Ca0.7Ti0.7La0.3Al0.3O3微波介质陶瓷微观组织结构与介电性能

采用固相反应法制备斜方晶系钙钛矿结构Ca07Ti07La0.3Al0.3O3微波介质陶瓷,研究了Al3+、Ca2、Ba2+和La3+离子掺杂对CTLA陶瓷微观组织结构和介电性能的影响.研究结果表明不同掺杂离子对于CTLA陶瓷的微观结构和介电性能有很大的影响,不同离子掺杂CTLA陶瓷的晶粒尺寸、气孔率、晶界析出相有很大的不同.Al3+、Ca2+、Ba2+和La3+离子掺杂可以有效降低CTLA陶瓷的谐振频率温度系数,但Ca2+、Ba2+离子掺杂同时也降低了CTLA陶瓷的致密度和Q×f值,Al3+、La3+离子掺杂不仅有效提高了CTLA陶瓷的致密度和Q×f值,并且有效降低了谐振频率温度系数.适量掺杂La3离子可以有效促进CTLA陶瓷的致密化,提高了CTLA陶瓷的微波介电性能.掺杂0.15mol％ La3+的CTLA陶瓷在4.7 GHz下测试介电性能为:εr=48.39,Q×f=32560 GHz,τf=23.68 ppm/C.     

溶胶-凝胶法制备La_(0.8)Sr_(0.2)MnO_3涂层的研究

采用溶胶-凝胶法在氧化铝基体制备La0.8Sr0.2MnO3涂层。通过热重分析、差示扫描量热分析、X射线衍射分析、扫描电镜等手段对涂层制备工艺、相组成以及表面形貌进行了分析。结果表明,用溶胶-凝胶法可制备La0.8Sr0.2MnO3单相涂层;涂层表面致密性好,但有裂纹,且不平整;涂层均匀且与基体间界面不明锐,涂层厚度约为0.5μm;另外,随Sr含量增加,La1-xSrxMnO3涂层方块电阻减小,当x=0.3时达到最小值。     

La0.7Sr0.3Ga0.6Fe0.4O3-δ氧离子导体材料的制备与表征

以相应的金属氧化物和盐为原料,通过甘氨酸-硝酸盐法(GNP)合成出La0.7Sr0.3Ga06Fe04O3-δ(LSGF)粉末,经压制、烧结后,得到LSGF烧结体试样.采用X射线衍射仪(XRD)对所得前驱体及其煅烧后粉体的相组成进行分析;采用扫描电镜(SEM)及X射线冠电子能谱仪(EDS)对烧结体的微观组织和成分进行了观察,还对烧结体的致密度、电导率和热膨胀系数等进行了测试分析.实验结果表明,甘氨酸-硝酸盐法所制备的前驱体粉末在700℃煅烧5h后可获得具有单一钙钛矿结构的LSGF粉末,其晶粒尺寸在45 nm左右,所制备的LSGF烧结体在400～900℃范围的电导率在3.97～4.42 S·cm-1之间,热膨胀系数在9.2 ×10-6 ～11.12 ×10-6 K-1之间.     

溶胶-凝胶法制备La0.65Sr0.35MnO3及其光催化性能

采用溶胶-凝胶法合成了以Sr取代部分稀土金属La的La0.65Sr0.35MnO3样品,经XRD衍射分析确定其具有钙钛矿的晶体结构,并对其进行了光催化活性实验.结果表明:在700℃时,La0.65Sr0.35MnO3样品平均粒径为19 nm;在太阳光照射下,LA0.65Sr0.35MnO3降解亚甲基蓝溶液120 min时,其降解率达到90%.     

Influence of molar ratio of citric acid to metal ions on preparation of La0.67Sr0.33MnO3 materials via polymerizable complex process

Polycrystalline La_0.67Sr_0.33MnO₃ (LSMO) nanometric sized powders and thin films are obtained from the resins synthesized by the polymerization of citric acid and ethylene glycol. Molar ratios of citric acid to metal ions were varied, and the resulting effects on the powder's properties were studied using TGA/DTA, FTIR, SEM and X-ray diffraction (XRD). The results indicated that with the molar ratio of citric acid/metal ions at 4, the resin contained a lower fraction of monodentate ligand and a higher portion of CCO structure obtained from ethylene glycol, which made it possible to synthesize the perovskite phase at temperature as low as 500 °C. The powder calcined at 550 °C exhibited a pure phase of perovskite, had a particle size of about 20–50 nm and a specific surface area of 25.24 m²/g. Thin films were prepared by using the as-prepared sols for spin coating on (1 0 0) Si substrate to investigate the properties of the films. As a result of the molar ratio of citric acid/metal cations at 3–4, the transformation of rhombohedral structure to cubic structure was observed.     

