Amorphous Mg-Cu-Y metallic glasses are established by density functional theory and simulated annealing method in this study. The mechanical properties of amorphous Mg-Cu-Y metallic glasses are investigated by molecular statics simulations for the nano-indentation and the nano-scratch process. In this study, some potential energy parameters are obtained by fitting for describing the Mg-Cu-Y system. The bulk modulus, the Young¡¦s modulus and X-ray structure of the Mg-Cu-Y system are calculated. Our results are within 10% error compared with experimental values, which prove the correctness of fitted potential parameters. For the cases of nanoindentations, the indentation force-displacement and the influenced depth are calculated. The mechanical properties are obtained are close to experimental results. The both ¡§slip vector¡¨ and Honeycutt-Andemen index (HA index) parameters are also used to study the deformation behavior and bond-type of a group of atoms. Our results indicate that the influenced depths can be affected by the tip indentation and the gather of copper atoms. The gather of copper atoms can provide the resistance and strengthen the mechanical properties of Mg-Cu-Y material. On the other hand, our results indicate that the amorphous structure of Mg-Cu-Y metallic glasses cannot be transferred to crystal structure during nano-indentation process by analysis of HA index. For the cases of nano-scratch, two different scratch depth (5Å and 15Å) are investigated to understand the understand the depth effect. the scratch force-displacement curve is also obtained. As the same with nano-indentation results, the scratch force will increase because the gather of copper atoms and provide the resistance.

The mechanical properties of the amorphous bulk metallic glassy (BMG) alloy, Mg58Cu31Y11, are examined by a non-traditional analytic method - nanoindentation scratch test. This thesis will discuss the influences of friction force, and fracture surface geometry on the BMG surface for load, depth of scratch, scratch velocity, and test temperature of the nano-scratch process. In this study, experimental factors, including load, depth of scratch, scratch velocity, and test temperature, are taken into consideration to investigate the effects of the friction force. And then, this research utilizes regression analysis to establish BMG machining experience formula. The significant parameters of the friction force on nano-scratch and the reliability of the prediction model are investigated by statistical software. According to the results, the friction force is nearly proportional to power of the load. The friction force exhibits a slightly dependence on the test temperature. Besides, the nano-scratch results show that the friction coefficient also increases as the load and test temperature increases. The results associated with the analysis of the variance can be practiced to assess the prominence among experimental factors. The analysis indicates that the load, test temperature play significant factors on the friction force. The results of the regression analysis using a statistical software can be applied to model the mathematical relationship between machining factors and friction force. It anticipates that the model is able to predict friction force over a wide variety of scratching conditions. The model is also proved in good agreement with experimental results.

On the toughening of bulk metallic glasses (BMGs), successful results in the phase-separated Zr63.8Ni16.2Cu15Al5 BMG have achieved compressive ductility over 15% through the computational-thermodynamic approach. In this study, the phase-separated Zr63.8Ni16.2Cu15Al5 BMG was compressed to nominal strains of 3%, 7%, and 10% at low strain rates (~10-4 s-1) and the results demonstrated that the BMG exhibited apparent uniform deformation initially, followed by visible local shear bands development. Afterwards, a single shear along the principal shear plane was soon developed and mainly dominated the whole deformation process. The principal shear contributed more than 2/3 of the overall plastic strain until failure. It was also found that the local shear strain varied along the principal shear plane and decreased monotonically from the shear band initiation site. Subsequently, in-situ compression experiments were conducted to monitor the change of sample shape during deformation in order to properly correlate with the stress-strain curve. The observed images showed that there was a one-to-one correspondence between the intermittent sample sliding and flow serration in the plastic region of stress-strain curve. Further investigations on flow serration were conducted on the Pd40Ni40P20 BMG through the compression experiments equipped with high-sensitivity strain gauges directly attached to two opposite sides of the test sample. There was an accompanied displacement burst when a shear band starts to propagate during deformation and this displacement burst would be accurately captured by the high-sensitivity strain gauges. Based on the displacement-time profile for one serration, shear-band propagating speed can be estimated and found to be insensitive to the applied strain rates (or the applied crosshead speeds). The disappearance of flow serration at high strain rates should be a result that the signal of displacement burst was overwhelmed by the applied strain rate. Using the shear strain rate data, the measured viscosity within a propagating shear band was found to be relatively low, which is in similar to the viscosity values reported in the supercooled liquid region during homogeneous deformation. In comparison with shear band propagation in the brittle Mg58Cu31Y6Nd5 and Au49Ag5.5Pd2.3Cu26.9Si16.3, moderately ductile Cu50Zr43Al7 and Pd40Ni40P20, and highly ductile phased-separated Zr63.8Ni16.2Cu15Al5 systems, the ductility of BMGs appears to be closely related to the dynamics during shear band propagation. The more ductile in nature the metallic glass is, the slower the shear band propagating speed would become. We also made attempts to investigate the shear band propagation in the porous Mo particles reinforced Mg58Cu28.5Gd11Ag2.5 bulk metallic glass composites (BMGCs) with up to 10% compressive failure strain. It was found that flow serration was absent in the stress-strain curve. Using high-sensitivity strain gauges, no distinct displacement burst was detected in the displacement-time profile. The diappearance of flow serration for the current porous Mo particles reinforced Mg58Cu28.5Gd11Ag2.5 BMGC is apparently associated with the lack of long-range shear band propagagtion. By employing the approach of separating the homogeneous amorphous matrix into many individual compartments, only short-range shear band propgagation is possible in the current Mg-based BMGC. An effective free spacing considering the spacing between two porous Mo particles and porous Mo particle size was applied to interpret the development of shear band propagation and is a useful indicator for the design of BMGC with high ductility.

