A review of the influence of

environmental humidity and

w a t e r on friction, lubrication
and wear
J. K. Lancaster*

A review is given of the various ways in which humidity and liquid water
can influence the friction and wear of metals, polymers, carbons and
graphite, lamellar solid lubricants and ceramics. Compared with dry
sliding, water usually reduces friction of materials to a limited extent,
except for MoS2, but wear rates change depending on the materials
concerned. Most of the fundamental mechanisms involved appear to be
reasonably well understood, but uncertainties still remain concerning the
role of humidity on the formation of third-body layers of aggregated
wear debris.

Keywords: humidity, water, friction, wear

Introduction system either accidentally, as a contaminant, or deliber-

It is a common complaint by reviewers of experimental
papers on unlubricated friction and wear that the
relative humidity of the environment concerned is
seldom controlled and often is not even stated.
Humidity measurement is a relatively simple matter
and there can be little excuse for its omission.
Environmental control, however, is more of a problem
and usually increases the complexity of the experiment.
It is thus important to be able to decide at the outset
of a research p r o g r a m m e whether or not humidity
control is likely to be 'cost-effective'. This paper
reviews what is known about the major effects of
humidity on friction and wear in order to provide a
background from which such a decision can rationally
be made. Two further reasons for this review were
also relewmt. First, a number of important investi-
gations into the role of humidity on friction and wear
were made many years ago and are now tending to be
forgotten because they are not always listed in com-
puter-based information-retrieval systems. Second, it
was thought to be of interest to see whether any areas
still remain in which the effects of humidity on friction
and wear are still not fully understood.
The discussion which follows divides the materials
concerned into five main groups: metals, polymers,
carbons and graphite, lamellar solid lubricants, and
ceramics. Within each group, comment is made on the
effects of both environmental humidity and liquid
water. It was considered important to include liquid
water because at humidities approaching saturation,
condensation may occur on contacting surfaces. In
addition, water is sometimes introduced into a sliding
:School of Engineering & lnJormation Sciences, Universio' ol'
Reading,,, Reading, Berkshire, UK.
ately, as a coolant.
Metals
It is now generally accepted that the friction of metals
results primarily from the shearing of adhesive junctions
which form over the localized areas of real contact
between two surfaces. The strength of these junctions
is extremely sensitive to the presence of adsorbed
contaminant films from the environment ~ and, indeed,
adhesion in ordinary atmospheres can only be observed
directly when normal loading is supplemented by
tangential m o v e m e n t to break down the contaminant
films-'. The main environmental effects on adhesion
and friction are primarily associated with the adsorption
of oxygen; the separate effects of water vapour appear
to have received little attention. In one particular
instance, however, it has been noted that surface
tension forces can lead to increased adhesion when
the surfaces are extremely smooth and the relative
humidity is sufficiently high to promote multilayer
adsorption of water 1. This effect becomes insignificant,
however, for surfaces with roughnesses typical of those
encountered in engineering practice. Even liquid water
is not an effective boundary lubricant for metals and
one comparison of friction coefficients for a range of
metals in air and water shows only very small
differences, except in the case of iron which gives
lower friction in water due to rusting-L
The influence of water on the wear of metals, however,
is much more significant than on friction. The greatest
effects occur during wear in the "corrosive' or "oxidative'
regime where chemical reactions with the environment
lead to the formation of surface films which can protect
against m e t a l - m e t a l contact. The presence of water
vapour influences both the rate of oxidation and the

TRIBOLOGY INTERNATIONAL © 1990 Butterworth-Heinemann Ltd

0301-679X/90/060371-19 371
J. K. Lancaster--The influence of environmentaf humidity and water on friction, /ubrication and wear

type of oxides formed 4. Barnes et al~ have examined

the unlubricated wear of an i r o n - 5 % chromium alloy
in controlled environments and shown that islands of
o8 - Ag
protective oxide gradually form on the surfaces leading
to reductions in both friction and wear. In ordinary 0.6
(moist) air there is a greater surface coverage by these
islands than in dry air and they therefore conclude
=0.4
that water vapour plays a significant role in forming
and compacting wear debris. Another example of ~U

water influencing the protection afforded by oxides

0.2
ve i
has been observed by Vaessen and deGee 6 during the
wear of copper alloys. At light loads, wear rates were 4
low because the films remained intact, but above a 0 1 • L~J
critical load there was a transition to higher wear, 0 I0 20 50 40 50

6!
%rh
simiIar to that frequently observed between the ~miId'
and 'severe' regimes 7. The transition load increased
with increasing relative humidity, suggesting that water
vapour facilitates the formation of a more protective
oxide. Above the transition, however, the wear rates
were greater at high humidities; to account for this it
was suggested that the adsorption of water vapour may
impede the aggregation and transfer of metallic debris. b
This interpretation conflicts with other work ~, however, c
where the prevention of debris aggregation and transfer
of a copper-zinc alloy by water was found to reduce
Ag I
the rate of wear. 2

If the adsorption of water vapour can affect both the ,me

rate of oxidation and the aggregation of oxide debris
into a third-body film, one would therefore expect to
find a significant influence of humidity on wear in
fretting conditions where debris tends to be retained
within the contact zone. This turns out to be so but
there is, unfortunately, no general agreement on the
trends observed. In one example from early work 9,
the fretting wear rates of mild steel were found
to decrease with increasing humidity and this was
interpreted by arguing that the hydrated oxides formed
at high humidities are less hard and abrasive than the
non-hydrated ones formed in dry air. A similar trend
was observed by Nield and Griffin m, also with ferrous
materials, during sliding in conditions approximating
to fretting. In contrast, however, Goto et al ~ find the
fretting wear of an aluminium alloy to be greater in
wet air than in dry, and a systematic study of the
influence of humidity during the fretting of a range of
pure metals shows maxima in both friction and wear
at some critical value which depends on the metal
concerned ~a. Examples of the ~atter are shown in Fig
1. These trends are explained by suggesting that at
low relative humidities water interferes with the
adsorption of oxygen, reduces the rate of oxidation
and so permits a greater amount of intermetallic
contact. At high humidities, the greater amount of
water adsorbed becomes sufficient to augment the
protection against intermetatlic contact provided by
the oxide and wear then decreases. The latter is not
entirely convincing, however, because reduced wear
at high humidities is not always associated with reduced
friction, for example Ag in Fig 1.
Abrasive wear
The abrasive wear regime for metals is associated with
extensive plastic deformation and debris production
via micro-cutting and/or low cycle fatigue. In view of
Or
O0 IO 20 50 4~0 50
%rh
Fig 1 Effect of relative humidity on the stead~-sla~e
friction and wear of pure metals during .fretting in air
(after Goto and BucMe/21
the poor boundary lubricating p r o p e m e s of water_ ~
is therefore somewhat surprising to find t.hat water
vapour can nevertheless influence this type of wear to
a considerable extent. Larsen-Basse "3 has exami,~ed
the three-body abrasion of various metals by SiC
particles against a polyurethane wheen and found
appreciable increases in the wear tale a:oove a critica~
relative humidity. Examples are shown in Fig 2(a). On
the basis of SEM examinations he concludes that the
main reason for the increased wear ~s moisture-assisted
fracture of the SiC grains which leads ,,o a ~self-
sharpening' effect. Differences between individuai
materials are associated with varying degrees of
protection afforded by the oxide films and the way in
which they are modified by humidity. This seems to
imply that the oxides on A1 and Zn are more likely
to be affected by moisture-assisted fracture than those
on Ni and Fe alloys. [t is certainly true that wa~er
accelerates crack growth rates in A120314 but no simi1_ar
information is available concerning the other axides.
In two-body abrasion against coarse (120 grade) SiC
paper, the effects of humidity on wear are somewhat
different ~s (Fig 2(b)). Self-sharpening of the SiC grains
is again proposed, but only up to a critical humidit?"
beyond this it is suggested that the rate of gram
deterioration becomes so high that the surfaces are
blunted, leading to lower wear. There may aiso be
softening of the resin binder when large amounts of

