivity of titanium. The appreciable i n c r e a s e i n d u c t i l i t y
a t temperatures of 200-300' and t h e slow deformation may be explained by t h e
s t r a i n aging of t i t a n i u m i n t h i s temperature i n t e r v a l ( r e f . 7).
T e s t s of t i t a n i u m specimens containing 0.03 p e r c e n t H2 revealed a d i s t i n c t
b r i t t l e n e s s t h r e s h o l d both under s t a t i c and impact loads.

I n conrplete conformity

Figure 2. Appearance of f r a c t u r e of t i t a n i u m
specimens under bending im-pact, x 100. Metal
was preheated i n a hydrogen-containing medium
a t 1100~.
w i t h t h e g e n e r a l r e g u l a r i t i e s of t h e cold b r i t t l e n e s s of s t e e l , a dynamic load
s h i f t s t h e b r i t t l e n e s s t h r e s h o l d i n t o a region of h i g h e r temperatures t h a n i n
static tests.
The r e s u l t s of s t a t i c bending t e s t s a t various temperatures of geometric a l l y s i m i l a r samples of t i t a n i u m containing 0.03 p e r c e n t H2 a r e shown i n t a b l e
2.

The S t r i b e c k c h a r a c t e r i s t i c was taken a s t h e measure of t h e d u c t i l i t y .

t o Stribeck
t i t a n i u m co
s t a t i c bend
anium con-

8.8
-60
--SO

cold b r i t t l e n e s s temperature (start a

decrease) OC

0.5

9.3-8.3
1.3
1.4

+SO

+20

244

+I0

-15

It should be noted t h a t t h i s c h a r a c t e r i s t i c ( r a t i o of t h e d i f f e r e n c e i n t h e
width of contracted and d i l a t e d f i b e r s t o t h e h e i g h t of t h e c r o s s s e c t i o n a t t h e
s i t e of r u p t u r e ) i s a p u r e l y a r b i t r a r y r e f l e c t i o n of t h e d u c t i l i t y , s i n c e t h e
c r o s s s e c t i o n of t h e f r a c t u r e can only be approximated by a t r a p e z o i d , f o r which
reason t h e absolute value of t h i s c h a r a c t e r i s t i c can vary appreciably. This
apparently explains t h e s u b s t a n t i a l d i f f e r e n c e i n t h e absolute values of t h e
deformation c h a r a c t e r i s t i c i n specimens of d u c t i l e t i t a n i u m . However, t h e r e l a t i v e change of t h i s c h a r a c t e r i s t i c w i t h decreasing temperature, which r e v e a l s
t h e b r i t t l e n e s s threshold, unquestionably e s t a b l i s h e s t h e c r i t i c a l b r i t t l e n e s s
temperature w i t h s u f f i c i e n t r e l i a b i l i t y . As i s evident from t a b l e 2, t h e c r i t i c a l b r i t t l e n e s s temperature r i s e s s y s t e m a t i c a l l y w i t h i n c r e a s i n g dimensions of
t h e specimens, and t h e c h a r a c t e r i s t i c i s -15' f o r specimens measuring 2.2 mm,
+lo0 f o r specimens measuring 5.5 mm, and + 800 f o r specimens measuring 20.20

mm

Thus, it may be concluded t h a t t h e cold b r i t t l e n e s s of t i t a n i u m a r i s i n g

from t h e presence of hydrogen and acted upon by t h e p r i n c i p a l e x t e r n a l f a c t o r s - e x t e n t of t h e s t r e s s condition, deformation r a t e and specimen s i z e - - i s manifested
w i t h t h e same r e g u l a r i t y a s i n s t e e l s .

It i s n a t u r a l t o assume t h a t t h e s i m i l a r i t y of t h e s e r e g u l a r i t i e s i s a
manifestation of t h e dual nature of t h e f r a c t u r e of titanium-containing hydrogen. These suggestions had a l r e a d y been expressed by L. S. Moroz ( r e f . 8) i n
connection w i t h an a n a l y s i s of t h e n a t u r e of t h e hydrogen b r i t t l e n e s s of
titanium.
The well-known i n t e r p r e t a t i o n 02 academician A.F. I o f f e i s based on t h e r e s u l t s obtained w i t h rock s a l t a t various temperatures. This i n t e r p r e t a t i o n presupposes two types of s t r e n g t h : a b r i t t l e and a d u c t i l e f r a c t u r e . The s t r e n g t h
of b r i t t l e f r a c t u r e , i . e . , t h e r u p t u r e s t r e n g t h , i s independent of e x t e r n a l
f a c t o r s ( s t r e s s condition, temperature and deformation r a t e ) , whereas on t h e
contrary, t h e s t r e n g t h i n d u c t i l e f r a c t u r e , i . e . , t h e deformation r e s i s t a n c e ,
depends s t r o n g l y on t h e s e f a c t o r s . The extension of A. F. I o f f e ' s i n t e r p r e t a t i o n
t o metals, suggested by N. N. Davidenkov, made it p o s s i b l e t o s e l e c t a s t r u c t u r a l
system of t h e o r e t i c a l i n t e r p r e t a t i o n s of t h e cold b r i t t l e n e s s of metals and t o
e s t a b l i s h many r e g u l a r i t i e s i n t h e v a r i a t i o n of b r i t t l e n e s s temperature w i t h
various f a c t o r s . However, t h e a p p l i c a t i o n of A. F. I o f f e ' s i n t e r p r e t a t i o n t o
metals was found very d i f f i c u l t . Only i n t h e case of i r o n phosphite was it poss i b l e t o o b t a i n ( r e f . 9) a curve of t h e change i n s t r e n g t h w i t h temperature
t h a t was c l o s e t o A. F. I o f f e r s i n t e r p r e t a t i o n . The d i f f i c u l t y of applying t h i s
i n t e r p r e t a t i o n t o metals was mainly due t o an attempt t o o b t a i n an i d e a l l y b r i t t l e f r a c t u r e (without any appreciable r e s i d u a l s t r a i n s ) which, a s was shown by
subsequent i n v e s t i g a t i o n s , does not e x i s t a t a l l . However, without changing i t s
e s s e n t i a l f e a t u r e s , one can r e - p r e s e n t A. F. I o f f e r s i n t e r p r e t a t i o n i n a somewhat d i f f e r e n t manner i f by b r i t t l e s t r e n g t h of metals i s meant t h e rupture
s t r e n g t h (independently of t h e p l a s t i c deformations), and i f t h e curve repres e n t i n g t h e temperature dependence of t h e y i e l d strerigth i s replaced by a curve
r e p r e s e n t i n g t h e temperature dependence of t h e s t r e n g t h a t d u c t i l e f r a c t u r e .
Considering t h e above refinements, we p l o t t e d curves of t h e change i n
t e n s i l e s t r e n g t h f o r t i t a n i u m containing d i f f e r e n t amounts of hydrogen ( f i g .
These curves provide a complete confirmation of A. F. I o f f e r s i n t e r p r e t a t i o n .

4).

t e s t i n g temperature,

OC

Figure 4. True rupture s t r e n g t h versus t e s t i n g

temperature f o r t i t a n i u m containing various amounts
of hydrogen: 1, vacuum-annealed titanium; 2, titanium containing 0.012 w t p e r c e n t Hz; 3, t i t a n i u m
containing 0.035 w t p e r c e n t H

2;

4, t i t a n i u m contain-

i n g 0.060 w t p e r c e n t H ~ .
The s t r e n g t h of vacuum-annealed t i t a n i u m i n c r e a s e s continuously a s t h e temperat u r e drops t o -196O. The i n t r o d u c t i o n of hydrogen l i m i t s t h e i n c r e a s e i n
s t r e n g t h t o t h e l e v e l of t h e cleavage s t r e n g t h , which i s p r a c t i c a l l y independent of temperature.
The l e v e l of t h e cleavage s t r e n g t h depends e n t i r e l y on t h e hydrogen content
of titanium. The more hydrogen i s p r e s e n t i n titanium, t h e lower i s t h e cleavage s t r e n g t h , o r s t r e n g t h a t b r i t t l e f r a c t u r e . Thus, t h e experimental d a t a show
t h a t a d i r e c t cause of t h e cold b r i t t l e n e s s of t i t a n i u m i s a sharp d e c l i n e i n
i t s cleavage s t r e n g t h under t h e i n f l u e n c e of hydrogen introduced i n t o t h e metal.
I n t h e l i g h t of t h e r e s u l t s obtained, it i s necessary once again t o r e t u r n t o
t h e i d e a of a p o s s i b l e g e n e r a l cause of cold b r i t t l e n e s s by r e l a t i n g it t o t h e
unavoidable presence i n metals of oxygen, n i t r o g e n and hydrogen i m p u r i t i e s o r
any o t h e r elements. It i s known t h a t such an explanation of cold b r i t t l e n e s s
has a l r e a d y been proposed i n a study of t h e b r i t t l e n e s s of chromium ( r e f s . 1 0
and 1 1 ) .

It i s p o s s i b l e t h a t even when t h e content of i m p u r i t i e s i s minute, t h e

cleavage s t r e n g t h of metals i n c r e a s e s sharply. The decrease i n cleavage s t r e n g t h
may be due t o t h e passage of t h e f i r s t s h i f t s causing a weakening of bonds along
c e r t a i n c r y s t a l l o g r a p h i c planes on which t h e i m p u r i t i e s can p r e c i p i t a t e .
App a r e n t l y , t h i s process i s c h i e f l y c h a r a c t e r i s t i c of metals w i t h a body-centered
o r hexagonal l a t t i c e .
The i n f l u e n c e of p l a s t i c deformation on t h e embrittlement p r o c e s s can be
confirmed by t e s t s f o r t h e impact s t r e n g t h of t i t a n i u m w i t h various hydrogen
contents. The curves r e p r e s e n t i n g t h e r e l a t i v e decrease i n t h e impact s t r e n g t h

Hz, w t percent
Figure 3. Relative change i n impact s t r e n g t h
versus hydrogen content : 1, t i t a n i u m workhardened t o t h e e x t e n t of 25 percent; 2, annealed titanium.

of cold-worked and annealed t i t a n i u m w i t h r i s i n g hydrogen content ( f i g 5 ) show

t h a t a d d i t i o n a l cold working s u b s t a n t i a l l y r e i n f o r c e s t h e d e c l i n e i n impact
s t r e n g t h . This means t h a t t h e cleavage s t r e n g t h decreases appreciably i n t h e
course of p l a s t i c deformation and t h a t t h e s e n s i t i v i t y of t i t a n i u m t o hydrogen
b r i t t l e n e s s increases.
Conclusions
1. The cold b r i t t l e n e s s of t i t a n i u m i s explained Ly t h e presence of hydro-

gen.

Cold b r i t t l e n e s s i s not displayed by t i t a n i u m f r e e from hydrogen.

2. The r e g u l a r i t i e s i n t h e change of t h e c r i t i c a l b r i t t l e n e s s temperature

of t i t a n i u m w i t h e x t e r n a l f a c t o r s - - e x t e n t of t h e s t r e s s condition (sharpness of
n o t c h ) , r a t e of applFcation of l o a d s and dimensions of specimens--are t h e same
as i n steel.

3. The a p p l i c a b i l i t y of A. I?. I o f f e t s i n t e r p r e t a t i o n t o t h e a n a l y s i s of
t h e conditions under which cold b r i t t l e n e s s i s displayed i n t i t a n i u m has been
confirmed. The main cause of t h e appearance of cold b r i t t l e n e s s i n t i t a n i u m i s
a decrease i n cleavage s t r e n g t h due t o t h e i n t r o d u c t i o n of hydrogen i n t o
titanium.

4. It was shown t h a t t h e p r i n c i p a l cause of t h e cold b r i t t l e n e s s of metals

may be t h e presence of i m p u r i t i e s which a r e bound t o be p r e s e n t i n metals of
technical purity.

REFERENCES
Davidenkov, N. N. and Chuchmin, T. N. In: Studies of Heat-Resistant Alloys
(~ssledovani~a
po zharoprochnym s~lavam) Ize-vo AN SSSR, Vol. 2, p. 9,

1957
Moroz, L. S., Chechulin, B. B., Polin, I. V., Butalov, L. V., Shulfkin,S. M.
and Goryachev, A. P. Coll. Titanium and Its Alloys i it an i yego splavy).
Sudpromgiz, Vol. 1, p. 120, 1960.
Davidenkov, N. N. Dynamic Tests of Metals (~inamicheskiyeispytaniya
metallov) OFTI, 1963.

Nikolayev, G. I. and Bruk, B. I. In: Physical Metallurgy (~etallovedeni~e)

Sudpromgiz, Vol. 2, p. 74, 1958.
Potak, Ya. M. and Sachkov, V. V.
P. 399, 1949.
Stribeck, VDI, Vol. 59, p.

Zhurnal Tekhnicheskoy Fiziki, No. 3,

57, 1915.

Rosi, F. D. and Perkins, F. C.

Trans. ASM, Vol.

45, p. 472, 1953.

Moroz, L. S. and Khesin, Yu. D. In: Physical Metallurgy (~etallovedeni~e)

Sudpromgiz, Vol. 3, p. 74, 1959.
Shevandin, Ye. M. Zav. Lab., No.

7, p. 858, 1947.

Wain, H., Henderson, F. and Lohnstone, S. J. Inst. Metals, Vol. 83, No. 4,
P. 133, 1954.
Savitskiy, Ye. N. and Terekhova, V. F. In: Studies of Heat-Resistant
Alloys (~ssledovaniyapo zharoprochnym splavam). Izd-vo All SSSR, Val. 2,
P. 141, 1957.

C m P OF ALLOY AT3 AT 350'

K. P. Markovich, V. S. Mikheyev and Z. G. Fridman

A t t h e p r e s e n t time, t h e only high-strength m a t e r i a l s w i t h a d e n s i t y of

4.4-4.6 g/cm3 f o r o p e r a t i o n a t 300-550' a r e titanium-base a l l o y s . For t h i s

reason, t h e development of t h e o r e t i c a l and experimental s t u d i e s i n t h e f i e l d of
high-temperature s t r e n g t h of t i t a n i u m a l l o y s assumes an exceptional importance.
One of t h e main problems i n t h i s f i e l d i s t h e study of t h e p r o p e r t i e s and behavior of t h e a l l o y s i n t h e course of creep.
The purpose of t h e p r e s e n t work was t o e s t a b l i s h t h e creep l i m i t of titanium a l l o y AT3 a t 350 f o r a t o t a l deformation of 1 p e r c e n t i n t h e course of
20,000 h r s o f t e s t i n g , and a l s o t o s t u d y t h e change i n t h e mechanical c h a r a c t e r i s t i c s of t h e a l l o y a f t e r it has been t e s t e d f o r creep under s e l e c t e d conditions.
Work conducted e a r l i e r i n t h i s d i r e c t i o n has shown ( r e f . 1 ) t h a t a l l o y AT3
a t 300 and 350 and a s t r e s s of 30 kg/mm2 following 5000 h r s of creep tests i s
c h a r a c t e r i z e d by a high creep r e s i s t a n c e and r e t a i n s a high thermal s t a b i l i t y .

An a l l o y melted under p l a n t conditions i n a vacuum a r c furnace by double

remelting was chosen f o r t h e i n v e s t i g a t i o n .
The following s t a r t i n g m a t e r i a l s
were used i n t h e p r e p a r a t i o n of t h e a l l o y : t i t a n i u m sponge TGO w i t h an u l t i m a t e
s t r e n g t h of 39-43 kg/mm2, t e c h n i c a l s i l i c o n KR, chromium X I , t e c h n i c a l i r o n ,
and a chromium-boron master a l l o y (up t o 10 percent 3 ) . The a l l o y i n g elements
were introduced i n t o t h e a l l o y i n t h e form of a complex master a l l o y . The chemi c a l composition of a l l o y AT3 was a s follows: base, Ti; 2.7 p e r c e n t AL; 0.6
p e r c e n t Cr; 0.30 p e r c e n t Fe; 0.36 p e r c e n t S i ; 0.01 percent B ( c a l c u l a t e d ) .
A f t e r forging, t h e mechanical c h a r a c t e r i s t i c s of a l l o y AT3 were a s follows:
ob = 86.4 kg/mm2; as = 84.9 kg/mm2; 6 =

14.5 percent; I#

= 43.2 p e r c e n t ; % =

7.7

.kgm/cm2. A f t e r annealing a t 8500 f o r 30 min and cooling i n a i r , t h e mechanical

c h a r a c t e r i s t i c s assumed t h e following values:
kg/mm2; 6 = 1 4 . 8 percent; I# = 44.75 percent;

ob = 86.3 kg/mm2; os = 85.0

a, =

6.8 kgm/cm2.

Specimens f o r creep t e s t s were prepared from a forged rod 20 mm i n diameter.

The t e s t s were made with an IP-5 machine a t a constant temperature of 350 and
s t r e s s e s of 15, 30, 33, 37, 45 and 50 kg/mm2. The d u r a t i o n of t h e t e s t s under
t h e above s t r e s s e s was r e s p e c t i v e l y 5,454, 6,662, 5,705, 5,215, 12,000 and 9,300
hrs

To determine t h e s t a b i l i t y of t h e a l l o y i n t h e course of long-time creep

t e s t i n g , t h e mechanical p r o p e r t i e s of t h e a l l o y were studied a t room temperature
a f t e r t h e creep t e s t . Standard r u p t u r e - t e s t specimens were c u t o u t of t h e
working p a r t of t h e creep-tested specimens.
Results
Creep of a l l o y AT3. Let us examine t h e d a t a on t h e creep following t e s t s
of a l l o y AT3 l a s t i n g from 5,000 h r s a t a constant temperature of 350 and creep

15, 30, 33, 37, 45 and 50 kg/mm2.

s t r e s s e s of

The shape of t h e creep curve a t s t r e s s e s of 15 and 30 kg/mm2 ( f i g . 1) i s

c l o s e t o l i n e a r . The s t a g e of t r a n s i e n t creep i s b r i e f . I t s d u r a t i o n does not
exceed

-200

h r s f o r s t r e s s e s of

15 and 30 kg/mm 2

As t h e creep s t r e s s i n -

creases t o 37 kg/mm2, t h e s t a g e of t r a n s i e n t creep i n c r e a s e s t o approximately

1,200 h r s , The s t a g e of s t e a d y - s t a t e creep i s f a i r l y long f o r a l l s t r e s s e s and
does not end a f t e r 5,000 h r s of t e s t i n g . Under t h e s e l e c t e d c r e e p - t e s t condit i o n s , t h e t h i r d stage, t h a t of accelerated creep, i s absent. The t o t a l deformation i n 5,000 h r s of t e s t i n g i n c r e a s e s w i t h r i s i n g creep s t r e s s from 0.18
percent a t

15 ks/mm2 t o 0.92 percent a t 37 kg/mm2.

A s shown by t h e creep curves f o r s t r e s s e s of 45 and 50 kg/mm2 ( f i g . 2 ) )

the s t a g e of s t e a d y - s t a t e creep begins a f t e r 400 h r s of t e s t s under a s t r e s s of

45 kg/mm2 and does not end a f t e r 12,000 h r s .

i s 1.2 percent.

The t o t a l deformation f o r 12,000 h r s

I n t e s t s of a l l o y AT3 under a s t r e s s of 50 kg/mm2, t h e s t a g e of steadys t a t e creep begins a f t e r t e s t i n g f o r 1,000 h r s . The t o t a l deformation f o r 9,300
h r s i s 4.8 percent.
The c-reep curves ( f i g s . 1 and 2) make it p o s s i b l e t o detemusne t h e r a t e of
steady-state creep on various p o r t i o n s of t h e curve. The r a t e of s t e a d y - s t a t e
creep v was defined a s t h e quotient of t h e d i v i s i o n of t h e elongation A 1 by t h e
P
time AT during which t h i s elongation took place.
The creep r a t e a t t h e s t e a d y - s t a t e stage increases with r i s i n g s t r e s s , but
does not exceed 2 * l 0 - 5 percent h r s f o r a s t r e s s of 37 kg/mm2.

An i n c r e a s e . i n

d u r a t i o n of t e s t , h r
Figure 1. Creep curves of a l l o y AT3 a t 350':

d u r a t i o n of t e s t , h r
Figure 2.

Creep curves of a l l o y AT3 a t 350'

creep s t r e s s e s o f

45 and 50 kg/mm 2

and

creep r a t e i s observed i n t e s t s under s t r e s s e s of 45 and 50 kg/mm2. I n t h e

presence of t h e s e s t r e s s e s , t h e creep r a t e a t t h e s t e a d y - s t a t e s t a g e i s equal
t o an average of 0 . 5 * 1 0 - ~and

1.6-

percent/hr r e s p e c t i v e l y , t h e c r e e p r a t e

remaining c o n s t a n t f o r 12,000 h r s of t e s t s under a s t r e s s of

45 kg/mm2.

We used t h e numerical values of creep r a t e s , obtained from t h e "elongationtime" curves, t o p l o t curves r e p r e s e n t i n g t h e change i n t h e creep r a t e i n semilogarithmic " s t r e s s - c r e e p r a t e " coordinates ( f i g . 3). Such a curve enabled u s
t o determine t h e l i m i t i n g s t r e s s a t 350' causing a s p e c i f i e d r e s i d u a l deformat i o n of 1 p e r c e n t a f t e r 20,000 h r s of t e s t s . The creep r a t e a t a r e s i d u a l
deformation of 1 percent a f t e r 20,000 h r s of t e s t s a t t h e i n d i c a t e d temperature

w i l l be 5.10'5

percent/hr.

7d3
v , percent/hr
P
Figure 3. Curves of t h e r e l a t i o n between o and
v f o r a l l o y AT3 w i t h 2.7 percent Al, 1.26 perP
;f'+

cent C (CR, Fe,

si)

a t 350.

Consequently, t h e l i m i t i n g s t r e s s causing a creep r a t e of 5 . 1 0 ~ e~r c e n t / h r

a t 350 f o r a l l o y AT3 containing 2.7 percent Al and 1.26 percent C ( ~ r Fe,
,
si)

w i l l be 42 kg/mm2.
Change i n Mechanical P r o p e r t i e s
Let us examine t h e dependence of t h e mechanical p r o p e r t i e s of a l l o y AT3 at
room temperature on t h e creep s t r e s s ( f i g . 4).

It i s apparent from the d a t a obtained t h a t t h e u l t i m a t e s t r e n g t h of t h e

a l l o y ob and t h e p l a s t i c i t y c h a r a c t e r i s t i c s o and $ do not undergo any apprec i a b l e changes following creep t e s t s a t various s t r e s s e s .

Thus, i n t h e i n i t i a l

s t a t e ( a f t e r f o r g i n g ) , t h e a l l o y had an u l t i m a t e s t r e n g t h of 86.4 kg/mm2 and an

elongation p e r u n i t l e n g t h of 16.3 percent, whereas a f t e r creep t e s t s a t 3500
and a creep s t r e s s of

45 kg/mm2 applied f o r 5,900 h r s , t h e u l t i m a t e s t r e n g t h was

85.8 kg/mm2, t h e elongation p e r u n i t l e n g t h was

percent.

16.4 percent and

I$

= 40.2

Consequently, t h e u l t i m a t e s t r e n g t h and t h e p l a s t i c i t y c h a r a c t e r i s t i c s of
the a l l o y do not undergo any s u b s t a n t i a l changes a f t e r s u f f i c i e n t l y long creep
tests.

Figure 4. Change i n t h e mechanical p r o p e r t i e s

of titanium a l l o y s AT3 with 2.7 percent A l and
1.26 percent C ( C r , Fe, ~ ia f)t e r a creep t e s t
of 5,000 h r s a t 350'.
I n t h e course of a prolonged creep t e s t , t h e a l l o y does not become emb r i t t l e d , independently of t h e s t r e s s . The s t r e n g t h and p l a s t i c p r o p e r t i e s of
t h e a l l o y a r e retained a t t h e l e v e l of t h e i n i t i a l s t a t e .
Summary

1. The creep of a l l o y AT3 of t h e six-component system Ti-Al-Cr-Fe-Si-B

with 3 percent A l and 1.26 percent C ( C r , Fe, ~ i a)t 350 was i n v e s t i g a t e d .
The t e s t s l a s t e d 5,000 h r s f o r creep s t r e s s e s of 15, 30, 33 and 37 kg/mm2 and
9,300-12,000 h r s f o r creep s t r e s s e s of 45 and 50 kg/mm2. Under t h e s e l e c t e d
t e s t i n g conditions, a l l o y AT3 i s characterized by a high creep s t r e n g t h .
2.

The creep r a t e of a l l o y AT3 does not exceed 2010-5 percent/hr f o r a

creep s t r e s s of 37 kg/mm2.
under s t r e s s e s of

45

equal t o 0 . 5 . 1 0 - ~ and
3.

An increase i n creep r a t e i s observed i n t e s t s

and 50 kg/mm2.

Under these s t r e s s e s , it i s r e s p e c t i v e l y

1 . 6 * 1 0 - percent/hr
~
a t t h e s t a g e of s t e a d y - s t a t e creep.

The l i m i t i n g s t r e s s a t 350'

a t which the r e s i d u a l deformation a f t e r

20,000 h r s of t e s t s corresponds t o 1 percent i s equal t o 42 kg/mm 2

1. Mikheyev, V. S., Markovich, K. P. and Fridman, Z. G. Coll. Titanium and I t s

Alloys i it an i yego splavy). Izd-vo AN SSSR, No. 10, p. 214, 1963.

2.

ICornilov, I. I . , Mikheyev, V. S., Chernova, T. S. and Markovich, K. P.

Coll. Titanium and I t s Alloys itan an i yego splavy). Izd-vo AN SSSR,
NO. 10,p . 224, 1963.

3.

N i k i t i n a , L. P. Coll. Titanium and Its Alloys

AN SSSR, No. 10, p. 224, 1963.

i it an

i yego splavy).

