无限稀释Igc技术测定聚苯胺导电态和非导电态表面物理化学性质和玻璃化转变的新方法

T. Hamieh, Khaled Chawraba, J. Lalevée, J. Toufaily
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引用次数: 1

摘要

我们的实验室进行了许多研究,通过使用反相气相色谱法(IGC)在无限稀释下测定聚合物和/或氧化物的物理化学和热力学性质。更具体地说,我们研究了固体基质与一些模型有机分子的相互作用及其酸碱性质,用刘易斯术语来说,就是通过确定酸性和碱性常数。本文拟结合IGC方法的新进展,对导电聚苯胺(PANI-HEBSA)和非导电聚苯胺(PANI-EB)的表面热力学热力学、跃迁现象、比相互作用和酸碱性质进行研究。利用该技术得到了正构烷烃在聚苯胺上吸附的净保留体积Vn和分散自由焓。PANI表面正构烷烃的表面能色散随温度的变化曲线表明,PANI- hebsa和PANI- eb分别在383K和430K处存在两个转变温度。正构烷烃的RTlnVn =f(1/T)曲线证实了上述结果。对吸附在聚苯胺上的极性分子的比自由焓的测定表明,聚苯胺- eb的玻璃化转变值发生了4K的变化。由其随温度的变化,推导出了不同极性分子的比焓值,并确定了表征固体底物的酸性常数KA和碱性常数KD。结果表明,聚苯胺的碱性比酸性强得多(约为碱性的2.6倍),在聚苯胺- eb的玻璃化转变附近,其酸碱性质显著增加。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
New Methods for the Determination of the Surface Physicochemical Properties and Glass Transition of Polyaniline in Conducting and Non-Conducting Forms by Using Igc Technique at Infinite Dilution
Many studies were devoted in our Laboratory to the determination of physico-chemical and thermodynamic properties of polymers and/or oxides by using the inverse gas chromatography (IGC) at infinite dilution. More particularly, we studied the interactions of solid substrates with some model organic molecules and their acid-base properties, in Lewis terms, by determining the acidic and basic constants. We proposed in this paper to study the surface thermodynamic energetics, transition phenomena, specific interactions and acid-base properties of both the conducting polyaniline (PANI-HEBSA) and the non-conducting form (PANI-EB) on the light of the new progresses of IGC methods. This technique was used to obtain the net retention volume Vn and then the dispersive free enthalpy of n-alkanes adsorbed on PANI. The curves of the dispersive component of the surface energy of n-alkanes adsorbed on PANI, as a function of the temperature highlighted the presence of two transition temperatures on 383K and 430K respectively for PANI-HEBSA and PANI-EB. There results were confirmed by the curves of RTlnVn =f(1/T) of n-alkanes. The determination of the specific free enthalpy of polar molecules adsorbed on PANI proved a shift of 4K in the value of the glass transition of PANI-EB. From the variation of as a function of the temperature, one deduced the values of the specific enthalpy of the various polar molecules and determined the acidic constant KA and basic constant KD, the two constants characterizing the solid substrate. It was showed that PANI is highly more basic than acidic (about 2.6 times more basic) and an increase of the acid-base character was highlighted near the glass transition for PANI-EB.
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