Doping-induced formation of bulk nanocrystalline alloy from metallic glass with controllable microstructure and properties

We report the formation of bulk nanocrystalline alloys from a Pr-based bulk metallic glass-forming alloy by doping iron. The microstructure of the alloys can be tuned progressively from full glassy state to composite with nanocrystalline particles in the glassy matrix, and finally into nanostructured state accompanying with the gradual magnetic and mechanical changes. The role of the addition in the control of microstructure and magnetic property, the mechanism for the nanocrystalline formation induced by addition, and the relation between the microstructure and properties are discussed.     

The structure and optical properties of GeO2-GeS2 glasses

Oxy-chalcogenide glasses with compositions of xGeO₂-(100 − x)GeS₂, where 0 ? x ? 100 mol%, have been prepared and studied in terms of their structures and optical properties. X-ray fluorescence spectroscopy shows that Ge:S ratio can deviate from GeS₂ by ∼10 at.%, depending critically upon the preparation conditions. Raman scattering spectroscopy suggests that stoichiometric GeO₂-GeS₂ glasses have a heterogeneous structure in the scale of 1-100 nm. The optical gaps are nearly constant at 3.0-3.5 eV for glasses with 0 ? x ? 80 mol% and abruptly increase to ∼6 eV in GeO₂. This dependence suggests that the optical gap is governed by GeS₂ clusters, which are isolated and/or percolated. Composition-deviated glasses appear as orange and brown, and these glasses seem to have more inhomogeneous structures.     

Influence of structural relaxation on atomic mobility in a Zr41.2Ti13.8Cu125Ni10.0Be22.5 (Vit1) bulk metallic glass

The effect of an annealing at a temperature above or below the glass transition temperature in a Zr_41.2Ti_13.8Cu₁₂₅Ni_10.0Be_22.5 bulk metallic glass was investigated using dynamic mechanical analysis. Structural relaxation influences both the storage modulus (elastic component) and the loss modulus (viscoelastic component). Kinetics can be captured by a stretched exponential relaxation function. Experimental results are correctly described using a physical model based on the concept of defects for the mechanical response of amorphous materials and especially for the characteristic time relative to atomic mobility.     

Thermal and some physical properties of glasses in the La2O3−CaO−B2O3 ternary system

Glasses in the La₂O₃−CaO−B₂O₃ ternary system were studied. The glass forming range as determined by the appearance of the annealed cast was found to match previously published findings. Clear glasses were formed in the composition range of 5.7−19.1 mol% La₂O₃ with constant B₂O₃ content of 71.4 mol%, and in glasses of constant La₂O₃:CaO ratio of 1:4 with B₂O₃ content in the range of 71.4-55.0 mol%. The non-linear optical crystalline phase La₂Ca₂B₁₀O₁₉ was crystallized from the clear glasses after heat treatments, as determined by powder XRD. Two types of the LaBO₃ crystalline phases were detected in the partially and the fully crystallized glass compositions outside the glass forming range. Data are reported for the glass transition temperature (T_g), dilatometric softening point (T_d), linear coefficient of expansion (α), onset crystallization temperature (T_x), exothermal peak temperature (T_P), density (ρ) and index of refraction (n_D) in the clear glasses.     

Structure and properties of Ni60(Nb100−xTax)34Sn6 bulk metallic glass alloys

Refractory bulk metallic glasses and bulk metallic glass composites are formed in quaternary Ni-Nb-Ta-Sn alloy system. Alloys of composition Ni₆₀(Nb_100−xTa_x)₃₄Sn₆ (x = 20, 40, 60, 80) alloys were prepared by injection-casting the molten alloys into copper molds. Glassy alloys are formed in the thickness of half mm strips. With thicker strips (e.g., 1 mm), Nb₂O₅ and Ni₃Sn phases and the amorphous phase form an in situ composite. Glass transition temperatures, crystallization temperatures, and ΔT_x, defined as T_x1 − T_g (T_x1: first crystallization temperature, T_g: glass transition temperature) of the alloys increase dramatically with increasing Ta contents. These refractory bulk amorphous alloys exhibit high Young’s modulus (155-170 GPa), shear modulus (56-63 GPa), and estimated yield strength (3-3.6 GPa).     

