LUBRICATION SCIENCE

Lubrication Science 2006; 18: 223–230

Published online 16 May 2006 in Wiley InterScience
(www.interscience.wiley.com) DOI: 10.1002/ls.19

Origins of the friction and wear properties of

antiwear additives

Hugh Spikes*,†
Department of Mechanical Engineering, Imperial College London,
Exhibition Road, London SW7 2AZ, United Kingdom

SUMMARY

Experimental techniques have been developed to measure the friction, antiwear film-forming and wear proper-
ties of lubricants in rolling–sliding contact. Friction measurements show that zinc dialkyldithiophosphates
(ZDDPs) and also some other phosphorus-based additives increase friction in mixed lubrication. Film thickness
measurements show that this increase in friction correlates with the thickness of antiwear film. They also reveal
some of the drivers of antiwear film formation and removal. A novel wear tester is described which enables the
mild wear resulting from ZDDP-containing oils to be monitored. Copyright © 2006 John Wiley & Sons, Ltd.

key words: antiwear; ZDDP; friction; film thickness; wear test

1. INTRODUCTION

Phosphorus-based antiwear additives and, in particular, zinc dialkyldithiophosphates (ZDDPs) have

been widely used in engine oils since the 1950s.1 Because of concern about the impact of phospho-
rus on exhaust after-treatment catalysts there have been considerable efforts in recent years to replace
these additives by other, phosphorus-free, alternatives. This has met with relatively little success and
instead most attention is now focusing on reducing the concentration of ZDDP in engine oils by opti-
mizing formulation and by augmenting ZDDP with other low- or zero-phosphorus supplements. This
phosphorus concentration constraint, together with the need to retain effective wear control over longer
and longer oil drain intervals, has made it very important to understand precisely how antiwear addi-
tives reduce wear.
An additional complication that has emerged in recent years is that some phosphorus-based anti-
wear additives, including ZDDPs, appear to enhance friction in boundary and mixed lubrication con-
ditions.2,3 This is unfortunate since modern engine oils are required to provide superior fuel economy

*Correspondence to: H. Spikes, Department of Mechanical Engineering, Imperial College London, Exhibition Road, London
SW7 2AZ, UK.
†
E-mail: [email protected]

Copyright © 2006 John Wiley & Sons, Ltd.

224 H. SPIKES

performance, which in turn implies very low friction coefficient. Clearly the ideal would be to iden-
tify an antiwear additive that gave very low wear and also low friction. Failing this, we need to achieve
the best compromise between friction and wear performance. To do this, we need to be able to quan-
tify and understand the origins of the influence of antiwear additives on both friction and wear.
This paper reviews studies by the author of the friction and wear performances of the antiwear addi-
tive ZDDP and shows how these help reveal the nature and properties of the films formed by this addi-
tive on rubbed surfaces.

2. TEST METHOD

The test apparatus consists of a minitraction machine (MTM) in which a steel ball is loaded and driven
in mixed rolling–sliding motion against the flat surface of a steel disc, as shown in Figure 1. Friction
is monitored using a load cell attached to the bearing housing of the ball drive shaft. Antiwear film
thickness is monitored by periodically halting ball and disc motion and loading a spacer-layer coated
glass disc, as shown in Figure 1, against the wear track on the ball. Interference images are then cap-
tured which enable a map of the thickness of antiwear film on the track to be determined (spacer-layer
imaging or SLIM).4 Wear is monitored by periodically sampling the test lubricant and using induc-
tively-coupled plasma optical emission spectroscopy (ICP) to measure the iron content of the sample.5
This combination of techniques enables friction, film formation and antiwear properties to be meas-
ured directly and correlated.

3. FRICTION BEHAVIOUR OF ZDDP

Figure 2 shows typical friction results.2 Periodically through a continuous rubbing test at 50%
slide–roll ratio, friction is measured over a range of entrainment speeds in order to obtain a ‘Stribeck

microscope +
spacer layer coated disc

steel ball
steel disc

lubricant
heaters

Figure 1. Schematic diagram of MTM rig with spacer-layer imaging optical attachment.

Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls
 FRICTION AND WEAR PROPERTIES OF ANTIWEAR ADDITIVES 225

0.16
100°C
100°C

0.12

Friction coefficient
0.08

0.04

initial 1 min 5 min 10 min

30 min 1 hr 3 hrs 4 hrs
0
0.001 0.01 0.1 1 10
Entrainment speed m/s

Figure 2. Variation of friction with rubbing time for a ZDDP in mixed sliding–rolling.2

curve’. It can be seen that, as the test time progresses and an antiwear film develops, this has the effect
of dramatically increasing friction at intermediate speeds. This behaviour has been seen with all
aliphatic ZDDPs studied as well as some other organophosphorus additives.
One possible origin of this behaviour is that the ZDDP antiwear film effectively roughens the sur-
faces, so that full film lubrication is only reached at a higher speed than would otherwise be the case.
ZDDPs are well known to form quite thick, pad-like structures on rubbed surfaces having diameter
typically 1–5 µm and height 100–200 nm.6 These pads are separated by deep fissures and it is possi-
ble that the latter act as drainage channels in the contact inlet so as to inhibit fluid entrainment.
This is an appealingly simple mechanism, but some recent work has suggested that even apparently
smooth ZDDP films show a friction increase and has indicated that the antiwear film may prevent fluid
entrainment by some other process.7 Whichever mechanism does occur, it appears that the ZDDP
inhibits fluid entrainment so that the contact remains in boundary and mixed lubrication over a wider
speed range than otherwise, and not, as sometimes suggested in the literature, by forming a boundary
film having high intrinsic friction properties.

4. FILM-FORMING BEHAVIOUR OF ZDDP

Figure 3 shows a series of optical interference images taken from the steel ball during a prolonged
rubbing test with ZDDP solution in mineral oil. From the interference pattern it can be seen that a film
gradually develops within the rubbing track. Negligible film is formed outside this track. Figure 4
shows how average antiwear film thickness increases with rubbing time, calculated from the images
in Figure 3.
Using this optical interference technique it is possible to explore the kinetics of antiwear film for-
mation and removal and also to identify the factors that drive antiwear film formation. By carrying
out tests at different entrainment and sliding speeds it has been shown that the film formation appears
to be stimulated by rubbing solid–solid contact itself and not from any local temperature or pressure
rise due to asperity contact.8

Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls
226 H. SPIKES

Initial 5 min 10 min

20 min 60 min 120 min

Figure 3. Interference image variation with rubbing time for ZDDP antiwear
additive solution in mixed sliding–rolling.

120
ZDDP reaction film thickness (nm)

80

40

0
0 1 2 3 4
Rubbing time (hours)

Figure 4. Variation of film thickness with rubbing time for a ZDDP in mixed sliding–rolling.

Figures 5 and 6 illustrate the impact of bulk oil temperature and ZDDP concentration for a primary
ZDDP.9 Clearly both the rate of formation and film thickness of film formed by ZDDP increases with
temperature, while the rate but not the final thickness increases with additive concentration.
This film thickness measurement method also enables the factors that promote removal of antiwear
films to be explored. To do this, films are first formed by rubbing the ball on the disc in a ZDDP
solution. Then this lubricant is drained and substituted by a ZDDP-free oil and rubbing continued.
When the ZDDP solution is replaced by base oil, the ZDDP antiwear film on the surfaces proves
to be remarkably resilient, showing no significant removal after several hours of rubbing.9 If,
however, a dispersant solution in mineral oil is used the film is quite rapidly removed, as shown in
Figure 7.9,10

Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls
 FRICTION AND WEAR PROPERTIES OF ANTIWEAR ADDITIVES 227

160
50°C
80°C

Film thickness (nm)

120 110°C
140°C

80

40

0
0 1 2 3 4
Rubbing time (hours)

Figure 5. Influence of temperature on film formation for 0.08% wt P concentration primary ZDDP.9

