Mechanical properties and frictional behavior of a mica-lled

poly(aryl ether ketone) composite

Daoji Gan
*
, Shiqiang Lu, Caisheng Song
1
, Zhijian Wang
2
Department of Materials Science and Engineering, Nanchang Institute of Aeronautical Technology, Nanchang, Jiangxi 330034,
People's Republic of China
Received 28 August 2000; received in revised form 2 January 2001; accepted 22 January 2001
Abstract
A composite material of a poly(aryl ether ketone) (PAEK), which was prepared from diphenyl ether, terephthaloyl
and isophthaloyl chloride, was developed using mica as a ller. Poly(p-phenylene terephthalamide) (PPTA) was em-
ployed for the purpose of improving the interfacial adhesion between mica and PAEK. Mechanical properties and
surface frictional behavior of these materials were examined as a function of mica content used. With increasing content
of mica in the materials, the tensile modulus increased and the ultimate elongation decreased while the tensile strength
exhibited a maximum value at a particular composition. Treatment of mica by PPTA improved the interfacial adhesion
between mica and PAEK as shown by improved mechanical strength, but did not aect the glass transition behavior of
the polymer. Coecient of friction and wearing rate of these materials were aected by the amount of mica
used. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Poly(aryl ether ketone); Mica; Composites; Mechanical properties; Frictional behavior
1. Introduction
Poly(aryl ether ketone)s (PAEK) are a type of high-
performance polymer which have outstanding thermal,
physical and mechanical properties. These polymers and
their composite materials have found many applications
in aerospace, coating and insulating material elds [14].
Many publications have reported signicant improve-
ment of physical, mechanical and frictional properties
after PAEK is reinforced by carbon or glass bers [58].
Mica is a plate-like crystalline aluminosilicate and
has been widely used as a reinforcing ller in polymeric
matrices due to its excellent mechanical, electrical and
thermal properties [9]. Commercial usage of mica as a
ller can be found in polymer composites involving
polyolens, polyesters, polyamides, epoxies and poly-
urethanes [9,10]. However, there are few reports on the
PAEK composites lled with mica [11].
In this study, PAEK composites lled with mica were
prepared. To enhance the interfacial adhesion between
mica and PAEK, the mica was treated by a polymer that
would provide good adhesion to both mica and PAEK.
Tensile tests, dynamic mechanical analysis and sliding
friction measurements were used to elucidate the eect
of mica content on the mechanical and frictional prop-
erties of the materials.
2. Experimental
Terephthaloyl chloride (TPC) (99% purity, mp 79
81C) and isophthaloyl chloride (IPC) (99% purity, mp
4344C) were obtained from Nanchang Agrochemical
European Polymer Journal 37 (2001) 13591365
www.elsevier.nl/locate/europolj
*
Corresponding author. Present address: School of Chem-
istry and Biochemistry, Georgia Institute of Technology, 770
State Street, Atlanta, GA 30332, USA. Tel.: +1-404-367-8645;
fax: +1-404-894-7452.
E-mail address: daoji.gan@chemistry.gatech.edu (D. Gan).
1
Present address: Jiangxi Normal University, China.
2
Present address: Chinese Academy of Sciences, China.
0014-3057/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S0014- 3057( 01) 00010- 6
Factory (Nanchang, China) and used as received. An-
hydrous AlCl
3
, diphenyl ether, formic acid and metha-
nol were purchased from Jiangxi Chemical Reagents
Company (Nanchang, China) and used without puri-
cation. 1,2-dichloroethane was distilled with P
2
O
5
before
use. N,N-dimethylformamide (DMF) was dried using
molecular sieves and distilled under reduced pressure.
Poly(p-phenylene terephthalamide) (PPTA) was a gift of
Guangdong Plastic Inc. (Guangzhou, China). Phlogo-
pite-type mica (average diameter >50 lm) was bought
from Shanghai Silica Inc. (Shanghai, China).
