In this dissertation, the ternary Mg-based amorphous ribbons are characterized and analyzed first. Among the three Mg65Cu25Y10, Mg65Cu25Gd10 and Mg65Ni25Gd10 amorphous ribbons, the Mg65Cu25Gd10 amorphous ribbon exhibits the best thermal properties in terms of the glass forming ability (GFA) indexes, such as 68 K of the supercooled liquid region (£GTx), 29 K of the liquidus region (£GTl), 0.582 of the reduced glass transition temperature (Trg), 0.427 of the £^ value and 0.768 of the £^m value. In spite that the Mg65Cu25Gd10 amorphous ribbons do not show the best performance in mechanical properties, such as micro-hardness value of 231 Hv (2.26 GPa), nano-hardness value is 3.24 GPa (300 Hv) and modulus from nano-indentation of 62.4 GPa, this composition is close to the two prediction compositions of Mg62Cu27Gd11 (the e/a-variant criterion) and Mg67Cu23Gd10 (the binary eutectic clusters criterion). However, among a series of ternary of Mg-Cu-Gd amorphous ribbons, the better overall thermal properties are seen in the Mg54Cu32Gd14 and Mg54Cu31Gd15 amorphous ribbons. In terms of the bulk Mg65Cu25Gd10 amorphous alloys, the 6 mm bulk metallic glass (BMG) rod can be fabricated successfully with minimum porosity. In order to improve the brittle properties of the Mg65Cu25Gd10 BMG rod, there are two methods applied in this study, namely, the intrinsic toughening method by heat treatment and the extrinsic toughening method of adding reinforcements. For the heat treated Mg65Cu25Gd10 BMG rod, both of the one-step and two-steps BMG rods show no distinct plastic deformation in the engineering stress-strain curves, while the micro-hardness and compressive stress are increased from 270 Hv to higher than 300 Hv and from 804 to 830 MPa. But, for the ductile metal-reinforced Mg-based BMG rods, the brittle properties are improved. For the Nb-reinforced Mg65Cu25Gd10 BMG rods, the compressive stress decreases from 804 to 595 MPa and the plastic strain increases from 0 to 0.48% with increasing volume fraction from 0 to 17.3%. But, for Mg65Cu25Gd10 BMG rod reinforced by 21.6% porous Mo, the compressive stress and plastic strain are 821 MPa and 1.63%, respectively. Moreover, for the porous Mo-reinforced Mg58Cu28.5Gd11Ag2.5 BMG rods, the compressive stress increases from 827 to 1111 MPa and the plastic strain increases from 0 to 7.84% with increasing volume fraction from 0 to 25.4%.

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

Metallic glasses can be considered for many commercial applications because of the higher mechanical strength, corrosion and wear resistance when compared to crystalline materials. To consider them for novel applications, the challenge of preparing metallic glasses from the liquid melt phase and how the properties of metallic glasses change due to relaxation need to be understood better. The glass forming ability (GFA) with variation in composition and inclusion of different alloying elements was studied by using thermal techniques to determine important GFA indicators for Zr-based bulk metallic glasses (BMG). The effect of alloying elements, annealing temperature and annealing time on the thermal and structural relaxation of the BMGs was studied by using an annealing induced relaxation approach. The thermal relaxation was studied by measuring specific heat of the samples using differential scanning calorimeter (DSC) and calculating the enthalpy recovery on reheating in the BMG samples. The structural relaxation was also studied by using extended X-ray absorption fine structure (EXAFS) technique on the as-obtained and relaxed samples. The effects of alloying elements and annealing on electrical resistance were studied by using a two point probe. From the study, it was found that the currently used GFA indicators are inadequate to fully capture and identify the best GFA BMGs. The fragility (beta) of the melt is a new criterion that has been proposed to measure and analyze GFA. The enthalpy relaxation of Zrbased BMGs was found to follow a stretched exponential function, and the parameters obtained showed the BMGs used in the current study are strong glass formers. EXAFS studies showed variations in the structure of BMGs with changes in alloying elements. Furthermore, alloying elements were found to have an effect on the structure of the relaxed BMGs. The resistance of BMGs was found to decrease with relaxation which can be attributed to short range order on annealing.