Izd-vo

STUDY OF THE CmEP I-WD THl3RMAL STABILITY OF ALLOY AT4 AT 500

I. I. Kornilov, 0. IY. Andreyev and B. M. Voshedchenko

The authors studied t h e creep and thermal s t a b i l i t y of titanium a l l o y AT4

of t h e six-component system Ti-Al-Cr-Fe-St-B a t 500 by using a standard method.
The a l l o y was melted under p l a n t conditions i n a vacuum a r c furnace by double
remelting.
The following charging m a t e r i a l s were used i n t h e preparation of t h e a l l o y :
titanium a l l o y 'E0 with an u l t i m a t e s t r e n g t h of 39-43 kg/mm2, t e c h n i c a l s i l i c o n
K r , chromium X I , t e c h n i c a l i r o n , and a chromium-boron master a l l o y (up t o 1 0
percent B)

The a l l o y i n g elements were introduced i n t o t h e composition i n t h e form of a

complex master a l l o y .
4.67 percent Al, 0.86
The chemical composition of a l l o y AT (base ~ iwas:
)
percent C r , 0.31 percent Fe, 0.27 percent S i , 0.001 percent B ( c a l c u l a t e d ) . The
content of i m p u r i t i e s was: 0.05 percent C , 0.024 percent N2, and 0.007 percent

The mechanical c h a r a c t e r i s t i c s of a l l o y AT& a t room temperature were:

forging (as-received condition) ab = 94 kg/mm2;

OS

= 8 9 kg/mm2;

after

6 = 15 percent;

Jr = 45 percent; a, = 6.5 kgm/cm2; a f t e r annealing f o r 30 min a t 8800 and cooling

i n a i r , ob = 94.2 kg/m2;

us

= 89.4 kg/mm2;

6 = 13.1 percent; Jr = 45.3 percent;

The creep of a l l o y AT^ a t 500' was studied by a standard extension method

on TSP-1 specimens with t h e working p a r t 100 mrn long and 10 mm i n diameter a t
s t r e s s e s of 2.5 and 5 kg/mm2 during 1,000 h r s .
For each s t r e s s , t h e t e s t s were c a r r i e d out on two specimens simultaneously
using IP-5 machines, and t h e same creep values were t h u s obtained.

Creep t e s t s of AT4 a t 500'

f o r 1,000 h r s showed t h a t a t t h e s t r e s s of

kg/mm2 t h e t o t a l deformation was 0.5 percent, and a t t h e s t r e s s of 2.5 kg/mm2,

it decreased t o 0.18 percent.
The "deformation-time" creep curves of a l l o y AT& a t s t r e s s e s of

5 and 2.5

kg/mm2 a r e s i m i l a r i n c h a r a c t e r ( f i g . 1).
The stage of t r a n s i e n t creep f o r a s t r e s s of 2.5 kg/mm2 does not exceed
650 h r s . As t h e s t r e s s increases t o
creases t o 750 hrs.

5 kg/mm2, t h e s t a g e of t r a n s i e n t creep in-

Thus, the s t a g e of s t e a d y - s t a t e creep i n t h e f i r s t case begins a f t e r 650

h r s of t e s t s , and i n t h e second, a f t e r 750 h r s and continues up t o 1,000 hrs.
The t e s t s a r e then terminated ( t h e specimens a r e removed).
Under t h e s e l e c t e d conditions of creep t e s t i n g , t h e t h i r d s t a g e of accelerated creep i s absent.
The t o t a l deformation f o r 1,000 h r s of t e s t s r i s e s with increasing creep
s t r e s s from 0.18 percent a t 2.5 kg/mm2 t o 0.5 percent a t

5 kg/mm2.

The creep curves ( f i g . 1) enabled us t o determine t h e r a t e of s t e a d y - s t a t e

creep.
The creep r a t e a t t h e s t e a d y - s t a t e s t a g e of creep i n c r e a s e s w i t h r i s i n g
creep s t r e s s .
A t s t r e s s e s of 2.5 and

5 kg/mm 2, t h e creep r a t e s a t the s t a g e of steady-

s t a t e creep a r e equal t o an average of 0.3.

and

1.6*10-~
percent/hr.

Hence, f o r a l l o y AT^, t h e l i m i t i n g s t r e s s causing a creep r a t e of 0 . 3 . 1 0 - ~

percent/hr a t 500'

w i l l be 2.5 kg/mm2.

This i n d i c a t e s a high creep r e s i s t a n c e

of a l l o y AT^ a t 500 and a s t r e s s of 2.5 kg/mm2.

Figure 1.

Creep curves of a l l o y AT^ a t 500 f o r 1,000 h r s :

The creep curves of t h e t i t a n i u m a l l o y s ( f i g . 2a) were p l o t t e d on t h e b a s i s

of d a t a obtained by I. I. Kornilov, V. S. Mikheyev, 0. N. Andreyev and P. S.
specimens were subjected t o bending by t h e c e n t r i f u g a l method
~ a ~ b o r 0 d a . The
l
a t 500'

and a s t r e s s of 20 kg/mm2.

The t e s t l a s t e d 100 hrs.

As i s evident from t h i s f i g u r e , t h e creep of a l l o y s of t h e six-component

system Ti-Al-Cr-Fe-Si-B,
AT3, AT^, AT^ and AT^ i s considerably l e s s t h a n t h a t
~
0 ~ 4 - 2 . The creep curves of
of t h e i n v e s t i g a t e d titanium a l l o y s , OT4, V T and
~ AT4 a r e shown i n f i g u r e 2b. The specimens were
a l l o y s OT4, VT5, VT5-1, V T and
subjected t o extension by a standard technique, and t h e t e s t i n g conditions were
t h e same a s before.
The d a t a on t h e creep r a t e obtained by t h e bending method and t h e standard
extension method a r e i n good mutual agreement.
Thus, of a l l t h e a l l o y s studied, t h e creep r a t e of a l l o y AT& i s t h e lowest.
Alloy AT&, w i t h a d e n s i t y of 4.5 g/cm3, i s very i n t e r e s t i n g a s a heatr e s i s t a n t titanium a l l o y whose s t r e n g t h i s c l o s e t o t h a t of l ~ h 1 8 N gs~t e e l and
which can be used a t working temperatures up t o 5 0 0 ~ .
a

Figure 2.

Creep curves of t i t a n i u m a l l o y s a t 500'

and a s t r e s s of

20 kg/m2 f o r 100 hrs: a, c e n t r i f u g a l method of bending t h e specimens

(1, a l l o y O T ~ ; 2, a l l o y AT1 without Al; 3, a l l o y V T ~ ;4, a l l o y OT4-2;
5, a l l o y AT3; 6, a l l o y AT&; 7, a l l o y AT^) ; b, standard extension method
(1, a l l o y OT4; 2, a l l o y VT5; 3, a l l o y VT5-1; 4, a l l o y ~ 6 5,; a l l o y
AT&).

'1. I. Kornilov, V. S. Mikheyev, 0. N. Andreyev and P. S. Mayboroda. Coll.

Titanium and I t s Alloys i it an i yego splavy). Izd-vo AN SSSR, No. 10, p. 234,
1963

A t t h i s temperature, a l l o y AT^ has a h i g h e r short-time and long-time

, VT5-1, V T ~and 0 ~ 4 - 2 . Furthermore,
s t r e n g t h than t i t a n i u m a l l o y s ~ 4 VT5,
a l l o y AT^ does n o t c o n t a i n any c o s t l y and s c a r c e components.
Alloy AT4 i s deformable: i t can be used t o make various semifinished
products, including p i p e s , by means of hot and cold r o l l i n g . Cold r o l l i n g can
be used t o make p i p e s 6-8 mm i n diameter w i t h a w a l l t h i c k n e s s of 0.3-0.6 mm
from t h i s a l l o y . Alloy AT^ welds s a t i s f a c t o r i l y when argon a r c and e l e c t r o s l a g
welding i s used.
To determine t h e thermal s t a b i l i t y of a l l o y AT4 i n t h e course of long-time
creep t e s t i n g , t h e mechanical p r o p e r t i e s were s t u d i e d a t room temperature a f t e r
t h e creep t e s t s .
Standard r u p t u r e - t e s t specimens LIM-1 ( l e n g t h of working p a r t 36 mm and
diameter 6 mm) were made from t h e working p a r t of specimens t e s t e d f o r creep.
The average mechanical c h a r a c t e r i s t i c s of a l l o y
h r creep t e s t were:
$ =

cfb = 98.15 kg/mm2;

c f =

AT^ a t 20' a f t e r a 1,000

92.7 kg/mm2;

6 = 14.4 percent;

44.9 p e r c e n t .

I n t h e course of t h e creep t e s t , t h e mechanical p r o p e r t i e s of a l l o y AT4

remain almost unchanged. The a l l o y r e t a i n s high p l a s t i c c h a r a c t e r i s t i c s , and
t h e u l t i m a t e s t r e n g t h and y i e l d s t r e n g t h i n c r e a s e t o an i n s i g n i f i c a n t e x t e n t .
These d a t a show t h a t a l l o y AT4 under c o n d i t i o n s of long t e s t i n g (up t o
1,000 h r s ) under s t r e s s a t 500 i s a thermally s t a b l e m a t e r i a l which does n o t
e m b r i t t l e ; t h i s i s an important performance c h a r a c t e r i s t i c .
I n a d d i t i o n t o t h e mechanical p r o p e r t i e s of a l l o y AT^, i t s microstruct u r e and hardness were i n v e s t i g a t e d before and a f t e r t h e creep t e s t s .
Etching was done i n a reagent c o n s i s t i n g of 1 p t . hydrofluoric a c i d , 1 p t .
n i t r i c acid and 2 p t s . g l y c e r i n . I n order t o prevent a s t r o n g o x i d a t i o n of
t h e s u r f a c e of t h e polished s e c t i o n , t h e specimens a f t e r being etched were
f i r s t washed w i t h a s o l u t i o n of soda and then w i t h water.
Let u s examine t h e m i c r o s t r u c t u r e s of a l l o y AT^ after forging, a f t e r annealing f o r 30 min a t 880 and co,oling i n a i r , and a f t e r c r e e p - t e s t i n g f o r 1,000
h r s ( f i g . 3 ) . I n t h e s t a t e a f t e r forging and i n t h e s t a t e a f t e r annealing
under t h e i n d i c a t e d conditions, a l l o y AT^ had t h e s t r u c t u r e of t h e a ' phase of
m a r t e n s i t i c type.
A f t e r 1,000 h r s of creep t e s t s a t 500' and a s t r e s s of 5 kg/mm2, t h e s t r u c t u r e of t h e a l l o y approaches t h e equilibrium s t a t e ; t h e a ' phase disappears, and
t h e a l l o y has t h e s t r u c t u r e of t h e a-phase w i t h a s l i g h t content of transformed
@-phase. The hardness of a l l o y AT^ i s almost t h e same a s i n t h e i n i t i a l s t a t e .

Figure 3. Microstructure of
a l l o y AT^, x 340: a, i n forged
s t a t e ; b, a f t e r annealing f o r
30 min a t 8800 and cooling i n
a i r ; c, a f t e r 1,000 h r s a t 500
and o = 5 kg/mt8.
Thus, t h e s t u d i e s showed t h a t of t h e a l l o y s s t u d i e d , t h e creep r a t e i s
I n i t s p r o p e r t i e s , AT4 i s of g r e a t i n t e r e s t a s a
lowest i n a l l o y AT4 a t 500'.
h e a t - r e s i s t a n t t i t a n i u m a l l o y which can be used a t working temperatures up t o
500.
Summary
1. I n t h i s work, s t u d i e s of t h e creep and thermal s t a b i l i t y of t i t a n i u m
a l l o y AT4 were c a r r i e d o u t f o r t h e f i r s t time by using t e s t s l a s t i n g 1,000 h r s .
2. I n a l l o y AT4 t h e creep i s considerably lower t h a n t n a l l o y s OT4, OT4-2
(of t h e system Ti-Al-Mn), a l l o y VT5-1 (of t h e system T i - ~ l - ~ nand
) a l l o y V T ~(of
t h e system Ti-Al-v).

3. The r e s i d u a l elongation a f t e r 1,000 h r s of t e s t i n g a t s t r e s s e s of 2.3

and 5 kg/mm 2 i s r e s p e c t i v e l y equal t o 0.18 and 0.5 percent.

4.

The l i m i t i n g s t r e s s causing a creep r a t e of 0 , 3 - 1 0 - ~p e r c e n t / h r a t 500'

i s 2.5 kg/mm2. This i n d i c a t e s a high creep r e s i s t a n c e of a l l o y AT4 under t h e

given conditions.

roducts including

DETERMINATION OF THE RELAXATION IIESISTmCE OF AZJ;OY AT3

L. P. N i k i t i n a

The r e l a x a t i o n of s t r e s s e s a s s o c i a t e d w i t h t h e transformation of e l a s t i c
i n t o p l a s t i c deformation, t h e dimensions of t h e p a r t being constant, i s frequently encountered i n engineering p r a c t i c e . For t h i s reason, a c h a r a c t e r i z a t i o n of t h e r e l a x a t i o n of an a l l o y i s required i n various cases. It i s necess a r y when an a l l o y i s t o be used f o r r e i n f o r c i n g p a r t s , f o r determining t h e
d u r a t i o n of t h e e f f e c t of undesirable i n t e r n a l s t r e s s e s i n t h e metal produced
during t h e assembly o r during welding, i n t h e choice of a s u i t a b l e mode of
heating t o r e l i e v e t h e i n t e r n a l s t r e s s e s i n t h e p a r t and o t h e r cases.
We know of few s t u d i e s on s t r e s s r e l a x a t i o n i n t i t a n i u m a l l o y s ( r e f . 1 and
o t h e r s ) . For t h i s reason, i n o r d e r t o determine t h e r e l a x a t i o n r e s i s t a n c e of
a l l o y AT3, r e l a t i v e l y labor-consuming t e s t s were required over a wide range of
temperatures and s t r e s s e s .
Te s t i n g Me tho4
The r e l a x a t i o n t e s t s were c a r r i e d o u t on I. A. Oding's r i n g specimens
( r e f . 2) made of b a r s of equal bending s t r e n g t h . The standard method o f t e s t i n g
f o r r e l a x a t i o n a t each temperature s p e c i f i e s a drop i n s t r e s s w i t h time from
two, t h r e e and f o u r l e v e l s of i n i t i a l s t r e s s . The i n i t i a l s t r e s s e s a r e u s u a l l y
chosen equal i n a b s o l u t e value f o r all t h e temperatures studied, and t h i s p l a c e s
t h e specimens under d i s s i m i l a r t e s t i n g conditions a t t h e lowest and h i g h e s t temp e r a t u r e i f i n t h e range under consideration t h e temperature has an a p p r e c i a b l e
e f f e c t on t h e short-time mechanical p r o p e r t i e s . Over a wider temperature range,
t h e loading t o e q u a l s t r e s s e s becomes completely impossible, s o t h a t one should
not use t h e g e n e r a l l y adopted methods of comparing t h e r e l a x a t i o n r e s i s t a n c e a t
various temperatures on t h e b a s i s of a dropof s t r e s s from t h e same a. values f o r
an equal t e s t i n g time.
To e l i m i n a t e t h e shortcomings of t h e method of r e l a x a t i o n t e s t s , w e adopted
i n i t i a l r e l a x a t i o n conditions such t h a t a t any t e s t i n g temperature t h e i n i t i a l
s t r e s s amounted t o a s p e c i f i e d f r a c t i o n of t h e y i e l d s t r e n g t h a t t h e given
temperature.

~ h u s ,f o r a l l o y AT3, we s e l e c t e d t h r e e s t r e s s l e v e l s :

0.375, 0.50 and 0.75

(the c o e f f i c i e n t s were r e s p e c t i v e l y bl = 0.375) b2 = 0.50) and

of ot
0.2

The determination of s t r e s s r e l a x a t i o n i n time was made on t h e b a s i s of

t h e r e l a t i v e value of t h e r e s i d u a l s t r e s s 07/00 and oT/oO.2, i n a d d i t i o n t o t h e
usual "absoluteff value of t h e r e s i d u a l s t r e s s aT.
This method of determining s t r e s s r e l a x a t i o n permitted c e r t a i n generalizat i o n s of t h e process of s t r e s s relaxation.
The r e l a x a t i o n t e s t s were c a r r i e d out i n the temperature range of 350-650
every 50'.
Materials Used
The r i n g specimens used i n t h e r e l a x a t i o n t e s t s were made from forged
pieces 70 mm i n diameter. The forged piece was f i r s t annealed i n a i r a t 900'
f o r 1 h r . The a x i s of t h e c y l i n d r i c a l p a r t of t h e specimens coincided w i t h
the a x i s of t h e forged piece. The mechanical c h a r a c t e r i s t i c s of a l l o y AT3 f o r
l o n g i t u d i n a l specimens are shown i n the t a b l e . The l a t t e r a l s o i n d i c a t e s value:
of t h e modulus of e l a s t i c i t y a t high temperatures (from the c e r t i f i c a t e d a t a of
a l l o y AT3).
MECRANICAL PROPERTIES OF FORGINGS FROM ALLOY AT3

Results of Experiments and Their Evaluation

The r e s u l t s of relaxation t e s t s made it possible t o examine t h e change of
t h e i n i t i a l s t r e s s and the buildup of p l a s t i c deformation i n t h e course of
relaxation.

The dependence between t h e r e s i d u a l s t r e s s on t h e value of t h e i n i t i a l

s t r e s s i s shown g r a p h i c a l l y . The f i r s t graph ( f i g . 1) i s a u s u a l graph of
0,-oo, c i t e d i n many r e l a x a t i o n s t u d i e s , w i t h t h e exception t h a t both q u a n t i t i e s
a r e divided by o

0.2'

This graph shows t h a t t h e higher t h e i n i t i a l s t r e s s , t h e

higher i s t h e r e s i d u a l s t r e s s f o r a s p e c i f i e d r e l a x a t i o n time.
I f t h e r e l a t i v e r e s i d u a l s t r e s s o,/ao

i s determined ( f i g . 2 ) , it i s appar-

e n t t h a t t h e h i g h e r t h e i n i t i a l s t r e s s , t h e f a s t e r i s t h e r e l a x a t i o n process,
f o r t h e same t e s t i n g time.
i .e., t h e s m a l l e r i s t h e r e l a t i v e value of
These experimental r e s u l t s a r e i n complete agreement w i t h t h e g e n e r a l concepts according t o which t h e r e l a x a t i o n and creep processes i n metals a r e of t h e
same nature.
To analyze t h e s t r e s s e s i n t h e course of r e l a x a t i o n , t h e primary " s t r e s s log time" r e l a x a t i o n curves were p l o t t e d i n t h r e e forms:
i n hours a t t = const:

a.

Absolute s t r e s s 0, i n kg/mm2--time

b.

R e l a t i v e s t r e s s %loo i n percent--time i n hours, i . e . ,

f r a c t i o n of

s t r e s s r e t a i n e d a t t = const and i n i n i t i a l s t r e s s of oO = b o:.2;

Figure 1. E f f e c t of t h e i n i t i a l s t r e s s o

stress o,

on t h e r e s i d u a l

(both q u a n t i t i e s divided by at ) :
0.2

b, 100 h r s ; c , 1,000 h r s .

a, 1 h r ;

c.

R e l a t i v e s t r e s s oT/oga2 i n percent--time i n hours, i . e . ,

s t r e s s r e t a i n e d r e l a t i v e t o value of y i e l d s t r e n g t h oh.

f r a c t i o n of

a t t = const and a

s p e c i f i e d value- of t h e i n i t i a l s t r e s s oo = b * o O n 2 .
A s an example, we c i t e t h e primary r e l a x a t i o n curves i n t h e c o o r d i n a t e s
" r e l a t i v e r e s i d u a l s t r e s s - t i m e " f o r values of i n i t i a l s t r e s s a t b = 0.5 and
b = 0.75 ( f i g . 3 ) .

I n o u r view, t h i s i s t h e most convenient form of r e p r e s e n t i n g primary

curves. Such primary curves make it p o s s i b l e t o e v a l u a t e t h e r a t e of t h e r e l a x a t i o n process a t various temperatures.
On t h e b a s i s of t h e primary curves f o r a l l t h r e e l e v e l s of i n i t i a l s t r e s s
(b1 - 0.375; b2 = 0.5; bg = 0.75), t h e time necessary f o r reaching a prede-

termined l e v e l of s t r e s s r e l a x a t i o n was determined:

= 0.8 oo; oT = 0.5 GO;

a, = 0.
The temperature dependence of t h e r e l a x a t i o n time up t o t h e s p e c i f i e d l e v e l
of r e l a t i v e s t r e s s i s p l o t t e d i n t h e coordinates I n T - 1 / ~
( f i g . 4). This graph
0

shows t h a t t h e following exponential r e l a t i o n e x i s t s between t h e r e l a x a t i o n time

and t h e temperatuxe:

Figure 2.

E f f e c t of i n i t i a l s t r e s s oO/oE.

t h e r e l a t i v e r e s i d u a l stress
100 h r s ; c, 1,000 h r s .

" at

on t h e value of

T = const:

a , 1 h r ; b,

Figure 3. Primary r e l a x a t i o n curves i n t h e

coordinates " r e l a t i v e r e s i d u a l s t r e s s - t i m e t t
a, a t

ture,

OK;

i s a constant.

o(1)

= 0.50 crOs2; b, a t GO = 0.75

06.~.

i s t h e time during which t h e given s t r e s s i s reached; T i s t h e tempera-

where

uo(l) i s t h e a c t i v a t i o n energy of t h e process; R i s t h e g a s constant;

The a c t i v a t i o n energy u

o(1)

75. lo3 cal/mole was c a l c u l a t e d from t h e ex-

perimental d a t a ; it c h a r a c t e r i z e s t h e r e s i s t a n c e of a l l o y AT3 t o t h e s t r e s s drop

a t high temperature. Without t h e values of t h e a c t i v a t i o n energy of t h e creep
process o r t h e a c t i v a t i o n energy of t h e process of s e l f - d i f f u s i o n o f a l l o y AT3
o r o t h e r t i t a n i u m a l l o y s , it i s d i f f i c u l t t o r e a l i z e t h e meaning of t h e value
obtained. However, t h e accumulation of s i m i l a r d a t a f o r a number of m a t e r i a l s
w i l l obviously permit a more e x t e n s i v e study of r e l a x a t i o n processes i n t h e
f u t u r e . I n p r a c t i c e , t h e graph shown i n f i g u r e 4 i s very u s e f u l i n s e l e c t i n g
t h e temperature and annealing time i n t h e case of r e l i e f of undesirable i n t e r n a l
s t r e s s e s , o r i n evaluating t h e r e l a x a t i o n r e s i s t a n c e of a l l o y AT3 a t v a r i o u s
working temperatures.

z,

td t-

0 b
+'\

2 be

z8
rn

cu a,
0 5
curl

G f

Figure
1- a t

4.

Temperature dependence of r e l a x a t i o n .

2
= 0.8; b = 0.5; 2_
a.

a~
at = 0.5;
00

b =50.5; 3

at

-= O;
*T

&= O;

'JE

Let us n o t e t h a t t h e a n a l y s i s of t h e temperature dependence of t h e r e s i d u a l

s t r e s s i t s e l f , not of t h e r e l a x a t i o n time, has not thus f a r permitted t h e establishment o f a simple a n a l y t i c a l r e l a t i o n s h i p between t h e r e l a x a t i o n stress
and t h e temperature on t h e standard o r logarithmic s c a l e e i t h e r .
An a n a l y s i s of t h e p l a s t i c deformation was c a r r i e d o u t on t h e b a s i s of
measurements of t h e r i n g specimens, s i n c e t h e r e l a x a t i o n s t r a i n "el = 0.0583

Arel

percent, where Arel

i s t h e i n c r e a s e i n t h e d i s t a n c e i n rnm

marks of t h e r i n g specimen.
ot

0.2

between t h e

These d a t a a r e shown a s an example f o r oo = 0.75

i n t h e form of primary "deformation-time" curves ( f i g .

5 ) . An a n a l y s i s of

t h e r e l a x a t i o n s t r a i n made it p o s s i b l e t o e s t a b l i s h c e r t a i n r e g u l a r i t i e s of t h e
process. Thus, an exponential r e l a t i o n was e s t a b l i s h e d between t h e time necess a r y f o r a s p e c i f i e d value of s t r a i n zrel t o be reached and t h e temperature

I n a d d i t i o n t o t h e a n a l y s i s of t o t a l r e l a x a t i o n s t r a i n based on t h e primary
curves erel-a, t h e minimum deformation r a t e s ( o r r a t e s c l o s e t o t h e minimum ones)
were determined.

It was found t h a t vmin and t h e i n i t i a l absolute r e l a x a t i o n

s t r e s s (kg/mm2) a r e r e l a t e d exponentially; t h i s r e l a t i o n i s s i m i l a r t o t h e one

f o r t h e creep process when o = const i n t h e course of each experiment.
A temperature a n a l y s i s of t h e minimum r a t e of r e l a x a t i o n deformation made
it p o s s i b l e t o e s t a b l i s h an exponential r e l a t i o n between vain, t, and t h e ac-

500
1000 1500 2000
d u r a t i o n of t e s t , h r
a

Fi,

d u r a t i o n of t e s t , h r
b
Figure 5. I n c r e a s e i n p l a s t i c deformation w i t h time a t
various r e l a x a t i o n temperatures (primary curves of relax'

a t i o n deformation):

1, 22.5 kg/mm2, 700';

2, 30 kg/mm2,

Thus, t h e analysxs of p l a s t i c r e l a x a t i o n deformation r e i n f o r c e s s t i l l more

t h e i d e a of an unquestionable r e l a t i o n between t h i s process and t h e p r o c e s s of
creep, and b r i n g s us c l o s e r t o a p o s s i b l e r e c i p r o c a l e v a l u a t i o n of both
processes.
Conclusion
Testing of a l l o y AT3 f o r r e l a x a t i o n i n t h e temperature range of 350-650'
makes it p o s s i b l e t o regard t h i s a l l o y a s being r e l a x a t i o n - r e s i s t a n t i n t h e
A drop i n s t r e s s t o 80-60 percent of t h e i n i t i a l
temperature range up t o 400'.
s t r e s s can be expected a f t e r a long period of time measured i n hundreds of
thousands of hours (see f i g . 4).
The d u r a t i o n of such r e l a x a t i o n i s determined not o n l y by t h e temperature,
but a l s o by t h e value of t h e i n i t i a l s t r e s s : t h e h i g h e r o
t h e more r a p i d t h e
0'
r e l a x a t i o n process, although t h e a b s o l u t e value of t h e remaining stress may be
even higher. Technological tempering t o r e l i e v e undesirable i n t e r n a l s t r e s s e s
I n s e l e c t i n g t h e t e m p e r a t u ~and
i s advisable a t temperatures of 600-650'.
d u r a t i o n of tempering of a c t u a l a r t i c l e s , it should be kept i n mind t h a t volume
s t r e s s e s a r e r e l i e v e d under somewhat more d r a s t i c conditions t h a n t h o s e which
we s t u d i e d and which involved a p l a n a r s t r e s s condition of t h e r i n g specimens.
The method which we used f o r s e l e c t i n g i n i t i a l s t r e s s e s amounting t o some
f r a c t i o n of t h e y i e l d s t r e n g t h a t each t e s t i n g temperature i s q u i t e e f f i c i e n t .
It enabled u s t o o b t a i n comparatively e x t e n s i v e d a t a f o r t h e minimum q u a n t i t y
of t e s t e d specimens and t o e s t a b l i s h a s e r i e s of new r e l a t i o n s h i p s i n t h e
process of r e l a x a t i o n i n a l l o y AT3 which w i l l undoubtedly prove v a l i d f o r o t h e r
metals a s well. The f i r s t checks of t h i s method on p e a r l i t i c s t e e l have confirmed t h i s assumption.
REFEIiENCES
1. Allsop, R. T.

