This thesis highlights a comprehensive research for the cell nucleation, growth and coarsening mechanisms during plastic foaming processes. Enforced environmental regulations have forced the plastic foam industry to adopt alternative blowing agents (e.g., carbon dioxide, nitrogen, argon and helium). Nevertheless, the low solubilities and high diffusivities of these viable alternatives have made the production of foamed plastics to be non-trivial. Since the controls of the cell nucleation, growth and coarsening phenomena, and ultimately the cellular morphology, involve delicate thermodynamic, kinetic, and rheological mechanisms, the production of plastics foams with customized cell morphology have been challenging. In light of this, the aforementioned phenomena were investigated through a series of theoretical studies, computer simulations, and experimental investigations. Firstly, the effects of processing conditions on the cell nucleation phenomena were studied through the in-situ visualization of various batch foaming experiments. Most importantly, these investigations have led to the identification of a new heterogeneous nucleation mechanism to explain the inorganic fillers-enhanced nucleation dynamics. Secondly, a simulation scheme to precisely simulate the bubble growth behaviors, a modified heterogeneous nucleation theory to estimate the cell nucleation rate, and an integrated model to simultaneously simulate cell nucleation and growth processes were developed. Consequently, through the simulations of the cell nucleation, growth, and coarsening dynamics, this research has advanced the understanding of the underlying sciences that govern these different physical phenomena during plastic foaming. Furthermore, the impacts of various commonly adopted approximations or assumptions were studied. The end results have provided useful guidelines to conduct computer simulation on plastic foaming processes. Finally, an experimental research on foaming with blowing agent blends served as a case example to demonstrate how the elucidation of the mechanisms of various foaming phenomena would aid in the development of novel processing strategies to enhance the control of cellular structures in plastic foams.

Chemical-looping combustion is an indirect oxygen combustion strategy, considered to be the most cost-effective power generation technology with the CO2 inherently concentrated. In this process, a solid oxygen carrier is used to transfer oxygen from the air reactor to the fuel reactor, which completely isolates nitrogen in air to meet with fuels. The oxygen carriers in the combustion process are subjected to the severe environments, such as high temperatures, multi-cycle operations, and thermodynamic limitations. Thus, the preparation of an oxygen carrier with high durability and better kinetics under harsh environment could be an essential part of Chemical-looping combustion development. In this study, modified wet impregnation and co-precipitation methods have been developed. The active ingredient is copper(II) oxide, and the supporting material is either directly from titanium(IV) oxide (anatase 99%) or that prepared from other titanium resources such as titanium tetrachloride and tetrabutyl titanate. Preliminary results showed the prepared oxygen carriers functioned properly in the multi-cycles of oxidization and reduction in TGA at different temperatures. Characterization of used oxygen carriers was carried out using techniques of XRD, and SEM-EDS, which provide information for the difference between oxygen carriers from different preparation methods. Through the comparison, the oxygen carrier from the sol-gel preparation method has better dispersion and oxidation activity than those from mechanical mixing, wet-impregnation, and cox precipitation method. Moreover, towards the oxygen carrier from sol-gel method, nucleation model and diffusion models were determined at different reaction periods.

Chemical vapor deposition (CVD) has been the main method for synthesizing diamond thin films on hetero substrate materials since 1980s. It has been well acknowledged that both nucleation and growth of diamond on non-diamond surfaces without pre-treatment are very difficult and slow. Furthermore, the weak adhesion between the diamond thin films and substrates has been a major problem for widespread application of diamond thin films. Up to now, Si has been the most frequently used substrate for the study of diamond thin films and various methods, including bias and diamond powder scratching, have been applied to enhance diamond nucleation density. In the present study, nucleation and growth of diamond thin films on Ti3SiC2, a newly developed ceramic-metallic material, using Microwave Plasma Enhanced (MPE) and Hot-Filament (HF) CVD reactors were carried out. In addition, synchrotron-based Near Edge Extended X-Ray Absorption Fine Structure Spectroscopy (NEXAFS) was used to identify the electronic and chemical structures of various NCD films. The results from MPECVD showed that a much higher diamond nucleation density and a much higher film growth rate can be obtained on Ti3SiC2 compared with on Si. Consequently, nanocrystalline diamond (NCD) thin films were feasibly synthesized on Ti3SiC2 under the typical conditions for microcrystalline diamond film synthesis. Furthermore, the diamond films on Ti3SiC2 exhibited better adhesion than on Si. The early stage growth of diamond thin films on Ti3SiC2 by HFCVD indicated that a nanowhisker-like diamond-graphite composite layer, different from diamond nucleation on Si, initially formed on the surface of Ti3SiC2, which resulted in high diamond nucleation density. These results indicate that Ti3SiC2 has great potentials to be used both as substrates and interlayers on metals for diamond thin film deposition and application. This research may greatly expand the tribological application of both Ti3SiC2 and diamond thin films. The results demonstrated that NEXAFS is a reliable and powerful tool to identify NCD films.

