Low Temperature Synthesis of （Pb,La）（Zr,Sn,Ti）O3 Powders by Citrate Process

Lead lanthanum zirconate stannate titanate （PLZST） powders with homogeneous composition were synthesized at a relatively low temperature of 650 ℃ by a citrate process based on the Pechini method. Clear aqueous solutions were prepared from inorganic salts, and citric acid was added as a chelating agent to attain precursor sols. Dried gel-precursors were calcined at different temperatures for various time. The perovskites powders were obtained at 650 ℃ for 1 hour. XRD and SEM results show that the powders were single-phase and ultrafine particles.     

Crystallization behavior of plasma-sprayed lanthanide magnesium hexaaluminate coatings

LaMgAl11O19 thermal barrier coatings （TBCs） were prepared by atmospheric plasma spraying. The crystallization behavior of the coatings and the synthesis mechanism of LaMgAl11O19 powders were researched. The results showed that the plasma-sprayed coatings conmined some amorphous phase, and LaMgAl11O19 powders were partially decomposed into Al2O3, LaAlO3, and MgAl2O4 in the plasma spraying process. The amorphous phase was reerystallized at a temperature of approximately 1174.9℃, at which level the decomposed Al2O3, LaAl2O3, and MgAl2O4 reacted again. The resynthesis temperature of LaMgAl11O19 in the plasma-sprayed coatings was lower than that of LaMgAl11O19 in the original raw powders. The synthesis mechanism of LaMgAl11O19 powders can be summarized as follows： during the first part of the overall reaction, La2O3 reacts with Al2O3 to form LaAl2O3 at approximately 900℃, and then LaAl2O3 further reacts with Al2O3 and MgAl2O4 to produce LaMgAl11O19 at approximately 1200℃.     

Temperature distribution for controlled-dwell extrusion of γ-TiAl

Ti-47Al-2Cr-2Nb-0.15B alloy (atom fraction) was extruded at temperatures(Ta) of 1250 and 1330℃,respectively. The method of adding a thermal insulating layer was used to overcome the problem associated with the flow stress mismatch between the can and the billet during extrusion. Effects of two kinds of insulations, ZrO2 powders and silica fibers, on the quality of extrude bar along the radial direction were studied, and the process parameters were optimized by combining with finite element method (FEM). Tensile properties of the extruded alloy at room and elevated temperature were tested. The results show that the silica fibers has better thermal insulating property than ZrO2 powders. The temperature distribution in radial is more homogeneous using silica fibers. The alloy has a good balance of yield strength and room temperature ductility and the values are 680 MPa and 3.5%, respectively.     

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 H4 TiO4 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-partieles after calcined at 550℃.     

Co-precipitation/hydrothermal synthesis of BiFeO<Subscript>3</Subscript> powder

A coprecipitation/hydrothermal route was utilized to fabricate pure phase BiFeO3 powders using FeCl3·6H2O and Bi（NO3）3·5H2O as starting materials, ammonia as precipitant and NaOH as mineralizer. The synthesized powders were characterized by XRD, SEM and DSC-TG analysis. In the process, single-phase BiFeO3 powders could be obtained at a hydrothermal reaction temperature of 180 ℃, with NaOH of 0.15 mol/L, in contrast to 200 ℃ and 4 mol/L for conventional hydrothermal route. Meanwhile, the micro-morphology of synthesized BiFeO3 powders changed with different reaction temperatures and concentrations of NaOH. The N6el temperature, Curie temperature and decomposition temperature of the synthesized BiFeO3 powders were detected to be 301 ℃, 828 ℃ and 964 ℃, respectively. The hydrothermal reactions mechanism to fabricate BiFeO3 powders were discussed based on the in-situ transformation process.     

Low-temperature Rapid Synthesis of Ultrafine Hafnium Carbide Ceramic Powders

Nano hafnium carbide(HfC) powders were synthesized by sol-gel combining hightemperature rapid heat treatment process using citric acid and hafnium tetrachloride as the raw materials. The effects of ball milling treatment on the phase and morphology of pyrolysis products(HfO_2-C) and final HfC product were investigated and the influences of heat treatment temperature and holding time on the structure and properties of the synthesized hafnium carbide powders were also studied. The experimental results showed that the HfO_2-C powders with good uniformity and small particle size were prepared by controlling the milling time. Pure HfC powders with an average particle size of 500 nm were obtained at 1 700 ℃ with a holding time of 3 min, and the oxygen content was about 0.69 wt%, lower than that of the hafnium carbide powders prepared by SPS(0.97%).     

