Wear 310 (2014) 90100

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Wear
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Wear and tribocorrosion behaviour of 304L SS, Zr-702, Zircaloy-4

and Ti-grade2
R. Priya, C. Mallika, U. Kamachi Mudali n
Corrosion Science and Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, Tamil Nadu, India

art ic l e i nf o a b s t r a c t

Article history: Passive materials like 304L stainless steel (SS), Zirconium-702, Zircaloy-4 and Titanium-grade2 exhibit an
Received 8 July 2013 activepassive behavior in an aqueous environment. Corrosion and wear interactions are of great
Received in revised form importance since the growth of a passive lm provides protection against corrosion, while wear may
23 November 2013
destroy the protective passive lm. Wear tests were carried out on a linear reciprocatory and pin on disc
Accepted 28 November 2013
Available online 17 December 2013
systems. Tribocorrosion experiments were performed using a pin on disc stand in 1 M HNO3. The results
revealed that the wear rate was low for 304L SS when compared to Zircaloy-4, Zr-702 and Ti-grade2. The
Keywords: lowering in open circuit potential (OCP) resulted during tribocorrosion test was a mixed potential which
Tribocorrosion indicates the surface state of unworn and worn surfaces. Potentiodynamic polarization and potentiostatic
Passive lm
sliding results revealed that the anodic current was higher with sliding than the anodic current measured
OCP
without sliding. This was due to more dissolution of the metal in the anodic potential range under sliding
Corrosion
Wear conditions. The current increase could then be attributed to the wear accelerated metal corrosion. The
wear tracks were analysed using SEM and surface prolometer. The synergy between wear and corrosion
was found in the above passive materials.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction
Development of materials for spent nuclear fuel reprocessing
applications is of considerable interest because these materials
should possess high corrosion resistance in nitric acid medium
[1,2] in order to have long service life in the plant. The perfor-
mance of moving components in the rotary equipment used in
nuclear reprocessing plants largely depends on the corrosion
resistance of the material combined with good wear resistance
in corrosive environment. The formation of a stable, adherent and
self-healing passive chromium oxide (Cr2O3) layer on AISI type
304 stainless steel makes it a candidate material in the reproces-
sing plants for applications in HNO3 medium of concentration
below 8 M and temperatures below 353 K [2]. Titanium does not
undergo transpassive dissolution with increase in nitric acid
concentration even above 8 M HNO3, as in the case of stainless
steel [3]. The protective thin titanium dioxide (TiO2) lm on the
surface of Ti facilitates its application as a dissolver material at
nitric acid concentrations as high as 11.5 M in the aqueous
reprocessing of plutonium-rich carbide/oxide fuels discharged
from Fast Breeder Reactors. However, titanium undergoes corro-
sion in the vapour phase of nitric acid [4]. Hence, zirconium and its
n
Corresponding author. Tel./fax: 91 44 27480121.
E-mail address: kamachi@igcar.gov.in (U.K. Mudali).
alloys are proposed as the suitable alternate choice for the
construction of dissolvers. Though zirconium and its alloys have
high corrosion resistance in nitric acid environment due to the
formation of a strong adherent protective oxide on the surface,
they exhibit passivetranspassive transition under certain condi-
tions unlike titanium, in nitric acid medium [5,6].
Tribocorrosion results due to the synergistic effect of corrosion
and wear acting together [710]. In the drive part of the contin-
uous dissolvers employed in nuclear fuel reprocessing plants, the
inner surface of the rotating drum and driving gear may undergo
wear and the components of the continuous dissolver are sub-
jected to scratching, abrasion, erosion and other forms of wear
damages in nitric acid environment. The tribocorrosion losses in
the passive materials are controlled by the kinetics of depassiva-
tion and repassivation of the material subjected to sliding wear in
a corrosive environment [1115]. The depassivation rate mainly
depends on the material behaviour in the contact, sliding velocity
and on the applied potential. Any mechanical damage on the
surface of a passive material leads to wear accelerated corrosion
[1620]. Achieving combined improvement in tribological and
corrosion properties in passivating materials is a challenge. There-
fore, it is of prime importance to study the tribocorrosion
behaviour of passive materials in nitric acid medium. The scope
of the present study is to understand the wear and tribocorrosion
issues of the materials employed for spent nuclear fuel reproces-
sing applications, for the purpose of improving the wear and

