Synthesis and characterization of potassium, rubidium, and cesium thiogermanate glasses

Glass-forming regions were investigated for the binary xM₂S + (1 − x)GeS₂ (M=K, Rb, Cs) systems. Glasses were prepared from 0?x?0.20 mole fraction alkali sulfide using a novel preparation route involving the decomposition of the alkali hydrosulfides in situ. At higher alkali concentrations near x=0.33, the glass-forming regions are limited by the readily formed adamantane-like M₄Ge₄S₁₀ crystals. Structural characterization of the glasses and polycrystals for x?0.33 were performed using Raman scattering and IR absorption. Terminal Ge-S⁻ vibrational modes, observed between 473 and 479 cm⁻¹, increased in intensity and decreased in frequency with increasing alkali modifier content. Glass transition temperatures decreased with increasing alkali modifier, ranging from 250 to 215 °C. Corresponding crystallization onset temperatures were between 340 and 385 °C. DC conductivity values of the glasses ranged from 10⁻¹⁰ to 10⁻⁷ (Ω cm)⁻¹ with activation energies between 0.54 and 0.93 eV for the temperature range of ∼100-250 °C. Higher ionic conductivities were observed with increasing alkali concentration and decreasing alkali radii. Additionally, an increase in the activation energy was observed above the glass transition temperature.     

High frequency acoustic attenuation of vitreous silica: New insight from inelastic x-ray scattering

We present new experimental results on the propagation and damping of the high frequency acoustic-like modes in vitreous silica. The new data are measured by means of the inelastic x-ray scattering technique down to an exchanged wavevector Q ∼ 0.9 nm ^− 1, at the limit of the instrument capabilities. Thanks to the continuous development of the technique, the new spectra are characterized by a very high signal to noise ratio when compared to previous experiments. The higher data quality finally allows for a reliable determination of the position and width of the inelastic excitations. The new data show that the sound damping Γ is marked by a frequency dependence compatible with the Rayleigh law, Γ ∼ ν⁴, for frequencies below the position of the excess vibrational modes at the boson peak. We show that the new data are in good agreement with estimates of the acoustic mean free path from the thermal conductivity, which take into account the peculiar plateau at a few Kelvin. The connection between the boson peak and the Rayleigh law is further confirmed by a comparison of the present data with literature data for the sound attenuation in a permanently densified silica sample.     

Structural changes during the crystallization of the Bi4Ge3O12 glasses

Bismuth-germanate glass ceramics with the composition 40% Bi₂O₃-60% GeO₂ (in molar percents) were prepared through controlled crystallization of melt-quenched glass. The Raman and FTIR spectra recorded in the as-made glasses show broad bands at 240, 400, 780 cm^− 1 and 400, 745 cm^− 1 have been assigned Ge-O bonds which appear right after preparation. X-ray diffraction has shown that the as-made glasses are amorphous, but after annealing above the crystallization temperature at 558 °C, BGO nano-crystallites with a size of about 50 nm precipitate in the glass matrix. The Raman and FTIR spectra reveal sharp peaks associated to the “internal” and “external vibrations” of GeO₄ tetrahedral groups inside the BGO nano-crystallites. In the glass ceramic sample the transparency region is shifted at longer wavelengths compared to as-made glass, due to the Rayleigh scattering on the BGO nano-crystallites.     

Generation and annealing of defects in virgin fused silica (type III) upon ArF laser irradiation: Transmission measurements and kinetic model

The transmission of ArF laser pulses in virgin fused silica (type III) samples changes during N = 10⁶ pulses at an incoming fluence H_in = 5 mJ cm⁻² pulse⁻¹. The related absorption is determined by the pulse energy absorption coefficient α(N, H_in) using a modified Beer’s law, yielding initial values α_ini around 0.005 cm⁻¹, a maximum α_max ? 0.02 cm⁻¹ at N = 10³-10⁴ and stationary values 0.0045 cm⁻¹ ? α_end ? 0.0094 cm⁻¹ after N ≈ 6 × 10⁵ pulses. The development α(N, H_in = const.) is simulated by a rate equation model assuming a pulse number dependent E′ center density E′(N). E′(N) is determined by a dynamic equilibrium between E′ center generation and annealing. Generation occurs photolytically from the precursors ODC II and unstable SiH structures upon single photon absorption and from strained SiO bonds via two-photon excitation. Annealing in the dark periods between the laser pulses is dominated by the reaction of E′ with H₂ present in the SiO₂ network. The development α(N, H_in = const.) is observed for the very first sample irradiation only (virgin state). The values α_end are not accessible by simple spectrophotometer measurements.     

