Wear 267 (2009) 1361–1370

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Wear
journal homepage: www.elsevier.com/locate/wear

Influence of temperature of sub-zero treatments on the wear

behaviour of die steel
D. Das a , K.K. Ray b , A.K. Dutta c,∗
a
Department of Metallurgy and Materials Engineering, Bengal Engineering and Science University, Shibpur, Howrah 711103, India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur 721302, India
c
Department of Mechanical Engineering, Bengal Engineering and Science University, Shibpur, Howrah 711103, India

a r t i c l e i n f o a b s t r a c t

Article history: This study examines the influence of temperature of sub-zero treatment on the wear behaviour of AISI
Received 1 September 2008 D2 steel. A series of dry sliding wear studies have been made under constant normal load at varying
Received in revised form sliding velocities. Emphasis has been laid to understand the operative modes and mechanisms of wear
25 November 2008
by the estimation of specific wear rates and detailed characterizations of the worn surfaces, wear debris
Accepted 25 November 2008
and subsurfaces with the help of scanning electron microscope (SEM) examinations coupled with energy
dispersive X-ray (EDX) microanalyses. The obtained results unambiguously infer that lower the temper-
Keywords:
ature of sub-zero treatment higher is the improvement in wear resistance. Wear resistance can increase
Sub-zero treatment
Cryogenic treatment
by 1.5–125 times depending on sliding velocity while hardness increases only by 4.2% at the lowest tem-
Die steel perature of sub-zero treatment (77 K) compared to the conventionally treated specimens. These results
Wear behaviour corroborate well with the reduction in retained austenite content associated with simultaneous increase
Mode of wear in the amount of secondary carbide particles with lowering of sub-zero treatment temperature. The oper-
Mechanism of wear ative modes and mechanisms of wear are identified as either mild oxidative or severe delaminative, which
depends on the temperature of sub-zero treatment and the sliding velocity of the wear test.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction The process of sub-zero treatment consists of controlled cool-

It is well established that sub-zero treatment improves several
mechanical properties of tool steels like wear resistance [1–10],
hardness [5–12], fatigue resistance [12], toughness [13], etc., apart
from improving dimensional stability of engineering components
[14]. The merit of sub-zero treatment is popularly attributed to the
transformation of retained austenite (␥R ) to martensite. As a con-
sequence, sub-zero treatment is being commercially used for the
improvement of wear resistance of tool/die steels. In a series of
recent investigations [7–10], the present authors have examined
the nature of phase transformation at deep cryogenic tempera-
ture and have studied their role on the wear behaviour of AISI
D2 steel. The outcomes of these investigations have indicated that
apart from the transformation of ␥R to martensite, nucleation and
growth of secondary carbides play an important role. In addition,
these studies have also shown that the degree of improvement in
wear resistance of tool steels is dependent on the selection of wear
test parameters.
∗ Corresponding author. Tel.: +91 33 2668 4561/62/63;
fax: +91 33 2668 4564/2916.
E-mail address: apurba@mech.becs.ac.in (A.K. Dutta).
ing of conventionally hardened specimens to a selected sub-zero
temperature followed by controlled heating of the specimens back
to the ambient temperature for subsequent tempering treatment.
The sub-zero treatment can be classified into three different tem-
perature regimes: cold treatment (CT, ≥193 K), shallow cryogenic
treatment (SCT, 193–113 K) and deep cryogenic treatment (DCT,
113–77 K). The influence of these temperature regimes on the wear
characteristics of sub-zero treated steels has not been systemati-
cally examined so far. The major aim of this report is to bring forth
the influence of temperature of sub-zero treatment on the wear
behaviour of steels under different wear test conditions.
Until recently, the accepted temperature for sub-zero treatment
has been 193 K where dry ice can be used for cooling. However,
the results of few recent studies [1–4] suggest that the tempera-
ture of sub-zero treatment should be <193 K in order to obtain the
maximum improvement in mechanical properties of tool steels; the
lowest temperature may be 77 K, the boiling temperature of liq-
uid nitrogen at normal atmospheric pressure. Mohan Lal et al. [2]
have shown that lower is the temperature higher is the improve-
ment in wear resistance for D3 and M2 steels. In contrast, Moore
and Collins [15] have suggested that there is an optimal tempera-
ture for sub-zero treatment of tool steel. Schiradelly and Diekman
[16] have applied Taguchi Design of Experiment (DOE) to identify
and to optimize the critical parameters of cryogenic treatment for a

