Wear 232 Ž1999.

168–175
www.elsevier.comrlocaterwear

Tribological properties of automotive disc brakes with solid lubricants

a,)
Luise Gudmand-Høyer , Allan Bach b, Georg T. Nielsen c , Per Morgen a

a
Physics Department, Odense UniÕersity, CampusÕej 55, 5230 Odense M, Denmark
b
Roulunds Fabriker, HestehaÕen 51, 5260 Odense S, Denmark
c
Tristan, KochsÕej 1, 2600 Glostrup, Denmark

Abstract

In automotive brake systems, high temperatures and pressures are generated at the contacting surfaces. This affects the pad and disc
materials, creating a friction film between the surfaces, which consists of wear particles and volatile reactants from the pad and disc. To
acquire suitable tribological properties, a pad matrix contains up to 20 different ingredients, mainly selected from experience. In the
present report the effect of solid lubricants has been studied in three different pad matrices with relatively few components as compared to
commercial brake pads. The components are Cu 2 S, PbS and Sb 2 S 3 , which are known to modify and stabilise the friction coefficient. The
friction coefficient and wear rates of the pads are examined on a dynamometer, which simulates series of real-life car brake events. Two
different energy levels and two ambient temperatures are included. After these tests, the brake disc surfaces are analysed with energy
dispersive X-ray ŽEDX. and Auger electron spectroscopy ŽAES. in combination with argon ion sputtering to study the microscopic lateral
and in-depth distribution of elements on and below the surface, looking for traces of the friction film. These experiments are used to
discuss the correlation between the tribological properties and the external variables — braking temperature, solid lubricants and pad
matrix. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: Tribology; Automotive brakes; Solid lubricants; Friction film; Surface analysis

1. Introduction original spare parts ŽOES.. Thus a better knowledge of the

The development of new pad materials is a complicated
matter as the components interact and synergetic effects
that are hard to disentangle arise. Quite often, the selection
of the different components is based on empirical experi-
ence, which means that some components are added for
reasons based more on tradition and less on knowledge
about their influence on the brake performance. In the
contact zone between the disc and pad, energy is trans-
ferred and heat is dissipated. As a consequence, a friction
film is created in the contact zone. The character of the
film depends on the friction pad formulation. Metal sul-
phides are known to modify and stabilise the friction
coefficient, though the more specific effects are not well
known. They are usually added though very expensive and
therefore primarily used for original equipment ŽOE. and
)
Corresponding author. Tel.: q45-65573509; fax: q45-65158760;
E-mail: lgh@fysik.ou.dk
effects of adding those components can improve the opti-
misation process and limit their use to minimise the price,
which is an important issue in the car industry.
Other groups have studied the formation of the friction
film. They looked for the influence of the film properties
on the friction coefficient. The chemistry of a solid transfer
film was studied with energy-dispersive X-ray ŽEDX. and
imaging XPS by Wirth et al. w1x. A wear-in period has
been described as the time during which the friction is
fluctuating with decreasing amount of material transfer as
stable conditions are reached. The specific role of additives
with respect to the relative amount of iron and oxygen in
the discs was discussed recently by Holinski w2x. The
formation of an iron layer on asbestos brake pads sliding
over steel surfaces has been investigated by Scieszka w3x
with SEM together with tribo-oxidation.
Experience from previous studies on friction film for-
mation under tribological testing with samples of hard ball
bearing steel indicated a very thin film of around 30 A ˚ w4x.
The references above have inspired us to study the
effects of metal sulphides on the formation of a friction

0043-1648r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 4 3 - 1 6 4 8 Ž 9 9 . 0 0 1 4 2 - 8
 L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175 169

Table 1
The composition of the friction materials is given in vol.%. The numbers in parenthesis indicate the reference friction material without metal sulphide
Main element Characteristic names Nmet Žvol.%. Low1 Žvol.%. Low2 Žvol.%.
Fibre Organic Žaramid. 5 Ž5.4. 11 Ž12. 5 Ž5.4.
Metal 9 Ž9.8.
Other inorganic 18 Ž19.6. 15 Ž16.3. 18 Ž19.6.
Fillers Barytes, friction dust, and vermiculite 41 Ž44.6. 25.5 Ž27.7. 29 Ž31.5.
Metals Brass 5 Ž5.4. 9 Ž9.8.
Abrasives Zirconium silicate 5 Ž5.4. 5 Ž5.4.
Aluminium oxide 0.5 Ž0.5.
Binders Resin, rubber 23 Ž25.0. 26 Ž28.3. 26 Ž28.3.
Metal sulphide Copper, lead or antimony sulphide 8 Ž0. 8 Ž0. 8 Ž0.
Total vol.% 100 100 100

