Dissertations / Theses on the topic 'Metals - Rapid Solidification Processing'

The main aim of this work is to investigate heterogeneous nucleation of solidification of metals and alloys by a combination of differential scanning calorimetry and transmission electron microscopy using a newly modified entrained particle technique. Attention is focused on investigating (a) heterogeneous nucleation of Cd, In and Pb particle solidification by Al in rapidly solidified Al-Cd, Al-In and Al-Pb binary alloys; (b) effects of various ternary additions such as Mg, Ge and Si on heterogenous nucleation of solidification of Cd and Pb solidification by Al; (c) heterogenous nucleation of solidification of Si by solid Al in hypoeutectic Al-Si alloys. In addition, the melting behaviour of Cd, In and Pb particles embedded in an Al matrix is investigated. The rapidly solidified microstructures of melt spun Al-Cd, Al-In and Al-Pb alloys consist of faceted 5-200nm diameter Cd, In and Pb particles homogeneously distributed throughout an Al matrix. Cd particles exhibit an orientation relationship with the Al matrix which can be described as {111}_Al//{0001}_Cd and andlt;110andgt;_Al//andlt;112and#773;0andgt;_Cd, and In and Pb particles exhibit a near cube-cube and cube-cube orientation relationship with the Al matrix respectively. Cd, In and Pb particles embedded in the Al matrix exhibit distorted truncated octahedral or truncated octahedral shapes surrounded by {111}_Al and {100}_Al facets. The solid Al-solid Cd, solid Al-solid In surface energy anisotropies are constant over the temperature range between room temperature and Cd and In melting points respectively. The solid Al-liquid Cd and solid Al-liquid In surface energy anisotropies decrease with increasing temperature above Cd and In melting points. Solidification of Cd, In, Pb particles embedded in an Al matrix is nucleated catalytically by the surrounding Al matrix on the {111}_Al faceted surfaces with an undercooling of 56, 13 and 22K and a contact angle of 42°, 27° and 21° for Cd, In and Pb particles respectively. Addition of Mg to Cd particles embedded in Al increases the lattice disregistry across the nucleating plane, but decreases the undercooling before the onset of Cd(Mg) particle solidification. Addition of Ge to Al decreases the lattice disregistry across the nucleating plane, but increases the undercooling before the onset of Pb particle solidification embedded in the Al(Ge) matrix. These results indicate that chemical interactions dominate over structural factors in determining the catalytic efficiency of nucleation solification in Al-Cd-Mg and Al-Pb-Ge alloys. Contact between Si precipitates and Pb particles embedded in an Al matrix decreases the undercooling before the onset of Pb particle solidification. The equilibrium melting point of Cd particle in the melt spun Al-Cd alloy is depressed because of capillarity, and the depression of equilibrium melting point increases with decreasing particle size. In the melt spun Al-In and Al-Pb alloys, however, most of the In and Pb particles embedded within the Al matrix grains are superheated, and the superheating increases with decreasing particle size. The heterogeneous nucleation temperature for Si solidification by Al depends sensitively on the purity of the Al. Na and Sr additions have different effects on the Si nucleation temperatures. With an Al purity of 99.995%, Na addition increases the Si nucleation temperature, while Sr addition does not affect or decreases the Si nucleation undercooling, depending on the amount of Sr addition. The solidified microstructure of liquid Al-Si eutectic droplets embedded in an Al matrix is affected by the Si nucleation undercooling. With low Si nucleation undercooling, each Al-Si eutectic liquid droplet solidifies to form one faceted Si particle, however, with high Si nucleation undercooling, each Al-Si eutectic liquid droplet solidifies to form a large number of non-faceted Si particles embedded in Al.

Orientadores: Amauri Garcia, Noe Cheung
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica
Made available in DSpace on 2018-08-14T16:40:44Z (GMT). No. of bitstreams: 1 Dias_AntonioCarlosPires_M.pdf: 13091267 bytes, checksum: c4c7c0e72c88328cba1119cc9cd6d650 (MD5) Previous issue date: 2009
Resumo: As ligas de solda à base de estanho apresentam excelente fluidez e temperaturas de trabalho ideais para a união de componentes eletrônicos. A solda com ligas do sistema estanho chumbo é a mais comum para soldas em eletrônica. Entretanto, há muitas preocupações com o uso do chumbo, devido aos diversos efeitos adversos na saúde humana e contaminação do meio ambiente. Por essas razões, na maioria dos países o chumbo já é condenado e proibido de ser incorporado em diversos produtos. Neste sentido, a indústria eletrônica está de olho em soldas livres de chumbo que possam substituir a clássica solda estanho-chumbo. É objetivo deste trabalho analisar a solidificação de ligas eutéticas dos sistemas Sn-Ag e Sn-Cu, que são duas ligas com potencial de substituição. Foram desenvolvidos experimentos para determinar a influência do acabamento superficial da chapa molde nos parâmetros térmicos de solidificação durante a solidificação direcional ascendente em regime transitório de extração de calor de ligas eutéticas Sn-Pb, Sn-Cu e Sn-Ag. Foram utilizados dois tipos de acabamentos superficiais na chapa molde: lixado e ranhurado, para investigar as condições de afinidade metal/substrato. Foi desenvolvida uma abordagem teórico-experimental para determinar quantitativamente as variáveis térmicas, tais como: coeficiente de transferência de calor global (hg) e velocidade de deslocamento da frente de solidificação. As micro estruturas de solidificação foram caracterizadas e os espaçamentos dendríticos secundários (?2) foram medidos na direção longitudinal dos lingotes, e correlacionados com as variáveis térmicas que atuaram durante a solidificação.
Abstract: Tin based alloys for welding applications have excellent fluidity and adequate temperature working range to join electronic components. The most used tin alloys for welding is the eutectic Sn-Pb alloy. However, there are some concerns about lead, due to hazardous effects to health and to environment. Due to theses reasons, many countries condemn and prohibit the use of lead in several products. In this sense, the electronic industries are looking for lead-free solder alloys with a view to replace the traditional Sn-Pb eutectic alloy. The aim of this work is to analyze the solidification of Sn-Ag and Sn-Cu eutectic alloys which are potential alloys candidates to replace the eutectic Sn-Pb alloy. Experiments were conducted to determine the influence of the mold wall roughness on the thermal solidification parameters during the upward unsteady-state directional solidification of eutectic Sn-Pb, Sn-Cu and Sn-Ag alloys. Two different kinds of surface mold finishing, sanded and grooved, were used in order to analyze metal/substrate affinity. A combined theoretical and experimental approach has been used to quantitatively determine such thermal variables, i.e., transient global heat transfer coefficient (hg) and solidification growth rates. The microstructures have been characterized and the secondary (?2) dendrite arm spacings were measured along the castings length and correlated to transient solidification thermal variables.
Mestrado
Materiais e Processos de Fabricação
Mestre em Engenharia Mecânica

Orientador: Amauri Garcia
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica
Made available in DSpace on 2018-08-14T11:35:39Z (GMT). No. of bitstreams: 1 Cante_ManuelVenceslau_D.pdf: 12795296 bytes, checksum: bd8bf91fcf479b66a28e7e3d6b5f7090 (MD5) Previous issue date: 2009
Resumo: O desenvolvimento de microestruturas otimizadas durante o processo de solidificação são de fundamental importância nas propriedades e desempenho de produtos acabados baseados em ligas metálicas. Neste estudo é analisada a cinética envolvida no processo de solidificação, seus efeitos nos parâmetros macro e microestruturais e a sua conseqüente influência nas propriedades mecânicas. Com esse intuito, ligas hipoeutéticas do sistema binário são estudadas Al-Ni por meio de experimentos de solidificação vertical ascendente sob regime transitório de condução de calor. Os espaçamentos dendríticos primários (?1) e secundários(?2) foram medidos ao longo de todos os lingotes para cada uma das ligas analisadas e correlacionados com as variáveis térmicas de solidificação. Uma abordagem teórico-experimental é utilizada na determinação quantitativa de tais variáveis térmicas: coeficiente de transferência de calor na interface metal/molde, velocidade de deslocamento da isoterma liquidus, gradientes térmicos, taxa de resfriamento e tempo local de solidificação. Os dados experimentais referentes à solidificação das ligas são confrontados com os principais modelos teóricos de crescimento dendrítico da literatura. Este estudo aborda, também, a influência do teor de soluto nos espaçamentos dendríticos para as ligas estudadas. Do ponto de vista macroestrutural, verifica-se que a transição colunar/equiaxial (TCE) ocorre para ligas hipoeutéticas Al-Ni para uma taxa crítica de resfriamento de 0,16 K/s. Por ensaios de tração as propriedades mecânicas das ligas do sistema Al-Ni são correlacionadas com parâmetros da micro-estrutura dendrítica resultante do processo de solidificação. Verifica-se que os limites de escoamento e de resistência à tração crescem com o aumento da concentração de soluto e decrescem com o aumento dos espaçamentos dendríticos, ?1 e ?2. O alongamento específico, por outro lado, mostra-se independente da composição e do arranjo dendrítico. Para a liga Al-5%Ni foi também realizado um estudo de solidificação rápida por refusão da superfície a laser para análise das variações microestruturais e de dureza entre as áreas não tratadas e tratadas superficialmente.
Abstract: The development of optimized microstructures during the solidification stage of processing is of fundamental importance to the mechanical properties and to the performance of finished products of metallic alloys. In this study the kinetics of solidification and its effects on macro and microstructural parameters, as well as the consequent influence on the final mechanical properties are analyzed. Hypoeutectic Al-Ni alloys are studied by upward unidirectional solidification experiments under transient heat flow conditions. Primary (?1) and secondary (?2) dendrite arm spacings are measured along the castings for all alloys analyzed and correlated with transient solidification thermal variables. A combined theoretical/ experimental approach is used to quantitatively determine such thermal variables, i.e., transient metal/mold heat transfer coefficients, tip growth rates, thermal gradients, tip cooling rates and local solidification time. The experimental data concerning the Al-Ni alloys solidification are compared to the main predictive dendritic models from the literature and the dependence of dendrite arm spacing on the alloy solute content is also analyzed. From the macrostructural point of view, it is found that the CET occurs for a critical value of cooling rate of about 0.16 K/s for hypoeutectic Al-Ni alloys.With a view to correlate mechanical properties to dendrite arm spacings, tensile testings were carried out. It is found that the ultimate tensile strength and the yield strength increase with increasing alloy solute content and with decreasing primary and secondary dendrite arm spacings. In contrast, the elongation is found to be independent of both alloy composition and dendritic arrangement. For the Al 5%Ni alloy a rapid solidification study is carried out by using laser surface remelting in order to permit microstructural and microhardness variations throughout the resulting treated and untreated zones, to be analysed.
Doutorado
Materiais e Processos de Fabricação
Doutor em Engenharia Mecânica

