Intrinsic correlation between fragility and bulk modulus in metallic glasses

A systematic study on the available data of 26 metallic glasses shows that there is an intrinsic correlation between fragility of a liquid and bulk modulus of its glass. The underlying physics can be rationalized within the formalism of potential energy landscape thermodynamics. It is surprising to find that the linear correlation between the fragility and the bulk-shear modulus ratio exists strictly at either absolute zero temperature or very high frequency. Further analyses indicate that a real flow event in bulk metallic glasses is shear dominant, and fragility is in inverse proportion to shear-induced bulk dilatation. Finally, extension of these findings to nonmetallic glasses is discussed.

Smaller Deborah number inducing more serrated plastic flow of metallic glass

Spherical nano-indentations of Cu46Zr54 bulk metallic glass (BMG) model systems were performed using molecular dynamics (MD) computer simulations, focusing specifically on the physical origin of serrated plastic flow. The results demonstrate that there is a direct correlation between macroscopic flow serration and underlying irreversible rearrangement of atoms, which is strongly dependent on the loading (strain) rate and the temperature. The serrated plastic flow is, therefore, determined by the magnitude of such irreversible rearrangement that is inhomogeneous temporally. A dimensionless Deborah number is introduced to characterize the effects of strain rate and temperature on serrations. Our simulations are shown to compare favorably with the available experimental observations.

Developing and characterizing bulk metallic glasses for extreme applications

Metallic glasses have typically been treated as a “one size fits all” type of material. Every alloy is considered to have high strength, high hardness, large elastic limits, corrosion resistance, etc. However, similar to traditional crystalline materials, properties are strongly dependent upon the constituent elements, how it was processed, and the conditions under which it will be used. An important distinction which can be made is between metallic glasses and their composites. Charpy impact toughness measurements are performed to determine the effect processing and microstructure have on bulk metallic glass matrix composites (BMGMCs). Samples are suction cast, machined from commercial plates, and semi-solidly forged (SSF). The SSF specimens have been found to have the highest impact toughness due to the coarsening of the dendrites, which occurs during the semi-solid processing stages. Ductile to brittle transition (DTBT) temperatures are measured for a BMGMC. While at room temperature the BMGMC is highly toughened compared to a fully glassy alloy, it undergoes a DTBT by 250 K. At this point, its impact toughness mirrors that of the constituent glassy matrix. In the following chapter, BMGMCs are shown to have the capability of being capacitively welded to form single, monolithic structures. Shear measurements are performed across welded samples, and, at sufficient weld energies, are found to retain the strength of the parent alloy. Cross-sections are inspected via SEM and no visible crystallization of the matrix occurs.

Next, metallic glasses and BMGMCs are formed into sheets and eggbox structures are tested in hypervelocity impacts. Metallic glasses are ideal candidates for protection against micrometeorite orbital debris due to their high hardness and relatively low density. A flat single layer, flat BMG is compared to a BMGMC eggbox and the latter creates a more diffuse projectile cloud after penetration. A three tiered eggbox structure is also tested by firing a 3.17 mm aluminum sphere at 2.7 km/s at it. The projectile penetrates the first two layers, but is successfully contained by the third.

A large series of metallic glass alloys are created and their wear loss is measured in a pin on disk test. Wear is found to vary dramatically among different metallic glasses, with some considerably outperforming the current state-of-the-art crystalline material (most notably Cu₄₃Zr₄₃Al₇Be₇). Others, on the other hand, suffered extensive wear loss. Commercially available Vitreloy 1 lost nearly three times as much mass in wear as alloy prepared in a laboratory setting. No conclusive correlations can be found between any set of mechanical properties (hardness, density, elastic, bulk, or shear modulus, Poisson’s ratio, frictional force, and run in time) and wear loss. Heat treatments are performed on Vitreloy 1 and Cu₄₃Zr₄₃Al₇Be₇. Anneals near the glass transition temperature are found to increase hardness slightly, but decrease wear loss significantly. Crystallization of both alloys leads to dramatic increases in wear resistance. Finally, wear tests under vacuum are performed on the two alloys above. Vitreloy 1 experiences a dramatic decrease in wear loss, while Cu₄₃Zr₄₃Al₇Be₇ has a moderate increase. Meanwhile, gears are fabricated through three techniques: electrical discharge machining of 1 cm by 3 mm cylinders, semisolid forging, and copper mold suction casting. Initial testing finds the pin on disk test to be an accurate predictor of wear performance in gears.