0043-1648/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2008.11.029
1362
Table 1
Nominal composition of the investigated AISI D2 steel.
Element C Mn Si S P Cr Mo
Weight (%) 1.49 0.29 0.42 0.028 0.029 11.38 0.80
martensitic stainless steel. Using the analysis of variance (ANOVA)
associated with the results of wear tests, these authors have shown
that the most significant parameter is the soaking temperature (72%
in contribution).
The reported improvements in wear resistance of die/tool steels
due to cryogenic treatment varies widely, for example from a few
percent to a few hundred percent for the same material [9]. Such
inconsistent reports are hindering the exploitation of the inherent
potential of cryogenic treatment for its commercial exploitations.
The lack of systematic studies of wear behaviour of cryogenically
treated tool steels with proper identification of the operative modes
and mechanisms of wear is mainly responsible for the reported
wide scatter in the degree of improvement of wear resistance of
tool steels by cryogenic treatment [8–10]. Therefore, it is necessary
to compare the wear resistance of tool/die steels subjected to dif-
ferent sub-zero temperature treatments with proper identification
of the operative modes and mechanisms of wear which is the focus
of this study.
2. Experimental procedure
2.1. Material and treatments
A commercial forged AISI D2 steel bar has been chosen for this
investigation. The nominal chemical composition of the steel is
presented in Table 1. Specimens of this steel have been subjected
to conventional treatment (CONT), cold treatment (CT), shallow
cryogenic treatment (SCT) and deep cryogenic treatment (DCT) in
separate batches. The CONT consists of hardening and tempering;
while in CT, SCT and DCT, an additional step of controlled sub-zero
treatment with lowest quenching temperature (TLQ ) as 198, 148 and
77 K, respectively, has been incorporated in-between hardening
and tempering treatments. In sub-zero treatment, conventionally
hardened specimens have been cooled from ambient tempera-
ture to the selected TLQ , held there for ∼5 min for homogenization
of temperature before heating back to the ambient temperature
for subsequent tempering treatment. Uniform cooling and heat-
ing rates of ∼0.75 K min−1 were maintained in each of the sub-zero
treatments. The hardening and single tempering treatments follow-
ing ASM standard [17] have been carried out at 1297 K for 30 min
and at 483 K for 120 min, respectively. In order to distinguish the
specimens subjected to different TLQ , these have been ascribed with
codes as shown in Table 2. These designations are followed in the
subsequent discussions. One can note here that TLQ for CONT is
303 K, i.e., with out any sub-zero treatment.
2.2. Microstructural characterizations
Microstructural examinations have been carried out on polished
and picral-etched specimens using both optical and scanning elec-
Table 2
Different heat treatments and the sample codes.
Sample code Description of heat treatment cycles
Hardening Lowest quenching
temperature, TLQ (K)
CONT 303
CT 198
1293 K, 30 min
SCT 148
DCT 77
D. Das et al. / Wear 267 (2009) 1361–1370
tron microscopes (SEMs). The carbide particles have been classified
as primary carbides (PCs) and secondary carbides (SCs) consider-
V Fe ing equivalent spherical diameter for PCs as >5 ␮m, while that for
0.68 Balance
SCs ≤ 5 ␮m. The volume percents of PCs and SCs have been esti-
mated by image analyses of digitally acquired suitable optical and
SEM micrographs using Leica QMetals software in Leica QWin V3
environment. Identification of the phases, and the measurement
of retained austenite (␥R ) following ASTM standard E975-00 have
been done by X-ray diffraction (XRD) analyses with Mo K␣ radiation
at 0.01◦ s−1 scan rate on bulk specimens with the help of PHILIPS
X’Pert software.
2.3. Hardness measurement
The bulk hardness of the differently treated specimens has been
measured by Vickers hardness tester using 60 kgf load. At least fif-
teen readings are considered for estimating the average value of
hardness, and the estimated standard errors associated with the
measured Vickers hardness numbers (VHN) were ±5.
2.4. Sliding wear tests
Dry sliding wear tests have been performed following ASTM
standard G99-05 by using a computerized pin-on-disc wear test-
ing machine. Cylindrical specimens of 4 mm diameter and 30 mm
length have been used as static pins, whereas, tungsten carbide
coated En 35 steel disc (surface hardness HV ≈ 1750) of diame-
ter 160 mm is selected as the rotating counter surface. The wear
tests have been carried out using a fixed normal load (FN ) of 98.1 N
(10 kgf) at different sliding velocities (SV ) of 1.00, 1.25 and 1.50 m s−1
and under ambient conditions of 298 K and 60% relative humid-
ity. The rpm of the disc was adjusted for a selected track diameter
(100–140 mm) for achieving a predetermined SV . The wear tests
were continued either for sliding distance of ∼2000 m or for the
duration that resulted into cumulative height loss of the pin speci-
men of ∼2 mm (equivalent to ∼25 mm3 of cumulative wear volume
loss), whichever occurred earlier. Average wear rates have been esti-
mated from the recorded cumulative height loss of the specimens
with respect to sliding distance in the steady-state wear regime