160
0.12 wt% P
0.08 wt% P
Film thickness (nm)

120 0.04 wt% P

0.01 wt% P

80

40

0
0 1 2 3 4
Rubbing time (hours)

Figure 6. Influence of ZDDP concentration on film formation for primary ZDDP at 80°C.9

This indicates that the well-known deleterious effect of succinimide dispersants on ZDDP antiwear
activity may be due not only to their complexing in solution with the ZDDP to reduce the latter’s
chemical activity but also to their weakening and helping solubilize the protective zinc phosphate glass
films formed by ZDDP on rubbed surfaces. Further work suggests that both of these effects can be
seen using the optical interference film mapping approach.

5. WEAR BEHAVIOUR OF ZDDP

We have recently developed a novel way of measuring mild wear.5 Most wear testers operate in ‘pure
sliding’ with one surface stationary, so that wear can be measured easily at the end of the test from
the dimensions of the wear scar on the stationary surface. Typical such tests are the four-ball wear

Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls
228 H. SPIKES

160
50 ppm N
500 ppm N

Film thickness (nm)

120 1000 ppm N

80

40

0
0 1 2 3 4
Rubbing time (hours)

Figure 7. Influence of succinimide dispersant concentration on removal of ZDDP

film in rolling–sliding contact at 80°C.10

test, the block on ring and the High Frequency Reciprocating Rig (HFRR). This approach creates a
number of problems. One is that, because all of the wear on one surface is highly localized, the contact
geometry and thus contact pressure usually fall markedly during a test, to the extent that the test often
ends up operating in mixed or fluid film lubrication. A second disadvantage is that such wear cannot
easily be monitored throughout a test, so that initial heavy wear that may occur before antiwear films
are generated cannot be distinguished from steady-state mild wear.
To address these problems, we have developed a test based on the MTM machine shown in Figure
1 operating in mixed sliding–rolling. Because both surfaces are moving, wear is distributed around
tracks on the ball and disc and thus does not result in significant change in contact conditions through-
out a test. To measure wear, chemical analysis of the lubricant is carried out using ICP. This is able
to measure concentration levels of Fe or other metals which, because of the MTM design, can only
originate from the ball–disc rubbing contact. ICP oil analysis means that wear rate can be monitored
throughout a test.
One particularly novel feature of the test is that, to achieve mixed sliding–rolling the ball and disc
are driven at different speeds in opposite directions, i.e. they are contra-rotated. This has the effect of
decoupling the entrainment speed (half the sum of the ball and disc velocities) from the sliding speed
(the difference between the ball and disc velocities). This overcomes the problem, endemic in all pure
sliding tests, that as the sliding speed is increased, so the entrainment speed and thus hydrodynamic
film thickness increase. Using contra-rotation, it is possible to rub the surfaces together at high sliding
speed (and thus high sliding distance) while remaining in controlled boundary or mixed lubrication.
Figure 8 shows results which explore the impact of P concentration on wear for a secondary ZDDP
in group II mineral oil at 80°C. All tests were carried out at an entrainment speed of 0.05 m/s (corre-
sponding to a specific film thickness of 0.5) and a sliding speed of 0.25 m/s. It can be seen that for P
concentrations above 0.03% wt there is a small amount of initial wear, presumably while an antiwear
film develops, but negligible wear thereafter. (It must, however, be noted that no other additives are
present and similar performance would be unlikely if dispersant were included.) At intermediate P
concentration, wear comparable to the base oil alone occurs, although with extended rubbing there is

Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls
 FRICTION AND WEAR PROPERTIES OF ANTIWEAR ADDITIVES 229

50
base oil
0.005% P
40 0.01% P
0.02% P

Fe concentration (ppm)
0.03% P
0.05% P
30 0.08% P

20

10

0
0 0.5 1 1.5 2 2.5
Rubbing time (hours)

Figure 8. Influence of ZDDP concentration on wear rate.5

some evidence of a fall in wear rate. At very low concentrations of ZDDP, wear rate is actually greater
than for the base oil alone. This is believed to occur because ZDDP reacts initially to remove iron
oxide from the surface and then forms a protective zinc/iron phosphate film.11 Low ZDDP concentra-
tions may be sufficient to remove the iron oxide and thus promote adhesive wear, but insufficient to
form a protective antiwear film.

