Document Type: Research Paper
CeFEMA/Depart. of Chem. Eng., IST, UL, Av. Rovisco Pais, 1, 1049-001 Lisbon, Portugal Depart. of Chem. Eng., ISEL, IPL, Rua Conselheiro Emídio Navarro 1, 1959-007 Lisbon, Portugal
Departamento de Química e Farmácia, FCT, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
Centro de Química-Física Molecular and IBB - Institute for Bioengineering and Biosciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1, 1049-001 Lisboa, Portugal
CeFEMA/Department of Chemical Engineering, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1, 1049-001 Lisbon, Portugal
Integral asymmetric cellulose acetate (CA) membranes were casted by phase-inversion with formamide varying content - 22, 30 and 34% - as pore promoter. These membranes, CA-22, CA-30 and CA-34, were analyzed by infrared spectroscopy in attenuated total reflection mode (ATR-FTIR) to investigate the porous membrane matrix influence on the polymer/water/solute interactions and the selective ultrafiltration of salts. The membranes covered a wide range of hydraulic permeabilities, from 3.5 to 81.0 kg.m-2.h-1.bar-1, and of molecular weight cut-offs, from 4.17 to 31.43 kDa. The experimental apparent rejection coefficients of neutral solutes of increasing molecular weight are related to their intrinsic rejection coefficients through the film model. The surface average pore radius, estimated by an iterative algorithm, ranges from 2.1 to 4.5 nm. The tighter membrane, CA-22, displays experimental apparent rejection coefficients to the Na2SO4, CaSO4, MgSO4 of 50% or higher values and this is in contrast with the lower values, between 14 and 18%, to the NaCl, CaCl2 and MgCl2 salts. The ATR-FTIR evidences that in the membranes with larger pores, CA-30 and CA-34, the water molecules are organized with a liquid-water-like structure, in which most molecules are hydrogen bonded to four or to two others; nevertheless, a fraction of water molecules is strongly bonded to the CA carbonyl groups. For the CA-22 membrane, there are more free carbonyl groups and a larger fraction of free water, both able to interact with solutes, such as the hydrated sulphate ions. Therefore, this ultrafiltration membrane has the capability of differentiating anionic species.