The final chapter explores an exciting technique in the field of additive manufacturing. Laser engineered net shaping (LENS) is a method whereby small amounts of metallic powders are melted by a laser such that shapes and designs can be built layer by layer into a final part. The technique is extended to mixing different powders during melting, so that compositional gradients can be created across a manufactured part. Two compositional gradients are fabricated and characterized. Ti 6Al¬ 4V to pure vanadium was chosen for its combination of high strength and light weight on one end, and high melting point on the other. It was inspected by cross-sectional x-ray diffraction, and only the anticipated phases were present. 304L stainless steel to Invar 36 was created in both pillar and as a radial gradient. It combines strength and weldability along with a zero coefficient of thermal expansion material. Only the austenite phase is found to be present via x-ray diffraction. Coefficient of thermal expansion is measured for four compositions, and it is found to be tunable depending on composition.

Pulse self-compression in normally dispersive bulk media

We experimentally demonstrate that high-power femtosecond pulses can be compressed during the nonlinear propagation in the normally dispersive solid bulk medium. The self-compression behavior was detailedly investigated under a variety of experimental conditions, and the temporal and spectral characteristics of resulted pulses were found to be significantly affected by the input pulse intensity, with higher intensity corresponding to shorter compressed pulses. By passing through a piece of BK7 glass, a self-compression from 50 to 20 fs was achieved, with a compression factor of about 2.5. However, the output pulse was observed to be split into two peaks when the input intensity is high enough to generate supercontinuum and conical emission. (c) 2005 Elsevier B.V. All rights reserved.

Orientation-controllable self-organized microgratings induced in the bulk SrTiO3 crystal by a single femtosecond laser beam

Self-organized microgratings were induced in the bulk SrTiO3 crystal by readily scanning the laser focus in the direction perpendicular to the laser propagation axis. The groove orientations of those gratings could be controlled by changing the irradiation pulse number per unit scanning length, which could be implemented either through adjusting the scanning velocity at a fixed pulse repetition rate or through varying the pulse repetition rate at a fixed scanning velocity. This high-speed method for fabrication of microgratings will have many potential applications in the integration of micro-optical elements. The possible formation mechanism of the self-organized microgratings is also discussed. (C) 2007 Optical Society of America.

Modifying Bulk Metallic Glasses: Composites and Configurational States

Bulk metallic glasses (BMGs) maybe be considered to share some of the same inherent trade-offs as engineering ceramics. While BMGs typically exhibit high yield strengths, and while some have surprising fracture toughness, they exhibiting little to no tensile ductility, and fail in a brittle manner under uniaxial loading. Speaking broadly, there are two complimentary approaches to improving on these shortcomings: 1) create bulk metallic glass matrix composites (BMGMCs) and 2) improve the properties of a monolithic BMG. The structure of this thesis mirrors this division, with chapters 2-7 focusing on creating and processing amorphous metal matrix composites, and chapter 8 focusing on modifying the properties of a monolithic BGM by altering its configurational state through irradiation.

Broadband near-infrared emission from transparent Ni2+-doped silicate glass ceramics

Transparent Ni2+-doped MgO-Al2O3-TiO2-SiO2 glass ceramics were prepared, and the optical properties of Ni2+-doped glass ceramics were investigated. Broadband emission centered at 1320 nm was observed by 980 nm excitation. The longer wavelength luminescence compared with Ni2+-doped Li2O-Ga2O3-SiO2 glass ceramics is ascribed to the low crystal field hold by Ni2+ in MgO-Al2O3-TiO2-SiO2 glass ceramics. The change in optical signals at the telecommunication bands with or without 980 nm excitation was also measured when the seed beam passes through the bulk gain host.(C) 2007 American Institute of Physics.

Photonic nanowires directly drawn from bulk glasses

High-uniform nanowires with diameters down to 50 nm are directly taper-drawn from bulk glasses. Typical loss of these wires goes down to 0.1 dB/mm for single-mode operation. Favorable photonic properties such as high index for tight optical confinement in tellurite glass nanowires and photoluminescence for active devices in doped fluoride and phosphate glass nanowires are observed. Supporting high-index tellurite nanowires with solid substrates (such as silica glass and MgF2 crystal) and assembling low-loss microcoupler with these wires are also demonstrated. Photonic nanowires demonstrated in this work may open up vast opportunities for making versatile building blocks for future micro- and nanoscale photonic circuits and components. (c) 2006 Optical Society of America.

Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with gamma-Alumina Nanoparticles

In the present work, the nematic glassy state of the non-symmetric LC dimer -(4-cyanobiphenyl-4-yloxy)--(1-pyrenimine-benzylidene-4-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of -alumina nanoparticles, in several concentrations.

