Preparation and structure characteristics of nano-Bi_2O_3 powders with mixed crystal structure

1INTRODUCTION Thefivekindsofcharacteristicphasesof Bi2O3areα ,β ,γ ,δ ,andω phases.Among them,themonoclinicα phaseandcubicδ phaseare alow temperaturestablephaseandahigh temper aturestablephase,respectively.Theothersare metastablephasesathightemperature[13].Each phaseobtainsadistinctcrystalstructureandsome physicalproperties(electrical,optical,photoelec trical,etc.).Forexample,at300K,thebandgap ofmonoclinicα Bi2O3is2.85eV,whilethatoftet ragonalβ phaseis2.58eV[4].Owingtothepe…     

Synthesis of γ-Al2O3 nanoparticles by chemical precipitation method

Highly pure active γ-Al₂O₃ nanoparticles were synthesized from aluminum nitrate and ammonium carbonate with a little surfactant by chemical precipitation method. The factors affecting the synthesis process were studied. The properties of γ-Al₂O₃ nanoparticles were characterized by DTA, XRD, BET, TEM, laser granularity analysis and impurity content analysis. The results show that the amorphous precursor Al(OH)₃ sols are produced by using 0.1 mol/L Al(NO₃)₃ · 9H₂O and 0.16 mol/L (NH₄)₂CO₃ · H₂O reaction solutions, according to the volume ratio 1.33, adding 0.024% (volume fraction) surfactant PEG600, and reacting at 40 °C, 1 000 r/min stirring rate for 15 min. Then, after stabilizing for 24 h, the precursors were extracted and filtrated by vacuum, washed thoroughly with deionized water and dehydrated ethanol, dried in vacuum at 80°C for 8 h, final calcined at 800 °C for 1 h in the air, and high purity active γ-Al₂O₃ nanoparticles can be prepared with cubic in crystal system, O _H ⁷ -FD3M in space group, about 9 nm in crystal grain size, about 20 nm in particle size and uniform size distribution, 131. 35 m²/g in BET specific surface area, 7 – 11 nm in pore diameter, and not lower than 99.93% in purity. Foundation item: Project(03JJY3015) supported by the Natural Science Foundation of Hunan Province     

Preparation and characterization of Bi4Ti3O12 platelets by a novel low-temperature molten salt system

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were prepared by molten salt method in a new salt system of CaC_l2-NaCl at 650–750 °C, using bismuth nitrate pentahydrate (Bi(NO₃)₃―H₂O) and titanium butoxide (Ti (OC₄H₉)₄) as raw materials. The synthesis temperature of Bi₄Ti₃O₁₂ platelets was decreased to 650 °C from 900–1100 °C. The phase compositions and crystalline morphology of Bi₄Ti₃O₁₂ platelets were investigated by XRD and SEM. The experimental results indicate that Bi₄Ti₃O₁₂ platelets containing tetragonal and orthorhombic phase with the size of 1–3 μm can be synthesized at 650 °C for 2 h, and the orthorhombic phase becomes the dominant phase at 750 °C for 5 h. The size and proportion of Bi₄Ti₃O₁₂ platelets increase with the increment of the calcining temperature and holding time. The proportion of platelets increases to about ninety percent, and the platelets grow up to about 3–10 μm at 750 °C for 5 h from 1–2 μm at 650 °C for 2 h. This technical route provides a new low-temperature molten salt system for preparing platelets by molten salt methods.     