372 December 90 Vo~ 23 No 6

 J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

water are available. The idea of self-sharpening of SiC

0.8
by moisture-assisted fracture is open to criticism on
Pyrex
the grounds that water does not normally increase
rates of crack growth in SiC m. The more usual
consequence of the presence of water, as will be
described later, is a tribochemical reaction ~7 which I
would tend to lead to blunting rather than fracture of z~
the grains. Mercer and Hutchings ~, in fact, find little 06 I
effect of humidity on wear rates during two-body
abrasion against fine (600 grade) SiC paper. It would
I
I
T
E o
% I
E
,£0.4
I
I
/ Ni
/ I
/ /ioi8 i
. 4
%/ B / /
% / / 0.2 I
E

o/
d 5 I
oL
6 /
/
/ o /
/ IO40 E040
{
~2 Itq
H20
1 t
o 0 50 I00
-- o o"" %rh
b

0 i i ~ [ I i z i i I
0 i0 20
PH20 , mm Hg
be of interest to repeat all these experiments using
6 0 6 3 ~T6 A1203 abrasives for which water-accelerated fracture
/ / is more probable.
/
/ / zn
7 // Lubricated conditions

In lubricated contacts, water can influence friction and

wear processes in three distinct ways. It may:
6
"//I / (1) modify the adsorption behaviour of long chain
organic compounds during boundary lubrication;
~7
(2) affect the interfacial chemistry of protective film
~:
%
5
"// formation by oxygen and/or additives present in
E // the lubricant:
*6 4
(3) lead to an increase in the pitting of rolling
elements.
//° ,&
~.o / Monomolecular layers of long-chain fatty acids are
well-known to be capable of providing boundary
3 __~.0__. Zn ~ Ii]/
~ _ ~. o=_::_ N /
lubrication for metals at relatively light loads and low
AA 7 Pyrex to moderate temperatures ~. The acids become much
2, //u [] more effective, however, when they react chemically
with a metal to form multilayers of soaps. The reaction
[] / proceeds via the oxide film and water plays a critical
~ o
I
role in 'conditioning' the oxide j'~, possibly by free-
[]
i
radical formation. Reactivity depends on the type of
oxide, where more than one exists as, eg with Cu and
o; ]- ,__ , , I , I L_ I Fe, and on the water concentration in the lubricant.
O IO 20 As little as 10 ppm of dissolved water is sufficient to
a PH20 ,mmHg initiate reaction 2°. An excellent review of all the early
Fi E 2 Variation of abrasive wear rates with humidity. work on water effects in boundary lubrication has been
(a) 3-body abrasion, 12Olin1 SiC, polyurethane wheel given by Campbell 2~.
(from Ref 13). (b) 2-body abrasion, 120 SiC paper. In all formulated lubricants, dissolved water and
(from Ref 15) oxygen are invariably present. Concentrations of water

TRIBOLOGY I N T ER N A TI O N A L 373
 J. K. Lancaster--The influence of environmental humidity and w a t e r on friction, lubrication and wear

depend on the type of base stock and are much greater,
for example, in synthetic diesters than in hydrocarbons.
Some types of additives may also increase the solubility
of water 22. Because of its high polarity, water competes
directly with other surface-active species in adsorption
processes and, in conjunction with oxygen, also contrib-
utes to the interracial chemistry of surface film
formation to provide protection against intermetailic
contact. The whole topic of additive interaction chemis-
try is too broad and complex to summarize in the
present context and a review has been given, for
example, by Fein 23. It must suffice here merely to
mention one or two examples of the rote of water.
Appeldoorn et at 24 have examined the lubricated wear
of steels in controlled atmospheres where the conditions
of sliding were insufficiently severe to lead to scuffing.
They postulate that in these conditions, wear is
primarily of the corrosive type in which oxide is
continuously being removed from the surfaces. As in
the case of dry sliding, mentioned earlier, the rate of
oxidation and the type of oxide can be affected by
water, and thus higher wear rates were observed in
wet air and argon than in dry air and argon. These
trends appeared to be largely independent of the type
of lubricant but other work conflicts with this. Fein 23
has shown that in hexadecane + 0.43% stearic acid,
for example, the wear of steel increases with increasing
environmental humidity whereas it decreases in a
neutral solvent. The interesting observation was made
that these humidity effects appeared to be associated
more with the atmospheric humidity present at the
time of cleaning the surfaces rather than with the
humidity of the air used to saturate the oils during
testing. 'Water-conditioning' of the surfaces may there-
relatively large fragments (compared with asperity
dimensions) are detached from the surface via fatigue
after a large number of repeated stress cycles. Pitting
occurs mainly in high stress conditions where the ,~,
ratio (elastohydrodynamic film thickness ro surface
roughness) is small and there is consequently a~
appreciable amount of solid-solid corttac~ occurring
through the lubricant film. [n this situation, crack
formation is believed to be initiated a~ the surface, in
contrast to that occurring with high )~ ratios where
sub-surface initiation is more probable 29. [t is now welt
known that the presence of water in the lubricant plays
a very important role in pitting failures and this has
been demonstrated both in simulation testing---rolling
four bal?°, 3~ and in comptete bearings 22, _~2.Examples
from both types of test are shown in Fig 3. As can be
seen from Fig 3(a) failure is accelerated even by the
very small amounts of water wkich dissolve in a
lubricant during exposure ~o humid air. It ha~ been
suggested 33 that such dissolved water may concert:rate
in developing cracks bv capillary condensation and
the presence of an immiscible water phase is thus not
an essential requirement. Pitting Iife decreases wit~
increasing water content (Fig 3(b)) but tends to approach
a limiting value beyond the point of satv.ration
solubility-;2o The presence of oxygen in addition to
water aiso influences pitting life. but the reported
8 i
90- t t o el /
& A
70-
I l i
,,t
o
I
®I t
t

fore have a long-term effect on their subsequent wear

behaviour, in a way reminiscent of that found in
Tingle's early experiments~9°
In most practical lubricated systems, oxygen and
2
¢e

"s
5O
i l
water alone are seldom sufficient to provide adequate 3O
protection against scuffing, although they may increase "5
the scuffing load to a limited extent 25. It is therefore 20
common practice to incorporate anti-wear additives in
lubricants to provide additional protection. The two CO

groups most widely used are the zinc organodithiophos- I0

phates (ZDPs) and triarylphosphates such as TCP
(tricresylphosphate). These materials decompose dur- I
0.5
I I I I I
1.0
I L ~ I
5.0
t I~1
t0.0
_

ing sliding and film formation occurs via reactions a Fatigue life, rnil lions of revolutions
between the decomposition products and the metal.
Decomposition studies 26 have shown that the presence
of water increases the rate of breakdown of ZDPs at
any one temperature and also increases the rate of
film formation on steel. With TCP, however, the
situation is more ambiguous. The wear-reducing action
of this additive is commonly attributed to hydrolysis27
leading to an acid phosphate which then reacts with
d

~5
o2
"2_

:f @ @

the metal surface. The presence of water, however,

does ~aot always seem to be beneficial and has been
shown to hinder film formation ~8. Some uncertainties,
therefore, still remain to be resolved. 0.1 I I L
25 100 400
b Water concentration, pprn