Universal critical-like scaling of dynamics in plastic crystals

Many theoretical models for the glassy dynamics have been proposed so far describing the changes in molecular dynamics along the extraordinary slowing down in the vitrification process of a disordered phase on cooling. Many of these theories share the concept of cooperative rearranging regions firstly proposed by Adam and Gibbs. Among them, the dynamical scaling model (DSM) is based on the random diffusion of free volume which creates random walking clusters formed by cooperatively rearranging entities.Within this framework a critical phenomenon relating a hidden phase transition at T_C (below T_g) implies the divergence of the relaxation time (τ) or viscosity (η) τ, η ∝ (T − T_C) ^− ? with a universal scaling exponent φ → 9. In this work we apply the DSM model to orientational glasses, obtained from the quenching of orientationally disordered phases (plastic crystals) via the application of the linearized derivative-based transformation of dielectric spectroscopy τ(T) data.     

Stark splitting of the ground state of Er in fluorozirconate glass at low temperature

Optical properties of Er³⁺-doped ZBLAN glass matrix have been studied by luminescence spectroscopy under 488 nm excitation. The spectrum of the ⁴S_3/2⁴I_15/2 transition, carried out at temperature T = 2 K, shows a new line in the lowest energy region. This new line, centered at 17 996 cm⁻¹, was attributed to the lower transition between the Stark components of the ⁴S_3/2⁴I_15/2 transition. Measurements from T = 2 K to room temperature show the disappearance of this new line. From the results we estimate the splitting of 415 cm⁻¹ for the ground state and 100 cm⁻¹ for the ⁴S_3/2 excited multiplet. The experimental result allows us to assign the positions of the eight Stark components of the ground state multiplet of the Er³⁺ in the ZBLAN glass matrix.     

Diffusion of the S isotope in soda-lime-silica and sodium trisilicate glass melts

The diffusivity of sulphur in nominal 10 Na₂O-16 CaO-74 SiO₂ (NCS) and 26 Na₂O-74 SiO₂ (NS3) melts was investigated in the temperature range 1273-1473 K using the ³⁵S radioactive isotope in a sandwich setup. Samples were sealed in platinum capsules and run with vertical alignment at 100 MPa confining pressure in an internally heated gas pressure vessel. Using the lowest diffusion coefficient D (m² s^− 1) for each temperature the Arrhenian relations logD = −(4.6 ± 0.3) − (216 ± 7) kJ mol^− 1/RT for NCS and logD = −(6.3 ± 0.6) − (167 ± 17) kJ mol^− 1/RT for NS3 were determined. Viscosity of the melts was used to test the applicability of the Stokes-Einstein (SE) and the Eyring (EY) equations to sulphur diffusion. The SE equation yields unrealistically low radii of the diffusing particles, a consequent of the non-molecular structure of the silicate melts. On the other hand, the Eyring relation yields reasonable jump distances of 550 pm (NCS) and 750 pm (NS3) by fitting the diffusion data to the EY equation. These large values imply that sulphate ions (ionic diameter = 290 pm) migrate as large entities through the silicate network.     