Ferroelectric properties of Bi3.4Ho0.6Ti3O12 thin films prepared by sol-gel method

We have prepared the Ho-substituted bismuth titanate (Bi_3.4Ho_0.6Ti₃O₁₂, BHT) thin films on Pt/Ti/SiO₂/Si substrates using sol-gel method. The crystal structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The BHT film shows a single phase of Bi-layered Aurivillius structure and dense microstructure. The 2Pr and 2Ec of the 600-nm-thick BHT film were 38.4 μC/cm² and 376.1 kV/cm, respectively at applied electric field 500 kV/cm. The dielectric constant and dielectric loss are about 310 and 0.015 at a frequency of 1 MHz, respectively. The Pr value decreased to 93% of its pre-fatigue values after 4.46×10⁹ switching cycles at 1 MHz frenquency, and the BHT film shows good insulating behavior according to the test of leakage current. Supported by the Hubei Province Natural Science Foundation (Grant No. 2007ABA309)     

Template effect on structure and morphology of Ni(OH)2 powders prepared by hydro-chemical method

The template effect controlling the structure and morphology of ultrafine particles was described. Ni(OH)₂ powders were prepared by NH₃ coordination-precipitation method. The effects of SO ₄ ²⁻ , NO ₃ ⁻ , Cl⁻, NH₃, pH value on Ni(OH)₂ structure and morphology were investigated experimentally, explained with the theoretical model that the growth units were the polyhedral structure of coordination anions. The results showed that the structure and morphology of Ni(OH)₂ were effectively controlled by the growth units, the dimensions and the linking patterns of the growth units vary with the changes of physical and chemical conditions in the aqueous solution. Foundation item: The National Natural Science Foundation of China(No.59774018) Biography of the first author: LIU Zhi-hong, professor, born in 1963, majoring in hydrometallurgical technology and control of structure and morphology of powders.     

Solvothermal preparation and characteristics of Sn-doped In2O3

Sn-doped In2O3 （ITO） nanopowders were prepared in ethanol solvent by solvothermal process. The effects of the solvothermal temperature, coprecipitation pH value and SnO2 content on the products phase and microwave absorption were investigated by X-ray diffractometry and microwave reflectance. ITO nanopowders with cubic structure can be respectively prepared at 250 and 270 ℃ for 6 h. The prepared product is InOOH or the mixture of InOOH and In3Sn4O12 when the solvothermal temperature is below 250℃. With rising solvothermal temperature and prolonging time, the absorption of the ITO powders gradually decreases. The products are ITO nanopowders by coprecipitating at pH=9 or 11, but ITO powders with Sn3O4 at pH=6. The absorption of powders prepared at pH=6 is better than that at any other pH value. The products are all ITO nanopowders and crystal size reduces with increasing SnO2 content. The microwave absorption of ITO nanopowders with SnO2 content of 8% （mass fraction） is the best among samples with different SnO2 contents.     

Luminescent properties of BaO-La2O3-B2O3 glasses with dopant

The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were stud{ed. The emissions spectra of Eu^2 and Eu^3 were observed in BaO-La2O3-B2O3-Eu2O3 glasses.The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu^2 , the sharp emission peaks at 592, 616, 650 and 250 nm correspond to 5^D0→1Fj(j=1--4) emission transition of Eu^3 ,respectively, which indicates that the BaO-La2O3a-B2O3-Eu2O3 glass can convert ultraviolet and green omponents of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent in--tensity of Eu^2 increases with increasing the molar ratio of Tb^3 in BaO-La2O3-B2O3-Eu2O3a-Tb4O3 glasses, whereas the luminescent intensity of Eua^3 decreases. So the luminescent intensity of Eu(Ⅲ,Ⅱ) is influenced by Tb^3 .These phenomena can be explained by electron transfer mechanism; Eu^3 (4f6) Tb^3 (4f^8)→Eu^2 (4f′) Tb^4 (4f′). Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.     

Pressureless sintered 3Y-TZP/20%Al2O3 composite ceramic

Nanometer 3Y-TZP/20%Al₂O₃ (mass fraction) composite powders prepared by the chemical coprecipitation method were pressureless sintered at 1550 °C for 2 h. Effects of calcining temperatures at 800 °C, 1 000 °C, and 1 200 °C on phase structure, relative density, and Vicker’s hardness of the sintered bodies were studied. The results show that 1 000 °C was the optimal calcining temperature, and the powder calcined was composed of tetragonal zirconia with the Scherrer crystalline size of 6.3nm. The relative density was up to 98.5% under pressureless sintering, and the sintered body was t-ZrO₂ (without m-ZrO₂)+α-Al₂O₃ with the average size of 0.4 μm. Foundation item: State Key Laboratory for Powder Metallurgy(No.9706-36) Biography of the first author: YIN Bang-yao, born in 1966, majoring in advanced ceramic materials.     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.     

