Comprehensive modelling strategy for gas transport in polymers: Analysis of swelling and non-swelling agents at high pressures

IF 2.7 3区 工程技术 Q3 CHEMISTRY, PHYSICAL Fluid Phase Equilibria Pub Date : 2024-12-10 DOI:10.1016/j.fluid.2024.114311
Roberta Di Carlo , Eleonora Ricci , Matteo Minelli
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Abstract

Gas transport in polymers is a process governed by the interplay between polymeric structure, gas properties, and operating conditions. This work analyzes the solubility and transport properties of different gases in five different industrially relevant polymeric systems, such as Matrimid/P84 polyimide blends, perfluorosulfonic acid membrane (PFSA) Nafion, as well as natural rubber (NR), silicone rubber (PDMS) and a fluorinated rubber (FKM), using a thermodynamic modeling framework, with focus on high-pressure conditions. Specifically, equations of state (EoS) and non-equilibrium thermodynamic for glassy polymers (NET-GP) approaches are able to describe gas solubility, and are combined to the Standard Transport Model (STM) to estimate diffusivity and permeability at various temperatures and pressures, with emphasis on the comparison of swelling and non-swelling penetrants, free-volume variations, and plasticization phenomena.
The results obtained reveal the ability of the models to describe the complex experimental behaviors, including challenging systems, such as glassy polymer blends or PFSA membranes. A thorough analysis of the gas transport and sorption properties in the different systems with the penetrant characteristics and with the polymer response to sorption is then performed to elucidate the prevailing effect shaping the behavior of the various systems. Therefore, the model proved to be a powerful tool to inspect the high-pressure induced changes in gas transport, and to predict the solubility and permeability properties in a wide range of conditions.

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聚合物中气体输运的综合建模策略:高压下膨胀剂和非膨胀剂的分析
聚合物中的气体输运是由聚合物结构、气体性质和操作条件之间的相互作用决定的过程。这项工作分析了五种不同工业相关聚合物体系中不同气体的溶解度和传输特性,如Matrimid/P84聚酰亚胺共混物,全氟磺酸膜(PFSA) Nafion,以及天然橡胶(NR),硅橡胶(PDMS)和氟化橡胶(FKM),使用热力学建模框架,重点是高压条件。具体来说,玻璃聚合物的状态方程(EoS)和非平衡热力学(NET-GP)方法能够描述气体溶解度,并与标准输运模型(STM)相结合,以估计不同温度和压力下的扩散率和渗透率,重点是溶胀渗透剂和非溶胀渗透剂、自由体积变化和塑化现象的比较。得到的结果表明,模型能够描述复杂的实验行为,包括具有挑战性的系统,如玻璃状聚合物共混物或PFSA膜。然后,对不同系统中具有渗透特性和聚合物对吸附的响应的气体传输和吸附特性进行了彻底的分析,以阐明形成各种系统行为的主要影响。因此,该模型被证明是一种强有力的工具,可以检测高压引起的气体输运变化,并预测各种条件下的溶解度和渗透率。
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来源期刊
Fluid Phase Equilibria
Fluid Phase Equilibria 工程技术-工程:化工
CiteScore
5.30
自引率
15.40%
发文量
223
审稿时长
53 days
期刊介绍: Fluid Phase Equilibria publishes high-quality papers dealing with experimental, theoretical, and applied research related to equilibrium and transport properties of fluids, solids, and interfaces. Subjects of interest include physical/phase and chemical equilibria; equilibrium and nonequilibrium thermophysical properties; fundamental thermodynamic relations; and stability. The systems central to the journal include pure substances and mixtures of organic and inorganic materials, including polymers, biochemicals, and surfactants with sufficient characterization of composition and purity for the results to be reproduced. Alloys are of interest only when thermodynamic studies are included, purely material studies will not be considered. In all cases, authors are expected to provide physical or chemical interpretations of the results. Experimental research can include measurements under all conditions of temperature, pressure, and composition, including critical and supercritical. Measurements are to be associated with systems and conditions of fundamental or applied interest, and may not be only a collection of routine data, such as physical property or solubility measurements at limited pressures and temperatures close to ambient, or surfactant studies focussed strictly on micellisation or micelle structure. Papers reporting common data must be accompanied by new physical insights and/or contemporary or new theory or techniques.
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