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Influence of Filler Size and Morphology in Controlling the Thermal Emissivity

of Aluminum/Polymer Composites for Space Applications

Article in Materials Science and Engineering B · April 2010

DOI: 10.1016/j.mseb.2009.11.009

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 Materials Science and Engineering B 168 (2010) 40–44

Contents lists available at ScienceDirect

Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Influence of filler size and morphology in controlling the thermal emissivity of

aluminium/polymer composites for space applications
Harshada A. Babrekar a,∗ , Naveen V. Kulkarni a , Jyoti P. Jog b , Vikas L. Mathe a , Sudha V. Bhoraskar a
a
Department of Physics, University of Pune, Ganeshkhind Road, Pune 411 007, India
b
National Chemical Laboratory, Pashan Road, Pune 411 008, India

a r t i c l e i n f o a b s t r a c t

Article history: The paper has addressed the problem of controlling the thermal emissivities from metal/polymer com-
Received 31 July 2009 posites prepared by solution method. Aluminium is used as a filler and polystyrene as a polymer–matrix.
Received in revised form 29 October 2009 Aluminium particles, with micrometer and nanometer dimensions having different morphologies, were
Accepted 3 November 2009
employed. The values of emissivities were reduced when the coarse grains and flakes of aluminium
were used as fillers, whereas, no significant change was observed when nano-aluminium was used in
Keywords:
the composite. Dielectric dispersion for the composites was measured and the results are analysed in
Thermal emissivity
view of Fresnel relation. The differences in the values of dielectric constants, between the experimen-
Dielectric constant
Camouflaging
tally measured and those which can be predicted theoretically, are thought to arise from the interfacial
Composite polarization.
Infra-red © 2009 Elsevier B.V. All rights reserved.

1. Introduction (by weight) of the filler into the polymer. Dielectric spectroscopy
also provides a promising method which can be used to control the
Thermal emissive property, of a solid surface, is of primary con- quality of products in industries [9].
cern in military applications for the purpose of camouflaging. Also, The paper reports the thermal (8–14 ␮m wavelengths) emissive
the thermal emissive properties of electronic components, in a properties of Al/polystyrene composites for three different mor-
satellite, are technologically important in determining its thermal phologies and sizes of the fillers. The kind of investigation provides
characteristics. Basically metals are known to exhibit low val- useful information in view of controlling the surface reflectivity in
ues of thermal emissivity, whereas polymers show high values. the IR range of frequencies. It is shown that the dielectric disper-
The emissivity can, therefore, be controlled to a desired value by sion can help in better understanding of the mechanism of thermal
forming the composites of metals with organic polymers. In fact emissivity in composite materials.
low thermal emissive paints have been recently reported [1]. The
experimental measurement of the values of thermal emissivities 2. Experimental procedure
of polymer/metal composites is strategically important, and inves-
tigation of different kinds of additives into the polymers provides The composites were prepared by mixing 5–40% (by weight)
useful information. of the three kinds of Al fillers into the base matrix polystyrene.
In the present paper we have investigated the thermal emissive Micron sized aluminium (Al-1) was obtained from Kamphasol,
behavior of composites of aluminum with polystyrene. Although India. To prepare the composites the flake-shaped aluminium (Al-
Al/polystyrene composites have been used in paints [2], as refrig- 2) was procured from Pidilite industries, India. Nano-aluminium
eration liners [3], in space crafts [4], as construction materials [5] (Al-3) was synthesized, in-house, by thermal plasma assisted gas
and in defense-applications [6–9]; there are no reports about its phase condensation method. The fillers were dispersed in toluene
thermal emission characteristics. at different concentrations in separate beakers and polystyrene was
The electrical and dielectric properties of metal/polystyrene also dissolved in toluene. These two solutions were mixed by stir-
composites have been very widely studied, since they offer appli- ring and ultrasonication. The solution was then poured into Petri
cations in the device technologies and packaging industries. The dishes and kept on a ground-leveled glass slab for solvent evap-
electrical performance is strongly related to the percent inclusion oration. Self-standing films, with thickness ranging between 200
and 210 ␮m, were obtained. The dispersion of Al particles into
the polystyrene matrix was studied by the morphological inves-
∗ Corresponding author. Tel.: +91 020 25692678; fax: +91 020 25691674. tigation of PS/Al composites using JSM-6360A Scanning Electron
E-mail address: harshada98@gmail.com (H.A. Babrekar). Microscope (SEM) of JEOL, Japan. The films were coated with thin

