Formation and laser patterning of perovskite-type KNbO3 crystals in aluminoborate glasses

Perovskite-type nonlinear optical KNbO₃ (KN) crystals are synthesized from 40K₂O-25Nb₂O₅-35B₂O₃ (KNB) and 40K₂O-25Nb₂O₅-25B₂O₃-10Al₂O₃ (KNBA) (mol%) glasses by using a conventional glass-ceramics method. It is found from X-ray diffraction analyses and Raman scattering spectrum measurements that the addition of Al₂O₃ to glass is effective for the formation of perovskite-type KN crystals. A continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) is irradiated onto the surface of CuO-doped (2 mol%) KNB and KNBA glasses, and in particular, perovskite-type KN crystals are patterned in the condition of the laser power of 0.9 W and laser scanning speed of 8 μm/s for KNBA glass containing Al₂O₃. The formation of metastable (not perovskite-type) KN crystals is also confirmed in the samples crystallized in an electric furnace and in laser-patterned lines. The formation behavior of KN crystals in the glasses is discussed from the point of view of glass composition.     

Thermal behavior of the amorphous precursors of the ZrO2-SnO2 system

Thermal behavior of the amorphous precursors of the ZrO₂-SnO₂ system on the ZrO₂-rich side of the concentration range, prepared by co-precipitation from aqueous solutions of the corresponding salts, was monitored using differential thermal analysis, X-ray powder diffraction, Raman spectroscopy, field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectrometry (EDS). The crystallization temperature of the amorphous precursors increased with an increase in the SnO₂ content, from 405 °C (0 mol% SnO₂) to 500 °C (40 mol% SnO₂). Maximum solubility of Sn⁴⁺ ions in the ZrO₂ lattice (∼25 mol%) occurred in the metastable products obtained upon crystallization of the amorphous precursors. A precise determination of unit-cell parameters, using both Rietveld and Le Bail refinements of the powder diffraction patterns, shows that the incorporation of Sn⁴⁺ ions causes an asymmetric distortion of the monoclinic ZrO₂ lattice. The results of phase analysis indicate that the incorporation of Sn⁴⁺ ions has no influence on the stabilization of cubic ZrO₂ and negligible influence on the stabilization of tetragonal ZrO₂. Partial stabilization of tetragonal ZrO₂ in products having a tin content above its solid-solubility limit was attributed to the influence of ZrO₂-SnO₂ surface interactions. In addition to phases closely structurally related to cassiterite, monoclinic ZrO₂ and tetragonal ZrO₂, a small amount of metastable ZrSnO₄ phase appeared in the crystallization products of samples with 40 and 50 mol% of SnO₂ calcined at 1000 °C. Further temperature treatments caused a decrease in and disappearance of metastable phases. The results of the micro-structural analysis show that the sinterability of the crystallization products significantly decreases with an increase in the SnO₂ content.     

The effect of MgO and SiO2 codoping on the properties of Nd:YAG transparent ceramic

Nd:YAG transparent ceramics were fabricated by a reactive sintering method under vacuum using SiO₂, MgO and compound additives (SiO₂ and MgO) as sintering aids. The effects of SiO₂ and MgO on the microstructure and sintering process of Nd:YAG ceramics were studied. High quality Nd:YAG ceramics with compound sintering aids obtained by vacuum sintering at 1780 °C are composed of grains of the size ∼10 μm, and their transmittance is 82% at 400 nm. It was found the absorption coefficient of 1.0 mol% Nd:YAG ceramic was 8.6 cm⁻¹ at 808 nm and its absorption cross section was calculated to be 6.26 × 10⁻²⁰ cm².     

Effect of ZrO2 addition on crystallization behaviour, porosity and chemical-mechanical properties of a CaO-TiO2-P2O5 microporous glass ceramic

2-6 mol% ZrO₂ was added to a base glass composition of P₂O₅ 31.25, CaO 43.75, TiO₂ 25 (mol%) at the expense of TiO₂. The prepared glasses were crystallized to bulk glass ceramics containing the major phases of β-Ca₃(PO₄)₂ and CaTi₄(PO₄)₆. DTA was utilized to determine the appropriate phase separation-nucleation and crystallization temperatures. The crystalline products and resulting microstructures were examined by XRD and SEM. The β-Ca₃(PO₄)₂ phase was dissolved out by leaching the resulting glass ceramics in HCl, leaving a porous skeleton of CaTi₄(PO₄)₆. It was shown that ZrO₂ addition resulted in reduction of volume porosity and mean pore diameter while the specific surface area was increased. The smallest median pore diameter and largest surface area were 8.6 nm and 32 m² g⁻¹ respectively obtained for the specimen containing 6 mol% ZrO₂. The ZrO₂ addition also improved the chemical durability and bending strength of porous glass ceramics.     

