Effect of Al2O3 Addition on Thermo-Electrical
Properties of Polymer Composites: An Experimental
Investigation
Alok Agrawal, Alok Satapathy
Department of Mechanical Engineering, National Institute of Technology, Rourkela 769008, India
To develop a new class of composites with adequately
high thermal conductivity and suitably controlled
dielectric constant for electronic packages and printed
circuit board applications, polymer composites are
prepared with microsized Al2O3 particle as filler having
an average particle size of 80–100 lm. Epoxy and poly-
propylene (PP) are chosen as matrix materials for this
study. Fabrication of epoxy-based composite is done
by hand lay-up technique and its counterpart PP-
based composite are fabricated by compression mold-
ing technique with filler content ranging from 2.5–25
vol%. Effects of filler loading on various thermal prop-
erties like effective thermal conductivity (keff), glass
transition temperature (Tg), coefficient of thermal
expansion (CTE) and electrical property like dielectric
constant (ec) of composites are investigated experi-
mentally. In addition, physical properties like density
and void fraction of the composites along with there
morphological features are also studied. The experi-
mental findings obtained under controlled laboratory
conditions are interpreted using appropriate theoretical
models. Results show that with addition of 25 vol% of
Al2O3, keff of epoxy and PP improve by 482% and 498%
respectively, Tg of epoxy increases from 98 C to 116 C
and that of PP increases from 214.9 C to 3.4 C. For
maximum filler loading of 25 vol% the CTE decreases
by 14.8% and 26.4% for epoxy and PP respectively
whereas the dielectric constants of the composites get
suitably controlled simultaneously. POLYM. COMPOS.,
00:000–000, 2014. VC 2014 Society of Plastics Engineers
INTRODUCTION
Polymers are widely used in packaging of electronic
devices such as in electronic moulding compound and glob
top encapsulation. Earlier, the main functions of packaging
devices are to protect the electronic devices from exposure
to various environmental hazards such as moisture, chemi-
cal agents, dusts and light. In addition to that it was also
providing mechanical strength to such devices [1]. High
thermal stability, low moisture absorption characteristics,
Correspondence to: Alok Agrawal; e-mail: alokag03@gmail.com
DOI 10.1002/pc.22918
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2014 Society of Plastics Engineers
V improved by surface modification of reinforced
POLYMER COMPOSITES—2014
and low cost are the various qualities of polymers which
make its use as an encapsulating material. But as the elec-
tronic technology is advancing day by day, more semicon-
ductor devices are integrated in a single device to increase
functionality and enhance performance. Such miniaturiza-
tion of microelectronics causes the problem of proper heat
dissipation which may limit the device reliability [2], as
polymer possesses certain poor thermal properties like, low
thermal conductivity and high coefficient of thermal expan-
sion. To overcome these problems, polymer composites
came into existence. The high thermal expansion coeffi-
cient of polymer resin is lowered with the addition of
ceramic filler like silica and quartz [3], but improvement in
thermal conductivity still remains a critical issue because
of low conductivity of silica filler. Therefore, particulates
with high thermal conductivity reinforced in polymer
matrix are emerging as a cost-effective mean to remove
heat accumulated from plastic packages [4].
The thermal conductivity of polymer composites can
be improved by reducing its thermal barrier resistance in
the direction of heat flow. The reduction of thermal bar-
rier resistance gives rise in the formation of thermal con-
ductive network within the composite. As the conductive
network form, the composite shows percolation behavior.
Formation of such conductive network depends on the
type, shape, size, volume fraction, dispersion characteris-
tics, and intrinsic thermal conductivity of the filler [2]. It
has been seen that, as the intrinsic thermal conductivity
of the filler increases, the thermal conductivity of com-
posite also increases, but Bigg [5] gave the limit of such
increase for a particular case of spherical particle rein-
forced composites and reported that as the thermal con-
ductivity of filler reaches a value about 100 times that of
matrix material, there is no significant increase in the
value of effective thermal conductivity of composite
material. The effect of shape, size, volume fraction, and
dispersion of filler in matrix to enhance heat conduction
behavior of composite material are reported in various lit-