2.

A i r c r a f t Production, Vol. 20, No, 1, 1958.

Oding, I. A. Trudy TsNIITMASh (proceedings of t h e C e n t r a l S c i e n t i f i c

Research I n s t i t u t e of Technology and ~ a c h i n e r y ) ,Bk. 23, Mashgiz, 1949.

CREEP OF ALLOYS OF TI33 QUATERNARY SYSTEM Ti-Zr-Al-Sn AT 750'

I. I. Kornilov, T. T. Nartova and M. M. Savellyeva

M e t a l l i c compounds of t i t a n i u m and a l l o y s based on them a r e of g r e a t

importance f o r t h e development of new h e a t - r e s i s t a n t a l l o y s (refs. 1-3). O f
t h e various m e t a l l i c compounds of titanium, t h o s e w i t h aluminum and t i n as
w e l l as s o l i d s o l u t i o n s based on them a r e of considerable i n t e r e s t a s s u b j e c t s
of i n v e s t i g a t i o n s .
The p r e s e n t work i s devoted t o a study of t h e creep of a l l o y s of t h e
quaternary system Ti-Zr-Al-Sn along t h e s e c t i o n extending from pure zirconium
t o a l l o y compositions corresponding t o t h e q u a s i - t e r n a r y system T i A1-Zr-Ti Sn

( f i g . 1).
The a l l o y s were prepared by a r c melting i n a furnace w i t h a nonconsumable
tungsten e l e c t r o d e i n an argon atmosphere. Titanium sponge TGOO w i t h an u l -

timate s t r e n g t h of 36 kg/mrn 2 i o d i d e zirconium of 99.9 p e r c e n t p u r i t y , aluminum

AVO00 and t i n of 99.9 p e r c e n t p u r i t y were used i n t h e p r e p a r a t i o n of t h e a l l o y s .
The a l l o y s were annealed f o r 30 minutes a t 8500.
To determine t h e creep r e g i s t a n c e a s a f u n c t i o n of t h e composition, phase
s t r u c t u r e and temperature, t h e a l l o y s were t e s t e d by t h e c e n t r i m g a l bending
method. On t h e b a s i s of t h e d a t a obtained, p l o t s were made of t h e creep curves
TL

Zr

AL
Sn

Figure 1. Section T i Al-Zr-Ti Sn of

3
3
quaternary system Ti-Zr-Al-Sn.

and diagrams of t h e composition versus t h e time necessary t o reach a given bending d e f l e c t i o n f o r t h e a l l o y s s t u d i e d , which comprise t h e q u a s i - t e r n a r y system
T i Al-Zr-Ti Sn.
3
3
Data on t h e creep of a l l o y s i n t h e t e r n a r y system Ti-Zr-Sn along t h e sect i o n T i Sn-Zr a r e c i t e d i n reference 5.

The high-temperature s t r e n g t h of a l l o y s of t h e t e r n a r y system Ti-Al-Sn

along t h e seckion passing through t h e compositions of t h e i n t e r m e t a l l i c compounds T i Al and T i Sn was studied a t 700-750 and a s t r e s s of 15-29 kg/mm2
3
3
with a t o t a l t e s t i n g time 'of 400 h r s ( r e f .

4).

We studied t h e creep r e s i s t a n c e of t h e a l l o y s of t h e t e r n a r y system

Ti-Al-Zr along t h e s e c t i o n T i Al-Zr a t 750'
3

and a s t r e s s of

15 kg/mm2.

The

t e s t l a s t e d 1,000 h r s .
The creep curves of a l l o y s of t h e s e c t i o n T i Al-Zr ( f i g . 2) show t h a t small
3
a d d i t i o n s of zirconium (1-5 p e r c e n t ) t o t h e compound T i Al have no a p p r e c i a b l e
3
e f f e c t on t h e h e a t - r e s i s t a n c e p r o p e r t i e s of t h i s compound. Alloys from t h e
region of zirconium concentration up t o 5 p e r c e n t r e t a i n a high degree of h e a t
r e s i s t a n c e , and ' a f t e r 1,000 h r s of t e s t i n g a t 750, t h e bending d e f l e c t i o n of
t h e specimens i s 10-12 mm. A s t h e zirconium content r i s e s f u r t h e r , t h e creep
r a t e of t h e a l l o y i n c r e a s e s . Alloys containing over 20 p e r c e n t Zr a r e not
o x i d a t i o n - r e s i s t a n t a t t h e t e s t i n g temperature of 750' and a r e t h e r e f o r e of no
interest.
On t h e b a s i s of t h e creep curves of a l l o y s of t h e s e c t i o n T i Al-Zr, a
3
diagram of t h e composition versus t h e time necessary t o reach bending d e f l e c t i o n s of 3 and 5 mm was p l o t t e d ( f i g . 3 ) . As i s evident from t h e f i g u r e , a l l o y s
containing 2-5 p e r c e n t Z r a r e t h e most h e a t - r e s i s t a n t . As t h e zirconium content
i n c r e a s e s f u r t h e r , t h e high- temperature s t r e n g t h of t h e a l l o y s decreases, which
may be due t o a f a s t e r drop i n t h e temperature of t h e polymorphic transformation.
L i t e r a t u r e d a t a ( r e f s . 4 and 5) and r e s u l t s of a study of t h e hightemperature s t r e n g t h of a l l o y s along t h e s e c t i o n T i Al-Zr have l e d t o t h e assump3
t i o n t h a t t h e most h e a t - r e s i s t a n t a l l o y s of t h e quaternary system Ti-Zr-Al-Sn
along t h e s e c t i o n T i Al-Zr-Ti Sn should be expected i n t h e region of composi3
3
t i o n s adjacent t o t h e s i d e of t h e s e c t i o n T i Al-Ti Sn.
3
3
I n t h i s connection, a study was made of t h e high-temperature s t r e n g t h of
a l l o y s of t h e q u a s i - t e r n a r y system T i Al-Zr-Ti Sn along two c r o s s s e c t i o n s

.-u

d u r a t i o n o f deformation, h r
Bending d e f l e c t i o n v e r s u s d u r a t i o n o f deformation

Figure 2.

of a l l o y s o f t h e s e c t i o n T i Al-Zr a t 750 and o =

1, T i Al; 2, T i Al

4, T i3Al

t-

15 kg/mm2:

1 p e r c e n t Zr; 3, T i Al t- 2 p e r c e n t Z r ;

5 p e r c e n t Zr; 5, T i Al
3

8 p e r c e n t Zr; 6, T i Al
3

20 p e r c e n t

Z r , w t percent

Figure 3. Time r e q u i r e d t o reach a g i v e n bending

d e f l e c t i o n v e r s u s zirconium c o n t e n t of a l l o y s o f
t h e s e c t i o n ' T i iU-Zr a t 750'

and o =

15 kg/mm2.

p a r a l l e l t o t h e s i d e of T i Al-Ti Sn a t a c o n s t a n t zirconium c o n t e n t of 1 and

p e r c e n t . The t e s t w a s c a r r i e d o u t a t 750'
t i o n of t h e t e s t w a s 500 h r s .

and a s t r e s s of

15 kg/mm2.

The dura-

L e t u s examine t h e "composition--high-temperature s t r e n g t h " diagram o f

a l l o y s o f t h e c r o s s s e c t i o n s p a r a l l e l t o t h e s i d e of T i Al-Ti Sn w i t h a c o n s t a n t

zirconium c o n t e n t of 1 and

5 p e r c e n t ( f i g . 4).

w t percent
Figure 4. Time required t o reach a given bending
d e f l e c t i o n versus composition of a l l o y s of t h e system T i Al-Zr-Ti Sn w i t h a c o n s t a n t zirconium con3
3
t e n t of 1 and 5 percent a t 750' and o = 15 kg/mm2:
1 and 2, 5 percent Zr; 3 and 4, 1 p e r c e n t Zr.
The curves r e p r e s e n t i n g t h e t i m e necessary t o reach a given bending d e f l e c t i o n versus a l l o y composition w i t h a constant content of 1 and 5 p e r c e n t Z r a r e
analogous t o t h e corresponding curves of a l l o y s of t h e s e c t i o n T i Al-Ti Sn ( r e f .
3
3

4 ) , t h e high-temperature s t r e n g t h of a l l o y s w i t h
higher t h a n t h a t of a l l o y s w i t h 1 percent Z r .

5 percent

Zr being somewhat

The broad maximum of high-temperature s t r e n g t h on t h e diagram covers a

region of a l l o y compositions containing 40-60 percent T i Sn and 60-40 p e r c e n t
3
Ti3Al.
The time necessary t o reach a bending d e f l e c t i o n of 8 mm under t e s t i n g
conditions of 750' and a s t r e s s of 15 kg/mm 2 f o r a l l o y s of t h e s e c t i o n s w i t h 1
and 5 percent Z r i n t h i s region of compositions amounts t o 100-200 h r s ; a bending d e f l e c t i o n of 10 mm i s not reached i n a l l o y s w i t h 5 p e r c e n t Z r a f t e r 500
h r s of t e s t i n g .
An a l l o y of optimum composition based on a s o l i d s o l u t i o n of t h e compound
Ti3Al with zirconium and t i n was chosen from t h e i n v e s t i g a t e d quaternary a l l o y s

of t h e q u a s i - t e r n a r y system T i Al-Zr-Ti Sn, t a k i n g i n t o account t h e p l a s t i c i t y

and t e c h n o l o g i c a l p r o p e r t i e s . This a l l o y was t h e base f o r a d d i t i o n a l a l l o y i n g

w i t h vanadium, niobium, molybdenum f o r t h e purpose of i n c r e a s i n g t h e technologi c a l plasticity.

We i l l u s t r a t e t h e creep curves based on bending a t 750' a f t e r t e s t i n g f o r

1,000 h r s t h e quaternary a l l o y based on t h e compound T i Al w i t h zirconium and

t i n and a l s o a l l o y s containing vanadium and niobium ( f i g . 5 ) . The creep curves

w i t h 0.5 and 1 p e r c e n t Mo a r e n o t i l l u s t r a t e d , s i n c e t h e y a r e t h e same a s t h e
curves with 1.5 and 2 p e r c e n t Nb.
A comparison of t h e r e s u l t s obtained shows t h a t vanadium, niobium, and
molybdenum r a i s e t h e high-temperature r e s i s t a n c e of t h e quaternary s o l i d solut i o n based on t h e compound T i Al, and t h a t molybdenum and niobium do s o t o a

much g r e a t e r e x t e n t t h a n vanadium. This i s explained by t h e f a c t t h a t niobium

and molybdenum d i f f e r more from t i t a n i u m i n t h e i r m e t a l l i c and chemical propert i e s than does vanadium.
The curves r e p r e s e n t i n g t h e time necessary t o reach a given bending def l e c t i o n of t h e a l l o y s versus t h e content of vanadium and niobium ( f i g . 6 )
i n d i c a t e t h a t a d d i t i o n s of up t o 0.5 p e r c e n t V t o t h e quaternary a l l o y r a i s e i t s
high-temperature s t r e n g t h . This a l l o y i s l o c a t e d i n t h e single-phase region of
t h e s o l i d s o l u t i o n based on t h e compound T i Al. I n t h e a l l o y s w i t h 1 and 1.3

p e r c e n t V, t h e r e i s observed a s l i g h t decrease i n high-temperature s t r e n g t h a s

a r e s u l t of t h e appearance of t h e two-phase a + B s t r u c t u r e .
The e f f e c t of niobium on t h e a l l o y based on t h e s o l i d s o l u t i o n of t h e compound T i Al w i t h zirconium and t i n i s analogous t o t h e e f f e c t of vanadium.

Figure 5. Bending d e f l e c t i o n versus r e l a t i o n

of deformation of T i Al-base alloys, containing

vanadium and niobium a t 750'

I

and o = 15 kg/m2.

- TlsAl + Zr 1- Sn; 2 - TIaAl -I-Zr + Sn + 0.5% V; 3 - TI,Al + Zr +

+ i % V; 4 - Ti, A1 + Zr 4- Sn + 2% V; 6 - TiaAl+ Zr + Sn + i %

-I- Sn
Nb;

- TlaAl + Zr + Sn + 1.5% Nb; 7 - Ti,Al + Zr + Sn + 2%

8 - TLA1 + Zr + Sn + 3% Nb

Nb;

k 7//0

cd Ej'Efffl
0

$"O

5oo

k 4-r

uoa g

408

.rl

g %a, 30fl

.rl

3c
a, a, ZOO

k a
a, ho
!
700

.A

-5

-I=

a,

2,s 3
w t percent
Figure 6. Time required t o reach a bending
d e f l e c t i o n of 8 mm versus composition of
T i Al-base a l l o y s containing vanadium and
P

45

4'5 2
V; NB,

niobium, a t 750 and o. =

15 kg/mm2.

Within t h e l i m i t s of i t s s o l u b i l i t y i n t h e compound T i Al (up t o 2.0 p e r c e n t ) ,

niobium g r a d u a l l y i n c r e a s e s i t s high-temperature s t r e n g t h . The lowest s t r e n g t h

i s displayed by t h e a l l o y w i t h 3 p e r c e n t Nb w i t h a two-phase a + B s t r u c t u r e .
A decrease i n t h e s t r e n g t h of t h e a l l o y s w i t h molybdenum i s observed a t a cont e n t a s low a s -1 p e r c e n t Mo, which is due t o t h e appearance of t h e @ phase i n
t h e s t r u c t u r e of t h e a l l o y s .
Such a c h a r a c t e r of t h e influence of vanadium, niobium, and molybdenum on
t h e change i n t h e high-temperature s t r e n g t h i n t h e s o l i d s o l u t i o n s of t h e compound T i Al corresponds t o t h e r e g u l a r i t i e s manifested by t h e i n f l u e n c e of t h e s e

elements on t h e high-temperature s t r e n g t h of titanium, a s was e s t a b l i s h e d e a r l i e r

i n references 6 and 7.
On t h e b a s i s of d a t a of m i c r o s t r u c t u r a l a n a l y s i s and a study of t h e hightemperature s t r e n g t h , it was shown t h a t a l l o y i n g elements (vanadium, niobium,
molybdenum) raise t h e high-temperature s t r e n g t h of a l l o y s based on t h e compound
Ti3A1 w i t h i n t h e l i m i t s of t h e i r s o l u b i l i t y i n t h i s i n t e r m e t a l l i c compound.
Thus, t h e above study makes it p o s s i b l e t o s e l e c t optimum compositions of
h e a t - r e s i s t a n t a l l o y s on t h e b a s i s of t h e i n v e s t i g a t e d system f o r working temp e r a t u r e s of 700-750

Bochvar, A. A.

Physical Metallurgy ( ~ e t a l l o v e d e n i y e ) Metallurgizdat, 1956.

Osipov, K. A. Problems of t h e High Temperature Strength of Metals and

Alloys (voprosy t e o r i i zharoprochnosti metallov i splavov). Izd-vo AN
SSSR, 1961.
Kornilov, I. I. Physicochemical P r i n c i p l e s of t h e High-Temperature Strength
of Alloys (~iziko-khimicheskiyeosnovy zharoprochnosti splavov). Izd-vo
AN SSSR, 1961.

---

Metallovedeniye i temicheskaya obrabotka metallov, No. 2, p.

Glazova, V. V. and Kurnakov, N. N.

Toplivo, No. 6, p. 193, 1962.

7, 1963.

Izv. AN SSSR, OTN, Metallurgiya i

Kornilov, I. I., Pylayeva, Ye. N, and Volkova, M. A. Coll. Titanium and I t s

Alloys itan an i yego splavy). Izd-vo AN SSSR, No. 7, p. 89, 1962.
Kornilov, I. I. and Vlasov, V. S.
Toplivo, No. 4, p. 31, 1958.

Izv. AN SSSR, OTN, Metallurgiya F

STUDY OF TAF, MECWCAL PROPERTIES OF TITANIUM ALLOYS

AT3, AT&, AT^ AND AT8 I N Rl3LATION TO TEEE TESTING TEMPERATURE

V. S. Mikheyev

Alloys AT3, AT&, AT^ and AT^ were developed on t h e b a s i s of t h e d a t a obt a i n e d from a study of phase diagrams of a p a r t of t h e six-component system
Ti-Al-Cr-Fe-Si-B ( r e f . 1) and diagrams of t h e mechanical and p h y s i c a l p r o p e r t i e s
of t h e a l l o y s ( r e f . 2 ) . The b a s i c p r o p e r t i e s of t h e a l l o y s a r e given i n r e f erence 3. Alloys AT contain d i f f e r e n t amounts of aluminum: 3 p e r c e n t ( a l l o y
AT^), 4.5 p e r c e n t ( a l l o y AT^), 6 p e r c e n t ( a l l o y AT^) and 7.5 percent ( a l l o y
AT^). The composition of each a l l o y includes chromium, i r o n , s i l i c o n and boron.
The t o t a l amount of t h e s e elements i s 1-1.6 percent. Boron i s introduced i n t o
C e r t i f i c a t e s have been i s s u e d f o r
t h e a l l o y s i n t h e amount of 0 . 0 1 p e r c e n t .
a l l o y s AT3, AT& and AT^.
The p r e s e n t work i s devoted t o a study of t h e mechanical p r o p e r t i e s of
i n d u s t r i a l melts of a l l o y s AT a t a t e s t i n g temperature from 20 t o 800-1000~.
Rods measuring 14 x 1 4 mm prepared by f o r g i n g were annealed f o r 30 min a t
730' and cooled i n a i r . Standard specimens 5 mm i n diameter and 25 mm long
were prepared from t h e s e rods by cold working.
The mechanical p r o p e r t i e s of each a l l o y were studied on 2-3 p a r a l l e l specimens of 4-5 melts.
The content of a l l o y i n g elements (chromium, i r o n , s i l i c o n ) of t h e s e a l l o y s
meets t h e c e r t i f i c a t e d a t a ; i n a l l o y s AT& ( a l l o y 1) and AT^ ( a l l o y 1) t h e r e i s
a h i g h e r sum of chromium, i r o n , and s i l i c o n (1.81 and 1.98 p e r c e n t r e s p e c t i v e l y ;
see table).
Alloys of t h e optimum composition a r e nonequilibrium a s o l i d s o l u t i o n s w i t h
a s l i g h t content of t h e f3 phase. Results of an i n v e s t i g a t i o n of t h e mechanical
p r o p e r t i e s of t h e a l l o y s a t temperatures up t o 800-1000~a r e shown i n t h e f i g u r e .
The l a t t e r a l s o i l l u s t r a t e s curves representing t h e change i n t h e mechanical.
c h a r a c t e r i s t i c s of iodide and magnesiothermic titanium. I n h i g h l y d u c t i l e iodide
titanium, a s t h e t e s t i n g temperature r i s e s t o 800, t h e u l t i m a t e s t r e n g t h dec r e a s e s approximately from 27 t o 1.5 kg/rnm2. The u l t i m a t e s t r e n g t h of t i t a n i u m
d e c l i n e s more a b r u p t l y a s t h e t e s t i n g temperature i s r a i s e d t o 200, and from
500 t o 800';
it changes i n s i g n i f i c a n t l y i n t h e temperature range from 200-500.
I n magnesiothermic t i t a n i u m TG1, i n which the content of i m p u r i t i e s (0.06-0.10
p e r c e n t Fe; 0.02-0.03 percent N i ; 0.03-0.05 percent Mg : 0.53-0.05 p e r c e n t S i ;

CHESIICAL COMPOSITION OF TITANIUM ALLOYS AT (IN w t PERCFNT).

Alloying elements

Alloy AT3
I
2
3
4
5

2.8
3.1
2.7
2.7
3.2

0.89
0.71
0.60
0.76
0.84

0.32
0.40
0.35
0.30
0.34

0.45
0.34
0.30
0.47
0.40

1.67
1.45
1.25
1.53
1.59

0.0023

0.004

0.01
0.01
0.01
0.01
0.01

0.0053
0.0053

0.01
0.01
0.02
0,Ol
0.01

0.030
0.027

0,033
0.021

0.01
0.01
0.01
0.01
0.01

0,043
0.067

Alloy AT4

Alloy AT6
I
4
5

5.13
5.13
5.90
5.75
5.60

1
2
3
4
5

6.81
6.49
6.20
6.50
6.3

'

0,86
0.67
0.83
0.64
0.52

0.32
0.23
0.27
0.32
0.33

0.45'
0.45
0.25
0.38
0.30

0.98
0,53
0.67
0.73
0.51

0.40
0.30
0.37
0.40
0.22

0.59
0.35
0.36
0.39
0.34

1.64
1.35
1.35
1.35
1.16

Alloy AT8

0.04-0.06

p e r c e n t C;

0.02-0.06

1.98
1.19
1.41
1.53
1.08

percent N; 0.005-0.008 p e r c e n t H ~ 0.15-0.25

;

p e r c e n t 02) and t h a t of o t h e r elements i s 5-7 times g r e a t e r t h a n t h e i r content

i n i o d i d e titanium, t h e u l t i m a t e s t r e n g t h , equal t o 50-60 kg/mm2, i s almost
twice a s high. The elongation of magnesiothermic t i t a n i u m i s 25-30 p e r c e n t ; t h e
contract-son of t h e c r o s s s e c t i o n i s 50-55 percent; t h e impact s t r e n g t h i s 7-10
kgm/cm2. The u l t i m a t e s t r e n g t h of t e c h n i c a l t i t a n i u m changes between 20 and
950' along a curve which d e c l i n e s a b r u p t l y toward. t h e abscissa; a t 8000, t h e
ultimarte s t r e n g t h of t i t a n i u m i s approximately equal t o 2.5 kg/mm2, and a t 9500,
t o about 1.5 kg/mm2.

A s can be seen from t h e diagram, t h e curve of t h e u l t i m a t e

s t r e n g t h of t e c h n i c a l t i t a n i u m d e c l i n e s s h a r p l y w i t h r i s i n g t e s t i n g temperature,
and approaches almost continuously t h e curve of t h e u l t i m a t e s t r e n g t h of i o d i d e
titanium.
The elements aluminum, chromium, i r o n , s i l i c o n and boron introduced i n t o
t i t a n i u m a l l o y s AT w i t h i n t h e above-indicated l i m i t s r a i s e t h e u l t i m a t e s t r e n g t h
of t h e a l l o y s considerably a s compared t o t h e u l t i m a t e s t r e n g t h of i o d i d e titanium, and decrease t h e i r d u c t i l e p r o p e r t i e s . A t room temperature, t h e u l t i -

A s t h e t e s t i n g temperature
mate s t r e n g t h of a l l o y AT3 i s equal t o 85-87 kg/mrn2.
r i s e s t o 200, t h e u l t i m a t e s t r e n g t h of t h e a l l o y d e c r e a s e s t o approximately
b

6 0 ~ 6 5kg/mm2, and i n t h e temperature range of 300-'j00~, changes from 57.1-63.2

t o 53-55.6 kg/rnrn2.
A s i s e v i d e n t from t h e course of t h e curve, when t h e
t e s t i n g temperature i s subsequently r a i s e d t o 700-8000, t h e u l t i m a t e s t r e n g t h
A s can be seen from t h e diagram,
of t h e a l l o y decreases s h a r p l y t o 14-8 kg/mm2.
a t t e s t i n g temperatures up t o 8000, t h e curve of t h e u l t i m a t e s t r e n g t h d u p l i c a t e s t h e course of t h e curve of i o d i d e t i t a n i u m . The u l t i m a t e s t r e n g t h of a l l o y s AT4, AT^ and AT^ changes i n s i m i l a r fashion. The diagram shows t h a t a s t h e
a s o l i d s o l u t i o n becomes i n c r e a s i n g l y s a t u r a t e d w i t h aluminum, t h e u l t i m a t e
s t r e n g t h of t h e a l l o y s i n c r e a s e s a t room temperature approximately from 85
kg/mm2 f o r a l l o y AT3 t o 93.5-102.9 kg/mm2 f o r a l l o y
f o r a l l o y AT^
of 20-9000 i n
mate s t r e n g t h
content. For

N4, t o 106-115.3 kg/mm2

and t o 116-124.5 kg/rnm2 f o r a l l o y m8. A t t e s t i n g temperatures

each successive ' a l l o y w i t h a higher aluminum content, t h e u l t i i s h i g h e r than i n t h e preceding a l l o y w i t h a lower aluminum
example, a t 500' t h e u l t i m a t e s t r e n g t h has t h e following values:

53-55.6 kg/mrn2 f o r a l l o y PIP3, up t o 60 kg/mm2 f o r a l l o y AT^, up t o 70 kg/mm2

f o r a l l o y AT^ and up t o 8 2 kg/mm2 f o r a l l o y AT^. A t temperatures above 450550, t h e u l t i m a t e s t r e n g t h of a l l t h e a l l o y s decreases a b r u p t l y . A t 800 i n
a l l o y s AT3, AT4, AT^ and m8, t h e u l t i m a t e s t r e n g t h i s r e s p e c t i v e l y e q u a l t o
\

10-14, 21.5, 30.7 and 33 kg/mm2; a t 900, t h e u l t i m a t e s t r e n g t h of a l l o y AT^

i s equal t o about 30 kg/mm2, and t h a t of a l l o y s AT^ and
lower than t h a t of a l l o y AT^.

AT^ i s

2 and 1.5 times

The dependence of t h e d u c t i l e p r o p e r t i e s of t i t a n i u m and i t s a l l o y s on t h e

t e s t i n g temperature i s very i n t e r e s t i n g . The diagram shows t h a t t h e e l o n g a t i o n
p e r u n i t l e n g t h i n c r e a s e s a t f i r s t a s t h e t e s t i n g temperature r i s e s t o 300,
t h e n s h a r p l y decreases i n t h e temperature range of 400-500~, then i n c r e a s e s
again a s t h e t e s t i n g temperature rises f u r t h e r . Beginning a t about 550, t h e
e l o n g a t i o n p e r u n i t l e n g t h oi magnesiothermic t i t a n i u m i s g r e a t e r than t h a t of
iodide titanium.