Properties characterization of the Cu68.5Ni12P19.5 alloy at elevated temperatures

The Cu_68.5Ni₁₂P_19.5 alloy was cast into the ribbons using melt spinning (23 m/s). The amorphous ribbon in the as-cast state was investigated by differential thermal analysis (DTA), dynamic mechanical analysis (DMA), resistivity measurements and X-ray diffraction ‘in situ’ at different temperatures. The work presents attempts to find correlation between the changes of the mechanical properties presented by DMA cycles and during the other tests. The measurements of the relative resistivity R/R₀ versus temperature for repeated heating and cooling cycles to different temperatures show changes of the temperature coefficient of resistivity (TCR) indicating reversible and irreversible transformations in the studied alloy.     

Crystallization behavior of Zr41Ti14Cu12.5Ni10Be22.5 bulk metallic glass under the action of high-density pulsing current

The crystallization behavior of Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass (Vit1 BMG) under the action of high-density pulsing current (HDPC) have been studied experimentally. It has been found that high-density pulsing current can directly induce the rapid nanocrystallization of Vit1 BMG. The multiple crystallization processes of Vit1 BMG induced by HDPC have been confirmed as Amorphous → Amorphous + i-phase → Be₂Zr + Zr₂Cu + Ni₇Zr₂ + FCC phase + other phases → Zr₂Cu + Ni₇Zr₂ + FCC phase + other phases. By comparing to the crystallization behavior of Vit1 BMG induced by isothermal annealing, the crystallization temperature is reduced and crystallizing process is significantly shortened, while the sequence of crystallization process in both cases is basically same. The present results show that the HDPC has significantly influenced the crystallizing kinetics of Vit1 BMG due to that it can greatly promote the movement and rearrangement of atoms, which will result in a rapid nanocrystallization. It suggests that HDPC treatment can be an effective way to induce the rapid nanocrystallization of BMGs.     

A glass with high crack initiation load: Role of fictive temperature-independent mechanical properties

The crack initiation load of a series of calcium aluminosilicate glasses and selected commercial glasses were evaluated using Vickers indentation. The results showed that a calcium aluminosilicate glass containing 80 mol% SiO₂, 10 mol% Al₂O₃ and 10 mol% CaO exhibited a high crack initiation load comparable to that of the less-brittle glass (LB glass) developed by Asahi Glass Co., Ltd. It has previously been determined that glasses experience a fictive temperature increase by indentation. The indented region of a glass, therefore, acquires, in general, different mechanical properties, such as hardness and elastic moduli, from the original, unindented glass. The extent of these mechanical property changes depends upon the glass composition and a certain glass composition with fictive temperature-independent mechanical properties can have the deformed region with matching mechanical properties to those of the undeformed region of the glass. It was found that the calcium aluminosilicate glass having no fictive temperature dependence on elastic moduli gave the highest crack initiation load. However, this composition did not coincide with fictive temperature-independence of hardness or density.     

Potentiodynamic polarization studies on amorphous Zr46.75Ti8.25Cu7.5Ni10Be27.5, Zr65Cu17.5Ni10Al7.5, Zr67Ni33 and Ti60Ni40 in aqueous HNO3 solutions

Potentiodynamic polarization studies were carried out on virgin specimens of Zr-based bulk amorphous alloys Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 and Zr₆₅Cu_17.5Ni₁₀Al_7.5, and conventional-type binary amorphous alloys Zr₆₇Ni₃₃ and Ti₆₀Ni₄₀ in solutions of 0.2 M, 0.5 M and 1.0 M HNO₃ at room temperature. The values of the corrosion current density (I_corr) for the bulk amorphous alloy Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 were found to be comparable with those of Zr₆₅Cu_17.5Ni₁₀Al_7.5 in 0.2 M and 0.5 M HNO₃, but the value of I_corr for the former was almost three times more than that of the latter in 1.0 M HNO₃. In the case of conventional binary amorphous alloys, Ti₆₀Ni₄₀ showed lower value of I_corr as compared to Zr₆₇Ni₃₃ in 0.5 M and 1.0 M HNO₃ and a comparable value of I_corr in 0.2 M HNO₃. In general, the binary Ti₆₀Ni₄₀ displayed the best corrosion resistance among all the alloys in all the cases and the corrosion current density (I_corr) for all the alloys was found to increase with the increasing concentration of nitric acid. It is noticed that the bulk amorphous alloys do not possess superior corrosion resistance as compared to conventional binary amorphous alloys in aqueous HNO₃ solutions. The observed differences in their corrosion behavior are attributed to different alloy constituents and composition of the alloys investigated.     

