By combining experiment and theory, we believe our study shed light on developing a new method for well investigating and controlling the different plasmonic modes and open their way for some great applications in biology, chemistry and photonics. / Finally, this thesis presents an approach to quantitatively evaluate the SP-mediated light emission. Based on this consideration, efforts are taken to find the temperature effect of SP on the light emission in semiconductor. On metal/ZnO system, a more realistic picture for the light emission is depicted by experimentally measuring the temperature-dependent photoluminescence and theoretically calculating the Purcell enhancement factor. The increasing plasmonic density of states with the lower temperature has been regarded as being responsible for the enhanced light emission. / Firstly, studies are performed on finding an in-depth understanding into the optical properties of two-dimensional (2D) metallic nano-cavity structure (grating). Structures are fabricated by interference lithography and thin film techniques. Grating geometries can be easily tuned by using these versatile techniques with high reproducibility and precision. Plasmonic dispersion in the 2D grating has been mapped out by angle-dependent reflectivity measurements. Two particular nanostructures, i.e., nano-bottle array and elliptical hole array, have been chosen to investigate the dependence of plasmonic properties on geometries change. Theories are also put forward to understand the origin and electromagnetic properties of the obtained plasmonic modes. / Surface plasmons (SP), the collective oscillations of the conduction electrons between the metal/dielectric interface, strongly influence the optical properties of metallic nanostructures and are of great interest for future photonic devices. Here, this thesis mainly focuses on the experimental and theoretical investigations on the optical properties of the metallic periodic nanostructures. / With an understanding into the different plasmonic properties of the metallic nanostructures, researches are then undertaken to explore how this associated electromagnetic field interacts with the molecules adsorbed onto a sample surface. The distinct and strong correlation between the plasmonic modes and surface enhanced Raman scattering (SERS) is verified on the one-dimensional silver grating. In particular, the detailed analysis of the enhancement factor from surface plasmons excitation and de-excitation process in SERS has been performed. On the other hand, the technique used to fabricate the controllable "hot spot" for enhancing Raman scattering has been introduced on the 2D metallic grating. Complemented by the theoretical simulation, the conditions for optimizing SERS enhancement effect are proposed. / Li, Jia = 週期性金屬鈉米結構光學特性的實驗和理論研究 / 李佳. / Adviser: Ong Hock Chun. / Source: Dissertation Abstracts International, Volume: 71-01, Section: B, page: 0388. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 135-144). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / Li, Jia = Zhou qi xing jin shu na mi jie gou guang xue te xing de shi yan he li lun yan jiu / Li Jia.

CaCu3Ti4O12 (CCTO), an unusual perovskite-like material, is known for extraordinarily high (often reaching 104) and relatively frequency independent dielectric constant. Recently, it has drawn a lot of attention, because of its potential applications in microelectronics and microwave devices. / In this investigation, CCTO powders were synthesized by two routes, a conventional solid-state reaction and a wet-chemistry method. Three kinds of materials, polyvinyl alcohol (PVA, an organic binder), boric oxide (B 2O3, a well-known glass former), hafnium oxide (HfO 2, a material with high dielectric constant ∼25), were added to the pre-reacted CCTO powder and sintered into ceramics. The effects of these additives on the microstructures, or electric and dielectric properties of CCTO ceramics were investigated. In addition, CCTO thin films were also successfully prepared. The AC conductivity, impedance, and complex dielectric permittivity were used to analyze the data. These observations were well explained in terms of an internal barrier layer capacitor (IBLC) model with Maxwell-Wagner (MW) dielectric relaxation. / Yuan, Wenxiang = 高介電常數材料CaCu₃Ti₄O₁₂χχχ / 苑文香. / Adviser: S.K. Hark. / Source: Dissertation Abstracts International, Volume: 73-01, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Yuan, Wenxiang = Gao jie dian chang shu cai liao CaCu₃Ti₄O₁₂ de yan jiu / Yuan Wenxiang.

I believe that my research work on the plasmonic spectroscopy of metallic nanostructures has provided an in-depth fundamental understanding of the localized surface plasmon resonance and will have a number of implications for the applications of metallic nanostructures in optics, optoelectronics, and biotechnology. / I will first describe my studies on the plasmonic properties of metallic nanostructures. Specific approaches of modifying the sizes and shapes of Au nanorods have been developed for tailoring their plasmonic properties, including surface plasmon wavelength, absorption, scattering, and extinction cross sections. Single-particle dark-field imaging and spectroscopy have proved that the scattering intensity of overgrown nanorods is larger than that of shortened nanorods from the same starting nanorods. Finite-difference time-domain (FDTD) calculations further show that the scattering-to-extinction ratio increases linearly as a function of the diameter of Au nanorods with a fixed aspect ratio. To obtain a deep understanding on the shape dependence of the localized surface plasmon resonance, I have emplyed FDTD on both Au nanorods and Au nanobipyramids. The results show that, when excited at their LSP wavelengths, Au nanobipyramids exhibit a maximal electric field intensity enhancement that is 3--6 times that of Au nanorods. Au nanorods have been further assembled into chains (end-to-end) and stacks (side-by-side). FDTD calculations have been performed on both Au nanorod chains and stacks with varying gap distances to obtain the dependence of the plasmon shift on the gap distance, which is then used as a plasmonic ruler to estimate the gap distance between assembled nanorods. Moreover, dye--Au nanorod hybrid nanostructures have also been successfully fabricated for the study of the coupling between the transition dipole resonance and the plasmonic resonance. The coupling-induced plasmon shift is found to be strongly dependent on molecular properties, the dye concentration in solutions, and the spacer thickness between dye molecules and the surface of Au nanorods. The coupling can be switched off by means of laser-induced photodecomposition of dye molecules. / Next, I will present my studies on the applications of metallic nanostructures. A SERS substrate has been constructed by assembling silver nanoparticles along silica nanofibers. The enhancement factors are found to be 2 x 10 5 for 4-mercaptobenzoic acid and 4-mercaptophenol, and 7 x 10 7 for rhodamine B isothiocyanate. A novel plasmonic optical fiber device has further been fabricated to detect small changes in the local dielectric environment. For individual Au nanorods, the index sensitivity and figure of merit (FOM) are found to be linearly dependent on the longitudinal plasmon resonance wavelength and reach 200 nm/RIU and 3.8, respectively. For nanorod ensembles, the index sensitivity and FOM of the longitudinal plasmon resonance are found to be 138 nm/RIU and 1.2, respectively. / The study of the plasmonic spectroscopy of metallic nanostructures is of great interest in nanoscale optics and photonics. Metallic nanostructures exhibit rich optical and electrical properties due to their localized surface plasmons (LSPs, collective charge density oscillations that are confined to metallic nanostructures). They can be widely used in a variety of application areas, such as surface-enhanced Raman scattering (SERS), plasmonic sensing, and metal enhanced fluorescence (MEF). In this thesis, a systematic study on the plasmonic spectroscopy of metallic nanostructures has been presented, both theoretically and experimentally. / Ni, Wei hai = 金屬納米結構的等離子體光譜 / 倪衛海. / Adviser: Jianfang Wang. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3580. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 135-154). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307. / Ni, Wei hai = Jin shu na mi jie gou de deng li zi ti guang pu / Ni Weihai.

A metal-oxide-silicon (MOS) tunneling diode is utilized to embed beta-FeSi 2 precipitates and give strong 1.5 tam electroluminescence at 80 K. And this simple MOS structure with beta-FeSi2 was fabricated by Fe ion implantation and rapid thermal oxidation (RTO) at 900°C, which is fully compatible with ultra-large scale integration (ULSI) processes. / beta-FeSi2 precipitates are also incorporated into a silicon-on-insulator (SOI) rib waveguide and a p+-i-n+ photodetector is monolithically integrated with this SOI rib waveguide. The photoresponse to 1550 nm laser of beta-FeSi2 precipitates was observed and compared to intrinsic silicon. / Beta-phase iron disilicide (beta-FeSi2) is a semiconductor that can act as a light emitting material at the wavelength of 1.55 mum and can also be grown epitaxially on Si substrates. In this thesis, Fe ion implantation into silicon using a metal vapor vacuum arc (MEVVA) ion source was performed to synthesize nano-scale beta-FeSi2 precipitates in silicon matrix. The implantation was performed at ∼-120°C and the effects of silicon substrate and conditions for the following