Small angle scattering characterisation of micellar systems and templated architectures

The work described in this thesis reports the structural changes induced on micelles under a variety of conditions. The micelles of a liquid crystal film and dilute solutions of micelles were subjected to high pressure CO2 and selected hydrocarbon environments. Using small angle neutron scattering (SANS) techniques the spacing between liquid crystal micelles was measured in-situ. The liquid crystals studied were templated from different surfactants with varying structural characteristics. Micelles of a dilute surfactant solution were also subjected to elevated pressures of varying gas atmospheres. Detailed modelling of the in-situ SANS experiments revealed information of the size and shape of the micelles at a number of different pressures. Also reported in this thesis is the characterisation of mesoporous materials in the confined channels of larger porous materials. Periodic mesoporous organosilicas (PMOs) were synthesised within the channels of anodic alumina membranes (AAM) under different conditions, including drying rates and precursor concentrations. In-situ small angle x-ray scattering (SAXS) and transmission electron microscopy (TEM) was used to determine the pore morphology of the PMO within the AAM channels. PMO materials were also used as templates in the deposition of gold nanoparticles and subsequently used in the synthesis of germanium nanostructures. Polymer thin films were also employed as templates for the directed deposition of gold nanoparticles which were again used as seeds for the production of germanium nanostructures. A supercritical CO2 (sc-CO2) technique was successfully used during the production of the germanium nanostructures.

Hollow core photonic crystal fibre as a viscosity and Raman sensor

This PhD thesis investigates the application of hollow core photonic crystal fibre for use as an optical fibre nano litre liquid sensor. The use of hollow core photonic crystal fibre for optical fibre sensing is influenced by the vast wealth of knowledge, and years of research that has been conducted for optical waveguides. Hollow core photonic crystal fibres have the potential for use as a simple, rapid and continuous sensor for a wide range of applications. In this thesis, the velocity of a liquid flowing through the core of the fibre (driven by capillary forces) is used for the determination of the viscosity of a liquid. The structure of the hollow core photonic crystal fibre is harnessed to collect Raman scatter from the sample liquid. These two methods are integrated to investigate the range of applications the hollow core photonic crystal fibre can be utilised for as an optical liquid sensor. Understanding the guidance properties of hollow core photonic crystal fibre is forefront in dynamically monitoring the liquid filling. When liquid is inserted fully or selectively to the capillaries, the propagation properties change from photonic bandgap guidance when empty, to index guidance when the core only is filled and finally to a shifted photonic bandgap effect, when the capillaries are fully filled. The alterations to the guidance are exploited for all viscosity and Raman scattering measurements. The concept of the optical fibre viscosity sensor was tested for a wide range of samples, from aqueous solutions of propan-1-ol to solutions of mono-saccharides in phosphate buffer saline. The samples chosen to test the concept were selected after careful consideration of the importance of the liquid in medical and industrial applications. The Raman scattering of a wide range of biological important fluids, such as creatinine, glucose and lactate were investigated, some for the first time with hollow core photonic crystal fibre.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials