Accepted Manuscript

Industrial waste fly ash cenosphere composites based broad band microwave
absorber

Pritom J. Bora, Mayuri Porwal, K.J. Vinoy, Kishore, Praveen C. Ramamurthy, Giridhar
Madras

PII: S1359-8368(17)32627-6
DOI: 10.1016/j.compositesb.2017.09.062
Reference: JCOMB 5309

To appear in: Composites Part B

Received Date: 1 August 2017

Revised Date: 23 September 2017
Accepted Date: 26 September 2017

Please cite this article as: Bora PJ, Porwal M, Vinoy KJ, Kishore , Ramamurthy PC, Madras G, Industrial
waste fly ash cenosphere composites based broad band microwave absorber, Composites Part B
(2017), doi: 10.1016/j.compositesb.2017.09.062.

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 ACCEPTED MANUSCRIPT

Industrial waste fly ash cenosphere composites

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based broad band microwave absorber

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Pritom J Bora1, Mayuri Porwal2, K.J. Vinoy3, Kishore2, Praveen C Ramamurthy*1, 2 and Giridhar

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Madras1, 4

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Interdisciplinary Centre for Energy Research (ICER),
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Department of Materials Engineering
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Department of Electrical and Communication Engineering,
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Department of Chemical Engineering
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Indian Institute of Science, Bangalore-560012, India.

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E–Mail: onegroupb203@gmail.com
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Abstract

The utilization of industrial waste fly ash cenosphere (FAC) for microwave absorption is explored in this

study. FAC, the industrial waste, was pre-treated with conventional acid-base wash. As soft magnetic metal oxides

are viewed with interest for microwave applications owing to their possessing many advantageous properties, in this

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work, NiO and CoOX was coated over FAC by chemical precipitation and thermal reduction method for studying the

microwave absorption property. The polyvinylbutyral (PVB)-FAC, PVB-CoOx-FAC and PVB-NiO-FAC

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composites were prepared by solution processing and dielectric property study was carried out in X-band (8.2-12.4

GHz) and Ku-band (12.4-18 GHz) microwave frequencies. The minimum reflection loss (RL) was observed for

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PVB-NiO-FAC composite in a large band width as compared to PVB-CoOx-FAC and PVB-FAC composites. In the

X-band, the lowest RL value of PVB-NiO-FAC composite was observed to be ~ -17 dB (~ 12.3 GHz) and it

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decreased to ~ -49.7 dB in the Ku-band (15.8 GHz). Additionally, the thickness dependent RL was also studied for
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all the composites. The enhancement of EM attenuation constant and loss factor (LF) was found to be intrinsically

high for PVB-NiO-FAC composite along with dielectric dissipation as compared to other composites (i.e., PVB-
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FAC and PVB-CoOx-FAC) pointing to its excellent microwave absorption property. Therefore, the prepared

composites are suitable for microwave absorption based applications such as radar, robotic engineering, military
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applications, electromagnetic gasket, aircraft and unmanned vehicles.

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1. Introduction

In the recent times, the rapid growth of the electronics industry, particularly the development of communication

systems and devices operating in the range of microwave frequencies, has given Filip to the development of

microwave absorbing materials (MAMs) [1-3]. This is due to the exigencies caused by the presence of

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electromagnetic interference issues [1-3]. Comprehensive efforts are being made by researchers to develop newer

and ideal electromagnetic wave absorbers that exhibit good absorbing properties. Further, they should be light

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weight, easy to process/handle, resist corrosion and be simple to synthesize as compared to conventional absorber

[2-8]. A single dielectric or magnetic loss material is disregarded as a result of its inefficiency in converging with

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desirous requirements of being light weight and having a lower thickness coupled with the difficulty in attaining

impedance matching [9]. Recent studies have been directed towards the development of such newer and attractive

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materials, especially polymer nanocomposites, as potential microwave absorbers [9, 10].
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Fly ash cenospheres (FACs) are hollow ceramic spheres of micrometer range. FAC is the by-product of

coal fired/ thermal power plants [11, 12]. Improper disposal of FACs lead to environmental-related problems [13].
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Consequently, efforts are continuously being made to utilize and recycle FAC [11-12]. Due to their unique

properties like low density [8-15], high mechanical strength of FAC loaded polymer [16], chemical resistance,
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thermal resistance, hydrophobic nature, excellent dispersive nature in polymer matrix, good fluidity, non-toxicity
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and reduced shrinkage, they are being utilized in a variety of applications such as fillers in cement, in ceramics and

in heterogeneous catalysis [17-19, 11]. Recently, researchers are investigating FAC core shell composites for EMI
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shielding and microwave absorption [15, 20, 21]. FAC and metal/metal oxide coated FAC loaded conducting

polymer (polyaniline) composite and their films are studied for EMI shielding applications [22-23]. However, as the
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conductivity of the conducting polymer’s decreases over a period due to de-doping, stability is a challenge [24]. On
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the other hand, metal backed lightweight microwave absorbers are recently in demand [4-10]. FAC-based

microwave absorbers have drawn keen interest due to advantages such as abundant availability and they are light

weight and inexpensive [20, 22, 25, 29]. For instance, Li et al. [20] synthesized barium ferrite-coated FACs

