C. Flight: George Mursbdll Space

https://ntrs.nasa.gov/search.jsp?
R=19660015720 2017-12-01T06:45:04+00:00Z
NASA TECHNICAL N.1S4 TM X- 53445

MEMORANDUM
April 20, 1966
x -N66 25009
0 - . a
5 (ACCESSION NUMBER) ITHRUJ
0
>
c
i
(PAGES) (CODE1 -
&
/(I~ASA'CR OR TUX OR AD NUMBER) TEQORI)
HEAT T R E A T M E N T O F T I T A N I U M A N D T I T A N I U M A L L O Y S
By F. F. Schmidt and R. A. Wood

c
Prepared Under the Supervision o f the

Research Branch, Redstone Scientific Information Center
Directorate of Research and Development
U. S. Army M i s s i l e Command
Redstone Arsenal, Alabama
NASA
George C. Mursbdll G P O PRICE s

Space Flight Center, CFSTl PRICE(S) $
Hard copy ':IC) -?

.ba
Microfiche !V F! .7f
ff 853 July 65
I .c- TECHNICAL MEMORANDUM X-53445
HEAT TREATMENT O F TITANIUM AND TITANIUM ALLOYS
F. F. Schmidt and R. A. Wood::
This r e p o r t reviews p r e s e n t h e a t t r e a t m e n t p r a c t i c e s f o r titanium

and titanium alloys. It d e s c r i b e s the methods, techniques, and equip-
m e n t c u r r e n t l y employed in the t h e r m a l t r e a t m e n t of titanium m a t e -
r i a l s , and the n e c e s s a r y p r o c e s s i n g considerations and precautions
I
that g o v e r n t h e s e t r e a t m e n t s . The m e t a l l u r g i c a l background i l l u s t r a t -
ing the p r i n c i p l e s u s e d in titanium h e a t t r e a t m e n t is a l s o d i s c u s s e d
with r e s p e c t t o alloy classifications, s t r u c t u r e s , and hardening
mechanisms.
+ P r i n c i p a l Investigators, Battelle Memorial Institute,

C o n t r a c t No. DA-Ol-O21-AMC-l1651(Z)
NASA-GEORGE C. MARSHALL SPACE FLIGHT CENTER

NASA-GEORGE C. MARSHALL SPACE FLIGH’I CENTER
TECHNICAL MEMORANDUM X-53445
BY
F. F. Schmidt and R. A. Wood
P r e p a r e d for
Manufactur ing Engine e r ing L a b o r at o r y
In Cooperation with
Technology Utilization Office
Under the supervision of
Redstone Scientific Information C e n t e r

U. S. A r m y M i s s i l e Command
Redstone A r s e n a l , A l a b a m a
M s F C O r d e r No. H-76715
Report No. RSIC-493
Subcontracted t o
Battelle M e m o r i a l Institute
505 King Avenue
Columbus, Ohio
C o n t r a c t No. DA-O1-02l-AMC-l1651(Z)
PREFACE
This r e p o r t i s one of a s e r i e s of s t a t e - o f - t h e - a r t r e p o r t s being

p r e p a r e d b y Battelle M e m o r i a l Institute, Columbus, Ohio, under
Contract No. DA-01-021-AMC-l1651(Z), in the g e n e r a l field of
m a t e r i a l s f a b r i c a t ion.
This r e p o r t on h e a t t r e a t m e n t of titanium and titanium alloys i s

intended to provide information useful to d e s i g n e r s , f a b r i c a t o r s , and
u s e r s of titanium m a t e r i a l s . The detailed d i s c u s s i o n s involving the
metallurgical background, methods, techniques, equipment, and p r e -
cautions a r e c o n s i d e r e d to b e r e l i a b l e guides underlying c u r r e n t
p r a c t i c e employed in the t h e r m a l t r e a t m e n t s of titanium and titanium
alloys.
The r e p o r t s u m m a r i z e s information collected f r o m books, techni-

c a l conferences, r e p o r t s on Government c o n t r a c t s , and interviews
with technical p e r s o n n e l actively engaged in titanium h e a t t r e a t m e n t .
A total of 27 r e f e r e n c e s , m o s t of which a r e y e a r 1965, a r e cited.
ii
.
. TABLE O F CONTENTS
Page
SUMMARY . . . . . . . . . . . . . . . . . . 1
INTRODUCTION . . . . . . . . . . . . . . . . 2
METALLURGICAL BEHAVIOR O F TITANIUM ALLOYS . . . 2
Classification of Titanium Alloys . . . . . . . . . 2

.
S t r u c t u r e of Titanium Alloys . . . . . . . . . 5
Alpha Alloys . . . . . . . . . . . . . . 5
Alpha-Beta Alloys . . . . . . . . . . . . 7
Beta Alloys . . . . . . . . . . . . . . . 9
Hardening M e c h a n i s m in Titanium Alloys . . . . . . 9
S t r e s s Relief and Annealing Titanium Alloys . . . . . 12
TYPICAL THERMAL TREATMENTS AND P R O P E R T I E S

O F REPRESENTATIVE TITANIUM ALLOYS . . . . . . 14
Alpha Alloy .Ti-5A1-2.5Sn . . . . . . . . . . 19

Structure . . . . . . . . . . . . . . . 19
. . . .
S t r e s s - R e l i e f Annealing . . . . . . . 19
Annealing . . . . . . . . . . . . . . . 20
.
Strengthening Heat T r e a t m e n t s . . . . . . . 20
.
T h e r m a l Stability . . . . . . . . . . . . 21
Alpha-Beta Alloy .Ti-6A1-4V . . . . . . . . . . 21
Structure . . . . . . . . . . . . . . . 21
. . . .
Annealing . . . . . . . . . . . . . . . 23
.
. .
Hardenability . . . . . . . . . . . 23
Solution Annealing . . . . . . . . . . . 23
. .
Aging Heat T r e a t m e n t s . . . . . . . 23
.
T h e r m a l Stability . . . . . . . . . . . . 26
B e t a Alloy .Ti.13V.llCr.3Al . . . . . . . . . . 26
Structure . . . . . . . . . . . . . . . 26
. . . .
Annealing . . . . . . . . . . . . . . . 27
.
.
Hardenability . . . . . . . . . . . . 27
Solution Annealing . . . . . . . . . . . 27
. .
Aging Heat T r e a t m e n t s . . . . . . . 29
. .
T h e r m a l Stability . . . . . . . . . . . 29
iii
TABLE O F CONTENTS
(Continued)
-
Page
TITANIUMHEAT-TREATMENT P R A C T I C E . . . . . . . 30
Contamination . . . . . . . . . . . . . . . 30
. .
Effect on P r o p e r t i e s . . . . . . . . . . 31
Oxidation . . . . . . . . . . . . . . . 33
Corrosion . . . .. . . . . . . . . . . 37
Contamination Control. . . . . . . . . . . . . 38
F u r n a c ing . . . . . . . . . . . . . . . . 45
Heat-TreatmentTechniques. . . . . . . . . . . 49
CONCLUSIONS AND RECOMMENDATIONS . . . . . . . 55
REFERENCES 56
iv
r
. LIST O F ILLUSTRATIONS
Figure Title Page
1. P r i n c i p a l Types of Titanium-Alloy Constitution

Diagrams . . . . . . . . . . . . . 3
2. M i c r o s t r u c t u r e s of Fully Annealed Titanium. . 6
3. T h e Effect of Solution-Treatment T e m p e r a t u r e on
the M i c r o s t r u c t u r e s of the Alpha-Beta Alloy
Ti-4.4% . . . . . . . . . . . . . . 8
4. R e p r e s e n t a t i v e H a r d n e s s Curve f o r a n Alpha-Beta
Alloy Quenched F r o m Alpha-Beta F i e l d and Aged
at 800 F . . . . . . . . . . . . . . 11
5. E f f e c t of Cooling Rate on P h a s e Relationships and

P r o p e r t i e s of a Typical Heat-Treatable Titanium
Alloy. . . . . . . . . . . . . . . . 14
6. Effect of T i m e and T e m p e r a t u r e on the Relief of

R e s i d u a l Stress in Ti-5A1-2. 5Sn. . . . . . . 19
7. T h e P h a s e Relationships f o r Ti-6A1-4V . . . . 21
8. Effect of T i m e and T e m p e r a t u r e on the Relief of

Residual Stress in Ti-6A1-4V . . . . . . . 22
9. End-Quench Hardenability Curves f o r Ti-6A1-4V . 24
10. T h e Effect of Aging on Hardness of a Ti-6A1-4V

S p e c i m e n End Quenched F r o m 1550 F . . . . . 24
11. The Effect of Section Size on the T e n s i l e P r o p e r t i e s

of Ti-6A1-4V . . . . . . . . . . . . . 24
12. T h e Effect of Solution T e m p e r a t u r e on Tensile

P r o p e r t i e s of Ti-6A1-4V . . . . . . . . . 25
13. T h e E f f e c t of Delayed Water Quenching F r o m 1750 and

1550 F on the T e n s i l e P r o p e r t i e s of Ti-6A1-4V. . . 25
V
LIST O F ILLUSTRATIONS
(Continued)
Figure Title Page
14. T h e Effect of Aging T i m e at 900 F on t h e T e n s i l e

P r o p e r t i e s of Ti-6A1-4V Solution T r e a t e d
at 1550 F . . . . . . . . . . . . . . . 26
15. P h a s e D i a g r a m of B- 120VCA With Variable C h r o m i u m

Content (Ti-13V-Cr-3A1-0. 5 0 2 ) . . . . . . . . 28
16. P h a s e D i a g r a m of B- l2OVCA With V a r i a b l e Aluminum

Content (Ti-13V-11Cr-A1-0. 5 0 2 ) . . . . . . . 28
17. T T T D i a g r a m f o r Ti-13V-11Cr-3A1-0. 1 5 0 2 a s D e t e r -
mined by Metallographic Techniques . . . . . . 28
18. Effect of Solution T e m p e r a t u r e on the Annealed a n d

Annealed-Plus-Aged H a r d n e s s of
Ti-13V-llCr-3A1 . . . . . . . . . . . . . 29
19. Effect of T h e r m a l E x p o s u r e at 6 0 0 F on t h e T e n s i l e
P r o p e r t i e s of Annealed-and- Worked
T i - 13V- 11C r .3A1 . . . . . . . . . . . . 30
20. Effect of Carbon, Oxygen, and Nitrogen on T e n s i l e

P r o p e r t i e s of Iodide Titanium. . . . . . . . . 32
21. Effect of Carbon, Oxygen, and Nitrogen on V i c k e r s

H a r d n e s s of Iodide Titanium. . . . . . . . . . 32
22. Effect of I n t e r s t i t i a l s on Toughness of Iodide

Titanium . . . . . . . . . . . . . . . 33
23. C h a r a c t e r i s t i c s of Hydrogen E m b r i t t l e m e n t in Alpha

Alloys, F r o m Data on Iodide T i t a n i u m . . . . . . 34
24. Oxidation R a t e s of T i t a n i u m in Oxygen in t h e 800 to

1100 F Range . . . . . . . . . . . . . . 36
25. C o m p a r i s o n of the Metal L o s s e s of C o m m e r c i a l

Titanium, Ti-5A1-2. 5Sn, and Ti-4A1-4Mn Heated
in A i r f o r 8 H o u r s . . . . . . . . . . . . 36
vi
c LIST O F ILLUSTRATIONS
( C ont inu ed )
Figure Title Page
26. S u m m a r y of H a r d n e s s - P e n e t r a t i o n Data f o r Unalloyed

Titanium Heated f o r Various T i m e s in A i r at
1600 F . . . . . . . . . . . . . . . . 37
27. Technique f o r Estimating the Depth of Contamination

of C o m m e r c i a l Titanium F r o m Combinations of T i m e
and T e m p e r a t u r e of Exposure t o A i r . . . .
. . 41
28. F o r E s t i m a t i n g the Depth of Contamination of

Ti-5A1-2. 5Sn F r o m Combination of T i m e and
T e m p e r a t u r e of Exposure t o A i r . . . . . . . 42
29. F o r E s t i m a t i n g the Depth of Contamination of Ti-4A1-

4% F r o m Combinations of Time and T e m p e r a t u r e
of E x p o s u r e t o A i r . . . . . . . . .
. . . 43
30. Vertical Gantry Type of Furnace. . . . . . . . 48
3 1. C a r Bottom Type of F u r n a c e . . . . . . . . . 48
3 2. Hot Sizing of Titanium . . . . . . . . . . . 53
33. T i m e - T e m p e r a t u r e - P e r Cent S t r e s s Relief Relation-

Ship f o r Ti-6A1-4V . . . . . . . . . . . . 54
vii
LIST O F TABLES -
Table Title Page
I. Heat T r e a t m e n t and Selected P r o p e r t i e s of Titanium

and Titanium Alloys . . . . . . . . . . . 15
11. P r o d u c e r Designations and F o r m s Available f o r

Titanium and Titanium Alloys . . . . . . . . 18
111. T e n s i l e P r o p e r t i e s of Annealed Ti-5A1-2. 5Sn

Extruded a t 1700 F . . . . . . . . . . . . 20
IV. Effect of T e m p e r a t u r e on the Oxide-Film T h i c k n e s s

of C o m m e r c i a l l y P u r e Titanium Heated in A i r f o r
1 / 2 Hour . . . . . . . . . . . . . . . 35
viii
TECHNICAL MEMORANDUM X-53445
I SUMMARY
The o c c u r r e n c e of a n allotropic t r a n s f o r m a t i o n i n p u r e titanium

c o n t r o l s the type of s t r u c t u r e s that c a n be produced by the h e a t t r e a t -
m e n t of t i t a n i u m - r i c h alloys and hence i n c r e a s e s the r a n g e of mechani-
c a l p r o p e r t i e s that c a n b e obtained f r o m the alloys. Titanium alloys
a r e divided into t h r e e c l a s s e s depending on the predominant phases
p r e s e n t : alpha o r n e a r alpha, alpha plus beta, o r beta. Specific heat-
t r e a t m e n t p r a c t i c e and its effect on p r o p e r t i e s f o r a r e p r e s e n t a t i v e
a-alloy (Ti-5A1-2. 5Sn), a-p alloy (Ti-6A1-4V), and P-alloy (Ti- 13V-
11Cr-3A1) a r e d i s c u s s e d in detail. Typical t h e r m a l t r e a t m e n t s for
other c o m m o n alloys of i n t e r e s t including the so-called "super-alpha"
alloys a r e tabulated.
T i t a n i u m is chemically v e r y a c t i v e at elevated t e m p e r a t u r e s , and

r e a c t s r e a d i l y with oxygen, nitrogen, carbon, and hydrogen i n a f u r -
n a c e a t m o s p h e r e . F u r t h e r m o r e , all contamination r e a c t i o n s c a u s e
d e g r a d a t i o n of p r o p e r t i e s and, with the exception of the hydrogen r e -
action, a r e i r r e v e r s i b l e . B e c a u s e of oxidation, heating t i m e s a r e kept
as s h o r t as is r e q u i r e d t o p e r f o r m the heat t r e a t m e n t . Because of its
v e r y r e a c t i v e n a t u r e , titanium should be h e a t t r e a t e d under conditions
as c l e a n a s possible which m e a n s keeping the workpiece s e p a r a t e d
f r o m all f o r e i g n s u b s t a n c e s , such as organics, i r o n oxides, r e f r a c t o r y
d e b r i s , etc. Titanium alloys a r e a l s o subject to s t r e s s c o r r o s i o n in
the p r e s e n c e of c h l o r i d e s (which might be r e s i d u a l f r o m s u c h things as
c h l o r i n a t e d cleaning solutions) when subsequently exposed to t e m p e r a -
t u r e s above about 550 F.
T h e r m a l t r e a t m e n t s f o r titanium m a t e r i a l s a r e n o r m a l l y c a r r i e d
out in conventional g a s - f i r e d , oil-fired, o r e l e c t r i c f u r n a c e s readily
a v a i l a b l e t o industry. The a t m o s p h e r e in the f u r n a c e should b e f r e e
f r o m w a t e r vapor and should be s l i g h t l y oxidizing. Both w a t e r vapor
and incompletely burned f u e l vapor c a n r e a c t with titanium to f o r m
a t o m i c hydrogen which is r e a d i l y absorbed by titanium. T h e s e prob-
lems m a y b e reduced by using protective coatings a n d / o r m o r e i n e r t
a t m o s p h e r e s , o r completely eliminated by using vacuum t r e a t m e n t .
Reducing a t m o s p h e r e s o r endothermic a t m o s p h e r e s should not be u s e d
in h e a t - t r e a t i n g titanium.
Most titanium m a t e r i a l s that a r e in the semifinished o r finished - -
condition a r e fixtured in jigs to control distortion during the h e a t -
t r e a t m e n t operation. S t r e s s -relieving t e m p e r a t u r e s a r e frequently
used to s t r a i g h t e n and c r e e p f o r m titanium p a r t s in hot-sizing p r e s s e s .
A n u m b e r of recommendations that a t t e m p t to identify p r o b l e m

a r e a s and advancements needed to f u r t h e r titanium h e a t - t r e a t m e n t
technology a r e included i n this r e p o r t .
INTRODUCTION
At the p r e s e n t t i m e (1965), titanium and titanium alloys a r e u s e d

extensively in a v a r i e t y of applications, ranging in sophistication f r o m
c r i t i c a l mis s ile and a i r c r a f t components to c o r r o s i o n - r e s is tant
anodizing r a c k s . Manufacturing c o n c e r n s that have had extensive
experience in fabricating this m a t e r i a l have found that i t i s only
slightly m o r e difficult t o handle than a r e m o s t of the other s t r u c t u r a l
m a t e r i a l s . A s with m o s t s t r u c t u r a l m a t e r i a l s , c e r t a i n p r o c e d u r e s
m u s t be followed to produce high-quality end i t e m s f r o m titanium.
This r e p o r t p r e s e n t s the m e t a l l u r g i c a l background underlying the h e a t
t r e a t m e n t of titanium and titanium a l l o y s , specific t h e r m a l t r e a t m e n t s
applied to the v a r i o u s alloys, and methods, techniques, and p r e c a u -
tions used in actual p r a c t i c e . Specific recommendations identifying
problem a r e a s and advancements needed to f u r t h e r titanium heat-
t r e a t m e n t technology a r e a l s o outlined.
METALLURGICAL BEHAVIOR O F TITANIUM ALLOYS
The v a r i o u s t h e r m a l t r e a t m e n t s applied to titanium and i t s alloys

to develop d e s i r a b l e s t r u c t u r a l c h a r a c t e r i s t i c s f o r metalworking and
end-product p r o p e r t i e s a r e b e s t understood f r o m a fundamental con-
sideration of titanium metallurgy. T h e r e f o r e , this section of the r e -
p o r t i s intended to i l l u s t r a t e the p r i n c i p l e s u s e d in titanium h e a t
treatment.
CLASSIFICATION O F TITANIUM ALLOYS
Titanium h a s two c r y s t a l s t r u c t u r e s . Alpha titanium, the low-

t e m p e r a t u r e modification, h a s a c 10se -packed hexagonal s t r u c t u r e
which i s s t a b l e up to about 1 6 2 5 F. B e t a t i t a n i u m , the high-
t e m p e r a t u r e allotrope, h a s a body-centered cubic s t r u c t u r e and is
2
.
stable f r o m the 1625 F t r a n s f o r m a t i o n t e m p e r a t u r e up t o the melting
Goint of 3035 F. The t e m p e r a t u r e a t which a-titanium begins to t r a n s -
f o r m t o beta is r a i s e d by the alloying of a-stabilizing e l e m e n t s and
lowered by the alloying of p- stabilizing elements. The t e m p e r a t u r e
at which the last remaining a-titanium t r a n s f o r m s t o p-titanium on
heating is called the p - t r a n s u s . Titanium alloys a r e c l a s s i f i e d as
containing principally a - p h a s e , p-phase, o r a m i x t u r e of a- and
/3-phas e s.
The t h r e e p r i n c i p a l types of phase d i a g r a m s f o r titanium alloys

a r e i l l u s t r a t e d in F i g u r e 1 . The alpha peritectoid type of s y s t e m is
c h a r a c t e r i s t i c of titanium alloys with aluminum, carbon, nitrogen,
and oxygen. T h e s e e l e m e n t s have a g r e a t e r solubility i n the a - p h a s e
than in the P-phase. The addition element s t a b i l i z e s the a - p h a s e and
the a - /3 region is elevated to high t e m p e r a t u r e s with i n c r e a s i n g
a-alloy content. Tin, zirconium, and possibly antimony .appear to b e
n e u t r a l , stabilizing neither a-phase n o r P-phase preferentially. In
g e n e r a l , however, t h e s e e l e m e n t s a r e considered a-stabilizing
elements.
TI Alloy Content - TI A I loy Content -

