A porous bulk metallic glass with unidirectional opening pores

Porous Zr-based bulk metallic glass (PMG) with unidirectional opening pores is prepared by electrochemical etching of tungsten wires of the W/bulk metallic glass (BMG) composites. The porosity and pore size can be controlled by adjusting the tungsten wires. The PMG showed no measurable loss in thermal stability as compared to the monolithic Zr-based BMG by water quenching and is more ductile and softer than the pore-free counterpart. The specific surface area of the PMGs is calculated to be 0.65, 3.96, and 10.54 m(2)/kg for 20, 60, and 80 vol % porosity, respectively. (c) 2007 The Electrochemical Society.

The characterization of plastic flow in three different bulk metallic glass systems

Plastic deformation behaviors of Zr52.5Al10Ni10Cu15Be12.5, Mg65Cu25Gd10 and Pd43Ni10Cu27P20 bulk metallic glasses (BMGs) are studied by using the depth-sensing nanoindentation, macroindentation and uniaxial compression. The significant difference in plastic deformation behavior cannot be correlated to the Poisson's ratio or the ratio of shear modulus to bulk modulus of the three BMGs, but can be explained by the free volume model. It is shown that the nucleation of local shear band is easy and multiple shear bands can be activated in the Zr52.5Al10Ni10Cu15Be12.5 alloy, which exhibits a distinct plastic strain during uniaxial compression and less serrated flow during nanoindentation. (c) 2006 Elsevier B.V. All rights reserved.

BONDING OF ALUMINA AND METAL USING BULK METALLIC GLASS FORMING ALLOY

Metal-alumina joints have found various practical applications in electronic devices and high technology industry. However, making of sound metal ceramic brazed couple is still a challenge in terms of its direct application in the industry. In this work we successfully braze copper with Al2O3 ceramic using Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glass forming alloy as filler alloy. The shear strength of the joints can reach 140 MPa, and the microstructrural analysis confirms a reliable chemical boning of the interface. The results show that the bulk metallic glass forming alloys with high concentration of active elements are prospective for using as filler alloy in metal-ceramic bonding.

Bonding Of Alumina And Metal Using Bulk Metallic Glass Forming Alloy

Metal-alumina joints have found various practical applications in electronic devices and high technology industry. However, making of sound metal ceramic brazed couple is still a challenge in terms of its direct application in the industry. In this work we successfully braze copper with Al2O3 ceramic using Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glass forming alloy as filler alloy. The shear strength of the joints can reach 140 MPa, and the microstructrural analysis confirms a reliable chemical boning of the interface. The results show that the bulk metallic glass forming alloys with high concentration of active elements are prospective for using as filler alloy in metal-ceramic bonding.

Synthesis Of Plastic Zr-Based Bulk Metallic Glass Matrix Composites By The Copper-Mould Suction Casting And The Bridgman Solidification

Zr-based bulk metallic glass matrix composites with the composition of Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.(5) were synthesized by the copper-mould suction casting and the Bridgman solidification. The composite, containing a well-developed flowery beta-Zr dendritic phase, was obtained by the Bridgman solidification with the withdrawal velocity of 0.8 mm/s and the temperature gradient of 45 K/mm, and the ultimate strength of 2050 MPa and fracture plastic strain of 14.6% of the composite were achieved, which was mainly interpreted by the homogeneous dispersion of bcc beta-Zr phase in the glass matrix. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.

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.

Electrical resistance and thermoelectric power of the metastable phases in tellurium-base alloys

By using techniques of rapid quenching from the melt, metastable phases have been obtained in ternary alloys which contain tellurium as a major component and two of the three noble metals (Cu, Ag, Au) as minor components. The metastable phases found in this investigation are either simple cubic or amorphous. The formation of the simple cubic phase is discussed. The electrical resistance and the thermoelectric power of the simple cubic alloy (Au₃₀Te₇₀) have been measured and interpreted in terms of atomic bondings. The semiconducting properties of a metastable amorphous alloy (Au₅Cu₂₅Te₇₀) have been measured. The experimental results are discussed in connection with a theoretical consideration of the validity of band theory in an amorphous solid. The existence of extrinsic conduction in an amorphous semiconductor is suggested by the result of electrical resistance and thermoelectric power measurements.

