A comparison of Ce~（3＋） luminescence in X_2Z（BO_3）_2（X=Ba,Sr;Z=Ca,Mg） with relevant composition and structure

The VUV-UV spectroscopic properties of Ce3+ in Ba2Mg(BO3)2,Ba2Ca(BO3)2 and Sr2Mg(BO3)2 were compared,and the relation between the energy of the 4f→5d transition of Ce3+ and the coordination environments of substituted alkaline earth ions was discussed.The chromaticity coordinates of Ce3+ activated X2Z(BO3)2(X=Ba,Sr;Z=Ca,Mg) phosphors were changeable from blue to whitish and further to green range by varying the doping concentration of Ce3+ or the types of substituted alkaline earth ions upon 172 nm excitation.     

固相反应法制备β″-Al_2O_3粉末的热力学研究

以Na2CO3和α-Al2O3为原料,Na2CO3与α-Al2O3的物质的量比为1:6,采用固相合成法制备β″/β-Al2O3粉末。通过热力学计算原料粉末在不同温度下可能发生的化学反应的吉布斯自由能,并结合Na2CO3/α-Al2O3混合粉末的DTA曲线,研究可能发生的化学反应的温度条件。同时,用X射线衍射仪(XRD)对固相合成粉末的物相组成进行分析。结果表明,Na2CO3/α-Al2O3混合粉末在1 150℃左右开始发生反应生成β″/β-Al2O3;最适宜的反应温度为1 250℃,α-Al2O3全部转化为β/β″-Al2O3,并且β″-Al2O3含量最高;当温度升高到1 400℃时,β/β″-Al2O3发生分解,生成α-Al2O3和Na2O,并且随温度升高,更多的β/β″-Al2O3发生分解,而Na2O在高温下挥发会促进β/β″-Al2O3的分解。当煅烧温度超过1 500℃时,β″-Al2O3分解还生成微量的Na Al O2。     

贵金属Pd-X(X=Ag,Ni,Sn)体系的相图热力学研究

对贵金属Pd-X(X=Ag,Ni,Sn)体系的相图热力学文献数据进行严格评估的基础上,采用替代溶液模型描述该3个二元系中液相和FCC＿A1相的吉布斯自由能,分别采用亚点阵模型(Pd,Sn)₁Sn₂、(Pd)_0.25(Pd,Sn)_0.75和(Pd)_0.2(Pd,Sn)_0.8描述Pd Sn₂、PdSn₃和PdSn₄相,通过CALPHAD(calculation of phasediagram)方法获得描述贵金属Pd-X (X=Ag,Ni,Sn)体系的热力学参数。相较于文献报道,本研究得到的热力学参数能更合理地描述Pd-X (X=Ag Ni,Sn)体系的实验相图数据和热力学数据,尤其在Pd-Ag相图、Pd-Ag体系和Pd-Ni体系FCC＿A1的混合焓及Pd-Sn相图富Sn端零变量反应的描述方面。计算结果与实验数据的比较表明本工作获得的热力学参数的准确性。     

高温超导体RBa2Cu3Oy超导转变热力学

研究了稀土氧化物高温超导体RBa₂Cu₃O_y(R:一般为稀土元素)超导转变的相变性质,认为在没有外界磁场作用时超导转变为二级相变,有外界磁场作用时为一级相变。推导出超导体RBa₂Cu₃O_y在超导转变时体系的Gibbs自由能关系式。     

Ca(OH)_2改性活性炭及其吸附CO_2的研究

采用Ca(OH)2为化学活化剂,对颗粒活性炭进行改性。结果表明,在Ca(OH)2用量为100mL、改性温度80℃、改性时间2h、干燥时间6h时,改性后的活性炭吸附容量达到最大,为3.91mmol/g。     

CaC2-CHCl3体系制备纳米碳球的反应热力学

利用CaC2-CHCl3体系反应合成纳米碳球,利用X射线衍射仪(XRD)和扫描电镜(SEM)对产物的物相、形貌和显微结构进行分析.对该体系进行吉布斯自由能和反应热效应计算,结合实验结果,研究采用无机化学反应法制备微纳米碳球的中间态成碳机理.结果表明:从理论上证实CaC2-CHCl3体系热解产物可能为石墨、金刚石和C3原...     