Mechanical p r o p e r t i e s versus t e s t i n g temperature:

1, iodide t i t a n i u m ; 2, magnesiothermic titanium;
3, a l l o y AT3; 4, a l l o y AT&; 5 , a l l o y AT^;
6, a l l o y AT^.
The e l o n g a t i o n p e r u n i t l e n g t h of a l l o y s AT i s considerably l e s s than t h e
e l o n g a t i o n of t i t a n i u m and changes between 20 and 400' along curves having a
s l i g h t trough i n t h e d i r e c t i o n of t h e a b s c i s s a . Above a temperature of about
4000, t h e e l o n g a t i o n curves of t h e a l l o y s , a f t e r passing through t h e minimum

p o i n t , rise s l i g h t l y a t f i r s t , t h e n more a b r u p t l y a t 500; a t t h e s e temperatures,

t h e a l l o y s acquire a high d u c t i l i t y .
The reduction of t h e c r o s s s e c t i o n a l a r e a of t i t a n i u m specimens a t temperat u r e s approximately up t o 450' changes along a r i s i n g curve w i t h a minimum a t
4 0 0 ~ . A t about 450, t h e curve changes d i r e c t i o n and as t h e t e s t i n g temperat u r e i s r a i s e d f u r t h e r , r i s e s s t i l l more s t e e p l y . A d e c l i n e i n d u c t i l e propert i e s , p a r t i c u l a r l y i n r e l a t i o n t o t h e elongation p e r u n i t l e n g t h of t i t a n i u m
from 300 t o 400 had been observed e a r l i e r by many i n v e s t i g a t o r s . However, t h e
cause of t h i s phenomenon has not y e t been e s t a b l i s h e d . It may be p o s t u l a t e d
t h a t t h e decrease i n t h e d u c t i l i t y of t i t a n i u m and a l s o t h a t of a l l o y s of t h e
system Ti-Al-Cr-Fe-Si-B i s p a r t i a l l y caused, i n a d d i t i o n t o o t h e r f a c t o r s , by
the i n f l u e n c e of hydrogen.
The dnfluence of aluminum on t h e d u c t i l i t y of t h e a l l o y s a t a given temp e r a t u r e can a l s o be followed on t h i s diagram. As t h e aluminum content of t h e
a s o l i d s o l u t i o n i n c r e a s e s , t h e d u c t i l i t y of t h e a l l o y s decreases ( s e e f i g u r e ) .
The t a b l e shows t h e change i n t h e content of t h e sum of chromium, i r o n ,
and s i l i c o n w i t h i n t h e l i m i t s of a given composition. A s t h e t o t a l content of
chromium, i r o n and s i l i c o n i n c r e a s e s , t h e u l t i m a t e s t r e n g t h of t h e a l l o y s i n c r e a s e s a s follows:

i n a l l o y AT3, from

t o 105 kg/mm2; i n a l l o y

75 t o 88 kg/mm2; i n a l l o y AT&, from 90

AT^, from 106 t o 115.3 kg/mm2; i n a l l o y AT8, t o 124

The d u c t i l e p r o p e r t i e s of t h e a l l o y s t h u s decrease: f o r i n s t a n c e , t h e
kg/mm2.
elongation decreases from 14-15.9 p e r c e n t i n a l l o y AT3 t o 8 p e r c e n t i n a l l o y
AT^ No. 1, i e a t t h e upper l i m i t , and t o 14.6 p e r c e n t i n a l l o y AT^, No. 2,
i . e . , a t t h e lower l i m i t .

. .,

Summary
1. Six-component a l l o y s of t h e system Ti-Al-Cr-Fe-Si-B of t h e optimum
compositions AT3, AT^, AT^, and AT^ b a s i c a l l y have t h e s t r u c t u r e of a n a s o l i d
s o l u t i o n w i t h a very small amount of t h e f3 phase; t h e y a= c h a r a c t e r i z e d by
high mechanical c h a r a c t e r i s t i c s a t room temperature and h i g h e r temperatures (up
t o 450- 600').

2. As t h e aluminum content of t h e six-component a l l o y s of t h e system TiAl-Cr-Fe-Si-B i n c r e a s e s from 3 t o 8 p e r c e n t , t h e t o t a l content of chromium,

i r o n , s i l i c o n , and boron being constant, t h e u l t i m a t e s t r e n g t h of t h e a l l o y s
increases. Thus, a l l o y AT3 h a s an u l t i m a t e s t r e n g t h of up t o 80 kg/mm*, and
a l l o y AT^, up t o 224 kg/mm2. The d u c t i l e c h a r a c t e r i s t i c s (elongation p e r u n i t
l e n g t h and t r a n s v e r s e c o n t r a c t i o n ) d e c l i n e .

3. A s t h e t e s t i n g temperature i s r a i s e d , t h e u l t i m a t e s t r e n g t h of t i t a n i u m
and t h a t of a l l o y s AT3, AT&, AT6 and m8 decreases, and does s o most r a p i d l y a t

a temperature above 450-500~. The elongation p e r u n i t l e n g t h and t r a n s v e r s e

c o n t r a c t i o n of t h e a l l o y s undergo l i t t l e change a s t h e temperature i s r a i s e d t o
approximately 450, b u t i n c r e a s e s h a r p l y a s t h e t e s t i n g temperature i s r a i s e d
further.

1. Kornilov, I. I., Mikheyev, V. S. and Chernova, T. S . Izv. AN SSSR, Om,

Metallurgiya, No. 3, P. 72, 1960.

I z v . AN SSSR, OTN, Metallurgiya i

2.

Mikheyev, V. S. and Chernova, T. S.

Toplivo, No. 5, p. 139, 1962.

3.

Kornilov, I. I., Mikheyev, V. S., Chernova, T. S. and Markovich, K. P.

Coll. Titanium and I t s Alloys i it an i yego splavy). Izd-vo AN SSSR,
NO. 7, p . 140, 1962.

STUDY OF THE COMPARATIVE FEAT RESISTANCE OF TITAlFIUM ALLOYS

SHEET AND ITS WELD JOINTS AT 450, 550, 650 and TOO0

I. I. Kornilov, 0 . N. Andreyev, V. M. Voshedchenko

and V. A. Kamanov

pp. 227-235 of o r i g i n a l document appears i n

J.P.R.S. T r a n s l a t i o n No. 28,176; TT:65-30080
pp. 11-23

BIGH-TEMPERATUEIF: STRENGTH OF ALLOYS OF THE QUATERNARY

SYSTEM Ti-Al-Mo-V

Ye. .?!I

Pylayeva and KO Chih-ming

The p r e s e n t a r t i c l e r e p o r t s on a study of t h e dependence of t h e hightemperature s t r e n g t h of a l l o y s of t h e systems Ti-A1-Mo and Ti-Al- (MO:V = 1:1)
on t h e i r composition and s t r u c t u r e . The p o s i t i o n of t h e s e systems i n t h e
tetrahedron of t h e quaternary system Ti-AL-Mo-V i s shown i n f i g u r e 1.
The method of long-time h o t hardness ( r e f . 1 ) and t h e c e n t r i f u g a l bendingt e s t method were used i n t h e study ( r e f . 2).
T e s t s f o r long-time hot hardness were c a r r i e d o u t on a V I M - 1 vacuum u n i t
( r e f . 1 3 ) a t a load of 1 kg and a deformation time of 1, 5, 1 0 and 20 min.
I n high-temperature s t r e n g t h t e s t s involving t h e c e n t r i f u g a l method, t h e

w a s v a r i e d from 550

No

Figure 1, Location of t h e systems Ti-Al-Mo

and T ~ - & - ( M o : v = 1 : l ) i n t h e tetrahedron of
t h e quaternary system Ti-AX-Mo-V.

Using t h e method proposed i n r e f e r e n c e 4, we c a l c u l a t e d t h e p l a s t i c deformation r a t e s vd from d a t a on t h e long-time h o t hardness of a l l o y s of t h e system

Ti-Al-Mo a t 700. The deformation r a t e , c a l c u l a t e d f o r t h e same s p e c i f i e d s i z e
of t h e i n d e n t a t i o n , corresponds t o conditions of p l a s t i c flow when t h e same
s p e c i f i c p r e s s u r e of t h e i n d e n t e r i s a c t i n g on t h e specimen. The r e l a t i v e hightemperature s t r e n g t h of t h e a l l o y s s t u d i e d can be evaluated from t h e values of
t h e deformation r a t e .
Let u s examine t h e curves r e p r e s e n t i n g t h e i n f l u e n c e of molybdenum concent r a t i o n on t h e logarithm of t h e deformation r a t e I n vd of t h e a l l o y s ( f i g 2)

. .

I n t h e b i n a r y a l l o y s of t h e system Ti-Mo ( f i g . 2, curve l ) , a d d i t i o n of up

t o 3 p e r c e n t Mo decreases t h e deformation r a t e somewhat, and as t h e molybdenum
content i n c r e a s e s t o 1 0 p e r c e n t , t h e e f f e c t of t h i s element i s almost unnoticeable.
I n t h e t e r n a r y a l l o y s w i t h 5, 15 and 20 p e r c e n t Al ( f i g . 2, curves 2, 3
and h ) , a s t h e molybdenum content i n c r e a s e s from zero t o 1 0 percent, t h e deformation r a t e of t h e a l l o y s decreases a t f i r s t (minimal values a r e reached a t a
molybdenum content of about 1 p e r c e n t ) , then a f t e r a c e r t a i n i n c r e a s e remains
p r a c t i c a l l y constant. This means t h a t t e r n a r y a l l o y s of t i t a n i u m w i t h 1 percent Mo containing r e s p e c t i v e l y 5, 15 and 20 p e r c e n t Al have a maximum hightemperature s t r e n g t h at 700' a s compared t o t h e r e s t of t h e a l l o y s .
These conclusions concerning t h e high-temperature s t r e n g t h of t e r n a r y
a l l o y s were confirmed by d a t a on bending t e s t s c a r r i e d o u t by t h e c e n t r i f u g a l
method. The "composition--high-temperature s t r e n g t h " diagrams of a l l o y s of t h e
system Ti-A1-Mo along s e c t i o n s w i t h 5 percent Al ( f i
3, curve 1 ) 1 0 p e r c e n t
Al ( f i g 3, curve 2 ) , 1 5 p e r c e n t Al ( f i g , 3, curve 3 and 20 p e r c e n t Al ( f i g .
3, curve 4) show t h a t t h e maxima on t h e curves r e p r e s e n t i n g t h e change i n hightemperature s t r e n g t h correspond t o a content of about 1 p e r c e n t Mo. This
corresponds t o t h e boundary of t h e t r a n s i t i o n from a s o l i d s o l u t i o n s t o t h e
region of a i- B phases on t h e phase diagram of t h e system Ti-Al-Mo.
From t h i s ,
one can conclude t h a t i n t h e i n v e s t i g a t e d p a r t of t h e system Ti-Al-Mo, t h e
maximum high-temperature s t r e n g t h a t 600-8000 i s displayed by those t e r n a r y titanium a l l o y s whose compositions are l o c a t e d i n t h e v i c i n i t y of t h e s o l u b i l i t y
l i m i t of molybdenum i n t h e a s o l i d s o l u t i o n .

f.

Let u s examine t h e dependence of t h e high-temperature s t r e n g t h of the a l l o y s

of t h e system Ti-Al-Mo along t h e s e c t i o n w i t h 5 percent Al on t h e molybdenum concentration (fig. 4).

Up t o 5 p e r c e n t Mo, t h e change i n t h e high-temperature s t r e n g t h i n t h e a l l o y s r e t a i n s t h e p a t t e r n e s t a b l i s h e d above, i . e . , as t h e molybden-m concentrat i o n r i s e s , t h e high-temperature s t r e n g t h i n c r e a s e s a t f i r s t w i t h i n t h e confines

of t h e a s o l i d s o l u t i o n and reaches a maximum n e a r t h e s a t u r a t i o n boundary a t a
content o f about 1 p e r c e n t Mo; when t h e a -t (3 region i s reached, t h e s t r e n g t h ,
a f t e r a s l i g h t decrease, remains p r a c t i c a l l y constant up t o 5 p e r c e n t Mo.

Mo, w t percent
Figure 2. Effect of molybdenum concentration on
1, binary a l l o y s
t h e values of I n vd a t 700':
of t h e system Ti-Mo; 2, t e r n a r y a l l o y with 5 percent Al; 3, t e r n a r y a l l o y with 1 0 percent A l ;
4, t e r n a r y a l l o y with 20 percent Al.

"

1 2 3 4 . 5

fro, w t percent
Figure 3. Time required t o reach a bending def l e c t i o n of 2 mm, versus molybdenum content f o r
a l l o y s of t h e system Ti-Al-Mo a t 600-8000 and
o = 1 5 kg/mm2:
1, s e c t i o n with 5 percent Al;
2, s e c t i o n with 1 0 percent Al; 3, s e c t i o n with
15 percent Al; 4, s e c t i o n with 20 percent Al.

Mo, w t percent
Figure 4. Time required t o reach a given bending
d e f l e c t i o n versus molybdenum content f o r a l l o y s of
t h e system Ti-Al-Mo w i t h 5 p e r c e n t Al a t 600-7000
and

CT

= 15 kg/rnm2.

A f u r t h e r i n c r e a s e i n molybdenum concentration causes a decrease i n hightemperature s t r e n g t h ; t h e s t r e n g t h curve, passing through a minimum a t -25
percent Mo, again rises s h a r p l y a s t h e composition of t h e a l l o y s approaches t h e
boundary between t h e f3 s o l i d s o l u t i o n and t h e a + f3 regions.

The a l l o y w i t h 5 percent Al and 35 p e r c e n t Mo, l o c a t e d n e a r t h e boundary

of t r a n s i t i o n from t h e p s o l i d s o l u t i o n t o t h e a + f3 region, s o f t e n s o n l y from
a temperature of 700'.
On t h e b a s i s of a systematic study of t h e experimental d a t a obtained from
the bending t e s t by t h e c e n t r i f u g a l method, we p l o t t e d t h e "composition--hightemperature strength'' diagram of a l l o y s of t h e system Ti-Al- (MO:V= 1:1) shown
i n f i g u r e 5.
The diagram i s divided Lnto a number of p o r t i o n s . These p o r t i o n s i n d i c a t e
t h e temperatures a t which a f t e r 100 h r s of bend-testing by t h e c e n t r i f u g a l method
a t a bending stress of 15 kg/mm2, t h e a l l o y s of t h e corresponding composition
reach a bending d e f l e c t i o n of 5 mm. From t h e i n d i c a t e d temperatures, one can
evaluate t h e r e l a t i v e high-temperature s t r e n g t h of a l l o y s of t h e system Ti-A1(MO:V = 1:l). The phase regions of t h e system a t 6000 a r e i n d i c a t e d by broken
l i n e s on t h e diagram.
The diagram shows t h a t a s t h e composition and s t r u c t u r e of t h e a l l o y s change,
t h e t e s t i n g temperature changes from 550 f o r a l l o y s adjacent t o t h e s i d e of Ti(MO:V = 1:l) t o 800' f o r a l l o y s from t h e region of t h e a s o l i d s o l u t i o n w i t h a
high aluminum content. For a l l o y s from t h e region of t h e y s o l i d s o l u t i o n based
on t h e compound T i m , t h e t e s t i n g temperature i s above 800'.
From t h e t e s t s performed it follows t h a t i n t h e system Ti-Al-(MO:V = 1:l)
t h e dependence of t h e high-temperature s t r e n g t h on t h e composition and s t r u c t u r e
of t h e a l l o y s obeys t h e r e l a t i o n s h i p s e s t a b l i s h e d f o r a l l o y s of t h e system
Ti-Al-Mo, i.e . , a maximum high-temperature s t r e n g t h c h a r a c t e r i z e s quaternary

titanium alloys whose compositions are located in the vicinity of the boundary
of transition from a solid solutions into the region of a + f3 phases.
Among the investigated alloys, those having the highest strength were from
the region of the quaternary y solid solutions based on the compound TiAl.
Thus, according to the physicochemical theory of high-temperature strength
(ref. 5), the diverse nature of the chemical interaction of the components in
the quaternary system Ti-Al-Mo-V permits the formulation of the following relationships in the change of the high-temperature strength of alloys of this
system.
As shown by the data obtained in the determination of the long-time hot
hardness at 700, in the binary system Ti-Mo the change in high-temperature
strength at molybdenum concentrations from zero to 10 percent corresponds to
the third type of 'lcomposition--high-temperature
strength" diagrams. Since
the concentration of the binary a solid solution in the system Ti-Mo is very
low (less than 0.8 percent) and is independent of temperature, a-Ti is practically devoid of the solution mechanism of hardening.
The high-temperature strength of the alloys depends primarily on the amount
of the f3 phase hardened by molybdenum and on the nature of the interaction at
the interface of the a and f3 phases.
In the systems Ti-Al-Mo and Ti-Al-(MO:V = 1:l) along the sections with a
constant aluminum content of 5, 10, 15 and 20 percent, the dependence of the
high-temperature strength of the alloys on the molybdenum concentration or the

Figure 5. Region of alloys of the system

~ i - ~(MO:V
l - = 1:l) with the same testing
temperature required to reach a bending deflection of

5 rnrn in

100 hrs at a =

15 kg/mm2.

sum of molybdenum and vanadium corresponds to the second type of "composition-high-temperature strengthttdiagrams. The introduction of aluminum into alloys
of these systems leads to an increase in the solubility of molybdenum and vanadium in the ternary and quaternary m solid solutions. Alloys hardened by
aluminum as a result of the formation of solid solutions and compounds are
additionally hardened by the solution mechanism and possibly dispersion mechanisms of hardening. The most heat-resistant titanium alloys at 600-800' are
those whose compositions are located near the boundary of the transition from
a solid solutions (ternary and quaternary) to the region of a + f3 phases.
Of the alloys which we studied, the most heat-resistant ones are those
with y solid solutions based on the compound TiAl. The great high-temperature
strength of the compound TiAl is due to the great stability of its chemical
bonding. However, alloys of this series are not deformed and may find applications as heat-resistant casting alloys.
rnFEFBNCES
1. Bochvar, A. A. Izv. AN SSSR, OTN, No. 10, p. 1369,
2. Kornilov, I. I. Zav. Lab., Vol. 15, NO. 1, p.

1947.

76, 1949.

3. Lozinskiy, M. G. High-Temperature Metallography (~ysokotemperaturnaya

metallografiya). Mashgiz, 1956.

4. Osipov, K. A, and T tien T$-cht eng . Izv. AN SSSR, OTN, Metallurgiya i

Toplivo, No. 4, p. 77, 1959.

5. Kornilov, I. I. Physicochemical Principles of the High-Temperature

Strength of Alloys (~iziko-khimicheskiyeosnovy zharoprochnosti splavov)
Izd-vo AN SSSR, 1961.

REAT RFISISTANCE OF TITANIUM ALLOY AT-8 I N

SHORT-TIME TESTS

N. M. P u l l t s i n , M. P. Rumanko and
V. B. Pokrovskaya

pp. 240-242 of o r i g i n a l document appears i n

J.P.R. S. Translation No. 28,176; TT: 65-30080
pp. 24-28

THE%

STABILITY OF ALLOYS AT3 AT TEBPERATURES OF 330

AND 400

K. P. Markovich and V. S. Mikheyev

I n connection w i t h t h e p o s s i b i l i t y of using a l l o y AT3 i n u n i t s o p e r a t i n g

f o r extended p e r i o d s of time a t temperatures of 350-400, a study of t h e s t a b i l i t y of t h i s a l l o y under operating conditions seemed of g r e a t i n t e r e s t .
Two i n d u s t r i a l melts of a l l o y AT3 w i t h t h e same content of aluminum and
boron (within t h e l i m i t s of t h e i r s o l u b i l i t y i n a - ~ i and
) d i f f e r e n t content of
) selected f o r the present int h e sum of a l l o y i n g elements C ( C ~ , Fe, ~ iwere
vestigation.
The chemical composition ( i n w t ~ e r c e n t )of t h e i n v e s t i g a t e d melts of a l l o y
AT3 was a s follows:
Alloy Ti
AT3-1 Base
At3-2 Base

A1

Cr

Fo

Si

2.7
2.8

0.60
0.79

0.30
0.44

0.36
0.30

0.01
0.01

I: (Cr, Be,

si)

1.26
1.53

Our e a r l i e r work on t h e determination of t h e s o l u b i l i t y of t h e sum of t h e

alloying elements C ( C ~ ,Fe, ~ ii n) t h e proportion of 1:l:1 i n a t e r n a r y a s o l i d
s o l u t i o n ( 3 p e r c e n t A l and 0.01 percent B ) showed t h a t t h e maximum s o l u b i l i t y
of t h e sum of t h e s e elements a t 500' i s equal t o about 0.75 percent ( r e f . 1) and
t h a t it i n c r e a s e s w i t h t h e temperature. Thus, it should be assumed t h a t t h e
compositions of a l l o y AT3 s e l e c t e d f o r t h e p r e s e n t i n v e s t i g a t i o n a r e l o c a t e d
near t h e l i m i t of t h e maximum s a t u r a t i o n a phase + excess phase i n a s t a t e c l o s e
t o equilibrium. Therefore, t h e i r phase composition i n t h e s t a t e of e q u i l i b r i u m
should correspond t o t h e s t r u c t u r e a phase + excess phase. It may be p o s t u l a t e d
t h a t embrittlement may t a k e p l a c e a s a r e s u l t of t h e p r e c i p i t a t i o n of t h e excess
phase when t h e a l l o y o p e r a t e s i n t h e i n d i c a t e d temperature range f o r a very long
time (up t o 20,000 h r s )
I n t h i s connection, a study of t h e aging of a l l o y AT3
was made a t temperatures of 350 and 400' f o r 10,000 h r s without s t r e s s and i n an
ordinary atmosphere.

The thermal s t a b i l i t y of t i t a n i u m a l l o y s of t h e AT s e r i e s was s t u d i e d by t h e

authors of reference 2 f o r various contents of aluminum and of t h e sum of t h e
a l l o y i n g elements besides i r o n and s i l i c o n f o r 100 h r s a t temperatures of 400,
450 and 500. The study e s t a b l i s h e d t h a t t h e t i t a n i u m a l l o y s AT3, AT&, AT^ and
AT^ t e s t e d under t h e s e l e c t e d conditions displayed a high thermal s t a b i l i t y .

The s t a b i l i t y of t i t a n i u m a l l o y s AT3, AT^ and AT^ was s t u d i e d a t 400 and

450O f o r 300-7,000 h r s ( r e f . 3 ) . The i n v e s t i g a t i o n showed t h a t a f t e r an aging
t e s t under t h e above-indicated conditions, t h e d u c t i l i t y of a l l o y AT3 decreases
during t h e i n i t i a l s t a g e of t h e aging and i s almost completely r e s t o r e d t o t h e
o r i g i n a l s t a t e a f t e r 3,000 h r s of aging.
I n an aging t e s t l a s t i n g 2,750 h r s i n a medium of s a t u r a t e d water vapor a t
100O without stress, a l l o y AT3 d i d not show any decrease i n d u c t i l i t y e i t h e r .
I n t h e p r e s e n t i n v e s t i g a t i o n , use was made of forged b a r s 1 4 x 1 4 mm i n
c r o s s s e c t i o n from two melts prepared by the vacuum method of double melting
under p l a n t c o n d i t i o n s . The following s t a r t i n g m a t e r i a l s were used t o prepare
t h e a l l o y s : t i t a n i u m sponge TGO w i t h an u l t i m a t e s t r e n g t h of 39-43 kg/mm2,
t e c h n i c a l s i l i c o n KR, chromium Khl, t e c h n i c a l i r o n , aluminum A l O O and a
chromium-boron master a l l o y (up t o 10 p e r c e n t B ) . The charge of t h e a l l o y
was c a l c u l a t e d t o c o n t a i n up t o 3 p e r c e n t Al and C ( C ~ Fe,
,
~ ia t) t h e i n t e r mediate and upper l i m i t .
Alloys AT3-1 and AT3-2 i n t h e forged s t a t e and a f t e r annealing had t h e
following mechanical c h a r a c t e r i s t i c s (determined by t h e standard method on
specimens prepared from forged b a r s 1 4 x 1 4 mm i n c r o s s s e c t i o n ) :

Alloy

A f t e r forging

After annealing f o r 30 min a t

850 and cooling i n a i r

The aging of a l l o y AT3 was studied on blanks taken from a forged b a r

The blanks were placed i n a heated f u r n a c e witho u t preliminary annealing. The mechanical p r o p e r t i e s and m i c r o s t r u c t u r e duri n g aging were s t u d i e d a f t e r holding times of 100, 500, 1,000, 2,000, 3,000,
5,000 and 10,000 h r s .

14 x 14 mm i n c r o s s s e c t i o n .

The e t c h i n g was c a r r i e d o u t i n a s p e c i a l s o l u t i o n ( 1 p t . EtF + 2 p t s .

H2N03 + 3 p t s . g l y c e r i n ) . I n o r d e r t o prevent a s t r o n g o x i d a t i o n of t h e
polished s e c t i o n s , t h e l a t t e r were washed i n a concentrated s o l u t i o n of soda,
t h e n i n water.
Results
1. Change i n t h e mechanical p r o p e r t i e s of a l l o y s i n the course of aging.
The change i n t h e mechanical p r o p e r t i e s of a l l o y s AT3-1 and AT3-2 i n t h e course
of aging l a s t i n g 10,000 h r s a t 350 and 400' i s shown g r a p h i c a l l y ( f i g s . 1-4).

I/U

CU

YO
'g-.

M 70

L4 30

4%

3 2.
Pw

z5
,'17

\a,sO

b 30

3
B

ZUBQ

40U0

6000

756'G'J

duration of aging, h r
Figure 1. Change i n t h e mechanical p r o p e r t i e s of a l l o y AT3-1
i n t h e course of aging a t 350' f o r 10,000 h r s .

duration of aging, h r
Figure 2. Change i n the mechanical p r o p e r t i e s of a l l o y
i n t h e course of aging a t 400' f o r 10,000 hrs.