(BFACs) and studied their microwave absorption properties. For 80 wt % BFAC-epoxy composite, they reported a

minimum reflection loss (RL) of -15.4 dB at 8.4 GHz at 3 mm thickness [20]. In another study by Wei et al. on La-

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doped magnetic FAC composites, it was reported that the FAC + FeLaO3 composites (thickness 2 mm) prepared

using pretreated FACs had a minimum RL of -24 dB at 5 GHz [29].

Metal oxide coated core-shell nanocomposites have recently aroused interest for potential microwave

absorption [26]. Magnetic metal oxides are also being used for absorption applications because of their novel

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functionalities [31]. Both nickel oxide (NiO) and cobalt oxide (Co3O4 and CoO) have dielectric properties and

therefore a shell of either NiO or CoOX (Co3O4 and CoO) can provide impedance matching [30, 31]. As a result,

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such composites exhibit higher absorption. Wang et al. studied the electromagnetic properties of graphene-SiO2-

NiO nanoflowers and reported a minimum RL of -20.5 dB at 11.3 GHz for a thickness of 3 mm and at 25 wt%,

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while the minimum RL of graphene-SiO2 was only -9.34 dB at 8.7 GHz for a thickness of 5 mm [32]. Liu et al.

studied the influence of microwave absorption property by NiO over Ni nanoparticles (Ni/NiO) [33]. They reported

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a minimum RL of -24.1 dB at 17.9 GHz at the thickness of 1.3 mm for the Ni/NiO-paraffin composite. However,
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for a thickness of 2 mm the RL was only ~-8 dB at 14 GHz. For the porous Ni/NiO-Paraffin composites, they

reported a RL of -49.1 dB at 14.4 GHz for a thickness of 1.5 mm [33]. Yang et al. studied the effect of elevated
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temperatures on microwave absorption of NiO nanorings/SiC composite [34]. From this investigation, they reported

that at 373 K, the minimum RL of SiC was only ~ -13 dB at 11 GHz whereas that of NiO/SiC composite was ~-18
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dB at 12.5 GHz for a thickness of 1.58 mm [34]. The lowest RL was observed at 673 K and was ~-14 dB for SiC
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and ~ - 47 dB for NiO-SiC composite. Liu et al. studied CoOx/ carbon fibres (CF) composites [30]. For the

prepared composites, they reported a minimum RL of only ~-2.5 dB for a thickness of 1.68 mm, whereas for the

composites annealed at 350˚C for 3 hours the minimum RL was reported as - 45.16 dB at 13.41 GHz for a thickness
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of 1.5 mm and 33.3 wt % [30]. Sun et al. studied CoO nanobelts and submicrometer spheres. They reported that for

CoO nanobelts the observed minimum RL was -12.3 dB at 14.4 GHz for a thickness of 3 mm and 70 wt %;
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however, for CoO sub-micrometer spheres, the observed minimum RL was only -5.4 dB at 1.4 GHz for the same
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thickness and composition [35].

Polyvinylbutyral (PVB) is a novel polymer and increasingly becoming popular as a matrix for composites

especially for organic electronics because of its unique blend of properties as well as weather resistivity [36]. PVB

is tough, amorphous, and transparent and it has good adhesive properties owing to which it provides a very

homogeneous distribution of the particles in the composites [36, 37]. The dielectric properties of PVB can be

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enhanced by loading FAC, which also decreases the water vapor transmission rates (WVTR) [38, 39]. The objective

of the present work is, to prepare FAC/PVB based broad band microwave absorber material that could be used by a

solution coating technique.