considering at least three test results under identical conditions.
2.5. Characterizations of the worn surfaces, wear debris and
subsurfaces
The worn surfaces at the end of the wear tests and gener-
ated debris collected in the steady-state wear regime have been
examined under SEM along with the energy dispersive X-ray (EDX)
microanalyses for all specimens at all wear test conditions. Some
selected worn samples were sectioned perpendicular to the worn
surface and parallel to the sliding direction using wire electro-
discharge machining. The sectioned faces of the specimens were
mounted, polished to 0.25 ␮m finish, etched using picral solution
and were examined using SEM in back-scatter mode to record the
subsurface features of the worn specimens.
3. Results and discussion
3.1. Microstructures and hardness
Fig. 1 depicts representative SEM micrographs of convention-
Tempering ally treated and a typical sub-zero treated specimens. These exhibit
large elongated dendritic type of primary carbides (PCs) and
nearly spherical secondary carbides (SCs) on tempered martensite
matrix. The occasional patches of retained austenite (␥R ) have been
483 K, 120 min
detected only in SEM micrographs of CONT [7] and CT specimens.
The volume fraction of ␥R has been estimated by XRD technique,
 D. Das et al. / Wear 267 (2009) 1361–1370
Fig. 1. Typical representative SEM micrographs of (a) CONT and (b) SCT specimens exhibiting primary carbides (PCs) and secondary carbides (SCs) of different sizes. The
smaller SCs are shown inside circles.
detailed procedure of which has been reported earlier [9]. The
amounts of ␥R in the different types of specimens are shown in
Fig. 2. The amount of ␥R in CT specimen is 4.6 ± 0.5 vol.% in compar-
ison to 9.8 ± 0.7 vol.% in CONT specimen. The amount of ␥R in both
SCT and DCT specimens is considered to be below the detection
limit (<2 vol.%) of XRD technique. This observation is in agreement
with the reported results for AISI D2 steel in DCT [6–10] and SCT
[14] conditions. The obtained results suggest that CT reduces the
␥R substantially as compared to CONT; while both SCT and DCT in
between conventional hardening and tempering treatments almost
completely remove it. Since the martensite finish (Mf ) temperature
for AISI D2 steel is ≈148 K, SCT and DCT with TLQ ≤ 148 K almost
completely transforms ␥R to martensite, and hence the observed
results are expected.
The amount of PCs is found to be invariant (≈7.0 vol.%) while
the amount of SCs varied in CONT, CT, SCT and DCT specimens. The
PCs in the investigated specimens have been identified mainly as
M7 C3 (M = Fe, Cr, Mo, V) with small amount of Cr7 C3 by XRD analy-
ses. The variations in the amounts of SCs with TLQ as determined by
image analyses are illustrated in Fig. 2. The SCs in all the specimens
have been identified as M23 C6 (M = Fe, Cr, Mo, V) type and this is
in agreement with earlier reports [7–10,13]. It is interesting to note
that the application of sub-zero treatments after conventional hard-
ening does not alter the nature of PCs and SCs. The amount of SCs
increases with decreasing temperature of sub-zero treatment. As
the temperature of sub-zero treatment is lowered, the amount of ␥R
Fig. 2. Variation of amount of retained austenite (␥R ) and secondary carbides (SCs)
as a function of lowest quenching temperature.
1363
decreases resulting in higher amount of martensite; the increased
amount of martensite naturally leads to higher amount of carbide
precipitation on subsequent tempering treatment as observed in
Fig. 2.
The variation of hardness with TLQ is shown in Fig. 3. The results
indicate that sub-zero treatment increases hardness of D2 steel
though by a smaller margin of up to 4.2%. The increase in hardness
is attributed to reduction in ␥R content with associated increase in
the amount of SCs (Fig. 2). It is observed from the results in Fig. 3 that
the rate of increase in hardness with TLQ diminishes with lowering
of TLQ . In addition, the nature of distribution of SCs (Fig. 1) can also
influence the increment in hardness with TLQ due to alteration in
the inter-particle spacing leading to the variation in micro-residual
stresses and sub-structural changes like dislocation density.
3.2. Wear rates
Typical plots of cumulative wear volume loss versus sliding dis-
tance for all the specimens tested at SV of 1.25 m s−1 under FN
of 98.1 N are shown in Fig. 4. The results in Fig. 4 exhibit distin-
guished regimes of ‘running-in’ and ‘steady-state’ wear [18–20] for
each specimen and the difference in the nature of variation in the
wear behaviour of these specimens. The results exhibit that the
volume losses for CONT and CT specimens are significantly higher
than those of the SCT and DCT specimens. Furthermore, volume
Fig. 3. Influence of lowest quenching temperature on the bulk hardness of differ-
ently treatment specimens.
1364 D. Das et al. / Wear 267 (2009) 1361–1370
Fig. 4. Typical plot of cumulative wear volume loss (CWVL) versus sliding distance
(SD ) for differently treated specimens tested at sliding velocity of 1.25 m s−1 . Inset
shows enlarged view of same for CONT and CT specimens. The arrow indicates the
transition of initial running-in wear to the final steady-state wear.
loss of CONT specimen is appreciably higher than that of CT spec-
