Highly conductive and thermally stable nanoparticle-conjugated polymer compounds through environmentally friendly in situ synthesis

doi:10.1016/j.porgcoat.2020.105606

Progress in Organic Coatings

Volume 142, May 2020, 105606

https://doi.org/10.1016/j.porgcoat.2020.105606 Get rights and content

Highlights

•
An environmentally-friendly in situ synthesis of nano-compounds is introduced.
•
The water-based synthesis enables the polymerization incorporating of nanoparicles.
•
The Ag nanoparticles enhanced the thermal stability and electrical conductivity of Ag-PPY:PSS.
•
The conductivity of Ag-PPY:PSS was well tuned by controlling the weight percentage of Ag nanoparticles.

Abstract

In this paper, an environmentally-friendly in situ synthesis of highly conductive and thermally stable nanoparticle-conjugated polymer nano-compounds is introduced. The water-based in situ chemical synthesis enables the successful polymerization of conductive, conjugated polypyrrole: polystyrene sulfonate (PPY:PSS) polymer and the incorporation of silver (Ag) nanoparticles without morphological deformation. The Ag nanoparticles dispersed within the PPY:PSS acted as a mass transport barrier, thus enhancing the thermal stability of the obtained Ag-PPY:PSS. In addition, the enhanced electrical conductivity of Ag-PPY:PSS was attributed to the embedded Ag nanoparticles generating a low-contact resistance conduction pathway, thereby facilitating inter-chain charge transport. Moreover, the conductivity of Ag-PPY:PSS was well tuned by controlling the weight percentage of Ag nanoparticles in the reaction mixture. The environmentally-friendly synthesis of highly conductive and thermally stable nano-compounds will contribute to the realization of next-generation green electronic applications.

Graphical abstract

Introduction

The synergistic physiochemical properties of nano-compound materials are attributed to the quantum size-effect and are expected to promote the utilization of such compounds in numerous fields such as optics, sensors, actuators, energy storage and memory devices [[1], [2], [3], [4], [5], [6], [7], [8], [9]]. Among the various organic and inorganic materials available for use as matrix materials in nano-compounds, the conjugated conducting polymers such as poly(aniline), poly(pyrrole), poly(acetylene), poly(3,4-ethylenedioxythiophene), poly(p-phenylenevinylene), poly(furan) and poly(thiophene) derivatives have been widely studied [10]. In particular, poly(pyrrole) or PPY is one of the most promising candidates due to a number of advantages, including relatively good conductivity, environmental stability and simplicity of synthesis [[11], [12], [13], [14]].

Many factors should be considered for a favorable material synthesis, such as improvement of electrical properties, stability, simplicity, processability, and environmental friendliness in response to recent global environmental issues [[15], [16], [17], [18], [19], [20], [21]]. Nevertheless, the synthetic methods proposed so far for PPY have a number of issues in this respect. While electrochemical polymerization is regarded as one of the most suitable techniques for growing a PPY thin-film on a working electrode, it is difficult to utilize for mass production and large-scale fabrication [22,23]. By contrast, the chemical oxidative polymerization technique is suitable for mass production of PPY, but it results in PPY with extremely poor processability [[24], [25], [26]]. However, the use of polystyrene sulfonate (PSS) dopant has been introduced as an effective way to overcome the processability and environmental problems [23,[27], [28], [29], [30], [31]]. Although water-dispersible PPY has been successfully prepared by using PSS as a dopant, the conductivity of the conjugated polymers was enhanced only up to a certain limit, which was insufficient for a wide range of electronic applications.

In the present work, an environmentally-friendly water-based synthesis of highly conductive and thermally stable PPY:PSS with incorporated Ag nanoparticles is suggested. The presence of embedded Ag nanoparticles in the PPY:PSS was confirmed by X-ray diffraction (XRD), ultraviolet-visible (UV–vis) absorption spectroscopy, energy dispersive X-ray (EDX) spectroscopy, and high resolution transmission electron microscopy (HR-TEM) study. The successful production of PPY:PSS was confirmed by Fourier transform infrared (FTIR) and solid state nuclear magnetic resonance (NMR) spectroscopy. The variation of current with the applied voltage of the prepared samples indicated that the presence of Ag nanoparticles as a guest material in the PPY:PSS polymer matrix improved the electrical charge transport mechanism and, hence, the conductivity, of the composite material. Furthermore, the decomposition temperature of Ag-PPY:PSS was increased compared to that of PPY:PSS because the Ag nanoparticles acted as a mass transport barrier, thereby restraining the polymer decomposition. The conductivity and thermal stability were well controlled by controlling the weight percentage of Ag nanoparticles.