Effects of heat treatment temperature on crystallization and thermal expansion coefficient of Li_2O-Al_2O_3-SiO_2

The basic glass of Li2 O-Al2 O3-SiO2 system using P2O5 as nucleator was prepared by means of conventional melt quenching technology, and the heat-treatment process was determined by using differential thermal analysis. The crystalline phases and the microstructure of the glass-ceramics were investigated by using X-ray diffraction and scanning electron microscopy. The results show that the glass based on Li2 O-Al2 O3-SiO2 oxides using P2 O5 as nucleator can be prepared at lower melt temperature of 1 450 ℃ and the glass-ceramics with lower thermal expansion coefficient of 21.6 × 10-7 ℃ 1 can also be obtained at 750 ℃. The glass-ceramics contain a few crystal phases in which the main crystal phase is β-quartz solid solution and the second crystal phase is β-spodumene solid solution. When the heat treatment temperature is not higher than 650 ℃, the transparent glass-ceramics containing β-quartzsolid solution can be prepared. β-quartz solid solution changes into β-spodumene solid solution at about 750 ℃. And the appearance of the glass-ceramics changes from translucent, part opaque to complete opaque with increasing temperature.     

Low-temperature oxidation behavior of MoSi2 powders

The oxidation behavior of molybdenum disilicide (MoSi2) powders at 400, 500, and 600℃ for 12 h in air were investigated by using X-ray diffraction (XRD) and transmission electron microscopic (TEM) techniques. Significant changes were observed in volume, mass, and color. Especially at 500℃, the volume expansion was found to be as high as 7-8 times, the color changed from black to yellow-white, and the mass gain was about 169.34% after 8 h, with SiO2 and MoO3 as main reaction products. The gains in volume and mass were less at 400 and 600℃ compared with those at 500℃, probably due to the less reaction rate at 400℃ and the formation of silica glass scale at 600℃, which would protect the matrix and restrain the diffusion of oxygen and molybdenum. Thus,the accelerated oxidation behavior of MoSi2 powder appeared at 500℃ and the volume expansion was the sign of accelerated oxidation.     

Preparation of Rod-like Aluminum Doped Zinc Oxide Powders by Sol-gel Technique Using Metal Chlorides and Acetylacetone Precursors

Al-doped ZnO(AZO) powders were prepared by using metal chloride precursors and the sol-gel technique. IR peaks observed at 1590 cm-1 and 1620 cm~(-1) indicated the formation of metal chelate as a consequence of the addition of acetylacetone to the metal chloride solution. TG-DSC analysis of the AZO gels confirmed the formation of metal chelate as evidenced by the development of several weight loss peaks accompanied by the introduction of new endothermic peaks. The resulting AZO gels were annealed at 500, 600, and 800 ℃ to study the effect of annealing temperature. XRD and SEM results showed that crystallization of AZO gels takes place around 600 ℃. Hexagonal wurtzite structure was identified as the main phase for all the samples. In addition, small shift of the XRD(002) peak coupled with XPS results from the AZO powders confirmed the successful doping of the ZnO powders. Micron sized rod-like AZO powders were uniform in dimension and morphology and remained stable even at 800 ℃.     

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.     

In-situ TEM Study on Mierostruetural Evolution of Nanostruetured TiO2

The effect of electron beam on the microstructures and phase transformation of nanostructured TiO2 heat treated at various temperatures for different time was studied by in-situ TEM and SAED. Anatase ex-situ heated at 250℃ and 360℃ transformed to rutile while irradiated by the electron beam. With the increasing sizes and distribution of the powders on the amorphous carbon, the process of phase transformation by the electron beam was encumbered. These evolutions may be due to the changes of vacuum atmosphere and the properties of powders.     

Preparation and characterization of nanocomposite MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript>

Nanocomposites MgFe₂O₄/SiO₂ were successfully synthesized by the sol-gel method in the presence of N, N-dimethylformamide (DMF). The formation of pure MgFe₂O₄ was confirmed by powder X-ray diffraction (XRD) and electron diffraction. The structural evolution of MgFe₂O₄ nanocrystals was followed by powder X-ray diffraction and IR absorption spectroscopy. The formation of spinel structure of MgFe₂O₄ started at 800 °C, and completed at 900 °C. The transmission electron microscopy (TEM) measurements suggest that the particle sizes increase with the increasing annealing temperature, and the mean particle sizes of the spherical samples annealed at 800 °C, 900 °C and 1 050 °C are ca. 3 nm, 8 nm and 11 nm, respectively. Magnetization measurements at room temperature and 78 K indicate superparamagnetic nature of these MgFe₂O₄ nanocrystals. Funded by the National Natural Science Foundation of China(No. 30771676), the Natural Science Foundation of Jiangsu Province (No. BK20081842), and the Foundation of Nanjing Bureau of Personal for the Returned Overseas Chinese Excellent Scholars     

Sensing characterization of Sn/In/Ti nanocomplex oxides for CO,CH<Subscript>4</Subscript> and NO<Subscript>2</Subscript>