Al2O3-V2O5体系的热力学优化

在对Al₂O₃-V₂O₅体系相图、热力学数据以及晶体结构数据进行综述与评估的基础上,采用相图计算方法对Al₂O₃-V₂O₅体系进行热力学优化.液相采用修正的似化学模型进行描述,利用对近似处理液相中存在的短程有序.将液相模型的最大短程有序设置在AlVO₄处,将VO₄3-当作液相中V₂O₅的基本组成单元.体系中AlVO₄相看作线性化合物.计算结果很好的重现了选定的实验数据,获得了一套合理、可靠、自洽的模型参数用来描述体系中各相的热力学性质,为Al₂O₃负载V₂O₅型催化剂催化性能的提高打下坚实的基础.      

Ca(OH)_2-NaOH分解混合稀土精矿的研究

采用TG-DTA热分析技术研究Ca(OH)2-NaOH体系分解混合稀土精矿的过程。并选择了焙烧温度、Ca(OH)2加入量、NaOH加入量、焙烧时间为影响因素,用二次正交回归实验设计方法研究并获得了矿物分解率受各因素影响的回归方程,实验表明,焙烧温度630℃;Ca(OH)2加入量23%(质量分数);NaOH加入量15%(质量分数);焙烧时间30 min,分解率为98.1%。     

稀土脯氨酸高氯酸盐配合物[RE_2(Pro)_6(H_2O)_4](ClO_4)_6(RE=Pr,Er)的低温热容及热力学性质

合成了两种纯度分别是 99.2 4%和 98.2 0 %的单晶稀土脯氨酸高氯酸盐配合物 [Pr2 (Pro) 6 (H2 O) 4](Cl O4) 6 和 [Er2 (Pro) 6 (H2 O) 4](Cl O4) 6 ,对该配合物进行了热容、热重、差热和标准燃烧热等测定。在 78～ 370 K温度区 ,用高精密全自动绝热量热仪测定了热容值 ,计算机拟合得其热容对温度的多项式方程分别为 :Cp=140 7.0 8 75 1.6 7X 170 .17X2 89.5 9X3- 76 .11X4和 Cp=1317.99 6 33.0 5 X 16 3.82 X2 15 0 .2 3X3- 86 .2 1X4,[Er2(Pro) 6 (H2 O) 4](Cl O4) 6 的 Cp- T曲线有一熔化峰 ,计算熔点为 35 5 .5 5 K,熔化熵为 6 9.5 42 J/(K m ol) ,熔化焓为2 472 5 .81J/m ol。 TG、DTA技术研究了其热分解过程 ,初步分析了配合物的分解机理。燃烧热实验给出了它们的标准燃烧热分别为 1772 0 .41k J/mol和 1810 1.6 5 k J/m ol     

Fe(III)-Mn(II)-As(V)-H_2O系相图的建立

依据实验数据利用DIASTAB计算机程序,建立了Fe(Ⅲ)-Mn(Ⅱ)-As(V)-H2O系的稳定性相图。所建立的相图表明,在pH=3 5～6 0范围内,体系内稳定存在的固体化合物为Fe(Ⅲ)-Mn(Ⅱ)-As(V)化合物、MnHAsO4和Mn3(AsO4)2,用DIASTAB计算机程序对实验数据进行逼近计算,算得前者的生成自由能为-245 5kcalmol1-;相图还表明,依靠所研究的体系,水相除砷不可能达到WHO规定的砷最大污染值0 05mg/L的标准。     

Thermodynamic Optimization of TmCl3-ACl （A = Na, K, Rb, Cs）Phase Diagrams

As well known, molten salt electrolysis was wide ly used for the production of rare earth metals andtheir alloys. And, phase diagrams are the most impor tant data for fused electrolytes. Dealing with the bina ry phase diagrams relating to rar…     

Thermodynamic Assessment of DyCl3-MCl （M= Na, K, Rb, Cs） Systems

Using the CALPHAD （Calculation of Phase Diagram） technique, the DyCl3-MCl （M = Na, K, Rb, Cs） systems were optimized and calculated. The modified quasi-chemical model in the pair approximation for short-range ordering was used to describe the Gibbs energies of the liquid phase in these systems. From the measured phase diagram data and experimental thermodynamic properties, a series of thermodynamic functions were optimized base on an interactive computer-assisted analysis. The optimized parameters and the experimental data were thermodynamically self-consistent. The optimized results were discussed.     

Thermodynamic optimization and calculation of phase diagrams of YbCl3-MCl (M=Na, K, Rb, Cs)

YbCl3-MCl (M = Na, K, Rb, Cs) systems were optimized and calculated using the CALPHAD (CALculation of PHAse Diagram) technique. The modified quasi-chemical model in the pair-approximation for short-range ordering was used to describe the Gibbs energies of liquid phase in the systems. On the basis of the measured phase diagram data and experimental thermodynamic properties, a series of thermodynamic functions were optimized and calculated through an interactive computer-assisted analysis. Furthermore, some reasonable discussions on the thermodynamic parameters for these strong interaction binary systems were carried out. The results showed that the optimized parameters and experimental data are thermodynamically self-consistent.     

