A new model for self-diffusion coefficients was proposed based oil both the concepts of molecular free volume and activation energy. The unknown parameters of this model were clearly defined and compared with the Chap...A new model for self-diffusion coefficients was proposed based oil both the concepts of molecular free volume and activation energy. The unknown parameters of this model were clearly defined and compared with the Chapman-Enskog model. At the same time a new method for calculating activation energy was devised and applied to the new model. In addition, the free volume was defined by implementing the generic van der Waals equation of state, the radial distribution function of which was obtained by using the Morsali- Goharshadi empirical formula. Under the same conditions, the new model was better than the original free volume model.展开更多
The diffusion behavior of methanol in different critical media （n-pentane, n-hexane, n-heptane and acetone） was investigated by the Monte Carlo （MC） method. From the simulation results, the diffusion constant of m...The diffusion behavior of methanol in different critical media （n-pentane, n-hexane, n-heptane and acetone） was investigated by the Monte Carlo （MC） method. From the simulation results, the diffusion constant of methanol molecule in the critical n-hexane is much larger than those in n-pentane, n-heptane and acetone. By analyzing the microscopic configurations of the critical mixtures, it is found that the diffusion constant of methanol is related to the local solvent clustering around methanol, but it does not exhibit strong dependence on the size of solvent cluster around methanol. Moreover, the survival time of the solvent cluster plays an important role in determining the diffusion constant.展开更多
A number of studies have been reported on the applications of supercritical fluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles m...A number of studies have been reported on the applications of supercritical fluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles must be reduced to a level below the maximum permissible limit. Conventional heat-relevant techniques for polymer devolatilization sometimes have limited effectiveness. Devolatilization with supercritical fluids, however, can enhance removal of volatiles from polymers. A model for diffusion-limited extraction is used to characterize dynamic supercritical fluid devolatilization of spherical polymer particles. The rate of supercritical fluid devolailization for styrene/polystyrene system is measured at 343 K and 18 MPa and at CO2 flow rate of 1.93, 3.27 and 5.62 L·min^-1, respectively. The model analysis, which is consistent with experimental results, indicates that the supercritical fluid devolatilization is not solubility-limited but diffusion-limited when CO2 flow rate is above 4.00 L·min^-1.展开更多
The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations....The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.展开更多
Microscopic structure and diffusion properties of benzene in ambient water (298 K, 0.1 MPa) and super critical water (673－773 K, 25－35 MPa) are investigated by molecular dynamics simulation with site-site models. It...Microscopic structure and diffusion properties of benzene in ambient water (298 K, 0.1 MPa) and super critical water (673－773 K, 25－35 MPa) are investigated by molecular dynamics simulation with site-site models. It is found that at the ambient condition, the water molecules surrounding a benzene molecule form a hydrogen bond network. The hydrogen bond interaction between supercritical water molecules decreases dramatically under supercritical conditions. The diffusion coefficients of both the solute molecule and solvent molecule at supercritical conditions increase by 30－180 times than those at the ambient condition. With the temperature approaching the critical temperature, the change of diffusion coefficient with pressure becomes pronounced.展开更多
Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in whi...Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in which the Fick＇s diffusion model was applied to analyze both the desorption and sorption processes. The equilibrium sorption amount of CO2 in PLLA increased with lowering temperature and elevating pressure at the temperature range from 40 to 60 ℃ and pressure from 10^4 to 2x10^4 kPa. Desorption diffusion coefficients were greatly influenced by the equilibrium sorption amount, and they were in the same order of magnitude as the sorption diffusion coefficients. The scan electron microscope （SEM） photos demonstrated that there was no foaming phenomenon of the PLLA film during desorption and sorption processes. The XRD spectra implied that the crystalline degree of PLLA film decreased after CO2 processing. It was concluded that PLLA polymer could be well swollen and plasticized by supercritical CO2.展开更多
The molecular dynamics (MD) was employed to simulate the diffusion coefficient of sodium chloride at infinite dilution in supercritical water from 703.2 K to 763.2 K and from 30 MPa to 45 MPa. Based on the simulated d...The molecular dynamics (MD) was employed to simulate the diffusion coefficient of sodium chloride at infinite dilution in supercritical water from 703.2 K to 763.2 K and from 30 MPa to 45 MPa. Based on the simulated data and the Patel-Teja(PT) equation of state and the Liu-Ruckenstein equation, an equation for calculating the diffusion coefficient of NaCl at infinite dilution in supercritical water is proposed. Both the agreement between the simulated and correlated data, and that between the simulated and predicted data of diffusion coefficients for NaCl in supercritical water ranging from 703.2K to 803.2 K and from 25 MPa to 50 MPa show that this equation is applicable for the calculation of diffusion coefficients.展开更多