Study of Ag/La0.6Sr0.4MnO3 catalysts for complete oxidation of methanol and ethanol at low concentrations

Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al₂O₃-supported catalysts, Ag/γ-Al₂O₃, Pt/γ-Al₂O₃, and Pd/γ-Al₂O₃. The results showed that the Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ in the temperature range of 370–573 K. Over a 6%Ag/20%La_0.6Sr_0.4MnO₃/γ-Al₂O₃ catalyst, the T₉₅ temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T₉₅ temperatures. Over a 6%Ag/La_0.6Sr_0.4MnO₃ catalyst, the T₉₅ temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH₃CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H₂-TPR) and oxygen temperature-programmed desorption (O₂-TPD) methods revealed that both the surface and the bulk phase of the perovskite La_0.6Sr_0.4MnO₃ played important roles in the catalytic oxidation of the alcohols, and that γ-Al₂O₃ as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag⁺ doped onto the surface of La_0.6Sr_0.4MnO₃ was able to partially occupy the positions of La³⁺ and Sr²⁺ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag⁺ to the surface of La_0.6Sr_0.4MnO₃ resulted in an increase in relative content of the surface O₂²⁻/O⁻ species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag₂O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO₃ would also lead to an increase in the content of the reducible Mnⁿ⁺ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.     

Microwave absorption properties of (1 − x)La0.85Ag0.15MnO3/x graphene (x = 0, 3, and 5 wt.%) composites

Composite of (1 − x)La_0.85Ag_0.15MnO₃/x graphene (x = 0, 3, and 5 wt.%) and epoxy resin with a ratio of 4:1 were prepared to investigate the influence of the addition of graphene in (1 − x)La_0.85Ag_0.15MnO₃/x graphene on real and imaginary parts of permittivity, permeability, as well as microwave reflection loss (RL), using a vector network analyzer in the 8–18 GHz of the frequency range. It is found that the value of RL is smaller at x = 3 wt.% (−20.74 dB at 14.85 GHz) and 5 wt.% (−14.81 at 16.50 GHz) compared to at x = 0 wt.% (−8.89 dB at 15.90 GHz). The result indicates that microwave absorption properties significantly improved as a result of the addition of graphene. It is suggested that the addition of graphene enhanced the dielectric loss–related mechanism such as interfacial polarization and conduction loss resulting in an improvement of microwave absorption performance for both x = 3 wt.% and x = 5 wt.% samples. It also shows that the observed enhanced microwave absorption properties may also be influenced by the resistivity of the sample as x = 3 wt.% sample exhibits enhanced microwave absorption properties and the lowest resistivity among the studied samples.     

CuCl/La0.5 Pb0.5 MnO3催化甲醇氧化羰基化合成碳酸二甲酯

通过混烧法制备了CuCl/La0.5Pb0.5MnO3负载型催化刺,采用BET、XRD对其进行了表征,研究了其对甲醇液相氧化装基化合成碳酸二甲酯反应的催化性能,并考察了反应温度、反应时间、压力及O2含量对催化反应的影响.结果表明,以溶胶-凝胶法制得的钙钛矿型复合金属氧化物La0.5Pb0.5MnO3为载体,CuCl负载量为10%、300℃焙烧6 h制备的催化剂,其比表面积为7.67 m2·g-1,晶相结构完整,CuCl高度分散,具有好的活性和选择性.当反应温度为120℃、总压力为2.5 MPa、O2含量为8%、反应时间为4 h时,碳酸二甲酯收率可达79.0%,选择性大于96.0%.     

