Elsevier

Applied Clay Science

Volume 184, January 2020, 105395
Applied Clay Science

Research paper
Synthesis and characterization of conducting aniline and o-anisidine nanocomposites based on montmorillonite modified clay

https://doi.org/10.1016/j.clay.2019.105395Get rights and content

Highlights

  • “in-situ synthesis” of polyaniline/derivatives based nanocomposites;

  • Montmorillonite increase the solubility of polyaniline;

  • The polyaniline based nanocomposite presents a capacitor behavior;

  • More efficient electrochemical process in montmorillonite based nanocomposites;

Abstract

A study on clay mineral polymer nanocomposites (CPN), namely polyaniline/montmorillonite-cetyltrimethylammonium bromide (PANI/Mt-CTAB), poly o-anisidine/montmorillonite-cetyltrimethylammonium bromide (poly(o-ANIS)/Mt-CTAB) and poly o-anisidine-co-aniline/montmorillonite-cetyltrimethylammonium bromide (poly(o-ANIS-co-ANI)/Mt-CTAB), synthesized by oxidative chemical polymerization method is presented. The nanocomposites have been characterized by Fourier transform infrared spectroscopy, UV–vis spectroscopy, and cyclic voltammetry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, cyclic voltammetry and thermogravimetry and differential scanning calorimetry analysis. By UV–vis measurements different electronic transitions for the CPNs were pointed out. The voltammograms indicate that the synthetized materials are electroactive. The FTIR analysis reveals the characteristic bands of the polymers and of the Mt-CTAB. The shift of the bands to higher/lower wavenumbers demonstrate the interaction between the pristine polymers macromolecular chains and the montmorillonite (Mt). The intercalation of the polymers inside the mineral clay was confirmed by the increased interlayer distance connected with the position of the 011 diffraction plane of the Mt., and the intercalation and exfoliation states were highlighted in the scanning and transmission electron microscopy images.

The obtained results are encouraging in respect with the purpose to use them in the field of photovoltaic applications.

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).

References (88)

  • S. Jain et al.

    Oral extended release of dexamethasone: montmorillonite-PLGA nanocomposites as a delivery vehicle

    Appl. Clay Sci.

    (2015)
  • R. Kandulna et al.

    Robust electron transport properties of PANI/PPY/ZnO polymeric nanocomposites for OLED applications

    Optik (Stuttg)

    (2017)
  • E.T. Kang et al.

    Polyaniline: a polymer with many intrinsic

    Prog. Polym. Sci.

    (1998)
  • M. Kotal et al.

    Polymer nanocomposites from modified clays: recent advances and challenges

    Prog. Polym. Sci.

    (2015)
  • V. Krupskaya et al.

    The influence of acid modification on the structure of montmorillonites and surface properties of bentonites

    Appl. Clay Sci.

    (2019)
  • L. Kulhánková et al.

    Montmorillonite intercalated by conducting polyanilines

    J. Phys. Chem. Solids

    (2012)
  • L. Kulhánková et al.

    Electrically conductive and optically transparent polyaniline/montmorillonite nanocomposite thin films

    Thin Solid Films

    (2014)
  • W. Li et al.

    Dendrimer-like assemblies based on organoclays as multi-host system for sustained drug delivery

    Eur. J. Pharm. Biopharm.

    (2014)
  • N.G.R. Mathebe et al.

    Electrochemistry and scanning electron microscopy of polyaniline/peroxidase-based biosensor

    Talanta

    (2004)
  • A.C. Mocanu et al.

    Internal and external surface features of newly developed porous ceramics with random interconnected 3D channels by a fibrous sacrificial porogen method

    Appl. Surf. Sci.

    (2019)
  • K.M. Molapo et al.

    Electronics of conjugated polymers (I): polyaniline

    Int. J. Electrochem. Sci.

    (2012)
  • L.B. de Paiva et al.

    Organoclays: properties, preparation and applications

    Appl. Clay Sci.

    (2008)
  • D. Patil et al.

    Humidity sensing properties of poly(o-anisidine)/WO3 composites

    Sensors Actuators B Chem.

    (2008)
  • D. Patil et al.

    Poly(o-anisidine)-tin oxide nanocomposite: synthesis, characterization and application to humidity sensing

    Sensors Actuators B Chem.

    (2010)
  • D. Profeti et al.

    Methanol electrooxidation on platinum microparticles electrodeposited on poly (o-methoxyaniline) films

    Electrochim. Acta

    (2004)
  • E.A. Sanches et al.

    Structural characterization of Chloride Salt of conducting polyaniline obtained by XRD, SAXD, SAXS and SEM

    J. Mol. Struct.

    (2013)
  • Z. Shen et al.