0 AlDhO Perltectotd b Beto Eutectold
TI Alloy Content - 1-52344
c Beta Isomorphous
FIGURE 1 . PRINCIPAL TYPES O F TITANIUM-ALLOY

CONS TIT UT ION DIAGRAMS
3
The P-eutectoid type of s y s t e m is c h a r a c t e r i s t i c of titanium alloys
with s u c h additions a s manganese, i r o n , chromium, nickel, copper,
and silicon. T h e s e p-stabilizing e l e m e n t s d i s s o l v e p r e f e r e n t i a l l y in
the p-phase causing a lowering of the t r a n s u s t e m p e r a t u r e with in-
c r e a s i n g alloy content. A eutectoid r e a c t i o n o c c u r s in this type of
s y s t e m a t a t e m p e r a t u r e between the t r a n s f o r m a t i o n t e m p e r a t u r e of
pure titanium and r o o m t e m p e r a t u r e in which the P-phase decomposes
to f o r m the a - s o l i d solution and a n i n t e r m e d i a t e phase r i c h e r in the
alloying e l e m e n t - usually a n i n t e r m e t a l l i c compound. Although under
equilibrium conditions, c h r o m i u m , manganese, and i r o n f o r m /3-
eutectoid s y s t e m s . The eutectoid reaction in t h e s e alloys is v e r y
sluggish, and in a c t u a l p r a c t i c e , t h e s e alloys behave a s i f the eutec-
toid r e a c t i o n did not occur. Additions of copper and silicon f o r m t r u e
eutectoid type of alloys.
The beta isomorphous type of s y s t e m includes alloys with molyb-

denum, vanadium, tantalum, and columbium. T h e s e e l e m e n t s a r e
appreciably m o r e soluble in the P-phase than in the a - p h a s e and the
p / ( a - p ) and a / ( a - p ) boundaries a r e d e p r e s s e d towards lower t e m -
p e r a t u r e s with increasing p-concentration. Sufficient amounts of t h e s e
additions r e n d e r e t i t a n i u m s t a b l e a t r o o m t e m p e r a t u r e . In a b i n a r y
a l l o y , t h e r e is a m i n i m u m amount of any p-stabilizing e l e m e n t that
enables the retention of 100 p e r cent m e t a s t a b l e beta on quenching
f r o m the P-phase field. F o r the c o m m o n p - s t a b i l i z e r s t h e s e amounts
a r e shown below (Ref. 1):k:
Approximate Weight P e r Cent
Stabilizing to P r o d u c e 100 P e r Cent
Element M e t a s t a b l e Beta on Quenching
Iron 4
C oppe r 12
Manganese 6
Chromium 7
Molybdenum 11
Vanadium 15
Columbium 36
Tantalum 40
In the foregoing d i s c u s s i o n , c o n s i d e r a t i o n h a s been given t o those

conditions which exist favoring a-type o r p-type of alloy s t r u c t u r e s .
Another m o s t important group of titanium a l l o y s a r e those that contain
both a- and P-phases. T h e s e a r e t e r m e d ( a - p ) type of alloys. Since
the P-phase is not r e t a i n e d in the a b s e n c e of a p-stabilizing alloy
.addition, s u c h a n e l e m e n t is a n e s s e n t i a l constitutent of the a-P type of
alloys. In addition t o the p-stabilizing e l e m e n t s , a-P-type of alloys
m a y contain a n a-soluble element, such as aluminum, to add g r e a t e r
s t r e n g t h t o the a-phase. The a-soluble e l e m e n t s a r e a l s o soluble to a n
appreciable extent in the P-phase. Thus, a-P types of alloys a r e not
only affected by the amount of ,8-stabilizing e l e m e n t p r e s e n t but a l s o
by the p r e s e n c e of a - p h a s e stabilizing additions.
The m e t a l l u r g i c a l changes that alloying b r i n g s about in titanium

f o r m the b a s i s f o r dividing titanium alloys into t h r e e c l a s s e s , depend-
ing on whether they a r e n o r m a l l y used in a condition in which they
c o n s i s t e n t i r e l y of a-phase, entirely of the P-phase, o r a m i x t u r e of
the two phases.
STRUCTURE O F TITANIUM ALLOYS
Alpha Alloys. In a-alloys, the p-phase t r a n s f o r m s c o m -

pletely to the a - p h a s e during cooling through the t r a n s f o r m a t i o n -
t e m p e r a t u r e range. E i t h e r a nucleation and growth Widmanststten
type alpha o r a m a r t e n s i t i c type alpha may be formed. The m a r t e n s i t i c
s t r u c t u r e f o r m e d during rapid cooling is designated a s a'. The a' is
of equilibrium composition even when the alloys a r e rapidly quenched
f r o m t e m p e r a t u r e s above the ,8-transus. (Ref. 2 ) The alloys a r e ,
t h e r e f o r e , not r e s p o n s i v e to heat treatment.
Alpha-stabilizing additions of aluminum in e x c e s s of about 6 p e r

cent introduce the probability of a s u p e r l a t t i c e s t r u c t u r e which h a s
been identified as a n o r d e r e d Ti3A1 s t r u c t u r e (a2). The o r d e r i n g m a y
be dilute long range, but i t s effect is generally t o i n c r e a s e s t r e n g t h
and c r e e p r e s i s t a n c e , while decreasing f r a c t u r e toughness and p e r h a p s
hot workability. (Ref. 3). Thus, long holding t i m e s o r slow cooling
in the c r i t i c a l o r d e r i n g t e m p e r a t u r e range (950 t o 1250 F f o r the
n e a r - a -Ti-8Al-lMo- 1V alloy) should be avoided in the f a b r i c a t i o n o r
h e a t - t r e a t m e n t c y c l e s f o r a-stabilized titanium alloys containing
a p p r e c i a b l e amounts of aluminum. (Ref. 1 )
A s indicated above, the Ti-8A1-1Mo-1V alloy is not a p u r e a - a l l o y

It is a n a-P alloy with s o little p-stabilizer content, it is often called a
n e a r - a alloy. Another popular t e r m used f o r this g r a d e and o t h e r
n e a r - a g r a d e s ( s u c h as the Ti-679 a l l o y ) is "super-alpha". Two all-a
g r a d e s , Ti-7A1-12Zr and Ti-SAl-SSn-5Zr, a l s o a r e called s u p e r -
alphas. The h e a t t r e a t m e n t and metallurgy of the l a t t e r follow
exactly t h a t of o t h e r p u r e o r a l l - a alloys. The h e a t t r e a t m e n t and
m e t a l l u r g y of the P-containing super-alpha alloys, Ti-8A1- 1Mo- 1V and
5
Ti-679 a r e in g e n e r a l s i m i l a r t o a-/3 alloys but differ b e c a u s e of the .*
small P-stabilizer content.
The m i c r o s t r u c t u r e of a-titanium alloys c o n s i s t s e s s e n t i a l l y of

100 per cent a-phase. Alpha alloys, such a s c o m m e r c i a l l y p u r e un-
alloyed titanium and Ti-5A1-2. 5Sn, contain a s m a l l amount of P-phase
as a r e s u l t of i m p u r i t i e s , such as i r o n ; however, this i s not in s u f -
ficient quantity to a l t e r t h e i r t r a n s f o r m a t i o n behavior.
Depending upon the method of t r e a t i n g the m e t a l , a - t i t a n i u m c a n

appear in s e v e r a l modifications. T h r e e d i f f e r e n t m i c r o s t r u c t u r e s of
fully annealed unalloyed titanium a r e shown in F i g u r e 2: equiaxed
alpha, Widmans t%tten alpha, and m a r t e n s i t i c alpha (a’). The l a t t e r
two a r e frequently lumped together under the n a m e a c i c u l a r alpha,
Widmanstxtten alpha o c c u r s by t r a n s f o r m a t i o n of beta to alpha on cool-
ing through the t r a n s f o r m a t i o n - t e m p e r a t u r e r a n g e a t a m o d e r a t e l y
slow r a t e . A m o r e r a p i d cooling r a t e l e a d s to the development of
m a r t i n s i t i c alpha (a’). Both f o r m s of a c i c u l a r alpha a r e t h e r e f o r e
t r a n s f o r m a t i o n products. Equiaxed alpha on the other hand, c a n only
be produced by r e c r y s t a l l i z a t i o n of m a t e r i a l that h a s been significantly
deformed in the a-field. The p r e s e n c e of a c i c u l a r alpha i s t h e r e f o r e a n
indication that the m a t e r i a l h a s been heated into the /3-field. (Ref. 4)
lOOX N15088 lOOX N15087 lOOX N15085

a . Equiaxed Alpha b . W idinanstatten Alpha c. Martensitic Alpha
Annealed 1 h o u r a t 1290 F
FIGUW 2 . MICROSTRUCTURES OF FULLY ANNEALED TITANIUM (REF. 4)
6
Alpha-Beta Alloys. Depending upon the P- stabilization e l e -
m e n t s and t h e i r r e l a t i v e amounts, a - p alloys m a y be c l a s s e d a s
s t r o n g l y o r weakly P-stabilized. By definition, m a r t e n s i t i c types of
a - p alloys contain a' a f t e r quenching f r o m a-p o r P-phase fields. The
amount of a' produced by quenching d e c r e a s e s with i n c r e a s i n g P-
s tabilizing-alloy content. T h e r e f o r e , weakly stabilized P-alloys a r e
g e n e r a l l y m a r t e n s i t i c . On the other hand, alloys containing a higher
p e r c e n t a g e of P - s t a b i l i z e r will r e t a i n m e t a s t a b l e b e t a upon quenching
f r o m t h e a - P o r P-phase fields.
Although a-p alloys a r e strengthened by quenching f r o m t e m p e r a -

t u r e s above the p - t r a n s u s , s u c h t r e a t m e n t s a r e not u s e d in c o m m e r -
c i a l h e a t - t r e a t i n g p r a c t i c e . R a t h e r , solution t r e a t m e n t s , followed by
aging, a r e u s e d to s t r e n g t h e n a-p titanium alloys. The solution t r e a t -
m e n t c o n s i s t s of (1) heating to t e m p e r a t u r e s approaching, but below,
the /3-transus, ( 2 ) holding at this t e m p e r a t u r e f o r a given period of
t i m e , and ( 3 ) cooling rapidly t o r o o m t e m p e r a t u r e . The solution-
t r e a t m e n t t e m p e r a t u r e d e t e r m i n e s the amount of P-phase that i s
p r e s e n t in the alloy and the composition of the P-phase. T h i s is
i l l u s t r a t e d in F i g u r e 3 . By p r o p e r t e m p e r a t u r e s e l e c t i o n and r a p i d
cooling, t h e P-phase, which is m e t a s t a b l e below t h e solution-
t r e a t m e n t t e m p e r a t u r e , is r e t a i n e d t o room t e m p e r a t u r e . The a l l o y s
a r e then a g e d at t e m p e r a t u r e s in the range of 900 t o 1100 F. During
aging, a - t i t a n i u m p r e c i p i t a t e s f r o m the P-phase and the alloy is
strengthened. In addition, as precipitation of alpha t a k e s place, the
r e m a i n i n g P-phase is e n r i c h e d in p-stabilizing content and becomes
stable. (Ref. 5)
P r o c e s s i n g and t h e r m a l h i s t o r y a l s o affect the m i c r o s t r u c t u r e of

a-p alloys ( F i g u r e 3 ) . If the a l l o y s a r e worked and h e a t t r e a t e d below
the p - t r a n s u s , fine - g r a i n e d equiaxed m i c r o s t r u c t u r e s result. T h e s e
s t r u c t u r e s give the b e s t combinations of s t r e n g t h and ductility. If a - p
a l l o y s a r e worked o r heated above the J3-transus, l a r g e 13-grains f o r m .
During subsequent cooling, the P-grains t r a n s f o r m t o a final s t r u c t u r e
that depends on a l l o y content and cooling r a t e . A c i c u l a r o r m a r t e n -
s i t i c s t r u c t u r e s a r e f o r m e d when alloys with low p-stabilizing contents
a r e cooled o r quenched. With higher /3-stabilizing contents, t r a n s f o r -
m a t i o n is m o r e sluggish and the a c i c u l a r s t r u c t u r e b e c o m e s finer and,
at high enough alloy contents, finally d i s a p p e a r s . After annealing, o r
a f t e r solution t r e a t m e n t s and aging, alloys with l a r g e p r i m a r y
P - g r a i n s h a v e the s a m e strength, but l e s s ductility, than fine-grained
a l l o y s in similar conditions. B e c a u s e of the l o w e r ductility, l a r g e -
g r a i n s t r u c t u r e s a r e g e n e r a l l y objectionable. (Ref. 5) The lower
ductility a s s o c i a t e d with a c i c u l a r a-p alloys, in conjunction with the
tendency f o r w - t r a n s f o r m a t i o n on cooling accompanying the heating of
7
250X 95258 250X 95265
a. Annealed 1 Hour a t 1200 F b. Annealed 1 Hour a t 1290 F
250X 95259 250X 95266

c. Annealed 1 Hour a t 1380 F d. Annealed 1 Hour a t 1490 F
Per Cent Beto Stabilizer-

4-52343
FIGURE 3. THE EFFECT OF SOLUTION-TREATMENT 25ox 95250

TEMI’EKATUKE ON THE MICROSTRUCTURICS OF TIIE Allllcalcd 1 I l w r ;IL 1!1:30 I:
ALPIHA-BLTA ALLOY T i - 4 . 4 M n (REF. 5)
All hpcciiiiciis w a t c r qucnclicd after aniical.
8
c
If the ,6-stabilizer p r e s e n t in the a l l o y i s l e s s than the c r i t i c a l

;mount, m e t a s t a b l e beta will not be retained a f t e r quenching from
the s o l u t i o n - t e m p e r a t u r e range. Rather, i t t r a n s f o r m s to m a r t e n s i t e
(a') by a s h e a r mechanism. M a r t e n s i t e f o r m a t i o n is c h a r a c t e r i s t i c
of weakly P-stabilized alloys, p a r t i c u l a r l y at high solution t e m p e r a -
t u r e . At low solution t e m p e r a t u r e s some /3-phase will be retained in
the m e t a s t a b l e condition on quenching if the solute composition of the
beta i s n e a r the c r i t i c a l . However, m o s t of the beta will t r a n s f o r m to
m a r t e n s i t e . Any m e t a s t a b l e beta p r e s e n t will t r a n s f o r m during aging
t o alpha in the m a n n e r d e s c r i b e d in F i g u r e 4.
100
600
I /
Note. If hardness is around 400 VHN. as q u e n c h ,
omega may form during quench. I
500
z
I
>
$400
c
al
gI
300
200
I00
I I I
As I IO 100
quenched
Aging Time, hours A-2578Q
FIGURE 4. REPRESENTATIVE HARDNESS CURVE F O R AN

ALPHA-BETA ALLOY QUENCHED FROM
ALPHA-BETA FIELD AND AGED AT 800 F
(REF. 7)
+:Some p r i m a r y alpha would a l s o b e p r e s e n t u n l e s s

alloy is quenched f r o m beta field.
Alpha p r i m e i s not a n equilibrium s t r u c t u r e in C L - ~ and P-alloys.