The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity (PDI) differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the polydispersity of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.

In the work presented in this dissertation, extensive molecular dynamics (MD) simulations have been performed to investigate various physical problems related to the solid-liquid transitions over a wide range of supercooling and superheating temperatures in model Lennard-Jones systems. The major focus of this work is to investigate the thermodynamics, kinetics, and underlying mechanisms of these problems. There are five topics in this work: (1) The classical nucleation theory (CNT) was tested for both liquid supercooling and solid superheating via different solid-liquid coexistence models. It is found that the CNT is valid for liquid supercooling but invalid for solid superheating. The arising elastic energy plays a significant role in affecting the liquid nucleation in a superheated solid. A new nucleation theory was proposed for describing the internal liquid nucleation of solid superheating. (2) Based on CNT, a new and accurate method was developed for calculating the crystal-melt interfacial free energy and its anisotropy. Our result is very close to Turnbulls experimental results. (3) The face, temperature, and size dependences of the crystallization rate were investigated in this work. The results show that the crystallization rate decreases substantially with the increasing system size. Different from the conventional models, a new model is developed to describe these dependences. (4) Melting from internal nanovoids was investigated in this work. It is found that the mechanism of void melting is quite different from bulk melting and nanoparticle melting. There are four different stages and three local melting temperatures in void melting. The mechanism of the complex melting sequence is systematically explained. (5) The homogenous melting at the upper limit of superheating was investigated in this work. For the first time, the ring diffusion is found to take place in superheated crystals and causes the spontaneous melting. The prevailing instability theories are unsuitable to describe this type of melting. The mechanism of the diffusion-loop mediated melting is carefully discussed in this work.

Soot and other products of incomplete combustion play an important role in the chemistry of the atmosphere. As particles are exposed to trace gases, such as ozone, their chemistry and physical properties can be altered leading to changes in their optical properties, as well as their cloud condensation nuclei and ice nucleation abilities. These alterations can lead to changes in the global radiative budget and cloud microphysical processes, which in turn affect the climate. In this study, the chemical and physical changes associated with the oxidation of pyrene, anthracene, and carbon (lampblack) by ozone were investigated. Fourier Transform Infrared Spectroscopy was used to identify oxidation products and track reaction progress for these representative aerosols. A C=O band attributed to a carboxylic acid formation was observed for all three substances, at each level of exposure to ozone - 20 ppm, 40 ppm, and 80 ppm. Second order reaction rate constants ranged from 9.58 x 10-16 cm2 molecules-1 s-1 to 7.71 x 10-13 cm2 molecules-1 s-1. Measurements of water uptake, ice nucleation efficiency, and optical properties were obtained to determine whether any physical changes associated with the oxidation process occurred. Optical measurements show an increase in the ultra-violet absorption of anthracene, but not for pyrene, while an increase in the visible absorption for pyrene was observed, but not for anthracene. Oxidized soot froze at a warmer temperature (-22.8 degrees C) then fresh soot (-25.6 degrees C), showing an increase in ice nucleation efficiency. Our data indicates that oxidation by ozone does alter the chemistry and physical properties of the substances study, leading to possible changes in how they interact with atmospheric processes.

Hexagonal boron nitride (h-BN) formation by carbothermic reduction of B2O3 under nitrogen atmosphere at 1500&deg / C and effect of CaO addition into the initial B2O3 &amp / #8211 / active C mixture were investigated during this study. Reaction products were characterized by powder X-ray diffraction, scanning electron microscopy (SEM) and quantitative chemical analysis. Main aim of this study was to investigate the presence of a second reaction mechanism that catalytically affects h-BN formation during CaO or CaCO3 addition into the initial mixture. It was found that similar to CaCO3 addition, CaO addition has a catalytic effect on carbothermic formation h-BN. In order to investigate the reaction mechanism experiments with B2O3 &amp / #8211 / CaO mixtures without active carbon addition into the mixture were conducted. Furthermore nucleation of h-BN from calcium borate melts had been investigated and experiments were conducted with h-BN addition into CaO &amp / #8211 / B2O3 mixtures. It was concluded that nucleation of h-BN in calcium borate slags under experimental conditions is not possible. Hexagonal BN should be present in the system in order to activate the second nitrogen dissolution followed by h-BN precipitation mechanism. Highest efficiency was achieved in the experiment conducted with CaCO3 addition and largest particle size was observed during the experiment conducted to investigate the effect of nucleation.

