Materials Science and Engineering, A 132 ( 1991 ) L5-L9 L5

Letter

On the tempered martensite embrittle-
ment in AIS1 4140 low alloy steel
F. A. Darwish
Department of Materials Science and Metallurj,% Catholic
Universi O' ( PU('/RJ), C.t'. 380(-)8, 22452-Rio de Janeiro, RJ
(Brazil)
L. C. Pereira and C. Gatts
D~Tmrtment of Metallur~.., and Materials Engineering, t:~'deral
Universi O' (("OPPE/Ut:RJ), Rio de Janeiro, RJ (Brazil)
M. L. Gra~za
Materials l)ivision, 7~'chnical Aero~v)ace ('enter (I>MR/CTA),
.~'dO Jos~; dos' ('ampos, M' (Brazil)
(Received June 11. 1990: in revised form September 10,
1990)
Abstract
from Fig. 1, both apparent and sharp crack
toughness (denominated KA and K[c respectively)
are significantly degraded as the tempering
temperature is increased from 200 to 350C.
Fractographic studies [9] have indicated that this
toughness degradation is associated with the
predominance of an intergranular cracking failure
mode along prior austenite grain boundaries of
the quenched-and-tempered material (Fig. 2).
The embrittlement of prior austenite grain
boundaries in quenched and low temperature
tempered commercially pure high strength low
alloy steels has been related by a number of
investigators (see for example refs. 4-7 and
10-12) to the combined effect of carbide
(cementite) precipitation as well as impurity-
element (notably phosphorus) segregation. While
phosphorus segregation occurs during austeniti-
zation [4, 7, 10], cementite forms by precipitation
from the tempered martensite and by thermal
decomposition of retained austenite at the
i

In the present investigation the Auger electron spec- P

troscopy CAES) technique was used to determine local 870 C AUST. - - . KI li }e
carbon and phosphorus concentrations on the fracture 240
0 1200 C AUST ....... KA i'
surfaces of as-quenched and q u e n c h e d - a n d - t e m p e r e d
(at 350 C) AISI 4 1 4 0 steel specimens austenitized at 200 I~/
low and high temperatures. T h e A E S results were
rationalized to conclude that, although carbide growth ~_ illI
as well as phosphorus segregation are expected to 160 Illl
contribute to tempered martensite embrittlement, w //
carbide precipitation on prior austenite grain b o u n d a -
ries during tempering is seen to be the microstructural
change directly responsible for the occurrence of the uJ J#~ xx /
referred embrittlement p h e n o m e n o n .

1. Introduction
i
f SO i
200 i
350 5 O0
Tempered martensite embrittlement (TME) TEMPERING TEMPERATURE ("C)
has long been observed in high strength low alloy
Fig. I. Variation with heat treatment conditions o f KLc and
steels (see for example refs. 1-7). Consistent with K.~ of AISI 4140 steel fracture tested at room temperature
an earlier finding by Wood [1], the phenomenon [9] (K,, is reported for a notch root radius of 0.25 ram). The
has recently been observed [8, 9] for quenched- data corresponding to the 500C tempering were not
reported in ref. 9 and are shown here to demonstrate the
and-tempered AISI 4140 steel austenitized at rapid increase in toughness as the steel softens. (Tempering
low and high temperatures. As can be noticed treatments were carried out for 1 h.)