A numerical study of the counterflow diffusion flames of methane/air at both subcritical and supercritical pressures,which have very important applications in the air-breathing rocket and advanced gas turbine engines,...A numerical study of the counterflow diffusion flames of methane/air at both subcritical and supercritical pressures,which have very important applications in the air-breathing rocket and advanced gas turbine engines,is conducted to obtain fundamental understanding of the flame characteristics.The analysis is based on a general mathematical formulation and accommodates a unified treatment of general fluids thermodynamics and accurate calculations of thermophysical properties.Results reveal that the maximum flame temperature occurs on the fuel-rich side for low-pressure conditions and shifts toward the stoichiometric position when the pressure increases.The maximum flame temperature increases with an increasing pressure,but decreases with an increasing strain rate.The flame width is inversely proportional to the square root of the product of the pressure and strain rate as■■1 p·a2/1.The total heat release rate varies with the pressure and strain rate in a relationship of Q release ■(p·a)0.518.An increased pressure leads to a slightly more complete combustion process near the stoichiometric position,but its effect on NO production is minor.Under the test conditions,variations of the strain rate have significant impacts on the formation of major pollutants.An increased strain rate leads to the decreased mole fraction of CO in the fuel-rich region and significantly reduced NO near the stoichiometric position.展开更多
Many researches on critical nozzles have been performed to accurately measure the mass flow rate of gas flow,and to standardize the performance as a flow meter.Recently,much interest is being paid on the measurement o...Many researches on critical nozzles have been performed to accurately measure the mass flow rate of gas flow,and to standardize the performance as a flow meter.Recently,much interest is being paid on the measurement of very small mass flow rate in industry fields such as MEMS applications.However,the design and performance data of the critical nozzles obtained so far have been applied mainly to the critical nozzles with comparatively large diameters,and the works available on miniature critical nozzles are lacking.In the present study,a computational fluid dynamics method has been applied to investigate the influence of the diffuser angle on discharge coefficient of the miniature critical nozzles.In computations,the throat diameter of critical nozzle is varied from 0.2 mm to 5.0 mm and the diffuser angle is changed from 2 deg to 8 deg.The computational results are validated with some experimental data available.The results show that the present computational results predict appropriately the discharge coefficient of the gas flows through miniature critical nozzles.It is known that the discharge coefficient is considerably influenced by the diffuser angle,as the throat diameter of nozzle becomes small below a certain value.This implies that the miniature critical nozzles should be carefully designed.展开更多
文摘A new model for self-diffusion coefficients was proposed based oil both the concepts of molecular free volume and activation energy. The unknown parameters of this model were clearly defined and compared with the Chapman-Enskog model. At the same time a new method for calculating activation energy was devised and applied to the new model. In addition, the free volume was defined by implementing the generic van der Waals equation of state, the radial distribution function of which was obtained by using the Morsali- Goharshadi empirical formula. Under the same conditions, the new model was better than the original free volume model.
文摘The diffusion behavior of methanol in different critical media （n-pentane, n-hexane, n-heptane and acetone） was investigated by the Monte Carlo （MC） method. From the simulation results, the diffusion constant of methanol molecule in the critical n-hexane is much larger than those in n-pentane, n-heptane and acetone. By analyzing the microscopic configurations of the critical mixtures, it is found that the diffusion constant of methanol is related to the local solvent clustering around methanol, but it does not exhibit strong dependence on the size of solvent cluster around methanol. Moreover, the survival time of the solvent cluster plays an important role in determining the diffusion constant.
基金Supported by the National Natural Science Foundation of China (No. 20576123).
文摘A number of studies have been reported on the applications of supercritical fluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles must be reduced to a level below the maximum permissible limit. Conventional heat-relevant techniques for polymer devolatilization sometimes have limited effectiveness. Devolatilization with supercritical fluids, however, can enhance removal of volatiles from polymers. A model for diffusion-limited extraction is used to characterize dynamic supercritical fluid devolatilization of spherical polymer particles. The rate of supercritical fluid devolailization for styrene/polystyrene system is measured at 343 K and 18 MPa and at CO2 flow rate of 1.93, 3.27 and 5.62 L·min^-1, respectively. The model analysis, which is consistent with experimental results, indicates that the supercritical fluid devolatilization is not solubility-limited but diffusion-limited when CO2 flow rate is above 4.00 L·min^-1.
基金Supported by the National Natural Science Foundation of China （20776066, 20476044） and the Specialized Research Fund for the Doctoral Program of Higher Education of China （20060291002）.
文摘The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.
基金Supported by the State Key Fundamental Research Plan (NO. G2000048) and the National High Performance Computing Foundation of China (No. 99118).
