Duarte Jocelei, Raota Camila Suliani, Baldasso Camila, Dos Santos Venina, Zeni Mara
Postgraduate Program in Process and Technologies Engineering (PGEPROTEC), University of Caxias do Sul, Caxias do Sul 95070-560, RS, Brazil.
Postgraduate Program in Materials Science and Engineering (PPGMAT), University of Caxias do Sul, Caxias do Sul 95070-560, RS, Brazil.
Membranes (Basel). 2025 Jan 1;15(1):7. doi: 10.3390/membranes15010007.
The starting point for the preparation of polymeric membranes by phase inversion is having a thermodynamically stable solution. Ternary diagrams for the polymer, solvent, and non-solvent can predict this stability by identifying the phase separation and describing the thermodynamic behavior of the membrane formation process. Given the lack of data for the ternary system water (HO)/hydrochloric acid (HCℓ)/polyamide 66 (PA66), this work employed the Flory-Huggins theory for the construction of the ternary diagrams (HO/HCℓ/PA66 and HO/formic acid (FA)/PA66) by comparing the experimental data with theoretical predictions. Pure polymer and the membranes produced by phase inversion were characterized to provide the information required to create the ternary diagrams. PA66/FA and PA66/HCℓ solutions were also evaluated regarding their classification as true solutions, and the universal quasi-chemical functional group activity coefficient (UNIFAC) method was used for determining non-solvent/solvent interaction parameters (). Swelling measurements determined the polymer/non-solvent interaction parameter () for HO/PA66 and the solvent/polymer interaction parameter () for PA66/FA and PA66/HCℓ. The theoretical cloud point curve was calculated based on "Boom's LCP Correlation" and compared to the curve of the experimental cloud point. The ternary Gibbs free energy of mixing and indicated FA as the best solvent for the PA66. However, for HCℓ, the lower concentration (37-38%), volatility, and fraction volume of dissolved PA66 () indicated that HCℓ is also adequate for PA66 solubilization based on the similar membrane morphology observed when compared to the PA66/FA membrane.
通过相转化制备聚合物膜的起点是获得热力学稳定的溶液。聚合物、溶剂和非溶剂的三元相图可以通过识别相分离并描述膜形成过程的热力学行为来预测这种稳定性。鉴于水(HO)/盐酸(HCl)/聚酰胺66(PA66)三元体系缺乏数据,本工作采用弗洛里 - 哈金斯理论,通过将实验数据与理论预测进行比较来构建三元相图(HO/HCl/PA66和HO/甲酸(FA)/PA66)。对纯聚合物和通过相转化制备的膜进行了表征,以提供创建三元相图所需的信息。还评估了PA66/FA和PA66/HCl溶液作为真溶液的分类,并使用通用准化学官能团活度系数(UNIFAC)方法确定非溶剂/溶剂相互作用参数()。溶胀测量确定了HO/PA66的聚合物/非溶剂相互作用参数()以及PA66/FA和PA66/HCl的溶剂/聚合物相互作用参数()。基于“Boom的LCP相关性”计算了理论浊点曲线,并与实验浊点曲线进行了比较。混合的三元吉布斯自由能和表明FA是PA66的最佳溶剂。然而,对于HCl,较低的浓度(37 - 38%)、挥发性和溶解的PA66的分体积()表明,与PA66/FA膜相比,基于观察到的相似膜形态,HCl对于PA66的溶解也是足够的。