Formation and thermal stability of Pd-based bulk metallic glasses

The glass-forming ability and thermal stability of bulk glassy Pd₇₉Cu₆Si₁₀P₅ alloy were studied by substitution of Cu with Ag and with Au + Ag from 0 to 6 at.%. The results indicated that the small addition of Ag strongly affects the thermal stability and glass-forming ability of the Pd₇₉Cu₆Si₁₀P₅ alloy. The alloy doped with 4 at.% Ag (Pd₇₉Cu₂Ag₄Si₁₀P₅) exhibits the largest glass-forming ability among the Pd₇₉Cu_6−xAg_xSi₁₀P₅ (x = 0–6 at.%) alloys. The critical diameter for glass formation of this alloy reaches as large as 7 mm by copper mold casting. On the other hand, the multi-addition of Au + Ag does not increase the glass forming ability though the Ag and Au are similar in atomic size. The largest glass forming ability is obtained at 1 at.% Au + 2 at.% Ag among the Pd₇₉Cu_6−x−yAu_xAg_ySi₁₀P₅ (x = 1–4 at.%, y = 1–3 at.%) alloys. The critical diameter of this alloy is 5 mm by copper mold casting.     

Structural and thermal properties of some tellurite glasses

Tellurium oxide glasses were prepared by the hammer and anvil technique. The glass systems are (0.85TeO₂ + 0.15Z), where Z = K₂O, TiO₂, V₂O₅, MnO, Fe₂O₃, CoO, NiO or CuO. A second group is a ternary system 0.85TeO₂+(0.15 − x)TiO₂ + xFe₂O₃) with x=0.0, 0.05, 0.1, 0.15 mol. X-ray diffraction, infrared spectroscopy and differential thermal analysis measurements were carried out. The present study showed the different glass-forming groups, the glass transition and crystallization temperatures as well as the crystallization processes.     

Influence of thermal history on the structure and properties of silicate glasses

We studied a set of float glass samples prepared with different fictive temperatures by previous annealing around the glass transition temperature. We compared the results to previous measurements on a series of amorphous silica samples, also prepared with different fictive temperatures. We showed that the modifications on the structure at a local scale are very small, the changes of physical properties are moderate but the changes on density fluctuations at a nanometer scale are rather large: 12% and 20% in float glass and silica, for relative changes of fictive temperature equal to 13% and 25% respectively. Local order and mechanical properties of silica vary in the opposite way compared to float glass (anomalous behavior) but the density fluctuations in both glasses increase with temperature and fictive temperature.     

The thermal conductivity of some chalcogenide glasses

The temperature-dependent thermal conductivities of several chalcogenide glasses were determined above 300 K. At 300 K, the thermal conductivity for most of these glasses is about 3 mW/cm · deg.     

The effects of microalloying on thermal stability,mechanical property and corrosion resistance of Mg-based bulk metallic glasses

(Mg₆₅Cu₂₀Y₁₀Zn₅)₉₈ M₂ (M = Ti, Cr) bulk metallic glasses with diameter of 3 mm were prepared by copper mold casting. The effects of Ti or Cr on thermal stability, mechanical property and corrosion resistance were systematically investigated. It's shown that the Glass forming ability of the Mg₆₅Cu₂₀Y₁₀Zn₅ bulk metallic glasses slightly decreases with the addition of the elements. Whereas, the strength and corrosion resistance significantly increase. The superior corrosion resistance of the amorphous sample containing Ti or Cr is presented for the forming of homogeneous passive layer with highly protective oxides.     

Thermal stability, spectra and laser properties of Yb: lead-zinc-telluride oxide glasses

A series of new glasses of 70TeO₂-(20 − x) ZnO-xPbO − 5La₂O₃-2.5K₂O-2.5Na₂O (mol%) doped with Yb³⁺ is presented. Thermal stability, spectra and laser properties of Yb³⁺ ions have been measured. It found that 70TeO₂-15PbO-5ZnO-5La₂O₃-2.5K₂O-2.5Na₂O composition glass had fine stability ((T_x−T_g)>190 °C), high-stimulated emission cross-section of 1.25 pm² for the ²F_5/2 → ²F_7/2 transition and existed measured fluorescence lifetime of 0.94 ms and the broad fluorescence effective linewidth of 72 nm. Evaluated from the good potential laser parameters, this system glass is excellent for short pulse generation in diode pumped lasers, short pulse generation tunable lasers, high-peak power and high-average power lasers.     

