International Journal of Mineral Processing, 22 (1988) 361-380 361

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

L a b o r a t o r y A b r a s i o n a n d E l e c t r o c h e m i c a l Test
M e t h o d s as a M e a n s o f D e t e r m i n i n g M e c h a n i s m
a n d R a t e s of C o r r o s i o n a n d W e a r in B a l l Mills

C.H. PITT, Y.M. CHANG, M.E WADSWORTH and D. KOTLYAR

Metallurgy Department, University o[ Utah, Salt Lake City, UT 84112 (U.S.A.)
(Received December 24, 1985; accepted after revision August 11, 1986)

ABSTRACT

Pitt, C.H., Chang, Y.M., Wadsworth, M.E. and Kotlyar, D., 1988. Laboratory abrasion and elec-
trochemical test methods as a means of determining mechanism and rates of corrosion and wear
in ball mills. Int. J. Miner. Process., 22: 361-380.

A review is given on general characteristics of corrosion and wear processes in both wet and dry
environments. Laboratory methods for corrosion and wear studies are also reviewed including a
detailed account of a jet slurry impingement apparatus used by Pitt and Chang at the University
of Utah to study grinding ball metal corrosion-wear processes. Workers in the field have found
that corrosion-wear processes are highly complex and subject to a great number of experimental
variables such as load, pH, oxygen partial pressure, relative hardness of two interacting surfaces,
impact and nature of the protective film formed on the metal surface. Effects of interactions of
particles and surfaces under varying conditions are discussed. Synergistic effects between corro-
sion and wear are also discussed. Larger particles, higher impingement velocities and more cor-
rosive conditions tend to increase the synergism between corrosion and wear. Methods of decreasing
the corrosion rate in grinding mills are discussed along with the role that laboratory tests can play
in preventing corrosion and wear of the ginding media.

INTRODUCTION

It is well known that a great deal of economic loss is experienced in grinding

mills due to wear and corrosion of grinding balls and mill liners. There have
been several different approaches taken by investigators in attempts to learn
about the factors which cause these losses. One of these is by direct measure-
ment in the operating mill where balls are weighed and marked, run for a cer-
tain length of time and then recovered and weighed to determine the wear rate
under actual mill conditions. Another approach has been to test balls in labo-
ratory ball mills under varying conditions of charge, pH, speed, temperature
and atmosphere to determine the effect of these variables on ball wear under
laboratory ball mill conditions. A third approach is to run corrosion/wear tests

0301-7516/88/$03.50 © 1988 Elsevier Science Publishers B.V.

362

on the grinding ball metal samples in specially designed apparatus to attempt

to determine the basic mechanisms of the corrosion/wear process. Each of these
methods has its drawbacks. The marked-ball wear test is good for determining
how particular balls will hold up under actual operating conditions in a partic-
ular mill, however, the same conditions may not hold for other mills with other
loads and types of charges. The laboratory ball mill test is good for determining
the effect of variables under the given conditions but the results obtained may
not be readily extrapolated to actual mill conditions. The third approach which
is the subject of this paper is good for determining basic mechanisms of cor-
rosion and wear which can be useful in limiting wear in the ball mill, but it
suffers from the fact that it is difficult to obtain experimental conditions which
simulate corrosion/wear conditions actually experienced in the mill. A review
of work accomplished previously in this area will first be given followed by a
summary of work accomplished in the corrosion/wear laboratory of the Com-
minution Center at the University of Utah.

GENERAL CHARACTERISTICSOF CORROSION/WEAR

When a non-noble metal surface is exposed to an atmosphere which could

be either air or solution there will be a chemical reaction between the metal
and the atmosphere which in many cases tends to protect the underlying metal
from further reaction. This chemical reaction is generally termed corrosion.
Wear is the removal of surface material by a mechanical action on the surface.
It is evident that corrosion can effect wear depending on the type of surface
compound formed during corrosion. The rate of formation, thickness, mechan-
ical properties, friction characteristics and adhesion of the film would deter-
mine the wear characteristics of the surface. It is also evident that wear can
effect corrosion by removing surface films which form and allowing further
reaction of the corrosive environment with the underlying metal. Perhaps less
well understood is the fact that there can be a synergistic interaction between
corrosion and wear in that more material is removed by the conjoint action of
both than would be by either process alone.

OXIDATIONAND WEARPROCESSES

Under non-aqueous conditions in the presence of air an oxide will form on

the metal surface. When wear occurs the oxide layer and its debris is thought
to assist the wear process. Increasing the oxidation rate should greatly enhance
the wear rate. Tao and his coworkers (Tao, 1968, 1969; Appledorn et al., 1969)
used a rotating ball on a cylinder device to study oxidation-assisted corrosive
wear at lubricated and unlubricated steel surfaces. It was found that the rate
of oxide build-up tended to control the rate of oxide removal in the corrosion
wear process and that the corrosive wear was not eliminated by using a corro-
 363

sion resistant metal but that a surface-active agent in the lubricant was greatly
beneficial. An in-depth review on the oxidational wear of metals was recently
done by Quinn (1983) who discussed the effects of the formation of oxide films
under dry contact conditions and lubricated conditions, the thickness of the
oxide film and the effect of temperature on oxidational wear rates. It was gen-
erally found that oxidation increases the overall wear rate in pin-on-disk type
wear tests.
Under aqueous environments the type of surface film formed is determined
by the solution chemistry. Oxidation can occur readily at the metal surface.
Allen and Ball (1981) and Noel and Ball (1982) studied the abrasion/corro-
sion of various ferrous alloys using a modified disc-belt sanding machine. They
measured the wear volume losses of samples corrosion-treated prior to the
abrasion tests. It was shown that the interactive effects of abrasion and cor-
rosion were very important in the overall wear rate under a wet corrosive en-
vironment. Corrosion-resistant alloys such as stainless steel were superior to
the wear-resistant alloys under low abrasive and high corrosive conditions while
the opposite was true for high abrasive and low corrosive conditions.
Fretting corrosion is a common form of corrosion-assisted wear which is
simply corrosion/wear occurring at two surfaces in close contact which are
undergoing small oscillating movements with respect to each other. Mecha-
nisms ascribed to fretting corrosion have included oxidation-wear, wear-oxi-
dation and a combination of the two (Fontana and Greene, 1978). Fretting is
generally influenced by the amplitude and relative velocity of motion of the
fretting surfaces and environmental factors such as temperature and chemical
reactivity. Most of the experimental work on fretting corrosion has not in-
volved determining electrochemical processes which may occur at the inter-
faces (Waterhouse, 1972), however, some work has been accomplished on
orthopedic implant materials. This work will be discussed in a later section of
this paper.

