Effects of Sn addition on the glass forming ability and crystallization behavior in Ni-Zr-Ti-Si alloys

The effect of Sn substitution for Si on the glass forming ability (GFA) and crystallization behavior has been studied in Ni₅₉Zr₂₀Ti₁₆Si_5 − xSn_x (x=0, 3, 5) alloys. A bulk amorphous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy with diameter up to 3 mm can be fabricated by injection casting. Partial substitution of Si by Sn in Ni₅₉Zr₂₀Ti₆Si_5 − xSn_x alloys improves the glass forming ability. The improved GFA of the Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy is can be explained based on the lowering of liquidus temperature. The crystallization sequence becomes completely different with addition of Sn. The amorphous Ni₅₉Zr₂₀Ti₁₆Si₅ alloy crystallizes via precipitation of only a cubic NiTi phase in the first crystallization step, whereas the amorphous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy crystallizes via simultaneous precipitation of orthorhombic Ni₁₀(Zr,Ti)₇ and cubic NiTi phases. Addition of Sn in the Ni₅₉Zr₂₀Ti₁₆Si₅ alloy suppresses the formation of the primary cubic NiTi phase. The bulk amorphous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy exhibits high compressive fracture strength of about 2.7 GPa with a plastic strain of about 2%.     

Particle size influence on crystallization behavior of Ge2Sb2Se5 glass

Differential scanning calorimetry was used to study crystallization in the Ge₂Sb₂Se₅ glass under non-isothermal conditions. The crystallization kinetics was described in terms of autocatalytic ?esták–Berggren model. An extensive discussion of all aspects of a full-scale kinetic study for a crystallization process was performed. Number of suggestions regarding the experimental part and importance of the particle size influence study was introduced in order to maximize precision, reproducibility and predicative potential of the experimental data. Complexity of the crystallization process was identified to be represented by closely overlapping consecutive competing surface and bulk mechanisms. Mutual interactions of both mechanisms as well as all other observed effects were discussed in relation to the ability of nowadays theoretical models to accurately and correctly describe the experimental data. Advanced error analysis was performed for each step of the kinetic study.     

Influence of UV-exposure on the crystallization and optical properties of photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a photosensitive multi-component silicate glass. Photoinduced crystalline phase precipitation results in refractive index variations in UV exposed areas of PTR glass. The precipitation of silver containing particles which occurs during photo-thermo-refractive process increases the optical absorption of the samples in the range 350 nm to NIR wavelengths and the growth of sodium fluoride crystals and their aggregation increases light scattering in visible and NIR regions. We show that one effect of the UV-exposure is a decrease in the crystallization temperature by ～50 °C compared to the unexposed areas as measured by differential scanning calorimetry, which we attribute to an increase in nucleation rate. Using spectro-photometric measurements, a linear function is fitted to the changes in the amplitude of the absorption band of the silver containing particles versus the UV-dosage. The root mean square scatter of the data from the linear function is better than 0.99 and the slope of the function is 0.32 ± 0.01 cm/J. The IR absorption of PTR sample, measured by laser calorimetry shows that the increase of the absorption in infrared region at 1.1 μm, is due to the tail of the absorption band of silver containing particles having maximum at 465 nm. We finally show that after hyper-development, one effect of UV-exposure at 325 nm on the crystallization kinetics of PTR glasses is a decrease in particle sizes from micron size to nanometers size. But additional investigations demonstrate that smaller dosage UV-exposures (a few tens of milliwatts) increase the optical scattering by one order of magnitude. Optical micrographs taken after UV-exposure and hyper-development reveal the use of smaller dosages enhances nucleation rate without preventing the growth of large crystals and therefore induces higher scattering.     

Effect of Ti addition on the crystallization behavior and glass-forming ability of Zr-Al-Cu alloys

The crystallization behavior of melt-spun (Zr₆₅Al_7.5Cu_27.5)_100−xTi_x (x = 0-15; in at.%) metallic glasses has been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The DSC traces showed an altered crystallization mode in the vicinity of 3 at.% Ti addition. A metastable icosahedral quasicrystal precipitated at the first crystallization stage of the Ti-bearing metallic glasses, which subsequently transformed to the stable Zr₂Cu-type phase in the followed exothermic reaction. The glass-forming abilities (GFAs) of these metallic glasses were assessed by the recognized GFA indicators T_rg, ΔT_x and γ. BMGs were easily made in the compositions containing 3-7 at.% Ti by means of copper mold casting. The validity of these parameters was clarified using the critical BMG forming diameter evidence.     

Influences of chemical aging on the surface morphology and crystallization behavior of basaltic glass fibers

The impact of aging in high humidity and water on the surface morphology and crystallization behavior of basaltic glass fibers has been studied using scanning electron microscopy, transmission electron microscopy, calorimetry and X-ray diffraction. The results show that interaction between the fibers and the surrounding media (high humidity or water at 70 °C) leads to chemical changes strongly affecting the surface morphology. The crystallization peak temperature of the basaltic glass fibers are increased without changing the onset temperature, this may be caused by a chemical depletion of network modifying elements.     