0921-5093/91/$3.50 Elsevier Sequoia/Printed in The Netherlands

L6
Fig. 2. Scanning electron micrographs of fracture surfaces
for room-temperature-fracture-tested quenched and 350 C
tempered AISI 4140 steel austenitized at (a) 870C and
(b) 1200C.
boundaries during tempering [2, 6, 7, 10-13].
Subsequent deformation-induced transformation
on loading of the remaining intergranular austen-
ite [2] adds more embrittling carbides (cementite)
to the grain boundaries.
The present study concentrated on using
Auger electron spectroscopy (AES) to determine
local carbon and phosphorus concentrations on
the fracture surfaces of in situ broken AISI 4140
steel specimens. The AES measurements, which
were made for both as-quenched and quenched-
and-tempered material, were then used to gain an
insight into the microstructural changes that can
lead to TME.
2. Experimental procedure
The material used in this investigation was
commercially pure AISI 4140 steel, having the
following composition (in weight per cent):
C 0.38; Mn 0.78; P 0.014; S 0.024; Si 0.29; Cr
0.90; Mo 0.17; Ni 0.25.
Pre-notched cylindrical specimens (25 mm
long and 2.7 mm in diameter) were machined
from the as-received steel plate and were then
subjected to different heat treatments to obtain
four distinct microstructures, representing, for
low (870C) and high (1200C) temperature
austenitizing, the as-quenched martensite and the
tempered martensitic structure produced on tem-
pering at 350 C. These microstructures, termed
8 7 0 - ' Q , 1 2 0 0 - ' Q , 8 7 0 - ' 3 5 0 and 1200---350
(where Q indicates the steel in the as-quenched
condition), reproduce those of the specimens
used to obtain the corresponding toughness data
reported in Fig. 1.
The heat-treated specimens were introduced
into the Auger spectrometer where they were
fractured at approximately liquid nitrogen tem-
perature. Intergranular and transgranular regions
on the resulting fracture surfaces were first iden-
tified and AES measurements were then made
for several spots within these regions using a
beam size of 1/~m and maintaining a high
vacuum ( 4 1 0 -1 Torr) throughout the whole
process. A primary beam energy of about 2 keV
was chosen and the current density was main-
tained at approximately 20 /~A cm -2. Approxi-
mate atomic percentages of phosphorus, carbon
and iron were determined from measurements of
the amplitude of the corresponding Auger peaks
in the differential d[N(E) E]/dE vs. kinetic
energy E spectrum using listed [14] sensitivity
factors. No attempt was made to determine the
sulfur concentration as it is believed [5] that the
presence of manganese in the steel could very
effectively precipitate free sulfur as MnS.
3. Results
Typical AES spectra are shown in Fig. 3 and
the analysis of the AES data are presented in
Table 1, where it is observed that, for a given
microstructural condition, the carbon concen-
tration on intergranular fracture facets is invari-
ably higher than that detected for transgranular
fracture regions. However, Table 1 indicates
no detectable presence of phosphorus on the
 L7

intergranular cracking was found to be the pre-

dominant failure mode (Fig. 2).
INTERGRANULAR A /~
High local carbon levels in as-quenched and
P C ' V r quenched-and-tempered steels were found [15[to
Fe be associated with retained austenite films
5 present in the steel after quenching. In addition to
an observed enrichment in the carbon level in the
~~,,~.qTRANSGRANULAR austenite films by a factor of about 2 with respect
._zz_.
"o 3 to the normal level in the steel, a particularly high
concentration of carbon (peak values in the range
Fe
of 10-24 at.%) at the martensite-austenite inter-
face was also detected. This very large concentra-
tion of carbon at the transformation interface is
considered to provide a simple and direct expla-
o ,~o ~o ~o ~o ~o ~o ~o ~' ,o'oo
KINETICENERGY,eV nation for the retardation of any subsequent reac-
tion [15]. Accordingly, Sarikaya et al. [16]
Fig. 3. Typical A u g e r spectra from intergranular and trans-
granular regions on the fracture surface of A E S specimens. conclude that TME accompanied by quasi-
T h e s e particular spectra were obtained for a sample analyzed cleavage fracture in alloy steels containing
in the 1200 ~ 350 microstructural condition. retained austenite after quenching is concurrent
with the decomposition on tempering of retained
TABLE 1 austenite into carbides (M3C) at the lath bound-
Analysis of A E S data
aries. However, Bhadeshia and Edmonds [3J
attribute TME detected in an Fe-V-C steel to the
Condition Fracture A m o u n t on fracture surface coarsening of interlath cementite resulting from
region (at.%) thermal decomposition of interlath retained
austenite. Transmission electron microscopy
Fe C P
observations [17] made it clear that the carbides
870 ~ Q Transgranular 83 14 3 nucleate at the austenite-martensite interface and
870~Q Intergranular 72 25 3 can grow into the austenite and/or martensite.
870 ~ 350 Transgranular 80 13 7
870 ~ 350 Intergranular 73 19 8 The driving force for this process is the high
1200 ~ Q Transgranular 86 14 -- carbon concentration at regions immediately
1200 ~ Q Intergranular 75 25 -- adjacent to the interface. An increased stability of
1200 + 350 Transgranular 82 13 5
1200 ~ 350 Intergranular 63 32 5 retained austenite during tempering favors car-
bide growth mainly into the martensite or along
the austenite-martensite interface. Thus coarsen-
ing of the carbide precipitates is not necessarily
fracture surface of 1 2 0 0 ~ Q AES specimens. related to decomposition of the retained austenite
Furthermore, the AES data indicate that phos- [17].
phorus segregation to both intracrystalline and If one considers the ambient-temperature frac-
intergranular fracture regions is favored by low ture behavior of the AISI 4140 steel tested in the
temperature austenitization as well as by the 1200-' Q condition some interesting conclusions
350 C tempering treatment. can be made. In particular, the observation [9]
that specimens in this microstructural condition
fail by a mixture of quasi-cleavage and inter-
4. D i s c u s s i o n
granular cracking should indicate that some sort
The results shown in Table 1 indicate a high of embrittlement had actually taken place, prob-
carbon concentration on the intergranular ably due to deformation-induced carbide precipi-
regions of the fracture surface of the quenched- tation in highly carbon enriched regions along the
and-tempered AES specimens. This in turn indi- retained austenite-martensite interfaces. The
cates the presence of high carbon constituents high carbon concentration detected on the frac-
along the fracture path, i.e. along prior austenite ture surface combined with the virtual absence of
grain boundaries in room-temperature-fracture- phosphorus segregation (Table 1) seems to indi-
tested quenched-and-tempered specimens, as cate that the precipitation of carbides is the
L8