CORROSION-ASSISTEDWEARIN WET ENVIRONMENTS

Corrosive wear of grinding media has been studied intensively. Marked-ball

wear tests have been described by a number of investigators (Ellis, 1942; Bond,
1957, 1964; Hoey et al., 1975, 1978; Lui and Hoey, 1977; Remark et al., 1976).
Significant increases in wear rates have been found under wet grinding con-
ditions as compared to dry conditions. Solution chemistry, chemical stability
of minerals present, mineral hardness, ball microstructure and hardness, and
corrosion-resistance of the balls have been established as important variables
in affecting the wear rates. The marked-ball wear test is widely accepted by
many investigators (Moroz and Lorenzetti, 1981; Moroz, 1983, 1985; Perez and
Moore, 1983; Iwasaki et al., 1984; Natarajan et al., 1984; Gangopadhyay and
364

Moore 1984; Perez et al., 1984; Jones, 1985) since it gives wear rates found
under actual in-plant operating conditions.
Erosion/corrosion likely plays an important role in corrosive wear experi-
enced by grinding balls (Pitt and Chang, 1985) due to the high relative rates
of motion between grinding balls and slurry experienced in large-diameter ball
mills. Erosion occurs due to the impact of particles and solution in the slurry
on the grinding media surfaces. The erosion component is influenced by the
characteristics of the solid particles and the velocity of the fluid. Experiments
for corrosion/erosion determinations can be carried out by means of a high
velocity jet impinging on a metal target or a rotating disk in a slurry. Details
have been discussed by a number of recent authors ( Natesan, 1978; Levy, 1979;
Levy et al., 1981, 1985; Levy and Yau, 1984; Wang et al., 1985). The rotating
disk technique is generally used where only mildly erosive conditions are de-
sired ( Scheifelbein, 1970; Weiser et al., 1973).
The effect of corrosion on wear in wet environments has been documented
in a number of instances (Lui and Hoey, 1973; Noel and Ball, 1982; Lebedev
et al., 1981; E1-Raghy et al., 1984; Wang et al., 1985; Pitt and Chang, 1985). In
order to determine the effect of corrosion by itself electrochemical measure-
ments can be made to determine the corrosion rate while wear is occurring
simultaneously. The experiment requires the use of a luggin capillary placed
near the eroding electrode to determine its change of potential when polarizing
currents are applied with a potentiostat in conjunction with a working elec-
trode. With the same apparatus the specimen can be cathodically protected to
stop chemical corrosion and the pure erosion rate is determined separately. A
number of factors have been found to control the wear rate utilizing these types
of experiments. The properties of the film formed on the metal and its rate of
formation are important. Film properties which are important are its coeffi-
cient of friction, its strength and adhesion and resistance to penetration by the
erosive particles. Films are removed completely or partially by the eroding
particles and the metal is much more reactive. If the film is not allowed to
reform the wear rate is controlled mainly by the wear and corrosion properties
of the metal itself. In addition to the corrosive and erosive effects there can be
synergistic interactions between corrosion and wear which enhance the wear
rate.

LABORATORYMETHODS FOR CORROSION/WEARSTUDIES

Since corrosion/wear studies involve generation of fresh metal surfaces it

may be of interest to consider studies involving electrochemical measurements
on freshly generated surfaces. Beck ( Beck, 1978) has reviewed these methods
among which the most common technique is to scrape or abrade the surface
following which the formation of passive surface films is studied (Tomashov
and Vershina, 1970;.Hashimoto et al., 1976; Burstein and Davies, 1981; Bar-
 365

bosa and Scully, 1982; Burstein and Marshall, 1983). More recently this tech-
nique has also been used to study the corrosion/wear process. E1-Raghy and
his coworkers have used this technique in the form of an electrochemically
instrumented pin-on-disk apparatus in studying the abrasion/corrosion char-
acteristics of stainless steel in aerated chloride solutions (E1-Kader and E1-
Raghy, 1985) and low-alloy steel in chloride solution (E1-Raghy et al., 1984).
It was found that mixed potentials and current densities were dependent on
surface roughness and the dissolution rate was independent of chloride con-
centration. Increasing the load of abrasion shifted the polarization curves neg-
atively to higher current densities but the curves reached a limit above which
they did not shift with increasing velocity of abrasion. The rate of passive film
renewal on stainless steel was dependent on the potential and solution pH.
The coefficient of friction of the surface film was found to be dependent on the
pH of the solution which was ascribed to the lubricating effect of NaOH. Typ-
ical anodic Tafel slopes were observed for metal dissolution. The dissolution
rate was independent of pH in the ranges 1-4 and 5.3-10 but was dependent
on pH in the ranges 4-5.3 and above 10. Tolley et al. (1984) modified a stan-
dard corrosion test cell by connecting an ultrasonic probe to the working elec-
trode which was immersed in a mineral slurry to measure the corrosion rates
of grinding media in mill water during ultrasonic scouring. They concluded
that corrosion would not account for more than about 10% of metal loss in
typical commercial ball mills but it seems ultrasonic scouring would not pro~
duce complete film removal under the given experimental conditions. Endo et
al. (1974) used an apparatus in which two test pieces of identical composition
rubbed together to study the effect of dissolved oxygen in saline solutions on
the corrosive wear of steel. He found that the thickness of the oxide layer which
varied with test conditions greatly affected the wear and the corrosion rate.
Adhesive wear was found to be important and he concluded lubrication should
lower the wear rate. Kim et al. (1981) designed a pin-on-disk type electro-
chemically instrumented corrosion/wear apparatus which was used to study
the effect of environment and rubbing under load on the corrosive wear of
bearing alloys. They found that in protective-film forming environments wear
increased corrosion rates significantly and that wear increased the corrosion
potential in the active direction. Yahagi and Mizutani (1984) using a pin-on-
disk type apparatus which was electrochemically instrumented found that the
wear rate of steel in gasahol was directly related to the corrosion rate. Buch-
anan et al. (1983) constructed an apparatus which had a corrosion sample-
wear pad design where the wear pads could be pressed against a rotating sample
for the study of corrosive wear of biomaterials. The load on the sample and the
wear speed could be adjusted. Using a similar design Kotylar et al. (1985)
constructed an apparatus to study the corrosive wear of grinding media in min-
eral slurries.
Most electrochemical investigations on fretting corrosion have been carried
366

