High-purity TeO2–WO3–(La2O3, Bi2O3) glasses for fiber-optics

TeO₂–WO₃, TeO₂–WO₃–La₂O₃ and TeO₂–WO₃–La₂O₃–Bi₂O₃ glasses were produced by high-purity oxides mixtures melting in crucibles of gold or platinum in purified oxygen atmosphere. The total content of Cu, Mn, Fe, Co and Ni impurities was not more than 0.1–2 ppm wt in glasses and below 0.1 ppm wt in the initial oxides. The hydroxyl groups absorption coefficients of the tellurite glasses at the maximum of the absorption band (λ ∼ 3 μm) lay in the region of 0.01–0.001 cm⁻¹. Stability to crystallization characterized by T_x − T_g = 150–190 °C was demonstrated for high purity 75TeO₂–25WO₃ glasses by DSC-measurements. There were no thermal effects of crystallization and crystallized phases fusion in case of La₂O₃-containing glasses.The optical absorption losses, measured by the laser calorimetry method at λ = 1.06, 1.56 and 1.97 μm, did not exceed 40–120 dB/km for glass samples. The multimode optical fibers with optical losses of 50–250 dB/km at 1.2–2.2 μm were produced from high-purity TeO₂–WO₃–(La₂O₃, Bi₂O₃) glasses.     

Glasses and glass-ceramics in the SrO–TiO2–Al2O3–SiO2–B2O3 system and the effect of P2O5 additions

The glass formation abilities of various compositions in SrO–TiO₂–Al₂O₃–SiO₂, SrO–TiO₂–B₂O₃–SiO₂, SrO–TiO₂–Al₂O₃–B₂O₃, and SrO–TiO₂–Al₂O₃–SiO₂–B₂O₃ systems were studied. Many new compositions were found to be suitable for the casting of crack-free, optically clear glasses of different color and with glass transition temperatures ranging from 595 to 775 °C. The crystallization behavior, structure, and thermal expansion behavior of selected glasses were analyzed by DTA, XRD, dilatometry, and heat treatment. The effect of P₂O₅ on the glass structure and crystallization behavior was also studied. P₂O₅ played a dual role depending on composition. In some glasses it acted as a nucleating agent while in others it suppressed crystallization. Heat treatment of borate and borosilicate glasses transformed them into glass-ceramics while comparable SrO–TiO₂–Al₂O₃–SiO₂ glasses showed a lower tendency to crystallize and form glass-ceramics under the same conditions.     

Effect of Al2O3 concentration on zirconolite (Ca(Zr,Hf)Ti2O7) crystallization in (TiO2,ZrO2,HfO2)-rich SiO2–Al2O3–CaO–Na2O glasses

Glass-ceramic matrices containing zirconolite (nominally Ca(Zr,Hf)Ti₂O₇) crystals in their bulk that would incorporate high proportions of minor actinides (Np, Am, Cm) or plutonium could be envisaged for their immobilization. Zirconolite-based glass-ceramics can be prepared by controlled crystallization of zirconolite in glasses belonging to SiO₂–Al₂O₃–CaO–Na₂O–TiO₂–ZrO₂–HfO₂ system. In this study, neodymium was used as trivalent actinides surrogate. Increasing Al₂O₃ concentration in glass composition had a strong effect on the nucleation rate I _z of zirconolite crystals in the bulk, on the amount of neodymium incorporated in zirconolite phase and on the crystal growth rate of silicate phases (titanite + anorthite) from glass surface. These results could be explained by the existence of competition—in favor of aluminum—between Al³⁺ and (Ti⁴⁺, Zr⁴⁺, Hf⁴⁺) ions for their association with charge compensators cations to facilitate their incorporation in the glassy network. Differential thermal analysis (DTA) was used to study exothermal effects associated with bulk and surface crystallization. ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra showed that aluminum enters glasses network predominantly in 4-fold coordination. Neodymium optical absorption and fluorescence spectroscopies showed that the Al₂O₃ concentration changes performed in this study had not significant effect on Nd³⁺ ions environment in glasses.     