Preparation and properties of 4.25Cu-0.75Ni／NiFe2O4 cermet

4.25Cu-0.75Ni/NiFe₂O₄ cermets were prepared by doping NiFe₂O₄ ceramic matrix with the mixed powders of Cu and Ni or Cu-Ni alloy powder as the electrical conducting metallic elements. The effects of technological parameters, such as the adding modes of metallic elements, the ball milling time, the sintering time and the sintering temperature, on the relative density and resistivity of the cermets were studied. The results show that the resistivity of 4.25Cu-0.75Ni/NiFe₂O₄ cermets decreases with increasing temperature, and has a turning point at 590 °C, which is similar to that of NiFe₂O₄ ceramic. The sintering temperature and adding modes of metallic elements have a great influence on the properties of 4.25Cu-0.75Ni/NiFe₂O₄ cermets. When the sintering temperature increases from 1200 °C to 1300 °C, the relative density increases from 89.86% to 95.33%, and the resistivity at 960 °C decreases from 0.11 Ω · cm to 0.03 Ω · cm, respectively. When the metallic elements are added with the mixed powders of Cu and Ni, the cermets of finely and uniformly dispersed metallic phase, high density and electric conductivity are obtained. The relative density and resistivity at 960 °C are 90.23% and 0.04 Ω · cm respectively for the cermet samples sintered at 1200 °C for 2 h, which are both better than those of the cermets prepared under the same technique conditions but with the metallic elements added as 85Cu-15Ni alloy powders. Foundation item: Project (G1999064903) supported by the National Key Fundamental Research and Development Program of China; project(2001AA335013) supported by the National High Technology Research and Development Program of China; project (50204014) supported by the National Natural Science Foundation of China     

Effects of drying method on preparation of nanometer α-Al2O3

Ammonium aluminum carbonate hydroxide （AACH） precursor was synthesized by the precipitation reaction of aluminum sulfate and ammonium carbonate. Then the precursor was dealt with five drying methods including ordinary drying, alcohol exchange, vacuum freeze-drying, glycol distillation, n-butanol azeotropic distillation respectively and calcined at 1 200℃ for 2 h to get α-Al2O3. The effects of drying methods on preparation of nanometer α-Al2O3 were discussed, and the optimal drying method was confirmed. The structural properties of powders were characterized by XRD, SEM and BET measurements. The results show that vacuum freeze-drying, glycol distillation and n-butanol azeotropic distillation can prevent the powders from aggregating, and among them the n-butanol azeotropic distillation is the best method. The nanometer α-Al2O3 powder with non-aggregation can be manufactured using n-butanol azeotropic distillation and the average particle size is about 40 nm.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Effects of In2O3 doping and sintering temperature on the electrical properties of ZnO varistors

ZnO varistors are prepared using the 0.1–0.3 mm ZnO powders. The effects of the sintering temperature, contents of In₂O₃ doping on the non-linear properties of ZnO varistors have been investigated. The results show that this kind of ZnO powder has a high sintering activity. It is suitable for making the low voltage varistors. The V _c decreases with the increase of sintered temperature, when the In₂O₃ content is fixed (0.98%, mass fraction), and increases with the increase of In₂O₃ contents when the temperature is steady. Project supported by the Nonferrous Metals Industry Corporation of China Synopsis of the first anthor Zhao Ruirong, born in Jan. 1935, majoring in nonferrous metal metallurgy and products exploition.     

