Investigation of glass forming ability in Ce–Al–Ni alloys

The compositional dependence of the glass forming ability (GFA), the correlation between their GFA and the GFA related parameters, and the thermal stability of the Ce–Al–Ni alloys were investigated. Rapidly quenched Ce₆₅Al_xNi_35 ? x (x = 2, 5, 10, 17, 20) and Ce₇₀Al_xNi_30 ? x (x = 2, 5, 10, 15, 20) ribbons were prepared by melt spinning, and their phase transformations were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The experimental results indicated that the GFA of Ce₆₅Al_xNi_35 ? x (x = 2, 5, 10, 17, 20) and Ce₇₀Al_xNi_30 ? x (x = 2, 5, 10, 15, 20) alloys increased firstly and then decreased with the increasing of the Al content up to 20 at.%, respectively. It was found that only one parameter, F₁, in evaluated currently available empirical GFA parameters searching for metallic glasses with a good GFA, can reflect the GFA of the Ce–Al–Ni alloys. It was indicated that the thermal stability of alloy with fully amorphous maybe lower than that of alloy with partial amorphous.     

Effect of Mo–Fe substitution on glass forming ability and thermal stability of Fe–C–B–Mo–Cr–W bulk amorphous alloys

Amorphous Fe_67?xC₁₀B₉Mo_7+xCr₄W₃ (x = 1–7 at.%) plates with 0.64 mm thickness were prepared by copper mold casting. The thermal properties and microstructural development during heat treatments were investigated by a combination of differential scanning calorimetry, differential thermal analysis, and X-ray diffraction. The glass forming ability (GFA) and activation energy for crystallization have a distinct dependence on Mo content. Fe₆₂C₁₀B₉Mo₁₂Cr₄W₃ was the best glass former in this study, demonstrating a supercooled liquid region, ΔT_x = 51 K, and an activation energy for crystallization, Q = 453 kJ/mol. The GFA of alloys in this system was governed by elastic strain optimization resulting directly from the variation in Mo content. Heat treatments were performed to demonstrate resistance to crystallization under typical processing conditions. Alloys in this system exhibited a three phased evolution during crystallization. A second set of heat treatments was performed to identify each phase. An analysis of phase evolution revealed a distinct dependence of phase evolution with stepwise substitution of Mo for Fe in this system.     

Solubility of tin dioxide in soda-lime silicate melts

In the present work, the solubility of tin dioxide is assessed as a function of time, temperature and basicity in simple ternary glasses: NC3S, NC4S, NC5S and NC6S (N: Na₂O, C: CaO, S: SiO₂). An increase of silica contents in the glass composition leads indeed to a decrease of the glass basicity. First, a kinetic study of the dissolution has been performed. Consequently, the solubility limits of tin dioxide have been determined after 2 h of heat treatment: this duration is long enough to reach the dissolution equilibrium, and short enough to limit the sodium oxide losses in the melt at high temperatures. Nevertheless the specific case of the most acid glass has been underlined, as its higher viscosity implies longer heating times. At equilibrium state, SnO₂ solubility depends on the temperature (Arrhenius law) and on the glass basicity. In the 1200 °C–1400 °C temperature range, in these soda–lime glasses, the solubility of tin dioxide is between 1.3 and 2.1 at.% Sn and the temperature dependence of solubility exhibits a single mechanism of dissolution. Furthermore, the basicity dependence of the solubilization process is also discussed, and the presence of another oxidation state of tin (Sn^II) is thus proposed.     

Magnetite nanoparticles prepared by the crystallization of Na2O–Fe2O3–B2O3–SiO2 glasses

A glass with the composition of 35Na₂O–24Fe₂O₃–20B₂O₃–20SiO₂–1ZnO (mol%) was melted, quenched, using a twin roller technique, and subsequently heat treated in the range 485–750 °C for 1–2 h. This led to the crystallization of magnetite as the sole or the major crystalline phase.Heat treatment at lower temperatures resulted in the crystallization of magnetite crystals 7–20 nm in diameter, whereas heat treatment at higher temperatures produced higher quantities of magnetite and much larger crystals. The room temperature magnetization and coercive force values were in the range of 6–57 emu g^? 1 and 0–120 Oe, respectively for the heat treated glasses.     