The primary focus of the present work is the development of macro-models for numerical simulation of binary alloy solidification processes, consistent with microscopic phase-change considerations, with a particular emphasis on capturing the effects of non-equilibrium species redistribution on overall macrosegregation behaviour. As a first step, a generalised macroscopic framework is developed for mathematical modelling of the process. The complete set of equivalent single-phase governing equations (mass, momentum, energy and species conservation) are solved following a pressure-based Finite Volume Method according to the SIMPLER algorithm. An algorithm is also developed for the prescription of the coupling between temperature and the melt-fraction. Based on the above unified approach of solidification modelling, a macroscopic numerical model is devised that is capable of capturing the interaction between the double-diffusive convective field and a localised fluid flow on account of solutal undercooling during non-equilibrium solidification of binary alloys. Numerical simulations are performed for the case of two-dimensional transient solidification of Pb-Sn alloys, and the simulation results are also compared with the corresponding experimental results quoted in the literature. It is observed that non-equilibrium effects on account of solutal undercooling result in an enhanced macrosegregation. Next, the model is extended to capture the effects of dendritic arm coarsening on the macroscopic transport phenomena occurring during a binary alloy solidification process. The numerical results are first tested against experimental results quoted in the literature, corresponding to the solidification of an Al-Cu alloy in a bottom-cooled cavity. It is concluded that dendritic arm coarsening leads to an increased effective permeability of the mushy region as well as an enhanced eutectic fraction of the solidified ingot. Consequently, an enhanced macrosegregation can be predicted as compared to that dictated by shrinkage-induced fluid flow alone. For an order-of-magnitude assessment of predictions from the numerical models, a systematic approach is subsequently developed for scaling analysis of momentum, heat and species conservation equations pertaining to the case of solidification of a binary mixture. A characteristic velocity scale inside the mushy region is derived, in terms of the morphological parameters of the two-phase region. A subsequent analysis of the energy equation results in an estimation of the solid layer thickness. It is also shown from scaling principles that non-equilibrium effects result in an enhanced macro-segregation compared to the case of an equilibrium model For the sake of assessment of the scaling analysis, the predictions are validated against computational results corresponding to the simulation of a full set of governing equations, thus confirming the trends suggested by the scale analysis. In order to analytically investigate certain limiting cases of unidirectional alloy solidification, a fully analytical solution technique is established for the solution of unidirectional, conduction-dominated, alloy solidification problems. The results are tested for the problem of solidification of an ammonium chloride-water solution, and are compared with those from existing analytical models as well as with the corresponding results from a fully numerical simulation. The effects of different microscopic models on solidification behaviour are illustrated, and transients in temperature and heat flux distribution are also analysed. An excellent agreement between the present solutions and results from the computational simulation can be observed. The generalised numerical model is subsequently utilised to investigate the effects of laminar double-diffusive Rayleigh-Benard convection on directional solidification of binary fluids, when cooled and solidified from the top. A series of experiments is also performed with ammonium chloride-water solutions of hypoeutectic and hypereutectic composition, so as to facilitate comparisons with numerical predictions. While excellent agreements can be obtained for the first case, the second case results in a peculiar situation, where crystals nucleated on the inner roof of the cavity start descending through the bulk fluid, and finally settle down at the bottom of the cavity in the form of a sedimented solid layer. An eutectic solidification front subsequently progresses from the top surface vertically downwards, and eventually meets the heap of solid crystals collected on the floor of the cavity. However, comparison of experimental observations with corresponding numerical results from the present model is not possible under this situation, since the associated transport process involves a complex combination of a number of closely interconnected physical mechanisms, many of which are yet to be resolved. Subsequent to the development of the mathematical model and experimental arrangements for macroscopic transport processes during an alloy solidification process, some of the important modes of double-diffusive instability are analytically investigated, as a binary alloy of any specified initial composition is directionally solidified from the top. By employing a close-formed solution technique, the critical liquid layer heights corresponding to the onset of direct mode of instability are identified, corresponding two a binary alloy with three different initial compositions. In order to simulate turbulent transport during non-equilibrium solidification processes of binary alloys, a modified k-8 model is subsequently developed. Particular emphasis is given for appropriate modelling of turbulence parameters, so that the model merges with single-phase turbulence closure equations in the pure liquid region in a smooth manner. Laboratory experiments are performed using an ammonium chloride-water solution that is solidified by cooling from the top of a rectangular cavity. A good agreement between numerical and experimental results is observed. Finally, in order to study the effects of three-dimensionality in fluid flow on overall macrosegregation behaviour, the interaction between double-diffusive convection and non-equilibrium solidification of a binary mixture in a cubic enclosure (cooled from a side) is numerically investigated using a three-dimensional transient mathematical model. Investigations are carried out for two separate model systems, one corresponding to a typical metal-ally analogue system and other corresponding to an actual metal-alloy system. As a result of three-dimensional convective flow-patterns, a significant solute macrosegregation is observed in the transverse sections of the cavity, which cannot be captured by two-dimensional simulations.