La0．8Ba0．2MnO3纳米晶的制备与表征

用溶胶-凝胶法制备了La0.8Ba0.2MnO3纳米粉体材料,对样品的凝胶进行热差热熏和红外光谱分析,结果表明,凝胶的加热煅烧过程中可以分为脱吸附水、有机物分解、硝酸根分解和钙态矿形成四个阶段。X射线衍射分析表明它是单一的钙态矿结构,扫描电子显微镜分析表明粉体呈球形巍径约80nm。     

Ferroelectric and ferromagnetic properties of Mn-doped 0.7BiFeO3–0.3BaTiO3 solid solution

Binary solid solutions 0.7BiFeO₃–0.3BaTiO₃–x wt.% MnO₂ (x = 0, 0.2, 0.3, and 0.5) were prepared by a traditional ceramic process. All ceramic samples show single perovskite phase. The effect of manganese doping on structure, dielectric, ferroelectric and ferromagnetic properties, and resistivity was investigated. Results show that Mn-dopant can improve the sintering ability of the materials when MnO₂ content is below 0.3 wt.%. When MnO₂ content exceeds 0.3 wt.%, the sintering ability is weakened and the phase structure of 0.7BiFeO₃–0.3BaTiO₃ solid solution changes from rhombohedral into tetragonal phase. With increasing concentration of MnO₂, the resistivity increases at first and then decreases. Whereas the coercive electric field decreases at first and then increases, the remanent magnetization M_r increases and the coercive magnetic field decreases.     

La0.8Sr0.2MnO3 MgAl2O4丝网蜂窝催化剂用于低浓度甲烷催化燃烧

首先,采用沉积-沉淀法制备了与镁铝尖晶石(Mg Al2O4,简称MA)载体复合的镧锶锰钙钛矿(La_(0.8)Sr_(0.2)MnO_3,简称LSM)催化剂LSMn,考察了MA与LSM的物质的量比(n)、前驱体老化和焙烧温度系列制备条件的影响,在程序升温微反应器中测试了LSMn粉体对低浓度甲烷催化燃烧反应的活性,并用FTIR、H2-TPR、BET、XRD和SEM手段对催化剂进行表征。结果表明:在10℃老化和800℃下焙烧的LSM4性能最佳,T50为489.4℃,活化能Ea=112.5 kJ/mol,BET比表面积仍有81.6 m2/g,表现出较好的抗烧结性能。然后,用浆料涂覆法依次将第二载体(MA)和LSM4粉体涂覆在Fe-Cr-Al合金丝网上制得了丝网蜂窝催化剂。考察了第二载体及LSM/4MA粉体涂覆量的影响,在空速40000 h–1条件下测试了蜂窝催化剂的活性,结果表明,MA的最佳涂覆厚度约20mm,LSM/4MA的最佳涂覆量约为2.65 mg/cm2,甲烷转化率30%以上。     

Enhanced resistance in Bi(Fe1-xScx)O3-0.3BaTiO3 lead-free piezoelectric ceramics: Facile analysis and reduction of oxygen vacancy

We reported a facile analysis and reduction of oxygen vacancy (${\mathrm{V}}_{\mathrm{O}}^{??}$) in 0.7Bi(Fe_1-xSc_x)O₃-0.3BaTiO₃ (0≤x≤0.08) ceramics. The leakage current mechanism was investigated intensively. Our results indicated that oxygen vacancies are the main cause for the high conductivity in BF-BT ceramics, and their concentration was quantitatively estimated from the Bi³⁺ content and the average oxidation state of iron. The ${\mathrm{V}}_{\mathrm{O}}^{??}$ concentration was effectively suppressed and the insulation resistance was enhanced by almost two orders of magnitude after doping 2%mol Sc³⁺. The enhanced insulation resistance contributed to excellent piezoelectric properties with d₃₃ = 165 pC/N, T_C = 505 °C, and k_p = 26%. The proposed analysis method used to quantify the ${\mathrm{V}}_{\mathrm{O}}^{??}$ concentration provides valuable indications to reduce the leakage current density and improve the piezoelectric properties of BF-BT based ceramic.     

