Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu(Ⅲ) with 1-(6-hydroxy-1-naphthyl)-1,3-butanedione (HNBD) was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu(Ⅲ) ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu3+ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods (Coat-Redfern equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation). The kinetic parameters of the first stage are E* = 164.02 kJ·mol-1, A = 1.31 × 1015 s-1, △S*= 42.27 J·K-1·mol-1, △H*= 159.51 kJ·mol-1, △G*= 136.54 kJ·mol-1, and n = 3.1, those of the second stage are E*= 128.52 kJ·mol-1, A = 1.44 × 106 s-1, △S*= - 136.89 J·K-1·mol-1,△H*= 120.41 kJ·mol-1, △G*=283.85 kJ·mol-1, and n = 1.1.     

Characterization and kinetic modeling of secondary phases in squeeze cast Al alloy A380 by DSC thermal analysis

Thermal analyses on squeeze cast aluminum alloy A380(SC A380) solidified under 90MPa were carried out to study the microstructure development of the alloy, in which a differential scanning calorimeter(DSC) was employed. During the DSC runs, heating and cooling rates of 1, 3, 10, and 20 °C·min~(-1) were applied to investigate the heating and cooling effects on dissolution of secondary eutectic phases and microstructure evolution. Various reactions corresponding to troughs and peaks of the DSC curves were identified as corresponding to phase transformations taking place during dissolution or precipitation suggested by the principles of thermodynamics and kinetics. The comparison of the identified characteristic temperatures in the measured heating and cooling curves are generally in good agreement with the computed equilibrium temperatures. The microstructure analyses by scanning electron microscopy(SEM) with energy dispersive X-ray spectroscopy(EDS) indicate that the distribution and morphology of secondary phases present in the microstructure of the annealed sample are similar to the as-cast A380, i.e., strip β(Si), buck bone like or dot distributed θ(Al_2Cu), β(Al_5Fe Si) and Al_(15)(FeMn)_3Si_2. Two kinetic methods are employed to calculate the activation energies of the three common troughs and three common peaks in DSC curves of SC A380. The activation energies of the identified reaction θ_(CuAl_2) = α(Al)+β(Si) is 188.7 and 187.1 k J?mol~(-1) when the activation energies of reaction α(Al)+β(Si)→θCu Al_2 is~(-1)22.7 and~(-1)21.8 k J?mol~(-1), by the Kissinger and Starink methods, respectively.     

纳米Eu0.12Y1.78La0.10O3-δ荧光粉的合成动力学

利用不同升温速率的差热-热重分析(DTA-TG)研究纳米Eu0.12Y1.78La0.10O3-δ荧光粉的合成动力学。研究表明,纳米Eu0.12Y1.78La0.10O3-δ荧光粉的前驱体为六方相Y(OH)3,利用Doyle-Ozawa法和Kissinger法计算得到前驱体2个分解阶段的表观活化能平均值分别为699.40、362.81kJ.mol-1。用Kissinger法确定反应级数和频率因子,确定纳米Eu0.12Y1.78La0.10O3-δ荧光粉2个合成阶段的反应速率方程分别为dα/dt=1.94×1046e-84120/T(1-α)1.17;dα/dt=5.89×1020e-43640/T(1-α)1.14。     

室温固相法制备Co/Mn包覆LiNiO_2正极材料(英文)

重点研究了室温固相法Co/Mn氢氧化物包覆Ni(OH)2的机理.采用XRD,SEM,TEM和EDS分析检测手段分析了未包覆与表面包覆材料的结构、形貌和表面成分.TEM实验结果表明,LiNiO2颗粒表面包覆了一薄层化合物;XPS实验结果表明,LiNiO2颗粒表面包覆了Co/Mn元素;SEM和EDS实验结果进一步表明,球形LiNiO2颗粒表面均匀包覆了Co/Mn化合物层.电化学性能测试结果表明,经Co/Mn包覆的LiNiO2正极材料显示了优越的循环性能.     

