Investigation of the Nucleation and Growth of Colloidal Indium Phosphide: from Molecular Precursors to Semiconductor Nanocrystals through In37P20(O2CR)51 as a Magic-Size Intermediate

Thesis (Ph.D.)--University of Washington, 2016-06

Effect of particle loss on soil behaviour.

Soil particle loss can result in strength and volume reductions which are difficult to predict. This paper investigates the influence of the removal of fractions of selected particle sizes under different confining pressures. The mass loss process was reproduced by the dissolution of selected salt particle sizes and fractions from uniform Leighton Buzzard sand. The dissolution tests were performed in a triaxial cell customised to allow circulation of pore-fluid thereby allowing the dissolution/removal of the salt fraction. Test results from previously conducted oedometric dissolution tests and subsequent triaxial dissolution tests all show increases in void ratio. From the triaxial tests, a reduction in shear strength with increasing ductility was observed. Volumetric and strength behaviour were found to be related to the particle size and fraction material removed while shear-wave measurements obtained pre- and post-particle removal indicate significant changes in small-strain stiffness.

CONTROL OF SIZE AND MAGNETIC PROPERTIES OF CARBOXYL-FUNCTIONALIZED MAGNETITE PARTICLES: SYNTHESIS PROCEDURES, CHARACTERIZATIONS, AND APPLICATIONS

Magnetic nanoparticles (MNPs) are known for the unique properties conferred by their small size and have found wide application in food safety analyses. However, their high surface energy and strong magnetization often lead to aggregation, compromising their functions. In this study, iron oxide magnetic particles (MPs) over the range of nano to micro size were synthesized, from which particles with less aggregation and excellent magnetic properties were obtained. MPs were synthesized via three different hydrothermal procedures, using poly (acrylic acid) (PAA) of different molecular weight (Mw) as the stabilizer. The particle size, morphology, and magnetic properties of the MPs from these synthesis procedures were characterized and compared. Among the three syntheses, one-step hydrothermal synthesis demonstrated the highest yield and most efficient magnetic collection of the resulting PAA-coated magnetic microparticles (PAA-MMPs, >100 nm). Iron oxide content of these PAA-MMPs was around 90%, and the saturation magnetization ranged from 70.3 emu/g to 57.0 emu/g, depending on the Mw of PAA used. In this approach, the particles prepared using PAA with Mw of 100K g/mol exhibited super-paramagnetic behavior with ~65% lower coercivity and remanence compared to others. They were therefore less susceptible to aggregation and remained remarkably water-dispersible even after one-month storage. Three applications involving PAA-MMPs from one-step hydrothermal synthesis were explored: food proteins and enzymes immobilization, antibody conjugation for pathogen capture, and magnetic hydrogel film fabrication. These studies demonstrated their versatile functions as well as their potential applications in the food science area.

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

Primary alkaline battery cathodes a three-scale model

A mathematical model for the galvanostatic discharge and recovery of porous, electrolytic manganese dioxide cathodes, similar to those found within primary alkaline batteries is presented. The phenomena associated with discharge are modeled over three distinct size scales, a cathodic (or macroscopic) scale, a porous manganese oxide particle (or microscopic) scale, and a manganese oxide crystal (or submicroscopic) scale. The physical and chemical coupling between these size scales is included in the model. In addition, the model explicitly accounts for the graphite phase within the cathode. The effects that manganese oxide particle size and proton diffusion have on cathodic discharge and the effects of intraparticle voids and microporous electrode structure are predicted using the model.

Wear mechanisms and scale effects in two-body abrasion

The ‘particle size effect’ and its manifestation in abrasion still attracts considerable debate as to its origins and the ranking of its likely causes. Experiments have been conducted to study the important contribution that the formation of wear debris can have on the progression of wear. The experiments consist of unlubricated (dry) pin-on-disk tests with silicon carbide coated paper of varying particle size, with different pin material, diameter and loads. It has been observed that the influence of debris formation on wear rate is more pronounced for fine abrasives and soft-wearing materials. Consequently, it is proposed that the particle size effect can be explained in terms of geometrical scaling and the evolution of third-body effects with diminishing particle diameter.

