Preparation and Characterization of a Cross-linked Matrimid/Polyvinylidene Fluoride Composite Membrane for H2/N2 Separation

A double layer composite membrane was fabricated by matrimid 5218 as a selective layer on polyvinylidene fluoride (PVDF), a porous asymmetric membrane, as a sublayer. The effect of chemical cross-linking of Matrimid 5218 by ethylenediamine (EDA) was investigated on gas transport properties of the corresponding membrane. The permeability levels of hydrogen (H2) and nitrogen (N2) were measured through the fabricated composite membranes at 25°C under pressure range of 2-8 bar. Scanning electron microscopy (SEM) was used for morphological observations of the composite membranes. The Matrimid membranes before and after cross-linking modification were characterized by the Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and density measurement. The FTIR results showed the conversion of imide functional groups into amide through the crosslinking reaction in Matrimid. The XRD results demonstrated a reduction in d-spacing between the polymer chains through cross-linking reaction. Measuring the density of each membrane's partial selective layer and calculating the corresponding fractional free volume revealed an increase in the density and reduced free volumes in Matrimid through the cross-linking reaction. Moreover, by increasing the EDA concentration, the gas permeability in each membrane decreased significantly for nitrogen compared to hydrogen which could be related to lower gas diffusivity through chain packing due to cross-linking of the polymer. The H2/N2 selectivity at 2 bar increased through the cross-linking modification from 56.5 for the pure Matrimid to 79.4 for the composite membrane containing 12 wt% EDA. The effect of pressure on gas permeability through the composite membranes was investigated and the results found to be in agreement with the behavior of less soluble gases in the glassy polymers. Moreover, the H2/N2 selectivity decreased first at low EDA content (0-4 wt%), before reaching a constant value at 8 wt% EDA and finally increasing by 12 wt% EDA content.