Antiplasticization of glassy polymers, arising from the addition of small amounts of plasticizer, was examined to highlight the developments that have taken place over the last few decades, aiming to fill gaps of knowledge in the large number of disjointed publications. The analysis includes the role of polymer/plasticizer molecular interactions and the conditions leading to the cross-over from antiplasticization to plasticization. This was based on molecular dynamics considerations of thermal transitions and related relaxation spectra, alongside the deviation of free volumes from the additivity rule. Useful insights were gained from an analysis of data on molecular glasses, including the implications of the glass fragility concept. The effects of molecular packing resulting from antiplasticization are also discussed in the context of physical ageing. These include considerations on the effects on mechanical properties and diffusion-controlled behaviour. Some peculiar features of antiplasticization regarding changes in Tg were probed and the effects of water were examined, both as a single component and in combination with other plasticizers to illustrate the role of intermolecular forces. The analysis has also brought to light the shortcomings of existing theories for disregarding the dual cross-over from antiplasticization to plasticization with respect to modulus variation with temperature and for not addressing failure related properties, such as yielding, crazing and fracture toughness.

For the application of proton exchange membrane fuel cells (PEMFCs) in a wide temperature range, an ionogel incorporated into poly(2,5-benzimidazole) (ABPBI) membranes with low phosphoric acid doping levels was designed. The natural sepiolite was first acid-treated to obtain one-dimensional silicon nanorods (SNRs) with a large specific surface area and a hierarchical porous structure. The SNRs were then filled with imidazolium ionic liquid (IL) to prepare IL@SNR ionogels. Analysis of related spectra and thermal behavior verified that the IL molecules were confined in the inner channels of SNRs. The as-prepared IL@SNRs were embedded in the ABPBI to form composite membranes (ABPBI/IL@SNRs) via in situ synthesis. By immobilizing proton conductors, the ABPBI/IL@SNR composite membranes markedly improved proton conductivity with low phosphoric acid doping levels in a wide temperature range. A single-cell based on 5 wt% IL@SNRs embedded in a composite membrane achieved a maximum power density of 0.15 and 0.28 W cm⁻² at 80 °C and 180 °C, respectively, with 0% RH. The proton conductivities were comparable to those of Nafion-based PEMFCs under the same temperature and humidity conditions and competed with those of reported polybenzimidazole–inorganic composite membrane-based PEMFCs at high temperatures. By using a facile method to prepare nanostructured fillers, the strategy of avoiding proton carrier wastage can be potentially used in the production of high-performance membranes for PEMFCs.

A new water-in-oil microemulsion, consisting of the non-ionic surfactant Triton X-114, cyclohexane as the oil phase and 1.0 M AlCl₃ aqueous solution as the aqueous phase, was developed and used to synthesise aluminium oxide (Al₂O₃) nanoparticles. The partial phase diagram of this ternary system was also determined at 38 °C. Syntheses of Al₂O₃ nanoparticles were carried out in a range of microemulsions with a fixed oil∶surfactant ratio of 70∶30 (w/w), but with different aqueous phase contents. For the purposes of comparison, Al₂O₃ particles were also synthesised in the corresponding emulsion and by direct precipitation from aqueous solution. Nano-sized Al₂O₃ particles were only obtained via microemulsions, whereas the emulsion route led to hollow ball-shaped particles with sub-micron apparent sizes and the direct precipitation process resulted in angular particles about 250 nm in dimension. The nanoparticles synthesised in the microemulsion with 20 wt% aqueous phase content have smaller particle sizes (5–15 nm) and a lower transformation temperature into α-form Al₂O₃ crystallites. Pure α-Al₂O₃ nanocrystals were obtained by calcination at 1000 °C for 12 h, while the nano-sized dimension of the particles retained though the apparent particle size increased to some extent. This transformation temperature is about 200 °C lower than that for the Al₂O₃ particles synthesised by direct precipitation.