No description available.

在近期的研究結果中, 相分離被發現發生在具非晶結構的Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅合金，而該合金的構成元素之間的有負值的混合焓。通過高分辨率透射電子顯微鏡的直接成像的方法，他們為Pd-Ni-P非晶系統相分離的發生提供了證據。 / 在這篇論文所論述的研究工作中，我們運用類似的技術來研究Pḍ₄₀₊₀₅{U+2093}Nị₄₀₊₀₅{U+2093}P₂₀₋{U+2093}的合金系統從 x = 0到3.5的非晶相分離。 / 實驗結果顯示，任何在空氣中冷卻到578 K再在613K退火一小時的樣品 (乙類樣本)，非晶相分離都沒有發生。然而，在613K退火一小時而沒有經過578K和613K溫度範圍的Pḍ₄₀₊₀₅{U+2093}Nị₄₀₊₀₅{U+2093}P₂₀₋{U+2093}大塊非晶金屬(丙類樣本)，卻在部分成分範圍中發生相分離。在丙類樣本中，當x>1，相分離發生；而當x≤1，相分離沒有發生。通過量度高角環形暗場影像中顯示的兩個相的平均波長，我們可得出其統計結果，而該統計結果與槓桿規則吻合。從此可見，在過冷的Pd-Ni-P熔合合金中存在著亞穩液態混溶間隙。並且這種出現在有負值混合焓的系統的亞穩液態混溶間隙，可以以短程有序的模型來解釋。 / Recently, the phase separation was found in the system of amorphous Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅ alloys which has negative heat of mixing among the constituent elements. In their work, the directly imaging method by technique of high resolution TEM provided the evidence of phase separation in amorphous Pd-Ni-P system. / In this work, by applying the similar technique of that previous studies, the alloy systems of Pḍ₄₀₊₀₅{U+2093}Nị₄₀₊₀₅{U+2093}P₂₀₋{U+2093} for x = 0 to 3.5were studied for amorphous phase separation. / The experimental result showed that for any sample which was allowed to cool down in air to 578 K before thermal annealing (B-type), there was no amorphous phase separation. But for the Pḍ₄₀₊₀₅{U+2093}Nị₄₀₊₀₅{U+2093}P₂₀₋{U+2093} BMG that was annealed at 613K for one hour without bypassing the temperature range between 578K and 613K (C-type), phase separation occurred with x>1 but absented when x≤1. The result of average wavelength measurement of the two phases in the HAADF images of the sample with phase separation obeyed the lever rule. This result suggested that in undercooled molten Pd-Ni-P alloys, there is a metastable liquid state miscibility gap. The formation of such miscibility gap in a system with negative heat of mixing can be explained by the model of unique short range orders. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Lau, Man Tat = 過冷鈀、鎳、磷熔化物中的亞穩液態互溶間隙 / 劉文達. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references. / Abstracts also in Chinese. / Lau, Man Tat = Guo leng ba, nie, lin rong hua wu zhong de ya wen ye tai hu rong jian xi / Liu Wenda. / Abstract --- p.i / Acknowledgement --- p.iv / List of Tables --- p.vii / List of Figures --- p.viii / Chapter Chapter 1 --- : Introduction --- p.1 / Chapter 1.1 --- Amorphous metal --- p.1 / Chapter 1.2 --- Phase Separation --- p.3 / Chapter 1.3 --- Nucleation --- p.6 / Chapter 1.4 --- Spinodal Decomposition --- p.10 / Chapter 1.5 --- Objective of the project --- p.16 / Figures --- p.18 / References --- p.26 / Chapter Chapter 2 --- : Experiment --- p.27 / Chapter 2.1 --- Preparation of sample --- p.27 / Chapter 2.2 --- Differential scanning calorimetry --- p.30 / Chapter 2.3 --- Preparation of TEM sample --- p.31 / Chapter 2.4 --- Microstructural analysis --- p.33 / Figures --- p.36 / References --- p.39 / Chapter Chapter 3 --- : A metastable liquid state miscibility gap in undercooled Pd-Ni-P melts --- p.40 / Chapter 3.1 --- Introduction --- p.40 / Chapter 3.2 --- Materials and experimental --- p.41 / Chapter 3.3 --- Results --- p.44 / Chapter 3.4 --- Discussions --- p.49 / Chapter 3.5 --- Conclusions --- p.52 / Table --- p.53 / Figures --- p.54 / References --- p.75

