Elastic properties of some bulk metallic glasses

The relationships between the elastic moduli, glass forming ability and response to deformation of bulk metallic glasses are investigated. Five bulk metallic glasses are prepared from high purity elements via suction casting. The results confirm that there exists a correlation between energy absorbed to failure during compression testing and the bulk to shear modulus ratio. This finding is developed such that it corresponds only to the elastic component of energy absorption, and that the bulk modulus dominates this. Plastic deformation appears to be favored by a reduced shear modulus, although it shows greater dependence on structural features that are frozen in during the glass transition, and so may well be dependent on the liquid fragility.     

A study of mechanical homogeneity in as-cast bulk metallic glass by nanoindentation

A surface softening effect induced during copper-mould suction casting of bulk metallic glass is investigated as a function of rod diameter and glass fragility index, m, by nanoindentation. A reduction in hardness and reduced modulus at the rod surface is found to be favoured in small diameter castings and in fragile systems, respectively resulting from limited in-situ annealing and from a greater diversity of metastable atomic environments in the potential energy landscape of fragile glasses. Enhanced propensity for shear transformation zone nucleation in the low moduli surface is explained in terms of reduced atomic connectivity arising from a reduction in local co-ordination number and a lowering of the shear modulus. Finally, the structure and mechanical diversity that is possible in as-cast bulk metallic glass rods is explored through a relative quantification of shear modulus and plastic zone size across the whole as-cast state and in a single rod. These findings illustrate the sensitivity of bulk metallic glass to preparation, especially in respect of thermal history, potentially making replication of mechanical data between researchers problematic.     

Effects of Zn addition on the improvement of glass forming ability and plasticity of Mg–Cu–Tb bulk metallic glasses

The effects of Zn addition on the glass forming ability and mechanical properties of Mg₆₅Cu_25?xZn_xTb₁₀ (x = 0, 2.5, 5, and 7.5) have been investigated. We show that small amounts of Zn addition improve the glass forming ability, strength, and ductility of the Mg–Cu–Tb bulk metallic glass. For the best glass forming composition, amorphous rods of Mg₆₅Cu₂₀Zn₅Tb₁₀ with a diameter of at least 7 mm have been prepared by a conventional copper mold casting method. Additionally, this composition exhibits obvious yielding and plastic deformation upon quasi-static compressive loading. The fracture strength, total strain to failure, and the plastic strain of the Mg₆₅Cu₂₀Zn₅Tb₁₀ bulk metallic glass reaches 1025 MPa, 2.05% and 0.15%, respectively. This is significantly superior compared to that exhibited by the original Zn-free Mg–Cu–Tb amorphous alloy.     

Characterization of plasticity-induced structural changes in a Zr-based bulk metallic glass using positron annihilation spectroscopy

Changes in the free volume distribution in Zr_58.5Cu_15.6Ni_12.8Al_10.3Nb_2.8 bulk metallic glass with inhomogeneous plastic deformation and annealing were examined using positron annihilation spectroscopy. Results indicate that the size distribution of open volume sites is at least bimodal prior to deformation. The size and concentration of the larger sites, identified as flow defects, changes with processing. The size of the flow defects initially increases with deformation. More extensive deformation shifts the distribution, with a third group of much larger sites forming at the expense of flow defects. This suggests that a critical strain is required for the growth of nanovoids observed elsewhere by HRTEM. Although these observations suggest the presence of three open volume size groups, further analysis indicates that all groups have a similar distribution of chemical species around them as evidenced by the same line shape parameter. This may be due to the disordered structure of the glass and the positron affinity to particular atoms surrounding the open volume regions.     

Enthalpy recovery and its effect on homogeneous flow stress during supercooled liquid region for Ti40Zr25Ni8Cu9Be18 bulk metallic glass

The homogeneous flow exhibits strain softening for Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ bulk metallic glass, which is related to increase in free volume concentration based on free volume model. When metallic glass is pre-annealed above T_g before deformation, the trend of strain softening becomes slow with pre-annealing time, indicating that the enthalpy recovery contributes to strain softening, because the enthalpy of metallic glass will recover towards equilibrium value above T_g, and leads to increase in free volume concentration. So the strain softening for Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ bulk metallic glass is related to enthalpy recovery.     

Plasticity induced by nanoparticle dispersions in bulk metallic glasses

We show room temperature plasticity in several ZrCu-based bulk metallic glasses (BMG) after dispersions of crystalline nanoparticles were generated prior to mechanical testing. BMGs are heated in synchrotron light in transmission such that annealing can be interrupted at the very first detection of nucleation of the crystallites. Effect of embedded nanocrystals on the mechanical properties of BMG-Composites was investigated by compressive testing. When nanocrystal dispersions were generated, zirconium-copper-based BMGs that initially showed no plastic deformation prior to fracture, exhibited ductile behavior in compression with about 10% deformation.     

