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.     

La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)-Ce_(0.9)Gd_(0.1)O_(1.95)高温电导弛豫的研究

通过直流四端法研究了钙钛矿型混合导体La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)和La0.6Sr0.4Co0.2Fe0.8O3-δ-Ce0.9Gd0.1O1.95(LSCF-GDC)复合材料的高温电学性质.通过电导率测试得出单相LSCF和LSCF-GDC的小极化子导电活化能分别为Ea1=9.72kJ/mol和Ea2=10.64kJ/mol.突然改变氧分压条件进行电导弛豫测试,进而研究了二者的氧表面交换性质.测定了温度范围在600~800℃、氧分压在21~34kPa之间变化时两种样品的表面交换系数为kchem为2.87×10-6~6.91×10-6cm/s.讨论认为GDC对氧表面交换过程的催化作用与引入GDC对材料微结构的影响共同促进了复合材料中的氧输运过程.根据两种样品氧表面交换系数和温度的关系估算了氧表面交换过程活化能.     

一种SiC/SixOyCz非连续增强陶瓷基复合材料的制备及性能

以聚硅氧烷类有机硅树脂YR3370(GE toshiba silicones)裂解生成的无定形Si_<em>xO_<em>yC_<em>z陶瓷为基质, 以0.8μm SiC颗粒为非连续增强介质, 制备了一种SiC/Si_<em>xO_<em>yC_<em>z非连续增强陶瓷基复合材料。含SiC颗粒50%的素坯在99.99%N₂气流中于1100~1300℃下保温1h, 所制备的陶瓷基复合材料密度可达2.27g/cm3, 维氏硬度可达741kg/mm2。通过结构模拟和强度计算分析了SiC/Si_<em>xO_<em>yC_<em>z陶瓷基复合材料的力学性能, 其结构特点是连续的无定形Si_<em>xO_<em>yC_<em>z陶瓷基质包围着分散的作为非连续增强介质的SiC颗粒, 基质与增强介质之间具有合理的热匹配, 并且可以改善单一陶瓷材料的脆性。     

Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

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.     

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.     

Electrochemical characteristics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ–Sm0.2Ce0.8O1.9 composite materials for low-temperature solid oxide fuel cell cathodes

In this paper, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ–xSm_0.2Ce_0.8O_1.9 (BSCF–xSDC, x = 0–60 wt.%) composite cathodes were prepared by soft chemical methods, and then examined for potential applications in lower temperature solid oxide fuel cells. Both DC polarization and AC impedance spectroscopy measurements indicated that the addition of SDC electrolyte into BSCF remarkably improved the electrochemical properties. The optimum composition was found to be BSCF–30SDC, which exhibited 5.5 times higher polarization current density and 15.1% polarization resistance, compared with the pure-phase BSCF cathode at 550 °C.     

Glass formation and conductivity in the Pb2P2O7–Ag4P2O7–AgI system

A large glass-forming domain has been identified in the Pb₂P₂O₇–Ag₄P₂O₇–AgI system. The physical properties have been determined as a function of AgI content. The ionic conductivity has been studied as a function of the Ag⁺ ion total concentration and the Ag⁺ ion concentration issued from the AgI component. The structure and electrical properties of obtained glasses are compared with those of ionic glasses of the Ag₄P₂O₇–AgI system.     

TeO_2-Nb_2O_5-P_2O_5系统玻璃的成玻特性和性能

研究了TeO₂--Nb₂O₅--P₂O₅三元系统的玻璃形成能力和相关理化性能。结果表明, 在TeO₂(80%--90%), Nb₂O₅(0--20%), P₂O₅(0--20%)(摩尔分数)成分范围内可以形成性能良好的透明玻璃, 碲氧、磷氧和少量的铌氧结构单元共同构建了稳定的链状玻璃网络骨架。TeO₂--Nb₂O₅--P₂O₅玻璃的转变温度为394--425℃、折射率为1.65--1.88。     

Calcium zinc manganites, Ca4Mn7Zn3O21 − δ (0.5 < δ < 2.5) with beta-alumina or magnetoplumbite-type structure and their nonlinear electrical transport and magnetic properties