Influence of europium ions on structure and crystallization properties of bismuth borate glasses and glass ceramics

Glasses of the xEu₂O₃ · (100?x)[2Bi₂O₃ · B₂O₃] system with 0 ? x ? 25 mol% have been characterized by X-ray diffraction and FTIR spectroscopy measurements. Melting at 1100 °C and the rapid cooling at room temperature permitted us to obtain glass samples. In order to improve the local order and to develop crystalline phases, the glass samples were kept at 625 °C for 24 h. After heat treatment two crystalline phases were put into evidence. One of the crystalline phases was observed for the host glass matrix, the x = 0 mol% sample, and belongs to the cubic system. The second one was observed for the x = 25 mol% sample and was find to be orthorhombic with two unit cell parameters very close to each other. For the samples with 0 < x < 25 mol% there is a mixture of the two mentioned phases. FTIR spectroscopy data suggest that both Bi₂O₃ and B₂O₃ play the glass network former role while the europium ions play the network modifier role in the studied glasses.     

Effect of crystallization behavior on the oxidation resistance of a Zr–Al–Cu metallic glass below the crystallization temperature

The crystallization behavior of Zr_65.0Al_7.5Cu_27.5 (at.%) metallic glass with 753 and 1053 K annealing treatment and its effect on oxidation resistance around the supercooled liquid region at 623 and 663 K was studied. The crystalline phase of bct-Zr₂Cu precipitates for the specimen annealed at 753 K was observed, while duplex structures of bct-Zr₂Cu and Zr₂Al formed in the specimen annealed at 1053 K. The oxidation resistance of the specimen depended on the amount of crystalline precipitates. Regardless of the exposure temperature, the annealed specimens showed higher oxidation resistance than the melt-spun one, especially for the specimen annealed at 1053 K. The formation of numerous crystalline phases of bct-Zr₂Cu and Zr₂Al from the matrix was responsible for improving the oxidation resistance due to their higher oxidation resistance and promotion of the development of Al₂O₃ and oxides of copper. The oxide constituents of the amorphous alloy after long exposure depended on the temperature. The oxide was composed of a large amount of CuO, some tetragonal and monoclinic-ZrO₂ and a minor amount of Cu₂O as well as a slight amount of Al₂O₃ for the melt-spun specimen during exposure at 623 K. Under the 663 K exposure, however, the oxide state of Cu³⁺ in the scale was also detected.     

Three-dimensionally nanostructured alumina film on glass substrate: Anodization of glass surface

We report fabrication of a three-dimensionally nanostructured porous alumina film on a glass substrate exhibiting an angle-insensitive optical transmission property using a robust anodization with ‘fictive critical anodizing-voltage’ estimation technique. The fictive critical anodizing-voltage is estimated from a resistance profile curvature; it offers a limit of a maximum cell size of an anodization system. Using this technique, we have obtained an extra-large cell (over 1 μm) and thick (～2.5 μm) alumina film. Observation of a fine structure on the current density profile at the initial anodizing stage is also presented with resistance profiling, cross-sectional scanning and transmission electron microscopies.     

Growth of LaBGeO5 crystal fibers by the micro‐pulling down technique

The LaBGeO₅ compound (LBGO) was prepared by solid state reaction at 1050°C and characterized by XRD and DTA analysis. The direct growth of LBGO fibers from the melt using micro‐pulling down technique was unsuccessful because of its high viscosity. The study of the LBGO‐LiF phase diagram showed that LiF could be considered as a convenient flux to reduce viscosity of the melt during the growth process. Several crystal fibers were then grown and characterized by Raman spectroscopy. To decrease the high volatility of LiF, B₂O₃ was added to the melt. A white cloudy fiber was obtained from LiF‐B₂O₃ flux and checked by Raman spectroscopy and scanning electron microscopy.     

Re-examination of effects of nucleation temperature and time on glass crystallization

The effects of nucleation temperature and time on the kinetics of non-isothermal glass crystallization have been re-examined to demonstrate the limitations of some approximate solutions used to extract kinetic parameters from differential thermal analysis (DTA) experiments. Those features were analyzed by numerical solutions of equations describing the dependence of fraction crystallized on the rates of nucleation and growth, and the corresponding transient time, reported for lithium disilicate. It was shown that the temperature of maximum nucleation rate varies on changing the nucleation time. Some guidelines were established to assist the selection of suitable conditions to perform crystallization studies by DTA, and to extract the values of activation energy and dimensionality of growth from the dependences of crystallization peak temperature on heating rate, and nucleation time. The main limitations of these methods were identified and discussed.     

Effects of phase separation on crystallization behavior

The effects of phase separation on the kinetics of crystal growth have been investigated for three compositions in the Na₂OSiO₂ system, containing about 1.5, 10 and 15 mol% Na₂O. In the two cases for which reliable data could be obtained over the full range of temperature (10 and 15% Na₂O), the measured growth rates are independent of time, for crystallization temperatures within as well as outside the miscibility gap. In both cases, the growth rate versus temperature relations are continuous through the region of the immiscible boundary. These results are related to previous data on the effects of phase separation on viscosity in the Na₂OSiO₂ system and on nucleation and crystallization in the Li₂OSiO₂ system. It is suggested that transport at the crystal-liquid interface in a phase-separating system involves different types of atomic rearrangements than those involved in viscous flow.     