thermal annealing on luminescence properties were studied. The samples were characterized by employing various analytical techniques including Rutherford backscattering spectrometry (RBS), transmission electron microscopy (TEM), atomic force microscope (AFM), photoluminescence (PL), and electroluminescence (EL). / It is found that the PL intensity is optimized in p-100 silicon substrates (with the resistivity of 15-25 O·cm) using Fe ion implantation at a voltage of 80 kV and dosage of 5x1015 cm -2. Formation of beta-FeSi2 can be completed after rapid thermal annealing (RTA) and strong photoluminescence is present. We also found that RTA could maintain the strain in beta-FeSi2 precipitates and there exists an epitaxial relationship between beta-FeSi2 and silicon. Additional furnace annealing at 850°C can relax the strain in beta-FeSi2 precipitates. / The development of both modern microelectronics and lightwave technologies has enabled the establishment of the Internet which has introduced a profound change in our everyday lives. Because of Moore's law, computing today is limited less by the computation ability of microprocessors than by the rate at which the processor can communicate with the outside world. Lightwave technology has had many successes in the long-haul communication field over the past decade. The advantages of lightwave technology over conventional electronics are becoming apparent for shorter and shorter reach applications and lightwave communications may eventually replace copper-based interconnects in microelectronics. To make possible optical interconnects, optical components, especially light emitters may be needed to be integrated on conventional silicon microchips. However, to date, no efficient on-chip silicon-based light emitter is fabricated in silicon photonics. / Sun, Caiming. / Adviser: Hon K. Tsang. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3703. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Shi Lei = 溶凝膠分佈反饋波導激光器之光學性質的研究 / 石蕾. / "September 2004." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references (p. 150-171) / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese. / Shi Lei = Rong ning jiao fen bu fan kui bo dao ji guang qi zhi guang xue xing zhi de yan jiu / Shi Lei.

In our research Hyper-Rayleigh scattering (HRS) is employed as an effective, simple investigation technique to study solutions of small molecules, pure liquids, nano-adsorbing systems and metal colloids. A set of apparatus has been built with good spectral resolution and high sensitivity to successfully measure characteristics of intensity and polarization properties of HRS. It was found that the consistency was different for pure liquid and solutions of small molecules when comparing experimental measurements of depolarized ratios and polarization patterns with theoretical expectations. This is due to the presence of both incoherent and coherent contributions to HRS in pure liquids, of which the origin of the coherent contribution is different for different pure liquids. In our results, pure liquid nitrobenzene was found to have strong coherent contribution to HRS caused by intermolecular interactions. Three different chemical compounds were used to mix with nitrobenzene to break the strong orientational correlations between molecules. Comparison between the results show different behaviors in the effectiveness in eliminating the coherent HRS signals, and the effectiveness was correlated to the molecular structures. Theory of second harmonic scattering from surface has been expanded as leading order contributions containing nonlocal electric dipole mode and local quadrupole mode, which can be exhibited in our experimental study of polarization patterns. Polarization patterns from polystyrene particles of different sizes adsorbed with different species of dyes were measured to investigate and compare with theoretical expectations. For small-size adsorbing system, measurements of polarization patterns were basically consistent with theory. However, for adsorbing system of polystyrene particles with a size of 900 nm, the polarization patterns showed discrepancies when comparing with theory, which indicated that higher order multipoles are needed in the theory. Silver and gold colloids were employed as the subject of investigation for measuring the polarization patterns of HRS. The results were found to be consistent when comparing with their extinction spectra and TEM images. We have managed to measure polarization patterns of HRS originated from surface of non-spherical colloids and the results showed that the origin of HRS can be qualitatively understood, although a more elaborated theory is needed to describe the data. / by Chen, Ji = 由有機液體以及金屬膠體產生的非線性光散射的研究 / 陳佶. / Source: Dissertation Abstracts International, Volume: 70-09, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 117-118). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307. / by Chen, Ji = You you ji ye ti yi ji jin shu jiao ti chan sheng de fei xian xing guang san she de yan jiu / Chen Ji.

