Preparation and Properties of Ti<Subscript>50</Subscript>Cu<Subscript>28</Subscript>Ni<Subscript>15</Subscript>Sn<Subscript>7</Subscript> Bulk Metallic Glass by Vacuum Hot Pressing

Amorphous Ti₅₀Cu₂₈Ni₁₅Sn₇ alloy powders were synthesized by a mechanical alloying (MA) technique. Differential scanning calorimetry (DSC) results showed that, after 7 hours of exposure to the milling process, amorphous Ti₅₀Cu₂₈Ni₁₅Sn₇ alloy powders exhibit a wide supercooled liquid region of 61 K. Consolidation of amorphous powders were performed at a temperature slightly higher than the glass transition temperature under a pressure of ∼1.2 GPa, and bulk metallic glass (BMG) discs can be prepared successfully. However, we noticed partial crystallization during the hot pressing process and were not able to achieve full densification of BMG. The Vickers microhardness of Ti₅₀Cu₂₈Ni₁₅Sn₇ BMG was 634 kg/mm², and the trace of the indentation revealed that pre-existing particle boundaries or interfaces between nanocrystals and amorphous matrix may serve as the crack initiation sites. Thus, typical brittle failure of Ti₅₀Cu₂₈Ni₁₅Sn₇ BMG was observed and resulted in relatively low fracture stress compared to that estimated by the microhardness. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Effects of Annealing and Pressure on Devitrification and Mechanical Properties of Amorphous Al<Subscript>87</Subscript>Ni<Subscript>7</Subscript>Gd<Subscript>6</Subscript>

Annealing studies at different temperatures, as well as those conducted with 940 MPa hydrostatic pressure, were conducted on amorphous ribbons of Al₈₇Ni₇Gd₆. The studies were performed to investigate the evolution of structure under different conditions and to particularly examine the effects of superimposed hydrostatic pressure during annealing. This amorphous alloy devitrifies at low temperatures via the precipitation of nano-crystalline α-Al particles. The effects of these various exposures on the amount of devitrification have been quantified using a variety of analytical techniques (i.e., X-ray diffraction (XRD), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM)). In addition, the effects of devitrification on the mechanical properties have been quantified using microhardness indentation and uniaxial tension tests. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.

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Mechanical behaviour of Ti<Subscript>5</Subscript>Si<Subscript>3</Subscript> based alloys and composites

The demand for materials to be used in the components operating above 1100°C in advanced aero-engines drives the development of the silicide-based intermetallic alloys and composites, including the titanium silicides. The mechanical behaviour of Ti₅Si₃ and its composites has been reviewed with emphasis on the microstructure-property relationships. It is found that the grain size is a critical parameter, and smaller grain sizes are desirable for reducing the magnitude of internal residual stress caused by the crystallographic anisotropy in coefficients of thermal expansion. The reduction in grain size leads to significant improvement in hardness, room temperature flexural strength and fracture toughness. On the other hand, the high temperature strength observed at slow strain rates and creep resistance are higher in the samples with the coarser grain sizes. Further improvements in the strength, fracture toughness and high temperature creep resistance are possible, either through the development of multiphase alloys, or by the use of ceramic reinforcements in composites.     

High-Accuracy X-Ray Diffraction Analysis of Phase Evolution Sequence During Devitrification of Cu<Subscript>50</Subscript>Zr<Subscript>50</Subscript> Metallic Glass

Real-time high-energy X-ray diffraction (HEXRD) was used to investigate the crystallization kinetics and phase selection sequence for constant-heating-rate devitrification of fully amorphous Cu₅₀Zr₅₀, using heating rates from 10 K/min to 60 K/min (10 °C/min to 60 °C/min). In situ HEXRD patterns were obtained by the constant-rate heating of melt-spun ribbons under synchrotron radiation. High-accuracy phase identification and quantitative assessment of phase fraction evolution though the duration of the observed transformations were performed using a Rietveld refinement method. Results for 10 K/min (10 °C/min) heating show the apparent simultaneous formation of three phases, orthorhombic Cu₁₀Zr₇, tetragonal CuZr₂ (C11_b), and cubic CuZr (B2), at 706 K (433 °C), followed immediately by the dissolution of the CuZr (B2) phase upon continued heating to 789 K (516 °C). Continued heating results in reprecipitation of the CuZr (B2) phase at 1002 K (729 °C), with the material transforming completely to CuZr (B2) by 1045 K (772 °C). The Cu₅Zr₈ phase, previously reported to be a devitrification product in C₅₀Zr₅₀, was not observed in the present study.     