erature as well [6–9]. Recently Cao et al. [10] reported
that the thermal conductivity of PS/PVDF blend is
nanoparticles which is another interesting way to enhance For series conduction model:
the heat conduction capability.
In addition to high thermal conductivity, low dielectric 1=keff 5ð12/f Þ=kp 1/f =kf (2)
constant is also required, as in application like printed circuit
boards. As the working frequency increases, signal intensity Effective thermal conductivity of composite, consider-
losses become more sensitive and will show inefficiency in ing geometric mean model is given by [18]
signal-conveying [11]. Low dielectric constant helps to / ð12/f Þ
keff 5kf f :km (3)
increase the velocity of signal propagation. So the material
used for these kinds of applications must have multifunc- Maxwell-Euken model [19] assumes well dispersed small
tional properties. Poor thermal conductivity of polymers can spherical filler within continues matrix to calculate the effective
be improved with the use of electrically resistive fillers, like thermal conductivity. The model is valid for low loading of fil-
aluminium nitride [12], boron nitride [13], aluminium oxide ler where the particles are not coming in contact with each
[14], silicon nitride [15] silicon carbide [16], etc, which other. The expression for Maxwell-Euken model is given as
maintains the low dielectric constant of polymer as well.  
keff kf 12kp 12/f ðkf 2kp Þ
In this study, effect of ceramic filler Al2O3 on two dif- 5 (4)
kp kf 12kp 2/ðkf 2kp Þ
ferent categories of matrix material, i.e. thermoset poly-
mer, epoxy and thermoplastic polymer, polypropylene are Bruggeman [20] derived an equation of thermal con-
under investigation. The shift in various physical, thermal, ductivity in terms of the solid loading for spherical fillers
and dielectric properties of composite with increase in fil- in a dilute suspension which is given as
ler content is reported. The crucial thermal conductivity  1
and important dielectric constant of the composites are keff 2kf kp 3
12/f 5 (5)
presented and discussed in detail. Other essential proper- kp 2kf keff
ties, such as density, void fraction, microstructure, glass Lewis and Nielsen [21] modified the effect of shape of
transition temperature, and coefficient of thermal expan- the particles and the orientation or type of packing and
sion are also examined. A suitable theoretical model to derived an equation which is expressed as
predict effective thermal conductivity of different matrix– !
filler combinations has been suggested in this study. It is 11AB/f
keff 5kp (6)
expected that this study will be of importance for new 12B/f w
packaging technologies of further increasing of working
frequency and miniaturization of electronic devices. where
!
ðkf =kp Þ21 12/p
B5 ; w511 /
ðkf =kp Þ1A /2p
ANALYTICAL MODELS FOR COMPOSITE
MATERIALS The values of A and /p depends on the geometric shapes
and the orientation of the fillers and are having specified
Models for Effective Thermal Conductivity values.
Tsao [22] derived an effective thermal conductivity equa-
To evaluate the effective thermal conductivity of com- tion for two-phase solid mixture which relates the conductiv-
posite materials, several predictive models have been pro- ity of the composite with that of conductivity of individual
posed in the past [17–23]. These models often contain components and also with the parameters which describe the
terms to account for the shape, size, and intrinsic thermal distribution of the individual phases. By assuming a parabolic
conductivity of the filler particles [24]. Brief descriptions distribution of discontinuous phase in the continuous phase, a
of few such models are listed below with their basic new model is derived by Cheng et al. [23] based on Tsao [22]
assumptions. Later the experimental values obtained for model. Here the parabolic distribution constant purely
the microsized particulate-filled polymer composites of depends on the volume fraction of discontinuous phase.
this study are compared with a various predictive models. For kf > kp:
For a two-component composite, the simplest alterna-
1 1
tives would be with the materials arranged in either series 5 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
or parallel with respect to heat flow, which gives the upper keff Cðkp 2kf Þ½kp 1Bðkf 2kp Þ
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi B pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
or lower bounds of effective thermal conductivity [17]. ½kp 1Bðkf 2kp Þ1 Cðkp 2kf Þ 12B
For the parallel conduction model: 3 ln pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi B2 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1
½kp 1Bðkf 2kp Þ2 2 Cðkp 2kf Þ kp
  (7)
keff 5 12/f kp 1/f kf (1)

