Int. J. Appl. Ceram. Technol.

, 7 [4] 475–481 (2010)

DOI:10.1111/j.1744-7402.2009.02483.x

Ceramic Product Development and Commercialization

Effect of Particle Size on the Microwave Dielectric

Properties of Alumina-Filled PTFE Substrates
Kodakkattu P. Murali, Surendran Rajesh, Kunnamkuzhakal J. Nijesh, and
Ravendran Ratheesh*
Centre for Materials for Electronics Technology (C-MET), Microwave Materials Division,
Thrissur 680 771, India

a-alumina of different particle sizes of 50 nm, 0.4, 3, and 7 mm have been incorporated into the PTFE matrix to prepare
flexible composite substrates. A proprietary process comprising of sigma mixing, extrusion, and calendering, followed by hot
pressing (SMECH process) has been used to obtain dimensionally stable ceramic-filled PTFE substrates. Variation of the
dielectric constant, loss tangent and moisture absorption of filled PTFE composites has been ascertained as a result of filler
loading.

Introduction above-mentioned requirements, low dielectric constant

The unprecedented growth in wireless communi-
cation demands lighter and faster microwave devices
with improved performance to keep up the market
demands. This has necessitated the development of
high-density packaging of electronic components and
high-speed signal transfer.1,2 In order to congregate the
*ratheeshr@yahoo.com
r 2010 Centre for Materials for Electronics Technology.
Journal compilation r 2010 The American Ceramic Society.
[Correction added after online publication Jan 22 2010: Copyright line corrected.]
and low loss tangent materials are required for the fab-
rication of base substrates. The electrical properties of
the materials such as dielectric constant (er 0 ), loss tan-
gent (tan d), and temperature coefficient of dielectric
constant (ter) are the main parameters that have a huge
influence on the performance compared with the stan-
dard printed circuit board laminates. The er 0 controls
the size of the circuit and the speed of signal propaga-
tion, whereas tan d determines the integrity of the signal
across distance. Minimum variation of these properties
in the applied frequency range is essential for the better
performance of the devices. Other important require-
476 International Journal of Applied Ceramic Technology—Murali, et al.
ments of these substrates are a low coefficient of thermal
expansion (CTE), low moisture absorption, and a better
tensile, and compressive modulus.3,4 The commonly used
materials for these high-end applications are copper-
cladded ceramic-filled PTFE composites because of their
excellent dielectric properties (very low tan do0.003 and
er 0 stable up to 20 GHz), superior chemical resistance, and
high operating temperature (B2501C).4–6
Recently, particulate fillers such as silica, alumina,
magnesia, strontium titanate, TiO2, BZN, and TeO2
have been incorporated into the PTFE matrix, and their
effects on the dielectric and thermal properties have
been extensively studied.7–12 These composites have an
effective dielectric constant ranging from 2.9 to 13.1,
together with loss tangento0.004. It is also reported
that particle size, distribution, and morphology have a
profound influence directly on the packing fraction and
subsequently on other properties of the composite sub-
strates.13–16 Chen et al.13 reported the variation of the
dielectric and thermal properties of 25 and 5 mm silica-
filled PTFE composites, whereas the effect of nanosilica
fillers on the PTFE composites has been studied by
Murali et al.,7 and the end properties have been com-
pared with micrometer-size silica-filled composites.
The role of nano- and micrometer size rutile-filled
PTFE composites has been studied by Rajesh et al.11 In
all these works, the particulate fillers were surface treated
using phenyltrimethoxy silane (PTMS) to preclude a
hydrophilic nature. However, to the best of our knowl-
edge, the effect of particle size on the dielectric and
moisture absorption properties of an alumina-filled
PTFE substrate has not been investigated. Hence, in
the present work, alumina fillers of sizes (D50) 50 nm,
0.4, 3, and 7 mm were loaded in the PTFE matrix and
the resultant density, microstructure, dielectric proper-
ties, optimum filler loading, and moisture absorption of
these composites were compared.
Experimental
The starting materials were PTFE, 50 mm powder,
H71 grade (Hindustan Fluoro Carbons, Hyderabad,
India), 0.4 and 3 mm a-Al2O3 powder, 99.99% pure
(Sumitomo, Tokyo, Japan), 50 nm and 7 mm a-Al2O3
powder, 499% pure (Sigma-Aldrich, St. Louis,
MO), and a short E-glass fiber having filament size
+10 mm and length 4–6 mm (Binani Glass, Goa, India).
Phenyl trimethoxy silane (PTMS) (Sigma-Aldrich) and
Vol. 7, No. 4, 2010
Dipropyleneglycol (Merck, Hohenbrunn, Germany) were
used as a silane coating agent and a lubricant, respectively.
In the present study, the silane coating (1 wt%) of
all alumina fillers has been performed using PTMS17 as
a silane coupling agent. Initially, the pH of water was
adjusted to obtain fine dispersion of the particulate fill-
ers with respect to the particle size. The slurry thus
obtained was vigorously agitated using a heavy duty
mixer. After 1 h of mixing, PTMS was added dropwise
and mixing was continued for about 30 min. The
resulting mixture thus obtained was transferred to a
glass container and dried at B1201C for 12 h to obtain
a silane-coated filler.
To address the anisotropy and porosity problems
associated with PTFE composite processing, a propri-
etary process comprising of sigma mixing, extrusion,
and calendering, followed by hot pressing (SMECH
process)7,9–11,15 has been used. Excellent dimensional
stability and bare minimum dielectric anisotropy are the
important end goals as far as ceramic-filled fluoropoly-
mer substrates are concerned for microwave circuit fab-
rication. To accomplish these objectives, a systematic
approach has been used to determine the optimum filler
loading in the present composite system that can yield
dense planar laminates. In the present work, 0.4, 3, and
7 mm alumina-filled composites were prepared with a
2 wt% interval in the higher filling fraction (50–
70 wt%) to determine optimum filler loading, whereas
fine tuning was restricted to a lower filler fraction
(o40 wt%) for 50 nm-filled composites considering
the high surface area. Two weight percent of chopped
microfiber glass is used as a reinforcing agent to improve
the mechanical and surface properties of all the com-
posites based on our previous studies.7,9–11
The microwave dielectric properties of the hot-
pressed samples were studied using the X-band wave-
guide cavity perturbation technique.18 The advantage of
the waveguide cavity perturbation technique is that it
requires only thin rectangular samples and measure-
ments are possible at several discrete frequencies in a
single setting covering the whole frequency band. Ag-
ilent (Palo Alto, CA) make PNA E8362B Vector Net-
work Analyzer was used in the X-band (8.2–12.4 GHz)
region for microwave dielectric property measurements.
The er 0 and tan d are calculated from the average of the
values obtained for five discrete frequencies in the entire
X-band range. The uncertainty in the dielectric mea-
surement using waveguide cavity perturbation is esti-
mated to be 72%.18,19
www.ceramics.org/ACT Effect of Particle Size on Alumina-Filled PTFE Substrates
The dimensional method was used to determine the
density of the PTFE composites. Moisture absorption of
the composite substrate samples was carried out as per
the IPC-TM-650.2.6.2.1 method. The average of the
results of three specimens is calculated and the test is
repeated if the results of the specimens varied 41%.
Surface morphology and filler distribution in the com-
posite samples were analyzed using Philips (Eindhoven,
The Netherlands), make SEM (Philips XL-30), with an
accelerating voltage of 15 kV. Samples were sputtered
with a gold layer and both planar and brittle fractured
cross-section surfaces were analyzed.
Results and Discussion
The SEM micrographs of alumina fillers of various
particle sizes (0.4, 3, and 7 mm) are shown in Fig. 1.
However, the micrograph of the 50 nm filler is not
shown because of poor clarity. It is expected that the
loading fraction and the associated end properties of the
PTFE composites vary with respect to the particle size of
the alumina fillers.
It can be seen from figure that 0.4 and 3 mm-size
alumina particles have a nearly spherical morphology
with a narrow particle size distribution, whereas the
7 mm alumina filler has a spherical and polygonal mor-
phology. Fillers having a submicrometer particle size
(0.4 mm) show agglomeration due to its high reactivity
Fig. 1. SEM micrographs of (a) 0.4 mm, (b) 3 mm, and (c) 7 mm alumina fillers.
477
resulting from a large surface area. SEM micrographs of
brittle fractured sections of PTFE composites prepared
using 0.4, 3, and 7 mm alumina fillers are shown in
Fig. 2. It is clear from the micrographs that particulate
fillers are well distributed in the PTFE matrix, especially
in the micrometer-size alumina-filled composites, which
establishes the effectiveness of the SMECH process
adopted for the fabrication of the composites.
Compared with micrometer-size alumina-filled com-
posites, the SEM micrographs of submicrometer
alumina-filled composites show slight agglomeration
due to the high surface area of the particulate filler.
Owing to the high surface area and the relatively high
surface charge, it is difficult to disperse nanosize fillers
uniformly in an aqueous medium during the silane
coating process. Moreover, 1 wt% of silane coating
may not be sufficient for providing a nanoscale silane
coating over the alumina particulates having a large sur-
face area, which further restricts the flow nature of the
filler and promotes agglomeration during hot pressing.
Hence, it can be inferred that a uniform distribution of
particulate fillers is difficult using nano- and submi-
crometer-size fillers due to their agglomerated nature,
which may lead to localized impedance mismatch when
used for circuit fabrication.
It has been reported7,9–11 in our earlier work that
optimum filler loading is preferred for filled PTFE
composites as microwave substrates. The optimum filled
PTFE substrates result in dimensionally stable laminates
478 International Journal of Applied Ceramic Technology—Murali, et al. Vol. 7, No. 4, 2010

Fig. 2. SEM micrographs of the brittle fracture surface of PTFE composites loaded with (a) 0.4 mm (56 wt%), (b) 3 mm (66 wt%), and (c)
7 mm (70 wt%) alumina fillers.

with reproducible properties. Hence, optimum filler

loading in all the composites has been determined
systematically by varying the filler percentage in 2 wt%
increment. It is interesting to note that the optimum
filler loadings were 28, 56, 66, and 70 wt% for 50 nm,
0.4, 3, and 7 mm alumina-filled PTFE composites,
respectively. The reason for the higher filling fraction
for composites prepared using the 7 mm alumina filler is
due to its comparatively wider particle size distribution
and relatively low surface area. Out of the four fillers,
50 nm and 0.4 mm alumina-filled composites exhibited
a bulk density of 2.48 and 2.62 g/cm3 at an optimum
loading level of 28 and 56 wt%, respectively, whereas
bulk densities of 2.8 and 2.84 g/cm3, respectively, were
obtained for 3 and 7 mm alumina fillers at optimum
filler loading (Table II). Further loading decreases the
effective density of the resulting composites (Fig. 3). er 0
and tan d obtained at optimum filler loading for 50 nm
0.4 mm alumina-filled samples were 2.8, 3.9, and
0.0064, 0.0046, respectively.
er 0 and tan d obtained at optimum filler loading for
3 and 7 mm alumina-filled substrates are 4.3, 4.34, and
0.0021, 0.0025, respectively (Figs. 4 and 5). It has been
reported that in addition to matrix and filler, their in-
terface region also has a profound influence in control- Fig. 3. Density variation close to the optimum filler loading for
ling the effective dielectric properties of a filled PTFE composites prepared using (a) 50 nm and 0.4 mm and (b) 3
composite. The interface region increases with respect and 7 mm size alumina fillers.
www.ceramics.org/ACT Effect of Particle Size on Alumina-Filled PTFE Substrates
Fig. 4. Variation of er 0 (average value over X-band) close to
optimum filler loading for PTFE composites prepared using (a)
50 nm and 0.4 mm and (b) 3 and 7 mm size alumina fillers.
to the filler loading and the surface area of particulate
fillers. Hence, the reason for the comparatively high tan
d for nano- and submicrometer alumina particulate-
filled composites can be attributed due to the presence
of a large volume of interface in the composite com-
pared with micrometer size alumina-filled samples.
Structural imperfections like lattice strains may also
contribute to a higher loss tangent in nanoalumina-
filled composites. A similar observation was made in the
case of nanosilica-filled PTFE composites.7,15
Hence, it can be concluded that particle size and its
morphology have a profound influence on the filler
fraction of PTFE composites. Fillers with larger mean
particle size and wider distribution result in higher op-
timum filling fractions, whereas greater interparticle at-
traction forces due to high surface area lead to poor
packing of the fillers as seen in the case of 50 nm and
0.4 mm particulate-filled composites.
Moisture absorption of PTFE/alumina composites
was ascertained as per the standard IPC-TM technique.
479
Fig. 5. Variation of tan d (average value over X-band) close to
optimum filler loading for PTFE composites prepared using (a)
50 nm and 0.4 mm and (b) 3 and 7 mm size alumina fillers.
Although there is not much of a variation in moisture
absorption between the composites prepared using mi-
crometer-size alumina as a filler, the nano- and submi-
crometer size alumina-loaded samples showed high
moisture absorption. The moisture absorption charac-
teristics of the composite substrates prepared using
50 nm, 0.4, 3, and 7 mm alumina fillers are compared
in Table I. It is clear from the table that the moisture
absorption of 50 nm and 0.4 mm alumina-filled com-
posites is comparatively higher than that of 3 mm and
7 mm alumina-filled PTFE samples. The increase in
moisture absorption of these samples even at a compar-
atively lower weight percentage may be due to the larger
surface area of the filler (Table II). Another plausible
reason for the high moisture absorption values could be
the agglomeration of the particulates, resulting in im-
proper silane coating. Further, during composite fabri-
cation, the agglomeration of the particulate fillers
prevents the formation of a better filler–matrix inter-
face, which in turn leads to porosity and thereby in-
creases the moisture absorption. Although the surface
480 International Journal of Applied Ceramic Technology—Murali, et al. Vol. 7, No. 4, 2010