Phase-field modeling of glass crystallization: Change of the transport properties and crystallization kinetic

In this work we present many-particle phase-field simulations of primary crystallization with a diffusion coefficient dependent on the local composition of the untransformed matrix. The results show that the experimental kinetics observed in primary crystallization of many metallic systems cannot be described by the soft-impingement effect but to the change of the transport properties of the matrix as the transformation proceeds.     

Behavior of water in glass during crystallization

The presence of water in glass has a large influence on the rate of crystallization. Furthermore, water can diffuse into or out of a glass during the heat-treatment for crystallization and influence the crystallization behavior of the glass surface. Water diffusion in a lithium alumino-silicate (LAS) glass and the corresponding LAS based transparent glass-ceramic was investigated using IR spectroscopy. IR spectra of water-related species changed drastically during crystallization, from an exclusively hydroxyl peak to a peak possibly containing molecular water. Both water solubility and diffusion coefficient were lower in the glass-ceramic than in the glass. These results were attributed to the expulsion of water from the crystalline phase and segregation into the remaining glassy phase, resulting in a high water concentration in the glassy phase.     

Kinetics of relaxation and crystallization of sodium metaphosphate glass

Kinetics of structural relaxation and crystallization of NaPO₃ glassforming melt is studied by means of thermal analyses. It is demonstrated that activation energy depends strongly on fictive temperature T_f. The dependence of the onset temperature T_o of the glass transition interval on the heating rate q⁺ is investigated for samples that were previously cooled down at a rate q⁻ of about 850 K/min. The dimensionless fragility F is a measure of the dependence of the activation energy for spatial rearrangement on the changes of structure. According to the present results F is large for NaPO₃ (i.e. phosphates are ‘fragile’ substances).     

Creep characterization of alumina particulate reinforced alumino-silicate glass

Compressive creep studies on alumino-silicate glass reinforced with alumina powders of 0.2 μm particle size as a function of volume fraction showed that there was a significant increase in the creep resistance by about an order of magnitude in the 20 vol.% composite. In order to study the effect of particle size on creep resistance, composites reinforced with 20 vol.% of 1.2 and 6.5 μm alumina particle size were also characterized. It was found that the composite with 1.2 μm particle sized reinforcement gave the highest creep resistance. All the composites exhibited Newtonian viscous creep and showed no strain hardening even at strains up to 10%.     

The effect of addition of 5 at% sulphur or tellurium to selenium on its electrical properties and on its rate of crystallization

The characteristic properties of selenium: density d, logarithm of electrical conductivity logσ, and the activation energy ΔE_g with addition of 5 at% sulphur and tellurium was measured for the glassy state and for the crystalline state. The process of transition of the amorphous into crystalline selenium was followed by measuring these quantities for all intermediate stages. Both S and Te decrease the rate of crystallization of selenium. In the crystalline state, the presence of S and Te increases the energy of activation of the conductivity process.     

Simulated effects of transient nucleation on the crystallization of glass samples

The kinetics of crystallization have been re-examined by taking into account the transient nucleation time and numerical methods were used to obtain the dependence of fraction crystallized on temperature, heating rate and nucleation conditions (temperature and time). These solutions were used to analyze the applicability of approximate models which were based on the assumption of steady state nucleation. The transient nucleation time, which precedes nucleation in as quenched samples, was taken into account to re-examine the deviations expected for relatively short nucleation time, and/or for cases when the actual nucleation temperature is displaced from the corresponding nucleation peak. Additional solutions were computed to obtain the dependence of crystallization peak temperature on the nucleation temperature. It was found that the crystallization peak temperature reaches its lowest value after nucleation at a temperature which can be significantly higher than the peak temperature of steady state nucleation.     

Influence of high temperature deformation on the fracture behavior of a bulk Zr-based metallic glass

Nanocrystalline/amorphous matrix composites obtained by isothermal compression at high temperatures and low strain rates were characterized using transmission electron microscopy. To study the influence of high temperature deformation on the fracture behavior and room temperature plasticity, compression tests with a constant strain rate of 1 × 10⁻⁴ s⁻¹ were applied to the deformed samples. Fracture features of as-cast alloy and deformed samples were analyzed using scanning electron microscopy. Compared with the as-cast alloy, the room temperature plasticity of deformed sample is not destroyed both in the range of 370-395 °C at 1 × 10⁻³ s⁻¹ and at 395 °C in 1 × 10⁻² to 1 × 10⁻³ s⁻¹, and deteriorated at higher temperatures and lower strain rates. Corresponding to the TEM images, the homogenously dispersed nanocrystals with small size contribute to the compressive plasticity, and the aggregated large nanoparticles destroy the plasticity of the sample after high temperature deformation.