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Wear 376-377 (2017) 12981306

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Micro abrasion-corrosion of ferritic stainless steels


W.S. Labiapari a,b, M.A.N. Ardila a, H.L. Costa a, J.D.B. de Mello a,n
a
Universidade Federal de Uberlndia, Uberlndia, Brazil
b
Aperam South America, Brazil

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

Article history: The synergistic effect between abrasion and corrosion has been widely investigated and debated, where
Received 21 December 2016 according to some works this synergy accentuates wear, and for others attenuates it. Despite the con-
Received in revised form siderable effort to understand the synergy between abrasion and corrosion, little progress has been made
19 January 2017
to understand this phenomenon for ferritic stainless steels. This paper analyses the micro abrasion-
Accepted 20 January 2017
corrosion performance of ferritic stainless steel with different chemical compositions (11%wt Cr with and
without Ti stabilization; 16%wt Cr with and without Nb stabilization) and, for comparative purposes,
Keywords: austenitic stainless steel (18%wt Cr  8%wt Ni) and carbon steel (0.2%wt C). The specimens were tested
Micro abrasion-corrosion for corrosion (turbulent and aerated environment), micro abrasion and micro abrasion-corrosion. For the
Synergy
corrosion tests, a 1 N H2SO4 solution was used, a 10%wt mixture of SiO2 in distilled water for the micro
ferritic stainless steels
abrasion tests, and an abrasive-corrosive environment of 10%wt SiO2 in 1 N H2SO4 for the micro abrasion-
Friction coefcient
Ti and Nb stabilization corrosion tests. In the micro abrasive wear tests there was not a clear trend between the different ma-
terials tested, despite differences in their chemical composition, mechanical properties and micro-
structure. On the other hand, their performance was ruled by their chemical composition, in particular
the Chromium content, under abrasion-corrosion conditions. This indicated the predominant role played
by corrosion in abrasive-corrosive environments in this particular tribo-system. For all materials tested,
micro abrasion wear coefcients were higher (4  ) than those measured under abrasion-corrosion
conditions. Friction coefcients could also be measured by a 3D load cell strategically positioned in the
specially developed micro abrasion-corrosion device, showing a strong reduction (2  ) in friction
coefcient under abrasion-corrosion conditions when compared with solely abrasion conditions. This
was attributed to the formation of a corrosion product, mainly constituted of iron sulphate (identied via
FTIR), which has lubricant properties.
& 2017 Elsevier B.V. All rights reserved.

1. Introduction passivating layers present in the metal surface. Exposed metal


surfaces may be highly reactive to the environment, which can
In various engineering applications, mechanical components accelerate corrosion [4]. Moreover, the presence of stresses chan-
are simultaneously subjected to a combination of mechanical wear ges the electrochemical response of mechanical components and
and corrosion [1,2]. Due to their high corrosion resistance, stain- structures [5].
less steels could be interesting candidates, despite their relatively Typically, corrosion and abrasion are investigated separately.
low mechanical resistance when compared to other hard wear- However, attempts to include the inuence of a corrosive en-
resistant materials. For example, in conditions of moderate cor- vironment on wear via a mathematical approach have incurred in
rosion in combination with mechanical wear, such as in the initial great dispersion and considerable errors [6]. According to Wood
stages of sugar cane plants for ethanol production, a previous work et al. [7], these errors may be reduced for tests that impose the
proved an exceptional performance of inexpensive ferritic stain- combined effect of corrosion and wear in situ. In this case, the
less steels at low cost-benet ratios [3]. mechano-electrochemical results dispense the mathematical ap-
In systems where corrosion and mechanical wear occur si- proach for the synergistic effects. The combined effect between
multaneously, phenomena such as plastic deformation inuence abrasion and corrosion, the so-called synergistic effect, has been
mechanical failure by wear, but also lead to the removal of widely debated in the literature. According to some authors,
abrasion accentuates corrosion [2,611], whereas for others abra-
n
Corresponding author. Tel.: 55 34 3239 4409; fax: 55 34 3239 4273. sion attenuates it [9,10]. However, even if considerable effort has
E-mail address: demello@ufu.br (J.D.B. de Mello). been done to understand the synergy between abrasion and

http://dx.doi.org/10.1016/j.wear.2017.01.083
0043-1648/& 2017 Elsevier B.V. All rights reserved.
W.S. Labiapari et al. / Wear 376-377 (2017) 12981306 1299

