Micro‐Raman study of Zr‐substituted Bi4Ti3O12 ceramics

We have studied the lattice vibrational modes of Zr‐substituted Bi₄Ti₃O₁₂ ceramics using micro‐Raman spectroscopy. Replacement of Zr at the Ti site in the perovskite block is found from the increase in the lattice parameters as a function of Zr contents. Combined X‐ray diffraction patterns and Raman analysis suggested less than 40 mole% Zr solubility in Bi₄Ti₃O₁₂. At 40 mole% of Zr substitution or above, the unreacted monoclinic‐phase ZrO₂ is observed in the X‐ray diffraction patterns and the Raman spectra. The incorporation of Zr in Bi₄Ti₃O₁₂ reduces the soft mode wavenumber and the transition temperature. Moreover, temperature dependent studies confirmed the ferroelectric to paraelectric transition in Bi₄Ti₃O₁₂ at about 675 °C. On increasing the Zr content up to 40% on the Ti sites of Bi₄Ti₃O₁₂, a systematic decrease in the phase transition temperature from 675 to 630 °C was observed. Copyright © 2007 John Wiley & Sons, Ltd.     

Mesoporous (ZrO2-TiO2)/Al2O3 ternary carriers as hydrodesulfurization catalysts support

Ternary systems at various compositions were synthesized by coprecipitating Zr and Ti (to get a ZrO₂-TiO₂ 40-60 mol%) chlorides in aqueous basic media (provided by urea thermal decomposition) over an alumina substrate. Materials characterization included N₂ physisorption, X-ray diffraction, thermal analysis, high-resolution electron microscopy and Raman and UV-vis spectroscopies. High interaction among components was clearly evidenced by various techniques. Textural properties of ternary oxides could be tuned depending on composition of formulations. Mixed oxides with 10 or 20 mol% of ZrO₂-TiO₂ (at 40-60% mol, in turn) had the most suitable combination of textural properties (surface area, average pore diameter and pore volume) for the intended application (support of catalyst for hydrodesulfurization de oil-derived middle distillates). The suitability of those ternary supports was demonstrated in the dibenzothiophene hydrodesulfurization where the corresponding supported MoS₂ catalysts (at 2.8 atom Mo nm⁻²) were much more active (on a per mass of catalyst basis) than when impregnated over either alumina or zirconia-titania oxides.     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.     

溶胶-凝胶ZrO2-TiO2高折射率光学膜层的抗激光损伤性能研究

采用溶胶-凝胶方法制备了ZrO₂-TiO₂(Ti含量为0—100mol%)高折射率光学薄膜. 借助激光动态光散射技术研究溶胶微结构. 采用傅里叶变换红外光谱、原子力显微镜、薄膜光学常数分析仪、漫反射吸收光谱及强激光辐照实验，对膜层的结构、光学性能及抗激光损伤性能进行了系统表征. 结果显示，溶胶-凝胶工艺可以在部分牺牲折射率的情况下，使膜层的抗激光损伤性能得到大幅度提升. 随Ti含量从0mol%增加至100mol%，膜层的平均损伤阈值呈下降趋势，当Ti含量从0mol%增加至60mol%时，平均损伤阈值从57.1J/cm²下降到21.1J/cm²(辐照激光波长为1053nm，脉冲宽度为10ns，“R/1”测试模式)，当Ti含量从60mol%增加至100mol%时，平均损伤阈值变化很小. 综合溶胶微结构、膜层光学性能和损伤实验结果可以推断，强激光诱导多光子吸收是引起膜层损伤的主要原因. 不同配比的复合膜之间光学带隙的显著差异导致相同辐照激光情况下多光子吸收的概率发生变化，从而导致损伤阈值的规律性变化. 关键词： 2-TiO₂薄膜')" href="#">ZrO₂-TiO₂薄膜 溶胶-凝胶 激光诱导损伤 光学带隙     

The effect of stoichiometry and Mg doping on the Raman spectra of LiNbO3:Mg crystals

