The Mechanism of Sol-Gel Synthesis of Normal Spinel LiMn_2O_4 with Chelation of Citric Acid

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Structure and electrochemical properties of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>−<Emphasis Type="Italic">x</Emphasis>F<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

LiMn₂O₄−_xF_x prepared by the sol-gel method has a perfect crystal formation. The crystal particle size of the material was medium and distributed uniformly. The substitution of F for O increased the specific capacity of the material at the cost of the cycleability. The explanation of this results is that the F decreases the valence of Mn, that is, more Mn³⁺ and less Mn⁴⁺ exist in the material. The increase of Mn³⁺ will improve the initial specific capacity and Mn³⁺ is the original reason for Jahn-Teller effect that caused the poor cycleability of the cathode material by the micro-distortion of the crystal structure. In addition, the expanded measurement of the crystal lattice is also the reason for the poor cycleability. Therefore, the results of F-substitution and cation-substitution are opposite. If the two methods are combined, they can compensate the inability each other and the satisfactory results may be obtained. XIA Jun-lei: Born in 1977 Funded by the National Natural Science Foundation of China (No. 59972026)     

Self-Propagating High-Temperature Reduetive Synthesis of TiB2-Al2O3 Composite Powders

TiB2-Al2O3 composite powders were produced by self-propagating high-temperature synthesis（SHS） method with reductive process from B2O3-TiO2-AI system. X-ray diffraction（XRD） and scanning electron microscopy（SEM） analyses show the presence of TiB2 and Al2O3 only in the composite powders produced by SHS. The powders are uniform and free-agglomerate. Transmission electron microscopy （TEM） and high resolution electron microscopy （HREM） observation of microstructure of the composite powders indicate that the interfaces of the TiB2-Al2O3 bond well, without any interfacial reaction products. It is proposed that the good interfacial bonding of the composite powders can be resulted from the TiB2 particles crystallizing and growing on the Al2O3 particles surface with surface defects acting as nucleation centers.     

Sol—Gel Synthesis of Normal Spinel LiMn2O4 and Its Characteristics

Normal spinel LiMn2O4 was synthesized by sol-gel method using lithium nitrate,manganese nitrate,citric acid and ethylene glycol as raw materials.LiMn2O4 was characterized by XRD,TG-DTA,IR,SEMand AAS,The optimum conditions for the synthesis were explored.Citric and ethylene glycol were mixed with molar ratio of 0.25,and the mixtrue was esterified at 140℃ for 4 hours.Then lithium nitrate and manganese nitrate were added with molar ratio of 0.6,In the system,the total molar of cations was equal to that of citric acid.At last,reflux the system at 105℃ for 2 hours,Dried gel was fired at 600℃ for 8 hours.Particle diameters of raw product were about 100nm mainly.Further research shows that lithium ion of LiMn2O4 is easy to be extracted,and normal spinel λ-MnO2 can be obtained after lithium ion extraction.     

Microstructures and mechanism of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al composites fabricated by the reaction between SiO<Subscript>2</Subscript> and molten aluminum

Al₂ O₃/Al composite was fabricated by the reaction between SiO₂ and molten aluminum. The microstructures of the composite obtained under different reaction conditions were analyzed. The formation mechanism of the composite microstructure was discussed. Results show that the reaction kinetics is influenced remarkably by the reaction temperature, reaction time and the quantity of SiO₂. The morphologies of Al₂O₃ have different features, depending on the reaction temperature. The composite has equaxed Al₂O₃ grains when materials reacted below 1200°C, and the composite is composed of a large number of fine Al₂O₃ grains and aluninum. The composite has a frame-shaped Al₂O₃ microstructure at the reaction temperature of above 1250°C. CHENG Xiao-min: Born in 1964 Funded by the National Natural Science Foundation of China (No. 91522)     

Manufacture Process of 8Y2O3 Stabilized ZrO2 from Nano Powders

The manufacture process of 8 mol% Y2O3 stabilized ZrO2 ( YSZ ) from nano powders, including the forming and sintering stages, was studied. During the forming process of YSZ powders, the relative density of YSZ increases lineally with the forming press, and the sintering linear shrinkage of YSZ to the forming press compiles to the parabola trend. When the forming press exceeding 500MPa, the samples with lower shrinkage and high density were obtained. The sintering temperature of YSZ decreases greatly because of the small size and high active surface of YSZ powders. As a result, the beginning sintering temperature of YSZ made in the experiment is as low as 825℃, and the end sintering temperature is 1300-1350℃ . The relative density of YSZ ceramic by solid sintering at 1300-1350℃ is more than 97% , with little and small pores in the uniform microstructure.     

