Análise termodinâmica do sistema ternário água/ácido clorídrico/poliamida 66

Abstract

The starting point for the preparation of polymer membranes by phase inversion is having a thermodynamically stable solution. The Flory-Huggins theory guided the construction of the ternary diagrams for water/formic acid/polyamide 66 and water/hydrochloric acid/ polyamide 66 systems by comparing the experimental data with theoretical, identifying the type of phase separation occurring, and describing the behavior of the thermodynamic processes of formation of asymmetric membranes prepared by phase inversion. In this work, the thermodynamic behavior of solutions of polyamide 66 (PA66) in formic acid (FA) and in hydrochloric acid (HC), was studied to evaluate their classification as true solutions. The viscosimetric average molar mass (Mw) of commercial PA66 was determined to be ≈ 11 600 g·mol-1. The PA66 and PA66 films in AF and in HC were characterized by differential scanning calorimetry (DSC), by X-ray diffraction (XRD), by Fourier transform infrared spectroscopy (FT-IR) and by scanning electron microscopy (SEM). The UNIFAC method (universal quasi-chemical funtional group activity coefficient) was used for the determination of non-solvent/solvent interaction parameters (g12) for the H2O/FA and H2O/HCsystems. From measurements of swelling, the polymer/non-solvent interaction parameter ( 13) for H2O/PA66 was found to be 2.77. The solvent/polymer interaction parameters ( 23) were determined as –9.0 and –7.74 by measuring the vapor pressure (VP) systems for PA66/FA and PA66/HC, respectively. 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 (ΔGm) and 23, indicate that the FA is the best solvent for the PA66, however, the concentration of HC (37-38%), its volatility and the volume fraction of dissolved PA66 ( 3), show that HC is also a good solvent for the PA66, which is proven by the membrane morphology obtained.