Polymer 45 (2004) 8211–8219

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Mechanical and thermal properties of graphite platelet/epoxy composites

Asma Yasmin*, Isaac M. Daniel
McCormick School of Engineering and Applied Science, Northwestern University, Evanston, IL 60208, USA
Received 21 April 2004; received in revised form 13 September 2004; accepted 21 September 2004

Abstract

Anhydride-cured diglycidyl ether of bisphenol A (DGEBA) reinforced with 2.5–5% by weight graphite platelets was fabricated. The
structural, mechanical, viscoelastic and thermal properties of these composites were studied and compared. XRD studies indicated that the
processing of composites did not change the original d-spacing of pure graphite. Tensile property measurements of composites indicated
higher elastic modulus and tensile strength with increasing concentration of graphite platelets. The storage modulus and glass transition
temperatures (Tg) of the composites also increased with increasing platelet concentration, however, the coefficient of thermal expansion
decreased with the addition of graphite platelets. The thermal stability was determined using thermogravimetric analysis. The composites
showed higher thermal stability in comparison with pure epoxy and increased char concentration for higher graphite concentration. The
effects of reinforcement on the damage mechanisms of these composites were investigated by scanning electron microscopy.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Graphite platelets; Epoxy; Composites

1. Introduction properties [1]. The most commonly used particles are

There is an increasing demand for advanced materials
with better properties to meet new requirements or to
replace existing materials. The high performance of
continuous fiber (e.g. carbon fiber, glass fiber) reinforced
polymer matrix composites is well known and documented.
However, these composites have some disadvantages
related to the matrix dominated properties which often
limit their wide application and create the need to develop
new types of composite materials. In the plastics industry,
the addition of filler materials to a polymer is a common
practice. This improves not only stiffness, toughness,
hardness, heat distortion temperature, and mold shrinkage,
but also reduces the processing cost significantly. In fact,
more than 50% of all produced polymers are in one way or
another filled with inorganic fillers to achieve the desired
* Corresponding author. Address: Center for Intelligent Processing of
Composites, 2137 Tech Drive, Room 330, Evanston, IL 60208, USA. Tel.:
C1 847 491 7961; fax: C1 847 491 5227.
E-mail address: a-yasmin@nothwestern.edu (A. Yasmin).
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.09.054
CaCO3, clay, mica, alumina trihydrate, glass beads, and
metal phosphates. The selection of filler is often made based
on the desired properties in the final product. The
improvement of mechanical and other properties of such
composites depends strongly on the particle content, particle
shape and size, surface characteristics and degree of
dispersion [2–5]. Consequently, the toughening of these
composites arises from a number of mechanisms such as
crack-tip pinning, crack-surface bridging, debonding/micro-
cracking, and crack deflection [2].
It is reported that the mechanical and thermomechanical
properties of composites filled with micron-sized filler
particles are inferior to those filled with nanoparticles of the
same filler [4]. In addition, the improved physical proper-
ties, such as surface smoothness and barrier properties
cannot be achieved by using conventional micron-sized
particles. Therefore, in recent years nanoparticle based
composites have drawn considerable attention. The most
promising of these are polymer/clay nanocomposites [6–
19], polymer/graphite nanoplatelet composites [20–27] and
polymer/carbon nanotube composites [28–31]. These
8212 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219

nanocomposites contain a very low amount of filler (!