Synthesis and characterization of a new Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> pillared triple-layered perovskite KSr<Subscript>2</Subscript>Nb<Subscript>3</Subscript>O<Subscript>10</Subscript>

A n-Hexyl NH₃Sr₂Nb₃O₁₀ is obtained by the stepwise ion-exchange reaction, then is dispersed in aqueous solution of trinuclear acetato-hydroxo iron (III) nitrate, [Fe₃(OCOCH₃)₇OH·2H₂O]NO₃, and the interlayer potassium cations of the perovskite niobate are exchanged with the partially hydrolyzed trinuclear acetato complex ions. On heating, the exchanged complex ions are converted into iron oxide pillars which keep the perovskite sheets apart. The product is characterized by XRD, SEM, EDAX and surface area measurement respectively. Zhang Hui: Born in 1970 Funded by the National Natural Science Foundation of China (No. 50002007), Major Program of Ministry of Education (No. 0201) and Open Foundation of State Key Lab of Advanced Tech. for Materials Synthesis and Processing.     

Nanocomposite films of V<Subscript>2</Subscript>O<Subscript>5</Subscript>−MoO<Subscript>3</Subscript> xerogel with poly ethylene oxide intercalation

Poly ethylene oxide (PEO)_x−V₂O₅−V₂O₅−MoO₃ (x=0, 0.5, 1) films were prepared by the sol-gel method. The synthesis and structure of the films were investigated by XRD, TG-DTA, FTIR, etc. The results show that V₂O₅−MoO₃ xerogel has a layered structure and its interlayer space increased from 1.3181 nm at x=0 to 1. 7898 nm at x=1 after the nanocomposite films were dried, and PEO in the interlayer changes the interface structure by forming hydrogen bonds with V=0 bands. CV measurement indicates that the intercalation of PEO improves insertion/extration properties of Li⁺ ions in the interlayer. ZHENG Jin-xia: Born in 1976 Funded by the National Natural Science Foundation of China (No. 50172036) and Natural Science Foundation of Hubei Province(No. 2001ABB083)     

Surface organic modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles

The surface organic modification of Fe3O4 nanoparticles with silane coupling reagent KH570 was studied. The modified and unmodified nanoparticles were characterized by FT-IR, XPS and TEM. The spectra of FT-IR and XPS revealed that KH570 was coated onto the surface of Fe3O4 nanoparticles to get Fe-O- Si bond and an organic coating layer also was formed. Fe3O4 nanoparticles were spheres partly with mean size of 18,8 nm studied by TEM, which was consistent with the result 17.9 nm calculated by Scherrer＇s equation. KH570 was adsorbed on surface and formed chemistry bond to be steric hindrance repulsion which prevented nanoparticles from reuniting. Then glycol-based Fe3O4 magnetic liquids dispersed stably was gained.     

Effect of La doping on microstructure and ferroelectric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by sol-gel method

The Bi4Ti3Oi2 and Bi3.25La0.75Ti3O12 thin films were prepared on the Pt/Ti/SiO2/Si substrate using the sol-gel method. The effect of La doping on the microstructure and ferroelectric properties of Bi4Ti3O12 films were investigated. Both the Bi4Ti3O12 and Bi3.25La0.75Ti3O12 thin films exhibited typical bismuth layered perovskite structure. The 2Pr （remanent polarization） value of Bi3.25La0.75Ti3O12 thin films is 18.6 μC/cm^2, which is much larger than that of Bi4Ti3O12 thin films. And the Bi3.2eLa0.75Ti3O12 films show fatigue-free behavior, while the Bi4Ti3O12 thin films exhibit the fatigue problem. The mechanism of improvement of La doping was discussed.     

Controlled synthesis and magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> walnut spherical particles and octahedral microcrystals

Magnetite Fe₃O₄ walnut spherical particles and octahedral microcrystals were successfully synthesized from K₄ [Fe (CN)₆], K₃ [Fe (CN)₆] and NaOH reagents via a simple hydrothermal process. And the uniform morphology of octahedral microcrystals was obtained in the presence of ethylene glycol. The morphology and structure of products were characterized by powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results showed that the Fe₃O₄ walnut spherical particles and octahedral microcrystals were single crystals with the face-center cubic structure and with size distributions from 2.2 to 8.6 μm and 1.6 to 12.5 μm, respectively. Their magnetic properties were detected by a vibrating sample magnetometer at room temperature. The walnut spherical particles exhibited a ferromagnetic behavior with the coercive force (Hc), saturation magnetization (Ms) and remanent magnetization (Mr) being 150.57 Oe, 97.634 and 12.05 emu/g, respectively. For the octahedral microcrystals they were 75.28 Oe, 101.90 and 6.69 emu/g, respectively. Different sizes of walnut spherical particles were controlled synthesized through adjusting the NaOH concentration. It was found that ethylene glycol molecules have a significant effect on the formation of Fe₃O₄ octahedra. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ products. Supported by Fund of weinan Teachers University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Dielectric Properties of B2O3 Doped MgTiO3-CaTiO3 System Ceramics

