Kinetics of Fe_3O_4 formation by air oxidation

1　INTRODUCTIONFe3O4 hasanumberofnovelpropertiesandper formances ,itsuniquemagnetic ,thermalandtribolog icalpropertiesmakeitanewtypeofmaterialspromis inginvariousapplicationssuchaspigment,toner ,in formationstorage ,ferrofluids ,bioprocessing ,elec tronicsandcatalyst[1,2 ] .Owingtothewideapplica tion ,majorityofresearchersfocusedontheprepara tionmethodsofmagnetite[310 ] ,however ,themech anismandkineticsofFe3O4 formationwerescarcelystudied .Thekineticsandmechanismofoxyhydrox idesformatio…     

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.     

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.     

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.     

Self-cleaning glass coated with Fe^3＋ -TiO2 thin film

The self-cleaning glass coated with Fe^3 -TiO2 photocatalytic thin film was prepared by sol-gel process from the system Ti(OC4H9),-NH(C2H4OH)2-C2H5OH-H2O containing FeCl3. The microstructure and properties of the film were studied using differential thermal analysis-thermogravimetry(DTA-TG), X-ray diffration (XRD) and scanning electron microscope(SEM). The transmittance of the self-cleaning glass was measured by using UV-Vis spectrometer. The effects of content of Fe^3 and the thickness of Fe^3 -TiO2 thin film on the photocatalytic ac-tivity were examined. The results show that the photocatalytic thin films are mainly composed of Fe3O4 and TiO2 particles within 10-100 nm. The appropriate amount of Fe^3 is effective for improving the photocatalytic activities of TiO2. The best photocatalytic activity is obtained when the molar ratio of Fe^3 to TiO2 is 0. 005 and the glass is coated with 9 layers.     

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)     

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     

水热辅助溶胶凝胶法制备纳米钛酸锌及其光催化性能

采用水热辅助的溶胶凝胶法制备纳米钛酸锌（ZnTiO₃）光催化剂,以罗丹明B为目标降解物,运用动力学模型分析罗丹明B（RhB）初始浓度对降解效果的影响。通过SEM、XRD、XPS、UV-Vis DRS对ZnTiO₃进行表征,并使用自由基捕获试验分析其降解机理。结果表明,ZnTiO₃为纯六方相,形貌为类球形,粒径50 nm左右。在催化剂用量为1 g/L、RhB初始浓度为5 mg/L、pH值为3的条件下,光催化反应150 min后,RhB降解率为93.2%。其动力学方程为k=0.132C₀^-1.253。ZnTiO₃光催化剂降解过程中,·OH、h⁺、·O₂^-均起到催化作用,产生·OH、h⁺的量相近且多于·O₂^-,说明·OH、h⁺在催化反应中起主要作用。     

Electrochemical behavior of K3Fe（CN）6 in water-in-oil microemulsion

A water-in-oil (W/O) microemulsion composed of Triton X-100, n-hexanol, n-hexane and water solution with hydrochloric acid was prepared. K₃Fe(CN)₆ was added in as a water-soluble electroactive probe, and its electrochemical behavior was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that the H⁺ concentration of the water phase has a great effect on the conductivity of the W/O microemulsion, and hence influences the electrochemical behavior of K₃Fe(CN)₆. When the pH value of water phase is about 7, the electrical conductivity of the W/O microemulsion is only 1.2×10⁻⁶ S/cm, and K₃Fe(CN)₆ almost cannot react at the glassy carbon electrode. But when the H⁺ concentration is more than 3 mol/L, the W/O microemulsion has a good electrical conductivity and K₃Fe(CN)₆ shows good electrochemical performance in it. The results of CV and EIS studies indicate that the electrochemical behavior of Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ in the W/O microemulsion is different from that in the aqueous solution. This may be due to the unique liquid structure of the W/O microemulsion and the unique mass transfer in the W/O microemulsion. Foundation item: Projects(20673036, J0830415) supported by the National Natural Science Foundation of China; Projects(05JT1026, 2007JT2013) supported by the Science Technology Project of Hunan Province, 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     

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.     

采用微生物覆铜板浸出液中铁离子制备 Fe2O3/石墨烯纳米复合材料的研究

针对微生物法覆铜板浸出液中的金属铁离子进行资源化处理,提高覆铜板浸出液的附加值。以水热法处理得到的铁离子溶液为原料,制备八面体和球形的Fe_2O_3/石墨烯复合材料,并将其作为锂离子电池负极材料,组装成扣式电池。结果显示:八面体形貌的Fe_2O_3/石墨烯复合材料的比容量高于球形的,其在100 mA/g电流下循环,首次放电和充电比容量分别高达1 343和970 mAh/g,在47次循环后,其放电及充电比容量分别为769和740 mAh/g。     

Effect of Fe(III) impurity on the electrochemical performance of LiFePO<Subscript>4</Subscript> prepared by hydrothermal process

