Metal Science and Heat Treatment Vol. 48, Nos.

3 4, 2006

UDC 620.178.742.5

DUCTILE-BRITTLE TRANSITION IN STEELS

AT NEAR-SOLIDUS TEMPERATURES

V. V. Zabilskii1 and R. M. Nikonova1

Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 4, pp. 9 20, April, 2006.

A complex study of the nature of the little-investigated phenomenon of high-temperature brittleness of steels,
i.e., the ductile-brittle transition observed in the temperature range t = (0.92 0.98)tmelt , is described. Regular
features in the behavior of mechanical properties of low-alloy steels in this temperature range are considered.
The effects of the chemical composition (carbon, impurities), preliminary plastic deformation, high-tempera-
ture annealing, and test medium on the mechanical properties are studied. Special features of the fracture
mechanism at the studied temperatures are described.

INTRODUCTION METHODS OF STUDY

It is known [1 4] that when heated to a temperature
close to that of melting (tmelt ) steels exhibit high-temperature
brittleness known as ductile-brittle transition at near-solidus
temperatures. This phenomenon is characterized by a marked
decrease in the strength and ductility characteristics, which
occurs in a narrow temperature range not exceeding 10C.
The main characteristic of the mentioned kind of brittleness
is the temperature of the ductile-brittle transition td/b , at
which the contraction has a zero value. Fracture of speci-
mens heated to t td/b develops over boundaries of austenite
grains in contrast to the known phenomenon of brittleness of
alloys cooled from the liquid state, in the temperature range
of which fracture occurs over dendrite boundaries [3].
The necessity for studying this very kind of high-tempe-
rature brittleness is explained by the fact that it is connected
with the appearance of hot cracks in continuous casting
[5, 6], welding [7], shaping in semifluid state [8], and other
operations. The present work completes a cycle of studies of
the authors [4, 9 13] devoted to the phenomenon of high-
temperature brittleness of the kind.
The aim of the work is to determine the main laws of
variation of the mechanical properties of steels in the tempe-
rature range of the ductile-brittle transition and the effect of
the chemical composition (carbon, impurities), preliminary
plastic deformation, high-temperature annealing, and test
medium on these properties and in studying special features
of the fracture mechanism of steels in the temperature range
of interest.
1 high-temperature brittleness we computed the content of
Physicotechnical Institute of the Ural Branch of the Russian
Academy of Sciences, Izhevsk, Russia.
High-temperature mechanical tests were performed in an
IMASh 20-75 installation in a medium of argon (99.992%
Ar, 0.0007% O, 0.006% N; steam content 0.007 g/m3 ) and
in vacuum at p = 1 and 10 2 Pa. Specimens 3 3 65 mm
in size were heated by the method of radiation with the help
of a tantalum heater placed around the functional part of the
specimen. In order to increase the uniformity of the distribu-
tion of temperature over the cross section and over the
length, the specimen was placed into a ceramic (BeO) tube.
The specimens were heated at a rate of 100 200 K/min to
1250C (with a stabilizing hold of 1 min) and then to the test
temperature. The tensile strength was tested at a rate of
4.1 10 3 sec 1. The temperature of the tested specimen
was controlled by a platinum-rhodium/platinum thermocou-
ple PP68, the thermal junction of which was welded directly
in the center of the functional part. The study was performed
by methods of high-temperature metallography, scanning
electron microscopy (RM-200), x-ray photoelectron and
Auger spectroscopy, and differential thermal analysis. The
objects of the study were low-alloy steels (Table 1), i.e.,
high-carbon steel ShKh15 (with cast and hot-deformed struc-
ture), low-carbon steels 17G1S and 09G2FB (with rated con-
tent of the S, P, Sn, and Sn + Cu impurities), steel 37KhN3A
(of special purity), and other grades.
The temperature of volume melting tmelt was determined
experimentally by the method of DTA and by visual observa-
tion of the melting process.
In order to evaluate the effect of the test medium on the
oxygen in the media with allowance for the fact that it took

150
0026-0673/06/0304-0150 2006 Springer Science + Business Media, Inc.
Ductile-Brittle Transition in Steels at Near-Solidus Temperatures 151

y t, %
20% of the air volume and under the assumption that the
contents of oxygen and nitrogen changed equally under the 80
conditions of vacuum.
60 Dt = 140C
RESULTS AND DISCUSSION 40 2 1
20
Main Laws of Variation of Mechanical Properties
0
The studies showed that the phenomenon of ductile-brit- srt , %
tle transition at near-solidus temperatures occurs in steels 1
10
with various chemical compositions and crystal structures, 2
namely, the tool steel R6M5, the high-carbon steel ShKh15, 5
tmelt
the low-carbon steel 17G1S, and the high-nickel steel 0
1220 1260 1300 1340 1380 1420
17G1SN27, which have the fcc structure of austenite at the ttest , C
test temperature [4]. A ductile-brittle transition was also de-
tected in complexly alloyed steel 04Kh24N7M3YuT and in Fig. 1. Temperature dependences of contraction yt and ultimate
alloys of type Fe 3% Si that have a ferrite structure (a bcc rupture strength str of steel ShKh15 (tmelt is the temperature of vo-
lume melting): 1 ) heating to the test temperature (ttest ) from room
lattice) at the temperatures studied. Brittleness is observed in temperature; 2 ) preliminary heating to 1310C, 3-min hold, cooling
alloys with a fine-grained structure (d = 10 20 mm, R6M5) to the test temperature.
and in alloys with a coarse-grained structure (d = 1000 mm,
Fe 3% Si).
As an example, let us consider the variation of high-tem- rature of the ductile-brittle transition (the temperature of zero
perature mechanical properties of commercial-purity high- ductility) of this steel td/b = 1290C (curve 1 in Fig. 1), which
carbon steel ShKh15 with cast structure (Fig. 1). The tempe- amounts to 0.92tmelt , where tmelt is the temperature of volume

