Polymer Quasicrystal Composite

Materials Science and Engineering 294296 (2000) 156159
Development of novel polymer/quasicrystal composite materials

Paul D. Bloom b , K.G. Baikerikar b , Joshua U. Otaigbe a , Valerie V. Sheares b,
a
Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011, USA
b Department of Chemistry, Iowa State University, Ames, IA 50011, USA
Received 3 September 1999; accepted 1 February 2000
Abstract
We report on a new class of materials, polymer/quasicrystal composites with useful properties for beneficial exploitation in applications,
such as dry bearings and composite gears. Our preliminary results indicate that our new composites are a means of enhancing the
properties of certain organic polymers while providing a new means of processing quasicrystals. AlCuFe quasicrystalline materials
significantly improved wear resistance to volume loss in polymer-based composites. Furthermore, mechanical testing results showed a
two-fold increase in the storage modulus of the reinforced composites compared with the polymer samples. The fabrication in addition to
the thermal, mechanical, and wear properties of these unique materials will be described. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Quasicrystal; Polymer; Composite; Filler; Additive
1. Introduction
Since the mid-1970s, the study of polymer additives has
emerged as one of the most important fields of polymer
science. Additives encompass a range of materials including plasticizers, stabilizers, flame-retardants, and fillers. The
use of fillers in the plastics industry began when it was discovered that the cost of plastics could be reduced by the
incorporation of inert materials to increase polymer bulk.
Consequently, the production of plastic products became less
expensive, earning fillers a low cost reputation which to date
remains. More recently, active fillers have been employed
which lead to improvements in certain mechanical and/or
physical properties and, thus, are also known as reinforcing fillers. In practice, the term reinforcement is not specifically defined. It can mean an increase in tensile strength,
flexural modulus, heat deflection temperature, etc. [1] all
of which add value to the product for the supplier and the
user. Here, we examine quasicrystals as a new additive to
create a novel class of materials, polymer/quasicrystal composites [2]. The materials described here, along with other
polymer/quasicrystal composites, have been described in our
previously filed patent.
Quasicrystals, first discovered in 1982 [3], are complex
metal alloys that are most comparable to ceramic particulate
fillers in polymer composites [4]. The unique properties of
the bulk quasicrystalline material include low surface energy
Corresponding author. Tel.: +1-515-294-2474; fax: +1-515-2940-105.
E-mail address: [email protected] (V.V. Sheares).
compared to most metals, low wettability in contact with

most aqueous solutions, low coefficients of friction, high
hardness, low thermal conductivity, and high softening temperatures. The major drawback in quasicrystal applications
is in the brittle nature of the materials up to a few 100 C.
Applications have been coatings prepared by thermal spray
or thin-film growth, precipitation-strengthened bulk materials, and Al-matrix quasicrystal composites [5,6]. Our results
have indicated that our new polymer/quasicrystal composites are a means of enhancing the properties of certain organic polymers while providing a new means of processing
quasicrystals. Specifically, we have investigated a semicrystalline polymer poly(p-phenylene sulfide) PPS, an amorphous polymer bisphenol A poly(aryletherketone) PAEK,
and two thermosetting polymers, novolac and diglycidyl
ether of bisphenol A (DGEBA) epoxies in comparison to
their polymer/AlCuFe quasicrystalline rich composites.
2. Experimental procedure
2.1. Materials
Quasicrystalline AlCuFe icosahedral phase rich powders, quasicrystal (QC) powder, with the composition
Al65 Cu23 Fe12 , were prepared at Ames National Laboratory [7]. AlCuFe powder was chosen based on several
factors including its potential low cost, low toxicity, and
availability. These powders were used as prepared by gas
atomization with an approximate composition of 60%
0921-5093/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 0 0 ) 0 1 2 3 0 - 2
P.D. Bloom et al. / Materials Science and Engineering 294296 (2000) 156159
157
icosahedral phase and 40% cubic phase [8]. Quasicrystalline powder was air classified to achieve various size
fractions. Morphology of the resulting powder was determined to be spherical by scanning electron microscopy. PPS
powder, Ryton-PR6, was provided by Phillips Petroleum
Company. PAEK was synthesized from bisphenol A
(Aldrich) and 4,40 -difluorobenzophenone (Aldrich). The
resulting PAEK had a number average molecular weight
by gel permeation chromatography of 1,06,000 g/mol
with polydispersity=1.93. Novolac resin D.E.N. 431TM
and DGEBA epoxy resin D.E.R. 331TM were provided
by Dow Chemical. Metaxylenediamine MXDA (Aldrich)
and diethylenetriamine DETA were used with D.E.N.
431TM and D.E.R. 331TM , respectively, to produce thermoset epoxy formulations. Epoxy samples were formulated
based on equivalent stoichiometry of amine and epoxy
functionality.
rate of 20 C/min. Measurements of storage modulus were

