热熔融流化床包衣过程中,颗粒的生长由颗粒团聚产生,颗粒团聚导致了颗粒粒径的非均一性。本研究采用群体平衡模型(Population Balance Model,PBM)对系统中各尺寸粒子建立守恒关系。为了求解PBM,对其进行离散化。颗粒的团聚核由基于气体...热熔融流化床包衣过程中,颗粒的生长由颗粒团聚产生,颗粒团聚导致了颗粒粒径的非均一性。本研究采用群体平衡模型(Population Balance Model,PBM)对系统中各尺寸粒子建立守恒关系。为了求解PBM,对其进行离散化。颗粒的团聚核由基于气体动力学理论的动能的等分(EKE)内核来描述。将EKE内核引入到离散的群体平衡(Discretized Population Balance,DPB)模型中,通过与基于质量的试验数据进行拟合,得出聚合速率常数β0=0.15×10^-3 kg m^-1/2 s^-1,为热熔融流化床包衣过程中颗粒的生长提供理论依据。展开更多
Time-dependent diffusion coefficient and conventional diffusion constant are calculated and analyzed to study diffusion of nanoparticles in polymer melts. A generalized Langevin equa- tion is adopted to describe the d...Time-dependent diffusion coefficient and conventional diffusion constant are calculated and analyzed to study diffusion of nanoparticles in polymer melts. A generalized Langevin equa- tion is adopted to describe the diffusion dynamics. Mode-coupling theory is employed to calculate the memory kernel of friction. For simplicity, only microscopic terms arising from binary collision and coupling to the solvent density fluctuation are included in the formalism. The equilibrium structural information functions of the polymer nanocomposites required by mode-coupling theory are calculated on the basis of polymer reference interaction site model with Percus-Yevick closure. The effect of nanoparticle size and that of the polymer size are clarified explicitly. The structural functions, the friction kernel, as well as the diffusion coefficient show a rich variety with varying nanoparticle radius and polymer chain length. We find that for small nanoparticles or short chain polymers, the characteristic short time non-Markov diffusion dynamics becomes more prominent, and the diffusion coefficient takes longer time to approach asymptotically the conventional diffusion constant. This constant due to the microscopic contributions will decrease with the increase of nanoparticle size, while increase with polymer size. Furthermore, our result of diffusion constant from mode- coupling theory is compared with the value predicted from the Stokes-Einstein relation. It shows that the microscopic contributions to the diffusion constant are dominant for small nanoparticles or long chain polymers. Inversely, when nanonparticle is big, or polymer chain is short, the hydrodynamic contribution might play a significant role.展开更多
The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer mol...The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.展开更多
The electrical, physical, mechanical and thermal properties of fluorine-containing alicyclic polyimides have been investigated. It was shown that the minimum value of the dielectric constant 1.91 at room temperature a...The electrical, physical, mechanical and thermal properties of fluorine-containing alicyclic polyimides have been investigated. It was shown that the minimum value of the dielectric constant 1.91 at room temperature and 1 kHz frequency was achieved for polymers containing only one fluorine atom in the structure. The dielectric loss tangent of new polymers was （I -4）~ 103. Electro-physical parameters were stable during polymer heating up to 300 ~C, and at the frequency from 1 to 20 kHz. Resistivity by heating in the air up to 320-380 ~C has been investigated depending on the polyimides structure. The coefficient of moisture absorption for the fluorine-containing polyimide based on dianhydride with 4,4＇-oxydianiline was determined at 50% humidity and 25 ℃. It was around 0.6, but after immersion in the water for 24 and 48 h was 0.8% and 1.2%, respectively. Manufactured films had tensile strength to 160-170 MPa, and elongation up to 55%.展开更多
Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very g...Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.展开更多
In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to ext...In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.展开更多
The color number Nc-dependence of the interplay between quark-antiquark condensates （q^-q） and diquark condensates （qq） in vacuum in two-flavor four-fermion interaction models is researched. The results show that ...The color number Nc-dependence of the interplay between quark-antiquark condensates （q^-q） and diquark condensates （qq） in vacuum in two-flavor four-fermion interaction models is researched. The results show that the Gs-Hs （the coupling constant of scalar （q^-q）2-scalar （qq）2 channel） phase diagrams will be qualitatively consistent with the case of Nc = 3 as Nc varies in 4D Nambu-Jona-Lasinio model and 219 Gross Neveu （GN） model, However, in 3D GN model, the behavior of the Gs-Hp （the coupling constant of pseudoscalar （qq）^2 channel） phase diagram will obviously depend on No. The known characteristic that a 3D GN model does not have the coexistence phase of the condensates （q^-q） and （qq） is proven to appear only in the case of Nc ≤ 4. In all the models, the regions occupied by the phases containing the diquark condensates （qq） in corresponding phase diagrams will gradually decrease as Nc grows up and finally go to zero if Nc → ∞, i.e. in this limit only the pure （q^-q） phase could exist.展开更多
文摘热熔融流化床包衣过程中,颗粒的生长由颗粒团聚产生,颗粒团聚导致了颗粒粒径的非均一性。本研究采用群体平衡模型(Population Balance Model,PBM)对系统中各尺寸粒子建立守恒关系。为了求解PBM,对其进行离散化。颗粒的团聚核由基于气体动力学理论的动能的等分(EKE)内核来描述。将EKE内核引入到离散的群体平衡(Discretized Population Balance,DPB)模型中,通过与基于质量的试验数据进行拟合,得出聚合速率常数β0=0.15×10^-3 kg m^-1/2 s^-1,为热熔融流化床包衣过程中颗粒的生长提供理论依据。
基金This work was supported by the National Natural Science Foundation of China （No.21173152）, the Ministry of Education of China （No.NCET-11-0359 and No.2011SCU04B31）, and the Science and Technology Department of Sichuan Province （No.2011HH0005）.
