The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This p...The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry ( DSC ) , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.展开更多
The oxygen evolution behavior in overcharged LiNil/3COl/3Mnl/3Oz-based electrode was investigated by differ- ential scanning calorimetry and thermal gravimetric (DSC/TG). Meantime, its thermal kinetic parameters wer...The oxygen evolution behavior in overcharged LiNil/3COl/3Mnl/3Oz-based electrode was investigated by differ- ential scanning calorimetry and thermal gravimetric (DSC/TG). Meantime, its thermal kinetic parameters were calculated by Kissinger's and Ozawa's method. As observed by DSC/TG, two exothermic peaks at 239 and 313℃ in washed cathode (4.6 V), were attributed to two steps of oxygen evolution. More importantly, the temperature of its oxygen release processes decreased obviously compared with that charged to 2.8 V. Activation energy (E) for the first and second oxygen evolution, both of which were assumed closely to be the first order reaction, between 200 and 350℃ in Lio.2o4NilnCol/3Mnl/3O2-based electrode were calculated as 113.63 and 158.13 kJ.mo1-1, respectively and the corresponding Arrhenius pre-exponential factors (A) of 1.05 × 10^11 and 6.46× 10^13 s-1 were also obtained. The different energy barrier of such two steps of oxygen evolution should probably be ascribed to the different bond energy of M--O (M=Mn, Co, Ni).展开更多
Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energ...Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.展开更多
The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniq...The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.展开更多
The complex of dysprosium chloride with glycine and L-tyrosine, Dy(Tyr)(Gly)3Cl3·3H2O, was synthesized and characterized. The standard molar formation enthalpy of Dy(Tyr)(Gly)3Cl3·3H2O at T=298.15 K ...The complex of dysprosium chloride with glycine and L-tyrosine, Dy(Tyr)(Gly)3Cl3·3H2O, was synthesized and characterized. The standard molar formation enthalpy of Dy(Tyr)(Gly)3Cl3·3H2O at T=298.15 K was determined to be (-4287.10±2.14) kJ/mol. The kinetics of thermal decomposition of the complex was studied by non-isothermal TG-DTG curves. The kinetic parameters and mechanism function of the thermal decomposition reaction for its second step were proposed. The kinetic equation could be expressed as;dα/dT=3.14×10^20 s^-1/βexp(-209.37 kJ·mol^-1/RT)(1 - α)^2.展开更多
In this article, high impact polystyrene/organo Fe-montmorillonite (HIPS/Fe-OMT) nanocomposites were prepared by melting intercalation. The thermal stability of HIPS/Fe-OMT nanocomposites increased significantly com...In this article, high impact polystyrene/organo Fe-montmorillonite (HIPS/Fe-OMT) nanocomposites were prepared by melting intercalation. The thermal stability of HIPS/Fe-OMT nanocomposites increased significantly compared to that of HIPS examined in thermal degradation conditions. Kinetic evaluations were performed by Kissinger, Flynn-Wall-Ozawa, Friedman methods and multivariate nonlinear regression. Apparent kinetic parameters for the overall degradation were determined. The resuRs showed that the activation energy of HIPS/Fe-OMT nanocomposites was higher than that of HIPS. A very good agreement between experimental and simulated curves was observed in dynamic conditions. Their decomposition reaction model was a single-step process of an nth-order reaction展开更多