Control of the thermal properties of slow bioresorbable glasses by boron addition

This work studied the properties of glasses with the molar composition 63.8SiO₂-(11.6-x)Na₂O-(0.7 + x)B₂O₃-19.2CaO-3MgO-1.5Al₂O₃-0.2P₂O_5, in which x = 0, 1, 2, 3. These glasses are of interest for the development of slowly dissolving fibers to be incorporated in composites for medical applications. The thermal properties were recorded using hot stage microscopy, differential thermal analysis, and heat treatments in the range of 800°-1000 °C. The glass crystallization behavior was determined based on calculated values of the activation energy of crystallization and the Johnson-Mehl-Avrami exponent. The structural units in the glass network were identified using infrared spectroscopy. Finally, in vitro dissolution was tested in SBF solution.The addition of B₂O₃ increased the glass transition temperature and reduced the working temperature. When heat treated at 900 °C, the glass with the smallest amount of B₂O₃ formed two crystalline phases: magnesium silicate MgSiO₃ and wollastonite CaSiO₃. In the other compositions, only CaSiO₃ was observed after heat treatment at 950 °C. All the glasses crystallized preferentially from the surface. Changes in the liquidus and crystallization temperatures were related to changes in the glass structure. The formation of [BO₃] units led to glasses with improved resistance to crystallization and decreased liquidus temperature. In the glasses with 2.7 and 3.7 mol% B₂O₃, [BO₃] units were transformed into [BO₄] units. The formation of [BO₄] led to an increase in fragility and a decrease in resistance to crystallization. All the glasses dissolved slowly in simulated body fluid.     

Formation and stability of nickel-zirconium glasses

Glasses may be formed in two composition ranges: 33–42 and 60–76 at.% Zr. The crystallisation temperatures (T_x), activation energies (Q_x), crystallisation morphologies, densities, Young's moduli and peak in the X-ray diffraction pattern (Q_p) are reported as a function of composition. T_x, Q_x and Q_p do not interpolate smoothly between the two composition ranges. Maximum thermal stability occurs at 36 at.% Zr, well away from the value predicted by the free electron approach of Nagel and Tauc. The glasses are denser than would be expected from a simple dense random packing of hard spheres. Some implications for the structure of all-metal glasses are discussed.     

Thermal properties of barium titanium borate glasses measured by thermal lens technique

In this paper, thermal lens spectrometry was used to determine the thermal properties of barium titanium borate glasses as a function of the amount of TiO₂ in the ratios 8/9 and 1/1 of BaO–B₂O₃. The thermal lens technique was shown to be sensitive to the variation of TiO₂ and the ratio of BaO/B₂O₃, through thermal diffusivity and conductivity, with different behavior for the ratios 1/1 and 8/9. An increase in thermal diffusivity and conductivity as a function of TiO₂ was observed, and this behavior was ascribed to the fact that titanium acts as a glassy-former, being more active in the ratio 8/9.     

Effect of microalloying of Nb on corrosion resistance and thermal stability of ZrCu-based bulk metallic glasses

Bulk metallic glasses (BMGs) of Zr_46−xNb_xCu_37.6Ag_8.4Al₈ with x = 0, 0.5, 1, 2 and 4 at.% were prepared by copper mould casting. The corrosion resistance of the ZrCu-based BMGs with different Nb contents was carefully examined by weight loss measurements and potentiodynamic polarization tests in 3 mass% NaCl, 1 N HCl and 1 N H₂SO₄ solutions, respectively. Nb addition improves the newly developed BMGs’ corrosion resistance in chloride-containing solutions and the alloys all exhibit excellent corrosion resistance in 1 N H₂SO₄. The corrosion behavior of the alloy containing 0 and 4 at.% Nb in phosphate-buffered solution was examined by electrochemical polarization tests. The influence of Nb addition on glass forming ability (GFA), thermal stability and mechanical property was investigated by X-ray diffraction, differential scanning calorimetry and compression tests, respectively. It is found that the addition of Nb can deteriorate the GFA and thermal stability of the base system, but little effect is observed on the mechanical properties, e.g., yielding strength and plasticity, of the ZrCu-based BMG alloys.     

Effect of OH-content on thermal and chemical properties of SnOP2O5 glasses

Glasses with 55–60 mol% SnO and 40–45 mol% P₂O₅ have shown extremely large differences in the chemical and thermal properties depending on the temperature at which they were melted. Glasses prepared at low melting temperature, 450–550 °C, had low T_g, 150–200 °C, and low chemical stability. Glasses prepared at high melting temperature, 800–1200 °C, had much higher T_g, 250–300 °C, and much higher chemical stability. No significant differences were found by ¹¹⁹Sn Mössbauer and ³¹P Nuclear Magnetic Resonance spectroscopy. Large differences in the OH-content could be detected as the reason by infrared absorption spectroscopy, thermal analyses, and ¹H Nuclear Magnetic Resonance spectroscopy. In samples with low T_g, a broad OH – vibration band around 3000 nm with an absorption intensity >20 cm^?1, bands at 2140 nm with intensity ～5 cm^?1, at 2038 nm with intensity ～2.7 cm^?1, and at 1564 nm with intensity ～0.4 cm^?1 were measured. These samples have shown a mass loss of 3–4 wt% by thermal gravimetric analyses under argon in the temperature range 400–1000 °C. No mass loss and only one broad OH-band with a maximum at 3150 nm and low absorption intensity <4 cm^?1 could be detected in samples melted at high temperature, 1000–1200 °C, which have much higher T_g, ～300 °C, and much higher chemical stability.     