The primary focus of the present work is the development of macro-models for numerical simulation of binary alloy solidification processes, consistent with microscopic phase-change considerations, with a particular emphasis on capturing the effects of non-equilibrium species redistribution on overall macrosegregation behaviour. As a first step, a generalised macroscopic framework is developed for mathematical modelling of the process. The complete set of equivalent single-phase governing equations (mass, momentum, energy and species conservation) are solved following a pressure-based Finite Volume Method according to the SIMPLER algorithm. An algorithm is also developed for the prescription of the coupling between temperature and the melt-fraction. Based on the above unified approach of solidification modelling, a macroscopic numerical model is devised that is capable of capturing the interaction between the double-diffusive convective field and a localised fluid flow on account of solutal undercooling during non-equilibrium solidification of binary alloys. Numerical simulations are performed for the case of two-dimensional transient solidification of Pb-Sn alloys, and the simulation results are also compared with the corresponding experimental results quoted in the literature. It is observed that non-equilibrium effects on account of solutal undercooling result in an enhanced macrosegregation. Next, the model is extended to capture the effects of dendritic arm coarsening on the macroscopic transport phenomena occurring during a binary alloy solidification process. The numerical results are first tested against experimental results quoted in the literature, corresponding to the solidification of an Al-Cu alloy in a bottom-cooled cavity. It is concluded that dendritic arm coarsening leads to an increased effective permeability of the mushy region as well as an enhanced eutectic fraction of the solidified ingot. Consequently, an enhanced macrosegregation can be predicted as compared to that dictated by shrinkage-induced fluid flow alone. For an order-of-magnitude assessment of predictions from the numerical models, a systematic approach is subsequently developed for scaling analysis of momentum, heat and species conservation equations pertaining to the case of solidification of a binary mixture. A characteristic velocity scale inside the mushy region is derived, in terms of the morphological parameters of the two-phase region. A subsequent analysis of the energy equation results in an estimation of the solid layer thickness. It is also shown from scaling principles that non-equilibrium effects result in an enhanced macro-segregation compared to the case of an equilibrium model For the sake of assessment of the scaling analysis, the predictions are validated against computational results corresponding to the simulation of a full set of governing equations, thus confirming the trends suggested by the scale analysis. In order to analytically investigate certain limiting cases of unidirectional alloy solidification, a fully analytical solution technique is established for the solution of unidirectional, conduction-dominated, alloy solidification problems. The results are tested for the problem of solidification of an ammonium chloride-water solution, and are compared with those from existing analytical models as well as with the corresponding results from a fully numerical simulation. The effects of different microscopic models on solidification behaviour are illustrated, and transients in temperature and heat flux distribution are also analysed. An excellent agreement between the present solutions and results from the computational simulation can be observed. The generalised numerical model is subsequently utilised to investigate the effects of laminar double-diffusive Rayleigh-Benard convection on directional solidification of binary fluids, when cooled and solidified from the top. A series of experiments is also performed with ammonium chloride-water solutions of hypoeutectic and hypereutectic composition, so as to facilitate comparisons with numerical predictions. While excellent agreements can be obtained for the first case, the second case results in a peculiar situation, where crystals nucleated on the inner roof of the cavity start descending through the bulk fluid, and finally settle down at the bottom of the cavity in the form of a sedimented solid layer. An eutectic solidification front subsequently progresses from the top surface vertically downwards, and eventually meets the heap of solid crystals collected on the floor of the cavity. However, comparison of experimental observations with corresponding numerical results from the present model is not possible under this situation, since the associated transport process involves a complex combination of a number of closely interconnected physical mechanisms, many of which are yet to be resolved. Subsequent to the development of the mathematical model and experimental arrangements for macroscopic transport processes during an alloy solidification process, some of the important modes of double-diffusive instability are analytically investigated, as a binary alloy of any specified initial composition is directionally solidified from the top. By employing a close-formed solution technique, the critical liquid layer heights corresponding to the onset of direct mode of instability are identified, corresponding two a binary alloy with three different initial compositions. In order to simulate turbulent transport during non-equilibrium solidification processes of binary alloys, a modified k-8 model is subsequently developed. Particular emphasis is given for appropriate modelling of turbulence parameters, so that the model merges with single-phase turbulence closure equations in the pure liquid region in a smooth manner. Laboratory experiments are performed using an ammonium chloride-water solution that is solidified by cooling from the top of a rectangular cavity. A good agreement between numerical and experimental results is observed. Finally, in order to study the effects of three-dimensionality in fluid flow on overall macrosegregation behaviour, the interaction between double-diffusive convection and non-equilibrium solidification of a binary mixture in a cubic enclosure (cooled from a side) is numerically investigated using a three-dimensional transient mathematical model. Investigations are carried out for two separate model systems, one corresponding to a typical metal-ally analogue system and other corresponding to an actual metal-alloy system. As a result of three-dimensional convective flow-patterns, a significant solute macrosegregation is observed in the transverse sections of the cavity, which cannot be captured by two-dimensional simulations.

Orientadores: Amauri Garcia, Noé Cheung
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica
Made available in DSpace on 2018-08-16T22:32:29Z (GMT). No. of bitstreams: 1 Bertelli_Felipe_M.pdf: 6382019 bytes, checksum: 7bc62ea83b7e721ef82e5669d236559f (MD5) Previous issue date: 2010
Resumo: Neste trabalho, o software ANSYS, baseado no Método dos Elementos Finitos, é adaptado para a simulação tridimensional do fluxo de calor no processo de refusão superficial a laser. A análise numérica é validada com resultados simulados por outros modelos existentes na literatura para casos de refusão superficial a laser de alumínio puro e com resultados simulados e experimentais de uma liga Al-5%Ni. Ensaios experimentais próprios foram realizados em amostras de uma liga Al-1,5%Fe, utilizando um laser à fibra dopado com Itérbio, com potência máxima disponível de 2 kW. Para efeito comparativo, as trilhas foram feitas variando-se valores de velocidade de deslocamento do feixe laser para um mesmo valor de potência. Observou-se que a microestrutura tanto do substrato quanto da zona tratada apresentou morfologia tipicamente celular. As microestruturas resultantes dos tratamentos a laser foram analisadas através de microscopia eletrônica de varredura, sendo observados espaçamentos celulares extremamente refinados na área tratada a laser refletindo no aumento significativo da dureza confirmado por ensaios de microdureza Vickers. Uma técnica de dissolução parcial das amostras tratadas a laser foi aplicada para evidenciar os intermetálicos no substrato e na região tratada a laser, mostrando a modificação da redistribuição dos intermetálicos no interior da poça fundida e dando indicações de aumento da resistência à corrosão na região tratada
Abstract: In this work, the software ANSYS, based on the Finite Element Method, is adapted to simulate the three-dimensional heat flux during the laser remelting surface treatment. The numerical analysis is validated against theoretical results furnished by other models from the literature for laser surface remelting of aluminum and against theoretical and experimental results of Al-5wt%Ni alloy samples. Laser remelting experiments with Al-1,5%wtFe samples have been carried out by using a 2kW Yb fiber laser. For comparative effects, the laser tracks were performed with different laser beam velocities for a fixed value of power. It was observed that both the substrate and the treated region had a typical cellular morphology. The microstructures resulting from the laser treatment were analyzed by using electron scanning microscopy and very refined cell spacing has been observed, which can induce a significant hardness increase confirmed by Vickers microhardness tests. A partial dissolution technique has been performed to foreground the intermetallics at the substrate and at the laser treated zone, showing the intermetallics redistribution inside the molten pool and giving indications of increased corrosion resistance on the treated region
Mestrado
Materiais e Processos de Fabricação
Mestre em Engenharia Mecânica

Rapid solidification processing is widely used in industry, but the underlying mechanisms are not completely understood. In the present work, an effort is made to understand the effects of rapid heat extraction and large undercooling on the solidification sequence, in particular: (1) the transition from diffusion-limited growth to impingement-limited growth; and (2) crystal nucleation in deeply undercooled liquids. Rapid solidification can be achieved either by (1) rapid quenching, or (2) large undercooling. Accordingly, two different methods are used in the present work. They are, (a) nanosecond pulsed laser quenching, and (b) bulk undercooling in a liquid flux. Thin films prepared by d.c. magnetron getter sputtering have been used in pulsed laser quenching. Both pure metals (Fe, Zr, Ti, Co, Ge) and binary alloys (Nb-Ni, Ti-Co) prepared by this method are investigated. Alloys Fe₄₀Ni₄₀B₂₀, Ni₇₅Si₈B₁₇ and elemental Ge have been used in bulk undercooling. The metastable structures obtained are analysed by optical microscopy, scanning electron microscopy, electron probe microanalysis, transmission electron microscopy and X-ray diffraction. The results obtained are discussed in terms of non-equilibrium crystal nucleation and growth processes.

In this thesis, the solidification behaviour and microstructure evolution of Ta-Al-Fe, Nb-Al-Co, Nb-Al-Fe, Ta-Al-Ti and Nb-Si-Ti alloys rapidly solidified via arc melting, suspended droplet alloying and additive manufacturing techniques were examined. Loss of interfacial equilibrium resulted in an extended solute solubility with significant undercooling due to nucleation constraints, leading to unexpected phases. For Ta-Al-Fe alloys, when Al < 10 at.% and Fe < 4 at.%, the peritectic reaction, L+A2 → σ, is suppressed and the eutectic, L → A2 + μ, occurs with formation of a halo of μ on primary σ phase. For Co-rich Nb-Al-Co alloys, when Nb > 20 at.%, the quasi-peritectic reaction, L+Co2AlNb → C36+CoAl does not occur, C36 and CoAl phases form through solid-state precipitation. A halo of C14 forms on primary CoAl but limited vice-versa. In Nb-Al-Fe alloys, failure to initiate coupled growth of NbAl3+C14 leads to a two-phase halo of C14+Nb2Al. The quasi-peritectic reaction, L+Nb2Al → (Nb)+μ is suppressed, forming the eutectic Nb2Al+μ instead. The ternary eutectic, L+C14+Nb2Al → μ, is limited with μ forming primarily. For Ti-Al-Ta alloys, the quasi-peritectic reactions, L+β → α+σ and L+σ → α+κ, occur at a very narrow window; good agreement for γ and ε phases is found with non-equilibrium formation of ε. For additive manufactured Nb-Si-Ti alloys, an increase in scanning speed led to microstructure refinement. Due to elemental additions, Nb3Si is suppressed with formation of Nbss+Nb5Si3. C15 Laves phase formed when Cr > 5 at.%, with HfO2 when Hf is added. For Ti > 22 at.% and SI > 18 at.%, a Ti-rich Nb5Si3 forms due to rejection of Ti solute. Hot isostatic pressing and heat treatment led to crystal structure changes, densification and phase coarsening. Diffusion and local super-saturation led to the split of Nbss into an energetically stable and homogeneous Tiss phase.

Solidification from the melt is an essential step in nearly all conventional processes to produce bulk materials for industrial applications. Rapid quenching from the liquid state at cooling rates of 102 to 106K/s or higher has developed into a new technology for processing novel materials. InxGa1 - xSb a ternary III-V compound semiconductor was synthesized by using the rapid spinning cup (RSC) technique. Several compositions of these alloys were batched and cast into ingots in evacuated sealed quartz tubes. These ingots were then melted and ejected onto a rapidly rotating copper disk. This resulted in the generation of flakes or powders depending on the rpm of the disk. Microstructural characterization of the flakes and powders was performed using XRD, SEM and TEM. Efforts were also made to measure the bulk resistivity of the annealed flakes to see the effect of annealing on ordering of the phases.

