The effect of deep cold induced nano-carbides on the wear of case

hardened components
Paul Stratton
a,
*
, Michael Graf
b
a
The Linde Group, Rother Valley Way, Holbrook, Shefeld S20 3RP, UK
b
The Linde Group, Carl-von-Linde-Str. 25, 85716 Unterschleissheim, Germany
a r t i c l e i n f o
Article history:
Received 21 November 2008
Received in revised form 13 March 2009
Accepted 13 March 2009
Keywords:
A. Metals
B. Nitrogen
F. Tribology
a b s t r a c t
Most studies of the wear improvements produced by the nano-carbides formed during deep cold treat-
ment have been carried out on tool steels. In this study a carburising steel 20MnCr5 was carburised
using typical industrial cycles, subjected to a range of cold treatments and its wear performance tested. It
was found that under the conditions examined, converting any retained austenite to martensite
increased wear. However, the nano-carbides formed by extended deep cold treatment at 196 C did sig-
nicantly improve wear. Deeper cold treatment at 269 C did not produce any further improvement,
even treatment for a much longer time.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Cold treatment for transforming retained austenite in the case
of carburising steels has been a common industrial practice for
decades [1]. Cooling the steel below the Mf temperature effectively
converts any retained austenite to martensite, increasing hardness.
Such treatments are generally considered a remedial measure after
imprecise control of the carburising process has resulted in too
much carbon in the case. However, some manufactures do over-
carburise and cold treat deliberately as they consider this to
improve wear. This type of treatment at 70 C was therefore
included in this study.
The benets of extended deep cold treatment on tool steels
have been widely reported [2]. Although some work on the effects
of deep cold on carburising steels has also been done, it did not
examine the effect on wear [3]. A typical deep cold treatment cycle
was therefore applied to case carburised samples to see if the same
effect occurred as in tool steels. It has been shown that the longer a
steel is held at the deep cold treatment temperature typically
196 C in liquid nitrogen the better the result, so a longer and
colder treatment was included in this study. Therefore, the samples
were cooled to 269 C for 168 h in liquid helium.
To ensure that the results were comparable to a previous study
of the wear of thermochemically treated steels [4], the same test
apparatus was used and the same test conditions applied.
Studies of the effects of deep cold treatment on carburised and
bearing steels have shown that it improves dry wear properties
signicantly [57]. This study set out to determine the extent of
this improvement and the effect of colder and longer treatment
cycles.
2. Experimental
The samples (Fig. 1) were manufactured from a typical carburis-
ing steel, 20MnCr5 with the analysis shown in Table 1. The heat
treatment cycles were carried out at the Linde Gas laboratory in
Unterschleibheim, Germany in an Ipsen TR25 sealed quench
furnace.
There were three carburising treatments followed by one of
four post-carburising treatments (Table 2). Care was taken to
ensure that the cold treatment followed the quench within 1 h to
prevent austenite stabilisation.
3. Wear testing
Wear testing was carried out at Swerea IVF AB in Sweden, on
the pin-disk machine shown in Fig. 2. The heat-treated test piece
is attached to the vertical bar as shown, and remains stationary
while the disk rotates. The resultant pressure is high initially,
equivalent to approximately 4 N/mm
2
after 50 m sliding.
The end of the large bar has a small angle against its length.
When the test pin is xed in a hole at the end of this bar the wear
mark will not be in the centre, but at a circle between centre and
the outer diameter as illustrated in Fig. 3. Between each test, the
test pin is turned a little and xed again. This makes it possible
to do 612 tests with each test pin. The wear mark diameter can
be read with a microscope with a resolution of 0.01 mm
0011-2275/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cryogenics.2009.03.007
* Corresponding author. Tel.: +44 1484328736.
E-mail address: paul.stratton@boc.com (P. Stratton).
Cryogenics 49 (2009) 346349
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The large horizontal grey beam in Fig. 2 can be xed in different
positions so that a new track on the horizontal wheel at a different
radius can be used for each test. In these tests only one disk was
used so that all the results were comparable. The disk was made
from a cold working tool steel hardened and tempered to 58RC.