AT3-1

duration of aging, h r
Figure 3 . Change i n t h e mechanical p r o p e r t i e s of a l l o y AT3-2
i n t h e course of aging a t 350' f o r 10,000 hrs.

d u r a t i o n of aging, h r
Figure 4. Change i n t h e mechanical p r o p e r t i e s of a l l o y AT3-2
i n t h e course of aging a t 400 f o r 10,000 h r s .
The lower p a r t of t h e graphs shows t h e dependence of t h e impact s t r e n g t h
on t h e d u r a t i o n of aging, t h e upper p a r t shows t h e change i n t h e u l t i m a t e
s t r e n g t h and y i e l d s t r e n g t h , and t h e middle p a r t shows t h e change i n t h e d u c t i l e
p r o p e r t i e s which took p l a c e during t h e elapsed aging-time i n t e r v a l .
The graphs show t h a t i n t h e course of aging a t 350 and 400 f o r 10,000 h r s
t h e s t r e n g t h of t h e a l l o y s c h a r a c t e r i z e d by t h e values of ob and os does n o t
change appreciably.
Thus, f o r example, t h e u l t i m a t e s t r e n g t h

% of a l l o y s AT3-1 and AT3-2 a f t e r

f o r g i n g i s equal r e s p e c t i v e l y t o 86.4 and 90.1 kg/mm2. A f t e r aging f o r 10,000

h r s a t 350, t h e i n d i c a t e d a l l o y s had an u l t i m a t e s t r e n g t h of 87.62 and 93.69

kg/mm2, r e s p e c t i v e l y , i.e . t h i s c h a r a c t e r i s t i c remained p r a c t i c a l l y unchanged.

The same dependence of -t h e u l t i m a t e s t r e n g t h on t h e d u r a t i o n of aging i s a l s o
observed a t 4 0 0 ~ .
The d u c t i l i t y of t h e a l l o y s 6 does not change during t h e aging p r o c e s s
e i t h e r , and i s represented by a s t r a i g h t l i n e on "properties--aging t i m e "
diagrams.
The elongation p e r u n i t l e n g t h 6 of a l l o y s i n t h e i n i t i a l s t a t e was 14.3-14
p e r c e n t , and a f t e r long aging became equal t o 15 percent i n a l l o y AT3-1 and 13.8
p e r c e n t i n a l l o y AT3-2.
The necking $ of a l l o y AT3-1 decreases from 43.2 p e r c e n t ( a f t e r f o r g i n g )
t o 36 percent ( a f t e r aging f o r 10,000 h r s a t 350) and 34.4 p e r c e n t ( a - ~ t e raging
f o r 10,000 h r s a,t 4 0 0 ~ ) . These values of t h e d u c t i l i t y a r e f a i r l y high f o r an
aging time of 10,000-12,000 h r s . The t r a n s v e r s e c o n t r a c t i o n of t h e neck decreases
more appreciably i n a l l o y AT3-2.
A f t e r 10,000 h r s of aging, $ decreases from 56.1 t o 46.13 percent ( a t an
aging temperature of 350) and t o 35.8 percent ( a t an aging temperature of 4 0 0 ~ ) .
The value $ = 35.8 percent i s a l s o s i g n i f i c a n t i n c h a r a c t e r i z i n g the d u c t i l L t y
o f t h e a l l o y a f t e r long aging.
293

The impact s t r e n g t h decreases during aging. However, i n t h e range of

holding times of 2,000-5,OOO h r s , it remains constant f o r both a l l o y s (an =

7.5-5.5 kgm/cm 2 ) and decreases t o 3.5-3.75 kgm/cm2 only a f t e r aging f o r 10,000

hrs

2. Change i n t h e microstructure of a l l o y AT3. A study of t h e microstruct u r e made it p o s s i b l e t o e s t a b l i s h t h a t a l l o y AT3 a f t e r forging has t h e s t r u c t u r e of an a s o l i d s o l u t i o n w i t h a small amount of r e s i d u a l p phase ( f i g . 5a)
independently of t h e t o t a l content of chromium, i r o n and s i l i c o n .
I n t h e course of long aging under t h e s e l e c t e d conditions, t h e s t r u c t u r e
undergoes l i t t l e change. This i s i n d i c a t e d by photomicrographs obtained a f t e r
d i f f e r e n t aging conditions a t 350 and 4.00~.
Microphotographs of a l l o y AT3-1 a f t e r f o r g i n g f o r 5,000 and 10,000 h r s a t
350 and 4000 ( f i g . 5) show a two-phase s t r u c t u r e and a t e x t u r e t h a t i s c o a r s e r
than i n t h e forged s t a t e .
The higher a l l o y AT3-2 has a s i m i l a r s t r u c t u r e a t 350 and 400'
corresponding holding times ( f i g . 6).

and t h e

A study of t h e microstructure of t h e aged a l l o y AT3 a t a s o n s t a n t aluminum

content and a v a r i a b l e t o t a l content of chromium, i r o n and s i l i c o n following
various holding times revealed t h a t the phase composition of t h e a l l o y under t h e
i n d i c a t e d aging conditions remains unchanged over such a long period of time.

The r e s i d u a l @ phase i n a l l o y s AT3-1 and AT3-2 i n t h e range of 500-6000

should e x h i b i t a e u t e c t o i d decomposition w i t h t h e formation of an a phase and an
i n t e r m e t a l l i c phase of complex composition. Since t h e aging of a l l o y AT3 took
p l a c e a t r e l a t i v e l y low temperatures (350 and 400), i n t h e range of which t h e
d i f f u s i o n processes a r e s t r o n g l y i n h i b i t e d , t h i s d i f f u s i o n d i d not occur. The
s t r u c t u r e of t h e a l l o y remains a nonequilibriurn s t r u c t u r e and c o n s i s t s c h i e f l y
of an a s o l i d s o l u t i o n andanundecomposed p phase. For t h i s reason, t h e prope r t i e s of t h e a l l o y (%, 0, and 6) remain a t t h e l e v e l of t h e o r i g i n a l ones
independently of a l l o y i n g a f t e r such long aging. However, long aging a t 400
causes a strengthening of t h e g r a i n s of t h e a phase, and t h i s a f f e c t s t h e
d u c t i l e c h a r a c t e r i s t i c s of t h e a l l o y , $ and an, t h e value of which decreases
with i n c r e a s i n g g r a i n s i z e .
I n a d d i t i o n , i n such long aging i n an atmosphere of a i r , t h e s u r f a c e oxid a t i o n of t h e a l l o y and t h e hydrogen, which s h a r p l y decreases t h e impact
s t r e n g t h , may a l s o e x e r t a c e r t a i n influence.
Summary
1. The aging of a l l o y AT3 containing 2.7-2.8 p e r c e n t Al and 1.26 and 1.53
percent C ( C ~ Fe,
,
~ iwas
) studied i n t h e course of 10,000 h r s a t temperatures of
350 and 4 0 0 ~ . The i n v e s t i g a t i o n showed t h a t , i r r e s p e c t i v e of a l l o y i n g , t h e phase
composition o f t h e a l l o y does not change under t h e s e l e c t e d aging conditions.

Figure 5. Microstructure of a l l o y AT3-1 a f t e r forging and aging a t 350

and 400, x 340: a , forged; b , 350, 5,000 hrs; c , 350, 10,000 h r s ;
d, 400, 5,000 hrs; e , 400, 10,000 h r s .

Microstructure cf a l l o y AT3-2 a f t e r aging a t 350 and 400,

a , 350, 500 h r s ; b, 350') 3,000 hrs; c, 350, 5,000 h r s ;
d , 350, 1,000 h r s ; e , 400, 500 h r s ; f , 400') 3,000 h r s ; g, 400,
5,000 h r s ; h, 400, 10,000 h r s .
Figure

x, 340:

6.

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EFFECT OF CONDITIONS OF PLASTIC DEFOPNATION AXD SUBSEQUENT TREATMENT

ON THE PROPEWIES OF CERTAIN TITANIUM ALLOYS

I. M. Pavlov, Yu. F. Tarasevich and A. Ye. S h e l e s t

I n t h e p r e s e n t work1 a study was made of t h e i n f l u e n c e of t h e magnitude of

p l a s t i c deformation and subsequent cooling a t various r a t e s on t h e mechanical
p r o p e r t i e s of c e r t a i n a: + $ a l l o y s
the O T m
~ a r t e n s i t i c - t y p e a l l o y and a l l o y s
V T and
~
VT14 i n which t h e $ phase may be p a r t l y f i x e d a t room temperature.

--

The treatment of t h e a l l o y s consisted i n r o l l i n g specimens of square c r o s s

s e c t i o n on a "200" r o l l m i l l w i t h reductions i n a r e a of 20, 40 and 60 p e r c e n t
over a temperature range of 1100-500' (every loo0). The r o l l i n g r a t e w a s 0 . 5
m/sec. For each experimental p o i n t , t h r e e specimens were r o l l e d of which one
was cooled i n water, t h e second i n a s b e s t o s , and t h e t h i r d i n a i r .
F i r s t , t h e cooling r a t e of t h e specimens i n t h e cooling media was measured
by means of thermocouples l o c a t e d on t h e s u r f a c e and a t t h e c e n t e r of t h e
specimens. Thus, f o r a l l o y V T ~ ,t h e following cooling r a t e s were obtained: i n
water, 60-70 deg/sec; i n asbestos, 4.5-5 deg/sec; i n a i r , 6-6.5 deg/sec.
The following mechanical c h a r a c t e r i s t i c s were determined: hardness RB,
proportional l i m i t a
y i e l d s t r e n g t h aOa2,u l t i m a t e s t r e n g t h aU, r e l a t i v e
P

c o n t r a c t i o n of c r o s s - s e c t i o n a l a r e a Jr and elongation p e r u n i t l e n g t h 6. The

hardness was determined on t h e s u r f a c e of t h e specimens a f t e r removing t h e gass a t u r a t e d l a y e r by p o l i s h i n g w i t h an emery wheel.
The remaining mechanical c h a r a c t e r i s t i c s were determined by s u b j e c t i n g t o
t e n s i l e t e s t s specimens 3 mm i n diameter which were c u t o u t of r o l l e d blanks i n
t h e d i r e c t i o n of t h e a x i s of r o l l i n g . The t e s t s were c a r r i e d o u t w i t h two
machines: a P-5 machine a t an extension r a t e of t h e specimen of -1 p e r c e n t /
sec and on a Gagarin p r e s s a t an extension r a t e of 4 . 0 5 percent/sec.
The t e n s i l e - t e s t diagrams obtained w i t h t h e Gagarin p r e s s showed l o a d s
corresponding t o t h e p r o p o r t i o n a l l i m i t and y i e l d s t r e n g t h ( r e f . 1). The dimens i o n s of t h e specimens before and a f t e r extension were measured w i t h an i n s t r u ment microscope. The gauge l e n g t h of t h e specimen taken was t h e d i s t a n c e between t h e t i p s (20 mm) minus t h e two r a d i i of curvature of t h e t i p s ( 2 mm),
l y e . G. Konstantinov p a r t i c i p a t e d i n t h i s work.

i . e . , 18 mm. Extension 61' specimens w i t h marks made a t a d i s t a n c e of 15 mm from

each o t h e r (corresponding t o standard quintuple specimens) showed t h a t t h e values
obtained f o r t h e elongation p e r u n i t l e n g t h should be enlarged by approximately
13-20 percent.
Given below a r e t h e r e s u l t s of hardness t e s t s of t h e s e a l l o y s and t h e res u l t s of t e n s i l e t e s t s of a l l o y 0 ~ 4 .
Hardness d a t a obtained w i t h a B r i n e l l p r e s s a s shown i n f i g u r e s 1-3. The
B r i n e l l hardness t e s t has advantages i n s t u d i e s of a l l o y s which a r e inhomogeneous i n s t r u c t u r e ; i n a d d i t i o n , t h i s method e s s e n t i a l l y corresponds t o t h e determination. of hardness from t h e degree of p e n e t r a t i o n of one body i n t o another
(ref. 2).
Cooling i n water from 900-1100~ sharply i n c r e a s e s t h e hardness of a l l t h e
a l l o y s . I n a l l o y ~ ~ ( f1i g . 4 3 ) ) t h e d i f f e r e n c e i n t h e hardness of specimens
cooled i n a i r and i n a s b e s t o s i s apparent, and t h e i n c r e a s e i n hardness t a k e s
place t o a l e s s e r e x t e n t .
The hardness of a l l t h e a l l o y s changes s l i g h t l y upon cooling from 500-800'
(region of e x i s t e n c e of t h e a phase) f o r a 20 p e r c e n t reduction. For a 40 percent reduction, an i n c r e a s e i n hardness i s apparent a s t h e r o l l i n g temperature
drops below 800'; t h i s may be explained by t h e prevalence of t h e phenomenon of
work hardness over t h e recovery phenomena occurring a t t h e s e temperatures.
The r e l a t i v e c o n t r a c t i o n of t h e c r o s s s e c t i o n a l a r e a and t h e elongation f o r
a l l o y O T were
~
t h e same i n extension on t h e P-5 machine and on t h e Gagarin p r e s s ,
and t h e u l t i m a t e s t r e n g t h determined by t e s t i n g w i t h t h e P-5 machine was found
t o be 5-7 p e r c e n t h i g h e r t h a n i n t e s t i n g w i t h t h e Gagarin p r e s s .
The dependence of t h e u l t i m a t e s t r e n g t h obtained by t e n s i l e t e s t s w i t h t h e
P-5 machine on t h e conditions of t h e treatment i s shown i n f i g u r e 4.
The i n f l u e n c e of t h e cooling r a t e on ou i s manifested o n l y a t r o l l i n g
temperatures above 900'.
C e r t a i n d a t a ( r e f . 3 ) i n d i c a t e t h e absence of response
t o hardening h e a t treatment i n a l l o y O T ~ ,although cooling i n water from t h e
temperatures of e x i s t e n c e of t h e p phase r a i s e s t h e u l t i m a t e s t r e n g t h of t h e
a l l o y t o 93-100 kg/mm2, which i s equal t o 82-85 kg/&
rates.
A t 20
i n rolling
confirming
properties

a t moderate cooling

percent reduction, t h e y i e l d s t r e n g t h changes smoothly w i t h a change

temperature. A t h i g h e r reductions, t h i s r e g u l a r i t y i s not manifested,
t h e i n f l u e n c e of t h e value of p l a s t i c deformation on t h e mechanical
of t h e a l l o y .

Over t h e e n t i r e range of r o l l i n g temperatures and a t a l l cooling r a t e s

(with t h e exception of a few cases a t 1 0 0 0 ~and cooling i n a i r ) , t h e r e l a t i v e

5flO

6flO

700

BOO

300

/UOO

//UO

Figure 1. Dependence of hardness on t h e r o l l i n g

temperature, r e d u c t i o n i n a r e a and c o o l i n g condit i o n s of a l l o y 0Tk: a, 20 p e r c e n t r e d u c t i o n ; b,
40 p e r c e n t r e d u c t i o n ; c , 60 p e r c e n t r e d u c t i o n ;
1, c o o l i n g i n water; 2, c o o l i n g i n a s b e s t o s ; 3,
cooling i n air.
c o n t r a c t i o n i n c r e a s e s w i t h an i n c r e a s e of t h e r e d u c t i o n i n a r e a , and t h e temp e r a t u r e dependence o f t h e curves of t h e r e d u c t i o n i n a r e a i s t h e same, having
a minimum a t 1 0 0 0 ~and a maximum a t TOO0.

;
76
\

2 3.50

-7

3;u
C

3?D

290

2 70

500

1100

700

8017

YflO

I000

IIflg

t, "C

Figure 2. Dependence of hardness on t h e r o l l i n g temperature,

reduction i n a r e a and cooling conditions of a l l o y V T ~ : a , 20
percent reduction; b y 40 percent reduction; c, 60 percent r e duction; 1, cooling i n water; 2, cooling i n asbestos; 3, cooling i n a i r .
300

6,

O r

F i g u r e 3. Dependence o f hardness on t h e r o l l i n g
t e m p e r a t u r e , r e d u c t i o n i n a r e a and c o o l i n g condit i o n s o f a l l o y ~ 1 4 : a , 20 p e r c e n t r e d u c t i o n ;
b, 40 p e r c e n t r e d u c t i o n ; c , 60 p e r c e n t r e d u c t i o n ;
1, c o o l i n g i n water; 2, c o o l i n g i n a s b e s t o s ; 3,
cooling i n a i r .
The e l o n g a t i o n p e r u n i t l e n g t h d e c r e a s e s on r o l l i n g from t e m p e r a t u r e s below

8000; t h e maximum v a l u e s of 6 a r e o b t a i n e d a t moderate r a t e s o f c o o l i n g from

llooO.

Figure 4. Dependence of t h e u l t i m a t e s t r e n g t h of
a l l o y O T on
~ t h e r o l l i n g temperature, reduction i n
a r e a and cooling conditions: a, 20 percent reduct i o n ; b, 40 p e r c e n t reduction; c, 60 percent reduct i o n ; 1, cooling i n water; 2, cooling i n asbestos;
3, cooling i n a i r .
The d a t a obtained i n t h e p r e s e n t work make it p o s s i b l e t o d i s t i n g u i s h t h e
p r i n c i p a l methods of r a i s i n g t h e mechanical p r o p e r t i e s of t i t a n i u m a l l o y s by
means of t h e i r thermomechanical treatment. It should.be kept i n mind, however,
t h a t t h e thermal s t a b i l i t y of a l l o y s a f t e r such treatment w i l l be f a i r l y low,
so t h a t a r t i c l e s made from them can be used only a t normal temperatures. The
p o s s i b i l i t i e s of using a r t i c l e s from t i t a n i u m a l l o y s subjected t o thermomechanical treatment a t h i g h e r temperatures r e q u i r e a d d i t i o n a l i n v e s t i g a t i o n s .

1. Avdeyev, B. A. Technique of Determining the Mechanical Properties of

Metals (~ekhnikaopredeleniya mekhanicheskikh svoystv metallov )
Mashgiz ,

1958.
2. Kishkin, S. T. and Petrusevich, R. L. Izv. AN SSSR, OTN, No. 1, p.

87,

1948.

3. Luzhnikov, L. P. and Moiseyev, V. I. Metallovedeniye i termicheskaya

obrabotka metallov, No. 7, p. 29, 1961.

STUDY OF THE BASIC PARAMETERS OF ROT AND MEDIUM TWERATURE

ROLLINC OF SOME TITANIUM ALLOYS UNDER SPECIAL CONDITIONS OF STRESS

I . M. Pavlov, Ye. G. Konstantinov, Yu. F. Tarasevich

and A. Ye. S h e l e s t

pp. 255-262 of o r i g i n a l document appears i n

J.P.R.S. Translation No. 28,176; TT:65-30080
pp. 29-40

SOME STUDIES OF TEE STRUCTURE AND PROPERTIES OF ALLOY V T ~ - 1

DURING AEATING FOR STAMPING

Ya. M. Dityatkovskiy, N. M. P u l ' t s i n , V. B. Pokrovskaya

and V. A. Vinogradov

The h o t working of t i t a n i u m a l l o y s i s hindered by t h e i r a c t i v i t y a t high

temperatures; t i t a n i u m combines w i t h atmospheric oxygen, and t h e components of
a i r d i s s o l v e i n t h e metal. P a r t of t h e metal i s t h u s converted i n t o s c a l e , and
i n the surface l a y e r of t h e blank t h e hardness and b r i t t l e n e s s a r e considerably
increased.
I n order t o preserve t h e t e c h n o l o g i c a l d u c t i l i t y of a blank, t h e l a y e r of
metal s a t u r a t e d w i t h t h e components of a i r i s removed e i t h e r by e t c h i n g o r by
machining. Thus, t h e h e a t i n g of t i t a n i u m a l l o y s e n t a i l s t h e l o s s of metal both
i n t h e s c a l e and i n t h e eliminated converted l a y e r .
The problem of t h e q u a n t i t y of metal l o s t i n technological heating, f o r
example, i n t h e process of stamping, r e q u i r e s s p e c i a l i n v e s t i g a t i o n s , s i n c e t h e
u s e of high h e a t i n g temperatures providing f o r an i n c r e a s e i n d u c t i l i t y and
f a c i l i t a t i n g t h e stamping causes an appreciable l o s s of t h e metal i n t h e s c a l e
and i n the eliminated l a y e r , and, although a decrease i n t h e heated temperature
causes a decreased metal l o s s , i t does not provide f o r t h e d e s i r e d d u c t i l i t y .
Such i n v e s t i g a t i o n s should aim a t t h e establishment of an optimum h e a t i n g temp e r a t u r e which provides f o r t h e d e s i r e d d u c t i l i t y of t h e metal and i t s minimum
l o s s i n t h e s c a l e and eliminated l a y e r . The i n c r e a s e i n t h e weight of t h e
blank during heating can be used a s a measure of t h e l o s s of metal.
To determine t h e weight i n c r e a s e , use was made of round specimens c u t from
a rod which a f t e r t u r n i n g were 35 mm i n diameter and 1 0 mm high. The weight of
t h e specimens was about 40 g.
The i n v e s t i g a t i o n s of t h e converted l a y e r , i t s thickness, hardness and
s t r u c t u r e were c a r r i e d o u t on wedge-shaped b a r s . This shape f a c i l i t a t e s t h e
p r e p a r a t i o n of oblique polished s e c t i o n s and t h e study of t h e depth of t h e
l a y e r . A s k e t c h of such a specimen i s shown i n f i g u r e 1.
Results of t h e i n v e s t i g a t i o n of weight i n c r e a s e ( t a b l e 1) showed t h a t i t s
magnitude i n c r e a s e s s u b s t a n t i a l l y a s t h e h e a t i n g temperature of t h e blanks i s
r a i s e d . Thus, f o r example, a f t e r a holding time of 0.5 h r , t h e s p e c i f i c weight
i n c r e a s e of t h e specimens a t 700'

i s 0.034 g/m2

h r , a t 800, 0.062 g/m2

hr,

Iff

t-l

F r n - - - I

Figure 1. Sketch of specimen f o r studying

t h e s t r u c t u r e and hardness of t h e l a y e r .

TABLE 1. INCREASE IN WEIGHT OF TITANIUM ALLOY V T ~DURING

-1
FEATIRG I N AN ATMOSPEIERF: OF A I R I R AN ELECTRIC FTJRNACE (IN
g/m2 m)
Holding time, h r

,.s;?""
$-Ir
n

.rl

1.0

2.0

2.4 gok
@ho

Experiment a 1
data

a t 900 0.46 g/m*

Experimental
data

&

we,

2+'
a,c.d~n
g

td
k

&.&a.

0s 0
0 0 s

e,

40

h r , a t 100oO, 0 . 8 g/m2 h r , and a t l l O o O , 0.94 g/m2 h r ,

If t h e weight i n c r e a s e a t 700' i s taken a s u n i t y , then, a s shown by c a l c u l a t i o n s , a t h i g h e r temperatures (800, 900, 1000, 1100 and 1200), it w i l l be,
r e s p e c t i v e l y , 2, 14, 24, 28 and 159. A s u b s t a n t i a l weight i n c r e a s e i s observed
i n passing from 800 t o 900 (sevenfold) and from 1100 t o 1200' ( s i x f o l d ) .
Analysis of t h e d a t a obtained shows t h a t i n h e a t i n g t i t a n i u m a l l o y VT5-1
f o r f o r g i n g and stamping, one should not use a temperature above 1100~
because
t h e metal l o s t i n t h e s c a l e and i n t h e eliminated s a t u r a t e d l a y e r i s t h u s
appreciably increased.

As t h e holding time i s increased, t h e s p e c i f i c weight i n c r e a s e decreases

s u b s t a n t i a l l y . Thus, f o r example, a t 900, an exposure of 0.5 h r i s a s s o c i a t e d

2
w i t h an i n c r e a s e of 0.46 g/m 2 h r , and an exposure of 2 h r s , w i t h o n l y 0.15 g/m
h r , i . e . , a l o s s 3.05 times smaller. A s i m i l a r p i c t u r e i s observed a t o t h e r
temperatures as w e l l .
A reduction i n t h e s p e c i f i c weight i n c r e a s e w i t h i n c r e a s i n g holding time
may be explained by t h e s e l f - i n h i b i t i o n of t h e s a t u r a t i o n process. The l a y e r
of oxides formed a s w e l l a s t h e l a y e r of t h e s o l i d s o l u t i o n of i m p u r i t i e s i n
t i t a n i u m h i n d e r a f u r t h e r absorption of t h e components of a i r by t h e metal t o
a c e r t a i n e x t e n t : t h e d i f f u s i o n of i m p u r i t i e s through t h e s c a l e and through
t h e converted l a y e r is slowed down.

It should be noted t h a t a s t h e temperature i s r a i s e d , t h e r e d u c t i o n i n t h e

weight i n c r e a s e s w i t h t h e holding time. Whereas a t 900 an i n c r e a s e i n holding
time from 0.5 t o 2 h r s causes a 3.05 f o l d drop i n t h e weight i n c r e a s e , a t 1100
t h e weight i n c r e a s e i s reduced only 1 . 4 times. This may be explained by an i n crease i n t h e r a t e of d i f f u s i o n a t h i g h temperatures and a decrease i n t h e s e l f inhibition effect.
The s t u d y of t h e modified l a y e r was made by means of metallographic a n a l y s i s
It was found t h a t t h e s u r f a c e l a y e r as a r e s u l t
and microhardness measurements.'
of s a t u r a t i o n w i t h atmospheric oxygen a c q u i r e s a g r e a t e r hardness, and t h a t the
a: s t r u c t u r e of t h e s o l i d s o l u t i o n undergoes a change which i s v i s i b l e under t h e
microscope.
The r e s u l t s of t h e i n v e s t i g a t i o n s a r e shown i n t a b l e 2 and f i g u r e 2.
TABLE 2. E ~ E C TOF A~EALING OF ~ L O YV T ~ON
-1
THE IVATURE: OF TAE
SUEACE LAYER FOR A HOLDING TIME OF 1 HR

Annealing
temperature,
Oc

900
1000
1200

Microstructure
Depth of
Microhardl ess,
modified l a y e r ,
kg/mm
of t r a n s i of s u r f ace
of core
of s u r f a c e of core
mm
tion layer

545

881
1140

300
300
300

0.12

0.15
0.28

CE
CE
CE

FE
CE
CE

+
+
+

FN
FN
CB

FE
FE

Symbols designating t h e s t r u c t u r e s : CE - coarse-grained e q u i a x i a l ,

FE - fine-grained e q u i a x i a l , FJT - fine-grained nonequiaxial, CB coarse-grained b a s k e t l i k e .

l y e . A. Bodrova p a r t i c i p a t e d i n t h e work.

307

+ FN
+ FN
CB

Figure 2. Microstructures of s p e c i
OY v
soaked f o r 1 h r , x 450: a, surface; b, t r a n s i t i o n l a y e r ; c, core;
I , a t 1 2 0 0 ~ ;11, a t 1 0 0 0 ~ ;111, a t 900.