The shrinkage during solidification of aluminium and iron based alloys has been studied experimentally and theoretically. The determined shrinkage behaviour has been used in theoretical evaluation of shrinkage related phenomena during solidification.

Air gap formation was experimentally studied in cylindrical moulds. Aluminium based alloys were cast in a cast iron mould while iron based alloys were cast in a water-cooled copper mould. Displacements and temperatures were measured throughout the solidification process. The modelling work shows that the effect of vacancy incorporation during the solidification has to be taken into account in order to accurately describe the shrinkage.

Crack formation was studied during continuous casting of steel. A model for prediction of crack locations has been developed and extended to consider non-equilibrium solidification. The model demonstrates that the shrinkage due to vacancy condensation is an important parameter to regard when predicting crack formation.

The centreline segregation was studied, where the contributions from thermal and solidification shrinkage were analysed theoretically and compared with experimental findings. In order to compare macrosegregation in continuous casting and ingot casting, ingots cast with the same steel grade was analysed. However, the macrosegregation due to A-segregation is driven by the density difference due to segregation. This is also analysed experimentally as well as theoretically.

19 Dec 2004.
Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2447" Amber Lynn Genau. 12/19/2004. Report is also available in paper and microfiche from NTIS.

Thesis (PhD) -- Stellenbosch University, 2014.
ENGLISH ABSTRACT: The process route for the production of base and platinum-group metals from natural sulfide ores commonly requires the conversion of high-iron furnace matte into an iron-lean converter matte. This is followed by pre-treatment through cooling of the iron-lean molten matte, physical processing of the solidified matte and hydrometallurgical metal extraction. Lonmin is the third largest producer of platinum-group metals in the world and utilizes Peirce-Smith converters for blowing high-iron furnace matte with air to a final iron concentration or endpoint. The molten matte is water granulated and solidification occurs via fast-cooling. The solidified matte is ground in a closed circuit ball mill with hydrocyclone classification and subjected to first stage atmospheric leaching. The specification of an ideal or desirable converter iron endpoint requires careful consideration. Most importantly, it must ensure the crystallization of converter matte with mineralogical qualities that are within the setpoints of the downstream unit processes and techniques. An additional consideration is for the final blown converter matte to achieve an optimum bulk concentration of the base metals Ni and Cu and platinum-group metals Pt, Pd, Rh, Ru and Ir. Mattes characteristic of variable iron endpoints were regularly produced at the Lonmin converter plant section. Uncertainty by plant metallurgists in knowing the desirable iron endpoint, particularly within the context of the Lonmin base metal refinery, and poor control has had detrimental effects on the mineralogical quality of the final matte and hence on the processing characteristics of the solidified matte particles downstream. A desirable iron endpoint required investigation, selection and implementation at Lonmin. The primary focus of this study was therefore to quantify the effect of a specific iron endpoint on the mineralogy and mineral chemistry of solidified converter matte. A fundamental examination of the solidification process upon cooling was regarded as critical to an in-depth understanding of the attained mineralogy and mineral chemistry as a function of a specific iron endpoint. It became equally important to quantify the effect of the resultant mineralogy, and hence iron endpoint, on the physical property of mineral structures in relation to downstream grinding, liberation and leaching characteristics. Despite considerable industry context, limited in-depth and coherent studies on the effect of a specific iron endpoint on fast-cooled converter matte systems were found in both industrial and scholarly literature. Previous findings in literature offered a limited quantitative understanding of the effect on mineralogy and mineral chemistry. Phase and cooling equilibria of multi-component, iron endpoint specific Ni-Cu-S matte systems were also not fully available. These would have been particularly useful in understanding the complexities of converter matte solidification as a function of iron endpoint. Physical property knowledge of converter matte mineral structures was hardly available and even less so in relation to grinding, liberation and leaching processes. A comprehensive investigation was therefore required to address these extensive knowledge gaps with respect to fastcooled converter matte systems in an industrial framework. Three Peirce-Smith converter production samples, representative of the extent in variability of iron endpoints attained at the converter plant, were used in a systematic investigation coupled to a novel combination of modern analytical techniques, computational thermochemistry and metallurgical testwork. The modern analytical techniques included the application of high resolution transmission electron microscopy and focused ion beam scanning electron microscopy tomography. Computational thermochemistry was applied through the use of MTDATA phase diagram software. Metallurgical testwork involved laboratory batch grinding at various specific energies. Closely associated leach experiments were also considered relevant to this wide-ranging investigation. The Peirce-Smith converter samples investigated were indicative of mattes that attained specific endpoints of 5.17%, 0.99% and 0.15 weight% Fe. The highest combined bulk concentration of the important base and platinum-group metals was achieved in the matte which attained a specific iron endpoint of 0.99%. The mineralogy of all three converter mattes was dominated by nickel sulfide mineral structures matched to the natural mineral of heazlewoodite. Mineral structures of copper sulfide, NiCu-alloy, spinel and OsRu-alloy were also constituents of the different converter mattes. The attainment of a specific iron endpoint was found to result in measurable mineralogical differences with respect to relative mineral abundances, external morphological characteristics and mineral chemistry. The mineralogical differences were particularly distinct between mineral structures of the high (5.17%) and low (0.99% and 0.15%) iron mattes. Subtle mineralogical differences were evident between mineral structures of the low iron mattes. The 0.99% Fe matte was characteristic of a significantly higher NiCu-alloy relative abundance, compared to the 5.17% Fe matte. The NiCu-alloy structures were found to act as the primary collectors of the economically significant platinum-group metals. Mineralogical observations were used to develop an understanding of the underlying mineralization mechanism of NiCu-alloy structures. High-fidelity color and grayscale 3D reconstructions were produced of the resultant mineralized structures. It was shown theoretically that variations in iron endpoint specific starting compositions of oxygen-free liquid matte systems alter the solidification pathway towards the eutectic. Moreover, a quantitative understanding of liquid phase solidification of the high and low iron matte systems, including oxygen, was developed to within ±2.5 oC. Most of the specific energy available for grinding was expended breaking the nickel sulfide matrix, particularly of the high iron matte. The breakage rates of copper sulfide mineral structures in the 5.17% Fe matte were calculated to be higher than in the 0.15% Fe matte at 25kWh/t specific energy. The degree of copper sulfide liberation was shown to be higher for the 5.17% Fe matte than for the 0.15% Fe matte at the same specific energy of grinding. A higher degree of Ni extraction and Cu cementation could be achieved when leaching low iron matte particles. The production of converter matte attaining a specific iron endpoint of 0.99% was found to be the most suitable with respect to endpoint selection criteria. A practical iron endpoint range of 1.6% to 1.0% was recommended for the production of converter matte with a resultant mineralogical quality within the constraints of the Lonmin base metal refinery. This study offers an integrated understanding of base and platinum-group metals production as a function of a desirable iron endpoint at Lonmin. This was not previously available in metal production literature. New technology for the monitoring and consistent control of such a practical iron endpoint range can subsequently be implemented.
AFRIKAANSE OPSOMMING: Die prosesroete vir die produksie van onedel en platinumgroepmetale uit natuurlike swawelertse vereis gewoonlik die omsetting van ’n ysterryke hoogoondmat in ’n ysterarm omsettermat. Hierna volg voorbehandeling deur die afkoeling van die ysterarm gesmelte mat, fisiese verwerking van die soliede mat, en hidrometallurgiese metaalekstraksie. Lonmin is die derde grootste produsent van platinumgroepmetale ter wêreld en gebruik Peirce-Smith-omsetters om ysterryke hoogoondmat met lug te blaas totdat dit ’n finale ysterkonsentrasie- of ystereindpunt bereik. Die gesmelte mat word met water granuleer, en solidifikasie vind deur middel van snelafkoeling plaas. Die soliede mat word in ’n geslotekringbalmeul met hidrosikloonklassifikasie gemaal en aan eerstestadium- atmosferiese loging onderwerp. Die spesifikasie van ’n ideale of gewenste ystereindpunt verg deeglike oorweging. Bowenal moet dit verseker dat die omsettermat kristalliseer met mineralogiese eienskappe wat binne die setpunte van die eenheidsprosesse en - tegnieke verder af in die prosesstroom val. ’n Bykomende oorweging is dat die uiteindelike geblaasde omsettermat ’n optimale massakonsentrasie van die onedel metale Ni en Cu en die platinumgroepmetale Pt, Pd, Rh, Ru en Ir moet bevat. Matte met die kenmerke van wisselende ystereindpunte is gereeld by die Lonminomsetteraanleg geproduseer. Die onsekerheid van metallurge by die aanleg oor die gewenste ystereindpunt – veral binne die konteks van die Lonmin-raffinadery vir onedel metale – sowel as swak beheer het ’n nadelige uitwerking gehad op die mineralogiese gehalte van die uiteindelike mat, en dus ook op die verwerkingskenmerke van die soliede matdeeltjies verder af in die prosesstroom. Die bepaling van die gewenste ystereindpunt het sorgvuldige ondersoek, seleksie en toepassing deur Lonmin vereis. Hierdie studie is dus hoofsaaklik uitgevoer om die uitwerking van ’n spesifieke ystereindpunt op die mineralogie en minerale chemie van soliede omsettermat te kwantifiseer. ’n Grondliggende ondersoek na die solidifikasieproses by afkoeling is as noodsaaklik beskou vir ’n diepgaande begrip van die verworwe mineralogie en minerale chemie as ’n funksie van ’n spesifieke ystereindpunt. Mettertyd het dit egter ewe belangrik geword om die uitwerking van die gevolglike mineralogie, en dus die ystereindpunt, op die fisiese eienskappe van minerale strukture met betrekking tot maling-, vrystellings- en loogprosesse verder af in die prosesstroom te kwantifiseer. Ondanks heelwat bedryfskonteks, het nóg bedryfs- nóg vakkundige literatuur veel diepte- en samehangende studies oor die uitwerking van ’n spesifieke ystereindpunt op snelafgekoelde omsettermatstelsels opgelewer. Vorige bevindinge in die literatuur het boonop ’n beperkte kwantitatiewe begrip van die uitwerking op mineralogie en minerale chemie getoon. Die fase- en afkoelingsekwilibriums van ystereindpuntspesifieke Ni-Cu-S-matstelsels met veelvuldige komponente was ook nie ten volle beskikbaar nie. Dít sou veral goed te pas gekom het om die kompleksiteite van omsettermatsolidifikasie as ’n funksie van ystereindpunt te verstaan. Kennis van die fisiese eienskappe van die minerale strukture van omsettermat was kwalik beskikbaar, terwyl selfs minder inligting oor maling-, vrystellings- en loogprosesse opgespoor kon word. Daarom was ’n omvattende ondersoek nodig om hierdie beduidende kennisleemtes met betrekking tot snelafgekoelde omsettermatstelsels in ’n nywerheidsraamwerk aan te vul. Drie Peirce-Smith-omsetterproduksiemonsters wat die wisselende bestek van ystereindpunte by die omsetteraanleg verteenwoordig, is in ’n stelselmatige ondersoek gebruik, tesame met ’n vernuwende kombinasie van moderne ontledingstegnieke, gerekenariseerde termochemiese bewerkings en metallurgiese toetswerk. Die moderne ontledingstegnieke sluit onder andere in hoëresolusie-transmissie-elektronmikroskopie (HRTEM) en gefokusdeioonstraalskandering-elektron-mikroskopie (FIB SEM) tomografie. Die gerekenariseerde termochemiese bewerkings is met behulp van MTDATAfasediagramsagteware uitgevoer. Metallurgiese toetswerk het die maling van laboratoriumlotte teen verskillende spesifieke energieë behels. Nou verwante loogproefnemings is ook as relevant vir hierdie omvattende studie beskou. Die bestudeerde Peirce-Smith-omsettermonsters het op matte met spesifieke eindpunte van 5.17%, 0.99% en 0.15 gewig% Fe gedui. Die hoogste gekombineerde massakonsentrasie van die belangrike onedel en platinumgroepmetale is in die mat met ’n spesifieke ystereindpunt van 0.99% gevind. Die mineralogie van ál drie omsettermatte is oorheers deur die minerale strukture van nikkelsulfied, wat met die natuurlike mineraal heazlewoodiet ooreenstem. Die verskillende omsettermatte het ook die minerale strukture van kopersulfied, NiCu-allooi, spinel en OsRu-allooi bevat. Daar is bevind dat die verkryging van ’n spesifieke ystereindpunt tot meetbare mineralogiese verskille in die relatiewe volopheid van minerale, die eksterne morfologiese kenmerke sowel as minerale chemie lei. Die mineralogiese verskille was veral duidelik te sien tussen die minerale strukture van die ysterryke (5.17% Fe) en ysterarm (0.99% en 0.15% Fe) matte. Fyn mineralogiese verskille is ook tussen die minerale strukture van die ysterarm matte bespeur. Die 0.99% Fe-mat het tipies beduidend meer NiCu-allooi as die 5.17% Fe-mat bevat. Die NiCu-allooistrukture tree oënskynlik op as die hoofversamelaars van die ekonomies belangrike platinumgroepmetale. Mineralogiese waarnemings is gebruik om ’n begrip te ontwikkel van die onderliggende mineralisasiemeganisme van NiCuallooistrukture. Die gevolglike gemineraliseerde strukture is met behulp van driedimensionele rekonstruksies met hoë kleurgetrouheid sowel as in grysskaal voorgestel. Daar is teoreties aangetoon dat variasies in ystereindpuntspesifieke beginsamestellings van suurstofvrye vloeibare matstelsels die solidifikasieroete na die eutetikum wysig. Daarbenewens is die vloeifasesolidifikasie van die ysterryke en ysterarm matstelsels, wat suurstof insluit, op sowat ±2.5 oC gekwantifiseer. Die meeste van die spesifieke energie wat vir maling beskikbaar was, is gebruik om die nikkelsulfiedmatriks te breek, veral vir die ysterryke mat. Berekeninge toon dat die breektempo’s van die minerale strukture van kopersulfied by die 5.17% Fe-mat hoër was as by die 0.15% Fe-mat teen ’n spesifieke energie van 25 kWh/t. Die mate van kopersulfiedvrystelling was hoër by die 5.17% Fe-mat as by die 0.15% Fe-mat by dieselfde spesifieke energie vir maling. ’n Hoër mate van Ni-ekstraksie en Cu-sementasie is verkry toe ysterarm matdeeltjies geloog is. Wat eindpuntseleksiemaatstawwe betref, is die produksie van ’n omsettermat met ’n spesifieke ystereindpunt van 0,99% as die mees geskikte aangewys. ’n Praktiese ystereindpuntbestek van 1.6% tot 1.0% word aanbeveel vir die produksie van ’n omsettermat met ’n gevolglike mineralogiese gehalte wat binne die perke van die Lonmin-raffinadery vir onedel metale val. Hierdie studie bied ’n geïntegreerde begrip van die produksie van onedel en platinumgroepmetale as ’n funksie van ’n gewenste ystereindpunt by Lonmin. Hierdie inligting was nie voorheen in literatuur oor metaalproduksie beskikbaar nie. Nuwe tegnologie vir die monitering en konsekwente beheer van so ’n praktiese ystereindpuntbestek kan dus op grond hiervan in werking gestel word.

