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Procedia Chemistry 19 (2016) 441 446

5th International Conference on Recent Advances in Materials, Minerals and Environment (RAMM) & 2nd
International Postgraduate Conference on Materials, Mineral and Polymer (MAMIP), 4-6 August 2015

Preparation and Characterization of Microwave-absorption of Sarulla North

Sumatra Zeolite and Ferric Oxide-filled Polyurethane Nanocomposites

Golfrid Gultoma,b, Basuki Wirjosentonoc, Kerista Sebayangd, Masno Gintinge

a
University of Sumatera Utara, Physics Post Graduate Program, Medan 20155, Indonesia
b
Polytechnic of Chemical Industry Technology, Medan 20228, Indonesia
c
University of Sumatera Utara, Chemistry Department, Medan 20155, Indonesia
d
University of Sumatera Utara, Physics Department, Medan 20155, Indonesia
e
Indonesian Institute of Science, Research Center for Physics, Serpong 15314 , Indonesia

Abstract

Microwave-absorptive polymeric composite materials are becoming important to protect interference of any communication sy stems due
to the increase in the use of microwave-inducing devices. In this work, the microwave-absorptive polyurethane composites are prepared
using natural zeolites of Sarulla North Sumatra and commercial ferric-oxide as fillers. Weight ratio of the natural zeolite to ferric oxide
were varied (18:2; 16:4; 14:6; 12:8 and 10:10) by weight. The fillers are prepared using ball milling technique and characterized using
Particle Size Analyzer for particle size distribution. The nanocomposites, prepared using in-situ reaction of polyethylene glycol and
toluene diisocyanate, is characterized for physical and mechanical properties using tensile strength, thermal properties with TGA
techniques, as well as morphological and chemical properties using scanning electron microscopy. Composition and loading of the
nanofillers against polyurethane matrices is 20% by weight. Microwave-absorption properties of the nanocomposites is characterized
using 8-12 GHz frequency. Tensile strengths of the natural zeolite-ferric oxides polyurethane nanocomposites shows higher values when
matrices filled with lower ferric-oxide, which could be due to the nanozeolites have functioned as reinforcement for the polyurethane
matrix through polar-polar interaction between the filler surfaces with the matrices. The microwave absorption properties, which
investigated by Vector Network Analyzer, of the nanocomposites filled in polyurethane with the ratio of nanozeolite to ferric oxide filler
of 12:8 shows reflection loss of 13.2 dB. This condition was observed at 11.1 GHz.

2016
2016 The
The Authors.
Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia.
Peer-review under responsibility of School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia
Keywords: Polyurethane, Nanozeolites, Microwave-absorption

*Corresponding author Tel: +6281361245428

Email: golfridg@gmail.com

1876-6196 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia
doi:10.1016/j.proche.2016.03.036
442 Golfrid Gultom et al. / Procedia Chemistry 19 (2016) 441 446

1. Introduction

Electromagnetic interference is worsening with the rapid development of wireless communications and circuit devices. The
high frequency electromagnetic wave is drawing more attention, due to the explosive growth in the utilization of
telecommunication devices in industrial, medical and military application 1,2.
In the past decades, the spinel ferrite have been utilized as the most frequent absorbing materials in various forms. The
absorbing characteristics of materials depend on the frequency, layer thickness, complex permittivity (Hr) and complex permeability
(Pr). All the parameters H, H, P and P are found to increase with the increased of ferrite contents and it is found that the
absorption properties in the composites are greatly improved with the increasing of ferrite contents in the polymer matrix4. But in
other side, it will increase the mass of the absorbing materials. Conducting polymer composites with micro/nanostructured have
attracted a significant academic and technological attention because of their unique physical properties and potential applications5-
8
.
Zeolite mineral is a compound of aluminium silicate hydrate with alkali metal which is group of several types of minerals.
Zeolite is aluminosilicate with a framework structure enclosing cavities occupied by a large ions and water molecules, both of
which have considerable freedom of movement, permitting ion-exchange and reversible dehydration.
Natural zeolite is natural mineral that composed of crystalline silica (SiO2) and alumina (Al2O3), with cavities of metal ions,
which is usually alkali and alkaline or earth metals, and water molecules. Unique characteristic, include very stable with very high
adsorption capacity and selectivity and have large active pore structure (microporous) and has a high specific surface area. Natural
resources have the potential to be further processed into products that can be used for broad applications, among others, as
supporting the catalyst or catalysts, and slow release substances. Zeolite crystal structure of alumina silicate shaped frame
(framework) three-dimensional, having cavities and channels as well as containing metal ions such as Na, K, Mg, Ca and Fe as
well as water molecules.
Sarulla natural zeolite chemical composition analysis using XRF showed the dominant chemical compounds are SiO2 and
Al2O3 as showed in Table 1.