These r e s u l t s confirmed t h e known l i t e r a t u r e d a t a t o t h e e f f e c t t h a t as t h e

heating temperature r i s e s , t h e hardness and depth ( t h i c k n e s s ) of t h e s u r f a c e
l a y e r of t h e t i t a n i u m a l l o y s i n c r e a s e . I n t h i s case, t h e r e i s observed an i n c r e a s e i n t h e microhardness i n t h e s u r f a c e l a y e r of a l l o y VT5-1 from 300 t o 545
kg/mm2 a f t e r soaking a t 900, t o 881 kg/mm2 a t 1 0 0 0 ~and t o 1140 kg/mm2 a t
1200. The depth of t h e l a y e r , defined a s t h e t h i c k n e s s of t h e zone of g r e a t e r
hardness, comprises r e s p e c t i v e l y 0.12, 0.15 and 0.28 mm.
The l i t e r a t u r e d a t a ( r e f . 1) on t h e influence of oxygen on t h e hardness of
t i t a n i u m and i t s a l l o y s make it p o s s i b l e t o s o l v e t h e problem of determination
of t h e amount of oxygen i n t i t a n i u m by means of t h e hardness.
Knowing the oxygen concentration i n t h e l a y e r , one can c o r r e c t l y analyze
t h o s e s t r u c t u r a l changes which a r e observed a s a r e s u l t of annealing t h e s i n g l e phase a a l l o y VT5-1.

Photomicrographs of t h e s t r u c t u r e s of t h e a l l o y a t t h e s u r f a c e , i n t h e
intermediate l a y e r and i n t h e core ( f i g . 2) a t various soaking temperatures i n d i c a t e t h a t the s t r u c t u r e v i s i b l e under t h e microscope depends not o n l y on t h e
soaking temperature but a l s o on t h e oxygen content; t h i s s t r u c t u r e changes from
t h e s u r f a c e of t h e specimen t o t h e core.

It would seem t h a t oxygen, which i s an a s t a b i l i z e r , should not change t h e

s t r u c t u r e , v i s i b l e under t h e microscope, of t i t a n i u m a l l o y VT5-1, which has a
single-phase s t r u c t u r e of t h e a s o l i d s o l u t i o n ( r e f . 2). However, t h e s t r u c t u r e s , v i s i b l e under t h e microscope, of t h e s u r f a c e l a y e r containing a s i g n i f i cant amount of oxygen, of t h e t r a n s i t i o n zone and of t h e core d i f f e r neverthel e s s ( f i g . 2). An e q u i a x i a l s t r u c t u r e of a s o l i d s o l u t i o n i s observed i n t h e
s u r f a c e l a y e r , whereas a b a s k e t l i k e s t r u c t u r e i s observed i n t h e core.
Such a d i f f e r e n c e i n s t r u c t u r e due t o a nonuniform content of oxygen, r e s u l t s from t h e f a c t t h a t oxygen r a i s e s t h e temperature of t h e a l l o t r o p i c t r a n s i t i o n of titanium.
Soaking of t h e a l l o y a t 1200' i s not a s s o c i a t e d by a s h i f t of t h e phase
transformation boundary on cooling and produces coarse e q u i a x i a l g r a i n s of t h e
a phase i n t h e s u r f a c e l a y e r ( f i g . 2a1).
I n t h e t r a n s i t i o n l a y e r , t h e e q u i a x i a l s t r u c t u r e i s obtained o n l y p a r t l y
It i s p r e s e n t t o g e t h e r w i t h t h e b a s k e t l i k e s t r u c t u r e of t h e a
( f i g . 2bI).
phase, obtained by cooling from t h e f3 s o l u t i o n a f t e r soaking i n t h e intermediate
region.

a + f3

The core, which i n t h e process of soaking a t 1200' c o n s i s t s of markedly

grown g r a i n s of t h e f3 phase, assumes a coarse b a s k e t l i k e s t r u c t u r e w i t h v e r y
l a r g e elements of t h e a phase on cooling ( f i g . 2cI).
Soaking of t h e a l l o y a t 1 0 0 0 ~produces almost t h e same r e s u l t s . The s u r f a c e l a y e r of t h e specimens has a coarse c r y s t a l l i n e e q u i a x i a l s t r u c t u r a l of t h e
a phase ( f i g . 2a,--) . Both an e g u i a x i a l and a nonequiaxial a phase i s observed
i n t h e t r a n s i t i o n l a y e r ( f i g . 2b

I1), while a f i n e l y c r y s t a l l i n e n o t co&rse

b a s k e t l i k e s t r u c t u r e i s observed i n the core ( f i g . 2cII), which i s explained by

t h e absence of overheating i n t h e f3 region.
The 900' isotherm f o r t h e a l l o y w i t h an equal content of oxygen does not
i n t e r s e c t t h e l i n e s of t h e phase transformations. For t h i s reason, almost no
nonequilibrium formations of t h e a phase a r e observed i n t h e s t r u c t u r e .
Summary
1. The weight i n c r e a s e of specimens during h e a t i n g f o r stamping i n c r e a s e s
considerably a t temperatures above 800 and p a r t i c u l a r l y on heating a t 1 1 0 0 ~ .

The magnitude of t h e s p e c i f i c weight i n c r e a s e a t various temperatures decreases

with an i n c r e a s e i n soaking time, i n d i c a t i n g a s e l f - i n h i b i t i o n of t h e absorption
of i m p u r i t i e s .
2. Heating of t i t a n i u m a l l o y VT5-1 i n an atmosphere of a i r a t various
temperatures i s accompanied by t h e formation of an a l t e r e d l a y e r whose t h i c k ness, microhardness and s t r u c t u r e depend on t h e soaking temperature.

3 . The maximum microhardness of t h e changed l a y e r i s observed i n t h e

surface and i t s value i s h i g h e r t h e higher t h e temperature. A s t h e temperature
i s r a i s e d , t h e depth of t h e l a y e r i n c r e a s e s and reaches about 0.3 mm a t 1 2 0 0 ~ .

4. The v i s i b l e s t r u c t u r e of t h e changed s u r f a c e l a y e r and of t h e t r a n s i t i o n

zone d i f f e r s from t h e s t r u c t u r e of t h e core, although t h e r e i s no fundamental
d i f f e r e n c e i n t h e s t r u c t u r e of a l l t h r e e regions: t h e s t r u c t u r e c o n s i s t s of a
s i n g l e phase--an a: s o l i d s o l u t i o n .
5. The s o l i d s o l u t i o n of t h e s u r f a c e zone has an e q u i a x i a l g r a i n s t r u c t u r e ,
while t h e s o l i d s o l u t i o n of t h e core has a b a s k e t l i k e o r f i n e l y c r y s t a l l i n e nonequilibrium s t r u c t u r e . Such a d i f f e r e n c e i n s t r u c t u r e i s due t o t h e f a c t t h a t
the s u r f a c e l a y e r h i g h l y s a t u r a t e d w i t h oxygen does not undergo any phase t r a n s formations during cooling a f t e r annealing; t h i s i s not t r u e of t h e core and
p a r t l y of t h e t r a n s i t i o n l a y e r .

6. The formation of t h e changed l a y e r (even a t h i n one) having a g r e a t

hardness and a coarse g r a i n seems t o be t h e cause of t h e appearance of cracks
i n t h e m a t e r i a l during i t s machining and perhaps during i t s s e r v i c e as w e l l .
REFErnCES
1. McQuillen, A. D. and McQuillen, M. C.

2.

P u l f t s k i n , N. M.
1962.

Titanium.

Metallurgizdat, 1958.

I z v . vyssh. uchebn. zaved., Tsvetnaya metallurgiya, No. 5 ,

SOME CHARACTERISTICS OF THl3 HEAT TREATMEVI! OF ALMY

AT3 WITH A LOW CONTENT OF ALLOYIEG ELEMENTS

S. A. Yudina and B. K. Vul'f

In the preceding studies (refs. 1-3), the influence of heat treatment on
the structure, properties, and thermal stability of alloys AT3, AT4, AT^
and AT8 of normal composition was elucidated.
The present investigation is devoted to the similar study of alloy AT3
containing the smallest amount of aluminum and a low content of alloying
elements; such an alloy is particularly interesting as a material for the
production of cold rolled pipes.
A practical objective of the present is the establishement of the optimum
conditions of thermal treatment permitting the best combination of mechanical
properties and, particularly, a sufficient difference in the value of the
ultimate strength and yield strength. This would facilitate the technological
process of pipe manufacture and would guarantee a high service reliability of
parts operating under complex load conditions.
MECMICAL CHARACTERISTICS OF TITANIUM ALLOY AT3 FOLLOWIBG
HEAT TRl3ATMEf\lT.

The alloy was melted in a vacuum arc furnace with a consumable electrode
by double remelting and was then subjected to forging at temperatures of 1000The procedure used in the preparation and the composition of the burden
1150'.
materials are indicated in reference 2.
The experimental alloy AT3 has the following chemical composition: 2.5 per+ Fe + Si + B ) 0.013 percent H2, 0.013 percent N2,
cent Al, 0.9 percent ( ~ r
and 0.06 percent C.

The blanks cut out of the rods were studied in the initial state, after
(at 50 intervals) and also after aging the
quenching in air from 750-1250~
quenched alloys for 100 hr at 300 and 400~. The holding time at quenching
temperatures of 750-1100~
was 1 hr and at 1150-1250~,15 min.
The mechanical properties were determined by tensile testing of Gagarin
6 and Y and impact testing of Menager specimens
specimens to determine ob
O0.2'
t~iththe determination of an. The data of the tests are shown in the table and
in figure 1.
From these data it is apparent that as the quenching temperature is raised,

cb and o0.2 decrease somewhat as a whole, but at a quenching temperature of

-served
goo0 in the case of aging at quenched alloys at 300' for
hr, there is oba small relative increase in the values of these characteristics. At
100

the other quenching temperatures, aging causes little change in the strength
characteristics.
Attention should also be drawn to the fact that as the quenching temperature rises, there is an increase in the difference between the values of o and
b
2
which for forged alloys in the initial state, as to 3-4kg/mm , and for
O0.2,
2
alloys quenched from 850 and higher, 9-10kg/mm

This is apparently due to the appearance of the $ phase at the heating

temperature, as confirmed by the data of reference 4 on the heat treatment of
alloys Ti - Cr and Ti - Cr - Al, in which it is stated that during the extension of specimens containing the $ phase in the structure there is observed
an increase in the difference between the ultimate strength and yield strength.
Aging also affects the relation between o and o
b
0.2'

At a quenching tem-

perature of 800-850, the difference between the values of ob and oOa2 is much
greater in the case of aging at 400' than at 300, since at higher quencfiing
temperatures this difference, being appreciable in absolute value, is practically independent of the aging temperature.

Figure 1. Influence

re on the mechanical

same + aging at jOoO, 100 hr; 3--same + aging at hOoO, 100 hr

The alloys preserve a high ductility up to a quenching temperature of

8500; a further rise in this temperature leads to a substantial decrease in

6 and particularly Y, owing to a rapid growth of the grains and beginning of

formation of the $ phase, which converts into a coarse platelike structure

of the a' phase during quenching. The lowest values of Y correspond to
quenching temperatures of 900-950'.
The highest values of the impact strength of the alloy were observed at
quenching temperatures of 825-850' (for example, at 825O an = 9.1 kw/cm2).

Figure 2. Microstructure of ally AT3, x 300. a-initial state; b-- quenching from 800~;c--quenching
from 850; d--quenching from 9
50'; e--quenching from
loooO.
It is interesting to note that aging at 300-400' sharply decreases the impact
strength of forged specimens (in the initial state), but practically does not
reduce the high values of impact strength characteristic of alloys quenched
from 800-8500. This result is a clear confirmation of the practical desirability of carrying out the quenching and should be attributed to an increased content of hydrogen in the alloy (0.Ol3 ~ercent).

It is known (ref. 5) that the solubility of hydrogen in titanium at 325O

is about 0.2 percent, and is close to zero at room temperature; all of the
hydrogen is contained in the y phase, which is titanium hydride. In the course
of slow cooling of titanium or a single-phase a alloy, this phase precipitates
along the grain boundaries of the solid solution and decreases the impact
strength of the alloy. As the alloy is heated, a complete dissolution of titanium hydride takes place, and the latter does not precipitate under quenching
conditions, so that a restoration of the original values of the impact strength
is observed, particularly in alloys with an increased hydrogen content.

Figure 3. Fractures of specimens of alloy after various

b-heat treatments. a--initial state + aging at 400';
quenching from 750' + aging at 400"; c--quenching from
800; d--quenching from 8500; c--quenching from 850' taging at 400~;
f--quenching from 950 + aging at 400~.
It should be noted
to different degrees if
and others, it is known
embrittle even at a low

in passing that the influence of hydrogen is manifested

the aluminum content is different. From reference 6
that alloys having a low aluminum content (2.5 percent)
hydrogen content (-- 0.008 perdent).

Apparently, an increase in aluminum content raises the solubility of hydrogen in the a phase or retards the precipitation of the hydride and decreases
the coefficient of the fusion of hydrogen in titanium.
However, at a low aluminum content of the alloy, the inclusions of hydride
are uniformly distributed, and at a high aluminum content, the inclusions precipitate primarily along the grain boundaries, as a result of which Y decreases
markedly.
The influence of heat treatment on the mechanical properties of alloy AT3
is confirmed by data of metallographi'c analysis and by the characteristics of
the breaks of specimens obtained under conditions of dynamic failure. In the
initial state and after quenching from 750, the alloy has a coarse platelike
structure of the a' phase (fig. 2a) and is characterized by a coarsely crystalline lustrous brittle fracture (fig. ga and b).
After quenching from the
optimum temper-ztures, there is formed a finely crystalline structure primarily
of the a phase with signs of steroidization (fig. 2b and c); in this case,

duration of aging, hr
Figure 4. Influence of temperature and
aging of the mechanical properties of a
50'. 1--after aging at 3
quenched from 8
aging at 400~.
the fracture becomes ductile, dull., and finely crystalline (fig. 3c, d
and e). On overheating to 950-1000, the coarse platelike structure of
the a t phase reappears (fig. 2d and e) with a coarse-grained brittle
fracture (fig. 3f) .
Aging at 300 and 400 for 100 hr of specimens quenched at the optimum
temperature of 8500 has practically little effect on the mechanical properties
of alloy AT3. The change in properties in the course of aging is also slight
(fig. 4). This indicates a high thermal stability of alloy AT3 in the quenched
state.
Summary

1. Alloy AT3, which has a low content of alloying elements and is characterized by a high ductility and resistance to dynamic loads, acquires the
best mechanical properties having quenching in air from 825-850'.
2 . The alloy quenched under these conditions as a high thermal stability
and has the following mechanical characteristics after aging for 100 hr at
4000: ob = 72 kg/mm2, oOa2 = 64 kg/mm2, o = 18 percent, Y = 52 percent, a, =

8 kgm/cm2.
3.
2

The considerable difference between ob and o0,2, amounting to about 8

kg/mrn , makes it possible to use the heat-treated alloy AT3 with a low content
of alloying elements for the preparation of parts operating under complex'conditions of stress application.

REFERENCES

i it an

1.

Vultf, B. K. and Yudina, S. A. Coll. Titanium and Its Alloys

yego splavy). Izd-vo AN SSSR, No. 7, p. 174, 1962.

2.

Kornilov, I. I., Vul'f, V. K. and Yudina, S. A. Metallovedeniye i

termicheskaya obrabotka metallov, No. 2, p. 54, 1963.

3.

Vullf,B. K. and Yudina, S. A. Coll. Titanium and Its Alloys

yego splavy) ~zd-voAN SSSR, NO. 10, p 207, 1963.

i it an

4. Moiseyev, V. N. Metallovedeniye i termicheskaya obrabotka metallov,

NO. 2, p. 24, 1963.
5.

Pul'tsin, N. M. Titanium Alloys and Their Use in Machine Construction

(~itanov~ye
splavy i ikh primeneniye v mashinostroyenii ) . Mashgiz,
1962.

SOME PROBLEMS OF FUSION WELDING OF TITANIUM

AND ITS ALLOYS

G. L. Petrov, M. D. Shchipkov, A. I . Lebedev

and A. A. Yazykov

pp. 273-282 of o r i g i n a l document appears i n

J.P.R.S. T r a n s l a t i o n No. 28,176; TT: 65-30080
PP. 41-55

SUBMERGED DOUBLE-ARC WELDING OF MEDIUM AND LARGE THICKNESS

SESIIFINISHED PRODUCTS OF TITAlCJIUM ALLOYS

S. M. Gurevich and S. D. Zagrebenyuk

pp. 283-288 of o r i g i n a l document appears i n

J.P.R.S. T r a n s l a t i o n No. 28,176; TT: 65-30080
pp. 56-62

STUDY OF TRE MUTUAL DIFFUSION OF TITANIUM WITH COPPER

AND OTHER METALS SUITABLE FOR BFAZING

A. Ya. Shinyayev, V. V. Bondarev and Ye. V. Sergeyeva

pp. 289-293 of o r i g i n a l document appears i n

J.P.R.S. T r a n s l a t i o n No. 28,176; TT:~?-30080
PP. 63-69

USE OF OPTICAL EMISSION MICROANALYSIS I N

THE STUDY OF TITANIUM ALLOYS

N. V . Korolev, S . A. Gorbunov and A. S . Bogdanov

Improvement of t h e device f o r emission microanalysis ( r e f s . 1, 2) has

opened up new v i s t a s f o r t h e s o l u t i o n of many problems. The s t u d i e s which were
c a r r i e d out made it p o s s i b l e t o c r e a t e conditions f o r t h e performance of analyses i n an atmosphere of i n e r t gases, t o improve t h e l o c a l i z a t i o n of t h e analys e s , and t o i n c r e a s e t h e i n t e n s i t y of t h e l o c a l a t t e n u a t e d microspark. Of p a r t i c u l a r value has been t h e use of a microspark i n argon i n analyses of a l l o y s
f o r oxygen and nitrogen.
Optical Diagram of Improved Device

. .

Let us consider t h e o p t i c a l diagram of t h e modified device ( f i g 1) The

e l e c t r i c spark formed between the s u r f a c e of t h e analyzed specimen 1 and t h e
t i p of t h e microelectrode 2, successively through t h e u l t r a v i o l e t microscope
o b j e c t i v e 3, a t i l t a b l e semialuminized mirror 4, a quartz l e n s 5, and an achromatic s e t of quartz and l i t h i u m f l u o r i d e l e n s e s 6, appears i n t h e plane of t h e
s l i t of t h e quartz spectrograph 7 on a s c a l e of 6:1.

F i g u r e 1. O p t i c a l diagram of apparatus f o r emission a n a l y s i s :

1, sample under analysis; 2, microelectrode; 3, microscope
objective; 4, semialuminized mirror; 5 , quartz l e n s ; 6, achromatic s e t ; 7, s l i t of spectrograph; 8, i l l u m i n a t i n g tube;
9, hinged prism; 10, l a t e r a l i l l u m i n a t o r ; 11, d e f l e c t i n g prism;
1 2 , eyepiece; 13, chamber; 14, nozzle of chamber; 15, d i r e c t i n g
cap.

321

The analyzed s u r f a c e of specimen 1 may be illuminated e i t h e r by l i g h t

coming from above through microobjective 3 o r by l a t e r a l l i g h t from i l l u m i n a t o r
1 0 . I n t h e former case, a hinged prism 9 which d i r e c t s the l i g h t from the
i l l u m i n a t i n g tube 8 i n t o t h e system of t h e microscope i s introduced i n order t o
provide i l l u m i n a t i o n between the s e t of l e n s e s 6 and t h e s l i t of t h e s p e c t r o graph

The s u r f a c e s of specimen 1 and of t h e t i p of microelectrode 2, i l l u m i n a t e d

by l i g h t coming from t h e s i d e or from above and r e p r o j e c t e d by o b j e c t i v e 3, a r e
observed i n eyepiece 1 2 by means of l i g h t which has p a r t l y passed through t h e
t i l t e d semialuminized mirror 4 and prism 11.

A r e t i c l e i n t h e eyepiece of t h e microscope makes it p o s s i b l e t o place t h e

s t r u c t u r e under a n a l y s i s and the t i p of the microelectrode i n t h e r e q u i r e d
p o s i t i o n r e l a t i v e t o t h e o p t i c a l a x i s of t h e instrument.

Figure 2. Construction of
microelectrode: a , s i d e
view; b , t o p view.

Figure 3. Attachment
with d i r e c t i n g groove.

Chamber 1 3 f o r c a r r y i n g out t h e analyses i n an atmosphere of i n e r t gases

i s screwed onto t h e housing of o b j e c t i v e 3. A d i r e c t i n g nozzle 14 i s provided
i n t h e bottom p a r t of t h e chamber. The i n e r t gas i s introduced i n t o t h e chamb e r by means of rubber tubing through a l a t e r a l connecting tube and i s d i r e c t e d
through t h e nozzle i n t o t h e burning zone of t h e microspark and onto t h e surface
being analyzed. The diameter of t h e gas j e t coming o u t of t h e nozzle i s 3 mm.
The d i s t a n c e from t h e t i p of t h e nozzle t o t h e s u r f a c e of t h e specimen i s 4 mm.
I n analyses f o r n i t r o g e n and oxygen, one must make sure t h a t no air i s
sucked i n t o t h e j e t of i n e r t gas. To t h i s end, a d i r e c t i n g cap 15 whose lower
t i p r e s t s on t h e s u r f a c e of analyzed sample 1 may be mounted on t h e nozzle.
The microelectrode i s i n s e r t e d i n s i d e t h e cap by means of a micromanipulator
through a square ( 2 x 2 mm) l a t e r a l aperture i n t h e cap. The i n e r t g a s comes
out of t h e chamber through t h i s aperture and through t h e gap between t h e lower
t i p of the cap and t h e specimen.
The c o n s t r u c t i o n of t h e microelectrodes used t o c a r r y out t h e microanalys e s i s shown i n f i g . 2.
The microanalysis involves t h e use of a d i r e c t i n g groove i n a quartz p l a t e

f o r t h e l o c a l i z a t i o n of spark discharges on t h e surface of t h e specimen.

construction of t h i s attachment i s shown i n f i g . 3.

The

The attachment, held i n t h e e l e c t r o d e holder by t h e round end of t h e e l e c t r o d e , i s placed on t h e surface of t h e specimen by means of t h e micromanipulat o r mechanism i n such a way t h a t t h e p o r t i o n under a n a l y s i s and under observat i o n i n t h e microscope i s l o c a t e d a t t h e apex of t h e d i r e c t i n g groove.
By carrying out t h e analyses i n an a t t e n u a t e d microspark by means of a
d i r e c t i n g groove, one can confine t h e e l e c t r i c discharges t o an a r e a up t o
0.05 mm i n diameter with a 10 p. minimum depth of t h e damaged l a y e r .
Microspark Generator

The e l e c t r i c c i r c u i t of the microspark generator now i n use ( f i g 4) makes

it possible t o obtain a hard and an a t t e n u a t e d microspark. The regime of t h e
hard microspark i s characterized by a higher concentration s e n s i t i v i t y and
g i v e s s p e c t r a of elements which a r e d i f f i c u l t t o e x c i t e ; t h e r e g i m of t h e
a t t e n u a t e d microspark i s used when it i s necessary t o have a highly l o c a l i z e d
analysis.
When switch S2 i s i n p o s i t i o n I , t h e c u r r e n t pulses which w e s t o r e d by
capacitor C before t h e arcing of t h e a u x i l i a r y gap AG, pass completely through
P
t h e a n a l y t i c a l gap AnG a f t e r t h e arcing of AG. I f t h e capacity of t h e weighti n g capacitor i s high ( C > 0.01 $), t h e s p e c t r a of ions of almost a l l e l e P
ments a r e r e a d i l y e x c i t e d i n such a microspark (hard regime of microspark).
I f t h e switch S2 i s i n p o s i t i o n 11, t h e c u r r e n t pulse

th

c a l gap under t h e influence of an induced emf a r i s i n g at t h e ends of t h e secondary winding of t h e a i r - c o r e transformer L2 when t h e current pulses pass
through t h e primary winding L1 of t h i s transformer.
The magnitude of t h e c u r r e n t pulses crossing the a n a l y t i c a l gap AnG depends on t h e capacitance of t h e conductors bringing t h e c u r r e n t from c o i l L2
t o t h i s gap, and not on t h e arcing voltage of t h e a n a l y t i c a l gaps. When t h e
supplementary gap SG i s absent, the pulses of t h e current crossing t h e analyt i c a l gap AnG a r e small, since t h e capacitance of t h e conductors and t h e arcing
voltage a r e s m a l l . As a r e s u l t , t h e b r i g h t n e s s of t h e spark i s we&.
The
i n t r o d u c t i o n of a supplementary gap SG r a i s e s t h e t o t a l a r c i n g voltage of gaps
S G and AnG, increasing t h e current pulses, as a r e s u l t of which t h e b r i g h t n e s s
of t h e microspark increases (regime of attenuated microspark).
The a d d i t i o n a l gap used i s a xenon pulse tube ISS~-100/1.