Structure formation in liquid and amorphous metallic alloys

Bulk metallic glasses developed in last 15 years represent a new class of amorphous metallic alloys. These multi-component metallic alloys can be obtained at relatively low cooling rates, which allow the production of large-scale materials by conventional casting processes. Furthermore, bulk metallic glasses show a glass transition well below the crystallization temperature enabling hot deformation, but also to investigate the glass transition phenomenon in a metallic system. The thermal behavior of Zr- and Pd-based bulk metallic glasses was studied by in situ X-ray diffraction at elevated temperatures. The temperature dependence of the X-ray structure factor of the glassy state can be well described by the Debye theory. At the caloric glass transition the temperature dependence of the structure alters, pointing to a continuous development of structural changes in the liquid state. The short-range order of the glass, of the super-cooled liquid, and of the equilibrium melt is found to be very similar. The existence of complex chemically ordered clusters in the melt is supposed to be related to the high glass-forming ability of the alloys. The microstructure of metallic glasses consisting of elements with negative enthalpy of mixing is homogeneous at dimensions above 1 nm. Phase separation in the liquid state appears in metallic systems with large positive enthalpy of mixing of the elements like Nb–Y. Thermodynamic calculations of the Ni–Nb–Y phase diagram show that the miscibility gap of the monotectic binary Nb–Y system extends into the ternary up to large Ni content. Experimental evidence of the phase separation in ternary Ni–Nb–Y melts is obtained by in situ X-ray diffraction at elevated temperatures and differential scanning calorimetry. The phase separated melt can be frozen into a two-phase amorphous metallic alloy by rapid quenching from the liquid. The microstructure depends on the chemical composition and consists of two amorphous regions, one Nb-enriched and the other Y-enriched, with a size distribution from several nanometers up to micrometer dimension. The experimental results confirm the close relationship between the structure of metallic glasses and the corresponding under-cooled liquids.     

Competition of time and spatial scales in polymer glassy dynamics: Rejuvenation and confinement effects

We use molecular-dynamics (MD) simulations and an original lateral contact experiment to explore the influence of mechanical history on polymer mechanical behavior and segmental mobility. Two typical glassy polymers are considered: bulk acrylate (experiments) and atactic polystyrene (aPS) in a bulk and in thin films (simulations). Stress-strain behavior has been investigated both experimentally for sheared, 50 μm thick, acrylate films and by MD simulations of an aPS in a bulk for two different strain rates in a closed extension-recompression loops. Cyclic shear strains applied in the plastic regime were found experimentally to induce a progressive transition of the mechanical response of the polymer glass toward a steady state which is characterized by a strong reduction of the apparent - non linear - shear modulus. The dynamics of the polymer glass in this yielded state was subsequently analyzed from a measurement of the time dependent linear viscoelastic properties at various imposed frequencies. Immediately after the cyclic plastic deformation, mechanical “rejuvenation” of the polymer is evidenced by a drop in the storage modulus and an increase in the loss modulus, as compared to the initial values recorded before plastic deformation. A progressive recovery of the viscoelastic properties is also measured as a function of time as a result of the enhanced aging rate of the system. This experimentally observed mechanical rejuvenation of polymer has been for the first time connected to the drastic increase in the simulated segmental mobility. A simulated distribution of relaxation times shows a shift to shorter times of the α and β relaxation processes which is consistent with the observed experimental changes in the viscoelastic modulus after rejuvenation. Finally, we present our first findings on the thickness- and substrate-dependence of the simulated glass transition temperature for thin aPS films. We observe the decrease of the glass transition temperature with film thickness, but for extremely thin (less than 2 nm) films.     

Properties of as-cast and structurally relaxed Zr-based bulk metallic glasses

We have studied the influence of the arc melting procedure of Nb-containing Zr-based bulk metallic glasses (BMGs) on their thermal and mechanical properties. We found that the strength and plastic strain to failure, determined at room temperature, increases by the addition of a few percentage of Nb into the Zr-based BMGs. High-resolution transmission-electron microscopy results show that the addition of 2 at.% Nb introduces the formation of as-cast nanocrystals. At the same time, thermal analyses indicate an increase in glass forming ability with the small addition of Nb. Contrary to the reported results in other amorphous alloys, we found that the plastic strain increases further after heat-induced structural relaxation in the Zr-based BMGs.     