Kinetic fragility of hydrous soda-lime-silica glasses

The effect of hydration on the kinetic fragility of soda-lime-silica glasses was investigated by viscometry in the glass transition range. Water-bearing glasses were prepared from industrial float glass (FG) and a ternary model glass (NCS = 16Na₂O 10CaO 74SiO₂ in mol%) by bubbling steam through the melt at 1480 °C and up to 7 bar. Additionally, a sodium borosilicate glass (NBS = 16Na₂O 10B₂O₃ 74SiO₂ in mol%) was hydrated under equal conditions. As detected by infrared spectroscopy water dissolves in the glasses exclusively as OH-groups. The hydration resulted in a total water content C_W up to ≈ 0.2 wt% for FG, NCS and NBS glasses. Kinetic fragility, expressed by the steepness index m, was determined from the temperature dependence of η at the glass transition. Viscosity data from previous studies on hydrous float glasses (C_W > 1 wt%) were surveyed together with literature data on the (H₂O)–Na₂O–CaO–SiO₂, (H₂O)–Na₂O–SiO₂ and (H₂O)–SiO₂ systems to expand the range of water concentration and bulk composition. We could demonstrate that m decreases for all glasses although water is dissolved as OH and should depolymerize the network. An empirical equation of the general type m = a ? b logC_W where a, b are fitting parameters, enables m to be predicted, for each glass series as function of the water content C_W. The enlarged data base shows that the parameter B of the Arrhenius viscosity-temperature relation decreases much stronger than the isokom temperature at the glass transition.     

Mixed alkali effect in physical and optical properties of Li2O–Na2O–WO3–B2O3 glasses

Glasses with composition xLi₂O-(30 ? x)Na₂O–10WO₃–60B₂O₃ (where x = 0, 5, 10, 15, 20, 25 and 30 mol%) have been prepared using the melt quenching technique. In the present work, the mixed alkali effect (MAE) has been investigated in the above glass system through density and modulated DSC studies. The density and glass transition temperature of the present gasses varies non-linearly, the exhibiting the mixed alkali effect. From the optical absorption studies, the values of direct optical band gap, indirect optical band gap energy (E_o) and Urbach energy(ΔE) have been evaluated. The values of E_o and ΔE vary non-linearly with composition parameter, showing the mixed alkali effect. The electronic polarizability of oxide ions, optical basicity and the Yamashita–Kurosawa's interaction parameter have been examined to check the correlation among them and bond character. Based on good correlation among electronic polarizability of oxide ions, optical basicity and the Yamashita–Kurosawa's interaction parameter, the present Li₂O–Na₂O–WO₃–B₂O₃ glasses were classified as normal ionic (basic) oxides.     

Performance investigation of Li2O–Al2O3–4SiO2 based glass–ceramics with B2O3, Na3AlF6 and Na2O fluxes

Influence of single fluxes (10 wt.% B₂O₃), bi-component fluxes (4 wt.% B₂O₃ + 6 wt.% Na₃AlF₆), and complex fluxes (4 wt.% B₂O₃ + 4 wt.% Na₃AlF₆ + 2 wt.% Na₂O) on the thermal kinetic parameters, microstructure, flexural strength and coefficient of thermal expansion (CTE) of Li₂O–Al₂O₃–4SiO₂ (LAS) glass–ceramics was investigated through differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscope (SEM). The results showed that complex fluxes could efficiently decrease transition temperature (T_g) and crystallization temperature (T_p), and accelerate the formation of needle-like β-spodumene crystals which benefit high flexural strength. The homogeneous LAS glass–ceramic (sample C₃) which has a high strength of 132.4 MPa and low CTE (100–650 °C) of 2.74 × 10^? 6/°C is obtained by doping of the initial LAS glass by complex fluxes of 4 wt.% B₂O₃, 4 wt.% Na₃AlF₆, and 2 wt.% Na₂O, nucleating at 630 °C/120 min and then crystallized at 780 °C/120 min. It is worthy of further investigation as a bonder of diamond composite material due to its outstanding prosperities.     