Since m o r e alloying addition can be maintained in a' than the
e q u i l i b r i u m amount soluble in a (Ref. 2), alpha p r i m e in highly
11
alloyed m a t e r i a l s upon aging r e v e r t s to alpha, producing p r o p e r t y
changes, including hardening. The m e c h a n i s m i s not completely
..
understood and a p p e a r s to v a r y depending on alloy composition. The
manifestation of this in s o m e alloys h a s been observed by the develop-
ment of a finely d i s p e r s e d p r e c i p i t a t e within the a'-needle, a f t e r aging
between 900 and 1400 F. (Ref. 1)
STRESS R E L I E F AND ANNEALING TITANIUM ALLOYS
S t r e s s relieving and annealing t r e a t m e n t s a r e c o m m o n p r a c t i c e

f o r a l l c o m m e r c i a l titanium alloys. T h e s e t r e a t m e n t s a r e n o r m a l l y
employed t o condition the m e t a l f o r subsequent fabrication o r to r e -
s t o r e d e s i r e d combinations of ductility and stability a f t e r fabrication.
A s t r e s s - r e l i e f t r e a t m e n t i s a t r e a t m e n t which produces a r e l a x a -
tion of r e s i d u a l s t r e s s e s induced f r o m mechanical operations o r weld-
joining operations. S t r e s s relieving i s conducted a t the lowest t e m -
p e r a t u r e a t which s t r e s s e s m a y be reduced to d e s i r e d l e v e l s in
p r a c t i c a l t i m e s . In addition, t r e a t m e n t s a r e s e l e c t e d s o that oxidation
and undesirable m e t a l l u r g i c a l f a c t o r s a r e minimized. The effective-
n e s s of a p a r t i c u l a r s t r e s s - r e l i e f t r e a t m e n t depends quite strongly
upon alloy type and alloy concentration. Recommended t i m e -
t e m p e r a t u r e combinations f o r s t r e s s relieving s e v e r a l of the m o r e
common alloys a r e given below: (Ref. 1)
S t r e s s -Relieving Conditions
Alloy Time, Temper atur e,
Alloy Type hours F
C o m m e r c i a l titanium a 1 / 4 to 4 9 0 0 - 1100
T i - 5A1- 2. 5Sn a 114 to 4 1000- 1200
Ti-8A1- 1Mo-1V Near a 112 t o 5 1100-1300
Ti-8Mn a- P 1 / 4 to 1 9 0 0 - 1100
Ti-4A1-3Mo- 1V a- P 112 to 8 9 0 0 - 1050
T i - 6A1- 4V a- P 1 to 24 900- 1200
Ti-6A1-6V-2Sn a- P 1 to 8 900-1200
Ti-13V-llCr-3A1 P 1 / 4 to 112 1300- 1350
P r e c a u t i o n s should b e taken t o avoid s t r e s s relieving strongly

P-stabilized alloys a t t e m p e r a t u r e s m u c h higher than 1150 F. Above
this t e m p e r a t u r e , a p p r e c i a b l e a m o u n t s of beta will f o r m . If the p a r t s
a r e then allowed to cool rapidly, t h i s b e t a w i l l be retained. If, at any
t i m e in their s e r v i c e life, t h e s e p a r t s a r e exposed to t e m p e r a t u r e s
12
a,lloys of this type into the P-field h a s occasionally been r e f e r r e d to as
"/3-embrittlement11. This t e r m is no longer in common usage.
Acicular a-p s t r u c t u r e s a r e generally observed in weldments and in
s o m e extruded and forged components. Alloy compositions have been
modified to m a k e t h e s e s t r u c t u r e s l e s s objectionable.
Beta Alloys. A P-phase alloy that i s thermodynamically stable

a t r o o m t e m p e r a t u r e c a n only be obtained i n titanium-alloy s y s t e m s in
which the addition e l e m e n t is, itself, body-centered cubic a t r o o m t e m -
p e r a t u r e and in which a continuous s e r i e s of p-phase solid solution
e x i s t s a t all concentrations of the addition e l e m e n t (Ref. 6). Alloys of
this type a r e r e p r e s e n t e d by the P-isomorphous s y s t e m in which the
p- stabilizing additions of vanadium, columbium, tantalum, and/ o r
molybdenum s u p p r e s s the formation of a-phase such that F-phase d e -
composition o c c u r s below r o o m t e m p e r a t u r e ( s t a b l e beta). Metastable-
beta a l l o y s , such a s T i - 13V- llCr-3A1, a r e s o heavily P-stabilized that
the P to a - t r a n s f o r m a t i o n is v e r y sluggish and the alloy r e m a i n s 100 p e r
cent beta when cooled f r o m above the F-transus t e m p e r a t u r e (about
1325 F). A i r cooling f r o m the solution t e m p e r a t u r e is sufficiently r a p i d
to r e t a i n P-phase in a m e t a s t a b l e condition. Thus, solution treating is
synonymous with annealing f o r alloys of this type. (Ref. 1)
HARDENING MECHANISM IN TITANIUM ALLOYS
In strongly /3-stabilized alloys, the tendency i s g r e a t f o r m e t a -

s t a b l e beta to be retained on quenching. A s the p-stabilization in-
c r e a s e s and the solution t e m p e r a t u r e d e c r e a s e s this tendency is
f u r t h e r enhanced. During subsequent e l e v a t e d - t e m p e r a t u r e exposure,
as in aging heat t r e a t m e n t , the /3-phase may p a r t i a l l y decompose.
The m e t a s t a b l e - b e t a decomposition during aging m a y be s u m m a r i z e d
a s follows: (Ref. 7 )
pr t w --f pr t w t a.
pr t w t a --f pu t a
isu t CL + t Ti,M
Y
(in active eutectoid s y s t e m s ) ,
where
9
Po = P-phase of original alloy content that e x i s t s a t the c
solution t e m p e r a t u r e and retained on quenching
Pu = P-phase of the equilibrium o r ' pseudo-equilibrium

alloy content that e x i s t s a t the aging t e m p e r a t u r e
Pr = P-phase of the alloy content i n t e r m e d i a t e between

that of Po and Pu (During the aging p r o c e s s , P-phase
gradually b e c o m e s r i c h e r in P-stabilizer e l e m e n t s ,
and eventually the composition r e a c h e s that value
indicated by the p - t r a n s u s . )
o = t r a n s i t i o n phase having a complex s t r u c t u r e
a = equilibrium alpha phase
TixMy = i n t e r m e t a l l i c compound phase.
In many alloys o is difficult to avoid on quenching o r in the initial

stages of reheating f o r aging. Omega f o r m a t i o n is m o s t likely t o
occur at the lower aging t e m p e r a t u r e s (below 900 F). It c a n be
avoided by s e v e r e quenching and r a p i d reheating to the higher aging-
t e m p e r a t u r e range. An aging t e m p e r a t u r e i s n o r m a l l y s e l e c t e d that
i s high enough t o i n s u r e that the a - r e a c t i o n is c a r r i e d t o completion
in p r a c t i c a l t i m e s and low enough to favor sufficient a-nucleation s i t e s
f o r the formation of a fine to m e d i u m a - p r e c i p i t a t e . (Ref. 1 )
An understanding of the n a t u r e of the phase changes t h a t take

place when a P-stabilized titanium alloy is quenched and subsequently
aged may b e obtained f r o m F i g u r e 4. This d i a g r a m m a y be applied,
in principle, to many titanium alloys. In the quenched condition, the
alloy contains a l a r g e p e r c e n t a g e of beta and h a s c o m p a r a t i v e l y low
h a r d n e s s u n l e s s the quench is not r a p i d enough t o s u p p r e s s the f o r m a -
tion of omega. (Ref. 7 )
After aging a s h o r t t i m e at t e m p e r a t u r e s below about 1000 F, the

P-phase s t a r t s to t r a n s f o r m to omega and the alloy i s hardened and
strengthened d r a s t i c a l l y . This high h a r d n e s s p e r s i s t s f o r long t i m e s
a t t e m p e r a t u r e s below 800 F. At aging t e m p e r a t u r e s between 800 and
1100 F, the alloy o v e r a g e s in p r a c t i c a l lengths of t i m e a s the h a r d n e s s
curve shows. This p a r t i a l softening p r o d u c e s the u s e f u l m e c h a n i c a l
properties f o r which titanium alloys a r e noted. It i s brought about by
the completion of the t r a n s f o r m a t i o n of o m e g a to alpha, leaving a f i n e ,
uniform d i s p e r s i o n of alpha i n a p - m a t r i x . (Ref. 7 )
10
hjgher than about 600 F, the beta could partially decompose t o
&-phase and the p a r t s might be s e r i o u s l y embrittled. (Ref. 7 )
It is thus a p p a r e n t that f o r titanium-alloy s h e e t which i s being hot

f o r m e d o r s t r e s s relieved, adequate t e m p e r a t u r e c o n t r o l is v e r y nec-
e s s a r y . If the s t r e s s - r e l i e f annealing t e m p e r a t u r e is too low, e. g . ,
800 o r 900 F, the s t r e s s e s m a y not be sufficiently relieved. If the
t e m p e r a t u r e is too high, m e t a s t a b l e beta might f o r m , and the p a r t m a y
fail during s e r v i c e if omega precipitates f r o m the beta.
In a - a l l o y s , annealing produces a r e c r y s t a l l i z e d equiaxed g r a i n

s t r u c t u r e f o r m a t e r i a l s worked in the a-field. Annealing of a - p o r
p-alloys produces a sluggish o r s t a b l e /3-phase and, in a-/3 alloys, a
slightly i n c r e a s e d amount of alpha. Annealing t r e a t m e n t s of a-P
alloys a r e n o r m a l l y designed t o develop m a x i m u m t h e r m a l stability.
Both the composition and the amount of ,h-phase i n a given a-P alloy
depend upon the t e m p e r a t u r e to which the alloy is heated and the r a t e
a t which it is cooled. F o r example, i n the Ti-8Mn alloy, the beta
which e x i s t s at 1325 F contains about 13 p e r cent manganese; a t
1525 F the beta contains only 8 p e r cent manganese, but m u c h m o r e is
present. T h e composition of the beta d e t e r m i n e s its stability. T h e r e -
f o r e , i f the alloy w e r e quenched f r o m 1325 F, the beta r e t a i n e d would
be m o r e s t a b l e than if the alloy w e r e quenched f r o m 1525 F. T o obtain
m a x i m u m stability of the beta phase, the alloy m u s t be cooled v e r y
slowly through the t e m p e r a t u r e r a n g e in which the a-phase is r e j e c t e d
m o s t readily. Since alpha w i l l dissolve v e r y l i t t l e m a n g a n e s e , it is
obvious t h a t the remaining beta m u s t become e n r i c h e d and, t h e r e f o r e ,
m o r e s t a b l e . Thus, f o r example, the beta phase in the Ti-8Mn alloy
cooled slowly to 1150 F would have a manganese content of about
16 p e r cent. (Ref. 7 )
Slow cooling through the t e m p e r a t u r e range 1300 to 1100 F i s

g e n e r a l l y u s e d by titanium p r o d u c e r s f o r mill products. In F i g u r e 5
t h e effects of t h r e e different cooling r a t e s on the m i c r o s t r u c t u r e s and
p r o p e r t i e s of a n a-p alloy a r e summarized. This shows that a po-
t e n t i a l s o u r c e of w-embrittlement is in the strongly p-stabilized alloys
which h a v e not been cooled slowly enough f r o m the final rolling t e m -
p e r a t u r e . Such m a t e r i a l i s unstable and, if r e h e a t e d f o r hot forming,
w i l l v e r y likely b e c o m e embrittled. L e s s strongly p-stabilized alloys,
s u c h as Ti-6A1-4V7 which do not undergo a n w r e a c t i o n c a n b e cooled
m o r e rapidly f r o m the stabilizing treatment.
13
/-B transus fl is stable
a and B ore stable
Solution
range
Stress relief and

stabilizing range
-Prirnory a i s Rimary a is retoined. Primary a is retoined.

retained. fl i s B portly retained i n Large quantity of secondary
retained in unstable unstable condition and Q formed Remoining beta is
condition A l l o y is portly transformed to w ond Q. enriched and stable. Alloy
soft and ductile. Alloy is slrong, m a y be brittle. is soft and ductile
Time - A-25781
FIGURE 5. E F F E C T O F COOLING RATE O N PHASE RELATION-

SHIPS AND PROPERTIES O F A TYPICAL HEAT-
TREATABLE TITANIUM ALLOY ( R E F . 7 )
TYPICAL THERMAL TREATMENTS AND PROPERTIES O F

REPRESENTATIVE TITANIUM ALLOYS
Although c u r r e n t l y t h e r e a r e about 30 t i t a n i u m a l l o y s c o m -
m e r c i a l l y a v a i l a b l e , about 10 of t h e s e account f o r 85 t o 90 p e r c e n t of
all applications. T h i s group includes t h r e e g r a d e s of unalloyed ti-
tanium and the a l l o y s , Ti-5A1-2. 5Sn, Ti-6A1-4V, Ti-8A1- 1Mo- l V ,
Ti-6A1-6V-2Sn, and T i - 1 3 V - l l C r - 3 A l . ( R e f , 4 ) T h e Ti-6A1-4V alloy
is by far t h e m o s t - u s e d g r a d e (about 60 t o 65 p e r c e n t of all t i t a n i u m
used). (Ref. 8) The Ti-5A1-2. 5Sn ( a - r e p r e s e n t a t i v e ) , Ti-6A1-4-d
(a-P r e p r e s e n t a t i v e ) , and T i - 13V- 1 1 C r - 3 A l ( p - r e p r e s e n t a t i v e ) a l l o y s
a r e d i s c u s s e d in the following s e c t i o n s in d e t a i l with r e s p e c t t o
specific h e a t - t r e a t m e n t p r a c t i c e a n d e f f e c t s on p r o p e r t i e s . The m o s t
common t h e r m a l t r e a t m e n t s f o r t h e s e and all o t h e r t i t a n i u m a l l o y s
n o r m a l l y encountered, together with t y p i c a l m e c h a n i c a l p r o p e r t i e s
obtainable, a r e s u m m a r i z e d in T a b l e I. T h e p r o d u c e r d e s i g n a t i o n s
and the f o r m s a v a i l a b l e f o r the v a r i o u s t i t a n i u m g r a d e s a r e l i s t e d in
Table 11.
14
.
c
-
c?
O
N d
C
-
F
4 -
m
i
5
>
VI
c
N " l o
0 0 1 9
-1
3:
$ n
iD o
o r
m
- Y
-
"l
N
t:
0
2
z
3
4
t:
G.
0
VI
w
a
W
0
a
0
c
U
r -
9 U
U
0 <
2
c
z
w U
c
4
W c
U N
c
c i
4
I -
0
0
n
I; -
m
Y
C
4
c
0 0 0
N
-
0 0
O
-
.
-
F
0
15
.
a- I:
1
0 3 U
I: b-
da
16
r-- m m o
2:: 2 '9:
x
? = P
L
1
a
c
C
-U
I
m m
-
"V
m
-
o
17
TABLE 11. PRODUCER DESIGNATIONS AND FORMS AVAILABLE FOR TITANIUM AND TITANIUM ALLOYS
Nomina 1 C o m p o s i t 1on
(Balance T i ) , Forms
Wright p ? r cent Available(b)
Unalloyed G r a d e s
39. 5Ti A-30, HA-1930, RMI-30, RD-30, Ti-35A, WC-30
39. 2Ti GOC-40, A-40, HA-1940, RMI-40, RD-40, Ti-55A, WC-40
99. OTi GOC-55, A-55, HA-1950, RMI-55, R D - 5 5 , T i - 6 5 A , WC-55
39. OTI GOC-70, A-70, HA-1970, RMI-70, RD-70, Ti-75A, WC-70

98. '?TI OMC-105, Ti-IOOA
I. 15-0. 2 0 P d A - 4 0 P d , H A - l 9 4 0 P d , OMC-103, R M I - 0 . ZPd, RD-015, T i - 0 . 1 5 P d
Alpha Alloys
5AI-2. 5Sn A - I I O A T , HA-5137, OMC-I66A, RMI-5A1-2. 5Sn, RD-110,
Ti-5AI-2. 5Sn
j A l - 2 . 5Sn ( l o w 0 2 ) A-95AT, HA-5137EL1, RMI-5AI-2. 5Sn E L I , T i - 5 A l - 2 . 5% E L I
5AI- 5Sn- 5 2 r T i - 5Al- 5%- 5Z r
7Al- l 2 Z r RMI-7AI- I 2 Z r , T i - 7 A l - l 2 Z r
7Al-2Ch-ITa RMI- 7Al-ZCb- 1 T a , T1-7Al-2Cb- I T a
3AI- I M o - I V HA-81 16, RMI-8AI- 1Mo- I V , RD-8-1-1, Ti-BAL- IMo- IV, WC-8- 1 - 1
E , 25AI-I I S n - 5 Z r - I M o - 0 . ZSi T i - 6 7 9 (1h4-679 B r i t i s h )
A l p h a - B e t a Alloys
3Mn C - I I O M , RMI-BMn, Ti-BMn, WC-8Mn
!Fe- 2C r - 2M0 T i - 140A
2. 5Al- I6V RMI- 16V-2. 5AI, RD- I 7 5
3AI-2. 5V RMI- 3A1-2. 5V, RD- IO0
%AI-4Mn C - 130AM, HA-4145, RMI-4A1-4Mn, RD- I 3 0
%AI-3Mo- I V RMI-4AI-3Mo- I V , T i - 4 A l - 3 M o - I V
jAI-I.25Fc-2.75Cr Ti-5Al-4FrCr
5AI- I . 5Fc- I . 4 C r - I . 2Mo T i - I55A
bA1-4V C-IZOAV, HA-6510, O M C - l 6 5 A , RMl-6AI-4V, RD-64,
T i - 6A1-4V, WC - 6-4
bA1-4V (low 0 2 ) C-IZOAV, HA-6510 E L I o r HA-6148, O M C - l 6 4 B , RMI-6AI-4V E L I ,
Ti-6AI-4V EL1
bA1-6V-ZSn-1 ( F r , C u ) C - 125 A V T , HA- 51 58, RMI- 6A1- 6V-ZSn, T i - 6Al- 6V-2Sn, WC- 6 - 6 - 2
7Al-4Mo C - I35A Mo, HA- 7 146, RMI- 7A1-4M0, T i - 7A1-4M0, WC- 7-4
Beta Alloys
IA1-8V-5Fe RMI- IAI-BV-5Fr
3Al-13V-IICr B-IZOVCA, R M I - I 3V-lICr-3A1, RD-120, T i - 1 3 V - I I C r - 3 A 1 ,
w c - 13- I I - 3
~ .
.
.
( a ) A-, D - , C - : C r u c i b l e S t r r l C o m p a n y (b) I3 - B i l l e t s a n d b a r s
G O C - : G. 0. C a r l s o n , Inc. F - Forgings
EIA-: H a r v e y Aluininiiln C o m p a n y S - P l a t e , s h r r f , and s t r i p
OMC - : O r P gon M t a I1 11r p I Ca1 C o r po r a t I on E -
Extrusions
RD-: R and D M e t a l s C o m p a n y ( w i r r s u p p l t e r ) T - Tubing
RMI-: Rc-active M c ~ t a l s , Inc. W - Wire
T I - : 'Titanitim M c l a l s C o r p . of Amc.ri< .I ('I'MCA)
W C - : Wah Chang C o r i m r a l i o n
18
c
ALPHA ALLOY - Ti-5A1-2.5Sn (Ref. 4 )
S t r u c t u r e . T h e s t r u c t u r e of Ti-5A1-2. 5Sn at r o o m t e m p e r a -
t u r e is e s s e n t i a l l y all alpha. T r a c e s of /3-phase c a n u s u a l l y b e de-
t e c t e d m e t a l l o g r a p h i c a l l y r e s u l t i n g f r o m the stabilization of this phase
by i r o n and m a n g a n e s e i m p u r i t i e s . This small amount of P-phase c a n
be d e t r i m e n t a l t o v e r y low t e m p e r a t u r e p r o p e r t i e s , however a low
i n t e r s t i t i a l g r a d e ( E L I ) which a l s o h a s a lower i r o n and m a n g a n e s e
content c a n be u s e d f o r t h e s e applications. The a - s t r u c t u r e h a s t w o
basic f o r m s - equiaxed and a c i c u l a r . The equiaxed s t r u c t u r e is ob-
tained by working and annealing in the a - p h a s e field. T h e a to a-p
t r a n s u s is about 1875 F and all p - s t r u c t u r e s e x i s t above about 1925 F.
The a c i c u l a r f o r m of alpha r e s u l t s f r o m cooling f r o m the a-p o r