铝热自蔓延法制备低氧高钛铁合金及表征

以金红石、钛精矿、Al为原料采用铝热自蔓延法制备出低氧高钛铁。研究相关反应体系的热力学及动力学问题,考察配料比、熔渣类型、发热剂等对铝热自蔓延过程的影响,采用XRD,SEM以及化学分析等技术对高钛铁合金进行表征。结果表明:反应体系的绝热温度大于1800K,反应能自我维持进行;Al还原TiO2反应的表观活化能为93.676kJ.mol-1,反应级数为0.01,Al还原TiO2和Fe2O3的表观活化能为300.740kJ.mol-1,反应级数为1.20;合金主要由TiFe2、TiFe以及Fe2TiO0.13等钛铁低氧固溶体相组成,夹杂相存在是导致合金中氧含量高及微观缺陷存在的直接原因;合金中钛、铝、铁、硅含量分别为:60.0%～62%、7.0%～11.0%、21.0%～25.0%以及3.0%左右;合金中的氧被有效去除,最低为1.85%。     

SYNTHESIZING KINETICS AND MICRO-CHARACTERIZATIONOF SPINEL LiMn2O4 FOR LITHIUM-ION BATTERYCATHODE MATERIAL

1. IntroductionLithiumion cells are the third generation of rechargeable batteries following by nickel-cadmium cells and nickel-hydrogen cells. They could be named aJs "green batteries" byvirtue8 of lower self resistance, little self discharge, no memorizing effect and no pollution.Recently, cathode materials has been much more studied such as lithiumrich transitionmetal oxides that are lithium-cobalt system, lithium-nickel system and lithium-manganesesystem[1l21. The consumption of cobalt is…     

新显色剂2-〔2，3，5-三氮唑〕-5-〔(N，N-二羧基甲基)氨基〕苯甲酸的合成及其与钯的显色反应

合成了新显色剂2-〔2,3,5-三氮唑〕-5-〔(N,N-二羧基甲基)氨基〕苯甲酸(简称TZACAB),并研究了性质及其与Pd显色反应的条件。结果表明：试剂的分子式C13H12N6O6,分子量349.27;在pH 3.18 HAc-NaAc缓冲溶液中,试剂与Pd形成1∶1蓝色络合物,λmax为661.4 nm,Pd量在0～1.2 μg*ml-1范围内遵守比耳定律,表观摩尔吸光系数为ε=1.72×104 L*mol-1*cm-1,大量的其它金属离子共存时,不经预分离也无需掩蔽剂可直接测定Pd-Pt催化剂中的微量Pd,操作简便,结果满意。     

利用高压DSC研究一水铝石在碱液中的溶出动力学

研究一水铝石(包括一水软铝石和一水硬铝石)在氢氧化钠溶液中溶出过程的机理函数并确定相应的动力学参数.将一水铝石矿和氢氧化钠溶液在高压DSC设备中以10 ℃/min的速度加热,用微分方程法分析得到DSC曲线,同时借助Matlab程序利用迭代法和线性最小二乘法计算微分方程,从30种机理函数的微分形式中分别逻辑地选择了两种一...     

Effect of Manganese substitution on hydrogen storage properties of LaNi4.25-xAl0.75Mnx alloy

The effect of Mn substitution on phase structure, hydrogen hydriding/dehydriding properties (plateau pressure and slope) and reaction heat enthalpy of LaNi4.25-xAl0.75Mnx alloys (x=0, 0.25, 0.35, 0.45, 0.55 and 0.65) were studied.The experimental results show that all LaNi4.25-xAl0.75Mnx alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy (CaCu5 type, P6/mmm).With increasing Mn substitution content, the cell parameters of LaNi4.25-xAl0.75Mnx alloy greatly increase, but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi4.25-xAl0.75Mnx alloy decrease from 1.38 wt.% to 1.18 wt.% and from 1.61 to 0.0712 MPa, respectively.Moreover, the hydrogen pressure plateau slope factor σ increases from 0.014 to 0.18, but the hysteresis factor is nearly constant.The heat enthalpy absolute value |ΔHplat| increases from 46.7 kJ·mol-1 H2 to 56.1 kJ·mol-1 H2 as the Mn content x increases from 0 to 0.65.     

Synthesis and characterization of LiNi0.95-xCoxAl0.05O2 for lithium-ion batteries

Samples of LiNi0.95-xCoxAl0.05O2 （x = 0.10 and 0.15） and LiNiO2, synthesized by the solid-state reaction at 725℃ for 24 h from LiOH-H2O, Ni2O3, Co2O3, and AI（OH）3 under an oxygen stream, were characterized by TG-DTA, XRD, SEM, and electrochemical tests. Simultaneous doping of cobalt and aluminum at the Ni-site in LiNiO2 was tried to improve the cathode performance for lithium-ion batteries. The results showed that co-doping （especially, 5 at.% A1 and 10 at.% Co） definitely had a large beneficial effect in increasing the capacity （186.2 mA.h/g of the first discharge capacity for LiNio.s.42OoaoAlo.0502） and cycling behavior （180.1 mA-h/g after 10 cycles for LiNio.85CooaoAlo.osO2） compared with 180.7 mA.h/g of the first discharge capacity and 157.7 mA.h/g of the tenth discharge capacity for LiNiO2, respectively. Differen- tial capacity versus voltage curves showed that the co-doped LiNio.95_xCoxmlo.osO2 had less intensity of the phase transitions than the pristine LiNiO2.     