文摘Microscopic structure and diffusion properties of benzene in ambient water (298 K, 0.1 MPa) and super critical water (673－773 K, 25－35 MPa) are investigated by molecular dynamics simulation with site-site models. It is found that at the ambient condition, the water molecules surrounding a benzene molecule form a hydrogen bond network. The hydrogen bond interaction between supercritical water molecules decreases dramatically under supercritical conditions. The diffusion coefficients of both the solute molecule and solvent molecule at supercritical conditions increase by 30－180 times than those at the ambient condition. With the temperature approaching the critical temperature, the change of diffusion coefficient with pressure becomes pronounced.
基金Supported by the National Natura Science Foundation of China （21076185）.
文摘Equilibrium sorption amount, desorption diffusion coefficients and sorption diffusion coefficients of CO2 in poly（l-lactic acid） （PLLA） films at elevated pressures were determined by the gravimetric method, in which the Fick＇s diffusion model was applied to analyze both the desorption and sorption processes. The equilibrium sorption amount of CO2 in PLLA increased with lowering temperature and elevating pressure at the temperature range from 40 to 60 ℃ and pressure from 10^4 to 2x10^4 kPa. Desorption diffusion coefficients were greatly influenced by the equilibrium sorption amount, and they were in the same order of magnitude as the sorption diffusion coefficients. The scan electron microscope （SEM） photos demonstrated that there was no foaming phenomenon of the PLLA film during desorption and sorption processes. The XRD spectra implied that the crystalline degree of PLLA film decreased after CO2 processing. It was concluded that PLLA polymer could be well swollen and plasticized by supercritical CO2.
基金Supported by the National Natural Science Foundation of China(No.20006008,20176020)and the Fundamental Research Foundation of Tsinghua University(JZ2002003).
文摘The molecular dynamics (MD) was employed to simulate the diffusion coefficient of sodium chloride at infinite dilution in supercritical water from 703.2 K to 763.2 K and from 30 MPa to 45 MPa. Based on the simulated data and the Patel-Teja(PT) equation of state and the Liu-Ruckenstein equation, an equation for calculating the diffusion coefficient of NaCl at infinite dilution in supercritical water is proposed. Both the agreement between the simulated and correlated data, and that between the simulated and predicted data of diffusion coefficients for NaCl in supercritical water ranging from 703.2K to 803.2 K and from 25 MPa to 50 MPa show that this equation is applicable for the calculation of diffusion coefficients.
基金supported by the National Natural Science Foundation of China(Grant No.11372277)
文摘A numerical study of the counterflow diffusion flames of methane/air at both subcritical and supercritical pressures,which have very important applications in the air-breathing rocket and advanced gas turbine engines,is conducted to obtain fundamental understanding of the flame characteristics.The analysis is based on a general mathematical formulation and accommodates a unified treatment of general fluids thermodynamics and accurate calculations of thermophysical properties.Results reveal that the maximum flame temperature occurs on the fuel-rich side for low-pressure conditions and shifts toward the stoichiometric position when the pressure increases.The maximum flame temperature increases with an increasing pressure,but decreases with an increasing strain rate.The flame width is inversely proportional to the square root of the product of the pressure and strain rate as■■1 p·a2/1.The total heat release rate varies with the pressure and strain rate in a relationship of Q release ■(p·a)0.518.An increased pressure leads to a slightly more complete combustion process near the stoichiometric position,but its effect on NO production is minor.Under the test conditions,variations of the strain rate have significant impacts on the formation of major pollutants.An increased strain rate leads to the decreased mole fraction of CO in the fuel-rich region and significantly reduced NO near the stoichiometric position.
文摘Many researches on critical nozzles have been performed to accurately measure the mass flow rate of gas flow,and to standardize the performance as a flow meter.Recently,much interest is being paid on the measurement of very small mass flow rate in industry fields such as MEMS applications.However,the design and performance data of the critical nozzles obtained so far have been applied mainly to the critical nozzles with comparatively large diameters,and the works available on miniature critical nozzles are lacking.In the present study,a computational fluid dynamics method has been applied to investigate the influence of the diffuser angle on discharge coefficient of the miniature critical nozzles.In computations,the throat diameter of critical nozzle is varied from 0.2 mm to 5.0 mm and the diffuser angle is changed from 2 deg to 8 deg.The computational results are validated with some experimental data available.The results show that the present computational results predict appropriately the discharge coefficient of the gas flows through miniature critical nozzles.It is known that the discharge coefficient is considerably influenced by the diffuser angle,as the throat diameter of nozzle becomes small below a certain value.This implies that the miniature critical nozzles should be carefully designed.