6. DISCUSSION

This paper has described the use of three experimental techniques, all based on the use of a ball on
disc tribometer. These techniques are able to monitor friction, film formation and wear respectively,
and thus enable the performance of antiwear films to be studied in considerable detail.
Friction tests on ZDDPs show that the films formed by these additives appear to inhibit the entrain-
ment of lubricant into the contact, resulting in higher friction in intermediate speed conditions. In prac-
tical terms this would mean that a lubricated system experiencing cyclically varying entrainment speed,
such as a piston ring-liner or cam-follower, would spend a larger proportional of the cycle in high fric-
tion boundary lubrication conditions than would otherwise be the case.
As discussed in Section 3 above, the mechanism of this inhibition of fluid entrainment is still not
fully clear. By combining friction and MTM-SLIM, it has been shown that the effect increases with
increasing ZDDP antiwear film thickness.12
The ability to monitor antiwear film thickness, as described in Section 4 above, enables the factors
that promote and inhibit antiwear film formation to be investigated. This shows that ZDDP antiwear
films are remarkably resistant to rubbing, at least in the relatively smooth surface conditions studied.
Their rapid removal is only accomplished by the intervention of some other aggressive species, such
as a succinimide dispersant, or soot.9,13 It is also found that some dispersants are more effective in
mitigating the effect of soot on antiwear films than others.13
One limitation of antiwear film thickness studies until very recently has been that, while it is obvi-
ously of scientific interest to measure and monitor film thickness, it has not been clear what thickness

Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls
230 H. SPIKES

of antiwear film is actually necessary or desirable to control wear. Some early work has indicated that
wear control levels out above a critical ZDDP film thickness of about 50 nm.14
With the development of the wear test method described in Section 5 of this paper, this issue can
now be addressed since it is possible to monitor wear and film thickness simultaneously in the same
test. This type of work has just begun.

7. CONCLUSIONS

New experimental tools have been developed which enable antiwear additive film thickness, friction
and wear to be monitored continuously throughout mixed sliding–rolling tests. These are able to
provide insights into the way that the antiwear additives control friction and wear.

ACKNOWLEDGEMENTS

The authors wishes to thank Dr Lisa Taylor and Dr Romeo Glovnea, who helped develop and apply the MTM-
SLIM method, Tina Fan who carried out the wear tests described and PCS Instruments Ltd who adapted and
advised on the use of the MTM.

REFERENCES

1. Spikes HA. The history and mechanisms of ZDDP. Tribology Letters 2004; 17:465–485.
2. Taylor LA, Glovnea R, Ribeaud M, Spikes HA. The nature and properties of antiwear additive films. ITC Conference,
Nagasaki, Oct. 2000, Vol. II. JST: Tokyo, 2001; 1257.
3. Taylor L, Spikes HA. Friction-enhancing properties of ZDDP antiwear additive. Part I. Friction and morphology of ZDDP
reaction films. Tribology Transactions 2003; 46:303–309.
4. Cann PM, Hutchinson J, Spikes HA. The development of a Spacer Layer Imaging Method (SLIM) for mapping elastohy-
drodynamic contacts. Tribology Transactions 1996; 39:915–921.
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tion of tribological contact time. Tribology Letters 2002; 12:155–162.
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9. Fujita H, Glovnea RP, Spikes HA. The study of ZnDTP anti-wear film formation and removal process. Part I: Experimen-
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10. Fujita H, Spikes HA. The study of ZnDTP antiwear film formation kinetics. Presented at ITC, Kobe, May 2005.
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Copyright © 2006 John Wiley & Sons, Ltd. Lubrication Science 2006; 18: 223–230
DOI: 10.1002/ls