LiNbO₃:Mg crystals doped with 0–8 mol. % Mg with stoichiometric, intermediate and congruent compositions were systematically investigated by Raman spectroscopy in backscattering y(zx)y, y(zz)y and z(xx)z geometries. The damping was found to be a very sensitive parameter for the characterization of the crystal composition. The half-widths of E(TO₃)–E(TO₉) and A ₁(TO₁)–A ₁(TO₄) bands having significant composition dependence for the undoped LiNbO₃ crystals show only a weak Mg concentration dependence below the photorefractive threshold, which is a consequence of the counteracting effect of the decreasing Nb_Li and increasing Mg_Li contents. The half-widths of the bands, however, increase linearly with growing Mg content for samples above the threshold, irrespective of the Li/Nb ratio. The change in the Mg concentration dependence at a given Li/Nb ratio determines the same threshold value as that concluded from IR and UV spectroscopic measurements. The half-width of the main A ₁(LO₄) band at 873 cm^-1 increases linearly with growing Mg concentration, but no threshold effect is observed. However, the ratio of the area of the main band and the high-frequency sideband shows a threshold effect that can be interpreted by the existing defect incorporation models. The small Raman band at about 740 cm^-1 attributed earlier to Nb_Li vibration is also detected in above-threshold LiNbO₃:Mg crystals, which can be explained by the vibration of Nb ions in Mg₄Nb₂O₉ defect clusters appearing at high Mg concentrations. PACS 77.84.Dy; 63.20.Mt; 42.70.Mp; 78.30.-j     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Study on the formation during the production of lead-free piezoceramics at the morphotropic phase boundary

Because of the environmental concerns, the manufacture of ceramics based on lead titanate zirconate [Pb(Zr_1−xTi_x)O₃−PZT] has been condemned because of the lead toxicity. In this context, the electromechanical properties of sodium, potassium and lithium niobate [(Na_0.5−x/2K_0.5−x/2Li_x)NbO₃−NKLN] at the morphotropic phase boundary granted these materials the position of most suitable candidate to replace PZT. However, the production of these ceramics is rather critical mainly because of a natural tendency of forming secondary phases. To help with the studies of the synthesis of this lead-free piezoceramic, this work presents an evaluation of the crystallization of the (Na_0.47K_0.47Li_0.06)NbO₃ phase by solid-state reactions. TG-DTA, XRD, dilatometric and ferroelectric hysteresis analyses indicated that a secondary phase (K₃Li₂Nb₅O₁₅) crystallizes at temperatures above 850 C and also during the sintering of the powders compacts at 1080 C. To prevent the formation of this phase, the addition of Na₂Nb₂O₆.nH₂O microfibers obtained through a microwave hydrothermal synthesis was performed in the sintering process. After to this addition, the suppression of the K₃Li₂Nb₅O₁₅ phase occurred and an increase of the NKLN electrical properties was then obtained.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Low- and infralow-frequency dielectric properties of the Pb(Mg1/3Nb2/3)O3 + 2 wt % Li2O ceramics

A dielectric response of the Pb(Mg_1/3Nb_2/3)O₃ ferroelectric ceramics with impurity of 2 wt % Li has been studied. The phase transition has been found to exhibit a relaxor character, as is the case in PMN without Li. However, unlike pure PMN, the dielectric response dispersion in PMN + 2 wt % Li₂O has been described by the Cole-Cole equation at temperatures below the temperature of the low-frequency maximum of the permittivity. An analysis of the dispersion parameters in a wide temperature range has demonstrated that it can be due to the relaxation of domain walls in PMN + 2 wt % Li₂O that appear most likely because of the existence of anomalously coarse grains in PMN + 2 wt % Li₂O.     

Characterization of ZrO2-promoted Cu/ZnO/nano-Al2O3 methanol steam reforming catalysts

Three Cu/ZnO/ZrO₂/Al₂O₃ methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO₂ from a monoclinic nanoparticle ZrO₂ precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO₂ produced by impregnation using a Zr(NO₃)₂ precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO₂ phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.     