Orientador: Ana Maria Martinez Nazar
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica
Made available in DSpace on 2018-07-22T16:31:39Z (GMT). No. of bitstreams: 1 Nunes_CarlosAngelo_D.pdf: 12292935 bytes, checksum: ea1a755d6645281ed644bfe2879a287c (MD5) Previous issue date: 1997
Resumo: Em trabalhos recentes têm-se proposto que materiais formados por um metal refratário em equilíbrio com uma fase intermetálica constituem a melhor opção para aplicações estruturais em temperaturas acima de 1400°C. Baseado em informações disponíveis na literatura foi identificada a existência de um campo bifásico envolvendo as fases Mo (solução sólida) e o intermetálico 'Mo IND. 5¿ ¿Si¿ ¿B IND. 2¿ ('T IND. 2¿) A 1600 º C no sistema Mo-B-Si. Tendo em vista o limitado número de informações relacionadas a este sistema objetivamos neste trabalho uma avaliação sistemática sobre estabilidade de fases na região rica em Mo. O trabalho consistiu em: determinar a relação de fases a 1600°C; desenvolver métodos de análise via microssonda eletrônica (WDS) para determinação da composição das fases; determinação da projeção liquidus; determinação da seção vertical Mo-'T IND. 2¿.A determinação da relação de fases a 1600°C confmnou a existência do campo bifásico Mo+ 'T IND. 2¿ naquela temperatura.A fase ternária 'T IND. 2¿ é rodeada pelos campos trifásicos ... Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital
Abstract: In recent investigations it has been proposed that equilibrium microstructures constituted by a refractory metal and an intermetallicphase are the best choice for high temperature structural applications at temperatures higher than 1400°C. Based on the information available in the literature it has been identified the existence of a Mo (solid solution) + intermetallic 'Mo IND. 5¿ ¿Si¿ ¿B IND. 2¿ two-phase field in the Mo-B-Si system. Considering the limited information related to this system it was the objective of this study to systematically evaluate the phase stability in the Mo-rich region. Specific objectives were: determination of the phase relations at 1600°C; development of microprobe methods of analysis to determine phase compositions; determination of the liquidus projection; determination of the Mo-'T IND. 2¿ vertical section. The Mo+ 'T IND. 2¿ two-phase field was confirmed to exist at 1600°C. The ternary phase ('T IND. 2¿) is surrounded by the following three-phase field ... Note: The complete abstract is available with the full electronic digital thesis or dissertations
Doutorado
Materiais e Processos de Fabricação
Doutor em Engenharia Mecânica