where, keff, kp, kf are the thermal conductivities of the where qffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffi
composite, matrix and filler, respectively, and /f is the
B5 3/f =2 C524 2=3/f
volume fraction of filler.

2 POLYMER COMPOSITES—2014 DOI 10.1002/pc

 All the models mentioned above are capable of esti-
mating the effective thermal conductivity of particulate
filled composites on the basis of volume fraction of the
filler but none of the model has actually taken care of the
arrangement of the filler within the matrix. However this
aspect has been considered in a recently proposed model
by the authors [25]. This model assumes an arranged dis-
tribution of filler particles within the matrix body and is
based on the following assumptions:
a. The distribution or dispersion of the spherical fillers in
the matrix is uniform.
b. Locally both the matrix and fillers are homogeneous and
isotropic.
c. The thermal contact resistance between the filler and the
matrix is negligible.
d. The composite body is free from voids.
e. The temperature distribution along the direction of heat
flow is linear.
The expression for keff as per proposed model is given
by [25]
1
keff 5  13 (8)
6/
1 1
kp 2 kp p
f
1    2  1 4  Kp /p 1Kf /f 1ð3Kp Kf =4Gp Þ
3 2/ 3
4p
kp 3/ 1 9pf 2pðkf 2kp Þ
f
where / represents the volume fraction and k is the ther-
mal conductivity, suffix f and p are for filler and matrix
material, respectively.
Models for Coefficient of Thermal Expansion
Thermal expansion is the tendency of a material to
change in its dimension when there is change in tempera-
ture. Coefficient of thermal expansion is an important
property to study in applications where high temperature
or fluctuating temperature is required. To evaluate the
effective coefficient of thermal expansion, the simplest
method is of rule of mixture which assumes that the total
expansion of the composite must be the sum of the
expansions of the constituents multiplied by their respec-
tive volume fraction [26], and is given as
ac 5ap /p 1af /f (9)
Where a and / are CTE and volume fraction, suffix c,
p, and f are for composite, matrix, and filler, respectively.
The CTE value calculated using ROM is based on the
assumption that there is a linear relationship between
CTE and volume fraction of each phase. However, the
thermal strain in one phase is constrained by the other
phase within a composite and the magnitude of such
strain depends on the shear transfer at the interface [27].
Thus, the elastic constants of individual effects the ther-
mal strain features strongly. In view of this, there are sev-
eral models available in the literature which takes into
account the elastic constant of material to evaluate CTE
DOI 10.1002/pc
[28–31]. Among them, Turner’s model [28] is based on
the fact that only uniform hydrostatic stresses exist in the
phases, Turner takes into account the mechanical interac-
tion between different materials in the composite. Based
on the assumption that all phases in the composite have
the same dimension change with temperature, he derived
a relationship that is expressed as
ap /p Kp 1af /f Kf
ac 5 (10)
/p Kp 1/f Kf
where K is the bulk modulus and is calculated by using
standard relationship:
E
K5 (11)
3ð32E=GÞ
E and G are Young’s and shear modulus, respectively;
subscript p and f are for matrix and filler respectively.
Kerner’s model [29] is given by the expression as
ac 5ap /p 1af /f 1/p /f ðaf 2ap Þ
Kf 2Kp (12)
3
The above model assumes the filler to be spherical
which is completely surrounded by the matrix phase and
the CTE of composite depends upon the volume fraction
of the individual phases.
According to Rosen-Hashin model [30], the expression
of evaluating the CTE of composite only provide bounds
of CTE which is divided into two parts i.e. upper bound
and lower bound, and is given as
4/p /f Gf ðKp 2Kf Þðap 2af Þ
auc 5 1ðap /p 1af af Þ (13)
3Kp Kf 1ð4Gf ðKp 1Kf Þ=2Þ
4/p /f Gp ðKp 2Kf Þðap 2af Þ
alc 5 1ðap /p 1af af Þ (14)
3Kp Kf 1ð4Gp ðKp 1Kf Þ=2Þ
where the superscript u and l are for upper and lower
bounds.
Models for Dielectric Constant
The dielectric constant of a material reflects the extent
to which it concentrates electrostatic lines of flux. It may
also be defined as the ratio of the amount of electrical
energy stored in a material by an applied voltage, relative
to that stored in a vacuum. For applications like printed
circuit board and encapsulation, material with low dielec-
tric constant is preferred to increase the signal transmit-
ting speed. Hence precise prediction of the dielectric
constant of polymeric composites is required. Among var-
ious analytical models available, few of them are used in
present study to calculate dielectric constant of the com-
posite material. Lichtenecker equation [31] to predict
POLYMER COMPOSITES—2014 3
dielectric constant of the composite material is simplest
among all and is given as
 