No description available.

The aim of this study is to investigate the bulk glass forming ability (BGFA) of Ti-based alloy systems. These investigations were carried out in two main parts that are complementary to each other: theoretical and experimental. For theoretical studies, which are based on electronic theory of alloys in pseudopotential approximation, Ti-Zr, Ti-Co and Ti-Cu alloys were chosen as the binary systems. Alloying element additions were performed to each binary for the investigation of the BGFA of multicomponent Ti-based alloys. Among the three studied binary systems, Ti-Cu was found to exhibit better BGFA, and Mn, Al and Ni elements were found to be suitable for improving the BGFA of Ti-Cu binary alloy system. BGFA of Ti-Cu binary and Ti-Cu-(Mn, Al, Ni) multicomponent alloys were investigated with the experimental studies that were carried out with performing arc melting and centrifugal casting operations. The characterizations of these alloys were done with scanning electron microscopy, X-ray diffraction analysis and differential scanning calorimetry. Ti60Cu35Mn5, Ti60Cu35Al5 and Ti60Cu35Ni5 alloys were produced and characterized as examples for ternary systems. Among them, Ti60Cu35Mn5 system was found to have better indications regarding to BGFA. Therefore, it was chosen as the main composition and multicomponent alloys of Ti59Cu35Mn5Al1, Ti59Cu35Mn5Ni1 and Ti58Cu35Mn5Al1Ni1 were synthesized and characterized.

This study is pertinent to setting a connection between glass forming ability (GFA) and topology of Fe-B based metallic glasses by combining intimate investigations on spatial atomic arrangements conducted via solid computer simulations with experimentations on high GFA bulk metallic glasses. In order to construct a theoretical framework, the nano-scale phase separation encountered in metallic glasses is investigated for amorphous Fe80B20 and Fe83B17 alloys via Monte Carlo equilibration and reverse Monte Carlo simulation. The phenomenon is identified regarding three topological aspects: 1) Pure Fe-clusters as large as ~0.9 nm and Fe-contours with ~0.72 nm thickness, 2) Fe-rich highly deformed body centered cubic regions, 3) B-centered prismatic units with polytetrahedral order forming distinct regions of high and low coordinations are found. All topological aspects are compiled into a new model called Two-Dimensional Projection Model for predicting contributions to short and medium range order (MRO) and corresponding spacing relations. The outcome geometrically involves proportions approximating golden ratio. After successfully producing soft magnetic Fe-Co-Nb-B-Si based bulk metallic glass and bulk nanocrystalline alloys with a totally conventional route, influences of alloying elements on structural units and crystallization modes are identified by the developed model and radial distributions. While Co atoms substitute for Fe atoms, Nb and Si atoms deform trigonal prismatic units to provide local compactions at the outset of MRO. Cu atoms alter the type of MRO which resembles crystalline counterparts and accompanying nanocrystals that precipitate. The GFA can be described by a new parameter quantifying the MRO compaction, cited as &amp / #934 / .

In this study molecular dynamics simulation program in NVT ensemble using Velocity Verlet integration was written in order to investigate the glass forming ability of two metallic systems. The Zn-Mg system, one of the frontiers of simple metal-metal metallic glasses and Fe-B, inquiring attention due to presence of many bulk glass forming alloy systems evolved from this binary with different alloying element additions. In addition to this, atomistic calculations on the basis of ordering were carried out for both Zn-Mg and Fe-B systems. Ordering energy values are calculated using electronic theory of alloys in pseudopotential approximation and elements which increase the ordering energy between atoms were determined. The elements which increase the ordering energy most were selected as candidate elements in order to design bulk amorphous alloy systems. In the experimental branch of the study centrifugal casting experiments were done in order to see the validity of atomistic calculations. Industrial low grade ferroboron was used as the master alloy and pure element additions were performed in order to constitute selected compositions. Fe62B21Mo5W2Zr6 alloy was successfully vitrified in bulk form using nearly conventional centrifugal casting processing. Specimens produced were characterized using SEM, XRD, and DSC in order to detect the amorphous structure and also the crystalline counterpart of the structure when the cooling rate is lower. Sequential peritectic and eutectic reaction pattern was found to be important for metallic glasses which can be vitrified in bulk forms with nearly conventional solidification methods.