PAEK (Scheme 1) was synthesized by low-tempera-
ture FriedelCrafts condensation of diphenyl ether with
TPC/IPC (molar ratio of 0.70.3) in the presence of
AlCl
3
as a catalyst and 1,2-dichloroethane/DMF as
solvents [12,13]. To remove the residual AlCl
3
in the
resin, the PAEK was reuxed in formic acid for three
days, and extracted with methanol for another two days
using a soxhlet apparatus. It has a glass transition
temperature (T
g
) of 160C, measured using dierential
scanning calorimeter (DSC) at a heating rate of 10C/
min. The reduced viscosity (g
inh
), measured using a
Ubbelohde-type viscometer in 95% H
2
SO
4
at 25C, is
0.95 dL/g. In some cases, the mica was treated by 2%
weight concentration of PPTA (g
inh
= 1:54, T
g
= 345C)
in sulfuric acid and then washed by water to generate a
thin layer of PPTA on the mica. PAEK was blended
with llers in a Brabender plastic-corder model PLE 330
at 360C. To obtain a nely dispersed composite, a ro-
tation speed of 90 rpm was maintained for 12 min. The
materials were then compressed at 165C in molds to
yield the specimen sheets. To minimize the eect of
polymer crystallization on the measurements, both sides
of the specimen sheets were placed on a heating stage at
350C for a short time and quenched immediately into
ice water. This method resulted in formation of amor-
phous glassy samples, as demonstrated by disappearance
of the crystallization peak during DSC measurements
[14].
The interaction of PPTA with mica was examined by
atomic force microscope (AFM) using a nanoscope III
scanning probe microscope (Digital Instruments, Santa
Barbara, CA, USA), equipped with a J-type vertical
engage scanner. Mica, treated by PPTA using the same
procedure as for preparing composites and annealed at
the same temperature, was examined by AFM at dif-
ferent stage. Approximate lm thickness was measured
by contact AFM using a silicon nitride tip with 0.58 N/m
for the spring constant of the cantilever. The measure-
ment was performed by applying a large force (~150
nN) to a small area of the surface until no further ma-
terials were displaced by the AFM tip. The force was
then minimized and a larger square of the AFM image
was collected to compare the height of the undisturbed
area with that of the machined area. The mica treated by
PPTA was also characterized by thermogravimetric an-
alyzer (TGA) (PerkinElmer TGS-7), at a heating rate
of 20C/min under nitrogen.
Tensile testing was carried out using an Instron ma-
chine, Model 5583 (Instron Inc., Canton, MA, USA),
having a video-monitored optical extensometer. Speci-
men sheets with a thickness of ~2 mm were cut into the
dumbbell shape specied in Fig. 1, using a steel die. All
tests were performed at room temperature with a cross-
head rate of 2 mm/min, according to ASTM D-638.
Tensile modulus was calculated from the initial slope of
the stressstrain curve while both tensile strength and
elongation were the values at the breaking point.
Dynamic mechanical analysis (DMA) was performed
on a Rheometrics, Model RSA II dynamic mechanical
tester (Rheometrics Scientic Inc., Piscataway, NJ,
USA), equipped with low-temperature units using liquid
nitrogen as a cooling medium [15]. The specimen lm
used for the test had a rectangular dimension of 20 mm
in length, 5 mm in width and ~1 mm in thickness. The
lms were placed in a sample holder; and 50150 g of
pre-tension was added at room temperature to avoid
sample buckling. After cooling to 0C, an additional 70
150 g of tension was added and measurements were
obtained at 5C increments with 0.1% applied strain at
2 Hz.
A MZ 200 friction-and-wear tester (Scientic In-
strument Inc., Beijing, China) (Fig. 2) was used to
measure the sliding friction and wearing loss. Before
experiments, the specimens were abraded by water-
abrasive paper. The specimens (rectangular dimension:
30 7 9 mm
3
) were held by a loading arm, which re-
corded the frictional force (F
f
). 50, 100 and 200 N of
normal loading forces (F
n
) were used for the tests. All
Scheme 1. Structure of Poly(aryl ether ketone) (PAEK).
Fig. 1. Schematic diagram of the sample used for tensile test.
1360 D. Gan et al. / European Polymer Journal 37 (2001) 13591365
the measurements were performed under ambient envi-
ronment at a sliding speed of 0.5 m/s. The coecient of
friction (f) was calculated as follows: f = F
f
=F
n
. The
weight of specimen before and after the test was deter-
mined by a balance with an accuracy of 10
4
g, and
converted into volume using the density of the sample,
which was measured by a specic gravity bottle using
absolute ethanol as the immersing medium. Wearing
rate (W
s
) was calculated by:
W
s
= (V
0
V
1
)=(F
n
L) (mm
3
=(Nm))
where V
0
is the volume of the sample before test, V
1
is
the volume after test and L is the sliding distance. For
tensile tests and sliding friction measurements, the data
shown here are the average values of six replicate tests.
3. Results and discussion
It is well known that the physical properties of
polymer composites are largely dependent on adhesion
between llers and the polymer matrices. Glass bers
and solid minerals such as micas have a high surface
energy, due to presence of hydroxyl groups on the sur-
face. Polar polymers (epoxy resin, nylon, etc.), capable
of forming H-bonds with the hydroxyl available on the
ller surface, have very strong adhesion to the llers.