TABLE 1. Chemical Composition of Steels

Content of elements, %
Steel Heat
C Mn Si Ti Al S P Cr Ni Cu Su Mo Other
ShKh15 (cast) 1 1.01 0.30 0.25 0.005 0.013 0.006 1.42 0.04 0.06
ShKh15 (hot-
deformed) 2 0.97 0.30 0.26 0.020 0.023 1.45
ShKh15 (ShP) 3 0.97 0.28 0.30 0.040 0.040 0.008 1.39 0.07 0.08 0.01
R6M5 4 0.81 0.38 0.31 0.015 0.017 3.90 0.32 5.26 5.7 W, 1.18 V
R6M5 6 0.85 0.20 0.35 0.006 0.025 4.04 0.42 4.82 5.59 W, 2.07 V
R18 7 0.87 0.30 0.47 0.011 0.025 3.90 0.38 0.40 16.5 W, 1.06 V
Fe 3% Si 8 0.06 0.29 2.73 0.350 0.005 0.009 0.05 0.08 0.17 0.01 Traces of W
and V
04Kh24N7M3YuT 9 0.04 0.150 0.009 0.030 22.8 7.78 3.00
17G1S 11 0.20 1.46 0.37 0.010 0.010 0.004 0.005 0.030 0.050 0.030 Traces
17G1S 16 0.19 1.45 0.41 0.005 0.220 0.024 0.005 0.010 Traces 0.020 0.001
G1 19 0.01 1.16 0.02 0.035 0.004 0.006 0.003 0.020 0.380 0.020
G1 20 0.01 1.20 0.003 0.013 0.080 0.005 0.004 0.023 0.270 0.005
17G1SN27 21 0.19 1.36 0.35 0.005 0.020 0.023 0.020 Traces 26.68 0.040
09G2FB 22 0.10 1.53 0.10 0.002 0.003 0.007 0.002 0.043 0.12 0.004 0.007 0.05 V,
0.036 Nb
09G2FB 24 0.11 1.60 0.23 0.002 0.003 0.028 0.040 0.052 0.012 0.004 0.007 0.08 V,
0.032 Nb
18Kh2N4MA 28 0.17 0.49 0.37 0.045 0.006 0.010 1.40 4.50 0.026
37KhN3A 29 0.34 0.001 0.001 0.001 0.0007 0.0005 1.40 3.20 0.001 0.001

Notes. 1. Out of the 29 heats tested, 3 heats were of steel R6M5, 6 heats of steel 09G2FB, 8 heats of steel 17G1S (in these cases the table pre-
sents the chemical composition of the heats with the highest and lowest content of impurities); the other steels were melted in one heat.
2. Heats 1 9 were of commercial purity; heats 10 29 were melted in laboratory.
152 V. V. Zabilskii and R. M. Nikonova

st, P
1

9
2

3
3 a b
10%
0
et, %

Fig. 2. Stress-strain diagrams of steel ShKh15 near the temperature

of ductile-brittle transition: 1 ) ttest = 1270C (t < td/b ); 2 ) 1290C
(t = td/b ); 3 ) 1310C (t > td/b ).
c d