10 vol%) compared to conventional particulate composites
where the usual filler content is in the range of 40–60 vol%.
Furthermore, these nanocomposites are quasi-isotropic and
can be processed by conventional means compared to the
composites reinforced with continuous fibers.
It is of interest to mention that both silicate clay
(montmorillonite) and graphite particles show a layered
structure by nature and possess high aspect ratios (O1000)
once intercalated or exfoliated by chemical processes
[7,21]. While nanocomposites with clay platelets show
improved strength, modulus, heat distortion temperature
and barrier properties, the nanocomposites with graphite
platelets show additional excellent electrical and thermal
conductivity. Carbon nanotubes also exhibit exceptional
mechanical (modulusZ1 TPa, strengthZ10 times that of
steel), thermal and electrical properties. Based on the above
considerations, it can be suggested that the development of
these nano-level particles will offer tailorability of desired
properties in a material. It is also reported that graphite
platelets, about 500 times less expensive than carbon
nanotubes, can be exfoliated and compounded in a
conventional way [25], whereas the nanotube-based com-
posites require development of processing techniques with
regard to dispersion, waviness and alignment of nanotubes. Fig. 1. Chemical formula of (a) diglycidyl ether of bisphenol A, (b) methyl
Therefore, graphite platelets are a potential alternative to tetrahydrophthalic, and (c) 1-methylimidazole.
carbon nanotubes with regard to cost and desired properties.
However, the fundamental understanding of the nanoscale Technologies LLC (Wilkes-Barre, PA). The properties of
reinforcement mechanisms is still important and necessary. the as-received graphite platelets are summarized in Table 1
Since, graphite is well known for its high strength and [32]. The graphite platelets were of sizes ranging from 4 to
high thermal conductivity, it offers the possibility of making 76 mm in diameter with a nominal average size of 22 mm. A
truly multifunctional composites in a cost effective way. SEM micrograph of the platelets is shown in Fig. 2. These
Polymers reinforced with such particles have many platelets consist of thin hexagonal plates or distorted
potential applications, e.g. CRTs and fuel cells, EMI clusters of flaky plates. It was difficult to measure the
shielding of electronic enclosures, radar absorbent coatings, thickness of as-received graphite platelets from SEM
and thermo-mechanically enhanced materials. The objec- micrographs though an attempt showed a typical thickness
tive of the present study is to fabricate composite materials of 150 nm. A simple relationship was developed to relate
that contain reinforcing graphite platelets in an epoxy the surface area and the thickness of platelet materials,
matrix and to evaluate their mechanical, thermal and
viscoelastic properties as well as the failure mechanisms 2
AZ (1)
as a function of platelet concentration. rt

