The reactions LnCl3 (s) + (3/2)Al2Cl6, (g) = LnAl3Cl12 (g) for Ln = La to Lu were studied by quenching experiments in roughly the same temperature and pressure ranges (588-851 K and 0.01-0.22 MPa). Stability constant...The reactions LnCl3 (s) + (3/2)Al2Cl6, (g) = LnAl3Cl12 (g) for Ln = La to Lu were studied by quenching experiments in roughly the same temperature and pressure ranges (588-851 K and 0.01-0.22 MPa). Stability constants Kθ of lanthanide complexes LnAl3Cl12 were calculated from the measurements. The values of Ig Kθ change linearly with the ionpotential (Z+/r) of lanthanide(Ⅲ) from La to Gd and from Tb to Lu, respectively, indicating the Gd break. There exist inclined W effect between Ig Kθ and the total angular momentum L of lanthanide(Ⅲ). And hereby lanthanide elements are divided into four segments, La-Nd, Pm-Gd, Tb-Ho, and Er-Lu. In each segment, the linearity is maintained.展开更多
Thermodynamic studies were carried out for the vapor complex of sodium chloride with zirconium tetrachloride at 718-778 K and 0.5-2.5 kPa by using high temperature phase equilibrium-quenching experiments, taking close...Thermodynamic studies were carried out for the vapor complex of sodium chloride with zirconium tetrachloride at 718-778 K and 0.5-2.5 kPa by using high temperature phase equilibrium-quenching experiments, taking closed Pyrex glass ampoules as the reaction containers. The results show that the sole predominant vapor complex is Na_2ZrCl_6 for the ZrCl4-NaCl system under the experimental conditions. The thermodynamic equilibrium constants and other thermodynamic functions of the reaction 2NaCl(s)+ZrCl4(g)=Na_2ZrCl_6(g) have been derived from the measurements. The results for the changes in enthalpy and entropy are △H0=(-70.1±1.5) kJ/mol and △S0=(-105.9±2.0) J/(mol·K) in the temperature range.展开更多
The bis(N-ethyl-5-methylsalicylaldimine)nickel(II) [Ni(5-me-saletN)2] complex was synthesized and characterized by elemental analyses, FT-IR, TG-DTA, mass spectrometry and vapour pressure measurement studies. The TG c...The bis(N-ethyl-5-methylsalicylaldimine)nickel(II) [Ni(5-me-saletN)2] complex was synthesized and characterized by elemental analyses, FT-IR, TG-DTA, mass spectrometry and vapour pressure measurement studies. The TG curve of the complex showed a single-step weight loss commencing from 490 K to nil residue at 600 K, without competing fragmentation step. The non-isothermal vaporization activation energy value determined by Coats-Redfern method yielded the value of 93.5 ± 7 kJmol–1. The dynamic TG run proved the complex to be completely volatile. And the equilibrium vapour pressure of the complex over the temperature range of 421 - 524 K, determined by the TG-based transpiration technique yielded the value of 94.2 ± 1.2 kJmol–1 for its standard enthalpy of vaporization . The entropy of vaporization was calculated from the intercept and found to be 249.4 ± 2.6 Jmol–1•K–1.展开更多
The complexes of bis[N-alkyl-2-hydroxonapthaldimine]nickel(II) (N-alkyl = methyl, ethyl, propyl, butyl or pentyl) were synthesized and their volatilization in N2 atmosphere was demonstrated by the TG-based transpirati...The complexes of bis[N-alkyl-2-hydroxonapthaldimine]nickel(II) (N-alkyl = methyl, ethyl, propyl, butyl or pentyl) were synthesized and their volatilization in N2 atmosphere was demonstrated by the TG-based transpiration technique. The equilibrium vapor pressure of the complexes over a temperature span of 470 - 590 K was determined by adapting a horizontal dual arm single furnace thermoanalyser as a transpiration apparatus. It yielded as 153.1 (±1.9), 122.9 (±0.3), 147.6 (±10.7), 151.8 (±10.9) and 114.7 (±5.3) k·Jmol–1 respectively. The entropies of vaporization for these complexes as calculated from the intercept of the linear fit expressions were found to be 319.7 (±3.9), 229.9 (±5.8), 317.8 (±17.2), 319.7 (±19.1) and 254.6 (±9.6) Jmo–1·K–1 respectively. The non-isothermal vaporization activation energy was determined from Arrhenius and Coats-Redfern methods.展开更多
Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl ...Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl n Cl 3 n +3 (Ln=RE elements). The bastnaesite was heated to 800 K and chlorinated between 800～1300 K with C+Cl 2+SiCl 4 to remove CO 2, SiF 4 and high volatile chlorides. At the temperature of 1300 K for 6 h, the resulted RE chlorides were chemically transported and mutual separated with the vapor complexes while CaCl 2 and BaCl 2 were remained in the residues. Significantly different CVT characteristics were observed for gradually decreased and wave form temperature gradients.展开更多
Catalyst enhanced chemical vapor deposition of nickel film on high Tg polymers such as teflon(PTFE), polyimide(PI), and polysulfone(PS) was investigated by hot wall and cold wall CVD, in which Ni(dmg)_2, Ni(acac)_2, N...Catalyst enhanced chemical vapor deposition of nickel film on high Tg polymers such as teflon(PTFE), polyimide(PI), and polysulfone(PS) was investigated by hot wall and cold wall CVD, in which Ni(dmg)_2, Ni(acac)_2, Ni(hfac)_2, Ni(TMHD)_2, and Ni(cp)_2 are used as precursors, and palladium complexes are used as catalysts. The films obtained were shiny with silvery color. The Ni was metallic and the purity of Ni was about 92%-95% from XPS analysis. SEM micrographs show that the film had good morphology. The conductivity of the film was about 0.5-4 W·cm^(-1). Ni films had good adhesion with polyimide and polysulfone.展开更多
通过热力学理论对物理气相传输(PVT)法AlN晶体生长过饱和度进行分析,分别从软件模拟和晶体生长实验对衬底表面的温度分布进行调控,进而控制衬底表面AlN晶体生长的驱动力。理论上,采用Comsol模拟软件对坩埚结构的温度分布进行模拟仿真,...通过热力学理论对物理气相传输(PVT)法AlN晶体生长过饱和度进行分析,分别从软件模拟和晶体生长实验对衬底表面的温度分布进行调控,进而控制衬底表面AlN晶体生长的驱动力。理论上,采用Comsol模拟软件对坩埚结构的温度分布进行模拟仿真,模拟结果表明:复合型衬底可以显著改变衬底表面的温度分布,达到改变衬底表面AlN气氛的过饱和度的目的;实验上,采用PVT法AlN晶体的生长实验验证了软件模拟结果。采用复合型衬底生长AlN晶体时,通过对衬底表面的温度分布调控可有效控制晶体生长驱动力,进而实现形核位置和形核数量的控制。经过6~8 h AlN晶体生长后,可获得尺寸约为12 mm、厚度约为3 mm的AlN单晶。喇曼光谱和XRD双晶摇摆曲线测试结果表明晶体质量良好。展开更多
文摘The reactions LnCl3 (s) + (3/2)Al2Cl6, (g) = LnAl3Cl12 (g) for Ln = La to Lu were studied by quenching experiments in roughly the same temperature and pressure ranges (588-851 K and 0.01-0.22 MPa). Stability constants Kθ of lanthanide complexes LnAl3Cl12 were calculated from the measurements. The values of Ig Kθ change linearly with the ionpotential (Z+/r) of lanthanide(Ⅲ) from La to Gd and from Tb to Lu, respectively, indicating the Gd break. There exist inclined W effect between Ig Kθ and the total angular momentum L of lanthanide(Ⅲ). And hereby lanthanide elements are divided into four segments, La-Nd, Pm-Gd, Tb-Ho, and Er-Lu. In each segment, the linearity is maintained.
基金Project(50274027) supported by the National Natural Science Foundation of China
文摘Thermodynamic studies were carried out for the vapor complex of sodium chloride with zirconium tetrachloride at 718-778 K and 0.5-2.5 kPa by using high temperature phase equilibrium-quenching experiments, taking closed Pyrex glass ampoules as the reaction containers. The results show that the sole predominant vapor complex is Na_2ZrCl_6 for the ZrCl4-NaCl system under the experimental conditions. The thermodynamic equilibrium constants and other thermodynamic functions of the reaction 2NaCl(s)+ZrCl4(g)=Na_2ZrCl_6(g) have been derived from the measurements. The results for the changes in enthalpy and entropy are △H0=(-70.1±1.5) kJ/mol and △S0=(-105.9±2.0) J/(mol·K) in the temperature range.
