Inverse gas chromatography of poly(n-butyl methacrylate): Effect of flow rate on specific retention volume and detection of glass transition temperature

Flow-rate effect on specific retention volume (V) was studied by eluting aliphatic, aromatic, and chlorinated aliphatic probes at infinite dilution on poly(n-butyl methacrylate) stationary phase at different temperatures from ?10 to 150°C, encompassing both the glass transition (T_g) and the softening temperatures of the polymer. The effect became pronounced as the temperature was reduced below 100°C. V decreased with an increase in the flow rate: first linearly at temperatures between 70 and 100°C, and then nonlinearly at all temperatures below 70°C. The retention diagrams of n-pentane, isooctane, and cyclohexane alone enabled the detection of glass transition. Dichloromethane gave a linear retention diagram through T_g without showing the flow-rate effect.