The nanocomplex oxides of Sn-In and Sn-In-Ti were prepared by controlled co-precipitation method as sensing materials of semiconductor gas sensors for detection of CO, CH4 and NO2. Through manipulating the Sn/In cation ratio, metal salt total concentration, precipitation pH value and aging time, the nanocrystalline powders were successfully derived with chemical homogeneity and superior thermal stability, compared with the single component oxides. The particle size and morphology, surface area, and thermal and phase stabilities were characterized using TEM, TG-DTA, BET and XRD. The sensing tests showed that the Sn-In composites exhibit high sensitivity and selectivity for CO and NO2. The introduction of TiO2 enhanced CH4 sensitivity and selectivity, particularly, additives of Pd and Al2O3 as a dopant and surface modification greatly enhanced the sensing properties. The sensitivity depended on the composition of composites, calcination temperature and operating temperature. The optimal values were (25%In2O3- 75%SnO2)-20%TiO2 for ternary composite, 600 and 300℃, respectively. Temperature-programmed desorption (TPD) studies were employed to explain the gas adsorption behavior displayed by the surface of nanocomposites and X-ray photoelectron spectroscopic (XPS) analysis was used to confirm the electronic interactions existing between oxide components. The sensing mechanism of the nanocomposites was attributed to chemical and electronic synergistic effects.     

Preparation of Fe-Al Intermetallie /TiC-Al2O3 Ceramie Composites from llmenite by SHS

Fe-Al intermetallic/TiC-Al2O3 ceramic composites were successfully prepared by selfpropagating high-temperature synthesis （SHS） from natural ilmenite, aluminium and carbon as the raw materials. The effects of carbon sources, preheating time and heat treatment temperature on synthesis process and products were investigated in detail, and the reaction process of the FeTiO3-Al-C system was also discussed. It is shown that the temperature and velocity of the combustion wave are higher when graphite is used as the carbon source, which can reflect the effect of the carbon source structure on the combustion synthesis; Prolonging the preheating time or heat treatment temperature is beneficial to the formation of the ordered intermetallics; The temperature and velocity of the combustion wave are improved, but the disordered alloys are difficult to eliminate with the preheating time prolonged. The compound powders mainly containing ordered Fe3Al intermetallic can be prepared through heat treatment at 750 ℃.     

Composite cathode Bi<Subscript>1.14</Subscript>Sr<Subscript>0.43</Subscript>O<Subscript>2.14</Subscript>-Ag for intermediate-temperature solid oxide fuel cells

Composites consisting of strontium stabilized bismuth oxide （Bi1.14Sr0.43O2.14, SSB） and silver were investigated as cathodes for intermediate-temperature solid oxide fuel cells with doped ceria electrolyte. There were no chemical reactions between the two components. The microstructure of the interfaces between composite cathodes and Ce0.8Sm0.2O1.9 （SDC） electrolytes was examined by scanning electron microscopy （SEM）. Impedance spectroscopy measurements show that the performance of cathode fired at 700 ℃ is the best. When the content of Ag2O is 70 wt%, polarization resistance values for the SSB-Ag cathodes are as low as 0.2 Ωcm^2 at 700℃ and 0.29 Ωcm^2 at 650℃. These results are much smaller than some of other reported composite cathodes on doped ceria electrolyte and indicate that SSB-Ag composite is a potential cathode material for intermediate temperature SOFCs.     

Preparation of TiO<Subscript>2</Subscript> thin film by the LPD method on functionalized organic self-assembled monolayers

In this paper, uniform titania (TiO₂) films have been formed at 50° on silanol SAMs by the liquid-phase deposition (LPD) method at a temperature below 100°C. OTS (Octadecyltrichloro-Silane) self-assembled monolayers (SAMs) on glass wafers were used as substrates for the deposition of titanium dioxide thin films. This functionalized organic surface has shown to be effective for promoting the growth of films from titanic aqueous solutions by the LPD method at a low temperature below 100°C. The crystal phase composition, microstructure and topography of the as-prepared films were characterized by various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results indicate that the as-prepared thin films are purely crystallized anatase TiO₂ constituted by nanorods after being annealed at 500°. The pH values, concentration of reactants, and deposition temperatures play important roles in the growth of TiO₂ thin films. Support by the National Natural Science Foundation of China (Grant No. 50672055) and National Key Technology R&D Program (Grant No. 2006BAF02A28)     

Microwave sintering of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript>-WC-Co cermets

Composite powders of nanocrystalline WC-10Co (15wt%),Y2O3 (8mol%) stabilized nanocrystalline ZrO2 (30wt%),industrial cobalt powder (4.5wt%) and submicron Al2O3 (55wt%) composite powders were fabricated by high-energy ball-milling process.The nanocomposite powders were consolidated by microwave sintering process at temperature ranged 1300℃-1550℃ for 15min,respectively.The optimum consolidation conditions,such as temperature,were researched during microwave sintering process.Vickers Hardness of the consolidated cermets was measured by using a Vickers indentation test,and density of specimens was also determined by Archimedes’ principle.Microwave sintering process could not only increase the density of Al2O3-ZrO2-WC-Co cermets and reduce the porosity,but also inhibit abnormal grain growth.     

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)