The Synthesis, Characterisation and Ion Exchange of Mixed Metal Phosphates by Victoria Anne Burnell
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The Synthesis, Characterisation and Ion Exchange of Mixed Metal Phosphates by Victoria Anne Burnell A thesis submitted to The University of Birmingham for the degree of Doctor of Philosophy The School of Chemistry College of Engineering and Physical Sciences University of Birmingham August 2011 University of Birmingham Research Archive e-theses repository This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder. Abstract Abstract This thesis presents work investigating the synthesis and characterisation of a range of mixed metal phosphates. The main aim of the project was to develop materials for the remediation of nuclear waste. In light of this, the materials developed were subject to ion exchange studies and leach testing. The thermal behaviour of the phosphates and nature of the decomposition products were also investigated. This study demonstrates that the true solid solution cannot be formed in any of the mixed metal series investigated, which included zirconium-titanium, germanium-titanium, germanium-zirconium, tin-titanium and tin-zirconium. In all cases a miscibility gap was observed and the reasons for these were established. The co-precipitates that formed were characterised by a variety of analytical techniques which included powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), pair distribution function (PDF) analysis and X-ray fluorescence (XRF). Structural characterisation was undertaken using both traditional Rietveld analysis of synchrotron X-ray powder diffraction data and PDF analysis of high energy synchrotron total scattering data. The results of the ion exchange studies yielded four exchanged products: strontium exchanged zirconium phosphate, a strontium exchanged zirconium-titanium phosphate and two sodium exchanged titanium phosphate products. Although it was not possible to solve the structures of these phases, they were further characterised by a number of methods and their use as potential stores were investigated by leach testing. The strontium exchanged zirconium phosphate product demonstrated good strontium retention and is recommended for further investigation as a possible strontium waste form. Acknowledgments Acknowledgments First and foremost I would like to acknowledge my supervisor, Dr. Joe Hriljac for all of his help and guidance throughout my PhD. I would also like to thank the members of fifth floor who have helped me over the last three years. Special mentions should go to Evin for her help with the SEM and to Colin, Julie and Jackie for the hours spent with the XRF! I would like to thank the EPSRC and the University of Birmingham for funding. I am also grateful to the following people who have helped with the acquisition of results included in this thesis: • Paul Jones from Bruker for his help with the XRF results. • Steve Baker, University of Birmingham for the ICP analyses • Peter Chupas and Karena Chapman at the APS for their help with the collection of the PDF data and for their guidance on how to use the PDF technique. • Chiu Tang, Julia Parker and Stephen Thompson at Diamond Light Source for their help in collecting the synchrotron X-ray diffraction data. • Dr. John Hanna, University of Warwick for the 31P NMR analysis Finally, but in no way insignificant in their part, I wish to thank my parents and Andy for their constant support and encouragement. Without them this work would not have been possible and though I may not say it enough they are very much loved. I would also like to thank my uncles Pat and Joe and Auntie Gina, who, had they have lived to see this would have been so very proud. Dedication ......for Andy 私の人生の愛 xx Abbreviations Abbreviations α-TiP α-Titanium Phosphate - Ti(HPO4)2.H2O α-ZrP α-Zirconium Phosphate - Zr(HPO4)2.H2O α-GeP α-Germanium Phosphate - Ge(HPO4)2.H2O α-SnP α-Tin Phosphate - Sn(HPO4)2.H2O α-PbP α-Lead Phosphate - Pb(HPO4)2.H2O α-HfP α-Hafnium Phosphate - Hf(HPO4)2.H2O PXRD Powder X-ray Diffraction XRD X-ray Diffraction XRF X-ray Fluorescence PDF Pair Distribution Function TGA Thermogravimetric Analysis DTA Differential Thermal Analysis NMR Nuclear Magnetic Resonance SEM Scanning Electron Microscopy EDX Electron Dispersive X-ray GSAS General Structural Analysis System Table of Contents Chapter 1: Introduction 1.1 Background – ‘The Big Picture’................................................................................ 1 1.2 Inorganic Ion Exchange Materials............................................................................ 4 1.3 Layered Metal (IV) Phosphates................................................................................ 7 1.3.1 Mixed Metal (IV) Phosphates............................................................................. 13 1.3.2 The Alpha Structure............................................................................................ 15 1.3.3 Ion Exchange of Layered Metal (IV) Phosphates................................................. 22 1.4 Aims.......................................................................................................................... 29 1.5 References................................................................................................................ 30 Chapter 2: Experimental 2.1 Introduction............................................................................................................. 34 2.2 Synthetic Procedures............................................................................................... 34 2.2.1 Synthesis of layered metal phosphates.............................................................. 34 2.2.1.1 α-TixZr1-x(HPO4)2.H2O for 0 ≤ x ≤ 1 ............................................................... 35 2.2.1.2 α-ZrxGe1-x(HPO4)2.H2O for 0 ≤ x ≤ 1 ............................................................. 38 2.2.1.3 α-TixGe1-x(HPO4)2.H2O for 0 ≤ x ≤ 1.............................................................. 38 2.2.1.4 Tin phosphate systems................................................................................ 40 2.2.2 Ion Exchange Reactions...................................................................................... 41 2.3 Crystallography........................................................................................................ 42 2.3.1 Crystal Structure................................................................................................. 42 2.3.2 Lattice Planes and Miller Indices........................................................................ 44 2.4 X-Ray Diffraction...................................................................................................... 45 2.4.1 Fundamentals of X-ray Diffraction...................................................................... 45 2.4.2 Generation of X-rays........................................................................................... 48 2.4.3 X-ray Intensity..................................................................................................... 51 2.4.4 Laboratory Equipment........................................................................................ 54 2.4.5 Synchrotron Sources........................................................................................... 56 2.5 Rietveld Refinements............................................................................................... 58 2.6 Pair Distribution Function (PDF) Analysis................................................................. 62 2.6.1 Introduction........................................................................................................ 62 2.6.2 Data Collection.................................................................................................... 66 2.6.3 PDF Structure Refinement.................................................................................. 66 2.7 Thermogravimetric Analysis + Mass Spectroscopy (TGA-MS)................................. 70 2.8 X-ray Fluorescence (XRF)......................................................................................... 72 2.8.1 Basics of XRF........................................................................................................ 72 2.8.2 Instrumentation................................................................................................... 73 2.8.3 Matrix Effects....................................................................................................... 76 2.8.3.1 Elemental interactions.................................................................................. 76 2.8.3.2 Physical effects............................................................................................. 77 2.8.4 Sample Preparation............................................................................................. 78 2.8.5 Calibrations.......................................................................................................... 81 2.9 Leaching Experiments............................................................................................... 85 2.9.1 Sample Preparation............................................................................................