ln ec 5/f ln ef 1 12/f ln ep
where ec, ep, and ef are the dielectric constant of compos-
ite, polymer matrix, and filler material, respectively, and
/f is volume fraction of filler material.
In early 90’s Jayasundere and Smith [32] derived an
equation which is one of the most popular and widely
used correlation for evaluating dielectric constant of com-
posite which is given as
h ih
3ep 3/f ðef 2ep Þ
ep ð12/f Þ1ef /f ef 12e p
11 ef 12e p
ec 5 h ih i (16)
3ep 3/f ðef 2ep Þ
ð12/f Þ1/f ef 12ep 11 ef 12ep
The developed expression is valid only when dielectric
constant of filler is more as compared to that of matrix
material. This deficiency of the above model is solved in
mid 2000 by Poon and Shin [33]; they derived an analytic
formula for prediction of dielectric constant of binary
composite material which is given as
1
ec 5ep 1/f ðef 2ep Þ
ef 12ep 2/f ðef 2ep Þ
/f 1ð12/f Þ 3ep
They validated their data with the experimental val-
ues for different type of filler-matrix combination and
concluded that the model is applicable for wide range
of ef/ep value. These analytical models have been used
widely to predict the thermal and dielectric properties
of composites. The predictions from the models have
successfully applied in some cases. However, the main
drawback has been that the models are applicable for
low volume fraction of fillers and with increase in fil-
ler content beyond certain value all this models are
either underestimating the measured value or starting to
show erratic behaviour for certain combination of filler
and matrix.
EXPERIMENTAL DETAILS
Materials Considered
Thermoset resin epoxy LY 556, chemically belonging
to the “epoxide” family is used as one of the matrix
materials in the present work. Its common name is
Bisphenol-A-Diglycidyl-Ether. It is used with its corre-
sponding hardener Triethylene tetramine (TETA, HY
951). Epoxy is most commonly used polymer and pos-
sesses low density (1.1 gm/cm3). In spite of low thermal
conductivity (0.363 W/m-K) and high CTE (66 3 1026/
 shown in Table 1. Typical images of epoxy/Al2O3 and
C), epoxy possesses low dielectric constant (4.3 at 1
MHz) which makes this polymer feasible for microelec-
tronics applications. PP, another most easily available
4 POLYMER COMPOSITES—2014
resin belonging to the thermoplastic group of polymer is
used for another set of composite material. It possesses
still lower density of 0.92 gm/cm3. CTE of PP is quite
(15) high (111.5 3 1026/ C) as compared to epoxy but it pos-
sesses a very low dielectric constant (2.25 at 1 MHz).
Both the polymers used in the present work are procured
from Ciba Geigy Limited, India. Aluminium oxide is alu-
minium based ceramic material used as the filler in the
present investigation were purchased from M/s Alfa Aesar
Limited-Beijing, China. These Al2O3 powder has a den-
sity of 3.89 gm/cm3. Al2O3 is chosen over other ceramics
because of its moderate heat conducting nature (35 W/m-
i K), moderate dielectric constant (9.8 at 1 MHz), low
coefficient of thermal expansion (8.1 3 1026/ C), and
stable crystal structure.
Composite Fabrication
Al2O3 particles with average size of 80–100 lm are
reinforced in epoxy resin to form particulate- filled com-
posites of different compositions. The low temperature
curing epoxy resin and the corresponding hardener are
mixed in a ratio of 10:1 by weight as per recommenda-
tion. Conventional hand-lay-up technique has been
(17) adopted to cast the composites. The dough (epoxy mixed
with Al2O3) is slowly decanted into the glass molds,
coated beforehand with wax and a uniform thin film of
silicone-releasing agent. The castings are left to cure at
room temperature for about 24 hours after which the glass
molds are broken and samples are released. The compo-
sites are cast in these molds so as to get disc type cylin-
drical specimens (diameter 50 mm, thickness 3 mm and
diameter 15 mm, thickness 1.6–2 mm). Composites of 10
different compositions with Al2O3 content ranging from
2.5 to 25 vol% are prepared. The number of samples
made for each individual composition is five. Another set
of composites having similar Al2O3 volume fraction with
PP as the matrix material is also fabricated by compres-
sion molding technique. Rheomix 600 batch mixer is
used to melt and mix the matrix phase and filler phase. In
present case the mixing temperature is set to 190 C,
whereas mixing time is of 12 minutes, the temperature
and time may differ for different sets of materials and
mainly depend on matrix phase as long as the fillers are
ceramics. The mixing is done as per ASTM standard D-
2538. As the mixing is over, the material is taken out
from the chamber and is cut into small pieces. Small
pieces are required to avoid trapping of air during com-
pression molding. Materials are kept in die which is used
to make a composite sheet of thickness 3 mm and area
60 3 60 mm2. Compression moulding is done as per
ASTM D-256 standard. Later the disc type specimens of
required dimensions are cut from the sheet. The composi-
tions of various samples prepared for present work is
PP/Al2O3 composites specimen used for experimentation
are shown in Fig. 1.
DOI 10.1002/pc
 TABLE 1. List of fabricated composites.