out on passive metals such as stainless steel or titanium which are typical met-
als used for implants. In one investigation ( Sherwin et al., 1971 ) a power os-
cillator was connected to a hemispherically ending rider on a flat plate where
both the rider and flat plate constituted the working electrode. Corrosion rate
changes and transient linear polarization curves of 304 stainless steel in 1%
NaC1 solution were studied. It was concluded that the major part of the ob-
served corrosion current increase was due to the plastic deformation of the
metal surface resulting in the emergence of active slip bands at the surface. A
modified design of this apparatus has also been used to study implant materials
in in-vitro environments during fretting ( Syrett and Wing, 1978 ). It was found
that the corrosion rate during fretting was significantly higher and that the
corrosion rate increased with time. Naherheim and Kendig (1985) studied the
influence of electrochemical potential on Nickel 200 in 1 M NaCl04 on fretting
and sliding wear using a modified pin-on-disk apparatus. It was found that the
overall wear rate of the working electrode could be significantly reduced by the
application of an appropriate potential to the surface.
The use of a rotating disk apparatus coupled with electrochemical measure-
ments has been a popular method to study corrosion/erosion in aqueous slur-
ries. The behavior of ferrous grinding ball alloys in mineral slurries was
investigated using this technique (Lui and Hoey, 1973). Cathodic protection
was used to determine the erosive wear in the absence of corrosion while the
overall weight loss was determined. They found that corrosive wear was a sig-
nificant factor in wear of mild steel, white cast iron and Ni-hard cast iron in
aerated slurries but was not a significant factor in the corrosive wear of stain-
less steel and chromium-plated steels due to their inherent corrosion-resis-
tance. Corrosion/erosion wear of steel in ore grinding equipment has been
studied by using the same approach (Lebedev et al., 1980) where it was found
that the abrasive action of pulp on carbon steel sharply accelerated the elec-
trochemical action and that the passive state of the steel was destroyed above
a critical rotation velocity of the disk. The rotating disk method has also been
used to study the electrochemical interactions between minerals and grinding
balls under slurry erosion conditions (Natarajan and Iwasaki, 1984; Adam et
al., 1985).
Jet impingement of slurries has also been used in electrochemically instru-
mented apparatus to study corrosion/erosion of slurries on grinding ball alloys
( Pitt and Chang, 1985). Separate components of corrosion and wear were de-
termined by measuring the corrosion rate electrochemically and the erosion
rate under cathodic protection. Comparing the separate components to the
total wear rate showed that a synergistic effect occurs between erosion and
corrosion in certain pH ranges and a~ certain jet velocities. A more complete
review of this work and the work by Kotlyar will be given in the following
section.
 367

Strip Chart Recorder

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or
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Iniversal Programmer
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Working
Electrode

•nce
rode

Fig. 1. Jet slurry apparatus.

LABORATORYCORROSION WEAR INVESTIGATIONSAT THE UNIVERSITYOF UTAH

Slurry jet impingement experiments

The apparatus constructed by Pitt and Chang (1985) to determine sepa-
rately the components of corrosion, erosion and total wear when jetting a min-
eral slurry against grinding ball alloys is shown in Fig. 1. The schematic drawing
for the test specimen container is shown in Fig. 2. The main plastic container
is air-tight and has a built-in cup to hold the Luggin capillary, the working
electrode and the counter electrode in contact with the slurry during the ex-
368
Working
Platinum Electrode Calomel
Electrode ,t ~. Electrode
( Counter I I Reference I
Gas Inletc.I~. __---..Gas Outlet

I',=i ,,
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--Nozzle
IOrificel

S et

Fig. 2. Schematic diagramof test cell.

periment. A perforated shield was placed around the impingement zone be-
tween the nozzle and the working electrode to minimize the turbulence near
the tip of the Luggin capillary. A hardened stainless steel tube with a 1/8-inch
diameter orifice delivers a solid jet stream which impinges on the working elec-
trode. A 1/8-inch diameter specimen is mounted in a cylindrical phenolic rod
and sealed with lacquer. The working electrode body is adjusted so that a 3-
mm gap is maintained between the electrode and the nozzle. The slurry is
forced through the nozzle at high velocities by a positive displacement pump.
An air-tight 10-liter tank is used to supply slurry to the pump. The experiments
were conducted with either air, nitrogen, or oxygen bubbling through the slurry.
The jet velocity is controlled by a valve and pressure gauge. Slurry jetting speeds
of up to 29 m/s were used for the various tests. The temperature of the slurry
can be controlled by the heat exchanger up to 80°C. To improve the ionic
strength of the slurry, reagent grade Na2S04 was added in the amount of 0.05
M. A platinum inlay electrode was used as a counter electrode and a saturated
calomel electrode was used as the reference electrode. Electrochemical mea-
surements were carried out using an EG&G Model 173 Potentiostat, a Model
 369

3o

E 2O
~o
o~
E

© Total weight l o s s
Q Erosive weight l o s s

Corrosive weight loss

i

4 6 8 10 12
pH

Fig. 3. Weight losses of high-carbon low-alloy steel specimens as a function of pH using quartz
slurry jet. Jet speed; 6.6 m/s.

20 " '. . . . . .

0 Total Weight L o s s
• Erosive Weight L o s s
J~

.T.

Corrosive Weight Loss

t , 410 . . . .
4 6 8 • 12
pH

Fig. 4. Weight losses of high-chromium cast iron specimens as a function of p H using quartz slurry
jet. Jet speed: 6.6 m/s.

