DEVELOPMENT OF POLYHIPE CHROMATOGRAPHY AND LANTHANIDE-DOPED LATEX PARTICLES FOR USE IN THE ANALYSIS OF ENGINEERED NANOPARTICLES A thesis submitted to The University of Manchester for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences 2013 Jonathan Mark Hughes School of Chemistry Table of Contents List of Figures 9 List of Tables 13 List of Abbreviations 17 ABSTRACT 19 DECLARATION 20 COPYRIGHT STATEMENT 20 Acknowledgements 22 Chapter 1Introduction 23 1.1 Aims and Objectives ...................................................................................................... 23 1.2 Nanoparticles (NPs) ....................................................................................................... 25 1.2.1 Summary of Techniques for Analysis of Nanoparticles in Aquatic Environments. ... 27 1.2.1.1 Electromagnetic (EM) Scattering Methods .............................................................. 27 1.2.1.1.1 Dynamic Light Scattering ..................................................................................... 27 1.2.1.1.2 Static Classical Light Scattering (SLS) ................................................................. 29 1.2.1.1.3 Laser Diffraction ................................................................................................... 30 1.2.1.1.4 Turbidimetry and Nephelometry ........................................................................... 31 1.2.1.1.5 Nanoparticle Tracking Analysis (NTA) ................................................................ 31 1.2.1.1.6 Small Angle X-ray Scattering (SAXS) & Small Angle Neutron Scattering (SANS) ................................................................................................................................. 32 1.2.1.2 Microscopy Techniques ........................................................................................... 33 1.2.1.2.1 Electron Microscopy ............................................................................................. 34 1.2.1.2.1.1Transmission Electron Microscopy (TEM) ........................................................ 34 1.2.1.2.1.2 Scanning Electron Microscopy (SEM) .............................................................. 35 1.2.1.2.1.3 Elemental Analysis and Electron Microscopy ................................................... 37 1.2.1.2.2 Scanning Probe Microscopy (SPM) ...................................................................... 38 1.2.1.2.2.1 Atomic Force Microscopy (AFM) ..................................................................... 38 1.2.1.2.2.2 Near-field Scanning Optical Microscopy (NSOM) ........................................... 38 1.2.1.2.2.3 Confocal Laser Scanning Microscopy (CLSM). ................................................ 39 1.2.1.2.3 X-ray Microscopy (XRM)..................................................................................... 39 1.2.1.3 Spectroscopic Methods ............................................................................................ 40 1.2.1.3.1 Optical Spectroscopy ............................................................................................ 40 2 1.2.1.3.2 Fluorescence Spectroscopy ................................................................................... 41 1.2.1.3.3 X-ray Photoelectron Spectroscopy (XPS) ............................................................. 41 1.2.1.3.4 X-ray diffraction (XRD) ....................................................................................... 41 1.2.1.3.5 Laser-induced breakdown detection Spectroscopy (LIBDS) ................................ 41 1.2.1.4 Fractionation and Separation Methods .................................................................... 42 1.2.1.4.1 Filtration ................................................................................................................ 42 1.2.1.4.2 Centrifugation ....................................................................................................... 42 1.2.1.4.3 Field Flow Fractionation (FFF) ............................................................................. 44 1.2.1.5 Chromatography Methods ........................................................................................ 45 1.2.1.5.1 Size Exclusion Chromatography (SEC) ................................................................ 45 1.2.1.5.2 Hydrodynamic Chromatography (HDC)............................................................... 47 1.2.2 Summation .................................................................................................................. 49 1.3 Introduction Emulsions and HIPEs ................................................................................ 53 1.3.1 Emulsions .................................................................................................................... 53 1.3.2 Surfactants ................................................................................................................... 54 1.3.2.1. The Hydrophilic-Lipophilic Balance (HLB) Concept ............................................ 56 1.3.3 High Internal Phase Emulsions (HIPEs) ..................................................................... 58 1.3.3.1 HIPE Formation ....................................................................................................... 59 1.3.3.2 HIPE Stability .......................................................................................................... 59 1.3.3.3 HIPE Rheology ........................................................................................................ 64 1.3.3.4 HIPE Geometry ........................................................................................................ 65 1.4 References ...................................................................................................................... 67 Chapter 2 Silica Materials Produced from High Internal Phase Emulsions, SiHIPEs 72 2.1 Introduction .................................................................................................................... 72 2.1.1 Aims and Objectives ................................................................................................... 72 2.1.2 HIPEs as a Route to Porous Materials ........................................................................ 73 2.1.3 SiHIPE ........................................................................................................................ 75 2.1.4 Other Inorganic Oxides ............................................................................................... 76 2.1.5 Organic-Silica Composites ......................................................................................... 77 2.1.6 Silica Sol-Gel .............................................................................................................. 79 2.2 Experimental .................................................................................................................. 81 2.2.1 Preparation of SiHIPE Materials. ................................................................................ 81 3 2.2.1.1 Materials ................................................................................................................... 81 2.2.1.2 Preparation of Sols ................................................................................................... 81 2.2.1.3 Formation of HIPEs ................................................................................................. 82 2.2.1.4 Formation of Beads from HIPEs .............................................................................. 82 2.2.1.5 Toluene Reservoir .................................................................................................... 83 2.2.1.6 Formation SiHIPE monoliths ................................................................................... 83 2.2.1.7 Monoliths from Sols Containing SiO2 Nanopowder ............................................... 84 2.2.1.8 Calcination ............................................................................................................... 84 2.2.2 Measurements ............................................................................................................. 85 2.2.2.1 Surface Area ............................................................................................................. 85 2.2.2.2 Scanning Electron Microscopy (SEM) .................................................................... 85 2.3 Results and discussion ................................................................................................... 86 2.3.1 Effect of Temperature upon Sol Aging ....................................................................... 86 2.3.2 Reservoir dispersion of the HIPE to control bead formation. ..................................... 93 2.3.3 Transition Metal Salts as Additional Porogens ........................................................... 95 2.3.4 SiHIPE Monoliths ..................................................................................................... 104 2.3.5 Copper Containing SiHIPE Monoliths ..................................................................... 108 2.4 Conclusions .................................................................................................................. 110 2.5 References .................................................................................................................... 112 Chapter 3 Synthesis and Characterisation of PolyHIPE Monoliths