0921-5107/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2009.11.009
 H.A. Babrekar et al. / Materials Science and Engineering B 168 (2010) 40–44 41

films (∼200 Å) of platinum so as to avoid the charging effects

while imaging under the SEM. The dielectric dispersion of these
films was recorded by broadband dielectric spectrometer (3 ␮Hz
to 20 MHz) with an Alpha-A: high performance frequency ana-
lyzer, having a ZGS-BDCS 41201 active sample cell (Novocontrol
Technologies, GmbH & Co. KG, Hundsangen, Germany). The instru-
ment has temperature controller and ‘WinFit’ software for data
analysis. The dielectric response of the films has been studied in
the frequency range of 0.01 Hz to 10 MHz at room temperature.
The sample was sandwitched between two 2 cm gold plated elec-
trodes. Silver paste, on the sample surfaces, was used to provide
better electrical contacts. The thermal emissivity, for the lower
surfaces, of these samples was measured by Thermal Imaging Cam-
era: Therma Cam TM S60 (FLIR, Israel), in the wavelength region of
8–14 ␮m. For monitoring the emissivity values, the samples were
kept at a distance of 50 cm from the thermal imager. The sample
temperature was maintained at 40 ± 0.01 ◦ C throughout the exper-
iment. The thermal imaging camera consisted of microbolometer
with an array of pixels made up of several layers. The spacial
resolution was 1.3 mrad and had a thermal sensitivity of 0.08 ◦ C. Fig. 1. X-ray diffraction patterns of (a) standard line intensity, (b) micron sized
The imaging frequency was 50 Hz. This was a compact camera particles, (c) nano-Al and (d) flakes of aluminium.
which was focused on the sample area to obtain the thermal
image as well to read the values of the emissivity directly on the
calculated using Scherrer’s formula [11] given by
camera-screen.
0.9 × 
t= (1)
ˇ × cos 
3. Results and discussions
where  = wavelength of X-rays used; ˇ = full width at half max-
The crystalline structure, of all the three Al fillers, was studied imum (FWHM) or integral breadth of diffraction line;  = Bragg
with the help of X-ray diffraction (XRD) technique. Fig. 1 shows the angle.
diffraction pattern of the three filler constituents; and is compared The average crystallite sizes of Al-1, Al-2 and Al-3 were 16 ␮m,
with the standard line pattern obtained from Joint Committee on 30 ␮m and 20 nm, respectively. Composites with PS of these Al
Powder Diffraction Standards (JCPDS) data [10]. No impurity was fillers have been prepared by solution casting method. It is observed
found and all the three samples are seen to possess crystalline cubic that the host polymer (polystyrene) exhibited the highest value of
Al. The morphology of three fillers are, however, seen to be differ- emissivity, i.e. 0.82. In all the composites, except in case of nano-Al,
ent as shown in the SEM and TEM micrographs in Figs. 2 and 3. The the values of emissivities (ε) were found to be reduced. Fig. 4(a)
shapes of the micron sized particles of Al-1 are seen to be irregu- shows that ε has reduced to a value of 0.58 for a concentration of
lar with average dimensions of 10–15 ␮m, as is shown in Fig. 2(a). 20% (by weight) of coarse grained Al and has remained stable at
On the other hand, Al-3 are flat flakes having average diameters this value. On the other hand, in case of flakes of Al we observe a
ranging between 20 and 30 ␮m. decrease in the emissivity at much lower value of the filler con-
The observed diffraction patterns (Fig. 1) were carefully ana- centration, i.e. at about 10% of metal inclusion. Further it has been
lyzed and were found to closely match with the standard line observed that its value is lowered to about 0.35 at the filler concen-
intensity patterns of fcc-Al. Based on these comparisons, the peaks tration, of 40%. For the filler concentration of 10–30%, the values of
have been indexed with the corresponding miller indices (hkl) emissivities in these three composites have remained almost con-
having closest resemblance with the standard XRD patterns and stant. However, the emissivity for the coarse-Al composite is seen to
identified by the lines occurring at 2 = 38.4◦ , 44.4◦ , 65.1◦ and 78.2◦ , remain constant beyond 20% of the filler concentration. The emis-
which correspond to the (hkl) values of (1 1 1), (2 0 0), (2 2 0) and sivity, for nano-Al composite, was not affected by the increase in
(3 1 1) planes of aluminium. The average crystallite size ‘t’ has been the filler concentration.