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2. Experimental Section:

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2.1 Materials

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The fly ash cenospheres (FAC) were obtained from National Thermal Power Corporation (NTPC), India. Cobalt

nitrate hexahydrate (Co(NO3)2.6H2O), and nickel nitrate hexahydrate (Ni(NO3)2.6H2O) were obtained from Sigma

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Aldrich (USA). Ammonium bicarbonate (NH4HCO3), polyethylene glycol (PEG 400), sodium hydroxide (NaOH),
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hydrochloric acid (HCl) and polyvinylbutyral were all procured from Polysales chemicals (India).
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2.2 Synthesis of CoOx/NiO-FAC :

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CoOX coated FAC was prepared by heterogeneous precipitation and thermal reduction technique. 1.5 g FAC and
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0.75 ml of poly ethylene glycol (PEG 400) was dispersed in 110 ml of DI water while being magnetically stirred.

Then 30 ml of 0.5 M cobaltous nitrate hexahydrate Co(NO3)2.6H2O was added to this solution. Subsequently, 15 ml
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of 1 M ammonium bicarbonate (NH4HCO3) was added drop-wise (~ 2 ml/min). To maintain the pH at ~7, few

drops of 3 M NaOH was added. The reaction mixture was stirred for another 4 hours and the resulting precipitate
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was washed with copious amount of DI water, then dried in the oven at 80±2˚C for 12 hours and the thermal

reduction was carried out at 600±4˚C for 2 hours. Similarly, the NiO-FAC was also synthesized under same
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conditions using Ni(NO3)2.6H2O.

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2.3 Synthesis of polyvinylbutyral (PVB) –CoOx/NiO-FAC composites:

PVB-FAC, PVB-NiO-FAC and PVB-CoOx-FAC composites were prepared by simple solution processing. PVB

was first dissolved in ethanol and 10 wt % of FAC, NiO-FAC, CoOX-FAC was added very slowly to PVB solution

and stirred for another 30 minutes. In the next step, few drops of DI water was added to the solution and the

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resulting gel was washed with DI water several times and poured to copper sample holders and kept in open air

drying for 48 hours.

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2.4. Characterizations

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The cross-sectional and surface morphology, energy dispersive X-ray (EDX) studies of the FAC, CoOx/NiO-FAC

and PVB-CoOx/NiO-FAC were carried out under field emission surface electron microscope (FESEM, Carl Zeiss).
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The focused ion beam (FIB) cut was carried out by using UHR dual beam FIB (Helios NanoLab 600i). The X-ray

diffraction (XRD) patterns of powdered samples were obtained by using Rigaku-XRD diffractometer. The dielectric
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and microwave absorption study of the as prepared composites in the X-band (8.2-12.4 GHz) and Ku-band (12.4-18

GHz) was carried out by using vector network analyzer (VNA, Agilent NS201). The thru-reflect-line (TRL)
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calibration of VNA is the standard calibration method to obtain the complex S-parameters (S11, S12, S21, S22) [37]. A
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complete two port TRL calibration was performed in the X-band and Ku-band frequencies, respectively, before

commencement of measurements. The sample holders were clamped tightly in respective coaxial to waveguide
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adaptors and the complex S-parameters were measured. From the obtained S-parameters, by using standard

Nicholsion-Ross-Weir (NRW) algorithm the complex permittivity (εr) and permeability (µ r) values were calculated
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for X-band and Ku-band respectively [40]. The reflection loss, RL, of metal backed samples was calculated from
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the obtained permittivity (εr) and permeability (µ r) data according to transmission line theory and cross-checked by

placing copper sheet behind the samples [3].

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3. Results and discussion:

3.1. Surface morphology and XRD analysis

The surface morphology of cleaned FAC and corresponding EDX results is shown in the Fig.1. It is

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observed that in the FAC, the Si and Al wt% is ~ 30% and ~ 20% respectively (constituent of FAC is mainly SiO2

and Al2O3).

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Fig.1. Surface morphology of (a) FAC, (b) broken FAC and (c) Major components.
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The surface morphologies of CoOx-FAC and NiO-FAC composites and corresponding EDX results are

shown in Fig. 2(a, b) and Fig.2 (c, d) respectively. Observed morphology suggests homogeneous coating of NiO

and CoOx over FAC surface. However, some agglomerated regions were also observed (especially in defect bearing

FACs). EDX results suggest that the presence of Ni wt% is ~ 43% in the case of NiO-FAC whereas Co wt% is ~

30% in the CoOx-FAC. The average NiO and CoO coating thickness on FAC was determined by FIB cut (Fig. 2 (e,

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f)). The shell thickness of FAC was found to be ~ 2±0.5 µm, average NiO coated layer obtained was ~ 700 nm in

the NiO-FAC and CoOx coated layer obtained was ~ 550 nm in CoOx-FAC.