Phonon dispersion in bulk metallic glass Zr55Cu30Al10Ni15

The expressions for the phonon frequencies of Zr₅₅Cu₃₀Al₁₀Ni₁₅ bulk metallic glass employing a simple model given by Bhatia and Singh for a hypothetical one-component metallic glass are derived both for longitudinal and transverse modes of excitations. The model assumes a central force, effective between the nearest neighbours, and a volume dependent force. Both types of excitations of phonons are computed for the Zr₅₅Cu₃₀Al₁₀Ni₁₅ bulk metallic glass for the first time both for self-consistent screening of conduction electrons with and without the inclusion of correlation effects. Phonon frequency expressions reproduce the main characteristic features of the dispersion curves. The theoretical results predicted are in a good agreement with available experimental data of different quaternary bulk metallic glasses having same constituents. These are also compared to the theoretical results of a quaternary glass to have an insight of the structural behavior of the glass under consideration.     

Superplasticity and superplastic forming ability of a Zr-Ti-Ni-Cu-Be bulk metallic glass in the supercooled liquid region

The superplastic deformation behavior and superplastic forming ability of the Zr_41.25Ti_13.75Ni₁₀Cu_12.5Be_22.5 (at.%) bulk metallic glass (BMG) in the supercooled liquid region were investigated. The isothermal tensile results indicate that the BMG exhibits a Newtonian behavior at low strain rates but a non-Newtonian behavior at high-strain rates in the initial deformation stage. The maximum elongation reaches as high as 1624% at 656 K, and nanocrystallization was found to occur during the deformation process. Based on the analysis on tensile deformation, a gear-like micropart is successfully die-forged via a superplastic forging process, demonstrating that the BMG has excellent workability in the supercooled liquid region.     

The correlation between the pressure sensitivity and the fragility/glass transition temperature in bulk metallic glasses

The correlations between the pressure sensitivity and the fragility/glass transition temperature have been addressed in various bulk metallic glasses in the present work. The results demonstrate that the pressure sensitivity of bulk metallic glasses is closely related to both the fragility index (m) and the glass transition temperature (T_g). The physical origin of the correlations has been discussed from their disordered structure, which is determined by the glass transition behavior and the glass transition temperature.     

Lutetium and thulium based rare earth bulk metallic glasses

We report the formation of lutetium and thulium based bulk metallic glasses based on the correlations between the thermodynamic, kinetic, elastic and other properties of metallic glasses. The two novel rare earth based bulk metallic glasses (REBMGs) exhibit excellent glass formation ability, high elastic moduli, considerable smaller Poisson’s ratio, high thermal stability, and even higher mechanical strength than that of typical high strength Zr-based BMGs. The reasons for the properties of the Lu- and Tm-based and other REBMGs are discussed.     

Crystallization kinetics in Cu46Zr45Al7Y2 bulk metallic glass by differential scanning calorimetry (DSC)

Crystallization transformation kinetics in isothermal and non-isothermal (continuous heating) modes were investigated in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass by differential scanning calorimetry (DSC). In isochronal heating process, activation energy for crystallization at different crystallized volume fraction is analyzed by Kissinger method. Average value for crystallization in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass is 361 kJ/mol in isochronal process. Isothermal transformation kinetics was described by the Johnson-Mehl-Avrami (JMA) model. Avrami exponent n ranges from 2.4 to 2.8. The average value, around 2.5, indicates that crystallization mechanism is mainly three-dimensional diffusion-controlled. Activation energy is 484 kJ/mol in isothermal transformation for Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass. These different results were discussed using kinetic models. In addition, average activation energy of Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass calculated using Arrhenius equation is larger than the value calculated by the Kissinger method in non-isothermal conditions. The reason lies in the nucleation determinant in the non-isothermal mode, since crystallization begins at low temperature. Moreover, both nucleation and growth are involved with the same significance during isothermal crystallization. Therefore, the energy barrier in isothermal annealing mode is higher than that of isochronal conditions.     

Zr-based bulk metallic glass with super-plasticity under uniaxial compression at room temperature

Commonly, bulk metallic glasses exhibit very limited plastic deformation (<2%) at room temperature. In this letter, through appropriate composition choices, rods of Zr_62.55Cu_17.55Ni_9.9Al₁₀ and Zr_64.80Cu_14.85Ni_10.35Al₁₀ bulk metallic glasses (BMGs) were prepared by using copper-mold suction-casting. X-ray diffraction and differential scanning calorimetry were utilized to determine their structures and thermal stabilities, and uniaxial compression tests were adopted to study their plastic deformation behaviors (PDBs) at room temperature. The results showed that T_g and T_x of the former are 651.5 K and 748 K, respectively, while those of the latter are 646 K and 750 K, respectively. Micro-hardness values are 693 ± 7 Hv and 595 ± 5 Hv for T1 and T2, respectively. During the compression tests, the former underwent about 2.5% engineering strain, i.e., 2.8% true strain, then fractured. While the latter was compressed into a flake-like form, of which, engineering strain values are larger than 70%, i.e., true strain exceeds 120%, showing super-plasticity at room temperature. It can be concluded that micro-hardness and PDBs of BMGs are very sensitive to composition.     