376 log current converter, and Model 175 Universal Programmer. The IR drop
between the working electrode and Luggin capillary was monitored by a Tec-
tronix Model Oscilloscope and compensated by a positive feedback circuit. The
corrosion current was determined by the polarization resistance technique ac-
cording to procedures given in ASTM G5. This apparatus enables the deter-
mination of the electrochemical corrosion component by polarization resistance
measurement and also the determination of erosive wear in the absence of
electrochemical corrosion by cathodic protection during weight loss determi-
370

nations. The total wear rate is determined by weight loss measurements under
normal operating conditions. Experiments have been run under various con-
ditions of jet velocity, pH, and aeration condition with quartz or chalcopyrite
slurries of controlled particle size jetting on to high-carbon low-alloy steel
(HCLA) and high-chrome cast iron (HCCI).
The results obtained have shown a synergistic effect between corrosion and
erosion. Generally the electrochemical corrosion is a small factor with the purely
erosive weight loss somewhat higher. The sum of the two in most cases does
not equal the total weight loss, subsequently a synergystic effect has been found
to occur as is illustrated in Figs. 3 and 4 for HCLA and HCCI alloys. In these
figures I mg h -1 c m - 2 = 1.24/tm h -1 cm -2.
Some of the findings in these experiments are summarized as follows.
(1) Pure erosive wear of HCLA and HCCI is strongly affected by the shape,
m o m e n t u m and hardness of the solid particles in the jet. The hardness and
microstructure of the target metal also affect the erosion rate. After a given
period of use the mineral particles tend to become rounded which cause a drop
in the erosive wear rate. Therefore mineral slurries were renewed periodically
so as to eliminate this factor.
(2) The electrochemical corrosion rate of HCLA and HCCI is affected by
factors such as pH, oxygen concentration, jet velocity and chemical reactivity
of the mineral particles. In general, increasing the pH above 10, lowering the
dissolved oxygen concentration and lowering the temperature reduced the
electrochemical corrosion rate. At high jet velocities of 20 m/s and above pro-
tective films were removed rapidly which resulted in increased corrosion rates
and weight losses.
(3) Synergistic effects due to interactions between corrosion and erosion
were generally found under all conditions. The major synergistic effects gen-
erally occur for larger particles at high jet velocities and high corrosion rates.
(4) The overall weight loss of the specimen is due mainly to erosion and the
synergistic relations between erosion and corrosion. The net corrosion rate in
terms of total weight loss rate is generally less than 10 per cent of the total.

Rotating cylinder and anvil experiments

As in the case of the impinging jet method the purpose of using the rotating
cylinder and anvil experiments was to quantify the separate effects of erosion
and corrosion, measured simultaneously. The apparatus permits the applica-
tion of predetermined load through opposing anvils brought into contact with
a rotating cylinder in the presence of a slurry. Specific goals were to determine
the separate erosion-corrosion contributions related to slurry pH, cylinder ro-
tating speed, anvil load, intermittent loading rate, ball hardness, ball compo-
sition and mineral chemistry.
A schematic drawing of the rotating cylinder and anvil apparatus is shown
 371

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CONTROL
VALVE RELAY-TIMER

Fig. 5. Schematic drawing of rotating cylinder and anvil abrasion-corrosion apparatus.

in Fig. 5. Details of the apparatus are included here since it has not been de-
scribed elsewhere. The apparatus consists of a rotating cylindrical part ( 1 ),
2.86 cm (1.125 in. ) in diameter and 0.32 cm (0.125 in. ) high. A variable speed
motor (2) controls the speed of rotation through a rotating shaft (3) and bevel
gear box (4). The rotating part is fixed by a phenolic nut (5) for ready removal
and weighing after each experiment. The rate of cylinder rotation is variable
between 30 and 238 rpm and is indicated on an electronic counter (6). Contact
pressure is applied to the rotating part through two opposing abrasive anvils
(7). The anvils are 0.32 cm (0.125 in. ) in diameter and are of metal or natural
or synthetic mineral as desired for a given experiment. The anvils are mounted
in phenolic holders on teflon-covered steel rods (8) and contact the specimen
with constant load or intermittently by hydraulic cylinders (9). The hydraulic
system consists of a pump, oil reservoir, directional control valve, flow control
valve, pressure gauges and a pressure regulator. Pressure gauges were cali-
brated using a dynamometer. A relay timer is connected to the directional con-
trol valve to regulate the speed of abrasive anvil displacement. The apparatus
also contains the elements of an electrochemical polarization cell permitting
the simultaneous recording of anodic and cathodic electrokinetic curves. The
polarization cell consists of a plastic cylinder container (10) with ring-shaped
gaskets around rods (8), a carbon brush electrical pickup ( 11 ), two platinum
reference electrodes (12), a Luggin probe for a saturated calomel electrode
(13), a stirrer (14) and controller (16) and gas diffuser (15). The working
372

1y
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80

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.: o
, jr ,) PH=7.5
20

PH=IO, O

10 20 25 30 35 40 50 10 15 20 25 30 4() 50
load, Ib load, Ib
Fig. 6. Effect of contact load on total wear rate (1, 1' ), on corrosion rate (2, 2' ) and on the
corrosion component as percent of total wear rate (3, 3' ) for HCLA steel in 15% quartz slurries
at pH 7.5 using HCLA anvils ( 1, 2, 3) and quartz anvil (1 ', 2', 3' ).

Fig. 7. Effect of contact load on total wear (1, 1' ), on corrosion rate (2, 2' ) and on the corrosion
component as percent of total wear rate (3, 3' ) for HCLA steel using HCLAanvils in 15% quartz
slurries at pH 7.5 (1, 2, 3) and pH 10.0 (1', 2', 3' ).

electrode body, except for the working area, was insulated by a lacquer coating.
Current and potential were measured using a Model 173 Potentiostat-
/Galvonstat, a Model 175 Universal Programmer and X-Y Recorder ( Prince-
ton Applied Research). The IR drop between the working electrode and the
Luggin capillary was monitored by a Tectronix Model 2213 Oscilloscope and
compensated by a positive feedback circuit.
In the initial experiment, reported in part in this presentation, the following
procedures and conditions were used: (1) anvil and cylinder contact and non-
contact times were 10 and 5 s, respectively; (2) weight loss was determined by
weighing the rotating cylinder after each experiment; (3) the specimen con-
sisted of a commercial high-carbon low-alloy steel ( H C L A ) with a hardness
of 59 RC and low alloy steel of hardness 14 RC; (4) anvils were either of the
same materials as the rotating cylinder or a quartz rod; (5) slurries consisted
of 15% quartz in solutions of variable pH; (6) weight loss was measured in
mg/h; and ( 7 ) the experiment duration varied between 1 and 2 h. To estimate
pure abrasion, cathodic protection was applied to the sample by applying - 1.7
V (vs. SCE). The metal weight loss was taken as pure abrasion under these
conditions. Corrosion rates were calculated from the electrochemical polari-
zation measurements and converted to mg/h. The synergistic effect between
corrosion and abrasion was calculated as a weight loss and was determined as
 373