Aromatic hydrocarbons constitute an important fraction (~20%) of total volatile organic compounds (VOCs) in the urban atmosphere. A better understanding of the aromatic oxidation and its association in urban and regional ozone and organic aerosol formation is essential to assess the urban air pollution. This dissertation consists of two parts: (1) theoretical investigation of the toluene oxidation initiated by OH radical using quantum chemical and kinetic calculations to understand the mechanism of O3 and SOA precursors and (2) experimental investigation of atmospheric new particle formation from aromatic acids. Density functional theory (DFT) and ab initio multiconfigurational calculations have been performed to investigate the OH-toluene reaction. The branching ratios of OH addition to ortho, para, meta, and ipso positions are predicted to be 0.52, 0.34, 0.11, and 0.03, respectively, significantly different from a recent theoretical study of the same reaction system. Aromatic peroxy radicals arising from initial OH and subsequent O2 additions to the toluene ring are shown to cyclize to form bicyclic radicals rather than undergoing reaction with NO under atmospheric conditions.Isomerization of bicyclic radicals to more stable epoxide radicals possesses significantly higher barriers and hence has slower rates than O2 addition to form bicyclic peroxy radicals. At each OH attachment site, only one isomeric pathway via the bicyclic peroxy radical is accessible to lead to ring cleavage. Decomposition of the bicyclic alkoxy radicals leads primarily to formation of glyoxal and methyl glyoxal along with other dicarbonyl compounds. Atmospheric aerosols often contain a considerable fraction of organic matter, but the role of organic compounds in new nanometer-sized particle formation is highly uncertain. Laboratory experiments show that nucleation of sulfuric acid is considerably enhanced in the presence of aromatic acids. Theoretical calculations identify the formation of an unusually stable aromatic acid-sulfuric acid complex, which likely leads to a reduced nucleation barrier. The results imply that the interaction between organic and sulfuric acids promotes efficient formation of organic and sulfate aerosols in the polluted atmosphere because of emissions from burning of fossil fuels, which strongly impact human health and global climate.

Nucleation of dislocation loop at the crack tip in a material subjected to uniaxial loading is investigated. Analytical expression for the total energy of rectangular dislocation loop at the crack tip is found. Depencence of the nucleation energy barrier on dislocation loop shape and stress intensity factor at the crack tip is determined. It is established that the energetic barrier for nucleation of dislocation loop strongly depends on the stress intensity factor. Nucleation of dislocation loop is very sensitive to stress field modifiers (forest dislocations, precipitates, clusters of point defects, etc.) in the crack tip vicinity.

<p>Admixtures like reactants and byproducts are solublenon-crystallizing compounds that can be present in industrialsolutions and affect crystallization of the main substance.This thesis provides experimental and molecular modellingresults on the influence of admixtures on crystal nucleation ofvanillin (VAN). Seven admixtures: acetovanillone (AVA),ethylvanillin (EVA), guaiacol (GUA), guaethol (GUE), 4-hydroxy-acetophenone (HAP), 4-hydroxy-benzaldehyde (HBA), andvanillic acid (VAC) have been used in this study. Classicalnucleation theory is used as the basis to establish arelationship between experimental induction time andsupersaturation, nucleation temperature, and interfacialenergy. A novel multicell device is designed, constructed, andused to increase the experimental efficiency in thedetermination of induction times by using 15 nucleation cellsof small volumes simultaneously. In spite of the largevariation observed in the experiments, the solid-liquidinterfacial energy for each VAN-admixture system can beestimated with an acceptable statistical confidence. At 1 mole% admixture concentration, the interfacial energy is increasedin the presence of GUA, GUE, and HBA, while it becomes lower inthe presence of the other admixtures. As the admixtureconcentration increases from 1 to 10 mole %, the interfacialenergy also increases. The interfacial energies obtained are inthe range 7-10 mJ m^-2. Influence of admixtures on metastable zone widthand crystal aspect ratio of VAN is also presented. Theexperimental results show that the admixtures studied arepotential modifiers of the nucleation of VAN. Molecularmodelling by the program Cerius2 is used to identify the likelycrystal growth faces. Two approaches, the surface adsorptionand the lattice integration method, are applied to estimatequantitatively the admixture-crystal interaction energy on thedominating crystal faces of VAN,<i>i.e</i>., {0 0 1} and {1 0 0}. However, a simple and clearcorrelation between the experimental values of interfacialenergy and the calculated interaction energies cannot beidentified. A qualitative structural analysis reveals a certainrelationship between the molecular structure of admixtures andtheir effect on nucleation. The determination of the influenceof admixtures on nucleation is still a challenge. However, themolecular and crystal structural approach used in this thesiscan lead to an improved fundamental understanding ofcrystallization processes. Keywords: Crystallization,nucleation, vanillin, admixtures, additives, impurities,induction time, interfacial energy, molecular modelling,interaction energy.</p>