film in a brake system and its effect on the surface of the
disc as indication of specific wear and friction behaviour.
2. Materials and experimental procedures
2.1. Friction pad formulation
Three different base matrices are designed especially
for this project, and they are simplified and compared to a
commercial brake pad. The matrices are: one with no
metal fibre ŽNmet. and two with a low content of metal
fibre ŽLow1 and Low2.. The Nmet is very simple with
only six components while Low1 and Low2 consist of
13–14 constituents. Three different metal sulphides are
added to the base matrices to examine their effects. We
labelled the different brake pads with the base matrix and
the respective additive, e.g., Low1-Cu is the label of base
matrix Low1 with 8 vol.% Cu 2 S added, and Low1-Ref
designates the base matrix Low1 without metal sulphide.
In this case the vol.% in Table 1 are adjusted to equal a
total of 100% of the components in the brake pads.
2.2. Tribological tests
The samples are tested on a dynamometer equipped
with a car brake caliper. Two test procedures — one at
low and one at high duty — are designed to examine the
effects of the metal sulphides at two different energy
inputs. The test at low duty Ž1A. consists of 600 braking
cycles performed from 50 kmrh down to rest. When the
temperature of the disc has decreased to 508C, the next
braking cycle begins. Each braking is performed with a
constant braking pressure. During braking the torque is
measured, from which the friction coefficient is extracted
as the ratio between measured momentum and braking
pressure multiplied by a constant value accounting for the
geometry. A similar procedure is performed at high duty
Ž2A., and the parameters are summarised in Table 2.
Before each test a new disc is mounted on the rig. The
discs used are Volvo standard rear discs, which are unven-
tilated. After testing, the discs are labelled according to
type of friction material and test procedure, e.g., Low1-Sb-
1A corresponds to base matrix Low1 with antimony sul-
phide tested at 1A.
After the dynamometer testing, the discs are cut into
pieces of 14 = 14 mm2 with a saw while cooling with a
commercial fluid to prevent heating. The samples are
stored in atmospheric air before analysis. The wear of the
pads is measured as change of thickness Žmm. and weight
loss Žg.. Compared to the friction material, the wear of the
discs is estimated to be much lower as it is immeasurable
using a micrometer screw.
2.3. Surface analysis
First, the samples of the disc are analysed in a Jeol 35
keV electron microscope with an EDAXe EDX system.
The analysis is performed as a spot analysis, using a
primary energy of 15 keV. The composition is calculated
from the peaks with the EDAXe computer program that
fits the background of the spectra with a smooth function
and subtracts it from the spectrum. The peaks are com-
pared to standard spectra from a database, and evaluated
with the ZAF-method w5x. The surfaces of the discs are
examined with SEM in which an image is created with
secondary electrons ejected from the surface. The combi-
nation SEMrEDX is a strong tool to get a quick overview
Table 2
Dynamometer tests 1A and 2A, indicating the initial velocity from which
the braking is performed, the initial temperature of the disc when each
braking cycle begin, and the applied brake pressure. The cycles are
repeated N times
Dynamometer Velocity Temperature Pressure Stop no.
test Žkmrh. Ž8C. Žbar. ŽN.
1A 50 70 30 600
2A 120 200 40 350
170 L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175

of both the topography and the main composition of the

surface of a large number of samples in a short time.
Afterwards, a selection of the samples is examined with
Auger electron spectroscopy ŽAES.. This is done with 3
keV primary electron energy combined with depth profil-
ing using 1 keV argon ion sputtering for 1 min between
each recorded spectrum. This analysis method is very
surface sensitive and gives the concentration of the compo-
nents with depth as spectra are recorded between each
cycle of argon iron sputtering. With AES it is possible to
see other elements than with EDX, e.g., oxygen and
carbon which are believed to play an important role in the
formation of a friction film.

3. Results

3.1. Friction and wear

The average friction levels measured for each braking

cycle for dynamometer tests 1A and 2A are shown in Fig.
1. The two graphs show how the friction level develops
from the beginning, during conditioning Žbedding-in. until
the end. At that stage the friction level is stable and the
surfaces are analysed to study the existence of a friction Fig. 2. Dynamometer results. The average friction of the different friction
materials tested against cast iron brake discs ŽB.. The pad wear Ž=.. Ža.
Dynamometer test 1A. Žb. Dynamometer test 2A.