corrosion, little progress has been made to quantify this phe- 18Cr8Ni (AISI 304), present higher cost, but are extremely versatile
nomenon for stainless steels [6]. in their use, with high corrosion resistance, good formability and
The corrosion resistance of stainless steels is attributed to the weldability.
formation of a protective passivated layer and they are generally This paper analyses the micro abrasion-corrosion performance
regarded as materials that are easily repassivated. The dynamics of ferritic stainless steel with different chemical compositions:
involving removal of the passive layer by mechanical action and
repassivation plays an important role on the abrasion-corrosion  11%wt Cr with (11CrTi) and without Ti (11Cr) stabilization;
resistance of stainless steels. The complex tribochemical me-  16%wt Cr with (16CrNb) and without Nb (16Cr) stabilization;
chanisms of stainless steels depend on the microstructure and  For comparative purposes, one austenitic stainless steels with
chemical composition of the material surface, the solution pH, the 18%wt Cr and 8%wt Ni (18Cr8Ni) and one carbon steel with 0.2%
abrasive (size, type and concentration), and the imposed electro- wt C (ASTM A36).
chemical conditions [7].
Bello et al. [6] performed abrasion-corrosion tests for AISI 304, The specimens were characterized in terms of corrosion, micro-
AISI 316 and duplex stainless steel using SiC (diameter 4.5 mm) abrasion and micro-abrasion-corrosion. For all materials tested,
abrasive in a 3.5%wt sodium chloride solution in distilled water. friction coefcients were measured by a 3D load cell.
The abrasion corrosion tests showed higher passivation current
densities than pure corrosion tests and this was attributed to the
removal of the passive layer. 2. Methodology
Another point regarding abrasion corrosion tests of passivating
materials such as stainless steels is that they usually show more 2.1. Materials
dispersion of the electrochemical current than pure corrosion
tests, which is partly attributed to competition between the re- Four ferritic stainless steels were selected for this work and
moval of the passive layer and repassivation [7]. were compared with one austenitic stainless steel for its great
Several studies have measured abrasion-corrosion for bioma- versatility in terms of use. The ferritic stainless steels had different
terials and various coatings [7,8,10], including CoCrMo alloys and Cr contents and were tested both in stabilized (with Ti or Nb) and
duplex stainless steels, materials that are easily repassivated. non-stabilized conditions. All the stainless steel specimens were
Those works showed higher current densities under abrasion- used after industrial hot rolling and annealing (see hot rolling
corrosion conditions when compared with pure corrosion condi- temperatures and annealing conditions in Table 1). The stainless
tions, due to removal or damage of the passive layer. steels were also compared with a commercial low carbon steel,
For carbon steels, current density increases with the applied ASTM A36, in the hot rolled condition, due to its low cost and large
normal load, showing the abrasive effect on the passive lm [2]. applicability in engineering applications.
For WC-metal composites tested using basic slurries, the me- Their chemical composition, which was evaluated by different
tallic matrices that formed passive layers showed higher resistance techniques [infrared absorption, (Leco, CS444s), thermo con-
under abrasion-corrosion conditions when compared with pure ductivity (Leco, TC436s), X-ray uorescence spectrometry (Ther-
abrasion conditions, i.e., a negative synergy between abrasion and mo ARL, 9900) and optical emission spectrometry (Thermo ARL,
corrosion. On the other hand, for the matrices where corrosion 4460)] is presented in Table 2.
resulted in the loss of matrix support for the carbides, resistance The specimens were thoroughly characterized in terms of
decreased under abrasion-corrosion conditions, showing a positive mechanical properties [tensile tests (Instron, 5583) and Vickers
synergy between abrasion and corrosion [9]. hardness (Instron Wolpert, Testor 930s)] and microstructure, de-
Most studies about abrasion-corrosion resistance of stainless tails can be found in [12]. Table 3 summarizes the main mechan-
steels are mainly focused on more traditional materials, such as ical properties of the materials tested.
AISI 304 and AISI 316 stainless steels, and, more recently, on AISI For each material, samples were cut into coupons with di-
2205 duplex stainless steels. The investigation of cost effective mensions of 35x25  5 mm3 and then sanded (grit sizes of 220 and
ferritic stainless steels for those applications is often neglected. 600). After this step, they were subjected to ultrasonic cleaning in
Despite this, they have found an important application niche in acetone for 15 min and dried. All materials were tested for pure
the biofuel industry [3], which certainly involves abrasion and corrosion, pure microabrasion and microabrasion-corrosion.
corrosion. Within ferritic stainless steels, it is relevant to in-
vestigate the effect of Cr content on tribocorrosion, as well as the 2.2. Corrosion tests
effect of stabilization. The cheapest stainless steel is 11Cr (DIN
14003) and it has vast application in the sugar-cane biofuel in- A standard 2 cm2 of active area for the corrosion and abrasion-
dustry. 11CrTi (ASTM S40910) is also a low-cost ferritic stainless corrosion tests was obtained using nail varnish and wax. A copper
steel stabilized with Ti, largely used in automobile exhausts sys- wire bonded by a silver glue established the electrical contact. To
tems. 16Cr (ASTM S43000) steels are slightly more expensive fer- ensure the solidication and xation of the wax on the specimen
ritic stainless steel, mainly used in the cutlery industry, but they and consequently the reproducibility of the results, the entire
are still cheaper than austentic steels. 16CrNb (ASTM S43000) is preparation process occurred at least 8 h before each test.
the same stainless steel stabilized with Nb, used in cutlery and The electrolyte was a 1 N H2SO4 (F. Maia Ind. e Com. Ltda -
stamping. On the other hand, austenitic stainless steels, such as Brazil) solution in distilled water. A platinum gauze was the

Table 1
Industrial hot rolling and annealing conditions.