Pitting of rolling elements
One of the main limitations in the life of rolling
element bearings is the incidence of pitting in which
374
Fig 3 Variation of pitting fatigue life with humidly~, :(a)
Rolling 4-ball tests in mineral oil (from Ref 29). (b)
Tapered roller bearings in SAE 20 oil containing rust
and oxidation inhibitors (from Ref 22)
December 90 VoR 23 No 6
 J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

trends are conflicting. Some experiments -+~ suggest humid air than in vacuum and attribute this to a
oxygen is beneficial and reduces the fatigue-inducing greater adhesion of the resins to the oxidized surface.
effects of water, whilst others indicate the opposite > . A similar increase in adhesion has been reported 4~- for
PTFE sliding on steel in moist air, but in this instance
The causative agent believed to be mainly responsible
the increased adhesion leads to the formation of a
for water-accelerated crack growth during pitting is
transfer film and the friction decreases rather than
atomic hydrogen which penetrates into the steel,
increases.
leading to embrittlement of the highly stressed surface
layers ~4. Direct evidence of reduced pitting life follow- Changes in the friction of polymers m the presence of
mg hydrogen penetration has been obtained ++`' bv liquid water also depend on the type of counterface
electrolytically pretreating balls before testing, and the against which they slide. Polymers fire not 'wetted' by
penetration of hydrogen during pitting has been water so that when sliding against themselves, the
followed using tritium as a radioactive tracer -~. There friction is little different from that observed in dry
arc several ways in which hydrogen can be liberated conditions. However, against hydrophilic surfaces, such
during lubricated sliding and it is still not certain which as glass or clean metals, friction usually decreases. The
is to he considered the most important. Interactions left-hand side of Table 1 shows some results from two
between water, oxygen find freshly exposed metal sources 4~44. Tanaka 44 attributes the reduced friction
surfaces lead to peroxide and hydrogen formation ~'' and in water to a sharing of load support between contact
electrochemical corrosion will also produce hydrogen in through the water film and that between the solids
the atomic state tit cathodic regions within a crack ~. themselves, i.e. to a 'mixed" lubrication process. This
In addition, the dissociation of organic lubricants, is supported by the fact that the extent of the friction
irrespective of their water content, also liberates reduction in water increases with increasing speed.
hydrogen, as shown by tracer experiments with deu- Because polymers, in general, have relatively low
terium-labelled paraffins :~r. Hydrocarbons dissociate elastic moduli, hydrodynamic effects can become
during chemisorption on clean metals but not on oxides, significant at much lower speeds than with metals ~-4~'.
whilst fatty acids can be catalytically decomposed on There are some complications in behaviour, however,
both metals find oxides -~*. It follows that there is likcl\ with those polymers, such as nyhm 6.6, which absorb
to bc a wide variability in the extent to which hydrogen appreciable amounts of water and become plasticized
can be liberated during rolling contact, depending on with a consequent reduction in strength. Cohen and
the type of lubricant, the additives present and the Tabor 47 have shown that when water is added to nylon
water content. In these circumstances, it is hardly 6.6 sliding against itself, there is an immediate reduction
surprising that large differences have beet) found in in friction as a rcsult of absorbed water reducing the
pitting fatigue lives with different oils a''. shear strength of the outermost surface layer. With
increasing time, however, the water penetrates further
One other aspect should also be mentioned. It was
into the polymer and reduces the sub-surface strength
suggested 4" many years ago that lubricants might
also: the real area of contact then increases and the
accelerate pitting failure bv penetrating into a
friction rises again.
deveh'ping crack and inducing a wedging action by
hydrostatic stresses when the crack mouth is tempor- Not a great deal of information is awulablc concerning
arily closed during contact. This 'hydraulic effect' is the influence of atmospheric humidity on the wear of
now no longer believed to be a major factor in pitting unfilled polymers but, as with friction, the effects do
fatigue of rolling elements, but it could well be not seem to be particularly large. Results from one
significant during lubricated sliding wear, as will be
seen l a t e r .
Table 1 Effects of w a t e r on the friction and wear of
unfilled polymers. A: On 0.15 # m Ra stainless steel,
L = 10 N, V = 0.2 m s 1 (Ref 43). B: On 0.05 g m Ra
Polymers
stainless steel, L = 10 N, V = 0.01 m s 1 (Ref 44)
Unlike metals, the friction of polymers is not, in
general, particularly sensitive to the presence of surface Polymer Friction
contamination. Semicrystalline polymers, such as poly- coefficient, W e a r rate,
ethylene, acetal, nylons etc. usually show only small wet/dry wet/dry
differences in friction coefficients in vacuum, air or
inert gases. On the other hand, amorphous thermoplas-
tics, such as polystyrene or polymethylmethacrylate, A B A B
and cross-linked thermosets, such as epoxies or phe-
nolics, arc rather more susceptible to the environment Poly(phenylene sulphide) 0.72 -- 2.9 --
and tend to show somewhat higher friction in vacuum Poly(phenylene oxide) 0.6 -- 1.25 --
than in air. Hydrogen bonding may play a part in Acetal 0.58 0.65 1.1 1.6
increasing the friction of polymers containing OH Nylon 6 -- 0.66 -- 3
groups in humid environments. When sliding against N y l o n 6.6 0.73 -- 0.8 --
metal counterfaces, however, the effects of water
PTFE 0.8 0.9 0.6 2.36
vapour on friction can become more significant L.D. p o l y ( e t h y l e n e ) 0.42 0.18 0.4 0.74
because, as already mentioned, water is able to modify H.D. p o l y ( e t h y l e n e ) I 0.58 -- 1.7
the state of oxidation of the metal. McLaren and UHMWPE 0.48 -- 0.35 --
Tabor at. for example, have found the friction of Polyimide 0.85 1.08 8 7.5
silicone and epoxy resins against steel to be greater in

TRIBOLOGY I N T E R N A T I O N A L 375
J. K. Lancaster--The influence of environmental h u m i d i t y and water on friction, lubrication and wear
series of experiments, comparing the wear rates of
three polymers in air ( ~ 5 0 % r h ) , and a rough vacuum
( ~ 1 0 -3 torr) are shown in Table 2. The wear rates
are greater in air only by factors of 2 to 3. The
mechanism by which particles are detached from a
polymer surface during wear is believed to involve
microfatigue on an asperity scale 4s'49, but there is no
evidence suggesting that rates of crack growth in
polymers are particularly sensitive to environmental
humidity. The most detailed investigation reported on
humidity effects in unfilled polymer wear is by Fusaro 5°
for a steel ball sliding on polyimide films. H e observed
a transition to relatively low wear (and friction) in dry
air at a t e m p e r a t u r e between 25 and 100 °C, which
was associated with a rearrangement of the polyimidc
chains to become parallel to the direction of sliding.
In wet air, this transition is deferred to a higher
temperature (100-200 °C) because, it is argued, hydro-
gen bonding of water to the potymer chains reduces
their mobility. Below the transition temperature, wear
rates were not greatly influenced by the environment
but above this temperature, the wear rates were greater
in wet air than when dry.
The influence of liquid water on unfilled polymer wear
is also, in general, relatively small. The right-hand side
of Table 1 shows some results and, with the exception
of the polyimide, the changes compared with dry
sliding are all within a factor of about three. Depending
on the particular polymer, however, water can either
increase or decrease the wear rate. T a n a k a 44 suggests
that the increases in wear rate are attributable to
penetration of water into the amorphous regions of
semicrystalline polymers leading to plasticization and
enabling polymer fibrils to be detached more easily.
The reasons for reduced wear are less obvious, but
they may be connected with lower friction reducing
the localized stresses over the asperity contacts. The
effects of water on transfer to the counterface with
these unfilled polymers did not appear to be significant.
Tanaka 44 found approximately similar amounts of
transfer under both wet and dry conditions. The
differences between wet and dry wear rates have also
been shown, in one particular instance, to be dependent
on counterface roughness 5~. For U H M W P E sliding
against stainless steel in dry conditions, there is a
minimum in wear rate at a roughness of around
0.02 ~m Ra. In water, this minimum no longer exists.
Thus, against very smooth steel, the wear rate of the
polymer is lower in water than in dry conditions
whereas against rough steel, the opposite is true.
Table 2 Wear rates ( x l 0 -8 m m a N ~ m -~} of unfilled
and carbon-fibre-reinforced polymers against 0.15
t~m Ra mild steel in air { ~ 5 0 % rh) and vacuum {10 -3
tort}
Air Vacuum
Polyimide 0.45 0.15
Polyimide/carbon fibre 0.15 22
PTFE 510 360
PTFE/carbon fibre 2 12
Aceta t 10 4.5
Acetal/carbon fibre 0.7 0.09
376
Composites
~n contrast to the relatively small effects of "water
and environmental humidity on the wear of unfilled
polymers, as described above, those on fitted and
reinforced polymers are very much greater. Schubert 52
has reported the results of an extremely comprehensive
series of experiments to examine the influence of water
vapour on the wear of filled P T F E composites ip..
different gases at constant temperature, 70°C. A
selection of his data is shown in Fig 4. repiotted ira
terms of specific wear rate in units m m 3 N-Zm - t From
this figure, and the additional information given m the
original paper, the following points may be noted.
(1) in any one gaseous environment, the type of
filler greatly affects the magnitude of the wear
rate and the way in which it varies with humidity
(Fig 4a).
(2) Fillers which lead to tow wear in one oarticu~ar
environnment do not necessarily do so in another.
For example, the wear of an {unspecified) metal
oxide-filled PTFE is very low in a r b~at up :o
t000 times greater in nitrogen or helium.
(3) The trend in wear rate with humidity for any one
material differs, depending on the gas in which
the water is present. A carbon-graphke filled
PTFE_ for example, shows low wear and no
sensitivity to humidity in some hydrocarbon
vapours, but higher wear and a rapid increase a~:
~ow humidities in nitrogen or helium (Fig 4(b)),
(4) The variauons in wear rates with different fillers
tend to b e c o m e less extreme when sliding agains~
I 3 % Cr steel rather than the cast iron used in
mos~ of the experiments tsee the shaded area in
Fig 4(b)).
Although Schubert did not provide any information
about the condition of the worn surfaces, the above
trends strongly suggest that counterface effects play a
major role in the wear at different humidities and in
the differem gases~ Such effects will include oxidation.
transfer film formation and/or abrasive damage by the
fillersS3~ Some of these aspects were, in fact. noZed
m a similar, though less comprehensive° series of
experiments on filled PTFEs by Fuchsluger and
Tuber 54 They also observed considerable variations in
wear behaviour. In air. the wear rates of compos~[es
containing glass fibre or carbon-graphite increased witiq
increasing humidity, whereas those for a bronze-filled
P T F E decreased. In nitrogen, these trends were largely
reversed. P, is difficult to compare their results directi}
with those of Schubert. however° because dee s~iding
conditions were such that there mus~ have been
considerable frictional heating and temperatures were
neither controlled nor measured.
The main problem in attempting to accoun~ for the
above environmental effects on wear is the ~otal tack
of any information from which to characterize the
fillers. Carbons and graphites, for example, can exhibit
a wide range of properties depending upon their source
(natural or artificial), particle size and shape, degree
of graphidzation, and content of organic and inorganic
~mpurities ss. The more graphitic materials will tend to
form transfer fitms on the metal counterfaee but the
extent to which this can occur wilI vary, depending o~
December 90 Vo! 23 No
 J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