melting. Tests at ttest > td/b have shown that the brittle state is
stable in a wide temperature range. For steel ShKh15 the
temperature range of embrittlement Dt = 140C. Note for
comparison that in the case of low-carbon steel 17G1S this
range is substantially lower, i.e., Dt = 45C [12].
Typical mechanical stress-strain diagrams illustrating the
variation of ductility and strength characteristics of steel
ShKh15 in the range of the ductile-brittle transition are pre-
sented in Fig. 2. At ttest < td/b the specimen fractures with a
high ductility (yt = 100%, curve 1 in Fig. 2). At ttest > td/b the
specimen fractures in the macroelastic domain (y t = 0%,
curve 3 in Fig. 2), which reflects a brittle fracture behavior.
As a rule, the fracturing stress is 2 4 MPa. At ttest = td/b the
specimen still possesses some deformability, which is mani-
fested in the form of a small ductile region on the
stress-strain curve (curve 2 in Fig. 2). It should be noted that
curve 2 in Fig. 1 was obtained by another test scheme, i.e.,
the specimens were stretched after preliminarily heating to
1310C (a temperature exceeding somewhat the value of
td/b ) and cooling to the test temperature. As a result we de-
tected a shift (hysteresis) of the ductile-brittle transition to-
ward lower temperatures (from 1290 to 1270C). It is obvi-
ous that the value of the hysteresis depends on the hold at
this temperature and on the rate of cooling to the test tempe-
rature.
High-temperature fracture of specimens at ttest td/b de-
velops in a brittle manner over grain boundaries (see Fig. 3)
without formation of a neck. The fracture surface has a typi-
cal fused structure. The fracture surface of steel 16GFR has a
specific relief in the form of a flat dendritic pattern (Fig. 3c
and d ), which indicates the presence of layers of a liquid
phase at the test temperature. In steel 17G1S at ttest = td/b
(1400C) grain boundaries bear river lines of hardened
melt located along grain boundary joints (Fig. 3f ). Similar
results reflecting the presence of a liquid phase on grain
boundaries were obtained for steels ShKh15,
04Kh24N7M3YuT (Fig. 3a, b, and e), and other grades.
e f
Fig. 3. Surfaces of high-temperature fracture of steels: a, b )
ShKh15, ttest = 1290C @ td/b ; c, d ) 16GFR, ttest = 1430C > td/b ;
e) 04Kh24N7M3YuT, ttest = 1320C @ td/b ; f ) 17G1S, ttest =
1400C @ td/b ; a, b, e, f ) SEM; c, d ) carbon extraction replicas;
a) 250; b ) 750; c) 8500; d ) 12,000; e) 500; f ) 110.
Effect of the Content of Carbon and Impurities
Generalization of the results obtained earlier [9 11] and
of the data of [1, 14] shows that high-temperature brittleness
of the kind considered is sensitive to the chemical composi-
tion of the steel, especially to the content of carbon and of the
S and P impurities. It has been shown for steel ShKh15 that
the decrease in the content of sulfur from 0.020 to 0.004%
and of phosphorus from 0.023 to 0.008% due to electroslag
remelting decreases the susceptibility to embrittlement, in-
creasing the value of td/b by 40C, i.e., from 1290 to 1330C
[9]. The temperature of volume meting remains unchanged
(1370 1390C). Similar results have been obtained for
low-carbon steels 17G1S and 09G2FB [9].
The effect of the S and P impurities on the temperature
td/b of the studied steels is generalized in Fig. 4. Straight line
1 corresponds to a low content of S and P impurities; straight
line 2 corresponds to their elevated content. It can be seen
that the decrease in the concentration of S and P to the level
specified increases td/b by 50C on the average.
The data of Fig. 4 also illustrate the effect of carbon;
growth in its content from 0.01 to 1.0% decreases td/b by
170C, which corresponds to 1.8C per 0.01 wt.% C. This re-
Ductile-Brittle Transition in Steels at Near-Solidus Temperatures
sult agrees with the data in the literature, according to which
this value is 1.6C [1]. The effect of carbon on the tempera-
ture of the ductile-brittle transition is similar to its effect on
the solidus temperature, which amounts to 1.8 2.0C per
0.01 wt.% C according to the Fe C phase diagram.
We processed statistically the results of high-temperature
mechanical tests of over 40 compositions of low-alloy steels
including the data of [1, 14]. This gave us an empirical de-
pendence of the temperature of the ductile-brittle transition
on the chemical composition of the steels, namely,
td/b = 1479 169[C] 547[S] 199[P] 8[Mn] 6[Si]. (1)
This equation makes it possible to predict the variation
of td/b upon changes in the content of elements in the compo-