Kinetics of SiO2 leaching from Al2O3 extracted slag of fly ash with sodium hydroxide solution

Kinetics of SiO₂ leaching from Al₂O₃ extracted slag of fly ash with sodium hydroxide solution was studied. The effect of leaching temperature, mass ratio of NaOH to SiO₂ and stirring speed on SiO₂ leaching rate was investigated. The results show that increasing leaching temperature, mass ratio of NaOH to SiO₂ and stirring speed increases SiO₂ leaching rate. The SiO₂ leaching rate is 95.66% under the optimized conditions. There are two stages for the SiO₂ leaching process, and the leaching reaction is very rapid in the first stage but quite slow in the second stage. The whole leaching process follows the shrinking core model, and the outer diffusion of no product layer is the rate-controlling step. The activation energies of the first and second stages are calculated to be 8.492 kJ/mol and 8.668 kJ/mol, respectively. The kinetic equations of the first and the second stages were obtained, respectively.     

Dissolution kinetics and thermodynamic analysis of vanadium trioxide during pressure oxidation

The dissolution kinetics of vanadium trioxide in sulphuric acid-oxygen medium was examined. It was determined that the concentration of sulphuric acid and stirring speed above 800 r min 1 did not significantly affect vanadium extraction. The dissolution rate increased with increasing temperature and oxygen partial pressure, but decreased with increasing particle size. The dissolution kinetics was controlled by the chemical reaction at the surface with the estimated activation energy of 43.46 kJ·mol-1. The l...     

ABSORPTION KINETICS OF HYDROGEN SULPHIDE USING ISOTHERMAL AND ISOVOLUMETRIC METHOD

ＡＢＳＯＲＰＴＩＯＮＫＩＮＥＴＩＣＳＯＦＨＹＤＲＯＧＥＮＳＵＬＰＨＩＤＥＵＳＩＮＧＩＳＯＴＨＥＲＭＡＬＡＮＤＩＳＯＶＯＬＵＭＥＴＲＩＣＭＥＴＨＯＤＨａｉＭｉｎｇｔａｎ；ＬｉｕＣｈａｎｇｑｉｎｇ；ＺｈａｎｇＰｉｎｇｍｉｎ；ＣｈｅｎＱｉｙｕａｎ（Ｄｅｐａ...     

三正辛胺从HCl介质中萃取钯(Ⅱ)的动力学研究

研究了三正辛胺从HCl介质中萃取Pd(Ⅱ)的动力学和萃取机理,结果表明:三正辛胺和Cl-的质量浓度对萃取速率有较大的影响,ln(kf (Pd)/kb(Pd))与lnCoTOA和ln[Cl-]分别成直线关系,直线斜率分别为2和-2.界面反应步骤是TOA萃取Pd(Ⅱ)速率的控制步骤,正向萃取反应活化能为21.154kJ· mol-1,推导得出了萃取速率和正、逆向萃取速率常数比(kf(Pd)/kb(Pd))的理论方程,当[Cl-]≥0.10mol·L-1 或 [H ]≥0.10mol·L-1时,理论计算值与实测值吻合.     

Kinetics of recovering germanium from lignite ash with chlorinating roasting methods

A process of recovering Ge by chlorinating masting was put forward. GeCl4 was separated and recovered from lignite ash because of its low boiling point. Kinetic analysis indicates that the chlorinating roasting process fits with the unreacted-core shrinking model and the reaction rate equation corresponds to 1 - 2a/3 - （1 - a）2/3 = kt. The apparent activation energy Ea is calculated to be 22.36 kJ·mol^-1. The diffusion of product layer serves as the rate-controlling step in this process. When the roasting temperature is 250℃, the roasting time is 60 min, the con- centration of hydrochloric acid is 10 mol/L, and the ratio of liquid to solid is 10 （mHCl/ash = 10）, and 90% Ge in lignite ash can be recovered.     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料,通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD),场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明,Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构,包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善,1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1,充放电循环500次后容量保持率分别为88.4%和78.2%,而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1,500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1,而未包覆材料的活化能为36.24 kJ?mol-1,包覆有效降低了材料Li+扩散所需克服的能垒,提高了材料的电化学性能。     