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Fig.2. FESEM images and corresponding EDX results of (a, b) CoOX-FAC, (c, d) NiO-FAC. (d, e) FIB cut of NiO-

FAC cenosphere.

XRD pattern of the as synthesized NiO/CoOx-FAC and FAC is shown in Fig.3. The XRD pattern of FAC

is similar to mullite [41]. In case of CoOx-FAC composite, the intense diffraction peaks observed at 2θ values of 38,

44, 68 º correspond to (311), (400), (440) planes of Co3O4 and the diffraction peaks observed at 2θ value of 42 and

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78 º corresponds to (200) and (222) planes of CoO, respectively [30]. Similarly, in NiO-FAC, the diffraction peaks

due to (111), (200), (220) and (311) planes of NiO is shown in the Fig.3 [42]. The cross-sectional surface

morphology of PVB-FAC composite is shown Fig.4. It shows that, the FAC and hence CoOx/NiO-FAC was grafted

in the PVB matrix.

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Fig.3. XRD diffractrogram of FAC, NiO-FAC and CoOx-FAC.

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Fig.4. Cross sectional surface morphology of PVB-FAC composite.
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3.2. Dielectric study of PVB-NiO/CoOx-FAC composite

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Fig. 5 shows the variation of the frequency dependent real (ε′) and imaginary (ε″) part of complex

permittivity ΄ ˝ and real (µ′) and imaginary (µ″) part of complex permeability (μ ΄ ˝ ) in the X-
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band (8.2-12.4 GHz). The real part of complex permittivity (ε′) represents the ability of the material to store electric

energy and is related to the amount of polarization whereas the imaginary part (ε″) represents the electric energy that
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dissipates [1]. Analogous to this, the real part of complex permeability (µ′) represents the magnetic energy storage

capacity of the material and the imaginary part (µ″) is the dissipation of magnetic energy [4]. From Fig. 5(a) it was
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observed that the ε´ remains almost constant for the PVB-FAC, PVB-NiO-FAC and PVB-CoOx-FAC composites,

for the entire the frequency range of 8.2-12.4 GHz. The PVB-FAC composite, the value of ε′ varies between 2.4 to

2.6, for the PVB-CoOx-FAC composite the values remains almost constant at about 4.2 and for the PVB-NiO-FAC

composite it about 4.5.

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Fig.5. Variation of (a, b) real and imaginary part of complex permittivity and (c, d) complex permeability of PVB-
FAC, PVB-NiO-FAC and PVB-CoOx-FAC composites in the X-band (8.2-12.4 GHz).
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It is also observed that the ε´´ remains almost constant for the PVB-FAC and PVB-CoOx-FAC composites
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at around 0.1 and 0.8, respectively (Fig. 5(b)). However, in case of the PVB-NiO-FAC composite, it was observed

that the ε´´ increases with increasing frequency (1.2-1.5). This increase in ε´´ of the PVB-NiO-FAC composite can
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be attributed to the conductivity as well as increased interfacial polarization. Due to the presence of different
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dielectrics such as PVB, NiO/CoOx, FAC and air (void) the interfacial polarization will be generated in PVB-

CoOx/NiO-FAC composite under the microwave irradiation [43, 44]. As change of ε´´ is higher for PVB-NiO-FAC

composite as compared to PVB-CoOx-FAC and PVB-FAC composite, therefore it can be concluded that, under

microwave irradiation, the interfacial polarization of PVB-NiO-FAC is the highest. The real part of complex

permeability (µ´) of all the three composites decreases with increase in frequency, as shown in Fig. 5(c). This

decrease in the value of µ′ can be attributed to the hysteresis effect of the magnetic domain walls and magnetic

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induction intensity. The relatively higher value of µ′ for the PVB-CoOx-FAC and PVB-NiO-FAC composites as

compared to PVB-FAC is a consequence of the presence of the soft magnetic CoOx and NiO particles in the

composites. The µ´´ was also observed to increase with frequencies for the PVB-CoOx-FAC and PVB-NiO-FAC

composites (Fig. 5(d)).

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Fig.6. Variation of (a, b) real and imaginary part of complex permittivity and (c, d) complex permeability of PVB-
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FAC, PVB-NiO-FAC and PVB-CoOx-FAC composites in the Ku-band (12.4-18 GHz).

