Crosland, James M (2021) Characterisation of a novel solution precursor to zirconia. PhD thesis, University of Warwick.

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Abstract

Aqueous nitrate-based solutions of zirconium (‘poly-zirconium nitrate’) of a range of compositions have been synthesised and then characterised with a number of analytical techniques including Fourier-transform infrared spectroscopy, Raman spectroscopy, smallangle X-ray scattering, extended X-ray absorption fine structure spectroscopy and X-ray pair distribution function analysis. Synthesis was carried out on the laboratory scale with a process mimicking the pilot plant production of analogous solutions as used in industry as precursors to a wide range of solid zirconium-based materials.

Raman spectroscopy has revealed the changes occurring in solution as a direct result of the hydrolysis of zirconium in these solutions due heating and aging and has been demonstrated to provide a useful measure of the extent of this reaction over time during synthesis. Results also suggest the presence of hydrolysed zirconium solution species similar to the zirconium tetramer.

How the sizes of solution species change with time and temperature has been seen via small-angle X-ray scattering, and manual extraction of size parameters from scattering data has been done so in a way consistent with the idea of particles growing in solution as if they were cylindrical, or predominantly growing along one axis.

The presence of, and presence of structures based upon, the zirconium tetramer in the specific aqueous zirconium solutions studied, regardless of exact solution composition, has been confirmed by Zr K-edge extended X-ray absorption fine structure measurements at the Diamond Light Source Synchrotron, and the growth of these species as ladder-like chains of connected tetramers has been seen via X-ray pair distribution analysis from data also collected at Diamond.

In addition, an optimised synthesis of the reference material and gravimetric analysis reagent zirconium mandelate, and its crystal structure, have been reported for the first time following work utilising NMR crystallography methods.

Item Type:	Thesis (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Zirconium, Zirconium -- Synthesis, Fourier transform spectroscopy, Raman spectroscopy, Hydrolysis
Official Date:	January 2021
Dates:	Date Event January 2021 UNSPECIFIED
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Walton, Richard I.
Format of File:	pdf
Extent:	vii, 236 leaves : illustrations
Language:	eng

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