imens, whereas the volume loss for SCT specimens is marginally
higher than that of DCT specimen. The results obtained for tests con-
ducted at SV of 1.00 and 1.50 m s−1 is similar in nature. The extent
of running-in wear depends on the experimental conditions like (i)
surface roughness of both the pin and the disc, (ii) perpendicularity
of the pin with respect to the disc and (iii) the rise in temperature
at the contact area, etc. [20]. The results in Fig. 4 indicate that (i) the
wear rates of all specimens are considerably higher in the running-
in regime than that in the steady-state regime and (ii) the wear
rates in the running-in regime decreases with lowering of TLQ .
Steady-state wear, which is known to depend on the material’s
characteristics [18–20], has been analyzed to reveal the effect of
TLQ on the wear behaviour of the selected steel. For this purpose,
the specific wear rate (WS ) has been calculated by the equation:
WS = VL /(FN × SD ); where VL is the wear volume loss of the pin
specimens in the steady-state regime in mm3 , FN is the applied
normal load in N and SD is the sliding distance corresponding to
the steady-state wear regime in mm. The magnitudes of WS esti-
mated at different SV for specimens with different TLQ are compiled
in Fig. 5. The results in Fig. 5 assist to infer that:
(i) at SV = 1.00 m s−1 , WS sharply decreases for TLQ = 303–198 K and
then its magnitude decreases marginally with further lowering
of TLQ ,
(ii) at SV = 1.25 m s−1 , WS marginally decreases between TLQ = 303
and 198 K and between TLQ = 148 and 77 K, whereas WS drasti-
cally decreases between TLQ = 198 and 148 K, and
(iii) at SV = 1.50 m s−1 , the magnitude of WS marginally decreases
for the entire range of investigated TLQ .
The nature of variation of WS for different specimens at the
selected SV or for the same specimen at different SV can be explained
only with the knowledge of the operative mechanisms of wear and
this is the content of the next section.
3.3. Mechanisms of wear
In order to identify the operative wear mechanisms, the topog-
raphy of the worn surfaces as well as the nature and morphology of
the generated wear debris have been characterized for all the tested
specimens. Some typical representative examples in Figs. 6–10
Fig. 5. Variation of estimated specific wear rate (WS ) with lowest quenching tem-
perature (TLQ ) of the specimens tested at different sliding velocities (SV ). Shading
has been used to demarcate WS into two different regimes based on the operative
modes and mechanisms of wear (see text for details).
illustrate the operative wear mechanisms of differently treated
specimens tested at varying SV . The micrographs in Figs. 6 and 7
bring to light the difference in the operative wear mechanisms for
CONT specimens compared to that for different sub-zero treated
specimens at SV = 1.00 m s−1 . The worn surface of CONT specimen
is rough but metallic in nature, and also exhibits fracture ridges and
deformation lips stretched parallel to the sliding direction (Fig. 6a).
The presence of deformation lip infers that the CONT specimen has
undergone heavy plastic deformation during wear test. In contrast,
the worn surfaces of the CT (Fig. 6b), SCT (Fig. 6c) and DCT (Fig. 6d)
specimens are smoother and exhibit presence of patches of oxide.
The micrograph of oxide depleted region of worn surfaces of these
specimens shows cracking and pull-out of PCs apart from the pres-
ence of surface grooves as illustrated in Fig. 6e. Surface grooves on
the worn surface are formed due to the trapping of loose hard PC
particles in-between the pin and disc surfaces. The micrograph of
the wear debris of CONT specimen (Fig. 7a) exhibits shiny metallic
appearance and a plate-like morphology. In contrast, the debris of
the CT (Fig. 7b), SCT (Fig. 7c) and DCT (Fig. 7d) specimens appear as
black coloured powder in naked eye; and these are much finer in
size and oxide in nature (Fig. 7e). These observations reveal that
the wear mechanism at SV = 1.00 m s−1 and FN = 98.1 N for CONT
specimen are plastic deformation induced delaminative wear [21],
whereas that for the sub-zero treated specimens is predominantly
oxidative [22] coupled with cracking and pull-out of PCs.
Representative features on the worn surfaces of CONT, CT, SCT
and DCT specimens tested at SV = 1.25 m s−1 are shown in Fig. 8;
the corresponding morphology of the wear debris and their typical
representative EDX profiles are presented in Fig. 9. The observed
features on the worn surfaces for both CONT and CT specimens
tested at SV = 1.25 m s−1 (Fig. 8a and b) closely resemble with that
observed for CONT specimen tested at SV = 1.00 m s−1 (Fig. 6a). Worn
surface features for SCT and DCT specimens tested at SV = 1.25 m s−1
(Fig. 8c and d) are similar to that of CT, SCT and DCT specimens
tested at SV = 1.00 m s−1 (Fig. 6b–d). However, the worn surfaces
of SCT and DCT specimens show regions of thick compacted oxide
layer at SV = 1.25 m s−1 (Fig. 8c and d) unlike that in the worn surface
of SCT and DCT specimens tested at SV = 1.00 m s−1 (Fig. 6c and d).
Furthermore, examinations of worn surfaces of SCT and DCT speci-
mens tested at SV = 1.25 m s−1 does not reveal any obvious signature
of cracking and/or pull-out of PCs even at higher magnifications.
 D. Das et al. / Wear 267 (2009) 1361–1370 1365