primary cause of the predominance of brittle formed on those boundaries are expected to
fracture modes since carbide coarsening is not increase with increasing austenitizing tempera-
likely to occur during loading of the as-quenched ture. This is reflected by the AES data (Table 1)
steel. where the carbon concentration on the intergran-
Based on the discussion presented above, it ular cleavage facets is seen to be higher for the
may be concluded that TME in the steel consid- 1200 ~ 350 specimens than for those analyzed in
ered in this investigation is primarily related to the 870--'350 microstructural condition. These
carbide precipitation during tempering along conclusions seem to be in agreement with the
prior austenite "grain boundaries already weak- toughness data shown in Fig. 1 (see also Table 2)
ened by phosphorus segregation (Table 1). where it can be noticed that the toughness
However, depending on the inherent toughness of degradation accompanying the 350 C tempering
the matrix, carbide precipitation alone can trigger is more pronounced for the 1200 C austenitizing
brittle failure modes as demonstrated by the frac- treatment. In fact, the 1200 C austenitization is
ture behavior of 1200--'Q specimens tested at so inducive to embrittlement in AISI 4140 steel
room temperature. that it can provoke intergranular cracking in the
The high carbon concentration associated with as-quenched material despite the absence of
retained austenite films present at prior austenite detectable phosphorus segregation to prior
grain boundaries favors carbide precipitation and austenite grain boundaries. For conventional
growth along those boundaries during tempering austenitization, on the other hand, a ductile
and this is reflected by the AES data (Table 1) failure mechanism was found to prevail in as-
indicating considerable carbon segregation on the quenched specimens [9]. Deformation-induced
intergranular cleavage facets of the specimens' carbide precipitation on loading was apparently
fracture surfaces. Carbide growth is expected to not sufficient to provoke brittle failure modes in
take place during the 1 h at 350C tempering room-temperature-fracture-tested 870--' Q speci-
treatment, and this together with phosphorus mens despite phosphorus segregation concurrent
segregation to prior austenite grain boundaries with low temperature austenitizing (Table 1).
leads to the predominance of intergranular crack- High temperature austenitization, on the other
ing as the failure mechanism in the quenched- hand, is thermodynamically and kinetically un-
and-tempered specimens. Considerable carbide favorable to phosphorus segregation [20]. This is
growth along prior austenite grain boundaries has borne out by t h e AES data which indicate that
recently been reported [18] for an AISI 4340 practically no phosphorus is present on the frac-
sample tempered at 350 C for 1 h after quench- ture surfaces of the 1200--'Q specimens. The
ing from 1200C. An elevated austenitizing AES results also indicate a considerable enrich-
temperature is expected to result in an increased ment in phosphorus at prior austenite grain
stability of the austenite in virtue of the excessive boundaries, for both austenitizing temperatures,
grain growth and extensive carbide dissolution in as a result of the 350 C tempering, in agreement
the austenitic matrix during high temperature with a finding by Paju and Moiler [21 ]. In addition
austenitization. Increased stability of the austenite to phosphorus diffusion enhanced by lattice
can result in increases in the amount [19] of defects, phosphorus rejection by the growing
etained austenite present at prior austenite grain carbides during tempering [22] can contribute to
boundaries as well as in the carbon content. the segregation of this element to prior austenite
Accordingly, the density and size of carbides grain boundaries.

