Corrosion Science, Vol. 26, No, 8, pp. 647-653, 1986 0010-938X/86 $3.00 + 0.

00
Printed in Great Britain Pergamon Journals Ltd.
WEAR-CORROSION MECHANISM OF STAINLESS STEEL
IN CHLORIDE MEDIA
H. ABD-EL-KADER and S. M. EL-RAGHY
Faculty of Engineering, Cairo University, Cairo, Egypt
Abstract--A laboratory technique to study the combined effects of mechanical and electrochemical
changes during a wear process in a corroding environment is presented. Cathodic protection is beneficial
because it stops corrosion, and the wear is merely mechanical. At anodic potentials, chemical reactions
lead to a wear rate almost twice the wear rate under cathodic protection. The difference between the two
levels represents the rate of corrosive wear. A model is proposed for the corrosive wear based on the film
growth rate and the rate of removal of the oxide layer. Experimental results verify this model.
INTRODUCTION
CORROSIVE wear takes place when an active environment produces a reaction product
on one or both of the rubbing surfaces and this reaction product is subsequently
removed by rubbing.1 The reaction products are, commonly, poorly adherent to the
surfaces, and further rubbing causes their removal. This corrosive wear requires both
corrosion and rubbing. The rate of growth of, for example, an oxide film on a steel
will decrease with time, and therefore unless the oxide film is removed by rubbing,
the oxidation of metal will rapidly become negligibly small.
It has been reported that the ability to re-form a surface oxide film is an important
factor in controlling the combined effects of the rubbing wear and corrosion on a
newly generated metal surface. 2-5
Corrosive wear of metals is encountered in many industries. In mineral processing,
wet grinding doubles the rate of grinding media consumption) The same
observation was noticed in a pilot investigation on the wear of grinding balls in a
tumbling mill. 7 Slurry transportation causes severe damage of the steel pipes due to
the joint effect of solid and liquid moving in the tube. s The same effect is observed
with moving parts of machines lubricated with oil containing an entrained aqueous
phase. 9
As an extension to our previous work, 1° this paper outlines a study directed to the
application of electrochemical techniques in the evaluation of abrasive and corrosive
wear.
EXPERIMENTAL METHOD
The apparatus used for continuous abrading of the electrode surface under potentiostatic control was
developed in our laboratory and has been described in detail in other papers. H.~2 The disc electrodcs used
were made from an annealed 18Cr-10Ni stainless steel. Solutions were made of AR grade NaCI and
NaOH in distilled water.
The stainless steel specimen was abraded under potentiostatic control. A Wenking Potentioscan
Model POS. 73 was used. The scanning range was from - 1400 or - 1200 to - l tl0 mV(SCE). The potential
Manuscript received 29 January 1985; in amended form 24 March 1986.
647
648 H. ABD-EL-KADER and S. M. EL-RAGHY
FIG. 1.
Vs 236 cm / sec. 2 = • • ~ •
"~' 3 u O
x __ v= ~_• • • /__/~____C ORROSi IV WEAR
7vv
C/ . . . . . . . . . . . . . .

I MECHANICAL WEAR
I , I ~ I L I i I ~ I -1200 -I000 -800 -600 -400 -200
E m¥
Wear rate vs potential in 1% NaCI, pH = 6.35 at normal loads of(D, 17.9; (1, 35.8;
V,53.7; A,71.6;O, 89.6gcm -2.
was made more positive in steps of 100 mV for 5 min. The wear rate and the current were recorded. UnLess
otherwise stated, potentials are referred to the saturated calomel electrode (SCE).
The surface topography was examined with a talysurf, Homel Tester T2-Germany.
EXPERIMENTAL RESULTS
Potentiostatic control and wear rate measurements
A series of wear rate measurements on stainless steel in different solutions and
various concentrations and pH values is presented in Figs 1 and 2. The wear rate
values shown represent the fitted values by the least square method. The figures show
an increase in the wear rate in the potential ranges -750 + 100 to -550 + 50
mV(SCE) and -1050 _+ 50 to -825 mV(SCE) in solutions of pH values 6.35 and
13.25, respectively. The upper limit potentials -550 _+ 50 and -825 mV(SCE)
correspond closely to the potentials at which Tafel slopes deviated toward higher
values. 12 It was stated that a surface film of appreciable coverage should be formed.
This gives evidence in support of the conclusion that continual rupture of the film
layer leads to corrosion.
Thermodynamic considerations
Possible reactions are the formation of oxides (for simplification iron oxides are
considered) according to: ~3
Erev. mV(SCE) Erev. mV(SCE)
pH 6.35 pH 13.25
Fe/FeO -663 - 1071 (1)
Fe/Fe304 - 700 - 1109 (2)
Fe/Fe20 3 - 667 - 1075 (3)
Fe/Fe (OH)2 -663 - 1071. (4)
Under dynamic conditions or rubbing, reaction (4) is favoured in the early stages
of film formation. 14 16 This reaction leads to repassivation of the abraded electrode.
Wear-corrosion mechanism of stainless steel in chloride media 649
Fie,. 2,
o
x
uE
o
c. u
i
i
-1400

