Towards A Better Understanding of The Reaction Between Metal Powders and The Solid Lubricant Sb2S3 in A..
Towards A Better Understanding of The Reaction Between Metal Powders and The Solid Lubricant Sb2S3 in A..
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2 authors, including:
AneMaite Martinez
Ecole Centrale de Lyon
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Article history:
Received 24 June 2015
Received in revised form
2 November 2015
Accepted 5 November 2015
Available online 29 November 2015
During braking, high temperatures can be generated on the contact surfaces and inside the brake pads.
Solid lubricants, i.e., metal sulphides, play an important role in brake performance, but they can react,
oxidise or decompose with exposure to temperature, modifying their tribological properties. This paper
investigates the chemical reactions between different metal powders (Cu, Fe, Sn and Zn) and Sb2S3 that
take place in a low-metallic brake pad during braking in conditions were high temperature is generated.
The reaction products were characterised by SEMEDS and the glancing XRD technique. Moreover,
thermal treatments (in air and argon) of binary mixtures, containing the same weight ratio of these metal
powders and Sb2S3 contained in the brake pad, were carried out and analysed via DSCTGA and XRD
techniques.
The paper nds that the reaction features and reaction products depend on the temperature generated during braking, the specic combination of metal/lubricant and the atmosphere conditions
(oxidant or inert). In general, the reaction products are a combination of an intermetallic (metallic
antimonide) and a metal sulphide (from the metal powder), which can be found both on the surface and
inside the brake pad.
& 2015 Elsevier B.V. All rights reserved.
Keywords:
Friction
Solid lubricant
Low-metallic brake pad
Transfer layer
DSCTGA
Glancing XRD
1. Introduction
In order to achieve the desired friction and wear performance,
automotive brake friction materials are complex composites consisting of a combination of more than 10 ingredients [1]. These
ingredients are frequently classied into four core classes: binder
resins, friction modiers, reinforcements and llers [2]. The type
and amount of these ingredients are determined mostly based on
experience, empirical observations [1,3,4] or a trial and error
method when making new formulations [4]. Among the friction
modiers used to produce brake pads solid lubricants play crucial
role in reducing the wear of both pad and disc, optimising friction
levels and controlling brake-induced vibrations [5].
While the temperature of the brake pad and disc increases
during braking due to the transformation of the kinetic energy of
the rotor into thermal energy, the degradation of the phenolic
resin takes place, leading to a dramatic decrease in the friction
coefcient and the increase in wear, the so-called fade (loss of
brake effectiveness at high temperature due to frictional heat). At
n
Corresponding author.
E-mail address: [email protected] (J. Echeberria).
http://dx.doi.org/10.1016/j.wear.2015.11.014
0043-1648/& 2015 Elsevier B.V. All rights reserved.
28
29
Fig. 1. SEM images of the metal powders (a) Cu, (b) Sn, (c) Sponge Fe, (d) Zn coarse, (e) Zn ultrane, and (f) lubricant Sb2S3 (black particles are impurities of SiO2).
Table 1
Details of the selected metal powders and the solid lubricant.
Powder
Cu
Sn
Supplier
Ave. Particle
size
o 45 mm
2.83.2
o 45 mm
499.7
3.8
475 mm
(69%)
Zn coarse
Pometon Powder-S 445 mm
(66%)
Zn ultrane COMETOX
34.5
QUARTZ-Anty65
o 45 mm
Sb2S3
Sponge Fe
2.15
499.7
3.03
98.5
77.2
4.6
Table 2
Relative content (wt%) of raw materials in the brake pads' friction materials.