Specimen 11Cr DIN 14003 11CrTi ASTM S40910 16Cr 16CrNb ASTM S43000 18Cr8Ni AISI 304

Final hot rolling temperature (C) 10007 50 950 7 50 1000 750 950 7 50 11007 50
Annealing soaking temperature (C) 7607 50 950 7 30 780 720 930 7 20 10407 20
Annealing time 8h 30 s 8h 30 s 30 s
1300 W.S. Labiapari et al. / Wear 376-377 (2017) 12981306

Table 2 0.7
0.56
Chemical composition of the specimens.
0.59 0.60
0.6
0.53 0.51
Specimen 11Cr 11CrTi 16Cr 16CrNb 18Cr8Ni A36 0.51

Friction Coefficient
0.5
C (%wt) 0.011 0.009 0.049 0.025 0.055 0.138
Cr (%wt) 11.23 11.29 16.10 16.19 18.28 0.01 0.4
Ni (%wt) 0.31 0.12 0.27 0.19 8.01 0.01
Nb (%wt) 0.006 0.002 0.014 0.416 0.005 0.001 0.3
Ti (%wt) 0.003 0.144 0.003 0.004 0.001 0.001
N (%wt) 0.0145 0.0087 0.0528 0.0202 0.0421 0.0026 0.2

0.1
Table 3
Mechanical properties of the materials tested. 0.0
18Cr8Ni A36 16CrNb 11CrTi 16Cr 11Cr
Specimen Vickers hard- Yield stress Ultimate Elongation to Materials
ness (MPa) (MPa) stress (MPa) fracture (%)
Fig. 3. Average friction coefcients during the pure microabrasion tests.
11Cr 14917 39 323 7 6 4127 2 38 71
11CrTi 14717 29 3167 4 4007 1 40 72 area, creating a saline bridge. The anodic polarization curve was
16Cr 1638 7 10 343 7 4 488 7 3 317 2
obtained using an increasing potential rate of 1 mV/s, which gives
16CrNb 1510 710 3367 3 4477 2 36 72
18Cr8Ni 19127 29 3477 9 7067 7 62 72 a test duration of 42 min. ASTM G5-94 (2004) [13] recommends a
ASTM A36 1402 7 10 305 7 4 4457 3 34 71 rate of 0.167 mV/s, which gives a test duration of 4 h. The reduc-
tion of the test time and consequent increase in the potential
variation rate was necessary because the subsequent micro-abra-
7 100
Fraction sion corrosion tests required a test time of around 40 min.
Accumulated 90 Therefore, the use of this higher rate ensures the imposition of
6
80 equivalent electrochemical conditions in both the corrosion and
5 abrasion-corrosion tests. Moreover, the rate of 1 mV/s has already
Accumulated [%]

70
Fractoin [%]

been used in other works [9,1416] or even higher values (2 mV/s)


60
4 as reported by Perret et al. [17].
50 For each condition tested, at least 3 repetitions were performed
3
40 to ensure the reproducibility of the results and the same applies to
30 the subsequent pure microabrasion and microabrasion-corrosion
2
tests.
20
1
10
2.3. Micro-abrasion tests
0 0
0.00
0.49

0.67
0.78
0.91
1.06
1.24
1.44

1.95
2.28
2.65
3.09

4.19

5.69
6.63
7.72
9.00
0.58

1.68

3.60

4.88

12.21
10.48

The so-called pure abrasion tests were carried out in a specially


Granulometry [mm] designed hybrid equipment, which allows both pure microabra-
sion and micro-abrasion-corrosion tests to be carried out. The test
Fig. 1. SiO2 particle size distribution analyzed by laser granulometry and abrasive
morphology by SEM.
rig consists of a xed-ball micro-abrasion tester, where the spe-
cimen is supported by a three-axis load cell, enabling the mea-
counter electrode and a saturated calomel electrode (SCE) was the surement of forces and moments acting on the contact. This test
reference electrode. The corrosion tests were carried out using a rig is well described in a previous paper [18].
Abrasive slurries composed of silica (SiO2) particles (Sigma-
potentiostat/galvanostat model Biologic SP150. During the tests,
Aldrich) suspended in distilled water, at a concentration of
the specimens were partially submerged in the solution. The same
10 g cm  3, were used. Distilled water can be considered as a
solution was then pumped at a rate of 1.7 ml/min over the exposed
neutral medium, leading to negligible corrosion of stainless steels,

2.0 10000
11Cr
3,030.0 3,158.7
11CrTi
1.5 16Cr
Potential [V] vs. SCE

16CrNb 1000
Ip [mA/cm2].10-3

1.0 18Cr8Ni
A36
0.5 100
35.7
0.0 19.8
11.5
10
-0.5

-1.0 1
1.E-05 1.E-03 1.E-01 1.E+01 1.E+03 18Cr8Ni 16Cr 16CrNb 11Cr 11CrTi
Current Density [mA/cm2] Materials
-a- -b-
Fig. 2. Abrasion behaviour. a- Typical potentiodynamic polarization curves. b- Average passivation current density.
W.S. Labiapari et al. / Wear 376-377 (2017) 12981306 1301

60 60

50 50

k [m3/N.m].10-15
k [m3/N.m].10-15
40 40

30 30

20 20 Test 1
Test 2
Test 1 Test 3
10 Test 2 10
Test 3
0 0
0 3 6 9 12 15 18 21 24 27 30 33 0 3 6 9 12 15 18 21 24 27 30 33
Time [min] Time [min]
-a- -b-
Fig. 4. Examples of the evolution of the micro-abrasive wear coefcient k with time: (a) 11Cr, (b) 11CrTi.