sition within the following ranges (in mass fractions):
0.01 1.90% C, 0.001 0.042% S, 0.001 0.040% P,
0.34 1.93% Mn, and 0.01 1.00% Si. The dependence
confirms that the value of td/b depends primarily on the con-
tent of carbon and on the S and P impurities.
In contrast to the impurities of sulfur and phosphorus, the
impurities of nonferrous metals, which are present in low-al-
loy steels in a low amount, does not affect substantially the
value of td/b. Such impurities have a low temperature of
melting (this is shown in [9] for two heats of steel 09G2FB
bearing 0.023% Sn and 0.025% Sn + 0.2% Cu, respectively).
No effect of retained metallurgical oxygen (0.0020
0.0078%) and nitrogen (0.0001 0.0090%) on td/b has been
detected either. The absence of the influence of impurities of
nonferrous meals on td/b reflects the low degree of enrich-
ment of grain boundaries with these elements at the test tem-
perature. The absence of the influence of metallurgical oxy-
gen and nitrogen is explainable by the high melting tempera-
tures of the nonmetallic inclusions (oxides, nitrides) present
in the composition of the steel. For example, the melting
temperature of MnO is 1780C; that of the AlN aluminum
nitride is 2200C [15].
Effect of Preliminary Treatment
The temperature of the ductile-brittle transition is sensi-
tive to preliminary treatment (hot plastic deformation and
high-temperature annealing) [12]. We studied steel 17G1S
after fractional casting at sulfur content ranging within
0.004 0.025%. In the case of testing after preliminary plas-
tic deformation the specimens were heated to 1350C (for
stabilization of the structure), cooled to the deformation tem-
perature td = 800C, deformed by stretching with degree
e = 6%, and then heated to the test temperature.
It turned out that the preliminary plastic deformation in-
tensified the high-temperature embrittlement, causing a sub-
stantial decrease in the temperature of the ductile-brittle tran-
sition. The negative effect of the deformation increased with
growth in the sulfur content in the steel. At 0.005% S the de-
crease in the temperature td/b was 18C; at 0.025% S it was
40C. The temperature of 800C was chosen for testing on
153
td/b , C
1450
1
1400
50
1350
2
1300
1250
0 0.2 0.4 0.6 0.8 C, wt.%
Fig. 4. Temperature of ductile-brittle transition td/b as a function of
the carbon content in low-alloy steels with different concentrations
of sulfur and phosphorus impurities: 1 ) 0.0007 0.007% S,
0.0005 0.005% P; 2 ) 0.008 0.034% S, 0.006 0.040% P.
the basis of the data of earlier studies [16], which showed
that deformation at this temperature caused growth in the
concentration of sulfur on grain boundaries. According to the
data of Auger spectroscopy [16], the mean concentration of
sulfur on grain boundaries in this case attains 4.0 wt.%,
which is more than three orders of magnitude higher than its
volume content. It is obvious that the decrease in the temper-
ature of the ductile-brittle transition after preliminary defor-
mation is explainable by the inherited elevated concentration
of sulfur on grain boundaries during heating to the tempera-
ture range of the ductile-brittle transition, i.e., it is preserved
in heating to a temperature exceeding td by more than 600C.
We performed preliminary annealing at 1250C for 6 h
in vacuum at a pressure p = 10 2 Pa. In contrast to hot plas-
tic deformation, high-temperature annealing decreased the
degree of embrittlement, causing an increase in td/b of the
studied steel. The positive effect of the annealing was inten-
sified upon a decrease in the sulfur content. Moreover, at
0.008% S and 0.004% P in the metal preliminary anneal-
ing ensured equality between the temperature td/b and the
temperature of volume melting tmelt , i.e., the given kind of
high-temperature embrittlement was fully eliminated.
It is known [17, 18] that in addition to changing the size
and shape of nonmetallic inclusions, high-temperature an-
nealing in vacuum causes formation of more stable com-
pounds with higher melting temperature. For example, in the
composition of the FeS MnS sulfide phase, high-tempera-
ture annealing raises the MnS/FeS proportion. Since the
melting temperature of FeS is 1190C and that of MnS is
1615C, it is obvious that the formation of more stable non-
metallic compounds is the main reason behind the observed
positive effect. It should be noted that high-temperature an-
nealing in vacuum can promote removal of another kind of
high-temperature brittleness in low-alloy steels, i.e., embrit-
tlement in the range 700 1000C [19].
154 V. V. Zabilskii and R. M. Nikonova