Transport property and structural characterization studies on (1 − x)[0.75AgI:0.25AgCl]:xTiO2 conducting composite electrolyte system

Transport property and structural investigation have been carried out on newly synthesized Ag⁺ ion conducting composite electrolyte system. The composite electrolyte system (1 − x)[0.75AgI:0.25AgCl]:xTiO₂, where 0 ? x ? 0.5 (in molar weight fraction) has been synthesized by melt quenching and annealing methods. The chemical compound TiO₂ (second phase dispersoid) dispersed in different compositions in a quenched (0.75AgI:0.25AgCl) mixed system/solid solution; this solid solution was used as a first phase host salt in place of AgI. The different preparation routes were adopted for the composite electrolyte system. Composition x = 0.1 exhibited highest conductivity at room temperature. The composite system 0.9[0.75AgI:0.25AgCl]:0.1TiO₂ was synthesized at different soaking times by melt quenching method. The system exhibited optimum conductivity at 20 min soaking time (σ_rt ≈ 1.4 × 10⁻³ S/cm). The ac conductivity has been measured from Z′-Z″ (Cole-Cole) complex impedance plots using impedance spectroscopic (IS) technique. The electrical conductivity as a function of temperature and frequency has been studied, and activation energy E_a, was calculated from Arrhenius plots for all compositions (0 ? x ? 0.5). The dc conductivity value has been evaluated from Log σ vs. log f plots. Structural characterization studies were carried out by X-ray diffraction (XRD) and differential thermal analysis (DSC) techniques.     

Thermo-optic properties of B2O3 doped Li2O-Al2O3-SiO2 glass-ceramics

Reduction in the temperature coefficient of the optical path length, dS/dT of Li₂O-Al₂O₃-SiO₂ glass-ceramics with near-zero thermal expansion coefficient was attempted using control of the temperature coefficient of electronic polarizability, ?, and the thermal expansion coefficient, α. The dS/dT value of 2.6 mol% B₂O₃-doped glass-ceramic was 12.5  × 10⁻⁶/°C, which was 0.9 ×  10⁻⁶/°C smaller than that of B₂O₃-free glass-ceramic. On the other hand, reduction in dS/dT through B₂O₃ doping was not confirmed in precursor glasses. Results showed that reduction in dS/dT of the glass-ceramic through B₂O₃ doping is caused by the reduction in ?. The reduction in ? from B₂O₃ doping was probably attributable to numerical reduction in non-bridging oxide ions with larger ? value by the concentration of boron ions in the residual glass phase. In addition, application of hydrostatic pressure during crystallization was effective to inhibit precipitation of β-spodumene solid solution, which thereby decreases dS/dT. The dS/dT value of B₂O₃-doped glass-ceramic crystallized under 196 MPa was 11.7 ×  10⁻⁶/°C. That value was slightly larger than that of silica glass. The α value of this glass-ceramic was smaller than that of silica glass.     

Occurrence of Kondo-like behavior in electrical-conductivity of Al70Pd20+xMn10−x (x = 0, 1 and 2) icosahedral quasicrystals

Zero-field and in-field (at 8 T) conductivity vs temperature (σ-T), magneto-resistance (Δρ/ρ), magnetization vs temperature (M-T) and magnetization vs field (M-H) of unannealed Al₇₀Pd₂₀Mn₁₀ and annealed Al₇₀Pd₂₀Mn₁₀, Al₇₀Pd₂₁Mn₉ and Al₇₀Pd₂₂Mn₈ quasicrystalline alloys have been studied in the temperature range of 1.4-300 K. Room temperature resistivity and the low-temperature magneto-resistance show a correlation with the corresponding magnetization. The σ-T for all the studied samples shows a pair of minima and maxima. The σ-T maxima show a correlation with the total magnetization. The analysis shows that σ-T is dominated by weak-localization effects. The minima are arising due to competing inelastic scattering times τ_i (e-ph scattering in the dirty metallic limit, τ_i ∝ T⁻²) and the Kondo-type spin-flip scattering time τ_sf whereas the maxima has been attributed to ‘Kondo-maxima’, occurring due to maxima in the spin-flip rate . The magneto-resistance of these samples shows a changeover from negative to positive where the negative component shows a correlation with the magnetization of the sample. The values of parameters derived from refinement give spin-flip scattering fields, which are found to be correlated with the total sample magnetization.     

