一步法合成碳氮化钒的动力学研究

通过三氧化二钒和碳的热重实验,发现三氧化二钒的碳热还原氮化过程可分为两个不同的反应阶段.反应过程存在多个吸热反应,并且不同的反应存在相当程度的重合.根据TG/DTG曲线,通过动力学分析方法得出三氧化二钒的碳热还原氮化反应的不同阶段的反应表观活化能Ea(1170～1340 K:Ea=205.46 kJ·mol-1;1340~1410 K:Ea=465.27 KJ·mkl-1)、频率因子A及动力学速率方程,反应符合反应控制机制(Rn模型).     

真空碳热还原制备碳氧钛的动力学研究

采用非等温固相模型对碳热还原TiO2历程和动力学条件进行研究。结果表明,真空碳热还原TiO2可分为四个阶段,第一阶段(1 373~1 523K)主要物相为C和TinO2n-1(n≥5),第二阶段(1 523~1 673K)主要物相为C、TiC0.5O0.5和TinO2n-1(2≤n≤4),第三阶段(1 673~1 833K)主要物相为C、Ti2O3和TiC0.5O0.5,第四阶段(1 833~1 973K)主要物相为TiC0.5O0.5;第一阶段动力学方程为α2=kt,受一维扩散控制,表观活化能为113.55kJ/mol,第二阶段动力学方程为(1-α)-1-1=kt,受二级化学反应控制,温度对还原率影响较大,表观活化能为303.36 kJ/mol,第三阶段动力学方程为2[(1-α)-1/2-1]=kt,受1.5级化学反应控制,还原剂不足对反应影响较大,表观活化能为53.93kJ/mol,第四阶段动力学方程为1-2α/3-(1-α)2/3=kt,受三维扩散控制,物料疏松成为晶核长大的限制环节,表观活化能为99.22kJ/mol。     

硫化铜精矿加碳酸钙焙烧表观动力学研究

通过DTA和TG结合X 射线衍射分析的方法,将硫化铜精矿加碳酸钙焙烧与硫化铜精矿焙烧的反应机理进行了对比研究。结果表明:加碳酸钙的硫化铜精矿焙烧在673～857K时铜的硫化物被氧化成硫酸盐;在857～1073K时生成的硫酸盐会发生分解。由数据分析可知它的两个阶段都受化学反应控制,其表观活化能和频率因子分别为E1=121.1kJ/mol,E2=182.9kJ/mol,A1=1.155×107s-1,A2=2.115×107s-1,其非等温动力学方程的表达式为:dαRT(1-α)2dT=Aβe-E     

二氧化氯浸出复杂硫化金精矿的动力学

以ClO2为浸出剂,研究了焙烧后的复杂硫化金精矿的浸出动力学.试验确定极限搅拌速度为800 r/min,反应表观活化能Ea=21.783 kJ/mol,Cl-和ClO2的表观反应级数分别为0.62和1.22,金的浸出速率方程为1-3(1-xB)2/3+2(1-xB)=4.56e-21783/RT·c0.62(Cl-)·c1.22(ClO2)·t.研究表明,金的浸出过程受固膜传质控制.     

高结晶水褐铁矿热分解非等温动力学研究

采用热分析(TG、DTG、DSC)技术,在不同升温速率下进行高结晶水褐铁矿热分解非等温动力学研究。结果表明:高结晶水褐铁矿热分解过程分为缓慢热阶段和快速热阶段,采用改良Coats-Redffen积分法进行了非等温动力学参数计算,拟合线性相关性都在0.98以上。缓慢阶段和快速阶段的表观活化能分别为18.69～20.63kJ/mol和94.31～102.55kJ/mol;升温速率对褐铁矿结晶水缓慢热分解阶段的影响不大,缓慢阶段热分解反应级数n=0.8,结晶水快速阶段热分解反应级数n=1。     

铌精矿微波碳热还原反应动力学

针对白云鄂博铌精矿利用工艺的成本高、过程复杂、能耗大的特点,引入微波场,考察温度对铌精矿还原的影响,并对其进行形貌及动力学分析。结果表明,微波场中铌精矿碳热还原反应机理属于三维扩散,动力学方程为y=1-(2/3)α-(1-α)2/3,表观活化能Ea=131.654 kJ/mol,微波加热相对于常规加热具有加快反应速率、降低反应活化能的效果。     