Bulk metallic glasses (BMGs) have received significant research interest due to their completely amorphous structure which results in unique structural and functional properties. Absence of grain boundaries and secondary phases in BMGs results in high corrosion resistance in many different environments. Understanding and tailoring the corrosion behavior can be significant for various structural applications in bulk form as well as coatings. In this study, the corrosion behavior of several Zr-based and Fe-Co based BMGs was evaluated to understand the effect of chemistry as well as quenched in free volume on corrosion behavior and mechanisms. Presence of Nb in Zr-based alloys was found to significantly improve corrosion resistance due to the formation of a stable passive oxide. Relaxed glasses showed lower rates compared to the as-cast alloys. This was attributed to lowering of chemical potential from the reduced fraction of free volume. Potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) techniques helped in quantifying the corrosion rate and polarization resistance. The effect of alloy composition was quantified by extensive surface analysis using Raman spectroscopy, energy dispersive x-ray spectroscopy and auger spectroscopy. Pitting intensity was higher in the as-cast glasses than the relaxed glasses. The electrochemical behavior of a Zr-Ti-Cu-Ni-Be bulk metallic glass subjected to high strain processing was studied. High strain processing caused shear band formation and an increase in the free volume. Potentiodynamic polarization and EIS showed a strong correlation between the enthalpy of structural relaxation and corrosion rate and polarization resistance. Pitting was observed to preferentially occur on shear bands in the processed samples, while it was stochastic in unprocessed glass. The corrosion analysis of Co-Fe glasses showed an increase in corrosion current density when Fe content was increased from 0 to 7 at%. The corrosion resistance improved when Fe content was further increased to 15 at%. Similar trend was seen in EIS studies. The improved corrosion resistance at 15 at% Fe can be attributed to the large supercooled region that facilitates the formation of completely amorphous alloy, in contrast to lower Fe containing alloys, where short range ordering may deteriorate the corrosion resistance. Porous metallic glass structure was developed by electrochemical dealloying via cyclic voltammetry. Mechanical properties and changes in electrical conductivity were measured as a function of depth from surface by nano-indentation and nano electrical contact resistance technique. The nanoporous layer was found have hardness of 0.41 GPa and elastic modulus of nearly 22 GPa. The resistivity of the nanoporous layer continuously decreased when moving towards the substrate as the indentation depth increased which is attributed to the gradient in pore size.

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.