The new organic-inorganic compound, [C_6H_7N_2O_2]_3TeCl_5·2Cl was synthesized and its structure was determined at room temperature in the triclinic system (P^-1) with the following parameters: a = 10.5330(11...The new organic-inorganic compound, [C_6H_7N_2O_2]_3TeCl_5·2Cl was synthesized and its structure was determined at room temperature in the triclinic system (P^-1) with the following parameters: a = 10.5330(11) ?, b = 10.6663(11) ?, c = 15.9751(16)?, α = 82.090(2)°, β = 71.193(2)°, γ = 68.284(2)°and Z = 2. The final cycle of refinement led to R = 0.057 and Rw = 0.149. The crystal structure was stabilized by an extensive network of N--H···Cl and non-classical C--H···Cl hydrogen bonds between the cation and the anionic group. Several thermal analysis techniques such as thermogravimetric analysis, differential scanning calorimetric analysis and evolved gas analysis were used. We used isoconversional kinetics methods to determine the kinetics parameters. We observe that the decomposition of [C_6H_7N_2O_2]_3TeCl_5·2Cl entails the formation hydrochloric acid of nitroaniline as volatiles. The infrared spectra were recorded in the4000–400 cm^(-1)frequency region. The Raman spectra were recorded in the external region of the anionic sublattice vibration 50–1500 cm^(-1). The optical band gap was calculated from the UV-Vis absorbance spectra using classical Tauc relation which was found to be 3.12 and 3.67 eV.展开更多
Gadolinium methacrylate(Gd(MAA)3) was synthesized by using gadolinium oxide and methacrylic acid as the starting materials and its self-polymerization kinetic was studied based on non-isothermal and isothermal ana...Gadolinium methacrylate(Gd(MAA)3) was synthesized by using gadolinium oxide and methacrylic acid as the starting materials and its self-polymerization kinetic was studied based on non-isothermal and isothermal analysis. Moreover, the monomer reactivity ratios of methyl methacrylate(MMA) and Gd(MAA)3 were evaluated by using Kelen-Tiidos method. The thermal neutron shielding properties of PMMA and poly(MMA-co-Gd(MAA)3) were calculated by MCNP program. The results show that the selfpolymerization of Gd(MAA)3 can be initiated by thermal and free radical and its activation energy is103.35 kJ/mol or 58.55 kJ/mol correspondingly in the solid state or aqueous solution. The polymerization rate,Rp,under low conversion at 65 ℃ is expressed as Rp = K[M]^(1.05)[I]^(0.60). The reactivity ratios of r1(MMA) and r2(Gd(MAA)3) are 0.225 and 1.340, respectively. The ability of thermal neutron shielding of poly(MMA-co-Gd(MAA)3) is increased by gadolinium contents and is far better than PMMA.展开更多
文摘The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry ( DSC ) , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.
基金Project supported by the National Natural Science Foundation of China (No. 50542004) and Graduate Degree Thesis Innovation Foundation of Central South University (No. 1960-71131100017).
文摘The oxygen evolution behavior in overcharged LiNil/3COl/3Mnl/3Oz-based electrode was investigated by differ- ential scanning calorimetry and thermal gravimetric (DSC/TG). Meantime, its thermal kinetic parameters were calculated by Kissinger's and Ozawa's method. As observed by DSC/TG, two exothermic peaks at 239 and 313℃ in washed cathode (4.6 V), were attributed to two steps of oxygen evolution. More importantly, the temperature of its oxygen release processes decreased obviously compared with that charged to 2.8 V. Activation energy (E) for the first and second oxygen evolution, both of which were assumed closely to be the first order reaction, between 200 and 350℃ in Lio.2o4NilnCol/3Mnl/3O2-based electrode were calculated as 113.63 and 158.13 kJ.mo1-1, respectively and the corresponding Arrhenius pre-exponential factors (A) of 1.05 × 10^11 and 6.46× 10^13 s-1 were also obtained. The different energy barrier of such two steps of oxygen evolution should probably be ascribed to the different bond energy of M--O (M=Mn, Co, Ni).
基金Project supported by the National Basic Research Program(973 Program,2012CBA01205)。
文摘Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.
文摘The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.
基金Project supported by the Science Foundation of Hubei Provincial Educational Department (No. 2001A27006), and the Teaching and Research Award Program for 0utstanding Young Professors in High Education Institute of Ministry of Education of China (2001).