Fig. 6. Representative secondary electron SEM micrographs of worn surfaces at the end of wear tests of (a) CONT, (b) CT, (c) SCT and (d) DCT specimens tested at SV = 1.00 m s−1 .
(e) A typical high magnification backscatter electron SEM micrograph of oxide depleted region as marked by area-1 in the worn surfaces of CT, SCT and DCT specimens.

The wear debris of CONT and CT specimens show large metallic
platelets unlike fine oxide debris shown by SCT and DCT specimens
(Fig. 9). Typical representative EDX profile of the wear debris of
CONT and CT specimens is shown in Fig. 9e and that for SCT and
DCT specimens is presented in Fig. 9f. The recorded EDX profiles
exhibit oxygen peak of higher intensity for SCT and DCT specimens
compared to that from CONT and CT specimens (Fig. 9f vis-à-vis
Fig. 9e). This observation suggests that the generated wear debris
for CONT and CT specimens is predominantly metallic in nature and
that for SCT and DCT specimens is predominantly oxide in nature.
The EDX profiles of both types of wear debris indicate the presence
of tungsten that has been transferred from the counter body to the
specimen surface by adhesion. Evidences in Figs. 8 and 9 assist to
reveal that the operative mechanisms of wear for both CONT and
CT specimens is delaminative at SV = 1.25 m s−1 , whereas that for
SCT and DCT specimens is oxidative wear under same experimental
condition.
The surface topography of all specimens tested at SV = 1.50 m s−1
indicates delaminative wear. Representative evidences are shown
in Fig. 10 for SCT and DCT specimens. The wear debris generated
during wear tests of these specimens is metallic platelets (inserts
in Fig. 10) corroborating with the observed features of the worn
surfaces. In summary, the observed wear mechanism for CONT
specimens for all tested SV is delaminative wear; whereas the
operative wear mechanisms change from predominantly oxida-
tive to delaminative at SV = 1.25 m s−1 for CT specimens and at
SV = 1.50 m s−1 for SCT and DCT specimens.
3.4. Transition of modes and mechanisms of wear
The modes of wear may be categorized using wear mechanism
map as suggested by Lim and Ashby [23] or by magnitude of WS
as suggested by Wang et al. [24] or through magnitude of wear
coefficient as suggested by Rabinowicz [20]. Identification of the
operative wear mechanisms at different test conditions is known to
assist in revealing the operative mode of wear [23]. In the present
investigation, the operative mechanisms of wear have been iden-
tified by the detailed characterizations (for all specimens tested
1366 D. Das et al. / Wear 267 (2009) 1361–1370

