Volume and viscosity of Zr–Cu–Al glass-forming liquid alloys

We examined the volume and viscosity of Zr–Cu–Al glass-forming liquid alloys to clarify the origin of a frozen free volume in glassy alloys. Since an excess free volume imparts toughness and ductility to glassy alloys, we attempted to increase this volume in glass structures so that they could be used as engineering materials. The maximum frozen excess free volume was observed in the ternary eutectic composition of the Zr–Cu–Al alloy system; however, its origin remains unclear. We attempted to reveal the mechanism of the formation of the frozen excess free volume in Zr–Cu–Al glassy alloys.     

The internal friction and elastic modulus of amorphous Pd–Si and Fe–P–C alloys

The internal friction and the shear modulus of the amorphous Pd₈₀–Si₂₀–, Fe₈₀–P₁₃–C₇ and Fe₅₀–Ni₃₃–P₁₂–C₅ alloys have been measured at about 0.5 Hz over a temperature range from room temperature to about 550°C. The internal friction rises steeply with temperature and shows maxima around the crystallization temperature. The activation energy for the steeply rising internal friction has been estimated by the two different procedures; from the shift of the curve by the frequency change and from the slope of the In Q^?1 versus 1/T plot. The two values are very different, which indicates the existence of a wide distribution of activation energies. Crystallization of the amorphous alloys resulted in an increase of about 30% in the shear modulus.     

Bulk glass formability for Cu–Hf–Zr–Ag and Cu–Zr–Ag–Si alloys

The effects of the gradual substitution of Zr by Hf on glass formability and thermal stability in the Cu₄₅Zr_45?xHf_xAg₁₀ alloys and the effects of small additions of Si on glass formability in the Cu₄₅Zr₄₅Ag₁₀ alloy are reported and discussed. The samples were prepared as ribbons of thickness in the range 25–200 μm by melt spinning and as conical bulk shapes, with a length of 50 mm and cone base diameters in the range 2–10 mm, by suction die casting. The alloy Cu₄₅Zr₄₅Ag₁₀ had a critical cylindrical rod diameter for glass formation, d_c, of 3.5 mm but substitution of 1.5 and 3.5 at.% Zr by Hf resulted in substantial increases to 5.5 and 4.5 mm, respectively. However, for x in the range 5–40 at.%, d_c was reduced to <1 mm_. The small addition of Si proved to be beneficial to the glass forming ability (GFA), increasing d_c up to 5.5 mm for 0.5 at.% Si. Thus the chemical and atomic size similarities of Hf and Zr do not guarantee that bulk glass formation will be maintained on substituting large proportions of Zr by Hf though small substitutions of Hf and of minor additions of Si were beneficial to the GFA. These effects are discussed in terms of the possible influence of the alloying additions on the liquid structure and on the number density of heterogeneous nucleants.     

Nano-crystallization behavior of Zr–Cu–Al bulk glass-forming alloy

The glass-forming ability and devitrification behavior of a Zr₅₅Cu₃₅Al₁₀ bulk glass-forming alloy were examined to elucidate the very high nanocrystallization product density (> 10²³ m^?3). The crystallization kinetics and structural changes in the glassy alloy were studied using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. The observed sequential phase formation during isothermal reaction and the high nanocrystal density are consistent with the influence of residual oxygen even at low levels (< 500 ppm) to promote nucleation.     

Hf–Cu–Ni–Al bulk metallic glasses: Optimization of glass-forming ability and plasticity

In the Hf–Cu–Ni–Al quaternary system, the Hf₅₁Cu_27.75Ni_9.25Al₁₂ bulk metallic glass (BMG) exhibits the best combination of the large glass-forming ability (GFA) and compressive plasticity. Minor substitution of Nb for Hf in Hf–Cu–Ni–Al BMGs degrades not only the GFA but also plasticity, while the substitution of Ta does not have an appreciable effect on both properties. For the investigated Hf-based BMGs, the shear modulus G is a more sensitive indicator to correlate with their plasticity than the Poisson′s ratio. Meanwhile, the correlation between the G and the glass transition temperature T_g for the Hf-based BMGs can be expressed as G = 9.9 + 576 (T_g/V_m)[1 ? 4/9(T/T_g)^2/3].     

Crystallization behavior during cooling and glass-forming ability of Al2O3-poor Li2O–Al2O3–SiO2 melts

The influence of K₂O/(MgO + K₂O) on some melt properties, including crystallization during cooling of melts and glass-forming ability, was investigated in the Li₂O–Al₂O₃–SiO₂ system with low Al₂O₃ content. The dependence of viscosity on K₂O/(MgO + K₂O) above 1000 °C showed a monotonic decrease due to the reduction of [MgO₄] concentration and the conductivity also decreased due to the larger ion radius of K. The temperature dependence of conductivity for all melts showed an abrupt change at one temperature due to crystallization in which temperature of crystallization decreases with increase of K₂O. The crystallization behavior near liquidus temperature was studied quantitatively by calculating the crystal volume fraction from apparent viscosity value. The glass-forming ability of the melts was discussed by using data related with viscosity and crystallization. Finally, it was suggested that the melts with K₂O/(MgO + K₂O) ? 0.75 have a good glass-forming ability.     