P-region. A l l m e t a l which w a s beta at the elevated t e m p e r a t u r e be-
c o m e s a c i c u l a r alpha d u r i n g cooling. Rapid cooling p r o d u c e s a s h a r p
a c i c u l a r m a r t e n s i t i c a - s t r u c t u r e . Slow cooling p r o d u c e s a l a r g e
rounded a c i c u l a r a - g r a i n s t r u c t u r e . All m e t a l which w a s not t r a n s -
f o r m e d to b e t a during the e l e v a t e d - t e m p e r a t u r e e x p o s u r e r e m a i n s in
the equiaxed a - f o r m .
S t r e s s - R e l i e f Annealing. S t r e s s - r e l i e f annealing is n o r m a l l y
conducted i n the 1000 to 1200 F t e m p e r a t u r e r a n g e f o r 1 / 4 to 1 hour
I followed by a i r cooling. F i g u r e 6 shows that little r e l a x a t i o n takes
FIGURE 6. E F F E C T O F TIME AND TEMPERATURE ON THE R E L I E F

O F RESIDUAL STRESS I N Ti-5A1-2. 5Sn (REF. 4 )
19
place at 7 0 0 F, only p a r t i a l relief of r e s i d u a l s t r e s s in p r a c t i c a l t i m e s
'
a t 900 F, and significant s t r e s s - r e l i e f annealing c a n be accomplished
i n 1 hour a t 1100 F.
Annealing. Ti-5A1-2. 5% is annealed f o r 1 / 4 t o 4 h o u r s in

the t e m p e r a t u r e r a n g e 1300 t o 1600 F. The s h o r t e r e x p o s u r e t i m e s
a r e used with the higher t e m p e r a t u r e s . T e m p e r a t u r e s above 1600 F
a r e not used b e c a u s e of e x c e s s i v e oxidation and g r a i n growth. Cool-
ing r a t e h a s l i t t l e effect on p r o p e r t i e s and m a t e r i a l is n o r m a l l y a i r
cooled although f u r n a c e cooling m a y be u s e d in vacuum annealing
(this annealing t r e a t m e n t r e s t o r e s b e s t ductility and toughness t o the
alloy).
Heating into the P-field without subsequent working in the a-field

c a u s e s lower ductility at r o o m t e m p e r a t u r e with l i t t l e effect on
tensile-strength p r o p e r t i e s (Table 111). Toughness can be i n c r e a s e d
b y P-heat t r e a t m e n t .
TABLE 111. TENSILE P R O P E R T I E S O F ANNEALED Ti-5A1-2. 5Sn

EXTRUDED A T 1 7 0 0 F ( a ) ( R E F . 4 )
__ - - -~~
Tensile Yield Reduction

Strength, Strength, Elongation, of A r e a ,
Annealing T r e a t m e n t 1000 p s i 1000 p s i 70 in 4 D %
- ~ _ _ _ _
2 1 0 0 F, w a t e r quench 153. 1 152.6 12.5 25. 0

2100 F, a i r cool 149.0 138. 8 8. 3 15. 2
2100 F, f u r n a c e cool 151. 8 141. 2 7. 5 13. 9
1850 F, w a t e r quench 146.3 131.4 16. 7 50. 0
1850 F, a i r cool 143. 5 139.0 16. 7 45. 7
1850 F, f u r n a c e cool 144. 2 141. 2 15. 5 43. 7
1600 F, a i r cool 138.4 131. 8 16. 7 50. 3
1200 F, a i r cool 146.0 143. 2 16. 7 43.4
__
(a) a -[jextrudcd.
Strengthening Heat T r e a t m e n t s . Since Ti-5A1-2. 5Sn i s

e s s e n t i a l l y an all a - a l l o y , heat t r e a t m e n t h a s l i t t l e o r no e f f e c t on
mechanical p r o p e r t i e s .
20
T h e r m a l Stability. Ti-5A1-2. 5Sn is metallurgically s t a b l e
hnder any conditions of s t r e s s , t e m p e r a t u r e , and t i m e up to the
annealing t e m p e r a t u r e .
ALPHA-BETA ALLOY - Ti-6A1-4V ( R E F . 4 )
S t r u c t u r e . Ti-6A1-4V i s a n a - p alloy in which a n a - s t a b i l i z e r ,

aluminum, and a p - s t a b i l i z e r , vanadium, a r e combined. The r e -
sponse of this alloy to t h e r m a l t r e a t m e n t c a n b e s t be d i s c u s s e d in
t e r m s of the phase relationships. F i g u r e 7 shows a s c h e m a t i c v e r t i c a l
section of the t e r n a r y phase diagram.
4 A- 5094 I
Vanadium, per cent
FIGURE 7. THE PHASE RELATIONSHIPS FOR Ti-6A1-4V ( R E F . 4 )
Annealing t e m p e r a t u r e s , indicated by Point A, usually a r e in the

r a n g e f r o m 1 2 0 0 to 1400 F. The resulting s t r u c t u r e is mainly a-phase,
with beta r e t a i n e d in the g r a i n boundaries. This high proportion of
alpha is a r e s u l t of the relatively high solubility of vanadium in alpha,
and the p r e s e n c e of aluminum, a n a - s t a b i l i z e r . By solution annealing
and quenching f r o m t e m p e r a t u r e s higher in the a - p field (Points B
to C), the alloy c a n be strengthened by subsequent aging. This in-
c r e a s e i n h e a t - t r e a t m e n t r e s p o n s e is caused both by the i n c r e a s e d
amount of p-phase in the s t r u c t u r e and the change in alloy content of
the P-phase with i n c r e a s i n g t e m p e r a t u r e . As the solution-annealing
t e m p e r a t u r e i s i n c r e a s e d , the vanadium content of the equilibrium
P-phase eventually is lowered below the l i m i t a t which p-phase is r e -
tained on quenching; the beta t r a n s f o r m s partially to alpha p r i m e
( m a r t e n s i t e ) a f t e r solution annealing at about 1750 F, w h e r e a s a t
21
1550 F, b e t a i s r e t a i n e d . At the l a t t e r solution-annealing t e m p e r a - .’
t u r e , however, the P-phase i s mechanically u n s t a b l e a f t e r quenching,
and m a r t e n s i t e c a n then be f o r m e d during p l a s t i c s t r a i n i n g . T h i s
condition is c h a r a c t e r i z e d by a low r a t i o of yield to u l t i m a t e t e n s i l e
s t r e n g t h s . Maximum h e a t t r e a t m e n t r e s p o n s e is a t t a i n a b l e a f t e r
solution annealing in the P-field (D); however, the s t r e n g t h i n c r e a s e
i s offset by a c o n s i d e r a b l e l o s s of ductility ensuing f r o m t h e t r a n s -
f o r m e d s t r u c t u r e , s o t h a t solution a n n e a l s usually a r e not c a r r i e d out
in the a l l - b e t a r a n g e but r a t h e r f r o m i n t e r m e d i a t e to high in the a-P
range ( P o i n t s B to C ) .
The i n t e r s t i t i a l e l e m e n t s c a r b o n , oxygen, and n i t r o g e n i n c r e a s e

t h e /3-transus with i n c r e a s i n g concentration. When t h e s e e l e m e n t s
a r e in excessof the n o r m a l l e v e l s , the /3 to a - r e a c t i o n is a c c e l e r a t e d
by the p r e s e n c e of t h e s e e l e m e n t s d i s s o l v e d in the /3-phase. At
n o r m a l concentrations m o s t of the i n t e r s t i t i a l s a r e d i s s o l v e d p r e f e r -
entially in the a - p h a s e s o that in p r a c t i c e little effect i s o b s e r v e d on
t h e t r a n s f o r m a t i o n kinetics.
S t r e s s - R e l i e f Annealing. T e m p e r a t u r e s of 1000 t o 1200 F

f o r periods of 1 / 2 to 1 h o u r , followed by a i r cooling, a r e commonly
u s e d to s t r e s s r e l i e v e Ti-6A1-4V. To m i n i m i z e oxidation, the t i m e
and t e m p e r a t u r e s should be a s low a s possible. Data covering the
effect of t i m e and t e m p e r a t u r e on r e s i d u a l s t r e s s a r e i l l u s t r a t e d in
F i g u r e 8.
Minutes 0 2 0 3 0 4 0 5 0
A-50940
Time
FIGURE 8. E F F E C T O F TIME A N D TEMPERATURE O N THE

R E L I E F O F RESIDUAL STRESS I N Ti-6A1-4V
( R E F . 4)
22
Annealing. Annealing heat t r e a t m e n t s usually involve holding
f o r 1 to 2 h o u r s a t 1300 to 1500 F, furnace cooling to about 1100 F,
and then a i r cooling to r o o m t e m p e r a t u r e . T i m e , t e m p e r a t u r e , and
cooling r a t e a r e s e l e c t e d s o that the annealing t r e a t m e n t achieves a
mixed a-p s t r u c t u r e that is ductile and stable. The m a j o r i t y of
Ti-6A1-4V product is supplied in the annealed condition.
Strengthening Heat T r e a t m e n t s . Generally the b e s t heat-

t r e a t e d p r o p e r t i e s a r e developed b y solution annealing at 1550 t o
1750 F, w a t e r quenching, and aging at t e m p e r a t u r e s f r o m 900 t o
1100 F.
Hardenability. Heat-treatable titanium alloys, s u c h as

Ti-6A1-4V, show a rather shallow hardenability. This is due t o the
low t h e r m a l conductivity of titanium alloys which allows t r a n s f o r m a -
tion of the /3-phase t o omega o r alpha during cooling f r o m the
solution-annealing t e m p e r a t u r e ( F i g u r e 9). Data shown in F i g u r e s 10
and 11 indicate that full strength in Ti-6A1-4V alloy sections o v e r
about 1 inch in thickness is not expected.
Solution Annealing. Solution annealing Ti-6A1-4V a t

about 1550 F r e s u l t s in m a x i m u m ductility and b e s t formability.
Solution annealing a t 1700 to 1750 F develops m a x i m u m s t r e n g t h
p r o p e r t i e s ( F i g u r e 12).
The solution t e m p e r a t u r e is effectively lowered when the work-

piece is not immediately quenched. The effect of time delay before
quenching on the t e n s i l e p r o p e r t i e s of Ti-6A1-4V is shown in
F i g u r e 13.
Aging Heat T r e a t m e n t s . The s t r e n g t h of Ti-6A1-4V is

improved through aging in the t e m p e r a t u r e r a n g e 900 to 1100 F f o r
1 to 24 h o u r s . Aging h e a t t r e a t m e n t s m u s t b e preceded by solution
annealing. Higher aging t e m p e r a t u r e s r e s u l t in overaging and a
c o n s i d e r a b l e l o s s in s t r e n g t h and only a slight improvement in
ductility. F i g u r e 14 shows the effect of aging t i m e at 900 F on the
t e n s i l e p r o p e r t i e s of Ti-6A1-4V m a t e r i a l solution t r e a t e d a t 1550 F.
Aging t i m e s i n e x c e s s of 8 h o u r s have little effect on p r o p e r t i e s .
23
50 I I I I
I n t e r s t i t i a l Level No. --
Carbon Oxygen N i t r o g e n
- I 0.05 0.06 0.0I
45
0 2 0.05 0.24 0.0I
-
- 3 0.05 0.08 0.07
0,
3 40 4 0.05 0.16 0.04
Y
0
0
5 0.20 0.08 0.0I
LT
m
m
- 35
Q,
c
72
30
25
0 I 2 3 4
Distance From Quenched End, inches
A-50939
FIGURE 9. END-QUENCH HARDENABILITY CURVES FOR T i - G h l - 4 V (REF. 4)
Solution teinpcraturcs werc 1 0 0 F above the beta traiisus.
iE
400 L 'SQF IC,wa
IKx)F24C1 IC, W O
W F
0 350
c
ul
In
Q,
6 300
0
I
250
200
Distance, inches
FIGURE 10. THE EFFECT OF AGING ON H A R D - FIGURE 11. THE EFFECT OF SECTION SILE
NESS OF A Ti-6A1-4V SPECIMEN END QUENCHED ON THE TENSILE PROPERTIES OF T1-6A1-4V
FROM 1550 F (REF. 4 ) (KEF. 4 )
24
0
._
c
0
E
0.95
0)
0.85
0.75 C
0.65 F
,
E
.-w
t
1300 1400 1500 1600 1700 1800

Temperature, F
FIGURE 12. THE E F F E C T O F SOLUTION TEMPERATURE ON

TENSILE PROPERTIES O F Ti-6A1-4V ( R E F . 4 )
..
GI20 0.90-;”
C 0
100 0.80
5i
0.70 5
0)
3 0.60
..
c
.- 40
- .o=
C
.-0
0
20
0 -
E S 0
wzU
B Log Time, seconds
T i m e , seconds A-50938
FIGURE 13. THE E F F E C T O F DELAYED WATER QUENCHING

FROM 1750 AND 1550 F ON THE TENSILE
PROPERTIES O F Ti-6A1-4V ( R E F . 4 )
25
FIGURE 14. THE E F F E C T O F
AGING TIME AT 9 0 0 F ON THE
TENSILE P R O P E R T I E S O F
Ti-6A1-4V SOLUTION TREATED
AT 1550 F ( R E F . 4 )
0 8 16 24
32 40 48
Time, hours
A- 50946
-
T h e r m a l Stability. In g e n e r a l , Ti-6A1-4V, a s annealed o r
a s aged under o r d i n a r y s e r v i c e conditions, is c o n s i d e r e d s t a b l e . T h e
alloy h a s the ability t o r e t a i n the o r i g i n a l m e c h a n i c a l p r o p e r t i e s a f t e r
prolonged t h e r m a l e x p o s u r e in a v a r i e t y of environments. Elevated-
t e m p e r a t u r e e x p o s u r e of solution-treated material, during o p e r a t i o n s
such as forming, m a y lead to s t r e n g t h i n c r e a s e s and a c o r r e s p o n d i n g
d e c r e a s e in ductility. In s u c h c a s e s the alloy should be s t a b i l i z e d by
aging o r annealing p r i o r t o s e r v i c e .
BETA ALLOY - Ti- 13V-llCr-3A1 ( R E F . 4)
S t r u c t u r e . T h e Ti- 1 3 V - l l C r - 3 A l s t r u c t u r e is e n t i r e l y beta
a t r o o m t e m p e r a t u r e a f t e r annealing f r o m above t h e /3-transus. T h e
s t r u c t u r e is e a s i l y obtained e v e n with slow cooling r a t e s b e c a u s e of
the ,B-stabilizing c h a r a c t e r i s t i c s of the high vanadium and c h r o m i u m
content of the alloy.
T h e effect of v a r i a b l e c h r o m i u m content on t h e phase relation-

ships of T i - 1 3 V - l l C r - 3 A 1 is shown i n F i g u r e 15. The alloy is
hypoeutectoidal with a p - t r a n s u s between 1200 and 1300 F. The high
vanadium content contributes t o the s t a b i l i z a t i o n of the j3-phase t o t h i s
low t e m p e r a t u r e .
F i g u r e 16 shows t h e effect of v a r i a b l e a l u m i n u m content. In-

c r e a s i n g a l u m i n u m content s t a b i l i z e s t h e a - p h a s e , which in t u r n
26
r a i s e s the p - t r a n s u s t e m p e r a t u r e . Oxygen a l s o r a i s e s the p - t r a n s u s
t k m p e r a t u r e . Without the m i n o r aluminum addition the p - t r a n s u s
t e m p e r a t u r e would be lowered by about 200 F.
The P-phase i s thermodynamically stable down t o about 1200 F

(with low oxygen content), however, the decomposition of the P-phase
is v e r y sluggish even a t lower t e m p e r a t u r e s . This is i l l u s t r a t e d in
F i g u r e 17. In addition to the decomposition products of the P-phase,
alpha and T i C r Z , and o-phase is believed to b e formed. The exact
conditions f o r the development of omega have not been established.
It is believed that omega is unstable and will decompose rapidly
above 1000 F.
S t r e s s - R e l i e f Annealing. S t r e s s - r e l i e f annealing of T i - 13V-

11Cr-3A1 is n o r m a l l y c a r r i e d out by annealing f o r 1 / 4 to 4 h o u r s at
900 to 1200 F. The s h o r t e r t i m e s a r e used with the higher
temper atur e s .
Annealing. N o r m a l cooling f r o m the annealing t e m p e r a t u r e
r e t a i n s the P-phase s t r u c t u r e . Thus, annealing t r e a t m e n t s f o r
Ti-13V- 11Cr-3A1 a r e the s a m e a s solution treating.
Strengthening Heat T r e a t m e n t s . High s t r e n g t h s a r e de-

veloped in Ti- 13V- 11Cr-3A1 by solution annealing above 1400 F, water
quenching o r air cooling, and aging a t 800 t o 1000 F. The Ti-13V-
11Cr-3A1 a l s o m a y be strengthened by cold working which is
i l l u s t r a t e d later.
Hardenability. Thick sections of Ti-13V- 11Cr-3A1 c a n

b e h a r d e n e d by aging solution-annealed m a t e r i a l . This r e s u l t is
obtainable due to the sluggishness of the P-phase which is r e t a i n e d
even i n t h e c e n t e r of v e r y thick sections and is subsequently a g e
hardenable.
Solution Annealing. Within the solution-annealing r a n g e

of about 1300 t o 1900 F t h e r e is little change in the h a r d n e s s ( F i g -
u r e 18) of annealed o r subsequent aged m a t e r i a l with t e m p e r a t u r e .
Cooling rate s e e m s to have e s s e n t i a l l y no effect due to the high
P- s t a b i l i z e r content of the alloy. However, long solution-annealing
p e r i o d s at high t e m p e r a t u r e s lower the ductility in aged m a t e r i a l
through e x c e s s i v e g r a i n growth and breakdown of favorable nucleation
s it e d i s tr ibution.
27
v9 IO II I2 13 14
Chromium Content, per cent
FIGURE 15. PHASE DIAGRAM OF BETA ALLOY WITH VARIABLE CHROMIUM CONTENT
(Ti-13V-Cr-3A1-0.05 0 2 ) (REF. 4)
-----r
I500 1400 ~
1 - r- - -
Beto tmnsus 1325 F
I400
I300
4
fe 1200
0)
n
El
I-
1100
IO00
900
500 -
Solution treoted
cent cold rolled
+ 25 per
-
I I
0 1 2 3 4 5 6 01 I IO I00 000 10,000
A-X¶bO
Aluminum Content, per cent Transformation Time, hours
A - 50955
FIGURE 16. PHASE DIAGRAM OF BETA ALLOY FIGURE 17. TTT DIAGRAM FOR T i - 1 3 V - l l C r -
WITH VARIABLE ALUMINUM CONTENT 3A1-0.15 0 2 A S DETERMINED BY METALLO-
(Ti-13V-11Cr-A1-0.5 0 2 ) (REF. 4) GRAPHIC TECHNIQUES (REF. 4)
28
FIGURE 18. E F F E C T O F
SOLUTION TEMPERATURE
ONTHEANNEALEDAND
ANNEALED-PLUS AGED
HARDNESS O F Ti-13V-11Cr-
3A1 ( R E F . 4)
1100 1300 1500 1100 1900 2100 2300

