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Abstract: The preparation of mesoporous carbons possessing a highly ordered body centred cubic (bcc) arrangement of pores by employing a halide- and metal-free synthesis method is reported. Products were characterised using gas physisorption, Small Angle X-ray Diffraction and X-ray Scattering, Raman spectroscopy and High Resolution Transmission Electron Microscopy (TEM). The materials produced in this work had Specific Surface Areas of between 422 and 988 m2g−1 and pore diameters of around 7 nm. From the TEM images, high quality Digital Diffraction Patterns, relating to the ordered mesopore structure, were obtained. On increasing calcination temperature from 350 to 1000°C the bcc structure was retained but its dimensions decreased progressively as the mesopore structure shrank. The effects on the structure and texture of the materials of the three key parameters of polymerisation time and the concentrations of the two catalysts employed, NH4OH and oxalic acid, were studied. Shorter polymerisation times and lower catalyst concentrations gave rise to the most well-ordered products whereas longer polymerisation times with higher concentrations of base and acid catalyst resulted in disordered pore structures.

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Abstract: As a result of the synthesis protocol polyoxyethylene sorbitan monooleate (polysorbate 80, PS80) is a highly complex mixture of compounds. PS80 was therefore separated into its main constituents, e.g. polyoxyethylene isosorbide esters and polyoxyethylene esters, as well as mono- di- and polyesters using preparative high-performance liquid chromatography. In this comprehensive study the individual components and their ethoxylation level were verified by matrix assisted laser desorption/ionization time-of-flight and their thermotropic behavior was analyzed using differential scanning calorimetry and X-ray diffraction. A distinct correlation was found between the average length of the ethylene oxide (EO) chains in the headgroup and the individual compounds’ ability to crystallize. Importantly, a critical number of EO units required for crystallization of the headgroup was determined (6 EO units per chain or 24 per molecule). The investigation also revealed that the hydrocarbon tails only crystallize for polyoxyethylene sorbitan esters if saturated. PS80 is synthesized by reacting with approximately 20 mol of EO per mole of sorbitol, however, the number of EO units in the sorbitan ester in commercial PS80 products is higher than the expected 20 (5 EO units per chain). The complex behavior of all tested compounds revealed that if the amount of several of the linear by-products is reduced, the number of EO units in the chains will stay below the critical number and the product will not be able to crystallize by the EO chains.

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Abstract: Gyroid‐nanostructured all‐solid polymer films with exceedingly high proton conductivity and low H2 gas permeability have been created via crosslinking polymerization of mixtures of a zwitterionic amphiphilic monomer and a polymerizable imide‐type acid that co‐organize into bicontinuous cubic liquid‐crystalline phases. The gyroid nanostructures are visualized by reconstructing a 3D electron map from the synchrotron X‐ray diffraction patterns. These films exhibit high proton conductivity of the order of 10−1 S cm−1 and extremely low H2 gas permeability of the order of 10−15 mol m m−2 s−1 Pa−1. These properties can be ascribed to the presence of the ionic liquid‐like layer along the gyroid minimal surface. Since these two characteristics are required for improving the performance of proton‐exchange membrane fuel cells, the present membrane design represents a promising strategy for the development of advanced devices, pertinent to establishing sustainable energy sources.

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Abstract: Ultra-SAXS can enhance the capabilities of existing synchrotron SAXS/WAXS beamlines. A compact ultra-SAXS module has been developed, which extends the measurable q-range with 0.0015 ≤ q (nm−1) ≤ 0.2, allowing structural dimensions in the range 30 ≤ D (nm) ≤ 4000 to be probed in addition to the range covered by a high-end SAXS/WAXS instrument. By shifting the module components in and out on their respective motor stages, SAXS/WAXS measurements can be easily and rapidly interleaved with USAXS measurements. The use of vertical crystal rotation axes (horizontal diffraction) greatly simplifies the construction, at minimal cost to efficiency. In this paper, the design considerations, realization and synchrotron findings are presented. Measurements of silica spheres, an alumina membrane, and a porous carbon catalyst are provided as application examples.

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Abstract: Terpenes are ideal candidates for sustainable polymer feedstocks, due to their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and that these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of Tg values are observed for the terpene (meth)acrylate homopolymers, from −3 °C for poly(limonene acrylate), up to +168 °C for poly(α-pinene methacrylate), and we exploit these to create renewably-sourced hard–soft block copolymers. We also report the synthesis of difunctional poly(α- and β-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(α-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.