Effect of pressure on the structural stability of iron phosphate glass: Role of trace water

Raman and infrared spectroscopic measurements were carried out on 40 mol% Fe₂O₃:60 mol% P₂O₅ iron phosphate glass samples to study the effect of increasing external pressure on the local structure of both anhydrous and water trapped glasses. In-situ high‐pressure Raman measurements, done up to 24.2 GPa on anhydrous samples, revealed hardening of the phonon modes accompanied by a loss of Raman intensity and ultimately leading to complete smearing of modes at very high pressures. These changes were found to be reversible upon quenching the sample back to ambient pressure. Raman and infrared spectroscopy of pressure quenched IPG samples containing trace amounts of water have revealed definite signatures of devitrification at room temperature.     

Pressure dependence of the Boson peak in glassy As2S3 studied by Raman scattering

A detailed pressure dependence study of the low energy excitations of glassy As₂S₃ is reported over a wide pressure range, up to 10 GPa. The spectral features of Boson peak are analyzed as a function of pressure. Pressure effects on the Boson peak are manifested as an appreciable shift of its frequency to higher values, a suppression of its intensity, as well as a noticeable change of its asymmetry leading to a more symmetric shape at high pressures. The pressure-induced Boson peak frequency shift agrees very well with the predictions of the soft potential model over the whole pressure range studied. As regards the pressure dependence of the Boson peak intensity, the situation is more complicated. It is proposed that in order to reach proper conclusions the corresponding dependence of the Debye density of states must also be considered. Comparing the low energy modes of the crystalline counterpart of As₂S₃, as well as the experimental data concerning the pressure dependencies of the Boson peak frequency and intensity, a structural or glass-to-glass transition seems to occur at the pressure ∼4 GPa related to a change of local dimensionality of the glass structure. Finally, the pressure-induced shape changes of the Boson peak can be traced back to the very details of the excess (over the Debye contribution) vibrational density of states.     

Preparation of mixed arsenic/antimony chalcogenide glasses and some optical and thermo-physical properties

The preparation of mixed glasses of As₂S_3−xSe_x (x = 0–3) and (1 − y) · As₂S₃y · Sb₂S₃ (y = 0–1) has been carried out by an in situ pouring technique. X-ray diffraction (XRD) was used to confirm the glassy nature of the materials and monitor devitrification. Visible-IR transmission, photoluminescence, refractive index and micro-Raman were measured as a function of composition. Microhardness (MH) and thermal expansion coefficient (TEC) were also measured. Raman peaks in As₂S₃ and As₂Se₃ were observed around 338 cm⁻¹ and 230 cm⁻¹, respectively in this first composition series in which S was replaced by Se. When As was replaced by Sb, in the case of second composition series, the As₂S₃ related Raman peak became broader and shifted to lower wave number, reflecting some structural change/devitrification. MH increased (1.31–1.50 GPa) with Se and Sb content while the TEC was found to decrease (2.5–1.4 × 10⁻⁵/K). The progressive increase in the content of either Se or Sb in As₂S₃ is anticipated to modify bond lengths and bond angles. The combined effect of these structural modifications would change the local structure of the glass forming a more rigid glass network thereby increasing the hardness and decreasing TEC.     

Growth of Zn3As2 on GaAs by liquid phase epitaxy and their characterization

Zn₃As₂ epitaxial layers were grown on GaAs (1 0 0) substrates by liquid phase epitaxy (LPE) using Ga as the solvent. Zinc mole fraction in the growth melt was varied from 1.07×10^?2 to 6×10^?2. X-ray diffraction spectrum exhibits a sharp peak at 43.3° characteristic of Zn₃As₂ crystalline layer. The peak intensity increases with increase in zinc mole fraction in the growth melt. The compositions of the as-grown Zn₃As₂ layers were confirmed by energy dispersive X-ray (EDX) analysis. Surface morphology was studied using scanning electron microscopy (SEM) and the thickness of the epilayers was also determined. The Hall measurements at 300 K indicate that Zn₃As₂ epilayers are unintentionally p-doped. With an increase of zinc mole fraction in the growth melt, carrier concentration increases and carrier mobility decreases. Infrared optical absorption spectroscopy showed a sharp absorption edge at 1.0 eV corresponding to the reported band gap of Zn₃As₂.     

Ex situ XRD,TEM, IR,Raman and NMR spectroscopy of crystallization of lithium disilicate glass at high pressure

The structure of Li₂O · 2SiO₂ (LS₂) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 °C, respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si–O–Si bond angle ∼7° lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa new high pressure form of lithium metasilicate crystallizes. This new phase, while having lithium metasilicate crystal symmetry, contains at least four different Si sites. NMR results for 6 GPa indicate the presence of Q⁴ species with (Q⁴)Si–O–Si(Q⁴) bond angles of ∼157°. This is the first reported occurrence of Q⁴ species with such large bond angles in alumina free alkali silicate glass. No five- or six-coordinated Si are found.     

