Fe-based bulk metallic glasses (BMGs) have gained considerable interest due to their excellent soft magnetic properties with high saturation magnetization, high electrical resistivity, very good corrosion resistance, low materials cost, extremely high mechanical strength and hardness. In spite of having excellent strength, Fe-based BMGs are not used as structural materials in service, so far. The major obstacle is their inherent brittleness under mechanical loading, once a crack is developed the material fails catastrophically. Owing to the ever growing industrial demand for the materials with outstanding properties, aside from exploring new alloy compositions, it is pertinent to understand why or why-not the existing system work and how to improve their properties. Recent reports suggested that the plastic deformability can be enhanced by introducing different microstructural heterogeneities such as free volume enhanced regions, separated phases, nano-crystals, atomic clusters caused by for instance additions of small amount of soft elements. Understanding the effect of addition of soft elements to Fe-based BMGs on thermal stability, structural evolution, magnetic and mechanical properties are the main point which this work addresses. In this work, a study on two different soft ferromagnetic Fe-based glass forming alloys are presented, both of them known to have very high mechanical strength and excellent soft magnetic properties but so far have not been used in any industrial applications. The important issue is with the brittle behavior of this BMGs, particularly under mechanical loading. In each glass forming alloys, the aim was to find out the optimum quantity of the soft elements (Cu and Ga), which can be added to improve their room temperature plastic deformability without affecting the glass forming ability (GFA) and soft magnetic properties. The first glass forming alloy that is studied is Fe36Co36B19.2Si4.8Nb4. This glass forming alloy is highly sensitive to the impurities, only pure elements were used to form this alloy. The addition of only 0.5 at.% Cu completely changes the thermal stability and structural evolution but it also improves the mechanical properties. In case of Ga addition up to 1.5 at.% the crystallization behavior remains unaltered and the thermal stability improves marginally. The addition of Ga improves the plastic deformability of the glass by forming soft zones, whose melting point is much lower compared to rest of the alloy. These soft zones are responsible for the plastic deformation of this glass. Thus addition of Ga is very beneficial in improving the mechanical properties of this Fe-based BMG. In the second part, Fe74Mo4P10C7.5B2.5Si2 glass forming alloy is studied. Unlike the aforementioned alloy, this glass forming alloy is not very sensitive to the impurities, industrial grade alloy elements can also be used to form this alloy. In this alloy addition of Cu is beneficial only up to 0.5 at.%, beyond that Cu addition deteriorates GFA and magnetic properties. In case of Ga addition up to 2 at.% the crystallization behavior remains unaltered and the thermal stability improves marginally. Similar to the FeCoBSiNb glass, the addition of Ga in FeMoPCBSi glass also improves the plastic deformability of the glass by formation of soft zones. Addition of small at.% Ga proved be an viable solution to improve the plastic deformability in the ferromagnetic Fe-based metallic glasses without compromising on thermal and magnetic properties of the glass. In the final part we tried to cast the Fe74Mo4P10C7.5B2.5Si2 glass in a complex shape using an industrial high pressure die casting (HPDC) set up. The important issues were with the casting alloy temperature, casting speed and die material. The aim of our work was to optimize the die material suitable for casting the BMGs and then address the issues with casting temperature and casting speed. We have thus attempted to gain a basic knowledge in casting the Fe-based BMG in industrial scale. Our effort was tremendously successful, we were able to produce fully amorphous complex shaped samples with excellent surface finish. We have thus made a considerable advancement towards understanding the basics behind improving the room temperature plastic deformability in Fe36Co36B19.2Si4.8Nb4 and Fe74Mo4P10C7.5B2.5Si2 ferromagnetic BMGs. We have also made a considerable progress in industrialization of bulk ferromagnetic BMGs.