0043-1648/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.wear.2013.11.051
 R. Priya et al. / Wear 310 (2014) 90100
tribocorrosion resistance, which in turn will prevent any critical
damage of the equipment and enhance the lifetime of the
components. Thus, the wear and tribocorrosion behaviour of
304L SS, Zr-702, Zircaloy-4 and Ti-grade2 were investigated by
employing linear reciprocatory and pin on disc systems with
in situ electrochemical measurements and the tribological proper-
ties of these passive materials had been compared in the
present work.
2. Experimental details
2.1. Materials and sample preparation
The materials used were 304L SS, Zircaloy-4, Zirconium-702
and Ti-grade2 samples of dimensions 12  12 mm. The samples
were polished mechanically by abrading with SiC emery paper up
to 1200 grit size. The surface of the specimens was subsequently
polished to mirror nish with diamond paste, washed with
distilled water and cleaned with acetone in an ultrasonic bath.
2.2. Microstructure and hardness
Microstructure of the samples was examined by optical micro-
scopy (Model LEICA). The micro hardness was measured using the
micro-hardness measurement device, Model SHIMADZU-HMV-2.
A load of 4.9 N (  500 g) was applied for the time duration of 15 s
and the average of 10 indentations was taken for each sample.
2.3. Dry sliding wear test by linear reciprocating and
pin-on-disc systems
A linear reciprocating and pin on disc (CM 9062) wear test
machine was used to study the wear behaviour of the four
materials. The initial weight of each specimen was recorded using
an electronic weighing machine with the least count of 0.01 mg.
The schematic of the experimental setup for linear reciprocatory
test (LRT) is shown in Fig. 1. During LRT an alumina ball of 6 mm
diameter was pressed against the reciprocating counter surface by
applying a load of 5 N at different reciprocating velocities (0.06,
0.12 and 0.18 m/s). The wear rate of the material was calculated by
weight loss method. Fig. 2 shows the schematic of the pin on disc
(POD) test setup. In the POD test, an alumina pin of 6 mm diameter
and 40 mm length with a hemispherical end of radius 3 mm was
used to contact the sample. The surface roughness of the alumina
counterpart was 1.4 m. The rubbing motion of the pin over the
sample was circular and a load of 9.8 N and sliding velocities of
0.018, 0.037 and 0.056 m/s were employed to measure the friction
force and coefcient of friction data.
Fig. 1. Schematic of linear reciprocatory test system.
91
Fig. 2. Schematic of tribocorrosion pin-on-disc experimental setup.
2.4. Tribocorrosion with in situ electrochemical measurements
by pin on disc rotary system
2.4.1. Potentiodynamic polarization studies
Tribocorrosion test was carried out using the POD setup, shown
in Fig. 2. A three-electrode cell setup made of teon was employed
for electrochemical measurements. The electrolyte was 1 M HNO3.
The cell comprised Pt as the counter electrode, Ag/AgCl in
saturated KCl as the reference electrode and the test specimen
(dimensions: 12  12  6 mm) as the working electrode. The
electrodes were connected to a potentiostat (Solatron 1287) and
the tests were carried out using the alumina pin described in
Section 2.3. Sliding tests were conducted with the sliding velocity
of 0.018 m/s and with a normal load of 9.8 N. Potentiodynamic
polarization studies were made without sliding (static condition)
and in the presence of sliding (tribo condition).
2.4.2. Open circuit potential (OCP) measurements
Initially, OCP measurements were performed without sliding
for 800 s and subsequently with sliding for a time period of 3600 s.
Sliding was then stopped and the OCP measurements were further
measured for 800 s.
2.4.3. Potentiostatic sliding test
The potentiostatic experiments were conducted at the applied
passive potential of 500 mV. Initially, current measurements were
carried out without sliding for 900 s and sliding was initiated
thereafter and continued for 3600 s. Sliding was then stopped and
the current measurements were further continued for 900 s.
2.5. Wear and corrosion synergistic experiments
Synergism experiments were conducted in the pin-on-disc
tribocorrosion experimental setup which facilitates the evaluation
of corrosion, wear and combined wear and corrosion behaviour.
Madsen [21] established a standard guide for determining the
synergism between wear and corrosion. Two wear tests were
conducted; one with the corrosion component (by applying a
passive potential of 500 mV) and the resultant degradation (T) due
to wear and corrosion. The other test was conducted by eliminat-
ing the corrosion component by applying 1 V cathodic to the open
circuit potential and the mechanical degradation estimated is
dened as W0. Electrochemical measurements were conducted
to obtain the polarization resistance Rp, according to ASTM
practice G59 and Tafel constants from potentiodynamic curve as
92 R. Priya et al. / Wear 310 (2014) 90100