Evaluation of structural and mechanical properties of aluminum oxide thin films deposited by a sol–gel process: Comparison of microwave to conventional anneal

Thin films of Al₂O₃ have been deposited on polished silica glass substrates at room temperature by sol–gel dip coating technique followed by two different exposure methods. One set was annealed at different temperatures ranging from 200 °C to 800 °C for 10 h and a second set was exposed to microwave (2.45 MHz) radiation at different powers for 10 min. The lower temperature and shorter time with microwave irradiation might be ascribed to the activating and facilitating effect of microwaves on solid phase diffusion. Unlike other preparation methods, microwave heating is generally quite faster, and energy efficient. X-ray diffraction (XRD) and scanning electron microscopy (SEM), energy dispersive X-ray analysis techniques have been employed to characterize structural, morphological and elemental compositions of the films. Adhesion strength failure measurements on films performed by scratch test in progressive loading sequence have shown critical loads up to 25 N (partial perforation) for both annealed films and films exposed to microwave irradiation. Nanohardness indentation tests of the films exposed (800 W) to microwave have shown hardness of 8.3 GPa with elastic modulus of 120 GPa compared to the conventional annealed film (800°) of 4.5 GPa with elastic modulus of 90 GPa.     

X-ray diffraction measurement of liquid As2Se3 by using third-generation synchrotron radiation

X-ray diffraction (XD) measurements of liquid As₂Se₃ were carried out in the temperature range up to 1600 °C where the temperature is well beyond the semiconductor to metal (SC–M) transition temperature around 1000 °C. The measurements were done by using third-generation synchrotron radiation at SPring-8 and the obtained structure factors have been much improved compared to previous in house XD measurements with regard to the momentum transfer range and the data statistics. The deduced pair distribution functions show that with increasing temperature, the position of the first peak does not change within the errorbar and the coordination number gradually decreases up to 1600 °C irrespective of the SC–M transition. These results coincide with those of the first-principle molecular dynamics simulation.     

Formation and structure of crystalline inclusions in As2S3–SbSI and As2Se3–SbSI systems glass matrices

The main aim of the study presented in this paper is the investigation of the structure of (As₂S₃)_100?x(SbSI)_x and (As₂Se₃)_100?x(SbSI)_x (0 ≤ × ≤ 40) glasses by Raman spectroscopy and X-ray methods, also the nature of the crystalline inclusions which arise up in their matrix at heat treatment. We have found that in conditions of continuous heating in the interval “glassforming temperature–crystallization temperature” a crystallization with predominant mechanism of stable phase SbSI separation is taking place. The formation mechanism of crystalline inclusions of antimony sulphoiodide in glass matrix is discussed in the light of our results. It was established that all investigated glasses have a nano-heterogeneous structure.     

Structural properties of Cr2O3–Fe2O3–P2O5 glasses,Part I

The structural properties of xCr₂O₃–(40 − x)Fe₂O₃–60P₂O₅, 0 ⩽ x ⩽ 10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr₂O₃ does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q¹, units. This is in accordance with O/P ≈ 3.5 for these glasses. The increase in glass density and T_g that occurs with increasing Cr₂O₃ suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe²⁺/Fe_tot ratio increases from 0.13 to 0.28 with increasing Cr₂O₃ content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr₂O₃–30Fe₂O₃–60P₂O₅ (mol%) sample was partially crystallized and contained crystalline β-CrPO₄ and Fe₃(P₂O₇)₂. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe₂O₃ (39.6 mol%) and P₂O₅ (54.9 mol%), but contained only 5.5 mol% of Cr₂O₃. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr₂O₃.     

In situ crystallization of lithium disilicate glass: Effect of pressure on crystal growth rate

Crystallization of a Li₂O · 2SiO₂ (LS₂) glass subjected to a uniform hydrostatic pressure of 4.5 and 6 GPa was investigated up to a temperature of 750 °C. The density of the compressed glass is ∼2% greater at 4.5 GPa than 1 atm and, depending on the processing temperature, up to 10% greater at 6 GPa. Crystal growth rates investigated as a function of temperature and pressure show that lithium disilicate crystal growth is an order of magnitude slower at 4.5 GPa than 1 atm resulting in a shift of +45 °C (±10 °C) in the growth rate curve at high pressure compared to 1 atm conditions. At 6 GPa lithium disilicate crystallization is suppressed entirely, while a new high pressure lithium metasilicate crystallizes at temperatures 95 °C (±10 °C) higher than those reported for lithium disilicate crystallization at 1 atm. The observed decrease in crystal growth rate with increasing pressure for the lithium disilicate glass up to 750 °C is attributed to an increase in viscosity with pressure associated with fundamental changes in glass structure accommodating densification.     

FT-IR and Raman study of silver lead borate-based glasses

Glasses from the xMnO · (100−x)[3B₂O₃ · 0.9PbO · 0.1Ag₂O] system with 0 ⩽ x ⩽ 20 mol% have been prepared and studied by means of FT-IR absorption and Raman scattering. We interpreted the spectroscopic data in conjunction with the structural information obtained by X-ray diffraction and scanning electron microscopy (SEM). The X-ray patterns have showed homogenous glasses over the entire compositional range while the SEM pictures have detected metallic silver or Ag₂O clusters dispersed in the glass network. Acting as complementary spectroscopic techniques, both types of measurements, FT-IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO₃ and BO₄ units placed in different structural groups, the BO₃ units being dominant. The influence of manganese-ion content (x), on the N_BO4/N_BO3 ratio evolution was investigated.     

Crystal growth of ZrW2O8 and its optical and mechanical characterization

ZrW₂O₈ is known for its isotropic negative thermal expansion over a wide of range of temperature from ?272 to 777 °C. However, ZrW₂O₈ melts incongruently at 1257 °C and is stable only over a short temperature interval between 1105 and 1257 °C. This makes the growth of single crystals a formidable challenge. In order to study the intrinsic properties of this compound, a repeatable, viable single crystal growth strategy is required. Here we report a simple, self-seeding, self-fluxing single crystal growth process which resulted in single crystals of ZrW₂O₈ up to about 4 mm in size. Grown crystals were characterized by X-ray diffraction (XRD), Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Mechanical properties of the crystals were studied using nanoindentation.     

Low-frequency Raman scattering and small-angle X-ray scattering of glasses inclined to phase decomposition

Low-frequency (<1000 cm⁻¹) Raman scattering of lithium aluminosilicate (12Li₂O : 15Al₂O₃ : 73SiO₂ with 4 mol% TiO2) glasses with addition of titanium dioxide has been studied. With a heat treatment at temperatures 660°C, 700°C, 720°C and 820°C and for various times and sequences of temperature, our samples decompose into nanometer sized dispersed aluminotitanate particles. In Raman spectra of these glasses an evolution of a boson peak was observed. The width of the relatively broad boson band decreases as does the frequency of the band. From small-angle X-ray scattering data we conclude that the boson peak is connected with elastic vibrations of amorphous or crystalline regions of inhomogeneity with a dimension of ∼1.7 nm in initial glasses or larger depending on the heat treatment sequences.     

Influence of manganese ions on spectroscopic and dielectric properties of LiF-SrO-B2O3 glasses

Transparent glasses, obtained through melt quenching technique, with composition 30LiF-10SrO-(60-x)B₂O₃-xMnO, with 0 ≤ x ≤ 3 mol% (x = 0, 1, 1.5, 2, 2.5 and 3), were characterized by X-ray diffraction (XRD) and then they were analyzed for physical, spectroscopic studies (optical absorption, electron spin resonance (ESR) and FTIR) and dielectric properties (dielectric constant ε′, loss tanδ ?and conductivity σ_ac etc.). The results were analyzed and correlated with each other in the light of local environment and oxidation states of manganese ion in the glass network. The increase in the area of optical absorption peak and ESR signal intensity indicate that both Mn²⁺ and Mn³⁺ ions exist in octahedral symmetry are increased with increasing MnO dopant in the glass matrix. The semi conducting nature of the glass network is found to increase due to the considerable increase in BO₃, MnO₆ structural units whenever B₂O₃ in the host glass is gradually replaced by MnO.     

The effects of ZnCl2 and ErCl3 on the vibrational spectra and structure of tellurite glasses

A series of zinc tellurite glasses, containing up to 40 mol% ZnCl₂ and doped with 1–10 mol% ErCl₃, was prepared by melting and casting and their structure was analyzed by polarized Raman and variable incidence infrared reflection spectroscopies. Kramers–Kronig analysis of the infrared reflectivity led to the identification of the vibrational mode components. The Raman spectra are dominated by an intense, depolarized boson peak at ∼45 cm⁻¹ and a high frequency, polarized peak at ∼767 cm⁻¹. The introduction of ZnCl₂ and ErCl₃ modifiers led to a blue shift of the high frequency peak, while the intensity of the boson peak was found to increase continuously with the Er³⁺ content. It is shown that the erbium and zinc compounds both break TeOTe bonds, introducing non-bridging chlorine species, connected mostly to the zinc atoms.     