Crystallization behavior of (GeS2)0.1(Sb2S3)0.9 glass

The crystal growth kinetics of antimony trisulfide in (GeS₂)_0.1(Sb₂S₃)_0.9 glass has been studied by microscopy and DSC. The linear crystal growth kinetics has been confirmed in the temperature range 492 ? T ? 515 K (E_G = 405 ± 7 kJ mol⁻¹). The applicability of standard growth models has been assessed. From the crystal growth rate corrected for viscosity plotted as a function of undercooling it has been found that the most probable mechanism is interface controlled 2D nucleated growth. The non-isothermal DSC data, corresponding to the bulk sample, can be described by the Johnson-Mehl-Avrami equation.     

Raman scattering in amorphous films of In1−xSex alloys

Raman scattering (RS) in amorphous films of In_1−xSe_x with 0.67±x?0.38 has been studied in backscattering geometry with the use of a microscope. Recorded RS spectra are revealing a mixed vibrational density-of-states and molecular character. The spectra spread from the Rayleigh line up to 200-250 cm⁻¹. The bands superimposed on the continua are related to zone center modes of the relevant crystal counterpart, Se-Se or In-In vibrations. The RS spectra suggest the structure of the In_1−xSe_x alloys to be the continuous random network built up of In centered tetrahedral clusters with In and Se atoms at the corners. The structure of the Se-rich alloys is similar to 4-2 networks with dominant InSe_4/2 clusters and two-fold coordination of Se bridging atoms. That of the In-rich alloys is expected to resemble 4-3 network with rather strong involvement of In atoms at corner of the In-centered tetrahedral clusters and Se atoms being linked to three In ones.     

Electron spin resonance and magnetic studies on CaO-SiO2-P2O5-Na2O-Fe2O3 glasses

Room temperature electron spin resonance (ESR) spectra and temperature dependent magnetic susceptibility measurements have been performed to investigate the effect of iron ions in 41CaO · (52 − x)SiO₂ · 4P₂O₅ · xFe₂O₃ · 3Na₂O (2 ? x ? 10 mol%) glasses. The ESR spectra of the glass exhibited the absorptions centered at g ≈ 2.1 and g ≈ 4.3. The variation of the intensity and linewidth of these absorption lines with composition has been interpreted in terms of variation in the concentration of the Fe²⁺ and Fe³⁺ in the glass and the interaction between the iron ions. The magnetic susceptibility data were used to obtain information on the relative concentration and interaction between the iron ions in the glass.     

Thermomagnetic study of the amorphous cobalt-erbium borides Co80ErxB20−x (0 ? x ? 4)

Calorimetric, magnetic and X-ray diffraction measurements have been used to study the magnetic susceptibility and thermal stability of Co₈₀Er_xB_20−x with (0 ? x ? 4) amorphous ribbons. The compounds are found to crystallize in Co₂B and β-Co, after precipitation of the tetragonal Co₃B phase. The addition of erbium shifts up the crystallization temperature leading to the increase in the stability of the amorphous state. Magnetic susceptibility measurements show that the addition of erbium increases the Curie temperature and induces noncollinear magnetic behavior. This latter fact is explained on the basis of random local magnetic anisotropy related to the rare earth atoms in amorphous materials.     

Disorder in LixFePO4: From glasses to nanocrystallites

Li_xFePO₄ glasses have been prepared by fast-quenching method in the whole range of composition 0 ? x ? 1. The amorphous state of glassy materials is confirmed by X-ray diffraction. Information concerning the local environment of Li and Fe cations and the configuration of (PO₄)³⁻ oxo-anions is obtained by Fourier transform infrared (FTIR) spectroscopy. While the LiFePO₄ crystalline materials undergo a transition from the paramagnetic to the antiferromagnetic ordering at 52 K, no magnetic ordering is observed in the vitreous samples that realize random field systems, so that a spin glass-like freezing is observed at low temperature. The paramagnetic Curie temperature of Li_xFePO₄ is independent of x and shifted to θ = −60 K in the glassy state, due to a significant distortion of the FeO₆ octahedra that alters the superexchange path inside the atomic FeO₄ layers of the crystallized structure. On another hand, the PO₄ tetrahedra are not significantly distorted in the glassy phase. The results are compared with highly disordered, but nanocrystallized LiFePO₄ recently obtained at the early stage of synthesis by solid state reaction at 300 °C. In this latter case, the lack of long-range antiferromagnetic ordering is due to substitutional disorder among the cationic sublattice.     

