The kinetics of formation of A AuGeSi metallic glass

The glass-forming ability of a Au_0.778Ge_0.138Si_0.084 alloy is analyzed theoretically by computing a time-temperature-transformation curve which describes the time required to produce a barely detectable fraction of crystallization, at various temperatures. The calculation is based on an interpolated viscosity-temperature curve, this alloy being exceptional among metallic glass formers in that experimental viscous-flow data are available at both high and low temperatures. Allowing for uncertainties, the critical cooling rate for glass formation lies within the range 10⁶?10⁸ K/sec which is in satisfactory agreement with experimental estimates of cooling rates in splat quenching. This and previous comparisons for Ni and PdSi alloys suggest that the approach may have useful and general applicability to metallic glasses.     

Mechanical damping of silver-containing SiAsChalcogenide glasses

Mechanical damping measurements were used to study the structural conditions responsible for the increase in thermal stability that has been observed when Ag and Se are substituted simultaneously in Si₃₅As_25?xAg_xTe_40?ySe_y glasses. Glasses containing Ag exhibited a mechanical damping peak whose magnitude was approximately proportional to the Ag content and which was absent in the more completely cross-linked Si₃₅As₂₅Te₄₀ base glass. This peak shifted to lower temperatures and split into two overlapping peaks with increasing Se content. The splitting of the peak has been tentatively attributed to phase separation which has been postulated to occur at higher Se contents.     

Composition dependence of the glass transition temperatures of PdNiP and PtNiP glasses

Thermal properties of glassy PdNiP and PtNiP alloys have been measured as a function of the concentration of transition metals. The glass transiion temperature, T_g, of these alloys glasses exhibits a negative linear deviation with transition metal content - which is in contrast to the increasing T_g of binary glassy alloys with increasing metalloids.It is suggested that the suppression of the glass transition temperature of these glassy alloys may be attributed to the excess configurational entropy of disorder associated with a mixture of hard spheres differing in radius. In contrast, the increasing T_g of binary glassy alloys with the metalloid content may be associated with the short-range order resulting from strong interactions between metal and metalloid atoms.     

Memory effect in CuAsSe glasses containing small amounts of Au

The Cu, As and Se contents of Au-containing CuAsSe glasses significantly affected both the resistivity in the memory state and the time required to reach the memory state, whereas the Au content affects only the latter. The main crystalline species formed in these glasses was a CuAsSe compound, and its formation was enhanced by the addition of Au. The role of Au in the memory effect was discussed on the basis of crystallization behavior of glasses.     

The leaching behavior of PbOSiO2 glasses

The leached layer of PbOSiO₂ glasses formed by diluted nitric acid solution has been investigated by ellipsometry and Auger electron spectroscopy (AES). The leaching behavior of PbOSiO₂ glasses in 10^?4 N aqueous solution of NHO₃ at 30°C was measured in real time using a Nikon auto-ellipsometer.The results were applied by curve fitting to the two-layer model from the concentration profile obtained by AES, and the refractive index profile against the film thickness was determined.The leached layer is inhomogeneous and consists of a low refractive index region and a transition region. The gradient of the refractive index in the former region is extremely small and the refractive index becomes nearly constant between 1.42 and 1.44. The shape of latter region becomes stable with its thickness at 100–310 Å, and moves in the direction of depth without changing the shape as the leaching proceeds.     

The study of transformation kinetics of the amorphous PdSi alloys

The kinetics of transformation behavior of roller-quenched amorphous Pd₈₃Si₁₇ and Pd₈₀Si₂₀ alloys after linear and isothermal heating is reported. The transformation was examined with electron microscopy, electron diffraction and electrical resistivity measurement. The crystallization of amorphous alloys with 17 at% Si begins with metastable ordered fcc solid solution. The ordered fcc solution is transformed to a ordered metastable phase with, probably, orthorhombic structure. The crystallization of amorphous alloys with 20 at% Si begins by formation of spherulites with lamellar structure. Using electron diffraction we found that spherulites consist of two phases - orthorhombic Pd₃Si silicide and Pd-rich silicide. From resistivity measurements, activation energies of 28.5 kcal/mol for Pd₈₃Si₁₇ and 80 kcal/mol for Pd₈₀Si₂₀, respectively, were calculated.     

Thermoelectric power of AsSeTe glasses

The result of the measurement of the thermoelectric power of glasses in the As₂Se₃As₂Te₃ system are reported. The results indicate that towards the As₂Te₃ end of the composition, there is an anomalous increase in thermoelectric power, the origin of which is not clear. Polaron hopping seems to contribute to conductivity in tellurium rich glasses. Structural restrictions on polaron hopping, such as the availability of AsTeAsTe chains seems to be important in discussing transport behaviour.     