y t, %
100
tile-brittle transition Dtd/b in steel ShKh15 ranged from 5
to 35C.
80 Evaluation of the content of oxygen in various media
60 1 2 3 showed that the growth in the temperature of ductile-brittle
transition was caused by a decrease in the partial pressure of
40 oxygen (Table 2). In accordance with the data obtained, oxy-
gen had the highest partial pressure in an argon medium
20
tmelt ( pO ~ 2 Pa) and the lowest partial pressure in the tests per-
2
0
srt , formed in vacuum in the presence of a copper getter ( pO ~
b 2
P 2
12
3 2 10 6 10 10 Pa [20]); the getter created conditions for
active desorption of oxygen from the surface of the specimen
8 1
to grain boundaries. In our opinion, the latter is the main
4 cause of the observed effect of growth in the temperature td/b
0
in the presence of oxygen getter.
1280 1320 1360 1400 ttest , C In order to determine the chemical composition of grain
boundaries including the content of oxygen, we quenched
Fig. 5. Temperature dependences of contraction y t and ultimate
specimens from 1295C (t ~ td/b ) and 1265C (t < td/b ).
rupture strength s tr of steel ShKh15 tested in different media: 1 ) ar-
gon; 2 ) vacuum ( p = 1 Pa); 3 ) vacuum ( p = 1 Pa) + copper getter Specimens 4 10 60 mm in size were heated in a labora-
(plate) placed close to the specimen. tory furnace in a protective atmosphere (argon) and then
quenched in a 10% aqueous solution of NaCl cooled to
4C. The quenched specimens were broken (by a striker) at
Role of the Test Medium room temperature. The specimens broken over boundaries of
austenite grains were studied by the methods of Auger and
When studying the effect of the test medium (inert gas, x-ray spectroscopy. For any of the quantitative difference in
vacuum) we established that the temperature of the duc- the results obtained by these methods (Table 3), the contents
tile-brittle transition was sensitive to the content of retained of S, Si, P, and oxygen increased in a jump at the temperature
oxygen in the test chamber [11, 12]. We studied high-carbon of the ductile-brittle transition.
steel ShKh15 in different (cast and hot-deformed) states. We Typical Auger spectra obtained from grain boundaries
have already mentioned that in tests in an argon medium after the quenching are presented in Fig. 6. Comparing spec-
td/b = 1290C (Fig. 1). In tests in vacuum ( p = 1 Pa) the tem- tra 1 and 2 we will see that growth in the temperature of
perature of the ductile-brittle transition increased by 15C, heating for quenching from 1265C (tq < td/b ) to 1295C
i.e., td/b = 1305C (curve 2 in Fig. 5). The use of an oxygen (tq ~ td/b ) enriches the grain boundaries with sulfur, silicon,
getter (a copper plate placed in direct vicinity of the speci- phosphorus, and (the most strongly) with the oxygen impu-
men and heated to 400C) increased the value of td/b by 20C rity. Specifically, the atomic fraction of sulfur on the grain
more, i.e., td/b = 1325C (curve 3 in Fig. 5). The test medium boundaries increases from 1.7 to 2.7%, that of silicon in-
produced a similar effect on the value of td/b of steel ShKh15 creases from 0.2 to 3.1%, and that of phosphorus increases
in the hot-deformed state (Table 2). Thus, depending on the from 0.9 to 3.1% (Table 3). The coefficient of enrichment of
conditions of the test (degree of evacuation, presence of a grain boundaries (the ratio of the concentrations of an impu-
copper-plate getter) the growth in the temperature of duc- rity on the boundary and in the body of a grain) increases
from 85 to 135 for S, from 0.42 to 6.46 for Si, and from 90 to