per ASTM Test Method G5. One set of corrosion tests was
performed to obtain the corrosion component, C0 alone (without
wear) and the other set of corrosion tests was conducted with
wear component Cw.
The total wearcorrosion degradation (T) can be calculated
from Eq. (1):
MTF
T 1
ADh
where M is the mass loss (g) without cathodic protection, A is the
surface area (cm2), D is the density (g/cm3), h is the time duration
of the experiment (h). TF is the time factor conversion from hour
to years and is equal to 8.76  103.
The wear volume W0 without corrosion can be determined
using Eq. (2):
Mc TF
W0 T and W 0 are given by mm3 =mm2 yr:
ADh
where Mc is the mass loss (g) with cathodic protection, A and
D are surface area (cm2) and density (g/cm3) of the specimen
respectively under cathodic protection.
The corrosion rates for the penetration equations are deter-
mined from the electrochemical parameters according to Eq. (3):
ba bc
icorr
2:303ba bc Rp
where ba is the anodic Tafel slope, bc is the cathodic Tafel slope and
Rp is the polarization resistance ( cm2). Faraday's Law can be
applied to calculate the corrosion rate (CR) in terms of penetration
rates using Eq. (4):
icorr K 1 EW
CR
D 3.1. Microstructure and hardness
CR is given in mm3/mm2-yr and icorr in mA/cm2. K1, the
corrosion conversion factor is equal to 3.27  10  3 (mm-g/mA-
cm-yr). EW is the equivalent mass of the material.
The total wearcorrosion synergism, S is the difference
between the total degradation and that due to the individual
components of corrosion and wear separately; i.e.
S T W 0  C 0 5
The synergistic component S can be divided into the two
components, Cw and Wc. Cw is the increase in corrosion due
to mechanical wear and Wc is the increase in mechanical wear
due to corrosion. S is given by
S C w W c S; DC w and DW c are given by mm3 =mm2 yr:
6
Cw and Wc are calculated using Eqs. (7) and (8) respectively.
C w C w  C 0 7
W c T  W 0  C w 8
2
2.6. Morphology of worn surface by SEM and contact prolometry
The worn morphology of the samples was examined by Scan-
ning electron microscope (SEM; SNE 3000 make). Taylor hobson
precision talysurf prolometer (CL1 1000), which is a scanning
surface topography instrument that moves the work piece under a
3 stationary gauge head was used to obtain the wear track prole.
Data were collected one point at a time with each point having a
discrete X, Y, Z location. Wear track width and depth of the worn
surface of the samples were obtained from the surface prole.
3. Results and discussion
4
The optical microstructure of 304L SS consists of austenitic
recrystallized grains (Fig. 3a). Zircaloy-4 (Fig. 3b) showed