Fig. 2. Morphology of coarse-Al particles as observed under scanning electron microscope for (a) micro-sized particles and (b) flakes.
42 H.A. Babrekar et al. / Materials Science and Engineering B 168 (2010) 40–44

Fig. 3. Morphology of nano-aluminium particles as observed from the (a) transmission electron micrographs and (b) corresponding size histogram of the nano-Al particles.

The results clearly point out that the metallic flakes yield much enclosed into the polymeric honey-comb-like structure as shown in
lower emissivities as compared to the other two fillers. This may be SEM image (Fig. 7). Consequently a large number of nano-particles
correlated to the large particle size, higher mass and flat surface of are seen to get agglomerated inside the cage thus filling all the
Al-2; which gets settled at the lower part of the composite during voids. In addition, the particles do not get settled down onto the
the process of casting. This results in reducing the roughness, helps lower part of the composite during the process of casting. Both the
in increasing the reflection coefficient R and in turn is responsible surfaces thus contribute towards high emissive layers. Since, PS and
in reducing the emissivity. It can be expected since the emissivity is Al have different densities, the emissivity can be supported by a two
inversely related to the reflectivity ‘R’ [12]. On the other hand, the layer model given by Ma and Ho [14]. In this model the polymer is
coarse particles of Al have very random shapes. They also get settled considered as one layer and the in-homogeneous composite layer
down; but yield a rough surface with low reflection coefficient. The as the second.
increase in the percentage of filler does not add to any increase in Fig. 5(a) and (b) present the plots of dielectric dispersion corre-
the value of reflectivity, might be, due to their irregular packing in sponding to the composites containing the coarse grained Al and
the polymer matrix. nano-Al with varying percentage by weight. It is observed that, the
In case of nano-Al (Fig. 3); the particles are too small, and exhibit dielectric constant remains almost constant over all the frequencies
very large surface to volume ratio making them highly reactive. for the composites of coarse-Al, whereas, for nano-Al the dielec-
The nano-particles of Al are reported to be inherently covered with tric constant is found to decrease with increasing frequency and it
an oxide layer [13]. The oxide, and possibly hydroxide terminated remains constant for higher frequency region; though the weight
Al surface, would show very low reflectivity. This would cause percent of the filler is increased. It is observed that, in case of coarse-
the emissivity to increase. Moreover, the particles are seen to get Al/PS composite, k is around 3.7 for highest concentration, i.e. 40%

Fig. 4. Variation of thermal emissivity of composite films with varying percentage loading of (a) coarse-Al, (b) nano-Al and (c) Al flakes.
 H.A. Babrekar et al. / Materials Science and Engineering B 168 (2010) 40–44 43

Fig. 5. Dielectric dispersion of metal/PS composites with frequency for five concentrations (5, 10, 20, 30 and 40%) of fillers (a) coarse grained (M1 to M5), (b) nano-Al (N1 to
N5) and (c) Al flakes (F1 to F5).