TABLE 2. Temperature of Ductile-Brittle Transition in Tests in

Media with Different Partial Pressure of Oxygen TABLE 3. Content of Impurities on Grain Boundaries in Steel
ShKh15 at Temperatures Close to td/b
Test medium n, m 3 pO , Pa td/b , C
2
Content of elements, at.%
Air 5 1024 2 104
Method of analysis t, C
Argon 2 1020 2 100 1290 S Si P O
Vacuum, p = 1 Pa 5 10 19
2 10 1 1295 X-ray spectrum 1265 (t < td/b ) 1.7 0.2 0.9 50
Vacuum, p = 10 2 Pa 5 1017 2 10 3 1300 1295 (t td/b ) 2.7 3.1 3.1 66
Vacuum, p = 10 2 Pa + Auger spectrum 1265 (t < td/b ) 3
getter (Cu) 1010 1014 10 6 10 10 1320 1295 (t td/b ) 0.3 2.2 24

Notations: td/b ) temperature of ductile-brittle transition; n ) num- Note. The content of the elements was determined at a depth
ber of oxygen molecules, pO ) partial pressure of oxygen. of 2 nm.
2
Ductile-Brittle Transition in Steels at Near-Solidus Temperatures
310 for P. According to the data of the Auger analysis the
mean atomic fraction of oxygen on a grain boundary (at a
depth of 0.4 nm) amounts to 24% (in some regions to 58%),
whereas in the body of a grain (on an intragrain fracture) it
does not exceed 3% (spectrum 3 in Fig. 6). The presence of
oxygen on the intragrain region of fracture is connected with
the fact that before the Auger analysis the specimen was bro-
ken in air.
The effect of retained oxygen in the test medium on td/b
can be explained by the development of oxidation reactions
of grain boundaries, which yield nonmetallic inclusions with
a lower melting temperature [21]. In the presence of oxygen
on the surface of a specimen and on grain boundaries of steel
ShKh15 bearing 0.25% Si, which is an active deoxidizer, the
process may develop by the reaction
4FeO + Si Fe2SiO4 + 2Fe. (2)
In accordance with reference data [15] the melting tem-
perature of the FeO oxide is 1368C and that of the Fe2SiO4
orthosilicate formed as a result of the interaction between the
FeO oxide phase and silicon is 1220C. In addition, the com-
position of steel ShKh15 includes such sulfide and oxide in-
clusions as (Fe, Mn)S, (Fe, Mn, Cr)S, MnO Cr2O3, etc.
[21, 27]. In a medium with a high content of retained oxygen
(argon) the composition of the inclusions can change toward
growth in the oxide component accompanied by the respec-
tive decrease in the melting temperature [21]. For example,
Si + O2 SiO2, (3)
2Mn + O2 2MnO, (4)
MnO + SiO2 MnO SiO2. (5)
The following reaction is also possible:
MnO Cr2O3 + SiO2 MnO SiO2 + Cr2O3. (6)
The oxides have the following melting temperatures:
1700C for SiO2, 1650C for MnO, over 2000C for the
MnO Cr2O3 spinel, and 1205C for the MnO SiO2 manga-
nese metasilicate [17, 22]. As a result of the interaction be-
tween the basic inclusions and oxygen from the test me-
dium, nonmetallic inclusions with considerably (hundreds of
degrees) lower melting temperature than that of the basic in-
clusions can form on grain boundaries; this explains the
changes in the temperature of the ductile-brittle transition of
the studied steel.
In the literature (for example, in [23]) the effect of the
test medium on the temperature of ductile-brittle transition is
explained by evaporation of low-melting impurities from
the surface of the metal in vacuum during high-temperature
deformation. However, in accordance with our data the test
medium can also change the chemical composition of grain
boundary segregations. This is confirmed by the data on the
155
I
1
C O
Fe
2
C
Fe
Si O
S
3
O Cr
C Fe
0 100 200 300 400 500 600 700 E, eV
Fig. 6. Auger spectra (I is the amplitude of the Auger signal) illus-
trating the variation of the chemical composition of grain boundaries
in heating for quenching to tq @ td/b : 1, 2 ) grain boundary, 1-min
ion etching of the surface (the etching depth is 2 nm); 3 ) grain body;
4 ) heating for quenching to 1265C (tq < td/b ); 2, 3 ) heating for
quenching to 1295C (tq ~ td/b ).
effect of S and P impurities presented above. The determin-
ing role of the impurity elements (nonmetallic inclusions) is
also confirmed by the fact that the ductile-brittle transition is
absent in steel 17G1S after high-temperature annealing
(td/b ~ tmelt ).
The study of alloys with a minimum amount of impuri-
ties also confirms the determining role of impurities. We
studied steel 37KhN3A of special purity (0.34% C, 0.0007%
S, 0.0005% P, 0.001% Mn, 0.001% Si, i.e., the total content
of S, P, Mn, and Si was below 0.004%), which was melted
under laboratory conditions, and high-purity Fe C alloys
(0.005 and 0.4%C, 0.0003% S, 0.005% P). It turned out that
in the tests performed in vacuum (with the use of oxygen get-
ter) the high-temperature brittleness was eliminated (Fig. 7),
i.e., the temperature of formation of liquid phase on grain
boundaries virtually corresponded to the melting temperature
of grain bodies (their difference Dt = 2C). Note for compari-
son that for commercial-purity steel ShKh15 Dt = 80C
(Fig. 5).
Thus, the studied phenomenon of high-temperature brit-
tleness of low-alloy steels in not their natural quality but is
determined by the presence of impurity elements (like S and
P) of metallurgical origin and by the content of retained oxy-
gen in the test medium.
Sources of the Liquid Phase and Fracture Mechanism
The data of fractographic analysis (Fig. 3) and the pre-
sence of hysteresis on the temperature dependences of me-
156 V. V. Zabilskii and R. M. Nikonova

