Preparation of ITO nano-powders by hydrothermal-calcining process

1 INTRODUCTIONSn-doped In2O3(ITO) is one kind of n-typesemiconductor material[1].It has excellent electro-optical properties , such as electrical conductivityand high transparency under visible light[2],andiswidely used in electronic , transparent electrode ,solar cells and electro-irradiance , especially inscreen display[3 ,4].Recently nearly half of the met-al indium has been used to prepare ITO materialsin the developed countries[5], such as Japan, A-merica ,France and so on.So the…     

Hydrothermal preparation and crystal habit of X-zeolite powder

The preparation of X-zeolite powder was investigatedin hydrothermal system, the crystal growth process of X-zeolite in hydrothermal condition was characterized by means of X-ray diffraction, scanning electron microscope and infrared ray. The results show that X-zeolite powder with uniform granularity and intact crystal shape can be obtained in hydrothermal system of acid-treated stellerite-NaOH-NaAl(OH)4-H2O; the crystallite size is in the range of 2 - 3μm. The best reaction time of hydrothermal preparation is 6 h. The formation phases of X-zeolite crystal are as follows: dissolution of feedstocks → formation of [SiO4]4- and [AlO4]5- tetrahedron, many-membered ring,β cage → formation of crystal nucleus and nano-particle → aggregation growth of nano-particle → coalescence growth of crystallite. The crystal habits of X-zeolite are intimately related with crystallization orientation ofβ cage in crystal and with its coupling stability on every crystal face family.     

Dendrite crystal morphology evolution mechanism of <Emphasis Type="Italic">β</Emphasis>-BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystal

Existence of [B₃-O₆]³⁻ hexagonal ring growth unit in melt solution of β-BaB₂O₄ crystal was proved by the results of high temperature Raman measurements. A morphology evolution process of β-BaB₂O₄ crystal was observed by a high temperature in-situ observation device. The crystal morphology varied with the supersaturation of growth melt solution. The mechanism of β-BaB₂O₄ crystal morphology evolution was analyzed through the growth unit model. Supported by the National Natural Science Foundation of China (Grant No. 60808026) and the Nanjing University of Aeronautics and Astronautics Scientific Research Fund (Grant No. S0764-081)     

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.     

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.     

Mechanism of zinc electroplating in alkaline zincate solution

The cathodic deposition properties and mechanism of Zn in alkaline zincate solution were studied by electrochemical techniques. The results show that Zn2 exists in the alkaline solution in the form of Zn(OH)42-. The apparent activation energy of the electrode reaction is 38.93 kJ/mol, which indicates that the discharge of Zn(OH)42- on cathode is controlled by electrochemical polarization, and accompanied by a preceding chemical reaction. The diffusion coefficient of Zn(OH)42- is 2.452×10-6 cm2/s. Zn(OH)2 is the species directly discharged on the cathode surface. Based on the above results the mechanism of zinc electroplating in alkaline zincate solution was put forward. The discharged species is Zn(OH)2 formed from the preceding chemical reaction, which becomes Zn(OH)ad when gaining one electron, and then gaining the second electron to become Zn. The first electron gaining step is rate determining one.     

Synthesis and characterization of arsenate antimonic acid AAAc(1 : 1)

The AAAc(1 : 1) was synthesized in water by As₂O₃ and Sb₂O₃ with molar ratio of 1 : 1. AAAc(1 : 1) was characterized by Raman, IR, TG/DTG, DSC, XPS and XRD. The results show that there are four peaks to v _s of As-OH, As-O-Sb, Sb-OH and Sb-O-Sb in Raman spectra of AAAc(1 : 1) at 100 – 1 000 cm⁻¹. The solution of AAAc(1 : 1) was also titrated with KOH solution. The titration results show that AAAc(1 : 1) is a hexabasic acid with dissociation constants of k ₁=3.62 × 10⁻², k ₂=3.05 × 10⁻³, k ₃=6.43 × 10⁻⁶, k ₄ =9.78 × 10⁻⁸, k ₅=1.32 × 10⁻¹¹, k ₆=3.87 × 10⁻¹². AAAc(1 : 1) has a good solubility and stability in water, its solid obtained by free volatilizing water from its solution under air at ambient temperature is amorphous. Chemical and thermal analysis show that the composition of AAAc(1 : 1) is As₂O₅ · Sb₂O₅ · 8H₂O in air at 25 °C. AAAc(1 : 1) has the structure of AsO(OH)₂-OH-Sb(OH)₄-O-Sb(OH)₄-OH-AsO(OH)₂ or As(OH)₃-O-Sb(OH)₄-O-Sb(OH)₄-O-As(OH)₃ (isomerism) through experimental determination and geometry optimization. Foundation item: Project(50274075) supported by the National Natural Science Foundation of China     

Microwave digestion polarography for determining seven trace elements in Salvia Miltiorrhiza Root and compound Salvia Miltiorrhiza Root injection simultaneously