Ku, Sin Yee = 添加鎳對網絡結構Fe₈₀C₂₀合金機械性能的影響 / 古倩儀. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Abstracts in English and Chinese. / Ku, Sin Yee = Tian jia nie dui wang luo jie gou Fe₈₀C₂₀ he jin ji xie xing neng de ying xiang / Gu Qianyi. / Abstract --- p.i / Acknowledgements --- p.v / List of Tables --- p.viii / List of Figures --- p.ix / Chapter Chapter 1: --- Introduction --- p.1 / Chapter 1.1 --- Composite Materials --- p.1 / Chapter 1.1.1 --- Parti culate-reinforced Composites --- p.2 / Chapter 1.1.2 --- Fibre-reinforced Composites --- p.2 / Chapter 1.1.3 --- Structural Composites --- p.3 / Chapter 1.1.4 --- Metal Matrix Composites --- p.3 / Chapter 1.2 --- Phase Transformations --- p.4 / Chapter 1.2.1 --- Introduction --- p.4 / Chapter 1.2.2 --- Stability and Equilibrium --- p.4 / Chapter 1.2.3 --- Undercooling --- p.6 / Chapter 1.2.4 --- Solidification of Undercooled Melts --- p.7 / Chapter 1.2.4.1 --- Nucleation --- p.8 / Chapter 1.2.4.1.1 --- Homogeneous Nucleation --- p.8 / Chapter 1.2.4.1.2 --- Heterogeneous Nucleation --- p.9 / Chapter 1.2.4.2 --- Growth --- p.11 / Chapter 1.2.5 --- Binary Systems with a Solid Miscibility Gap --- p.12 / Chapter 1.2.6 --- Phase Separation Mechanisms in a Solid Miscibility Gap --- p.14 / Chapter 1.2.6.1 --- Nucleation and Growth --- p.14 / Chapter 1.2.6.2 --- Spinodal Decomposition --- p.15 / Chapter 1.2.6.2.1 --- Uphill Diffusion --- p.16 / Chapter 1.2.6.2.2 --- Diffusion Equation of Spinodal Decomposition --- p.17 / Chapter 1.2.6.2.3 --- Solution to the Diffusion Equation --- p.19 / Chapter 1.2.7 --- Metastable Liquid Miscibility Gap --- p.21 / Chapter 1.3 --- Mechanical Properties --- p.22 / Chapter 1.3.1 --- Hardness --- p.22 / Chapter 1.3.2 --- Strength --- p.23 / Chapter 1.3.3 --- Ductility --- p.23 / Chapter 1.3.4 --- Strengthening Mechanisms --- p.25 / Chapter 1.3.4.1 --- Grain Boundary Strengthening --- p.25 / Chapter 1.3.4.2 --- Solid Solution Strengthening --- p.26 / Chapter 1.4 --- Objectives of This Project --- p.27 / Figures --- p.29 / References --- p.42 / Chapter Chapter 2: --- Experimental --- p.43 / Chapter 2.1 --- Formation of Bulk Network Nanostructured Alloys --- p.43 / Chapter 2.1.1 --- Preparation of Fused Silica Tubes --- p.43 / Chapter 2.1.2 --- Weighing and Alloying --- p.44 / Chapter 2.1.3 --- Fluxing and Quenching --- p.45 / Chapter 2.2 --- Sample Preparation --- p.46 / Chapter 2.2.1 --- "Cutting, Grinding and Polishing" --- p.46 / Chapter 2.2.2 --- Etching --- p.47 / Chapter 2.2.3 --- Sample Preparation for Transmission Electron Microscopy Analysis --- p.48 / Chapter 2.3 --- Mechanical Tests --- p.49 / Chapter 2.3.1 --- Microhardness Test --- p.49 / Chapter 2.3.2 --- Compression Test --- p.50 / Chapter 2.4 --- Microstructural Analysis --- p.51 / Chapter 2.4.1 --- Scanning Electron Microscopy Analysis --- p.51 / Chapter 2.4.2 --- Transmission Electron Microscopy Analysis --- p.52 / Chapter 2.4.2.1 --- Indexing Diffraction Patterns --- p.52 / Chapter 2.4.2.2 --- Energy Dispersive X-Ray Analysis --- p.53 / Chapter 2.4.2.3 --- Electron Energy Loss Spectroscopy --- p.53 / Figures --- p.55 / References --- p.62 / Chapter Chapter 3: --- Dependence of the Mechanical Properties of FesoC2o Network Alloys on the Addition of Ni --- p.63 / Chapter 3.1 --- Abstract --- p.63 / Chapter 3.2 --- Introduction --- p.64 / Chapter 3.3 --- Experimental --- p.64 / Chapter 3.4 --- Results --- p.66 / Chapter 3.5 --- Discussions --- p.74 / Chapter 3.6 --- Conclusions --- p.79 / Tables --- p.80 / Figures --- p.82 / References --- p.100 / Bibliography --- p.101

