Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R'2O3)y(P2O5)1-(x+y), where (R, R') denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å-1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with 'dial-up' lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P-O and PO bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials. © 2013 The Owner Societies.

Effect of cooling rate on intercritically reheated microstructure and toughness in high strength low alloy steel

High strength low alloy steels have been shown to be adversely affected by the existence of regions of poor impact toughness within the heat affected zone (HAZ) produced during multipass welding. One of these regions is the intercritically reheated coarse grained HAZ or intercritical zone. Since this region is generally narrow and discontinuous, of the order of 0.5 mm in width, weld simulators are often employed to produce a larger volume of uniform microstructure suitable for toughness assessment. The steel usedfor this study was a commercial quenched and tempered steel of 450 MN m -2 yield strength. Specimen blanks were subjected to a simulated welding cycle to produce a coarse grained structure of upper bainite during the first thermal cycle, followed by a second thermal cycle where the peak temperature T p2 was controlled. Charpy tests carried out for T p2 values in the range 650-850°C showed low toughness for T p2 values between 760 and 790°C, in the intercritical regime. Microstructural investigation of the development of grain boundary martensite-retained austenite (MA) phase has been coupled with image analysis to measure the volume fraction of MAformed. Most of the MA constituent appears at the prior austenite grain boundaries during intercritical heating, resulting in a 'necklace' appearance. For values of T p2 greater than 790°C the necklace appearance is lost and the second phase areas are observed throughout the structure. Concurrent with this is the development of the fine grained, predominantly ferritic structure that is associated with the improvement in toughness. At this stage the microstructure is transforming from the intercritical regime structure to the supercritically reheated coarse grained HAZ structure. The toughness improvement occurs even though the MA phase is still present, suggesting that the embrittlement is associated with the presence of a connected grain boundary network of the MA phase. The nature of the second phase particles can be controlled by the cooling rate during the second cycle and variesfrom MA phase at high cooling rates to a pearlitic structure at low cooling rates. The lowest toughness of the intercritical zone is observed only when MA phase is present. The reason suggested for this is that only the MA particles debond readily, a number of debonded particles in close proximity providing sufficient stress concentration to initiate local cleavage. © 1993 The Institute of Materials.

Thermochemical characterisation of various biomass feedstock and bio-oil generated by fast pyrolysis

The projected decline in fossil fuel availability, environmental concerns, and security of supply attract increased interest in renewable energy derived from biomass. Fast pyrolysis is a possible thermochemical conversion route for the production of bio-oil, with promising advantages. The purpose of the experiments reported in this thesis was to extend our understanding of the fast pyrolysis process for straw, perennial grasses and hardwoods, and the implications of selective pyrolysis, crop harvest and storage on the thermal decomposition products. To this end, characterisation and laboratory-scale fast pyrolysis were conducted on the available feedstocks, and their products were compared. The variation in light and medium volatile decomposition products was investigated at different pyrolysis temperatures and heating rates, and a comparison of fast and slow pyrolysis products was conducted. Feedstocks from different harvests, storage durations and locations were characterised and compared in terms of their fuel and chemical properties. A range of analytical (e.g. Py-GC-MS and TGA) and processing equipment (0.3 kg/h and 1.0 kg/h fast pyrolysis reactors and 0.15 kg slow pyrolysis reactor) was used. Findings show that the high bio-oil and char heating value, and low water content of willow short rotation coppice (SRC) make this crop attractive for fast pyrolysis processing compared to the other investigated feedstocks in this project. From the analytical sequential investigation of willow SRC, it was found that the volatile product distribution can be tailored to achieve a better final product, by a variation of the heating rate and temperature. Time of harvest was most influential on the fuel properties of miscanthus; overall the late harvest produced the best fuel properties (high HHV, low moisture content, high volatile content, low ash content), and storage of the feedstock reduced the moisture and acid content.