Ingredients (wt%)/Designation
Parent composition
Sb2S3
Copper
Sn
Sponge iron
Zn (coarse)
Zn (ultrane)
Carbon Fibres (CF)
F1
F2
F3
F4
F5
84
6
10
84
6
84
6
84
6
84
6
10
10
10
6
4
a
Binder (Phenolic resin) 6.5 wt%; friction modiers (alumina, magnesia, graphite, coke, iron oxide) 28 wt%; reinforcements (steel bre, aramid bre) 26 wt%;
llers (NBR powder, barite) 23.5 wt%.
this study to test the friction materials. This test was divided into
two different sections, cold and hot. In the cold section sensitivity
to speed and pressure changes were studied in the friction
material, while in the hot section the temperature in the interface
reached 500 C, simulating extreme braking conditions. Most of
the results from the AK-Master test were reported in the Eurobrake congress EB2014-DF-002 paper [17]. These dyno tests were
used mainly for obtaining the worn brake pads to be characterised
30
Table 3
SAE J2522 AK-Master dynamometer test procedure.
Section
Description
as tin, barite and Sb2S3 show similar contrast but again different
particle size. In the F1 mixture with Cu powder, the steel bres and
Cu powders show a similar contrast, but while copper powder
show rounded and smaller particles, steel bres are longer.
On the other hand, the open structure of the sponge iron powder
used in F3 formulation is clearly observed, and it is very different
from the steel bre morphology. Finally, the most signicant feature
is the difference in the size and morphology of the Zn particles on
the surface of formulations F4 and F5. While in F4 large particles of
zinc are well distributed around the surface, in F5 the zinc ultrane
particles are in general observed as agglomerates.
3.2. Friction performance at high temperature
The friction behaviour of the different brake pads during Fade
1 and Recovery 1 sections is shown in Fig. 3, where the effect of
the temperature on m is studied. F5 is not included to its similarity
with F4. It could be observed how formulations F1 and F4, with Cu
and Zn powder respectively, show the highest fade resistance with
a smother reduction of the m, more obvious in the rst brakings at
temperature 4500 C. Formulation with Sn powder (F2) appears
to have the lowest fade resistance with the highest decrease of m,
while F3 with sponge Fe show an intermediate behaviour.
3.3. Study of the worn brake pads
In Fig. 4, the surfaces of the worn brake pads for formulations
F1 (Cu), F2 (Sn), F3 (Fe) and F5 (Zn ultrane) are shown. F4 with Zn
coarse powder is not included due to its similarity to F5. These
SEM micrographs of the friction surfaces show how a friction layer
formed on the surface of all brake pads tested and that it covers a
large part of the worn surface (in a grey contrast). In all cases the
presence of some of the initial constituents of the brake pad formulations (graphite particles and steel bres) can also be distinguished in a dark and lighter grey contrast, respectively. In
addition, some white contrast zones can be observed on these
bres, which apparently indicate areas where the steel bre had
reacted during dyno testing with some of the constituents in the
formulation (Sb2S3 and/or the different metal powders).
The extent of this reaction depends on the metal powder present in the pad formulation. While in F1(Cu) the steel bres nearly
maintain their morphology and chemical composition (only minor
amounts of Cu and Sb have been found on their surface), in F2(Sn)
these bres have a very white contrast, indicating that they have
reacted with Sb2S3 and/or with Sn to a higher degree. Fig. 5 shows
31
32
0,5
F1
F2
F3
0,5
F4
F1
0,4
F2
F3
F4
0,4
0,3
0,3
0,2
n of braking (Fade 1)
0,2
n of braking (Recovery 1)
Fig. 4. SEM micrographs of the worn brake pad surfaces after dyno testing.
formulations. In this case it seems that Zn powder is easily oxidised and it transfers to the surface of the cast iron disc, protecting
it from the tribo-oxidation as it is known to work as a solid
lubricant at elevated temperature [18]. Furthermore, the identication of zinc sulde, ZnS, in the X-ray pattern would corroborate
the reaction between Zn and Sb2S3.
Most of the peaks belonging to barite could be distinguished in
the transfer layer (see Fig. 6) even after dyno testing, but no Sb2S3
was detected. A unique property of copper and other soft constituents, such as graphite, barite [25], MgO and certain metal
sulphurs (Sb2S3, MoS2, SnS) is that they seem to transform into an
equiaxed nanocrystalline structure with that easily incorporate
into the transfer layer, which basically formed by magnetite [26].