Yin, Weixin = 非晶液態鈀-鎳-磷合金相位分離的證據 / 殷瑋欣. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Abstracts in English and Chinese. / Yin, Weixin = Fei jing ye tai ba-nie-lin he jin xiang wei fen li de zheng ju / Yin Weixin. / Acknowledgement --- p.i / Abstract --- p.ii / Contents --- p.iv / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- A Brief Introduction to Metallic Glass --- p.1 / Chapter 1.2 --- Homogeneous Nucleation Frequency --- p.3 / Chapter 1.3 --- Heterogeneous Nucleation Frequency --- p.4 / Chapter 1.4 --- Spinodal Decomposition --- p.5 / Chapter 1.5 --- Conditions for Metallic Glasses Formation --- p.8 / Chapter 1.6 --- How to Get Large Undercooling --- p.9 / Chapter 1.7 --- Liquid Phase Separation --- p.10 / References --- p.12 / Figures --- p.13 / Chapter Chapter 2 --- Experimental Procedures and Techniques of Transmission Electron Microscopy --- p.18 / Chapter 2.1 --- Sample preparation --- p.18 / Chapter 2.1.1 --- Ni2P Preparation --- p.18 / Chapter 2.1.2 --- Alloying --- p.18 / Chapter 2.1.3 --- Fluxing --- p.18 / Chapter 2.2 --- Introduction to TEM Specimen Preparation --- p.19 / Chapter 2.2.1 --- "Grinding, Polishing and Punching" --- p.19 / Chapter 2.2.2 --- Final Thinning by Ion Miller --- p.20 / Chapter 2.2.3 --- Final Thinning by Twin Jet --- p.20 / Chapter 2.3 --- Introduction to Transmission Electron Microscopy Techniques --- p.21 / Chapter 2.3.1 --- Basic Instrumentations of TEM --- p.21 / Chapter 2.3.2 --- Elastic Scattering and Inelastic Scattering --- p.21 / Chapter 2.3.3 --- Image Contrast --- p.22 / Chapter 2.3.4 --- Dark Field Image and Bright Field Image --- p.24 / Chapter 2.3.5 --- EDX Mapping --- p.24 / Chapter 2.3.6 --- High Resolution Images --- p.25 / References --- p.26 / Figures --- p.27 / Chapter Chapter 3 --- Evidence of amorphous/liquid phase separation in Pd41.25Ni41.25P17.5 alloy --- p.32 / Chapter 3.1 --- Introduction --- p.32 / Chapter 3.2 --- Experimental --- p.34 / Chapter 3.3 --- Discussions --- p.42 / References --- p.44 / Figures --- p.45 / Chapter Chapter 4 --- Conclusions --- p.68

過去幾十年當中，金屬玻璃（包括塊狀金屬玻璃）中非晶相分離的發生已經成為了一個具有爭議性的課題。一些報告報導在具有負混合熱的Pd-Ni-P合金體系中發生了非晶相分離。然而，有一些報告聲稱相分離不能在Pd-Ni-P非晶合金中被觀察到。文獻分析表明，困難在於缺乏直接的實驗證據。 / 為了解決這個難題，示差掃描量熱儀、高分辨電子顯微鏡、掃描透射模式下的高角環射暗場相、以及能量色散X射線光譜儀等檢測儀器在我們實驗當中被使用。同時為了清楚展示非晶相分離反應，在過冷Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅熔體被冷卻為固態非晶樣品之前引入了中間熱退火處理。 / 實驗研究了三種經由不同路徑製備的A、B、C型號樣品。結果表明在非晶/液態Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅合金中可能存在獨特的短程有序結構，它會導致相分離的發生。同时研究發現，在大約625 K，調幅分解的持續時間的下限大概是200 s。調幅分解的時間常數R在大約625 K 下為0.002 s⁻¹。三种类型样品在不同的溫度下被退火從而獲得部分的結晶。A型號和B型號具有相似的行為。在低溫下，圓形的核心首先形成，接著發生共晶反應。在高溫下，出現了一種形狀為立方體的析出相。在C型號的樣品當中，核心和立方的析出物同時被發現。但是核心的成分分佈與A和B型號中出現的不同。同時，隨著退火時間的加長形核的數量也具有獨特的行為表現。作為對比，Pd₄₀Ni₄₀P₂₀塊狀金屬玻璃的結晶行為也被展開了研究。同樣的，以形成核心開始，但是它的成分分佈異於A和B型號的樣品。 / Amorphous phase separation in metallic glass (including bulk metallic glass) has been a controversial issue in the past several decades. There are reports saying that amorphous phase separation occurs in Pd-Ni-P, which has a negative heat of mixing among its constituent elements. However, there are also as many reports claiming that phase separation is absent in amorphous Pd-Ni-P alloys. The lack of direct experimental evidence makes the issue to be difficult to be resolved. / To solve this problem, differential scanning calorimetry (DSC), high resolution transmission electron microscopy (HRTEM), high angle annular dark field (HAADF) in scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy (EDX) have been employed. Intermediate thermal annealing is introduced before an undercooled Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅ melt is cooled down to become a solid amorphous specimen. / A-type, B-type, and C-type specimens of composition, Pd₄₁.₂₅Ni₄₁.₂₅ P₁₇.₅, have been prepared via three different cooling paths. It was found that amorphous phase separation indeed occurs in C-type specimens. Results suggest that there may be unique short range orders in amorphous/liquid Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅, which are responsible for the phase separation. Experimental arrangements were made to study the occurrence of spinodal reaction in undercooled molten Pd₄₁.₇₅Ni₄₁.₇₅P₁₇.₅ alloys as a function of time. The lower bound of the duration of the spinodal decomposition at a temperature of {U+2248}625 K is about 200 s and the time constant R of the spinodal decomposition at a temperature of {U+2248}625 K is 0.002 s⁻¹. / A-type and B-type specimens have similar crystallization behavior. At low temperature, it starts with the formation of a spherical core and then eutectic crystallization takes over. At higher temperatures, an additional phase in the shape of a cube appears. In annealed C-type specimens, cores and cubic precipitates are also found. However, the composition profile of the cores is different and the number of nucleation events versus time has peculiar characteristics. The crystallization behavior of Pd₄₀Ni₄₀P₂₀ BMG was studied for comparison. It again starts out with the formation of a core, but with a composition profile different from those of A-type and B-type specimens. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Lan, Si = 對於具有負混合熱的塊狀金屬玻璃非晶相分離的研究 / 蘭司. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references. / Abstract also in Chinese. / Lan, Si = Dui yu ju you fu hun he re de kuai zhuang jin shu bo li fei jing xiang fen li de yan jiu / Lan Si. / Abstract of thesis --- p.i / Acknowledgements --- p.v / List of Tables --- p.x / List of Figures --- p.xi / Chapter Chapter 1 --- Introduction and literature review --- p.1 / Chapter 1.1 --- Introduction to metallic glasses --- p.1 / Chapter 1.1.1 --- Background of metallic glasses --- p.1 / Chapter 1.1.2 --- Glass transition --- p.2 / Chapter 1.1.3 --- The undercooling of liquids --- p.3 / Chapter 1.1.4 --- Crystal nucleation and growth in liquids --- p.3 / Chapter 1.1.4.1 --- Crystal Nucleation in liquids --- p.3 / Chapter 1.1.4.2 --- Crystal growth in liquids --- p.5 / Chapter 1.1.4.3 --- TTT diagram --- p.6 / Chapter 1.1.4.4 --- Crystallization in metallic glasses --- p.6 / Chapter 1.1.5 --- Glass formation methods and systems --- p.6 / Chapter 1.1.6 --- Glass forming ability and criteria --- p.8 / Chapter 1.1.7 --- Properties and applications --- p.9 / Chapter 1.2 --- The basic theory of phase separation in a binary system --- p.10 / Chapter 1.2.1 --- Thermodynamic background --- p.10 / Chapter 1.2.2 --- Solid state phase separation --- p.11 / Chapter 1.2.2.1 --- A miscibility gap of binary mixture --- p.11 / Chapter 1.2.2.2 --- Nucleation and growth mechanism --- p.12 / Chapter 1.2.2.3 --- Spinodal decomposition mechanism --- p.13 / Chapter 1.2.3 --- Liquid state miscibility gap in a binary system --- p.21 / Chapter 1.3 --- Literature review for phase separation in metallic glasses --- p.23 / Chapter 1.4 --- The aim of this thesis --- p.28 / Figures --- p.30 / References --- p.39 / Chapter Chapter 2 --- Experiments and characterization --- p.44 / Chapter 2.1 --- Introduction and the outline of the experiments --- p.44 / Chapter 2.2 --- Sample preparation --- p.45 / Chapter 2.2.1 --- Bulk metallic glasses preparation --- p.45 / Chapter 2.2.1.1 --- Preparation of clean fused silica tubes --- p.45 / Chapter 2.2.1.2 --- Weighing --- p.46 / Chapter 2.2.1.3 --- Alloying --- p.46 / Chapter 2.2.1.4 --- Fluxing --- p.47 / Chapter 2.2.2 --- Thermal annealing --- p.49 / Chapter 2.2.3 --- Specimens preparation for characterization --- p.50 / Chapter 2.2.3.1 --- Cutting, molding, grinding and polishing --- p.50 / Chapter 2.2.3.2 --- Etching --- p.51 / Chapter 2.2.3.3 --- Thinning for TEM foils --- p.51 / Chapter 2.3 --- Characterization --- p.55 / Chapter 2.3.1 --- Differential scanning calorimetry (DSC) --- p.55 / Chapter 2.3.2 --- Scanning electron microscopy (SEM) --- p.55 / Chapter 2.3.3 --- Transmission electron microscopy (CTEM and HRTEM) --- p.57 / Chapter 2.3.4 --- High angle annular dark field (HAADF) in Scanning transmission electron microscopy (STEM) --- p.58 / Chapter 2.3.5 --- Energy dispersive X-ray spectroscopy (EDX) --- p.59 / Figures --- p.62 / References --- p.69 / Chapter 3 --- p.70 / Chapter 3.1 --- Introduction --- p.70 / Chapter 3.2 --- Materials and Experimental --- p.73 / Chapter 3.3 --- Results --- p.75 / Chapter 3.3.1 --- Thermal behaviors of three types of specimens --- p.75 / Chapter 3.3.2 --- Microstructures of three types of specimens --- p.75 / Chapter 3.3.2.1 --- A-type specimens --- p.75 / Chapter 3.3.2.2 --- B-type specimens --- p.76 / Chapter 3.3.2.3 --- C-type specimens --- p.76 / Chapter 3.4 --- Discussion --- p.78 / Chapter 3.5 --- Conclusions --- p.79 / Chapter 3.6 --- Afterward --- p.79 / Figures --- p.80 / References --- p.89 / Chapter Chapter 4 --- The time constant of the spinodal decomposition in Pd₄₁.₇₅Ni₄₁.₇₅P₁₇.₅ bulk metallic glasses --- p.92 / Chapter 4.1 --- Introduction --- p.92 / Chapter 4.2 --- Materials and experimental --- p.92 / Chapter 4.3 --- Results --- p.94 / Chapter 4.3.1 --- Thermal behaviors --- p.94 / Chapter 4.3.2 --- Microstructures --- p.94 / Chapter 4.4 --- Discussion --- p.96 / Chapter 4.5 --- Conclusions --- p.98 / Figures --- p.100 / References --- p.123 / Chapter Chapter 5 --- Crystallization in homogeneous and phase-separated Pd₄₁.₂₅Ni₄₁.₂₅P₁₇.₅ bulk metallic glasses --- p.125 / Chapter 5.1 --- Introduction --- p.125 / Chapter 5.2 --- Experiments --- p.126 / Chapter 5.3 --- Results --- p.128 / Chapter 5.3.1 --- Low temperature thermal annealing at 613 K with 0≤t{U+2090} ≤ 8 h --- p.128 / Chapter 5.3.1.1 --- A-type and B-type specimens --- p.128 / Chapter 5.3.1.2 --- C-type specimens --- p.130 / Chapter 5.3.1.3 --- Pd₄₀Ni₄₀P₂₀ BMG --- p.132 / Chapter 5.3.2 --- High temperature thermal annealing --- p.133 / Chapter 5.3.2.1 --- A-type and B-type specimens --- p.133 / Chapter 5.3.2.2 --- C-type specimens --- p.135 / Chapter 5.3.2.3 --- Pd₄₀Ni₄₀P₂₀ BMG --- p.137 / Chapter 5.4 --- Discussion --- p.137 / Chapter 5.4.1 --- Formation of spherical cores --- p.138 / Chapter 5.4.1.1 --- A-type and B-type Pd₄₁.