Solution kmperature, F
A-50956
Aging Heat T r e a t m e n t s . Aging T i - 13V- 11Cr-3A1 in-

c r e a s e s s t r e n g t h p r o p e r t i e s through the modification of the
m e t a s t a b l e - b e t a s t r u c t u r e to p-plus-decomposition products. De-
composition of m e t a s t a b l e - b e t a phase does not o c c u r below about
6 0 0 F. N o r m a l aging of solution-annealed m a t e r i a l i s conducted a t
800 t o 950 F f o r relatively long periods of t i m e , 20 t o 100 h o u r s .
Overaging does not o c c u r for up t o 500 h o u r s a t 1000 F and it a p p e a r s
that m a x i m u m aging r e s p o n s e o c c u r s at about 900 F. The aging r e -
a c t i o n is a c c e l e r a t e d i n cold- o r w a r m - w o r k e d m a t e r i a l . A signifi-
cantly h i g h e r s t r e n g t h level can b e achieved by cold working the alloy
between t h e solution h e a t t r e a t m e n t and the aging t r e a t m e n t .
T h e r m a l Stability. The ability of the solution-annealed

P-alloy t o m a i n t a i n mechanical p r o p e r t i e s is limited to relatively
s h o r t e x p o s u r e t i m e a t t e m p e r a t u r e s to about 600 F. F i g u r e 19
i l l u s t r a t e s the e f f e c t of t i m e on the 600 F stability of annealed and
cold w o r k e d Ti- 13V- 11Cr-3A1. The t h e r m a l stability of aged m a t e -
rial is b e t t e r than that of annealed m a t e r i a l . However, the t e m p e r a -
t u r e limit f o r alloy stability r e m a i n s in the range 575 to 600 F f o r
l o n g - t i m e exposure.
29
FIGURE 19. E F F E C T O F
THERMAL EXPOSURE AT 600 F
ON THE TENSILE PROPERTIES
O F ANNEALED-AND- WORKED
T i - 1 3 V - l l C r - 3 A l ( R E F . 4)
E w s u r e Tome 01 600 F. hours A-50949
TITANIUM HEAT- TREATMENT PRACTICE
S t r e s s relieving titanium a l l o y s r e l a x e s r e s i d u a l s t r e s s e s and

i m p r o v e s ductility and toughness. Heating titanium a l l o y s higher into
the r e c r y s t a l l i z a t i o n - t e m p e r a t u r e r a n g e followed by a i r o r f u r n a c e
cooling (depending on composition) develops the m a x i m u m ductility
and toughness. F o r strengthening p u r p o s e s , titanium a l l o y s a r e
f i r s t solution t r e a t e d a t r e l a t i v e l y high t e m p e r a t u r e s , w a t e r
quenched, and finally aged at s o m e i n t e r m e d i a t e t e m p e r a t u r e . T h u s ,
the r e a s o n s f o r the heat t r e a t i n g of titanium and t h e m e t a l l u r g i c a l
phenomena that heat t r e a t m e n t s b r i n g about a r e s i m i l a r in principle
t o those employed in other m e t a l - a l l o y s y s t e m s . However, s i n c e
titanium r e a c t s with m o s t a t m o s p h e r e s under n o r m a l h e a t - t r e a t i n g
conditions, consideration of contamination e f f e c t s and t h e i r c o n t r o l
i s of utmost importance. This s e c t i o n of the r e p o r t d e a l s with con-
tamination, furnacing, and, finally, a d i s c u s s i o n of techniques now
being employed f o r the t h e r m a l t r e a t m e n t of t i t a n i u m m a t e r i a l s .
CONTAMINATION
Titanium is chemically v e r y a c t i v e a t elevated t e m p e r a t u r e s and

r e a c t s with a l m o s t all e l e m e n t s including t h o s e which a r e m o s t
30
r-eadily available - carbon, oxygen, nitrogen, and hydrogen. T i -
tanium r e a c t s with, and i s contaminated by, m o s t gaseous c o m -
pounds, including CO, C 0 2 , H 2 0 vapor, "4, and many volatile
organic m a t e r i a l s . The r e s u l t s of such g a s r e a c t i o n s a r e m o r e
s e r i o u s f o r titanium than f o r many other m e t a l s , s i n c e the gaseous
e l e m e n t s not only f o r m compounds a t the s u r f a c e , but a l s o p e n e t r a t e
the m e t a l l a t t i c e causing loss of ductility and toughness. F u r t h e r -
m o r e , with the exception of hydrogen, the contaminating g a s e s cannot
be removed by v a c u u m h e a t t r e a t m e n t , since the r e a c t i o n s a r e
irreversible.
Effect on P r o p e r t i e s (Ref. 1 0 ) S m a l l quantities of the i n t e r -

s t i t i a l e l e m e n t s r e m a i n in titanium a f t e r the v a r i o u s metal-winning
p r o c e s s e s and additional quantities a r e picked up during p r i m a r y
and secondary fabrication p r o c e s s e s . Heavy concentrations of
carbon, oxygen, and nitrogen in the m e t a l s u r f a c e , picked up during
fabrication and/ o r h e a t - t r e a t m e n t operations, h a r d e n and s t r e n g t h e n
titanium. Both nitrogen and oxygen a r e used to s u r f a c e h a r d e n
titanium f o r i n c r e a s i n g w e a r r e s i s t a n c e i n friction applications.
Carbon i s effective as a s t r e n g t h e n e r only up to its l i m i t of solubility
in alpha. Although hydrogen h a s a strengthening effect in titanium
alloys, the effect is a l m o s t nil in unalloyed titanium. Ductility and
toughness d e c r e a s e with increasing amounts of i n t e r s t i t i a l content i n
unalloyed titanium. S u m m a r y c u r v e s showing the i n t e r s t i t i a l effects
on titanium s t r e n g t h , ductility, and h a r d n e s s a r e given in F i g u r e s 20
and 21.
The m o s t d e l e t e r i o u s effect of the i n t e r s t i t i a l s on the p r o p e r t i e s

of unalloyed titanium is on toughness. High-purity titanium i s v e r y
tough to quite low t e m p e r a t u r e s , but the p r e s e n c e of i n t e r s t i t i a l s
l o w e r s toughness p r ogr e s sively with increasing i n t e r s t i t i a l content
until transition-type behavior o c c u r s ( F i g u r e 22). A tendency toward
t r a n s i t i o n type of behavior o c c u r s at 0. 2 4 p e r cent oxygen equivalent,
and definite t r a n s i t i o n behavior o c c u r s at 0. 36 p e r cent oxygen
equivalent. The e f f e c t s of combinations of i n t e r s t i t i a l s on toughness
a p p e a r t o be additive on the same basis a s t h e i r effects on s t r e n g t h ,
that is 3C = 20 = IN. Oxygen equivalent concentrations of c a r b o n o r
nitrogen m a y be calculated using this relationship.
31
- 130
0
8 140
130
5 120
ri 110
;
E IW
e
I-y 90
eo
- 70
60
50
i
a
40
30
6 20
j
(L
10
0
0 01 0 2 0 3 0 4 O S 0 6 0 1 0 8 O I X 0.yp.n
0 03 06 09 12 X Carbm
0 01 02 03 04 X N1Irog.n
4 DIW@
FIGURE 20. E F F E C T O F CARBON, OXYGEN, AND NITROGEN ON

TENSILE PROPERTIES O F IODIDE TITANIUM
(REF. 10)
.
FIGURE 21. E F F E C T O F CARBON, OXYGEN, AND NITROGEN ON
VICKERS HARDNESS O F IODIDE TITANIUM ( R E F . 1 0 )
32
- 200 0 200 - 200 0 200 - 200 0 200
A-51561
Testing Temperature. F
FIGURE 22. E F F E C T O F INTERSTITIALS O N TOUGHNESS

O F IODIDE TITANIUM ( R E F . 1 0 )
Hydrogen h a s a s i m i l a r effect upon the toughness of titanium,

although a t much lower concentration than that o b s e r v e d f o r carbon,
oxygen, o r nitrogen. F o u r i n t e r r e l a t e d v a r i a b l e s have been found to
a f f e c t the tend e nc y tow a r d e m b r it t 1e m e nt : h y d r og e n c ont e n t , s t r a in
r a t e , s t r e s s concentration, and t e m p e r a t u r e . Typical effects a r e
shown in F i g u r e 23. F r o m t h e s e plots, it c a n be s e e n that t r a n s i t i o n
t e m p e r a t u r e i s i n c r e a s e d (i. e . , e m b r i t t l e m e n t b e c o m e s m o r e
s e v e r e ) a s hydrogen content i s increased, loading r a t e is i n c r e a s e d ,
o r notches a r e introduced into the samples. A s might be expected,
the e f f e c t s a r e magnified i n the p r e s e n c e of the o t h e r i n t e r s t i t i a l
elements.
The effects of i n t e r s t i t i a l content on the m e c h a n i c a l p r o p e r t i e s of

titanium alloys a r e much the same a s for unalloyed titanium. In
g e n e r a l , s t r e n g t h is i n c r e a s e d while ductility and toughness a r e de-
c r e a s e d in the p r e s e n c e of i n t e r s t i t i a l s . However, with r e g a r d t o
e m b r i t t l e m e n t e f f e c t s and especially e m b r i t t l e m e n t effects promoted
by hydrogen, c e r t a i n alloys of titanium c a n t o l e r a t e m o r e i n t e r -
s t i t i a l s than o t h e r s and the embrittlement phenomenon o c c u r s a t
d i f f e r e n t t e m p e r a t u r e s f o r the different a l l o y s . (Ref. 1 0 )
Oxidation (Ref. 11). Titanium is noted f o r its excellent r e s i s -

t a n c e t o many c o r r o s i v e environments. This r e s i s t a n c e t o c o r r o s i o n is
r e l a t e d t o the thin, n a t u r a l oxide film that f o r m s on titanium. This
oxide film d o e s not grow significantly thicker at a m b i e n t t e m p e r a t u r e s
33
E 100 r I I I I 1
$ 10bprn H2
L
g 80 /
-
0
w
L
60
a Slow-speed test,
.-c 40
U
a. Effect of Hydrogen Content
EWu ' O O E
d
80 '
60 -
40
Unnotched test,
U
b. Effect of Loading Rote
2 I00
W
V
80
60
40
20
n
"
-300 -200 -100 0 I00 200
Temperature, F
c. E f f e c t of Stress Concentration
FIGURE 23. CHARACTERISTICS O F HYDROGEN EMBRITTLEMENT

IN ALPHA ALLOYS, FROM DATA ON IODIDE
TITANIUM ( R E F . 10)
34
0 2 4 6 8 IO 12
J T i m e , min A-51595
FIGURE 24. OXIDATION RATES OF TITANIUM IN OXYGEN IN THE

800 T O 1100 F RANGE (REF. 11)
70
60 w
Temperature, F 1.515%
FIGURE 25. COMPARISON OF THE METAL LOSSES OF COMMERCIAL TITANIUM, Ti-5A1-2.5Sn.

AND Ti-4A1-4Mn HEATED IN AIR FOR 8 HOURS (REF. 11)
36
n o r at t e m p e r a t u r e s up through about 1000 F. Thus, oxidation of ti-
tanium in the s e r v i c e - t e m p e r a t u r e r a n g e is not a problem. In f a c t ,
it would take about 300 y e a r s to f o r m a n oxide l a y e r 1 mil thick on
titanium a t 500 F, o r about 6 months a t 9 0 0 F. However, at higher
t e m p e r a t u r e s , p a r t i c u l a r l y those u s e d f o r fabrication and heat t r e a t -
m e n t of titanium, the oxidation r a t e b e c o m e s significant and, in
addition, oxygen diffuses into the solid metal. Table I V shows the
effect of t e m p e r a t u r e on the oxide-film thickness of titanium.
TABLE IV. E F F E C T O F TEMPERATURE ON THE

OXIDE-FILM THICKNESS O F
COMMERCIALLY P U R E TITANIUM
HEATED IN AIR F O R 1 / 2 HOUR
(REF. 1)
M e a s u r a b l e Oxide T h i c k n e s s ,
Temperature, F mils
600 None
800 None
1000 None
1200 <o. 2
1400 0.3
1500 <1
1700 <2
1800 2
1900 4
2000 14
Both the osidation and diffusion p r o c e s s e s a r e t i m e and t e m p e r a -

t u r e dependent. At low t e m p e r a t u r e , 1000 F and below, t h e oxidation
of titanium follows a parabolic r a t e law. A p r o t e c t i v e oxide film is
f o r m e d , and the oxidation r a t e d e c r e a s e s with t i m e . In t h e s e r v i c e -
t e m p e r a t u r e r a n g e (up t o 1000 F ) , the oxidation p r o c e s s is s e l f -
healing, and a protective s c a l e is slowly f o r m e d . An e x a m p l e of the
oxidation r a t e s of titanium a t low t e m p e r a t u r e s is given i n F i g u r e 24.
However, a t t e m p e r a t u r e s in the f a b r i c a t i o n and h e a t - t r e a t m e n t

r a n g e s (1400 t o 2 0 0 0 F ) , the oxidation rate of t i t a n i u m and titanium
alloys becomes v e r y r a p i d , a s shown by the d a t a i n F i g u r e 25.
M o r e important than oxidation at high t e m p e r a t u r e s is the d i f f u -

sion of oxygen into titanium and titanium a l l o y s . T h e d i f f u s i o n of
oxygen into titanium h a r d e n s the s u r f a c e and c a u s e s e m b r i t t l e m e n t .
35
hydrochloric, s u l f u r i c , phosphoric, oxalic, and f o r m i c a c i d s ) , ioniz- -
able-fluoride compounds, s o m e low-pH s a l t solutions (including hot,
I concentrated aluminum and calcium c h l o r i d e s ) , and c e r t a i n powerful
oxidizing agents ( s u c h as r e d fuming n i t r i c acid, high concentrations
of hydrogen peroxide, liquid and gaseous oxygen), and d r y chlorine
g a s (Ref. 13).
Titanium displays excellent r e s i s t a n c e to s t r e s s - c o r r o s i o n

cracking i n aqueous solutions. F a i l u r e s a r e o b s e r v e d only on r a r e
occasions and then only i f the right combination of s t r e s s , m e t a l -
l u r g i c a l h i s t o r y , and environmental f a c t o r s is p r e s e n t w i l l the c r a c k s
initiate and propagate.
Titanium alloys have a tendency t o c r a c k under s t r e s s in the

p r e s e n c e of chloride s a l t s a t a threshold t e m p e r a t u r e of 550 F and
above. (Refs. 14, 15, 16) This phenomenon h a s been t e r m e d hot-
s a l t s t r e s s c o r r o s i o n . The extent of damage i s a d i r e c t function of
t i m e , t e m p e r a t u r e , and s t r e s s level employed, but it a l s o v a r i e s with
the alloy and the environment. The phenomenon h a s been observed in
titanium p a r t s which w e r e f o r m e d and subsequently h e a t t r e a t e d
( s t r e s s - r e l i e f annealing) without proper cleaning p r i o r to h e a t t r e a t -
ment. S t r e s s e s w e r e r e s i d u a l f r o m the forming operation. Chloride
ions w e r e believed to be p r e s e n t f r o m e i t h e r f i n g e r p r i n t s o r f r o m
chlorinated hydrocarbon r e s i d u e s (left by cleaning and d e g r e a s i n g
solutions). T h e r e is evidence that the r e s i d u e f r o m chlorinated
hydrocarbon solvents contained hydrochloric acid. (Ref. 17) Thus,
the i m p o r t a n c e of p r o p e r cleaning to eliminate chloride-containing
r e s i d u e s and p r o p e r handling to eliminate fingerprinting p r i o r to heat
t r e a t m e n t cannot be overemphasized. Mill s t e n c i l s , o i l s , and
g r e a s e s should a l s o always be removed f r o m titanium m a t e r i a l s
p r i o r to pickling, s t r e s s - r e l i e v i n g , and annealing operations.
CONTAMINATION CONTROL
Mill products m a y be supplied in the annealed condition o r in the

h e a t - t r e a t e d condition. In general, b a r stock and forgings c a n be
h e a t t r e a t e d to high s t r e n g t h p r i o r to a final grinding o r machining
operation. In t h e s e c a s e s , neither a i r contamination nor quench
d i s t o r t i o n p r e s e n t s any g r e a t difficulty since the final m e t a l - r e m o v a l
o p e r a t i o n g e t s r i d of the contamination o r distortion defects. F o r
products of this type, heating i n almost any kind of f u r n a c e including
g a s - and oil-fired f u r n a c e s , e l e c t r i c r--.:Efle f u r n a c e s , in a n e u t r a l
s a l t bath, o r in induction furnaces is suitable.
38
The only way that this contamination c a n be eliminated is by removing
the contaminated l a y e r f r o m the s u r f a c e of the m e t a l .
T h e oxidation and contamination of titanium alloys do not r e s u l t

in a uniformly hardened c a s e but in a diffusion zone that extends well
into the metal. The depth of this zone i s both t i m e and t e m p e r a t u r e
dependent. F i g u r e 26 shows the effect of t i m e a t 1600 F on the depth
of contamination in unalloyed titanium b a s e d on h a r d n e s s m e a s u r e -
m e n t s . This type of information i s useful in s e l e c t i n g t i m e and t e m -
p e r a t u r e combinations f o r h e a t - t r e a t m e n t and fabrication operations.
Information of this s a m e type i s available f o r titanium alloys f r o m
Reference 12.
400
350
ul
Y)
0
= 250
E0
I
Q
8 200
C
Y
I50
100
0 IO 20 30 40 50 60 70
Penetration ,mils PI- 3 1597
FIGURE 26. SUMMARY O F HARDNESS-PENETRATION DATA F O R