110^＊树脂吸附镥的行为研究

在pH=5.70的HAc-NaAc缓冲体系中,110*树脂对镥(Ⅲ)的静态饱和吸附容量为319mg/g,用0.3～0.5 mol/L HCl溶液可定量解吸镥(Ⅲ).测得表观吸附速率常数k298=3.00×10-5s-1.树脂吸附镥(Ⅲ)的行为遵守Freundlich方程.测得298 K时吸附反应热效应△H=16.54kJ/mol,表观吸附活化能Ea=9.57kJ/mol.用红外光谱法探讨了树脂吸附镥(Ⅲ)的反应机理,认为110*树脂对镥(Ⅲ)的吸附为化学吸附.     

FeS热分解动力学的热分析

FeS诱发含硫油品自燃的事故受到了业界的日益关注.通过在不同升温速率(2,5,8,10,15℃/min)下的热分析实验,应用模型和非模型拟合研究了FeS的热分解动力学机理,结果表明:FeS受热氧化是FeS与氧气物理吸附、化学吸附和化学反应过程,对FeS的模型拟合结果不稳定,可靠性较差;采用等转化率法得到FeS热分解的表观活化能E=(135.81±8.27)kJ/mol;通过Satava-Sestak方程确定了FeS的受热分解符合成核和生长模型函数A2:g(α)=[-ln(1-α)]1/2,其表观活化能E=148.43 kJ/mol,表观指前因子A=3.82×109K/s.     

三氧化二铋碳热还原反应的动力学

由于铋元素密度较大,在工业硅碳热还原冶炼过程中容易沉淀,导致冶炼所得工业硅中杂质分布不均,质量下降,因此研究铋在碳热还原反应中的动力学行为,为工业硅冶炼中铋含量的控制提供理论指导具有重要意义。通过热重分析方法研究了不同碳质还原剂对铋氧化物（三氧化二铋）碳热还原的影响。结果表明,石油焦相较于石墨活性更高,石油焦作还原剂具有更好的还原性能。对不同温度下三氧化二铋还原熔炼产物进行了物相分析,其还原反应产物物相转变顺序为：Bi2O3→Bi2O2.5→Bi。通过热重分析法研究了不同升温速率下三氧化二铋碳热还原反应动力学,应用等转化率法、Kissinger法和?atava-?esták法进行动力学分析,得到三氧化二铋碳热还原反应平均表观活化能E0=142.41 kJ/mol,指前因子A0=2.96×109 s-1;反应机理属于相边界反应,对应的动力学方程微分形式为3(1—α)2/3。     

铋-过硫酸钾-氨基黑10B催化动力学光度法测定痕量铋

在醋酸钠溶液介质中,过硫酸钾能将氨基黑10B氧化为红色,加入铋(III)能加快反应速率,据此,建立了测定痕量铋的催化动力学光度法。考察了反应介质种类和用量、过硫酸钾溶液和氨基黑10B溶液用量、温度和时间等因素对反应的影响。在最佳实验条件下,用1cm比色皿,在波长615nm处,用水作参比分别测定催化体系与非催化体系吸光度,计算得到吸光度差ΔA。结果表明,铋(III)质量浓度在0.02~0.12μg/mL范围内与ΔA呈良好的线性关系,相关系数为 0.9958。反应的表观速率常数为k=2.23×10^-4/s,表观活化能Ea=48.52kJ/mol,方法检出限为1.15×10^-9 g/mL。将实验方法结合铜试剂-氯仿萃取、硝酸反萃取分离方法测定了磷石膏中的铋,测定结果与原子荧光光谱法基本一致,相对标准偏差(RSD,n=6)为2.9%~3.3%。     

Reactions in the systems MoSi3N4 and NiSi3N4

The reaction products, formed during annealing of porous powder mixtures of Si₃N₄ with non-nitride forming metals like Ni or Mo, will depend on the partial pressure of N₂ in the atmosphere. In a diffusion couple, however, nitrogen has to be released at the Si₃N₄-interface during the formation of a metal silicide. It cannot escape easily and builds up a higher pressure of nitrogen at this interface. Therefore, the reaction products are different from those in porous pellets. This has been verified for NiSi₃N₄ and MoSi₃N₄ couples. The role of traces of oxygen on these reactions will be discussed.     