The dielectric ceramics with a main crystal phase of MGTiO3 and additional crystal phase of CaTiO3 were prepared by the conventional electronic ceramics technology .the strucures of MgTiO3 are ilmenitetype,and belong to hexagonal syngony.the ratio of MgTiO3 to Ca TiO3 doping on the dielectric properties of MGTiO3-CaTiO3(MCT)ceranics were inrestigated.the addition of B2O3 decreases the sintering temperatnre and results in rapid desification without obrious negative effect on the Q values of the system(Q=1/tan ).B2O3 exists as liquid phase in the sintering process,promoting the reactions as a singering agent.     

Domain structure and defects of highly ordered Bi<Subscript>4</Subscript>Si<Subscript>3</Subscript>O<Subscript>12</Subscript> micro-crystals

Highly ordered Bi₄Si₃O₁₂ micro-crystals were prepared at normal atmosphere. Phase identification of the prepared crystals was accomplished by X-ray diffractometer (XRD). Domain structure and defects were characterized by environmental scanning electron microscopy (ESEM). XRD shows that the obtained micro-crystals are of eulytite structure with chemical formulation of Bi₄Si₃O₁₂. A highly ordered growth pattern is confirmed due to the faster growth of the {124} faces than that of the {204} faces by ESEM. The growing process of the domain structure is of pollen parent and filial generation pattern. The filial generations of Bi₄Si₃O₁₂ crystals are generated from the pollen parent. Cracks generate from the defect areas and propagate along the {124} faces due to their lower binding energy under a proper temperature gradient, contributing to the total transcrystalline fracture. It is confirmed that the generation and development of the voids in the crystal grains can be developed when unmatched dimensions of the two opposite faces are formed. And the development of the voids is dependent on the dimensions and orientations of the two opposite faces. Supported by the Innovation Research Team Funds of Shaanxi University of Science & Technology (Grant No. SUST-A04)     

Novel preparation and XPS analysis of V<Subscript>2</Subscript>O<Subscript>5</Subscript> xerogel

The V₂O₅ sol was fabricated by ultra-fast quenching. The vanadium with low valence (V⁴⁺) was found in V₂O₅ xerogel films by XPS analysis. The technology of oxygen top-blown was applied to analyze the XPS spectrum difference of V₂O₅ xerogel when the powder of V₂O₅ was melting in air or in oxygen atmosphere. The results show that the different melting atmosphere has certain influences on the chemical valence of V₂O₅ xerogel. ZHU Quan-yao: Born in 1968 Funded by the National Natural Science Foundation of China (No. 50172036, No. 59802009)     

Molten Salt Synthesis of Ba（ Mgl／3Nb2／3 ）O3 Powder

The single-phrase Ba(Mgl/3Nb2/3)O3(BMN) powder was saccessfully prepared by the KCImolten salt synthesis(MSS) method. The temperature for single-phase BMN powders by MSS was about 400℃ lower than that by the solid-phase method. The average particle size (APS) was about 0.91,u.m at 900℃ and increased with increasing synhesis temperature. Based on the APS, the activation energy for particle growth in theMSS, whose value was 64. 1kJmol^-1.was attained. The sinterability of the powder prepared by MSS method wasbetter than that pretared by solid-phase method.     

Preparation of Nanometer-structured TiO2 Thin Films by-Sol-Gel Method

The transparent anatse TiO2 nanometer thin films were prepared by the sol-gel method on soda-line glass,X-ray diffraction,thermal analysis and UV-visible spectrophotometer were used to analyze the formation of the phases,Only increasing the heat-treatment time,the average graing size has no obvious change,The mechanism of grain growth in TiO2 thin film is probably as follows:the grain of coating will become grain core later;TiO2 sol constantly deposited on the surface of TiO2 grain and formed membrance with increasing of coating cylce time ;TiO2 grain in the film grow steadily.     

Structure and dielectric properties of ZnO and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> doped BaO-TiO<Subscript>2</Subscript> system microwave ceramics

The microwave dielectric properties and microstructure of BaTi4.3ZnyO9.6＋y ＋0.02 mol% SnO2＋0.01 mol% MnCO3＋x mol% Nb2O5（x=0-0.05, y=0-0.08） system ceramics were studied as a function of the amount of ZnO and Nb2O5 doped. Addition of （y=0-0.05） ZnO and （x=0-0.025） Nb2O5 enhanced the reactivity and decreased the sintering temperature effectively. It also increased the dielectric constant ε r and quality factor Q（=1/tan 8） of the system due to the substitution of Ti^4＋ ions with incorporating Zn^2＋and Nb^5＋ ions, which was analyzed by the reaction ZnO＋Nb2O5＋ 3 TiTxTi →ZnTi＋ 2NbTi＋3TiO2. When the system doped with （y=0.05） ZnO and （x=0.025） Nb205 were sintered at 1 160 ℃ for 6 h, the εr. Qf0 value and rfwere 36.5, 42 000 GHz, and＋1.8 ppm/℃, respectively, at 5 GHz.     