304L Zircaloy-4

Zr-702 Ti grade2

Fig. 3. Optical microstructure of (a) 304L SS, (b) Zircaloy-4, (c) Zr-702 and (d) Ti-grade2.
 R. Priya et al. / Wear 310 (2014) 90100
-microstructure with recrystallized equiaxed grains and second
phase particles. Zr-702 and Ti-grade2 (Fig. 3c and d) consisted of
-structure. The 304L SS microstructure was revealed by electro-
lytic etching in 10% oxalic acid whereas Zircaloy-4 and Zr-702
were chemically polished and etched in a solution comprising
45 ml HNO3, 10 ml HF and 45 ml H2O. The Ti-grade2 microstruc-
ture was swab etched in Kroll's reagent (4 ml HNO3, 1.5 ml HF and
94 ml H2O). Vicker's microhardness values of 304L SS, Zircaloy-4,
Zr-702 and Ti-grade2 were 180, 182, 149 and 198 Hv respectively.
Ti-grade2 was observed to have higher hardness than 304L SS,
Zircaloy-4 and Zr-702. Pure Zr-702 had lower hardness than the
nuclear grade Zircaloy-4. 304L SS and Zircaloy-4 exhibited hard-
ness in the same range.
3.2. Dry wear test by LRT and POD methods
3.2.1. Effect of sliding speed on coefcient of friction
The variation in the coefcient of friction as a function of time
for 304L SS, Zircaloy-4, Zr-702 and Ti-grade2 by LRT and POD
methods is shown in Figs. 4 and 5 respectively. The results
indicated that the coefcient of friction increased remarkably with
the sliding time and gradually stabilized. The probable reason
could be that the passive materials were readily oxidised in air and
at the initial period of rubbing, the oxide lm breaks up and fresh
Fig. 4. Coefcient of friction measured using LRT method for (a) 304L SS, (b) Zircaloy-4, (c) Zr-702 and (d) Ti-grade2.
93
surface comes in contact which increases the coefcient of friction
between the contacting surfaces. As the sliding distance increases
the contact pressure decreases due to increase in contact area. The
report by Hua et al. [22] that the wear between a pair of mating
surfaces tends to be stabilized with the gradual increase in sliding
distance corroborates the observation in the present study. The
increase in sliding speed resulted in the increase of friction
coefcient at the contacting surface. The coefcient of friction
was observed to uctuate more at higher frequency due to the
interaction of third body particles from wear debris during sliding.
Thus, any entrapment of wear particles increases the friction force
due to the increase of ploughing effect.
3.2.2. Effect of sliding speed on wear rate
Wear rates were calculated for 304L SS, Zircaloy-4, Zr-702 and
Ti-grade2 at different sliding speeds by LRT and POD methods
(Fig. 6a and b). The results showed that the wear rate increased
with sliding speed. The sliding velocity determines the relative
importance of heat conduction away from the surface [23].
At lower sliding speed, the heat generated at the interface will
be rapidly conducted away whereas at higher sliding speed, only
limited heat conduction can occur and this leads to higher inter-
face temperature. As a consequence of high interface temperature,
high chemical reactivity of the surface resulting in rapid surface
94 R. Priya et al. / Wear 310 (2014) 90100

Fig. 5. Coefcient of friction measured using POD method for (a) 304L SS, (b) Zircaloy-4 (c) Zr-702 and (d) Ti grade2.

Fig. 6. Comparison of wear rate of all the samples using (a) LRT and (b) POD methods.

oxidation occurs. Increase in interface temperature also reduces Removal of oxide produces wear debris and abrasion of these hard
the mechanical strength of asperities of contact. The rate of oxide particles leads to more wear. Thus, increase in sliding speed
oxidation inuences the transition between mild and severe wear. increases the wear rate. Both the test methods indicated that
 R. Priya et al. / Wear 310 (2014) 90100 95

Fig. 7. Surface proles by (a) LRT and (b) POD methods.

Fig. 8. Potentiodynamic polarization behaviour in 1 M HNO3 with and without sliding (a) 304L SS, (b) Zircaloy-4, (c) Zr-702 and (d) Ti-grade2.