Phase-pure calcium zinc manganite, Ca₄Mn₇Zn₃O_21 − δ has been synthesized by the solid-state reaction between CaMnO₃, ZnO and Mn₃O₄ at ∼ 1300 °C. Conversion of Ca₄Mn₇Zn₃O_21 − δ to Ca₄Mn₇Zn₃O_19 ± δ occurs at 1330-1350 °C which is influenced by the oxygen nonstoichiometry associated with increasing Mn³⁺/Mn⁴⁺ ratio. The Ca₄Mn₇Zn₃O_21 − δ phase is rhombohedral (space group = R3¯m) and has the β″-alumina (BA)-type structure consisting dominantly of Mn⁴⁺ (3d³) ions. The Ca₄Mn₇Zn₃O_19 ± δ is hexagonal (space group = P6₃/mmc) having the magnetoplumbite (MP)-type structure containing dominantly Mn³⁺ (3d⁴) ions. The electrical transport properties of Ca₄Mn₇Zn₃O_21 − δ and Ca₄Mn₇Zn₃O_19 ± δ are indicative of the activated-type small polaron hopping conductivity below 366 and 392 K respectively. The anisotropic charge transport is influenced only in a limited way by the mixed-valency of Mn prevailing in the manganite spinel blocks. Highly nonlinear current-voltage (I-V) curves with nonlinearity coefficient, α, up to 64 was achieved at the turn-on field strength E_t ∼ 110-160 V/mm. Magnetic properties of Ca₄Mn₇Zn₃O_21 − δ and Ca₄Mn₇Zn₃O_19 ± δ have been investigated which showed the antiferromagnetic-insulating (AFI) behavior with T_N = 103 and 80 K and with an AF-ordered effective magnetic moment, μ_eff = 3.54 and 4.28 μ_B/Mn respectively. The Ca₄Mn₇Zn₃O_19 ± δ phase showed the ferrimagnetic interaction below T_N (at ∼ 20 K).     

Photoinduced nonlinear optics in Sb2Se3–BaCl2–PbCl2 glasses

Photoinduced structural transformations in amorphous Sb₂Se₃–BaCl₂–PbCl₂ glasses were studied using a differential IR spectroscopy Fourier technique in the spectral region between 100 and 300 cm⁻¹. A stage of the reversible photodarkening is realized in the Sb₂Se₃ fragments after the first cycle of photoexposure and thermoannealing. The whole scheme of the photo- and thermoinduced transformations in the amorphous system may be explained as a coordination of formation and annihilation of defects. The vibrational density of states calculated using quantum chemical solid state methods confirms our experimental results and their interpretation. Photoinduced photodarkening changes using a CO₂ pulse laser (λ=10.6 μm) in new synthesized Sb₂Se₃–BaCl₂–PbCl₂ glasses were investigated. At the same time we have studied photoinduced second harmonic generation (SHG) and two-photon absorption (TPA). The possibility of using this glass as perspective materials for IR optoelectronics and nonlinear optics was shown.     

Photoconductive properties of organic-inorganic hybrid perovskite (C6H13NH3)2(CH3NH3)m − 1PbmI3m + 1:TiO2 nanocomposites device structure

Photoconductive devices, with remarkable photoconductive performance, of fluorine doped tin oxide/TiO₂/(C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2):TiO₂/Pt were fabricated. An electron injection mechanism from the (C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2) to TiO₂ was proposed for the photoconductive effects, where organic-inorganic hybrid perovskite (C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2), self-organized into mesoscopic TiO₂ films from solution directly, served as the electron donor. The photoconductive performance of the devices can be adjusted by the inorganic sheet thickness (tuned by m) of the hybrid perovskite. The photocurrent value increased as m value increased at the same illumination. Further, when bias voltage was 1.0 V, the ratio of photocurrent and dark current for (C₆H₁₃NH₃)₂(CH₃NH₃)_2⁻ Pb₂I₇:TiO₂ reached as high as 7.05 × 10³. The devices could be potentially used as light detectors and light-controlled switch.     

Physical properties of a new cuprate superconductor Pr2Ba4Cu7O15−δ

We present studies of the thermal, magnetic, and electrical transport properties of reduced polycrystalline Pr₂Ba₄Cu₇O_15−δ (Pr247) showing a superconducting transition at T_c=10–16 K, and compare them with those of as-sintered non-superconducting Pr247. The electrical resistivity in the normal state exhibited T² dependence up to approximately 150 K. A clear specific heat anomaly was observed at T_c for Pr247 reduced in a vacuum for 24 h, proving the bulk nature of the superconducting state. By the reduction treatment, the magnetic ordering temperature T_N of Pr moments decreased from 16 to 11 K, and the entropy associated with the ordering increased, while the effective paramagnetic moments obtained from the DC magnetic susceptibility varied from 2.72 to 3.13μ_B. The sign of Hall coefficient changed from positive to negative with decreasing temperature in the normal state of a superconducting Pr247, while that of the as-sintered one was positive down to 5 K. The electrical resistivity under high magnetic fields was found to exhibit T^α dependence (α=0.08–0.4) at low temperatures. A possibility of superconductivity in the so-called CuO double chains is discussed.     

Sol–gel synthesis and characterization of Li2O–As2O5–SiO2 glassy system

The ternary 10% Li₂O + 90% (xAs₂O₅ + (1 − x) SiO₂) (x = 0.025, 0.05, 0.075 and 0.1) (LAS) glassy system with different compositions were prepared using sol–gel technique. All the prepared samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry techniques. The observed peak-free XRD patterns confirm the amorphous phase of the prepared LAS compounds. Structural coordination of LAS glassy samples was confirmed by Fourier transform infrared spectroscopy. Thermal behavior of the glassy samples was characterized by differential scanning calorimetry. Bulk conductivity of all the LAS glassy samples was calculated by analyzing the impedance data measured at different temperatures. Activation energy (E_a) is evaluated from the log σT vs. 1000/T plot and it is found to be 0.837 eV.     