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.     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

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)     

Preparation and sintering of nano Fe coated Si3N4 composite powders

Fe/Si₃N₄ composite powder was synthesized by the heterogeneous precipitation-thermal reduction process, and then pressed into flakes under a pressure of 10 MPa. Flakes were sintered by pressureless and hot-pressing at 1 600 °C under 0.1 MPa N₂. The chemical composition, phases and microstructure of composite powder and sintered flakes were investigated by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the structure of composite powders is Si₃N₄ coated by nano Fe. The crystal phases of sintered flakes by pressureless are Fe(Si) compound, SiC and Si₃N₄. The crystal phases of the sintered samples by hot-pressing are Fe, Fe(Si) compound and Si₃N₄. It is found that crystal phases flakes obtained by pressureless and hot-pressing are very different. Foundation item: Project(50804016) supported by the National Natural Science Foundation of China     

Effect of Bi content in precursor solutions on microstructure and ferroelectric properties of bismuth cerium titanate thin films

Sol-gel derived bismuth cerium titanate (BCT) thin films with different Bi contents in precursor solutions were deposited on the Pt/Ti/SiO₂/Si substrates. The effect of Bi content in the precursor solutions on the microstructure and ferroelectric properties of the films was investigated. It is found that with Bi content increasing from 90% to 110% of the nominal value in the precursor solutions, the dissipation factor and leakage current density of the BCT films obtained decrease, while the grain sizes, dielectric constant and remanent polarizations (2Pr) increase, and concurrently, a Bi-deficient phase of Bi₂Ti₂O₇ gradually disappears. The film prepared from solution with 110% of the nominal Bi content exhibits pure Bi-layered Aurivillius polycrystalline phase, and the 2Pr value and coercive field value are 67.1 μC/cm² and 299.7 kV/cm, respectively. Their dielectric constant and the dissipation factor are about 172 and 0.033 at 1 kHz, respectively. Moreover, this film shows no polarization fatigue after 4.46×10⁹ switching cycles. Supported by the Hubei Province Natural Science Foundation (Grant No. 2007ABA309)     

Thermodynamic equilibrium of bismuth hydrometallurgy in chloride and nitrate solutions

Simultaneous equilibrium was applied to the thermodynamic analysis and calculation of Bi( Ⅲ )-X(Cl- ,NO3- )-H2O systems, based on which the diagrams of the logarithm of equilibrium concentration of Bi( Ⅲ ) of series precipitation vs pH value of these two systems at 25 ℃ were obtained, and the pH ranges of the stable zones of various precipitations were analyzed and determined. In Bi( Ⅲ )-Cl -H2O system, the variations of c0 (Bi3 ) and c0 (Cl-) have little effect on the equilibria of Bi(OH)3-solution and BiOOH-solution, but has great influence on the equilibrium of BiOCl-solution. However, in Bi( Ⅲ )-NO3-H2O system, the variations of c0 (Bi3 ) and C0 (NO3-)have little effect on equilibria of Bi(OH)3-solution, BiOOH-solution and Bi2O3-solution. When pH value is high,Bi2O3 is the thermodynamic stable phase, its stable zone is the widest, almost including the stable zones of BiOCl or BiONO3, Bi(OH)3 and BiOOH. Bi(OH)3 cannot be obtained from Bi( Ⅲ )-Cl--H2O system, even strong alkaline media. Bi2O3 can be obtained from the solution directly, and highly pure BiOCl or BiONO3 can also be obtained through strictly controlling pH value.     

Properties of plasma sprayed NiCrAlY+(ZrO2+Y2O3) coating on refractory steel surface

NiCrAlY+(ZrO₂+Y₂O₃) thermal barrier coating was prepared on the surface of refractory steel 1Cr18Ni9Ti with plasma spraying technique. The phases and microstructure of the thermal barrier coating were determined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that the bonding between thermal barrier coating and substrate is sound. The surface hardness of 1Cr18Ni9Ti reaches up to 1 000 HV, but that of substrate is only 300 HV. The patterns sprayed with CoNiCrAlY+(ZrO₂+Y₂O₃) ceramic coating have a good heat insulation effect at 800 °C for heat insulation temperature difference reaches 54 °C, which increases the operating temperature and service life of refractory steel. Foundation item: Project (5040202140) supported by Scientific Research Common Program of Beijing Municipal Commission of Education