20 in the abrasioncorrosion tests. For that, an electrolyte of 1 N


18 17.3 H2SO4 instead of distilled water was used in the abrasive slurry at
16 13.6 the same abrasive concentration (10%wt. SiO2 4.5 mm).
To minimize the effect of transients, the abrasioncorrosion
14
k [m3/N.m].10-15

12.7
tests were performed only after the abrasion process reached a
12 11.3
10.2 steady state condition. For that, the tests started without applying
10 9.0 any external potential difference during 15 min. The use of the
8 corrosive slurry assured a pickling process that was able to remove
6
the passive layer. This initial time of 15 min was established as the
time necessary to reach a steady-state abrasion condition under
4
pure microabrasion conditions, as it will be shown in the Results
2 section.
0 After that, a potentiodynamic corrosion test was triggered, so
A36 11CrTi 11Cr 16CrNb 16Cr 18Cr8Ni
that a micro-abrasion-corrosion test could be carried out. The
Materials conditions for the potentiodynamic scan were identical to those
Fig. 5. Average wear coefcients k. used in the pure corrosion tests.
In order to verify whether corrosion occurs mainly in the wear
so that the microabrasion tests carried out using this abrasive crater, after the abrasion-corrosion test, one sample (11Cr) was
slurry were considered pure microabrasion tests [18]. The granu- immersed in a solution containing potassium ferricyanide, which
lometric distribution of the abrasive particles, determined by laser helps to evidence the corrosion products. In fact, the corrosion
granulometry (Malvern Instruments - Mastersizers), is shown in products ow from the wear crater, evidencing that corrosion and
Fig. 1, where the abrasives have semi angular shape and an abrasion indeed occur in the same location [12].
asymmetric normal size distribution, mean particle size of After the tests, the surfaces were investigated by optical mi-
3.4 70.2 mm, 85% of the particles with diameter between 1 and croscopy and scanning electron microscopy (SEM- Philips, XL-30s)
10 mm. to identify wear mechanisms.
The counter body used was a zirconia ball (S Esferas- Brazil)
with diameter 25.4 mm. As reported by some authors [20] and
quantied by Costa et al. [21], the ball roughness strongly inu- 3. Results and discussion
ence the wear mechanisms and wear rates. In order to maintain
this inuence negligible, the arithmetic surface roughness (Ra) was 3.1. Corrosion tests
controlled and kept in the range 0.32 mm o Ra o0.38 mm. The ro-
tary speed was set to 150 rpm, and the normal load was set to Fig. 2 synthesizes the corrosion behaviour of the materials in-
1.42 N. vestigated in this work. In Fig. 2-a, typical potentiodynamic po-
For each test, wear coefcients (k) were calculated as k (b4 larization curves for all studied steels are illustrated. Different
/64R)/(s.N), where b is the diameter of the wear scar, R is the repetitions for each material tested showed very stable and re-
sphere radius, s is the sliding distance and N is the normal load, as producible results, so that for clarity only one curve is presented
proposed in [19]. The tests were interrupted at every 3 min to for each material. Fig. 2-b presents the average value of the pas-
evaluate the evolution of k with time. After the tests, the spherical sivation current density for the stainless steels. The arrow in this
shape of the wear craters was veried by 3D laser interferometry, gure indicates that materials with lower passivation current
since this equation for k only applies to spherical craters. densities exhibit higher corrosion resistance. There is a strong
inuence of the Chromium content on the passivation current
2.4. Micro-abrasion-corrosion tests density and the shape of the passivation curves. The higher Cr
content (18Cr8Ni steel) induced the lower passivation current
The microabrasion tests were carried out using the electro- whereas the higher passivation currents corresponded to the
chemical cell present in the same hybrid equipment used for the lower Cr content regardless of the stabilization by Ti (11CrTi and
pure abrasion tests. The same imposed parameters used for the 11Cr). The effect of stabilization by Nb on current density was also
separate abrasion and corrosion tests were applied simultaneously negligible for the intermediate Cr content, 16%wt [22]. The low
1302 W.S. Labiapari et al. / Wear 376-377 (2017) 12981306

Fig. 6. SEM of wear craters after the pure abrasion tests: (a) A36 (b) 18Cr8Ni (c) 16Cr.