Multistage etching process for microscopically smooth tellurite glass surfaces in optical fibers

Bulk samples of tellurite glass with composition 75TeO(2)-20ZnO-5Na(2)O (TZN) were fabricated by melting and quenching techniques. In order to improve the surface quality of optical fiber preform made with this tellurite glass, the authors developed a multistage etching process. The relationship between successive etching treatments and roughness of the TZN glass surface was probed by using an atomic force microscope. The results demonstrate that this multistage etching method effectively improves this tellurite glass surface smoothness to a level comparable with that of a reference silica glass slide, and the corresponding chemical micromechanisms and fundamentals are discussed and confirmed by atomic force microscopy, potentially contributing to the development of multicomponent soft glass fibers and devices. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3437017]

Shear transformation zone volume determining ductile–brittle transition of bulk metallic glasses

Three-point bending experiments were performed on as-cast and annealed samples of Zr52.5Cu17.9Ni14.6Al10Ti5 (Vit105) bulk metallic glasses over a wide range of temperatures varying from room temperature (293 K) to liquid nitrogen temperature (77 K). The results demonstrated that the free volume decrease due to annealing and/or cryogenic temperature can reduce the propensity for the formation of multiple shear bands and hence deteriorate plastic deformation ability. We clearly observed a sharp ductile-to-brittle transition (DBT), across which microscopic fracture feature transfers from micro-scale vein patterns to nano-scale periodic corrugations. Macroscopically, the corresponding fracture mode changes from ductile shear fracture to brittle tensile fracture. The shear transformation zone volume, taking into account free volume, temperature and strain rate, is proposed to quantitatively characterize the DBT behavior in fracture of metallic glasses.

Strain rate-dependent shear band behavior in bulk metallic glasses

In this article, we review our recent advances in understanding the deformation behavior of a typical tough Zr41.2Ti13.8Cu12.5Ni10Be22.5 (Vit 1) bulk metallic glass (BMG), as a model material, under various loading modes and strain rates, focusing particularly on the rate-dependence and formation mechanism of shear-banding. Dynamic and quasi-static mechanical experiments, including plate shear, shear punch and spherical indentation, and continuum as well as atomistic modeling on shear-banding are discussed. The results demonstrate that higher strain rate slows down the annihilation process of free volume, but promotes the free-volume coalescence, which is responsible for the rate-dependent shear banding. The physical origin of shear bands, that is the free volume softening underpinned by irreversible rearrangements of atoms, is unveiled. Finally, some concluding remarks are given.

Fracture behavior of a Zr-metallic glass under dynamic compression

Dynamic planar compressive experiments on a typical tough Zr-BMG (Bulk Metallic Glass) were carried out under impact velocity of 500-600 m/sec and strain rate of 10(6)/s. The fracture surface of samples exhibits different fracture patterns at different parts of the sample. At a corner close to the front loading boundary, fracture patterns from the free edge toward the centre changed from equiaxial veins in microscale to periodic corrugations in nanoscale; in the middle of the sample, the fracture surface contains glazed zones laid out orderly along the same boundary. FEM simulation was performed to investigate the stress distributions in the impacted sample under a short duration impact loading. It has revealed that the fracture patterns changing from the free edge toward the centre were resulted from the fracture modes' changing from the tensile dominant fracture to the shear dominant fracture. Whereas at the middle part of the sample, fracture initiated from several parallel shear bands propagating close to the same boundary is due to a large strain or much higher shear stress in this area.

Glass formation ability and mechanical properties of Ti40Cu40Zr10Ni10 alloy

Melt-spun ribbon and bulk samples in cylindrical rod form with diameter ranging from 2 mm to 4 mm of Ti40Cu40Zr10Ni10 alloy were prepared by melt-spinning technique and copper mould casting method, respectively. The microstructure, thermal stability and mechanical properties of the bulk samples were investigated. A completely glassy single phase is formed in the 2 mm rod sample. Increasing the diameter of the rod samples resulted in the formation of CuTi crystalline phase in the 3 mm and 4 mm rod samples.

Investigation of Chemical Bond Characteristics, Thermal Expansion Coefficients and Bulk Moduli of alpha-R2MoO6 and R2Mo2O7 (R = rare earths) by Using a Dielectric Chemical Bond Method

Theoretical researches are performed on the alpha-R2MoO6 (R = Y, Gd, Tb Dy, Ho, Er, Tm and Yb) and pyrochlore-type R2Mo2O7 (R = Y, Nd, Sm, Gd, Tb and Dy) rare earth molybdates by using chemical bond theory of dielectric description. The chemical bonding characteristics and their relationship with thermal expansion property and compressibility are explored. The calculated values of linear thermal expansion coefficient (LTEC) and bulk modulus agree well with the available experimental values. The calculations reveal that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the lanthanides: the LTEC decreases from 6.80 to 6.62 10(-6)/K and the bulk modulus increases from 141 to 154 GPa when R goes in the order Gd, Tb Dy, Ho, Er, Tm, and Yb in the alpha-R2MoO6 series; while in the R2Mo2O7 series, the LTEC ranges from 6.80 to 6.61 10(-6)/K and the bulk modulus ranges from 147 to 163 GPa when R varies in the order Nd, Sm, Gd, Tb and Dy.