Characterization of Ti4AlN3

Bulk samples of Ti₄AIN₃ were fabricated by reactive hot isostatic pressing (hipping) of TiH₂, AlN, and TiN powders at 1275 °C for 24 hours under 70 MPa. Further annealing at 1325 °C for 168 hours under Ar resulted in dense, predominantly single-phase samples, with <1 vol pct of TiN as a secondary phase. This ternary nitride, with a grain size of ≈20 μm on average, is relatively soft (Vickers hardness 2.5 GPa), lightweight (4.6 g/cm³), and machinable. Its Young’s and shear moduli are 310 and 127 GPa, respectively. The compressive and flexural strengths at room temperature are 475 and 350 MPa, respectively. At 1000 °C, the deformation is plastic, with a maximum compressive stress of ≈450 MPa. Ti₄AlN₃ thermal shocks gradually, whereby the largest strength loss (50 pct) is seen at a ΔT of 1000 °C. Further increases in quench temperature, however, increase the retained strength before it ultimately decreases once again. This material is also damage tolerant; a 100 N-load diamond indentation, which produced an ≈0.4 mm defect, reduces the flexural strength by only ≈12 pct. The thermal-expansion coefficient in the 25 °C to 1100 °C temperature range is 9.7±0.2 × 10⁻⁶ °C⁻¹. The room-temperature electrical conductivity is 0.5 × 10⁶ (Θ · m)⁻¹. The resistivity increases linearly with increasing temperature. Ti₄AlN₃ is stable up to 1500 °C in Ar, but decomposes in air to form TiN at ≈1400 °C. graduated from the Department in June of 1999 with an MS thesis.     

Phase Stability and Ionic Conductivity of NASICON-Like Phases in ScPO4-Na3PO4-Li3PO4 Ternary System

Phase formation in ternary system of complex Sc, Na and Li phosphates was studied at 950 ℃ and synthesis of new phases of definite composition was carried out. Obtained specimens were investigated with X-ray powder diffraction, infrared and impedance spectroscopy. Compositions of fields of homogeneity with NASICON-like structure were discovered. Temperature dependency of ionic conductivity was measured.     

Coumarins XIV: high-resolution mass spectra of 3',4'-disubstituted 3',4'-dihydroseselins

High-resolution mass spectra of 14 3',4'-disubstituted 3',4'-dihydroseselins were examined. The nature of the substituents determinines the mode of fragmentation. Compounds having one or two acyloxy substituents fragment mainly by a pathway leading to the stable coumarinopyrilium ion. Coumarins with alkoxy or hydroxy substituents proceed by way of fission of the chroman ring, accompanied by the loss of two ring carbon atoms. Several generalizations are formulated which will aid in the interpretation of the mass spectra of this class of coumarins from a structural standpoint.     

Fe_3O_4@SiO_2@Co_3O_4三元核壳结构催化剂的制备及表征

本文中采用均相沉淀法制备了Fe3O4@SiO2@Co3O4核壳结构纳米材料。通过X射线衍射仪,X射线能谱仪,透射电镜,振动样品磁力计,对其结构形貌和磁性能进行了表征。结果表明,所制备纳米粒子包覆结构比较完整,粒径约300nm,内核为磁性Fe3O4,中层为无定形SiO2,外层为Co3O4纳米线,具有海胆状三元核壳结构。该材料有望应用于具有可回收性的磁性纳米催化剂。     

4-Phenyl-4-oxo-butanoic acid derivatives inhibitors of kynurenine 3-hydroxylase

Kynurenine 3-hydroxylase (KYN 3-OHase) is a key enzyme in the kynurenine pathway of tryptophan degradation and its inhibition may be an effective mechanism for counteracting neuronal excitotoxic damage. We present here a new class of inhibitors derived from a structure-activity relationship (SAR) study of the benzoylalanine side-chain of 1. 2-hydroxy-4-(3,4-dichlorophenyl)-4-oxobutanoic acid (8) and 2-benzyl-4-(3,4-dichlorophenyl)-4-oxo-butanoic acid (10) emerged as the most interesting derivatives. Enantiospecific synthesis for both enantiomers of 8 and diastereomeric salt resolution for those of 10 were successfully applied.