Bulk metallic glasses and multi-principal element alloys represent relatively new classes of multi-component engineering materials designed for satisfying multiple functionalities simultaneously. Correlating the microstructure with mechanical behavior (at the microstructural length-scales) in these materials is key to understanding their performance. In this study, the structure evolution and nano-mechanical behavior of these two classes of materials was investigated with the objective of fundamental scientific understanding of their properties. The structure evolution, high temperature nano-mechanical behavior, and creep of two Zr-based alloys was studied: Zr41.2Ti13.8Cu12.5Ni10.0Be22 (Vitreloy1) and Zr52.5Ti5Cu17.9Ni14.6All0 (Vitreloy105). Devitrification was found to proceed via the formation of a metastable icosahedral phase with five-fold symmetry. The deformation mechanism changes from inhomogeneous or serrated flow to homogenous flow near 0.9Tg, where Tg is the glass transition temperature. The creep activation energy for Vitreloy1 and Vitreloy105 were 144 kJ/mol and 125 kJ/mol, respectively in the range of room temperature to 0.75Tg. The apparent activation energy increased drastically to 192 kJ/mol for Vitreloy1 and 215 kJ/mol for Vitreloy105 in the range of 0.9Tg to Tg, indicating a change in creep mechanism. Structure evolution in catalytic amorphous alloys, Pt57.5Cu14.7Ni5.3P22.5 and Pd43Cu27Ni10P20, was studied using 3D atom probe tomography and elemental segregation between different phases and the interface characteristics were identified. The structure evolution of three multi-principal element alloys were investigated namely CoCrNi, CoCrFeMnNi, and Al0.1CoCrFeNi. All three alloys formed a single-phase FCC structure in as-cast, cold worked and recrystallized state. No secondary phases precipitated after prolonged heat treatment or mechanical working. The multi-principal element alloys showed less strain gradient plasticity compared to pure metals like Ni during nano-indentation. This was attributed to the highly distorted lattice which resulted in lesser density of geometrically necessary dislocations (GNDs). Dislocation nucleation was studied by low load indentation along with the evaluation of activation volume and activation energy. This was done using a statistical approach of analyzing the "pop-in" load marking incipient plasticity. The strain rate sensitivity of nanocrystalline Al0.1CoCrFeNi alloy was determined by in situ compression of nano-pillars in a Pico-indenter. The nanocrystalline alloy demonstrated a yield strength of ~ 2.4 GPa, ten times greater than its coarse grained counterpart. The nanocrystalline alloy exhibited high strain rate sensitivity index of 0.043 and activation volume of 5b3 suggesting grain boundary dislocation nucleation.