Magnetic moments in amorpous palladium-cobalt-silicon alloys

The magnetic moments of amorphous ternary alloys containing Pd, Co and Si in atomic concentrations corresponding to Pd_(80-x)Co_xSi_(20) in which x is 3, 5, 7, 9, 10 and 11, have been measured between 1.8 and 300°K and in magnetic fields up to 8.35 kOe. The alloys were obtained by rapid quenching of a liquid droplet and their structures were analyzed by X-ray diffraction. The measurements were made in a null-coil pendulum magnetometer in which the temperature could be varied continuously without immersing the sample in a cryogenic liquid. The alloys containing 9 at.% Co or less obeyed Curie's Law over certain temperature ranges, and had negligible permanent moments at room temperature. Those containing 10 and 11 at.% Co followed Curie's Law only above approximately 200°K and had significant permanent moments at room temperature. For all alloys, the moments calculated from Curie's Law were too high to be accounted for by the moments of individual Co atoms. To explain these findings, a model based on the existence of superparamagnetic clustering is proposed. The cluster sizes calculated from the model are consistent with the rapid onset of ferromagnetism in the alloys containing 10 and 11 at.% Co and with the magnetic moments in an alloy containing 7 at.% Co heat treated in such a manner as to contain a small amount of a crystalline phase. In alloys containing 7 at.% Co or less, a maximum in the magnetization vs temperature curve was observed around 10°K. This maximum was eliminated by cooling the alloy in a magnetic field, and an explanation for this observation is suggested.

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.

Lattice anomalies and magnetic states in Fe_5Si_3-Mn_5Si_3 alloys

The lattice anomalies and magnetic states in the (Fe_100-xMn_x)₅Si₃ alloys have been investigated. Contrary to what was previously reported, results of x-ray diffraction show a second phase (α') present in Fe-rich alloys and therefore strictly speaking a complete solid solution does not exist. Mössbauer spectra, measured as a function of composition and temperature, indicate the presence of two inequivalent sites, namely 6(g) site (designated as site I) and 4(d) (site II). A two-site model (TSM) has been introduced to interpret the experimental findings. The compositional variation of lattice parameters a and c, determined from the x-ray analysis, exhibits anomalies at x = 22.5 and x = 50, respectively. The former can be attributed to the effect of a ferromagnetic transition; while the latter is due to the effect of preferential substitution between Fe and Mn atoms according to TSM.

The reduced magnetization of these alloys deduced from magnetic hyperfine splittings has been correlated with the magnetic transition temperatures in terms of the molecular field theory. It has been found from both the Mössbauer effect and magnetization measurements that for composition 0 ≤ x ˂ 50 both sites I and II are ferromagnetic at liquid-nitrogen temperature and possess moments parallel to each other. In the composition range 50 ˂ x ≤ 100 , the site II is antiferromagnetic whereas site I is paramagnetic even at a temperature below the bulk Néel temperatures. In the vicinity of x = 50 however, site II is in a state of transition between ferromagnetism and antiferromagnetism. The present study also suggests that only Mn in site II are responsible for the antiferromagnetism in Mn₅Si₃ contrary to a previous report.

Electrical resistance has also been measured as a function of temperature and composition. The resistive anomalies observed in the Mn-rich alloys are believed to result from the effect of the antiferromagnetic Brillouin zone on the mobility of conduction electrons.

Structure and properties of amorphous thin film for optical data storage

In this paper the magnetic and magneto-optical properties of amorphous rare earth-transition metal (RE-TM) alloys as well as the magnetic coupling in the multi-layer thin films for high density optical data storage are presented. Using magnetic effect in scanning tunneling microscopy the clusters structure of amorphous RE-TM thin films has been observed and the perpendicular magnetic anisotropy in amorphous RE-TM thin films has been interpreted. Experimental results of quick phase transformation under short pulse laser irradiation of amorphous semiconductor and metallic alloy thin films for phase change optical recording are reported. A step-by-step phase transformation process through metastable states has been observed. The waveform of crystallization propagation in micro-size spot during laser recording in amorphous semiconductor thin films is characterized and quick recording and erasing mechanism for optical data storage with high performance are discussed. The nonlinear optical effects in amorphous alloy thin films have been studied. By photo-thermal effect or third order optical nonlinearity, the optical self-focusing is observed in amorphous mask thin films. The application of amorphous thin films with super-resolution near field structure for high-density optical data storage is performed. (c) 2007 Elsevier B.V. All rights reserved.

