Polyanilines (PANI)/reduced graphene oxide (RGO) nanocomposites are chemically synthesized. Their structure and morphology are characterized by scanning and transmission electron microscopies, x-ray diffraction and Raman spectroscopy. In addition, the nanocomposites' electrical, thermal and thermoelectric (TE) transport characteristics are investigated as a function of RGO content. The power factor and figure of merit (ZT) of PANI/RGO hybrids are deduced from measurements of the electrical conductivity (σ), Seebeck coefficient (α) and thermal conductivity (κ). Experimental results reveal that the properties of PANI/RGO composites are inherently dependent on the volume fraction of RGO. It is observed that electrical percolation follows a 2D conduction process which takes place for samples having 0.099 vol% RGO content. Unlike electrical conductivity, the thermal conductivity of PANI/RGO increases only slightly with the RGO fraction and is successfully fitted using a modified MG-EMA model which provides an interfacial (PANI/RGO nanoplatelets) resistance (Rk) of 4.9 × 10(-10) m(2) K W(-1). This low Rk value is attributed to good interactions between the planar geometry of RGO platelets and PANI aromatic rings through π-π stackings as evidenced by Raman spectroscopy and x-ray studies. Compared to that of pure PANI, the TE performance of PANI/RGO composites exhibits a ZT enhancement of two orders of magnitude.
Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes.
Intrinsically conducting polymer (ICP) thin films are used as driving electrodes for Polymer-Dispersed Liquid-Crystals (PDLC) display devices. In order to investigate the electro-optical efficiency of these organic electrodes, three different kinds of conducting polymers, i.e. polyaniline doped with 10-camphorsulfonic acid (PANI(HCSA)), polypyrrole doped with dodecylbenzenesulfonic acid (PPY(DBSA)), and polyethylenedioxythiophene doped with polystyrenesulfonate (PEDOT(PSS)), were prepared or purchased, and coated either on glass or plastic substrates. Optical absorption studies in the UV-Vis range of the conducting polymer-coated substrates were first performed showing the presence of conducting species for the three types of polymers. The electrical characteristics of the resulting films were measured with the four-probes technique. PANI(HCSA) exhibits a higher conductivity sigma approximately 122 S x cm(-1) (RS=1.2x10(3) Omega x (-1)) compared to PPY(DBSA) sigma approximately 2.6 S x cm(-1) (RS=150.7x10(3) Omega x (-1)), and PEDOT(PSS) sigma approximately 1.6 S x cm(-1) (RS=637.3x10(3) Omega x (-1)). It is also shown that for a given conducting polymer, its electrical conductivity decreases when a plastic substrate is used. These observations have been related to significant morphological changes observed by scanning electron microscopy (SEM). A mixture of Norland Optical Adhesive 65 and nematic liquid-crystal E7 in the weight ratio (35:65) was used as precursor of the PDLC material. Better electro-optical responses (transmission properties, drive voltages and switching times) of PDLC films were obtained for devices prepared with (PPY(DBSA))-based electrodes. The electro-optical performances of the PDLC display devices also depend on the nature of the ICP substrate used.
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