Defects, i.e. hot tears, macrosegragation, and pores, formed in metal castings are a result of stresses and strains in the solid-liquid mushy zone. Numerical simulation of solidification of deforming dendrite crystal promises to improve insight into the mechanical behavior of mushy zones under an applied load. The primary goal of this thesis is to develop numerical methodologies for performing solidification simulation of deforming dendrites. Such simulation encounters difficulties associated with the interface dynamics due to phase change or interaction among the dendrites, and large visco-plastic deformation applied to them. Phase-field simulation of dendritic solidification is promising for the treatment of the complex interface dynamics. Free energy based formulation allows the model to incorporate bridging and wetting phenomena occurring at grain boundaries through an extra energy term which arises from a mismatch of the crystallographic orientation. The particle method would be attractive to handle large inelastic deformation without suffering mesh entanglement. In order to investigate the effect of solid deformations on the evolving microstructure, the material point method with elasto-visco-plasticity constitutive model is developed to couple to a phase-field model of solidification. The changes in the crystallographic orientation of a growing dendrite crystal due to solid deformation are carefully accounted for through the coupling methodology. The developed numerical framework is applicable to the simulation for single and multiple crystals, and is capable of handling complex morphological change. The wide variety of validations and practical problems solved in this thesis demonstrates the capability of investigating deformation behavior of growing crystals.

This dissertation examines the applicability of the iron-based degradative solidification/stabilization (DS/S-Fe(II)) to various chlorinated aliphatic hydrocarbons (CAHs) that are common chemicals of concern at contaminated sites. The research focuses on the transformation of 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloro-ethane (1,1,2,2-TetCA) and 1,2-dichloroehtane (1,2-DCA) by Fe(II) in cement slurries. It also investigates the degradation of 1,1,1-TCA by a mixture of Fe(II), cement and three iron-bearing phyllosilicates. Transformation of 1,1,1-TCA and 1,1,2,2-TetCA by Fe(II) in 10% cement slurries was characterized using batch reactors. Dechlorination kinetics of 1,1,1-TCA and TCE* (TCE that was produced by transformation of 1,1,2,2-TetCA) was strongly dependent on Fe(II) dose, pH and initial target organic concentration. Degradation of target organics in DS/S-Fe(II) process was generally described by a pseudo-first-order rate law. However, saturation relationships between the rate constants and Fe(II) dose or between the initial degradation rates and target organic concentration were observed. These behaviors were properly described by a modified Langmuir-Hinshelwood kinetic model. This supports the working hypothesis of this research that reductive dechlorination of chlorinated ethanes occurs on the surface of active solids formed in mixtures of Fe(II) and cement. Transformation products for 1,1,1-TCA and 1,1,2,2-TetCA in mixtures of Fe(II) and cement were identified. The major product of the degradation of 1,1,1-TCA was 1,1-DCA, which indicates that the reaction followed a hydrogenolysis pathway. However, a small amount of ethane was also observed. TCE* was rapidly produced by degradation of 1,1,2,2-TetCA and is expected to undergo β-elimination to produce acetylene. Dechlorination of 1,1,1-TCA in suspension of Fe(II), cement and three soil minerals (biotite, vermiculite, montmorillonite) was characterized using batch reactors. A first-order rate model was generally used to describe the dechlorination kinetics of 1,1,1-TCA in this heterogeneous system. The rate constants for 1,1,1-TCA in mixtures of Fe(II), cement and soil minerals were influenced by soil mineral types, Fe(II) dose and the mass ratio of cement to soil mineral. It was demonstrated that structural Fe(II) and surface-bound Fe(II) in the soil minerals affect dechlorination kinetics and the effects vary with mineral types. Furthermore, it suggests that the reductant formed from Fe(II) and cement hydration components is also effective in systems that include soil minerals.

Heterogeneous nucleation of bubbles on an advancing solidification front during freezing of water containing a dissolved gas has been experimentally and analytically studied. The formation of bubbles resulting from supersaturation of liquids is commonly encountered in different fields such as heat transfer, manufacturing, and bioscience.In this work, sizes of nucleating bubbles and concentration profiles of dissolved oxygen and carbon dioxide gases in water ahead of the solidification front have been measured.From successful comparisons between the measured and predicted critical radii of nucleating bubbles and distributions of dissolved gas content, phenomena of heterogeneous nuc leation in a binary weak solution during the freezing process are quantitatively confirmed.

Proposing a math model and using enthalpy method to solve the temperature and flow field distribution around the bubble. Find the influence for different coefficients.