Crystallization of CaHf1? x Zr x Ti2O7 (0?≤ x ≤?1) zirconolite in SiO2–Al2O3–CaO–Na2O–TiO2–HfO2–ZrO2–Nd2O3 glasses

Glass-ceramics containing (Hf,Zr)-zirconolite crystals (nominally CaHf_1−x Zr _x Ti₂O₇ with 0 ≤ x ≤ 1) were envisaged to immobilize minor actinides and plutonium. Such materials were prepared in this study by controlled crystallization of glasses belonging to the SiO₂–Al₂O₃–CaO–Na₂O–TiO₂–HfO₂–ZrO₂–Nd₂O₃ system. Neodymium was used as trivalent actinides surrogate. The effect of total or partial substitution of ZrO₂ by HfO₂ (neutron poison for fission reactions) on glass crystallization in the bulk and near the surface is presented. It appeared that Hf/Zr substitution had not significant effect on nature, structure, and composition of crystals formed both on glass surface (titanite + anorthite) and in the bulk (zirconolite). This result can be explained by the close properties of Zr⁴⁺ and Hf⁴⁺ ions and by their similar structural role in glass structure. However, strong differences were observed between the nucleation rate I_Z of zirconolite crystals in glasses containing only HfO₂ and in glasses containing only ZrO₂. Hf-zirconolite (CaHfTi₂O₇) crystals were shown to nucleate only very slowly in comparison with Zr-zirconolite (CaZrTi₂O₇) crystals. Composition changes - by increasing either HfO₂ or Al₂O₃ concentration or by introducing ZrO₂ in parent glass - were performed to increase I_Z in hafnium-rich glasses. The proportion of Nd³⁺ ions incorporated in the zirconolite phase was estimated using ESR.     

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.     

Production and properties of high purity TeO2–ZnO–Na2O–Bi2O3 and TeO2–WO3–La2O3–MoO3 glasses

High-purity TeO₂–ZnO–Na₂O–Bi₂O₃ and TeO₂–WO₃–La₂O₃–MoO₃ glasses were produced by melting the high-purity oxides mixtures in platinum or gold crucible at 800 °C in hermetic chamber in the purified oxygen atmosphere. The content of limiting impurities in the produced initial oxides and glasses, the optical properties as well as the stability to crystallization were investigated. The optical fibers were produced from high-purity tellurite glasses with losses at the level of several hundreds of dB/km.The total content of 3d-transition metals in the glasses was not more than 1 ppm wt and content of hydroxyl groups corresponded to the absorption level of 0.001–0.002 cm⁻¹ at ∼3 μm. The absorption band, monotonically increasing with the increase in MoO₃ content, was observed in dry TeO₂–WO₃–La₂O₃–MoO₃ glasses with the maximum at about 3.7 μm.     

Characterization of Al2O3/ZrO2 nano multilayer thin films prepared by pulsed laser deposition

Microstructural characterization of pulsed laser deposited Al₂O₃/ZrO₂ multilayers on Si (1 0 0) substrates at an optimized oxygen partial pressure of 3 × 10⁻² mbar and at room temperature (298 K) has been carried out. A nanolaminate structure consisting of alternate layers of ZrO₂ and Al₂O₃ with 40 bi-layers was fabricated at different zirconia layer thicknesses (20, 15 and 10 nm). The objective of the work is to study the effect of ZrO₂ layer thickness on the stabilization of tetragonal ZrO₂ phase for a constant Al₂O₃ layer thickness of 5 nm. The Al₂O₃/ZrO₂ multilayer films were characterized using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1473 K. The studies showed that the thickness of the zirconia layer has a profound influence on the crystallization temperature for the formation of tetragonal zirconia phase. The tetragonal phase content increased with the decrease of ZrO₂ layer thickness. The cross-sectional transmission electron microscope (XTEM) investigations were carried out on a multilayer thin films deposited at room temperature. The XTEM studies showed the formation of uniform thickness layers with higher fraction of monoclinic and small fraction of tetragonal phases of zirconia and amorphous alumina.     

Fabrication and optical properties of fibers with an Al2O3-P2O5-SiO2 glass core

A process has been developed for the fabrication of preforms and fibers with Al₂O₃-P₂O₅-SiO₂ glass cores, and their optical properties have been investigated. The results demonstrate that the refractive index and optical losses of the glasses studied are nonadditive functions of Al₂O₃ and P₂O₅ contents in the range 0–20 mol %. Original Russian Text ? M.M. Bubnov, V.N. Vechkanov, A.N. Gur’yanov, K.V. Zotov, D.S. Lipatov, M.E. Likhachev, M.V. Yashkov, 2009, published in Neorganicheskie Materialy, 2009, vol. 45, No. 4, pp. 496–501.     