Photocatalytic properties of TiO2-P2O5 glass ceramics

Binary TiO₂-P₂O₅ glasses with 69 mol% and 76 mol% TiO₂ were prepared and converted into glass ceramics by heat-treatments. XRD measurements show that the main crystalline phases precipitated in the glass ceramics are anatase-type TiO₂ crystals or (TiO)₂P₂O₇ crystals, depending on the concentration of titanium constituent. Photocatalytic activities of the glass ceramics were evaluated by the decomposition of methylene blue (MB) and measuring the water contact angle. It is found that the glass ceramics containing anatase crystals exhibit both photocatalytic oxidation activity and highly photo-induced hydrophilicity under UV irradiation with intensity of 1.0 mW/cm².     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Sol-gel preparation and properties of TiO2-P2O5 bulk glasses

Monolithic transparent and colorless, or Ti³⁺-free TiO₂-P₂O₅ glasses containing very large amounts of TiO₂ (up to 93 mol%) were successfully prepared by heat-treating the xerogels, which were made from titanium tetraisopropoxide and triethyl phosphate, through the sol-gel reaction. The density and refractive index n_632.8 nm of the sol-gel-derived glasses were higher than the melt-derived glasses of the corresponding compositions. The glasses of TiO₂ content of larger than 80 mol% seemed somewhat porous, but n_632.8 nm of these glasses was very high as 2.2-2.3. Higher density and higher n_632.8 nm than the melt-derived glasses were considered to be due to more abundance of six-fold coordinated Ti⁴⁺ ions.     

The effect of P2O5 on the structure,sintering and sealing properties of barium calcium aluminum boro-silicate (BCABS) glasses

The effect of P₂O₅ incorporation on the sintering, flow and crystallization characteristics of BCABS glasses of composition (mol%) 35BaO–15CaO–5Al₂O₃–(37 − x)SiO₂–8B₂O₃–xP₂O₅ (0 ≤ x ≤5) is investigated. It is observed that addition of P₂O₅, removes cations (Ba²⁺ and Ca²⁺) from the silicate network, resulting in an increase in polymerization. This is reflected by a reduction in TEC and an increase in sealing temperature. In addition, the removal of cations for charge compensation causes a change in major crystalline phases formed, from BaSiO₃ to Ba(Al₂Si₂O₈). In addition, beyond 3 mol% P₂O₅, crystallization of phosphate phases is evident. Based upon the flow temperature, glasses with 0, 1 and 2 mol% P₂O₅ are selected for sealing. In these glasses, conversion of Cr to Cr₂O₃ is observed_, yielding improved adhesion. However, the 2 mol% P₂O₅ glass showed an increased crystallization tendency, resulting in incomplete sintering. Therefore, 1 mol% P₂O₅ seems a good compromise for sealing with improved adhesion.     

Mixed cation effect in xR2O-(40 − x)Na2O-50B2O3-10Bi2O3 (R = Li, K) glasses

Mass density, glass transition temperature and ionic conductivity are measured in xLi₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ and xK₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ glass systems with 0 ≤ x ≤ 40 mol%. The strength of the mixed alkali effect in T_g, dc electrical conductivity and activation energy has been determined in each glass system. The magnitudes of the mixed alkali effect in T_g for the mixed Li/Na glass system are much smaller than those in the mixed K/Na glasses. The impact of mixed alkali effect on dc electrical conductivity in mixed Li/Na glass system is more pronounced than in the K/Na glass system. The results are explained based on dynamic structure model.     

Synthesis and properties of GeS2-Ga2S3-PbI2 chalcohalide glasses

The glass-forming region in the GeS₂-Ga₂S₃-PbI₂ system was determined and the basic parameters of thermal and optical properties (glass transition temperature, density, microhardness and transmission window) for these glasses have been measured. Better thermal stability originated from their larger difference between T_x and T_g in the range of 107-161 °C, higher glass transition temperatures between 252 and 398 °C and wide optical transmission window from 0.5 to 12.7 μm make these glasses the promising candidate materials for rare earth doped fiber amplifiers and nonlinear optical devices.     

Eu ions and CaF2-containing transparent glass-ceramics

Transparent glass-ceramics have been prepared by heat-treating 45SiO₂-20Al₂O₃-10CaO-25CaF₂ glasses doped with Eu²⁺ ions (in mol%). The precipitated crystalline phase in the glass-ceramics was CaF₂. TEM observation showed the precipitated crystalline phase had a size of 11-18 nm and dispersed in the amorphous phase without clustering. Fluorescence measurements showed that Eu²⁺ ions entered into the CaF₂ crystalline phase and gave a much stronger emission in the glass-ceramics than in the corresponding glass.     