The sensitive second derivative waves of Cu(Ⅱ),Pb(Ⅱ),Cd(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Fe(Ⅱ)and Mn(Ⅱ),forming in the substrate solution(pH=9.26)consisting of ammonia,ammonium chlorid,gelatin and ascorbic acid were researched.The peak potentials of the polarographic waves of the seven ions are at about 0.48,0.63,0.79,1.04,1.28,1.44 and 1.60 V respectively.Combining with microwave technique,a new method for the simultaneous determination of the seven trace elements in Chinese traditional medicine was developed.The method is easy to operate,rapid,simple and convenient.When the signal-to-noise rate equals 3,the detection limits of Cu,Pb,Cd,Ni,Zn,Fe and Mn are 4.2×10 3,5.3×10 3,2.1×10 3,5.8×10 4,3.0×10 3,7.7×10 4 and 1.1×10 3 μg/mL respectively.Well linear relationships exist between the concentrations and the peak currents when Cu,Pb,Cd,Ni,Zn,Fe and Mn concentrations are within 8.5×10 3 10,9.7×10 3 10,4.5×10 3 10,1.2×10 3 10,6.4×10 3 10,1.5×10 3 10 and 2.8×10 3 10 μg/mL,respectively.The method has been used to the simultaneous determination of the seven trace elements in Salvia Miltiorrhiza Root and compound Salvia Miltiorrhiza Root injection,the relative standard deviations(RSDs)of the Cu,Pb,Cd,Ni,Zn,Fe and Mn in the two medicines are 3.9% and 5.8%,4.0% and 4.1%,4.3% and 5.7%,4.9% and 5.3%,4.4% and 4.7%,3.5% and 4.0%,0.51% and 2.8%,respectively;the comparisons of the determination results with the values obtained by the standard method indicate that the presented method has very well veracity.     

Formation mechanism of barium titanate nanocrystals under hydrothermal conditions

Growth units and the crystallization habit of BaTiO₃ nanocrystals have been investigated. It has been proposed that the growth units of BaTiO₃ were surface hydroxylated Ti(OH)₆²⁻ octahedra. The relationship between crystal morphology and the variation of the current intensity in the solution has been obtained through the measurement of the OH⁻ in the solution and the hydrothermal experiment with superimposed direct electric field. Based on the computation of the stability energy of the growth units, the relationship between the crystallized morphology of crystallites and the most favorable growth units under different conditions has been derived. It has been found that there is structure similarity between anatase (TiO₂) and BaTiO₃ from the crystal chemistry viewpoint, so they are soluble in each other, which can serve as a reasonable explanation for the abnormal phenomenon of the retention of cubic substable phase at room temperature. Project supported by the National Natural Science Foundation of China.     

Effects of La^3＋ doping on MnZn ferrite nanoscale particles synthesized by hydrothermal method

MnZn ferrite nanoscale particles were synthesized by hydrothermal method. The effects of amount of addition La³⁺ on the products were discussed. The product was characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM). The results show that the sample with 0.2% La³⁺ (mass fraction) or without La³⁺ has only spinel phase, but the sample with mass fraction of La³⁺ exceeding 0.4% posses second phase besides the spinel one; and the nano-MnZn ferrites change from cube to hexagon when the mass fractions of La³⁺ is up to 1.2%. TEM image of the sample with 1.2% La³⁺ indicates that the homogeneous hexagonal crystal is obtained and the particles are larger than those of undoped; the addition of La³⁺ has great influence on the crystallization of hydrothermal process and can change the shape of particles and improve their growth. The saturation magnetization of the sample with 1.2% La³⁺ (2.64 A · m² · kg⁻¹) is lower than that of undoped (17.54 A · m² · kg⁻¹) and it behaves superparamagnetically. Foundation item: Project (2001BA90A09) supported by the Tenth Five-Plan of China     

Impedance spectroscopy study on Mn1＋xFe2-2xTixO4 （0≤x≤0.5） ferrites

The complex impedance spectroscopy and surface morphology of Mn_1+x Fe_2−2x Ti _x O₄ (0⩽x⩽0.5) system, prepared using a conventional solid state reaction technique, were investigated. The impedance spectroscopy measurements were carried out at room temperature in the frequency range of 42–5 MHz. The electrical processes in the samples were modeled in the form of an equivalent circuit made up of a combination of two parallel RC circuits attributed to grain and grain boundaries. The DC conductivity obtained by extrapolation of AC data using impedance spectroscopy and four-probe method increases at 10% doping of Ti ions. The energy-dispersive X-ray (EDX) pattern confirmed the homogeneous mixing of the Mn, Fe, Ti and O atoms in pure and doped ferrite samples.     

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.     