[
J

10-SL 10-5

/ \ Materials I- II on
XI5% Cr steel

N
9 \
10-6 __ 10-6
z z \ \ ~ ~ " Air
w l O

2
b
~. 10-7 / cJ

10-7

._____.__ N 2

He
10-8 10-8 _
-- C3H6
.. C3H8,H4HIo

C2H6

I
~0 -9 ____ I L J I J to -9 L J I 1 J ] I
10-2 I0 -I I iO 102 I03 104 10-2 I0 -t I I0 I02 I03 104
a ppm H20 ~ ppm H20

Fig 4 Variations of wear rate with humidity for PTFE composites (cd'ter Schuhert~-'). (a) Materials 1-II on cast iron
in N>. (b) Material 1 on cast iron ill various atmospheres

the level of abrasive impurity present and on the 10-5

1"
counterface hardness. Organic impurities may volatilize x
/

under the influence of frictional heating and act as a / / Hm

/
substitute for water vapour in preventing excessive
// No transfer
wear at low humidities, as will be described later. The iO -4 _ / or pohshing
/
size and shape of the filler particles will also affect the /
/
extent to which they can support the load preferentially. /
/
In any future work on environmental effects in E x/
composite wear it is therefore imperative that the ~ 2 : 1 0 -5 -- /' J Water
~x
fillers should be characterized as completely as possible. L-x . . . . . x~
E
Hs
The effects of liquid water on the wear of filled or Polishing
reinforced polymers are also considerably greater than 2
those on unfilled polymers. A detailed examination of
~ 10-6 _

the wear of carbon fibre-reinforced polymers ~' has

Transfer +
shown that when sliding against steel in dry conditions, Hs polishing
the fibres lead to reduced wear mainly by reducing the
i0 -7 _
initial counterface roughness by transfer or polishing, or
both. When water is added to a system in which a Dry
transfer film has been formed during dry sliding, the Transfer
film is almost instantaneously disrupted and the wear
t0 -8 _ _ I ~ _ _ t I J f
rate increases to a level characteristic of the initial 0 02 04 06
surface topography. This situation occurs with polymers Initial counterfoce roucjhness,iJm Ra
reinforced with high-modulus (graphitic) fibres. In
Fig 5 Effects o f .'uter o , the wear rates of 60% vol.
contrast, high-strength (carbon) fibres are considerably carbon fibre-reinforced epoxy resin sliding on stainless
more abrasive and lead to polishing of the counterface:
steel. H, = high strength fibre, H,,, = high modulus
the wear rates in both wet and dry conditions then
fibre. (from Ref 56)
become almost insensitive to the initial roughness.
These trends are all illustrated in Fig 5 for epoxy
composites. It may also be noted from this figure that additional factor relevant to wear in water other than
even when counterface polishing occurs with Hs fibres, the level of counterface roughness. It has been
the wear rates in water are still much higher than suggested ~7 that this could well be the hydraulic effect,
in dry conditions. There must, therefore, be some mentioned earlier in connection with pitting fatigue.

TRIBOLOGY INTERNATIONAL 377

J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

SEM examination of worn polymer composite surfaces

almost invariably reveals the presence of numerous
cracks or discontinuities, mainly at the filler-matrix
interfaces. The hydraulic effect may also be invoked
to account for the rapid disruption of the transfer films
formed during dry sliding when water is added to the
z
system.
The deleterious effects of water on the wear of polymer E