From the characterisation of the worn surface by SEM and Xray diffraction, it was observed that the Sb2S3 lubricant had reacted with the metallic constituents of the brake pad during braking.
In order to study the extent of these reactions, analyses underneath the worn brake surface were performed. For this purpose
cross-section of the worn pads were prepared and analysed by
SEM and EDS up to a maximum depth of 9 mm (bottom of
the pad).
Although all the brake pad formulations were analysed, Fig. 7
shows as an example the SEM micrographs taken at different
depths (from the surface up to 9 mm in depth) for copper content
formulation F1. The analysis of these micrographs reveals that Cu
and Sb2S3 reacted during braking tests since no individual Cu and
33
Relative intensity
20
25
30
35
40
45
2 (deg)
Fig. 6. GAXRD patterns taken at glancing angle from the brake pad surfaces. The
dotted line represents pre-dyno and the solid line represents post-dyno testing;
where
is barite and
is Fe3O4..
sulphide (Cu2S), and the white zones correspond to the intermetallic Cu2Sb. Moreover, the darker grey zones correspond to
copper-zinc sulphide (CuZnS). Therefore, the reaction between Cu
and Sb2S3 results in copper sulphide and copper antimonide. The
presence of copper zinc sulphide can be explained by the presence
of Zn in the parent formulation. It is important to note that similar
behaviour was found for the rest of the formulations.
In Fig. 8b a particle of Sn in the cross-section of a worn F2 pad
that had reacted with Sb2S3 is shown. In this case the white and
grey zones were identied as intermetallic tin antimonide (SnSb)
and tin sulphide (SnS), respectively. This reaction was observed up
to a depth of 6 mm, similar to the cross-section of F3 containing
sponge iron powder, whose reaction details are shown in Fig. 8c.
The reaction between sponge iron and Sb2S3 is shown at the edge
of an iron sponge particle where iron sulphide (FeS) (grey areas)
and iron antimonide (FeSb) (white areas) could be distinguished.
On the other hand, the characteristics of this reaction for the
formulations containing zinc powder (F4 and F5) differ from the
difference in the particle size of the Zn powder used in each case.
Fig. 8d shows that for F4 the reaction between coarse Zn and Sb2S3
produces zinc sulphide (ZnS), which appears in the dark grey
contrast surrounding the zinc particle, and zinc antimonide
(ZnSb), which is revealed with a white contrast. Meanwhile, Fig. 8e
shows how this reaction and the reaction products found in F4 are
limited by the presence of Zn agglomerates. These agglomerates
were partially oxidised during the dyno test, forming a thin layer
of ZnO around the particles. It seems that the presence of such an
oxide layer around the Zn particles prevented the reaction
between Zn and Sb2S3, and only Zn particles that had not been
oxidised or located at the border of the Zn agglomerates and were
in contact with Sb2S3 had reacted, forming zinc sulphide (ZnS) and
zinc antimonide (ZnSb).
In summary, analyses carried out on cross-sections of the brake
pads revealed that Sb2S3 reacts with Cu, Sn, Fe and coarse Zn to
produce metal antimonides and metal sulphides up to different
34
Fig. 7. Evolution of the reaction between Cu and Sb2S3 (marked with x) along pad depth. Only at 9 mm can unreacted Sb2S3 be found.
(1)
(2)
35
Fig. 8. Detail of metal particles that reacted with Sb2S3 lubricant in worn pad cross-sections: (a) F1 (Cu) pad, (b) F2 (Sn) pad, (c) F3 (Fe) pad, (d) F4 (Zn coarse) pad and (e) F5
(Zn ultrane) pad.
Table 4
Reaction products and the depth up to where these reactions were observed on the
worn brake pad cross-section.