文摘The bis(N-ethyl-5-methylsalicylaldimine)nickel(II) [Ni(5-me-saletN)2] complex was synthesized and characterized by elemental analyses, FT-IR, TG-DTA, mass spectrometry and vapour pressure measurement studies. The TG curve of the complex showed a single-step weight loss commencing from 490 K to nil residue at 600 K, without competing fragmentation step. The non-isothermal vaporization activation energy value determined by Coats-Redfern method yielded the value of 93.5 ± 7 kJmol–1. The dynamic TG run proved the complex to be completely volatile. And the equilibrium vapour pressure of the complex over the temperature range of 421 - 524 K, determined by the TG-based transpiration technique yielded the value of 94.2 ± 1.2 kJmol–1 for its standard enthalpy of vaporization . The entropy of vaporization was calculated from the intercept and found to be 249.4 ± 2.6 Jmol–1•K–1.
文摘The complexes of bis[N-alkyl-2-hydroxonapthaldimine]nickel(II) (N-alkyl = methyl, ethyl, propyl, butyl or pentyl) were synthesized and their volatilization in N2 atmosphere was demonstrated by the TG-based transpiration technique. The equilibrium vapor pressure of the complexes over a temperature span of 470 - 590 K was determined by adapting a horizontal dual arm single furnace thermoanalyser as a transpiration apparatus. It yielded as 153.1 (±1.9), 122.9 (±0.3), 147.6 (±10.7), 151.8 (±10.9) and 114.7 (±5.3) k·Jmol–1 respectively. The entropies of vaporization for these complexes as calculated from the intercept of the linear fit expressions were found to be 319.7 (±3.9), 229.9 (±5.8), 317.8 (±17.2), 319.7 (±19.1) and 254.6 (±9.6) Jmo–1·K–1 respectively. The non-isothermal vaporization activation energy was determined from Arrhenius and Coats-Redfern methods.
文摘Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl n Cl 3 n +3 (Ln=RE elements). The bastnaesite was heated to 800 K and chlorinated between 800～1300 K with C+Cl 2+SiCl 4 to remove CO 2, SiF 4 and high volatile chlorides. At the temperature of 1300 K for 6 h, the resulted RE chlorides were chemically transported and mutual separated with the vapor complexes while CaCl 2 and BaCl 2 were remained in the residues. Significantly different CVT characteristics were observed for gradually decreased and wave form temperature gradients.
基金Funded by the National Natural Science Foundation of China(51566005)
文摘Catalyst enhanced chemical vapor deposition of nickel film on high Tg polymers such as teflon(PTFE), polyimide(PI), and polysulfone(PS) was investigated by hot wall and cold wall CVD, in which Ni(dmg)_2, Ni(acac)_2, Ni(hfac)_2, Ni(TMHD)_2, and Ni(cp)_2 are used as precursors, and palladium complexes are used as catalysts. The films obtained were shiny with silvery color. The Ni was metallic and the purity of Ni was about 92%-95% from XPS analysis. SEM micrographs show that the film had good morphology. The conductivity of the film was about 0.5-4 W·cm^(-1). Ni films had good adhesion with polyimide and polysulfone.
文摘通过热力学理论对物理气相传输(PVT)法AlN晶体生长过饱和度进行分析,分别从软件模拟和晶体生长实验对衬底表面的温度分布进行调控,进而控制衬底表面AlN晶体生长的驱动力。理论上,采用Comsol模拟软件对坩埚结构的温度分布进行模拟仿真,模拟结果表明:复合型衬底可以显著改变衬底表面的温度分布,达到改变衬底表面AlN气氛的过饱和度的目的;实验上,采用PVT法AlN晶体的生长实验验证了软件模拟结果。采用复合型衬底生长AlN晶体时,通过对衬底表面的温度分布调控可有效控制晶体生长驱动力,进而实现形核位置和形核数量的控制。经过6~8 h AlN晶体生长后,可获得尺寸约为12 mm、厚度约为3 mm的AlN单晶。喇曼光谱和XRD双晶摇摆曲线测试结果表明晶体质量良好。