Table 1. Sarulla natural zeolite chemical compositions.

Compound % wt
Na2O 1.76
P2O5 0.61
MgO 0.12
Al2O3 14.19
SiO2 80.3
K2O 1.45
CaO 0.14
TiO2 0.52
Fe2O3 0.91

In this paper in-situ reaction of polyethylene glycol and toluene diisocyanate with nanofillers of zeolite and ferric oxide is used
to fabricate PU nanocomposites. The effect of alumino silica as the higher compound in natural zeolite combined with ferric oxide
as the most frequent absorbing materials were observed as microwave absorption.

2. Experimental

The fillers used for nanocomposite fabrication are natural zeolite and commercial ferric-oxide (J-Fe2O3). The polyurethane
matrix used was a commercial type which contains two-part urethane monomers i.e. 60% wt polyethylene glycol and 40% wt
toluene diisocyanate.
The PU nanocomposites reinforced with natural zeolite and ferric-oxide were fabricated with in-situ reaction. The
activated natural zeolite crushed to the size of 74 Pm using planetary ballmill for 10 hours. Natural zeolite and ferric-oxide with
ratio of 18:2; 16:4; 14:6; 12:8 and 10:10 by weight were mixed for 4 hours using planetary ballmill. Nanofillers of natural zeolite
and ferric oxide is 20 % wt of the Polyurethane. The homogen nanofillers divided into the same ratio and mixed with PPG and
TDI for 1 minute. Polyethylene glycol and toluene diisocyanate with nanofillers of zeolite and ferric oxide are using in-situ
reaction. Polyurethane, with the sample thickness of 5 mm, is hold and pressed for 30 minutes.
 Golfrid Gultom et al. / Procedia Chemistry 19 (2016) 441 446 443

3. Result and Discussion

Fig.1 shows the X-Ray Diffraction spectrum of Sarulla natural zeolite. Observed from the XRD spectrum shows intensity at 2
= 29.76; 27.67 and 27.92. Maximum peak occur at 29.76 with FWHM 0.124 which is at the aluminium silicate phase. Mordenite
standard have a high intensity at 2 = 27; 25.63 and 23. Compare with Sarulla zeolite, it shows that natural zeolite is mordenite,
but another peak at natural zeolite at 29.76 shows that crystaline at Sarulla natural zeolit is not only modernit but also mixed with
other crystalline and other impurities

Fig. 1. X-Ray diffraction of Sarulla natural zeolite.

b c

Zeolit particle

Pore

Ferric oxide particle

Fig.2. (a) SEM micrograph of Sarulla natural nanozeolite; (b) SEM micrograph of PU filled zeolit and ferric oxide 50 x magnification; (c) SEM micrograph
of PU filled zeolit and ferric oxide 500 x magnification.
444 Golfrid Gultom et al. / Procedia Chemistry 19 (2016) 441 446