Removed B m
Material 1.2 m Profile BB
0.2
1.0
Height

0
0.8 -0.2 Removed
0.6 -0.4 Material
0.4 -0.6
83.5 m
1.3 m -0.8
0.2
0 10 20 30 40 50 60 70 80 m
0.0 Length [m]
B 35.2 m
-a- -b-
Fig. 7. Topographic analysis of the wear craters evidencing large portions of material removal, 18Cr8Ni: (a) 3D map and (b) 2D prole.

carbon steel (A36) did not exhibit passivation in this medium, as Average wear coefcients were calculated for each material. To
normally reported in the literature [23,24]. compute the average values, all points in the steady-state regime
(after 15 min of test) for each repetition (3) were used, which gives
3.2. Micro-abrasion tests 18 values for each material. Fig. 5 summarizes the average wear
coefcients k obtained.
Due to the use of the 3D load cell, friction coefcients could be The ferritic steels showed higher abrasion resistance than the
obtained during the tests. Average friction coefcients were low carbon steel A36. The best performance was presented by the
computed for each material (Fig. 3). austenitic stainless steel. Attempts were carried out to correlate
No signicant difference was detected between the friction wear coefcients with hardness and some microstructural char-
coefcients presented by the different materials. acteristics, such as grain size, but no clear pattern was identied.
Fig. 4 exemplies the evolution of the microabrasion wear Fig. 6 shows SEM images of some selected wear craters pro-
coefcient k with time for two of the materials tested. It shows duced after the microabrasion tests. In all tests the prevailing
that after a transient period of around 15 min, a steady-state re- mechanism was the sliding of the abrasive particles (grooving)
gime is achieved. This initial transient period during microabra- [27]. It is noteworthy the detachment of large portions of material
sion tests has been widely reported in many other works for the carbon steel (A36, Fig. 6-a) and for the austenitic stainless
[21,25,26]. Similar behaviour was observed for all the materials steel (18Cr8Ni, Fig. 6-b), indicated by arrows. Similar localized
tested. removal did not occur for the ferritic stainless steels (Fig. 6-c),
W.S. Labiapari et al. / Wear 376-377 (2017) 12981306 1303

2.0 2.0
18Cr8Ni: Aerated - Turbulent 16CrNb: Aerated - Turbulent
18Cr8Ni: Abrasion - Corrosion 16CrNb: Abrasion - Corrosion
1.5 1.5

Potential [V] vs. SCE


Potential [V] vs. SCE
1.0 1.0

0.5 0.5

0.0 0.0

-0.5 -0.5

-1.0 -1.0
1.E-06 1.E-04 1.E-02 1.E+00 1.E+02 1.E-06 1.E-04 1.E-02 1.E+00 1.E+02
Current Density [mA/cm2] Current density [mA/cm2]

-a- -b-
1.0
0.9 Abrasion
Abrasion-Corrosion
0.8
Friction Coefficient

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 30 60 90 120 150 180
Time [s]
-c-
Fig. 8. Typical results for the microabrasion tests. (a) potentiodynamic curve, 18Cr8Ni, (b) potentiodynamic curve, 16CrNb. (c) Evolution of friction coefcient with test time,
18Cr8Ni.

90 0.8
Abrasion 81.3 Abrasion
80 0.7 Abrasion-Corrosion
Abrasion-Corrosion
70 63.5 0.59 0.60
Friction Coefficient

0.6
k [m3/N.m].10-15

0.53 0.51 0.55


60 0.52
50.6 0.5
50 0.33
42.0 0.4
40 36.7 0.28 0.31 0.34
33.9 0.26 0.27
0.3
30

17.3 0.2
20
13.6 12.7 11.3 10.2 9.0
10 0.1

0 0.0
A36 11CrTi 11Cr 16CrNb 16Cr 18Cr8Ni A36 11CrTi 11Cr 16CrNb 16Cr 18Cr8Ni
Materials Materials
-a- -b-
Fig. 9. Evaluation of (a) wear rate coefcient k, and (b) friction coefcient in pure micro-abrasive and micro-abrasive-corrosive environment.

which showed lower wear coefcients than the carbon steel and whole potential range investigated (42 min) was longer than the
the austenitic stainless steel. A 3D topographic assessment of the transient period in the pure microabrasion tests (15 min), so that
worn surfaces by laser interferometry (Fig. 7) conrms that the the nal portion of the test should occur after a steady-state wear
regions indicated by arrows correspond indeed to areas with in- regime was achieved. First, it was observed for all material an
tense material removal. increase in the passivation current density when compared with
the pure corrosion tests. The curves obtained for pure corrosion
3.3. Micro-abrasion-corrosion test are again presented in this gure for comparison. In the literature
[2,7,28], this increased passivation current density Ip observed in
Fig. 8-a and Fig. 8-b shows some selected potentiodynamic abrasion corrosion tests is attributed to a competition between of
curves obtained during the microabrasion-corrosion tests. It the removal of the passive layer and repassivation. In our tests, the
should be again pointed out that the time necessary to scan the current density showed a slight increase in the passivation
1304 W.S. Labiapari et al. / Wear 376-377 (2017) 12981306