S
IIItIrILI,IL
-I000 -600 -200
E my
w

Wear rate vs potential at V, = 236 cm s t, and normal load of 71.6 gcm -'. C), 3, 6
and 10% NaCI, pH = 6.35; O, 0.2 M NaOH or 3% NaCI, pH = 13.25.
The passive state will only exist for a short time due to continual abrading.
Accordingly, the corrosion will proceed as long as rubbing is taking place. ]7
The lower wear rate shown in Figs 1 and 2 at potentials <-750 + 100 mV(SCE)
for solutions of pH 6.35 and <-1050 + 50 mV(SCE) for solutions of pH 13.25
represents purely mechanical wear, since in this region the steel is cathodically
protected. Apparently, this type of wear is independent of potential.
At higher potentials >550 + 50 and -825 mV(SCE) the wear rates were found
to be independent of potential. In the static oxidation, the oxide film formed would
act as a barrier between the base metal and the electrolyte, and the rate of oxidation
would slow down. In the dynamic case, however, the oxide layer is rubbed away
almost immediately. The oxidation rate is therefore always at its initial high value .4
The independence of the corrosive wear rate of potential in this range suggests that a
layer-rupturing action, which is constant at fixed conditions of abrasion, has become
rate controlling for the corrosive wear. Accordingly, the layer-repairing process is
also independent of potential. ]7
At the most noble potentials, where the corrosion reaction would occur, the wear
rates reached a constant higher level almost twice the wear rate level below the
characteristic potential. The difference between the two levels represents the rate of
corrosive wear.
An attempt to determine the corrosive wear from current-potential measurements
is shown in Fig. 3. An assumption was made that the total anodic current
density passed through the circuit is consumed in the active dissolution of the metal
as Fe 2+. The Faradaic equivalent of the total anodic current passed was calculated to
be electrochemical corrosion (the hatched area in Fig. 3). The electrochemical
corrosion at -200 mV(SCE) is less than 7% of the total wear.
A profilometric trace of the abraded surfaces shows typical grooves and ridges
(Fig. 4). Since the abrading particles only penetrate a fraction of their diameter, the
groove widths shown are a measure of the minimum particle size. There are spaces
between the abrading particles. The surfaces' roughness increased by load.
DISCUSSION
A model is proposed based on a theoretical analysis to show the relative
importance of the rate of oxidation and the rate of remowd of the oxide layer. This
650 H. ABD-EL-KADER and S. M. EL-RAGHY
FIG. 3.

T
~o 3 WEAR
x
CORROSIVE 9
i
~2
N
MECHANICAL
,~. I WEAR
!
Ii~iIiIiI~I
-1200 -800 -400
E my
Wear rate vs potential in ! % NaC], pH = 6.35 at V s = 236 cm s-1 and normal load
of 71.6 g cm-;. Hatched area represents the electrochemical corrosion.
will be applied to experimental wear data, making the assumption that all of the
corrosive wear proceeded by a corrosion mechanism and rubbing, and that all the
mechanical wear was due to cutting by abrasive particles. The experimental evidence
makes this assumption justifiable.
Theoretical model
Corrosive wear is assumed to proceed by successive stages of build-up and
removal of oxides on the rubbing surface. 18 The proposed model is shown in Fig. 5.
The model assumes a gradual growth of the oxide layer which is removed instantaneously
by the rubbing action when a certain depth (AS) is reached.18'19 A continuous
curve of the wear is shown in Fig. 6.
0,22 #rn
2 029
0.4
0.49
0.51
300
5 I.um
FIG. 4. A profilometric trace of a surface with a talysurf, at various normal loads. 1, 17.9;
2, 35.8; 3, 55.7; 4, 71.6 g cm -2 in 1% NaCI, pH = 6.35; 5, 71.6 g cm 2 in 0.2 M NaOH,
pH = 13.25.
Wear-corrosion mechanism of stainless steel in chloride media 651

OXIDER EMOVAL
TIME
FIG. 5. Theoretical model for corrosive wear.
The oxidation rate follows a logarithmic iaw,ll'2° and this may be written as: 21'22
A~ = CI log t + C2 (5)
where A6 is the increase in film thickness, C1 is the logarithmic rate constant, C2 is
constant and t is the time. By differentiating equation (5):
d6 CI
--- (6)
" dt 2.303t
or
d6
- - - C,. (7)
d log t
Since AS is very small, the step function of wear rate can be linearized as shown
in Fig. 6 with a slope which is approximated to the slope of the logarithmic segment,
at points of intersections, so that:
dS d6
- (8)
dt dt
The wear depth can be represented by:
AS = kt. (9)
Since at t = 0, AS = 0, i.e. the line passes through the origin:
dS
.-. -- = k. (lO)
dt
FIG. 6.
o')

Lb~IEAR ~ /
APPROXlMATIO~Eo~
/OGARIT:~ °VAL
OXIDATION
Tilde l
Linear approximation of oxidation model for corrosive wear.
652 H. ABD-EL-KADER and S. M. EL-RAGHY
7
II
Z
0
e~
<
Z<
0
Z
0
O'
0
Z r,
0
Z
0
<
0
en
Z
<
<
N
0
0
Zm
m
Z
0
N<
M
0

o
×
t~
<1
0
0
0

~x
'N eZ
<
e'~
0
¢0aO

z~
~~z~
zzzzz~z
Wear-corrosion mechanism of stainless steel in chloride media 653
From equations (6), (8) and (10):
... k- C1 (11)
2.303t
... kt = 0.43CI. (12)
Substitute the value of kt from equation (9) in equation (12):
... AS = 0.43C1. (13)
C1 was determined from the oxide growth rate by open-circuit potential.ll Since
every cm depth of oxide as Fe(OH)2 -= 0.267 cm depth of metal, 21 the right hand side
of equation (13) must be multiplied by the conversion factor 0.267, to determine the
depth of metal lost as oxide. Equation (13) becomes:
AS = 0.43C1 x 0.267 = 0.1G (14)
where AS is the wear rate/1 cm sliding distance. The data of Table 1 confirm the
proposed model.
CONCLUSIONS
1. At anodic potentials, an oxide film is formed and the wear rate is almost twice
the wear rate under cathodic protection. The difference between the two levels
represents the rate of corrosive wear.
2. The total wear rate is an additive product of the mechanical and corrosive
wear.
3. Corrosive wear is mainly due to surface oxide film formation.
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