film. These results are typical for all friction materials,

Fig. 1. The friction levels of different brake couples measured on a
dynamometer. The shown friction material is base matrix Low1 with
Cu 2 S, PbS or Sb 2 S 3 , and the reference without a metal sulphide. Ža.
Dynamometer test 1A. Žb. Dynamometer test 2A.
though with some variations in the friction level between
the three base matrices.
The results of wear and friction are visualised in Fig. 2.
The friction value is the average value of the measured
friction after the bedding-in period when the friction has
stabilised, which is respectively after 200 and 100 stops for
dynamometer test 1A and 2A. A comparison of the differ-
ent friction materials for dynamometer test 1A shows little
variation of the wear, around 0.1–0.3 mm. The friction
varies from 0.36–0.53. For all three base matrices the
friction is highest for Sb 2 S 3 , around 0.47–0.49, and a little
lower for PbS, around 0.40–0.47. The largest variations
are seen with Cu 2 S, from 0.37–0.53. For dynamometer
test 2A, the wear varies much more with the friction
material, from 1.5–6.5 mm. The wear is by far highest for
base matrix Nmet and much lower for Low1 and Low2.
The addition of one of the metal sulphides to Low1
improves the wear, and the situation is opposite for Low2.
Addition of Cu 2 S leads to relatively higher wear and
Žsometimes. lower friction.
The repeated measurements show some variations for
both friction and wear. The variation is 5–10% on the
friction, and 20–30% on the pad wear. Several factors
cause the large variations of wear. Before the weight
 L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175
measurement, wear particles are not removed. The thick-
ness is affected by the permanent swell of the pads after
heating. The roughness of the discs varies, which can
cause different wear during bedding-in. The result is there-
fore to be used merely as indication of the trend.
3.2. SEM
The surfaces of the discs are examined with SEM in
which the image is created with secondary electrons ejected
from the surface. The image reflects a dependency both on
topography and composition. Fig. 3 shows an image of a
new disc before and after testing scanned with 15 keV and
magnified 400 = . The underlying longitudinal lines are
from the machining of the disc. Apart from that, two
different areas are circled. One area looks smooth Ž S . and
the other area is rough Ž R .. Both types of areas are found
on all the discs including the new disc. The next paragraph
presents the results of EDX examinations of the rough and
smooth areas to demonstrate the character of the friction
film.
3.3. EDX analysis
After testing, all the discs have been analysed with
EDX at a smooth and rough area. The overall results are
discussed by comparing two discs, one tested against the
reference material without a metal sulphide and the other
tested against a friction material with antimony sulphide.
The variation from sample to sample is comparable to the
differences between the individual friction materials. The
scatter from spot to spot on one sample reflected the
surface topography; thus, the smooth areas were similar in
composition.
Fig. 3. Typical SEM images of a cast iron disc before and after testing on a dynamometer. The rough Ž R . and smooth Ž S . areas are indicated with a circle.
Ža. New disc. Žb. Low1-Sb-2A.
171
A typical example of the EDX analysis of the discs is
shown in Figs. 4 and 5 of Low1-Sb-1A and Low1-Sb-2A,
respectively, giving the composition of both a rough Ž R .
and a smooth Ž S . part of the discs. The spectra in Fig. 4a
and Fig. 5a are both recorded at a smooth Ž S . area. The
former shows no other components than those from the
disc: silicon, iron and manganese. The latter shows some
similarities with Fig. 4b and Fig. 5b, which are recorded at
rough Ž R . areas on the discs. These spectra contain peaks
from components with origin in the pad matrix.
The existence of several components with origin in the
pad indicates a transfer of friction material. The ratios
between antimony and sulphur, and barium and sulphur,
which are original compounds in the pads, are especially
interesting. If chemical changes have taken place, their
ratios in the discs should have changed from the values of
the original material.
The element concentrations for Low1-Sb-1A and 2A
and Low1-Ref-1A and 2A are calculated from the spectra,
as shown in Table 3. For all eight measurements shown,
except for Low1-Ref-1A, the ratio MnrFe is almost the
same. At the rough areas, the ratio BarS and SbrS are the
same for Low1-Sb-1A Ž R . and Low1-Sb-2A Ž R ., but the
concentrations are different. This indicates that the surface
layers are similar and that the same reactions have taken
place, but the thickness of the layers is different.
At the smooth areas no antimony and barium is found
for Low1-Sb-1A Ž S ., only sulphur, copper, and zinc. This
is in contrast with the spectrum of Low1-Sb-2A Ž S ., which
contains the same elements as Low1-Sb-2A Ž R . but the
ratios between the elements are different. Compared to
Low1-Sb-2A Ž S ., Low1-Ref-2A Ž S . contains 10 times less
sulphur and no barium, indicating that no friction material
 172
L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175
Fig. 4. Typical EDX-spectra measured on the cast iron disc surface tested against friction material Low1-Sb-1A. The spectra are recorded on Ža. a smooth area and Žb. a rough area.
 L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175
Fig. 5. Typical EDX-spectra measured on the cast iron disc surface tested against friction material Low1-Sb-2A. The spectra are recorded on Ža. a smooth area and Žb. a rough area.

173
174 L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175

has been transferred at the smooth areas for the reference

material. The ratio ZnrCu is the same for Low1-Ref-1A
Ž S . and Low1-Ref-2A Ž S ..