Thin film shape memory alloys for optical sensing applications

Based on shape memory effect of the sputtered thin film shape memory alloys, different types of micromirror structures were designed and fabricated for optical sensing application. Using surface micromachining, TiNi membrane mirror structure has been fabricated, which can be actuated based on intrinsic two-way shape memory effect of the free-standing TiNi film. Using bulk micromachining, TiNi/Si and TiNi/Si 3N 4microcantilever mirror structures were fabricated. © 2007 IOP Publishing Ltd.

Light absorption and electrical transport in Si:O alloys for photovoltaics

Thin films (100-500 nm) of the Si:O alloy have been systematically characterized in the optical absorption and electrical transport behavior, by varying the Si content from 43 up to 100 at. %. Magnetron sputtering or plasma enhanced chemical vapor deposition have been used for the Si:O alloy deposition, followed by annealing up to 1250 °C. Boron implantation (30 keV, 3-30× 1014 B/cm2) on selected samples was performed to vary the electrical sheet resistance measured by the four-point collinear probe method. Transmittance and reflectance spectra have been extracted and combined to estimate the absorption spectra and the optical band gap, by means of the Tauc analysis. Raman spectroscopy was also employed to follow the amorphous-crystalline (a-c) transition of the Si domains contained in the Si:O films. The optical absorption and the electrical transport of Si:O films can be continuously and independently modulated by acting on different parameters. The light absorption increases (by one decade) with the Si content in the 43-100 at. % range, determining an optical band gap which can be continuously modulated into the 2.6-1.6 eV range, respectively. The a-c phase transition in Si:O films, causing a significant reduction in the absorption coefficient, occurs at increasing temperatures (from 600 to 1100 °C) as the Si content decreases. The electrical resistivity of Si:O films can be varied among five decades, being essentially dominated by the number of Si grains and by the doping. Si:O alloys with Si content in the 60-90 at. % range (named oxygen rich silicon films), are proved to join an appealing optical gap with a viable conductivity, being a good candidate for increasing the conversion efficiency of thin-film photovoltaic cell. © 2010 American Institute of Physics.

Elastic properties of crystalline-amorphous core-shell silicon nanowires

The pressure behavior of Raman frequencies and line widths of crystalline core-amorphous shell silicon nanowires (SiNWs) with two different core-to-shell ratio thicknesses was studied at pressures up to 8 GPa. The obtained isothermal compressibility (bulk modulus) of SiNWs with a core-to-shell ratio of about 1.8 is ∼20% higher (lower) than reported values for bulk Si. For SiNWs with smaller core-to-shell ratios, a plastic deformation of the shell was observed together with a strain relaxation. A significant increase in the full width at half-maximum of the Raman LTO-peak due to phonon decay was used to determine the critical pressure at which LTO-phonons decay into LO + TA phonons. Our results reveal that this critical pressure in strained core-shell SiNWs (∼4 GPa) is different from the reported value for bulk Si (∼7 GPa), whereas no change is observed for relaxed core-shell SiNWs. © 2013 American Chemical Society.

Elasticity, band structure, and piezoelectricity of BexZn1-xO alloys

Lattice constants, elasticity, band structure and piezoelectricity of hexagonal wideband gap BexZn1-xO ternary alloys are calculatedusing firstprinciples methods. The alloys' lattice constants obey Vegard's law well. As Be concentration increases, the bulk modulus and Young's modulus of the alloys increase, whereas the piezoelectricity decreases. We predict that BexZn1-xO/GaN/substrate (x = 0.022) multilayer structure can be suitable for high-frequency surface acoustic wave device applications. Our calculated results are in good agreement with experimental data and other theoretical calculations. (c) 2008 Elsevier B.V. All rights reserved.