W-Zr体系的热力学优化

综合评估了W-Zr体系的实验结果。采用Redlich-Kister多项式描述体系液相、bcc和hcp相的过剩自由焓。利用第一性原理和德拜理论得到化合物W2Zr的自由焓，并结合选取合理的实验数据，优化得到W-Zr二元体系各相的热力学参数，用优化结果计算的相图与实验结果吻合较好。     

Optimization and Calculation of TbCl3-ACl（A = Li, Na, K, Rb, Cs）Phase Diagrams

Thermodynamic information of the melts involvingrare earth halides and alkali halides plays an importantrole in the preparation of rare earth metals by moltensalt electrolysis and by metallothermic reduction. Theknowledge of thermodynamics of molten s…     

Phase equilibria calculation of LaI3-MI （M=Na, K, Cs） binary systems

The Gibbs energies of liquid phases in the LaI3-MI (M=Na, K, Cs) systems were described by the modified quasi-chemical model. From the measured phase equilibrium data of these binary systems, a set of thermodynamic functions were optimized by using the CAL-PHAD technique. The enthalpy of mixing and the interaction parameter of the liquid phase were predicted from known data for the LaI3-MI systems.     

Formation and Characterization of Li0.24 ＋ 2x La0.59-x Mx TiO3-LaPO4 （M = K, Na） System

Ionic conductingsolid materials has received con-siderable attention in the last few years due to theirpotential utilityin high energy batteries and other elec-trochemical devices . Several systems of lithium fastion conductors ,such as γ-Li3PO4-type sol…     

碳热还原法制备锂离子电池正极材料Li3V2(PO4)3的研究

以LiCO3、V2O5、NH4H2PO4为原料,采用碳热还原法合成锂离子电池正极材料Li3V2(PO4)3(LVP).根据TG分析得到制备样品的温度范围.对所得材料分别进行了XRD、粉末微电极循环伏安及恒电流充放电测试.XRD分析表明, 850 ℃煅烧所得样品特征衍射峰型尖锐,晶体结构发育良好,为纯相的Li3V2(PO4)3;循环伏安测试表明,锂离子脱嵌分三步进行,循环伏安曲线对称性好;合成的正极材料在7 mA/g恒流充放电,首次充、放电比容量分别为129.8 mA·h/g、116.8 mA·h/g,充放电效率达90%,循环性能有待提高.材料中过量碳的加入提高了其充、放电比容量,使其循环性能有所改善.     

Experimental Study and Thermodynamic Optimization of the FeO-V_2O_3 System

Optimization of the phase diagram of FeO-V2O3 system is a part of an on-going research project to develop a self-consistent multi-component thermodynamic database for vanadium slag from hot metal.Due to the lack of experimental data for optimization,a novel experimental investigation has been carried out by thermal analysis(DSC)with a series of slags on different V2O3 contents(i.e.3mass%-12mass%).All available thermodynamic and phase diagram data for the binary systems have been simultaneously optimized with CALPHAD(Calculation of Phase Diagrams)methods to give one set of model equations for the Gibbs free energy of the liquid slag as functions of composition and temperature.The modified quasi-chemical model was used to describe the binary slag system.It was demonstrated that the calculated phase diagram with the optimized parameters was in good agreement with the experimental data.     

Thermodynamic Calculation of Inclusion Formation in Mg-Al-Si-O System of 430 Stainless Steel Melts

 A phase diagram was drawn through thermodynamic calculation to understand the equilibrium conditions of 2MgO·SiO2, MgO·Al2O3, 3Al2O3·2SiO2, and 2MgO·2Al2O3·5SiO2 formation in Mg-Al-Si-O system of 430 stainless steel melts at 1873 K. Further, the thermodynamic formation and transformation conditions of MgO·Al2O3 inclusion were discussed. The following results are obtained when wSi=026% and wO=10×10-5 in molten steel. The uniphase cordierite inclusion is difficult to exist stably; MgO·Al2O3 inclusion cannot be formed in case of wAl being less than 1×10-6; 3Al2O3·2SiO2 would change to MgO·Al2O3 and 2MgO·SiO2 in turn with increasing the Mg content when wAl is above 17×10-6; with the formation of MgO·Al2O3 inclusion, Al content increases with increasing Mg content when wMg is over 17×10-9. For equilibrium condition and calculated steel composition, 2MgO·SiO2 inclusion would be formed ultimately and MgO·Al2O3 is almost inexistent.