Dotsenko, Olga A.

Kachusova, Anastasia O.

Polivanova, Anna S.

Ulianova, Olga A.

English

Tomsk State University Repository

48 17th INTERNATIONAL CONFERENCE ON MICRO/NANOTECHNOLOGIES AND ELECTRON DEVICES EDM 2016Abstract – Nanostructured composite materials have opened a new era for multifunctional materials (such as reflection, absorbing, conducting etc.). In particular, multiwalled carbon nanotubes (MWCNTs) can be applied in order to improve electromagnetic properties in composites. Polymer composite materials based on MWCNTs were obtained. In this paper, microwave properties of polymer composites based on MWCNTs have been analyzed. Frequency dependences of permittivity of MWCNTs/varnish composite films were investigated in the range 3 – 14 GGz. The multiwall carbon nanotubes used in the composite were about 9.4 nm and 18.4 nm in diameter. The results show that the ultrasonic treatment modifies the dielectric permittivity of the composite. The dependence of the real and imaginary parts of the permittivity of sonication time is non linear. Index Terms – MWCNT, composite, permittivity, ultrasonic treatment, microwave I. INTRODUCTIONPOLYMER COMPOSITE materials are used in widely industries and science. They have more suitable mechanical properties than ceramic composite. Multiwall carbon nanotubes (MWCNTs) are promising in different fields of material science. Carbon nanotubes have a wide range of non-studied potential applications in various technological areas due to their attractive structural, mechanical, end electrical properties [1] – [3]. Conductivity of carbon nanotubes is very high. Polymer composite, containing conductive fillers are very perspective for electromagnetic application in gigahertz [4] – [7] regions even at low concentration of nanotubes. The binder material for production of polymer composite should have a good adhesive properties, high fluidity and high polymerization rate. The microwave properties of a composite are described by the frequency dependence of complex permittivity ε(ω) = εʹ(ω) – jεʹʹ(ω), where εʹ(ω) and εʹʹ(ω) are the real and imaginary parts characterizing the dielectric polarization and losses in the composite, respectively. The permittivity depends on the nanotubes concentration in a composite [2], aspect ratio and the residues of catalytic metals [1], [7].Methods of changes of electromagnetic properties of composite materials in external influence on their structure have been investigated [2], [3]. One way to change the internal structure of composite materials is ultrasonic treatment [8]  – [11]. Ultrasonication can produce thermodynamically stable MWCNTs mixture and after sonication MWCNTs are separated. The aim of this work is to study the electromagnetic properties that are present in varnish/MWCNTs polymer composites obtained by ultrasonic treatment. The impact of two types of MWCNTs on polymer composite’s electromagnetic properties is also studied.II. EXPERIMENTAL RESULTSA. MWCNT/varnish composite film preparationThe filler of composites was multi-walled carbon nanotubes (MWCNTs–2 and MWCNTs–3). Nanotubes were obtained by catalytic gas-phase deposition of ethylene in the presence of FeCo/Al2O3 catalyst in Institute of Catalysis SB RAS [12]. It is a lightweight, fluffy black powder containing individual nanotubes, tensions and aggregates of nanotubes, impurity of metal particles which were encapsulated in nanotubes, as well as the particles of the oxide supporter. The average MWCNTs–2 diameter is 9.4 nm, length > 15 µm, purity > 97.5%. The average MWCNTs–3 diameter is 18.4 nm, length > 15 µm, purity > 90.0 %. MWCNTs–3 contain remainders of catalyst about 7.0 %.Urethane alkyd varnish Tikkurila Unika Super (Tikkurila, Finland) was used for production of experimental samples. In the liquid state its viscosity is known to be small. This allows a filler to be moved easily.The technology of obtaining experimental samples was described in Ref. [7]. For the production of mix for experimental samples 0.25, 0.5, 1.0, 2.0 wt. % of MWCNT was added to varnish. The mixture was placed in a glass beaker. The mixture was sonicated by the ultrasonic device “Alena” (Biysk Technological Institute, Russia). Probe was inserted into a glass beaker with mixture. The mixture was sonicated for 1, 2, 3, 4 and 5 minutes at 50 VA power. Mixtures were molded into a planar plate, which size is 70.0 × 25.0 × 0.5 mm3. Notice that when volume concentration was increased, viscosity of mixture was increased. It was restricted to a concentration of MWCNTs at composite mixture.The process of polymerization was carried out for 48 h at the room temperature. The experimental samples used for microwave studies were thin strips 70.0 × 2.0 × 0.5 mm.Effect of Ultrasonic Treatment on Electromagnetic Properties of Composites Based on Multiwall Carbon Nanotubes at Microwave Frequency RangeAnastasia O. Kachusova, Olga A. Ulianova, Olga A. Dotsenko, Anna S. PolivanovaTomsk State