12

11

10 100

9 90

• 4 8
1
E 7 7o ~o
q; E
~3 6

5
//f .~_
so ~
o

1 30 ~

10
2' •
13 14 o:2 o:6 ,.o
pH hs/ha

Fig. 8. Influence of pH on total wear rate (1, 1' ) and on corrosion rate (2, 2' ) of HCLA steel
abraded by H C L A anvils (1, 2) and quartz anvils (1', 2' ) for 15% quartz slurries and contact
loads of 10 lb. (1, 2) and 15 lb. (1', 2 ' ) .

Fig. 9. Influence of the ratio of metal specimens hardness (hs) to anvil hardness (ha) on the total
wear rate (1), on corrosion rate (2) and on the corrosion component as percent of total wear (3)
for specimen/anvil couples H C L A / H C L A , HCLA/quartz and mild steel/HCLA; 15 % quartz slur-
ries and pH 10.2.

the difference between the total measured weight loss and the sum of the weight
loss due to pure abrasion plus corrosion.
Fig. 6 illustrates the effect of load on the total wear and corrosion compo-
nents of wear for different anvil materials. The rotation specimen for all tests
was HCLA steel and the anvils were either HCLA steel or quartz. The slurry
contained 15% quartz with a pH of 7.5. Curves 1, 2 and 3 refer to results ob-
tained using anvils of HCLA steel and curves I', 2', and 3' indicate results
obtained using quartz anvils. Solid curves refer to the left ordinate and dashed
curves refer to the right ordinate. Curves 1 and 1' illustrate the total wear of
HCLA steel with HCLA and quartz anvils, respectively. Quartz is 2 to 3 times
as abrasive as the HCLA steel. The increase in total wear is approximately
linear with load for both anvil materials with a somewhat steeper increase for
quartz. Curves 2 and 2' represent measured corrosion for the HCLA and quartz
anvils, respectively. Corrosion is somewhat greater for quartz anvil abrasion
374

TABLE I

The effect of the ratio of the specimen hardness (hs) to the abrasive hardness (ha) on the total
wear rate, pure abrasion rate, corrosion rate and synergistic effect of H C L A steel and mild steel
in 15% quartz slurry

hs/ha Total Pure Electro- Synergistic

abrasive abrasion chemical effect
wear rate rate* 1 corrosion (mg/h)
(mg/h) (mg/h) rate
(mg/h)

HCLA steel abraded by HCLA steel

p H = 10.0 + 0.2 1.0 1.127 0.0 0.436 0.690
p H = 9.0+0.2 1.0 1.49 0.21 0.670 0.468
p H = 8.0+0.2 1.0 1.69 0.66 0.520 0.505
load= 15 lb.
HCLA steel abraded by quartz
p H = 10.2 + 0.2 0.50 3.87 1.57 0.393 1.9
load = 10 lb.
Mild steel abraded by HCLA steel
p H - - 10.2 + 0.2 0.2 10.3 5.41 0.451 4.44
load = 15 lb.

*1Measured during abrasion with applied cathodic protection.

than for HCLA anvil abrasion. In either case corrosion is relatively insensitive
to load. Curves 3 and 3' are calculated curves illustrating the percent of total
wear attributable to corrosion for HCLA and quartz anvils, respectively. It is
apparent that corrosion is a smaller component of total wear for quartz/HCLA
abrasion than for HCLA/HCLA abrasion. Fig. 7 illustrates total wear, corro-
sion and the corrosion component for HCLA/HCLA abrasion in a 15% quartz
slurry at two pH values (7.5 and 10.0). Total wear and corrosion are greater
at pH 7.5 than at pH 10.0. The disproportionate increase in total wear at pH
7.5 illustrates the synergistic contribution of corrosion to total wear. Fig. 8
represents the influence of pH for both HCLA/HCLA and quartz/HCLA abra-
sion at a constant load of 10 lb. A marked linear decrease in total wear with
pH is apparent. Only a modest decrease in pure corrosion was observed. These
results again illustrate the important synergistic contribution of pure corrosion.
Table I and Fig. 9 illustrate the influence of the ratio of the specimen hard-
ness ( hs ) to the abrasive hardness (ha) of the anvil on the total wear rate, pure
abrasion and corrosion rate for 15% quartz slurries. For various hs/ha values,
Table I lists total abrasion, pure abrasion (measured with applied cathodic
protection), electrochemical corrosion and the calculated synergistic contri-
bution. The pure abrasion rate increases with decreasing pH. These results are
plotted in graphical form in Fig. 9 for pH = 10.2. A marked decrease in total
wear rate occurs (curve 1 ) for increasing hJha values. The corrosion rate (curve
 375