Microstructural characterization of electron beam evaporated tungsten oxide films for gas sensing applications

Tungsten trioxide is one of the potential semiconducting materials used for sensing NH3, CO, CH4 and acetaldehyde gases. The current research aims at development, microstructural characterization and gas sensing properties of thin films of Tungsten trioxide (WO3). In this paper, we intend to present the microstructural characterization of these films as a function of post annealing heat treatment. Microstructural and elemental analysis of electron beam evaporated WO3 thin films and iron doped WO3 films (WO3:Fe) have been carried out using analytical techniques such as Transmission electron microscopy, Rutherford Backscattered Spectroscopy and XPS analysis. TEM analysis revealed that annealing at 300oC for 1 hour improves cyrstallinity of WO3 film. Both WO3 and WO3:Fe films had uniform thickness and the values corresponded to those measured during deposition. RBS results show a fairly high concentration of oxygen at the film surface as well as in the bulk for both films, which might be due to adsorption of oxygen from atmosphere or lattice oxygen vacancy inherent in WO3 structure. XPS results indicate that tungsten exists in 4d electronic state on the surface but at a depth of 10 nm, both 4d and 4f electronic states were observed. Atomic force microscopy reveals nanosize particles and porous structure of the film. This study shows e-beam evaporation technique produces nanoaparticles and porous WO3 films suitable for gas sensing applications and doping with iron decreases the porosity and particle size which can help improve the gas selectivity.

Determining a set of surrogate parameters to evaluate urban stormwater quality

This thesis details methodology to estimate urban stormwater quality based on a set of easy to measure physico-chemical parameters. These parameters can be used as surrogate parameters to estimate other key water quality parameters. The key pollutants considered in this study are nitrogen compounds, phosphorus compounds and solids. The use of surrogate parameter relationships to evaluate urban stormwater quality will reduce the cost of monitoring and so that scientists will have added capability to generate a large amount of data for more rigorous analysis of key urban stormwater quality processes, namely, pollutant build-up and wash-off. This in turn will assist in the development of more stringent stormwater quality mitigation strategies. The research methodology was based on a series of field investigations, laboratory testing and data analysis. Field investigations were conducted to collect pollutant build-up and wash-off samples from residential roads and roof surfaces. Past research has identified that these impervious surfaces are the primary pollutant sources to urban stormwater runoff. A specially designed vacuum system and rainfall simulator were used in the collection of pollutant build-up and wash-off samples. The collected samples were tested for a range of physico-chemical parameters. Data analysis was conducted using both univariate and multivariate data analysis techniques. Analysis of build-up samples showed that pollutant loads accumulated on road surfaces are higher compared to the pollutant loads on roof surfaces. Furthermore, it was found that the fraction of solids smaller than 150 ìm is the most polluted particle size fraction in solids build-up on both roads and roof surfaces. The analysis of wash-off data confirmed that the simulated wash-off process adopted for this research agrees well with the general understanding of the wash-off process on urban impervious surfaces. The observed pollutant concentrations in wash-off from road surfaces were different to pollutant concentrations in wash-off from roof surfaces. Therefore, firstly, the identification of surrogate parameters was undertaken separately for roads and roof surfaces. Secondly, a common set of surrogate parameter relationships were identified for both surfaces together to evaluate urban stormwater quality. Surrogate parameters were identified for nitrogen, phosphorus and solids separately. Electrical conductivity (EC), total organic carbon (TOC), dissolved organic carbon (DOC), total suspended solids (TSS), total dissolved solids (TDS), total solids (TS) and turbidity (TTU) were selected as the relatively easy to measure parameters. Consequently, surrogate parameters for nitrogen and phosphorus were identified from the set of easy to measure parameters for both road surfaces and roof surfaces. Additionally, surrogate parameters for TSS, TDS and TS which are key indicators of solids were obtained from EC and TTU which can be direct field measurements. The regression relationships which were developed for surrogate parameters and key parameter of interest were of a similar format for road and roof surfaces, namely it was in the form of simple linear regression equations. The identified relationships for road surfaces were DTN-TDS:DOC, TP-TS:TOC, TSS-TTU, TDS-EC and TSTTU: EC. The identified relationships for roof surfaces were DTN-TDS and TSTTU: EC. Some of the relationships developed had a higher confidence interval whilst others had a relatively low confidence interval. The relationships obtained for DTN-TDS, DTN-DOC, TP-TS and TS-EC for road surfaces demonstrated good near site portability potential. Currently, best management practices are focussed on providing treatment measures for stormwater runoff at catchment outlets where separation of road and roof runoff is not found. In this context, it is important to find a common set of surrogate parameter relationships for road surfaces and roof surfaces to evaluate urban stormwater quality. Consequently DTN-TDS, TS-EC and TS-TTU relationships were identified as the common relationships which are capable of providing measurements of DTN and TS irrespective of the surface type.