where A, specific surface area per unit mass (m2/g); r,

density (g/cc); t, platelet thickness (nm).
2. Experimental
The thickness of as-received graphite platelets was as
high as 250 nm when calculated from Eq. (1) considering
2.1. Materials
surface area and density of graphite platelets of 3.56 m2/g
and 2.25 g/cc, respectively, as given in Table 1. This gives
The matrix material was a three component epoxy
system consisting of diglycidyl ether of bisphenol A Table 1
(DGEBA) cured with an anhydride hardener, methyl Properties of graphite platelets [32]
tetrahydrophthalic anhydride (MTHPA) and an accelerator, Composition Carbon
1-methylimidazole. This three-component system was Color Dark gray to black
obtained from Ciba-Geigy and was processed in proportions Hardness 1–2
of 100:85:1 by weight. The chemical structure of these Specific gravity (g/cc) 1.9–2.3
Surface area (m2/g) 3.56
materials is shown in Fig. 1. The reinforcing particles were
Mean particle size (mm) 22
net crystalline graphite platelets developed by Cornerstone
 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219
Fig. 2. SEM micrograph of graphite platelets.
an aspect ratio of 15–300. Therefore, these graphite platelets
are relatively thick compared to graphite nanoplatelets of
less than 100 nm thick as reported elsewhere [21]. Further
information on the synthesis of these graphite platelets is
proprietary with Cornerstone Technologies, LLC. In gen-
eral, natural graphite is exfoliated by a combination of
chemical and thermal treatments [22,23]; graphite is
intercalated by an acid treatment followed by exfoliation
by a thermal shock at an elevated temperature. Such a
process can generate exfoliated graphite platelets with a
surface area of 40 m2/g and thickness of less than 50 nm as
observed in a recent study [26]. However, with the aid of the
right intercalant and process it is possible to produce
graphite nanosheets or ‘graphene’ that correspond to surface
areas of more than 2600 m2/g with a thickness of less than
1 nm. It is also reported that the acid treatment of natural
graphite generates oxygen containing functional groups
(–OH and –COOH) that facilitate both physical and
chemical interactions between graphite and polymer [23,24].
2.2. Composite fabrication
The graphite platelet/epoxy composites were prepared
following standard procedures. First, the epoxy resin
(DGEBA) was mixed with 85 wt% hardener. Next, graphite
platelets were added and mixed using a magnetic stirrer over
a hot plate at approximately 60 8C for 1 h. Finally, an
accelerator of 1 wt% was added to the mixture at ambient
temperature with slow agitation. The accelerator was added
at the end since it helps to start the curing process of the
mixture. The mixture was then poured in an aluminum mold
that was prepared following the ASTM standard D638-99.
The mold was then placed in an oven and cured at 138 8C for
1 h. In this study, composites were prepared with graphite
concentrations of 2.5 and 5 wt%. The reason for adding a
higher concentration of graphite was to observe its effect on
pure epoxy. However, above 5 wt%, the mixture became
very viscous and difficult to process. Tensile specimens
165 mm long and 2.5 mm thick with a gage length of 50 mm
and width of 13 mm were prepared.
8213
2.3. Characterization techniques
2.3.1. Wide angle X-ray diffraction (WAXD)
WAXD was used to verify the structure of the composite.
WAXD was performed on a Rigaku diffractometer with
Cu Ka radiation (lZ1.541 Å) operating at 40 kV and
20 mA. The scanning range was 4–608 with a scanning
speed of 0.5 8/min.
2.3.2. Mechanical testing
Tensile tests were performed on an Instron 8500
servohydraulic testing machine at a crosshead rate of
0.25 mm/min which corresponds to a strain rate of 0.01%
per second. The strains were recorded with strain gages. At
least six tests were carried out for each case.
2.3.3. Microscopy
Following tensile testing, the fracture surfaces were
examined using a Hitachi S4500 FE Scanning Electron
Microscope to identify the mode of failure. The fracture
surfaces were gold coated prior to SEM investigation to
avoid charging and were examined at 15 kV accelerating
voltage. Since graphite is conductive, the particles could be
examined at 3 kV accelerating voltage without gold coating.
The distribution of graphite platelets in the composite was
also examined using an optical microscope.
2.3.4. Dynamic mechanical analysis (DMA)
DMA of both pure epoxy and graphite platelet/epoxy
composites were performed on a model 2980 DMA
Dynamic Mechanical Analyzer (TA Instruments, USA) to
determine their thermomechanical properties, such as
storage modulus E 0 , loss modulus E 00 damping factor tan d
and glass transition temperature (Tg). The experiments were
carried out on prismatic samples (30 mm!8 mm!2 mm)
under single cantilever mode. A frequency of 1 Hz
(corresponding to a strain rate of 0.05% per second) with
a temperature ramp of 3 8C/min and a scanning temperature
range from 30 to 200 8C were employed. The glass
transition temperature, Tg, was determined from the peak
of the tan d curve. At least three tests were carried out for
each case.
2.3.5. Coefficient of thermal expansion
The coefficient of thermal expansion (CTE) of pure
epoxy and its composites was determined using a strain
gage technique. The slope of the thermal strain versus
temperature curve measures the CTE of the composite. The
samples were heated in an oven from room temperature to
200 8C (well above the Tg) at a rate of 2 8C/min. The thermal
strains were recorded using high temperature strain gages.
The gages were bonded on the specimen surface following
the Micro Measurements, Inc. standard procedures. Strain
gage readings were calibrated using a titanium silicate
sample and the error due to the purely thermal output of the
strain gage was taken into account and corrected for.
8214 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219
2.3.6. Thermogravimetric analysis (TGA)
The thermal stability of the composites was investigated
using a TGA-SDT 2960 Thermogravimetric Analyzer (TA
Instrument, USA). The TGA scans were recorded at
20 8C/min under constant nitrogen flow of 100 ml/min
from room temperature to 800 8C. At least three tests were
carried out for each case.
3. Results and discussion
3.1. Microstructure
Optical micrographs of the cross-section of graphite
platelet/epoxy composites with concentrations of 2.5 and
5 wt% of graphite platelets are shown in Fig. 3(a) and (b),
respectively. The distribution of graphite platelets is found
to be nearly uniform without segregation after curing. The
pure epoxy matrix is transparent but the addition of graphite
platelets made the composites opaque.
3.2. WAXD measurements
Fig. 4 shows the WAXD patterns for pure graphite
Fig. 3. Optical micrographs of the cross-section of graphite platelet/epoxy
composites. (a) 2.5 wt% graphite and (b) 5 wt% graphite.
platelets and the composites. Both pure graphite platelets
and the graphite platelet/epoxy composites exhibit an
intense peak at a 2q value of 26.58, corresponding to a
basal spacing of 3.36 Å. This basal spacing is exactly the
same as that observed for pure crystalline graphite [33]. This
confirms that the graphite platelets, w250 nm in thickness
(calculated), are still in order and multilayer, and thus,
maintain their original d-spacing. This, further, indicates
that the processing technique used in this study was unable
to affect the order in the structure or exfoliate the graphite
platelets in the epoxy matrix.
3.3. Density
Epoxy materials are well known for their low density.
However, the density of the filler is usually higher than that
of pure epoxy. It is, therefore, important to know the change
in density with filler addition. The variation of density with
graphite platelet concentration was measured by conven-
tional means. The density of the composite was also
calculated using the rule of mixtures. The corresponding
equations are:
w=rp
fZ (2)
w=rp C ð1 K wÞ=rm
rc Z f rp C ð1 K f Þrm (3)
where f is the volume fraction of graphite platelets, w the
weight fraction of graphite platelets, rp the graphite platelet
density, rm the matrix density, and rc the composite density.
It is reported that the density of graphite particles (rp)
varies in the range of 1.9–2.3 g/cc (Table 1). Using rpZ
1.9 g/cc and rmZ1.2 g/cc (density of pure epoxy measured
in this study), the density of a 2.5 wt% graphite platelet/
epoxy composite becomes 1.208 g/cc. Using rpZ2.3 g/cc,
the density of a 2.5 wt% graphite platelet/epoxy composite
becomes 1.211 g/cc. Both numbers are very close to the
Fig. 4. XRD patterns of pure graphite and its composites.
 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219 8215

measured value (1.21 g/cc). However, the density of the

5 wt% graphite platelet/epoxy system should range between
1.219 and 1.226 g/cc, which is lower than the measured
density of 1.244 g/cc. This discrepancy may be due to the
occasional presence of inclusions (e.g. clay) in the graphite
particles, which becomes more pronounced as the graphite
content increases. However, it can be suggested that the
increase in density due to the addition of graphite platelets
in pure epoxy is still negligible.

3.4. Mechanical properties

The tensile properties of pure epoxy and graphite

platelet/epoxy composites reinforced with 2.5 and 5 wt%
graphite platelet concentrations are summarized in Table 2.
From this table, it can be seen that both composites show
higher elastic modulus and strength than the pure epoxy
matrix. They also show failure at a higher strain than the
pure epoxy.
The variation of elastic modulus with graphite platelet
concentration is shown in Fig. 5(a). The composite
reinforced with 2.5 wt% graphite platelets showed about
10% increase in elastic modulus, whereas the composite
reinforced with 5 wt% of graphite platelets showed about
25% increase in elastic modulus over the pure epoxy matrix.
However, the variation in tensile strength with graphite
concentration did not follow the same trend. In Fig. 5(b), the
graphite platelet/epoxy composites showed about 21%
higher tensile strength with the addition of 2.5 wt% but
only 9% increase with the addition of 5 wt% of graphite
platelets compared to the pure epoxy. Agag et al. [17] also Fig. 5. Effect of graphite platelet concentration on the tensile properties of
reported that the addition of low clay content (1%) in graphite platelet/epoxy composites. (a) Elastic modulus and (b) tensile
strength.
polyimide matrix increased the tensile strength, however,
the higher clay content (4%) decreased the tensile strength.
It can be assumed that the increased concentration of produce a high stress concentration and cause premature
graphite platelets made the composite more brittle and failure [14,15].
reduced its failure strain. The improvement in strength and Attempts were also made to calculate the elastic modulus
modulus can be attributed to the high strength and high of the composites as a function of particle content using
aspect ratio of graphite platelets as well as to the uniform existing micromechanical models. The constituent materials
distribution and good interfacial adhesion between the properties used in the analysis are: matrix Young’s
platelets and the epoxy matrix. All these characters provide modulusZ3 GPa, matrix Poisson’s ratioZ0.34, graphite
good load transfer from the matrix to the platelets. However, in-plane modulusZ600 GPa, graphite out-of-plane modu-
the lower strength at higher graphite platelet concentration lusZ10.5 GPa, graphite Poisson’s ratioZ0.25, graphite
(R5 wt%) can be attributed to the inevitable aggregation of platelet widthZ22 mm, and thicknessZ250 nm. The
platelets at high concentration. The cluster of platelets Reuss (series) model predicted moduli of 3.03 and
shown in Fig. 3 also confirms this. Therefore, when the 3.07 GPa for 2.5 and 5 wt% graphite/epoxy composites,
composites are under load, the platelets in the cluster may respectively, whereas, the Mori–Tanaka model [34]
Table 2
Mechanical properties of pure epoxy and graphite platelet/epoxy composites