La_(0.8)Sr_(0.2)MnO_3的燃烧法制备及对HMX热分解的影响(英文)

Perovskite-type La0.8Sr0.2MnO3 was prepared by stearic acid gel combustion method. The obtained powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron micrograph (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic activity of La0.8Sr0.2MnO3 was investigated on thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by thermal gravity-differential scanning calorimetry (TG-DSC) techniques. The experimental results show that La0.8Sr0.2MnO3 is an effective catalyst for HMX thermal decomposition. The surface-adsorbed species such as H2O, OH&;#61485; and adsorbed oxygen (Oad) could result in an advance in the onset temperature of HMX thermal decompo-sition. The mixture system of Mn3+ and Mn4+ ions and lattice oxygen could play key roles for the increase of the decomposition heat of HMX because these exothermic reactions could be catalyzed by La0.8Sr0.2MnO3 between CO and NOx (from the thermal decom-position of HMX) and the oxidation reaction of CO. According to the previous researches and our results, perovskite-type La0.8Sr0.2MnO3 may be used as a novel catalyst or modifier for nitrate ester plasticized polyether (NEPE) propellant.     

稀土Mn氧化物中的电子双交换机制

首先综述了钙钛矿结构稀土Mn氧化物中的电子双交换模型以及掺杂效应所引起的Jahn-Teller畸变.接着利用该模型结合晶格Jahn-Teller畸变效应对CMR效应的产生机理进行了分析.     

New BST–silica suspension coating material for dielectric thin films fabricated at low temperatures

Abstract

A new Ba_0·7Sr_0·3TiO₃ (BST)–silica suspension has been developed as a coating material for dielectric thin films. Using a spin on glass (SOG) wet process, a thin layer consisting of nanoparticles of BST and silica was formed on an Al/SiO₂/Si wafer. The BST–silica suspension was made by mixing a BST nanoparticle dispersion with methyl siloxane oligomer. A silicon wafer was coated with the BST–silica suspension using a spin coater and heat treated. The sample was then coated with methyl siloxane oligomer and heat treated again, and finally, a top electrode was applied. The Al/SiO₂/BST–SiO₂/Al/SiO₂/Si stack thus prepared is a metal insulator metal (MIM) capacitor. The electrical properties of the MIM capacitor were evaluated and its capacitance, dissipation factor and voltage coefficient of capacitance were determined to be 1054 pF mm^?2, <0·1 and <100 ppm V^?1 respectively.     

WO3/BiOCl0.7I0.3光催化剂的制备及其光催化降解机理

通过简单的煅烧法和原位沉淀法制备了WO₃/BiOCl_0.7I_0.3复合光催化材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)等表征手段对合成材料的微观形貌、化学组成等进行表征。并通过可见光催化降解20mg/L盐酸四环素来评价材料的光催化性能,结果显示,WO₃/BiOCl_0.7I_0.3复合材料较单一的BiOCl_0.7I_0.3和WO₃具有更优的光催化性能,其中W与Bi摩尔比为1∶15时,复合材料具有最高的光降解率,可见光下60min达到最高值93.84%,且四次循环试验后仍具有较好的光催化活性。对自由基捕获试验结果及电子自旋共振光谱进行分析,明确了h⁺和·O₂^-为光催化主要活性物质,提出WO₃/BiOCl_0.7I<...     

Ce_(0.7)Zr_(0.3)/γ-Al_2O_3纳米固溶体的制备及其结构

以氯氧化锆、硝酸铈、硝酸铝为原料,按n(Ce)∶n(Zr)=0.7∶0.3的比例,采用化学共沉淀法与有机物共沸蒸馏法,将CeO2、ZrO2分散到γ-Al2O3表面上使其形成Ce0.7Zr0.3O2/γ-Al23固溶体。用XRD考察纳米固溶体在不同温度下焙烧后的相结构。结果表明:Ce0.7Zr0.3O2/γ-Al2O3纳米固溶体为立方晶型,且随着焙烧温度的升高,样品的衍射峰依次变强,峰宽变窄。     

Catalytic oxidation of trichloroethylene in two-component mixtures with selected volatile organic compounds

The activity of two noble metal catalysts (Pt and Pd) on metallic monolithic support and one perovskite (La_0.5Ag_0.5MnO₃) on cordierite monolith was tested in the oxidation of selected volatile organic compounds (VOCs) and trichloroethylene (TCE), oxidized alone and in two-component mixtures of TCE with a non-halogenated compound. Only over the Pt catalyst each compound in the reaction mixtures strongly enhanced TCE oxidation. Over Pd, promoting effect on TCE oxidation was observed for toluene and ethanol only. Over perovskite, each non-chlorinated compound was found to inhibit TCE oxidation. The presence of TCE was found to inhibit the oxidation of each compound added over both noble metal catalysts, but it had no influence on the oxy-derivatives oxidation over the perovskite catalyst.