Composition Composition
(Hand lay-up (Compression
Sample technique) molding technique)

1 Epoxy 1 2.5 vol% filler Polypropylene 1 2.5 vol% filler

2 Epoxy 1 5.0 vol% filler
3 Epoxy 1 7.5 vol% filler
4 Epoxy 1 10.0 vol% filler
5 Epoxy 1 12.5 vol% filler
6 Epoxy 1 15.0 vol% filler
7 Epoxy 1 17.5 vol% filler
8 Epoxy 1 20.0 vol% filler
9 Epoxy 1 22.5 vol% filler
10 Epoxy 1 25.0 vol% filler
Polypropylene 1 5.0 vol% filler
Polypropylene 1 7.5 vol% filler
Polypropylene 1 10.0 vol% filler
Polypropylene 1 12.5 vol% filler
Polypropylene 1 15.0 vol% filler
Polypropylene 1 17.5 vol% filler
Polypropylene 1 20.0 vol% filler
Polypropylene 1 22.5 vol% filler
Polypropylene 1 25.0 vol% filler

FIG. 2. The SEM micrographs of Al2O3.

ec 5C:d=e0 :A (18)

where d is the thickness of the discs, e0 is vacuum dielec-

FIG. 1. The pictorial view of fabricated composites (a) Epoxy/ Al2O3
composite (b) PP/ Al2O3 composite
Characterization
Scanning electron microscopic (SEM) observations to
determine either filler or composites morphologies are
performed with JEOL JSM-6480 LV. The density of the
fabricated polymer-based composites is measured by the
Archimedes principle using distilled water as a medium.
UnithermTM Model 2022 is used to measure thermal con-
ductivity of the composite material under study. The tests
are done at room temperature (27 C) in accordance with
ASTM E-1530 standard. Circular sample of 50 mm diam-
eter and 3 mm of thickness with flat surface on both side
are used for the measurement. This instrument works on
the principle of guarded heat flow meter test method.
Glass transition temperature and coefficient of thermal
expansion are measured with the help of Perkin-Elmer
thermal mechanical analyzer (TMA-7). The temperature
range used to measure the properties is from 50 C to
150 C for epoxy/Al2O3 composites and 250 C to 50 C
for PP/Al2O3 composites with a heating rate of 5 C/min.
The tests are in accordance with ASTM D 618 for evalu-
ating glass transition temperature and ASTM E 831 for
CTE. Dielectric constant measurements are taken at room
temperature on a Hioki 3532-50 Hi Tester LCR analyzer
with an applied AC voltage of 500 mV in the frequency
range 1 kHz–1 MHz. The used samples are disc-shaped
with 15 mm diameter and 1.6–2 mm thickness. The
dielectric constant is calculated from capacitance, and is
given as:
tric constant that is 8.85 3 10212 farad per m, A is the
disc area and C is the parallel capacitance. All the experi-
ments performed are repeated three times for each fabri-
cated samples and each data point is the average of
results obtained from three replications.
RESULTS AND DISCUSSION
Microstructural Study
It is well known that the properties of particulate-filled
polymer composites are strongly affected by the degree
of compatibility between the matrix and the filler phase.
In view of this, the scanning electron microscopy of the
filler particles and the composite surfaces are taken and
some typical SEM images are presented in Figs. 2 and 3.
Figure 2 reveals the almost spherical shape of the Al2O3
particles with an average particle size of 80–100 lm. Fig-
ure 3a and b show the morphology of the cross-sectional
areas of epoxy/Al2O3 and PP/Al2O3 composites, respec-
tively. These images are for typical composites with
Al2O3 content of 20 vol%. From images it is clear that
there is almost homogeneous dispersion of microsized
Al2O3 particle in both the matrix material. The degree of
particle dispersion is different for composites of epoxy
and PP because of the difference in their respective fabri-
cation routes. PP/Al2O3 composite is fabricated by com-
pression molding technique in which the mixing is done
by batch-mixer Rheomix 600 under ASTM D2538 stand-
ard, whereas epoxy/Al2O3 composite is fabricated by
hand lay-up technique.
Density
The density of composite materials depends on the
densities of the constituent components and also on their