Effect of Internal Interfaces on Hardness and Thermal Stability of Nanocrystalline Ti<Subscript>0.5</Subscript>Al<Subscript>0.5</Subscript>N Coatings

The effect of microstructure on the thermal stability and hardness of the cathodic arc evaporated Ti_0.5Al_0.5N coatings was investigated with the aid of the in-situ high-temperature X-ray diffraction experiments, which were accompanied by high-resolution transmission electron microscopy (HRTEM) and nanoindentation measurements. The microstructure of the coatings was modified through the choice of the bias voltage in the deposition process. It was found that the bias voltage affects strongly the uniformity of the local distribution of titanium and aluminum in the coatings. The nonuniform distribution of the elements contributes to the formation of lattice strains at the crystallite and phase boundaries. The lattice strains at the crystallite boundaries increase the hardness of the coatings; the lattice strains at the phase boundaries improve their thermal stability. A certain nonuniformity of the distribution of the metallic species in the coatings is regarded as advantageous. However, a great nonuniformity in the distribution of the metallic species accelerates the degradation of the coatings at high temperatures. As a measure for the nonuniformity of the distribution of the atomic species in the as-deposited (Ti, Al) N samples, the stress-free lattice parameter of fcc-(Ti, Al) N is suggested.     

Ferroelectric and Dielectric Behavior of Samarium-Substituted Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Nanomaterials Synthesized by Gel Combustion Method

Samarium (Sm) substituted bismuth titanate (Bi₄Ti₃O₁₂, BT) nanoparticles with compositions of Bi_4?xSm_xTi₃O₁₂ (BSmT) (where x = 0.0, 0.25, 0.50, 0.75, 1.0) were prepared by using the gel combustion method. X-ray diffraction pattern of prepared nanoparticles confirmed that all the BSmT compositions were of the single phase orthorhombic structure with the space group of B2ab. The dielectric loss at 100 Hz varied from 0.0925 to 0.056 with an increase in Samarium content. Dielectric loss confirmed the lower leakage current of BSmT nanoparticles. The ferroelectric behavior of BSmT nanoparticles showed that the Bi_3.50Sm_0.50Ti₃O₁₂ had good ferroelectric property and also had minimum leakage current. The increase of coercive field (Ec) and the increase of remnant polarizations (Pr) were pronounced with the increase in Sm content confirming to the fact that the substitution of Sm³⁺ had improved the ferroelectric properties of BT.     

Deformation and failure of Zr<Subscript>57</Subscript>Nb<Subscript>5</Subscript>Al<Subscript>10</Subscript>Cu<Subscript>15.4</Subscript>Ni<Subscript>12.6</Subscript>/W particle composites under quasi-static and dynamic compression

We have investigated the mechanical behavior of a composite material consisting of a Zr₅₇Nb₅Al₁₀Cu_15.4Ni_12.6 metallic glass matrix with 60 vol pct tungsten particles under uniaxial compression over a range of strain rates from 10⁻⁴ to 10⁴ s⁻¹. In contrast to the behavior of single-phase metallic glasses, the failure strength of the composite increases with increasing strain rate. The composite shows substantially greater plastic deformation than the unreinforced glass under both quasi-static and dynamic loading. Under quasi-static loading, the composite specimens do not fail even at nominal plastic strains in excess of 30 pct. Under dynamic loading, fracture of the composite specimens is induced by shear bands at plastic strains of approximately 20 to 30 pct. We observed evidence of shear localization in the composite on two distinct length scales. Multiple shear bands with thicknesses less than 1 μm form under both quasi-static and dynamic loading. The large plastic deformation developed in the composite specimens is due to the ability of the tungsten particles both to initiate these shear bands and to restrict their propagation. In addition, the dynamic specimens also show shear bands with thicknesses on the order of 50 μm; the tungsten particles inside these shear bands are extensively deformed. We propose that thermal softening of the tungsten particles results in a lowered constraint for shear band development, leading to earlier failure under dynamic loading.     

Precursor Dependent Structural Phase Evolution in Hydrothermally Prepared Cu<Subscript>2</Subscript>O Octahedrons and Cu Micro-Flakes and Their Structural and Optical Properties

Cuprous oxide (Cu₂O) and metallic copper particles with different microstructures have been prepared by a single-step hydrothermal method by using copper acetate monohydrate and sodium hydroxide as precursors, d-glucose as reducing agent, and poly (vinylpyrrolidone) as stabilizing agent. It was found that the concentration of the NaOH in the reactant solution played a significant role in the structural phase formation of the product. Further, it was also optimized to get either the single phase of Cu₂O or Cu or the mixed phase of Cu₂O and Cu depending on the NaOH content in the reaction mixture. The product material was systematically investigated by x-ray diffraction (XRD), Rietveld refinement, UV–Vis, Raman spectroscopies, scanning electron microscopy (SEM), and X-ray energy dispersive spectroscopy (XEDS). A thorough analysis of the XRD patterns in a standard method as well as by Rietveld refinement have shown the cubic phases for both Cu₂O and Cu. The same phases have been retained in the mixed phase sample also. Optical band gap was determined through Tauc plot to be 1.95 eV. Microstructural studies by SEM showed that the Cu particles were formed as micro flakes whereas the Cu₂O particles were formed with the well-defined octahedral morphology. The XEDS analysis confirmed the chemical composition in Cu₂O. This work reports the dependence of NaOH concentration in the reactant solution on the type of product (single phase or a mixed phases of Cu₂O and Cu) and their structural and optical properties.     