Morphotropic phase boundary in high temperature ferroelectric xBi(Zn1/2Ti1/2)O3 − yPbZrO3 − zPbTiO3 perovskite ternary solid solution

A bismuth and lead oxide based perovskite ternary solid solution xBi(Zn_1/2Ti_1/2)O₃ − yPbZrO₃ − zPbTiO₃ (xBZT − yPZ − zPT) was investigated as an attempt to develop a high T_C ferroelectric material for piezoelectric sensor and actuator applications. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was determined through an XRD study on a pseudobinary line 0.1BZT − 0.9[xPT − (1 − x)PZ] for composition 0.1Bi(Zn_1/2Ti_1/2)O₃ − 0.5PbZrO₃ − 0.4PbTiO₃. Enhanced piezoelectric and ferroelectric activities were observed for MPB composition with dielectric constant ε_r′ ~ 23,000 at Curie temperature (T_C) ≈ 320 °C, remanent polarization (P_r) = 35 μC/cm², piezoelectric coefficient (d₃₃) = 300 pC/N, unipolar strain = 0.15%, and electromechanical coupling coefficient (k_P) = 0.45.     

White-emitting phosphors Ca6La2Na2(PO4)6F2:Dy and luminescence enhancement through Ce → Dy energy transfer

Ce³⁺ and Dy³⁺ activated fluoro-apatite Ca₆La₂Na₂(PO₄)₆F₂ with chemical formulas Ca₆La_2−xLn_xNa₂(PO₄)₆F₂ (Ln = Ce³⁺, Dy³⁺) were prepared by a solid state reaction technique at high temperature. The vacuum-ultraviolet (VUV) and ultraviolet (UV) spectroscopic properties are investigated. The results indicate that Ce³⁺ ions show the lowest 5d excitation band at ∼305 nm and a broad emission band centered at ∼345 nm. Dy³⁺ ions exhibit intense absorption at VUV and UV range. White-emitting under 172 nm excitation is obtained based on two dominant emissions from Dy³⁺ ions centered at 480 and 577 nm. In addition, the energy transfer from Ce³⁺ to Dy³⁺ in the co-doped samples are observed and discussed.     

Preparation of La0.8Sr0.2Cr0.97V0.03O3 − δ films for solid oxide fuel cell application

La_0.8Sr_0.2Cr_0.97V_0.03O_3 − δ (LSC) is commonly studied as a ceramic interconnect material as well as a coating material for metallic interconnects for solid oxide fuel cell applications. However, it is difficult to sinter this type of material to high density. In order to overcome this problem and to study the material in form of a thin film we have used Pulsed Laser Deposition to obtain a dense, uniform film with the right stochiometry. Investigation of preparation-parameter dependence of the LSC films deposited on a stainless steel substrate during pulsed-laser deposition was carried out. The LSC films were deposited with KrF excimer laser (248 nm) on a stainless steel substrate at different oxygen pressure and substrate temperatures. The substrate temperature (873-1073 K) and the oxygen background pressure (5-20 Pa) were varied in order to obtain optimal growth conditions. The surface morphology and structural information of the films were obtained using scanning electron microscope (SEM) and X-ray diffraction, respectively. Under the optimal preparation-parameter conditions: substrate temperature of 1023 K and an oxygen pressure of 10 Pa the structure of the film agreed with the target structure and the SEM micrographs show that the surfaces are homogeneous, smooth, crack-free and dense.     

Observation of a Sub-10-Hz Linewidth 88Sr+ 2S1/2–2D5/2 Clock Transition at 674 nm

In this paper, a pair of diode lasers at 674 nm, locked to two independent ultralow-expansion high-finesse cavities, have been characterized by monitoring the beat frequency between them. The individual laser linewidth of 1.4 Hz for a 3-s averaging time broadened to 4 Hz at 30 s. The relative frequency stability of the beat at 1s is 2.5 10^-15. One of the lasers has been used to interrogate the ⁸⁸Sr^{+ 2}Si_1/2-²D _5/2 transition at 674 nm, and a transition linewidth of 9 Hz has been observed     

Optical bistability for ZnO–Nb2O5–TeO2 glasses

We examined the optical nonlinear properties of ZnO–Nb₂O₅–TeO₂. The absorption and Raman spectra were measured, the third-order nonlinear susceptibility was determined by degenerated four wave mixing technique. The magnitude of χ⁽³⁾ is about 1.0 × 10⁻¹² esu, larger than that of silica glasses, and the optical bistability was observed in a Fabry–Perot cavity.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.