This paper numerically simulates flow and concentration fields in a supersaturated liquid in front of the solidification front during freezing. The supersaturated liquid usually produces bubbles. This phenomenon often occurs in different fields, for example, heat transfer, manufacture, biochemistry , etc. The research is based on micro theory to analyze different phenomena of a single bubble, which involve the unsteady interactions between flow and concentration fields, and rising and resistance forces etc. The results contribute to an improved understanding of bubble dynamics generally encountered in technological industries.

The sizes of a bubble trapped in solid after nucleation on the solidification front during an upward freezing of water containing a dissolved oxygen or carbon dioxide gas are experimentally measured and quantitatively predicted in this work. From an in situ measurements of bubble shapes in solid at cold temperatures of -25 and -15 C, it quantitatively shows that pore formation can be divided into five regimes: (1) nucleation on the solidification front, (2) spherical growth, (3) solidification rate-controlled elongation, (4) disappearance of the bubbles, and (5) formation of the pores in solid. To interpret experimental results, equations incorporated with the growth rate of a spherical bubble and solidification rate to predict bubble shapes in the solid during the spherical growth and solidification rate-controlled elongation are successfully proposed. Experimental data show the effects of initial gas concentration and solidification rate on geometries of the bubble in solid.

Heterogeneous nucleation of bubbles on an advancing solidification front during freezing of water containing a dissolved gas has been experimentally and analytically studied. The formation of bubbles resulting from supersaturation of liquids is commonly encountered in different fields such as heat transfer, manufacturing, and bioscience. In this work, sizes of nucleating bubbles and concentration profiles of dissolved oxygen and carbon dioxide gases in water ahead of the solidification front have been measured. From successful comparisons between the measured and predicted critical radii of nucleating bubbles and distributions of dissolved gas content, phenomena of heterogeneous nucleation in a binary weak solution during the freezing process are quantitatively confirmed. The results show that an increase in gas content at the solidification front in the liquid decreases the free energy barrier and critical radii of bubbles that are formed on the solidification front. In the early stage of solidification, sizes of the critical radii decrease and the number of nucleating bubbles increase. As solidification rates decrease later, content of the dissolved gas in the liquid on the advancing interface decreases and the critical radii of nucleating bubbles increase.

This dissertation examines the applicability of the iron-based degradative solidification/stabilization (DS/S-Fe(II)) to various chlorinated aliphatic hydrocarbons (CAHs) that are common chemicals of concern at contaminated sites. The research focuses on the transformation of 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloro-ethane (1,1,2,2-TetCA) and 1,2-dichloroehtane (1,2-DCA) by Fe(II) in cement slurries. It also investigates the degradation of 1,1,1-TCA by a mixture of Fe(II), cement and three iron-bearing phyllosilicates. Transformation of 1,1,1-TCA and 1,1,2,2-TetCA by Fe(II) in 10% cement slurries was characterized using batch reactors. Dechlorination kinetics of 1,1,1-TCA and TCE* (TCE that was produced by transformation of 1,1,2,2-TetCA) was strongly dependent on Fe(II) dose, pH and initial target organic concentration. Degradation of target organics in DS/S-Fe(II) process was generally described by a pseudo-first-order rate law. However, saturation relationships between the rate constants and Fe(II) dose or between the initial degradation rates and target organic concentration were observed. These behaviors were properly described by a modified Langmuir-Hinshelwood kinetic model. This supports the working hypothesis of this research that reductive dechlorination of chlorinated ethanes occurs on the surface of active solids formed in mixtures of Fe(II) and cement. Transformation products for 1,1,1-TCA and 1,1,2,2-TetCA in mixtures of Fe(II) and cement were identified. The major product of the degradation of 1,1,1-TCA was 1,1-DCA, which indicates that the reaction followed a hydrogenolysis pathway. However, a small amount of ethane was also observed. TCE* was rapidly produced by degradation of 1,1,2,2-TetCA and is expected to undergo β-elimination to produce acetylene. Dechlorination of 1,1,1-TCA in suspension of Fe(II), cement and three soil minerals (biotite, vermiculite, montmorillonite) was characterized using batch reactors. A first-order rate model was generally used to describe the dechlorination kinetics of 1,1,1-TCA in this heterogeneous system. The rate constants for 1,1,1-TCA in mixtures of Fe(II), cement and soil minerals were influenced by soil mineral types, Fe(II) dose and the mass ratio of cement to soil mineral. It was demonstrated that structural Fe(II) and surface-bound Fe(II) in the soil minerals affect dechlorination kinetics and the effects vary with mineral types. Furthermore, it suggests that the reductant formed from Fe(II) and cement hydration components is also effective in systems that include soil minerals.