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)     

Structure and electrochemical properties of LiCoO2 synthesized by microwave heating

Microwave synthesis method was applied to the fast preparation of LiCoO₂. The structure of the synthesized oxides was analyzed by using X-ray diffraction. Only single-phase LiCoO₂ was obtained. Electrochemical behaviors of LiCoO₂ were investigated by charge-discharge cycling properties in the voltage range of 3.00 – 4.35 V (vs Li). The results show that the prepared LiCoO₂ powders calcinated at 900 °C for 120 min exhibit an initial charge and discharge capacity of 168 and 162 mA · h · g⁻¹ at 0.1C current rate, respectively, as compared to 159 and 154 mA · h · g⁻¹ of LiCoO₂ synthesized by conventional means. In addition, more than 95% of the capacity is retained even after 10 cycles. But with the increase of calcinating time, its electrochemical properties deteriorate. Compared with the conventional method, the microwave heating method is simple, fast, and with high energy efficiency.     

IR Spectra Analysis of SiO2-TiO2-GeO2 Gel Glass of CO2 Laser Transmitting Hollow Waveguide

Both titanium and germanium were introduced into silicon dioxide system by sol-gel method to move its region of anomalous dispersion caused by IR resonance absorption towards the wavelength of CO₂ laser. It is indicated by IR absorption spectra that as the content of SiO₂ decreases in this glass system TiO₂ and GeO₂ tends to exist in their own phases. As for the gel glass with a composition of 40 SiO₂·30TiO₂·30GeO₂, when the temperature is below 600°C, germanium atoms exist mainly in Ge−O−Ge bonds. With the temperature increasing from 800°C to 1000°C, titanium atoms in Si−O−Ti bonds abmost transform into Ti−O−Ti bonds. Furthermore, a large number of Si−O−Ti and Si−O−Ge bonds formed when the temperature approaches 800°C, which makes a notable IR absorption band round the wavelength of CO₂ laser. Therefore, sol-gel based SiO₂−TiO₂−GeO₂ gel glass is a candidate material for CO₂ laser hollow waveguide. JING Cheng-bin: Born in 1974. This work was partly financially supported by the Foundation of Key Teachers of Ministry of Education, China.     

Kinetics of Fe3O4 formation by air oxidation

The kinetics of Fe₃O₄ formation by air oxidation of slightly acidic suspension of Fe(OH)₂ was studied. The effects of initial concentration of Fe(II), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe₃O₄ formation is composed of two-step reaction, the first step is the formation of Fe(OH) ₂ ⁺ by oxidation of Fe(OH)⁺ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)⁺ and Fe(OH) ₂ ⁺ . The oxidation reaction is zero-order with respect to the concentration of Fe(II) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ · mol⁻¹.     

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.     

Effect of matrix composition on physical properties of Al<Subscript>3</Subscript>CON in-situ reaction reinforced corundum composite

60% white corundum used for aggregate, 5% aluminium powder for fixed additions and 35% various additives for matrix were prepared for specimens 1#,2#,3#. They were mixed uniformly with the suitable resin as a binder and pressed under pressure of 315 ton forging press, then dried at 200℃ for 24 h. Effects of various additives on 1500 ℃×2 h creep properties of Al3CON reinforced corundum composite were researched. The experimenal results show that creep coefficients of specimens 1#,2#,3# at 1500 ℃×2 h are 1.4×10^- 4, -9.4×10^-4, -22.6×10^-4, respectively. Crushing strength of the slide plate added with suitable additive A after fired at 1500 ℃ ×3 h reaches to 225 MPa, the creep rate is positive all the time from 0% to 0.014% at 1500 ℃ for 2 h. The microstructure result analysis shows that reinforced phases of Al3CON fiber composite have been formed after fired with Al powder in coke at high temperatures for specimen 1#, and the strength of the composite is increased. The hot modulus of rupture is up to 59 MPa at 1400 ℃ and the RUL is obviously higher than that at 1700 ℃. Its service life is two times as that of Al2O3-C slide plate when used in the process of pouring steel. The mechanism of creep rate resistance of the composites can be discovered by means of SEM and EDAX analysis. It is concluded that the active Al3CON and Al2O3 multiphases that were formed by N2 in gas, C, Al and Al2O3 inside the matrix of the composites during in-situ reaction,which gives the composites outstanding creep rate resistance for the dense zone resuiting from Al3CON oxidation that inhibits contraction at the high temperature. Besides, the matrix will turn into the multiphase with high refractoriness, N content and its Al3CON reinforced fiber will further increase accordingly. In addition, Al3CON formed by Al2O3 and C, Al in the matrix with N2 in gas will inhibit the creep rate and also greatly improve the creep rate resistance of the composites.     