Properties Epoxy Epoxy—2.5 wt% graphite Epoxy—5 wt% graphite

Elastic modulus, E (GPa) 3.0G0.1 3.3G0.1 3.75G0.2
Tensile strength, sult (MPa) 34G3 41G4.6 37G3
Ultimate tensile strain, 3ut (%) 1.24G0.2 1.5G0.2 1.3G0.3
Poisson’s ratio, n 0.34 0.35 0.33
8216 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219
predicted moduli of 3.78 and 4.61 GPa for 2.5 and 5 wt%,
respectively. The Voigt model predicted even higher values.
The experimental results are not in agreement with these
models. The most obvious reasons would be the random
distribution of platelets and numerous aggregates instead of
good exfoliation, and orientation of graphite platelets.
Therefore, a processing technique that provides better
dispersion, exfoliation and orientation of platelets is highly
desirable. In addition, the values of Young’s modulus and
the thickness of graphite platelets used in the calculations
were assumed. It is, therefore, important to measure the
Young’s modulus as well as the geometry of the graphite
platelets to predict the modulus of composites more
accurately.
3.5. Viscoelastic properties
A dynamic mechanical analyzer is often used to study the
viscoelastic properties of polymers under stress and
elevated temperature. Fig. 6 shows the variation of storage
modulus and tan d with temperature for pure epoxy and its
composites. For the purpose of clarity, only one representa-
tive curve for each case is shown. At 30 8C, the 2.5 and
5 wt% graphite platelet/epoxy composites showed about 8
and 18% higher storage modulus than the pure epoxy
matrix. As the temperature increased, both pure epoxy and
its composites showed a gradual drop in storage modulus
followed by a sudden drop at the glass transition
temperature (Tg). The drop in modulus is related to the
material transition from a glassy state to a rubbery state. Fig.
6 shows that at the onset of glass transition temperature
(w125 8C), both 2.5 and 5 wt% graphite platelet/epoxy
composites showed similar improvements in storage
modulus as observed at 30 8C. A higher storage modulus
with the higher graphite content was also observed above
Tg, or in the rubbery region. At 150 8C, the 2.5 and 5 wt%
graphite platelet/epoxy composites showed about 34 and
Fig. 6. (a) Dynamic mechanical properties of pure epoxy and its
composites.
53% higher storage modulus, respectively, than the pure
epoxy, a much higher increase than observed at room
temperature. In the present study, the graphite platelet/
epoxy nanocomposites showed consistently higher storage
modulus over pure epoxy, increasing with the concentration
of graphite particles. The DMA analysis also revealed that
the effect of graphite is more pronounced on the viscoelastic
behavior.
From Fig. 6, it can also be seen that the glass transition
temperature of pure epoxy increased slightly with the
incorporation of graphite platelets. The Tgs were 143, 145
and 146 8C for graphite contents of 0, 2.5 and 5 wt%,
respectively. These results are more promising compared to
clay/epoxy nanocomposites, where a decrease in Tg with
increased clay content is a common problem [10,12,16]. In
general, the increase in Tg is attributed to the good adhesion
between the polymer and the reinforced particles so that the
nanometer size particles can restrict the segmental motion
of cross-links under loading [16,17]. It is reported that the
acid treatment of natural graphite generates oxygen
containing functional groups that facilitate both physical
and chemical interactions between graphite and polymer
[23,24]. The other important factors that can affect Tg are
degree of particle dispersion and curing conditions. The
degree of particle dispersion includes size, homogeneity,
orientation and spacing between particles, whereas curing
conditions include curing speed and degree of cross-linking.
The small improvement in Tg observed in this study for
graphite platelet/epoxy composites may arise from some of
these factors.
3.6. Thermal expansion coefficient
The thermal expansion coefficient is an important issue
for polymers in engineering applications. A low thermal
expansion coefficient is often desirable to achieve dimen-
sional stability and can be achieved by incorporation of a
rigid and low CTE filler material. In the present study, the
graphite platelets were added to pure epoxy to study the
CTE of the resultant composites. It was found that both pure
epoxy and the graphite platelet/epoxy composites showed
an initial linear slope followed by a sudden discontinuity in
thermal expansion. However, in contrast to pure epoxy and
5 wt% graphite platelet/epoxy composite, the 2.5 wt%
graphite platelet/epoxy composite showed a bilinear
response with an initial slope of 36!10K6/8C. This was
slightly smaller than the final value of 41!10K6/8C; the
transition in slope occurred at 77 8C. Tandon et al. [35] also
reported a bilinear behavior when they measured the CTE of
graphite–epoxy composites using a strain gage technique. In
the present study, the CTE of pure epoxy was found to be
60!10K6/8C, and the addition of 2.5 wt% graphite platelets
reduced it to 36–41!10K6/8C, therefore, about 30–40%
lower than the CTE of pure epoxy. The lowering of CTE can
be attributed to the fine dispersion and rigidity of graphite
platelets in the epoxy matrix, which can inhibit the
 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219 8217