obtained using a Perkin-Elmer DMA 7e equipped with a
three-point bending measuring system with a 15 mm span
length. Rectangular bars of the polymers and composite samples were machined to dimensions of 17 mm wide, 1.00 mm
high and 3.25 mm in depth from compression molded disks.
The scan rate was set at 5 C/min for PPS samples and
2 C/min for epoxy samples with a static force, dynamic
force and frequency of 110 mN, 100 mN and 1 Hz. Wear tests
were performed using a pin-on-disk type configuration. The
wear testing analysis for polymer and composite disks were
run using a Falex Friction and Wear test machine Model #
ISC450PC. A linear speed of 0.15 m s1 , a 10 N load, and a
total linear distance of 1 km were used in the wear testing.
Chrome steel 52,100 balls with a diameter of 0.635 cm were
used as the stationary pin materials.
2.2. Composite fabrication
3. Results and discussion
Desired amounts of polymer and quasicrystal powders

were weighed, added together and shaken vigorously in a
sealed container for 10 min to provide optimum mixing.
The volume fraction of the quasicrystals in the composite
materials studied was in the range 1060%. The resulting
QC/polymer powder mixture was placed in a die mold that
had a diameter of 2.50 cm and a final volume of 1.58 cm3
when fully compressed. The mold was equipped with a thermocouple to monitor temperature during the compression
molding process. The filled mold was heated in a variable
temperature hydraulic press (American Steel Foundries
Elmes Engineering Division) under a pressure of 7 MPa
to 310 C. The samples were held at the set temperatures
for 10 min before cooling under pressure to room temperature. The resulting composite surfaces were polished
with 320-grade emery paper followed by washing with
deionized water. The same procedure was used to prepare
compression-molded samples of neat PPS. Disks of PAEK
and PAEK/QC composites were compression molded at
250 C in a similar manner.
Epoxy samples were prepared from a two-part mix of
epoxy resin and amine cure agent. Test samples were made
as neat epoxy and at 30 vol.% of the QC powder in the
epoxy matrix. The epoxy resin, cure agent, and AlCuFe
icosohedral rich alloy were mechanically mixed together and
poured into a Teflon mold. The mold was heated at 85 C for
4 h. The epoxy/QC composite was then removed from the
mold and post-cured at 175 C for 2 h and 225 C for 2 h.
TGA analysis of the neat PPS sample gave a 5% weight

loss in air at 530 C. The PPS/quasicrystal composite material showed little change in thermal stability with a 5%
weight loss in air at 533 C. The 5% weight loss temperatures of the PAEK and epoxy samples also showed little
difference from their AlCuFe composites. The glass transition temperatures Tg of PPS and PAEK did not show any
change upon quasicrystal addition. The thermal properties
of the polymer in the composite samples were unaffected by
the QC fillers, suggesting no adverse interactions between
the filler and polymer.
Storage modulus (E0 ), which is a measure of the stiffness
or rigidity of a material, showed a two-fold increase in a
30 vol.% QC-enriched PPS sample. The magnitude of the
storage modulus increased in the PPS/QC composite with
increasing QC filler content above a critical QC volume
fraction of 10%, especially below the glass transition temperature of the polymer matrix (Fig. 1). Comparison of the
mechanical properties of D.E.R. 331TM /DETA-QC composites to unfilled D.E.R. 331TM /DETA epoxy thermosets
showed an increase in storage modulus for the QC filled
2.3. Characterization
Differential scanning calorimetry was performed on a
Perkin-Elmer DSC 7 under a nitrogen purge at a heating and
cooling rate of 20 C/min. Thermogravimetric analysis was
carried out on a Perkin-Elmer TGA 7 in air with a heating
Fig. 1. Storage modulus curves for PPS filled with 515 m AlCuFe
powder at (A) 30.0; (B) 20.0; (C) 10.0 and (D) 0.0 vol.%.
158
Fig. 2. Storage modulus curves for D.E.N. 331TM /DETA filled with
515 m AlCuFe powder at (A) 30.0 and (B) 0.0 vol.%.
Fig. 3. Loss modulus curves for D.E.N. 331 filled with 515 m AlCuFe
powder at (A) 30.0 (Tg =142 C) and (B) 0.0 vol.% (Tg =135 C).
samples (Fig. 2). The Tg of the D.E.R. 331TM /DETA/QC

