Coupled isomorphic substitution and exsolution of pyroxene,rutile, apatite and quartz in supersilicic garnet

Dissolution of pyroxene in garnet at ultrahigh pressures produces supersilicie garnet with the coupled substitutions of Si^Ⅵ M^Ⅵ= A^Ⅵ A^Ⅵ and Si^Ⅵ Na^Ⅷ=A^Ⅵ M^Ⅷ,which are enhanced by rising pressure. The supersilicic garnet and exsolution of pyroxene, rutile, apatite and quartz in garnet during decompression were found in natural rocks,pointing to the importance in studying mantle-derived rocks and ultrahigh pressure metamorphism related to plate deep subduction. Ti, P, K and H2O enters garnet via the substitutions of Ti = Si, P^Ⅵ Na^Ⅷ = Si^Ⅵ CaⅧ, Si^Ⅵ K^Ⅷ = AI^Ⅵ M^Ⅷ, and [(OH)4]^4- = [SiO4]^4- or [4H]^4 = Si^4 respectively. The possible entering of Eskola pyroxene component M0.5AlSi2O6 in clinopyroxene, together with the common pyroxene component M2Si2O6, into garnet can lead to the presence of the substitution of Si^Ⅵ 0.5□^Ⅷ= A^Ⅵ 0.5M^Ⅷ in garnet structure, which plays a key role in the exsolution of rntile, apatite and quartz in garnet. Two new breakdown reactions are thus proposed on the basis of the new coupled substitution, which can be regarded as a theoretical model for the exsolntion of the 3 minerals in garnet. The real exsolution may be a combination of several breakdown reactions.     

压电悬臂梁式微型电场传感器的设计与制备

提出并研制一种新型压电悬臂梁式微型电场传感器,该传感器是基于压电(PZT)薄膜驱动的悬臂梁式微型电场传感器;同时介绍了传感器的工作原理、结构设计、制作工艺以及初步测试结果。该微型电场传感器由多根压电悬臂梁构成,每根悬臂梁能同时具有屏蔽电场和感应电荷功能。对传感器感应电荷的能力进行了计算;并根据计算结果和工艺要求设计了传感器的参数。该微型电场传感器采用微加工技术制作,每根悬臂梁为多层复合结构(Al/Si3N4/Pt/PZT/Pt/Ti/Si O2/Si),其中PZT薄膜采用溶胶-凝胶法制备。测试结果证明,传感器具有良好的响应特性。     

Li1+xAlxTi2-x(PO4)3(x=0~0.4)溶胶-凝胶法合成及其性质

以乙酸锂、硝酸铝、钛酸丁酯、磷酸二氢铵为原料,利用溶胶-凝胶法合成锂离子Li_1+xAl_xTi_2-x(PO₄)₃(x=0~0.4)固体电解质体系,检测结果表明：Li_1+xAl_xTi_2-x(PO₄)₃体系具有较好的结晶性,合成的粉末与烧结片之间的结晶性与结构差异不大;当Al³⁺掺杂量逐步增加时,离子电导率逐渐增大,并在x=0.3时达到最大值,但掺杂量进一步增加时,离子电导率迅速下降;活化能的变化趋势与离子电导率相反.     

Subsolidus phase relations in the system MgO-ZnO-SiO2 at high pressure

The subsolidus phase relations were determined experimentally in the system MgO-ZnO-SiO2 at 1.0 GPa and 1 200℃, by use of the high-pressure apparatus "piston-cylinder". The results showed characteristics of the phases assemblage different from that in similar ternary systems. It is impossible to form complete Mg2SiO4-Zn2SiO4 olivine and Mg2Si2O6-Zn2Si2O6 pyroxene solid solution. This is controlled by the properties of Zn2+ with an outer layer of electron (Ar)3d10, different from others transition metal ions, like Fe2+ , Ni2+ , Co2+ .     