304L SS had minimum wear rate when compared to Zircaloy-4, resistance of Zr is inferior to stainless steel [2729]. At lower
Zr-702 and Ti-grade2. sliding speeds, the wear resistance of Zircaloy-4 was observed to
Though Ti has higher hardness, it undergoes more wear owing be better than that for Zr-702 and this is attributed to the higher
to the highly reactive nature of the metal [2426]. The wear hardness of Zircaloy-4 than Zr-702. When the sliding speed
96 R. Priya et al. / Wear 310 (2014) 90100
increased, the wear rate of Zircaloy-4 and Zr-702 were comparable
and this could be due to the accelerated wear caused by oxide
wear debris. As Zircaloy-4 and Zr-702 have similar oxidation rates,
removal of the oxide layers at higher sliding speed resulted in
similar wear rates. 304L SS had enhanced wear resistance than
Zircaloy-4, Zr-702 and Ti-grade2. Zandrahimi et al. [30] and
Van Herpen et al. [31] observed mechanically induced martensite
transformation in 304L SS due to the inuence of plastic strain.
This friction induced transformation of 0 to 0 phase could have
strengthened the matrix and improved the wear resistance of 304L
stainless steel when compared to Zr and Ti based materials.
3.2.3. Characterisation of worn surface by surface prolometry
The wear proles obtained by LRT and POD methods for 304L
SS, Zircaloy-4, Zr-702 and Ti-grade2 (Fig. 7a and b) were analysed
using surface prolometer. The wear track proles by LRT method
at 6 Hz showed signicant increase in the width and depth for
Ti-grade2 when compared to other materials. Nevertheless, the
wear track comparison by POD method at 60 rpm showed that the
wear track width and depth for Zr-702 were higher than those
values for Ti-grade2 and Zircaloy-4. The wear track surface prole
of 304L SS showed the lowest wear track width and depth than
Fig. 9. Open circuit potential behaviour in 1 M HNO3 with and without sliding (a) 304L SS, (b) Zircaloy-4, (c) Zr-702 and (d) Ti-grade2.
Zircaloy-4, Zr-702 and Ti-grade2. Thus, the wear prole values for
the investigated materials upheld their wear rates.
3.3. Tribocorrosion assessment by POD rotary test system coupled
with electrochemical studies
3.3.1. Potentiodynamic polarization measurements
The polarization curves obtained for 304L SS, Zircaloy-4, Zr-702
and Ti-grade2 immersed in 1 M HNO3 (with and without sliding)
are shown in Fig. 8ad. The polarization curves under static
condition showed that 304L SS exhibited transpassive behaviour
at 1200 mV, while transpassive behaviour of Zircaloy-4 and Zr-702
was observed at about 2100 mV. Ti-grade2 exhibited a very wide
passive region and excellent corrosion resistance than 304L SS,
Zircaloy-4 and Zr-702, implying that the passive lm stability is
high for Ti-grade2 among the four materials. It has been reported
by Jayaraj et al. [3] that commercially pure (CP)-Ti exhibited non-
transpassive behaviour even at 11.5 M HNO3. The passive current
density of 304L SS (41.31 mA/cm2) was marginally higher than
Zircaloy-4 (31.45 mA/cm2), Zr-702 (37.27 mA/cm2) and Ti-grade2
(31.78 mA/cm2). Higher passive current density and earlier trans-
passive behaviour of 304L SS indicates the poor passive lm
stability of 304L SS than Ti and Zr based materials. Hence the
 R. Priya et al. / Wear 310 (2014) 90100
corrosion resistance of 304L SS is inferior to Zircaloy-4, Zr-702 and
Ti-grade2.The difference in the polarization behaviour of Zircaloy-
4 and Zr-702 was negligible. The uctuations observed in the
polarization curves under tribo-condition could be due to the
activepassive transitions taking place in the wear track. Further-
more, in the passive region marginally higher current was noticed
for 304L SS under tribo condition than under static condition. The
impact of sliding motion was found to have a marked effect on the
passive current density. The current increase was attributed to the
wear accelerated metal corrosion [1618]. The measured current is
assumed to be the sum of the current originated from worn and
unworn surfaces of the samples. Similar to 304L SS, the polariza-
tion curves of Zircaloy-4 and Zr-702 under sliding condition
showed higher current in the passive region and a transpassive
behaviour around the potential of 1800 mV. In the static condition
Zircaloy-4 and Zr-702 showed a passive region with wide potential
range, whereas under tribocorrosion condition, the passive region
diminished. In tribo-condition, Ti-grade2 showed an increase in
passive current density and transpassive behaviour was observed
in 1 M HNO3 medium just like 304L SS, Zircaloy-4 and Zr-702. This
could be due to the masking effect of the wear debris on the
unworn passive lm surface. More wear debris gets accumulated
on the surface owing to the inferior wear behaviour of Ti-grade in
nitric acid medium. Hence, the working electrode area represents
the worn surface which is the active region and it undergoes
passivation and depassivation cycles.
Fig. 10. Current transients recorded before, during and after sliding tests at an applied passive potential for (a) 304L SS, (b) Zircaloy-4, (c) Zr-702 and (d) Ti-grade2.
97
3.3.2. Open circuit potential measurements
The open circuit potentials were recorded before, during and after
the sliding wear test. The variation in OCP with time as a result of
sliding wear for 304L SS, Zircaloy-4, Zr-702 and Ti-grade2 in 1 M
HNO3 is shown in Fig. 9ad. As expected, sliding wear resulted in a
cathodic shift of OCP. In static condition, the OCP of a passive material
is higher and stable. But during sliding, the OCP shifted towards
cathodic potential. It is reported that the OCP recorded during sliding
was a mixed potential reecting the active state of the material inside
the wear track and the passive state of the unworn area outside the
wear track [1114]. Thus, the lowering of OCP during sliding was due
to the depassivation of the wear track area. The comparatively lower
value of OCP shift in 304L SS than the OCP shift of Zircaloy-4, Zr-702
and Ti-grade2 during sliding wear was attributed to the low wear
observed in 304L SS compared to the other three materials. When the