High-temperature oxidation behavior of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiAl matrix composite in air

The oxidation behavior of Al₂O₃/TiAl in situ composites fabricated by hot-pressing technology was investigated at 900° in static air. The results indicate that the mass gains of the composites samples decrease gradually with increasing Nb₂O₅ content and the inert Al₂O₃ dispersoids effectively increase the oxidation resistance of the composites. The higher the Al₂O₃ dispersoids content, the more pronounced the effect. The primary oxidation precesses obey approximately the linear laws, and the cyclic oxidation precesses follow the parabolic laws. The oxidized sample containing Ti₂AlN and TiAl phases in the scales exhibits excellent oxidation resistance. The oxide scale formed after exposure at 900°C for 120 h is multiple-layered, consisting mainly of an outer TiO₂ layer, an intermediate Al₂O₃ layer, and an inner TiO₂+Al₂O₃ mixed layer. From the outer layer to the inner layer, TiO₂+Al₂O₃ mixed layer presents the transit of Al-rich oxide to Ti-rich oxide mixed layer. Near the substrate, cross-section micrograph shows a relatively loose layer, and micro- and macro-pores remain on this layer, which is a transition layer and transferres from Al₂O₃+TiO₂ scale to substrate. The thickness of oxide layer is about 20 μm. It is also found that continuous protective alumina scales can not be observed on the surface of oxidation scales. Ti ions diffuse outwardly to form the outer TiO₂ layer, while oxygen ions transport inwardly to form the inner TiO₂+Al₂O₃ mixed layer. Under long-time intensive oxidation exposure, the internal Al₂O₃ scale has a good adhesiveness with the outer TiO₂ scale. No obvious spallation of the oxide scales occurs. The increased oxidation resistance by the presence of in situ Al₂O₃ particulates is attributed to the enhanced alumina-forming tendency and thin and dense scale formation. Al₂O₃ particulates enhance the potential barrier of Ti ions from M/MO interface to O/MO interface, thereby the TiO₂ growth rate decreases, which is also beneficial to improve the oxidation resistance. Moreover, the multi-structure of the TiO₂+Al₂O₃ mixed layer decreases the indiffusion of oxygen ions and also avails to improve the high temperature oxidation resistance of the as-sintered composites. Supported by the Special Program for Education Bureau of Shaanxi Province, China (Grant No. 08JK240) and Scientific Research Startup Program for Introduced Talents of Shaanxi University of Technology, China (Grant No. SLGQD0751)     

The film-forming behavior on the interface between air and hydrosol of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The film forming behavior on the interface between air and hydrosol of Fe₂O₃ nanoparticles was investigated by the surface pressure-time isotherms, the surface pressure-trough area isotherms, Brewster angle microscopy and transmission electron microscopy. It is found that the freshly prepared hydrosol of Fe₂O₃ nanoparticles is not stable. The surface pressure increases with the aging time and finally approaches a constant, and the smaller the concentration is, the smaller the surface pressure is stabilized at and the shorter the time the hydrosol reaching stable needs. The surface pressure also increases with compression until collapsed, and the longer the hydrosol is aged, the higher the collapsing pressure is. A uniform and compact film composed of nanoparticles with an average diameter of about 2–3 nm on the air-hydrosol interface is observed by Brewster angle microscope and transmission electron microscope. Funded by the National Natural Science Foundation of China (50672089), the Encouraging Foundation for the Scientific Research of the Excellent Young and Middleaged Scientists in Shandong Province(2006BS04034)     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> content on residual stress and properties of CAS glass-ceramics

The structure and properties of the glass-ceramics were tested with X-ray diffraction testing instrument,correlative software,and other modern testing means.Then the effect of Al2O3 content on internal stresses in CaO-Al2O3-SiO2 glass-ceramics was studied deeply.In order to study the relationship of Al2O3 to the residual stress of CaO-Al2O3-SiO2 glass-ceramics,X-ray diffraction ＂sin2ψ＂ was used.The means utilized the x radial incidence produced from cathode radial tube,and took the space between crystals as measurement of strain.When the stresses produced,the space between crystals changed and the diffraction peak moved during Bragg diffraction.The magnitude of movement is related to the stresses.The experimental results show the residual stress is considerably high and Al2O3 can influence the mechanical properties of this material hugely.