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.     

Performance and durability of octadecyltrichlorosilane coated borosilicate glass

While a coating may alter the surface properties and the performance of a material, it is unclear if these thin barrier layers can effectively inhibit environmentally-assisted cracking processes. In this research a nanoscale, hydrophobic film of octadecyltrichlorosilane was applied to bulk borosilicate glass rods. The resistance of the coated and uncoated rods to environmentally-assisted cracking was then evaluated in a room temperature, deionized water environment. While the coating procedure did not damage the glass surface or affect the probability of completing a successful test, it did not provide protection the glass samples against environmentally-assisted cracking. Analytical models based on linear elastic fracture mechanics suggest that the coating thickness must be on the order of the crack mouth opening displacement for the barrier layer to be effective. This finding suggests that nanoscale barrier coatings are best suited for micron and nanometer-scale substrates when superior structural performance is required.     

Degradation of nickel (86 MeV) ion irradiated polystyrene

Samples of polystyrene films were irradiated under vacuum at room temperature with ⁵⁸Ni⁷⁺ (86 MeV) ion with fluences ranging from 1 × 10¹¹ to 1 × 10¹³ ions cm⁻². Ion induced structural modifications were studied by means of atomic force microscopy atomic force microscopy (AFM), X-ray diffraction (XRD), UV-visible absorption spectroscopy (UV-Vis) and Fourier transform infrared spectroscopy (FTIR) techniques. Atomic force microscopy shows that the root mean square (RMS) roughness of the irradiated polystyrene surface increases with the increment of ion fluence. XRD analysis reveals that in addition to the increase of amorphization of polymer with the increase of ion fluence there is also an increase of ordering (to a small extent) in some of the micro-domains. These results have further been supported by the study of optical and chemical analysis. The analysis of present study shows that the increase of full width at half maximum (FWHM) of first peak of XRD spectra, decrease of optical band gap and the formation of new alkyne group may be attributed to the increase of amorphization of polystyrene. Similarly, sharpening of second X-ray diffraction peak, decrease of Urbach’s energy and increase in the absorbance ratio of I₁₂₂₂/I₁₁₈₃ may be owed to the increase of ordering in some domains.     

Anionic structure and elasticity of Na2O-MgO-SiO2 glasses

The structure and elastic properties of a series of xNa₂O · MgO · 4SiO₂ glasses have been studied using both Raman and Brillouin spectroscopy. Relative to Na₂O-SiO₂ glasses, the maximum abundance for phyllosilicate structural units in the present glasses shows a lag of 0.5 units in the number of non-bridging oxygen per silicon atom (NBO/Si). This phenomenon has been attributed to the decrease in the average coordination number of modifying cations due to the presence of Mg²⁺. It has also been found that the decomposition of both metasilicate and disilicate (dimerized SiO₄) anionic structural units in Na₂O-SiO₂ glasses are enhanced by the addition of MgO. However, the presence of Mg²⁺ does not cause a considerable effect on the decomposition of phyllosilicate structural unit. The acoustic data have revealed that both shear and Young’s moduli of the present glasses decrease with increasing NBO/Si (the variation in bulk modulus is reversed, however). The resistance to shear deformation for the anionic structural units in silicate glasses has been found to decrease in the following order: tectosilicate > phyllosilicate > metasilicate > disilicate > orthosilicate. The relative contribution of the various anionic structural units to the bulk modulus of a glass remains to be determined. The ideal mixing model using Makishima-Mackenzie’s relationship for predicting Young’s modulus is not applicable to the present glasses.     

Effect of antimony addition on the thermal and electrical-switching behavior of bulk Se-Te glasses

The thermal properties and electrical-switching behavior of semiconducting chalcogenide Sb_xSe_55−xTe₄₅ (2 ? x ? 9) glasses have been investigated by alternating differential scanning calorimetry and electrical-switching experiments, respectively. The addition of Sb is found to enhance the glass forming tendency and stability as revealed by the decrease in non-reversing enthalpy ΔH_nr, and an increase in the glass-transition width ΔT_g. Further, the glass-transition temperature of Sb_xSe_55−xTe₄₅ glasses, which is a measure of network connectivity, exhibits a subtle increase, suggesting a meager network growth with the addition of Sb. The crystallization temperature is also observed to increase with Sb content. The Sb_xSe_55−xTe₄₅ glasses (2 ? x ? 9) are found to exhibit memory type of electrical switching, which can be attributed to the polymeric nature of network and high devitrifying ability. The metallicity factor has been found to dominate over the network connectivity and rigidity in the compositional dependence of switching voltage, which shows a profound decrease with the addition of Sb.     