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-04T20:26:12Z No. of bitstreams: 1 ALANA PEREIRA RAMOS - DISSERTAÇÃO PPG-CEMat 2014..pdf: 2592489 bytes, checksum: 5e82ab454a76e1050981da9019ce8fec (MD5)
Made available in DSpace on 2018-04-04T20:26:12Z (GMT). No. of bitstreams: 1 ALANA PEREIRA RAMOS - DISSERTAÇÃO PPG-CEMat 2014..pdf: 2592489 bytes, checksum: 5e82ab454a76e1050981da9019ce8fec (MD5) Previous issue date: 2017-08-07
As ligas ternárias de Ti-Cu-Ni com memória de forma são conhecidas por apresentarem transformação de fase característica e propriedades semelhantes às ligas binárias Ti–Ni. Estudos realizados com ligas ricas em cobre mostraram que a adição de cobre nas ligas de Ti-Ni reduz a histerese de resposta do efeito de memória de forma e aumenta a TFA (tendência de formação de fase amorfa) ainda pouco estudada com altas porcentagens de cobre. Diante disso, este trabalho teve como objetivo avaliar a influência da velocidade de resfriamento nas temperaturas de transformação e na tendência de amorfização em fitas de Ti-CuNi resfriadas rapidamente. Para tanto, foram produzidas duas fitas Ti01 (Ti 43,5 Cu 37,8 Ni 18,7) e Ti02 (Ti 58,4 Cu 25,6 Ni 16,0) pelo processo melt spinning, variando-se a velocidade linear da roda em 21 m/s e 63 m/s. As amostras foram caracterizadas utilizando-se técnicas DSC, DR-X, RET e MO. Após essa caracterização pode-se afirmar que a técnica de melt spinning permite a produção de fitas muito finas, da ordem de micrômetros, em apenas uma etapa de processamento, assim como também foi possível a produção de fitas amorfas, do sistema Ti-Cu-Ni, sem nenhuma fase cristalina como observado na fita Ti01 e Ti 02 obtidas com velocidade linear de 63m/s. O tratamento térmico foi suficiente para remover todos os defeitos produzidos pelo processo de solidificação rápida e produzir um rápido crescimento de grão, favorecendo o aumento das temperaturas de transformação martensíticas e austeníticas.
Ternary alloys with shape memory Ti-Cu-Ni are known to submit a characteristic phase transformation and properties similar to the and Ti-Ni binary alloy . Studies with rich-copper alloys showed that the addition of copper in alloys Ti-Ni reduces the hysteresis response of the shape memory effect and increases the TFA (tendency to form amorphous phase) still little studied with high percentages of copper. Thus, this study aimed to evaluate the influence of cooling rate on the transformation temperatures and on the tendency of Cu-Ni-Ti ribbons rapidly solidified. Therefore, two ribbons TI01 (Ti 43.5 Cu 37.8 Ni 18.7) and Ti02 (Ti 58.4 Cu 25.6 Ni 16.0) were produced by melt spinning process, varying the wheel linear velocity 21 m/s and 63 m/s. The samples were characterized using DSC, X-DR, RET and MO and techniques. Melt spinning technique allows the production of very thin ribbons of the order of microns, in one processing step, as it was also possible to produce amorphous ribbons, the system Ti-Cu-Ni, without crystalline phase as observed in TI01 and 02 Ti02 with linear velocity of 63m/s. The heat treatment was sufficient to remove all defects produced by rapid solidification process and produce a rapid grain growth, favoring the increase of temperatures of martensitic and austenitic transformation.

Yeung Man Hau.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1998.
Includes bibliographical references (leaves 52-53).
Text in English; abstract also in Chinese.
Yeung Man Hau.
Chapter Chapter 1 --- Introduction
Chapter 1. --- Background of solidification --- p.1
Chapter 1.1 --- The driving force for solidification
Chapter 1.2 --- Capillarity effect (or Gibbs-Thomson effect)
Chapter 2. --- Nucleation --- p.3
Chapter 3. --- Growth --- p.4
Chapter 3.1 --- Constrained growth and unconstrained growth
Chapter 3.2 --- Directional solidification
Chapter 4. --- Growth of pure substances --- p.6
Chapter 4.1 --- Metals
Chapter 4.2 --- Stability of planar S/L interface
Chapter 4.3 --- Non-metals
Chapter 5. --- Solidification of single-phase binary alloys --- p.7
Chapter 5.1 --- Equilibrium solidification
Chapter 5.2 --- Constitutional undercooling
Chapter 5.3 --- Stability of planar S/L morphology
Chapter 5.4 --- Minimum scale of perturbation in directional growth
Chapter 5.5 --- Development of growth morphology
Chapter 5.6 --- Growth rate of cell/dendrite tip
Chapter 5.7 --- Arm spacing and coarsening
Chapter 6. --- Solidification of binary eutectic alloys --- p.11
Chapter 6.1 --- Classification
Chapter 6.2 --- Growth of lamellar eutectics
Chapter 6.3 --- Stability of planar morphology
Chapter 6.4 --- Coupled zone (Competitive growth of eutectic and dendrites)
Chapter 6.5 --- Off-eutectic solidification
Chapter 7. --- Solidification of ternary eutectic alloys --- p.14
References --- p.16
Figures --- p.17
Chapter Chapter 2 --- Experimental Methods
Chapter 1. --- Fused silica tube cleaning --- p.37
Chapter 2. --- Alloy preparation --- p.37
Chapter 3. --- Undercooled specimen preparation --- p.38
Chapter 4. --- Specimen examination --- p.38
Chapter 5. --- TEM sample preparation --- p.39
References --- p.40
Figures --- p.41
Chapter Chapter 3 --- Solidification of Undercooled Molten Pd60 .5Cu25Si14.5 Alloy
Chapter 1. --- Introduction --- p.44
Chapter 2. --- Experimental --- p.46
Chapter 3. --- Results --- p.46
Chapter 3.1 --- Thermal profiles
Chapter 3.1.1 --- Temperature-time chart plotter (plotter)
Chapter 3.1.2 --- Differential thermal analysis (D TA)
Chapter 3.2 --- Microstructures
Chapter 3.2.1 --- Effect of undercooling on the microstructure
Chapter 3.2.2 --- Effect of quenching after 1st exothermic peak on the microstructure
Chapter 3.2.3 --- Effect of annealing at the onset temperature of 1st exothermic peak on the microstructure
Chapter 3.2.4 --- Effect of using slower cooling rate on the microstructure
Chapter 4. --- Discussions --- p.50
Chapter 5. --- Conclusion --- p.51
References --- p.52
Figures --- p.54

by Chan Kim Wai.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1997.
Includes bibliographical references.
by Chan Kim Wai.
Chapter Chapter I --- Introduction
Chapter 1.1 --- Rapid solidification
Chapter 1.1.1 --- Rapid quenching --- p.1-1
Chapter 1.1.2 --- Undercooling --- p.1-2
Chapter 1.2 --- Grain refinement
Chapter 1.2.1 --- What is grain refinement? --- p.1-5
Chapter 1.2.2 --- Previous results in grain refinement
Chapter 1.2.2.1 --- Pure metals (or dilute alloys) --- p.1-5
Chapter 1.2.2.2 --- Alloys --- p.1-9
Chapter 1.2.2.3 --- Semiconductor --- p.1-10
Chapter 1.2.3 --- Critical crystal growth velocity V* --- p.1-11
Chapter 1.2.4 --- Proposed models to grain refinement
Chapter 1.2.4.1 --- Dynamic nucleation and cavitation --- p.1-12
Chapter 1.2.4.2 --- Remelting (melt-back) --- p.1-14
Chapter 1.2.4.3 --- Interdendritic fluid flow --- p.1-15
Chapter 1.2.5 --- Volumetric manifestation of grain refinement --- p.1-15
Chapter 1.3 --- Aim of this project --- p.1-16
References
Figures
Chapter Chapter II --- Experimental
Chapter 2.1 --- Pure palladium
Chapter 2.1.1 --- Sample preparation and procedure --- p.2-1
Chapter 2.1.2 --- Limitation and choice of flux --- p.2-2
Chapter 2.1.3 --- High temperature furnace --- p.2-3
Chapter 2.1.4 --- Measurement of specific volume
Chapter 2.1.4.1 --- Theory --- p.2-4
Chapter 2.1.4.2 --- Setup --- p.2-5
Chapter 2.1.5 --- Observing internal morphology --- p.2-5
Chapter 2.2 --- Palladium with insoluble impurity
Chapter 2.2.1 --- Choice of insoluble impurities --- p.2-6
Chapter 2.2.2 --- Sample preparation --- p.2-7
References
Figures
Chapter Chapter III --- Results and Discussion
Results
Chapter 3.1 --- Pure palladium
Chapter 3.1.1 --- Specific volume --- p.3-1
Chapter 3.1.2 --- Grain structure and internal voids --- p.3-2
Chapter 3.2 --- Palladium with insoluble impurity
Chapter 3.2.1 --- Pinning effect of insoluble impurities --- p.3-3
Chapter 3.2.2 --- Pd-Ni-S system
Chapter 3.2.2.1 --- Grain refinement in Pd99.9Ni-S)0.1 --- p.3-4
Chapter 3.2.2.2 --- Change of ΔT* with addition of sulfur --- p.3-5
Chapter 3.2.2.3 --- Internal voids --- p.3-5
Discussion
Chapter 3.3 --- Dynamic nucleation of Pd-Ni-S system --- p.3-6
Chapter 3.4 --- Void formation of pure palladium and Pd-Ni-S --- p.3-6
Chapter 3.5 --- Grain refinement and specific volume --- p.3-7
Reference
Figures

Thesis (M.S.)--University of Wisconsin--Madison, 1991.
Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 157-163).