Synthesis of magnesium borates using sodium borate and magnesium sulfate

Synthesis conditions of magnesium borate compounds in aqueous medium using Na₂B₄O₇ · 10H₂O and MgSO₄ · 7H₂O were determined. The effects of B/Mg mole ratio, pH, reaction time and precipitation temperature on the reaction performed at 90 °C were examined. 0.04Na₂O · MgO · 1.23B₂O₃ · 3.42H₂O and 0.06Na₂O · MgO · 1.65B₂O₃ · 3.34H₂O were synthesized at optimum B/Mg mole ratios of 3.60 and 4.80 by precipitation at 5 °C and the amorphous compounds formed were identified by B, Mg, Na and XRD analyses and some physical tests.     

Electrical properties of SrBi2(Nb0.7V0.3)2O9−δ in the SrO–Bi2O3–0.7Nb2O5–0.3V2O5–Li2B4O7 glass system

Glasses in the system (100 − x)Li₂B₄O₇–x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (where x = 10, 30 and 50, in molar ratio) were fabricated via melt quenching technique. The compositional dependence of the glass transition (T_g) and crystallization (T_cr) temperatures was determined by differential thermal analysis. The as-quenched glasses on heat-treatment at 783 K for 6 h yielded monophasic crystalline strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) in lithium borate (Li₂B₄O₇ (LBO)) glass matrix. The formation of nanocrystalline layered perovskite SBVN phase was preceded by the fluorite phase as established by both the X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The dielectric constants for both the as-quenched glass and glass–nanocrystal composite increased with increasing temperature in the 300–873 K range, exhibiting a maximum in the vicinity of the crystallization temperature of the host glass matrix. The electrical behavior of the glasses and glass–nanocrystal composites was characterized using impedance spectroscopy.     

In2O3 and tin-doped In2O3 nanocrystals prepared by glass crystallization

Glasses in the system Na₂O/B₂O₃/Al₂O₃/In₂O₃/(SnO₂) were melted and subsequently tempered in the range from 540 to 700 °C. This led to the crystallization of In₂O₃, besides also NaBO₂ and Na₂Al₂B₂O₇ were formed. The crystallite sizes were in the range from 12 to 34 nm, depending on the temperature of thermal treatment, as calculated from XRD-line broadening. Crystal sizes determined by TEM were in the same range. Particle size histograms show a narrow crystal size distribution. After crystallization, the glass matrices and the non indium-containing crystalline phases were dissolved in diluted acetic acid. Spectra of the obtained suspensions containing tin-doped In₂O₃ nanocrystals exhibited a sharp UV-cut off, high transmission in the visible range and strongly decreasing transmission at wavelengths >1000 nm.     

BaO–B2O3–SiO2–Al2O3 sealing glass for intermediate temperature solid oxide fuel cell

Glasses in the formulation close to BaSiO₃–BaB₂O₄ eutectic compound are developed for sealing of intermediate-temperature (500–650 °C) solid oxide fuel cell (IT-SOFC). Thermal and microstructural analyses of the glasses with 0–10 mol% Al₂O₃ are also conducted. Detailed crystallization kinetics and interfacial stability of the glass in contact with yttria-stabilized zirconia (YSZ) and samaria-doped ceria (SDC) are investigated and compared. The results show that the formulation, 47BaO–21B₂O₃–27SiO₂–5Al₂O₃ (G1A5), performs the best on glass forming ability (GFA) among all tested formulations, and shows matched thermal expansion and working temperature to CeO₂-based electrolytes of IT-SOFC. Two major crystalline phases that precipitate from G1A5 above 750 °C are platy hexacelsian and BaSiO₃ grains.     