DOI 10.1002/pc POLYMER COMPOSITES—2014 5

 FIG. 3. The SEM micrographs for 20 vol% filler: (a) Epoxy/ Al2O3 composite and (b) PP/ Al2O3 composite.
respective volume percentage. The density is measured
using Archimedes method and compared with the rule of
mixture model [34] which is given as
 
qc 5/f qf 1 12/f qm
where q and / are the density and volume fraction, suffix
c, f, and m represents the composite, filler, and matrix
material. The density of neat epoxy and PP resins are
measured by Archimedes method are found to be 1.1 and
0.92 g/cm3, respectively. Later, the densities of fabricated
composites are also measured by the same method. Figure
4 depicts the measured and theoretical densities of epoxy-
Al2O3 and PP-Al2O3 composites for different volume
fractions of Al2O3. It is seen from Fig. 4 that the densities
of both the sets of composite for lower filler content
agree well with the theoretical values. Also with increases
in filler content the density of the composites are increas-
ing as expected because of higher density of Al2O3 as
compared to resins.
It is to be noted that the theoretically calculated den-
sity are on a higher side as compare to the measured den-
FIG. 4. Variation in density with filler content: (a) Epoxy/ Al2O3 composite and (b) PP/ Al2O3 composite.
6 POLYMER COMPOSITES—2014
sity and the difference in theoretical and measured value
is increasing with filler content. The reason for this is,
while calculating the density theoretically, there is no
consideration of voids and defects, while is actual prac-
(19) tice, fabrication of composite gives rise to considerable
amount of voids which increases with filler loading as
reflected in Table 2. This table presents the theoretical
and measured densities of the composites along with the
corresponding void content.
The maximum volume fraction of voids in the ther-
moset composites reaches to 6.51% for maximum filler
loading of 25 vol% which is more than those of ther-
moplastic composites where void content reaches to
maximum of 4.33% for similar filler loading. This can
be attributed to the routes adopted for fabricating these
two different classes of composites. Compression mold-
ing has always been more effective than hand lay-up
technique as far as the uniformity of particle dispersion
and void formation are concerned. In hand lay-up route,
formation of pores and voids becomes inevitable,
whereas in compression molding the possibility of voids
is usually much less.
DOI 10.1002/pc
 TABLE 2. Theoretically and experimentally obtained density of composite along with volume fraction of voids.

Density (gm/cm3) Density (gm/cm3)

Epoxy/Al2O3 Polypropylene/Al2O3
Filler content
S.No. (Vol.%) Theoretical Experimental Void content (%) Theoretical Experimental Void content (%)

1 5 1.239 1.20 3.14 1.068 1.06 0.75

2 10 1.379 1.33 3.55 1.217 1.19 2.21
3 15 1.518 1.46 3.82 1.365 1.33 2.56
4 20 1.658 1.57 5.30 1.514 1.46 3.56
5 25 1.797 1.68 6.51 1.662 1.59 4.33

Thermal Conductivity the composite is noticed is called the percolation thresh-

old of that particular filler in the resin. For epoxy/Al2O3
The thermal conductivity of the epoxy/Al2O3 compo-
composite, the percolation threshold reaches when filler
sites as a function of the filler content is shown in Fig. 5.
content increases beyond 15 vol%. Beyond this no theo-
It is clear from the figure that the thermal conductivity of
retical model is estimating the conductivity value cor-
the composite increases with the increase in filler content
rectly including the model proposed by the authors
which is obvious because of high thermal conductivity of
previously. This can be attributed to the fact that, while
reinforcement phase as compared to matrix phase. The
deriving the correlation, the authors have not taken care
value of thermal conductivity calculated from various
of the interconnectivity between the filler particles which
established theoretical models along with the value
are built up at higher filler concentrations in the real
obtained from the mathematical model proposed by
composite.
authors is their earlier work [25] and experimental meas-
The entire experimental procedure is repeated for simi-
ured values are reflected in the figure. For low volume
lar set of composites made up of PP with same filler and
fraction of filler particles, a marginal increase in the value
it is observed that the percolation threshold reaches after
of thermal conductivity is observed as they can disperse
17.5 vol% of filler loading as shown in Fig. 6. With this
randomly in the epoxy matrix and has weak interaction
it is noted that the value of percolation threshold is not
with one another. It is observed that the model proposed
same for all composite systems; rather it varies with
by the authors is in good agreement with measured data
change in either the matrix material, filler material or
whereas other established models are underestimating the
both. It is further noticed that the measured value are less
value of effective thermal conductivity. The deviation of
as compared to the calculated value upto percolation
values obtained from the existing models from the meas-
threshold which is because of the air trapped while fabri-
ured ones might be attributed to the assumptions of the
cation. Also the difference between the measured value
respective models most of which are often unrealistic. As
and the predicted value are relatively higher for epoxy/
the volume fraction of filler increases, the particles begin
Al2O3 composites as compared to PP/Al2O3 composites
to touch each other, resulting in the formation of conduc-
as low void content is observed in case of composite fab-
tive path, because of which a sudden jump in the value of
ricated by compression molding technique. Within the
thermal conductivity is observed. The limiting filler con-
percolation limit, the percentage error of the theoretical
tent (volume fraction) at which such sudden rise in keff of

FIG. 5. Variation of effective thermal conductivity with volume frac- FIG. 6. Variation of effective thermal conductivity with volume frac-
tion of Al2O3 fillers in epoxy matrix. tion of Al2O3 fillers in polypropylene matrix.