Chemial Bond and Stability of Adsorption of [Au（ AsS3 ）]^2- on the Surface of Kaolinite

Density function theory and discrete variation method (DFT-DVM) were used to study the adsorption of [Au( AsS3 )]^2- on the surface of kaolinite. The correlation among structure, chemical bond and stability was discussed. Several models were selected with [ Au( AsS3)]^2- in different directions and sites. The results show that the models with gold on the edge of kaolinite basal layer contain pincerlike bond among gold and several oxygen atoms and form strong Au - 0 covalent bond, so these models are more stable than those with gold above or under the layer. The models with gold near to [ AlO2(OH)4] octahedra are more stable than those with gold near to the vacancy withont aluminium. These two stable tendencies in kaolinite- [ Au( AsS3)]^2- are stronger than that in kaolinite-Au systems. The interaction between [ Au( AsS3 )]^2- and kaolinite is stronger than that between gold and kaolinite, and this interaction is strong enough to form the surface complexes.     

Effects of different iron sources on the performance of LiFePO4/C composite cathode materials

Olivine LiFePO₄/C composite cathode materials were synthesized by a solid state method in N₂ + 5vol% H₂ atmosphere. The effects of different iron sources, including Fe(OH)₃ and FeC₂O₄·2H₂O, on the performance of as-synthesized cathode materials were investigated and the causes were also analyzed. The crystal structure, the morphology, and the electrochemical performance of the prepared samples were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), laser particle-size distribution measurement, and other electrochemical techniques. The results demonstrate that the LiFePO₄/C materials obtained from Fe(OH)₃ at 800°C and FeC₂O₄·2H₂O at 700°C have the similar electrochemical performances. The initial discharge capacities of LiFePO₄/C synthesized from Fe(OH)₃ and FeC₂O₄·2H₂O are 134.5 mAh·g⁻¹ and 137.4 mAh·g⁻¹ at the C/5 rate, respectively. However, the tap density of the LiFePO₄/C materials obtained from Fe(OH)₃ are higher, which is significant for the improvement of the capacity of the battery.     

Investigation on the surface active sites variation of mineral dusts

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Technology of black coloring for stainless steel by electrochemical method

The technology of black coloring for stainless steel by electrochemical method was studied. The optimum bath compositions and operating conditions were obtained as follows. 40 - 50 g/L K2Cr2O7, 15 - 20 g/L MnSO4, 15 -20 g/L （NH4）2SO4, 20 -40 g/L H3BO3, 20 -30 g/L additive A, 2 g/L （NH4）6Mo7O24 ; time 9 -20 min; temperature 15 - 30 ℃ ; potential 3 V and current density 1 - 2 mA/cm^2. The effects of the compositions of the bath on the quality of black colored film were discussed. The influences of passivation process on the black coloring velocity and performances of black colored film layer were investigated. The results show that the passivation process can improve the corrosion resistance and the stability to bear color-change; （NH4）2 SO4 can control the black coloring velocity and prolong black coloring bath life remarkably; and additive A can improve the evenness and compactness of black colored film layer. The results of scanning electron microscopy and energy dispersive spectra show that the microstructure is of cylindrical lump, the filling process can decrease the crackles, and the main elements of black colored film are Fe, Cr, Mn and Ni.     

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/℃.     

Spectra and DNA-binding properties of two novel mixed-ligand complexes containing organosulfonate

Two novel mixed-ligand complexes, [M(phen)₂(ans)₂]·H₂O (M = Cd(II) 1, Zn(II) 2; phen is 1, 10-phenanthroline, and ans is 4-aminonaphthalene-1-sulfonate), were obtained from the reaction of 1, 10-phenanthroline, sodium 4-aminonaphthalene-1-sulfonate tetrahydrate and acetate in mixed solvents. Interaction of the complexes with calf thymus DNA (ctDNA) were investigated using UV-vis absorption spectra, luminescence titrations, steady-state emission quenching by [Fe(CN)₆]⁴⁻, DNA competitive binding with ethidium bromide (EB) and viscosity measurements. The experimental results indicate that there exist two interaction modes between the complexes and DNA, namely the electrostatic interaction and intercalation, with the binding constants of 1.82 × 10⁵ M⁻¹ for 1 and 4.78 × 10⁴ M⁻¹ for 2 in buffer of 50 mM NaCl and 5 mM Tris-HCl (pH 7.0). Funded by Key Project of the National Natural Science Foundation of China (No. 60537050)     

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.     

Formation and dielectric properties of Mn-Doped BSTN composite ceramics

The influence of Mn doping on the formation and dielectric properties of 0.7BaO·0.3SrO·(1−y)TiO₂·yNb₂O₅ (BSTN) composite ceramics were investigated. The Mn was doped according to the formula 0.7BaO·0.3SrO·(0.7−z)TiO₂·0.3Nb₂O₅·zMnO₂ (BSTNM). The results show the two phases, perovskite phase BST and the tungsten bronze phase SBN, are coexistence in BSTNM as they are in BSTN composite ceramics. The Mn ions doped in BSTN substitute for Nb⁵⁺ ions in the tungsten bronze phase, and then, the Nb⁵⁺ ions substitute for Ti⁴⁺ ions in the perovskite phase. With the increasing of Mn dopant, the content of the perovskite phase increases while that of the tungsten bronze phase decreases, and the grain size of the perovskite phase decreases. As well as, the phase transition temperature of tungsten bronze phase increases with value z increasing from 0 to about 0.05.