composites are particularly evident with filled P T F E c3

formulations. These materials normally exhibit low
wear in dry conditions as a consequence of transfer ?~ 10 - 5
films reducing the effective roughness of the coun-
terrace. Table 3 shows a selection of results. It should
be emphasized that the transfer films involved here
(in dry sliding) are mixtures of PTFE with degraded
filler debris and are relatively thick in comparison with ~o-6 </_ I I t iJ
the thin, smeared films characteristic of the unfilled 0 0.01 O, I I0 i0
polymer. The varying extent to which the wear rates % wf At203
increase in water with different fillers depends on the Fig 6 Effect of additions of 3p,m AI20~ o~ the wear
effectiveness of the fillers in promoting transfer under rate of PTFE containing 25% voL high modulus carbon.
dry conditions and their abrasiveness to the counterface fibres during sliding against stainless steel. Full curve:
under wet conditions. Different types of fillers vary in water; broken curve: dr)' (from Ref 59)
widely in their abrasiveness aS. In general, composites
containing the more abrasive fillers tend to show the
lowest increases in wear rate in water. In some
drcumstances, it may even be advantageous -~') to over 50 years ('°. It first assumed practical s~gnificance
incorporate small quantities of finely divided polishing during the Second World War. when the carbon
agents, such as A1203, into a composite to minimize brushes in electrical equipmew: of aircraft flying aT
wear in water; an example illustrating this is given in high altitudes were found to exhibit extremely high
Fig 6. rates of wear m. Similar effects were subsequently
In general terms, the most effective fillers for use in observed for graphite sliding in vacuum 6a inert gases ~'~
water-lubricated conditions are unlikely to be the same and even in ordinary environments at high loads
as those for dry sliding. In applications involving speeds and/or temperatures 64,(~5 An example of the
intermittent wet/dry operation, therefore, the choice latter is shown in Fig 7 for a graphitlc carbon sliding
of the most appropriate filler formulation will usually against a harder, non-graphitic one. In all cases the
be a compromise. phenomena appear to be very similar: the coefficient
of friction is high (0.5-1.0}o the rate of wear as typically
102-103 rJmes greater than the 'normal' rate. the
Carbons and graphite surfaces become severely roughened and the debris is
The sensitivity of the friction and wear behaviour of extremely finely divided. Dusting is initiated when the
graphite to environmental humidity has been known for partial pressure of water vapour relative ~o the
saturation vapour pressure. P/P,,, falis below some
critical value which depends on the environment and
Table 3 Influence of water on the wear of some
the contac~ temperature. In normal, water-containing
PTFE composites during sliding against 0.15 # m Ra
environments, the friction and wear of graphite are
stainless steel. L = 20 N, V = 1 m s -~
low because the basal planes become oriented approxi
mately parallel to the surfacd'~ and these planes are
low-energy surfaces which exhibit only weak adhesion
Fillers Dry wear Ratio
for each other ~'7. However. when a basal plane becomes
rate, wet/dry
t0 -7 mm 3 w e a r rate
damaged, high-energy edge sites are exposed for which
adhesior~ can be much greater. Friction and wear then
N-lm-~
only remain low if these edge sites can be neutralized
by the adsorption of water. [t is widely believed that
25% carbon fibre (HM) 3 500 adsorption is physicaP s. i.e. reversible, although this
Molybdenum* 13 310 view has recently been challenged '9 and the suggestion
25% glass fibre* 20 50 made that the adsorbed water may, in fact. dissociate o
Bronze-graphite* 2 45 The amount of water physically adsorbed is controlled
25% mica* 80 62 by the ra~io P/Po and can. therefore, be in~.uenced
25% asbestos fibre* 25 5 either by altering the amount of vapour present. P. or
25% coke* 8.5 4.5 by changing the temperature which affects Po. Ie
25% carbon fibre (HS) 7 1~7 ordinary, wate r-containing air. dusting is initiated when
25% carbon fibre (HM) + 5 1.6 P/Po falls below about 0.001: this corresponds to the
1% 3 ixm AI203 attainment of a critical temperature at the asperky
contacts of the order of 150 180°C. depending on the
*Commercial materials ambient relative humidity'~C This value of P/P, i,~

378 December 90 Vol 23 No 6

 J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

SLIDING ENVIRONMENT

06
g Increased severity of
sliding conditions
F_
4,
"6 0 4 I Higher contact temperature Reduction in partial pressure
"E I of water vapour, p
I
I
I
Po increases
~ Q2 B l
x x

,o/,oo falls below critical value

I I I _ _ I
8 12 24 4,
Increased adhesion

iO -2 Increased friction
f A
4,
Disruption of surface films
4,
Increased roughness
4,
Fewer contact areas

'E ~0 -B I __7,
4,
Higher contact temperatures Higher contact stresses

E
aJ
• I Brittle fracture of asperities
o

o) Carbon properties ~ Breakdown of debris in contacts

i0 -4
Increased s u r f a c e r o u g h n e s s

X
,,,X--
--x- X
i0 5 _ ~___ [ I~ I I
0 8 12
Speed, ms -I
Fig 7 Variation qf friction and wear rate with speed for
an electrographite sliding on carbon-graphite in air
(~50% rh, 20°0; load = 22 N. (A) Clean. (B)
Containing -~7°/i, wt of (NH4)e HP04 (from Re]" 74)
appreciably lower than that needed in vacuum (0.1)
because the adsorption of oxygen from the air sup-
plements that of water vapour 7". The attainment of a
critical temperature depends on the interactions
between two groups of parameters TM. On the one hand
are those which influence the rate of heat generation
and dissipation--load, speed, coefficient of friction,
thermal properties of the materials and ambient
temperature--whilst on the other are the factors
influencing the number, size and distribution of the
localized contacts--surface roughness, apparent con-
tact area, and third-body formation. In general, dusting
occurs most readily for rough surfaces with small
apparent contact areas sliding against counterfaces of
low thermal conductivity. The sequence of events
involved is shown in Fig 8.
The onset of dusting can be inhibited in a number of
ways. Organic vapours can substitute for water, and
the critical ratios of P/Po for hydrocarbons and alcohols
decrease monotonically with increasing chain
length ~'~-72. With heptane, for example, the critical
P/P,, at 30°C is only of the order of 10 5 compared
with that of 10 ~ for water vapour at the same
temperature. It follows that small traces of organic
TRIBOLOGY INTERNATIONAL
X--
1 STATEDUST,NG I
l~ig 8 Sequence of events involved in dusting (/?ore Ref
71)
I _ _
24
contamination present in carbons, which may volatilize
under the influence of frictional heating, could greatly
affect their friction and wear behaviour in dry environ-
ments. Most manufactured carbons and graphites are
porous and organic contamination is neither easy to
detect nor to remove. One interesting example of the
role of organic materials in preventing high wear in
the absence of water vapour is given by some results
for high-strength carbon fibre-reinforced polymers
sliding in air and vacuum. Table 2 shows that, as would
be expected, the wear rates of polyimide and PTFE
containing carbon fibre are both appreciably greater
in vacuum than in ordinary (moist) air. With the
acetal composite, however, the reverse occurs. In the
particular conditions of sliding used, the localized
surface temperatures were sufficiently high ( > 180°C)
to degrade the acetal, liberating formaldehyde which
could then substitute for the absent water. The greater
thermal stabilities of PTFE and polyimide effectively
preclude the formation of sufficient quantities of
organic vapour. Dusting can also be inhibited by
the incorporation into carbons of certain inorganic
compounds which tire widely used as anti-oxidants.
These compounds, for example POCI3 or
(NH4)2HPO4, function by adsorbing on dislocations
exposed on basal planes which tire the nuclei for
oxygen attack 73. One would therefore also expect them
to be effective substitutes for water in preventing
dusting and this turns out to be so TM. Line B in Fig 7
shows that the incorporation of 7 wt% of (NH4)2HPO4
into a graphitic carbon eliminates the transition to
dusting within the range of speeds, and hence contact
temperatures, examined.
379
J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear
Under very severe conditions of sliding for which the
critical temperatures reach values well in excess of
those needed to initiate the transition to high friction
and wear, dusting wear rates increase with increasing
partial pressure of water vapour, as shown in Fig 9.
This rather unexpected trend has been attributed 75 to
the idea that the mechanism of particle detachment in
dusting conditions involves crack propagation leading
to brittle fracture on a localized, asperity scale. Water
vapour then increases the rate of crack propagation in
proportion to its availability, ie pressure. In this
respect, therefore, carbons appear to behave in a very
similar way to some ceramics, as will be described
later. Crack propagation and fatigue are also believed
to be the predominant mechanism of particle detach-
ment in the normal, low-wear regime of carbons 7~ but
here there is no significant effect of environmental
vapour pressure 7"~. The difference arises because in
ordinary environments sufficient amounts of adsorbed
vapour are already available to migrate to a developing
crack tip77; the crack growth rate is therefore already
at its maximum value irrespective of the surrounding
vapour pressure providing, of course, that it always
remains above the critical minimum to avoid dusting.
Some particular grades of manufactured carbons,
usually incorporating metals or synthetic resins to
minimize porosity, are widely used for seals and
bearings in water-lubricated applications. Their wear
rates thus, presumably, remain adequately Iow for this
purpose. There appears to be no information available,
however, which directly compares these wear rates in
water with those in air. Most carbons give reIadv-eiy
low wear rates in air as a consequence of transfer fiIm
(x 10-4") 5
E
E at the appropriate specimen temperature on a single
e3
(3
L
I by the removal of adsorbed water from :he surfaces
VGCUGJm
(-IO-I Tort)
O IO 20
Pressure ,Torr
Fig 9 Variation of the dusting wear rate of electrograph-
ite on non-graphitic carbon with pressure of water
vapour. Load = 20 N, speed = 27m s ~, temperature
= 300°C (from R e f 72)
380
formation on a metal counterface and, by analogy with
what has already been described for P T F E composites,
water is likely to lead to increased wear by disrupting
these films. This has been observedS6; the wear rates
of a partially graphitized carbon and a non-graphitic
one sliding against 0.15 pm Ra stainless steel increased
in water by factors of 830 and 25 times, respectively.
The lower factor for the non-graphitic carbon is
attributable to its greater ability to polish the steel.
counterface in wet conditions. In view of the fact that
these materials were porous~ there could also have
been some cot~tribution to the increased wear in water
from the previously mentioned hydratflic effect. An
additional feature of significance in the wear of
carbons ,in water is electrochemical corrosio~ of metal
counterfaces because of the electronegativity of carbon
with respect to metals. A limited amount of corrosion~
however, can sometimes be beneficial to wear by
reducing the initial roughness of the counterface-~%
Lamellar solid lubricants
Most of the information concerning the influence of
water and water vapour on the performance of lame!far
solid lubricants is confined to McS2. Some limited dat
are available on related dichalcogenides of Mo. W
Nb. and Ta 7s but. in general, their behaviour parallels
that of MoS2. Unlike graphite. MoS2 is an intrinsic soIid
lubricant whose low friction is a direct consequence of
its lamellar structure and does not depend critically on
the presence of adsorbed vapours. This is not to say,
however, that vapour adsorption is irrelevant: on the
contrary, as will be seen° ~t can significantly affect
both the magnitude of the friction coefficient and the
wear life of deposited films.
It was first shown by Peterson and Johnson 7') that the
friction coefficient of a rubbed film of MoS2 powder
on a metal substrate in air containing water vapour
increased up to a relative humidity of 70% ann
then decreased again. The increase was subsequently
confirmed on numerous occasions 8°-u3 and a review of
some of this early work has been given by Wirier s~
An example of the scale of the humidity effect on
friction is shown in the top half 0 ~ Fig
" 10 w,h ere vabaes
of the static friction obtained at various ~emperamres
and air humidities are plotted against relative humidity
master curve. It has also been suggested 8° that tb.e
reductions in friction of MoS2 films which usually occur
with increasing load and speed can be who~iy explained
as a consequence of frictional heating. This idea
appears to be supported by Barry and Binkelman s-5
who found the friction of rubbed MoS2 films in dry
atmospheres to be independent of load and speed (Fig
11). The absence of any variation with load. however.
seems a little surprising because other experiments s'~
have shown that. irrespective of any humidity effects.
the friction of thin-film lubricants tends ~0 decrease
with increasing load because the constraining influence
of the substrate prevents the real area of contac~ from
~ncreasing proportionately with load.
The increased friction in humid environments of rubbed
MoS~ films is generally associated with an appreciable
December 90 Vo] 23 No 6
 J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