sample was also increased over the neat epoxy sample
(Fig. 3). The storage modulus of D.E.N.431TM /MXDA and
D.E.N. 431TM /MXDA/QC (30 vol.% loading) at 30 C were
3.5109 and 8.2109 Pa, respectively.
Pin-on-disk wear testing results showed that the quasicrystalline reinforced composites exhibited enhanced
wear resistance to volume loss. PPS/AlCuFe composites
were evaluated at 30 and 60 vol.% loading levels versus unfilled PPS. The quasicrystalline filled PPS samples showed
less volume loss due to wear than did the unfilled PPS
(Fig. 4). In addition to wear testing done on semi-crystalline
PPS, an amorphous polymer PAEK synthesized in our
laboratory was blended with quasicrystals in solution and
then precipitated. The resulting composite material was
compression molded into disks and wear properties were
evaluated. PAEK/AlCuFe quasicrystalline composites,
filled at 30 vol.%, displayed 0.47 mm3 less volume loss to
wear than the unfilled PAEK. Dow epoxies were used to
formulate the QC-filled composites. Dow epoxy D.E.N.
431TM (novolac resin) was cured with metaxylenediamine. The results show that the novolac epoxy/QC composites had better wear resistance than the neat D.E.N.
431TM formulation. The addition of 30 vol.% QC in the
novolac formulation resulted in an improvement in the
Fig. 4. Volume loss results of PPS composite wear at various volume

percentages of QC powder from pin-on-disk testing. Particle size fraction
in microns listed in parenthesis.
Fig. 5. PAEK and D.E.N. 431TM / MXDA composite volume loss results
from pin-on-disk wear testing. Samples were tested neat (unfilled) and
filled at 30 vol.% AlCuFe powder. Particle size fraction in microns
listed in parenthesis.
wear resistance (Fig. 5). This result is similar to that displayed by the thermoplastic PPS/QC composites described
earlier.
4. Conclusions
AlCuFe gas atomized powder was used as reinforcing
filler in the polymer matrices of this study. The addition of
AlCuFe quasicrystal rich powder to amorphous, semicrystalline, and thermosetting polymers showed improved wear
resistance to volume loss compared to the unfilled polymers.
The corresponding reduction in wear was attributed to the
low coefficient of friction and high hardness of the quasicrystal rich powders. The storage modulus (E0 ) of the composite materials was found to increase with increasing volume
fraction of the QC powder, as expected for a filled polymer
composite containing rigid fillers [9]. In the thermoplastic
polymers, the glass transition temperatures were unaffected
by the addition of the QC filler. However, QC powder caused
the Tg of the D.E.R. 331TM epoxy composite to increase
by 7 C, slightly extending the useful temperature range of
the epoxy. Based on these results, polymer/QC composites
may find applications as dry bearing materials [10]. In addition, polymer/QC composites may find uses as other high
wear components, such as composite gears. Future studies
will include more detailed investigation of composite wear,
thermal conductivity, and other composite properties of the
interesting and technologically relevant materials described
in this paper.
Acknowledgements
This work was supported by the Director, Office of Energy Research, Office of Basic Energy Sciences, Material
Sciences Division of the US Department of Energy under
contracts No. DE-AC03-765F00098 and W-405-Eng-82
and Iowa State University. The authors would also like to
thank Dr. Daniel Sordelet and Mr. Matt Besser of Ames
Laboratory and Ms. Melissa McConnell of Iowa State
University.
159
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(1984) 1951.
[4] J.M. Durand, M. Vardavoulias, M. Jeandin, Wear 833 (1995) 181
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[5] D. Lutz, Putting quasicrystals to work, Ind. Phys. 26 (1996) 24.
[6] M. Brown, Quasicrystals: novel alloys for tough, non-stick coatings,
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[7] J.E. Shield, A.I. Goldman, I.E. Anderson, T.W. Ellis, R.W.
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Materials Science and Engineering 294296 (2000) 156159

Development of novel polymer/quasicrystal composite materials

compared to most metals, low wettability in contact with

rate of 20 C/min. Measurements of storage modulus were

2.2. Composite fabrication

3. Results and discussion

Desired amounts of polymer and quasicrystal powders

TGA analysis of the neat PPS sample gave a 5% weight

samples (Fig. 2). The Tg of the D.E.R. 331TM /DETA/QC

Fig. 4. Volume loss results of PPS composite wear at various volume

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