CuO-TiO_2复合助剂低温烧结氧化铝陶瓷的机理(Ⅱ)

固定CuO(0.4%)和TiO₂(4%)的添加量、改变TiO₂(0--32%)和CuO(0--3.2%)的添加量(质量分数, 下同), 研究了CuO--TiO₂复合助剂对氧化铝陶瓷烧结性能、微观结构、物相组成以及烧结激活能的影响, 以揭示复合助剂的低温烧结机理。结果表明, 在1150--1200℃TiO₂固溶入Al₂O₃生成Al₂Ti₇O₁₅相, 并生成大量正离子空位提高了扩散系数, 从而以固相反应烧结的作用机理促进了氧化铝陶瓷的致密化; TiO₂在Al₂O₃中的极限固溶度为2%--4%, 超过固溶极限的TiO₂对陶瓷烧结没有促进作用; 添加适量的CuO(0.4%)可将TiO₂在Al₂O₃中的固溶温度降低到1100℃以下, 并以液相润湿作用促进氧化铝陶瓷的致密烧结。陶瓷烧结激活能的计算结果定量地印证了上述烧结机理; 当在Al₂O₃中添加4%的TiO₂和2.4%的CuO, 可将烧结激活能降低到54.15 kJ ? mol-1。     

Structural properties of Al2O3-La2O3 binary oxides prepared by sol-gel

The structural properties of La₂O₃ and Al₂O₃-La₂O₃ binary oxides prepared by sol-gel were studied by XRD, HRTEM and UV-vis. The binary oxides with high lanthana contents show an amorphous structure after calcination at 650 °C. At calcination temperatures higher than 1000 °C there is a phase transformation from the amorphous state to the crystalline LaAlO₃ with a perovskite structure. The structure of La₂O₃ is consistent with the hexagonal system; however, some crystalline microdomains with a monoclinic structure were detected by HRTEM. Islands of La₂O₃ and LaAl₁₁O₁₈ phases were detected at high lanthana concentration in the binary oxide. The modification in the coordination shell of the Al³⁺ cations due to the interaction with La³⁺ cations confirms the formation of phases with a perovskite structure and the presence of islands of the LaAl₁₁O₁₈ phase.     

Fabrication of nanostructure Al2O3/ZrO2 (Y2O3) eutectic by combustion synthesis melt-casting under ultra-high gravity

A novel method for preparing Al₂O₃/ZrO₂ (Y₂O₃) eutectic was developed by combining combustion synthesis with melt-casting under ultra-high gravity (CSMC-UHG). The application of UHG = 800 g resulted in a high relative density of 99.8%, and an orientation-growth along the UHG direction. The microstructure was composed of aligned growth regimes containing a triangular dispersion of orderly ZrO₂ rods in Al₂O₃ matrix with a spacing of 300 nm. The eutectic had a high fracture toughness up to 17.9 MPa·m^1/2, which was mainly attributed to the nanostructure and the elastic bridge effects of the aligned ZrO₂ rods.     

Structure and property changes of ZrO2/Al2O3/ZrO2 laminate induced by low-temperature NH3 annealing applicable to metal-insulator-metal capacitor

Phase transformation and morphology evolution of ZrO₂/Al₂O₃/ZrO₂ laminate induced by the post-deposition NH₃ annealing at 480 °C were studied and the effect on the electrical property of the TiN/ZrO₂/Al₂O₃/ZrO₂/TiN capacitor module was evaluated in dynamic random access memory cell. Experimental results indicated N could indeed be incorporated into the dielectric laminate by the low-temperature NH₃ annealing, resulting in tetragonal-to-cubic phase transformation and small crystallites in the ZrO₂ layers. The C residue and Cl impurity in the ZrO₂/Al₂O₃/ZrO₂ laminate, which derived from the dielectric film formation and capping TiN layer deposition, respectively, could also be reduced by the nitridation process. As a result of the better surface morphology and less impurity content, lower dielectric leakage current and longer reliability lifetime were observed for the nitrided ZrO₂/Al₂O₃/ZrO₂ capacitor. This study demonstrates the low-temperature NH₃ annealing on ZrO₂/Al₂O₃/ZrO₂ dielectric can be applicable to the metal-insulator-metal capacitor structure with nitride-based electrode, which brings advantages over mass production-wise property improvements and extends the practical applicability of the ZrO₂/Al₂O₃/ZrO₂ dielectric.     

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.     

Low-temperature sintering characteristics of nano-sized BaNd2Ti5O14 and Bi2O3–B2O3–ZnO–SiO2 glass powders prepared by gas-phase reactions

Nano-sized BaNd₂Ti₅O₁₄ (BNT) powders were prepared by spray pyrolysis from solutions containing ethylenediaminetetraacetic acid and citric acid. Treatment at temperatures ≥900 °C and subsequent milling resulted in nanoparticle powders with orthorhombic crystal structures. The mean particle size of the powder post-treated at 1000 °C was 160 nm. Nano-sized Bi₂O₃–B₂O₃–ZnO–SiO₂ glass powder with 33 nm average particle size was prepared by flame spray pyrolysis and used as a sintering agent for the BNT. BNT pellets sintered at 1100 °C without the glass had porous structures and fine grain sizes. Those similarly sintered with the glass had denser structures and larger grains.     