2) is essentially independent of the hJha ratio. The synergistic component

(curve 3) consequently increases with increase in the hJha ratio.
The synergistic effect between corrosion and abrasion is apparent for both
HCLA and mild steel. The magnitude of the synergistic effect is considerable
and decreases with increasing hs/ha. The corrosion rate of steel in a 15% quartz
slurry, pH 10.2, is practically independent of the hJh~ ratio. When soft mild
steel is abraded by high-hardness HCLA steel abrasive (hdha=0.23), the
magnitude of the total wear increases as compared to the magnitude of the
total wear of the high-hardness HCLA steel abraded by the high-hardness
HCLA abrasive ( h,/ha = 1.0; Fig. 9 ). The corrosion component ( curve 3 in Fig.
9) of the total wear of HCLA steel and mild steel also depends on the h d h a
ratio. It varies from 60.5% for the high-hardness HCLA steel abraded by the
high-hardness abrasive ( h d h , - - 1 ) to 4% for the soft steel abraded by the high-
hardness abrasive ( hJha = 0.23 ).
Based on the above results the following conclusions may be drawn.
(1) The corrosion rate of HCLA steel in an aerated 15% quartz slurry under
abrasive conditions depends on the extent of oxide film removal and abrasion
resistance of the oxide films formed by anodic reactions.
(2) For high pH slurry values the corrosion rate of HCLA steel decreases
significantly. It appears that oxide films generated in high-alkaline slurries are
more protective than films formed in neutral, 15% quartz slurries.
( 3 ) With increasing applied load the corrosion rate of HCLA steel increases.
The effect may be related to the nearly complete removal of the oxide film
from the metal surface at high load and the associated exposure of the fresh
metal surface in the corrosive slurry.
(4) Pure abasion (cathodically protected) of HCLA steel abraded by HCLA
steel decreases with increasing pH of the quartz slurry. This effect may be
related to the reduction of the coefficient of friction from increasing the pH.
(5) The magnitude of pure abrasion of HCLA steel abraded by quartz in-
creases markedly compared to that of HCLA steel abraded by the same steel.
The abrasion is intensified by the corrosion action.
(6) The magnitude of the synergistic effect is Considerable even if the cor-
rosion component of the wear is small. It is believed that the removal of metal
particles produces the synergistic effect and is due to the development and
propagation of surface cracks assisted by anodic corrosion.
( 7 ) The total abrasive wear of HCLA steel, which is the sum of pure abra-
sion, corrosion and the synergistic contribution increases with an increase of
applied load, increased hardness of the abrasive and with decreasing slurry pH.

DISCUSSION AND SUMMARY

Many investigators have studied various aspects of corrosion and wear in

the laboratory. The investigations have included oxide formation in the pres-
376

ence of wearing surfaces, fretting corrosion, wear and corrosion of orthopedic

implants, erosion/corrosion of turbine blades, and erosion/corrosion and abra-
sion/corrosion of grinding ball alloys.
Laboratory methods for studying corrosion/wear phenomena also vary widely
ranging from wear apparatus such as pin-on-disk, rotating disk and jet type
equipment to laboratory ball mills and commercial ball mills. Experimental
measurements have included simple weight loss, friction and dimensional
change measurements, and highly sophisticated electrochemical measure-
ments to separate the wear and corrosion components.
Workers in this field have found that corrosion/wear processes are complex
and subject to a great number of experimental variables. Variations in the load,
pH or oxygen partial pressure of the environment, relative hardness of the
abrasive particles or of the wearing surfaces, duration of the load, impact and
the nature of the protective films formed are some of the important factors
which affect the amount of metal lost during the corrosion/wear process.
Consideration of the basic process of particle impact on a metal surface leads
to the following conclusions. The particle, upon impact, if it is traveling suffi-
ciently fast and is sufficiently hard and sharp, gouges the surface it encounters.
The surface may be covered with a film or be of fresh metal. The gouge may
remove part of the surface and/or produce loose material which may be re-
moved easily by subsequent particle impacts. In any event material is removed
from the surface. If the particles are arriving at a sufficient rate and with enough
energy protective films can be removed from the surface and fresh metal ex-
posed. On the other hand the particles themselves undergo changes also. Sharp
corners which may have originally existed are rounded upon repeated impacts
and the particle over a period of time loses its ability to cut or gouge. Particle
impact on the surface if sufficiently strong can also cause plastic flow and
deformation of the surface metal layers. Abrasive wear caused by two surfaces
rubbing together may be looked at in a fashion similar to particle impact. In
this case there are surface asperities which interact in a similar rubbing, goug-
ing or plowing fashion. The main difference is that the surface asperities can
be larger, may shear off material and can have a greater load sustained on the
surface for a longer time. So abrasive wear can have a more severe effect in
removing surface material.
If the surface is in a chemically reactive environment chemical and/or elec-
trochemical reactions will occur there along with the wear process which takes
place. The chemical reactions may produce surface films which can be subse-
quently removed, or they may simply remove metal ions from the surface. From
this aspect chemical reactions generally tend to occur more readily at the more
reactive sites on the surface such as grain boundaries, ledges or dislocation
sites. Consequently the surface is not generally corroded in a uniform manner
but non-uniformly since crevices and undercutting are possible. When this
occurs there is the chance that during particle impact, film or metal particles
 377

may be removed from the surface of a size greater than could be removed by
the basic abrasion process in the absence of corrosion. This leads to the so
called "synergistic effect" between corrosion and wear. The process can be
looked at from the "wear point of view" also. The wear process acts to remove
protective films which when removed allow corrosion to proceed more rapidly.
Thus wear assists corrosion and corrosion assists wear.
A number of investigators cited in this paper have found synergistic effects
between corrosion and wear that support this view. Their method of investi-
gation using electrochemical techniques consists of measuring the corrosion
rate by electrochemical methods and subsequently protecting the surface cath-
odically from corrosion and then measuring the wear rate separately. The total
corrosion-wear rate is measured and the difference between this rate and the
sum of the separately determined corrosion and erosion rates gives the syner-
gistic effect. The synergistic effect has been found in both abrasive wear ex-
periments and erosive wear experiments. Larger particles, higher impingement
velocities and more corrosive conditions tend to increase the effect. Tougher
films, lower-friction surfaces, lower particle and sliding surface velocities and
less corrosive conditions tend to decrease the effect.
In grinding mills for comminution a number of processes tend to cause metal
loss from grinding balls and mill liners. Some of the more important processes
are erosive-corrosive wear, abrasive-corrosive wear and impact fatigue. Im-
pact fatigue has not been discussed in this paper and is considered to be a
separate topic which needs to be investigated more thoroughly. In view of the
basic processes described in this paper prevention of metal loss in grinding
media could be accomplished by the following means.
(1) Decreasing the basic corrosion rate. This in turn might be done by: (a)
maintaining a high pH - - this increases the tendency to form a tough passive
film with lower friction on the surface which in turn is a protection against
both wear and corrosion; (b) cathodic protection - - the best method for cath-
odic protection would likely be inclusion of metals in the mill charge which are
more active electrochemically than the grinding balls; (c) use of inhibitors - -
organic or inorganic inhibitors can aid in corrosion prevention by several
mechanisms; (d) removal of oxygen from the slurry - - cathodic reduction of
oxygen has been shown to be one of the most important reactions which en-
hances corrosion; removal might be aided by oxygen scavenging chemicals; (e }
use of more corrosion resistant materials for grinding media - - forged rather
than cast high-chrome grinding balls may be more corrosion-resistant and pro-
vide for less corrosive wear.
( 2 ) Improving the wear resistance of the grinding media. Finding materials
and heat treatments which produce better abrasion- and erosion-resistance.
Basically this means harder materials with the best microstructure for wear
resistance.
(3) Optimizing grinding mill performance for lower wear rates. It is not pos-
378

