Solid–liquid–liquid phase envelopes from temperature-scanned refractive index data

Abstract

A novel method for estimating the upper critical solution temperature (UCST) of N,N-diethyl-m-toluamide (DEET)-polyethylene systems was developed. It was validated using data for the dimethylacetamide (DMA)-alkane systems which showed that refractive index mixing rules, linear in volume fraction, can accurately predict mixture composition for amide-alkane systems. Furthermore, rescaling the composition descriptor with a single adjustable parameter proved adequate to address any asymmetry when modeling the DMA-alkane phase envelopes. This allowed the translation of measured refractive index cooling trajectories of DEET-alkane systems into phase diagrams and facilitated the estimation of the UCST values by fitting the data with an adjusted composition descriptor model. For both the DEET- and DMA-alkane systems, linear behavior of UCST values in either the Flory–Huggins critical interaction parameter, or the alkane critical temperature, with increasing alkane molar mass is evident. The UCST values for polymer diluent systems were estimated by extrapolation using these two complimentary approaches. For the DEET-polyethylene system, values of 183.4 and 180.1 °C respectively were obtained. Both estimates are significantly higher than the melting temperature range of polyethylene. Initial liquid–liquid phase separation is therefore likely to be responsible for the previously reported microporous microstructure of materials formed from this binary system.