Use of Emission Microanalysis

Microspectral a n a l y s i s can f i n d various applications i n t h e s t u d y of t i t a n -

i u m a l l o y s because of i t s advantages over ordinary s p e c t r a l a n a l y s i s . One of

t h e main advantages of t h e microspectral a n a l y s i s i s t h e small q u a n t i t y of substance r e q u i r e d f o r t h e analysis ( 1 0 - ~ - 1 0 ' ~ g ) ,which permits an i n v e s t i g a t i o n
without damage t o t h e analyzed items. A f t e r t h e a n a l y s i s , only minor f i n i s h i n g
of t h e s u r f a c e i s necessary. Many years of experience with t h i s device l e a d s
us t o b e l i e v e t h a t t h e construction of a p o r t a b l e microspectral apparatus f o r
checking l a r g e - s i z e d items i s p o s s i b l e .
The a n a l y s i s may be performed at a s t r i c t l y defined s i t e of t h e part,where
changes i n t h e composition of t h e a l l o y can be expected. This advantage i s
i r r e p l a c e a b l e when- it i s necessary t o account f o r - t h e causes of various surf ace
defects.
F i n a l l y , t h i s method of a n a l y s i s permits t h e determination of elements
which a r e d i f f i c u l t t o e x c i t e and a r e present i n t h e a l l o y s .
The e x i s t i n g methods of checking f o r gaseous impurities i n t i t a n i u m ( spect r a l methods, vacuum f u s i o n , e t c .), r e q u i r e t h e d e s t r u c t i o n of t h e p a r t s , so
t h a t t h e s e methods cannot be used t o perform l a y e r analyses f o r oxygen, n i t r o gen and carbon, whereas t h e improved design of t h e microspectral u n i t opens up
broad perspectives i n t h i s d i r e c t i o n .
A s e r i e s of examples given below i n d i c a t e s various means and methods of
microspectral a n a l y s i s drawn from t h e experience of studying t i t a n i u m a l l o y s .
Microspectral Analysis of Gaseous Impurities
I n t h e process of oxidation of t e c h n i c a l l y pure titanium VT1, t h e impurity
elements a r e r e d i s t r i b u t e d between t h e oxides and t h e metal l a y e r l o c a t e d under
t h i s c r u s t of oxides.
The purpose of t h e i n v e s t i g a t i o n was t o determine t h e chemical composition
of t h e metal ( p r i m a r i l y gaseous impurities) on t h e surf ace of specimens of
a l l o y VT1 heated i n air a t various temperatures and f o r various periods of time.
The study of t h e chemical composition of t h e surface l a y e r s of t h e metal
yielded t h e following r e s u l t s .l
A t oxidation temperatures of 1100 and 1200, carbon, s i l i c o n and n i t r o g e n ,
present i n t h e composition of t h e metal a s i m p u r i t i e s , concentrate i n t h e s u r f a c e l a y e r of t h e metal t o a depth of 10-15 p . This l a y e r i s extremely s t a b l e
chemically and has a g r e a t hardness close t o t h a t of titanium carbides and

%his i s discussed i n more d e t a i l i n an a r t i c l e by N. V. Korolev ( s e e t h i s

c o l l e c t i o n , p 146)

Figure 4. E l e c t r i c c i r c u i t of microspark generator: HR,

high-voltage r e c t i f i e r ; Rc charging r e s i s t o r ; S1, capaci-

t a n t switch; Cw, working capacitors; AG, a u x i l i a r y gap;

S2, switch f o r microspark regimes; L1 and L2, primary and
secondary winding of air core transformer ;

L12 '

a i r core

transformer; SG, supplementary gap; AG, a n a l y t i c a l gap;

S3, on -off switch of supplementary gap.
n i t r i d e s . The concentration of carbon and nitrogen on t h e surface of t h e metal
a f t e r the oxidation i n air of samples of a l l o y VTl a t various temperatures and
t e s t i n g times can be evaluated from t h e r e s u l t s of t h e a n a l y s i s shown i n t h e
t a b l e below:
CONTENT OF NITROGEN AND CARBON I N SURFACE LAYERS OF SPECIMENS OF TITANIUM ALLOY VT1 ( I N PERCENT).
Testing
temperature,
OC

Duration of
testing,
Hr

0 .05
1200
0.1
1200
0.2
1200
1200
0.5
1
1200
4
1200
4
1100
8
1100
16
1100
8
1-000
16
1000
8
900
16
900
8
800
800
96
Note: S e n s i t i v i t y of determination:
0.03 percent f o r carbon.

0 .O
0*5
0.7
3.6
3.3
1.7
3.5
1.7
3-5

0.04
O -02
0.04
0.12
0.65
1.16

--

0 3
0.35
0.04
o .o
o .06
o .o
0 .O
0 .05
o .06
o .o
0.1
o .o
0.14
o .o
0.3 percent f o r nitrogen,

The oxygen content i n t h e surface l a y e r s of t h e titanium samples was 0.1

percent and higher.
325

Layer Microspectral Analysis Involving Transfer

of t h e Analyzed Substance Onto Copper P l a t e s
The n a t u r e of t h e d i s t r i b u t i o n of a l l o y i n g elements i n t h e oxide l a y e r was
s t u d i e d on t h e b i n a r y a l l o y T i + 10 percent Sn.
The technique of t h e a n a l y s i s of t h e oxides c o n s i s t s i n t h e following: a
small amount of powder of t h e oxides from t h e l a y e r l o c a t e d a t a c e r t a i n depth
i s removed by means of a corundum or s i l i c o n carbide scraper and placed on a
copper p l a t e ( f i g . 5)

The oxide powder i s t h e n rubbed i n t o t h e surface l a y e r of t h e p l a t e by

means of t h e same s c r a p e r , o r i s spread over t h i s surf ace. The surf ace l a y e r
of t h e p l a t e with t h e powder rubbed i n t o it i s then t r e a t e d with pulsed d i s charges of a hard microspark i n t h e u n i t f o r emission microspectral a n a l y s i s .
The s p e c t r a obtained i n t h e spark a r e photographed. The photographic f i l m cont a i n i n g t h e s p e c t r a i s subjected t o photometric treatment by using t h e t e c h nique described i n r e f . 2. A r e s u l t of t h e photometric treatment of t h e f i l m
i s t h e determination of t h e r a t i o of t h e weight concentration of t h e a l l o y i n g
element t o t h e concentration of t i t a n i u m f o r oxide l a y e r s l o c a t e d a t d i f f e r e n t
depths.

/7

F i g u r e 5. Diagram of t h e transf'er of oxide onto metal backing: 1, copper p l a t e ; 2, specimen with oxide c r u s t ; 3, oxide
c r u s t ; 4, scraper made of A 1 0 and S i c ; 5, oxide powder.
2 3
Let us examine t h e nature of the change i n t h e r a t i o of t h e concentration
of t i n CSn t o t h e concentration of t i t a n i u m CTi i n t h e layer of oxides formed
on t h e s u r f a c e of the a l l o y with 10 percent S n during oxidation of a specimen
i n a i r f o r 8 h r at 1 1 0 0 ~ :
Outer oxide l a y e r from the s u r f ace
Inner surface of o u t e r l a y e r
Outer surf ace of monoxide
Inner surface of monoxide
Top l a y e r from the metal s u r f a c e
Average composition of a l l o y

0.018

o .036
0 .029

0.105
0 33
0.11

The a n a l y s i s shows a very high concentration of t i n i n t h e l a y e r adjacent

t o t h e metal.

Emission Microspectral Analysis of Surf ace Layers

Tnis method i s indispensable i n explaining t h e causes of t h e varibus def e c t s a s s o c i a t e d with a change i n t h e composition of t h e a l l o y at t h e l o c a t i o n
of t h e d e f e c t s .
A microanalysis of r e l a t i v e l y small ( 3 x 3 mm) a r e a s of t h e i n v e s t i g a t e d
specimens makes it p o s s i b l e t o determine t h e composition of l a y e r s up t o 0 . 1 p
t h i c k . We s h a l l i l l u s t r a t e t h e a p p l i c a b i l i t y of t h i s method by two examples:

a. The r o l l i n g of t h i c k s h e e t s of a l l o y AT5 i s sometimes accompanied by

cleavage of t h e s h e e t . B r i g h t , b r i t t l e p r e c i p i t a t e s can be observed on t h e
surf ace of t h e cleavage. When t h e specimen i s s t r u c k with a hammer, l u s t r o u s
metal granules come off the cleavage surface. The m i c r o s t r u c t u r a l method was
used t o analyze these granules i n argon. It was found t h a t t h e oxygen content
of t h e granules was approximately 2.5 percent. The aluminum content of t h e
granules was only 1 percent. The analyses confirm t h e hypothesis t h a t p a r t of
t h e titanium sponge had been contaminated with oxygen. Such sponge h a s a
higher melting point than pure sponge, and f o r t h i s reason it apparently r e mained s o l i d during t h e melting of a l l o y AT5. This i s i n d i c a t e d by a lower
aluminum content i n t h e b r i t t l e granules of t h e cleavage surf ace a s compared
t o t h e o r i g i n a l content.
b. The e f f e c t of oxygen i m p u r i t i e s on t h e s t r e n g t h c h a r a c t e r i s t i c s of
a l l o y VT15 was studied. According t o t h e microscopic a n a l y s i s , specimens cont a i n i n g 0 . 1 percent O2 a f t e r being kept f o r 1 hour a t 8500 have only t h e

s t r u c t u r e of $-Ti.

I n specimens containing 0.4 percent 02, a small amount of

i s present a f t e

heat treatment.

I n order t o convert i t

t h e s e specimens f o r 3 hours a t 9 5 0 ~ .After

t i s necessary
t h i s h e a t treatment, t h e specimens with 0.4 percent 0 a r e c h a r a c t e r i z e d by a
2
low impact s t r e n g t h .

The impact s t r e n g t h of specimens with 0 . 4 percent 0

heated f o r 3 hours a t 950'

heated f o r 1 hour a t

i s 0 . 7 kgm/cm2.

Specimens with 0 . 1 percent O2

850' have an impact s t r e n g t h of 8 kgm/cm 2 .

The chemical composition ( i n percent) of f r a c t u r e s u r f a c e s of specimens

with 0 . 1 and 0.4 percent O2 and of t h e same s u r f a c e s a f t e r e t c h i n g was d e t e r mined by t h e microspectral method; t h i s made it p o s s i b l e t o evaluate t h e i n i t i a l a l l o y composition:
Fracture of specimen with 0 . 1 percent O2 a f t e r
heating f o r 1 hour a t 850':
Before etching
A f t e r etching

Mo

Cr

Al

7.5

9-9
9.8

2.00
2.06

8.2

O2
0.5

---

F r a c t u r e of specimen with 0.4 percent O2

a f t e r h e a t i n g f o r 3 hours a t 950'
Before etching
A f t e r etching

Mo

Cr

A1

02

5.6
8.1

8.8

2.1
2.1

1.5

9.5

--

The f r a c t u r e of t h e specimen with 0 . 4 p e r c e n t O2 t a k e s place i n a r e a s enriched with oxygen and impoverished i n molybdenum and chromium.

It w a s shown by means of an e l e c t r o n microscope t h a t a - T i i n t e r l a y e r s a r e

present i n t h i s case along t h e boundaries of t h e @ g r a i n s i n the a l l o y with
0.4 percent 0 2 .
Microspectral Analysis w i t h Localization of
Charges by Means of a Directing Groove
This method of a n a l y s i s was used t o determine t h e n a t u r e of t h e d i s t r i b u t i o n of a l l o y i n g elements i n g r a i n s of t h e c a s t a l l o y T i + 5 percent A 1 -I- 2
percent V. The a n a l y s i s showed t h a t t h e g r a i n boundaries of transformed @-Ti
are r i c h i n aluminum and vanadium. The a n a l y s i s was c a r r i e d out on g r a i n s
approximateiy 0 .5 mm2 i n s i z e . A t t h e g r a i n boundaries, even i n t h e zone of a
l o c a l spot 50 ~1 i n diameter, t h e presence of 6 percent A l w a s e s t a b l i s h e d i n s t e a d of t h e average concentration of 5 percent. On t h e g r a i n boundary i t s e l f ,
t h e aluminum content w i l l probably be s t i l l higher.
The enrichment of the boundaries with vanadium i s minor. A t a n average
concentration of 2 percent V , i z s content i n t h e boundary zone i s 2.2 percent.
The enrichment of t h e g r a i n boundaries with aluminum seems t o be an important
f a c t o r which accounts f o r t h e f a c t t h a t when t h e heated a l l o y i s cooled, t h e
transformation of @-Ti i n t o a - T i begins a t t h e g r a i n boundaries. Occasionally,
when t h e g r a i n s of transformed @-Ti a r e very l a r g e , boundasy l m e l l a e of CX -Ti
o r i e n t e d along t h e boundaries of @ g r a i n s can be observed on t h e s u r f a c e of t h e
microsections. A s t h e a l l o y i s cooled, t h e s e lamellae a r e apparently t h e f i r s t
t o form from @-Ti, and t h i s i s followed by t h e growth of i n t e r l a y e r s of t h e a
phase w i t h i n t h e g r a i n .
Microspectral Analysis i n Combination with
Selected Etching of Microstructure
I n solving c e r t a i n m e t a l l u r g i c a l problems, it becomes necessary t o d e t e r mine t h e content of elements i n t h e i n d i v i d u a l s t r u c t u r a l components. To t h i s
end, a reagent i s chosen which e t c h e s one s t r u c t u r a l component t o a l e s s e r ext e n t than another. A s a r e s u l t of s e l e c t i v e e t c h i n g , t h e weakly etched s t r u c t u r e r i s e s above t h e s u r f a c e of t h e microsection. After the etching, a micros p e c t r a l a n a l y s i s of t h e protuberances i s performed. The presence of r i d g e s
can be determined by refocusing the microscope when various phases a r e observed,
and a l s o when a microinterferometer i s used ( r e f . 3). I n a d d i t i o n , t h e solut i o n of t h e e t c h a n t can be analyzed a f t e r t h e s e l e c t i v e e t c h i n g . To t h i s end,

a drop of t h e s o l u t i o n i s placed on t h e specimen and, a f t e r a s u i t a b l e exposure,

i s t r a n s f e r r e d with a p i p e t t e onto a copper p l a t e . The e t c h a n t on t h e copper
p l a t e i s d r i e d over a burner. The s a l t d e p o s i t which p r e c i p i t a t e s on t h e copp e r p l a t e i s t r e a t e d by discharges with a has6 microspark. Such a n a l y s i s r e g ) . The use of such
q u i r e s a very small amount of t h e elements (10'7-10'8
Thus,
f
o
r
example,
microspectral a n a l y s i s
methods gives i n t e r e s t i n g r e s u l t s .
of t h e low a l l o y s T i + 5 percent A 1 + 0.8 percent Mo, Ti + 5 percent A 1 t- 0.8
percent F e , T i + 5 percent A 1 + 2 percent V confirmed t h e presence of the soc a l l e d @ b r i t t l e n e s s of these a l l o y s . During slow cooling from t h e region of
@ - T i i n t o t h e region of a - T i , a drop i n impact s t r e n g t h and a decrease i n t r a n s verse c o n t r a c t i o n a r e observed i n t h e s e a l l o y s . Microscopic and microinterferometric analyses of t h e surfaces of s e c t i o n s etched with hydrofluoric a c i d
showed t h a t t h i n i n t e r l a y e r s p r o j e c t i n g above t h e surface of t h e s e c t i o n remain
between t h e lamellae of a - T i .
Comparative s p e c t r a l a n a l y s i s of t h i n surface l a y e r s of s e c t i o n s which
were and were not etched with hydrofluoric a c i d showed t h a t a f t e r t h e etching,
t h e surface l a y e r i s enriched with f3 s t a b i l i z e r s -- i r o n o r molybdenum. This
a n a l y s i s shows t h a t t h e r i d g e s p r o j e c t i n g above t h e surface a f t e r etching with
hydrofluoric a c i d may be t h e remainders of a f3 phase enriched with molybdenum
and i r o n during cooling. Photometric treatment of the spectrograms obtained
from t h e polished s u r f a c e s of t i t a n i u m a l l o y s before and a f t e r e t c h i n g with
hydrofluoric a c i d gave t h e following r e s u l t s :

Object of a n a l y s i s

Change i n t h e content of
a l l o y i n g elements

Here t h e concentration of elements i n t h e surface l a y e r before e t c h i n g i s

taken a s u n i t y .
For t h e q u a n t i t a t i v e a n a l y s i s of t h e i n t e r l a m e l l a r l a y e r s , t h e specimens
with B b r i t t l e n e s s were etched with hydrofluoric a c i d and washed with d i s t i l l e d
water. A t h i n copper p l a t e was then applied on t h e etched s u r f a c e by hammering.
The p r o j e c t i n g i n t e r l a m e l l a r l a y e r s thus become p a r t l y wedged i n t h e s u r f a c e
l a y e r and remain i n t h e p l a t e . Microspectral a n a l y s i s of t h e p a r t i c l e s stuck
t o t h e surface l a y e r of t h e copper p l a t e showed t h a t i n t h e l a y e r with 0 . 8 perc e n t Mo t h e y contain 14 percent Mo; i n t h e a l l o y with 0.8 percent Fe, about 4
percent Fe i s present i n t h e i n t e r l a y e r s .

Metallographic Study of Titanium Alloys

A thorough metallographic a n a l y s i s of microsections i n both ordinary and
polarized l i g h t should precede a microspectral a n a l y s i s , s i n c e it r e v e a l s t h e

s t r u c t u r e of t h e a l l o y and permits a q n a l i t a t i v e determination of t h e degree of

inhomogeneity present. I n a d d i t i o n t o ordinary and s e l e c t i v e etching, a simple
and r e l i a b l e method of developing t h e microstructure of titanium a l l o y s i s t h e
etching of t i t a n i u m and i t s a l l o y s by oxidation i n air at 300-500~. Such oxidat i o n may b e accomplished by heating on an ordinary e l e c t r i c h o t p l a t e u n t i l
f i r s t - o r d e r temper c o l o r s appear. The thickness of t h e oxide f i l m Ti02 formed
on t h e s t r u c t u r a l component of t h e specimen under c e r t a i n conditions of oxidat i o n i s r e l a t e d t o t h e c r y s t a l l a t t i c e of t h e s t r u c t u r e , i t s chemical composit i o n , and the o r i e n t a t i o n of t h e c r y s t a l l o g r a p h i c axes of t h e g r a i n r e l a t i v e
t o t h e polished s u r f a c e of t h e s e c t i o n .
Most u s e f u l i n t h e development of t h e a l l o y s t r u c z u r e i s the formation of
Ti02 f i l m s whose thickness v a r i e s between 300 and 750 A on t h e surface of t h e
section.

It may be t e n t a t i v e l y estimated t h a t a f i l m 260-460

a f i l m 480-530
blue

1t h i c k

i s purple, and a f i l m 600-750

1t h i c k

i s yellow,

t h i c k i s blue and dark

It was noted t h a t a f t e r h e a t i n g t o 500' and exposure t o t h i s temperature

f o r s e v e r a l minutes, t h e t h i c k e s t f i l m was formed on a - T i on t h e polished s u r a l l o y . I n t h e oxidation of s i n g l e -phase titanium,
f ace of a two -phase a +
t h e thickness of t h e oxide l a y e r formed depends on t h e oxygen concentration:
t h e more oxygen has dissolved i n a - T i , t h e t h i c k e r i s t h e Ti02 f i l m formed.
For example, i f a - T i i s oxidized t o a yellow color without oxygen, t h e n i n t h e
presence of oxygen a - T i under t h e same conditions oxidizes t o a purple and even
dark-b lue color.

The i n t e r l a y e r s beThe s t r u c t u r e s of t i t a n i u m a l l o y s may be very f i n e

tween lamellae of a-Ti and t h e i n t e r l a y e r s along t h e g r a i n boundaries a r e f i n e .
For t h i s reason, t h e oxidized surface of t h e specimen under a metallographic
microscope should be examined with t h e s t r o n g e s t o b j e c t i v e s . Immersion apochromatic o b j e c t i v e s 90 x 1.30 and acromats 90 x 1.25 a r e attached t o metallographic microscopes f o r t h i s purpose. When an achromatic objective 90 x 1.25
is employed, it i s d e s i r a b l e t o use polarized l i g h t , which makes it p o s s i b l e
t o o b t a i n more s a t u r a t e d i n t e r f e r e n c e c o l o r s of t h e s t r u c t u r e s .

Before carrying o u t a microanalysis of t h e surf aces of f r a c t u r e s s p l i t s ,

and cleavages, it i s d e s i r a b l e t o c a r r y out t h e oxidation and t o abserve them
through t h e microscope a t various megnifications, including t h e h i g h e s t ones,
i n polarized l i g h t . Unfortunately, t h i s cannot always b e done, s i n c e immersion
objectives have a very small working distance.

REFERENCES
1. Korolev, N . V .
2.

Zav. Lab., No. 8, p. 1014, 1959.

Genkin, A. D . and Korolev, N . V .

p. 64, 1961.

Geologiya rudnykh mestorozhdeniy, No. 5 ,

3. Korolev, N . V . and Molchanov, V. S .

Zav. Lab., No. 7, p , 913, 1961.

DEFECT INCLUSIONS IN TITANIUM INGOTS

E. S. Fal'kevich, Ye. A. Lyukevich
and A. N. Kucherenko
At the present time, much attention is concentrated on the study of the
nature of defect inclusions in titanium ingots and semifinished products and
on the causes of the formation of these inclusions.
Defect inclusions in ingots in forged or rolled semifinished products differ
from the base metal by a very appreciable hardness and brittleness which often
cause breaks in the continuity of the metal.
The nature of these inclusions and the cause of their appearance remain
largely unclear.
The existing magnesiothermic method of production of titanium sponge does
not permit the preparation of a sufficiently homogeneous sponge mass. Investigations have shown that films at the points of contact of the sponge mass
with the material of the apparatus ("lining film") and portions located in
the bottom part of the lump ("dark gray sponge") differ most strongly in chemical composition from the bulk of the sponge.
Furthermore, when the continuity of the apparatus is impaired, and also
because of several other factors, a partial oxidation of the sponge in the
course of its preparation is possible. Such sponge often has a straw-yellow
color and less frequently a bluish-violet color. In the total mass of titanium sponge, the oxidized sponge of yellow and bluish-violet color is found
in extremely low amounts (in the form of discrete fragments whose total weight
is less than 0.3 percent of the whole batch).
When the lump is knocked out of the reactor, the sponge sometimes ignites.
The burned sponge acquires a grayish-white color (certain fragments may have a
reddish-brown and yellowish-red color). Such sponge is included in the waste,
and its presence even in the form of individual fragments in the batch is
eliminated, since it does not even reach the crushing system. The chemical
composition of the above-described forms of the sponge of the 2-5 mm fraction
is shown in the table. The content of all the elements (except oxygen) was
determined directly in the sponge. A control ingot could not be melted out of
each type of sponge because of difficulties in pressing and subsequent melting.
For this reason, the oxygen content was determined indirectly. To this
end, 0.5, 1, 2, 3 and 5 percent of sponge of each type was added to the highgrade sponge of known composition. Ingots were melted from such charges.

CHEMICAL COMPOSITION OF SOME TYPES OF SPONGES (wt PERCENT).

Type of
sponge

/ 1 I
Po

Oxidized,
Oxidized, bluish
yiolet
0.03
Oxxd-szed,
g r a y i s h - h i 0.04
Lining film
*

7.23

ci

1 1

xi

si

0.06

0,013 0.04

1 1I

0.10

0.10

1% of
addition

0.04

0.026 0 . 0 1 0 0.04

1,831 4.021 -1
10.5 /1.99 10.09

Note: Numerator, for units made of steel 1 K h 1 8 ~ g ~ ;

denominator, for units made of steel 3.

From the oxygen content of the ingots, its content in the corresponding
type of sponge was calculated.
X-ray structural ana,lysis of all the types of sponge (with the exception
of oxidized sponge of grayish-white color) of the 2-5 mm fraction showed the
presence of mainly one phase, titanium.$ The oxidized grayish-white sponge
consists of a mixture of two phases: rutile, titanium nitride, and titanium.
The lattice constant of titanium nitride for samples of burned sponge
containing various quantities o; yellowish-red or reddish-brown fragments
varies between 4.212 and 4.221 A.

As we know, titanium nitride ?as a cubic lattice of NaCl type with

a lattice constant of 4.213-4.235A depending upon the composition of the
nitride (refs. 1, 2). It is apparent that the lattice constant found for the
burned sponge corresponds to titanium nitride. Nevertheless, it will be more
correct to assume that the burned sponge does not contain pure titanium
nitride but an oxynitride (solid solution of Ti0 in T~N),whose composition
is close to the nitride. Ti0 and TiN form a continuous series of solid solutions. An increase in the oxygen content of titanium nitride will cause a
decrease in the lattice constant, since the l9ttice constant of Ti0 varies
with the composition between 4.184 and 4.153 A (ref. 1).
At the first stage, under laboratory conditions, it appeared of interest
to elucidate the influence of the above-described types of sponge (see table)

l ~ e r eand subsequently a "titanium" phase will designate a solid solution of impurities, primarily gases, in titanium.

on the formation of inclusions in the ingots, and<also to study on laboratory

ingots the inclusions which appear upon the introduction of pieces of hard
alloys into the charge.
In addition, it is very important to find relatively simple and widely
applicable methods which can be used to identify the nature of the inclusion
in each specific case when a small amount of sample is used.l
Method of Investigation
The investigations were carried out on ingots of technical titanium,l30
mm in diameter melted in a laboratory vacuum arc furnace.
In the melting of the alloys, use was made of consumable electrodes 80 mm
in diameter. The electrodes were prepared by pressing into a piercing die with
a 100 ton hydraulic press. The current intensity during the melting was 1.82.4 ka. The weight of the ingot was 7 kg. The residual pressure before melting was 2-10mm Hg. The ingot was melted from a sponge with a hardness HB =
113-120.
Sponge of various types of a 2-16 mm fraction (see table) was introduced
into the electrode in two ways:
(a) During the pressing;
( b ) Into apertures drilled at four points (along the height) of the consumable electrode.

In the latter case, the sponge was placed next to the central axis of
the electrode. 5-10 pieces were placed in each aperture. In all, 50 ingots
were prepared which contained various types of sponge: 10 ingots with the
addition of oxidized sponge of yellow, bluish-violet and dark-gray color, 5
ingots containing lining film, and 15 ingots containing oxidized grayish-white
sponge. In approximately one-half of the ingots the additions were introduced
during pressing, and in the other half, into the apertures.
In addition, eight ingots were prepared by adding 3-10 fragments of hard
alloys VK8 and T15K6 measuring 2-12 mm into each aperture drilled in the consumable electrode.
After roughing and face grinding, the ingots were etched in a mixture of
solutions of nitric and hydrofluoric acid. After the etching, the macrostructure of the faces was studied, and the hardness was measured. The hardness
was measured at 25 points on each face surface using a TSh-2 hardness tester
at a load of 3000 kg and a ball 10 mm in diameter.
l1t is obvious that in most cases the microchemical and microstructural analyses
are amply sufficient to determine the nature of the inclusion. However, these
methods are quite complex and cumbersome and have been adopted by only a few
enterprises.