Call number: LD2668 .T4 1985 O83 / Master of Science

A falta de ordenamento atômico de longo alcance dos vidros metálicos produz propriedades superiores em comparação com as mesmas ligas em condição cristalina. Ligas amorfas à base de Zr se oxidam facilmente, tornando-se frágeis, além do aumento do oxigênio levar a um aumento na taxa crítica de resfriamento necessário para a formação de vidro. O presente estudo mostrou a influência do oxigênio e da taxa de resfriamento (representada pelo diâmetro da amostra) na formação de fases cristalinas em duas ligas amorfas baseadas em Zr: Zr48Cu46,5Al4Nb1,5 e Zr52,5Cu17,9Ni14,6Al10Ti5 (Vit 105). As amostras de cada liga foram produzidas por fusão à arco elétrico com coquilhamento em molde de cobre refrigerado à água obtendo-se amostras de 2, 3, 4, 5 e 6 mm de diâmetro. As técnicas de caracterização empregadas foram medidas de oxigênio em equipamento LECO pelo princípio de fusão em gás inerte, quantificação da fração amorfa por análise de imagem de microscopia ótica, identificação das fases cristalinas por difração de raios-X (DRX) convencional e síncrotron, realização de refinamento Rietveld para quantificação da fração amorfa pelo método do grau de cristalinidade no software TOPAS e da fração das fases cristalinas, análises de microscopias eletrônicas de varredura (MEV) e de transmissão (MET). A fração amorfa formada nas ligas tende a diminuir com o aumento do oxigênio e com o aumento do diâmetro da amostra. Foram criados os mapas de formação de fases para ambas as ligas, onde observou-se que a liga Vit 105 possui uma maior tendência de formação vítrea (TFV) do que a liga Zr48Cu46,5Al4Nb1,5. / The lack of long-range atomic ordering in metallic glasses produces better properties when compared with the same alloys in crystalline condition. Zr-based amorphous alloys easily oxidize and becomes brittle with oxygen increases, leading to an increase in the critical cooling rate required for glass formation. This study aimed to analyze the influence of oxygen and cooling rate (represented as sample diameter) on the crystalline phase formation in two amorphous alloys based on Zr: Zr48Cu46.5Al4Nb1.5 and Zr52.5Cu17.9Ni14.6Al10Ti5 (Vit 105). The samples were produced by electric arc-melting followed by suction casting in a water-cooled copper mold producing samples with 2, 3, 4, 5 and 6 mm in diameter. The characterization techniques used were: oxygen measurement in LECO equipment by the fusion inert gas principle, optical microscopy to amorphous fraction quantification by image analysis, conventional and synchrotron X-ray diffraction (XRD) to identification of crystalline phases by Rietveld refinement with quantification of the amorphous fraction by the degree of crystallinity method on TOPAS software along with quantification of crystalline phases, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The amorphous fraction formed in the alloys tended to decrease with increasing oxygen content and sample diameter. Phase formation maps were created for both alloys, where it was observed that Vit 105 alloy has a higher glass forming ability (GFA) than Zr48Cu46.5Al4Nb1.5 alloy.

Chan Fu-wai = 非晶態鐵磁性鐵-磷-碳合金的製作 / 陳輔偉. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / Chan Fu-wai = Fei jing tai tie ci xing tie-lin-tan he jin de zhi zuo / Chen Fuwei. / Acknowledgments --- p.i / Abstract --- p.ii / Table of Content --- p.iv / Chapter Chapter 1: --- Introduction --- p.1 / Chapter 1.1 --- Nucleation --- p.1 / Chapter 1.1.1 --- Homogenous nucleation --- p.1 / Chapter 1.1.2 --- Heterogeneous nucleation --- p.4 / Chapter 1.2 --- The crystal growth --- p.5 / Chapter 1.2.1 --- The solid-liquid interface --- p.5 / Chapter 1.2.2 --- Lateral growth --- p.6 / Chapter 1.2.3 --- Continuous growth --- p.6 / Chapter 1.3 --- Non-equilibrium process --- p.8 / Chapter 1.3.1 --- Reduction of impurities --- p.8 / Chapter 1.3.2 --- Suppression of crystal growth --- p.8 / Chapter 1.4 --- The change in metallurgy --- p.9 / Chapter 1.4.1 --- The metallic glass --- p.9 / Chapter 1.4.2 --- The properties of glass --- p.10 / Chapter 1.4.3 --- The development of amorphous alloy --- p.11 / Chapter 1.5 --- Preparation methods of amorphous alloy --- p.12 / Chapter 1.6 --- The criterion of glass formation --- p.14 / Chapter 1.7 --- The study of this project --- p.15 / Reference --- p.16 / Figure --- p.19 / Chapter Chapter 2: --- Experiment --- p.36 / Chapter 2.1 --- Preparation --- p.36 / Chapter 2.2 --- Experimental procedure --- p.37 / Chapter 2.3 --- Sample analysis --- p.38 / Reference --- p.41 / Figure --- p.42 / Chapter Chapter 3: --- The formation of bulk ferromagnetic Fe-P-C amorphous alloy --- p.45 / Abstract --- p.45 / Introduction --- p.46 / Experiment --- p.47 / Result --- p.48 / Reference --- p.49 / Figure --- p.52 / Chapter Chapter 4: --- Compaction of bulk ferromagnetic Fe-P-C amorphous alloy --- p.57 / Abstract --- p.57 / Introduction --- p.58 / Experiment --- p.58 / Result --- p.60 / Reference --- p.61 / Figure --- p.62 / Chapter Chapter 5: --- Conclusion --- p.65

"Apr 2002." / The numerals in title is subscript. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / 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.

