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Materials combining conducting polymers and noble metals
Bober, Patrycja Magdalena ; Stejskal, Jaroslav (advisor) ; Omastová, Mária (referee) ; Pron, Adam (referee)
Polyaniline-silver composites combine the electrical properties of metals and the material properties of polymers. Polyaniline is one of the most studied conducting polymers on account of high electrical conductivity (units S cm-1 ), environmental stability, ease of preparation from common chemicals, good processibility and low cost. Silver is well known because of its highest conductivity among metals (500 000 S cm−1 ), antibacterial properties, and low price compared to other noble metals. Aniline was oxidized with silver nitrate in acidic aqueous medium to polyaniline-silver composite. The presence of different organic acids was studied. The most promising became methanesulfonic acid solution, in which most problems (such as inhomogeneity of samples and limited solubility of silver salts) got solved. The oxidation of aniline with silver nitrate is slow and takes over several months to get a reasonable yield. An addition of a small amount of p-phenylenediamine, even 1 mol. % relative to aniline, shortens the reaction time to several hours or even to tens of minutes. Small amounts of ammonium peroxydisulfate had similar effect. The content of silver in composites is fixed by the stoichiometry of reaction, and composites always contain ≈70 wt.% of silver. By using mixed oxidants, silver nitrate and...
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Catalytic synthesis of polyanilines
Bláha, Michal ; Vohlídal, Jiří (advisor) ; Omastová, Mária (referee) ; Trchová, Miroslava (referee)
This Ph.D. thesis is dealing with catalytic polymerization of aniline (ANI) and partially also of substituted anilines with FeCl3/H2O2 catalyst system, in which according to obtained results both active species, Fe3+ and HO , participate in the overall polymerization mechanism, creating a synergic system. The Fe3+ /H2O2 catalyst system, also called Fenton's system can considerably lower contamination of forming neat polyanilines (PANIs) by side-products characteristic of stoichiometric polymerization. However, catalytically prepared PANIs exhibit reduced conductivity related most probably to side reactions involving radicals generated as integral components of the FeCl3/H2O2 system. Catalytic polymerization of ANI with FeCl3/H2O2 system was found to be the reaction of approx. 2nd order with respect to ANI and gives PANIs of a good quality only when [H2O2] in the reaction mixture was kept low, i.e., at under- stoichiometric ratios [H2O2]/[ANI]. At over-stoichiometric ratio [H2O2]/[ANI], PANIs of lowered conductivity, worse spectroscopic characteristics and increased size of PANI nanostructures were obtained; nevertheless, these PANIs were not over-oxidized to pernigraniline state. The reaction-time profiles of the open-circuit potential of reaction mixtures exhibited an inflection related to the...
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Materials combining conducting polymers and noble metals
Bober, Patrycja Magdalena ; Stejskal, Jaroslav (advisor) ; Omastová, Mária (referee) ; Pron, Adam (referee)
Polyaniline-silver composites combine the electrical properties of metals and the material properties of polymers. Polyaniline is one of the most studied conducting polymers on account of high electrical conductivity (units S cm-1 ), environmental stability, ease of preparation from common chemicals, good processibility and low cost. Silver is well known because of its highest conductivity among metals (500 000 S cm−1 ), antibacterial properties, and low price compared to other noble metals. Aniline was oxidized with silver nitrate in acidic aqueous medium to polyaniline-silver composite. The presence of different organic acids was studied. The most promising became methanesulfonic acid solution, in which most problems (such as inhomogeneity of samples and limited solubility of silver salts) got solved. The oxidation of aniline with silver nitrate is slow and takes over several months to get a reasonable yield. An addition of a small amount of p-phenylenediamine, even 1 mol. % relative to aniline, shortens the reaction time to several hours or even to tens of minutes. Small amounts of ammonium peroxydisulfate had similar effect. The content of silver in composites is fixed by the stoichiometry of reaction, and composites always contain ≈70 wt.% of silver. By using mixed oxidants, silver nitrate and...
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Catalytic synthesis of polyanilines
Bláha, Michal ; Vohlídal, Jiří (advisor) ; Omastová, Mária (referee) ; Trchová, Miroslava (referee)
This Ph.D. thesis is dealing with catalytic polymerization of aniline (ANI) and partially also of substituted anilines with FeCl3/H2O2 catalyst system, in which according to obtained results both active species, Fe3+ and HO , participate in the overall polymerization mechanism, creating a synergic system. The Fe3+ /H2O2 catalyst system, also called Fenton's system can considerably lower contamination of forming neat polyanilines (PANIs) by side-products characteristic of stoichiometric polymerization. However, catalytically prepared PANIs exhibit reduced conductivity related most probably to side reactions involving radicals generated as integral components of the FeCl3/H2O2 system. Catalytic polymerization of ANI with FeCl3/H2O2 system was found to be the reaction of approx. 2nd order with respect to ANI and gives PANIs of a good quality only when [H2O2] in the reaction mixture was kept low, i.e., at under- stoichiometric ratios [H2O2]/[ANI]. At over-stoichiometric ratio [H2O2]/[ANI], PANIs of lowered conductivity, worse spectroscopic characteristics and increased size of PANI nanostructures were obtained; nevertheless, these PANIs were not over-oxidized to pernigraniline state. The reaction-time profiles of the open-circuit potential of reaction mixtures exhibited an inflection related to the...
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