sible to use smaller mills with lower abrasion and wear characteristics but it
m ay be possible to optimize t he mill speed and charge c o n t e n t to give the best
p e r f o r m a n c e with regard to ore grinding rates and wear rates.
No n e of the above possible p r e v e n t i o n methods has been analyzed as to their
economic impact on t he grinding process. T h e methods need to be analyzed as
to their cost effectiveness under actual operating conditions to provide guid-
ance to mill operators.
In conclusion it m ay be said t h a t laboratory c o r r o s i o n - w e a r test methods
have served to clarify t he role t h a t the various p a r a m e t e r s experienced in com-
mercial grinding mills play in the c o r r o s i o n - w e a r process. Also t h e y have pro-
vided a means to quantify the synergistic effects which occur between corrosion
and wear and to enable the f u r t h e r devel opm ent of likely mechanisms of cor-
rosion an d wear which occur u n d e r operating mill conditions. T h e laboratory
tests methods point t he way toward procedures which m ay be tried in com-
mercial ball mills to lower corrosion a nd wear and provide for more economical
operation, however, these methods m us t be tested and evaluated under oper-
ating mill conditions to de t e r m i ne t he i r cost effectiveness.

ACKNOWLEDGEMENTS

T h e authors express their gratitude to the C o m m i n u t i o n Center of the Uni-

versity of U t a h and the U ni t ed States B u r e a u of Mines whose funding assist-
ance helped to make this pa pe r and research possible.

REFERENCES

Adam, K., Natarajan, K.A., Iwasaki, I. and Riemer, S.C., 1985.Electrochemicalaspects of grinding
media-mineral interaction in sulfide ore grinding. NACE Preprint Paper 362. Corrosion 85.
Boston, Mass.
Allen, C. and Ball, A., 1981. The abrasive corrosivewear of stainless steels. Wear, 74: 287-305.
Appledorn, J.K., Goldman, I.B. and Tao, F.F., 1969. Corrosive wear by atmospheric oxyenand
moisture. ASLE Trans., 12: 140-150.
Barbosa, M. and Scully, J.C., 1982. The role of repassivation kinetics in the measurement of the
pitting potential ofAIS1304 stainless steel by the scratch method. Corros. Sci., 22: 1025-1035.
Beck, T.R., 1978. Techniques for studying initial film formation on newly generated surfaces of
passive metals. In: R. Baboian (Editor), Electrochemical Techniques for Corrosion. NACE,
1977, Houston, Texas.
Bond, F.C., 1957. Wet versus dry grinding. Min. Congr. J., 43: 38-41.
Bond, F.C., 1964. Lab equipment and tests help predict metal consumption. Eng. Min. J., 665:
Brown, S.A. and Merritt, K., 1981. Fretting corrosion in saline and serum. J. Biomat. Res., 15:
479-488.
Buchanan, R.A., Turner, G.D., Gray, P.D., Melendez,J.G., Talbot, T.F. and McDonald,J.L., 1983.
A new apparatus for synergistic studies of corrosivewear. Corrosion,39: 377-378.
Burstein, G.T. and Davies, D.H., 1980. The effects of anions on the behavior of scratched iron
electrodes in aqueoussolutions. Corros. Sci., 20: 1143-1155.
 379

Burstein, G.T. and Davies, D.H., 1981. The electrochemical behavior of scratched iron surfaces
in aqueous solutions. J. Electrochem. Soc., 128: 33-39.
Burstein, G.T. and Marshall, P.I., 1983. Growth of passivating films on scratched 304L stainless
steel in alkaline solution. Corros. Sci., 23: 125-137.
E1-Kader, H.A. and E1-Raghy, S.M., 1985. Electrochemical kinetics of stainless steel in aerated
chloride solutions during wear process. Electrochim. Acta, 30: 841-849.
E1-Kader, H.A., E1-Raghy, S.M. and EI-Hassan, M.E.A., 1984. Film thickening on abraded 18-10
stainless steel in chloride solutions. Br. Corros. J., 19; 139-142.
E1-Koussy, R., E1-Raghy, S.M. and E1-Mehairy, A.E., 1981. Effect of heat treatment conditions
and composition on the wear resistance of some chromium steels. Tribol. Int., 14: 323-328.
Ellis, O.W., 1942. Wear tests on ferrous alloys. Trans. ASM, 30: 249-286.
EI-Raghy, S.M., E1-Kader, H.A. and Abou-E1-Hassan, M.E., 1982. Electrochemistry of abrasion
corrosion of low alloy steel in 1% NaC1 solution. Corrosion, 40:60-61.
Endo, K., Komai, K. and Shiomi, H., 1974. Effects of dissolved oxygen in saline on corrosive wear
of steel. Wear, 30: 285-297.
Fontana, M.G. and Greene, N.D., 1978. Corrosion Engineering. McGraw-Hill, New York, N.Y.,
475 pp.
Gangopadhyay, A. and Moore, J.J., 1984. An assessment of wear mechanisms in grinding media.
SEM-AIME fall meeting, Denver, Colo., Preprint No. 84-342.
Hashimoto, K., Osada, K. Masumoto, T. and Shimodaira, S., 1976. Characteristics of passivity of
extremely corrosion-resistant amorphous iron alloys. Corros. Sci., 16: 71-76.
Hoey, G.R. Dingley, W. and Freeman, C., 1975. Corrosion inhibitors reduce ball wear grinding in
sulphide ore. CIM Bull., pp. 120-123.
Hoey, G.R., Dingley, W. and Freeman, C., 1978. Corrosive wear of grinding media in grinding a
complex zinc-lead-copper sulfide ore. Proc. Aust. Inst. Min. Met. 265: 27-32.
Isaacson, A.E. and Huiatt, J.L., 1985. An electrochemical study of grinding media corrosion. Pre-
sented at Corrosion 85. Paper No. 364.
Iwasaki, I., Reimer, S.C. and Orlich, J.N., 1984. Erosive wear in taconite grinding. Presented at
SME-AIME fall meeting, Denver, Colo., Preprint No. 84-316.
Jones, D., 1985. Fundamentals of corrosive wear in wet ore grinding sysems. Presented at Corro-
sion 85. Annual NACE Meeting, Boston, Mass. Paper No. 363.
Kim, K.Y., Bhattacharyya, S. and Agarwala, V., 1981. An electrochemical polarization technique
for evaluation of wear-corrosion in moving components under stress. ASME, pp. 772-778.
Kotlyar, D., Wadsworth, M.E. and Pitt, C.H., 1985. Unpublished data. Metallurgy Department,
University of Utah.
Lebedev, A.N., Shcherbakov, O.K. and Balashov, G.V., 1980. Corrosion and erosion wear of steel
in ore-grinding equipment. Z. Metallov., 16: 251-254.
Levy, A. (Editor), 1979. Proc. Corrosion/Erosion of Coal Conversion Systems. Materials Conf.
NACE, Houston, Texas.
Levy, A. and Yau, P., 1984. Erosion of steels in liquid slurries. Wear, 98: 163-182.
Levy, A.V., Yan, J. and Arora, V.D., 1985. Sand-water slurry erosion of carburizsed AISI 8620
steel. Wear, 101: 117-126.
Li, S.K., Humphrey, J.A.C. and Levy, A.V., 1981. Erosive wear of ductile metals by a particle-
laden high velocity liquid jet. Wear, 73: 295-309.
Lui, A.W. and Hoey, G.R., 1973. Corrosive and erosive wear of metals in mineral slurries. Can.
Metall. Q., 12: 185-190.
Lui, A.W. and Hoey, G.R., 1977. Use of alkaline additives to reduce wear on steel balls in grinding
low grade copper ore. Br. Corros. J., 12: 51-53.
Moroz, P.J., Jr., 1983. Proc. 56th Annual Meeting of the Minnesota Sec. AIME.
Moroz, P.J., Jr., 1985. Factors affecting the wear of grinding media during wet ore grinding when
380