文摘The complex of dysprosium chloride with glycine and L-tyrosine, Dy(Tyr)(Gly)3Cl3·3H2O, was synthesized and characterized. The standard molar formation enthalpy of Dy(Tyr)(Gly)3Cl3·3H2O at T=298.15 K was determined to be (-4287.10±2.14) kJ/mol. The kinetics of thermal decomposition of the complex was studied by non-isothermal TG-DTG curves. The kinetic parameters and mechanism function of the thermal decomposition reaction for its second step were proposed. The kinetic equation could be expressed as;dα/dT=3.14×10^20 s^-1/βexp(-209.37 kJ·mol^-1/RT)(1 - α)^2.
文摘In this article, high impact polystyrene/organo Fe-montmorillonite (HIPS/Fe-OMT) nanocomposites were prepared by melting intercalation. The thermal stability of HIPS/Fe-OMT nanocomposites increased significantly compared to that of HIPS examined in thermal degradation conditions. Kinetic evaluations were performed by Kissinger, Flynn-Wall-Ozawa, Friedman methods and multivariate nonlinear regression. Apparent kinetic parameters for the overall degradation were determined. The resuRs showed that the activation energy of HIPS/Fe-OMT nanocomposites was higher than that of HIPS. A very good agreement between experimental and simulated curves was observed in dynamic conditions. Their decomposition reaction model was a single-step process of an nth-order reaction
基金partially funded by the Tunisian Ministry of Higher Education and Scientific Research,the Spanish Programa Nacional de Materiales through project MAT2014-51778-C2-2-Rby the Universitat de Girona contract No.MPCUd G2016/059.Dfinancial support of the Tunisian Ministry of Higher Education and Scientific Research
文摘The new organic-inorganic compound, [C_6H_7N_2O_2]_3TeCl_5·2Cl was synthesized and its structure was determined at room temperature in the triclinic system (P^-1) with the following parameters: a = 10.5330(11) ?, b = 10.6663(11) ?, c = 15.9751(16)?, α = 82.090(2)°, β = 71.193(2)°, γ = 68.284(2)°and Z = 2. The final cycle of refinement led to R = 0.057 and Rw = 0.149. The crystal structure was stabilized by an extensive network of N--H···Cl and non-classical C--H···Cl hydrogen bonds between the cation and the anionic group. Several thermal analysis techniques such as thermogravimetric analysis, differential scanning calorimetric analysis and evolved gas analysis were used. We used isoconversional kinetics methods to determine the kinetics parameters. We observe that the decomposition of [C_6H_7N_2O_2]_3TeCl_5·2Cl entails the formation hydrochloric acid of nitroaniline as volatiles. The infrared spectra were recorded in the4000–400 cm^(-1)frequency region. The Raman spectra were recorded in the external region of the anionic sublattice vibration 50–1500 cm^(-1). The optical band gap was calculated from the UV-Vis absorbance spectra using classical Tauc relation which was found to be 3.12 and 3.67 eV.
基金Project supported by Graduate Student Research Innovation Project(KYLX_1337)
文摘Gadolinium methacrylate(Gd(MAA)3) was synthesized by using gadolinium oxide and methacrylic acid as the starting materials and its self-polymerization kinetic was studied based on non-isothermal and isothermal analysis. Moreover, the monomer reactivity ratios of methyl methacrylate(MMA) and Gd(MAA)3 were evaluated by using Kelen-Tiidos method. The thermal neutron shielding properties of PMMA and poly(MMA-co-Gd(MAA)3) were calculated by MCNP program. The results show that the selfpolymerization of Gd(MAA)3 can be initiated by thermal and free radical and its activation energy is103.35 kJ/mol or 58.55 kJ/mol correspondingly in the solid state or aqueous solution. The polymerization rate,Rp,under low conversion at 65 ℃ is expressed as Rp = K[M]^(1.05)[I]^(0.60). The reactivity ratios of r1(MMA) and r2(Gd(MAA)3) are 0.225 and 1.340, respectively. The ability of thermal neutron shielding of poly(MMA-co-Gd(MAA)3) is increased by gadolinium contents and is far better than PMMA.