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.     

The optical properties of Bi3.25La0.75Ti3O12 thin films with different thickness prepared by chemical solution deposition

Bi_3.25La_0.75Ti₃O₁₂(BiLT) thin films with different thickness were successfully deposited onto fused quartz by chemical solution deposition. X-ray diffraction analysis shows that BiLT thin films are polycrystalline with (0 0 2)-preferred orientation. The dispersion of refractive indices of the BiLT thin films was investigated by the optical transmittance spectrum. The optical band gap energy was estimated from the graph of (hνα)² versus hν. The results show that the refractive index and band-gap energy of the BiLT thin films decrease with the films thickness.     

Chemical stability and dielectric properties of RO-La2O3-B2O3 (R = Ca, Mg, Zn)-based ceramics

New lanthanum borate (La₂O₃-B₂O₃) glasses modified with divalent oxides, such as CaO, MgO and ZnO were investigated as potential low temperature dielectrics by understanding compositional dependence of dielectric properties and chemical leaching resistance. Firing behavior, such as densification and crystallization, depended strongly on the glass composition and is found to influence the resultant dielectric performance. Specifically, the dielectric composition of 20ZnO-20La₂O₃-60B₂O₃ glass with 40 wt% Al₂O₃ as a filler showed distinct enhancements of dielectric properties, i.e., k ∼ 8.3 and Q ∼ 1091 at the resonant frequency of 17.1 GHz, as a result of 850 °C firing. The result was believed related to earlier densification and unexpected evolvements of ZnAl₂O₄ and La(BO₂)₃ phases during firing. The Mg-containing glass sample was most stable in strong acid solutions and did not show any significant changes in microstructure even after 300 min exposure. The Ca-containing glass sample was not regarded as a promising candidate for low temperature dielectrics from the observed low quality factor and weak chemical durability.     

Sintering and dielectric properties of 0.88Al2O3-0.12TiO2 microwave ceramics by glass addition

The microwave characteristics and the microstructures of 0.88Al₂O₃-0.12TiO₂ with various amounts of MgO-CaO-SiO₂-Al₂O₃ (MCAS) glass sintered at different temperatures have been investigated. The sintering temperature can be lowered to 1300 °C by the addition of MCAS glass. The densities, dielectric constants (ε_r) and quality values (Q×f) of the MCAS-added 0.88Al₂O₃-0.12TiO₂ ceramics decrease with the increase of MCAS glass content. The temperature coefficients of the resonant frequency (τ_f) are shifted to more negative values as the MCAS content or the sintering temperatures increase. The change of the crystalline phases of Al₂TiO₅ phase and rutile-TiO₂ phase has profound effects on the microwave dielectric properties of the MCAS-added Al₂O₃-TiO₂ ceramics. As sintered at 1250 °C, 0.88Al₂O₃-0.12TiO₂ ceramics with 2 wt.% MCAS glass addition exists a ε_r value of 8.63, a Q×f value of 9578 and a τ_f value of +5 ppm/°C.     

Ultrapure SiO2 and Al2O3 for the preparation of low-loss compound glasses

The application of glass fibers for optical communications requires the preparation of glasses with ultralow transition metal contents. If the glasses are made by melting, raw materials in the form of powders with a purity at least equal to that required for the glass fibers must be available. This paper describes the preparation of ultrapure SiO₂ and Al₂O₃ powders by liquid state hydrolysis of alcoholates.     

Electrical properties of Pb0.97La0.02(Zr0.95Ti0.05)O3 antiferroelectric thin films on TiO2 buffer layer

Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ antiferroelectric thin films with thickness of 500 nm were successfully deposited on TiO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates via sol-gel process. Microstructure of Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was studied by X-ray diffraction analyses. The antiferroelectric nature of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was confirmed by the double hysteresis behaviors of polarization and double buffer fly response of dielectric constant versus applied voltage at room temperature. The capacitance-voltage behaviors of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films with and without TiO₂ buffer layer were studied, as a function of temperature. The temperature dependence of dielectric constant displayed a similar behavior and the Curie temperature (T_c) was 193 °C for films on both substrates. The current caused by the polarization and depolarization of polar in the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films was detected by current density-electric field measurement.