Research paperSynthesis and characterization of conducting aniline and o-anisidine nanocomposites based on montmorillonite modified clay
Graphical abstract
Introduction
Montmorillonite (Mt) is a 2:1 layered hydrous aluminium silicate, having a nanolayer structure of 1 nm thickness and 200–300 nm the lateral dimension (Xue et al., 2007a). Member of the smectites group, characterized by high cation exchange capacities, surface area and adsorptive properties, is one of the most utilised for the preparation of the polymer nanocomposites (CPN), (Lee et al., 2000; Sinha Ray and Okamoto, 2003; Kulhánková et al., 2014; Bouabida et al., 2016; Verma and Riaz, 2019; Zhu et al., 2019), improving their properties when compared to the polymer alone or to the conventional micro/macro composites (Sinha Ray and Okamoto, 2003; Gupta et al., 2014; Zhu et al., 2019). These type of materials are frequently proposed for packaging, environmental or (bio)medical applications (Özdemir et al., 2006; Soon et al., 2007; de Paiva et al., 2008; Feng et al., 2009; Haroun et al., 2014; Li et al., 2014; Jain and Datta, 2015). Because the mineral clays have a hydrophilic nature that inhibit their capacity to disperse in a polymeric matrix, organic/inorganic emulsifying agents are used to replace interlayer cations, modifying their polarity, thus, increasing their affinity to organic components (Xu et al., 2008; Azeez et al., 2013; De León-Almazan et al., 2018). Usually, the CPNs are prepared by: a) melt-intercalation (Shen et al., 2002)-adequate for thermoplastic polymers, involving physical mixing and melting of the components and, b) solution intercalation (Feng et al., 2009) –adequate for water-soluble polymers due to the fact that implies a solvent in which both polymer and clay mineral can be mixed due to the solubility of the polymer and the clay swelling c) in-situ polymerization intercalation-characterized by the use of the monomers that are functionalised with the clay mineral before polymerization (Bober et al., 2010; Yamase and Goto, 2018).
Recently, the organic/inorganic compounds get interest in the worldwide technology due to the possibility to obtain hybrid materials with complimentary behaviour for further applications in electronics and electromagnetics (Hule and Pochan, 2007; Lerari and Benaboura, 2015; Daud et al., 2016; Nosheen et al., 2017). The hybrid materials combine the properties of the organic materials (e.g. flexibility, processability, variety) with those of the inorganic materials (e.g. thermal stability, conductivity) (Visakh et al., 2017). Moreover, it was reported that the conjugated polymer based nanomaterials can be implied in the fabrications of biocaptors, electrochemical devices, transistors, display nanowires or used as a corrosion inhibitor (Kim et al., 2005; Huang, 2006; Yeum et al., 2012; Naik and Shah, 2016; Vollick et al., 2017; Ouyang, 2018).
From the organic materials, the polyaniline (PANI), a conductive polymer, is often used to prepare nanocomposites due to its easy way of synthesis, low cost, environmental stability and large domain of application, mostly in electronic technology such as organic light emitting diodes (Kandulna and Choudhary, 2017), organic field effect transistors (Amer et al., 2017), transparent electrodes (Devarayan et al., 2015), microwave shield (Sasikumar et al., 2017) and gas detection (Sandaruwan et al., 2018; Zhu et al., 2018). The drawback of PANI is connected with its poor solubility, thus PANI/clay nanocomposites with different combination of the two components and with increased electrical, thermal and mechanical stability have attracted more and more attention due to the fact that the aniline monomer can be introduced into the interlayer space by ion exchange (Kim et al., 2005; Daud et al., 2016; De León-Almazan et al., 2018; Ouyang, 2018).
In the present case, the mineral clay was organomodified by the use of cetyltrimethylammonium bromide (CTAB) through cation exchange, replacing the metal ions with the organic cetyltrimethylammonium cations, thus increasing the interlayer distance that enables the monomers to enter between the layers and to polymerize (Kotal and Bhowmick, 2015). Further, the in-situ polymerization reaction of the aniline and o-anisidine monomers between the lamellar layers of the organo-modified clay (OMt) was done using ammonium peroxydisulphate (APS) as oxidizing agent. The resulting nanocomposites can be found in one or all three forms: exfoliated, intercalated or separated (Kim et al., 2002; Bober et al., 2010; Kazim et al., 2012).
In this context, this study is oriented on the synthesis and characterization of new nanocomposite materials based on different content of Mt-CTAB and conductive polymers: PANI/Mt-CTAB, poly(o-ANIS)/Mt-CTAB and poly (o-ANIS-co-ANI)/Mt-CTAB.
Section snippets
Materials
The utilised monomers, aniline (ANI), o-anisidine(o-ANIS) and the intercalation agent, (quaternary ammonium salt, cetyltrimethylammonium bromide-CTAB) have been bought from Sigma-Aldrich. The montmorillonite (also named Maghnite), a clay of Maghnia was extracted from a mine situated in Tlemcen (west of Algeria) and provided by ENOF Maghnia.
A distillation system (ElgaLab Water Purelab Ultra) was involved in the purification of water necessary for the preparation of NaCl and CTAB aqueous
Solubility tests
The solubility fundamentally depends on the physical and chemical properties of the solute and solvent as well as on temperature, pressure, polarization and presence of other chemicals properties of the solution (including changes to the pH) (Zhu et al., 2019). It is very important to know the solubility of the materials in various solvents, because depending on this can be chosen the deposition method for the preparation of thin films from the studied materials for further device applications (
Conclusion
The PANI/Mt-CTAB, poly(o-ANIS)/Mt-CTAB and poly(o-ANIS-co-ANI)/Mt-CTAB nanocomposites have been synthesized and characterized quantitatively and qualitatively. For the characterization, series of physicochemical analyses are realized such the XRD, UV–vis, FTIR, SEM, TEM, CV, TG and DSC. Nine different conducting nanocomposites materials were successfully synthesized by in-situ oxidative polymerization with high solubility in acetone, NMP and Chloroform.
The synthetized nanocomposites show both
Acknowledgments
All authors acknowledge Romanian Ministry of Research and Innovation in the framework of Core Program PN19-03 (contract no. 21 N/08.02.2019), and Algerian Ministry of Higher Education and Scientific Research for the financial support. A.K. acknowledges Algerian Ministry of Higher Education and Scientific Research for the received mobility research grant (no. 304/PNE/2018-2019) in the frame of Algerian Programme National Exceptionnel (PNE).
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