or accelerating repassivation. The exact mechanism still needs to


be elucidated and should be a niche of further research.
Fig. 9-b compares the average friction coefcients of each
material measured during the pure abrasion and the micro-abra-
sion tests. No signicant difference was observed between the
different materials, which was conrmed by Analysis of Variance
(ANOVA). This gure conrms the lower friction coefcients under
abrasion-corrosion conditions when compared with pure
microabrasion.
When Wu et al. [30] measured the friction coefcient of AISI
304 stainless steel during sliding corrosion tests (fretting condi-
tions) using H2SO4 solution, they found friction coefcients be-
tween 0.25 and 0.3, which is the same range found here under
microabrasion-corrosion conditions.
Fig. 10. FTIR analysis of 11Cr steel before and after immersion in 1 N H2SO4
According to Kolesnichenko et al. [31], the formation of FeSO4
solution.
in tribocorrosive systems containing sulfuric acid is the main
factor responsible for the reduction of the friction coefcient. Re-
region, i.e. a less effective repassivation occurred.
ciprocating sliding-corrosion tests of iron also showed a reduction
Fig. 8-c exemplies, for the stainless steel, a comparison be-
tween friction coefcients obtained during pure abrasion and of the friction coefcient when sliding in H2SO4 solutions when
abrasion-corrosion tests. Under abrasion-corrosion conditions the compared with pure sliding tests using water [32]. Rowson and
friction coefcients obtained were substantially lower. Similar Azouz [33] associated friction reduction to the formation of FeSO4
behaviour was observed for the other materials tested. as an extreme pressure agent to the contact. We had tried, using
Average wear coefcients were calculated for the microabra- FTIR, to detect the presence of FeSO4 in the wear scars. It was
sion-corrosion tests using the same methodology described for the impossible to detect any variation by comparing the spectrum
pure microabrasion tests. Fig. 9-a presents the values obtained, obtained outside and within the wear mark. In fact, the instrument
which for comparison also presents the values obtained under indicated that the bands were very weak and therefore unreliable.
pure microabrasion conditions. The thickness of FeSO4 lms formed on iron surfaces in the
The rst strong fact evidenced by this gure is the substantially presence of H2SO2 was measured by Auger microscopy in the lit-
lower wear coefcient (38  lower) observed under microabra- erature as around 3 nm [34]. Therefore, it is difcult to identify this
sion-corrosion conditions when compared with pure microabra- lm, but it induces signicant smoothening of the surface. In
sion conditions. A similar tendency was also observed using NaCl presence of a H2SO4 solution as electrolyte, iron dissolution leads
solutions by Bateni et al. [29] for AISI 304 stainless steels and AISI to the formation of FeSO4 on the metallic surface, as indicated by
1045 carbon steel and by Sinnett-Jones et al. [14] for AISI 304 the reaction shown in Eq. (1).
stainless steels. This behaviour was associated to the change in the Fe(s) + H2 SO4 (aq) FeSO4 (aq) + H2 (g) (1)
repassivation kinetics due to the presence of the corrosive media
and to the external application of a potential difference. To demonstrate the formation of this lm, a 11Cr steel sample
The comparative behaviour between the different materials was immersed in a 1 N H2SO4 solution at room temperature for
was very different from that observed under pure abrasion con- 1 h. Then the sample was subjected to FTIR analysis, Fig. 10.
ditions, where the austenitic stainless steels had presented the The FTIR spectrum identied humidity bands in the region
worst behaviour. Under abrasion-corrosion conditions, the in- between 3570 and 2940 cm  1 and 1650 cm  1, and more im-
crease in Chromium content resulted in a steady reduction of the portantly, it conrmed the formation of FeSO4 in the region be-
wear coefcient. Higher Cr contents increase the stability of the tween 1168 and 1068 cm  1.
passive lm in most corrosive environments [22]. Under abrasion- In order to verify the kinetics response of the effects of corro-
corrosion conditions, the passive lm stability seems to govern the sion on friction coefcient, two further test sequences were car-
behaviour of stainless steels [6,14]. The increase in Cr content ried out. In the rst, the abrasion-corrosion test started using a
could improve the lm stability by either hindering depassivation slurry of abrasive and water, which was then changed to a slurry of

Fig. 11. Friction coefcients measured during microabrasion-corrosion tests of 18Cr8Ni:(a) started with water slurry and replaced by 1 N H2SO4 slurry; (b) started with 1 N
H2SO4 slurry and replaced by water slurry.
W.S. Labiapari et al. / Wear 376-377 (2017) 12981306 1305

Fig. 12. Analysis by SEM of the surfaces of steel samples after testing 18Cr8Ni: (a) micro-abrasion-corrosion and (b) micro-abrasion test.

4000 scars for all the materials tested under pure microabrasion and
Microhardeness HV0.05 [MPa]

Before test
3500
microabrasion-corrosion conditions. The results are shown in
Abrasion 3255
2972
2972 Fig. 13.
Abrasion - Corrosion 2810
3000 First, all the samples showed an increase in hardness when
2527
2500 2400 2363 2363
compared with microhardness of the samples before the tests.
2145 2301
2143 2186 2186
2143 Strain hardening is a common phenomenon during abrasion of
1971 1971
2000 1842 1842 metals and has been vastly reported in the literature [35]. How-
1500
ever, strain hardening was less intense under abrasion-corrosion
conditions than under pure abrasion conditions. Comparing pure
1000 microabrasion, which is mechanically dominated, with abrasion-
500
corrosion, less energy is used in mechanical phenomena such as
strain hardening. This agrees with the lower friction values mea-
0 sured under abrasion-corrosion than under pure abrasion, since
A36 11CrTi 11Cr 16CrNb 16Cr 18Cr8Ni
Materials abrasion-corrosion only needs frictional energy for the mechanical
removal of passive lm, but not for the tribocorrosion of the active
Fig. 13. Micro hardness Vickers HV0,05 at the samples of the material measured areas.
within the wear scar before and after micro-abrasion and micro-abrasion-corrosion
test.