A Comparative Study on the Microstructure and Mechanical Properties of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> and Cu<Subscript>3</Subscript>Sn Joints Formed by TLP Soldering With/Without the Assistance of Ultrasonic Waves

In this study, the microstructure and mechanical properties of Cu₆Sn₅ and Cu₃Sn intermetallic joints, formed by the transient liquid phase (TLP) soldering process with and without the assistance of ultrasonic waves (USWs), were compared. After the application of USWs in the TLP soldering process, Cu-Sn intermetallic compounds (IMCs) exhibited a novel noninterfacial growth pattern in the molten solder interlayer. The resulting Cu₆Sn₅ and Cu₃Sn joints consisted of refined equiaxed IMC grains with average sizes of 3 and 2.3 µm, respectively. The Cu₆Sn₅ grains in the ultrasonically soldered intermetallic joints demonstrated uniform mechanical properties with elastic modulus and hardness values of 123.0 and 5.98 GPa, respectively, while those of Cu₃Sn grains were 133.9 and 5.08 GPa, respectively. The shear strengths of ultrasonically soldered Cu₆Sn₅ and Cu₃Sn joints were measured to be 60 and 65 MPa, respectively, higher than that for reflow-soldered intermetallic joints. Ultrasonically soldered Cu₆Sn₅ and Cu₃Sn joints both exhibited a combination of transgranular and intergranular fractures during shear testing.     

Phase composition and some properties of titanium carbonitride-titanium nickelide alloys with Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The phase formation in and the microstructure of titanium carbonitride-titanium nickelide alloys with aluminum oxide Al₂O₃ nanopowder additions are studied by X-ray diffraction, electron-microscopic, and electron-probe microanalyses. The phase interaction is characterized by the redistribution of nonmetallic elements and aluminum between refractory and binding phases with the formation of a nonstoichiometric titanium-aluminum (Ti,Al)(C,N) carbonitride and a titanium-aluminum nickelide. The number of forming phases and their compositions are controlled by the kinetic parameters of the process.     

Phase equilibrium and distribution of minor elements between Ni-S melt and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-MgO Slag at 1873 K

Distribution of nickel and minor elements such as Au, Ag, Fe, Co, Cu, As, and Sb between the Ni-S alloy and the CaO-Al₂O₃ based slag phases in a magnesia crucible was studied at 1873 K. Partial pressure of SO₂ was controlled at 10.1 kPa, while partial pressures of O₂ and S₂ ranged between the point of NiO precipitation (po₂ of 10.1 Pa) and the point at which Ni₃S₂ is formed (ps₂ of 4.0 kPa). The nickel content in the slag and the sulfur and oxygen contents in the metal at a given po₂ or pso₂ decrease when the temperature is increased from 1773 to 1873 K. The distribution ratios of iron, cobalt, and copper, defined by (wt pct X in slag)/{wt pct X in alloy}, where X is the minor element in the slag, have larger values than that of nickel, while the values of Au, Ag, Sb, and As are lower than that of nickel. The distribution behavior of nickel and minor elements is discussed based on the concept of oxidic and sulfidic dissolution.     

Structural Transitions and Magnetic Properties of Ni<Subscript>50</Subscript>Mn<Subscript>36.7</Subscript>In<Subscript>13.3</Subscript> Particles with Amorphous-Like Phase

The high-energy ball-milling method was used for fabricating Ni₅₀Mn_36.7In_13.3 fine-sized particles. The as-melt polycrystalline Ni₅₀Mn_36.7In_13.3 alloy exhibits a 14 M modulated martensite structure at room temperature (RT). The atomic pair distribution function analysis together with the differential scanning calorimetry technique proved that the 14 M modulated martensite transformed to a metastable amorphous-like structure after ball milling for 8 hours. Annealing of the ball-milled particles with the amorphous-like phase first led to the crystallization to form a B2 structure at 523 K (250 °C), and then an ordered Heusler L2₁ structure (with a small tetragonal distortion) at 684 K (411 °C). The annealed particles undergo different structural transitions during cooling, tailored by the atomic arrangements of the high-temperature phase. Low-field thermomagnetization measurements show that the ball-milled particles with the amorphous-like structure or the atomically disordered crystalline structure exhibit a magnetic transition from the paramagnetic-like to the spin-glass state with decreasing temperature, whereas the crystalline particles with the ordered Heusler L2₁ structure present a ferromagnetic behavior with the Curie temperature T _c ≈ 310 K (37 °C).