Deformation behavior of a Ni59Zr20Ti16Si2Sn3 metallic glass matrix composite reinforced by copper synthesized by warm extrusion of powders

A metallic glass matrix composite (MGMC) reinforced by copper short fibers has been prepared by warm extrusion of powders, and its deformation behavior at room temperature and in the supercooled liquid region of the metallic glass has been investigated. A mixture of Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ metallic glass powders and copper powders is extruded in the supercooled liquid region of the metallic glass with an extrusion ratio of 5. The volume fraction of the copper phase is 0.2. After extrusion, initially spherical powders are elongated along the extrusion direction; no pores are visible. The MGMC shows a high failure strength of around 1.85 GPa, slightly lower than that of the as-cast Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ metallic glass, under uniaxial compression. However, due to the crack bridging mechanism produced by the randomly distributed copper short fibers, the MGMC does not catastrophically fail by a single shear band propagating across the whole monolithic sample. In the supercooled liquid region of the metallic glass, the MGMC shows large elongation to failure but fails by cavitation due to the preexisting Ni-based crystalline powders.     

Icosahedral ordering in Cu60Zr40 metallic glass: Molecular dynamics simulations

The atomic structure of bulk metallic glasses has long been mysterious for the lack of long range order. Although the solute-centered cluster packing model has recently been proposed to disclose the nanoscale medium-range order (MRO), the atomic packing scheme in systems with large solute concentration remains obscure. In this work, the atomic structure of Cu₆₀Zr₄₀ metallic glass is investigated via molecular dynamics simulations with the Finnis–Sinclair potential. It is found that the fragments of icosahedra are dominant in the model metallic glass. The icosahedra are completely centered by solvent atoms. Extended clusters composed of two icosahedra interpenetrate and form MRO with 3–11 icosahedra. It is suggested that the structure of Cu₆₀Zr₄₀ metallic glass can be described by the aggregation of icosahedra.     

Enhanced plasticity of a Zr50Cu48Al2 bulk metallic glass

In this work, a Zr₅₀Cu₄₈Al₂ bulk metallic glass (BMG) with improved glass forming ability and mechanical properties was synthesized by adding a small amount of Al to a Zr-Cu binary glass-forming alloy. The as-cast Zr₅₀Cu₄₈Al₂ glassy rod does not exhibit macroscopic failure under compression at room temperature indicating the excellent plasticity of the BMG. The deformation behavior of the BMG was studied intensively by examining the true stress-strain curve and the surface morphology of the post-deformation sample. The effect of minor Al addition on the mechanical properties including the fracture stress, the modulus, and the kinetic characteristics of the BMG was also investigated. The enhanced plasticity of the BMG is considered to be related to its reduced fragility parameter m value.     

Superplastic flow of a Mg-based bulk metallic glass in the supercooled liquid region

The tensile flow behavior of Mg₆₅Cu₂₅Y₁₀ bulk metallic glass was investigated over a range of strain rates (10⁻³–10⁻¹/s) and deformation temperatures (150–170 °C) in the supercooled liquid region. In this region, the relationship between peak flow stress, strain rate and absolute deformation temperature was described adequately by the classic Sellars–Tegart constitutive relationship. There was also a good correlation between the Zener–Hollomon parameter, Z, and the flow characteristics of the material such as the transition from Newtonian to non-Newtonian flow and maximum achievable tensile elongation; the latter was used for determining the optimum conditions for superplastic flow in the material.     

Surface stress relaxation and resulting residual stress in glass fibers: A new mechanical strengthening mechanism of glasses

Glass surfaces exhibit faster relaxation than the bulk at a constant temperature in the presence of either a liquid water or water vapor atmosphere. Permanent bending of glass fibers at temperatures lower than their glass transition temperatures in an atmosphere containing water vapor or in liquid water was attributed to and analyzed in terms of surface stress relaxation and the resulting surface residual stress. It was found that the fiber bending kinetics are controlled by water diffusion into the glass surface and that glasses with a faster transition crack velocity from region I (linear relation between logarithm of crack velocity and stress intensity factor) to the fatigue limit exhibited a faster rate of surface stress relaxation. It was suggested that this surface stress relaxation and resulting residual stress is the cause of various strengthening phenomena of glasses such as static fatigue limit and coaxing.