Thin film deposition and characterization of pure and iron-doped electron-beam evaporated tungsten oxide for gas sensors

Pure Tungsten Oxide (WO3) and Iron-doped (10 at%) Tungsten Oxide (WO3:Fe) nanostructured thin films were prepared using a dual crucible Electron Beam Evaporation techniques. The films were deposited at room temperature in high vacuum condition on glass substrate and post-heat treated at 300 oC for 1 hour. From the study of X-ray diffraction and Raman the characteristics of the as-deposited WO3 and WO3:Fe films indicated non-crystalline nature. The surface roughness of all the films showed in the order of 2.5 nm as observed using Atomic Force Microscopy (AFM). X-Ray Photoelectron Spectroscopy (XPS) analysis revealed tungsten oxide films with stoichiometry close to WO3. The addition of Fe to WO3 produced a smaller particle size and lower porosity as observed using Transmission Electron Microscopy (TEM). A slight difference in optical band gap energies of 3.22 eV and 3.12 eV were found between the as-deposited WO3 and WO3:Fe films, respectively. However, the difference in the band gap energies of the annealed films were significantly higher having values of 3.12 eV and 2.61 eV for the WO3 and WO3:Fe films, respectively. The heat treated samples were investigated for gas sensing applications using noise spectroscopy and doping of Fe to WO3 reduced the sensitivity to certain gasses. Detailed study of the WO3 and WO3:Fe films gas sensing properties is the subject of another paper.

Nutrients build-up and wash-off processes in urban land uses

This thesis describes outcomes of a research study conducted to investigate the nutrient build-up and wash-off processes on urban impervious surfaces. The data needed for the study was generated through a series of field investigations and laboratory test procedures. The study sites were selected in urbanised catchments to represent typical characteristics of residential, industrial and commercial land uses. The build-up and wash-off samples were collected from road surfaces in the selected study sites. A specially designed vacuum collection system and a rainfall simulator were used for sample collection. According to the data analysis, the solids build-up on road surfaces was significantly finer with more than 80% of the particles below 150 ìm for all the land uses. Nutrients were mostly associated with the particle size range below 150 ìm in both build-up and wash-off samples irrespective of type of land use. Therefore, the finer fraction of solids was the most important for the nutrient build-up and particulate nutrient wash-off processes. Consequently, the design of stormwater quality mitigation measures should target particles less than 150 ìm for the removal of nutrients irrespective of type of land use. Total kjeldahl nitrogen (TKN) was the most dominant form of nitrogen species in build-up on road surfaces. Phosphorus build-up on road surfaces was mainly in inorganic form and phosphate (PO4 3-) was the most dominant form. The nutrient wash-off process was found to be dependent on rainfall intensity and duration. Concentration of both total nitrogen and phosphorus was higher at the beginning of the rain event and decreased with the increase in rainfall duration. Consequently, in the design of stormwater quality mitigation strategies for nutrients removal, it is important to target the initial period of rain events. The variability of wash-off of nitrogen with rainfall intensity was significantly different to phosphorus wash-off. The concentration of nitrogen was higher in the wash-off for low intensity rain events compared to the wash-off for high intensity rain events. On the other hand, the concentration of phosphorus in the wash-off was high for high intensity rain events compared to low intensity rain events. Consequently, the nitrogen washoff can be defined as a source limiting process and phosphorus wash-off as a transport limiting process. This highlights the importance of taking into consideration the wash-off of low intensity rain events in the design of stormwater quality mitigation strategies targeting the nitrogen removal. All the nitrogen species in wash-off are primarily in dissolved form whereas phosphorus is in particulate form. The differences in the nitrogen and phosphorus wash-off processes is principally due to the degree of solubility, attachment to particulates, composition of total nitrogen and total phosphorus and the degree of adherence of the solids particles to the surface to which nutrients are attached. The particulate nitrogen available for wash-off is removed readily as these are mobilised as free solids particles on the surface. Phosphorus is washed-off mostly with the solids particles which are strongly adhered to the surface or as the fixed solids load. Investigation of the nitrogen wash-off process using bulk wash-off samples was in close agreement with the investigation of dissolved fraction of wash-off solids. This was primarily due to the predominant nature of dissolved nitrogen. However, the investigation of the processes which underpin phosphorus wash-off using bulk washoff samples could lead to loss of information. This is due to the composition of total phosphorus in wash-off solids and the inherent variability of the wash-off process for the different particle size ranges. This variability should preferably be taken into consideration as phosphorus wash-off is predominantly in particulate form. Therefore, care needs to be taken in the investigation of the phosphorus wash-off process using bulk wash-off samples to ensure that there is no loss of information and hence result in misleading outcomes. The investigation of different particle size ranges of wash-off solids is preferable in the interest of designing effective stormwater quality management strategies targeting phosphorus removal.