Viscosity, relaxation and elastic properties of photo-thermo-refractive glass

Viscometry, ultrasonic echography and mechanical spectroscopy were applied to explore the thermo-mechanical properties of a photo-thermo-refractive (PTR) glass. Newtonian shear viscosity and ultrasonic velocity were used to determine the Maxwell time of structural relaxation. Two fast relaxation modes are found in PTR glass below glass transition temperature, which are attributed to alkali and mixed cation mobility. Respective activation energies, E_γ = 72 ± 4 kJ mol⁻¹ and E_β = 117 ± 4 kJ mol⁻¹, are considerably lower than that of viscous flow at the glass transition E_α ≈ 465 kJ mol⁻¹ as quantified from mechanical spectroscopy. Decoupling ratios of E_γ/E_α = 0.155 and E_β/E_α = 0.255 are similar to those of sodium trisilicate glass but at considerably longer timescales. These observations imply that β- and γ-relaxations are delayed as local structural arrangements are more complex for the multi-component PTR glass.     

Properties and structure of copper ultraphosphate glasses

The structures of xCuO · (1 − x)P₂O₅ glasses (0 ? x ? 0.50) prepared in vacuum sealed silica ampoules were investigated using vibrational spectroscopies. With the addition of CuO, both infrared and Raman spectra indicate a systematic transformation from a three-dimensional ultraphosphate network dominated by Q³ tetrahedra into a chain-like metaphosphate structure dominated by Q² tetrahedra. IR spectra clearly show two distinct Q³ sites with bands at 1378 and 1306 cm⁻¹, assigned to PO bonds on isolated Q³ tetrahedra and PO bonds on tetrahedra that participate in the coordination environments of the Cu-octahedra, respectively. As CuO content increases, the intensity of the PO band associated with the tetrahedra increases to a maximum x ∼ 0.33, then decreases with a concomitant increase of the intensity of the band at 1265 cm⁻¹, due to the asymmetric vibration of the PO₂ groups on Q² tetrahedra. When x > 0.33 the isolated Cu-octahedra begin to share common oxygens to form a sub-network in the phosphate matrix. The effects of glass structure on the glass properties, including density, refractive index, and glass transition temperature, are discussed.     

Insulator-like electrical transport in structurally ordered Al65Cu20+xRu15−x (x = 1.5, 1.0, 0.5, 0.0 and −0.5) icosahedral quasicrystals

Low-temperature resistivities, in zero-field and 8 T field, and magnetoresistance have been measured down to 1.4-300 K for stable icosahedral quasicrystals Al₆₅Cu_20+xRu_15−x (x = 1.5, 1.0, 0.5, 0.0 and −0.5). The analysis of the magnetoresistance data shows an overwhelming presence of anti weak-localization effect (τ_so ∼ 10⁻¹² s). But the sample with x = −0.5 shows anomalous magnetoresistance and the anti weak-localization effect breaks down (τ_so to be 10⁻¹⁵ s). The in-field σ-T between 5 K and 20 K, for x = 1.0, 0.5, 0.0 and −0.5 samples, and between 1.4 K and 40 K for x = 1.5 sample, follow a power-law behavior with an exponent of 0.5 and above ∼30 K the exponent ranges from 1.17 to 1.58. The observed power-laws basically characterize the presence of critical regime of the metal-insulator (MI) transition, dominated by electron-electron and electron-phonon inelastic scattering events respectively. In samples with x = 1.0, 0.5, 0.0 and −0.5 the in field σ-T has been found to follow ln σ-vs-T^1/4 below 5 K, which indicates the presence of variable range hopping. The observed transport features indicate the occurrence of proximity of metal-insulator transition in these Al-Cu-Ru quasicrystal samples.     

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.