Meta powder
Reaction products
Cu
Sn
Sponge Fe
Zn (coarse)
Zn (ultrane)
Cu2Sb, Cu2S
SnSb, SnS
FeSb, FeS
ZnS, ZnSb
ZnS, ZnO, ZnSb
9
6
6
6
6
36
Fig. 9. DSCTGA curves for Sb2S3 (a) in air atmosphere (b) in argon atmosphere.
between Sb2S3 and Cu take place during heating. First, in the DSC
curve peak (1) arises between 300 and 450 C, peak (2) between
450 and 500 C, and peak (3) starts at 500 C. XRD patterns from
the M1 mixture and the mixture heat-treated at 400 C and 650 C
are shown in Fig. 11c to assist in the identication of the reactions
involved in the DSC peaks.
The XRD pattern for M1 heated at 400 C may help to explain
the reaction or reactions related to DSC peak (1). Four different
compounds were identied from this pattern: Sb2O3 (mainly ,
with some residual ), Cu, Cu2O and Cu2S. Firstly, as happened
with the primary Sb2S3 powder, the Sb2S3 present in the M1
mixture is completely oxidised to Sb2O3. However, from the TGA
curve of the M1 mixture (Fig. 11b), this reaction is combined with
a mass gain of about 5%, differing from the mass loss observed for
primary Sb2S3 (Fig. 9). Therefore, the SO2 produced from the oxidation of Sb2S3 according to Reaction (1) is not liberating, and it
may react with Cu according to Reaction (3) to form copper sulphide, Cu2S, and copper oxide, Cu2O. Furthermore, some Cu2O can
be formed from the direct oxidation of Cu, which according to the
XRD pattern it is not completed oxidised after 1 hour at 400 C.
6Cu SO2-Cu2S2Cu2O
(3)
(4)
(5)
Sb2S3_650C Air
Sb2S3_400C Air
Sb2S3
20
25
30
35
40
45
3.4.2.2. M2 (Sn Sb2S3). Fig. 13 shows the DSC and TGA curves in
air (a) and in argon (b) for Sn and the binary mixture M2. In
addition, Figs. 13c and 13d also shows the XRD patterns for M2
heat treated at 400 C and 650 C in air and argon respectively. For
primary Sn powder, only an endothermic peak (1) associated with
its melting point at 225 C is observed (Fig. 13a), without any mass
change throughout the whole heating cycle. Evidently, this peak is
also observed in the M2 mixture. For this mixture two additional
exothermic peaks are clearly seen (2 and 3), the rst one occurring
50
2 (deg)
Fig. 10. XRD patterns of Sb2S3 solid lubricant without treatment, heating up to
400 C and 650 C in air where:
Sb2S3,
SiO2,
-Sb2O3,
Sb2O3 and
37
-Sb2O4..
20%
M1
15%
Sb S
2
10%
m (%)
5%
Cu
0%
2
Cu
Sb S
-5%
1
M1
-10%
0
-1
100
150
200
250
300
350
400
450
500
-15%
100
550
150
200
250
Temperature (C)
300
350
400
450
500
550
Temperature (C)
M1_650C Air
M1_400C Air
M1
20
25
30
35
40
45
50
2 (deg)
Fig. 11. (a) DSC and (b) TGA curves in air for Sb2S3, Cu and M1 mixture; (c) XRD patterns of M1 initial mechanical mixture, M1 after heating up to 400 C and 650 C in air
where:
Sb2S3,
Cu,
Cu2O,
-Sb2O3,
-Sb2O3,
Cu2S,
Cu (Sb2O6), and
Cu2O(SO4).