expansion of polymer chains as the temperature is raised.

However, further addition of graphite platelets, w5 wt%,
increased the CTE to 50!10K6/8C. This can be explained
with regard to the inevitable aggregation of graphite
platelets at higher concentration. It is expected that the
lack of uniform distribution or graphite platelets in cluster
form should not provide enough obstacles to the expansion
of polymer chains. A similar behavior is also reported
elsewhere [17], where the addition of low clay content (2%)
in polyimide matrix decreased the CTE, but the higher clay
content (4%) increased the CTE. Therefore, it can be
suggested that the graphite content influences the thermal
behavior of the composites significantly. The effects of
processing techniques as well as the orientation and aspect
ratio of platelet materials can also influence the thermal
expansion behavior of composites significantly as reported
by Yoon et al. [36] for a nylon 6/clay composite system. A
Fig. 7. TGA of pure graphite, pure epoxy and the composites.
similar study for graphite platelet/epoxy composites is now
under investigation. char content of 10%, the composites show about 13 and
15% for 2.5 and 5 wt% graphite platelet/epoxy composites,
3.7. Thermal stability respectively. Therefore, the incorporation of the graphite
platelet resulted in pronounced improvement in thermal
The thermal stability of composites was determined stability. This can be attributed to the homogeneous
using a thermo-gravimetric analyzer. The TGA curves of distribution of graphite particles as well as the tortuous
pure epoxy and the composites with different graphite path in the composites that hinders diffusion of the volatile
content are shown in Fig. 7. It is observed that pure graphite decomposition products in the composites compared to that
exhibits very high thermal stability with only 1.6% total in pure epoxy. The improvement of thermal stability due to
weight loss up to 800 8C. On the other hand, both pure the addition of nanoparticles has also been reported for other
epoxy and the composites show thermal degradation at composites [17–19].
much lower temperatures and significant weight loss with
temperature. The onset and the end set of thermal 3.8. Fractography
degradation temperature were determined from the inter-
section of two tangents. The TGA values of pure epoxy and Fig. 8(a) shows the fracture surface of pure epoxy. The
its composites (onset; end set; degradation temperatures at crack usually initiates from surface defects or high stress
5, 10 and 50% weight loss; non-volatile part or char content) regions. The mirror-like region in Fig. 8(a) represents the
are given in Table 3, which indicate that the thermal slow growth of crack-like defects. The lines next to the
stability of the pure epoxy was enhanced by the incorpor- mirror-like region are shear cusps developed by nucleation
ation of graphite particles. For pure epoxy, the onset and propagation of micro shear zones within the matrix
temperature is 360 8C, while for the composites it increases ligament. These shear cusps are also found to be oriented at
to 366 8C for 2.5 wt% graphite platelet/epoxy and 368 8C 458 with the loading direction with almost equal widths.
for the 5 wt% graphite platelet/epoxy. In all cases, the This observation is consistent with the brittle failure
thermal degradation occurs in one step, which is mainly due mechanisms of epoxy materials as mentioned elsewhere
to the degradation of cross-linking. Further, the incorpor- [37]. Fig. 8(b) shows the shear cusp at higher magnification.
ation of 2.5 and 5 wt% graphite particles in pure epoxy Fig. 9(a) shows the fracture surface of a composite
matrix increases the 5% decomposition temperature of pure reinforced with 5 wt% of graphite platelets. As in the case of
epoxy by 13 and 25 8C, respectively. The composites also pure epoxy, it also shows shear cusps but only at the
show higher char content or reduced weight loss at 800 8C beginning when the crack growth rate is low. Further, the
as the graphite content increases. While pure epoxy shows a shear cusps appear to be shorter and smaller compared to
Table 3
TGA values for pure epoxy and its composites