文摘Time-dependent diffusion coefficient and conventional diffusion constant are calculated and analyzed to study diffusion of nanoparticles in polymer melts. A generalized Langevin equa- tion is adopted to describe the diffusion dynamics. Mode-coupling theory is employed to calculate the memory kernel of friction. For simplicity, only microscopic terms arising from binary collision and coupling to the solvent density fluctuation are included in the formalism. The equilibrium structural information functions of the polymer nanocomposites required by mode-coupling theory are calculated on the basis of polymer reference interaction site model with Percus-Yevick closure. The effect of nanoparticle size and that of the polymer size are clarified explicitly. The structural functions, the friction kernel, as well as the diffusion coefficient show a rich variety with varying nanoparticle radius and polymer chain length. We find that for small nanoparticles or short chain polymers, the characteristic short time non-Markov diffusion dynamics becomes more prominent, and the diffusion coefficient takes longer time to approach asymptotically the conventional diffusion constant. This constant due to the microscopic contributions will decrease with the increase of nanoparticle size, while increase with polymer size. Furthermore, our result of diffusion constant from mode- coupling theory is compared with the value predicted from the Stokes-Einstein relation. It shows that the microscopic contributions to the diffusion constant are dominant for small nanoparticles or long chain polymers. Inversely, when nanonparticle is big, or polymer chain is short, the hydrodynamic contribution might play a significant role.
基金supported by the National Natural Science Foundation of China(No.21573027)
文摘The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.
文摘The electrical, physical, mechanical and thermal properties of fluorine-containing alicyclic polyimides have been investigated. It was shown that the minimum value of the dielectric constant 1.91 at room temperature and 1 kHz frequency was achieved for polymers containing only one fluorine atom in the structure. The dielectric loss tangent of new polymers was （I -4）~ 103. Electro-physical parameters were stable during polymer heating up to 300 ~C, and at the frequency from 1 to 20 kHz. Resistivity by heating in the air up to 320-380 ~C has been investigated depending on the polyimides structure. The coefficient of moisture absorption for the fluorine-containing polyimide based on dianhydride with 4,4＇-oxydianiline was determined at 50% humidity and 25 ℃. It was around 0.6, but after immersion in the water for 24 and 48 h was 0.8% and 1.2%, respectively. Manufactured films had tensile strength to 160-170 MPa, and elongation up to 55%.
基金supported by the National Natural Science Foundation of China(No.21773251 and No.21973098)the Youth Innovation Promotion Association CAS(No.2018045)the Beijing National Laboratory for Molecular Sciences。
文摘Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.
基金financial support provided by Islamic Azad University of Mahshahr Branch,Iran
文摘In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.
基金supported by the National Natural Science Foundation of China under Grant No. 10475113
文摘The color number Nc-dependence of the interplay between quark-antiquark condensates （q^-q） and diquark condensates （qq） in vacuum in two-flavor four-fermion interaction models is researched. The results show that the Gs-Hs （the coupling constant of scalar （q^-q）2-scalar （qq）2 channel） phase diagrams will be qualitatively consistent with the case of Nc = 3 as Nc varies in 4D Nambu-Jona-Lasinio model and 219 Gross Neveu （GN） model, However, in 3D GN model, the behavior of the Gs-Hp （the coupling constant of pseudoscalar （qq）^2 channel） phase diagram will obviously depend on No. The known characteristic that a 3D GN model does not have the coexistence phase of the condensates （q^-q） and （qq） is proven to appear only in the case of Nc ≤ 4. In all the models, the regions occupied by the phases containing the diquark condensates （qq） in corresponding phase diagrams will gradually decrease as Nc grows up and finally go to zero if Nc → ∞, i.e. in this limit only the pure （q^-q） phase could exist.
