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Title: The structure of rare-earth gallate and aluminium glasses dertermined by neutron and x-ray diffraction and spectroscopy
Author: Kidkhunthod, Pinit
ISNI:       0000 0004 2725 6057
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2011
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Recently glasses based on gallate and aluminate networks have aroused interest in laser technology, for example, for the use as the host for .Iaser active ions. As these glasses are not good glass-formers other ingredients such as silica are normally added to improve their glass abilities. In this work I have succeeded in producing these glasses without the need for these additions. The structures of these pure rare-earth gallate and aluminate glasses made by aerodynamic levita- tion and laser heating techniques have been studied including neutron and X-ray diffraction and spectroscopy. The following results have been obtained. The structures of rare-earth gallate glasses, R2Ga6012 and R3Ga5012 where R = Pr and Nd, were studied using neutron diffrac- tion with the isomorphic substitution technique. A good agreement between the structural models from MD simulation and MD-RMC for the difference functions and the full experimental data sets was achieved. The mean Ga-O coordination number was found to be 4.1(1). The results also show a mixture of 6, 7 and 8-fold coordinated sites for the rare-earth ions with an average coordination number of 7.7(1). A more detailed study using a combination of neutron diffraction, Extended X-ray Absorption Fine Structure (EXAFS), MD simulation and MD-RMC refinement was applied to obtain the detail of the local structure of Pr3Ga5012 glasses at Pr and Ga K-edges. The nucleation and phase separation in the (Y203)x(Al203)1-x glassy systems produced by an aerodynamic levitation and laser heating was studied using micro-focus EXAFS. Turbidity was found to occur in the x < 0.25 and x > 0.35 glasses. At x < 0.25, even though no large inclusions (> 1μm) were seen in the turbid glasses, a phase separation into a polycrystalline sample of YAP (x = 0.50) and pure alumina was found. It is concluded that the turbidity in glassy samples at x ≤ 0.25 is due to the formation of nano meter size crystallites. For x = 0.36 and 0.375 (known as YAG), a nucleation of YAG crystals as spherical inclusions was found in a glass matrix giving rise to the turbidity in these glasses. Finally, a study of the structures of BaTiAl206 glasses was made in order to understand the processes giving rise to their unusual properties. Black and opaque, and clear and transparent BaTiAb06 glasses produced by aerodynamic levitation and laser heating by fast and slow quench rates were studied. Neutron and X-ray diffraction, MD simulation, MD-RMC refinement and X-ray absorption spectroscopy have been used and combined to determine the structure of the glass especially with regard to the coordination structure around the Ti ions. Evidence is found to show that the Ti ions occur in four fold and higher fold oxygen coordinated sites while the Al ions remain to- tally four fold coordinated. Very small differences in the structure of the two glasses are observed confirming that the opacity arises largely due to a small number of optical defects in present in the same overall glass structure.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available