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Similar to the observations of X-band, it is observed from Fig. 6(a) that the real part of complex

permittivity vacillates around 2.25, 4.25 and 4.5 for the PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC

composites, respectively, in the Ku-band (12.4-18 GHz). The ε´´ values of the PVB-CoOx-FAC and PVB-NiO-FAC

composites are observed to increase with frequency as compared to the PVB-FAC composite. The increase in the

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ε´´ value of PVB-NiO-FAC is from 1.6 to 1.9. From Fig. 6(b), it was observed that a similar decreasing tendency of

µ′ is observed for the Ku-band as well, although, it is observed that the decrease is sharper for the PVB-NiO-FAC

composite. The µ′ value decreases from 1.03-0.98 for PVB-FAC, 1.06-0.99 for PVB-CoOx-FAC and 1.04 -0.93 for

the PVB-NiO-FAC composites. However, the µ´´ value was also observed to increase with frequency for NiO-FAC

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and CoOx-FAC loaded PVB composites. In both, X-band and Ku-band, µ´´ values show multiple peaks (especially

PVB-NiO-FAC), it indicates the resonance behaviors of the polymer composite [44].

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3.3. Microwave absorption property of PVB-NiO/CoOx-FAC composite

The microwave absorption property of a material is determined in terms of reflection loss, (RL). The

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mathematical interpretation of RL of metal backed samples is [1, 3],
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20 (1)

Z = input impedance and it can be written as,

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in

"$ "$
μ μ ⁄ # %&'ℎ )*2+, μ μ ⁄ #- (2)
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Z = characteristic impedance of free space and

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d = thickness of the absorber

- 10 dB RL is believed as an adequate level of absorption limit for practical applications [45, 1, 3]. Fig.7.
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and Fig.8 show the obtained RL of PVB-NiO/CoOx-FAC composites in the X-band and Ku-band respectively. The

minimum RL value of - 2 dB was obtained for PVB-FAC (3 mm) composite in the X-band and it decreased to – 4.5
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dB in the Ku-band. The thickness dependent variation of RL of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC
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composites in X-band is shown in Fig. 7(a), Fig. 7(b) and Fig. 7(c) respectively. In the X-band, the minimum RL of

PVB-CoOx-FAC composite (3.5 mm) was found to be -16 dB with a bandwidth of 2 GHz (11-12 GHz). Similarly,

the RL value of PVB-NiO-FAC composite also decreases with frequency and thickness in the X-band and reaches

the minimum RL value of -32 dB, at thickness of 3 mm. However, the bandwidth was observed for the thickness

3.5 mm with a minimum RL value of -26 dB. The comparison of RL value of PVB-FAC, PVB-CoOx-FAC and

PVB-NiO-FAC composite for the same thickness (3.5 mm) in the X-band is shown in the Fig. 7(d).

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Fig.7. Variation of reflection loss (RL, dB) of (a) PVB-FAC, (b) PVB-CoOx-FAC, (c) PVB-NiO-FAC composites
at various thicknesses, (d) comparison of RL value of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites
in the X-band (8.2-12.4 GHz).
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Fig.8. Variation of reflection loss (RL, dB) of (a) PVB-FAC, (b) PVB-CoOx-FAC, (c) PVB-NiO-FAC composites
at various thicknesses, (d) comparison of RL value of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites
in the Ku-band (12.4-18 GHz).
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In Ku-band, for all the composites, the RL value and bandwidth vary at less thicknesses as compared to X-
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band. In case of PVB-CoOx-FAC composite, the RL value was obtained as -24 dB at 17.8 GHz (2 mm), -27 dB at
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15.8 GHz (2.5 mm) and -23 dB at 13.8 GHz (3 mm). The RL value of PVB-NiO-FAC composite was found to

gradually decrease to -2.5 dB to -11.5 dB and -7.2 dB to -39.5 dB for thicknesses of 1.5 mm and 2 mm, respectively

(Fig. 8(c)). When thickness was increased to 2.5 mm, the minimum RL value was found - 47.5 dB at ~ 15.8 GHz

with a wide band width in the frequency range of 13.8-18 GHz. Moreover, it shifts to low frequency region while

thickness was further increased (3 mm). This observed interesting behavior can be explained by EM cancellation

effect, dielectric loss, EM attenuation and impedance matching [46]. The EM cancellation effect takes place on the

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surface of the absorbing surface if the phase difference between the incident wave and emerged wave is 180 º.

Therefore, the ideal coating thickness (dm) and the incident wavelength (λ) must obey the following conditions [46],

/
. (3)
0

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Here, n is the cardinal number (n =1, 3, 5…..)