sliding was stopped, the material resumed back to its initial OCP
condition. Thus, passivation is restored in the depassivated worn areas
of the sample.
3.3.3. Potentiostatic sliding wear test
Sliding tests were performed under potentiostatic conditions
for 304L SS, Zircaloy-4, Zr-702 and Ti-grade2 at an applied passive
potential of 500 mV and the results are reproduced in Fig. 10ad.
Zero time corresponds to the onset of passive potential. After
900 s, rubbing was initiated and the increase in current observed
98 R. Priya et al. / Wear 310 (2014) 90100
was due to depassivation resulting from abrasion. Current decreased
when rubbing was stopped. The phenomenon observed in passive
systems by many investigators [1518] corroborates this observation.
Under tribocorrosion condition, at the applied passive potential of
500 mV, the passive materials showed higher evolution of current.
Thus, under sliding, the depassivation kinetics leads to wear accel-
erated corrosion. The current evolved in the wear track during
tribocorrosion tests is the difference between the current evolved
with sliding and the current measured without sliding. Higher
current noticed during rubbing implies that rubbing leads to
signicant increase in chemical reactivity of the passivated materials.
The surface proles measured after potentiostatic sliding test
are shown in Fig. 11. The wear track proles revealed that Zr-702
had higher wear track width and depth than Zircaloy-4, Ti-grade2
and 304L SS. This is reected in the mechanical volume loss for
Zr-702 in 1 M HNO3, which value is more in Zr-702 than in
Zircaloy-4, Ti-grade2 and 304L SS. The tribocorrosion mechanism
of the passive materials could be explained based on the depen-
dence of mechanical volume loss and chemical volume loss on the
depassivation and repassivation kinetics of the materials in nitric
acid medium at the contact interval of sliding and these materials
were found to suffer from wear accelerated corrosion.
3.4. Wearcorrosion synergism
The standard penetration rate equations (Eqs. (1)(8)) have
been used to interpret the data obtained from tribocorrosion test
described in Section 2.5 [21]. The calculated penetration rates for
the passive materials are given in Table 1. The total material loss T
comprises the following components: the wear rate in the absence
of corrosion W0, the corrosion rate C0 in the absence of wear and
Fig. 11. Surface proles recorded after potentiostatic sliding wear test.
Table 1
Wear and corrosion synergistic data.
Material Material loss rate, (mm3/mm2/yr)
T W0 C0
304L SS 27.137 1.02 23.36 7 1.50 0.71 70.08
Zircaloy-4 69.377 1.80 61.477 1.65 0.66 70.05
Zr-702 86.617 2.02 78.127 1.43 0.69 70.05
Ti-grade2 64.07 1.68 55.86 7 2.10 0.45 70.04
T Total material loss due to wear-corrosion synergism, W0 Mechanical volume loss by applying cathodic protection, C0 Corrosion volume loss with wear, Cw Corrosion
volume loss due to wear, S Synergistic component, Cw Change in corrosion rate due to wear, Wc Change in wear rate due to corrosion.
the synergistic component S and it is the sum of the interactions
between corrosion and wear processes, which is given in Eq. (9).
T W 0 C0 S 9
The total material loss (T) was found to be higher for Zr-702 than
Zircaloy-4, Ti-grade2 and 304L SS. The contribution of pure corrosion
loss to total material loss was less than the pure mechanical wear loss
by cathodic protection in 1 M HNO3. Pure corrosion rate was margin-
ally higher for 304L SS than Zr and Ti based materials. This is due to
the inferior passive lm resistance of 304L SS when compared to Zr
and Ti materials in nitric acid medium. The presence of wear had
inuenced the corrosion rate (Cw) and the change in corrosion rate
(Cw) of these passive systems remains more or less the same. This
could be due to the same recovery rate of the passive lms broken by
wear for these passive systems in 1 M HNO3. Similar accelerative effect
of wear on the corrosion of passive material (austenitic stainless steel)
was studied by Jiang et al. [32]. The change in wear rate (Wc) due to
corrosion was found to be higher for Zr and Ti based materials than
304L SS. This is attributed to the inferior wear resistance of these
materials. The synergistic component (S) was observed to be lower for
304L SS than Ti and Zr based materials. The poor wear resistance of
Ti and Zr based materials resulted in more material degradation than
304L SS in 1 M HNO3 medium.
3.5. Worn morphology by SEM
The worn morphology of 304L SS, Zircaloy-4, Zr-702 and Ti-grade2
revealed by SEM is shown in Fig. 12al. Plastically deformed surface
was observed in all cases. The worn morphology under dry sliding
condition revealed that the wear track of 304L SS had minimum
deformation with very less coverage of oxide particles, whereas
Zircaloy-4, Zr-702 and Ti-grade2 showed severe deformation with
more patches of oxides covering the surface of the wear track. This
could be due to the higher wear resistance of 304L SS when compared
to other materials. The presence of oxide layers is due to the tribo-
mechanical interaction between the contacting surfaces. The wear
debris particles accumulated would have acted as a third body in the
tribo contact and induced abrasion on the sliding surface [23,31].
Grooves parallel to the sliding direction evidenced the abrasivity of the
generated particles. Voids and crack initiated under the worn surface
had led to delamination and pull out from the surface under repeated
loading. Smooth surface appeared in 304L SS at OCP and at anodic
potential, while rough wear tracks with more ploughing were
observed in Ti and Zr-based materials.
4. Conclusions
The following conclusions were drawn from the present study:
1. Wear resistance determined by reciprocatory and unidirectional
sliding modes revealed that the wear resistance value is high for
304L SS when compared to Zircaloy-4, Zr-702 and Ti-grade2.
Cw S Cw Wc
1.09 7 0.06 3.05 7 1.20 0.38 7 0.04 2.677 0.90
1.117 0.05 7.247 1.40 0.447 0.05 6.7 7 0.80
1.187 0.07 7.80 7 1.36 0.497 0.04 7.3 7 1.10
0.87 7 0.08 7.687 1.24 0.42 7 0.05 7.277 1.22
 R. Priya et al. / Wear 310 (2014) 90100 99