ESR study of Mn2+ in GeTe and GeTeSi glasses

The electron spin resonance spectra of Mn²⁺ ions have been studied in Ge_xTe_100?x with x = 15, 17.5 and 20, and Ge_20?xTe₈₀Si_x with 0 ?x? 20. All samples are found to exhibit six hyperfine lines centered at g = 4.3 with hyperfine interaction constant A = 56 × 10^?4cm^?1. The g = 4.3 line is interpreted as being caused by Mn²⁺ ions incorporated in the amorphous network and surrounded by four Te atoms in an arrangement of orthorhombic symmetry. Some of the samples of GeTe show a g = 2.0 line. This line also appears after heat treatment in air at temperatures above the glass transition temperature. It is concluded that the g = 2.0 line is caused by Mn²⁺ ions in phase separated microcrystalline or concentrated regions of MnO in the glass.     

Sensitivity of the photo-darkening effect in CuAsSe glasses

When CuAsSe glasses are irradiated, they exhibit higher concentrations of darkening than AsSe glasses. Since darkening depends on the composition, the darkening centers in CuAsSe glasses to be of the same kind as those in AsSe glasses, i.e. arsenic clusters. Concerning the kinetics of erasing, it was found that the activation energy and the rate constant of erasing in CuAsSe are almost equal to those in AsSe glasses, but for the kinetics of darkening, it was found that the activation energy of darkening is equal to that of AsSe but α₀, which is proportional to the number of latent darkening centers, and the darkening rate constant k₁ are about twice as high as the corresponding constants of AsSe glasses. This may be the reason for the greater darkening in CuAsSe glasses. The high value of α₀ was attributed to the generation of more AsAs bonds on the addition of Cu to the AsSe glass network. The high value of k₁ was attributed to the increase in efficiency of photo-decomposition because of the many impurity levels in the band gap and also because of the narrow optical energy gap in the CuAsSe glasses.     

Quenched-in excess volume and structural relaxation in Ni- and FeNi based metallic glasses

The amount of quenched-in excess volume (ΔV_R) in various Ni- and FeNi based metallic glasses, which is defined by the volume change due to the structural relaxation, was estimated from measurements of length changes caused by isochronal annealing. It was found that the values of ΔV_R depend greatly on the kind of transition metals (Fe, Ni) and metalloids (Si, B, P) and their ratios (Fe/Ni, Si/B). In non-magnetic Ni-based metallic glasses, almost a linear relationship was observed between the changes in volume and electrical resistivity during the low temperature annealing below around 275°C. Furthermore, a large ΔV_R was observed in the metallic glasses which have a large thermal expansion coefficient such as Ni₇₅Si_12.5B_12.5 or which exhibit a well-defined glass transition such as Fe₂₇Ni₅₃P₁₄B₆, as a general trend. These results indicate that the amount of quenched-in excess volume is very sensitive to the local atomic arrangement and is attributed mainly to the distribution in bond lengths, angles and coordination numbers in the short range structure and the difference in packing of basic structural units between as-quenched and relaxed glassy states.     

Raman scattering study of BaF2ZrF4FeF2 glasses

Several BaF₂ZrF₄ glasses containing 5 mol% FeF₂ have been studied to elucidate the fraction of nonbridging fluorine atoms (−F⁻) in a ZrF₆ octahedron constituting a zigzag chain. A continuous increase in the fraction of nonbridging fluorine atom in a ZrF₆ octahedron is deduced from the increase in the integrated peak intensity of the symmetric stretching-vibrational mode (ν^s) for the Zr-nonbridging fluorine atom when the BaF₂ (+ FeF₂) content is lower than 38 mol%, i.e., in the composition region where the average coordination number of Zr is regarded as six. This result is well consistent with the previous results obtained from Raman studies of binary BaF₂HfF₄ glasses, and also with those of Mössbauer and Raman studies of ternary BaF₂ZrF₄FeF₂ glasses. A drastic decrease in the symmetric-stretching vibrational mode (ν^s) in 42BaF₂·53ZrF₄·5FeF₂ glass suggests that a friction of ZrF₆ octahedron is reduced when BaF₂ (+FeF₂) content is close to 50 mol%. The zigzag chain is therefore considered to be constituted of ZrF₇ units in such glasses.     

Thermal expansion and density of glassy PdNiP and PtNiP alloys

Thermal expansion and density of (Pd_1?xNi_x)_0.80P_0.20 and (Pt_1?yNi_y)_0.75P_0.25 alloys in their various states have been measured from room temperature to the glass transition temperature T_g. The thermal expansion of the glassy alloys at room temperature varies linearly with x and y and is 10 to 20% higher than that of corresponding pure metals. The thermal expansion of the undercooled alloy liquids near T_g as well as the molar volume $\text{v}\text{?}$ deduced from the density of glasses in contrast exhibits a negative deviation with composition x and y.This behavior is in line with the previously reported negative deviation of the glass transition temperature of these glassy alloys with metal content and may be explained in terms of excess volume associated with a mixture of hard spheres.     

Formation of glass in the GeSiS system

The formation of glass in the GeSiS system was investigated. After synthesis of material with the general formula Ge_1?xSi_xS_y, where x was chosen to be 0.05, 0.1, 0.2, 0.3 and y was in the range 1.28–3.6, cylindrical samples were prepared and used for the characterization of glass by means of DTA. It was found that the substitution of germanium with silicon does not lead to any expressive change of the glass transition temperature, crystallization and the onset of melting.     