Synthesis and characterization of a multicomponent Fe-based bulk amorphous alloy

A new bulk metallic glass (BMG) Fe₆₀B₁₅Zr₁₀Co₇Mo_5.5Y₂Si_0.5 was synthesized by Cu mold casting. The alloy was characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) techniques. The thermal stability and glass-forming ability (GFA) of the alloy have been discussed by evaluating a number of thermal parameters. The maximum values of the key thermal parameters like T_rg (T_g/T_m, T_g/T_l), γ, δ and β parameters were found to be ～(0.66, 0.64), 0.407, 1.84 and 3.83, respectively. The alloy showed double stage crystallization process. The activation energies for crystallization were found to be 606.6 and 623.1 kJ/mol by Kissinger and Ozawa equations, which indicate the high thermal stability. Crystallization behavior of the alloy was explored by XRD. Mechanical properties like Vicker’s hardness, nanohardness and elastic modulus are found to be very promising.     

Continuous compositional changes of crystal and liquid during crystallization of a sodium calcium silicate glass

This paper deals with a systematic study of crystal nucleation and growth kinetics in a 14.6Na₂O–34.0CaO–51.4SiO₂ mol% glass, which is close to the CaO · SiO₂–Na₂O · SiO₂ pseudo-binary section, just left of the stoichiometric Na₂O · 2CaO · 3SiO₂ (N₁C₂S₃) compound. We show that crystallization begins with nucleation of a Na_4+2xCa_4−x[Si₆O₁₈] (0 < x < 1) solid solution that is enriched in sodium as compared with both parent glass and the N₁C₂S₃ compound; while a fully crystallized sample is composed only by a solid solution that is stable at very high temperatures, but is metastable in the temperatures under investigation. We thus confirm a continuous compositional change of the crystals during the course of crystallization.     

Soda lime zirconia silicate glasses as prospective hosts for zirconia-containing radioactive wastes

Na₂O–CaO–ZrO₂–SiO₂ glass compositions with ZrO₂ contents of up to 20 mol% were melted. Up to 12.3 mol% ZrO₂ could be dissolved into the glasses. Melting temperatures ⩾1450 °C were required to remove seed and produce a melt that could be cast. Addition of ZrO₂ caused an increase in the glass transition and crystallization temperatures. Glasses crystallized at temperatures ⩾1050 °C with Keldyshite and Parakeldyshite (Na₂O · ZrO₂ · 2SiO₂) as the crystalline phases. Addition of up to 4.6 mol% ZrO₂ caused an increase in the hydrolytic resistance of the glass, with further additions having little effect. The suitability of these glasses as hosts for ZrO₂-containing radioactive wastes is discussed.     

Roughness of glass surfaces formed by sub-critical crack growth

This paper presents a study on the roughness of glass fracture surfaces formed as a consequence of sub-critical crack growth. Double-cantilever-beam specimens were used in these studies to form fracture surfaces with areas under well-defined crack velocities and stress intensity factors. Roughness depends on crack velocity: the slower the velocity, the rougher the surface. Ranging from approximately 1 × 10⁻¹⁰ m/s to approximately 10 m/s, the velocities were typical of those responsible for the formation of fracture mirrors in glass. Roughness measurements were made using atomic force microscopy on two glass compositions: silica glass and soda lime silica glass. For silica glass, the RMS roughness, R_q, decreased from about 0.5 nm at a velocity of 1 × 10⁻¹⁰ m/s to about 0.35 nm at a velocity of 10 m/s. For soda lime silica glass, the roughness decreased from about 2 nm to about 0.7 nm in a highly non-linear fashion over the same velocity range. We attributed the roughness and the change in roughness to microscopic stresses associated with nanometer scale compositional and structural variations within the glass microstructure. A theory developed to explain these results is in agreement with the data collected in the current paper. The RMS roughness of glass also depends on the area used to measure the roughness. As noted in other studies, fracture surfaces in glass exhibit a self-affine behavior. Over the velocities studied, the roughness exponent, ζ, was approximately 0.3 for silica glass and varied from 0.18 to 0.28 for soda lime silica glass. The area used for these measurements ranged from (0.5 μm)² to (5.0 μm)². These values of the roughness exponent are consistent with values obtained when the scale of the measurement tool exceeds a critical size, as reported earlier in the literature.     