UNALLOYED TITANIUM HEATED F O R VARIOUS
TIMES I N AIR A T 1 6 0 0 F ( R E F . 1 1 )
Corrosion. T i t a n i u m ' s c o r r o s i o n p r o p e r t i e s , unlike those of

m o s t m e t a l s , c a n be defined within f a i r l y s i m p l e l i m i t s . The m e t a l i s
highly r e s i s t a n t t o a l l n a t u r a l environments (including s e a w a t e r , m i n e
w a t e r s , body fluids, f r u i t j u i c e s , e t c . ) and a g r e a t m a n y aqueous
c h e m i c a l s up to a t l e a s t t h e i r boiling t e m p e r a t u r e s . T i t a n i u m is used
m o s t extensively in cnvironments containing c h l o r i d e s a l t s , s u l f i d e s ,
hypochlorides, n i t r i c a c i d , chlorine dioxide, and w e t chlorine.
(Ref. 1 3 )
Chemicals which a t t a c k titanium include hot o r c o n c e n t r a t e d solu-

tions of the reducing type of acids (including s o m e concentrations of
37
C
A m e r i c a is now using a p r o p r i e t a r y coating f o r application t o s h e e t

b a r that affords good protection and h a s self-peeling p r o p e r t i e s at
the p r o p e r s t a g e s of s t r i p rolling. (Ref. 20)
In g e n e r a l , solution-annealing t e m p e r a t u r e s and t i m e s n o r m a l l y
r e c o m m e n d e d f o r specific alloys r e s u l t in about 3 t o 8 mils depth of
contamination. F i g u r e s 27, 28, and 29 show c u r v e s f o r estimating
the depth of contamination f o r titanium and two alloys f o r any given
t i m e - t e m p e r a t u r e conditions. It i s g e n e r a l l y accepted that the
v a r i o u s , c o m m e r c i a l l y available, protective coatings f o r titanium
cut down the depth of contamination but do not eliminate the p r o b l e m
entirely. Unpublished work at Battelle (Ref. 21) indicated that f o r
thin s h e e t m a t e r i a l of Ti-6A1-4V, exposed f o r s h o r t periods of t i m e
up to 1800 F, contamination w a s reduced by a t l e a s t one-half over that
of unprotected m a t e r i a l . In ahy c a s e , s c a l e a n d / o r coating m u s t be
r e m o v e d a f t e r t r e a t m e n t by chemical milling o r by mechanical tech-
niques s u c h as grinding o r sandblasting. Titanium Metals Corporation
of A m e r i c a r e p o r t s that the development of a u n i v e r s a l effective coat-
ing f o r all titanium alloy s u b s t r a t e s is probably out of the r e a l m of
p r a c t i c a l i t y . However, specific coating s y s t e m s have been proven f o r
specific titanium alloys. (Ref. 20) Thus, each individual t h e r m a l -
p r o c e s s i n g t r e a t m e n t m u s t b e considered with r e s p e c t t o allowable
depth of contamination and t o the compatibility and usefulness of any
given protective coating. A detailed examination of the s u r f a c e t r e a t -
m e n t s and conditioning of titanium and titanium alloys, with r e s p e c t
t o mechanical, e l e c t r o c h e m i c a l , nonmetallic, and s p r a y coatings
t r e a t m e n t s , is covered in another NASA r e p o r t . (Ref. 2 2 )
On the b a s i s of r e c e n t data, the heat t r e a t m e n t of titanium in a

tank of w a t e r - s o l u b l e molten g l a s s a p p e a r s a t t r a c t i v e f o r protecting
titanium a g a i n s t contamination. (Ref. 23) Solution treating Ti-4A1-
3 M o - l V s h e e t 1 / 4 hour a t 1625 F by i m m e r s i n g it in a f r i t t e d molten
g l a s s (82. 8 p e r cent b o r i c oxide-6. 5 p e r cent alkali oxide-10. 7 p e r
cent a l u m i n a ) r e s u l t e d in no surface contamination o r any d e l e t e r i o u s
effect on m i c r o s t r u c t u r e . Although g l a s s n o r m a l l y a c t s a s a n in-
s u l a t o r , s p e c i m e n s heat t r e a t e d in the above mix and quenched in
w a t e r f r o m 1625 F cooled to l e s s than 900 F within 10 seconds.
R e s i d u a l g l a s s remaining in contact with the alloy can be completely
r e m o v e d in hot (180 F) running water. Considerable additional effort
is r e q u i r e d before compatibility p a r a m e t e r s a r e f i r m l y established,
however, e a r l y r e s u l t s appear promising f o r the u s e of t h e s e molten
g l a s s e s f o r protection against contamination.
Descaling h a s been accomplished by various methods. A sodium

h y d r i d e o r a Virgo bath h a s been frequently used. (Ref. 7 ) Titanium
Near-finished and finished machined p a r t s and s h e e t titanium .
p r e s e n t s e r i o u s heat-treating problems. Unlike s t e e l , titanium can-
not be protected f r o m oxidation by conventional a t m o s p h e r e s s u c h a s
hydrogen, c a r b o n monoxide, o r c r a c k e d ammonia, s i n c e it r e a d i l y
r e a c t s with t h e s e gases. I n e r t g a s e s such a s a r g o n and helium c a n
afford protection of finished titanium p a r t s , and even t h e s e i n e r t
g a s e s must be highly purified, i. e . , f r e e f r o m m o i s t u r e and other
t r a c e i m p u r i t i e s to avoid contamination of the metal. High-purity
g a s furnaces a r e used extensively in l a b o r a t o r i e s f o r solution t r e a t i n g
of titanium, but c o m m e r c i a l f u r n a c e s of this type a r e few. T h r e e
a l t e r n a t i v e s a r e ( 1 ) t o solution t r e a t f o r a s s h o r t a period a s possible,
( 2 ) to u s e the b e s t i n e r t a t m o s p h e r e economically p r a c t i c a l , o r (3) to
p e r f o r m the t r e a t m e n t under vacuum. In the f o r m e r c a s e s , it will
be n e c e s s a r y to follow the heat t r e a t m e n t with a pickling o r light-
grinding operation. N o cleanup should be n e c e s s a r y a f t e r vacuum
t r e a t m e n t . A word of caution should be i n t e r j e c t e d h e r e r e g a r d i n g
the u s e of a i r o r i n e r t - g a s a t m o s p h e r e s in f u r n a c e s that a r e a l s o
u s e d f o r a t m o s p h e r e heating of steel. Such f u r n a c e s should be purged
f o r s e v e r a l h o u r s with the gas to be used to prevent contamination
with hydrogen f r o m r e s i d u a l g a s remaining in the c r e v i c e s and r e -
f r a c t o r y p a r t s of the furnace. In air-blown f u r n a c e s , used a l s o f o r
the a t m o s p h e r e heat t r e a t m e n t of f e r r o u s a l l o y s , a n air-flow purge
of considerable volume and duration (e. g . , 150 cu f t / m i n for 4 h o u r s )
is r e c o m m e n d e d p r i o r to using the furnace for any t h e r m a l t r e a t m e n t s
involving titanium products. (Ref. 18) Of c o u r s e t h e s e oxidation and
contamination p r o b l e m s m a y be circumvented by using vacuum-heat-
t r e a t m e n t facilities for h e a t t r e a t m e n t s not t e r m i n a t e d by rapid
cooling.
P e r h a p s one of the b e s t methods f o r protecting l a r g e titanium

p a r t s o r sheets of s i m p l e g e o m e t r i c configuration is to encapsulate
them in low-carbon s t e e l c o n t a i n e r s . The p r o c e d u r e c o n s i s t s
simply of s e a m welding the s t e e l envelope around the titanium p a r t ,
putting a fitting in the envelope to p e r m i t evacuation of the a i r , and
sealing. (Ref. 18) An a l t e r n a t i v e to this p r o c e d u r e is t o provide two
fittings s o that a continuous purge of i n e r t g a s , s u c h a s a r g o n o r
helium, i s p r e s e n t e d to the workpiece in the container. (Ref. 19)
In e i t h e r c a s e the s t e e l envelope containing the i n e r t a t m o s p h e r e p r o -
t e c t s the titanium f r o m oxidation and hydrogen, and d o e s not s e r i o u s l y
affect the cooling rate.
S o m e organizations, including both p r o d u c e r s and end-product

f a b r i c a t o r s , a r e using coatings, with varying d e g r e e s of s u c c e s s , to
protect titanium during t h e r m a l t r e a t m e n t s . On the o t h e r hand, other
organizations do not favor coatings. Titanium M e t a l s C o r p o r a t i o n Of
39
40
50
60
70
80
90
100
I10
AKHN F
Key: Drow o line from LSKHN to 1 ,

mork m.
Drow o line from m to F, r a d X
A- I2911
FIGURE 28. NOMOGRAPH F O R ESTIMATING THE D E P T H O F CON-

TAMINATION O F Ti-5A1-2. 5Sn FROM COMBINATIONS
O F TIME AND TEMPERATURE O F EXPOSURE TO
AIR (REF. 12)
T h i s is b a s e d on the solution of log x = C t 0. 5 log t -
-
6430 and C = f (AKHN).
T
Note: The t e m p e r a t u r e , T, i n the equation is in
d e g r e e s Kelvin.
42
V
.25 2100
50
- 20
-15
k
60
70
80
-2
X , mils
90 -15
F
-I
I 00
-0 7 K e y : Drow a line from A K H N to 1,

I IO mark m
-0.5 Draw o line from m to F,
.O 4
120 reod x
-0.3
130
-0 2
AKHN A - 12916
m t hours
FIGURE 27. NOMOGRAPH FOR ESTIMATING THE D E P T H O F CON-

TAMINATION O F COMMERCIAL TITANIUM FROM
COMBINATIONS O F TIME AND TEMPERATURE O F
EXPOSURE TO AIR ( R E F . 1 2 )
T h i s i s b a s e d on the solution of l o g x = C t 0. 5 l o g t -
l o ' 7 0 0 and C ' = f (AKHN).
T
Note: The t e m p e r a t u r e , T , in the equation is in
41
- 2100
-
-2Ooo
- 1900
0 -I800
0
0
- 1700
-
- 1600
- 1500
-
- 1900
A KHN
m t
t 0.3
0.2
, hours
Key: Drow o line from
m r k m.
A K H N to 1 ,
Drow o line from m to F, Rad x
A12918
I FIGURE 29. NOMOGRAPH FOR E S T I W T I N G THE D E P T H O F CON-

TAMINATION O F Ti-4A1-4Mn FROM COMBINATIONS
O F TIME AND TEMPERATURE O F EXPOSURE TO
AIR ( R E F . 12)
T h i s is b a s e d on the solution of log x =
ct 0 . 5 log t - -
6050 and C = f (AKHN).
T
Note: The t e m p e r a t u r e , T, i n the equation is i n
43
Metals Corporation of A m e r i c a u s e s a l o w - t e m p e r a t u r e (400 to 425 F )
s a l t bath, composed of p o t a s s i u m compounds with additives and in-
hibitors to control oxidation, to d e s c a l e a l m o s t a l l titanium alloys
rolled and annealed a t 8 0 0 to 1900 F. (Ref. 2 0 ) Operating a t this low
t e m p e r a t u r e , well below the 700 to 1000 F r a n g e c o m m o n to many
salt-bath descaling p r o c e s s e s , s c a l e c a n be removed without a g e
hardening o r causing e x c e s s i v e hydrogen pickup. The p r o c e s s is
c a r r i e d out in two batch-type descaling and pickling installations in
which billets, s l a b s , tubing, plate, s h e e t , and w i r e a r e p a s s e d
through the s a l t bath, a cold-water r i n s e , 35 p e r cent s u l f u r i c acid,
a hot-water r i n s e , and finally through a nitric-hydrofluoric a c i d
solution and another hot-water rinse. Short, repetitive c y c l e s -
about 10 minutes in the s a l t bath and 5 minutes in the s u l f u r i c a c i d -
have proved to be m o r e effective than one longer cycle.
Shot blasting and grinding a l s o have been used t o d e s c a l e titanium

alloys. Pickling is accomplished n e a r l y u n i v e r s a l l y in a HF-"03
water solution a t slightly elevated t e m p e r a t u r e s . Although this solu-
tion will a l s o c a u s e hydrogen pickup, it is now s t a n d a r d p r a c t i c e t o
minimize this by maintaining the H F concentration below about
3 per cent and the H N 0 3 concentration above about 15 p e r cent. T O O
high a concentration of " 0 3 will c r e a t e fuming and m a k e the bath
difficult, i f not dangerous, to handle. (Ref. 7 )
In s u m m a r y , a few points should be r e e m p h a s i z e d r e g a r d i n g the

mechanics of titanium h e a t t r e a t m e n t . Titanium is chemically v e r y
active at elevated t e m p e r a t u r e s , and r e a c t s r e a d i l y with oxygen,
nitrogen, carbon, and hydrogen in a f u r n a c e a t m o s p h e r e . In all h e a t -
treating operations, oxidation c a n be a v e r y i m p o r t a n t f a c t o r , due t o
the embrittling effect of titanium oxides on the p r o p e r t i e s of a p a r t .
P r i m a r i l y b e c a u s e of oxidation, heating t i m e s a r e kept as s h o r t as is
r e q u i r e d to p e r f o r m the h e a t t r e a t m e n t . T h i s is p a r t i c u l a r l y t r u e f o r
s h e e t products, w h e r e the s u r f a c e to volume r a t i o is l a r g e and the
difficulty of s c a l e r e m o v a l i s the g r e a t e s t . Most titanium forgings
a r e fully machined a f t e r hot working and h e a t t r e a t m e n t . S o m e
forgings a r e ground o r otherwise machined to r e m o v e contamination
only in the a r e a s of h i g h - s t r e s s concentration. (Ref. 1 )
The danger of hydrogen pickup during h e a t - t r e a t i n g operations is

probably m o r e important. C u r r e n t specifications l i m i t hydrogen con-
centrations in titanium alloys to u n d e r 200 ppm. At high hydrogen
concentrations, the titanium b e c o m e s e m b r i t t l e d , showing a reduced
impact and notched t e n s i l e strength. T o m i n i m i z e the possibility of
hydrogen pickup o r to avoid oxidation, h e a t t r e a t m e n t i s s o m e t i m e s
accomplished in a n i n e r t a t m o s p h e r e s u c h a s a r g o n o r helium, o r
44
*
in a vacuum. Because t h e s e methods a r e expensive, m o s t h e a t t r e a t -
in’g is done in a slightly oxidizing a t m o s p h e r e ; this r e d u c e s the p a r t i a l \
p r e s s u r e of hydrogen that m a y be i n the surrounding a t m o s p h e r e

f r o m the breakdown of w a t e r vapor o r unburned hydrocarbons.
(Ref. 1)
Oxidation r a t e s v a r y with the titanium alloy. Generally a-alloys

show slightly less scaling than P-alloys. Nitrogen is a b s o r b e d by
titanium during h e a t t r e a t m e n t a t a m u c h slower rate than oxygen,
and does not produce a s e r i o u s contamination problem. (Ref. 1)
Titanium alloys a r e a l s o subject t o s t r e s s c o r r o s i o n when ex-

posed to c h l o r i d e s at t e m p e r a t u r e s above about 550 F in the p r e s e n c e
of a n applied o r r e s i d u a l t e n s i l e s t r e s s . F i n g e r p r i n t s o r c h l o r i d e s
f r o m cleaning solutions m u s t b e cleaned off of the titanium p a r t
p r i o r t o h e a t - t r e a t m e n t operations. (Ref. 1)
In addition, since titanium m a t e r i a l s a r e v e r y r e a c t i v e at n o r m a l

h e a t - t r e a t i n g t e m p e r a t u r e s , c a r e m u s t be e x e r c i s e d t o eliminate mill
s t e n c i l s , o i l s , and g r e a s e s p r i o r t o s t r e s s relief and annealing o p e r a -
tions. The r e a c t i o n of c e r t a i n furnace r e f r a c t o r i e s and mill s c a l e
c a r r i e d o v e r f r o m f e r r o u s heat-treating operations with titanium
m a t e r i a l s should a l s o b e carefully considered and r e m o v e d i f pos-
s i b l e b e f o r e any t h e r m a l t r e a t m e n t s a r e performed.
FURNACING
In d i s c u s s i n g f u r n a c e s f o r the heat t r e a t m e n t of titanium, a r e -

view of t h e p r a c t i c e s followed by titanium p r o d u c e r s , f a b r i c a t o r s ,
and u s e r s a f f o r d s a n insight into the most acceptable methods of
heating titanium.
Since the production of titanium m i l l products h a s been c a r r i e d

out a l m o s t e n t i r e l y in facilities which a r e owned and operated by s t e e l
c o m p a n i e s , the heating and heat-treating equipment u s e d for s t e e l
h a v e a l s o been used f o r titanium. This h a s been a r a t h e r s a t i s f a c t o r y
a r r a n g e m e n t s i n c e the t e m p e r a t u r e s required f o r shaping and heat
t r e a t i n g of titanium a r e not v e r y different f r o m those used f o r s t e e l
products. Unlike s t e e l , titanium and its alloys a r e v e r y r e a c t i v e
with the a t m o s p h e r e a t mill-processing and heat-treating t e m p e r a -
t u r e s as explained e a r l i e r in t h i s report.
T i t a n i u m ingots and semifinished products a r e heated and forged

