Mass spectrometric inverse gas chromatography: Investigation of polymeric phase transitions

An improved inverse gas chromatographic method involving the use of a mass-specific detector for the determination of the glass transition temperature of polymeric materials is described, The new method allows the use of several probe solutes simultaneously with an automated, closed-loop injector and stepped temperature programming, The result is a single continuous chromatogram for each probe solute over a range of temperatures encompassing the glass transition temperature, T-g. Several different methods for the exact determination of T-g from the chromatogram were investigated, including the classical van't Hoff-type plots with retention volumes calculated from both the peak maximum and first moment values of the elution peaks, Two new methods are also proposed for the evaluation of T-g from either the temperature dependence of the second moments of the elution peaks for probe solutes or simple inspection of the variation of elution peak height (width) with temperature, All four methods for the determination of T-g are evaluated with three probe solutes and four different polymers, viz., poly(methyl methacrylate), poly(ethylene terephthalate), polycarbonate, and two batches of polystyrene with different molecular weights and T-g values, Three phenomenological models were used to interpret the chromatographic retention mechanisms of the solute probes in glassy and rubbery polymers. These are (i) the classical adsorption/absorption model for glass and rubber polymers, (ii) the single absorption mechanism model, and (iii) a dual-mode model previously used to explain the sorption of gases, such as CO2, in glassy polymers. It is concluded that no single approach is adequate to interpret the experimental results for all of the systems, although each model is adequate for some individual solute/polymer combinations.