The lack of a thorough understanding of the solidification behaviors of the proeutectic Al₃Sc and the Al-Al₃Sc eutectic in a hypereutectic Al-Sc alloy stimulates the present dissertation. The major findings for the single-phase growth of the proeutectic Al₃Sc is summarized as follows: At a low cooling rate (~1 ºC·s^-1), the proeutectic Al₃Sc phase’s formation was governed by the lateral growth, exposing six flat {100} facets. At an intermediate cooling rate (~400 ºC·s^-1), the proeutectic Al₃Sc grew in a dendritic manner, with well-defined backbones extending in eight <111> directions and paraboloidal dendrite tips, although the dendrite tips and side-branches turned into faceted steps at a late growth stage,when the lateral growth prevailed. At a high cooling rate (~1000 ºC·s^-1), the proeutectic Al₃Sc primarily crystallized into an entirely seaweed-structured particle, which was composed of interior compact seaweeds and exterior fractal seaweeds. In order to verify the proposed dendritic and seaweed growth mechanisms for the proeutectic Al₃Sc, various morphological stability criteria were used, and fair agreement between the observed and the estimated characteristic length scales was reached.

On the Al-Al₃Sc eutectic side, it was found that a rod-typed Al₃Sc eutectic phase prevalently existed in an as-cast hypereutectic Al-Sc alloy that solidified via both slow cooling in air (~1 ºC·s⁻¹) and rapid cooling in a wedge-shaped copper mold (up to ~3000 ºC·s⁻¹). Al-Al₃Sc eutectic dendrites were identified within a narrow region near the edge of the wedge. The eutectic dendrites had an equiaxed dendritic contour and a rod eutectic structure inside. Quantitative assessments revealed that an interface undercooling of 48.2 ºC was required to form the eutectic dendrites, or in other words, to enter the coupled zone of the Al-Al₃Sc phase diagram. Furthermore, a phenomenon of scientific interest was discussed: When crystallizing under a near-equilibrium condition, the eutectic Al₃Sc phase formed a non-faceted morphology, in contradiction to its faceted nature. Based on the competitive growth criterion, it was deduced that the non-faceting of the eutectic Al₃Sc phase essentially reduced the interface undercooling for the resultant regular eutectic, in comparison to an otherwise irregular eutectic that would contain a faceted eutectic Al₃Sc phase.

Hong Sin Yi, Grace.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1997.
Includes bibliographical references (leaves 50-51).
Acknowledgments
Abstract
Chapter Chapter 1 --- Introduction
Chapter 1.1 --- Metallic Glass and its application --- p.1
Chapter 1.2 --- Glass Forming Ability (GFA) --- p.2
Chapter 1.3 --- Equilibrium Phase --- p.3
Chapter 1.4 --- Nucleation and Growth --- p.6
Chapter 1.5 --- Spinodal Decomposition --- p.8
Chapter 1.6 --- Morphology Comparison between Nucleation and Growth and Spinodal --- p.13
Figures --- p.14
References --- p.24
Chapter Chapter 2 --- Experimental Method
Experimental Method --- p.25
Figure --- p.29
References --- p.30
Chapter Chapter 3 --- Metastable liquid miscibility gap in Pd-Si and its glass forming ability
Introduction --- p.32
Experimental --- p.33
Results --- p.34
Discussion --- p.36
Figures --- p.40
References --- p.49
Bibliography --- p.50

The aim of the present thesis is to understand the phase transformation behavior of embedded alloy nanoparticles embedded in immiscible matrices. Embedded alloy inclusions have been dispersed in immiscible matrix via rapid solidification method. The present work deals with synthesis of embedded particles, evolution of microstructure, morphology and crystallographic orientation relation relationships among different phases, phase transformation and phase stability behavior of embedded alloy inclusions in different matrices. In the present investigation the systems chosen are Bi-Sn and Bi-Pb in Zn matrix and Cd-Sn in Al matrix. Chapter 1 gives the brief introduction of present work Chapter 2 gives a brief review of nanoscale materials, various synthesis techniques, microstructure evolution, solidification and melting theories. Chapter 3 discusses the processing and experimental techniques used for characterization of the different samples in the present work. Melt-spinning technique used to synthesize the rapidly solidified ribbons. The structural characterization is carried out using X-ray diffraction and transmission electron microscopy. Chapter 4 illustrates the size dependent solubility and phase transformation behavior of Sn-Cd alloy nanoparticles embedded in aluminum matrix. X-ray diffraction study shows the presence of fcc Al, bct Sn, hcp Cd solid solution and hcp Cd phases. Based on Zen’s law, the amount of Sn present Cd solid solution is estimated. Using overlapped sterograms, the orientational relationships among various phases are found. Microscopy studies reveal that majority of the alloy nano inclusions exhibit a cuboctahedral shape with 111 and 100 facets and they are bicrystalline. STEM-EDS analysis shows that both phases exhibit size dependent solubility behavior and for particles size smaller than 18 nm, single phase solid solution could only be observed. Calorimetric studies reveal a depression in eutectic melting point of bimetallic particles. In situ heating studies show that melting initiates at triple line junction corner and melt first grows into the interior of the Sn rich phase of the particle and then later the melt grows into the interior of the Cd phase of the particle. During cooling first Cd phase solidifies later Sn phase solidifies and on further cooling at low temperatures entire particle transforming into complete solid solution phase particle. Size dependent melting studies show that during heating smaller particles melted first, later bigger particles melted. During cooling first bigger particle solidified later smaller particles solidified. High resolution imaging indicates presence of steps across particle-matrix interface that may get annihilated during heating. During cooling, molten particles in the size range of 16-30 nm solidify as solid solution which for molten particles greater than 30 nm solidify as biphasic particle. Insitu heating studies indicates that for solid particles less than 15 nm get dissolved in the Al matrix at temperatures at around 135°C. Differential scanning calorimetry (DSC) studies show in the first heating cycle most of the particles melt with an onset of melting of at 166.8°C which is close to the bulk eutectic temperature of Sn-Cd alooy. The heating cycle reveals that the melting event is not sharp which can be understood from in-situ microscopy heating studies. In the second and the third cycles, the onset of melting observed at still lower temperatures 164.3°C and 158.5°C .The decrease in onset melting point in subsequent heating cycles is attributed to solid solution formation of all small particles whose size range below 30 nm during cooling. cooling cycles exhibit an undercooling of 90°C with respect to Cd liquidus temperature. Thermal cycling experiments using DSC were carried out by arresting the run at certain pre-determined temperatures during cooling and reheating the sample to observe the change in the melting peak position and area under the peak. The areas of these endothermic peaks give us an estimate of the fraction of the particles solidified upto the temperature when the cycling is reversed. Based on experimental observations, a thermodynamic model is developed, to understand the solubility behavior and to describe the eutectic melting transition of a binary Sn-Cd alloy particle embedded in Al matrix. Chapter 5 discusses the phase stability and phase transformation behavior of nanoscaled Bi-Sn alloys in Zn matrix. Bi-Sn alloys with eutectic composition embedded in Zn matrix using melt spinning technique. X-ray diffraction study shows the presence of rhombohedral Bi, pure BCT Sn and hcp Zn phases. In X-ray diffractogram, there are also other new peaks observed, whose peak positions (interplanar spacings) do not coincide either with rhombohedral Bi or bct Sn or hcp Zn. Assuming these new phase peaks belong to bct Sn rich solid solution(based on earlier work on Bi-Sn rapidly solidified metastable alloys) whole pattern fitting done on x-ray diffractogram using Lebail method. The new phase peaks indicated as bct M1(metastable phase1), bct M2(metastable phase2) phases. The amount of Bi present in M1, M2 solid solution is estimated using Zens law. Two sets of inclusions were found, one contains equilibrium bismuth and tin phases and the other set contains equilibrium bismuth and a metastable phase. In-situ TEM experiments suggest that as temperature increases bismuth diffuses into tin and becomes complete solid solution. Melting intiates along the matrix–particle interface leading to a core shell microstructure. During cooling the entire inclusion solidify as solid solution and decomposes at lower temperatures. High temperature XRD studies show that as temperature increases M1, M2 phases peaks merge with Sn phase peaks and Bi phase peak intensities slowly disappear and on further increasing temperature Sn solid solution phase peaks also disappear. During cooling diffraction studies show that first Sn solid solution phase peaks appear and later Bi phase peaks appear. But, the peaks belong to metstable phases not appeared while cooling. Chapter 6 presents morphology and phase transformation of nanoscaled bismuth-lead alloys with eutectic (Pb44.5-Bi55.5) and peritectic (Pb70-Bi30) compositions embedded in zinc matrix. using melt spinning technique. In alloy1[ Zn-2at%(Pb44.5-Bi55.5)] inclusions were found to be phase separated into two parts one is rhombohedral Bi and the other is hcp Pb7Bi3 phase. X-ray diffraction study shows the presence of rhombohedral Bi, hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb44.5-Bi55.5) melt spun sample. The morphology and orientation relationships among various phases have been found. In-situ microscpy heating studies show that melt initially spreads along the matrix–particle interface leading to a core-shell microstructure. And in the core of the core-sell particles, first Bi phase melts later Pb7Bi3 phase will melt and during cooling the whole particle solidify as biphase particle with large undercooling. In-situ heating studies carried out to study the size dependent melting and solidification behavior of biphase particles. During heating smaller particles melt melt first later bigger particle will melt. In contrast, while cooling smaller particles solidifies first, later bigger particles will solidify. Detailed high temperature x-ray diffraction studies indicate there increases first Bi phase peaks disappear later Pb7Bi3 phase peaks disappear and during cooling first Pb7Bi3 phase peaks appear and later Bi phase peaks appear. In alloy2[ Zn-2at%(Pb70-Bi30)] inclusions were found to be single phase particles. X-ray diffraction study shows the presence of hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb70-Bi30) melt spun sample. The crystallographic orientation relationship between hcp Pb7Bi3 and hcp Zn phases. In-situ microscpy heating studies show that melting initiates across the matrix–particle interface grows gradually into the interior of the particle. Three phase equilibrium at peritectic reaction temperature is not observed during insitu heating TEM studies. Size dependent melting point depression of single phase particles is not observed from in-situ heating studies. Detailed high temperature x-ray diffraction studies show that while heating the Pb7Bi3 phase peak intensities start decreasing after 170°C and become zero at 234°C. And during cooling Pb7Bi3 phase peaks starts appearing at 200°C and on further cooling the Pb7Bi3 phase peak intensities increase upto 150°C, below this temperature peak intensities remain constant.