Influence of different microstructure of La-based fully amorphous samples and its composites on the impact fracture energy were investigated and discussed. Results showed improvement in fracture energy of glassy metals with the presence intermetallic phases, but deteriorated in the presence of dendrite phases and high volume % of crystalline phases. / Singapore-MIT Alliance (SMA)

Glass forming ability (GFA) in the Pr-rich Pr-(Cu, Ni)-Al alloys at or near the eutectic points was systematically studied. It was found that the GFA in the pseudo-ternary alloys of Pr-(Cu, Ni)-Al is higher than that of the ternary alloys of Pr-Cu-Al. Two eutectic compositions in Pr-(Cu, Ni)-Al alloys were found by DSC, namely, Pr₆₈(Cu₀.₅Ni₀.₅)₂₅Al₇ and Pr₅₂(Cu₀.₅Ni₀.₅)₂₅Al₂₃ (at %). The later one shows better GFA than the first one. However, the best GFA was obtained at an off-eutectic composition of Pr₅₄(Cu₀.₅Ni₀.₅)₃₀Al₁₆, which can be formed in fully amorphous rod with diameter of 1.5 mm by copper mould casting. The deviation of the best GFA composition from the eutectic point [Pr₆₈(Cu₀.₅Ni₀.₅)₂₅Al₇] was explained in terms of the asymmetric coupled eutectic zone and the higher glass transition temperature Tg on the hypereutectic side. / Singapore-MIT Alliance (SMA)

The elastic properties of a solid are of considerable interest to both science and technology. Not only do they contain fundamental information about the nature of the inter-atomic bonding in the material, but they also determine the mechanical behavior of solids. In the past few years, considerable effort has been devoted to the study of elastic properties of bulk metallic glasses (BMGs), a relatively new class of metallic materials that display a unique combination of mechanical and physical properties. Our research has focused on Zr-based, Cu-based and Ca-based metallic glasses. Zr-based BMGs are known to have superior glass forming ability and high strength, but their ductility is too low for wide-spread practical applications. Cu-based BMGs recently received wide interest because of their low cost and good mechanical properties. Ca-based BMGs have low glass transition temperature Tg, around 390 K, which make them very attractive to be studied near Tg. In this work, resonant ultrasound spectroscopy (RUS) has been applied to study the elastic properties of above mentioned BMGs from 5 K to their glass transition temperature Tg. RUS is a novel technique for determining the elastic moduli of solids, based on the measurement of the resonances of a freely vibrating body. In an RUS experiment, the mechanical resonances of a freely vibrating solid of known shape are measured, and an iteration procedure is used to “match” the measured lines with the calculated spectrum. This allows determination of all elastic constant of the solid from a single frequency scan. Below Tg, the elastic constants of the BMGs under investigation show “normal” behavior, i.e. with increasing temperature, all moduli decrease and Poisson ratio increases. Above Tg changes in the trends occur due to structural relaxation and crystallization. We confirmed the suggested link between ductility and Poisson ratio: BMGs showing good ductility display high Poisson ratio. By increasing palladium content in Zr50Cu40-xAl10Pdx alloys, BMGs with high Poisson ratio and thus good ductility have been obtained. In addition, we developed a simple model to provide fast and good estimate of the temperature dependence of elastic constants of BMGs from room temperature measurements. Keywords: Elastic properties; Bulk metallic glasses (BMGs); Resonant ultrasound spectroscopy (RUS); Internal friction.