Section snippets

Chemicals

Pyrrole (Alfa Aesar) was used after purification by low-pressure distillation. Ammonium peroxydisulfate (APS) and silver nitrate (AgNO₃ were provided by Samchun Chemicals. Camphor sulfonic acid CSA, Sigma Aldrich and PSS Alfa Aesar, MW 70,000 were used as received. Deionized DI water was produced using a pure RO 15 reverse osmosis system and used for further chemical processes.

Synthesis

In the present work, PSS-doped PPY with incorporated Ag nanoparticles was synthesized via an in situ chemical

Results and discussion

The presence of Ag nanoparticles embedded in the PSS-doped PPY was first confirmed by XRD and UV–vis absorption, as shown in Fig. 2. The XRD profiles of PPY:PSS and Ag-PPY:PSS with varying concentration of Ag nanoparticles are presented in Fig. 2(a). The presence of only one broad peak around 2θ = 24° in the XRD profile of the PPY:PSS indicates the formation of PSS-doped semi-crystalline PPY [32]. The XRD patterns of the Ag-PPY:PSS 1, Ag-PPY:PSS 2, and Ag-PPY:PSS 3 compounds exhibit one broad

Conclusion

A water-based environmentally-friendly in situ chemical polymerization process is proposed for the synthesis of PPY:PSS conjugated polymer with incorporated Ag nanoparticles. The PPY was successfully doped with PSS and Ag nanoparticles were incorporated into the PPY:PSS conjugated polymer matrix by stirring for a few hours at 1000 rpm and 0–5℃. This procedure allowed the successful synthesis of highly conductive and thermally stable Ag-PPY:PSS nano-compounds. The Ag nanoparticles embedded in

Author contributions

Conceptualization of this work was performed by Swarup Biswas, Do-Kyung Kim, Jin-Hyuk Bae and Hyeok Kim. Experiments were conducted by Swarup Biswas, Do-Kyung Kim and Il-Woo Nam. Data curation was performed by Swarup Biswas and Do-Kyung Kim and Il-Woo Nam. Formal analysis was performed by Do-Kyung Kim, Swarup Biswas. The results were analyzed by Do-Kyung Kim, Swarup Biswas, Muhan Choi and Jin-Hyuk Bae. The methodology was devised by Swarup Biswas. Muhan Choi, Jin-Hyuk Bae and Hyeok Kim were in

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by the Basic Science Research Program through the NRF funded by the Ministry of Education (NRF-2018R1D1A3B07049992) and Ministry of Trade, Industry, & Energy (MOTIE, Korea) under the Industrial Technology Innovation Program (No. 10063473), and Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2018R1A2B6008815). M. Choi also would like to acknowledge the National Research Foundation of Korea

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¹: These authors contributed equally to this work.

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Highly conductive and thermally stable nanoparticle-conjugated polymer compounds through environmentally friendly in situ synthesis

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals

Synthesis

Results and discussion

Conclusion

Author contributions

Declaration of Competing Interest

Acknowledgements

Inorg. Chem. Commun.

J. Mol. Catal. A Chem.

Nano Energy

J. Power Sources

Compos. Part B Eng.

Carbohydr. Polym.

J. Ind. Eng. Chem.

J. Ind. Eng. Chem.

J. Alloys Compd.

Appl. Catal. A Gen.

Sens. Actuators B-Chem.

Surf. Coat. Technol.

Colloid Surf. A Physicochem. Eng. Asp.

Polymer

Mater. Sci. Semicon. Proc.

Compos. B Eng.

Compos. Sci. Technol.

Eur. Polym. J.

Polymer

Synth. Met.

Colloids Surf. B

J. Ind. Eng. Chem.

Chem. Eng. J.

Solid State Commun.