Its rotation speed was kept at the same sliding speed of 0.4 m/s
for all the tests. After a xed wear distance the large vertical bar
with the pin xed at its end was put under a microscope to mea-
sure the diameter of the wear mark. The sample carrier was then
replaced in the exactly same position and the test continued.
Although the diameter of the wear mark (Fig. 4) can be used as
the measure of wear, this investigation found that the calculated
wear volume was more discriminating. Each sample was subjected
to three tests and the results averaged.
4. Metallurgical examination
Separate samples of the same dimensions as the wear test
pieces were treated in each batch. Sections were prepared and
examined for hardness proles and microstructure. Near surface
retained austenite was determined by X-ray diffraction.
5. Results
5.1. Metallurgical
The hardness gradients for the case after carburising treatment
1 and various cold treatments are shown in Fig. 5. It can be seen
that all the cold treatments increased the hardness near the surface
Table 1
Sample analysis.
%C %Si %Mn %P %S %Cr
0.195 0.40 1.25 0.35 0.35 1.10
Table 2
The heat and cold treatments.
Treatment Conditions
Carburising treatments
1 Carburised to 0.8% carbon and a total case depth of 0.75 mm and direct
oil quenched from 850 C
2 Carburised to 1.0% carbon and a total case depth of 0.75 mm and direct
oil quenched from 850 C
3 Carburised to 1.0% carbon and a total case depth of 0.75 mm, cooled
out, reheated, and oil quenched from 850 C
Cold treatments
a Tempered at 150 C for 1 h
b Cooled to 70 C for 1 h then tempered at 150 C for 1 h
c Cooled to 196 C for 24 h then tempered at 150 C for 1 h
d Cooled to 269 C for 168 h then tempered at 150 C for 1 h
Fig. 2. The pin-disk machine used for the wear testing.
Fig. 3. Wear marks at the end surface of the test pin.
Fig. 4. The test pin with one large and one small wear mark.
Fig. 1. The wear test samples.
Fig. 5. The case proles for carburising treatment 1 after various cold treatments.
P. Stratton, M. Graf / Cryogenics 49 (2009) 346349 347
by a small amount because of conversion of retained austenite to
martensite. The total case depth was 0.65 mm and the effective
case depth (to 550 HV) was 0.45 mm. The hardness gradients for
carburising treatment 2 and 3 samples were very similar with
the same total and effective case depths.
The retained austenite in the case of the samples after carburis-
ing and cold treatment is shown in Table 3.
The microstructures of the carburising treatment 2 as-quenched
and tempered and after the various cold treatments are shown in
Fig. 6. The reduction in retained austenite produced by the cold
treatments can clearly be seen.
As may have been expected the microstructure of the near-sur-
face case of carburising treatment 2 exhibits some ne globular
carbides (Fig. 7) produced by the cool-out, reheat, and quench
treatment. The retained austenite was correspondingly lower than
was found in the direct quenched treatment (carburising treat-
ment 2).
5.2. Wear
The results of the wear tests are shown in Figs. 810. For the
two treatments where there was little retained austenite present
(Figs. 8 and 10) the changes in wear rate due to the cryogenic treat-
ments were small, but signicant, with rates comparable to those
found in a previous study of carburised steel using the same wear
measurement technique [6]. As might have been expected the
Table 3
Retained austenite percentage for all the treatments at 50 lm.
Carburising
treatment 1
Carburising
treatment 2
Carburising
treatment 3
Tempered 9.1 31.0 6.4
70 C, tempered 3.3 13.5 4.1
196 C, tempered 3.0 9.6 4.0
269 C, tempered 2.6 8.3 2.9
Fig. 6. The microstructure of treatment 2 after quench and temper (a) and after various cold treatments (b, c, and d {see Table 2}).
Fig. 7. The microstructure of carburising treatment 2 after reheat, quench and
temper.
Fig. 8. The wear of 20MnCr5 carburised to 0.8% carbon and direct quenched and
subjected to various cold treatments.
348 P. Stratton, M. Graf / Cryogenics 49 (2009) 346349
differences between the wear rates of the different cryogenic treat-
ments were much larger when the initial retained austenite level
was high (Fig. 9).