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.     

Effect of tin on the reaction synthesis of ternary carbide Ti3AlC2

The effect of tin on synthesis of Ti₃AlC₂ by spark plasma sintering (SPS) from TiC/Ti/Al powders was investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for phase identification and microstructure evaluation. The experimental results show that addition of tin can considerably accelerate the synthesis reaction of Ti₃AlC₂ and fully dense, essentially single-phase polycrystalline Ti₃AlC₂ could be successfully obtained by sintering 2TiC/1Ti/1Al/0.2Sn powders at 1200–1250 °C under a pressure of 30 MPa. SEM images show that Ti₃AlC₂ samples in about 2–5 μm thick and 10–25 μm long platelets can be obtained. The fracture toughness and flexural strength of Ti₃AlC₂ were 6.5±0.2 MPa·m^1/2 and 560±10 MPa, respectively. Funded by the National Natural Science Foundation of China (No.20771088, No.50572080) and Doctoral Foundation of Wuhan University of Technology (No.471-38650142)     

Effect of catalyst on structure of （PEO）8LiClO4-SiO2 composite polymer electrolyte films

（PEO）8LiClO4-SiO2 composite polymer electrolytes（CPEs） were prepared by in-situ reaction, in which ethyl-orthosilicate （TEOS） was catalyzed by HCl and NH3·H2O, respectively. The ionic conductivity, the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra, contact angle method and TEM. The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10^-5 and 1.1×10^-5 S/cm respectively at 30 ℃. The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2, and influences the surface energy and conductivity of CPE films directly. Meanwhile, the ionic conductivity is related to the surface energy.     

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     

High temperature cyclic oxidation behavior of Y2O3-ZrO2 thermal barrier coatings irradiated by high-intensity pulsed ion beam

The high-temperature oxidation resistance behavior of 7% (mass fraction) Y₂O₃-ZrO₂ thermal barrier coatings (TBCs) irradiated by high-intensity pulsed ion beam (HIPIB) was investigated under the cyclic oxidation condition of 1 050 °C and 1 h. The columnar grains in the TBCs disappear after the HIPIB irradiation at ion current densities of 100–200 A/cm² and the irradiated surface becomes smooth and densified after remelting and ablation due to the HIPIB irradiation. The thermally grown oxide (TGO) layer thickness of the irradiated TBCs is smaller than that of the original TBCs. After 15 cycles, the mass gains of the original TBCs and those irradiated by ion current densities of 100 and 200 A/cm² due to the oxidation are found to be 0.8–0.9, 0.6–0.7, and 0.3–0.4 mg/cm², respectively. The inward diffusion of oxygen through the irradiated TBCs is significantly impeded by the densified top layer formed due to irradiation, which is the main reason for the improved overall oxidation resistance of the irradiated TBCs. Foundation item: Projects supported by The 2nd Stage of Brain Korea and Korea Research Foundation     

Antibiotic properties of Al2O3 doping silver

The preparation technique and properties of Ag-type inorganic antibiotic material carried by Al₂O₃ were studied. The results show that the material has good antibiotic and safety properties, the acute toxicity taken by stomata is LD ₅₀>8 000 mg/kg (little and big white rats), and the normal quantity in subacute toxicity test is 80 mg/(kg · d). The better mass fraction of doping Ag₂O in antibiotic material carried by Al₂O₃ is 4%–8%, and the optimal sintering temperature is from 1 000 °C to 1 100 °C. Foundation item: Project (2002AA327090) supported by National High Technology Research and Development Program of China     

Electrical conductivity of （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts

The effects of contents of AlF3 and Al2O3, and temperature on electrical conductivity of （Na3AlF6-40%K3AlF6）- AlF3-Al2O3 were studied by continuously varying cell censtant （CVCC） technique. The results show that the conductivities of melts increase with the increase of temperature, but by different extents. Every increasing 10 ℃ results in an increase of 1.85 × 10^-2, 1.86× 10^-2, 1.89 × 10^-2 and 2.20 × 10^-2 S/cm in conductivity for the （Na3AlF6-40%K3AlF6）-AlF3 melts containing 0%, 20%, 24%, and 30% AlF3, respectively. An increase of every 10 ℃ in temperature results an increase about 1.89× 10^-2, 1.94 × 10^-2, 1.95 × 10^-2, 1.99× 10^-2 and 2.10× 10^-2 S/cm for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts containing 0%, 1%, 2%, 3% and 4% Al2O3, respectively. The activation energy of conductance was calculated based on Arrhenius equation. Every increasing 1% of AlF3 results in a decrease of 0.019 and 0.020 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3 melts at 900 and 1 000 ℃, respectively. Every increase of 1% Al2O3 results in a decrease of 0.07 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts. The activation energy of conductance increases with the increase in content of AlF3 and Al2O3.     