Investigation on the phase separation in undercooled Cu–Fe melts

On the basis of the gravity difference and the temperature dependence of the interfacial energy of the separated phases, the amalgamation of the droplets of minor phase was affected by Stokes sedimentation and Marangoni motion during the liquid-phase separation. Moreover, the velocity of Stokes motion increased distinctly with the undercooling, while the velocity of Marangoni motion was slightly impacted. At the beginning of the liquid-phase separation, the droplets of minor phase were dominated by Marangoni motion when the droplets radius was small. As the droplets radius increased by combination, the effect of Stokes sedimentation strengthened gradually. Additionally, the coagulation process was mainly controlled by Stokes sedimentation when a critical radius r_d was far exceeded.     

Structural Features and Mutual Influence of the Layers in PZT–LNO–SiOx–Si and PZT–LNO–Si Compositions

Crystallography Reports - The phase composition and specific features of the microstructures of layers in the Pb(Zr0.52Ti0.48)O3–LaNiO3–Si and...     

The solidification behavior and phase equilibrium of o-Nitroaniline-β-Naphthol binary eutectic system

Phase diagram studies of o-nitroaniline-β-naphthol system have been made by the thaw melt method. Simple eutectic type phase diagram was formed. Formation of eutectic mixture occurred at 0.7222 mole fractions of o-nitroaniline and melted at 326.85 K. The heat of fusion of components and eutectic mixtures were determined with the help of DSC technique and excess thermodynamic functions were calculated. Experiments were performed to study the undercooling, microstructure and linear velocities of crystallization. Flexural strength measurements were also made. Eutectic mixture showed higher flexural strength as compared to the components.     

Hardness and refractive index of Ca–Si–O–N glasses

Vickers hardness and refractive index was determined for Ca–Si–O–N glasses with 14.6–58 e/o N and 19–42 e/o Ca. By applying slow cooling rates, transparent glasses were obtained for compositions near Ca_9.94Si₁₀O_17.73N_8.14, while the majority of the glasses were opaque due to small inclusions of elemental Si and/or Ca-silicide. Determined glass densities varied between 2.80 and 3.25 g/cm³. Hardness was found to vary from 7.3 to 10.1 GPa at a load of 500 g and, respectively increase and decrease linearly with N and Ca content. The refractive index was found to increase linearly with N content from 1.62 to 1.95 and showed no significant dependence on Ca content.     

Effect of rare-earth elements on the plasma etching behavior of the RE–Si–Al–O glasses

The effect of rare-earth elements on the plasma etching behavior of oxide glasses were investigated to develop the window glass for a plasma processing chamber in the semiconductor industry. Aluminosilicate glasses with various rare-earth elements (Y, Gd and La) were prepared and their optical transmittance and plasma etching depth were evaluated. The plasma etching behavior of the glasses was estimated by X-ray photoelectron spectroscopy analysis at the fluorine plasma exposure surface of the glasses. The rare-earth element in the glass was highly related to various properties such as density, molar volume, mechanical properties and plasma etching depth. The cationic field strength of the rare-earth element more strongly affected the plasma etching depth of the glasses than the sublimation point of the fluorine compounds and this may be related to the plasma etching condition.     

Three-dimensional visualization and characterization of morphology and internal microstructural features of primary silicon crystals in a cast Al–Si base alloy

Primary Si crystals are usually present in the cast microstructures of near-eutectic, eutectic, and hyper-eutectic Al–Si base alloys. Three-dimensional digital images of individual primary Si crystals present in a permanent mold cast unmodified Al-12 wt% Si-1 wt% Ni base alloy are reconstructed using a combination of montage serial sectioning and three-dimensional digital image processing techniques. Octahedral, prismatic, and plate-like three-dimensional morphologies of the primary Si crystals are present in the microstructure. Some of the primary Si crystals contain interior regions/islands of Al-alloy that are completely enclosed in the corresponding Si crystals indicating certain variations in the crystal growth velocities during the evolution of these crystals. The boundaries of these interior regions/islands are non-faceted smooth and curved indicating re-melting of the Al-rich islands and re-dissolution of some Si near these internal boundaries in the Al-alloy as a result of the heat generated by liquid-to-solid transformation of Si away from the islands.     

Growth and Morphological Study of Graded-Gap Si–Si1 – xGex–GaAs Structures

Crystallography Reports - Single-crystal films of Si1&nbsp;–&nbsp;xGex (0 &lt; x &lt; 1) solid solution have been grown on Si substrates by liquid-phase epitaxy, and a...     