A f t e r t h e hardness w a s measured, a l a y e r 5 mm t h i c k w a s removed by f a c e

h-white c o l o r i s
gnificant quantities
of dark g r a y

changes most s u b s t a
introduced. The i n
(up t o 5 p e r c e n t ) ,
sponge causes a n i n

47 42 43 44 45 46 4 7 48 43 lfl ll
d i s t a n c e from i n c l u s i o n , mm
Figure 1. Change i n t h e hardness of an i n g o t made of t e c h n i c a l
t i t a n i u m upon i n t r o d u c t i o n of v a r i o u s types of sponge. 1--oxid i z e d yellow sponge; 2--oxidized b l u i s h - v i o l e t sponge; 3--oxid i z e d grayish-white sponge; 4--dark-gray sponge; 5--lining f i l m .
I n c l u s i o n s were not observed i n any of t h e i n g o t s containing dark-gray
sponge, l i n i n g f i l m , and oxidized sponge of yellow and b l u i s h - v i o l e t c o l o r .
No appreciable change i n macrostructure and hardness was observed along t h e
cross s e c t i o n s of t h e ingots ( f i g . 1).
O f t h e 25 i n g o t s melted with t h e a d d i t i o n of oxidized sponge of grayishwhite c o l o r , i n c l u s i o n s were observed i n only one ingot ( f i g . 2 a ) . This i n g o t

Figure 2. Photomicrographs of inclusions in

laboratory ingots, formed upon introduction
into the charge of burned sponge of grayishwhite color (a), pieces of alloy Tl5K6 (b),
pieces of alloy VK8 ( c ) .
was melted by adding the sponge through the apertures. Five inclusions were
observed at various locations along the height of the ingot. The inclusions
were situated close to the lateral surface of the ingot. The phase composition
of the inclusion was titanium oxynitride and $itanium. The lattice constant
of titanium oxynitride was found to be 4.201 A. A certain decrease in the
lattice constant as compared to its value in the initial phase in the grayishwhite burned sponge is apparently due to an increase in the oxygen content of
the oxynitride during the melting.
Thus, the grayish-white rutile present in the oxidized grayish-white
sponge dissolved during melting, and an inclusion formed because of the presence of titanium nitride (more exactly oxynitride, close to the nitride in

composition) in the phase composition of the sponge. Titanium nitride has a

higher melting point (- 2950~)than rutile (1855O). This apparently explains
the different solubilities of these compounds.
The microhardness of the base metal increases sharply as the inclusion
is approached (fig. 3).

2 loo
a
u
distance from inclusion, mrn
Figure 3. Change in the microhardness of regions
of base metal adjacent to inclusions, 1--burned
grayish-white sponge; 2--pieces of alloy ~ 1 5 ~ 63-;
pieces of alloy VK8.
A check with an ultrasonic flaw detector revealed an inclusion along the
axial line of the ingot at a distance approximately one-third of the height
from the lower end in one of the large industrial titanium ingots.

An x-ray structural analysis of the inclusion sh9wed the presence of

titanium oxynitri.de with a lattice constant of 4.203 A and titanium. The
nature of the change in microhardness in the region adjacent to the inclusion is shown in figure 3.
The following remark may be made with regard to the location of a defect
inclusion in an industrial ingot. Titanium nitride has a density of the order
of 5.44 g/cm3, calcuated from x-ray structural data (refs. 1, 2). As a result, when a piece of sponge, shaving or chip whose composition includes titanium nitride falls from the consumable electrode into the liquid bath, it will
go down to the bottom of the bath.
When pieces of hard alloys were inserted into the consumable electrode,
inclusions were observed in all the ingots. It is important to note that despite the insertion of 4-5 large fragments (10-12 mm In size) into each electrode, inclusions of this size were observed in only one ingo-c (in the lower
part). In the remaining cases, instead of a large inclusion, a series of fine
ones was found. Apparently, thermal stresses cause the hard alloys to be
broken up into smaller particles in the course of the melting.

The inclusions were chiefly observed in the lower half of the ingot, close
to the lateral surface,
The phase composition of the inclusions upon the introduction of the solid
alloy T15~6was titanium and titanium carbide with a lattice constant of 4.235
~ 6 had the phase composiA. In the initial state, the pieces of alloy ~ 1 5 used
tion of titanium carbide and tungsten carbide.
When pieces of alloy VK8 are inserted, inclusions are formed which consist mainly of s mixture of titanium and tungsten carbide phases (in the initial
state, alloy VK8 has tungsten carbide as its main phase).
The microhardness of the portions of the base metal adjacent to the carbide inclusions also changes (fig. 3). However, the extent of the increase in
microhardness and the size of the region having an increased hardness are considerably smaller than in the case of oxidized sponge.
A thermodynamic calculation shows that i
2200, the reaction

temperature range of 1700-

should proceed at a high rate.

Consequently, the phase composition of the inclusions formed when fragments of the hard alloys VK8 and ~ 1 5 % drop into the charge should be close
to the composition of titanium carbide. It should be noted that an analysis
which we carried out on two inclusions found in industrial al&oys showed the
presence of titanium carbide with a lattice constant of 4.29 A and the presence of a "titanium" phase.
As can be seen from the above results,
ng upon the cause
e
appearance of inclusions in the ingots, their phase composition and the microhardness of the regions adjacent to them are completely different from one
another.
Summary

1. Oxidized sponge titanium of yellow and bluish-violet color, darkgray sponge and lining film do not cause the formation of defect inclusions
in laboratory ingots of technical titanium.
In some cases, oxidized sponge of grayish-white color having the
2.
phase composition of rutile and titanium nitride (more exactly oxynitride with
a composition close to nitride) may cause the appearance of defect inclusions
in the ingots. Titanium nitride seems to be responsible for the appearance of
inclusions in this case.

3. The introduction of fragments of hard alloys measuring 2-12mrn into

the consumable electrode caused the appearance of inclusions in the ingots in
all cases.

4. X-ray structural phase analysis and measurement of microhardness in

the region adjacent to the inclusion may be used as simple methods for determining the nature of the inclusions.

1. Yeremenko, V. N. Titanium and Its Alloys

AN USSR, Kiev, 1960.
2.

i it an

i yego splavy)

Izd-vo

Samsonov, G. V. and Wnskiy, Ya. S. Solid Compounds of Refractory

Metals (Tverdyye soyedineniya tugoplavkikh metallov) Metallurgizdat,

1957

METASTABLE PHASES OF TITANIUM ALLOYS AND

CONDITIONS OF THEIR FORMATION

S. G. Fedotov

Introduction
The physical and mechanical properties of alloys are known to be strongly
dependent on their structure. By using methods of thermal and mechanical
treatment together or separately, one can change considerably the crystal and
phase structure of alloys, thus causing not only a change in properties, but
frequently giving rise to completely new ones.
Despite the practical development of certain modes and techniques of
thermal and thermomechanical treatment of alloys, many problems still remain
unsolved as regards the physical picture of the processes of hardening and
change in properties, and the meehanism of phase transformation and its
kinetics.
For titanium alloys, which are relatively new structural materials, the
basic tenets of the theory of thermal and thermomechanical treatment have not
been formulated, and the practical conditions of such treatment have been
determined to a lesser extent than for steels.
For this reason, the study of the mechanism and conditions of formation
of metastable phases characteristic of titanium alloys and the accumulation of
new experimental data in this direction are very important.
Brief Characterization of Metastable Phases
As we know, several metastable phases are formed in alloys of titanium
with many transition elements (vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron and other important alloying elements) on
quenching from the f3 region. According to the classification of Yu. A.
Bagaryatskiy et al. (ref. 1), such phases may be the a ' , CY,", w and the f3 metastable phase.
Soviet scientists have made a substantial contribution to the determination of the nature of the metastable phases and to the establishment of the
characteristic features .of their formation (refs 1-6). According to the
studies of the authors of ref. 1, a brief characterization of metastable phases
amounts to the following:

The atphase is a supersaturated solid solution based on the hexagonal

crystal lattice of a-Ti. The formation of the a' phase substantially increases
the hardness of the alloys.
phase differs from the a' phase by a decrease in symmetry from
The at'
hexagonal to rhombic as a result of considerable supersaturation of the a solid
solution with the alloying element. This phase is formed in alloys of titanium
with transition elements whose atomic radii are close to the atomic radius of
titanium (v, Nb, Ta, W, Mo, Re). The hardness of alloys with the a" phase is
considerably lower than that of alloys with the a' phase.
The w phase, detected only by x-ray diffraction, has a hexagonal crystal
structure. Like the atphase, it forms in all alloys of titanium with transition metals, but only at a definite "critical" concentration of the alloying
element.
The metastable a', a" and w phases are martensitic in their mechanism of
formation. This means that according to the concepts given in refs. 3, 7, 8,
the martensite transformation takes place without a change in the concentration
of the solid solution, i.e., without diffusion, as a polymorphic transformation
in a single-component system.
The microstructure of the a' and a" phase has an acicular texture characteristic of all martensitic phases. The w phase does not have an acicular
texture and for this reason is referred to (refs. 1-3) as a martensitic phase
of a special kind.
The fixation of the metastable $ solid solution should be associated with
a low hardness, high ductility indices, a low yield strength and a large difference in the values of the yield strength and ultimate strength as compared
to the analogous characteristics of the other metastable phases (refs. 9, 10).
Characteristic Features of the w Phase
The w phase occupies a special place among the indicated metastable phases.
It causes the most substantial change in the physical and mechanical properties
of the alloys, and its formation is characterized by a series of special features. We shall therefore dwell at some length on their discussion and analysis.
The first reports of the w phase were made in 1954 by Frost et al. (ref.
ll), who observed it in binary alloys of titanium with chromium and manganese.
Later, the w phase was found in many other titanium alloys as well.
The formation of the o phase causes the ernbrittlement of alloys; their
hardness and strength increase greatly, and their elestic constants rise markedly (refs. 12, 13).
The w phase also forms during the tempering of more highly alloyed metastable $ solid solutions.

It was found that the w phase is formed in zirconium- (refs. 14, 15, 6)
and hafnium-base alloys (ref. 16). A state analogous to the w phase with a
similar change in properties was observed in hardened alloys of uranium with
zirconium, niobium and other elements (ref. 17)

For this reason, a great number of investigations have been

nature of the w phase and to the establishment of the conditions
of its formation, since the solution of this problem is of great
practical importance reaching beyond the scope of the problem of
alloys.

devoted to the
and mechanism
scientific and
titanium

As indicated above, the w phase is observed only by x-ray diffraction. It

does not show up under the microscope. There are no reliable data on its
detection by the electron microscope. "It must be admitted" - writes Yu. A.
Bagaryatskiy et al. (ref. 1) - "that neither the shape nor the size of the
formations of the w phase within the $ phase have as yet been reliably established.I
'
There is no consensus of opinion concerning the crystal structure of the w
phase among researchers.
The authors of some studies (refs. 18, 19), asserting that the crystal
structure of the w phase is described in hexagonal axes, stress the similarity
of this lattice to the cubic lattice. Other investigators (refs. 20, 21)
ascribe a pseudocubic crystal structure with a tripled lattice constant to
the w phase.
Other evaluations of the structure of the crystal lattice of the w phase
have been published (ref. 22).

Later, Yu A. Bagaryatskiy (ref. 23) made a critical review of the literature data and confirmed the results of his investigations, which agreed with
the data of Silcock (ref. 24) to the effect that the w phase has a hexagonal
crystal lattice.
Nature of the w Phase
Yu. A. Bagaryatskiy et al. (ref. 2) considered the w phase to be a metastable low-temperature modification of the $ solid solution; this modification
is an electron-type compound. The basis for this interpretation was the fact
that the w phase is formed during the hardening of alloys of only a certain
definite composition which they termed "critical" and which corresponds a$proximately to a constant electron concentration per atom or a constant difference
between the number of vacancies in the d-orbital and the number of s electrons.
V. N. Gridnev and V. I. Trefilov (ref. 6) deem it physically sound to use the
electron concentration as a criterion for the determination of the chemical
composition at which the w phase is formed during the hardening of the alloys.
On this basis, they attempted (ref. 6) to generalize the existing literature
data on the physical and mechanical properties of alloys with the w phase to
the kinetics and mechanism of the $
w transformation as well.
-+

N. V. Ageyev and L. A. Petrova (ref. 5) have also concluded that the role
of the electron concentration is important in stabilizing the metastable J3
solid solutions of titanium with various transition elements which follow the
w phase in composition.
Another group of researchers, mainly foreign ones (refs. 11, 25-29),
regard the w phase as an intermediate phase forming as a result of a redistribution of the alloying elements in the J3 solid solution in the course of
hardening or tempering of alloys. They do not, however, explain the role of
the "critical" concentration of the alloying elements in the formation of
this phase and do not discuss the nature of the mechanism of its formation.

A serious impediment to the treatment of the w phase as an electron-type

compound is, in our view, the experimental fact that the w phase has been
observed in alloys of titanium with zirconium (refs. 14, 3l), in which the
electron concentration remains unchanged over the entire region of compositions, according to the method of calculation adopted in refs. 2, 6.
In our view, the following facts are important in understanding the nature
of the w phase and in the establishment of the conditions and mechanism of its
formation:

1. The w phase is the product of transformation of the metastable J3 solid

solution. The process of the J3 4 w transformation never reaches completion,
i.e., the disappearance of the J3 solid solution; the w phase always coexists
with the metastable $ phase.
2. The lattice constants of the w phase are practically independent of
the conditions of formation (hardening or tempering) or of the type of alloying elements.

3. The process of B w transformation on hardening alloys from the

"critical" concentration takes place at approximately the same or neighboring
indepenmartensite temperatures ( M ~ )which are relatively low (--300-500~),
dently of the alloying elements.

4. The temperature of formation of the w phase during the tempering of

more highly alloyed metastable solid solutions is approximately 180- 500' and
is practically equal to the temperature of formation of the w phase during
hardening ( M ~ )

5. The formation of the w phase is always accompanied by an increase in

the density of the alloys.

6. As was noted above, a characteristic feature of the w phase is that it

does not show up under the microscope or the electron microscope and that difficulties arise in the interpretation of its crystal structure.
The above experimental facts lead to the following conclusions:
First, the constancy and independence of the lattice constants of the w
phase from the conditions of formation (hardening of the alloys from the

"critical" concentration and tempering of more highly alloyed metastable @

solid solutions) indicate its identical chemical composition in the case of
alloys of the same lcind,
Second, the constancy of the lattice constants of the w phase in alloys of
various systems indicates the same contribution made by different elements to
the formation of the structure and parameters of the w phase. Therefore, the
chemical composition at which the w phase is formed in titanium alloys of various systems can be termed the "equivalent" composition.
In this connection, it should be expected that individual volume elements
of an individual fj solid solution which have undergone the f3
w transformation should generally have, independently of the alloying element, the same or
a similar state characterized primarily by a closeness in the value of the
lattice constant. This assumption should be obviously more applicable to
alloys with the "critical" concentration of the alloying elements, since in
the latter the greatest number of volume elements undergo the $
w transformation on hardening, and hence, the original chemical composiLion of these alloys
will provide the truest and most reliable reflection of the changes which they
induce in the lattice constant of @-Ti.
+

The data available in the literature constitute a sufficiently reliable

confirmation of this conclusion. The authors of ref. 1 found that the lattice
constant of the $ solid solution of the systems Ti - W, Ti - Mo, Ti - Cr,
w transformation on hardening, has approximately
Ti - Mn, which undergoes a f3
the same value equal to 3.255-3.26 kX.
+

The data of ref. 1 and the results of other investigations (refs. 32-37)
of the lattice constant of the phase also indicate its linear variation with
the composition for various alloying elements over a wide region of existence
of $ solid solutions. Alloy compositions during the hardening of which the w
phase is formed also follow this dependence. Hence, the main and overriding
significance of the chemical composition of an alloy in the formation of a metastable phase including the w phase does not lie in a special function or special
nature of the initial composition as such, but in the change which this composition induces in the principal parameter of the martensite transformation, i.e.,
the temperature Ms, since the structure of the products of the transformation,
their chemical composition, and the degree of metastability will depend on the
level of the temperature of the martensite transformation and the time during
which they are exposed to this temperature.
Thus, the analogy and similarity in the structure of various metastable
phases in the systems of titanium with various elements characterized by the
same type of interaction result from a similarity or closeness of the values
of the temperatures of martensite transformations. Furthermore, the similarity
in the values of the temperatures of martensite transformations and tempering
temperatures at which the w phase forms in the alloys may indicate an identity
of its physical nature and a single common mechanism of formation, not two
mechanisms, which would be the diffusionless, i.e., martensitic mechanism, and
the diffusion mechanism, as is sometimes indicated in the literature (refs. 30,

38) *

By analogy w i t h t h e conditions of formation of t h e w phase, one can expect

t h a t o t h e r $ s o l i d s o l u t i o n s of various systems w i t h d i f f e r e n t contents of
a l l o y i n g elements w i l l a l s o undergo a f3 + a transformation during hardening a t
t h e same m a r t e n s i t e temperatures ( M ~ i)f t h e value of t h e constant of t h e i n i t i a l $ s o l i d s o l u t i o n s was t h e same,
From t h e above t h e r e follows a s c i e n t i f i c a l l y and p r a c t i c a l l y important
statement of t h e problem which e s s e n t i a l l y amounts t o t h e following: s i n c e t h e
temperature l e v e l of the m a r t e n s i t e transformations determines t h e s t r u c t u r e
of t h e a l l o y s hardened from t h e $ region and hence t h e i r p r o p e r t i e s , then i n
order t o be a b l e t o c o n t r o l t h e process of phase transformations including t h e
martensite k i n e t i c s , i n order t o c o r r e c t l y determine t h e chemical composition
of t h e a l l o y s and t o know t h e optimum p o s s i b i l i t i e s of t h e s e a l l o y s , one must
know t h e p h y s i c a l n a t u r e of t h e temperatures of t h e m a r t e n s i t e transformations
( M ~ ) i,. e . , e s t a b l i s h t h e causes of such pronounced influence of chemical comp o s i t i o n on Ms, t h e independence of Ms from t h e cooling r a t e when t h e c r i t i c a l
r a t e i s reached, e t c .
According t o r e f s . 40-42,t h e temperature range of formation of t h e w phase
during t h e hardening of a l l o y s i s , a s was noted above, characterized by a comp a r a t i v e l y low value (-- 3 0 0 - 5 0 0 ~ ) . A t such temperatures, t h e displacements of
t h e atoms i n t h e t i t a n i u m a l l o y s a r e markedly hindered, but a r e s t i l l p o s s i b l e
under c e r t a i n s p e c i f i c conditions. Therefore, it may be assumed t h a t t h e process of t h e @ - + atransformation which has s t a r t e d a t comparatively low temp e r a t u r e s i n various volume elements and which t a k e s p l a c e a t t h e s e temperatures
during an extremely s h o r t time i n t e r v a l ( i n t h e course of hardening) does not go
t o completion, i . e . , does not reach t h e formation of t h e low-temperature hexagonal c r y s t a l l a t t i c e of a - T i , but s t o p s a t some intermediate s t a g e ( a c t u a l l y ,
t h i s process a l s o t a k e s place a t room temperature a t an extremely slow r a t e ) .
For t h i s reason, such a s t a t e of t h e a l l o y , c h a r a c t e r i z e d by a p a r t i a l d i s placement of t h e atoms i n various volume elements of t h e metastable $ s o l i d
s o l u t i o n s and c a l l e d t h e w phase, shows up n e i t h e r under t h e microscope n o r
under t h e e l e c t r o n microscope, does not cause t h e formation of an a c i c u l a r r e l i e f , and i s a c t u a l l y observed only by means of x-ray d i f f r a c t i o n . This i s
what causes t h e o b s t a c l e s encountered i n t h e i n t e r p r e t a t i o n of t h e c r y s t a l
s t r u c t u r e of t h e w phase.
The formation of t h e w phase i n t h e course of tempering a l s o i n d i c a t e s t h e
n e c e s s i t y of r e d i s t r i b u t i o n of t h e a l l o y i n g elements i n t h e i n i t i a l $ s o l i d
s o l u t i o n over impoverished spaces which s a t i s f y t h e j3
w transformation i n comp o s i t i o n , and over enriched portions, which become more s t a b l e . This has been
experimentally confirmed by s e v e r a l authors ( r e f s . 14, 39) who s t u d i e d t h e decomp o s i t i o n k i n e t i c s . Such a phenomenon i s c a l l e d t h e demixing of f3 s o l i d s o l u t i o n s .
+

Data on t h e d e n s i t y of metastable a l l o y s seemed very important t o us f o r

expanding and deepening t h e concepts of t h e transformation processes. Based on
t h e d i f f e r e n c e i n t h e c r y s t a l s t r u c t u r e of t h e end products of t h e transformat i o n of t i t a n i u m ( a - and $-Ti) and t h e g r e a t d i f f e r e n c e i n t h e parameters a
and c of t h e hexagonal c r y s t a l l a t t i c e , it may be assumed t h a t i n t h e process of
t h e $ 4 a t r a n s f o r m a t i o n , c e r t a i n atoms of t h e o r i g i n a l u n i t c e l l execute d i s p l a c e ments which a r e d i f f e r e n t i n magnitude. Apparently, t h e atoms which form parame t e r c I n t h e a l a t t i c e (we s h a l l r e f e r t o them a s c atoms) a r e displaced t o a

greater extent in the process of the a

making up parameter a.

si: $

transformation than are the a atoms

The observed increase in the density of the alloys upon the formation of the

w phase as compared to the density of the equilibrium alloys with the a + $

structure makes it possible to state that in the process of the rearrangement of

a cubic lattice into a hexagonal one, the c atoms come closer together. The fixation of this state constitutes the essence of the formation of the w phase, i.e.,
the first stage of the $ - a transformation. A further displacement of these
atoms, executed as the temperature is raised, carries the formation of the hexagonal crystal lattice to completion and leads to the appearance of an acicular
microrelief, i.e., to the formation of supersaturated a' solid solutions. The
decrease in density and the formation of an acicular microstructure observed
during the second stage of the transformation indicate that in the course of
their further movement, having passed the energy barrier during their approach,
the atoms diverge in different directions to somewhat greater distances than in
the equilibrium a lattice. This process can be visibly manifested only during
heating, when conditions are created for the expulsion of the excess quantity of
atoms from regions undergoing the $ a transformation, to a composition corresponding to the formation of supersaturated a' solid solutions. The $ + a
transformatio'n and the process of redistribution of the alloying elements in
the initial $ solid solution constitute one and the same process, since the
latter involves the same moving forces and the same mechanism of the elementary
event of displacement of atoms. This process constitutes the essence of
kinetics of martensite transformations.
Thus, the polymorphic $ za transformation occurs in at least two stages.
In alloys with a lower content of alloying elements up to pure titanium,
the process of the martensite $ a transformation does not, in our opinion,
differ in mechanism from the above-described case of the w phase, The difference lies only in the kinetics, i.e., in the rate at which the individual
stages of transformation take place. In the case under consideration, the intermediate state with the w phase cannot be fixed because the displacements of
the atoms occur at an appreciably higher rate and are carried to completion,
resulting in the formation of an a crystal lattice.
-+

However, if conditions are created which hinder such a transformation,

for example, by means of hydrostatic pressure, then it might be possible to
identify a state similar to the w phase in alloys with lower contents of alloying elements and in pure titanium. 1
Another indirect proof of the two-stage occurrence of the
alloys of titanium and in titanium itself are voluae changes,
the volume effect in a $
w transformation, one should expect
rence of the first stage of the $ a transformation should be
+

-+

process in low
By analogy with
that the occuraccompanied by

'After the manuscript of the article was sent to the publisher, the paper of
J.C. Jamilson appeared (science, 1963, 140, No. 3562) which reported the
formation df the w phase in titanium and zirconium at high temperatures.

an increase in density, i.e,, a decrease in volume, and that the occurrence of

the second stage ( w -+ a t ) should be associated with a decrease in density.
Finally, in alloys with a higher content of alloying elements than the
"critical" concentration, the process of - + atransformation does not begin
at all, i.e., does not manifest itself to any appreciable extent, since the
temperature of the martensite transformation in the case of extrapolation of
the corresponding curves is close to room temperature.
Such a state has been termed stabilization of an unstable f3 solid solution. A study of its decomposition on slight heating makes it possible to
follow and identify all the stages of the @ a transformation under conditions where its course has been slowed down.
+

Conclusion and Formulation of New Investigations

Summing up the results of the examination of the available data and their
analysis, one can conclude that the w phase, which is the product of an incomplete polymorphic /3
a formation, constitutes one of the stages or steps
of this process. The incompleteness of the process results from the low temperature of the start of its appearance. At such a temperature, the redistribution of the alloying elements in the initial metastable $ solid solution
over impoverished and enriched regions as well as its further expansion and
occurrence in a hard elastic medium preventing this transformation are hindered
before the formation of a close-packed hexagonal crystal lattice. In this
process, the stage of formation of the w phase has a beginning, but no end.
+

the @

The other metastable phases essentially express the step of completion of

a transformation.
+

In crystal structure, a' and a" phases are the products of the completed
transformation, whereas in the metastable $ phase such processes have not begun at all, i.e., this phase is one with the greatest nonequilibrium character.
In evaluating the pmblem of the @ + a transformation, the physical nature
of the elementary event of the process of $
w transformation and its moving
forces remain unclear, and the kinetics of the transformation and formation of
metastable phases have not been determined. The physical meaning of the temperature of martensite transformations and its strong dependence on the chemical
composition have not been accounted for. The factors determining a definite
chemical composition of the w phase which frequently but not always corresponds
to approximately the same electron concentration per atom have not been established. Because these and other problems have not been solved, the causes of
such pronounced influence of the structure of metastable alloys on the physical
and mechanical properties and the completely new properties acquired by them
remain insufficiently clear.
-)

Hence, it becomes necessary to conduct further investigations which will

bring us closer to the knowledge of the phenomena taking place in metals and
alloys.

In planning new investigations, we proceed from the concepts that the process of polymorphic @ -;t a transformations, i.e., the process of rearrangement
of one order in the distribution of atoms into another under the influence of
temperature, pressure of composition, consists in the loss of elastic stability
of one crystal lattice and its transfer into another, more stable state under
the given conditions.
Important information in this regard may be obviously obtained by studying elastic properties. To this end, we have carried on for a number of years
systematic investigations of elastic constants (young's modulus, shear modulus
and Poisson's ratio) of binary, ternary and more complex titanium alloys as a
function of the composition and structure.
It is well known that the metastable a', a", w and $ phases discussed
above are formed in alloys of titanium with transition elements whose interaction is characterized by:

(1) An unlimited solubility in @-Ti and a low solubility in a-Ti, but

(molybdenum, vanadium, niobium,
one that increases with rising
tantalum);
(2) A high or unlimited solubility in @-Ti and a very low and decreasing
solubility in a-Ti with decreasing temperature below the eutectoid temperature,
at which the f.3 solid solution undergoes a eutectoid decomposition (chromium,
iron, manganese, cobalt, nickel,etc )

..

Thus, in order to attempt an observation of the common and diverse phenomena of the formation of metastable phases and to be able to compare these
data with one another and with the phase diagram, we studied the elastic
properties of alloys of a series of systems both of the first type1 (Ti - Mo,
Ti - V, Ti - Nb, Ti - Ta, Ti-Mo-V, Ti - Mo - Nb, Ti - V - Nb and Ti - Mo V - Nb) and second type2 of interaction (Ti - Cr, Ti - Fe, Ti - Co, Ti - Mn,
Ti - ~i).
The results of the investigation and their analysis will be. presented in
the next paper.

'1n cooperation with 0 . K. Belousov.

In cooperation with Ye. P. Sinodova.

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Translated f o r t h e National Aeronautics and Space Administration

by John F. Holman and Co. Inc.

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