The Effect of Bi2O3 on the Structure and Microwave Dielectric Properties of Ba6-3xNd8＋2xTi18O54 System（x=2/3）

The structures and dielectric properties of Ba6-3xNd8＋2xTi18O54 system（x=2/3） doped with different contents of Bi2O3, whose final molecular formula is Ba6-3x（Nd1-yBiy）8＋2xTi18O54 were investigated. It is indicated that the dielectric constant increases greatly whereas Q value（f0=4 GHz） decreases with the increase of Bi2O3 content. However, the temperature coefficient could be controlled below 0±30×10^-6/℃ in the experiment. These phenomena are related to the appearance of a new phase, Bi4Ti3O12, which has high dielectric constant. Also, that Bi^3＋（0.13 nm） substitutes for Nd^3＋（0.099 5 nm） will increase the unit cell volume, which will lead to the enlargement of the octahedron B site occupied by Ti^4＋. So the spontaneous polarization of Ti^4＋ ions will be strengthened. Besides, Bi^3＋ will fill up some vacancies which Ba^2＋ or Nd^3＋ ions leave in two A1 sites and four A2 sites. More positive ions polarize, which also contributes to higher dielectric constant. The samples got with the optimium properties are sintered at 1 200 ℃ for 4 h, when y=0.25, ε≈110, Q≈5 400（f0=4 GHz）, TCC=-4.7×10^-6/℃; When y=0.3, ε≈120, Q≈5 000（f0=4 GHz）, TCC=-24×10^-6/℃.     

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.     

复合活性钎料钎焊Cu与Al2O3的接头组织及性能

为改善紫铜与Al_2O_3陶瓷的连接强度,采用纳米-Al_2O_3增强的AgCuTi复合钎料(Ag Cu Tip)对紫铜与Al_2O_3陶瓷进行了真空钎焊.采用扫描电镜、能谱分析以及剪切试验对钎焊接头微观组织及力学性能进行了分析.钎焊接头典型界面组织为紫铜/扩散层/铜基固溶体+银基固溶体+Ti_2Cu+Ti_3(Cu,Al)3O/Al_2O_3.纳米-Al_2O_3的添加抑制了Al_2O_3侧反应层的生长,并促进钎缝中形成弥散分布的Ti_2Cu相.随着保温时间的延长,铜侧扩散层和Ti_3(Cu,Al)_3O反应层的厚度逐渐增大.保温时间为20 min时,铜母材向钎料过度溶解,降低了接头性能.当钎焊温度为880°C,保温10 min时,接头抗剪强度最高为82 MPa.纳米颗粒的加入细化了钎缝组织并降低了母材与钎缝热膨胀系数的不匹配,因此提高了接头的连接性能.保温时间可影响界面组织及反应层的厚度,进而影响接头的连接强度.     

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.     

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 of Al2O3-SiO2-TiO2-ZrO2 Composite Ceramic Membranes by Sol-Gel Method

Al2O3-SiO2- TiO2-ZrO2 supported membranes were prepared by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al2O3, TiO2 ( anatase ), Al2 SiO5 , and ZrO2 in these membranes. Changing the molar ratio of Al:Si: Ti : Zr ,the kinds and content of crystal phases of composite membranes could be different, which may lend to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investigated by XRD, SEM, AFM, EPMA. The effects of additives and heat treatments on the surface nanoscale topography and microstracture of composite ceramic membranes were also analyzed.     

Chemical reaction of in-situ processing of NiAl/Al2O3 composite by using thermite reaction

NiAl/Al₂O₃ composite were synthesized by thermite reaction of nickel oxide and aluminum powder mixtures. The phase, the microstructure of the composite, as well as the thermite reaction mechanism, were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM) combined with differential scanning calorimetry (DSC). The experimental results show that the thermite reaction leads to the interpenetrating network structure of NiAl/Al₂O₃ at 1223K for 60 min and the chemical reaction apparent activation energy is E_ap=166.960±13.496 kJ·mol⁻¹ in the NiO/Al system. Funded by the Younger Teacher Foundation of High School of Anhui Province (No. 2003jq158)