Fig. 7. Representative secondary electron SEM micrographs of generated wear debris corresponds to the steady-state wear regime of (a) CONT, (b) CT, (c) SCT and (d) DCT
specimens tested at SV = 1.00 m s−1 . All these micrographs are taken at the same magnification of 250X, whereas (e) is a typical high magnification view of wear debris of CT,
SCT and DCT specimens.

at different SV ) of worn surfaces and generated debris. These are
shown in Fig. 5, which reveals that the data related to the WS clus-
ters into two different regimes depending on the mechanisms of
wear, and the magnitude of WS between these regimes varies about
an order of magnitude. Considering the magnitude of WS and the
wear mechanisms, these regimes are termed as ‘mild-oxidative’ and
‘severe-delaminative’, in which ‘mild’ and ‘severe’ refer the mode
of wear.
The results in Fig. 5 indicate that the transition SV for mild-to-
severe wear for CT is 1.00 m s−1 and that for SCT and DCT specimens
are 1.25 m s−1 . Within the tested range of SV (1.00–1.50 m s−1 ), the
WS for CONT specimens lies in the severe wear regime (Fig. 5) and
corresponding wear mechanism has been identified as delamina-
tive wear (Figs. 6–9). These results suggest that transition SV for
mild-to-severe wear for CONT specimens occurs at SV lower than
1.00 m s−1 . Additional experiments were carried out to find out the
transition SV for CONT specimens and this has been found to be
0.75 m s−1 corresponding to predominantly oxidative wear. The WS
of the CONT specimen at the transition SV is 8.10 × 10−8 mm3 N−1
mm−1 . The transition SV for mild-to-severe wear is a function of
microstructure and mechanical property of tested pin specimens,
when the other wear test parameters remain constant [23,24].
The observed variation in the transition SV for CONT, CT and SCT
specimens is expected, since these specimens exhibit significant
differences in their microstructures (Fig. 2) and hardness values
(Fig. 3). The obtained transition SV for both SCT and DCT specimens
are same (1.25 m s−1 ), because the microstructures of SCT and DCT
specimens are nearly similar, both being free from ␥R and having
almost identical amounts of SCs (Fig. 2). In addition, the difference
in hardness values of these specimens is <0.5%. Hence, it is natural
that both SCT and DCT specimens exhibit same transition SV .
It is also interesting to note that the WS of both SCT and DCT
specimens decreases about an order of magnitude with increase
of SV from 1.00 to 1.25 m s−1 even when the operative mode and
mechanism of wear (mild-oxidative) remain unchanged. Similar
observation has been reported earlier for dry sliding wear of steel
specimens; for example, Sullivan and Hodgson [25] have shown
that the wear rate of 52100 steel decreases by an order of magnitude
with increase in SV , when SV lies below transition SV for mild-
to-severe wear. This behaviour is related to the rate of formation
and retention of oxide at the contact surface of the pin specimen.
Increase in SV increases the flash temperature that, on one hand,
accelerates the formation of tribochemical reactions at the con-
tact junctions [22,23]. On the other hand, it increases the degree
of work-hardening of the material beneath the contact junctions
leading to the development of increased depth of work-hardened
layer with enhanced hardness [25]; this, in turn, assists in retain-
ing oxides at the contact junctions resulting into development of
thicker oxide layer [22,25]. Therefore, increased SV increases the
thickness of oxide layer at the contact surfaces which is evident
 D. Das et al. / Wear 267 (2009) 1361–1370 1367

Fig. 8. Representative secondary electron SEM micrographs of worn surfaces at the end of wear tests of (a) CONT, (b) CT, (c) SCT and (d) DCT specimens tested at SV = 1.25 m s−1 .

from the SEM micrographs of wear debris of both SCT and DCT spec-
imens (Fig. 7 vis-à-vis Fig. 9). Development of thicker oxide layer is
thus responsible for the reduction in the WS values with increasing
SV from 1.00 to 1.25 m s−1 for both SCT and DCT specimens [22,25].
The results in Fig. 5 assist to infer that the maximum value
of WS for mild-oxidative wear and the minimum value of WS
for severe-delaminative wear are 9 × 10−8 and 4 × 10−7 mm3 N−1
mm−1 , respectively. Wang et al. [24] have earlier suggested for
steel specimens that the upper limit of WS for mild-oxidative wear
is 1 × 10−8 mm3 N−1 mm−1 and the lower limit of WS for severe-
delaminative wear is 2 × 10−8 mm3 N−1 mm−1 . These authors have
also indicated that one can use the term ‘transition wear’, if the
WS is in the region of 1 × 10−8 to 2 × 10−8 mm3 N−1 mm−1 . The
present results, however, indicate that the demarcating lines for
transition wear could be wider than that suggested by Wang et al.
[24]. Kato [26] has earlier suggested that the WS of steel specimens
can vary over a wide range, from 10−5 to 10−13 mm3 N−1 mm−1 ,
and the exact magnitude of WS are influenced by several statis-
tical variables involved in the wear tests. The major variables that
determine the magnitude of WS are macro-material structures, sur-
face roughness, flash temperature, local contamination, adhesive
transfers, free wear particles and tribochemical reactions on the
micro-scale on the contact surfaces [26]. Thus, the differences in
the magnitudes of WS as obtained in the present investigation and
that reported by Wang et al. [24] for demarcating the mild and the
severe wear regimes may be attributed to the differences in the
microstructures and properties of the selected materials, employed
wear test methodologies and the chosen test conditions. Wang et
al. [24] have studied the wear behaviour of 52100 and 1080 steels
employing pin-on-ring testing method, whereas the material and
test methodology of the present study are AISI D2 steel and pin-on-
disc.

Table 3
Ratio of specific wear rates (WS ) and the operative modes and mechanisms of wear.

Sliding velocity (m s−1 ) Specimen codes Wear rate ratio, a Mode and mechanism of wear

Mode Mechanism

CONT 1 Severe Delaminative

CT 6.5 Mild Oxidative
1.00
SCT 7.3 Mild Oxidative
DCT 7.9 Mild Oxidative

CONT 1 Severe Delaminative

CT 1.8 Severe Delaminative
1.25
SCT 103 Mild Oxidative
DCT 125 Mild Oxidative

CONT 1 Severe Delaminative

CT 1.2 Severe Delaminative
1.50
SCT 1.3 Severe Delaminative
DCT 1.5 Severe Delaminative
a
 is ratio of WS of CONT specimen to that of CT, SCT and DCT specimens.
1368 D. Das et al. / Wear 267 (2009) 1361–1370

Fig. 9. Representative SEM micrographs of generated wear debris corresponds to the steady-state wear regime of (a) CONT, (b) CT, (c) SCT and (d) DCT specimens tested at
SV = 1.25 m s−1 . All micrographs taken at the same magnification of 250×, whereas the insets in (c) and (d) at 1500× are detailing the features of the same micrographs. (e) and
(f) are representative EDX profiles taken from the rubbed surfaces of the wear debris as marked by area-1 in (a) and (b), and by area-2 in the inset of (c) and (d), respectively.