Influence of mixed alkali on the spectral properties of vanadyl ions doped xNa2O-(30 − x)K2O-60B2O3 glasses—an EPR and optical study

Electron paramagnetic resonance (EPR) and optical investigations have been performed in the mixed alkali borate xNa₂O-(30 − x)K₂O-60B₂O₃ (5 ≤ x ≤ 25) glasses doped with 10 mol% of vanadyl ions in order to look for the effect of ‘mixed alkalis’ on the spectral properties of the glasses. The observed EPR spectra have structures for x > 5 mol% which are characteristic of a hyperfine interaction arising from an unpaired electron with the ⁵¹V nucleus and it builds up in intensity as x increases. It is observed that the mixed alkali play a significant role in accommodating the vanadyl ions in these mixed alkali glasses and for x > 5 mol%, shows a well resolved hyperfine structure typical for isolated VO²⁺ ions. The spin-Hamiltonian parameters (g and A), the dipolar hyperfine coupling parameter (P) and Fermi contact interaction parameter (k) have been evaluated. It is observed that the spin-Hamiltonian parameters do not vary much with the change in composition. It is observed that with increase of x, an increase occurs in tetragonal distortion for VO²⁺. The number of spins (N) participating in resonance and the paramagnetic susceptibility (χ) have been calculated. It is observed that N and χ increase with x. The optical bandgap energies evaluated for these glasses slightly increase with x and reach a maximum around x = 20 and thereafter decrease showing the mixed alkali effect. Optical band gap energies obtained in the present work vary from 2.73 to 3.10 eV for both the direct and indirect transitions. The physical parameters of the glasses are also determined with respect to the composition.     

Crystallization kinetics and thermal properties of 20Li2O-80TeO2 glass

In this work, X-ray diffraction, Raman spectroscopy and differential scanning calorimetry techniques were used to understand the crystallization process on 20Li₂O-80TeO₂ glass. X-ray diffraction results reveal the presence of three distinct alpha γ-TeO₂, α-TeO₂ and α-Li₂Te₂O₅ crystalline phases in the glass matrix. The Raman spectroscopy band structure of this glass is similar to the one observed in glassy TeO₂. Raman results clearly reveal the metastable character of the γ-TeO₂ phase in the 20Li₂O-80TeO₂ glass, whose associated vibration modes disappear completely at temperatures higher than 315 °C. On the other hand, the Raman modes associated to α-TeO₂ and α-Li₂Te₂O₅ phases persists up to temperatures close to the final stages of the crystallization in the studied glass (around 420 °C). From DSC measurements, the activation energies 296 ± 3 and 298 ± 1 kJ mol⁻¹ were associated to γ-TeO₂ and α-TeO₂ phases crystallization, indicating that these phases crystallizes at temperatures very close in the studied glass.     

Second Harmonic Generation induced by optical poling in new TeO2-Tl2O-ZnO glasses

New tellurite glasses with a large glass forming domain were elaborated within the TeO₂-Tl₂O-ZnO ternary system. The evolution of the glass transition (T_g) and onset crystallization (T₀) temperatures for such tellurite glasses was studied, in particular, as a function of the Tl₂O addition. A decrease of both T_g and T₀ temperatures was observed; the former being more affected. Structural modifications induced by the addition of the modifiers were studied by Raman spectroscopy. For a fixed ZnO concentration, the increase in the Tl₂O content leads to a destruction of the glass framework, characterized by the transformation of TeO₄ disphenoids into isolated TeO₃²⁻ trigonal pyramid-like ortho-groups. For a fixed Tl₂O concentration, the ZnO addition induces similar effects on the glass structure. The optical transmission of the ((80 − x)TeO₂-xTl₂O-20ZnO) (x = 10, 20 and 30 mol%) glasses was measured in the 300-2000 nm range. Their good transparency was evidenced and a clear reduction of the optical band-gap was noticed with the increase in the Tl₂O content. Finally, Second Harmonic Generation was unambiguously detected for each glass composition. The second order non-linearity amplitude is found to be increasing as a function of the Tl₂O concentration, in the tested range.     

Raman spectroscopic study of structure of WO3La2O3B2O3 glasses with no color and crystallization of LaBWO6

Glasses with the nominal compositions of xWO₃25La₂O₃(75 − x)B₂O₃ (mol%) with x = 15, 25, and 50 were prepared using a conventional melt quenching method, and their structure and crystallization behavior were examined from Raman scattering spectra and X-ray diffraction analyses. The glasses are colorless in the visible light region and give the optical band gap energy of 3.49-3.61 eV. The glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing WO₃ content. The strong Raman bands at 840 and 940-960 cm⁻¹ suggest that the main coordination state of W⁶⁺ ions in the glasses is isolated (WO₄)²⁻ tetrahedral units. The formation of WO₆ octahedral units is also suggested in the glasses with high WO₃ contents. The main crystallization mechanism in the glasses is the surface crystallization, and the glass of 50WO₃25La₂O₃25B₂O₃ shows the crystallization of LaBWO₆ single phase. The present study proposes that WO₃La₂O₃B₂O₃ glasses and crystallized glasses are very interesting as optical functional materials.     