The encapsulation of gold nanoparticles using RAFT, ATRP and miniemulsion polymerisation techniques

The investigation into the encapsulation of gold nanoparticles (AuNPs) by poly(methyl methacrylate) (PMMA) was undertaken. This was performed by three polymerisation techniques including: grafting PMMA synthesised by reversible addition-fragmentation chain transfer (RAFT) polymerisation to AuNPs, grafting PMMA synthesised by atom transfer radical polymerisation (ATRP) from the surface of functionalised AuNPs and by encapsulation of AuNPs within PMMA latexes produced through photo-initiated oil-in-water (o/w) miniemulsion polymerisation. The grafting of RAFT PMMA to AuNPs was performed by the addition of the RAFT functionalised PMMA to citrate stabilised AuNPs. This was conducted with a range of PMMA of varying molecular weight distribution (MWD) as either the dithioester or thiol end-group functionalities. The RAFT PMMA polymers were characterised by gel permeation chromatography (GPC), ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), Fourier transform Raman (FT-Raman) and proton nuclear magnetic resonance (1H NMR) spectroscopies. The attachment of PMMA to AuNPs showed a tendency for AuNPs to associate with the PMMA structures formed, though significant aggregation occurred. Interestingly, thiol functionalised end-group PMMA showed very little aggregation of AuNPs. The spherical polymer-AuNP structures did not vary in size with variations in PMMA MWD. The PMMA-AuNP structures were characterised using scanning electron microscopy (SEM), transition electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and UV-vis spectroscopy. The surface confined ATRP grafting of PMMA from initiator functionalised AuNPs was polymerised in both homogeneous and heterogeneous media. 11,11’- dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane] (DSBr) was used as the surface-confined initiator and was synthesised in a three step procedure from mercaptoundecanol (MUD). All compounds were characterised by 1H NMR, FTIR-ATR and Raman spectroscopies. The grafting in homogeneous media resulted in amorphous PMMA with significant AuNP aggregation. Individually grafted AuNPs were difficult to separate and characterise, though SEM, TEM, EDAX and UV-vis spectroscopy was used. The heterogeneous polymerisation did not produce grafted AuNPs as characterised by SEM and EDAX. The encapsulation of AuNPs within PMMA latexes through the process of photoinitiated miniemulsion polymerisation was successfully achieved. Initially, photoinitiated miniemulsion polymerisation was conducted as a viable low temperature method of miniemulsion initiation. This proved successful producing a stable PMMA with good conversion efficiency and narrow particle size distribution (PSD). This is the first report of such a system. The photo-initiated technique was further optimised and AuNPs were included into the miniemulsion. AuNP encapsulation was very effective, producing reproducible AuNP encapsulated PMMA latexes. Again, this is the first reported case of this. The latexes were characterised by TEM, SEM, GPC, gravimetric analysis and dynamic light scattering (DLS).