o r r o l l e d with and without protection f r o m the air. P r o p r i e t a r y coat-
ings a r e used in many of the p r i m a r y metalworking operations
45
although not u n i v e r s a l l y so. Heating m a y be c a r r i e d out in any type .
>
of furnace, and g a s - o r o i l - f i r e d f u r n a c e s commonly found in s t e e l
plants have been used with s u c c e s s . The m o s t important precaution
to be observed with fuel f u r n a c e s is that the stock should not be ex-
posed d i r e c t l y to the f l a m e if this can be avoided. If complete
muffling is not possible, the a t m o s p h e r e in the f u r n a c e should be
f r e e f r o m w a t e r vapor and should be slightly oxidizing. Both w a t e r
vapor and incompletely burned fuel vapor c a n r e a c t with titanium to
f o r m a t o m i c hydrogen which i s readily a b s o r b e d by the titanium.
Thus, one of the principal s o u r c e s of hydrogen contamination in
titanium products i s the fuel-fired furnace. The only p r a c t i c a l
method for removing hydrogen f r o m titanium i s by vacuum annealing.
F u r n a c e s for solution treating m a y be g a s f i r e d o r e l e c t r i c , with the
l a t t e r being p r e f e r r e d to m i n i m i z e hydrogen pickup. R e s i s t a n c e and
induction types of heating a r r a n g e m e n t s a r e a l s o used to m i n i m i z e
contamination through reduced heating t i m e s . The effectiveness of a
solution-treatment operation i s tied v e r y c l o s e l y to the way the
quenching m e d i u m o p e r a t e s in conjunction with the furnace. In many
c a s e s of production p a r t s , the f u r n a c e s a r e built together s o that the
p a r t can b e dropped o r rolled f r o m the hot zone into the quenching
a r e a in a v e r y s h o r t time. Quench delay t i m e i s c r i t i c a l with r e g a r d
to obtaining optimum p r o p e r t i e s . Water is the m o s t widely u s e d
quenching medium, although low-viscosity o i l and w a t e r containing
about 3 p e r cent NaOH a r e a l s o employed. (Ref. 1) The NaOH addi-
tion provides f o r a b e t t e r wetting action and consequently m o r e
efficient heat dissipation. (Ref. 18) T h e r e have been s o m e r e p o r t s
that solution-treated and aged Ti-6A1-4V exhibits c o n s i d e r a b l e i m -
provements in s t r e n g t h combined with good ductility when m o r e
effective water-quenching techniques a r e employed. (Ref. 24) It
a p p e a r s that this is facilitated for titanium a l l o y s by incorporating
the c o r r e c t quench media with violent agitation through a n o v e r s i z e d
pumping s y s t e m . (Ref. 18) F o r example, i f a 5-hp pump i s sufficient
to agitate a bath, a much l a r g e r pump, s a y 50-hp, might t r u l y be
required to m o r e ideally quench the p a r t f o r o p t i m u m p r o p e r t y
development.
Vertical gantry types of f u r n a c e s a r e quite popular f o r the h e a t

t r e a t m e n t of titanium. (Refs. 18, 25) T h e s e f u r n a c e s a r e n o r m a l l y
e l e c t r i c o r g a s f i r e d with a m a x i m u m operating t e m p e r a t u r e of 2000
to 2100 F f 25 F. Effective working a r e a s of up t o a t l e a s t 29 f e e t
in height (Ref. 25) and 13 f e e t in d i a m e t e r a r e available. Quench
tanks a r e located in pits below the f l o o r and the f u r n a c e t r a v e l s on a
t r a c k to the p a r t i c u l a r quench tank in u s e . T r a n s f e r t i m e f r o m
f u r n a c e t o quench m e d i a can be a c c o m p l i s h e d in l e s s than 5 seconds.
Sheet quenched f r o m v e r t i c a l f u r n a c e s is r e l a t i v e l y f r e e f r o m
46
.
d i s t o r t i o n b e c a u s e it is suspended vertically. However, v e r y s h o r t
t r a n s f e r t i m e s c a n c a u s e degradation of the p a r t through m e c h a n i c a l
vibration c a u s e d by speeding up the quenching p r o c e s s . (Ref. 18)
California-Doran Heat T r e a t i n g Company h a s found in solution t r e a t -
ing Ti-6A1-4V heavy s e c t i o n p a r t s that no d e t r i m e n t in p r o p e r t i e s
o c c u r s when using up t o a n 8-second quench delay t i m e provided t h e
cooling r a t e is v e r y r a p i d once the p a r t e n t e r s the quench
medium. (Ref. 18) A v e r t i c a l f u r n a c e of this type u s e d in the h e a t
t r e a t m e n t of t i t a n i u m is shown in F i g u r e 30.
V e r y l a r g e g a s - f i r e d f u r n a c e s , such as the one shown in F i g -

u r e 31, a r e available for s t r e s s relieving and aging of t i t a n i u m p a r t s
and s t r u c t u r e s . C r e e p flattering of l a r g e titanium plates h a s been
proposed using t h i s type of furnace.
Although vacuum h e a t t r e a t m e n t is normally m o r e expensive than

conventional furnacing, many applications of titanium h e a t t r e a t m e n t
a r e ideally suited for vacuum. Many t i m e s when comparing v a r i o u s
h e a t - t r e a t m e n t p r o c e s s e s in their entirety, the vacuum t r e a t m e n t
b e c o m e s m o r e economical s i n c e p r o b l e m s a s s o c i a t e d with contamina-
tion and n e c e s s a r y cleanup a r e eliminated. Of c o u r s e , final machined
p a r t s and t h i n - s h e e t s t r u c t u r e s r e q u i r i n g h i g h - t e m p e r a t u r e t h e r m a l
e x p o s u r e while maintaining c l o s e dimensional t o l e r a n c e s a r e ex-
cellent candidates for vacuum f u r n a c e s . Also, the only p r a c t i c a l way
of lowering d e t r i m e n t a l hydrogen content in titanium m a t e r i a l s is by
vacuum exposure. This is u s u a l l y done at a t e m p e r a t u r e between
1000 and 1400 F for 2 to 4 h o u r s at p r e s s u r e s of l e s s than 0. 5 m i c -
ron. (Ref. 26) Under t h e s e conditions, chemically m i l l e d and
hydrogen- c ontaminated T i - 6A1-4V containing 5 50 - ppm hydrogen c a n
b e p u r i f i e d t o 25 to 35-ppm hydrogen after vacuum t r e a t m e n t .
(Ref. 26)
Vac-Hyd C o r p o r a t i o n h a s a v e r y l a r g e vacuum f u r n a c e that is

being u s e d for t i t a n i u m h e a t t r e a t m e n t . (Ref. 26) The f u r n a c e
m e a s u r e s 5 f e e t in d i a m e t e r , 5 f e e t high ( 5 - 1 / 2 feet with a lower
t e m p e r a t u r e r e t o r t ) , and c a n maintain h e a t - t r e a t m e n t t e m p e r a t u r e s
u p to 2250 F ( m a x i m u m ) at 0. 1 to 0.3 micron. Heating e l e m e n t s
a r e contained outside the evacuated retort. Thin t i t a n i u m sheet,
30 to 40 mils, is n o r m a l l y u s e d a s a getter to p r o t e c t the t i t a n i u m
p a r t s . T h e s e t i t a n i u m s h i e l d s a r e mounted around the workpiece and
a r e u s e d f i v e t i m e s before recleaning. Cooling i s n o r m a l l y slow.
However, a n a r g o n back-fill can be used to give a quench r a t e of
100 F / m i n u t e . Vac-Hyd h a s plans for a production vacuum unit
c a p a b l e of quenching f r o m vacuum which will duplicate an oil quench.
47
FIGURE 30. VERTICAL GANTRY TYPE OF
FURNACE
6 fcet in diaineter, 8 f e e t -
6 inches high, 2000 l b a t
2000 F or 3000 lb a t 1600 I;,
15 I; gradicnt.
Courtesy of California-Doran
H c a t Treating Co.
FIGURE 31. CAR BOTTOM TYPE OF

FURNACE
Fririiace iiieasures 12 fcet

by 12 feet by 42 fcet.
Courtcsy of Cahfornis-
Doraii Heat Treating Co.
48
-the solution
b Salt baths, s u c h as NaCl o r BaClZ, a r e and have been used in
t r e a t m e n t of titanium p a r t s . However, s o m e experience
in the application of a n e u t r a l BaC12 s a l t bath during solution anneal-
ing r e s u l t e d i n i n t e r g r a n u l a r attack of the titanium, s u c h that e x c e s s
m a t e r i a l w a s r e q u i r e d to allow for contamination cleanup. If e x c e s s
m a t e r i a l is available, the h e a t t r e a t m e n t can n o r m a l l y be effected
b e t t e r i n a i r . (Ref. 18) In addition, the salt-bath r e s i d u e , if not
p r o p e r l y and completely removed, m a y have a d v e r s e effects in
promoting salt s t r e s s c o r r o s i o n as d i s c u s s e d e a r l i e r i n t h i s r e p o r t .
F o r the production h e a t t r e a t m e n t of f l a t - r o l l e d mill products,

Titanium Metals Corporation of A m e r i c a h a s a continuous e l e c t r i c -
r o l l e r h e a r t h f u r n a c e outfitted with r o l l e r - l e v e l e r - spray-quench
a p p a r a t u s on one end and a 16-foot-long tank at the other. (Ref. 1 )
Production s h e e t s a r e heated. to the solution- t r eating t e m p e r a t u r e ,
going through a p r e h e a t zone f i r s t . They a r e finally held a t the
solution t e m p e r a t u r e f o r about 5 minutes and then heavily s p r a y
quenched, top and bottom, a s they e m e r g e f r o m the f u r n a c e j u s t
b e f o r e they e n t e r the r o l l e r l e v e l e r and a l s o during r o l l e r leveling.
The t h r e e zones in this furnace a r e controlled to *5 F, and the t e m -
p e r a t u r e is uniform in each zone. The r o l l e r - s p r a y - q u e n c h
a p p a r a t u s is designed to provide a n even quench, and is positioned
t o m i n i m i z e the t r a n s f e r t i m e f r o m furnace t o quench.
Titanium Metals Corporation of A m e r i c a a l s o h a s a continuous-

vacuum-annealing f u r n a c e in operation in conjunction with a
S e n d z i m e r Mill, and other cutting and cleaning equipment f o r the
production of c o m m e r c i a l l y pure and alloy s t r i p . (Ref. 1) S t r i p to
b e i n t e r m e d i a t e o r final annealed e n t e r s the f u r n a c e tower through a
s e r i e s of r o l l e r s , coming f i r s t to a cold zone. It then p a s s e s into
the hot zone i n the top, front quadrant of the tower. A f t e r annealing,
the s t r i p p a s s e s over r o l l e r s in the top of the f u r n a c e and down the
back s i d e ; the back half of the f u r n a c e is a l s o cold. Vacuums in the
c h a m b e r s a r e in the 0. 1 to 0.5-micron p r e s s u r e range. S t r i p up to
48 i n c h e s wide m a y be accommodated. T h i s continuous-vacuum-
annealing equipment is a tremendous improvement over conventional
line air -annealing techniques, a s postanneal descaling i s avoided,
along with the gage control and pitting, and other p r o b l e m s it
creates.
HEAT TREATMENT TECHNIQUES
T h e r e a r e s e v e z a l r e a s o n s for heating titanium p a r t s back up to

elevated t e m p e r a t u r e s a f t e r the p r i m a r y fabrication of mill products.
49
Secondary fabrication, that is m e t a l shaping, is the f o r e m o s t r e a s o n ,
and v a r i o u s h e a t t r e a t m e n t s f o r the development of optimum p r o p e r -
t i e s account f o r the r e m a i n d e r . Some of the difficulties and p r o b l e m s
that might be encountered, and s o m e of the solutions t o these situa-
tions have been reviewed in the preceding sections. Thus, it r e -
mains to review s o m e of the operations r e q u i r e d to h e a t - t r e a t titanium
using techniques that have been found to give s u c c e s s f u l finished
parts.
F o u r distinct types of h e a t t r e a t m e n t need be considered: s t r e s s

relief annealing, f u l l annealing, solution annealing o r solution h e a t
treatment, and aging. As d e s c r i b e d in the m e t a l l u r g i c a l sections of
this r e p o r t , s o m e titanium alloys a r e not given a l l types of t r e a t -
ments, and in p r a c t i c e a l l types of t r e a t m e n t s a r e n e v e r used in
producing a single p a r t even though the alloy used might be a m e n a b l e
to all four types. F o r example, the Ti-6A1-4V alloy m a y be given
a l l four heat t r e a t m e n t s , but this is never done in producing Ti-6A1-
4 V p a r t s . Instead, the alloy i s used in one of s e v e r a l conditions a s
follows.
(1) Ti-6A1-4V mill product supplied f r o m the m i l l in the

annealed c ond i t i on
May be shaped and conditioned to final p a r t s i z e

then used without any additional h e a t t r e a t m e n t
May be shaped and conditioned to final p a r t s i z e

then s t r e s s - r e l i e f annealed p r i o r to u s e
May be shaped ( d r a s t i c deformation) and condi-

tioned to final p a r t s i z e then fully reannealed p r i o r
to u s e
May be shaped and solution heat t r e a t e d , quenched,

conditioned to final p a r t s i z e , and aged p r i o r to
use
May be solution heat t r e a t e d , quenched, shaped

and conditioned to f i n a l p a r t s i z e , and aged p r i o r
to use.
50
8
(2) Ti-6A1-4V mill product supplied f r o m the mill in the
s olu t i on - he at -t r e a t ed c ondit ion
(a) May be shaped and conditioned to f i n a l p a r t s i z e

and then aged p r i o r t o u s e
(b) May be shaped ( d r a s t i c deformation) resolution

heat t r e a t e d , quenched, conditioned t o f i n a l p a r t
s i z e , and aged p r i o r t o use.
( 3 ) Ti-6A1-4V mill product supplied in the solution-treated-

and-aged condition
( a ) May b e u s e d without additional heat t r e a t m e n t
( b ) May be mildly deformed and shaped by additional

aging in f i x t u r e s p r i o r to use.
Note: A s is d i s c u s s e d l a t e r in t h i s section, s t r e s s - r e l i e f
annealing and aging heat t r e a t m e n t s c a n b e incorporated
into t h e f o r m i n g operation.
In the c a s e of non-heat-treatable titanium g r a d e s , s u c h a s unalloyed

g r a d e s a n d a - a l l o y s , only s t r e s s - r e l i e f annealing o r full reannealing
t r e a t m e n t s a r e u s e d t o condition the p a r t f o r use. T h e r e a r e no
m e t a l l u r g i c a l r e a s o n s f o r solution treating and aging g r a d e s of this
type.
Until recently, the h i g h - t e m p e r a t u r e ( a s in solution heat t r e a t -

m e n t ) h e a t t r e a t m e n t of titanium w a s not utilized by titanium u s e r s .
Instead, m o s t of the titanium u s e d w a s in the annealed o r s t r e s s -
relief-annealed condition, o r e l s e , in a few c a s e s , u s e r s aged the
m a t e r i a l a f t e r f o r m i n g f r o m a producer-supplied solution-annealed
condition. With the advent of rocket technology, solution heat t r e a t -
m e n t of titanium p a r t s (and subsequent u s e in the aged condition)
b e c a m e m o r e common among titanium u s e r s . At f i r s t , and s t i l l the
p r e d o m i n a n t p r a c t i c e today, heavy section p a r t s w e r e those m o s t
frequently destined f o r u s e in the higher strength, solution-treated,
quenched, and aged condition. The p r a c t i c e was to shape, rough
m a c h i n e (leaving considerable e x c e s s stock), solution heat t r e a t ,
quench, f i n i s h machine and otherwise finish the fabrication, and age.
The h e a v i e r contamination picked up during solution heat t r e a t m e n t
w a s r e m o v e d by the finish-machining operation while light contamina-
tion, often j u s t a s u r f a c e t a r n i s h , picked up during aging w a s
e l i m i n a t e d by v a r i o u s c h e m i c a l and mechanical methods. Heat
51
t r e a t m e n t in air w a s , and is, the m o s t c o m m o n p r a c t i c e , although ,
t h e r e i s definitely a t r e n d toward m o r e usage of the sophisticated
h e a t - t r e a t m e n t techniques, i n e r t gas o r v a c u u m protection f r o m the
contaminates.
At a somewhat l a t e r point in t i m e , solution heat t r e a t m e n t and

aging to develop high s t r e n g t h in titanium alloys, s t a r t e d to be
applied to all s o r t s of titanium p a r t s including s h e e t p a r t s . F o r
example, the XB-70 r e p r e s e n t s the f i r s t application of h e a t - t r e a t e d
titanium-alloy s h e e t f o r a i r f r a m e s t r u c t u r e s . In this c a s e , the
transition f r o m fabrication of the lower strength, annealed, c o m -
m e r c i a l l y p u r e and Ti-8Mn m a t e r i a l s to that of higher s t r e n g t h ,
h e a t - t r e a t e d Ti-6A1-4V and Ti-4A1-3Mo- 1V was accomplished. The
forward fuselage of the XB-70 c o n s i s t s a l m o s t e n t i r e l y of the above
m a t e r i a l s , in addition to h e a t - t r e a t e d Ti-6A1-4V forgings and ex-
t r u s i o n s and h e a t - t r e a t e d Ti-7A1-4Mo b a r and forgings. In t h e s e up-
to-date applications, the alloys a r e h e a t t r e a t e d to t h e i r m a x i m u m
t e n s i l e - s t r e n g t h levels of 160, 000 to 200, 000 p s i and u s e d a s s h e e t ,
b a r , extrusions, and forgings in many s i z e s and configurations. In
e a c h p a r t , the alloys a r e s e l e c t e d and p r o c e s s e d to achieve m a x i m u m
strength, closely controlled f r a c t u r e toughness, and c l o s e dimen-
sional t o l e r a n c e s . (Ref. 2 7 )
Forming, f o r the production of p r e c i s i o n XB-70 p a r t s in heat-

t r e a t e d m a t e r i a l s , is a highly refined p r o c e s s , involving r o o m -
t e m p e r a t u r e forming and hot sizing at about 1200 F in p r e c i s i o n m e t a l
d i e s ( F i g u r e 32). This is n e c e s s a r y to compensate f o r the low
amount of plasticity and the v e r y high spring-back r a t e of high-
strength titanium. A final aging c y c l e develops the 170, 000-psi
strength level in the p a r t s . (Ref. 2 7 )
Elsewhere in the industry, hot sizing and c r e e p forming a r e also

becoming commonplace. The f u r t h e r advancement of incorporating
e i t h e r simultaneous sizing - s t r e s s - r e l i e f annealing o r c r e e p f o r m -
ing - aging schedules into the production of p a r t s i s being made.
(Ref. 25) T h e s e operations a r e usually a c c o m p l i s h e d in a i r , s i n c e
t e m p e r a t u r e s a r e not high enough to r e s u l t in s e v e r e contamination,
although a s noted e a r l i e r , t h e r e is a t r e n d t o m o r e and m o r e u s a g e
of protective devices that m i n i m i z e contamination.
52
8
Port before
After
Principal heot ond pressure
Hot-size press
0 0 0 0 0 0 0
Heated ploten
A-52341
Part
FIGURE 32. HOT SIZING O F TITANIUM ( R E F . 27)
Most titanium p a r t s and s t r u c t u r e s a r e fixtured in jigs con-

s t r u c t e d of i r o n - b a s e o r nickel-base alloys to p r e v e n t d i s t o r t i o n
during h e a t treatment. (Refs. 18, 19, 25, 26) It i s generally r e c o m -
mended that the titanium p a r t be s e p a r a t e d f r o m the f i x t u r e s by thin
titanium s h e e t (Ref. 26) o r s p r a y e d A1203 (Ref. 25) t o p r e v e n t any
possible contamination f r o m the jigging. P r i o r t o u s e , the f i x t u r e s
a r e usually thoroughly cleaned and "burned off" in a i r o r vacuum,
depending upon the method of heat treatment.
S t r e s s relieving is u s e d extensively t o r e m o v e high r e s i d u a l

s t r e s s e s induced during forming and fabrication operations. It i s
a l s o being u s e d t o r e m o v e w a r p a g e f r o m f o r m e d p a r t s and f r o m
s h e e t o r p a r t s that a r e d i s t o r t e d a f t e r solution treating. In s o m e
c a s e s , the s t r e s s - r e l i e v i n g forming operation is a l s o a p a r t of the
aging cycle.
In the p a s t , Boeing (Ref. 7) investi.gated the extent of w a r p a g e

r e m o v a l that o c c u r s when Ti-6A1-4V p a r t s a r e r e s t r a i n e d during a
s t r e s s - r e l i e f h e a t treatment. F i r s t , the t h e o r e t i c a l s t r e s s relief
that o c c u r s when the alloy i s exposed to v a r i o u s t e m p e r a t u r e s f o r
d i f f e r e n t t i m e s was d e t e r m i n e d . The r e s u l t s a r e plotted a s the
monograph shown in F i g u r e 33. Data of this type m a y be used a s a
guide f o r predicting w a r p a g e r e m o v a l in a given p a r t , but allowance
m u s t be made f o r configuration. Boeing points out that the extent of
w a r p a g e r e m o v a l is roughly proportional to the s t r u c t u r a l stability of
the p a r t . Thus, in n a r r o w flat s t r i p s w a r p a g e r e m o v a l will be v e r y
c l o s e t o the p e r c e n t a g e of s t r e s s relief indicated on the monograph;
53
9oc IO6 -
-
- 20,000
-- 10,000
-
-- 5000
-- 4000
- 3000
IO -
- - 2000
-
--
- 1000
-
--500
- -400
-300
- 200
loo( -
-
-
-
-
LL -
c 50 2
E3! 1140 2
-30
c
E!
0,
,
--20 g
I-"
I IOC O2
IO
I200
A - 52 342
FIGURE 3 3 . TIME-TEMPERATURE-PER CENT STRESS R E L I E F

RELATIONSHIP F O R Ti-6A1-4V ( R E F . 7 )
54
however, in f o r m e d p a r t s the w a r p a g e r e m o v a l would b e g r e a t e r .
T h e difference is due p r i m a r i l y to the very high s t r e s s e s c r e a t e d by
clamping the f o r m e d p a r t .
CONCLUSIONS AND RECOMMENDATIONS
This review of p r e s e n t p r a c t i c e s for. heat-treating titanium alloys

b r i n g s out s e v e r a l a r e a s which r e q u i r e additional r e s e a r c h and
development.
With the i n c r e a s e d demands and u s e s of titanium m a t e r i a l s , a

continued effort i s r e q u i r e d to d i s s e m i n a t e p r a c t i c a l information
which d e s c r i b e s the p r o p e r technique normally employed in handling
titanium alloys. A continued p r a c t i c a l p r o g r a m of this type would
eliminate many p r o b l e m s encountered by the initiate s u c h a s heat
t r e a t m e n t in i n c o r r e c t a t m o s p h e r e s (i. e. , hydrogen o r nitrogen).
A m o r e c o m p r e h e n s i v e and p r a c t i c a l a p p r o a c h t o r e d u c e con-
t a m i n a t i o n of titanium alloys during heat t r e a t m e n t is needed. The
need f o r b e t t e r and m o r e compatible protective coatings which r e -
duce o r p r e v e n t contamination is especially great. F u r t h e r m o r e ,
the development of n o n r e a c t i v e molten baths, s u c h as s a l t s and
g l a s s e s , would p e r m i t a m o s t economical technique for heat-treating
titanium alloys.
It a p p e a r s that p r i o r r e s e a r c h and development work which

e s t a b l i s h e d specifications f o r the quench delay and quench r a t e s of
t i t a n i u m alloys h a s neglected the p r a c t i c a l a s p e c t s of adapting t h e s e
p a r a m e t e r s to l a r g e - s c a l e production heat t r e a t m e n t s . F o r example,
r a p i d t r a n s f e r t i m e s of l a r g e titanium p a r t s to the quench media c a n
r e s u l t in s e v e r e d e f o r m a t i o n of p a r t s due t o handling p r o b l e m s that
could h a v e b e e n avoided by relaxing the t r a n s f e r t i m e by only a few
s e c o n d s . . ( L a r g e , thick section p a r t s do not r e q u i r e e x t r e m e l y s h o r t
q u e n c h delay t i m e s b e c a u s e they do not l o s e h e a t quickly. ) In addi-
tion, w o r k is r e q u i r e d to b e t t e r establish the effect on the p r o p e r t i e s
of titanium alloys a s a function of quench-media, volume available,
and amount of agitation.
A relaxation of the aging-time specification of titanium alloys

is r e q u i r e d . T h i s would allow the heat t r e a t m e n t of complex t i -
t a n i u m p a r t s and s h a p e s in the c r e e p - f o r m - a g i n g operation t o be
done u n d e r a m o r e r e a l i s t i c and p r a c t i c a l s e t of conditions t o m e e t
r equi r ed d i m e n s ional s pec if i c a t ions.
55
REFERENCES
1. Broadwell, R. G . , "The P r a c t i c a l H e a t T r e a t m e n t of T i t a n i u m
Alloys", p a p e r presented a t the Titanium Metallurgy C o u r s e ,
New Y o r k U n i v e r s i t y , School of Engineering and Science
( S e p t e m b e r 13-15, 1965) (RSIC 1264).
2. Maykuth, D. J . , Holden, F. C . , Williams, D . N . , Ogden, H. R . ,

and J a f f e e , R . I . , "The E f f e c t s of Alloying E l e m e n t s i n T i t a n i u m ,
Vol. B. P h y s i c a l and C h e m i c a l P r o p e r t i e s , Deformation and
T r a n s f o r m a t i o n C h a r a c t e r i s t i c s " , DMIC R e p o r t 136B, B a t t e l l e
M e m o r i a l Institute (May 29, 1961) (RSIC 1291).
3. Maykuth, D. J . , Ogden, H. R . , and J a f f e e , R . I . , "The Effects

of Alloying E l e m e n t s in T i t a n i u m , Vol. A . Constitution", DMIC
Report 136A, B a t t e l l e M e m o r i a l I n s t i t u t e ( S e p t e m b e r 15, 1960)
(RSIC 1292).
4. A i r c r a f t D e s i g n e r ' s Handbook f o r T i t a n i u m and T i t a n i u m Alloys,

SST 65-8, C o n t r a c t FA-SS-65-6, p r e p a r e d f o r F e d e r a l Aviation
Agency by B a t t e l l e M e m o r i a l I n s t i t u t e (August, 1965) (RSIC 0575).
5. F a u l k n e r , G. E . , L e w i s , W . J . , and M a r t i n , D. C . , "The S t a t u s
and P r o p e r t i e s of T i t a n i u m Alloys f o r T h i c k Plate", DMIC R e p o r t
185, B a t t e l l e M e m o r i a l I n s t i t u t e ( J u n e 14, 1963) (RSIC 0693).
6. McQuillan, A. D . , and McQuillan, M. K . , T i t a n i u m , Metallurgy

of the R a r e r Metals-4, B u t t e r w o r t h & Co. ( P u b l i s h e r s ) L i m i t e d
(RSIC 0600).
7. G r i e s t , A . J . , and F r o s t , P. D, , " P r i n c i p l e s and Application of

Heat T r e a t m e n t f o r Titanium Alloys", T M L R e p o r t No. 87,
Battelle M e m o r i a l I n s t i t u t e ( D e c e m b e r 27, 1957) (RSIC 1265).
8. Minkler, W , W . , "Titanium i n 1965", p a p e r p r e s e n t e d a t the

Titanium Metallurgy C o u r s e , New Y o r k U n i v e r s i t y , School of
L-
Engineering and Science ( S e p t e m b e r 13-15, 1965) (RSIC 1308).
9. Wood, R . A . , "A Tabulation of D e s i g n a t i o n s , P r o p e r t i e s , and

T r e a t m e n t s of Titanium and T i t a n i u m Alloys", DMIC M e m o r a n -
dum 171 (Revision of DMIC M e m o r a n d u m l o ) , Battelle M e m o r i a l
Institute ( J u l y 15, 1963) (RSIC 0293).
56
Wood, R. A . , "Effect of I n t e r s t i t i a l s on the Mechanical P r o p e r -
ties of T i t a n i u m and Its Alloys", paper p r e s e n t e d at the Titanium
Metallurgy C o u r s e , New York University, School of Engineering
and Science ( S e p t e m b e r 13-15, 1965) (RSIC 1302).
Ogden, H. R. , "The Behavior of Titanium a t Elevated T e m p e r a -

tures", p a p e r p r e s e n t e d a t the Titanium Metallurgy C o u r s e , New
Y o r k University, School of Engineering and Science (Septem-
ber 13-15, 1965) (RSIC 1301).
Reynolds, J. E . , Ogden, H. R , , and J a f f e e , R. I., "A Study of

the A i r Contamination of T h r e e Titanium AlloysBy,T M L R e p o r t
No. 10, B a t t e l l e M e m o r i a l Institute (July 7 , 1955) (RSIC 1335).
B o m b e r g e r , H. B. , "Fund+rnentals of C o r r o s i o n of Titanium",
p a p e r p r e s e n t e d at the Titanium Metallurgy C o u r s e , New York
U n i v e r s i t y , School of Engineering and S c i e n c e ( S e p t e m b e r 13-15,
1965) (RSIC 1304).
B r a s k i , D. N . , and H e i m e r l , G. J . , "The Relative Susceptibility

of F o u r C o m m e r c i a l T i t a n i u m Alloys to S a l t S t r e s s C o r r o s i o n a t
550 F", NASA TN D-2011, National A e r o n a u t i c s and S p a c e
A d m i n i s t r a t i o n ( D e c e m b e r , 1963) (RSIC 1306).
P r i d e , R. A . , and Woodard, J. M., "Salt-Stress-Corrosion

C r a c k i n g of Residually S t r e s s e d Ti-8A1- 1Mo-1V B r a k e - F o r m e d
S h e e t at 550 F (561 K)", NASA TM X-1082, National A e r o n a u t i c s
and S p a c e A d m i n i s t r a t i o n (April, 1965) (RSIC 1307).
Boyd, W. K . , and F i n k , F. W . , "The Phenomenon of Hot-Salt-

S t r e s s - C o r r o s i o n Cracking of Titanium Alloys", NASA CR- 1 1 7 ,
C o n t r a c t No. NASr- 100( 04), p r e p a r e d by Battelle M e m o r i a l
I n s t i t u t e f o r the National Aeronautics and Space Administration
( O c t o b e r , 1964) (RSIC 1184).
P e a r s o n , R. E. , "Fundamentals of Design Considerations", paper

p r e s e n t e d a t the Titanium Metallurgy C o u r s e , New York U n i -
v e r s i t y , School of Engineering and Science ( S e p t e m b e r 13- 15,
1965) (RSIC 1303).
P r i v a t e communication with R. H. Lundquist of California-Doran

H e a t T r e a t i n g Company, Los Angeles, California (October 13,
1965) (RSIC 1333).
57
19. P r i v a t e communication with S. S m i t h of M e n a s c o Manufacturing P .
Company, Burbank, California (October 12, 1965) (RSIC 1330).
20. P r i v a t e communication with G. A. Lenning of T i t a n i u m M e t a l s

C o r p o r a t i o n of A m e r i c a , H e n d e r s o n , Nevada (October 13- 14,
1965) (RSIC 1334).
21. P r i v a t e communication with R. H. E r n s t and D. N. Williams of

B a t t e l l e M e m o r i a l I n s t i t u t e , Columbus, Ohio (October 18, 1965)
(RSIC 1328).
22. Mallett, M. W . , "Surface T r e a t m e n t and Conditioning of

Titanium and Titanium Alloys", unpublished r e p o r t p r e p a r e d by
B a t t e l l e M e m o r i a l Institute f o r Redstone Scientific Information
C e n t e r under C o n t r a c t DA-01-021-AMC-11651 ( Z ) . (RSIC 1327).
23. Unpublished data u n d e r C o n t r a c t A F 33(615)-1386, N o r t h

A m e r i c a n Aviation, Columbus Division ( J a n u a r y - J u n e , 1965)
(RSIC 1305).
24. P r i v a t e communication with H. G i l b e r t and J. J . Shaw of H a r v e y

Aluminum Company, T o r r a n c e , California (October 13, 1965)
(RSIC 1332).
25. P r i v a t e communication with K. T . McDonald of N o r t h A m e r i c a n

Aviation, Los Angeles, California (October 12, 1965) (RSIC 1329).
26. P r i v a t e communication with H. A. K r a a k e of Vac-Hyd C o r p o r a -

tion, T o r r a n c e , California ( O c t o b e r 13, 1965) (RSIC 1331).
27. Rogerson, D. B. , "Technological Advancements Resulting f r o m

X B - 7 0 P e r f o r m a n c e R e q u i r e m e n t s " , p a p e r p r e s e n t e d a t the
National Aeronautic and S p a c e Engineering and Manufacturing
Meeting, SAE 650798, Los A n g e l e s , C a l i f o r n i a ( O c t o b e r 4-8,
1965) (RSIC 1343).
58
APPROVAL NASA TM X-53445
By F. F. Schmidt and R. A. Wood
The information in t h i s r e p o r t has been reviewed f o r s e c u r i t y

classification. Review of any information concerning D e p a r t m e n t of
Defense o r Atomic E n e r g y Commission p r o g r a m s has been m a d e by
the MSFC Security Classification Officer. This r e p o r t , in its
entirety, has been d e t e r m i n e d to be unclassified.
This document h a s a l s o been reviewed and approved f o r technical

accuracy.
&fl- W. A. WILSONfL
Chief, Methods Development Branch
~J. P. .RR
Manufacturing R e s e a r c h and
echnology Division
+,WERNER R. KUERS
j D i r e c t o r , Manufacturing Engineering
Labor atory
59

C. Flight: George Mursbdll Space

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

C. Flight: George Mursbdll Space

Uploaded by

Copyright:

Available Formats

https://ntrs.nasa.gov/search.jsp?

NASA TECHNICAL N.1S4 TM X- 53445

By F. F. Schmidt and R. A. Wood

Prepared Under the Supervision o f the

George C. Mursbdll G P O PRICE s

Hard copy ':IC) -?

HEAT TREATMENT O F TITANIUM AND TITANIUM ALLOYS

F. F. Schmidt and R. A. Wood::

This r e p o r t reviews p r e s e n t h e a t t r e a t m e n t p r a c t i c e s f o r titanium

+ P r i n c i p a l Investigators, Battelle Memorial Institute,

NASA-GEORGE C. MARSHALL SPACE FLIGHT CENTER

TECHNICAL MEMORANDUM X-53445

HEAT TREATMENT O F TITANIUM AND TITANIUM ALLOYS

Manufactur ing Engine e r ing L a b o r at o r y

Technology Utilization Office

Under the supervision of

Redstone Scientific Information C e n t e r

This r e p o r t i s one of a s e r i e s of s t a t e - o f - t h e - a r t r e p o r t s being

This r e p o r t on h e a t t r e a t m e n t of titanium and titanium alloys i s

The r e p o r t s u m m a r i z e s information collected f r o m books, techni-

METALLURGICAL BEHAVIOR O F TITANIUM ALLOYS . . . 2

Classification of Titanium Alloys . . . . . . . . . 2

TYPICAL THERMAL TREATMENTS AND P R O P E R T I E S

Alpha Alloy .Ti-5A1-2.5Sn . . . . . . . . . . 19

CONCLUSIONS AND RECOMMENDATIONS . . . . . . . 55

Figure Title Page

1. P r i n c i p a l Types of Titanium-Alloy Constitution

2. M i c r o s t r u c t u r e s of Fully Annealed Titanium. . 6

5. E f f e c t of Cooling Rate on P h a s e Relationships and

6. Effect of T i m e and T e m p e r a t u r e on the Relief of

8. Effect of T i m e and T e m p e r a t u r e on the Relief of

9. End-Quench Hardenability Curves f o r Ti-6A1-4V . 24

10. T h e Effect of Aging on Hardness of a Ti-6A1-4V

11. The Effect of Section Size on the T e n s i l e P r o p e r t i e s

12. T h e Effect of Solution T e m p e r a t u r e on Tensile

13. T h e E f f e c t of Delayed Water Quenching F r o m 1750 and

Figure Title Page

14. T h e Effect of Aging T i m e at 900 F on t h e T e n s i l e

15. P h a s e D i a g r a m of B- 120VCA With Variable C h r o m i u m

16. P h a s e D i a g r a m of B- l2OVCA With V a r i a b l e Aluminum

18. Effect of Solution T e m p e r a t u r e on the Annealed a n d

20. Effect of Carbon, Oxygen, and Nitrogen on T e n s i l e

21. Effect of Carbon, Oxygen, and Nitrogen on V i c k e r s

22. Effect of I n t e r s t i t i a l s on Toughness of Iodide

23. C h a r a c t e r i s t i c s of Hydrogen E m b r i t t l e m e n t in Alpha

24. Oxidation R a t e s of T i t a n i u m in Oxygen in t h e 800 to

25. C o m p a r i s o n of the Metal L o s s e s of C o m m e r c i a l

Figure Title Page

26. S u m m a r y of H a r d n e s s - P e n e t r a t i o n Data f o r Unalloyed

27. Technique f o r Estimating the Depth of Contamination

28. F o r E s t i m a t i n g the Depth of Contamination of

29. F o r E s t i m a t i n g the Depth of Contamination of Ti-4A1-

30. Vertical Gantry Type of Furnace. . . . . . . . 48

3 2. Hot Sizing of Titanium . . . . . . . . . . . 53

33. T i m e - T e m p e r a t u r e - P e r Cent S t r e s s Relief Relation-

I. Heat T r e a t m e n t and Selected P r o p e r t i e s of Titanium

11. P r o d u c e r Designations and F o r m s Available f o r

111. T e n s i l e P r o p e r t i e s of Annealed Ti-5A1-2. 5Sn

IV. Effect of T e m p e r a t u r e on the Oxide-Film T h i c k n e s s

HEAT TREATMENT O F TITANIUM AND TITANIUM ALLOYS

The o c c u r r e n c e of a n allotropic t r a n s f o r m a t i o n i n p u r e titanium

T i t a n i u m is chemically v e r y a c t i v e at elevated t e m p e r a t u r e s , and

A n u m b e r of recommendations that a t t e m p t to identify p r o b l e m