TABLE 2
r o m p a r i s o n of t o u g h n e s s values for a s - q u e n c h e d and q u e n c h e d - a n d - t e m p e r e d AISI 4 1 4 0 steel [9]

Condition Ktc Reduction in Kjc KA Reduction in K A

(MPa m I/2) due to T M E (%) (MPa m I/z) due to T M E (%)

870-Q 57+1 -- 1/3+4 --

870~350 52+ 1 8.8 102+3 9.7
1200-Q 71 + 4 -- 85+2 --
1200~350 56+2 21.1 68-3 20

5. Conclusions
(1) TME detected by room-temperature
fracture testing in commercial-purity AISI 4140
steel is concurrent with carbide precipitation
during tempering along prior austenite grain
boundaries. Although carbide growth as well as
impurity element segregation, notably of phos-
phorus, are expected to contribute to TME,
carbide precipitation is seen to be the microstruc-
rural change directly responsible for the occur-
rence of this embrittlement phenomenon.
(2) Compared with the conventional 870C
austenitizing treatment, high temperature austen-
itization was found to be associated with a more
pronounced TME, apparently owing to more
intensive carbide precipitation and growth during
tempering.
(3) Considerable phosphorus segregation to
prior austenite grain boundaries was shown to
result from tempering for 1 h at 350 C, and this
is expected to contribute to the observed TME.
(4) Phosphorus segregation is not a prerequi-
site for the occurrence of TME in AISI 4141
steel austenitized at 1200 C. As demonstrated by
the fracture behavior of as-quenched specimens,
high temperature austenitization was found to
favor brittle failure modes despite the virtual
absence of phosphorus segregation.
Acknowledgments
The authors gratefully acknowledge the finan-
cial support by FINEP and CNPq.
References
1 W. E. Wood, Eng. Fract. Mech., 7 (1975) 219.
L9
2 R. M. Horn and R. O. Ritchie, Metall. Trans. A, 911978)
1 (/39.
3 H. K. D. H. Bhadeshia and D. V. Edmonds, Met. Ak'i., 13
11979) 325.
4 C.L. Briant and S. K. Banerji, Memll. Trans. A. 10 (1979)
123.
5 C.L. Briant and S. K. Banerji, Metall. 7?arts. ,,t, 1011979)
1151.
6 J. R Materkowski and G. Krauss, Memll. 7?ans. A, 10
11979) 1643.
7 C. k. Briant and S. K. Banerji, Metall. Trans. A. 1011979)
1729.
8 M. L. Graqa, F. A. Darwish and L. C. Pereira, in S. R.
Valluri, D. M. R. Taplin, E Rama Rao, J. F. Knott and R.
Dubey (eds.), Advances in Fracture Research 1984-1Cf6,
Vol. 2, Pergamon, Oxford, 1984, p. 1533.
9 F. A. Darwish, L. C. Pereira and M. L. Graqa, in K.
Salama, K. Ravi-Chandar, D. M. R. Taplin and R Rama
Rao (eds.), Advances in Fracture Research 1989-I('F7,
Vol. 4, Pergamon, Oxford, 1989, p. 2475.
10 S. K. Banerji, C. J. McMahon, Jr., and H. C. Feng, Metall.
Trans. A. 9 (1978) 237.
11 N. Bandyopadhyay and C. J. McMahon, Jr., Metall.
I?ans. A, 1411983)1313.
12 H. Kwon and C. H. Kim, J. Mater. Sci., 18 (1983) 3671.
13 X. Zuyao and C. Siwei, Mater. Sci. Tech., 1 (1985) 1025.
14 L. E. Davis, N. C. MacDonald, P. W. Palmberg, G. E.
Riach and E. R. Weber, Handbook of Auger Electron
Spectroscopy, Physical Electronics Industries, Eden
Prairie, MN, 1976.
15 S. J. Barnard, G. D. W. Smith, M. Sarikaya and G.
Thomas, Scr. Metall., 15 ( 1981 ) 387.
16 M. Sarikaya, A. K. Jhingan and G. Thomas, Metall.
Trans. A, 1411983)1121.
17 J. A. Peters, J. V. Bee, B. Kolk and G. G. Garrett, Acta
Metall.. 37 (1989) 675.
18 C. L. Briant, Mater. Sci. Tech., 5 (1989) 138.
19 C. N. Sastry and W. E. Wood, Mater. Sci. Eng., 45 (198tl)
277.
2 0 G. Clark, R. O. Ritchie and J. F. Knott, Aimere Phys. Sci..
239(1972) 104.
21 M. Paju and R. Moiler, Scr. Metall., 18 (1984) 813.
22 P. Bowen, C. A. Hippsley and J. F. Knott, Acta Metall., 32
11984) 637.