Lithium iron phosphate (LiFePO₄) was synthesized from LiOH, FeSO₄ and H₃PO₄ by a hydrothermal process at 180°C. The samples were characterized by X-ray diffraction, scanning electron microscopy and chemical analysis. Electrochemical performance of the samples was tested in terms of charge-discharge capacity and cycling behavior. The results indicated that Fe(III) impurity had obviously effect on the electrochemical properties of LiFePO₄, and the formation of Fe³⁺ was caused by the oxidation of Fe²⁺ in the dissolving and feeding processes accompanying the increase of pH value. It was found that the precipitation separation was effective in decreasing the content of Fe³⁺ in the solution of FeSO₄ and the sealed feeding was useful in preventing the conversion of Fe²⁺ to Fe³⁺. When the content of Fe³⁺ < 0.5 wt%, the hydrothermally synthesized LiFePO₄ calcined at 750°C with sucrose as carbon source exhibited an initial discharge capacity of 154.9 mAh·g⁻¹ at the rate of 0.1 C (1 C = 150 mA·g⁻¹) and the cycling retention rate could reach 98% after 50 cycles at room temperature.     

Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction

LiNi_0.5Mn_1.5O₄ was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry (XRD), scanning electron microscopy (SEM) and electrochemical measurement. XRD patterns show that LiNi_0.5Mn_1.5O₄ synthesized under various conditions has cubic spinel structure. SEM images exhibit that the particle size increases with increasing calcination temperature and time. Electrochemical test shows that the LiNi_0.5Mn_1.5O₄ calcined at 700 °C for 24 h delivers up to 143 mA · h/g, and the capacity retains 132 mA · h/g after 30 cycles. Foundation item: Project (76600) supported by Postdoctoral Science Foundation of Central South University     

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     

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.     

N掺杂Co3O4纳米片的制备以及活化过一硫酸盐的性能研究

采用牺牲模板法合成N掺杂Co₃O₄纳米片（N-Co NS）,通过透射电子显微镜（TEM）、原子力显微镜（AFM）和光电子能谱（XPS）对制备材料的形貌结构、化学组成进行分析,并通过催化活化过一硫酸盐（PMS）降解水中双酚A （BPA）来探究催化剂的催化性能.实验结果表明与Co₃O₄纳米颗粒（Co NP）、Co₃O₄纳米片（Co NS）相比,N-Co NS表现出了较高的催化性能.在PMS浓度为2 mmol·L^-1、BPA初始质量浓度为50 mg·L^-1的反应条件下,N-Co NS在10 min内完全降解水中的BPA,表明N掺杂和二维纳米片结构有利于催化剂性能的提升.通过pH及离子影响实验证实N-Co NS在复杂水化学环境中仍具有较高的活性.此外结合自由基捕获实验和电子顺磁共振（EPR）测试证实反应体系中产生了高氧化活性的羟基自由基和硫酸根自由基.     

Cu2O/Cu2S 复合材料制备及可见光催化降解甲基橙的研究

通过水热法制备Cu₂O/Cu₂S 复合材料对甲基橙(MO) 进行光催化降解实验。在Cu₂O 中引入S 元素, 通过 改变Cu/S 投加摩尔比, 从而得到不同Cu/S 的复合材料。利用XRD、SEM、UV-vis、EIS 等手段对材料进行表征, 并 对MO 进行光催化降解实验。XRD 结果表明, 随着S 含量的增多, Cu₂S 的衍射强度逐渐上升, Cu₂O 的f111g 晶面 衍射强度逐渐降低。SEM 结果表明Cu₂S 能较好地包覆在Cu₂O 八面体的表面。通过UV-vis 和EIS 结果计算得知, 复合材料带隙为1.49 eV, 电荷转移电阻大幅降低。降解实验结果表明复合材料最佳Cu/S 投加摩尔比为15 : 1, 其在 100 min 时对MO (100 mL, 10 mg/L) 降解率达到91.4%, 明显高于纯Cu₂O 对于MO 的降解率(60.3%)。猝灭实验表 明了?OH 和 ?O₂ ^-在光催化过程中起到主要作用。     

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     

Modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles by L-dopa or dopamine as an enzyme support

Fe3O4 magnetic nanoparticles were prepared by co-precipitation of Fe^2＋ and Fe^3＋ in an ammonia solution, and its size was about 36 nm measured by an atomic force microscope. Fe3O4 magnetic nanoparticles were modified by L-dopa or dopamine using sonication method. The analysis of FTIR clearly indicated the formation of Fe-O-C bond. Direct immobilization of trypsin （EC： 3.4.21.4） on Fe3O4 magnetic nanoparticles with L-dopa and dopamine spacer was investigated using glutaraldehyde as a coupling agent. No significant changes in the size and magnetic property of the three kinds of magnetic nanoparticles linked with or without trypsin were observed. The existence of the spacer molecule on magnetic nanoparticles could greatly improve the activity and the storage stability of bound trypsin through increasing the flexibility of enzyme and changing the microenvironment on nanoparticles surface compared to the naked magnetic nanoparticles.