    Comparison of solution intercalation and melt intercalation of polymer-clay nanocomposites

    Polymer (Guildf)

    (2002)
  • D.T.C. Silva et al.

    Tamoxifen/montmorillonite system – effect of the experimental conditions

    Appl. Clay Sci.

    (2019)
  • S. Sinha Ray et al.

    Polymer/layered silicate nanocomposites: a review from preparation to processing

    Prog. Polym. Sci.

    (2003)
  • Z.M. Sui et al.

    Capping effect of CTAB on positively charged Ag nanoparticles

    Phys. E Low-Dimensional Syst. Nanostructures

    (2006)
  • J. Tang et al.

    Infrared spectra of soluble polyaniline

    Synth. Met.

    (1988)
  • Y. Xi et al.

    Structure of organoclays - an X-ray diffraction and thermogravimetric analysis study

    J. Colloid Interface Sci.

    (2004)
  • W. Xue et al.

    FTIR investigation of CTAB-Al-montmorillonite complexes

    Spectrochim. Acta A Mol. Biomol. Spectrosc.

    (2007)
  • W. Xue et al.

    FTIR investigation of CTAB–Al–montmorillonite complexes

    Spectrochim. Acta A Mol. Biomol. Spectrosc.

    (2007)
  • O. Yayapao et al.

    CTAB-assisted hydrothermal synthesis of tungsten oxide microflowers

    J. Alloys Compd.

    (2011)
  • W.H. Yu et al.

    Clean production of CTAB-montmorillonite: formation mechanism and swelling behavior in xylene

    Appl. Clay Sci.

    (2014)
  • H. Zengin et al.

    Synthesis and characterization of polyaniline/activated carbon composites and preparation of conductive films

    Mater. Chem. Phys.

    (2010)
  • T.T. Zhu et al.

    Exfoliation of montmorillonite and related properties of clay/polymer nanocomposites

    Appl. Clay Sci.

    (2019)
  • K. Amer et al.

    Organic field effect transistor based on polyaniline-dodecylbenzene sulphonic acid for humidity sensor

    Natl. Radio Sci. Conf. NRSC Proc.

    (2017)
  • C.O. Baker et al.

    Polyaniline nanofibers: broadening applications for conducting polymers

    Chem. Soc. Rev.

    (2017)
  • A.D. Bhagwat et al.

    Facile rapid synthesis of polyaniline (PANI) nanofibers

    J. Nano-Electron. Phys.

    (2016)
  • J.L. Bishop et al.

    Infrared spectroscopic analyses on the nature of water in montmorillonite

    Clay Clay Miner.

    (1994)
  • J.L. Bonczek et al.

    Monolayer to bilayer transitional arrangements of hexadecyltrimethylammonium cations on Na-Montmorillonite

    Clay Clay Miner.

    (2002)
  • A.D. Borkar et al.

    Oxidative copolymers of aniline with o-anisidine: their structure and ion exchange properties

    Mater. Res. Innov.

    (2011)
  • Cited by (17)

    • Nanocomposite-based functional materials: Synthesis, properties, and applications

      2022, Functional Materials from Carbon, Inorganic, and Organic Sources: Methods and Advances
    • Novel trends in conductive polymeric nanocomposites, and bionanocomposites

      2021, Synthetic Metals
      Citation Excerpt :

      Hence, from this perspective, researches on designing of electrically conducting substrates for biotechnologically and biomedically usages have garnered high interests [211]. CPs are presently essential materials capable of being utilized within biotechnologically and biomedically focused fields like biosensing devices [212,213], neural electrode devices [214], bio-activating agents [215], wound repairing and manipulative releasing mechanisms [216], and tissue scaffolding [217,218], because of inherent electrically aligned attribute, along with biocompatibility [219]. Usage of CPs in these applications is further enabled through CPs preparation within super-porously biocompatible cryogels (CG).

    • Conducting Polymer-Based Nanocomposites: Fundamentals and Applications

      2021, Conducting Polymer-Based Nanocomposites: Fundamentals and Applications
    • Synthesis and characterization of montmorillonite/polyaniline composites and its usage to modify a commercial separator

      2021, Journal of Electroanalytical Chemistry
      Citation Excerpt :

      The bands occurring at 1288 and 1239 cm−1 in MMT/PANI_12/88 are attributed to the stretching vibration of C-N+ benzenoid and quinoid (υC-N+), respectively. These bands are generally related to the delocalization of the π-electron induced in the polymer by protonation [9,20] and confirm the existence of PANI as emeraldine salt. In MMT/PANI_87/13 sample, these bands are shifted to 1308 and 1254 cm−1 respectively, indicating the interaction between the N+ groups and the negative surface of the clay [37], in agreement with TG analyses.

    View all citing articles on Scopus
    View full text