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

Metallic glasses are amorphous alloys that do not possess long-range structural order in contrast to crystalline alloys. Ni-free Ti-based bulk metallic glasses (BMGs) have potential for biomedical applications due to their attractive properties such as high strength, good corrosion resistance and excellent micro-formability, which cannot be obtained for conventional crystalline alloys. In this PhD thesis, Ni-free Ti-based BMGs, i.e. Ti40Zr10Cu34Pd14Sn2 and Ti40Zr10Cu36-xPd14Inx (x = 0, 2, 4, 6, 8), were prepared in the shape of rods by suction casting. Both alloy classes were systematically characterized in terms of glass forming ability, thermal stability, phase formation and mechanical properties. The largest diameter obtained in the fully glassy state for Ti40Zr10Cu34Pd14Sn2 alloy is 3 mm and for Ti40Zr10Cu36-xPd14Inx (x = 2, 4, 6, 8) alloys is 2 mm. Base alloy (Ti40Zr10Cu36Pd14) contains some crystalline phase(s) in the glassy matrix for a 2 mm diameter rod. The structural transformations of Ti40Zr10Cu34Pd14Sn2 BMG upon heating were thoroughly analyzed by utilizing different combination of methods. Firstly, we used differential scanning calorimetry (DSC), X-Ray diffraction (XRD) and transmission electron microscopy (TEM) to investigate the first crystallization event. The main products of the first crystallization are possibly -(Ti, Zr) and Cu3Ti (orthorhombic) phases. Secondly, we employed in situ x-ray diffraction in transmission mode using synchrotron beam to deeply study the thermally-induced structural changes like relaxation, glass transition and crystallization. Since the first peak in the diffraction patterns reflects the structure of the glassy phase on the medium-range scale, the position, width and intensity of this peak in diffraction patterns are fitted through Voigt function below 800 K. All the peak position, width and intensity values show a nearly linear increase with increasing temperature to the onset temperature of structural relaxation, Tr = 510 K. However, these values start to deviate from the linear behavior between Tr and glass transition temperature Tg. The changes in the free volume, which was arrested during rapid quenching of the BMG, and the coefficient of volumetric thermal expansion prove that the aforementioned phenomenon is closely related to the structural relaxation. Above 800 K, three crystallization events are detected and the first exothermic event is due to the formation of metastable nanocrystals. For the Ti40Zr10Cu34Pd14Sn2 alloy, 2 mm diameter rods exhibit the best combination of mechanical properties (e.g. large plastic strain and high yield strength) among all the diameters (ø2, ø3 and ø4 mm) under the room-temperature compression tests. With the aim to improve its room-temperature mechanical properties, the processes of pre-annealing and cold rolling have been applied for the 2 mm diameter rods. Annealed and quenched specimens below Tg and in the supercooled liquid region (between Tg and onset crystallization temperature Tx) do not lead to the enhancement of the plasticity compared to as-cast alloys due to annihilation of excess free volume and crystallization. Cold rolling can effectively improve the plasticity of this BMG by inducing structural heterogeneities. Rolled samples up to a thickness reduction of 15% result in the largest plasticity of 5.7%. Low yield strength and visible work hardening ability are observed in the both 10%-rolled and 15%-rolled samples. The deformation behavior of Ti40Zr10Cu34Pd14Sn2 BMG at the elevated temperatures slightly below Tg and in the supercooled liquid region has been investigated. The stress-strain relations for this BMG over a broad range of temperatures (298 ~716 K) and strain rates (10-5 to 10-3 s-1) were established in uniaxial compression. Under compression tests at the highest test temperature of 716 K, the Ti-based BMG partially crystallizes and low strain rates can lead to the formation of larger volume fractions of crystals. In order to further improve the plasticity of Ti-Zr-Cu-Pd BMGs and simultaneously reduce the content of Cu (considering harmful element for the human body), the Ti40Zr10Cu36-xPd14Inx (x = 2, 4, 6, 8) BMGs have been newly developed with different short- or medium-range order in the structure. The compressive global strain of Ti40Zr10Cu36-xPd14Inx (x = 0, 2, 4, 6, 8) can be significantly improved from 4.5% for the In-free alloy to 10.2% for x = 4. However, a further increase of the indium content to 8 at.% results in a decrease of the plasticity. Among all the monolithic Ni-free Ti-based BMGs reported so far, the novel Ti40Zr10Cu32Pd14In4 BMG shows the largest plasticity. Inspired by the dislocation concept in crystalline materials, we propose a strategy for the design of ductile BMGs through minor substitution using relatively large atoms, which make the bonding nature become more metallic and with it less shear resistant. Such a locally modified structure results in topological heterogeneity, which appears to be crucial for achieving enhanced plasticity. This strategy is verified for Ti-Zr-Cu-Pd glassy alloys, in which Cu was replaced by In, and seems to be extendable to other BMG systems. The atomic-scale heterogeneity in BMGs is somewhat analog to defects in crystalline alloys and helps to improve the overall plasticity of BMGs.