The effect of TiO2 on phase separation and crystallization of glass-ceramics in CaO–MgO–Al2O3–SiO2–Na2O system

The experiments were carried out on studying the effect of phase separation on nucleation and crystallization in the glass based on the system of CaO–MgO–Al₂O₃–SiO₂–Na₂O. In the experiments, TiO₂ was chosen as nucleating agent. Three batches of 5, 8 and 10 wt% TiO₂ substitution were investigated by the techniques of DSC, XRD, FTIR and FESEM equipped with EDS. XRD and FTIR analysis indicated that the super cooled glasses were all amorphous, the heat treatment leading to nucleation would cause a disruption of silica network which followed phase separation. The phase separation followed the generation of crystal seeds Mg(Ti, Al)₂O₆. FESEM observation and EDS analysis revealed that the more TiO₂ content of glass, the more droplet separated phase and crystal seeds after nucleation heat treatment. The main crystal phase is clinopyroxene, Ca(Ti, Mg, Al)(Al, Si)O₆, of crystallized glass.     

Preparation of TiO2–Na2O glass by sol–gel method and structural characterization

The applicability of sol–gel process in glass formation of binary system, (100 − x)TiO₂–xNa₂O (x = 10, 20, 30), was investigated and the glasses were prepared successfully by the sol–gel process for the first time. The process of glass formation was checked by using X-ray diffraction measurement and DTA–TG analysis. In the baking step, a DTA peak related to the crystallization of gel was found. The short-range structure of glassified samples was studied by neutron scattering measurement. It is found from the results of neutron scattering measurement that the coordination number of O atom around Ti atom is about 4, and the O atoms around Ti atom form a planer square rather than a regular tetrahedron.     

Multicomponent phosphate invert glasses with improved processing

Owing to their structure of small phosphate units, phosphate invert glasses have high crystallisation tendencies, which make processing of the melt challenging. The aim was to improve their processing by (1) increasing the number of glass components and (2) incorporating intermediate oxides (TiO₂, MgO and ZnO). Glasses (P₂O₅–CaO–MgO–Na₂O) were produced by a melt-quench route. In series 1, TiO₂ was partially substituted for Na₂O, and the number of components was increased by partially substituting strontium for calcium, zinc for magnesium and potassium for sodium on a molar base. In series 2, the MgO + ZnO content in the multicomponent glass was varied between 0 and 20 mol% in exchange for CaO + SrO. Differential scanning calorimetry showed a significant increase of the processing window in the multicomponent glasses, explained by an increased energy barrier for crystallisation owing to increased entropy of mixing. The MgO + ZnO content also significantly improved the processing window from 117 K (0 mol% MgO + ZnO) to 185 K (20 mol%), owing to their large field strength. These results show that the processing of phosphate invert glasses for biomedical applications can be improved significantly by incorporating ions such as strontium or zinc which are also known to have therapeutic effects.     

Phosphate speciation in sodium borosilicate glasses studied by nuclear magnetic resonance

The structure of RNa₂O · B₂O₃ · KSiO₂ · xP₂O₅ (0.5 < R < 2; 0.86 < K < 3) borosilicate glasses has been studied by nuclear magnetic resonance (NMR). ³¹P magic angle spinning (MAS), double quantum-magic angle spinning (DQ-MAS) and ³¹P–¹¹B transfer of populations under double resonance magic angle spinning (TRAPDOR MAS) NMR were used to determine the phosphate speciation in the glasses and their connectivity with the borosilicate network. The structure of the glass network was characterized with ¹¹B, ²⁹Si and ²³Na MAS NMR. Ab initio calculations of the ³¹P chemical shielding were carried out in order to confirm the connectivity between phosphorus and the structural units of the borosilicate glass network. Na₃PO₄ (monophosphate), Na₄P₂O₇ (diphosphate) and P–O–B species (mono- and diphosphate groups with borate units as the next nearest neighbors) are found all along the compositional range studied. The proportion of the P–O–B groups increases as the glass optical basicity decreases, while the proportions of mono- and diphosphate species decrease. The change in the glass transition temperature of the phospho-borosilicate glasses with respect to that of the borosilicate ones is discussed in terms of the structural characterization. The formation of phosphate species gives rise to the increase in T_g, which is attributed to the re-polymerization of the silicate network, while the formation of P–O–B bonds weakens the glass network and produces a decrease in the glass transition temperature.