Preparation and electromagnetic properties of chitosan-decorated ferrite-filled multi-walled carbon nanotubes/polythiophene composites

doi:10.1016/j.compscitech.2014.05.013

Composites Science and Technology

Volume 99, 30 July 2014, Pages 141-146

https://doi.org/10.1016/j.compscitech.2014.05.013 Get rights and content

Abstract

The chitosan-decorated ferrite-filled multi-walled carbon nanotubes (MWCNTs)/polythiophene composites were synthesized through in situ chemical polymerization of thiophene in the presence of the chitosan-decorated ferrite-filled MWCNTs. The structure of the samples was characterized by Fourier transform infrared spectroscopy, X-ray diffraction. The shape and size were observed by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The properties of the samples were tested with the vibrating sample magnetometer and the four-probe conductivity tester. The results showed that chitosan has been decorated onto the surface of MWCNTs. And the MWCNTs have been filled with a large number of ferrite crystals. And the chitosan-decorated ferrite-filled MWCNTs have also been coated with polythiophene. The magnetic saturation value of the chitosan-decorated ferrite-filled MWCNTs/polythiophene composites has achieved 0.18 emu/g, and the conductivity is 1.613 S/cm. Finally, based on the experimental results, the probable formation mechanism of this composite has been investigated.

Introduction

In recent years, functional materials have played an important role in the field of civilian economic construction and national defense. In particular, materials with electromagnetic function have been the subject of extensive research. For example, nanoscale particles of oxides have been dispersed in conductive polymers such as polyaniline [1], [2], [3], [4], [5], [6], [7], [8], polypyrrole [9], polythiophene derivatives [10], [11], polyacrylamide [12] and phenylalanine [13]. The resulting composites of nanoscale magnetic particles and organic polymeric materials have been extensively studied. Because the combination of these materials has the potential to create new electromagnetic materials.

Meanwhile, Carbon nanotubes (CNTs) have been characterized by their high aspect ratio, high Young’s modulus, chemical stability, nanometric dimensions, and interesting electrical properties, especially high permittivity [14]. Multiwalled carbon nanotube (MWCNT)-magnetic composites have been created through the assembly of Zn single bond Sn substituted strontium ferrite film onto the surface of MWCNTs [15]. Wang et al. [16] have synthesized the ferrite-MWCNT composites using a sol–gel method. And the CNTSrFe₁₂O₁₉ composites have been produced using a sol–gel method by Li et al. [17]. The CoFe₂O₄/MWCNT composites were produced by electrospinning a dispersion of MWCNTs in a solution of polyvinylpyrrolidone, iron (Ш) nitrate nonahydrate, cobalt (П) acetate tetrahydrate, absolute ethanol, and H₂O [18]. The γ-Fe₂O₃/carbon composites exhibit strong absorption characteristics with an absorption peak of −32.0 dB at 6.4 GHz [19]. Despite significant progress with the above studies, new approaches to prepare the multifunctional MWCNT-magnetic composites with control are highly needed.

Herein, we present a general approach to obtaining a new electromagnetic composite. This approach used a wet chemical online-filled method to prepare the ferrite-filled MWCNTs and in situ chemical synthesis of the chitosan-decorated ferrite-filled MWCNTs/polythiophene composites. The decoration of chitosan onto the surface of the ferrite-filled MWCNTs has improved the dispersion of the ferrite-filled MWCNTs in the matrix of polythiophene. And it reduces the agglomeration of the ferrite-filled MWCNTs. Furthermore, this method has been expected to be applicable for the preparation of other MWCNT-magnetic composites such as surfactant-decorated M_xFe₂₋_xO₄-filled MWCNTs/conductive polymer composites (M = Co, Zn, Ni, Mn, Cu) for use in the electromagnetic devices.

Section snippets

Materials

In this study, MWCNTs (O.D. 20–30 nm, length 10–30 μm, purity >95%, Ash <0.5 wt.%, EC >10⁴ S/m), purchased from Beijing DK Nanotechnology Co. Ltd., were used directly without further purification. Chitosan (with a degree of deacetylation >90.0%) was obtained from Sinopharm Chemical Reagent Co. Ltd., and thiophene monomer was purchased from Sigma. All other chemicals were all analytical grade.

Preparation of the ferrite-filled MWCNTs

The composites were obtained through a wet chemical filled route. The typical preparation procedure for the

Polymerization

Fig. 1 illustrates the polymerization procedure for the chitosan-decorated ferrite-filled MWCNTs/polythiophene composites. First, Fe³⁺ was self-adsorbed into the inner surface of the MWCNTs through a gross suction effect in the mixed acid environment. The mixed acid environment was produced with a ratio of 3:1 concentrated nitric acid and concentrated sulfuric acid. Ferrite was formed onto the inner wall of MWCNTs during high-temperature calcination under argon. Second, chitosan was deposited

Conclusions

The results of FTIR, XRD, SEM and TEM indicate that the ferrite-filled MWCNTs, the chitosan-decorated ferrite-filled MWCNTs, and the chitosan-decorated ferrite-filled MWCNTs/polythiophene composites have been prepared successfully in this work, and there are interactions between chitosan and the ferrite-filled MWCNTs as well as between the chitosan-decorated ferrite-filled MWCNTs and polythiophene. VSM illustrates that the chitosan-decorated ferrite-filled MWCNTs/polythiophene composites

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 20904019 and 51273089), the Aviation Science Fund (Nos. 2011ZF56015 and 2013ZF56025), the Natural Science Foundation of Jiangxi Province (No. 20132BAB203018), the Key Laboratory of Photochemical Conversion and Optoelectronic Materials, TIPC, CSA (Nos. PCOM201228 and PCOM201130), the Jiangxi Province Education Department of Science and Technology Project (No. GJJ13491), the Jiangxi Province Youth

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Preparation and electromagnetic properties of chitosan-decorated ferrite-filled multi-walled carbon nanotubes/polythiophene composites

Abstract

Introduction

Section snippets

Materials

Preparation of the ferrite-filled MWCNTs

Polymerization

Conclusions

Acknowledgements

React Funct Polym

Eur Polym J

Mater Chem Phys

Colloids Surf A: Phys Eng Aspects

J Magn Magn Mater

Colloids Surf A: Phys Eng Aspects

J Phys Chem Solids

J Alloys Compd

Synth Met

Synth Met

Electrochim Acta