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1

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(4)
34|67 | |87 |

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Here, c is the velocity of light and f is the frequency. Therefore,

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. (n= 1, 3, 5…..) (5)
034|67 | |87 |

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Thus Eqn. (3) indicates EM cancellation effect takes place at a specific frequency for a given thickness. In

other words, the RL curves shift towards lower frequency with increasing absorber thickness. That is why the RL

value of PVB-CoOx/NiO-FAC composites shifted to low frequency regions on increasing thickness. Fig. 8(d)
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shows the comparison of RL values of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites in the Ku-band
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(thickness 2.5 mm). The better microwave absorption property of the prepared composites can be understood in
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terms of microwave absorption efficiency [1], RE, which is expressed as, R: , where, >? @ ,AB≤ " CD [1,
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45]. The RE values of PVB-CoOx-FAC and PVB-NiO-FAC composites were calculated for X-band and Ku-band

and it is respectively shown in the Fig. 9(a) and Fig. 9(b) (the RL value does not reach -10 dB for PVB-FAC
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composite). In the X-band, the maximum R : value was obtained 14.32 dB GHz / mm for PVB-NiO-FAC composite

(3.5 mm) which is much higher as compared to PVB-CoOx-FAC composite (3.66 dB GHz / mm). Similarly, in the
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Ku-band, the microwave absorption efficiency of PVB-NiO-FAC was found to be very high as compared to the
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PVB-CoOx-FAC composite. The optimal R: value of PVB-NiO-FAC composite (2.5 mm) was obtained 53.79 dB

GHz / mm, whilst optimal R : value of PVB-CoOx-FAC composite was 25.35 dB GHz / mm. Thus, it shows the

excellent microwave absorption rate of PVB-NiO-FAC composite as compared to PVB-CoOx-FAC composite.

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(a)

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Fig.9. Variation of microwave absorption efficiency (RE) of the PVB-CoOx-FAC composite and PVB-NiO-FAC

composite in the (a) X-band and (b) Ku-band respectively.

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The electromagnetic loss mechanism i.e., dielectric loss tangent (%&' EF ´´$ ) and magnetic loss tangent
´

μ´´
(%&' E. $μ´) is another reason for obtained low RL (dB) value. Fig. 10(a) and Fig. 10(b) shows the variation

of %&' EF and %&' E. of PVB-NiO/CoOx-FAC composites in the X-band, respectively. The %&' EF value of FAC

loaded PVB (PVB-FAC) was found to be 0.2, which increases to ~ 0.35 and ~ 0.45 respectively when CoOx-FAC

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and NiO-FAC were loaded to PVB. The %&' E. value also found to be high for PVB-NiO-FAC composite as

compared to PVB-CoOx-FAC and PVB-FAC composite. Like X-band, in Ku-band (Fig. 10(c)) the %&' EF values of

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PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC were found to increase with frequency. Similarly, the

%&' E. value was also found to be highest for PVB-NiO-FAC composite (Fig. 10(d)).

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Fig.10. Variation of (a) dielectric loss tangent (%&' EF ) and (b) magnetic loss tangent (%&' E. ) in the X-band.
Variation of (c) dielectric loss tangent and (d) magnetic loss tangent in the Ku-band.

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The incident microwave energy is dissipated in the composite materials through damping forces which

arises due to materials electronic structure. Hence, by using Poynting theorem [47], for a closed surface (S) having

volume V, the dissipated power (Pdiss) can be written as [47],

" R
HC II J K ∮ M × O∗ ?Q ∭ ´´|M|# + μ μ´´|O|# U (6)

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# 0

Here, ω (=2πf) is the angular frequency and ε0 is the permittivity of the free space.

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Eqn. (6) indicates that the real part of propagation constant (γ) is important for EM attenuation, i.e., EM

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attenuation constant (α). Therefore, α is given by following equation [4],

\
R \
# # [] ]
V J W × ) μʹʹ ʹʹ μʹ ʹ + Z μʹʹ ʹʹ μʹ ʹ + μʹ ʹʹ + μʹʹ ʹ - (7)

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Here c is the velocity of light.

Thus, α is the intrinsically important factor for EM absorption. Fig. 11(a) and Fig. 11(b) shows the
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variation of α of the PVB-CoOx/NiO-FAC composites in X-band and Ku-band, respectively. In both the bands, the

α value was found to increase with frequency, viz., in X-band, the obtained α value of PVB-FAC, PVB-CoOx-FAC
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and PVB-NiO-FAC were 10-15, 37-53 and 57-100, respectively. In Ku-band, it increased to ~ 25, 78-100 and 109-
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200 for PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC samples, respectively. Thus, the analysis of data indicates

the excellent EM absorption property of PVB-NiO-FAC composite. Further, it can be correlated in terms of loss
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factor (LF), which is given by following relation [48, 49],

^ % 100 × 1 |?"" |# |?#" |# (8)

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Where, S11 and S21 are the linear reflection coefficient and transmission coefficient respectively.