38
M1_650C Ar
7
6
5
M1_400C Ar
M1_200C Ar
2
1
M1
Sb S
M1
0
-1
100
150
200
250
300
350
400
450
500
550
20
25
30
35
40
45
Fig. 12. (a) DSC curves in argon for Sb2S3 and M1 mixture; (b) XRD patterns of M1, M1 after heating up to 200 C, 400 C and 650 C in argon where:
CuSbS2,
Cu2Sb and
4%
6
M2
2
3
0%
2
Sn
3%
2%
M2
1%
0%
2
-1%
M2
Sb S
-2%
-3%
-1
-2
200
M2
150
4%
-2%
100
Cu,
250
300
350
400
450
500
-4%
550
m (%)
2%
m(%)
-1
Sb2S3,
Cu2S.
50
2 (deg)
Temperature (C)
-2
100
150
200
250
Temperature (C)
300
350
400
450
500
-4%
550
Temperature (C)
M2_650C Ar
M2_650C Air
M2_400C Air
M2_400C Ar
M2_200C Ar
M2
20
25
30
35
40
45
50
20
25
30
35
40
45
50
2 (deg)
2 (deg)
Fig. 13. DSC and TGA curves in air (a)and in argon(b) for Sn and M2 mixture; XRD patterns of M2 and M2 heat treated at 400 C and 650 C in air (c) and argon(d) where:
Sb2S3,
Sn,
SnO2,
SnS,
SbSn,
-Sb2O3 and
-Sb2O4.
between 340 and 440 C and related to a mass gain of 2%, and
the second one occurring between 450550 C and with no
apparent mass change. The XRD pattern obtained from M2 heattreated at 400 C (Fig. 13c) shows that the reaction between Sn (in
liquid state) and Sb2S3 that yields tin sulphide, SnS, and tin
seen, with no related mass change in the TGA curve. At the same
time, the lack of a melting point endothermic peak related to the
melting point of Sb2S3, could indicate that the reaction between
the lubricant and Sn takes place in the temperature range where
the low intense DSC peaks are shown. The XRD patterns (Fig. 13d)
conrm this observation. Although at 200 C no reaction is
observed in M2 at this temperature, at 400 C the formation of SnS
and SbSn from the reaction between Sn and Sb2S3 (Reaction (6)) is
determined, with some residual Sn and a certain amount of SnO2,
which means than some oxygen is remaining in the atmosphere.
However, no Sb2S3 is found, in agreement with the lack of its
melting point peak in the DSC curve. The only difference between
the XRD patterns at 400 C and 650 C is that the peaks belonging
to Sn disappeared at 650 C.
For this mixture the correlation between the analyses performed in argon also coincides with the characterisation of the
cross-section of the worn brake pads. However, the correlation
between the heat treatments in air and the surface of the worn
pad is more complicated. In both cases SnO2 is found, but SnS and
SbSn are barely found on the worn surface.
(6)
Sn 1/2 O2-SnO2
(7)
2%
7
6
6
Fe
1%
1
4
2 3
0%
2
1
M3
m (%)
39
4
3
2
M3
-1%
0
Sb S
M3
-1
-1
-2
-2
-2%
100
150
200
250
300
350
400
450
500
100
550
150
200
250
300
350
400
450
500
550
Temperature (C)
Temperature (C)
M3_650C Air
M3_650C Ar
M3_400C Ar
M3_400C Air
M3
M3_200C Ar
20
25
30
35
40
45
50
20
25
30
35
40
45
50
2 (deg)
2 (deg)
Fig. 14. DSC and TGA curves in air (a)and in argon(b) for Sn and M3 mixture; XRD patterns of M2 and M3 heat treated at 400 C and 650 C in air (c) and argon(d) where:
Sb2S3,
Fe,
Sb2O3,
Sb2O3,
Fe2O3,
Sb2O4 and
Fe3O4.
40
(8)
(9)
35
5%
M4
30
4%
M5
3%
20
m (%)
25
15
M4
2%
M5
10
Zn ultrafine
1%
Zn ultrafine
Zn coarse
5
0%
0
Zn coarse
-1%
-5
100
150
200
250
300
350
400
450
500
100
550
150
200
250
300
350
400
450
500
550
Temperature (C)
Temperature (C)
M4_600C Air
M5_600C Air
M4_400C Air
M5_400C Air
M4
M5
20
25
30
35
40
45
50
20
25
30
Fig. 15. DSC (a), TGA (b) curves and XRD patterns in air for M4 (c) and M5 (d) mixtures. Where:
ZnSb and
ZnSb2O4.