University, Tomsk, Russia17th INTERNATIONAL CONFERENCE ON MICRO/NANOTECHNOLOGIES AND ELECTRON DEVICES EDM 2016 49B. Measuring equipmentThe cavity perturbation techniques were used for the evaluation of permittivity of experimental samples at SHF range. This technique is applicable for low loss samples and volume of the sample inserted should be very small in comparison to the volume of the empty cavity In this technique, a cavity was designed with a very small slot at the centre of the broad/short wall of rectangular waveguide in order to insert the sample material. The device consists of vector network analyzer, Agilent Technologies E8363B, and different volume multimode rectangular cavities that cover the frequency range 3 – 14 GHz. Measurements were made at temperature of 24 ± 1 °С.C. SHF range measurement The complex permittivities of experimental samples with different time of ultrasonic treatment at SHF range are shown in Fig. 1 – 4. The concentration of MWCNTs is equal to 0.5 wt. %. The complex permittivities of experimental samples 0.25, 1.0, 2.0 wt. % of MWCNTs have same character. The measurement error is about 5 percent for real part of permittivity and about 10 percent for imaginary part of permittivity. Fig. 1. Real permittivity of composites based on MWCNT – 2 for different time of ultrasonic treatmentFig. 2. Imaginary  permittivity of composites based on MWCNT – 2 for different time of ultrasonic treatmentFig. 3. Real permittivity of composites based on MWCNT – 3 for different time of ultrasonic treatmentFig. 4. Imaginary  permittivity of composites based on MWCNT – 3 for different time of ultrasonic treatmentIII. DISCUSSION OF RESULTSUrethane alkyd varnish has values of the permittivity 4 arb. un. at the frequency range 3 – 14 GHz [13]. Figs. 1 and 3 show that the composite based on 0.5 wt. % nanotubes has increased values of permittivity. The values of permittivity of composites based on MWCNTs–2 and MWCNTs–3 are different. The ratio of imaginary permittivity of MWCNTs–3 to imaginary permittivity of MWCNTs–2 is equal to 8 (see Figs. 2 and 4). The large values of the real and imaginary permittivity of composite based on MWCNTs–3 are caused by a large percentage of impurities. Firstly, MWCNTs–3 contain remainders of catalyst about 7.0 %. Secondly, MWCNTs–3 diameter is twice as much as MWCNTs–2 diameter. The ultrasonic treatment modifies the dielectric properties of the composite. For example, the sonication during 2 min MWCNTs–2 increased the value of real permittivity from 4.0 till 7.5 arb. un. (Fig. 1) The frequency dependenсe of both real and imaginary permittivity was not observed. Under such conditions polymer composite is nonpolar dielectric. 50 17th INTERNATIONAL CONFERENCE ON MICRO/NANOTECHNOLOGIES AND ELECTRON DEVICES EDM 2016The increase of treatment time leads to emergence of the orientational polarization and there appears the frequency dependences of permittivity. This may be caused by the distraction of MWCNTs agglomerates is a reason of this fact. The sonication during 2 min MWCNTs–3 decreased the value of real permittivity from 9.0 till 5.0 arb. un. (Fig. 3). MWCNTs–3 have many defects. They are destroyed by the ultrasonic treatment. The volume content of the amorphous part is increased in the composite. It leads to decreasing both real and imaginary permittivity (Figs. 3, 4).IV. CONCLUSIONIn this paper we investigated MWCNTs composite materials. Polymer composite materials, containing 0.5, 0.5, 1.0, 2.0 wt. % concentrations of multiwall carbon nanotubes and varnish as matrix were prepared. Multiwall carbon nanotubes/varnish mixtures were treated ultrasonically before polymerization [8]. The time of ultrasonic treatment was 1 – 5 minutes. The differences in electrical behaviors of varnish/MWCNTs polymer composites are traceable to the ultrasonic treatment. It is shown that adding nanotubes increases permittivity of materials. The main conclusion is that electromagnetic responses of multiwall carbon nanotubes/varnish composite are very sensitive to the time of ultrasonication.ACKNOWLEDGMENTThe authors would like to thank the Center Radiophysical measurements, diagnostics and research parameters of natural and artificial materials of Tomsk State University for the equipment provided. Authors are thankful to V. A. Zhuravlev, V.I. Suslyaev and K.O. Dorozhkin of National Research Tomsk State University for helping in measurements and discussions during the course of this work.Synthesis of materials is supported by Tomsk State University Competitiveness Improvement Program. Measurements of elec-tromagnetic parameters are supported by Russian Federation Presidents grant МК-6957.2015.8.REFERENCES[1] Muradyan V.E., Sokolov E.A., Babenko S.D., Moravsky A.P. Microwave Dielectric Properties of Composites Modified by Carbon Nanostructures // Technical Physics. 2010. Vol. 55. No. 2. pp. 242-246.