Other polymers, however, have relatively poor adhesion
and wettability to the llers. To improve the ller
polymer interaction, interfacial modiers such as cou-
pling agents are commonly used. Among these, silane
derivatives are the most universal modern coupling
agents, and they may improve ller/matrix adhesion,
protect the ller surfaces from micro-aws that initiate
failure, reinforce the interface layer, improve the ller
wetting and dispersion conditions, and increase hydro-
phobicity of the surface [16].
Unfortunately, none of silane coupling agents is
thermally stable at the high temperature that melt ex-
trusion and injection of PAEK requires. PPTA, con-
taining both aromatic and amide groups, has high
thermal stability and good compatibility with PAEK,
and can also form hydrogen bond with the surfaces of
minerals [7,17].
The interaction of mica and PPTA was examined by
AFM following the procedure for preparing composites.
Fig. 3a shows an AFM image of pure mica, where a
small area in the center was scratched by applying a
large force (~150 nN) by contact AFM with a silicon
nitride tip. Since mica is relatively hard and thus cannot
be broken by silicon nitride tip, the AFM image of a
relatively large area, captured after minimization of
force on the cantilever, shows no materials displaced by
the AFM tip. Correspondingly, the section analysis does
not show much dierence in height between the scrat-
ched area and the unscratched area. For the mica treated
by PPTA solution and washed by water, the AFM image
(Fig. 3b), however, shows a hole made by the AFM tip
during the rst stage applying large force in the small
area. Considering the hardness of mica, the displaced
materials should be PPTA on the mica. This indicated
that a layer of PPTA was formed on the mica surface,
due to possible H-bonds between the amide groups of
PPTA and the hydroxyl groups on mica surface. The
PPTA layer has a thickness ~40 nm, as indicated by the
section analysis prole through the hole. Fig. 3c shows
the AFM image and its section analysis prole after this
sample was annealed at 360C for 12 min and washed by
water. Again, a hole could be made by the AFM tip and
the thickness of PPTA layer was still ~40 nm. It thus can
be assumed that the layer of PPTA on mica would be
stable for the processing of PAEK/mica composites.
Further evidence by TGA shows that ~1.8 wt.% of
PPTA was coated on mica as determined by heating the
sample to 700C to cause decomposition of the polymer.
Tensile properties of PAEK and its composites were
measured using an Instron tester at a cross-head rate of
2 mm/min. Typical stressstrain curves are shown in Fig.
4. As expected, PAEK, a plastic polymer, displayed a
yielding point in the curve and showed a relatively high
value of elongation at break. Both mica/PAEK and
treated mica/PAEK composites showed an increased
mechanical strength, although the elongation of the
materials decreased due to incorporation of rigid mica.
The treated mica/PAEK composites exhibited higher
values of elongation than the mica/PAEK composites.
Fig. 5 shows the tensile properties of PAEK and its
composites. Obviously, tensile modulus of these mate-
rials increased rapidly with the content of mica, which
Fig. 2. Schematic diagram of the friction-and-wear tester.
D. Gan et al. / European Polymer Journal 37 (2001) 13591365 1361
Fig. 3. Contact AFM image (left) and its section analysis prole (right) for (a) pure mica. A small area in the center was scratched by a
silicon nitride tip through applying large force (~150 nN) on cantilever. Section prole through the scratched area shows no material
displaced by AFM tip due to the high hardness of mica, (b) the mica treated by PPTA and washed by water. A hole was made by AFM
tip and the layer of PPTA has a thickness of ~40 nm and (c) the PPTA treated mica after annealing at 360C for 12 min and water
washing. A hole with ~40 nm in depth was made by the AFM tip.
1362 D. Gan et al. / European Polymer Journal 37 (2001) 13591365
was responsible for the high modulus of these compos-
ites. Treatment of mica by PPTA before blending did
not cause much dierence in the tensile modulus of these
composite materials if the same content of mica was
used.
Tensile strength of these materials initially increased
with the content of mica; after reaching a maximum
value at ~30 wt.% of mica used, it began to drop. The
eect of the ller on the tensile strength may be attrib-
uted to the counterbalance of two phenomena as in-
creased ller contents in the polymer composites:
increased eective surface fracture energy, and increased
sizes of voids and agglomeration of ller particles
[16,18]. As addition of ller to polymer matrix, dispersed
particles make the crack propagation path longer, ab-
sorb a portion of the energy and enhance the plastic
deformation. Therefore, the surface fracture energy in-
creases and the strength of the composites should in-
crease with the volume percentage of the ller [16].