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.     

Development of optical nonlinearity, high dielectric constant and ferromagnetic behavior in a silicate glass nanocomposite by suitable heat treatment

We have explored the development of multifunctionalities viz, optical nonlinearity, high dielectric constant and ferromagnetic behavior in a nanostructured silica based glass of 14.0Na₂O, 26.0BaO, 26.0TiO₂, 16.0B₂O₃, 17.0SiO₂, 1.0NiO (mol%) composition. A heat treatment at 863 K for 4 h led to nonlinear refractive index and absorption coefficients at wavelength 800 nm of 0.11 × 10⁻¹⁹ m²/W and 1.15 × 10⁻³ cm/GW, respectively. A heat treatment at 1073 K for 2 h followed by 1113 K for 3 h increased the dielectric constant from 11 to 50, apparently due to the formation of nanocrystals of BaTiO₃ within the glass medium. Glass samples reduced at 923 K for 1 h exhibited ferromagnetic behavior due to the presence of nickel nanoparticles.     

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.     

Fabrication and characterization of metallic glasses with a specific microstructure for micro-electro-mechanical system applications

Metallic glass microstructures with high aspect ratios for micro-electro-mechanical system applications have been fabricated by micro-electro-discharge machining and selective electrochemical dissolution methods. Micro-holes and three-dimensional microstructures machined on the La₆₂Al₁₄Ni₁₂Cu₁₂, Zr₅₅Al₁₀Ni₅Cu₃₀ and Cu₄₆Zr₄₄Al₇Y₃ bulk metallic glasses by micro-electro-discharge machining are evaluated by using X-ray diffraction, scanning electron microscopy, and nanoindentation. The experimental results demonstrate that the machined samples kept their amorphous structure without devitrification, and their machining characteristics are related to the thermo-physical properties of the alloys and the electrode diameters. Porous, single-pore and thin-walled Zr-based metallic glass tubes with micro-pore structures can be prepared by selective electrochemical dissolution method. The high aspect ratio microstructures fabricated by the two methods have the potential applications as micro-nozzles, polymer micro-injection molding tools, micro-channels or micro-flow meters in micro-electro-mechanical system devices.     

Population dynamics of the F4 and H4 levels in highly-doped Tm:ZB(L)AN glasses

Population dynamics of the ³F₄ and ³H₄ levels in Tm³⁺ doped ZB(L)AN glasses was studied for Tm³⁺ concentrations from 0.5 to 12 mol%. Fluorescence waveforms from these levels were measured at 1.8 μm (³F₄) and 800 nm (³H₄) with both direct and indirect pumping. Decay from the ³F₄ level was found to be exponential with non-radiative decay rates proportional to the square of the Tm concentration. This indicated a process of energy migration by diffusion within the excited Tm³⁺ ions followed by quenching at sites to which the ions could migrate. The decay of the directly pumped ³H₄ level exhibited both exponential and non-exponential behavior depending on the concentration. For the lowest concentration (0.5 mol%) the decay was exponential, but at concentrations of 1, 2, 4 and 6 mol% the decay waveforms were distinctly non-exponential. The non-exponential waveforms could be fitted by the Yokota-Tanimoto model for diffusion of excited donors and dipole-dipole interactions with acceptors. This model produced values for C_DD and C_DA, the donor-donor and donor-acceptor energy transfer parameters, respectively. At the higher concentrations (8, 10, 12 mol%) the waveforms were exponential with decay rates from which the cross-relaxation parameter for the process ³H₄, ³H₆ → ³F₄, ³F₄ was obtained. When the ³F₄ level is pumped at 1660 nm, the decay of the ³H₄ level confirmed the influence of the up-conversion energy transfer process ³F₄, ³F₄ → ³H₄, ³H₆.     