Dynamics of transformation and fragmentation of composite liquid nano-particles

Recent research on particle size distributions and particle concentrations near a busy road cannot be explained by the conventional mechanisms for particle evolution of combustion aerosols. Specifically they appear to be inadequate to explain the experimental observations of particle transformation and the evolution of the total number concentration. This resulted in the development of a new mechanism based on their thermal fragmentation, for the evolution of combustion aerosol nano-particles. A complex and comprehensive pattern of evolution of combustion aerosols, involving particle fragmentation, was then proposed and justified. In that model it was suggested that thermal fragmentation occurs in aggregates of primary particles each of which contains a solid graphite/carbon core surrounded by volatile molecules bonded to the core by strong covalent bonds. Due to the presence of strong covalent bonds between the core and the volatile (frill) molecules, such primary composite particles can be regarded as solid, despite the presence of significant (possibly, dominant) volatile component. Fragmentation occurs when weak van der Waals forces between such primary particles are overcome by their thermal (Brownian) motion. In this work, the accepted concept of thermal fragmentation is advanced to determine whether fragmentation is likely in liquid composite nano-particles. It has been demonstrated that at least at some stages of evolution, combustion aerosols contain a large number of composite liquid particles containing presumably several components such as water, oil, volatile compounds, and minerals. It is possible that such composite liquid particles may also experience thermal fragmentation and thus contribute to, for example, the evolution of the total number concentration as a function of distance from the source. Therefore, the aim of this project is to examine theoretically the possibility of thermal fragmentation of composite liquid nano-particles consisting of immiscible liquid v components. The specific focus is on ternary systems which include two immiscible liquid droplets surrounded by another medium (e.g., air). The analysis shows that three different structures are possible, the complete encapsulation of one liquid by the other, partial encapsulation of the two liquids in a composite particle, and the two droplets separated from each other. The probability of thermal fragmentation of two coagulated liquid droplets is discussed and examined for different volumes of the immiscible fluids in a composite liquid particle and their surface and interfacial tensions through the determination of the Gibbs free energy difference between the coagulated and fragmented states, and comparison of this energy difference with the typical thermal energy kT. The analysis reveals that fragmentation was found to be much more likely for a partially encapsulated particle than a completely encapsulated particle. In particular, it was found that thermal fragmentation was much more likely when the volume ratio of the two liquid droplets that constitute the composite particle are very different. Conversely, when the two liquid droplets are of similar volumes, the probability of thermal fragmentation is small. It is also demonstrated that the Gibbs free energy difference between the coagulated and fragmented states is not the only important factor determining the probability of thermal fragmentation of composite liquid particles. The second essential factor is the actual structure of the composite particle. It is shown that the probability of thermal fragmentation is also strongly dependent on the distance that each of the liquid droplets should travel to reach the fragmented state. In particular, if this distance is larger than the mean free path for the considered droplets in the air, the probability of thermal fragmentation should be negligible. In particular, it follows form here that fragmentation of the composite particle in the state with complete encapsulation is highly unlikely because of the larger distance that the two droplets must travel in order to separate. The analysis of composite liquid particles with the interfacial parameters that are expected in combustion aerosols demonstrates that thermal fragmentation of these vi particles may occur, and this mechanism may play a role in the evolution of combustion aerosols. Conditions for thermal fragmentation to play a significant role (for aerosol particles other than those from motor vehicle exhaust) are determined and examined theoretically. Conditions for spontaneous transformation between the states of composite particles with complete and partial encapsulation are also examined, demonstrating the possibility of such transformation in combustion aerosols. Indeed it was shown that for some typical components found in aerosols that transformation could take place on time scales less than 20 s. The analysis showed that factors that influenced surface and interfacial tension played an important role in this transformation process. It is suggested that such transformation may, for example, result in a delayed evaporation of composite particles with significant water component, leading to observable effects in evolution of combustion aerosols (including possible local humidity maximums near a source, such as a busy road). The obtained results will be important for further development and understanding of aerosol physics and technologies, including combustion aerosols and their evolution near a source.

Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Porous PLGA microspheres effectively loaded with BSA protein by electrospraying combined with phase separation in liquid nitrogen

Polymer microspheres loaded with bioactive particles, biomolecules, proteins, and/or growth factors play important roles in tissue engineering, drug delivery, and cell therapy. The conventional double emulsion method and a new method of electrospraying into liquid nitrogen were used to prepare bovine serum albumin (BAS)-loaded poly(lactic-co-glycolic acid) (PLGA) porous microspheres. The particle size, the surface morphology and the internal porous structure of the microspheres were observed using scanning electron microscopy (SEM). The loading efficiency, the encapsulation efficiency, and the release profile of the BSA-loaded PLGA microspheres were measured and studied. It was shown that the microspheres from double emulsion had smaller particle sizes (3-50 m), a less porous structure, a poor loading efficiency (5.2 %), and a poor encapsulation efficiency (43.5%). However, the microspheres from the electrospraying into liquid nitrogen had larger particle sizes (400-600 m), a highly porous structure, a high loading efficiency (12.2%), and a high encapsulation efficiency (93.8%). Thus the combination of electrospraying with freezing in liquid nitrogen and subsequent freeze drying represented a suitable way to produce polymer microspheres for effective loading and sustained release of proteins.

Delamination of kaolinite - potassium acetate intercalates by ball-milling

Structural changes in intercalated kaolinite after wet ball-milling were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), specific surface area (SSA) and Fourier Transform Infrared spectroscopy (FTIR). The X-ray diffraction pattern at room temperature indicated that the intercalation of potassium acetate into kaolinite causes an increase of the basal spacing from 0.718 to 1.42 nm, and with the particle size reduction, the surface area increased sharply with the intercalation and delamination by ball-milling. The wet ball-milling kaolinite after intercalation did not change the structural order, and the particulates have high aspect ratio according SEM images.