Evolution of pressure-amorphized zirconium tungstate upon annealing

Zirconium tungstate Zr(WO₄)₂ exhibits irreversible amorphization at high pressure. Upon heating, the pressure-amorphized phase transforms into different phase/phases depending on the pressure applied during heating. Transformation of pressure-amorphized samples to metastable cubic phase during isochronal annealing at ambient pressure is investigated using X-ray diffraction and Raman spectroscopy. Though the X-ray diffraction and Raman spectra show only monotonic changes up to 850 K in the amorphous state, the sample exhibits dramatic changes in the color from gray to black to white. The relaxation of the amorphous phase during annealing suggests gradual irreversible volume increase by about 6%, whereas the tungstate tetrahedra are found to shrink. Crystallization to cubic phase at 900 K is accompanied by a large increase in the sample volume. The specific volumes of the amorphous phases obtained from cycling the samples to different pressures suggest the possibility of polyamorphism in this system.     

Waveguides based on Te2As3Se5 thick films for spatial interferometry

Planar waveguides were obtained by deposition of Te₂As₃Se₅ films on polished As₂S₃ glass substrates by RF-sputtering or thermal evaporation. The RF-sputtered films were porous and had a column-like structure. By contrast, the thermal evaporated films were homogeneous and dense. They were adhesive, transparent up to 18 μm and characterized by a refractive index of 2.821 ± 0.005 at 10.6 μm. M-lines measurements highlighted the existence of several guided mode lines, proving that the manufactured structures behaved as waveguides. The geometry of the film was modified by physical or reactive ion etching. Some quasi vertical ribs up to 2.11 μm in depth were etched by reactive ion etching under a CF₄/O₂ atmosphere.     

Characterization of B2O3 and/or WO3 containing tellurite glasses

Characterization of B₂O₃ and/or WO₃ containing tellurite glasses was realized in the 0.80TeO₂–(0.20 ? x)WO₃ ? xB₂O₃ system (0 ≤ x ≤ 0.20 in molar ratio) by using differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectrometry techniques. Glasses were prepared with a conventional melt-quenching technique at 750 °C. To recognize the thermal behavior of the glasses, glass transition and crystallization temperatures, glass stability value, glass transition activation energy, fragility parameter were calculated from the thermal analyses. Density, molar volume, oxygen molar volume and oxygen packing density values were determined to investigate the physical properties of glasses. Fourier transform infrared spectra were interpreted in terms of the structural transformations on the glass network, according to the changing B₂O₃ and/or WO₃ content. Crystallization behavior of the glasses was investigated by in situ X-ray diffraction measurements and microstructural characterization was realized by scanning electron microscopy and energy dispersive X-ray spectrometry analyses.     

Ultra-high thermal expansion glass–ceramics in the system MgO/Al2O3/TiO2/ZrO2/SiO2 by volume crystallization of cristobalite

Glasses in the system MgO/Al₂O₃/TiO₂/ZrO₂/SiO₂ with and without the addition of As₂O₃ and Sb₂O₃ were thermally treated. Up to a temperature of 950 °C, this resulted in the formation of ZrTiO₄, sapphirine and high quartz solid solution. Annealing at higher temperatures led to the formation of low quartz solid solutions, ZrTiO₄ and sapphirine. This resulted in a continuous increase of density, hardness, fracture toughness and thermal expansivity. In the glass doped with As₂O₅ and Sb₂O₅ annealing temperatures >1000 °C resulted in the formation of cristobalite instead of quartz. Then the density, hardness and strength decreased again, while the fracture toughness (up to 2.8 MPa m^1/2) and the thermal expansion coefficient increased strongly. In the dilatometric curves, a steep increase in expansion is observed in the temperature range from 100 to 200 °C, which is attributed to the transformation of low cristobalite to high cristobalite. The mean linear thermal expansion coefficient (25–200 °C) is 20 × 10^?6 K^?1 and the largest up to now reported in the literature for alkali-free silicate glass–ceramics.     

Phase evolution on heat treatment of sodium silicate water glass

Heat treatment of sodium silicate water glass of the nominal composition Na₂O/SiO₂ = 1:3 was carried out from 100 °C up to 800 °C and the advancement of the resulting phases was followed up by powder X-ray diffraction, scanning electron microscopy and thermogravimetry along with differential thermal analysis. The water glass, initially being an amorphous solid, starts to form crystals of β-Na₂Si₂O₅ at about 400 °C and crystallizes the SiO₂ modification cristobalite at about 600 °C that coexists along with β-Na₂Si₂O₅ up to 700 °C. At 750 °C Na₆Si₈O₁₉ appears as a separate phase and beyond 800 °C, the system turns into a liquid.