Bulk metallic glasses have interesting combination of physical, chemical, mechanical, and magnetic properties which make them attractive for a variety of applications. Consequently there has been a lot of interest in understanding the structure and properties of these materials. More varied applications can be sought if one understands the reasons for glass formation and the methods to control them. The glass-forming ability (GFA) of alloys can be substantially increased by a proper selection of alloying elements and the chemical composition of the alloy. High GFA will enable in obtaining large section thickness of amorphous alloys. Ability to produce glassy alloys in larger section thicknesses enables exploitation of these advanced materials for a variety of different applications. The technique of mechanical alloying (MA) is a powerful non-equilibrium processing technique and is known to produce glassy (or amorphous) alloys in several alloy systems. Metallic amorphous alloys have been produced by MA starting from either blended elemental metal powders or pre-alloyed powders. Subsequently, these amorphous alloy powders could be consolidated to full density in the temperature range between the glass transition and crystallization temperatures, where the amorphous phase has a very low viscosity. This Dissertation focuses on identifying the various Fe-based multicomponent alloy systems that can be amorphized using the MA technique, studying the GFA of alloys with emphasis on improving it, and also on analyzing the effect of extended milling time on the constitution of the amorphous alloy powder produced at earlier times. The Dissertation contains seven chapters, where the lead chapter deals with the background, history and introduction to bulk metallic glasses. The following four chapters are the published/to be published work, where the criterion for predicting glass formation, effect of Niobium addition on glass-forming ability (GFA), lattice contraction on amorphization, effect of Carbon addition on GFA, and observation of mechanical crystallization in Fe-based systems have been discussed. The subsequent chapter briefly mentions about the consolidation of amorphous powders and presents results of hot pressing and spark plasma sintering on one of the alloy systems. The final chapter summarizes the Dissertation and suggests some prospective research work that can be taken up in future. The Dissertation emphasizes the glass-forming ability, i.e., the ease with which amorphization can occur. In this work the milling time required for amorphization was the indicator/measure of GFA. Although the ultimate aim of this work was to consolidate the Fe-based amorphous alloy powders into bulk so as to undertake mechanical characterization, however, it was first necessary to study the glass forming aspect in the different alloy systems. By doing this a stage has been reached, where different options are available with respect to amorphous phase-forming compositions and the knowledge to improve glass-forming ability via the mechanical alloying technique. This will be ultimately useful in the powder compaction process into various shapes and sizes at optimum pressure and temperature. The study on mechanical crystallization indicates, or in a way defines, a limit to the process of amorphization, and it was also demonstrated that this phenomenon is more common in occurrence than and not as restricted as it was earlier reported to be.