DOI 10.1002/pc POLYMER COMPOSITES—2014 7

 FIG. 7. Variation of glass transition temperature with filler content: (a) Epoxy/ Al2O3 and (b) PP/ Al2O3
composites.

value with respect to the measured value lie in the range from Eqs. (7–17) are also shown in Fig. 8, which take
of 2–9% for epoxy-based composites and 0.5–3% for PP- into account the elastic constants into the calculation of
based composites. CTE. As expected, the incorporation of particles into the
The intrinsic thermal conductivity of epoxy matrix is polymers results in a reduction in the value of CTE of the
as low as 0.363 W/m-K; however, with 25 vol% of filler composites because of the restricted mobility of the poly-
content the effective thermal conductivity of epoxy/Al2O3 mer molecules arising out of adsorption of Al2O3
composite reaches to 2.114 W/m-K which is around 5.8
times that of neat epoxy. Similarly, addition of same vol-
ume fraction of filler increases the thermal conductivity
of homo-polymer PP from 0.11 to 0.658 W/m-K, which
is 5.98 times that of unfilled PP. The rate of increase of
effective thermal conductivity for PP-based composite is
more as compared to epoxy-based composite for same
volume fraction of filler. The reason for higher rate of
increase in PP-based composite is because of their prepa-
ration method. The presence of more percentage of voids
in composite fabricated by hand lay-up technique is the
reason for low rate of increase in thermal conductivity,
whereas composite fabricated by compression moulding
technique possesses very low percentage of such voids.

Glass Transition Temperature and Coefficient of Thermal

Expansion
Figure 7 shows the variation in glass transition temper-
ature of epoxy and PP resin with increasing Al2O3 con-
tent. In the present study, experimentally measured Tg of
epoxy is 98 C, and it is gradually increases to 116 C
when 25 vol% of microsized Al2O3 is reinforced in
epoxy. The similar effect of Al2O3 is noticed on PP
matrix, where Tg of PP increases from 214.9 C to 3.4 C.
The reason for such increase is that, as the filler is rein-
forced into the polymers, a network structure is formed
between them and because of this network structure, the
movement of molecular segment is limited in it and hence
the glass transition temperature increases [35].
The variations in the measured values of CTE of the
fabricated composites are shown in Fig. 8. The calculated FIG. 8. Variation of CTE with filler content: (a) Epoxy/ Al2O3 and (b)
CTE as a function of volume fraction of Al2O3 results PP/ Al2O3 composites.

8 POLYMER COMPOSITES—2014 DOI 10.1002/pc

 FIG. 9. Variation of dielectric constant with frequency and filler content: (a) Epoxy/ Al2O3 and (b) PP/
Al2O3 composites.