Fig. 10. Representative SEM micrographs of worn surfaces at the end of wear tests of (a) SCT and (b) DCT specimens tested at SV = 1.50 m s−1 . Insets represent the generated
wear debris corresponds to the steady-state wear regime for the same samples.
 D. Das et al. / Wear 267 (2009) 1361–1370
Fig. 11. Representative back scattered SEM subsurface micrographs of worn surfaces at the end of wear tests of (a) CONT, (b) CT, (c) SCT and (b) DCT specimens tested at
SV = 1.25 m s−1 . WL: while layer; PDL: plastically deformed layer.
3.5. Influence of temperature of sub-zero treatments on wear
behaviour
In order to assess the influence of temperature of sub-zero treat-
ments on the degree of improvement in wear resistance, a new
parameter  has been incorporated here which is considered as
the ratio of WS of CONT specimen to that of the different sub-zero
treated specimens at a given SV . The estimated values of  for differ-
ent SV are compiled in Table 3 along with the operative modes and
mechanisms of wear. The results in Table 3 reveal that the improve-
ment in wear resistance by sub-zero treatment is marginal when
the operative mode and mechanism between CONT and sub-zero
treated specimens are similar (severe-delaminative). Under this
condition, the value of  is 1.8 for CT specimen at SV = 1.25 m s−1
and it varies from 1.2 to 1.5 at SV = 1.50 m s−1 for all the sub-zero
treated specimens. In contrast, the magnitude of  varies over two
orders of magnitude when the operative mode and mechanism of
wear for CONT specimens is severe-delaminative and that for the
sub-zero treated specimens is mild-oxidative. Such wide variation
in the magnitudes of  is due to the similar or dissimilar operative
modes and mechanisms of wear amongst the specimens considered
(Table 3). These findings are in excellent agreement with the recent
reports by the present authors [8,10] on the deep cryogenically
treated and conventionally treated tool steels.
However, comparison of  values for SCT and DCT specimens
at SV = 1.00 and 1.25 m s−1 indicates that the  increases signifi-
cantly at higher SV for these specimens, though the operative mode
and mechanism of wear for the CONT (severe-delaminative) and
that for the SCT and DCT (mild-oxidative) remains unchanged for
above-mentioned SV values (Table 3). Such variation in  occurs
due to increase in WS for the CONT specimens and reduction of
the same for the SCT and DCT specimens when SV increases from
1.00 to 1.25 m s−1 (Fig. 5). This apparent contradiction, however,
is in agreement with earlier suggestions by Welsh [18,19]. He elu-
cidated that the WS of steels increases with increasing SV, if the
SV lies between the characteristics critical SV related to the mild-
to-severe and the severe-to-mild wear transitions. Identification of
operative wear mechanism as delaminative for CONT specimen for
1369
all the tested SV (1.00–1.50 m s−1 ) confirms that these SV indeed lie
in between the two transitions SV for this specimen. Thus, accord-
ing to this explanation of Welsh [18,19] it is natural that WS would
increase with the increase in SV from 1.00 to 1.25 m s−1 as observed
for the CONT specimens (Fig. 5).
Welsh [18,19] and Sullivan and Hodgson [25] have earlier also
shown that the WS of steels tend to decrease with increasing SV ,
if the applied SV is lower than the transition SV at which mild-
to-severe transition takes place. For both SCT and DCT specimens,
mode and mechanism of wear are ‘mild-oxidative’ at SV = 1.00
and 1.25 m s−1 and ‘severe-delaminative’ at SV = 1.50 ms−1 . Thus,
SV = 1.00 and 1.25 ms−1 are below the transition SV for these spec-
imens. Therefore, it is natural that WS of these specimens would
decrease with the increase of SV from 1.00 to 1.25 m s−1 (Fig. 5).
This behaviour is related to the rate of tribochemical reaction at the
contact surfaces as the increase in SV increases the flash tempera-
ture, which accelerates the formation of oxide layer at the contact
junctions. At higher SV , development of more compacted oxide
layer at the contact is expected to reduce the magnitude of WS as
observed in the present study for the SCT and DCT specimens when
SV increased from 1.00 to 1.25 m s−1 . This is well supported from
the observations that (i) the area of worn surface covered by the
compacted oxide layer increases with increasing SV (Fig. 6c and d
vis-à-vis Fig. 8c and d) and (ii) the generated oxide debris are much
thicker at higher SV (Fig. 7e vis-à-vis insets in Fig. 9c and d).
An attempt to correlate the results of wear tests in Table 3 with
the results of microstructural analyses in Figs. 1 and 2 reveal that
TLQ has considerable influence on generating the nature of the
microstructures and hence on the resulted wear properties of the
selected steel. In order to get insights on the role of microstructural
constituents on the variation of wear behaviour, the subsurfaces
of all types of specimens tested at SV = 1.25 m s−1 were examined