Conductivity and water uptake of Sr4(Sr2Nb2)O11·nH2O and Sr4(Sr2Ta2)O11·nH2O

The hydrated oxygen deficient complex perovskite-related materials Sr₄(Sr₂Nb₂)O₁₁·nH₂O and Sr₄(Sr₂Ta₂)O₁₁·nH₂O were studied at high water vapour pressures over a large temperature range by electrical conductivity measurements, thermogravimetry (TG), and X-ray powder diffraction (XRPD). In humid atmospheres both materials are known to exhibit protonic conductivity below dehydration temperatures, with peak-shaped maxima at about 500 °C. In this work we show that the peaks expand to plateaus of high conductivity from 500 to 700 °C at a water vapour pressure of 1 atm. However, in situ synchrotron XRPD of Sr₄(Sr₂Nb₂)O₁₁·nH₂O as a function of temperature shows that these observations are in fact coincident with melting and dehydration of a secondary phase Sr(OH)₂. The stability of Sr₄(Sr₂Nb₂)O₁₁·nH₂O and Sr₄(Sr₂Ta₂)O₁₁·nH₂O in humid atmospheres is thus insufficient, causing decomposition into perovskites with lower Sr content and SrO/Sr(OH)₂ secondary phases. This, in turn, rationalizes the observation of peaks and plateaus in the conductivity of these materials.     

Barium borate glass and transparent glass ceramics doped with Pb4Lu2YbF17

Barium borate glasses doped with complex Pb₄Lu₂YbF₁₇ fluoride have been synthesized and investigated. Heat treatment produced glass ceramics containing the crystalline BaF₂:Yb³⁺ phase. The changes in the structural and optical properties of the glass ceramics were revealed by X-ray diffraction, Raman spectroscopy, and luminescence spectroscopy of Yb³⁺ ions in polycrystalline Pb₄Lu₂YbF₁₇, initial glass, and glass ceramics.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Electrical characteristics and low-temperature sintering of BiFeO3-modified Pb(Zr,Ti)O3–Pb(Fe2/3W1/3)O3–Pb(Mn1/3Nb2/3)O3 ceramics with ZnO addition

Effects of ZnO addition on electrical properties and low-temperature sintering of BiFeO₃-modified Pb(Zr,Ti)O₃–Pb(Fe_2/3W_1/3)O₃–Pb(Mn_1/3Nb_2/3)O₃ were investigated. The investigations revealed that the sintering temperature can be decreased to 950 °C, and the favorable properties were obtained with 0.10 wt% ZnO added ceramics. The electrical properties were as follows: d₃₃ = 313 pC/N, K_p = 0.56, tan δ = 0.0053, ε_r = 1407 and T_c = 295 °C, which showed that this system was a promising material for the multilayer devices application.     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

Effects of (LiCe) co-substitution on the structural and electrical properties of CaBi2Nb2O9 ceramics

The piezoelectric, dielectric, and ferroelectric properties of the (LiCe) co-substituted calcium bismuth niobate (CaBi₂Nb₂O₉, CBNO) are investigated. The piezoelectric properties of CBNO ceramics are significantly enhanced and the dielectric loss tanδ decreased. This makes poling using (LiCe) co-substitution easier. The ceramics (where □ represents A-site Ca²⁺ vacancies, possess a pure layered structure phase and no other phases can be found. The Ca_0.88(LiCe)_0.04□_0.04Bi₂Nb₂O₉ ceramics possess optimal piezoelectric properties, with piezoelectric coefficient (d₃₃) and Curie temperature (T_C) found to be 13.3 pC/N and 960 ℃, respectively. The dielectric and piezoelectric properties of the (LiCe) co-substituted CBNO ceramics exhibit very stable temperature behaviours. This demonstrates that the CBNO ceramics are a promising candidate for ultrahigh temperature applications.     

Disorder‐induced symmetry lowering in Ba(Y1/2Nb1/2)O3 ceramics probed by Raman spectroscopy

This work investigates the evolution of the crystal structure of microwave‐hydrothermal synthesized Ba(Y_1/2Nb_1/2)O₃ powders as a function of firing temperature by Raman spectroscopy. The samples were produced at 200 °C and fired at temperatures ranging from 600 to 1600 °C. Raman spectra were obtained at room temperature for all samples and the results showed that materials fired at 1600 °C exhibited tetragonal (I4/m or ) structure, whereas those fired at lower temperatures exhibited the triclinic (P1 or C_i¹) structure. The results were compared with those observed for ceramics obtained by conventional solid‐state methods. It is believed that the lowering of the symmetry verified in materials fired below 1600 °C is a consequence of the local disorder of Y⁺³ and Nb⁺⁵ ions in octahedral sites. Copyright © 2008 John Wiley & Sons, Ltd.     