35
40
45
50
2 (deg)
2 (deg)
Sb2S3,
Zn,
ZnO,
-Sb2O3,
ZnS
Zn4Sb3,
the TGA curves; it seems that the mass gain, which is related to the
oxidation of Zn, starts after the reaction between Zn and Sb2S3 is
almost completed, at 350 and 460 C for M5 and M4, respectively.
The XRD diffraction analyses carried out on the mixtures heattreated in air at 400 and 650 C, also corroborated the effect of
particle size on the reactivity of Zn with Sb2S3. Thus, even though
in both binary mixtures ZnS is formed at 400 C, the stoichiometry
of the intermetallic formed in each case is different, -Zn4Sb3 and
-ZnSb for M4 and M5 respectively. In both mixtures a certain
amount of Zn is unreacted (the molar relation of the binary mixture is 9Zn/Sb2S3, meaning there is an excess of Zn). Additionally,
in line with the different mass gains determined in the TGA analyses, the ultrane Zn powder in M5 is more oxidised, since the
intensity of the ZnO peaks in the XRD pattern is higher than in M4.
The different surface area of the Zn powders, which also implies a
different oxidation tendency, may be responsible for the different
products formed. At 400 C only traces of Sb2O3 were determined
by XRD, which combined with the mass gain of 3% determined by
TGA, this proves that the SO2 produced from oxidation according
to Reaction (1) is not liberating and may react with Zn to form ZnS
and ZnO (as it was the case for the M1 mixture).
In addition, at 650 C minor differences are observed between
M4 and M5, where Zn is fully reacted or oxidised, At this temperature, the antimonide formed on both is the same: ZnSb, with a
large amount of ZnO. ZnSb2O4 in M4 is identied, which would be
due to the reaction between ZnO and Sb2O4 that formed during
the oxidation of Sb2O3 (Reaction (2)), meaning that the reaction
mechanism would be the same as in the case of M1 with Cu.
Fig. 16 shows the DSC curves and the XRD patterns for M4 and
M5 for the mixture heat-treated in argon. The TGA curves are not
included since no mass change was observed. It is important to
mention that in contrast to the rest of the mixtures, broad peaks
are observed in the DSC curve (Fig. 16a). Once again, the particle
size of Zn affects the reaction with Sb2S3. For M4 the exothermic
reaction starts at a similar temperature as in air, 350 C, although
in argon it seems to nish just before the melting temperature of
Zn, whose peak is also noted. Otherwise, for M5 two exothermic
peaks are observed, the rst one at very low temperatures (200
325 C) and the second one is similar to what happens in M4, but
at a lower temperature ( o30 C). The Zn melting transitions also
take place after the last reaction nishes.
The XRD patterns obtained from the mixtures heat-treated at
200, 400 and 650 C (Fig. 16b) do not show the differences found
in the DSC curves for both mixtures. The patterns from M4 and M5
mixtures heat-treated in argon at 400 and 650 C are the same.
41
Apart from ZnS, Zn4Sb3 and ZnSb are found at 400 and 650 C,
respectively. Therefore, the stoichiometry of the intermetallic
formed depends on the temperature at which the reaction
takes place.
For M4 and M5 binary mixtures, with regard to the reaction
products, few differences between the heat treatments carried out
it air or in argon have been found. Apart from the higher amount
of ZnO formed in air, in both cases zinc sulphide and zinc antimonide are formed. Since no agglomerates are present in binary
mixture M5 with Zn ultrane, the reaction is complete in comparison to the reaction found in the cross-section of the worn
F5 pad.