Fig.2(a) above shows the surface of the zeolite have a crystal lattice in the form of pores of the zeolite surface , this is in-line
with the report stating that zeolite microporous crystalline solid is hollow and grooved and has a pore size of 3 to 10 called as
molecular sieves. SEM photograph shows that dark colors are pores or cavities and a bright color is a natural zeolite nanoparticles,
particle size of > 50 nm stated that zeolite is the mordenite type. Fig.2(b) show the PU nanocomposites foams distribution and
Fig.2(c) shows where zeolit and ferric oxide distributed in PU matrices.
Based on the measurement data, it is shows that the best mechanical properties of tensile strength at 3.23 MPa with natural
zeolite to ferric oxide ratio is 18:2, larger ferric oxide ratio will affect to the tensile strength degradation. This is probably due to
the polar to polar interaction between nanozeolite and PU matrices. The layer silicates in nanometer-sized natural zeolites can be
dispersed randomly and evenly that give structure to the nano composites. Silicate layers that exist in scattered individual zeolite
has a large surface contact area which caused to a strong bind with the matrix PPG and TDI and further gives effect to the increase
in tensile strength.

3.5
Tensile Strength (MPa)

3
2.5
2
1.5
1
0.5
0
10 : 10 12 : 8 14 : 6 16 : 4 18 : 2
Zeolite to ferric oxide ratio

Fig.3. Polyurethane nanocomposite filled natural zeolite and ferric-oxide tensile strength.

Termogram (TGA) curve analysis shows samples of PU with no filler, PU with ratio of nanozeolite and ferric-oxide of 16:4
(PU A-2) and PU with ratio of nanozeolite and ferric-oxide of 10:10 (PU A-5) have lost its weight when the temperature increased,
all samples will release the water in the compounds at the temperature of 200oC. Decomposition of PU at 336oC and 410oC will
lose its weight of 27.07% and 40.68% respectively. PU A-2 is decomposed at 335oC and 406oC and the weight is reduced of
23.17% and 28.74 % respectively. After heating to the temperature of 680oC, PU will have 16.44% residue, PU A-2 with 29.03 %
residue and PU A-5 with 30.18 % residue. Thermal stability will increase according to the increase of ferrite oxide content in the
composite.

Fig. 4. TGA curve of PU- natural nanozeolite and ferric oxide.

 Golfrid Gultom et al. / Procedia Chemistry 19 (2016) 441 446 445

Reflection loss measurement using Vector Network Analyzer for polyurethane nanocomposites reinforcement with 20% wt
nanofillers of natural zeolite and ferric-oxide ratio of 18:2; 16:4; 14:6; 12:8 and 10:10 as a function of frequency in X-band (8-12
GHz) shows in Fig.5 PU nanocomposites with ratio of natural zeolite and ferric-oxide ratio of 12:8 fillers have the optimum
reflection loss of -13.2 dB at 11.1 GHz. The reflection loss of less than -10 dB means the microwave absorption more than 90%.
The microwave absorption being dependent on the ratio of SiO2 and Al2O3 which is to dominant compounds of natural zeolite and
ferric-oxide, the content of ferric-oxide in natural zeolite will modify the reflection loss and microwave absorption of the
nanocomposite and will affect the complex permittivity and complex permeability of the nanocomposite. To satisfy the zero-
reflection condition where maximum absorption would occur, the impedance of the composite should be 1 to prevent reflection.
This can be ideally achieved when the materials present complex permittivity equal to complex permeability. Ferrite itself usually
presents electromagnetic characteristics of complex permeability less than complex permittivity. Minimum loss occurs when the
thickness is about an odd multiple of one quarter of the wavelength of the incident frequency 4.

Fig.5. Reflection loss of polyurethane natural zeolite and ferric oxide nanocomposites

4. Conclusion

Polyurethane filled nanozeolite and ferric-oxide has prepared using in-situ reaction. Natural zeolite and ferric oxide ratio as a
filler in PU matrices will cause a different effect in mechanical properties and microwave absorption properties. Tensile strength
properties show a better value when matrices filled with larger ratio of natural zeolite. Binding of zeolite with PU will increase the
mechanical properties. The nanocomposite absorb microwave at X band frequency for > 90 % absorption. This is due to the effect
of aluminum silicate and ferric oxide binding with polar polar reaction between filler and matrices. These reaction cause
difference in input impedance and this will make a difference in the resonance at high frequency. Ferrite-oxide particle have a
great microwave absorption characteristic, but in this case, the ratio between zeolite and ferric-oxide will affect the best microwave
absorption.

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