Study on the isothermal oxidation behavior in air of Ti3AlC2 sintered by hot pressing

The isothermal oxidation behavior at 900–1300°C for 20 h in air of bulk Ti₃AlC₂ with 2.8 wt% TiC sintered by means of hot pressing was investigated in the work. The isothermal oxidation behavior generally followed a parabolic rate law. The parabolic rate constants increased from 1.39×10⁻¹⁰ kg²·m⁻⁴·s⁻¹ at 900°C to 5.56×10⁻⁹ kg²·m⁻⁴·s⁻¹ at 1300°C. The calculated activation energy was 136.45 kJ/mol. It was demonstrated that Ti₃AlC₂ had excellent oxidation resistance due to the continuous, dense and adhesive protect scales consisted of a mass of α-Al₂O₃ and a little of TiO₂ and/or Al₂TiO₅. In principle, the oxide scale was grown by the inward diffusion of O²⁻ and the outward diffusion of Ti⁴⁺ and Al³⁺. The rapid outward diffusion of cations usually resulted in the formation of cracks, gaps, and holes.     

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.     

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.     

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     

Microstructural Probing of （1-x） GeS2- x Ga2S3 System Glasses By Raman Scattering

Roman scattering measurement of （ 1 - x ） GeS2-x Ga2S3 system glasses was conducted in order to understand the microstructural change caused by the addition of Ga2S3 . According to the change of Raman spectra with the addition of Ga2S3, two main structural transformations were deduced ： the gradual enhancement of ethane- like structural units S3 Ge- GeS3 （ 250 cm ^- 1） and S3 Ga- GaS3 （270 cm ^- 1 ） and the appearance of charge imbalanced units [ Ga2 S2 （ S1/2 ）4 ]^2- and [Ga（ S1/2 ）4 ]^- . And this change of structural aspect seems to give as a clue to understanding the cause of the increased rare-earth solubility.     

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)     

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.     

基于数值模拟的CO2地质封存项目井筒泄漏风险定量化评价方法

为评估CO₂地质封存场地的CO₂沿井筒泄漏风险，介绍了自主研发的可对CO₂井筒泄漏风险进行定量化评价的数值模拟WellRisk软件，将软件应用于实际CO₂地质封存场地--神华鄂尔多斯CO₂咸水层封存示范工程，定量评估该场地CO₂沿注入井和监测井的泄漏量，并将软件模拟结果与美国能源部开发的NRAP–IAM–CS（The national risk assessment partnership–integrated assessment model–carbon storage）软件模拟结果进行对比，实现了CO₂沿井筒泄漏风险的定量化评价。定义了井筒泄漏系数，即井筒发生泄漏的有效截面积和井筒总截面积的比值，并将井筒泄漏系数作为量化表征井筒固井质量的重要参数。当泄漏系数取值为10^–6时，神华CO₂地质封存场地在1 000 a内的总泄漏量为720 tCO₂，占总注入量的0.24%，小于IPCC的风险阈值1%。因此，泄漏系数为10^–6或更低的井筒是低风险泄漏井，具有良好的固井质量，对应于NRAP–IAM–CS软件中井筒渗透率低于10^–12 m²的情况。泄漏系数为10^–5或更高的井筒是高风险泄漏井，具有较差的固井质量。WellRisk和NRAP–IAM–CS的计算结果均表明，当注入井和监测井的固井质量良好时，神华CO₂地质封存场地基本不存在CO₂泄漏风险。     

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.     

Leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system

The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size, reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching efficiency of zinc were examined. The leaching kinetics of low-grade zinc oxide ore in NH3-NH4Cl-H2O system follows the kinetic law of shrinking-core model. The results show that diffusion through the inert particle pores is the leaching kinetics rate controlling step. The calculated apparent activation energy of the process is about 7.057 kJ/mol. The leaching efficiency of zinc is 92.1% under the conditions of ore particle size of 69μm, holding at 80℃ for 60 min, sum ammonia concentration of 7.5 mol/L, the molar ratio of ammonium to ammonia being 2：1, and the ratio （g/mL） of solid to liquid being 1：10.     

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     

Preparation of λ-MnO2 by Column Method and Its Ion-Sieve Property

λ-MnO₂ was prepared by column method from normal spinel LiMn₂O₄ with purity of 99.38%. The influence of LiMn₂O₄ grain size and acidity of leaching solution on the lithium leaching process was studied. The results show that the appropriate range of LiMn₂O₄ grain size was 60–160 meshes and the concentration of leaching solution HCl was 0.1 mol·L⁻¹. The adsorption capacity Q of λ-MnO₂ for lithium increased with the increase of pH and changed markedly at pH 6.0–10.0. It was 3.80mmol/g at pH 12.0 The distribution coefficients K_d of Li⁺ and Na⁺ were 3.406×10⁴ and 2.300 respectively, and the separation coefficient a _Na ^Li was 1.481 ×10⁴ at pH 6.5. As a result, λ-MnO₂ is a high performance ion-sieve material for lithium ion. LEI Jia-heng: Born in 1957. Funded by the National Natural Science Foundation of China (No. 59972027) and the Natural Science Foundation of Hubei Province (No. 2002AB074)).     