Sr位Nd掺杂对SrBi$lt;sub$gt;2$lt;/sub$gt;Nb$lt;sub$gt;2$lt;/sub$gt;O$lt;sub$gt;9$lt;/sub$gt;性能的影响及机理研究

采用传统固相法制备了（Sr_1-3x/2A_x/2Nd_x）Bi₂Nb₂O₉（x=0,0.05,0.1和0.2）陶瓷,并系统研究了Nd离子取代Sr离子对SrBi₂Nb₂O₉性能的影响及其作用机理.研究结果表明：Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉的介电常数和介电损耗随温度变化的行为具有明显的离子松弛极化特征.Nd³⁺对Sr²⁺的部分取代,导致Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉剩余极化强度P_r稍有下降,但其压电系数d₃₃却有所增加,根据铁电热力学理论,这是Nd³⁺对Sr²⁺取代导致材料介电常数增大所致.Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉的居里温度（T_C）没有随Nd含量的增加而变化,拉曼光谱技术分析表明这是其NbO₆八面体畸变程度没有发生变化所致.Nd³⁺取代Sr²⁺提高了材料的介电常数ε_r、压电系数d₃₃、机电耦合系数K_p,同时降低了机械品质因数Q_m,但是谐振频率温度系数C值没有改变. 关键词： 压电陶瓷 介电性能 压电性能 拉曼光谱     

Preparation and characterization of visible light responsive Fe2O3-TiO2 composites

In this study we present the effects of iron oxide (Fe₂O₃) on titanium dioxide (TiO₂) in synthesising visible-light reactive photocatalysts. A Fe₂O₃-TiO₂ composite photocatalyst was synthesized from Fe₂(SO₄)₃ and Ti(SO₄)₂ by a ethanol-assisted hydrothermal method. The preparation conditions were optimized through the investigation of the effects of hydrothermal temperature and time as well as molar ratio of Ti to Fe on the photocatalytic activity. The visual, physical and chemical properties of the Fe₂O₃-TiO₂ composites were investigated. The results showed that α-Fe₂O₃ and anatase TiO₂ were present in the composites. The Fe₂O₃-TiO₂ synthesized under optimum condition consisted of mesoporous structure with an average pore size of 4 nm and a surface area of 43 m²/g. Under visible and solar light irradiation, the photocatalytic activity of optimized sample was significantly higher than that of pure TiO₂. This sample led to a photodegradation efficiency of 90% and 40% of auramine under visible light and solar light, respectively.     

Thermoluminescence studies on Cu-doped Li2B4O7 single crystals

Lithium tetraborate (Li₂B₄O₇) is a tissue equivalent material and single crystals of this material doped with Cu are promising for dosimetric applications. In the present study highly transparent single crystals of lithium tetraborate (Li₂B₄O₇) doped with Cu (0.5 wt%) have been grown using the Czochralski technique. The Li₂B₄O₇:Cu crystals were studied using photoluminescence, X-ray diffraction (XRD), UV-vis transmission, time resolved fluorescence and thermoluminescence (TL) techniques. The TL readout of Li₂B₄O₇:Cu crystals showed two well-defined glow peaks at 402 K (peak-1) and 513 K (peak-2) for a 4 K/s heating rate. While the low temperature TL peak-1 fades completely within 24 h at room temperatures, the main dosimetric peak-2 remains the same. The TL sensitivity of the grown single crystal is found to be 3.3 times that of a conventional TL phosphor, TLD-100. The Li₂B₄O₇:Cu crystals showed a linear TL dose-response in the range from 1 mGy to 1 kGy. The TL analysis using a variable dose method revealed first order kinetics for both the peaks. Trap depth and frequency factor for peak-1 were found to be 0.81 eV and 5.2×10⁹ s⁻¹, whereas for peak-2 the values were 1.7 eV and 1.7×10¹⁶ s⁻¹, respectively.