abrasive in 1 N H2SO4 solution. In the second, the abrasion-cor- 4. Conclusions


rosion test started using a slurry of abrasive in 1N H2SO4 solution,
which was then changed to a slurry of abrasive and water. The Abrasion-corrosion of stainless steels was assessed using xed-
results are shown in Fig. 11. Both curves show a short interval ball microabrasion tests with 1 N H2SO4 solution slurry and si-
between the two situations that corresponds to the time necessary multaneous imposition of potentiodynamic curves. The results
to remove the test load and change the slurry. When H2SO4 is showed that:
added to the slurry (Fig. 11-a), the lm seems to form very
1. The mechanical effects of turbulence and abrasion accelerate
promptly, reducing friction coefcient. In Fig. 11-b, abrasion re-
the corrosion process, mainly evidenced by increase in the
moves the lm, which is not restored in the absence of H2SO4,
passivation current density.
causing friction to increase.
2. Although the austentic stainless steel stainless steel (18Cr8Ni),
We believe that the FTIR technique does not present sufcient
with the highest Cr content within the materials tested, showed
sensitivity and is therefore not suitable for the detection of FeSO4
the worst performance under pure abrasion conditions, it pre-
in the wear marks produced by abrasion-corrosion. More sensitive
sented the best performance in the microabrasion-corrosion
techniques such as Auger Microscopy, XPS and TOF-SIMS are ne- tests. Under abrasion-corrosion conditions, the tribological
cessary and will be used in further investigations. performance improved with the increase in Cr content.
Fig. 12 compares for the austenitic stainless steel the wear 3. The test rig allowed the measurement of friction coefcients
crater produced after abrasion-corrosion (Fig. 12-a) with that during microabrasion tests. This allowed to detect a reduction in
produced after pure abrasion (Fig. 12-b). This gure shows that friction coefcient during abrasion-corrosion conditions when
abrasion-corrosion leads to the formation of a signicantly compared with pure abrasion tests. Friction reduction was at-
smoother surface, which gives lower friction. On this way, it was tributed to the presence of FeSO4 as a corrosion product, which
observed the smoother surface, Fig. 12-a compared to Fig. 12-b, as was conrmed by FTIR analysis.
a consequence of low friction coefcient. 4. Microhardness Vickers measurements inside the wear scars
The reduction of friction coefcient under microabrasion cor- showed a less intense strain hardening under abrasion corr-
rosion conditions decreases the amount of mechanical energy that osion conditions than under pure abrasion conditions. This
is dissipated in the active interface in the form of friction. Vickers is probably due to the reduction in the energy dissipated as fric-
microhardness measurements were carried out inside the wear tion in the contact and therefore available for plastic deformation.
1306 W.S. Labiapari et al. / Wear 376-377 (2017) 12981306