06

O,t5 - ~ ' ~ ' ~ " 4 L , - L = 1155N

0.5 _ o o
O.IC
A =L

0 0 5 0 % rh
0.05
0.4 Dry
g
_o A Z~ O
I I I _ I _ I I I
I 2 3 4 5 6 7
o Speed, I0 -2 m s -I
g0.3
o
0.15
_o
~ ~ - - ~ , j ~ 6 0 % rh

0.2 OiO
:=L
V = 7 . S m m s -I
,oc
0 05
0.1 Dry

I I I I I_ I
0 200 4-00 600 800 1000 1200
Load, N
0 _ _ ~ J__ I I I I
0 I0 20 30 40 50 60 70 Fig 11 Variation or friction with load and speed Jot a
a Relativehumidifyofspecimenfemperoture,% rubbed M o S 2 film on stainless ,steel in wet and dry air
(after Barry and Binkehnan '~-~)
o 4-5 - ( specimen femperofure,°C )
9000

of the contact zone. In moist environments, however,

there is oxidation of the MoS~ to MoO~ ~'~ which inhibits
E
the flow properties by increasing intcrparticle cohesion.
'Blistering" of the films then occurs, presumably as a
5
6000, consequence of the build-up of compressive stresses,
and failure is initiated by the break-up of these blisters
x~ and exposure of the underlying metal surface '~'. The
fact that water adsorption facilitates interparticle
cohesion in rubbed MoS~ films has been clearly
:6
demonstrated by Johnstone and Moore'" who found
o 40
•~ 5 0 0 0 increases in the film density, as assessed by x-ray
fluorescence, of 7-8 times when the humidity was
increased from 6 - 8 5 % . The films formed by burnishing
\ 030 at high humidities also exhibited a greater degree of
preferred orientation. There are thus two competing
0 140~ I 30 °125 I I I 025 effects: burnishing of MoS2 powder in humid air leads
0 I0 20 30 40 50 60 70 to thicker and more uniform films, but wear life is
b Relative humidity af specimen temperature, % greatest, and friction lowest, in dry air. It may also be
Fi~ lO Variation of (a) static friction and (b) wear life noted that there is some similarity to the behaviour of
with humidity' for a run-in film of MoS2 powder. Mild MoS2 in the influence of humidity on graphite fluoride,
steel discs', load = 600 N, speed = 0.35 m s ~ (front ( C F , ) , , films. Fusaro '~2found thicker and more uniform
Re,[ 83) ( C F , ) , films when burnishing in moist air. However,
in contrast to MoS:, the wear lives of films burnished
in moist air were always greater than those burnished
in dry air, irrespective of the humidity of the test
reduction in their life to failure, i.e. to an increase in
environment.
their wear rate. An example is given in the lower part
of Fig 10, obtained from thrust washer tests at various Although the reasons for the increased wear of MoS2
temperatures and humidities, and the same trend has powder films in humid environments seem to be
also been confirmed by others ~7's~. The processes reasonably well understood, those for the increased
occurring during the wear of an MoS film appear friction remain more obscure. Consider the situation
to be rather complex, Microscopic observation has of contact between an MoSe*covered surface and a
shown ~s that there is considerable flow and re- metal in a dry environment. In the initial stages of
coalescence of particles and, in dry environments, sliding, the magnitude of the friction coefficient will
failure ultimately occurs as a result of lateral flow out be determined by the shear strength of the surface