y t, %
100

80

1 2
60

40

20 tmelt

0 b
1420 1440 1460 ttest , C

Fig. 7. Temperature dependence of contraction y t of special-purity

steel 37KhN3A: 1 ) tests in an argon medium; 2 ) tests in vacuum
( p = 10 2 Pa).

chanical properties (Fig. 1) allow us to assume that the

c
embrittlement of grain boundaries at the temperature of duc-
tile-brittle transition is a result of the development of pro-
cesses of localized melting, i.e., formation of a liquid phase
on grain boundaries. We studied the sources of the liquid
phase by the method of high-temperature metallography on
the surface of specimens of steel ShKh15. At 1225C the liq-
uid phase was absent (Fig. 8a ). The first portions of the liq-
uid phase appeared on the surface at a temperature of
1275C, which is somewhat lower than td/b (Fig. 8b ). With d
further growth in the temperature the amount of the liquid
phase increased (Fig. 8c and d ). The liquid phase formed pri-
marily on grain boundaries in the places of location of non-
metallic inclusions. In the process of deformation the liquid
propagated over grain boundaries as a result of slip (Fig. 8e ),
which promoted brittle fracture.
The results of an analysis of fracture surfaces of speci-
mens quenched from 1310C (tq > td/b , Fig. 9a and b ) con-
firm the results of fractographic analysis of surfaces after e
high-temperature fracture of steels (Fig. 3). They show that
Fig. 8. Microstructure ( 185) of steel ShKh15 at different tempera-
the nonmetallic inclusions are sources of the liquid phase. In tures (high-temperature metallography): a) 1225C; b ) 1275C;
addition, single pores with a special (tubular) shape with c) 1290C; d ) 1300C; e) 1300C + deformation of degree e = 2%.
transverse size of 2 10 mm occur over triple joints
(Fig. 9c e). Similar tubular pores have been detected on a
surface of high-temperature fracture in steel 17G1S (see the FeS MnS sulfides is intermediate between the melting
Fig. 3f ). A detailed comparative analysis has shown that af- temperatures of FeS (1190C) and MnS (1615C); the tem-
ter quenching from tq < td/b traces of liquid phase are absent perature of melting of the FeO FeS oxysulfides is interme-
on grain boundaries, including places where nonmetallic in- diate between the melting temperatures of FeO (1368C) and
clusions are located; the same concerns tubular pores FeS [17]. It follows from the data of [17, 24] that low-melt-
(Fig. 9f ). ing inclusions in steel ShKh15 with melting temperatures
Figure 10 presents a fracture surface and Auger spectra close to td/b can also be FeP and MbP phosphides
obtained from fused inclusions. Analysis of these spectra (tmelt 1190C), 2CaO P2O5 phosphate (tmelt = 1230
shows that inclusions of the type of FeS MnS sulfides and 1300C), MnO SiO3 metasilicate, and 2MnO SiO2 ortho-
FeO FeS oxysulfides fuse. The temperature of melting of silicate (tmelt = 1290 1300C).
Ductile-Brittle Transition in Steels at Near-Solidus Temperatures
a b
c d
e f
Fig. 9. Fracture surface of steel ShKh15 (tests at room temperature)
after quenching from different temperatures: a e) tq = 1310C > td/b ;
f ) tq = 1265C < td/b ; a, b ) 1280; c e) 3500; f ) 1800. oxysulfides, etc.) at the temperatures of interest and, proba-
The liquid phase can also be supplied by lighter refrac-
tory inclusions. Figure 11 presents the Auger spectra ob-
tained from different fused regions on the surface of a speci-
men. The spectrum of the center of a nonmetallic inclusion
(Fig. 11a and b ) has considerable peaks of Fe, Ti, and O.
Therefore, it is most probable that the inclusion analyzed is
the FeO TiO2 titanate. The temperature of its melting is
1370C [15], which is 80C higher than the value of td/b of
the studied steel. It can be seen from the spectra presented in
Fig. 11c and d that the region where the liquid spreads and
the adjoining unfused matrix have virtually similar chemical
compositions. This means that in this case it is not the inclu-
sion that fuses, but rather the phase boundary. The develop-
ment of the processes of formation of liquid phase is stimu-
lated by the presence of stresses on the phase boundary,
which is detectable by the method of high-temperature
metallography from the appearance of a characteristic
strain-induced texture on the phase boundary (Fig. 12). The
stresses appear due to the difference in the physical and me-
chanical properties of the inclusion and of the matrix, for
157
C
Mn
Fe
S
S O
Fe
b
0 400 800 1200 E, eV
Fig. 10. Auger spectra obtained from the surface of low-melting in-
clusions located on a fracture surface (temperature of heating for
quenching tq = 1295C, ion etching of surface contaminations for
2 min): a) FeS MnS sulfide (the circle on the photograph of the
fracture surface marks the place from which the spectrum is taken);
b ) FeO FeS oxysulfide.
example, due to the difference in the coefficients of their
thermal expansion [17].
It is obvious that the intense development of the pro-
cesses of melting of nonmetallic inclusions (sulfides, oxides,
bly, their dissolution explains the considerable enrichment of
grain boundaries with surface-active S, Si, P, and O impuri-
ties.
The presence of tubular pores observed at a temperature
t > td/b (Fig. 9c e) is important for the explanation of the
mechanism of brittle fracture over grain boundaries. Such
pores can play the role of crack nuclei causing a catastrophic
decrease in the high-temperature ductility characteristics of
steels. Judging by the tubular shape such pores can be gene-
rated by emission of gas. In an oxygen-bearing medium the
FeO oxide can react with dissolved carbon and then yield CO
monoxide on grain boundaries, i.e.,
FeO + C Fe + CO. (7)
The formation of CO at t ~ td/b can lead to considerable
local pressure on grain boundaries and thus give rise to
pores.
The possibility of the emission of gaseous CO at the tem-
peratures of ductile-brittle transition follows from the results
of an Auger analysis made directly on the walls of tubular
pores (Fig. 13). The surface of the pores is enriched with car-
bon to up to 93 at.% (spectrum 1 in Fig. 13); after etching to
a depth of 35 nm the carbon content is preserved at a level of
158 V. V. Zabilskii and R. M. Nikonova

C
O
Fe
Ti

b
0 200 400 600 800 E, eV
I I

C O Cr C O Cr Fig. 11. Microstructure of a refractory inclu-

sion surrounded by petals of liquid phase (a)
and Auger spectra obtained from its surface
Fe
(b d ): a) high-temperature metallography
Fe c d (1300C), 50-min ion etching, 230; b ) center
of nonmetallic inclusion; c) region where the
0 200 400 600 800 E, eV 0 200 400 600 800 E, eV liquid spreads; d ) adjoining unfused matrix.

1
3% O2 4% Fe

93%

6% O2 8% Fe

86%
Fig. 12. Characteristic texture around an inclusion, which illus- 3
trates the appearance of high mechanical stresses on the phase
31%
boundary. High-temperature metallography, heating to 1300C, 2.7% S 20% Fe
450.
46% O2
0 200 400 600 800 E, eV
37 at.%. Though these values of carbon content can be over-
Fig. 13. Typical Auger spectra obtained from different regions of a
estimated substantially due to the difference in the rates of fracture surface (tq = 1310C > td/b ): 1 ) region of a pore before ion
ion etching in the region of the pore and on the smoother sur- etching; 2 ) region of a pore after ion etching to a depth of 4 nm;
face of the grain boundary, the enrichment of the pore sur- 3 ) triple joint without a pore (no ion etching).
face with carbon is quite high. In the absence of pores in a
triple joint the amount of carbon is considerably lower, i.e.,
as a result of decomposition of CO according to the reaction
31 at.% (spectrum 3 in Fig. 13). On the surfaces of the grain
(with Fe as catalyst)
boundaries (outside the joint) the average content of carbon
is 13 at.%. Note that Auger analysis at room temperature 2CO CO2 + C, (8)
shows the presence of what is known as pure carbon on
grain boundaries (a graphite form of the Auger peak instead the occurrence of which is most probable at a temperature
of a carbide one). The presence of pure carbon is possible below 720C, i.e., after cooling of the specimen [25].
Ductile-Brittle Transition in Steels at Near-Solidus Temperatures 159

b c

CO
Slip Channel
(pore)
direction of liquid phase

Liquid
phase P

Fig. 14. Diagram of formation of liquid phase and pores on grain

boundaries: a) t < td/b ; b ) t = td/b ; c) t = td/b + a load P; &, =) low-
melting (FeS MnS, FeO FeS) and refractory (FeO TiO2 ) in-
clusions respectively.