Characterization of Bi4−xRxTi3O12 (Rx = Pr, Nd, Gd, Dy, x = 0.8) layered electroceramics by a photoacoustic method

We have carried out photoacoustic experiments to study the layered electroceramics Bi_4−xR_xTi₃O₁₂ (R_x=Pr, Nd, Gd, Dy), with x=0.8. Results are shown in terms of successive analyses performed on functions, PA(t, T_i), which result from the interaction of the laser beam with the crystalline lattice. Previous permittivity experiments performed in the materials suggested anomalous ferroelectric behavior. Using a pulsed Nd:YAG laser (10 Hz, 5 ns pulse width), photoacoustic experiments were run from room temperature up to 800 °C. Perturbations in the resultant correlation curves can be interpreted as the existence of a wide set of different transition temperatures in the material, such as are believed to occur in relaxors. From these experiments, we conclude that the temperature dependence of non-classical ferroelectrics can be more closely monitored.     

Microstructure and electrical properties of Sm2O3 doped Bi2O3-based ZnO varistor ceramics

The dependence of the bulk density, microstructure and dc electrical properties of bismuth oxide (Bi₂O₃)-based zinc oxide (ZnO) varistor ceramics for various samarium oxide (Sm₂O₃) contents was investigated. The value of bulk density was found to 5.43-5.50 g cm⁻³ with Sm₂O₃ (mol%) content. The maximum value of bulk density is observed to be 5.50 for 0.30 mol% Sm₂O₃ containing varistor ceramics. The grain sizes for all the samples calculated from the scanning electron micrographs were found to decrease as Sm₂O₃ increases. The presence of ZnO phases, Bi-rich phases, spinel phases and Sm₂O₃ phases were observed in the samples by the energy dispersive X-ray analysis and X-ray diffraction analysis. As the Sm₂O₃ amount increased in the Bi₂O₃-based ZnO varistor ceramics, the nonlinear coefficient, α increased up to 0.10 mol%, reaching a maximum value of 58 and then decreased. The breakdown electric field, E_b, increased with the increase of Sm₂O₃ content with a maximum value of 3220 V cm⁻¹ for the 0.75 mol% Sm₂O₃ doped ZnO varistor ceramics. The leakage current, I_L, showed a minimum value of 1.10 μA for the composition of 0.30 mol% Sm₂O₃ doped Bi₂O₃-based ZnO varistor ceramics. The 0.30 mol% Sm₂O₃-doped Bi₂O₃-based ZnO varistor ceramics sintered at 1200 °C exhibited a good stability for dc accelerated aging stress of 0.90 V_1 mA/90 °C/12 h.     

Structural characterization of 0.5PbMg1/3Nb2/3O3-0.5BaxPb(1−x)TiO3 powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5Pb(Mg_1/3Nb_2/3)O₃-0.5(Ba_xPb_(1−x)TiO₃) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 nm for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 °C for 4 h.     

Study of thermal and optical properties of GeS2-Ga2S3-Ag2S chalcogenide glasses

Chalcogenide glasses in the GeS₂-Ga₂S₃-Ag₂S pseudo-ternary system were prepared by melt-quenching technique. The structural evolvement of the glasses was studied by Raman spectroscopy. The Raman results show that the addition of Ag₂S involves the breaking of [S₃Ge-GeS₃] ethane-like units and the formation of Ag-S ionic bonds. The results of differential scanning calorimetry (DSC) show that the glasses have relatively high-glass transition temperatures and good thermal stabilities. These GeS₂-Ga₂S₃-Ag₂S glasses have a wide range of transmission approximately from 0.50 to 12.5 μm. In addition, with the method of Maker fringe, SHG was observed in the 0.9GeS₂-0.05Ga₂S₃-0.05Ag₂S glass irradiated by an electron beam. The value of second-order nonlinear optical susceptibility d is as large as 6.6 pm/V, and the poling mechanism of electron beam irradiation was also discussed in this work.     

Glass formation and properties of GeSe2-Ga2Se3-MX (MX is alkali halide) chalcohalide glasses

The glass forming, optical, thermal, and mechanical properties of GeSe₂-Ga₂Se₃-MX (MX is alkali halide) chalcohalide glasses are reported. A unique property of the glasses is that they have excellent transparency in red-light region in addition to the 8-14 μm atmospheric window. This property is interesting and important for improving the quality control of infrared systems. These glasses also present good thermal stability. They could be promising materials for infrared transmitting applications, although their thermo-mechanical properties are relatively weak.