SiC/Ti6Al4V复合材料界面反应产物的形成序列及扩散路径

通过SiC/Ti6Al4V钛基复合材料的制备及在不同条件下的热处理试验，利用SEM，EDS及XRD分析技术研究复合材料界面反应产物相的形成及反应元素的扩散路径。结果表明：反应元素如C，Ti，Si在界面反应层中出现浓度波动，合金元素Al并没有显著扩散进入界面反应产物层，而是在界面反应前沿堆积，其界面反应产物被确认为Ti3SiC2，TiCx，Ti5Si3C，和Ti3Si；在界面反应初期，存在着TiC＋Ti5Si3Cx双相区，当形成各界面反应产物单相区时，SiC／Ti6Al4V复合材料界面反应扩散的完整路径应为：SiC ｜ Ti3SiC2 ｜ Ti5Si3Cx ｜ TiCx ｜ Ti3Si｜ Ti6Al4V＋TiCx；界面反应产物层的生长受扩散控制，遵循抛物线生长规律，其生长激活能Q^k及k0分别为290.935 kJ·mol^-1,2.49× 10^-2 m·s^-1/2.     

Effect of Ni on Mg based hydrogen storage alloy Mg3Nd

Magnesium-neodymium based alloys were prepared by induction melting in an alumina crucible under protection of pure argon atmosphere. XRD patterns show that the as-melted Mg-Nd and Mg3NdNi 0.1 diffraction peaks can be excellently indexed with D03 structure (BiF3 type, space group Fm3m ). The lattice constant of Mg3Nd phase is 0.7390 nm, which is determined by XRD analysis using Cohen's extrapolation method. The reversible hydrogen storage capacity reaches 1.95wt.% for Mg3Nd and 2.68wt.% for Mg3NdNi0.1 . The desorption of hydrogen takes place at 291 ℃ for Mg3Nd and at 250 ℃ for Mg3NdNi 0.1 . The alloys could absorb hydrogen at room temperature with rapid hydriding and dehydriding kinetics after only one cycle. The enthalpy (ΔH ) and entropy (ΔS ) of Mg3Nd-H dehydriding reaction were -68.2 kJ·mol-1 H2 and -0.121 kJ·(K·mol)-1 H2 determined by using van't Hoff plot according to the pressure-composition-isotherms (P-C-I) curve measured at different temperatures. Hydrogen absorption kinetic property of Mg3NdNi 0.1 alloy was also measured at room temperature.     

Dissolution kinetics of molybdite in KOH media at different temperatures

The dissolution kinetics of synthetic molybdite (MoO₃) in a potassium hydroxide (KOH) medium was studied by varying the system temperature, KOH concentration, and particle size. Additionally, the effects of the stirring rate and different reagents such as barium hydroxide (Ba(OH)₂), calcium hydroxide (Ca(OH)₂), and sodium hydroxide (NaOH) were also evaluated. The experiments were performed in a reactor with controlled temperature and agitation. The results indicated that the dissolution reaction mechanism of molybdite generates potassium molybdate (K₂MoO₄) without intermediate compounds. Temperature (6–80 °C), KOH concentration (0.0005–0.025 mol/L), and particle size (5–40 μm) positively affected the dissolution of molybdite. The maximum Mo recovery was 67.5% in 0.25 h for 80 °C and 0.01 mol/L KOH. At the lowest temperature (6 °C), which is near the freezing point of water (0 °C), a substantial amount of Mo was recovered (17.8% in 45 min). The kinetics equation describing the molybdite dissolution in a KOH environment indicated that diffusion occurs through the porous layer. The activation energy was calculated to be 47.81 kJ/mol. A reaction order of 1.0 with respect to KOH concentration was obtained and was found to be inversely proportional to the squared particle size. The kinetics equation was obtained. The dissolution of molybdite resulting from the oxidation of a molybdenite concentrate (MoS₂) led to a low molybdenum recovery, which was primarily caused by the consumption of KOH by impurities such as CaCO₃ and Cr(MO₄)₃.     

Gas chromatographic thermodynamics on hydration processes of magnesium chloride with low water

1　INTRODUCTIONMagnesiumchlorideisabasicmaterialforchem icalindustry ,andithaswideapplicationsinmetallur gy,architecturalmaterialandtextileindustry .Itisalsoamaterialforfire resistantproducts ,cryogenandcompoundfertilizerproductions[1] .Thefullydehy dratedmagnesiumchlorideisagoodmaterialforelec trolyticmetalmagnesium production .Becausemag nesiumchloridehasastrongadsorptiveability ,itisalsousedasadryingagent .Manysuccessfulworkshavebeendoneonthedehydrationofbischophite[2 10 ] .Butinfact,…