DC conductivity of ZnOV2O5 glasses

This work presents for the first time results regarding the DC conductivity of glasses belonging to ZnOV₂O₅ system. It is shown that the conduction can be described by a small polaron hopping model. The high temperature activation energy and conductivities are close to the values determined for V₂O₅P₂O₅ glasses of similar composition. The analysis of the pre-exponential factor shows strong evidence for a non-adiabatic conduction regime.This fact agrees with the conclusion drawn for the majority of vanadate glasses. The strong variation of α suggests the presence of fluctuations in the V⁵⁺ surroundings.     

Electrical conductivity of GeTe glasses under hydrostatic pressure

The electrical conductivity of some GeTe bulk glasses has been measured between 10 and 80°C under hydrostatic pressure up to 3000 bar. The electrical conductivity (σ) of as-prepared, amorphous samples can be expressed by an equation: σ = A exp (?B/kT). For Ge₁₇Te₈₃ glass, the pressure dependences of the constants, A and B, are: (d ln A/dp) = ?3.2 × 10^?4 bar^?1 and (dB/dp) = ? 2.1 × 10^?5 eV · bar^?1. The results are analysed in terms of the low-mobility band model of Mott-CFO for amorphous semiconductors.     

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.     

Kinetics of crystallization process of Mg–Cu–Gd based bulk metallic glasses

The crystallization behavior of Mg₆₁Cu₂₈Gd₁₁ and (Mg₆₁Cu₂₈Gd₁₁)₉₈Cd₂ bulk metallic glasses was studied using DSC in the mode of continuous and isothermal heating, and its crystallization process and microstructure were confirmed by XRD and TEM. In continuous heating, the activation energies of glass transition, onset and peak crystallization were determined by the Kissinger method, which yields 110 ± 12, 77 ± 9 and 79 ± 10 kJ/mol, respectively, for Mg₆₁Cu₂₈Gd₁₁ glassy alloy, and 144 ± 10, 126 ± 6 and 131 ± 5 kJ/mol, respectively, for (Mg₆₁Cu₂₈Gd₁₁)₉₈Cd₂ glassy alloy. The isothermal kinetics was modeled by the Johnson-Mehl-Avrami equation. The Avrami exponent of the base alloy was in the range from 1.98 to 2.56 (± 0.01), which indicated a decreasing nucleation rate and a diffusion-controlled growth. For Cd-added glassy alloy, the Avrami exponent was in the range from 3.26 to 4.08, which indicated an increasing nucleation rate. The activation energies in isothermal process were calculated to be 88 ± 2 and 132 ± 2 kJ/mol, respectively, for the base and Cd-added glassy alloys. It was found that Mg₂Cu phase was the primary phase in the initial crystallization and the strong affinity between Cd and Mg/Gd tended to impose resistance to the formation of Mg₂Cu phase and thus improves the thermal stability.     

Melting enthalpy ΔHm for describing glass forming ability of bulk metallic glasses

A new melting enthalpy ΔH_m criterion for the prediction of glass forming ability (GFA) of alloys is proposed and five Zr–Al–Ni–Cu bulk metallic glasses (BMG) with critical dimension Z_max up to ? 7.5 mm are also developed by us in the light of the optimum ΔH_m of Zr–Al–Ni–Cu alloy system. And then, we researched the relationships between ΔH_m and two GFA parameters (critical cooling rate R_c and Z_max) of five bulk metallic glass (BMG) systems, such as Mg–Ni–Nd, Pd–Cu–Si, La–Al–Ni–Cu, Zr–Al–Ni–Cu and Zr–Ti–Ni–Cu–Be, respectively. The results show that the relationships between ΔH_m and R_c are all concave upward parabolas, and the optimum ΔH_ms for Mg–Ni–Nd, Pd–Cu–Si, Zr–Al–Ni–Cu, Zr–Ti–Ni–Cu–Be and La–Al–Ni–Cu are 10.3960 kJ mol^?1, 21.2202 kJ mol^?1, 19.7146 kJ mol^?1, 18.1455 kJ mol^?1 and 13.1558 kJ mol^?1, respectively. On the contrary, the relationships between ΔH_m and Z_max are all concave downward parabolas, and the optimum ΔH_ms for Mg–Ni–Nd, Pd–Cu–Si, Zr–Al–Ni–Cu, Zr–Ti–Ni–Cu–Be and La–Al–Ni–Cu are 10.5530 kJ mol^?1, 21.0830 kJ mol^?1, 19.6603 kJ mol^?1, 19.7231 kJ mol^?1 and 13.1173 kJ mol^?1, respectively. Furthermore, other BMGs’ R_cs or Z_maxs predicted by above-mentioned relationships satisfactorily agree with the tested results, which indicates that these relationships are reliable. However, the predicted results are reliable only if the main components are similar with the fitted BMGs or the additive is sparkle enough that the alloy’s character does not change. On the whole, the ΔH_m can act as a criterion for quickly predicting the alloy’s GFA and be helpful for the development of new BMGs.