Ti-Si复合氧化物催化剂的合成、表征及邻苯二酚O-单醚化反应性能

采用溶胶-凝胶法制备了不同Ti/Si比的钛硅氧化物及纯SiO₂和TiO₂样品, 通过XRD, FT-IR, UV-vis, NH₃-TPD和氮吸附等手段对材料的物理化学性质进行了表征. 结果表明, Ti-Si复合氧化物以无定形状态存在, 随着硅量的增加, 钛的存在形态由六配位为主向四配位为主转变, 表面酸量降低; 样品在以邻苯二酚和甲醇为原料气相法合成愈创木酚反应中的活性结果表明, n(Ti) ∶n(Si)＝6 ∶1的样品活性最高68％, 随着Ti/Si的减小活性降低, 这可能与样品表面酸量和酸类型变化有关.     

Photoluminescence from Si-based SiNxOy films

B⁺, C⁺, Si⁺, and As⁺ with dose of 5 × 10¹⁶ cm⁻² were implanted into SiN_xO_y, films grown on crystalline silicon by plasma-enhanced chemical vapor deposition. The ion-implanted samples exhibit their photoluminescence with different intensities and different peak wavelengths after thermal annealing. Especially, the C⁺-implanted SiN_xO_y, films show very intense photoluminescence at green-yellow color region.     

Effects of alloying and high-temperature heat treatment on the microstructure of Nb–Ti–Si based ultrahigh temperatur e alloys

The phase co mpositions, microstructure and especi ally phase i nterfaces in the as-cast and heat-treated Nb– Ti–Si based ultrahigh temperature alloys have been investigated. It is shown that β(Nb,X)5Si3 and γ(Nb,X)5Si3 are the primary p hase s in the Nb–22Ti–16Si–5Cr–5Al (S1) (at%) and Nb–20Ti–16Si–6C r–4Al–5Hf–2B–0.06Y (S2) (at% ) alloys, respectively. The Nb solid solution (Nbss) is the primary phase in Nb–22Ti–14Si–5Hf–3Al–1. 5B –0.0 6Y (S3) (at%) alloy . An orientation relationship between Nbss and γ(Nb,X)5Si3 was determine d to be (1-10)Nb//(101-0)γ and [111]Nb//[0001]γ in the as-cast S2 and S3 alloys. Some original β(Nb,X)5Si3 transfor med into α(Nb,X)5Si3 because Al and Cr diffused from the β(Nb,X)5Si3 to Nbss during heattreatment at 1500 °C for 50 h in the S1 alloy. Mean while, Ti diffused from Nbss to β(Nb,X)5Si3, which induced a Ti to generate near the interface between Nbss and Ti-rich β(Nb,X)5Si3. The orientation relationship between the newl y-formed a Ti and previous Nbss was (110 )Nb//(1-10-1) αTi and [001]Nb//(12-3-1)αTi. Among the ( Nb,X)5Si3 phases , the contents o f Cr and Al in β(Nb,X)5Si3 are n earl y the same as those in γ(Nb,X)5Si3 but obviously hi gher than those in the α(Nb,X)5Si3, where as the content of Si in α(Nb,X)5Si3 is nearly the same a s that in γ(Nb,X)5Si3 but higher than that in the β(Nb,X)5Si3     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Novel trichromatic phosphor Co-doped with Eu, Tb in SiO2 gel matrix

The Eu, Tb co-doped SiO2 matrix tricolor fluorescence system was prepared by sol-gel technique. Red emission at 618 nm, green emission at 543 nm and blue emission at 350-500 nm were observed in the PL spectra of the sample, indicating that Eu^3＋, Eu^2＋ and Tb^3＋ ions coexisted in the matrix. In the co-doped sample, the blue emission of Eu^2＋ was much stronger than that of the sample single doped with Eu, which implied that the electron transfer between Eu^3＋ and Tb^3＋ maybe happened in the SiO2 matrix. The influences of the annealing temperature and Tb concentration on the PL spectra of the samples were investigated. The optimal doped concentration of Tb was determined to be 0.2% and the optimal annealing temperature 850℃. Annealed at 600℃, Tb^3＋ had a sensitizing effect on Eu^3＋ in the SiO2 matrix, and the emission intensity of Eu^3＋ in the Eu, Tb co-doped sample was more than four times that of the single doped sample, which could be attributed to the energy transfer from Tb^3＋ to Eu^3＋.     