TRIBOLOGY INTERNATIONAL 381

J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear
layers. According to Briscoe and Smith 93, the value at
high pressures becomes approximately equal to the
pressure coefficient of the shear strength which for
MoS2 is around 0.15. Transfer then occurs to the metal
and, as a consequence of sub-surface shear and flow,
the surfaces of the films gradually become oriented
with the basal planes parallel to the surface. These
planes are low energy surfaces for which adhesion is
lOW94 and so the friction eventually decreases to a
relatively low value of around 0.05. The implication
now is that there must be true interfacial sliding
occurring between these basal planes. If a vapour is
admitted into the system at this stage, the consequent
rise in friction can only result from the re-introduction
of sub-surface shear by one of the following methods.
(1) Vapour penetrating the porosity within the films,
leading to reduced adhesion, film disruption and
a greater proportion of metal-to-metal contact.
(2) Adsorption of vapour onto the basal planes,
increasing the adhesion between them to a level
exceeding the sub-surface shear strength.
The former is inconsistent with observations that
vapours affect the friction of MoS2 compacts in just
the same way as for films on metats 9s and that the rise
in friction following v a p o u r admission is virtually
instantaneousS~: The latter is also difficult to reconcile
with the fact that vapours adsorb much more strongly
on the edge surfaces of MoS2 crystallites than onto
the basal planes 96. Further work thus seems to be
needed to clarify the role of vapours in MoS2 friction
more precisely.
To obtain thicker films and potentially longer wear
lives than is possible with burnished MoS2 films,
synthetic resins are commonly added to produce
'bonded coatings'. Other constituents may also be
incorporated into the formulations to improve particu-
lar properties, such as anti-oxidants or corrosion
inhibitors. The possibility of corrosion of ferrous
substrates by MoSz has been the subject of much
debate in the past because in the presence of oxygen and
water vapour, the most thermodynamically favourable
oxidation route is the one liberating sulphuric acid:
2Mo82 + 4H20 + 902--> 2M003 + 4H2SO4.
It is for this reason that there are p H limits of aqueous
extracts required in many specifications of MoS2
quality 9s and that the powder is often protected during
storage by containment in an inert gas atmosphere or
by the adsorption of long-chain organic inhibitors.
Environmental performance trends for bonded coatings
are much more difficult to categorize than those for
burnished films because the results depend so much
on the particular formulation involved. Fig 12, for
example, shows opposing trends in the wear
life-humidity relationship for two different formu-
lations 99. In liquid water, the effects on wear life are
less ambiguous: wear lives tend to decrease because
of the hydraulic effect mentioned earlier. Water has
been shown to reduce the life of burnished films s2,
whilst fluids in general reduce lives of both burnished
films m° and bonded coatings m~. In the latter case, the
extent of life reduction depends greatly on the precise
coating formulation.
382
(xtO4)
20
~15--
o~
1,4
L I f __i
0 20 40 60 80 I00
Relative hurnidity~ %
Fig 12 Effect of humidity on the wear life Gf two
bonded coatings. (i) MoS2 + modified epoxy resin;
(2) M o ~ + graphite + vinyl butyraI resin (after
DiSapio 99)
Ceramics
The friction and wear behaviour of ceramics ~s currently
attracting a considerable amount of research effort and
one of the most significant aspects is in attempting to
elucidate the role of environmental water. The evidence
so far available is confusing. Environmental humidkv
and liquid water appear ~0 increase friction and wear
in some instances and reduce them in others. Table 4
illustrates this variability with a selection of p u n i s h e d
information, whilst Fig 13(a) shows examples of the
differing friction trends for Ai203 and SiC.
Reduction of the coefficient of friction cart be attributed
to three main causes. First. adsorbed water molecules
may provide a limited amount of boundary lubrication.
as found with other material groups such as polymers.
Water could atso lead to shear s~rength reductions
in the surface layers by Rehbinder-type effects n2
Enhanced dislocation mobility and plasticity in the
presence of water has been demonstrated, for example.
with MgO n3 but similar effects with engineering
ceramics of more practical utility remain ,~0 be proven.
Second. with many ceramics tribochemicai reactions
can occur with water leading to the formation of
hydrated surface layers with shear strengths lower than
those of the parent materials, i.e. the reaction layers
function as solid lubricant films. The ro!e of these
layers will be discussed in more detail later in
connection with wear. Finally, the continuous removal
of reaction layers during sliding sometimes ieads t o
the generation of extremely smooth surfaces which are
then. in water, able to be lubricated hydrodynamically
even a~ very low speeds of sliding ~7. Increased friction
m the presence of liquid water seems most likely ~o
result from the fact that. as with other material groups.
water will prevent the aggregation of wear debris into
a coherent, protective, third-body ~ayer. In humid
environments, however, where such layers can still be
formed, adsorbed water may increase the interparticle
bonding within the layer, as already noted for MoS29~ _
and thus increase friction by increasing the shear
strength.
The effects of water on the wear of ceramics are
generally greater than those on friction: ~0 see why
December 90 Vo~ 23 No 6
 J. K. L a n c a s t e r - - T h e i n f l u e n c e o f e n v i r o n m e n t a l h u m i d i t y a n d w a t e r on friction, l u b r i c a t i o n a n d w e a r

Table 4 S o m e examples of the trends in friction and w e a r caused by increasing humidity or the addition of
liquid w a t e r for various ceramic combinations

Combination Experimental Environment Effect of water on Ref

configuration
friction wear rate

AI203/AI203 Pin/disc Varying rh Decrease Decrease 102)

Ball/disc " Increase Increase 103)
4-ball Water Decrease Decrease 104)
Pin/disc " -- Increase 105)
Si3N4/Si3N 4 Pin/disc Varying rh Decrease Decrease 102)
Pin/disc ",water . . . . 106)
SiC/SiC Pin/disc Varying rh Decrease Decrease 102)
Fretting . . . . . . 107)
ZrO2/ZrO2 Pin/disc Varying rh Increase Increase 108)
Fretting " Unchanged Decrease 109)
Pin/plate Water Increase Increase (110)
Pin/ring " Decrease Increase (111)

06 this should be so it is necessary to comment briefly on

current understanding of the ways in which ceramics
are damaged during sliding. There appear to be three
main processes 114

0.4 -- ~~'~,,~ o • AI205 (1) Plastic deformation leading to grooving. This is

often observed on a microscale e.g. Ref 115, but
"6 the extent to which it can make a significant
contribution to the total wear is still uncertain.
_ • • (2) Fracture, as a consequence of crack growth,
"~
--~ 02
(D • •
• ~ C which in the extreme may lead to the detachment
of whole grains but, more usually, results either
in grain chipping (transverse cracks) or flaking
(lateral cracks).
(3) Tribochemical reactions, usually with environ-
o___ ~ _ ~ _ I I mental water, which can either lead directly to
0 20 40 60 80 ioo wear by the continuous removal of reaction
a % rh
1©-5y product or may mitigate wear due to microfrac-
ture, as above, by providing surface protection,
lower friction and lower contact stresses.

It is therefore apparent that the presence of water

could either increase wear via water-accelerated crack
growth, or reduce wear by tribochemical film forma-
~ SiC
tion. These processes will compete with each other
E
g and the final outcome must obviously depend on the
particular ceramic involved,
J AI203 It is well known that water can accelerate the rates of
slow (sub-critical) crack growth in many non-metallic
IO-8 • • • materials~L The best known example is fl)r glass,
and results obtained by Wiederhorn ~7 are shown
schematically in Fig 14. Three regimes are identified.
At low stress intensities, I, the rate of crack propagation
jo9 I t L~ I I is controlled by the rate of reaction with water at the
O 20 40 60 80 IOO crack tip and increases rapidly with stress intensity.
b % rh At intermediate stresses, II, the rate of diffusion of
Fig 13 Variation with relatiw" humidity of (a) friction water becomes the controlling parameter in crack
and (h) wear rate Jor Al_,O.~/Al20.~ and SiC~SiC after growth. Finally. at very high stress intensities, I11,
lO~m of sliding. Ball on disc, load = 10 N, speed = rapid fracture occurs and the growth rate is no
O.l m s i (after Kapelski m~) longer dependent on water vapour concentration.

TRIBOLOGY INTERNATIONAL 383

J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear

10-41 B°r°silicafy'xxT H20 ~ 11

H20
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i0 -4 _
10-8 I I " I I I
4 5 6 7 8
Stress intensity Ki, N m-s/e (x 105)
Fig 14 Schematic variation of the rate of crack growth E
with stress intensity for soda-lime glass at different
humidities (after Wiederhorn n7)
;
-~: -5
'\
Experiments on the wear of glass, sliding against
smooth (0.02 Ixm Ra) tungsten carbide in conditions O %NkN X~
where the localized contact stresses remain well below \% \ weo~
T
the elastic limit, have shown that the wear rate E X
W
z \
increases with humidity in exactly the same way as the \
rate of slow crack growth in regime I (Fig 15(a)). % N
E \
Crack growth rates for glass in liquid water are also ¢o \
known to increase exponentially with temperature t19 ~10-6 -- N
®N
and Fig 15(b) shows that the wear rate again exhibits N
a similar trend, it is therefore of interest to examine \ I
N i
the extent to which ceramics might show similar \ x Crack growth
behaviour.
\ \o !
Al203 is known to be susceptible to water-accelerated
crack growth in an almost identical manner to glass !4
I0-7
80
I
60 40 20 ' 0 r,°C I
and increased wear rates have been observed in humid
environments (for example Fig 13(b)) and in water m3, 0.0030 0.0052 0.0034 0,0056 0.00:58
ms,ira,us. In support of this correspondence between b //fig)
wear and crack growth rates, it has also been found a2° Fig I5 Variation of the wear rate of glass against smooth
that the susceptibility of A1203 to increased wear in (0.02 # m Ra) tungsten carbide-cooak' " ' (a) rdative
w,,tn
water can be reduced by incorporating small pro- humidity in air; (b) temperature in water (from Ref
portions of ZrO2 into the Al203. These improve the zig)
fracture properties by limiting the extent of crack
propagation. However, the opposite trend of reduced
wear in water is also well documented m2,m4,n~. observed 121 when water is added to a fluid labricant0
Although A1203 has commonly been supposed in the as shown in Fig 16(a), and again attributed to
past to be essentially inert with respect to water, this the consequences of a tribochemical reaction, h is
does not seem to be correct. It has recently been interesting to note from Fig 16(b), however, that when
s h o w n m4 that tribochemical reactions can occur during sliding against rough surfaces the trend in the w e a r
sliding in water leading to the formation of an rates of A1203 with water content of the fluid is
atuminium hydroxide film which has a layer-lattice reversed: the higher stresses imposed by the rough
structure and is able to reduce both friction and wear. surface now lead to water-accelerated crack growth
Reductions in the wear rate of A1203 have also been becoming the dominant wear mechanism.