Sample Onset (8C) Endset (8C) T (8C) for 5% loss T (8C) for 10% loss T (8C) for 50% loss Char (%)
Pure epoxy 360 442 305G1.0 348G2.0 407G1.5 10G2.0
2.5 wt% graphite/epoxy 366 448 318G5.3 355G5.0 412G2.0 13G4.0
5 wt% graphite/epoxy 368 450 330G2.1 357G0.7 414G2.8 15G3.5
8218 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219

Fig. 8. SEM fractographs of pure epoxy. (a) Low magnification and (b) high
magnification.

those in pure epoxy. This may be due to the interference of

graphite platelets to the flow stress, where the graphite
platelets restrict the free movement of polymer chains by
crack tip pinning. Fig. 9(b) shows a combination of shear
cusps and coarse features which indicate the transition from
slow to fast crack growth. Finally, Fig. 9(c) shows only
coarse features due to fast fracture. A similar type of fracture
surface is also observed for the composite with 2.5 wt%
graphite concentration.
Further investigation of the fracture surface of the
5 wt% graphite platelet/epoxy composite at higher magni-
fication shows debonding between matrix and graphite
platelets at different locations, as shown in Fig. 10. It can
Fig. 9. SEM fractographs of 5 wt% graphite/epoxy composite. (a) Slow
be assumed that the platelets debonded from the epoxy
crack growth region, (b) transition from slow to fast fracture region and (c)
matrix under loading and generated microcracks. Upon fast fracture region.
further loading, these microcracks joined together to form
a single dominant crack, and the final failure of the 4. Summary
specimen occurred by microvoid coalescence. The 5 wt%
graphite platelet/epoxy composite also failed at both lower The excellent combination of lightweight and superb
stress and lower strain than the 2.5 wt% graphite platelet/ thermal, mechanical, electrical, and flame retardant proper-
epoxy composite. This can be attributed to the lower ties of graphite has drawn attention to the development of
particle spacing in the former case and as a result the multifunctional polymer based nanocomposites in recent
microvoids coalesced earlier. years. In the present study, graphite platelets of around
 A. Yasmin, I.M. Daniel / Polymer 45 (2004) 8211–8219
Fig. 10. Fracture surface of 5 wt% graphite/epoxy composite showing
debonding at different locations (arrows).
250 nm thickness were used to prepare 2.5–5 wt% graphite
platelet/epoxy composites. XRD studies of composites
revealed that there was no change in d-spacing of graphite
platelets. This indicates that the graphite platelets were in
order and multilayer, and the processing technique used in
this study was unable to affect the order in the structure or
exfoliate the graphite platelets in the epoxy matrix.
However, the addition of graphite platelets increased both
elastic modulus and tensile strength of the composites. The
DMA also showed increased storage modulus and Tg with
increased graphite concentration. The CTE of pure epoxy
(60!10K6/8C) decreased to almost half of its original value
with the addition of 2.5 wt% of graphite platelets (34–41!
10K6/8C). The composites also showed higher thermal
stability than pure epoxy. Finally, the fractographic analysis
of graphite platelet/epoxy composites showed failure
mechanisms consisting of crack tip pinning, debonding
and void coalescence, which were absent in the case of pure
epoxy.
It can be suggested that the 2.5 wt% graphite platelet/e-
poxy showed the best balance of mechanical (modulus,
strength), viscoelastic (storage modulus, Tg) and thermal
(CTE, thermal stability, decomposition temperature) prop-
erties due to the homogeneous dispersion of stiff and rigid
graphite platelets. The influence of expanded or exfoliated
graphite nanoplatelets of less than 50 nm thick on the
mechanical and thermal properties of pure epoxy is now
under investigation and will be communicated later.
Acknowledgements
This research was sponsored by the Office of Naval
Research (ONR). We are grateful to Dr Y. D. S. Rajapakse
of ONR for his encouragement and cooperation. We are also
thankful to Dr Peter A. Kanjorski of Cornerstone Technol-
ogies LLC, PA for supplying the graphite materials for our
experiments. Thanks are also due to Dr Jyi-Jiin Luo for his
help in modeling the composites.
8219
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