and is found to remain constant for all the frequencies. In case of inter-phase surface. Thus a small filler size leads to relatively large
nano-Al, the value of k is high for lower frequencies and reduces increase in dielectric constant [2]. High dielectric constant at low
to a low values remaining almost stable at a value of 3.0 for high- frequencies and sluggish behavior at high frequencies, in case of
est filler concentration. For the composites of PS with 40% Al-3 the nano-Al composite, reflects such behavior.
maximum value of k is observed to be 21.8 at 10−2 Hz and 2.1 at Fig. 5(c) shows the dielectric dispersion for the composites of
107 Hz. PS with the Al flakes. It is interesting to note that the variation in
Thus the frequency response of the dielectric constant, for the the dielectric constant has increased with increasing percentage
three composites, are not similar; although the dielectric constants, of flakes. The low frequency dielectric constant for filler (40%) has
for all the three composites, are high compared to that of the host reached a value of 4.6 and has dropped to a value of approximately
polymer over all the frequencies. 3.7 for high frequencies. The increased dielectric constant seems
In addition, the composite materials will contribute to inter- to be responsible in reducing the emissivity for these composites.
faces at the boundaries of each metal particle, as shown in Fig. 6 The variation is not as drastic as is observed for nano-composites.
[15]. Inside is a high electron concentration due to the metal parti- The highest value of dielectric constant (3.8) is shown by flakes/PS
cles and surrounding is a layer of polymer. The polymeric interface composites having 40% of Al which has indicated an emissivity as
will get charged positively and thus the particle/polymer interface low as 0.35. Thus, it can be said that, one of the deciding factors
can behave like a dipole. Fig. 6 shows the expected inter-phases in in controlling the thermal emissivity can be considered to be the
the close vicinity of metal particles. Also, at a given volume frac- dielectric constant. Further; the correlation between the dielectric
tion of filler, the smaller particle size has more polarization in the constant ‘k’ and the emissivity ‘ε’ can be established on the basis of
Fresnel relation [16]. According to this relation the emissivity ‘ε’ is
related to the reflectivity ‘R’ by,

ε=1−R (2)

Here the absorption coefficient of the emitting surface is

assumed to be negligible. ‘R’ is related to the dielectric constant
‘k’ by
√ 2
( k − 1)
R= √ 2
(3)
( k + 1)
If we take an overview of the values of dielectric constant, it is
observed that all the composites of metal fillers exhibit increased
values of dielectric constant, which is in accordance with Fres-
nel’s theory. However, the structure of these composites is very
Fig. 6. Schematic of (a) Al/PS composites consisting of filler, inter-phase and matrix. in-homogeneous due to the settling down of the metal particles
44 H.A. Babrekar et al. / Materials Science and Engineering B 168 (2010) 40–44

Fig. 7. Cross-sectional view of Al/PS composites (a) coarse-Al/PS and (b) nano-Al/PS.

(except in case of nano-Al). The dielectric constant is measured for be a minimum. Oxidation and agglomeration of nano-particles
the total film whereas the emissivity is only a surface property. of Al and the formation of cage like structures are shown to be
The overall behavior can be appropriately, explained by the model detrimental parameters. In all the cases the dielectric constant has
shown in Fig. 5. On account of this, if we calculate the dielectric been reported to be increased; and thus it is concluded that the
constant from the observed values of emissivities of the different emissivity follows the Fresnel relation.
composites using Fresnel relation, there seems to be a large dif-
ference. The calculated values of dielectric constant would be too Acknowledgements
high, wherein the measured values are low.
The cross-sectional morphology of Al/PS composites have been Authors Mrs. Harshada A. Babrekar, and Dr. (Mrs.) Sudha V. Bho-
shown in Fig. 7. Fig. 7(a) refers to coarse-Al and (b) refers to nano-Al raskar wish to acknowledge the Council for Scientific and industrial
at 40% loading respectively. From the observations in Fig. 7(a) and Research (CSIR), New Delhi as well as Defence Laboratory, Jodhpur,
(b) it can be stated that the aluminium particles are caged into the for financially supporting the project.
polymer matrix and form a well defined honey-comb kind of set-
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