Effect of ZnO and Bi2O3 addition on linear and non-linear optical properties of tellurite glasses

Glasses in the system TeO₂-Bi₂O₃-ZnO were studied with respect to their linear refractive indices and optical absorption in the UV-vis range. The third order non-linear refractive indices were measured using degenerated four wave mixing (DFWM). The optical Kerr susceptibilities calculated hereof were in the range from 5.49 to 6.58 × 10⁻¹³ esu and hence 34-41 times larger than that of fused SiO₂. They are roughly proportional to values theoretically calculated by the theory of Lines.     

Development and properties of a glass made from MSWI bottom ash

A uniform shiny black-coloured glass was obtained using bottom ash produced by a Portuguese municipal solid waste incinerator (MSWI). The bottom ash was the single batch material used in the formation of the glass, which was obtained by vitrification of the solid waste at 1400 °C for 2 h. Under these conditions, a homogeneous melt with an appropriate viscosity to be shaped was obtained, indicating the suitability of this waste material to be employed in the development of vitreous products. The characterization of the resulting glass was performed in order to assess its structural, physical, mechanical, thermal and chemical features. The glass had a density of 2.69 g cm⁻³, a hardness of 5.5 GPa, a fracture strength of 75 MPa, a thermal expansion coefficient of 9.5 × 10⁻⁶ °C⁻¹ and it exhibited a very good chemical stability. In summary, the MSWI bottom ash glass has good mechanical and chemical properties and may, therefore, be used in several applications, particularly as a construction material.     

Nanomechanical properties of commercial float glass

The float process produces flat glass with a tin-rich surface due to contact with the molten metal bath. The incorporation of tin into the glass network is expected to modify the mechanical properties of the surface and the relative durability of the two sides of the material. In this work nanoindentation was used to evaluate the elastic modulus and hardness of a 2 mm thick commercial float glass. The near-surface elastic modulus (depths < 400 nm) of both sides of the glass was elevated by up to 10%, and could not be attributed solely to the presence of tin. However, slight differences in hardness (<10%) between the air and tin sides of the float glass were observed. These results suggest that tin may alter the flow properties of the glass, but the elastic modulus changes are masked by other structural and chemical differences between the air and tin sides of the float glass.     

Elasticity, thermal expansion and compressive behavior of Mg65Cu25Tb10 bulk metallic glass

The existence of special covalently bonded short-range ordering structures in a Mg₆₅Cu₂₅Tb₁₀ bulk metallic glass (BMG) is confirmed by thermal expansion and compression behavior. Under ambient conditions the linear thermal expansion coefficient obtained is almost constant in the glassy state with a value of 4.0 × 10⁻⁵ K⁻¹. By fitting the static equation of state at room temperature under ambient conditions we find the value for bulk modulus B of 48.7 GPa, which is in excellent agreement with the experimental study by pulse-echo techniques of 44.7 GPa. Unlike many bulk metallic glasses, such as Zr- and Pd-based, which bulk modulus is much larger than 100 GPa, the value B of Mg₆₅Cu₂₅Tb₁₀ BMG falls into the range of SiO₂ and fluorozirconate glass ZBLAN. Moreover, the elastic constant of the Mg₆₅Cu₂₅Tb₁₀ BMG is almost the same as those of ZBLAN. No evidence for the high-pressure phase transitions of the Mg₆₅Cu₂₅Tb₁₀ BMG has been found up to 31.19 GPa at room temperature.     

Sulfur behavior in silicate glasses and melts: Implications for sulfate incorporation in nuclear waste glasses as a function of alkali cation and V2O5 content

The presence of sulfur in radioactive waste to be incorporated in borosilicate glasses entails difficulties mainly due to the relatively low solubility of sulfates in the vitreous phase. In this work a study is presented on the effects of the ratio R = [Na₂O]/[B₂O₃], the type of sulfate added and the addition of V₂O₅ on the incorporation of sulfates in borosilicate glasses. Glass samples were prepared at the laboratory scale (up to 50-100 g) by melting oxide and sulfate powders under air in Pt/Au crucibles. XRF and ICP/AES chemical analysis, SEM/EDS, microprobe WDS and Raman spectroscopy were employed to characterize the fabricated samples. The main experimental results confirm that the incorporation of sulfates in borosilicate glasses is favored by the network depolymerization, which evolves with the ratio R. The addition of V₂O₅ seems to accelerate the kinetics of sulfur incorporation in the glass and, probably, increase the sulfate solubility by modifying the borate network and fostering the formation of voids of shape and size compatible with the sulfur coordination polyhedron in the glassy network. The kinetics of X₂SO₄ incorporation in the glass seems to be slower when X = Cs.     