3.5. Relation between the friction performance of the brake pads and
the interfacial chemistry
Generally, it was observed that the friction transfer layer
formed on the brake pad and disc surfaces was not a homogenous
lm and that its composition depends largely on the tribooxidation of the disc, on the initial composition of the brake
pads and, also, on the reaction between the solid lubricant and the
metal constituents (powders and bres).
The presence of Cu and Cu2O in the transfer layer of the formulation F1 may act as lubricants at high temperatures and,
therefore, contribute to the lower pad and disc wear during
braking tests helping to obtain a steady friction coefcient at high
temperatures. Similar friction behaviour was observed in F4 formulation (Zn). In this case a high concentration of Zn was determined in the transfer layer. It is believed that the Zn powder is
easily oxidised protecting the cast iron disc from the tribooxidation. Additionally, ZnO and ZnS, present in the transfer
layer, could be acting as lubricants, as is reported by [18], so that
supporting this friction behaviour.
On the other hand, F2 formulation with Sn powder seems to
have the lowest fade resistance with the highest decrease of m. In
this case, the steel bres have actively been reacted with the soli
lubricant and with the Sn powder, as it was determined on the
worn surface of the pad, affecting on its friction behaviour.
Moreover, the presence of Fe3Sn and SnO2 compounds on the
worn disc surface may also be impairing this worse friction
behaviour.
Finally, sponge iron powder in F3 modies the tribo-oxidation
behaviour of the friction disc. It could be noticed that it is the only
formulation in which the intermetallic FeSb and a high amount of
FeO are found in the disc transfer layer. Therefore, both
5
M4_650C Ar
M4
3
M4_400C Ar
2
M5
1
Sb S
M4_200C Ar
-1
100
150
200
250
300
350
400
450
500
550
20
25
30
Temperatura (C)
Fig. 16. (a) DSC curves and (b) XRD patterns for M4 (coarse Zn) and M5 (Zn ultrane) after heat treatments in argon. Where:
ZnSb,
Zn4Sb3.
35
40
45
50
2 (deg)
Sb2S3,
Zn,
ZnO,
ZnS,
42
4. Conclusions
The chemical reaction that occurs between the different metal
powders (Cu, Sn, Fe, Zn) and the solid lubricant (Sb2S3) in the
brake pad during braking depends on the nature and morphology
of the metal powder, the temperature attained during braking and
the atmosphere conditions. In general, inside the brake pad a
combination of a metal sulphide and a metal antimonide is formed
in all formulations, whereas the transfer layer on the worn surface
is composed of a mixture of metal oxides and, depending on the
combination of the powder metal and Sb2S3, some reaction products can also be found.
The low angle glancing X-ray technique was successfully used
to determine the constituents of the transfer layer on the worn
brake pad surface. In all cases, magnetite, Fe3O4, is the main
constituent, expect for the Zn content formulations, in which Zn is
easily oxidized to ZnO, which protects the cast iron disc from the
tribo-oxidation.
It is possible to explain the chemical reactions between the
metal powders and the lubricant included in the brake pad formulation by the preparation of the binary mixtures and the use of
DSCTGA and X-ray diffraction techniques to determine the reaction products formed during thermal treatments in argon and air
atmospheres. Whereas the thermal treatments carried out in air
could be used to reproduce the braking conditions on the pad
surface (except pressure), the thermal treatments performed in
argon could reproduce the reactions that take place inside the
brake pad.
The reaction between the metal powders and the lubricant
starts at temperatures between 350 and 400 C, except for the Cu
Sb2S3 system, where it starts at a lower temperature (200 C). This
observation could be used to estimate the maximum temperature
inside the brake pad during the complete braking dyno test.
According to these data, 400 C can be attained at a depth of 6 mm.
Acknowledgements
The authors acknowledge POMETON S.p.A. (130018/11) for its
nancial support while carrying out this work and GAMA S.p.A. for
providing the friction material and dynamometer test results.
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