Phase analysis and thermal conductivity of in situ O′-sialon/β-Si3N4 composites

Typical O??-sialon-based ceramics, with a formula of Si_2?x Al _x O_1+x N_2?x , where x was set as 0.25, were fabricated by in-situ synthesis. Si₃N₄, Al₂O₃, and SiO₂ powders were used as raw materials, and MgO and Y₂O₃ were added as sintering additives. All the samples were sintered at different temperatures under a nitrogen pressure of 0.25?C0.30 MPa, and their microstructure, phase content, and thermal conductivity were evaluated. The effects of O??-sialon and ??-Si₃N₄ on the thermal conductivity were analyzed by numerical calculation in detail. In the case of the similar porosity, the thermal conductivity of O??-sialon-based ceramics decreased with the ratio of O??-sialon/??-Si₃N₄ increasing. When the ratio was 12, the thermal conductivity of O??-sialon ceramics sintered at 1360°C was 1.197 W·m^?1·K^?1.     

Zr~(4+)/F~– co-doped TiO_2(anatase) as high performance anode material for lithium-ion battery

Zr~(4+) and F~– co-doped TiO_2 with the formula of Ti_(0.97)Zr_(0.03)O_(1.98)F_(0.02) was facilely synthesized by a sol-gel template route.The crystal structure,morphology,composition,surface area,and conductivity were characterized by Raman spectroscopy,energy-dispersive X-ray analysis,scanning electron microscopy,Brunauer-Emmett-Teller measurements,X-ray photoelectron spectroscopy,and electrochemical impedance spectroscopy.The results demonstrate that Zr~(4+)and F~–homogeneously incorporated into TiO_2,forming solid solution with an anatase structure.Ti_(0.97)Zr_(0.03)O_(1.98)F_(0.02)shows outstanding electrochemical properties as Li-ion battery anode in comparison with Ti_(0.97)Zr_(0.03)O_2.In particular,upon 35-fold cycling at 1C-rate Zr~(4+)/F~–co-doped TiO_2delivers a reversible capacity of 163 mAh g~(–1),whereas Zr~(4+)-doped TiO_2gives only 34 mA h g~(–1).Additionally,Zr~(4+)/F~–co-doped TiO_2retains a capacity of 138 mA h g~(–1)during cycling even at 10 C.The enhance performance originates from improved conductivity of Zr~(4+)/F~–co-doped TiO_2material through generation of Ti~(3+)(serving as electron donors)into the crystal lattice and,possibly,due to F-doping blocked the anode surface from attack of HF formed as electrolyte decomposition product.     

Y2O2S:Eu3+,Zn2+,Ti4+荧光体的缺陷及红色长余辉发光性质

采用高温固相法合成了红色长余辉材料Y2O2S:Eu3+,Zn2+,Ti4+,实现了余辉发光中心和缺陷中心之间的能量传递。通过XRD、荧光发射和激发光谱、余辉发射光谱与衰减曲线、色坐标和热释光谱测试手段对Y2O2S:Eu3+,Zn2+、Y2O2S:Eu3+,Ti4+、Y2O2S:Eu3+,Zn2+,Ti4+和Y2O2S:Eu3+,Mg2+,Ti4+进行了结构与性能的表征,发现其荧光发射与余辉发射基本一致,红色余辉发光主峰位于625 nm附近,来源于Eu3+的5D0→7F2跃迁发射。相比而言,Y2O2S:Eu3+,Zn2+,Ti4+余辉发光性能最好,可持续1.5 h左右。     