Solubility of glasses in the system P2O5-CaO-MgO-Na2O-TiO2: Experimental and modeling using artificial neural networks

Phosphate glasses in the system P₂O₅-CaO-MgO-Na₂O-TiO₂ for use as degradable implant materials were produced. In order to classify their solubility behavior, dissolution experiments were performed in deionized water for 60 min at 98 °C. Resulting solutions were analyzed using ICP-OES. In addition, pH measurements were carried out in physiological NaCl solution. With increasing phosphorus oxide content, the glasses showed a higher solubility and gave lower pH values in aqueous solution. This was caused by changes in the glass structure, as long phosphate chains are more susceptible to hydration than smaller phosphate groups. These changes in glass structure were followed by ³¹P MAS-NMR experiments. Increasing sodium oxide concentrations in exchange for calcium or magnesium oxide also increased the glass solubility by disrupting ionic cross links between chains. By contrast, addition of titania made the glasses more stable towards dissolution by cross linking smaller phosphate groups. The aim of this study was to find a relationship between glass composition and solubility behavior. As classical linear methods of data analysis were unsuitable due to the complexity of the relationship, preliminary artificial neural networks analyses were performed and were found to be an interesting tool for modeling the solubility behavior of phosphate glasses.     

Synthesis and mechanical properties of Zr-based bulk amorphous alloys

Design and characterization of bulk amorphous alloys has been an active area of research due to their promising thermal and mechanical properties. An alloy composition Z₆₅Cu₁₇Ni₁₀Al₈ was designed and synthesized by Cu mold casting. In the base alloy 2 at.% Gd was added to study its effect on thermal and mechanical properties. Characterization of the alloys was done by techniques of X-ray diffraction (XRD), differential scanning calorimetry (DSC) and field emission scanning electron microscopy (FESEM). Many thermal parameters were evaluated to investigate the thermal stability and glass-forming ability of the alloys. In addition, the mechanical properties like nanohardness, elastic modulus and elastic recovery were measured. Thermal properties and activation energy reduced while mechanical properties like nanohardness, elastic modulus and percentage elastic recovery (% R) increased with Gd addition.     

The structure of GeO2-SiO2 glasses and melts: A Raman spectroscopy study

We have investigated a series of glasses and melts along the GeO₂-SiO₂ join using insitu Raman spectroscopy. The results for both the glasses and melts are consistent with a continuous random network in which there are ‘regions’ that are SiO₂-like, GeO₂-like and mixed GeO₂-SiO₂-like. Incorporation of GeO₂ into the SiO₂ network is initially accommodated via the 3- and 4-membered SiO₄ rings which are lost as they convert to larger mixed Ge/Si rings. The LO-TO mode behavior is also consistent with a network that is composed of different ‘regions’ and is similar to that expected from the Bruggeman effective media model. At the highest temperatures there are indications that the mixed Ge/Si rings convert back to small 3-membered GeO₄ rings and large SiO₄ rings; the small 3- and 4-membered SiO₄ rings are not reformed.     

Remark on the optical gap in ZnO-Bi2O3-TeO2 glasses

Four ZnO-Bi₂O₃-TeO₂ glasses were prepared from high purity (4N5) oxides. From measurements of the optical transmission on very thin bulk samples the optical gap was determined at around 3.55 eV for the glasses studied. The temperature dependence of the optical gap was also determined from the room temperature close up to 500 K. Preliminary Raman scattering measurements indicate that with a decrease in TeO₂ content, TeO₄ trigonal bipyramid transformation proceeds into TeO₃ trigonal pyramids.     

Kinetic analysis of the isochronal crystallization of Ti40Zr25Ni8Cu9Be18 metallic glass

The isochronal crystallization kinetics of the Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ metallic glass has been investigated by differential scanning calorimetry (DSC). Results indicate that the two crystallization events of this metallic glass cannot be well-described by the classic Johnson-Mehl-Avrami (JMA) kinetic equation. The kinetic equation considering the impingement effect has been found more applicable for describing the isochronal crystallization kinetics of this amorphous alloy. Accurate values of kinetic parameters were determined by fitting the theoretical DSC data to experimental curves. The kinetic parameters change in different crystallization stages and show strong heating rate dependence. Reasons of the deviation from the JMA kinetics for the isochronal crystallization of Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ metallic glass were discussed.