Materials Dry OCP condition Potentiostatic condition

304L SS

Zircaloy-4

Zr-702

Ti-grade2

Fig. 12. SEM images of worn morphology.

2. Higher coefcient of friction was noticed for Ti-grade2 and
Zr-based materials when compared to that of 304L SS. Wear depth
prole by surface prolometry also substantiated that the wear
depth is higher for Ti-grade2 and Zr-based materials than 304L SS.
3. Cathodic shift in OCP was observed under sliding condition in
1 M HNO3 and the OCP measured was the mixed potential
resulting from the state of unworn and worn surfaces.
4. Under tribocorrosion condition, the potentiodynamic polarization
measurement of the investigated materials showed marginal
increase in passive current density compared to that of static
condition. Ti-grade2 exhibited transpassive behaviour under rub-
bing condition in 1 M HNO3.
5. Potentiostatic sliding wear test revealed the evolution of higher
current during rubbing due to the depassaviation resulting
from rubbing. Also the wear rate of 304L SS is comparatively
lower in 1 M HNO3 than Zr and Ti based materials.
6. The synergistic effect of wear and corrosion is more pro-
nounced in Ti and Zr based materials than 304L SS.
100 R. Priya et al. / Wear 310 (2014) 90100
Thus, the synergy between wear and corrosion led to degrada-
tion of the passive materials in tribocorrosion condition. Though
304L SS has minimum wear loss in nitric acid medium compared
to Zr-702, Zircaloy-4 and Ti-grade2, it is not a suitable material for
plant conditions due to its poor corrosion resistance in higher
concentrations of nitric acid, envisaged in the processes. Hence, Zr
and Ti based materials will be the better choice for rotary
equipment in the plant. Thus, improving the wear resistance of
these materials by surface modication would be more effective in
enhancing the tribocorrosion resistance and extending the service
life of the rotary dissolver.
Acknowledgements
The authors are grateful to Mr. K. Thyagarajan, CSTG, IGCAR for
his assistance in the experimental work. The authors would like to
thank Dr. N.L. Parthasarathy, and Mr. M. Aravind of MTD, IGCAR for
their support in the surface prolometry analysis.
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