Heteroseneous oxidation of carbonyl sulfide on mineral oxides

Heterogeneous oxidation of carbonyl sulfide （OCS） on mineral oxides including SiO2, Fe2O3, CaO, MgO, ZnO and TiO2, which are the main components of atmospheric particles, were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy （in situ DRIFTS）, ion chromatography （IC）, temperature-programmed desorption （TPD）, X-ray diffraction （XRD） and Brunauer-Emmett-Teller （BET） methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely, OCS can be catalytically oxidized to produce surface SO4^2- species and gaseous CO2 through the surface hydrogen thiocarbonate （HSCO2-） and HSO; species. The activity series for heterogeneous oxidation of OCS follows： Al2O3 ≈ CaO 〉 MgO 〉 TiO2 ≈ ZnO 〉 Fe2O3 〉 SiO2. The specific area, basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.     

Structural investigation and luminescent properties of BaZr(BO<Subscript>3</Subscript>)2:Eu<Superscript>3+</Superscript> phosphors containing Si

Si⁴⁺-doped BaZr(BO₃)₂:Eu³⁺ phosphors are prepared by a conventional solid-state reaction. The influence of Si⁴⁺ addition on the charge transfer state of Eu³⁺-O^2– and photoluminescence (PL) properties of BaZr(BO₃)₂:Eu³⁺ are discussed. Room temperature PL spectra indicated that efficient emission is obtained by Si doping. Increased values for the peak-peak ratio (PPR) of BaZr(BO₃)₂:Eu³⁺ at higher Si doping concentrations implied that the Eu³⁺ ion is located in a more asymmetric environment in BaZr_0.8Si_0.2(BO₃)₂:Eu³⁺ than in the undoped samples. The Judd-Ofelt parameters Ω_λ (λ=2,4) were calculated from the PL data, giving results that were consistent with those from the PPR. The maximum radiative quantum efficiency was achieved at a Si doping concentration of 20 mol%.     

Preparation and photocatalytic activity of Cu-doped TiO2/SiO2

Cu²⁺-doped nanostructured TiO₂-coated SiO₂ (TiO₂/SiO₂) particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO₂ colloids were synthesized by the sol-gel method using TiOSO₄ as a precursor. The experimental results showed that TiO₂ nanopowders on the surface of SiO₂ particles were well distributed and compact. The amount of TiO₂ increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550°C. The 2-layer coated TiO₂ particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu²⁺-doped TiO₂/SiO₂ was higher than that of undoped TiO₂/SiO₂. The optimum dopant content was about 0.10wt%.     

Synthesis and luminescence properties of Eu3+, Sm3+ doped (YxGd1-x)2O3:Si4+, Mg2+ long-lasting phosphor

A novel red long-lasting phosphor, (Y_1−x Gd _x )₂O₃:Eu³⁺, Sm³⁺, Si⁴⁺, Mg²⁺, was synthesized by the co-precipitation method using oxalate precipitation as the precursor. X-ray diffraction (XRD), scanning electronic microscopy (SEM), integrated thermal analyzer (TG), and photoluminescence spectra (PL) as well as the ST-900PM weak light photometer were used to study the synthesis conditions, morphology, luminescence properties, and the decay time of the phosphor. The XRD results show that the products synthesized at 1400°C for 4 h have good crystallization without any detectable impurity phases. Based on the PL spectra, the optimal conditions are as the following. The molar ratios of Y³⁺ to Gd³⁺ and Eu³⁺ to Sm³⁺ are 2:8 and 3:1, respectively, and the contents of Mg²⁺ and SiO₂ are 5mol% and 3mol%, respectively. The decay time monitored by the ST-900PM weak light photometer is 7200 s, increasing 44% and 100%, respectively, compared with the Eu³⁺ and Sm³⁺ single-doped phosphors. The results indicate that the energy transfer is from Sm³⁺ to Eu³⁺ ion, and Sm³⁺ is a good sensitizer to Eu³⁺.     