surfaces. CTE of the composite reduces from 66 3 greatly influences the signal-carrying capacity and the
1026/ C to 56.2 3 1026/ C for epoxy-based composite speed of the device to propagate signals. The delay in sig-
and from 111 3 1026/ C to 81.7 3 1026/ C for PP-based nal propagation in such device can be determined as [4]
composites with increasing Al2O3 content (0–0.25 Uf).
It can be seen that in case of PP/Al2O3 composites, the l pffiffiffiffi
Td 5 ec (20)
CTE values obtained lies in between the upper and lower c
bounds of Rosen-Hasin model for all volume fraction of
where c and l are the velocity of light and transmission
filler. The measured value for CTE of PP/Al2O3 compos-
distance of the signal, respectively. From Eq. 20 it can be
ite are close to the value obtained from upper bound of
seen that the time delay caused in signal propagation is
the model as well as from the values obtained from Ker-
directly proportional to the square root of dielectric con-
ner’s model whereas Turner’s model is far from satisfac-
stant. So the low dielectric constant is needed to reduce
tion. This is not surprising for Turner’s model as it does
the delay time. The dielectric constant variations of the
not describe the actual stress state in the composites and
composites for various filler concentrations as a function
consider only uniform hydrostatic stresses existing in the
of frequency in the range of 1 kHz to 1 MHz of respec-
phases, while the stresses inside the composite are very
tive polymer-ceramic composites are shown in Fig. 9a
complex. Similar trend is observed by Wong and Bollam-
and b. The figures demonstrate that the dielectric constant
pally [36] as well. Also the CTE values calculated using
on the composites increases with an increase in Al2O3
rule of mixtures is slightly higher than the corresponding
content. The dielectric constants of neat epoxy as well as
experimental values for PP/Al2O3 composite. This may be
its composites show a marginal reduction in the measured
because of the difference in microstructure, bulk modulus
frequency range. The decrease in the dielectric constant
and thermal softening of the components in the compo-
with an increase in frequency is because of the reason
sites, which are not accounted in this relation [18]. In
that the interfacial dipoles have less time to orient them-
case of epoxy/Al2O3 composite, for higher filler loading,
selves in the direction of the alternating field [37]. For
not much reduction in the value of CTE is obtained and
epoxy/Al2O3 composites, dielectric constant reaches to
after 15 vol% of filler loading, the experimental value are
6.25 for maximum loading of 25 vol% at 1 kHz, whereas
coming out of the range of lower and upper bound of
for PP/Al2O3 composite it goes to 4.28 for similar loading
both the models and also value calculated from Kerner’s
and frequency.
model and rule of mixture are slightly lower than the
The predicted values of dielectric constant using equa-
experimental value. The possible reason for such trend
tion (12–14) for both the sets of composites are calculated
might be because of inevitable agglomeration of Al2O3
and are compared with the experimental results at 1 MHz
particles at higher concentration as epoxy/Al2O3 compo-
and the results are shown in Fig. 10. It can be seen from
sites are fabricated by hand lay-up technique.
both the figure that the models are valid for low volume
fraction and thereafter they deviate, though Lichteneck-
er’s model is in closest approximation to the experimen-
Dielectric Constant
tally measured values. Also the experimental values are
The materials used in integrated circuits must possess always lower than the theoretical value. As it is known
low dielectric properties for better device performance. that the dielectric constant of the composite depends on
The dielectric constant is very important parameter which two factors, i.e. the polarization associated with matrix

DOI 10.1002/pc POLYMER COMPOSITES—2014 9

 FIG. 10. The measured and calculated dielectric constant at 1MHz for (a) Epoxy/ Al2O3 and (b) PP/ Al2O3
composites.
material and filler particles, and it is also influenced by
the interfacial polarization at the interface between matrix
and filler.
The deviations of the theoretical from the experimental
values are because of the reason that the equations have
been developed without considering the effect of interface
together with voids and defects. It can also be seen from
the figure that as the filler content increases, the gap
between the theoretical and experimental values increases,
it can be explained that with the increase in filler content,
the interfacial area between the matrix and filler
increases, and hence the influence of interface polariza-
tion on the dielectric constant also increases [38].
CONCLUSIONS
The present investigation leads to the following spe-
cific conclusions:
 Successful fabrication of polymer composites with ceramic
fillers Al2O3 as a reinforcement in possible by hand lay-up
technique when epoxy is chosen as matrix material and by
compression moulding technique when PP is chosen as
matrix material.
 Thermal conductivities of these fabricated composites are
measured experimentally and are compared with the theo-
retically calculated values obtained from some existing
models and with the model developed and proposed by
the authors in their earlier work. It is found that measured
points fit well with the values obtained from the proposed
mathematical model within the percolation threshold invar-
iably for both matrices.
 Effective thermal conductivity of composites increases as
the volume fraction of the fillers increases for both epoxy
as well as polypropylene based composites. For maximum
loading of 25 vol%, Al2O3 particle enhances thermal con-
ductivity of epoxy by 5.8 times whereas 5.98 times
increase in thermal conductivity is noticed in case of PP
matrix for the same filler content.
10 POLYMER COMPOSITES—2014
 For same filler loading, Tg increases from 98 C to 116 C
whereas the CTE reduces from 66 3 1026/ C to 56.2 3
1026/ C for epoxy based composite.
 Under similar condition, for PP based composites, Tg
increases from 214.9 C to 3.4 C and a remarkable
decrease in CTE from 111 3 1026/ C to 81.7 3 1026/ C
is noticed.
 The dielectric properties of the composites in a wide range
of frequency from 1 kHz to 1 MHz are studied. It is found
that dielectric constant increases with increase in Al2O3
content and decreases with increase in frequency. The
maximum value of dielectric constant reaches to 6.25 for
epoxy/Al2O3 composite and 4.28 for PP/Al2O3 composite
for maximum filler loading at the lowest operating
frequency.
 With light weight, improved thermal properties and con-
trolled dielectric constant, this new class of Al2O3 filled
polymer composites can find potential applications in the
areas of electronic packages, communication devices,
encapsulations, and printed circuit board substrates.
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