[2] Mazov I.N., Kuznetsov V.L., Moseenkov S.I., Ishchenko A.V., Romanenko A.I., Anikeeva O.B., Buryakov T.I., Korovin E.Yu., Zhuravlev V.A., Suslyaev V.I. Electrophysical and Electromagnetic Properties of Pure MWNTs and MWNT / PMMA Composite Materials Depending on Their Structure // Fullerenes, Nanotubes and Carbon Nanostructures. 2010. Vol. 18. No. 4. pp. 505-515.[3] Dotsenko O.A., Frolov K.O. Microwave Composite Absorbers Based on Barium Hexaferrite/Carbon Nanotubes for 0.01– 18 GHz Applications // Key Engineering Materials. 2016. Vol. 685. pp. 535-557.[4] Zarate-Triviño D.G., Prokhorov E., Luna-Bárcenas G., Mendez-Nonell J., Gon-zález-Campos J.B., Elizalde-Peña E., Mota-Morales Josué D., Santiago-Jacinto P., Terrones M., Gómez-Salazar S., Nuño-Donlucas S.M., Sanchez I.C. The effect of CNT functionalization on electrical and relaxation phenomena in MWCNT/chitosan composites // Materials Chemistry and Physics. 2015. Vol. 155. pp. 252-261.[5] Kuleshov G.E., Dotsenko O.A., Ulyanova O.A., Suslyaev V.I. Interaction of microwave radiation with composites containing nanosized hexaferrite, multiferroics, carbon nanostructures and silicon binder // Int. J. Nanotechnol. 2015. Vol. 12. No. 3/4. pp. 200-208.[6] Sedelnikova O.V., Kanygin M.A., Korovin E.Y., Bulusheva L.G., Suslyaev V.I., Okotrub A.V. Effect of fabrication method on the structure and electromagnetic response of carbon nanotube/polystyrene composites in low-frequency and Ka bands // Composites Science and Technology. 2014. Vol. 102. No. 6. pp. 59-64.[7] Savi P., Miscuglio M., Giorcelli M., Tagliaferro A. Analysis of Microwave Absorbing Properties of Epoxy MWCNT Composites // Progress In Electromagnetics Research Lett   ers. 2014. Vol. 44. pp. 63-69.[8] Dotsenko O.A., Kachusova A.O. Influence of Ultrasonic Treatment on Electromagnetic Characteristics of Composites Based on Multiwall Carbon Nanotubes at Microwave Frequencies // Key Engineering Materials. 2016. Vol. 683. pp. 65-70.[9] Emelyanov E.V., Suslyaev V.I., Dunaevskii G.E., Zhuravlev V.A., Kuznetsov V.L., Moseenkov S.I., Mazov I.N. Terahertz transmission spectra of composite materials based on MWCNT with different time of ultrasonic processing // 37th IRMMW-THz International Conference, Wollongong, Australia, Sept. 23-28, 2012. p. 6380147.[10] Frmyr T R, Hansen F K, Olsen T. The optimum dispersion of carbon nanotubes for epoxy nanocomposites: evolution of the particle size distribution by ultrasonic treatment // J. of Nanotechnol. 2012. Vol. 2012. Article ID 545930, 14 p.[11] Ponnamma D., Sadasivuni K.K., Grohens Y., Guod Q., Thomas S. Carbon nanotube based elastomer composites – an approach towards multifunctional materials // J. Mater. Chem. C. 2014. Vol. 2.No. 40. pp. 8446-8485.[12] Mazov I., Kuznetsov V., Romanenko A. and Suslyaev V. Properties of MWNT-Containing Polymer Composite Materials Depending on Their Structure” in Composites and Their Properties / Edited by Ning Hu. – INTECH, ISBN: 978-953-51-0711-8, DOI: 10.5772/48245[13] Dotsenko O.A., Kochetkova O.A., Wagner D.V., Chernobrova D.A., Zhuravlyova Y.V. Influence magnetic and dielectric nanostructures fillers on electromagnetic characteristics of composite // International Siberian Conference on Control and Communications (SIBCON) Proceedings, Siberian Federal University, Krasnoyarsk, 2013, pp. 019n437-1-5. (In Russian)Anastasia O. Kachusova (1994) is student of National Research Tomsk State University, Faculty of Radiophysics. Her research activities deal with influence of ultrasonic treatment on electromagnetic characteristics of composites based on multiwall carbon nanotubes at microwave frequencies.Olga A. Ulianova (1990) is postgraduate student of National Research Tomsk State University, Faculty of Radiophysics. Her research activities deal with electromagnetic properties of radio materials in the microwave range and the analysis of measurement methods for the microwave characterization of materials.Olga A. Dotsenko (1968) received the Ph.D. degree in radiophysics from the Tomsk State University, Russia, in 2007.Presently, she is lecturer at National Research Tomsk State University, Faculty of Radiophysics. Her research activities deal with electromagnetic wave propagation in magnetic and dielectric materials and the analysis of measurement methods for the microwave characterization of materials, and modeling of magnetic and dielectric materials.17th INTERNATIONAL CONFERENCE ON MICRO/NANOTECHNOLOGIES AND ELECTRON DEVICES EDM 2016 51Anna S. Polivanova (1995) is a student of Na-tional Research Tomsk State University, Facul-ty of Radiophysics. Her research interests – nu-merical modeling of electrodynamics waveguide devices.

Effect of ultrasonic treatment on electromagnetic properties of composites based on multiwall carbon nanotubes at microwave frequency range

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Effect of ultrasonic treatment on electromagnetic properties of composites based on multiwall carbon nanotubes at microwave frequency range

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