The loss factor of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC are shown in Fig.12. The LF was

found to increase with frequency. In X-band, LF of PVB-FAC was 40 % which increases to 60 % for PVB-CoOx-

FAC and 70 % for PVB-NiO-FAC composites, respectively (Fig. 12(a)). As shown in Fig. 12(b), the LF of PVB-

NiO-FAC is increased to 79 % in Ku-band. Thus it signifies the enhancement of microwave absorption property of

NiO/CoOx coated FAC loaded PVB composite and PVB-NiO-FAC composite is better for microwave absorption.

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(a)

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(b)

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Fig.11. Variation of EM attenuation constant (α) of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites in
(a) X-band (8.2-12.4 GHz) and (b) Ku-band (12.4-18 GHz).
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(a)

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Fig.12. The loss factor of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites in the (a) X-band and (b)
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Ku-band.
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When incident electromagnetic wave falls on the polymer composites (PVB-CoOx/NiO-FAC), three

phenomena takes place, namely, reflection, absorption and multiple reflections. Schematic is shown in the Fig.13.

Multiple reflections are more prominent for multiphase porous structures [7]. As incident microwave has to pass

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through the polymer, soft magnetic metal oxide coated layer and followed by FAC, therefore, impedance matching

is another important factor for PVB-CoOx/NiO-FAC composite. The EM matching degree (∆) is expressed as [45],

> |a 'ℎ# b, c| (9)

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Here, K and M depends on the permittivity and permeability of the medium [45]. As it was observed, the

dielectric dissipation of PVB-NiO-FAC composite is more than the PVB-CoOx-FAC composite and expected value

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of M is high which results in low ∆ value. According to the literature [50], hollow microsphere based material also

favors impedance matching through effective permittivity.

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Fig.13. Schematic of prepared composites for microwave absorption, ri and ro denotes the inner and outer radii
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respectively.
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To better understand the contribution of NiO/CoOx coating over FAC for microwave absorption property,

the EM simulation (CST microwave studio) was carried out for the prepared composites. As loss due to dielectrics

is the major factor for microwave absorber therefore loss in dielectrics of the incident power is investigated for the

present polymer composites (metal backed) and is shown in the Fig. 14 and Fig. 15 for X-band and Ku-band

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respectively. As observed in Fig. 14(a, b, c), with increasing absorber thickness the loss in dielectric also increases

which also corresponds to RL change. In the X-band, the maximum dielectric loss was obtained for PVB-NiO-FAC

composite (44-95 % for the thickness 3 mm). Similarly, in the Ku-band, the dielectric loss of PVB-NiO-FAC

composite reached 99.9 % for a lesser thickness (2.5 mm, Fig. 15(c)). On the other hand, PVB-CoOx-FAC shows

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maximum dielectrics loss of 95 % for the thickness of 3 mm. Since the maximum dielectric loss of PVB-FAC

composite (3 mm) is 12 % and 63 %, for X-band and Ku-band respectively, therefore it can be easily understand that

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CoOx/NiO coating over FAC enhances dielectric loss of PVB-CoOx/NiO-FAC and is predominant for NiO. That is

why, PVB-NiO-FAC composite shows the best microwave absorption property.

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Fig.14. The dielectric loss (%) of (a) PVB-FAC, (b) PVB-CoOx-FAC, (c) PVB-NiO-FAC in various thicknesses,
(d) comparison of dielectric loss (%) of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites (3 mm) in the
X-band.

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Fig.15. The dielectric loss (%) of (a) PVB-FAC, (b) PVB-CoOx-FAC, (c) PVB-NiO-FAC in various thicknesses,
(d) comparison of dielectric loss (%) of PVB-FAC, PVB-CoOx-FAC and PVB-NiO-FAC composites (3 mm) in the
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Ku-band.