The influence of Ag substitution for Cu on glass-forming ability and thermal properties of Mg-based bulk metallic glasses

A group of pseudo-ternary Mg–(Cu–Ag)–Dy bulk metallic glasses (BMGs) was developed by copper mold casting. The glass-forming ability (GFA) is significantly improved by the coexistence of similar elements of Ag and Cu. The critical diameter for glass formation increases from 10 mm for ternary Mg_56.5Cu₃₂Dy_11.5 alloy to 18 mm for pseudo-ternary Mg_56.5Cu₂₇Ag₅Dy_11.5 alloy. Thermal stability, crystallization and melting behaviors of the Mg-based BMGs were evaluated. The decrease of Gibbs free energy difference between undercooled liquid and crystalline phases caused by similar element substitution with optimal amount can be responsible for the increase in GFA of the resulting alloys.     

The thermal stability and activation energy of crystallization of (Cu61.8Zr38.2)1−xAlx bulk metallic glasses

The present paper reports on the thermal stability and activation energy of crystallization of bulk metallic glasses (BMGs) (Cu_61.8Zr_38.2)_1−xAl_x. The (Cu_61.8Zr_38.2)_1−xAl_x composition series, prepared by copper mould suction casting into bars with a diameter of 3 mm, form BMGs with an e/a range of 1.24–1.3. These BMGs manifest increased thermal stability with increased e/a ratios. The activation energies (ΔE) of crystallization as derived from thermal analysis at different heating rates follow a similar tendency to that of the thermal stability, indicating stronger short-range ordering with increasing e/a ratios. The optimum BMG Cu_58.1Zr_35.9Al₆ exhibits the highest thermal stability and the largest ΔE.     

Calculation of thermal expansion coefficient of glasses

Thermal expansion of oxide glasses has been theoretically studied to derive an equation for the calculation of the thermal expansion coefficient of glass from chemical composition. Grüneisen's constant may be correlated with packing density and a ratio of cation-to-anion radius and, considering the packing density and dissociation energy per unit volume, a semi emprical equation was derived. The agreement between observed and calculated values was satisfactory over 150 glasses of the binary, ternary and quarternary systems.     

Effect of B2O3 addition on the thermal properties and density of barium phosphate glasses

Variations in glass transition temperature, onset of crystallization, thermal expansion coefficient, density and molar volume with B₂O₃ concentration were studied in a series of xB₂O₃–(100 − x)Ba(PO₃)₂ glasses with 0–10 mol% B₂O₃. DTA analysis and isothermal treatments for powdered glass samples reveal that ⩾7.5 mol% B₂O₃ addition suppresses surface crystallization during softening process. Raman spectroscopy suggests that the properties are related to the glass structure consisting of PO₄ Q² units with diborate and PO₄–BO₄ groups.     

Study of thermal and optical properties of the Ge-Te-CdI2/ZnI2 far infrared transmitting glasses

A systematic series of (100 ? x)(GeTe_4.3) ? xCdI₂/ZnI₂ far infrared transmitting glasses were prepared by traditional melt-quenching method. ZnI₂ (20 mol%) can be introduced in the glassy matrix, while only 10 mol% CdI₂ can be incorporated in the Ge-Te-CdI₂ glass system. Based on differential thermal analysis (DTA) data, most of the glass samples have good thermal stability. A maximum ΔT value of 115 °C was obtained for the glass composition 90(GeTe_4.3)–10ZnI₂. The allowed indirect transition optical band gap was calculated according to the classical Tauc equation. It is found that the indirect optical band gap decreased from 0.619 to 0.569 eV with the CdI₂ addition and increased from 0.628 to 0.677 eV with the ZnI₂ addition. According to infrared transmission spectra, the Ge-Te-CdI₂/ZnI₂ glasses show wide IR transparency.     

The defect diffusion model and the properties of glasses and liquids

Several previously unexplained relaxation phenomena are interpreted quantitatively in terms of the defect diffusion model (DDM). These include widely different pre-exponentials, exponents and consequently fragility. In addition, the DDM is used to give a qualitative explanation of many properties that glasses and liquids exhibit. This includes interpretations of the glass transition (T_g), the liquid–liquid transition (T_B), the crystalline melting temperature (T_m), and the different values of the characteristic temperature, T_C, that some materials exhibit for different types of physical measurements. Next, qualitative explanations of the origin of secondary relaxations such as the excess wing and the β relaxation are given. In addition, the boson peak is discussed in terms of the DDM. Finally, it is pointed out that in the DDM, universality is embodied in the defects i.e. free volume.