Microstructure and field emission properties of the Si–TaSi2 eutectic in situ composites by electron beam floating zone melting technique

The directionally solidified Si–TaSi₂ eutectic in situ composites, which have highly aligned and uniformly distributed TaSi₂ fibers embedded in the Si continuous matrix, are obtained by electron beam floating zone melting (EBFZM) technique at the solidification rate range 0.3–9.0 mm/min. The preferential orientation of the Si–TaSi₂ eutectic is also studied by selected area electron diffraction (SAED), which is [0 1¯ 1¯]Si∥[0 0 0 1]TaSi₂ and (0 1¯ 1)Si∥(0 1¯ 1 1)TaSi₂. Moreover, field emission properties of the Si–TaSi₂ eutectic in situ composites are investigated by transparent anode imaging technology. Approximately straight F–N curves show that this material has excellent field emission properties.     

Short-range order and dynamic viscosity of liquid Cu–Ge alloys

We report an investigation of the dynamic viscosity and the atomic structure of liquid Cu–Ge alloys. The concentration as well as the temperature dependence of the viscosity obtained experimentally has been modelled by use of a thermodynamic approach. An excess viscosity above mixing rules has been observed for Cu-rich alloys which – in relation with the diffraction experiments – can be explained in terms of a micro-heterogeneous structure.     

The effect of Ag addition on the glass-forming ability of Mg–Cu–Y metallic glass alloys

The effect of Ag substitution for Cu on the glass forming ability was studied in Mg₆₅Cu_25−xAg_xY₁₀ (x=0,5,10,15,20,25) alloys by using thermal analysis and X-ray diffractometry (XRD). With increasing x from 0–25, the glass transition temperature, T_g, of melt spun Mg₆₅Cu_25−x Ag_xY₁₀ alloys increases slightly from 426 to 436 K, and the crystallization temperature, T_x, decreases from 494 to 459 K, resulting in a decrease in the supercooled liquid region. However, a partial substitution of Cu by Ag in Mg₆₅Cu₂₅Y₁₀ promotes the glass formation. The maximum diameter for amorphous phase formation by injection casting increases from 4 mm in Mg₆₅Cu₂₅Y₁₀ to 6 mm in Mg₆₅Cu₁₅Ag₁₀Y₁₀ alloy. Both amorphous Mg₆₅Cu₁₅Ag₁₀Y₁₀ alloys prepared by melt spinning and injection casting showed similar crystallization process during continuous heating in differential scanning calorimetry (DSC). The relationship between the critical diameter for the formation of an amorphous phase in injection casting and the parameters reflecting glass-forming ability was examined.     

Fabrication and ionic conductivity of amorphous Li–Al–Ti–P–O thin film

Li⁺ ion conducting Li–Al–Ti–P–O thin films were fabricated on ITO-glass substrates at various temperatures from 25 to 400 °C by RF magnetron sputtering method. When the substrate temperature is higher than 300 °C, severe destruction of ITO films were confirmed by XRD (X-ray diffraction) and the abrupt transformation of one semi-circle into two semi-circles on the impedance spectra. These as-deposited Li–Al–Ti–P–O solid state electrolyte thin films have an amorphous structure confirmed by XRD and a single semicircle on the impedance spectra. Good transmission higher than 80% in the visible light range of these electrolyte thin films can fulfill the demand of electro-chromic devices. Field emission scanning electron microscopy and atomic force microscopy showed the denser, smoother and more uniform film structure with the enhanced substrate temperature. Measurements of impedance spectra indicate that the gradual increased conductivity of these Li–Al–Ti–P–O thin films with the elevation of substrate temperature from room temperature to 300 °C is originated from the increase of the pre-exponential factor (σ₀). The largest Li-ion conductivity can come to 2.46 × 10^? 5 S cm^? 1. This inorganic solid lithium ion conductor film will have a potential application as an electrolyte layer in the field such as lithium batteries or all-solid-state EC devices.     

Crystal and molecular structure of calcium L(–)-malate trihydrate

The new crystal and molecular structures of a less common hydrated calcium L(–)-malate (calcium (2S) 2-hydroxybutanedioate trihydrate) Ca(C₄H₄O₅)3H₂O, are reported. X-ray crystallographic data are as follows: a = 6.6460(3) Å, b = 8.3795(3) Å, c = 8.2707(4) Å, = 112.640(2)°, V = 425.1(4) ų, space group P2₁ (No. 4), Z = 2, D _calc = 1.767 g cm^–3. The calcium ion coordination number is seven. One of the three water molecules present in the unit cell is less strongly bound, only interacting with a calcium ion. In aqueous or hydroalcoholic solution, both di- and trihydrated species crystallize simultaneously.