The high microwave absorption property of hollow microspheres is also due to the central region (void)
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which has a constant refractive index (RI) and due to this spatial dispersion is predominant [27]. The maximum

value of the refractive index (nh) of hollow microsphere is (Fig. 13) [27],
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#
'd , e'I , + f f # + 'g 4f #
+ f #
f # i⁄4f #
(10)
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Where, ns(f) is the RI of the coated region and n0 is RI of air (=1). ri and ro corresponds to inner and outer

radii respectively. The effect of coating thickness on absorption performances can be explained based on the model

proposed by Bychanok et al. [27]. According to that, the microwave absorption ability of the present structure can

be increased by increasing the size (outward radius, ro), at constant coating thickness. The coating thickness of NiO

on FAC can be controlled during synthesis. For increasing NiO coating thickness on FAC, the precursor and

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reducing agent amount was increased to 1 M (NiNO3.6H2O) and 2 M (NH4HCO3) respectively while the remaining

procedure was same. The resulted thickness was found ~ 850 nm (Fig. S3, Supporting information). The PVB

composite was prepared by same procedure and the composite was named as PVB-NiO (850 nm)-FAC (NiO coating

over FAC is ~850 nm). The thickness dependent RL of PVB-NiO (850 nm)-FAC composite in X-band and Ku-

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band is shown in the Fig. 16(a) and Fig. 16(b) respectively ( and μ were shown in the Fig. S4 and Fig. S5

respectively, Supporting information). It was observed that, while thickness was increased, the RL value was not

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decreased significantly in the X-band (the optimum RL value is – 25 dB). While a significant difference of RL

value was observed in the Ku-band (minimum RL value - 33 dB), which indicates less microwave absorption

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property of PVB-NiO(850 nm)-FAC composite in the Ku-band. This is believed due to that, while coating was

increased, the reflection and scattering of incident microwaves is high and due to that less wave enters into the

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hollow structure resulting in lesser absorption [50].
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(a)

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Fig.16. Thickness dependent RL of PVB-NiO (850 nm)-FAC composite in X-band and Ku-band.

A comparison of the RL value of the present composite materials with reported materials has been

tabulated in the Table 1. From the tabulation, it can be observed that present PVB-NiO-FAC composite is one of

the superior, inexpensive and lightweight polymer composite for microwave absorption. As hollow microsphere

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based microwave absorbers are always attractive. Therefore, the present polymer composite materials are most

useful for military applications, electromagnetic gasket, aircraft and unmanned vehicle applications.

Table 1. Comparison of recently reported RL values of absorbing materials with present material.

Sr. Material Frequency RL (dB) Filler Thickness Reference

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No (GHz) (wt %) (mm)
1 Graphene SiO2-Paraffin 11.3 -20.5 25 3 32

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2 Graphene SiO2 -NiO ~16.56 -12.5 25 2 32
nanoflowers-Paraffin
3 Ni/NiO-Paraffin 17.9 -24.1 50 1.3 33

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4 Porous-Ni/NiO-Paraffin 14.4 -49. 50 1.5 33
5 NiO/SiC 12.5 -18 - 1.58 51

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6. Co/CF precursor 14 -25 33.33 1.68 30
7 Co/CF precursor 13.41 -45.16 33.33 1.5 30
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annealed (300˚C)
8 Paraffin wax-Co/CoO 13.68 -14.5 60 1.7 52
nanocrystals air dried at 300˚C
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9 CoO nanobelts/Paraffin wax 14.4 -12.3 70 3 35

10 CoO submicrometer 10.4 -5.4 70 3 35
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spheres/paraffin wax
11 Barrium Ferrite coated 8.4 -15.4 80 3 20
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FAC/Epoxy
12 La doped magnetic FAC 5 -24 - 2 29
(FAC+FeLaO3)
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13 PVB-CoOx-FAC ~ 15.8 ~ -27 10 2.5 Present Work

14 PVB-NiO-FAC ~ 15.8 ~ -47.5 10 2.5 Present Work
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4. Conclusions

The solid waste FAC is metal oxide (NiO and CoOx) coated by two step chemical synthesis and PVB-NiO/CoOx-

FAC composites were prepared by solution processing. The PVB-NiO-FAC composite was found to be more

suitable for microwave absorption as compared to PVB-FAC and PVB-CoOx-FAC composites. The lowest RL

value, obtained for PVB-NiO-FAC composite, was ~ -17 dB and ~ - 47.5 dB in the X-band and Ku-band

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respectively for the thickness of 2.5 mm. High loss factor (~ 79 %) and EM attenuation constant of PVB-NiO-FAC

composite along with dielectric dissipation were found to be intrinsically dominant factors for obtained low RL

values. Thus, the study suggests that this light weight, industrial waste coating material is a novel composite

candidate material for microwave absorption.

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Acknowledgments

Authors gratefully acknowledge the financial support by Department of Science and Technology (DST)

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(SB/S3/ME/51/2012) and technical support from MNCF (CeNSE) for this work. Kishore would like to place on

record the AICTE for offering Emeritus position. Giridhar Madras thanks DST for J.C. Bose fellowship.

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Graphical Abstract
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