Table I. Comparison of Moisture Absorption Characteristics of 50 nm, 0.4, 3, and 7 lm

Alumina-Filled PTFE Composites
7 lm alumina-filled 3 lm alumina-filled 0.4 lm alumina-filled 50 nm-alumina filled
composites composites composites composites

Loading Moisture Loading Moisture Loading Moisture Loading Moisture

(wt%) absorption (%) (wt%) absorption (%) (wt%) absorption (%) (wt%) absorption (%)
64 0.058 60 0.055 50 0.12 24 0.080
66 0.068 62 0.055 52 0.14 26 0.099
68 0.089 64 0.060 54 0.18 28 0.305
70 0.099 66 0.065 56 0.23 30 1.150
72 0.135 68 0.095 58 0.30 32 1.250

Table II. Comparison of the End Properties of Filled PTFE Substrates Fabricated Using Alumina Particulates of
Different Sizes at Optimum Filler Loading
Size of alumina Surface Area Optimum filler Dielectric constant Loss tangent Moisture
filler (D 50 ) (m2 /g) loading (wt%) (X-band) (X-band) absorption (%)
50 nm 40.00 28 2.80 0.0064 0.305
0.4 mm 4.00 56 3.90 0.0048 0.230
3 mm 0.40 66 4.30 0.0021 0.065
7 mm 0.25 70 4.34 0.0025 0.071

area of the 7 mm alumina filler is smaller than that of the
3 mm filler, comparatively higher moisture absorption is
seen for the composites fabricated using the former one
because of its irregular particle morphology.
Table II shows the comparison of the microwave
dielectric and moisture absorption characteristics of filled
PTFE substrates fabricated using different-size alumina
fillers. It can be seen from the table that by using alumina
fillers of different sizes, the end properties of the resulting
composites can be tailored. However, the present study
shows that nano-size fillers are not preferred for filled
PTFE substrate fabrication due to the comparatively high
loss tangent and moisture absorption characteristics.
Conclusions
Dimensionally stable PTFE composite substrates
have been fabricated through the SMECH process using
alumina particulates of sizes 50 nm, 0.4, 3, and 7 mm.
The ceramic fillers have been silane coated before sigma
mixing to preclude the moisture absorption. The vari-
ations of the dielectric properties, density, and moisture
absorption of these alumina fillers in the PTFE matrix
were studied as a function of filler loading. Among the
composites, the highest optimum filler fraction of
70 wt% was obtained for the 7 mm alumina filler,
whereas the lowest optimum loading fraction of
28 wt% was obtained for 50 nm fillers. The composite
samples exhibited er 0 of 2.8, 3.9, 4.3, and 4.34 and
tan d of 0.0064, 0.0048, 0.0021, and 0.0025 for com-
posite substrates prepared using fillers of sizes 50 nm,
0.4, 3, and 7 mm, respectively, at optimum filler load-
ing. SEM micrographs show homogeneous filler distri-
bution for micrometer-size particulate-filled composites,
whereas agglomerated filler distribution is observed for
submicrometer and nano-size alumina-filled compos-
ites. It is concluded that micrometer size fillers are ideal
for the fabrication of planar PTFE/ceramic flexible mi-
crowave substrates.
Acknowledgment
We are grateful to Dr. K. R. Dayas, Director,
C-MET Thrissur, for extending facilities to carry out
www.ceramics.org/ACT Effect of Particle Size on Alumina-Filled PTFE Substrates
this work. We acknowledge Sumitomo Corporation,
Japan, for providing alumina fillers.
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