384 December 90 Vo~ 23 No 6

 J. K. Lancaster--The influence of environmental h u m i d i t y and water on friction, lubrication and wear

(xlO 4) IO that of the oxide ceramics. Although crack growth and

microfracture certainly contribute to the wear of these
materials ~23, water does not significantly affect their
rates of crack growth ~6. Tribochemical reactions gener-
ally dominate the trends in wear behaviour with
increasing humidity. These reactions are as follows:
Si.~N4 + 6H20 ~ 3Si02 + 4NH3
SiC+02+H20~SiO2+CO+ He
SiO~ + 2H20 --+ Si(OH)4
They lead to the formation of protective films of
hydrated amorphous silica which inhibit the contri-
bution to wear from microfracture. Wear rates thus
tend to decrease in the presence of water. Such
reductions have now been observed many times: SiC "j>
. 2-- / x
E PSZ IO3,107 Si3N41(12.1o6.123.124, and Fig 17 shows an example
-TZ .---~-X "~-'" X~ for SieNa. The protection afforded by the reaction
film against microfracture, however, depends on the
o2 0 - - I I____ I I imposed conditions of sliding, such as load, surface
a 0 25 50 75 IO0 roughness (contact stress level) and speed (time of
a exposure between repeated contacts~LS). The relative
[ contributions of microfracture and tribochemical wear
(x104) / are thus likely to vary between different types of
experiments.
150~
c The aspect of ceramics" wear which is currently least
understood is the part played by the third-body layers
AI203 of aggregated wear debris. The formation of such
I00 -- layers has often been reported (e.g. Refs 126,127)
le,- and, like reaction films, they reduce wear by protecting
/ x the original surfaces from direct contact. By analogy
PSZ
with the other material groups, the introduction of
5c ~- any fluid, including water, should increase wear by

I I I I 10-8 !
0
0 25 ,50 75 I00
Soturc]tion of diester with woter. %
b o DISC in Ar+ H20
Fig, lO Variation of wear rates of Al,O¢ and PSZ I ~ ~ • PIN in Ar+ H20
with water content in di-2-ethylhexylsebacate. (a) on E] DISC in Air+ H2O
"Syndite", (b) on 35 tzm diamond-impregnated poly- • PINin Air +H20
DISC in H20
ester strip (from Ref 121) • PIN in H2O

10-9
o
"vE
There is also some ambiguity about the role of water 'z
in the wear of ZrO2. Wear rates, or the level of surface
damage, have been observed to increase in water "'s d
.m,~,~Js,,z2 and when water is added to a lubricant
(Fig 16) or to decrease m2'u'~. In general, the number
of reported increases outweigh the decreases. Much
less seems to be known about the effects of water on 10-t0
crack-propagation and tribochemical reactions with
Z r O : than for other ceramics. It has been stated ~2-~ O0 Z~
following microscopic examination of worn surfaces, •
that water increases the rate of crack propagation and o
recent evidence, also from wear experiments, suggests
that tribochemical reactions can occur as well. Sasaki m2
has shown that the wear rate of Z r O , first of all
increases with relative humidity up to about the 20% 10-11 I_ I I I I
20 40 60 80 I O0
level, then decreases again. This trend is qualitatively Humidity,%
explained in terms of the competing effects of water-
accelerated crack growth and tribochemical reaction. Fig 17 Wear rates of S(¢N4 sliding against itself in
air and argon as a function of relative humidity.
The wear behaviour of SigN4, SiC, and Sialon in water Hemispherical pin on disc, load = 10 N, speed =
or humid environments is much more consistent than 1 rnm s i (from Re,[ 123)

TRIBOLOGY INTERNATIONAL 385

J. K. Lancaster--The influence of environmental humidity and water on friction, lubrication and wear
disrupting, or preventing the formation of, these third-
body layers. This was observed by Ajayi and Ludema ~26
during slow-speed sliding of a diamond hemisphere
o v e r A 1 2 0 3 , Si~N4,SiC and ZrO2, and has also been
noted with similar ceramics during sliding against a
metal-bonded diamond disc--'Syndite' ~Zl. Some results
from the latter experiments are given in Table 5. The
steady-state wear rates in air were all associated with
third-body formation, but such layers were no longer
obtained when sliding in water and the diester lubricant.
It is interesting to note that the wear rates in water
are all appreciably lower than those in the dried
diester, in agreement with the contention that water
can promote a tribochemical reaction.
Concluding remarks
The information presented in this review has revealed
a wide variety of different roles played by water in
friction and wear processes. Many of the effects of
varying humidity on the magnitudes of the coefficient
of friction and the rate of wear are relatively small,
but they are nevertheless still likely tobe of significance
when considering power requirements and life predic-
tions for components in service. Measurements of the
environmental humidity should, therefore, always be
included in any materials-testing or research pro-
gramme concerned with friction and wear. There are
three effects of water, however, which stand out as
being of major importance, namely its influence on
the following:
(1) crack propagation;
(2) reactions with the sliding surfaces;
(3) modifications to third-body layers of aggregated
wear debris.
When the friction and wear processes of particular
materials include any of these elements, some form of
humidity control during testing would appear to be
highly desirable. The first two are affected by water
in both its liquid and vapour phases. The fundamental
mechanisms involved appear to be reasonably welt
understood, although there is still some uncertainty
about how vapour adsorption leads to increased friction
with MoS2 films. The last of the three effects above,
however, is most important with liquid water and is
common to all material groups. Water effectively
Table 5 Wear rates of four ceramics sliding against
a 'Syndite' diamond counterface (~ 0.10 i~m Ra) in
air {~ 50% rh) water, and dried di-2-ethylhexylse-
bacate (from Ref 121}
Ceramic Wear rates, 10 5 mm a N-~m
Air Water Di-2-ethyihexylsebacate
AI203 1.5 5 40
SiC 6 !10 2OO
Sialon 0.5 6 105
PSZ 0.8 1.5 8 corrosio~ of ionic and mixed ionic/covalent so]ids. J. A m
386
prevents the formation of third-body debris layers or,
if introduced after such layers have formed during dry
sliding, leads to their rapid disruption via the 'hydraulic
effect'. The presence of water in the vapour phase
does not seem to inhibit the formation of third-body
layers but it must almost certainly affect their properties
as, for example, with burnished MoSz films9.. Little
is known so far about this aspect, the main problem
being that there is no convenient way in which to
characterize the properties of debris layers, such as
their cohesive strength or stiffness. One way of
approaching the problem might be via some form
of 'scratch' test on layers produced in different
environmental conditions. This, however, remains a
challenge for the future.
Acknowledgements
This paper was prepared during a period spent at the
Institut National des Sciences Appliqu6es de Lyon.
The author is greatly indebted to Prof. R. Hamelin.
Director of the [NSA and Prof. M. Godeto Director
of the Laboratoire de Mdcanfq~e des Contacts for the
provision of facilities, and to the Reglo~ Rh6ne-Alpes
and the Fondation Scientifique de Lyon e~ Sud-Est for
financial support.
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