the corrosive component of wear is small. Corrosion 85. Paper N. 366. NACE annual meeting.
Boston, Mass.
Moroz, P.J., Jr. and Lorenzetti, J.J., 1981. The effects of matrix hardness and microstructure on
the wear of steel grinding balls during wet copper ore grinding. In: Wear of Materials, ASME,
280.
Naherheim, Y. and Kendig, M.W., 1985. The influence of electrochemical potential on wear. Wear,
104: 139-150.
Natarajan, K.A. and Iwasaki, I., 1984. Electrochemical aspects of grinding media-mineral inter-
actions in magnetite ore grinding. Int. J. Miner. Process., 13: 53-71.
Natarajan, K.A., Riemer, S.C. and Iwasaki, I., 1984. Influence of phyrrhotite on the corrosive wear
of grinding balls in magnetite ore grinding. Int. J. Miner. Process., 13: 73-81.
Natesean, K. (Editor), 1978. Corrosion Erosion Behavior of Materials. Metallurgical Society of
AIME. Symposium Proceedings, Warendale, Pa.
Noel, R.E.J. and Ball, A., 1982. On the synergistic effects of abrasion and corrosion during wear.
Wear, 74: 351-361.
Perez, R. and Moore, J.J., 1983. The influence of grinding ball composition and wet grinding
conditions on metal wear. In: Wear of Materials, ASME, New York, N.Y.
Perez, R., Moore, J.J. and Smith, K.A., 1984. Interaction of corrosion and abrasion in grinding
media wear. SME-AIME fall meeting, Denver, Colo., Preprint 84-611.
Pitt, C.H. and Chang, Y.M., 1985. Electrochemical determination of erosive wear of high carbon-
steel grinding balls. Min. Met. Proc., 2 (3) :166-173.
Pitt, C.H. and Chang, Y.M., 1985. Jet slurry corrosive wear of high chromium cast iron and high
carbon steel grinding balls. Corrosion, 42: 312-317.
Quinn, T.J.F., 1983. Review of oxidational wear, I. The origins of oxidational wear; II. Recent
developments and future trends in oxidational wear research. Tribol. Int., 16: 257-271; 305-315.
Remark, J.F. et al., 1976. Corrosion control in ball and rod mills. Presented at Corrosion 76.
Houston, Texas, NACE, Paper 121.
Schiefelbein, G., 1970. Performance of alloys against erosion-corrosion attack. Mater. Prot. Per-
form., 9: 11-13.
Sherwin, M.P., Taylor, D.E. and Waterhouse, R.B., 1971. An electrochemical investigation of
fretting corrosion in stainless steel. Corros. Sci., 11:419-429.
Syrett, B.C. and Wing, S.S., 1978. An electrochemical investigation of fretting corrosion of sur-
gical implant materials. Corrosion, 34: 379-386.
Tao, F.F., 1968. The role of diffusion in corrosive wear. Am. Soc. Lubric. Eng., 11: 121-130.
Tao, F.F., 1969. A study of oxidation phenomena in corrosive wear. Am. Soc. Lubric. Eng., 12:
97-105.
Thomashov, N.D. and Vershinina, L.P., 1970. Kinetics of some electrode processes on a contin-
uously renewed surface of solid metal. Electrochim. Acta, 15: 501-517.
Tolley, W.K., Nicols, J. and Huiatt, J., 1984. Corrosion Rates of Grinding Media in Mill Water.
U.S. Bureau of Mines Report, NO. 8882.
Wang, Q., Peien, X., Shuiumei, S. and Cuizhen, X., 1985. On the mechanism of wet abrasive
erosion. Tribol. Int., 18: 113-119.
Waterhouse, R.B., 1972. Fretting Corrosion. Pergamon Press, Oxford, 253 pp.
Weiser, P.F., Beck, F.H. and Fontana, M.G., 1973. Resistance to erosion-corrosion of commer-
cially cast steels. Mater. Perform., 12: 34-38.
Yahagi, Y. and Mizutani, Y., 1984. Corrosive wear of steel in gasoline-ethanol-water mixtures.
Wear, 97: 17-25.