A study on the bonding structure of CaO−SiO2 slag by means of molecular dynamics simulation

The investigation results of the bonding structure of CaO−SiO₂ slag by means of molecular dynamics simulation are presented. The characteristics of partial radial distribution functiong _ij(r) are in good agreement with the measurement of X-ray diffraction, and the variation ofQ _n with different SiO₄ tetrahedra following the change ofX _CaO is consistent with the results of Raman spectroscopy. The partial vibrational density of states Γ_Si(ω) shows that two bands appear in the range of 636–737 cm⁻¹ and 800–1200 cm⁻¹ respectively which are also consistent with Raman spectroscopy. Project supported by Shanghai Natural Science Foundation.     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

Preparation and structure characteristics of nano-Bi2O3 powders with mixed crystal structure

The nano-Bi2O3 powders were prepared by a chemical precipitation method with Bi(NO3)3, HNO3 and NaOH as reactants. The structural characteristics and morphology of nano-Bi2O3 powders were investigated by X-ray diffraction and transmission electron microscopy, respectively. The results show that under the optimum condition that 300g/L Bi(NO3)3 reacts at 90℃ for 2 h, the Bi203 powders with 60 nm on the average and 99.5% in purity are obtained. The prepared nano-Bi2O3 powders contain a mixed crystal structure of monoclinic and triclinic instead of traditional structure of monoclinic α-Bi2O3. And the mixed crystal structure is stable in air. The reason for the appearance of the mixed crystal structure may be that the ionic radius ratio of Bi^3 to O^2- changes easily during the formation of nano-Bi2O3 particles by a chemical precipitation method.     

Preparation of BN／SiO2 ceramics by PIP method

The precursor infiltration and pyrolysis(PIP) method for preparation of BN/SiO2 composites was used to improve mechanical properties, dielectric properties and feasibility of high temperature dielectric parts with large dimensions and complex shapes. In the processing procedure, the porous BN ceramic matrix was first successfully prepared by compacting the mixed powders of B and BN and then sintering them at a certain temperature under normal pressure of N2. The polycarbosilane(PCS) solution was vacuum infiltrated into porous BN ceramics at the room temperature and then at 800℃ in the air to depolimerize out amorphous SiO2, and sintered further at 1 300℃ in N2 to get BN/SiO2 composites. The microstructure of materials was studied by means of X-ray diffraction and electron probe micro analysis. The thermo-decomposition mechanism of PCS was investigated by a TG-DTA and infrared (IR) spectrum analysis. The flexural strengths were measured by the three-point bending method. The dielectric constant and the loss tangent were measured by the wave-guide method. The results show BN/SiO2 composites were fabricated. The obtained composites posses a flexural strength of 61.96 - 93.31 MPa, the dielectric constant in the range of 3.50 - 3.78 and the order of magnitude of the loss tangent at 10^-3 , which are good for the high tempera turedielectric parts with large size and complex shapes.     

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn₂O₄ used as cathode materials for lithium-ion batteries was synthesized by mechano-chemistry fluid activation process, and modified by doping rare-earth Sm. Thesting of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn₂O₄ cathode materials and the modified materials. The results show that the cathode materials doped rare earth Li _x Mn_2−y Sm _z O₄ (0.95⩽x⩽1.2, 0⩽y⩽0.3, 0⩽z⩽0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discharge. In EC: DMC(1 : 1)+1 mol/L LiPF₆ electrolyte with discharge capacity more than 130 mA · h/g, and its capacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55°C. At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element. Foundation item: Project (02JJY2081) supported by the Natural Science Foundation of Hunan Province     

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 modified D401 chelating resin and its adsorption properties for Pb^2＋

A novel chelating resin with sulfonic group was synthesized by chemical modification of D401 resin with sulphonation reaction and characterized by FT-IR spectrometry. The adsorption properties of the novel chelating resin for Pb²⁺ were studied by batch adsorption, and the adsorption process was analyzed from thermodynamics and kinetics aspects. The adsorption mechanism of Pb²⁺ on the modified D401 chelating resin was discussed by FT-IR spectrometry. Experimental results show that in the Pb²⁺ concentration range of 200–400 mg/L, the adsorption capacities of the modified D401 chelating resin for Pb²⁺ increase by 77%–129%, and Langmuir isothermal adsorption model is more suitable for the equilibrium adsorption data. Adsorption is an endothermic process that runs spontaneously. Kinetic analysis shows that the adsorption rate is mainly governed by liquid film diffusion. The best pH value under adsorption condition is 4–5. The saturated resin can be regenerated by 3 mol/L nitric acid, and the adsorption capacity remains stable after five consecutive adsorption-desorption cycles. The maximal static saturated adsorption capacity of the resin is 206 mg/g at 333 K in the Pb²⁺ concentration range of 200–400 mg/L. The modified D401 chelating resin is an efficient adsorbent for the removal of Pb²⁺ from its single-metal ion solution. Foundation item: Project(708049) supported by the Important Item Cultivation Foundation of Scientific Innovation Project of Colleges and Universities of China     

Effects of temperature and initial molar ratio of Na2O to Al2O3 on agglomeration of fine Al（OH）3 seed in synthetic Bayer solution

Fine Al（OH）3 crystals were aggregated from supersaturated aluminate solution in the batch reaction tanks. By means of laser particle size analyzer and scanning electron microscopy, the influences of temperature and initial molar ratio of Na2O to Al2O3 （aK） on agglomeration of fine seed in Bayer process were investigated. The results show that agglomeration is almost finished in 8 h, and seeds with size less than 2 μm are easily aggregated together, and almost disappear in 8 h under the optimal process conditions. In the aluminate solution with the same moderate initial aK, when the reaction temperature reaches 75 ℃, the secondary nucleation does not occur, and the effect of agglomeration is better. And at the same reaction temperature, when the initial aK is 1.62, the initial supersaturation of aluminate solution is moderate, the binders on the surfaces of the seed are enough to maintain the agglomeration process, and the agglomeration degree is better. From SEM images, agglomeration mainly occurs in the fine particles, the combinations among the fine particles are loose and the new formed coarse crystal shapes are irregular.