The aim of the present thesis is to understand the phase transformation behavior of embedded alloy nanoparticles embedded in immiscible matrices. Embedded alloy inclusions have been dispersed in immiscible matrix via rapid solidification method. The present work deals with synthesis of embedded particles, evolution of microstructure, morphology and crystallographic orientation relation relationships among different phases, phase transformation and phase stability behavior of embedded alloy inclusions in different matrices. In the present investigation the systems chosen are Bi-Sn and Bi-Pb in Zn matrix and Cd-Sn in Al matrix. Chapter 1 gives the brief introduction of present work Chapter 2 gives a brief review of nanoscale materials, various synthesis techniques, microstructure evolution, solidification and melting theories. Chapter 3 discusses the processing and experimental techniques used for characterization of the different samples in the present work. Melt-spinning technique used to synthesize the rapidly solidified ribbons. The structural characterization is carried out using X-ray diffraction and transmission electron microscopy. Chapter 4 illustrates the size dependent solubility and phase transformation behavior of Sn-Cd alloy nanoparticles embedded in aluminum matrix. X-ray diffraction study shows the presence of fcc Al, bct Sn, hcp Cd solid solution and hcp Cd phases. Based on Zen’s law, the amount of Sn present Cd solid solution is estimated. Using overlapped sterograms, the orientational relationships among various phases are found. Microscopy studies reveal that majority of the alloy nano inclusions exhibit a cuboctahedral shape with 111 and 100 facets and they are bicrystalline. STEM-EDS analysis shows that both phases exhibit size dependent solubility behavior and for particles size smaller than 18 nm, single phase solid solution could only be observed. Calorimetric studies reveal a depression in eutectic melting point of bimetallic particles. In situ heating studies show that melting initiates at triple line junction corner and melt first grows into the interior of the Sn rich phase of the particle and then later the melt grows into the interior of the Cd phase of the particle. During cooling first Cd phase solidifies later Sn phase solidifies and on further cooling at low temperatures entire particle transforming into complete solid solution phase particle. Size dependent melting studies show that during heating smaller particles melted first, later bigger particles melted. During cooling first bigger particle solidified later smaller particles solidified. High resolution imaging indicates presence of steps across particle-matrix interface that may get annihilated during heating. During cooling, molten particles in the size range of 16-30 nm solidify as solid solution which for molten particles greater than 30 nm solidify as biphasic particle. Insitu heating studies indicates that for solid particles less than 15 nm get dissolved in the Al matrix at temperatures at around 135°C. Differential scanning calorimetry (DSC) studies show in the first heating cycle most of the particles melt with an onset of melting of at 166.8°C which is close to the bulk eutectic temperature of Sn-Cd alooy. The heating cycle reveals that the melting event is not sharp which can be understood from in-situ microscopy heating studies. In the second and the third cycles, the onset of melting observed at still lower temperatures 164.3°C and 158.5°C .The decrease in onset melting point in subsequent heating cycles is attributed to solid solution formation of all small particles whose size range below 30 nm during cooling. cooling cycles exhibit an undercooling of 90°C with respect to Cd liquidus temperature. Thermal cycling experiments using DSC were carried out by arresting the run at certain pre-determined temperatures during cooling and reheating the sample to observe the change in the melting peak position and area under the peak. The areas of these endothermic peaks give us an estimate of the fraction of the particles solidified upto the temperature when the cycling is reversed. Based on experimental observations, a thermodynamic model is developed, to understand the solubility behavior and to describe the eutectic melting transition of a binary Sn-Cd alloy particle embedded in Al matrix. Chapter 5 discusses the phase stability and phase transformation behavior of nanoscaled Bi-Sn alloys in Zn matrix. Bi-Sn alloys with eutectic composition embedded in Zn matrix using melt spinning technique. X-ray diffraction study shows the presence of rhombohedral Bi, pure BCT Sn and hcp Zn phases. In X-ray diffractogram, there are also other new peaks observed, whose peak positions (interplanar spacings) do not coincide either with rhombohedral Bi or bct Sn or hcp Zn. Assuming these new phase peaks belong to bct Sn rich solid solution(based on earlier work on Bi-Sn rapidly solidified metastable alloys) whole pattern fitting done on x-ray diffractogram using Lebail method. The new phase peaks indicated as bct M1(metastable phase1), bct M2(metastable phase2) phases. The amount of Bi present in M1, M2 solid solution is estimated using Zens law. Two sets of inclusions were found, one contains equilibrium bismuth and tin phases and the other set contains equilibrium bismuth and a metastable phase. In-situ TEM experiments suggest that as temperature increases bismuth diffuses into tin and becomes complete solid solution. Melting intiates along the matrix–particle interface leading to a core shell microstructure. During cooling the entire inclusion solidify as solid solution and decomposes at lower temperatures. High temperature XRD studies show that as temperature increases M1, M2 phases peaks merge with Sn phase peaks and Bi phase peak intensities slowly disappear and on further increasing temperature Sn solid solution phase peaks also disappear. During cooling diffraction studies show that first Sn solid solution phase peaks appear and later Bi phase peaks appear. But, the peaks belong to metstable phases not appeared while cooling. Chapter 6 presents morphology and phase transformation of nanoscaled bismuth-lead alloys with eutectic (Pb44.5-Bi55.5) and peritectic (Pb70-Bi30) compositions embedded in zinc matrix. using melt spinning technique. In alloy1[ Zn-2at%(Pb44.5-Bi55.5)] inclusions were found to be phase separated into two parts one is rhombohedral Bi and the other is hcp Pb7Bi3 phase. X-ray diffraction study shows the presence of rhombohedral Bi, hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb44.5-Bi55.5) melt spun sample. The morphology and orientation relationships among various phases have been found. In-situ microscpy heating studies show that melt initially spreads along the matrix–particle interface leading to a core-shell microstructure. And in the core of the core-sell particles, first Bi phase melts later Pb7Bi3 phase will melt and during cooling the whole particle solidify as biphase particle with large undercooling. In-situ heating studies carried out to study the size dependent melting and solidification behavior of biphase particles. During heating smaller particles melt melt first later bigger particle will melt. In contrast, while cooling smaller particles solidifies first, later bigger particles will solidify. Detailed high temperature x-ray diffraction studies indicate there increases first Bi phase peaks disappear later Pb7Bi3 phase peaks disappear and during cooling first Pb7Bi3 phase peaks appear and later Bi phase peaks appear. In alloy2[ Zn-2at%(Pb70-Bi30)] inclusions were found to be single phase particles. X-ray diffraction study shows the presence of hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb70-Bi30) melt spun sample. The crystallographic orientation relationship between hcp Pb7Bi3 and hcp Zn phases. In-situ microscpy heating studies show that melting initiates across the matrix–particle interface grows gradually into the interior of the particle. Three phase equilibrium at peritectic reaction temperature is not observed during insitu heating TEM studies. Size dependent melting point depression of single phase particles is not observed from in-situ heating studies. Detailed high temperature x-ray diffraction studies show that while heating the Pb7Bi3 phase peak intensities start decreasing after 170°C and become zero at 234°C. And during cooling Pb7Bi3 phase peaks starts appearing at 200°C and on further cooling the Pb7Bi3 phase peak intensities increase upto 150°C, below this temperature peak intensities remain constant.