Origin of Rayleigh scattering and anomaly of elastic properties in vitreous and molten GeO2

Vitreous (v) and molten (m) GeO₂ were studied by Rayleigh and Mandel’shtam–Brillouin scattering spectroscopy and high-temperature acoustics. Original measurement apparatus and procedure were used that included Bayseian deconvolution of light scattering spectra of vGeO₂ and a specially designed high-temperature (up to 1500 °C) acoustic interferometer to measure temperature and frequency dependence of ultrasonic (US) velocity and attenuation in mGeO₂. Landau–Placzek ratios for vGeO₂ were found optically (from the light scattering spectrum) and acoustically (through the Schroeder’s formalism). Dispersion of optical and other physical parameters of vGeO₂ found by many authors is explained by the existence of small amount of GeO in the samples. It means that properties of vGeO₂ are under the influence of redox synthesis conditions controlling the GeO₂ ↔ GeO and coordination [GeO₄] ↔ [GeO₆] equilibrium in vGeO₂. Measurements of temperature dependencies of longitudinal ultrasonic velocities in mGeO₂ and in the PbO–GeO₂ glass melts as a function of PbO concentration shows existence of ‘water-like anomaly’ in mGeO₂ and in liquid germanates with the rich content of GeO₂ where equilibrium sound velocity increases with the temperature.     

The presence of a thermally reversing window in Al-Te-Si glasses revealed by alternating differential scanning calorimetry and electrical switching studies

Alternating differential scanning calorimetric (ADSC) studies and electrical switching experiments have been undertaken on Al₁₅Te_85−xSi_x (2 ? x ? 12) system of glasses. These glasses are found to exhibit two crystallization reactions (T_c1 and T_c2), for compositions with x < 8. Above x = 8, a single-stage crystallization is seen. Further, a trough is seen in the composition dependence of non-reversing enthalpy (ΔH^NR), based on which it is proposed that there is a thermally reversing window in Al₁₅Te_85−xSi_x glasses, in the composition range 4 ? x ? 8. Electrical switching studies indicate that Al₁₅Te_85−xSi_x glasses exhibit a threshold type electrical switching at ON state currents less than 2 mA. Further, the switching voltages are found to increase with the increase in silicon content. It is interesting to note that the start (x = 4) and the end (x = 8) of the thermally reversing window are exemplified by a kink and a saturation in the composition dependence of switching voltages, respectively.     

Effect of P2O5 content in two series of soda lime phosphosilicate glasses on structure and properties - Part II: Physical properties

The effect of the variation in phosphate (P₂O₅) content on the properties of two series of bioactive glasses in the quaternary system SiO₂-Na₂O-CaO-P₂O₅ was studied. The first series (I) was a simple substitution of P₂O₅ for SiO₂ keeping the Na₂O:CaO ratio fixed (1:0.87). The second series (II) was designed to ensure charge neutrality in the orthophosphate (), therefore as P₂O₅ was added the Na₂O and CaO content was varied to provide sufficient Na⁺ and Ca²⁺ cations to charge balance the orthophosphate present. Network connectivity’s of the glasses were calculated, and densities and thermal expansion coefficients predicted using the Appen and Doweidar models, respectively. Theoretical densities were measured using the Archimedes principle. Characteristic temperatures, namely the glass transition temperature, T_g, and crystallization temperatures, T_x, were obtained using differential analysis (DTA). Two crystallization exotherms were observed for both glass series (T_xi and T_xii). Both T_g and T_x decreased with P₂O₅ addition for both series. The working range of the glasses, T_x-T_g was shown to increase to a maximum at around 4 mol% P₂O₅ then decrease at higher P₂O₅ contents for both series. Thermal expansion coefficients were measured using dilatometry increasing with P₂O₅ addition and showed good agreement with the Appen values. Dilatometric softening points, T_s, were also measured, which increased with P₂O₅ addition. X-ray diffraction (XRD) was performed on the glasses to confirm their amorphous nature. The glass containing 9.25 mol% P₂O₅ from series I exhibited well-defined peaks on the XRD trace, indicating the presence of a crystalline phase.     

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.     

Local structure and its effect on the oscillator strengths and emission properties of Ho in chalcohalide glasses

The formation of structural units in Ge-Ga-S glass with CsBr addition and its effect on the optical band gap and several spectroscopic properties of Ho³⁺ were investigated. The optical band gap of the host glasses and the oscillator strengths of Ho³⁺ absorption decreased sharply when the ratio of CsBr/Ga became close to unity. These property changes were associated with the formation of structural units of [GaS_3/2Br]⁻ and they have a crucial effect on the changes of the local structure around Ho³⁺ ions. The local structure was not sensitive to the As or Br addition but was critically dependent on the concentration of CsBr.     