Desde a descoberta das ligas amorfas em 1960, os motivos pelos quais algumas ligas podem ser facilmente amorfizadas enquanto outras não podem, não é claramente conhecido, assim não há teoria universal para predizer a habilidade de formação vítrea em sistemas metálicos. No presente trabalho, um critério de seleção foi aplicado ao sistema Ni-Nb-Zr com o objetivo de predizer as melhores estequiometrias com as mais altas tendências de formação vítrea. As habilidades de formação vítrea das ligas foram avaliadas pelo parâmetro térmico &#947;m e os resultados mostraram uma pobre correlação com as predições. Este critério preditivo correlaciona as taxas de resfriamento para a formação vítrea com a instabilidade topológica de estruturas cristalinas, as diferenças médias de função trabalho e densidade eletrônica entre os elementos constituintes da liga. O parâmetro térmico depende de temperaturas características de transformações de fases que podem ser facilmente determinadas a partir de curvas de calorimetria exploratória diferencial dos vidros metálicos. As hipóteses iniciais para explicar a pobre correlação entre os resultados e as predições foram atribuídas às influências de fatores não considerados nos cálculos como os compostos intermetálicos desconhecidos e contaminação por oxigênio. Assim, algumas ligas solidificadas rapidamente foram investigadas com mais rigor com o objetivo de entender a formação das fases cristalinas que competem contra a formação vítrea. As fases cristalinas foram caracterizadas e comparadas com estruturas cristalinas encontradas na literatura como também alguns diagramas de fases. Os diagramas de fases foram utilizados como guias para o melhor entendimento do comportamento de cristalização. Em adição, o critério de seleção também foi utilizado para predizer o melhoramento da tendência de formação vítrea de uma liga do sistema Ni-Nb-Zr com pequenas adições dos elementos terras-raras Y ou Er. É bem conhecido que uma pequena adição de um elemento terra-rara apropriado pode aumentar significativamente a habilidade de formação vítrea de algumas ligas. As tendências de formação vítrea da liga base e das ligas dopadas com terras-raras também foram avaliadas pelo parâmetro térmico &#947m e os resultados concordaram muito bem com a tendência predita pelo cálculo. As amostras amorfas volumosas foram produzidas por injeção em molde de cobre. A natureza amorfa foi analisada por difração de raios-X e calorimetria exploratória diferencial. As fases cristalinas foram analisadas por microscopia eletrônica de transmissão, microscopia eletrônica de varredura, espectroscopia de raios-X por dispersão em energia e difração de raios-X. A contaminação por oxigênio foi quantificada pelo método de fusão em gás inerte. / Since the discovering of amorphous alloys in 1960, the actual causes of why some alloys can be easily formed into glasses while others cannot, are not clearly known, thus there is no universal theory to predict the glass forming ability in metallic systems. In the present work, a selection criterion was applied in the Ni-Nb-Zr system in order to predict the best stoichiometries with high glass forming ability. The actual glass forming ability of alloys were evaluated by the thermal parameter &#947;m and the results have shown a poor correlation with the predictions. This criterion correlates critical cooling rate for glass formation with topological instability of stable crystalline structures; average work function difference and average electron density difference among the constituent elements of the alloy. The thermal parameter depends on the characteristic temperatures of phase transformations which can be easily measured from differential scanning calorimetry curves of metallic glasses. The initial hypotheses to explain the poor correlation between the experimental results and the predictions concerned with the influence of factors not considered in the calculation, such as unknown intermetallic compounds and oxygen contamination. Thus some rapidly quenched alloys were investigated with more accuracy in order to understand the formation of crystalline phases which compete against the glass formation. We characterized the crystalline phases and compared them to crystalline structures found in literature as well as some phase diagrams. The phase diagrams were used as guides in order to understand the crystallization behavior. In addition, the selection criterion also was used to predict the glass forming ability improvement of a Ni-Nb-Zr alloy with minor additions of rare-earth elements Y or Er. It is well known that the minor amount addition of proper rare-earth elements can greatly enhance the glass forming ability of some glass-forming alloys. The actual glass forming ability of the base alloy and rare-earth doped alloys also were evaluated by the thermal parameter &#947m and the results agree very well with the tendency predicted by the calculation. Bulk amorphous specimens were produced by injection casting. The amorphous nature was analyzed by X-ray diffraction and differential scanning calorimetry. The crystalline phases were analyzed by transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and x-ray diffraction. Oxygen contamination was quantified by the inert gas fusion method.