₇₅Ni₄₁.₇₅P₁₇.₅ specimens --- p.138 / Chapter 5.4.1.2 --- C-type Pd₄₁.₇₅Ni₄₁.₇₅P₁₇.₅ specimens --- p.139 / Chapter 5.4.1.3 --- Pd₄₀Ni₄₀P₂₀ BMG --- p.140 / Chapter 5.4.2 --- Formation of cubic precipitates --- p.141 / Tables --- p.142 / Figures --- p.144 / References --- p.188 / Chapter Chapter 6 --- Conclusions --- p.190 / Bibliography --- p.192

by Yuen Cheong Wing. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves [138]-[142]). / by Yuen Cheong Wing. / Acknowledgments --- p.ii / Abstract --- p.iii / Table of Contents --- p.v / Chapter Chapter 1: --- Introduction --- p.1-1 / Chapter 1.1 --- What is Metallic Glass? --- p.1-1 / Chapter 1.2 --- Use of Metallic Glass --- p.1-3 / Chapter 1.3 --- A Dilemma --- p.1-4 / Chapter 1.4 --- Glass Forming Ability --- p.1-5 / Chapter 1.5 --- Role of Liquid State Phase Separation in GFA --- p.1-6 / References --- p.1-9 / Figure --- p.1-10 / Chapter Chapter 2: --- Phase Separation Theory --- p.2-1 / Chapter 2.1 --- Free Energy Curve --- p.2-1 / Chapter 2.2 --- Nucleation and Growth --- p.2-2 / Chapter 2.2.1 --- Liquid state nucleation and growth --- p.2-2 / Chapter 2.2.2 --- Nucleation and growth during solidification --- p.2-4 / Chapter 2.3 --- Spinodal Decomposition --- p.2-5 / Chapter 2.3.1 --- Cahn-Hilliard linearized equation --- p.2-6 / Chapter 2.3.2 --- Temporal evolution --- p.2-9 / References --- p.2-12 / Figures --- p.2-15 / Chapter Chapter 3 ： --- Experimental Setup and Techniques --- p.3-1 / Chapter 3.1 --- Technique in Achieving High Undercooling --- p.3 -1 / Chapter 3.1.1 --- Effects and limitation of B203 --- p.3-1 / Chapter 3.1.2 --- Preparation of B203 --- p.3-3 / Chapter 3.1.3 --- Cleansing of apparatus --- p.3-4 / Chapter 3.2 --- Experimental --- p.3-5 / Chapter 3.2.1 --- Sample preparation --- p.3-6 / Chapter 3.2.2 --- Experimental setup --- p.3-7 / Chapter 3.2.3 --- Procedures --- p.3-8 / Chapter 3.3 --- Observing the Microstructure --- p.3-9 / Chapter 3.3.1 --- Cutting --- p.3-10 / Chapter 3.3.2 --- Molding --- p.3-10 / Chapter 3.3.3 --- Polishing --- p.3-11 / Chapter 3.3.4 --- Etching --- p.3-12 / Chapter 3.3.5 --- Observation --- p.3-12 / References --- p.3-14 / Table --- p.3-15 / Figures --- p.3-16 / Chapter Chapter 4: --- Metastable liquid phase separationin undercooled molten PD40. 5]\l40.5P19 --- p.4-1 / Abstract --- p.4-1 / References --- p.4-9 / Figures --- p.4-10 / Chapter Chapter 5 ： --- Transformation in undercooled molten PD40.5NI40.5P19 --- p.5-1 / Chapter 5.1 --- Abstract --- p.5-1 / Chapter 5.1 --- Introduction --- p.5-2 / Chapter 5.3 --- Experimental --- p.5-4 / Chapter 5.4 --- Results --- p.5-6 / Chapter 5.5 --- Discussions --- p.5-13 / References --- p.5-20 / Figures --- p.5-22 / Chapter Chapter 6 ： --- Solidification of liquid spinodal in undercooled PD40.5NI40.5P19 --- p.6-1 / Chapter 6.1 --- Abstract --- p.6-1 / Chapter 6.2 --- Introduction --- p.6-2 / Chapter 6.3 --- Experimental --- p.6-3 / Chapter 6.4 --- Results --- p.6-5 / Chapter 6.5 --- Discussions --- p.6-10 / References --- p.6-17 / Figures --- p.6-18 / Chapter Chapter 7: --- Conclusion --- p.7-1 / References --- p.7-4 / Bibliography --- p.B-1