For decades, Metallic Glass, with its isotropic featureless structure while exhibiting outstanding mechanical properties was possible only at a high rate of quenching and with at least one dimension in the submicron regime.  This limitation was overcome with the discovery of Bulk Metallic glasses, BMGs, containing three or more elements following the additional two empirical rules of optimum geometric size differences and negative energy of mixing among the constituent elements. Since then thousands of Fe-, Ni-, Al-, Mg-, Ti- based BMGs have been discovered and comprehensively investigated mainly by groups in Japan and USA. Yet the discovery of new combinations of elements for BMGs is alchemy. We do not know with certainty which element when added will make possible a transition from being a ribbon to a bulk rod.    In this thesis we report a discovery of castable BMGs rods on substitution of Fe by nickel in an alloy of FeBNb which could otherwise have been only melt-spun into ribbons.  For example, we find that substitution of just 6 at.% of Fe raises the glass forming range, GFA, to as much as ∆Tx =40K while the other parameters for GFA like Trg, γ, and δ reach enhanced values 0.57, 0.38, and 1.40 respectively.  Furthermore, the electrical conductivity is found to increase by almost a factor of two.  Magnetically it becomes softer with coercivity 260mOe which further reduces to much lower values on stress relaxation.  Ni does not seem to carry a magnetic moment while it enhances the magnetic transition temperature linearly with Ni concentration. We have investigated the role of Ni in another more stable BMGs based FeBNbY system in which case ∆Tx becomes as large as 94K with comparable enhancement in the other GFA parameters. Due to the exceptional soft magnetic properties, Fe-based bulk metallic glasses are considered potential candidate for their use in energy transferring devices. Thus the effect of Ni substitution on bulk forming ability, magnetic and electrical transport properties have been studied for FeBNb and FeBNbY alloy systems. The role of Ni in these systems is densification of the atomic structure and its consequence. We have exploited the superior mechanical properties of BMGs by fabricating structures that are thin and sustainable.  We have therefore investigated studies on the thin films of these materials retaining their excellent mechanical properties. Magnetic properties of FeBNb alloy were investigated in thin films form (~200-400nm) in the temperature range of 5-300K. These Pulsed Laser deposited amorphous films exhibit soft magnetism at room temperature, a characteristic of amorphous metals, while they reveal a shift in hysteresis loop (exchange anisotropy, HEB=18-25Oe), at liquid helium temperature. When thickness of films is reduced to few nanometers (~8-11nm), they exhibit high transparency (&gt;60%) in optical spectrum and show appreciably high saturation Faraday rotation (12o/μm, λ= 611nm). Thin films (~200-400nm) of Ni substituted alloy (FeNiBNb) reveal spontaneous perpendicular magnetization at room temperature. Spin-reorientation transition was observed as a function of film thickness (25-400nm) and temperature (200-300K), and correlated to the order/disorder of ferromagnetic amorphous matrix as a function of temperature. These two phase films exhibits increased value of coercivity, magnetic hardening, below 25K and attributed to the spin glass state of the system.    Using the bulk and thin films we have developed prototypes of sensors, current meters and such simple devices although not discussed in this Thesis.                                         Ti-based bulk metallic glasses have been attracting significant attention due to their lower density and high specific strength from structural application point of view. High mechanical strength, lower values of young’s modulus, high yield strength along with excellent chemical behaviors of toxic free (Ni, Al, Be) Ti-based glassy metals make them attractive for biomedical applications. In the present work, toxic free Ti-Zr-Cu-Pd-Sn alloys were studied to optimize their bulk forming ability and we successfully developed glassy rods of at least 14mm diameter by Cu-mold casting. Along with high glass forming ability, as-casted BMGs exhibit excellent plasticity. One of the studied alloy (Ti41.5Zr10Cu35Pd11Sn2.5) exhibits distinct plasticity under uniaxial compression tests (12.63%) with strain hardening before failure which is not commonly seen in monolithic bulk metallic glasses. / <p>QC 20120906</p> / Hero-m