Effects from various initial molar ratios of aniline (AN), ammonium peroxydisulfate (APS) and HCl ( [AN]: [APS]: [HCl]) on the polymerization of AN were investigated. First, a scheme derived from a molecular point of view was proposed to distinguish formation mechanisms based on their initial conditions. Thereafter, by choosing a relatively low ratio of Keywords: aniline; formation mechanism; phenazine-like oligomers; polyaniline INTRODUCTION Polyaniline (PANI) is one of the most important conducting and semi-conducting polymers widely used in organic optoelectronic devices and has attracted considerable attention recently because of its tunable electrical conductivity, easy preparation from common chemicals and excellent thermal and environmental stabilities. 1,2 The electrical properties of PANI are sensitively dependent on its oxidation and protonation states, of which the emeraldine state (see Figure 1) with a wide range of electrical conductivity can be achieved by simple doping/dedoping chemistry based on acidic/basic reactions. 1-3 The conventional chemical oxidative polymerization of aniline (AN) is carried out in a strong acidic solution and initiated by adding an oxidant (such as ammonium peroxydisulfate, APS). 3 From a technical point of view, the above-mentioned preparation for PANI is a simple process, but the formation mechanism involves an intricate interplay of consecutive chemical and physical reactions. [3][4][5][6][7][8][9][10][11][12] To account for the formation of PANI, the following basic mechanisms were reported. The redox reaction of neutral ANs with APS produces AN radicals. 4 Under a neutral or alkaline condition, the mixed ortho-para coupling of AN radicals together with oxidative intramolecular cyclization forms AN oligomers with phenazine-like structures at the initial stage (see Figures 2a and b for phenazine and phenazine-like trimer). 9-13 The oxidation of AN and AN oligomers with APS both release protons, and the pH of the solution falls. [12][13][14][15][16][17][18][19][20] In a strong acidic environment, the formation of a para-coupled structure
A series of sol-gel derived organic-inorganic hybrid coatings consisting of organic epoxy resin and inorganic silica were successfully synthesized through sol-gel approach by using 3-glycidoxypropyl-trimethoxysilane as coupling agent. Transparent organicinorganic hybrid sol-gel coatings with different contents of silica were always achieved. The hybrid sol-gel coatings with low silica loading on cold-rolled steel coupons were found much superior improvement in anticorrosion efficiently. The as-synthesized hybrid sol-gel materials were characterized by Fourier-transformation infrared spectroscopy, 29 Si-nuclear magnetic resonance spectroscopy and transmission electron microscopy. Effects of the material composition of epoxy resins along with hybrid materials on the thermal stability, Viscoelasticity properties and surface morphology were also studied, respectively.
A new and effective method has been developed where self-assembled gold nanoparticles (Au-NPs) of ∼10 nm diameter are successfully attached onto the surface of sidewalls and ends of thiol-terminated multi-walled carbon nanotubes (MWNTs) functionalized with orthomercaptoaniline, acting as a bridging agent. It can bridge the carbon nanotubes (CNTs) and Au-NPs via the bi-functional moiety with benzene unit at one end and thiol group at the other end by self-assembly. The ortho-mercaptoaniline was first grafted onto the surface of the CNTs via π-π interaction between the benzene ring of the mercaptoaniline and π-conjugated body of MWNTs surface to produce thiol-terminated CNTs. The bare surface of Au-NPs facilitates to attach on the thiol group of the thiol-terminated CNTs. Attenuated total reflectance FTIR, UV-visible, Raman spectroscopy and X-ray powder diffraction studies were used to verify whether the mercapto-benzene moieties have been attached to the π-conjugated body of functionalized MWNTs. The direct evidence is obtained from transmission electron microscope (TEM) images where selfassembled Au-NPs are attached onto the functionalized MWNTs.
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