Acknowledgements 452460.
[16] H.B. Lee, D.S. Wuu, C.Y. Lee, C.S. Lin, Wear and immersion corrosion of NiP
electrodeposit in NaCl solution, Tribol. Int. 43 (2010) 235244.
The authors would like to thank Capes/Proex, CNPq (Gant [17] J. Perret, E. Boehm-Courjault, M. Cantoni, S. Mischler, A. Beaudouin, W. Chitty,
477286/2011-9), CBMM S.A. (Grant FEMEC01-2011) and Fapemig J.P. Vernot, EBSD, SEM and FIB characterisation of subsurface deformation
for nancial support. during tribocorrosion of stainless steel in sulphuric acid, Wear 269 (2010)
383393.
[18] M.B. Santos, W.S. Labiapari, M.A.N. Ardila, W.M. da Silva Jr, J.D.B. de Mello,
Abrasioncorrosion: new insights from force measurements, Wear 332333
References (2015) 12061214.
[19] D.N. Allsopp, R.I. Trezona, I.M. Hutchings, The effects of ball surface condition
in the micro-scale abrasive wear test, Tribol. Lett. 5 (1998) 259264.
[1] M.M. Stack, K. Chi, Mapping sliding wear of steels in aqueous conditions, Wear
[20] P.H. Shipway, The role of test conditions on the microabrasive wear behaviour
255 (2003) 456465.
of soda-lime glass, Wear 233 (1999) 191199.
[2] M.M. Stack, H. Jawan, M.T. Mathew, On the construction of micro-abrasion
[21] H.L. Costa, M.A.N. Ardila, W.S. Labiapari, W.M. Silva, J.D.B. de Mello, Effect of
maps for a steel/polymer couple in corrosive environments, Tribol. Int. 38
surface topography on the dynamics of the abrasive particles during micro-
(2005) 848856.
[3] W.S. Labiapari, C.M. Alcntara, H.L. Costa, J.D.B. de Mello, Stainless steel as an abrasion, Wear 324325 (2015) 129139.
antiwear material for the bio-fuel industry, Wear 302 (2013) 15361545. [22] A.J. Sedriks, Corrosion of Stainless Steels, Wiley-Interscience Publication, New
[4] D. Landolt, S. Mischler, M. Stemp, S. Barril, Third body effects and material York, 1996.
uxes in tribocorrosion systems involving a sliding contact, Wear 256 (2004) [23] Y.F. Cheng, J. Bullerwell, F.R. Steward, Electrochemical investigation of the
517524. corrosion behavior of chromium-modied carbon steels in water, Electrochim.
[5] V. Vignal, N. Mary, P. Ponthiaux, F. Wenger, Inuence of friction on the local Acta 48 (2003) 15211530.
mechanical and electrochemical behaviour of duplex stainless steels, Wear [24] J.A.L. Dobbelaar, E.C.M. Herman, J.H.W. de Wit, The corrosion behaviour of
261 (2006) 947953. iron-chromium alloys in 0.5 M sulphuric acid, Corros. Sci. 33 (1992) 765778.
[6] J.O. Bello, R.J.K. Wood, J.A. Wharton, Synergistic effects of micro-abrasion [25] W.M. da Silva, R. Binder, J.D.B. de Mello, Abrasive wear of steam-treated sin-
corrosion of UNS S30403, S31603 and S32760 stainless steels, Wear 263 tered iron, Wear 258 (2005) 166177.
(2007) 149159. [26] J. D. B de Mello, A. A. Polycarpou, Abrasive wear mechanisms of multi-com-
[7] R.J.K. Wood, D. Sun, M.R. Thakare, A. de Frutos, Rozas, J.A. Wharton, Inter- ponents ferrous alloys abraded by soft, ne abrasive particles, Wear, 269,
pretation of electrochemical measurements made during micro-scale abra- 2010, 911-920.
sion-corrosion, Tribol. Int. 43 (2010) 12181227. [27] R.I. Trezona, D.N. Allsopp, I.M. Hutchings, Transitions between two-body and
[8] D. Sun, J.A. Wharton, R.J.K. Wood, Micro-abrasion mechanisms of cast CoCrMo three-body abrasive wear: inuence of test conditions in the microscale
in simulated body uids, Wear 267 (2009) 18451855. abrasive wear test, Wear 225 (1999) 205214.
[9] M.R. Thakare, J.A. Wharton, R.J.K. Wood, C. Menger, Exposure effects of alka- [28] F. Ferrer, H. Idrissi, H. Mazille, P. Fleischmann, P. Labeeuw, A study of abrasion
line drilling uid on the microscale abrasioncorrosion of WC-based hard- corrosion of AISI 304L austenitic stainless steel in saline solution using
metals, Wear 263 (2007) 125136. acoustic emission technique, NDT E Int. 33 (2000) 363371.
[10] M.R. Thakare, J.A. Wharton, R.J.K. Wood, C. Menger, Investigation of micro- [29] M.R. Bateni, J.A. Szpunar, X. Wang, D.Y. Li, The effect of wear and corrosion on
scale abrasioncorrosion of WC-based sintered hardmetal and sprayed coating internal crystalline texture of carbon steel and stainless steel, Wear 259
using in situ electrochemical current-noise measurements, Wear 267 (2009)
(2005) 400404.
19671977.
[30] P.-Q. Wu, J.P. Celis, Electrochemical noise measurements on stainless steel
[11] A.J. Gant, M.G. Gee, A.T. May, The evaluation of tribo-corrosion synergy for
during corrosionwear in sliding contacts, Wear 256 (2004) 480490.
WCCo hardmetals in low stress abrasion, Wear 256 (2004) 500516.
[31] L.F. Kolesnichenko, P.V. Trushko, Formation of boundary layers during friction
[12] W.S. Labiapari, Abrasion-Corrosion of Ferritic Stainless Steels (Doctoral Thesis),
in the presence of sulfur, Sov. Powder Metall. Met. Ceram. 9 (1970) 993997.
Universidade Federal de Uberlandia 2015, p. 186, p, Uberlandia, MG, Brazil (in
[32] K. Miyoshi, Studies of mechanochemical interactions in the tribological be-
Portuguese).
[13] ASTM, Standard Reference Test Method for Making Potentiostatic and Po- havior of materials, Surf. Coat. Technol. 43 (1990) 799812.
tentiodynamic Anodic Polarization Measurements, G5-94, 2004. [33] D.M.Rowson, A.Azouz, An investigation of extreme pressure lms formed
[14] P.E. Sinnett-Jones, J.A. Wharton, R.J.K. Wood, Micro-abrasioncorrosion of a during wear test, Vacuum 31 (1981) 593596.
CoCrMo alloy in simulated articial hip joint environments, Wear 259 (2005) [34] S. Mischler, E. Rosset, G.W. Stachowiak, D. Landolt, Effect of sulphuric acid
898909. concentration on the rate of tribocorrosion of iron, Wear 167 (1993) 101108.
[15] I. Garc a, D. Drees, J.P. Celis, Corrosion-wear of passivating materials in sliding [35] K.L. Zum Gahr, Microstructure and Wear of Materials, Tribology Series 10,
contacts based on a concept of active wear track area, Wear 249 (2001) Elsevier, Amsterdam, 560p, 1987.