Carbothermal synthesis of Si3N4 powders using a combustion synthesis precursor

Si₃N₄ powders were synthesized by a carbothermal reduction method using a SiO₂ + C combustion synthesis precursor derived from a mixed solution consisting of silicic acid (Si source), polyacrylamide (additive), nitric acid (oxidizer), urea (fuel), and glucose (C source). Scanning electron microscopy (SEM) micrographs showed that the obtained precursor exhibited a uniform mixture of SiO₂ + C composed of porous blocky particles up to ～20 μm. The precursor was subsequently calcined under nitrogen at 1200–1550°C for 2 h. X-ray diffraction (XRD) analysis revealed that the initial reduction reaction started at about 1300°C, and the complete transition of SiO₂ into Si₃N₄ was found at 1550°C. The Si₃N₄ powders, synthesized at 1550°C, exhibit a mixture phase of α- and β-Si₃N₄ and consist of mainly agglomerates of fine particles of 100–300 nm, needle-like crystals and whiskers with a diameter of about 100 nm and a length up to several micrometers, and a minor amount of irregular-shaped growths.     

Micro-arc oxidization fabrication and ethanol sensing performance of Fe-doped TiO<Subscript>2</Subscript> thin films

In-situ pure TiO₂ and Fe-doped TiO₂ thin films were synthesized on Ti plates via the micro-arc oxidation (MAO) technique. The as-fabricated anatase TiO₂ thin film-based conductometric sensors were employed to measure the gas sensitivity to ethanol. The results showed that Fe ions could be easily introduced into the MAO-TiO₂ thin films by adding precursor K₄(FeCN)₆·3H₂O into the Na₃PO₄ electrolyte. The amount of doped Fe ions increased almost linearly with the concentration of K₄(FeCN)₆·3H₂O increasing, eventually affecting the ethanol sensing performances of TiO₂ thin films. It was found that the enhanced sensor signals obtained had an optimal concentration of Fe dopant (1.28at%), by which the maximal gas sensor signal to 1000 ppm ethanol was estimated to be 7.91 at 275°C. The response time was generally reduced by doped Fe ions, which could be ascribed to the increase of oxygen vacancies caused by Fe³⁺ substituting for Ti⁴⁺.     

Thermal degradation of BaAl2Si2O8：Eu2＋ phosphor excited by near ultraviolet light

Eu2+ doped BaAl2Si2O8 phosphor was synthesized by one-step calcination of precursors that were prepared by chemical co-precipitation.The thermal degradation properties of BaAl2Si2O8:Eu2+ were investigated by photoluminescence,lifetime and chromaticity coordinate measurements.BaAl2Si2O8:Eu2+ is efficiently excited by incident light of 250-400 nm,which matches the emission of near ultraviolet LED chips well.BaAl2Si2O8:Eu2+ exhibits broad blue emission at 470 nm because of the 4f65d1-4f7(8S7/2) transition of Eu2+ ions,and the emission band shows an unusual blue shift with bandwidth broadening and emission intensity decreasing as the annealing temperature is increased.The luminescence decay and CIE chromaticity coordinates of BaAl2Si2O8:Eu2+ were determined to investigate its application in white LEDs.     

Brazing of micrograin-filled quartz fiber reinforced silica composites and Invar using Ag-21Cu-4.5Ti alloy

Brazing of quartz fiber reinforced silica composites (QFSC) to Invar alloy was carried out in a vacuum at 1173 K for 10 min using Ag-21Cu-4.5Ti metal filler.Experiments indicated that composites prefilled with CaCO3 micrograins had good wettability.The CaCO3 decomposed to CaO during brazing.After brazing,a joint of structure QFSC/3CaO·2SiO2+Ti3O5+Fe2Ti+NiTi+Ag(s,s)+ Cu(s,s)/Invar was established.The shear strength of the brazed joint reached 11.6 MPa at room temperature,which is about five times the shear strength of that obtained without surface filling.