2011-05-15

A method for compositional characterization of friction materials

used in brake linings and pads
Marcos. R. F. Soares
Felipe G. Pandolfo
Albertina Artmann
Fras-le S/A.

Edison M. Serbino
Volkswagen do Brasil Indstria de Veculos Automotores Ltda.
Copyright 2011 Society of Automotive Engineers, Inc

ABSTRACT
This paper presents a procedure for compositional
characterization of brake pads and linings based on X-Ray
Fluorescence (XRF) and Thermogravimetrical (TG)
analysis. The compositional characterization of brake pads
is considered relevant by the Original Equipment Market
(OEM) manufactures since it could assist the failure
analyses of brakes systems, and it can be considered a
fingerprint of the material. Results of chemical analysis of
four different brake pads compositions produced at Fras-le
S/A were investigated. The comparison of XRF and TG
analysis of as received and tested pads shows a very
good ability to distinguish among the different
compositions. TG analyses were also essential as an
evidence to identify the changes on material composition
due to the influence of heat generated during braking in a
dynamometer bench.
INTRODUCTION
Brake pads and linings are composite materials
classified by the literature either as Polymer or Organic
Matrix Composites, which can use approximately 10 to 20
different raw materials in their composition [1, 2]. The
complexity of establishing the role those raw-materials
have on the performance of the final product is well known
in the automotive industry, and there are several
experimental studies to investigate the effect of the friction
material components in tribological properties of the discpad system [3, 4, 5, 6, 7].

Consequently, friction material composition is still an

open issue in automotive industry since it is considered as a
black box and its effect on product performance is not fully
understood due to the complexity of the braking
phenomena. Besides this, the great variety of constituents
imposes an extra analytical difficulty to establish a reliable
procedure to analyze and homologate a friction material
composition.
The approach adopted in this paper uses both semiquantitative XRF and TG analysis to present a procedure
for compositional characterization of brake pads and linings
which can be traceable to its raw-material constituents.
These techniques are complementary and together provide
both inorganic (XRF) and organic (TG) chemical
composition information of the friction material
ingredients. The goal is to define chemical features capable
to clearly distinguish among brake pads with different
composition and/or performance. Another goal of this study
is to establish an analytical condition to detect chemical
modifications on the brake pad surface induced by the
braking phenomena.
MATERIALS AND METHODS
Four different brake pads compositions corresponding
to regular materials produced by Fras-le S/A were used in
this investigation. According to the brake pad classification
used by Chan and Stachowiak [2] one pad material is
designed as a Non Asbestos Organic NAO formulation
while the other three have a common Semi-Metallic base,

that has been slightly modified to adjust the performance

requirements of different applications. Table 1 presents an
overview of their major components according to the
functionality of the raw materials used in their formulation.

under controlled conditions in a Scale Dynamometer

specially adapted for friction material evaluation [9]. This
equipment uses the same fixture to reproduce the kinetic
energy per friction material unit area; the specific pressure
at pad surface; and the angular speed of the real vehicle
application. Performance results obtained in this Scale
Dynamometer have a very good correlation with those of
Figure 1 for an Inertial Dynamometer [10].

Table 1 Friction materials selected and their respective

formulation according to the different raw materials
functionality, in wt%.

Sample preparation for chemical analysis was

performed on the powder obtained from drilling the brake
pad surface. While the as received pads were probed on
their whole bulk composition, the tested brake pads had
several drills performed at depths <1 mm from the worn
surface.
CHEMICAL ANALYSIS The response to
temperature change of the organic ingredients present in the
friction materials was measured by Thermogravimetrical
Analysis TG, in a Perkin Elmer TGA 7 equipment. A
temperature rate of 5oC/min with a synthetic air atmosphere
and aliquots of 7 to 8 mg of sampled powder were used in
each run. Results of TG analysis are obtained through a plot
of mass versus temperature coupled with its corresponding
derivative (DTG). An illustration of a typical thermal event
is shown in Figure 2. The weight variation is obtained from
the variation of the percentage of either loss or gain of
weight, between points B and C of the TG curve on the
thermograph (Figure 2), which is selected with the aid of
the DTG derivative curve.

The comparison of their performance is indicated at

Figure 1, which uses as reference the industry standard AK
Master Test Procedure [8] for Inertial Dynamometer. This
figure presents the fade step of the procedure, which shows
the typical friction level variation against temperature of
each material. Test results presented are representative of a
period of 2 years, where each value is the average of 4 to 5
measurements while the vertical bars indicate the standard
deviation of the measurement. Dotted lines display the
respective temperature reached at disc brake surface during
the test. One can verify that the performance of NAO
material has a distinct tendency for lower friction level,
compared with the semi-metallic compositions, material
507 has an intermediate friction value, while there is no
clear distinction between -level of materials 011 and 079.

Figure 2 Indication of a thermal effect detected by the

TG method for a typical organic weight variation.
Inorganic composition of the friction materials was
determined by X-Ray Fluorescence Analysis XRF in a
Philips PW2400 fluorescence spectrometer with dispersive
x-ray wavelength (WDS), a Rh tube at 3KW, and aliquots
of up to 5 g for as received and up to 0,2 g for tested
samples. The loose powders were supported by a polyester
film with a background of boric acid due to the small
quantity sampled. Results were calculated using a Philips
software for semi-quantitative analysis using a correction
for the absorption of polyester film. The computation was
performed in terms of elements normalized to the residue
found by TG analysis, informing the loss on Ignition (LOI)
as mass percent of carbon.

Figure 1 Insert of the AK Master Procedure [8]

comparing the friction level at the fade step for the
materials investigated [10]. Temperature is indicated by
the dotted lines.
The tested materials of this study were obtained
using the same AK Master Test Procedure, performed

equipment calibration accepts a variation of 5oC on the

informed Tp values.

RESULTS AND DISCUSSION

Table 2 presents the chemical composition of the as
received friction materials. It shows clear differences from
NAO material to the other semi-metallic materials,
specially the lower amounts of Mg and Al, usually found in
abrasives; the moderate quantity of Sb and the absence of
Mo, both commonly found on lubricant raw materials; the
remarkable amount of Ba, present in the fillers; and the
reduced quantity of Fe coupled with a corresponding
increase in the Cu amount. As expected the semi-metallic
materials are very similar to each other, but the analysis still
can differentiate them either by the presence or absence of
Mo and Sn, which are elements present in the lubricants; or
the amounts of remaining elements like Ba, Si, Ca and Fe,
which are present simultaneously in different raw materials.

TG

DTG

Figure 3 Thermograph of the four as received friction

materials with their major weight loss events up to 950oC.

Table 2 Chemical composition of the as received brake

pads, obtained by XRF semi-quantitative analysis, in wt%.

Table 3 Weight loss at each peak temperature (Tp)

identified on the as received and tested friction
materials. It is accepted a temperature variation of 5oC on
Tp values.

TG results of the as received friction materials are

presented in Figure 3 and summarized on Table 3. All
materials on Figure 3 show a minor (<1 wt%) weight loss
for temperatures below 250oC, while for temperatures
above 600oC the weight loss ranges from 12 to 20 wt%. At
these higher temperatures TG shows a weight gain, as
observed for materials 011 and 079. It is an effect that is
accounted to the oxidation of metallic Fe present in those
formulations [11].

The combination of XRF with TG analysis is capable

to identify different kinds of brake pads compositions. The
above results demonstrated that either very distinct
products, such as the NAO and semi-metallic formulations,
or similar products, as the three semi-metallic formulations
investigated, can be successfully identified. This feature is
maintained and can easily be displayed in a qualitative
approach like the one presented on Figure 4. This figure
illustrates that only five chemical elements together with
the weight loss in two distinct temperature ranges can
univocally distinguish the four compositions investigated in
this study.

Also in agreement with the observations of Ramousse

et all [11] the major differences among the materials were
detected from 250 to 600oC. Within this range both 539
(NAO) and 079 (semi-metallic) compositions display two
thermal events: the first one close to 445 460oC and the
second one at a higher temperature, close to 540 550oC.
The other semi-metallic materials display only one thermal
event in the same range, both at a lower peak temperature,
close to 420 430oC. In this range of temperature the

These effects are summarized on Figure 5. Comparing

with Figure 4 it is possible to verify that all the
representative inorganic elements of the materials are still
present within the tested samples, while the most
different pattern appears on the sample weight loss, related
to the thermal change of their organic ingredients.

Figure 4 Selected elements and weight loss values used to

qualitatively distinguish the investigated compositions.
Tested samples XRF chemical composition of the
tested friction materials is summarized on Table 4 and
TGA results were already presented on Table 3. The most
distinguishing feature displayed by the chemical
composition of tested pads is their Fe enrichment, due to
iron transfer from disc brake. It is a well known effect that
has been described before [12]. Variation of the results of
the other elements is within the measurement error and can
be analytically related to the Fe enrichment of the samples.

Figure 5 Qualitative chemical composition and weight

loss values of the tested pad compositions. The scale is
the same of Figure 4.
CONCLUSIONS

TG analysis displays the most remarkable difference

from the as received materials. All the weight loss events
that once occurred in the 250 600oC range are not
displayed by the tested samples anymore. This effect
could be clarified if one considers that temperatures
measured in an AK Master Procedure could exceed 600oC,
at 2 mm below the disc surface, and the temperature of the
brake pad surface could be even higher. This scenario could
easily cause thermal degradation of friction material during
the test, which eliminates those organic components once
present in the as received materials.

The combination of XRF and TG analysis is capable

to identify different compositions of brake pads friction
materials, since its feature is maintained in a product. It also
can easily be displayed in a qualitative approach, as long it
uses enough elements to univocally distinguish the
compositions investigated. TG analysis results is also a
good indicative of the temperature level that the brake pads
have been exposed by the braking phenomena, through the
chemical degradation presented by their organic
ingredients.
The procedure is feasible to establish reference values
used for the characterization of brake pads composition that
may be used in specific failure analyses of brakes systems.
To establish tolerances of each value presented demands a
larger amount of time and carefully defined on a case by
case evaluation, which may be suggested for future works.

Table 4 Chemical composition of tested brake pads

determined by XRF semi-quantitative analysis, in wt%.

AKNOWLEDGEMENTS
The authors thank the fruitful discussions for material
selection and evaluation with MSc. Ademir Menetrier and
also to Fras-le S/A, represented by Mr. Paulo Varante and
Gilberto Crosa, for the great support of this investigation.

[12] R. Hinrichs, M. A. Z. Vasconcellos, M. R. F.

Soares. Magnetite generated by tribo-reactions on the
surface of brake pad material. In: 28 SAE Brake
Colloquium and Engineering Display - Friction Material,
2010, Phoenix, Arizona, USA. SAE 2010 Brake
Colloquium, 2010.

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