Preparation and characterization of new fluorotellurite glasses for photonics application

Glasses based on (85 − x)TeO₂-xZnF₂-12PbO-3Nb₂O₅ (x = 0-40) system have been studied for the first time for fabricating mid-infrared optical fiber lasers. The thermal and optical properties including UV-Vis, Raman as well as FTIR spectra are reported. It is demonstrated that increasing the ZnF₂ concentration to 30 mol% significantly increased the thermal stability of the glass. Adding ZnF₂ also reduced the hydroxyl (OH) content of the glass resulting in lower optical absorption in the mid-infrared region, which is crucial for infrared laser applications. The glass absorption cut-off edge near 400 nm blue-shifts with increasing ZnF₂ addition. Raman spectra show a depolymerization of the glass network with increasing transformation of TeO₃₊₁ to TeO₃ structures.     

Influence of metal organic and inorganic precursors on spray pyrolyzed ceramic MgO (2 0 0) thin films for epitaxial over layers

The MgO (2 0 0) surface is widely used as a substrate for epitaxial growth of superconducting and ferro-electric films. Highly oriented, single crystalline, extremely flat and transparent MgO films have been successfully deposited on quartz substrates by the chemical spray pyrolysis technique using economically viable metal organic and inorganic precursors under optimized conditions at the substrate temperature of 600 °C. Thermal analysis (TGA/DTA) in the temperature range 30-600 °C with the heating rate of 10 °C/min revealed the decomposition behavior of the precursors and confirmed the suitable substrate temperature range for film processing. The heat of reaction, ΔH due to decomposition of metal organic precursor contributed additional heat energy to the substrate for better crystallization. The intensity of the (2 0 0) peak in X-ray diffraction (XRD) measurements and the smooth surface profiles revealed the dependency of precursor on film formation. The compositional purity and the metal-oxide bond formation were tested for all the films. UV-Vis-NIR optical absorption in the 200-1500 nm range revealed an optical transmittance above 80% and the absorption edge at about 238 nm corresponding to an optical band gap E_g = 5.25 eV. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) micrographs of MgO films confirmed better crystallinity with larger grain size (0.85 μm) and reduced surface roughness (26 nm), respectively.     

Fabrication and properties of novel low-melting glasses in the ternary system ZnO-Sb2O3-P2O5

Glasses in the ternary system ZnO-Sb₂O₃-P₂O₅ were investigated as potential alternatives to lead based glasses for low temperature applications. The glass-forming region of ZnO-Sb₂O₃-P₂O₅ system has been determined. Structure and properties of the glasses with the composition (60 − x)ZnO-xSb₂O₃-40P₂O₅ were characterized by infrared spectra (IR), differential thermal analysis (DTA) and X-ray diffraction (XRD). The results of IR indicated the role of Sb³⁺ as participant in glass network structure, which was supported by the monotonic and remarkable increase of density (ρ) and molar volume (V_M) with increasing Sb₂O₃ content. Glass transition temperature (T_g) and thermal stability decreased, and coefficient of thermal expansion (α) increased with the substitution of Sb₂O₃ for ZnO in the range of 0-50 mol%. XRD pattern of the heat treated glass containing 30 mol% Sb₂O₃ indicated that the structure of antimony-phosphate becomes dominant. The improved water durability of these glasses is consistent with the replacement of easily hydrated phosphate chains by corrosion resistant P-O-Sb bonds. The glasses containing ?30 mol% Sb₂O₃ possess lower T_g (<400 °C) and better water durability, which could be alternatives to lead based glasses for practical applications with further composition improvement.     

Effect of method of preparation and drying time on photophysical properties of coumarin 1 laser dye embedded in HCl catalysed sol-gel glasses

Coumarin 1 (C1) dye is impregnated in transparent sol-gel glass samples prepared by sol-gel process using three methods - (I) using HCl as catalyst and glycerol as a drying control chemical additive (DCCA), (II) using HCl as catalyst at 60 °C subsequent drying at room temperature, and (III) using HCl as catalyst at 60 °C and heated at 600 °C for 3 h. The sol-gel matrices prepared by Methods I and II are given dip treatment with methanol/distilled water (50/50 volume) for 16 h before dipping into dye solution. The effect of method and drying time of matrix on spectroscopic properties of C1 dye doped glass samples has been studied. The optical density (OD) at absorption maximum wavelength and fluorescence intensity (FI) at fluorescence maximum wavelength of all C1 dye doped samples prepared by Methods I and II decrease, where as there is no change in photophysical properties (OD/FI) is observed in samples prepared by Method III with the time of drying of the sol-gel samples. These absorption/fluorescence properties of C1 dye in sol-gel glass matrices are compared with its respective properties in methanolic solution in acidic environment.