Formation and electrical interfacing of nanocrystal-molecule nanostructures

The objective of this thesis work is to develop methods for forming and interfacing nanocrystal-molecule nanostructures in order to explore their electrical transport properties in various controlled environments. This work demonstrates the potential of nanocrystal assemblies for laterally contacting molecules for electronic transport measurements. We first propose a phenomenological model based on rate equations for the formation of hybrid nanocrystal-molecule (respectively: 20 nm – 1.2 nm) nanostructures in solution. We then concentrate on nanocrystals (~ 60 nm) assembled between nano-gaps (~ 40 nm) as a contacting strategy for the measurement of electronic transport properties of thiophene-terminated conjugated molecules (1.5 nm long) in a two-terminal configuration, under vacuum conditions. Similar devices were also probed with a three-terminal configuration using thiophene-terminated oxidation-reduction active molecules (1.8 nm long) in liquid medium for the demonstration of the electrolytic gating technique. The experimental and modelling work presented in this thesis project brings into light physical and chemical processes taking place at the extremely narrow (~1 nm separation) and curved interface between two nanocrystals or one nanocrystal and a grain of a metallic electrode. The formation of molecular bridges at this kind of interface necessitates molecules to diffuse from a large liquid reservoir into the region in the first place. Molecular bonding must occur to the surface for both molecular ends: this is a low yield statistical process in itself as it depends on orientation of surfaces, on steric hindrance at the surface and on binding energies. On the other hand, the experimental work also touched the importance of the competition between potentially immiscible liquids in systems such that (organo-)metallic molecules solvated by organic solvent in water and organic solvent in contact with hydrated citrate stabilised nanocrystals dispersed in solutions or assembled between electrodes from both experimental and simulations point of view.

The formulation, testing and stability of 16% fat cream liqueurs

Cream liqueurs manufactured by a one-step process, where alcohol was added before homogenisation, were more stable than those processed by a two -step process which involved addition of alcohol after homogenisation. Using the one-step process, it was possible to produce creaming-stable liqueurs by using one pass through a homogeniser (27.6 MPa) equipped with "liquid whirl" valves. Test procedures to characterise cream liqueurs and to predict shelf life were studied in detail. A turbidity test proved simple, rapid and sensitive for characterising particle size and homogenisation efficiency. Prediction of age thickening/gelation in cream liqueurs during incubation at 45 °C depended on the age of the sample when incubated. Samples that gelled at 45 °C may not do so at ambient temperature. Commercial cream liqueurs were similar in gross chemical composition, and unlike experimentally produced liqueurs, these did not exhibit either age-gelation at ambient or elevated temperatures. Solutions of commercial sodium caseinates from different sources varied in their calcium sensitivity. When incorporated into cream liqueurs, caseinates influenced the rate of viscosity increase, coalescence and, possibly, gelation during incubated storage. Mild heat and alcohol treatment modified the properties of caseinate used to stabilise non-alcoholic emulsions, while the presence of alcohol in emulsions was important in preventing clustering of globules. The response to added trisodium citrate varied. In many cases, addition of the recommended level (0.18%) did not prevent gelation. Addition of small amounts of NaOH with 0.18 % trisodium citrate before homogenisation was beneficial. The stage at which citrate was added during processing was critical to the degree of viscosity increase (as opposed to gelation) in the product during 45 °C incubation. The component responsible for age-gelation was present in the milk-solids non fat portion of the cream and variations in the creams used were important in the age-gelation phenomenon Results indicated that, in addition to possibly Ca++, the micellar casein portion of serum may play a role in gelation. The role of the low molecular weight surfactants, sodium stearoyl lactylate and monodiglycerides in preventing gelation, was influenced by the presence of trisodium citrate. Clustering of fat globules and age-gelation were inhibited when 0.18 % citrate was included. Inclusion of sodium stearoyl lactylate, but not monodiglycerides, reduced the extent of viscosity increase at 45 °C in citrate containing liqueurs.

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.

Exploring the physicochemical basis of cheese texture, rheology and functionality, with emphasis on cation-casein interactions

The physicochemical properties of cheese and milk gels are greatly influenced by molecular interactions between the casein proteins involving calcium. Novel experiments were designed to investigate the relationship between insoluble caseinbound cations and rheological properties of Cheddar cheese and rennet-induced milk gels. Cheddar cheese and rennet-induced milk gels were supplemented with Mg2+ or Sr2+ to compare their effects on their rheological properties to those previously reported in literature for Ca2+ supplementation. Sr2+ displayed behaviour similar to Ca2+ as observed by its ability to increase the rigidity of cheese and rennet milk gels and also decrease cheese meltability. Mg+2 had no influence on cheese rheological properties and was greatly inferior to Ca2+ and Sr2+ in its ability to increase rennet milk gel elasticity. Cheddar cheese was supplemented with the calcium-chelating salts trisodium citrate, disodium hydrogen phosphate or disodium EDTA, in an attempt to reduce the CCP content of cheese and thereby modify its rheological and functional properties. TSC and EDTA were successful in decreasing cheese CCP, whereas DSP caused an initial increase in CCP content. Cheddar cheese was supplemented with chlorides of iron, copper and zinc at salting to investigate the effects of concentrations of these elements in excess of those found innately or commonly in fortification studies, with emphasis on mineral equilibria changes and resultant alteration of rheological properties. Zinc addition was the only added metal that significantly influenced cheese rheological properties, leading to an increase in cheese rigidity and decreased cheese melt at elevated temperatures. Gum tragacanth was used as a fat-replacer in the manufacture of reduced-fat Cheddar cheese, in an attempt to improve the rheological, functional and sensory properties of reduced-fat Cheddar. Overall, the experimental work reported in this thesis generated new knowledge and theories about how casein-mineral interactions influence rheological properties of casein systems.