However, with increase of ller contents, the size of the
voids formed when the polymer matrix becomes de-
tached from the ller particles due to deformation will
become critically large and may initiate the main crack
[16]. In addition, the inevitably increased agglomeration
of dispersed ller particles results in decreased mechan-
ical strength due to the low strength of the agglomerates
themselves [18]. It is also worth mentioning that the
composite materials made using mica treated by PPTA
generally have higher values of tensile strength in com-
parison with those generated using untreated mica. This
shows that PPTA improves the interfacial adhesion be-
tween PAEK and mica.
Ultimate elongation of these materials decreased with
increase of the mica content. This is due to development
of cracks around the ller particles and possible for-
mation of particle agglomerates and voids resulting
from local detachment of the matrix from the particles
Fig. 4. Typical stressstrain curves of PAEK and its compos-
ites.
Fig. 5. Tensile properties as a function of mica content in the
composite materials.
D. Gan et al. / European Polymer Journal 37 (2001) 13591365 1363
[16]. If the same content of mica is used, the composites
containing mica treated by PPTA have relatively higher
value of ultimate elongation than those using untreated
mica. Again, this can be attributed to the improved in-
terfacial adhesion between PAEK and mica by use of
PPTA.
DMA scans at a constant frequency of 2 Hz are
shown in Fig. 6. Storage modulus (G
/
) decreased slowly
as a function of temperature up to the T
g
, where a very
rapid decrease of G
/
could be observed. The modulus of
these materials, especially at lower temperatures, was
aected by the content of mica used. Addition of mica to
the polymer matrix leads to an increase of the modulus
of the resulting materials, which is in agreement with the
results of tensile tests. Although mica treated by PPTA
shows relatively good interfacial adhesion to PAEK as
observed by the tensile tests, incorporation of mica into
these materials has little inuence on the glass transition
behavior of PAEK. All the materials have the same T
g
as the virgin PAEK. This is an indication that the in-
teraction between mica and PAEK is not enough to
aect the macromolecular mobility of PAEK.
Fig. 7 shows the frictional properties as a function of
mica used. Compared to materials containing untreated
mica, those containing mica treated by PPTA did not
lead to regular change in the coecient of friction and
wearing rate since the data scattered largely. For the
same materials, the coecient of friction and wearing
rate generally increased with the loading forces used.
With 50 N of loading force used in the test, not much
dierence in coecient of friction and wearing rate was
found for the composite materials containing dierent
ratios of mica. If large loading forces (100 or 200 N)
were employed for tests, both coecient of friction and
wearing rate decreased with increasing content of mica,
reaching a minimum value at 20 wt.% of mica used, and
then increasing as a function of mica content. There are
several basic established modes, which are commonly
used to deal with the tribological behavior [19,20]. For
polymer composites, both components, rigid particles
and deformable polymers, make contributions to the
friction of the resulted materials and are interactive
during the frictional process. It has been assumed that
the coecient of friction and wearing rate are propor-
Fig. 6. DMA temperature scans at a constant frequency of 2
Hz and a heating rate of 5C/min for PAEK and its composites.
The mica was treated with PPTA.
Fig. 7. Friction properties as a function of mica content in the
composite materials measured by using 50, 100 and 200 N of
loading forces.
1364 D. Gan et al. / European Polymer Journal 37 (2001) 13591365
tional to the real contact area, which decreases with
increasing modulus of the materials in a given system
[20]. In another word, the larger the modulus of the
polymer composite, the lower the coecient of friction
and wearing rate it exhibits. Therefore, mica is an e-
cient component for reducing the coecient of friction
and wearing rate of polymer composites, considering the
increased modulus of polymer composites as observed
by tensile test. However, as the ller fraction increases to
a high level, the friction-induced thermal and mechani-
cal eects, leading to enhanced softening and plastic
deformation of polymer matrix and detachment of the
ller from polymer matrix, become dominant and nally
lead to increase of frictional coecient and wearing rate
of the materials [20].
4. Summary
In summary, both untreated mica and mica treated
by PPTA were used as llers in PAEK to prepare
composite materials. The treated mica gave stronger
interfacial adhesion to the polymer than the untreated
mica, but neither caused a change in glass transition
behavior of the polymer. The mechanical properties and
frictional behavior of these materials were aected by
the content of mica used. Based on these observations,
the properties of these materials can be tuned, to some
extent, by changing the compositions of these materials.
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