Desde a descoberta das ligas amorfas em 1960, os motivos pelos quais algumas ligas podem ser facilmente amorfizadas enquanto outras não podem, não é claramente conhecido, assim não há teoria universal para predizer a habilidade de formação vítrea em sistemas metálicos. No presente trabalho, um critério de seleção foi aplicado ao sistema Ni-Nb-Zr com o objetivo de predizer as melhores estequiometrias com as mais altas tendências de formação vítrea. As habilidades de formação vítrea das ligas foram avaliadas pelo parâmetro térmico &#947;m e os resultados mostraram uma pobre correlação com as predições. Este critério preditivo correlaciona as taxas de resfriamento para a formação vítrea com a instabilidade topológica de estruturas cristalinas, as diferenças médias de função trabalho e densidade eletrônica entre os elementos constituintes da liga. O parâmetro térmico depende de temperaturas características de transformações de fases que podem ser facilmente determinadas a partir de curvas de calorimetria exploratória diferencial dos vidros metálicos. As hipóteses iniciais para explicar a pobre correlação entre os resultados e as predições foram atribuídas às influências de fatores não considerados nos cálculos como os compostos intermetálicos desconhecidos e contaminação por oxigênio. Assim, algumas ligas solidificadas rapidamente foram investigadas com mais rigor com o objetivo de entender a formação das fases cristalinas que competem contra a formação vítrea. As fases cristalinas foram caracterizadas e comparadas com estruturas cristalinas encontradas na literatura como também alguns diagramas de fases. Os diagramas de fases foram utilizados como guias para o melhor entendimento do comportamento de cristalização. Em adição, o critério de seleção também foi utilizado para predizer o melhoramento da tendência de formação vítrea de uma liga do sistema Ni-Nb-Zr com pequenas adições dos elementos terras-raras Y ou Er. É bem conhecido que uma pequena adição de um elemento terra-rara apropriado pode aumentar significativamente a habilidade de formação vítrea de algumas ligas. As tendências de formação vítrea da liga base e das ligas dopadas com terras-raras também foram avaliadas pelo parâmetro térmico &#947m e os resultados concordaram muito bem com a tendência predita pelo cálculo. As amostras amorfas volumosas foram produzidas por injeção em molde de cobre. A natureza amorfa foi analisada por difração de raios-X e calorimetria exploratória diferencial. As fases cristalinas foram analisadas por microscopia eletrônica de transmissão, microscopia eletrônica de varredura, espectroscopia de raios-X por dispersão em energia e difração de raios-X. A contaminação por oxigênio foi quantificada pelo método de fusão em gás inerte. / Since the discovering of amorphous alloys in 1960, the actual causes of why some alloys can be easily formed into glasses while others cannot, are not clearly known, thus there is no universal theory to predict the glass forming ability in metallic systems. In the present work, a selection criterion was applied in the Ni-Nb-Zr system in order to predict the best stoichiometries with high glass forming ability. The actual glass forming ability of alloys were evaluated by the thermal parameter &#947;m and the results have shown a poor correlation with the predictions. This criterion correlates critical cooling rate for glass formation with topological instability of stable crystalline structures; average work function difference and average electron density difference among the constituent elements of the alloy. The thermal parameter depends on the characteristic temperatures of phase transformations which can be easily measured from differential scanning calorimetry curves of metallic glasses. The initial hypotheses to explain the poor correlation between the experimental results and the predictions concerned with the influence of factors not considered in the calculation, such as unknown intermetallic compounds and oxygen contamination. Thus some rapidly quenched alloys were investigated with more accuracy in order to understand the formation of crystalline phases which compete against the glass formation. We characterized the crystalline phases and compared them to crystalline structures found in literature as well as some phase diagrams. The phase diagrams were used as guides in order to understand the crystallization behavior. In addition, the selection criterion also was used to predict the glass forming ability improvement of a Ni-Nb-Zr alloy with minor additions of rare-earth elements Y or Er. It is well known that the minor amount addition of proper rare-earth elements can greatly enhance the glass forming ability of some glass-forming alloys. The actual glass forming ability of the base alloy and rare-earth doped alloys also were evaluated by the thermal parameter &#947m and the results agree very well with the tendency predicted by the calculation. Bulk amorphous specimens were produced by injection casting. The amorphous nature was analyzed by X-ray diffraction and differential scanning calorimetry. The crystalline phases were analyzed by transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and x-ray diffraction. Oxygen contamination was quantified by the inert gas fusion method.