6. Discussion
It is quite clear from the wear test results that regardless of the
carburising treatment, cooling below 196 C, to 269 C, is of no
benet. This is probably because at 269 C the dislocations do not
coalesce to form nucleation sites for the nano-sized g-carbides,
that are the basis of the wear improvements in the 196 C treat-
ment [3,7,8], at these very low temperatures; diffusion is so slow
that even a 168 h treatment is insufcient. Even at 196 C the
process takes a minimum of 24 h.
Both when the surface carbon is close to optimum (0.8%C
(Fig. 5)) and when the high surface carbon is mitigated by forming
carbides that leave the matrix with the optimum carbon (1.0% car-
bon, cooled out, then reheated, and quenched (Fig. 7)), the wear
rate is minimised by the deep cold treatment at 196 C for 24 h.
It is highly likely that the mechanism for the improvement in wear
is the precipitation of g-carbides, as has been shown to be the case
for tool steels [7,8]. Compared to the untreated sample, the overall
wear rate was reduced by approximately 20% by deep cold treat-
ment at 196 C for 24 h. In the 1.0% carbon sample that was direct
quenched, the effect of transforming the retained austenite to mar-
tensite swamped any effect due to deep cold treatment.
It might be expected that transforming the retained austenite in
the high carbon, direct quenched samples (Fig. 8) would reduce the
wear rate, but in fact the reverse was found, with the as-quenched
and tempered sample giving the lowest wear rate of all. It is prob-
able that stress during wear dynamically transforms the retained
austenite, minimising the wear rate. For most components it will
still be necessary to remove the retained austenite because of the
problems associated with grinding crack formation [9].
7. Further work
Although not considered in this study, it is recognised that the
improvement of resistance to sliding wear, due to cold or cryogenic
treatments, is more or less signicant as a function of the sliding
speed [10]. Further work is required to elucidate this effect for
the materials and treatments studied.
8. Conclusions
The dry wear rate of optimally carburised 20MnCr5 was reduced
by approximately 20% by deep cold treatment at 196 C for
24 h.
Deep cold treatment at very lowtemperatures (269 C in liquid
helium) has no benet for carburised steel.
When high levels of retained austenite are present in the case of
carburised 20MnCr5, cold treatment converts most retained
austenite to martensite, consequently the dry wear rate
increases.
References
[1] Moore C. The development of the BOC Ellenite process (cold treatment of
metals with liquid nitrogen. In: Heat treatment 73. The Metals Society; 1975.
p. 15761 [book no. 163].
[2] Cold and cryogenic treating of steel. Heat Treat Prog; One-min Mentor
2007;2(48).
[3] Stratton PF. Optimising nano-carbide precipitation in tool steels. Mater Sci Eng
A 2007;449451:80912.
[4] Surberg CH, Stratton P, Lingenhle K. The effect of deep cold treatment on two
case hardening steels. Acta Metall Sin 2008;21(1):17.
[5] Stojko A. Sub-zero treatment of tool steels. M.Sc. Thesis, DTU, Lyngby; 2001.
[6] Stratton PF, Segerberg S. A comparative study of the dry adhesive wear of
various thermochemical surface treatments. In: Proceedings of international
heat treat 2004. India: ASM; 2004. paper I-3.
[7] Gerson A, Cavallaro G, Xu N. Microstructure of cryogenically treated high
performance tool steels. Mater Aust 2007;40(5):489.
[8] Rhyim Y-M, Han S-H, Na Y-S, Lee J-H. Effect of deep cold cryogenic treatment
on carbide precipitation and mechanical properties of tool steels. Solid State
Phenom 2006;118:914.
[9] Totten GE. Steel heat treatment: metallurgy and technologies. CRC Press; 2006.
p. 387.
[10] Bensely A, Prabhakaran A, Mohan Lal D, Nagarajan G. Enhancing the wear
resistance of case carburized steel (En 353) by cryogenic treatment. Cryogenics
2005;45(12):74754.
Fig. 10. The wear of 20MnCr5 carburised to 1.0% carbon, reheated, and quenched,
then subjected to various cold treatments.
Fig. 9. The wear of 20MnCr5 carburised to 1.0% carbon and direct quenched and
subjected to various cold treatments.
P. Stratton, M. Graf / Cryogenics 49 (2009) 346349 349