y t, %

60

40

20

srt , P
b
40
Fig. 16. Surface of high-temperature fracture of steel R6M5 at
20 1260C (ttest > td/b ): a) 1400, b ) 6000.

0
1180 1200 1220 1240 1260 1280 t, C
Fig. 15. Temperature dependences of contraction y t and ultimate
rupture strength s tr of tool steels: =, ), ^, &) R6M5 (four heats);
p) R18.
The mechanism of formation of liquid phase and pores
on grain boundaries during heating is presented schemati-
cally in Fig. 14. Formation of liquid phase on grain bound-
aries meets the condition t = td/b . We have shown that the
sources of the liquid phase are low-melting nonmetallic in-
clusions and melting of the refractory inclusion matrix
phase boundary. In addition, pores form in triple joints in
carbon-bearing steels due to high local pressures arising
upon the emission of CO. The presence of stresses gives rise
to grain boundary slip typical for high-temperature deforma-
tion. As a result, a tubular pore (crack) propagates rapidly in
the plane of grain boundaries weakened by the presence of
liquid phase and causes a catastrophic decrease in the ductil-
ity and strength characteristics of the steel (to virtually zero
values).
Another mechanism of formation of liquid phase is im-
plemented in high-alloy tool steels of type R6M5 and R18.
Results of high-temperature mechanical tests of these steels
are presented in Fig. 15. The temperature td/b in these steels
coincides with the range of the temperatures of heating for
quenching (the hatched region in Fig. 15), which should be
taken into account in heat treatment of tool steels. In accor-
dance with the data of fractographic analysis (Fig. 16) and
electron microscopy (carbon extraction replicas), fusion of
grain boundaries in this case occurs as a result of dissolution
of grain boundary carbides and subsequent formation of a
carbide eutectic on the boundaries. In addition, an Auger
spectrum analysis has shown that the boundaries, primarily
the carbide matrix interphases, are enriched considerably
by sulfur (6.8 at.%), which corresponds to a coefficient of
enrichment of carbide matrix interphases b = 409
[26, 27]. The curves of differential thermal analysis have
three melting peaks for steel R6M5 and two melting peaks
for steel R18 (Fig. 17). The first peaks correspond to the tem-
perature td/b of these steels. Judging by the data of electron
microscopy of steel R6M5 [27] the appearance of the duc-
tile-brittle transition is caused by melting of eutectics based
on a Me6C carbide and on V(C, N) carbonitride.
CONCLUSIONS
1. The ductile-brittle transition at near-solidus tempera-
tures is not a natural property of low-alloy steels but is de-
termined by the presence of impurity elements of metallurgi-
160
Dt
20
R65
td/b = 1230
R18 td/b = 1290
600 800 1000 1200 1400 t, C
Fig. 17. Curves of differential thermal analysis of steels R6M5 and
R18 illustrating the correspondence between the temperatures of
ductile-brittle transition td/b and the first melting peaks of these
steels. The heating rate is 20 K/min.
cal origin, primarily of S and P, and by the content of re-
tained oxygen in the test medium. A decrease in the total
content of impurities to 0.004% and a simultaneous de-
crease in the amount of oxygen in the test medium promote
complete removal of the embrittlement.
2. The temperature of the ductile-brittle transition (td/b )
depends on the preliminary treatment. Preliminary plastic de-
formation (td = 800C) decreases td/b due to the inherited ele-
vated concentration of sulfur on grain boundaries, which ap-
pears at the temperature of the preliminary deformation. Pre-
liminary high-temperature annealing in vacuum, which
changes the composition and morphology of grain boundary
segregations, produces a positive effect that causes removal
of the high-temperature embrittlement.
3. The appearance of ductile-brittle transition in low-al-
loy steels is connected with local formation of a liquid phase
on grain boundaries, primarily in the places of triple joints.
Formation of liquid phase in combination with processes of
gas emission (CO monoxide) gives rise to the appearance of
extended tubular pores with a diameter of 2 10 mm on grain
joints. The tubular pores play the role of crack nuclei that
cause brittle fracture in the macroelastic region.
4. The phenomenon of ductile-brittle transition in high-
alloy tool steels of type R6M5 is caused by formation of li-
quid eutectics based on carbides of type Me6C and vanadium
carbonitride V(C, N).
5. Highly accurate (with an error of 1C) determination
of the temperature of the beginning of formation of the liquid
phase on grain boundaries is ensured by the method of
high-temperature mechanical tests used for determining the
temperature of the ductile-brittle transition.
V. V. Zabilskii and R. M. Nikonova
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