3.4. AES depth profile

The existence of antimony on the surface can be ob-

served in Fig. 6 showing a decreasing concentration with
depth; thus, antimony has been transferred and dissolved at
the very upper surface of the disc. The amounts of iron,
oxygen and carbon also change with depth. The oxygen
concentration follows the iron concentration closely, in-
creasing with depth whereas the carbon concentration de- Fig. 6. A typical AES depth profile measured on the cast iron disc surface
creases. The ratio between iron and oxygen indicates that a tested against friction material Low1-Sb-1A. Intensity of the signals from
homogeneous phase of FeO has formed at the surface. This oxygen, carbon, iron, antimony and sulphur is mounted against sputter
time in minutes.
iron oxide phase is stable compared to higher oxidation
levels and is discussed by Jansson et al. w6x. A further
tored by EDX shows a much higher concentration of
discussion of the AES analysis of all samples is to be
sulphur in Low1-Sb-2A Ž S . compared to the other sam-
published later in relation to a discussion of the general
ples. The presence of oxygen and carbon is monitored by
concepts of formation of the friction film.
AES, showing an oxidised surface covered or passivated
by a thin carbon layer. The systematic changes of friction
and wear with temperatures are seen from Figs. 1 and 2. It
4. Discussion
is noted how a higher brake temperature minimises the
bedding-in time, before friction stabilises. The addition of
It takes many small bits of information to create a full
copper sulphide causes a gradual loss of friction while lead
picture of the effects, e.g., to see which constituents have
sulphide and antimony sulphide stabilise the friction, at
been transferred and which are gone or not active. Also,
both the higher and lower temperatures. For antimony
the atomic stoicheiometric percentages indicate if there has
sulphide, the absolute friction level decreases strongly at
been any chemical change. When one component is pre-
the higher temperature while for lead sulphide it stays at
sent with a different relative amount than the original
the same level. In the absence of metal sulphides, the
constituent, as in the case of barium sulphate and antimony
friction varies more between the two temperatures, increas-
sulphide, it indicates a chemical reaction.
ing with temperature.
The present measurements and procedures allow for at
The wear generally increases with temperature, and in
least a partial understanding of the friction film formation
particular for pads without metal fibre content. The wear is
process. This is definitely demonstrated here with Low1-
generally much smaller and roughly independent of the
Sb-2A where a friction film forms at 120 kmrh, 2008C,
pad matrix and the content of metal sulphide for dy-
and a brake pressure of 40 bar at the presence of antimony
namometer tests at low duty in contrast to high duty
sulphide in the pad. In this case, even smooth-looking
testing. Discs with considerably fewer wear tracks than the
areas of the disc have undergone compositional modifica-
average show higher wear of the brake pads, under other-
tion, as shown with EDX. The presence of sulphur moni-
wise similar conditions.

Table 3
Surface concentration measured with EDX of the cast iron discs tested 5. Conclusion
with the friction materials Low1-Sb and Low1-Ref analysed at smooth
Ž S . and rough Ž R . areas on the discs The variation in friction and wear between different pad
Element Low1-Sb-1A Low1-Sb-2A Low1-Ref-1A Low1-Ref-2A matrices is much larger when braking is performed at high
Ž S. Ž R. Ž S. Ž R. Ž S. Ž R. Ž S. Ž R. temperature and pressure than at low temperature and
At.% At.% At.% At.% pressure, where, furthermore, there is no significant effect
SiK 2.7 5.1 4.8 5.6 3.1 6.5 3.3 10.3
of the metal sulphides. This correlates with the surface
SK 0.1 4.9 1.2 10.0 0.1 3.0 0.1 12.1 analysis, which indicates that no friction film is formed on
SbL – 2.1 0.4 4.2 – – – – the disc at low duty.
BaL – 2.7 0.4 5.6 – 2.9 – 14.9 The evidence for the existence of a friction film is most
MnK 1.2 1.2 1.2 0.8 0.6 1.2 1.4 0.8 clearly obtained from the studies of the smooth areas of
FeK 95.4 75.2 89.5 58.7 95.1 78.0 93.9 53.9
CuK 0.5 6.5 1.2 10.8 0.9 5.9 0.9 6.7
the discs. Here the surface contained elements from the
ZnK 0.1 2.1 1.3 4.1 0.3 2.5 0.4 0.5 pad matrix with a changed material composition compared
to the pad matrix.
 L. Gudmand-Høyer et al.r Wear 232 (1999) 168–175
From the microscopic pictures of the surfaces together
with the surface analysis, it is clearly indicated how the
wear and contact to the pad influences the disc surface
topography and composition.
Acknowledgements
This project is supported by ATV and STVF, Denmark.
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