under SEM. Typical micrographs of the subsurfaces are presented
in Fig. 11. The features beneath the worn surface of CONT and
CT specimens are markedly different than that for SCT and DCT
specimens (Fig. 11). The SCT and DCT specimens show only plas-
tically deformed layer; in contrast, the CONT and CT specimens
exhibit a well-defined ‘heavily deformed layer’, termed popularly
1370 D. Das et al. / Wear 267 (2009) 1361–1370
in the literature as white (non-etching) layer [27], and followed by
a plastically deformed layer. The presence of the white layer is the
signature of deformation induced delaminative wear [21] which is
indeed the governing wear mechanism for CONT and CT specimens
at SV = 1.25 m s−1 . The presence of only plastically deformed layer
and the absence of any white layer in the subsurfaces of SCT and
DCT specimens are indicative of mild-oxidative wear for these spec-
imens. The white layer of CONT specimen (Fig. 11a) shows presence
of cracks that originated at a given depth beneath the worn surface
and propagated parallel to the sliding direction; whereas, the crack-
ing of white layer is less prominent for CT specimen (Fig. 11b). This
observation is in agreement with the lower estimated WS of the CT
specimen than that of CONT specimen at identical test conditions
(Fig. 5).
Severe-delaminative wear of steels occurs by continued plastic
deformation at the contact surfaces of a test specimen leading to
nucleation of cracks followed by its propagation as suggested by
Suh [21]. The presence of soft ␥R associated with lower amount
of hard SCs in the CONT and CT specimens as compared to those
in the SCT and DCT specimens (Fig. 2) suggests that the former
specimens are more prone to plastic deformation during wear at
a lower SV for a constant FN or at lower FN at a constant SV . There-
fore, specimens having less resistance to plastic deformation are
expected to undergo mild-to-severe wear transition at a lower FN
and/or SV . Thus, the present observation of higher SV for mild-to-
severe wear transition for SCT and DCT specimens as compared to
that for CONT and CT specimens is natural. Moreover, the fact that
at SV = 1.00 m s−1 , the operative wear mechanisms for CONT and
CT specimens are delaminative and oxidative wear, respectively,
also supports the above argument; since CT specimen possesses
higher amount of SCs and lower amount of ␥R than those in CONT
specimens (Fig. 2). In summary, this investigation highlights the
influence of temperature of sub-zero treatments on the microstruc-
ture and wear behaviour of die steel.
4. Conclusions
The experimental results related to the influence of temperature
of sub-zero treatments on the wear behaviour of selected AISI D2
steel and their pertinent analyses assist to infer the following major
conclusions:
(i) All types of sub-zero treatments appreciably improve the wear
resistance of the die steels compared to the conventional
treated (CONT) ones. However, the improvement in wear resis-
tance by shallow (SCT) and deep cryogenic treatment (DCT) is
significantly higher than that achieved by CT, and the maxi-
mum improvement is obtained by DCT. This is attributed to
the decrease in the retained austenite content associated with
the increasing amount of secondary carbide particles with low-
ering of temperature of the sub-zero treatments.
(ii) The obtained hardness of AISI D2 steel for CONT and
DCT are 759 and 791 VHN, respectively and typical val-
ues of their specific wear rates (WS ) are 1.03 × 10−6 and
8.26 × 10−9 mm3 N−1 mm−1 , respectively, at sliding velocity
(SV ) of 1.25 m s−1 .
(iii) Estimation of WS and detailed characterization of worn
surfaces, generated debris and subsurfaces of all types of speci-
mens assist to reveal that the severe mode of wear is associated
with the deformation induced delaminative wear mechanism,
whereas the mild mode of wear is associated with the predom-
inantly oxidative wear mechanism coupled with occasional
cracking and pull-out of primary carbide particles.
(iv) The modes and mechanisms of wear are synergistically
affected by the temperature of sub-zero treatments and the
SV of wear tests at a constant normal load. The mild-to-severe
wear transition occurs at SV = 0.75 m s−1 for CONT specimen
and at SV = 1.00 m s−1 for CT specimen, and at SV = 1.25 m s−1
for both SCT and DCT specimens.
(v) The obtained results unambiguously lead to infer that lower
the temperature of sub-zero treatment higher is the improve-
ment in wear resistance. However, the degree of improvement
is dependent on the SV of wear tests and/or the temperature
of sub-zero treatment, which govern the operative modes and
mechanisms of wear.
Acknowledgement
The financial assistance received from the University Grants
Commission, Government of India [Grant No. F. No. 31-48/
2005(SR)] to carry out a part of this research is gratefully acknowl-
edged.
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