The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns(2D TRLS) has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in which ...The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns(2D TRLS) has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in which the secondary phase separation takes place.The results of the 2D TRLS provided more detailed information that was not readily observed in the 1D TRLS patterns.(i) During the first process of phase separation,the sequential order of coarsening in size of the domains among the larger and smaller ones has been reversed between the diffusion regime and the hydrodynamic regime. (ii) The change of the larger domains in size,due to the hydrodynamic flow in the late stage of the first phase separation process,keeps on taking place earlier than that of the new domains appeared in the secondary phase separation process. (iii) During the secondary phase separation process the size growth of the smaller domains takes place earlier than that of the larger ones,probably due to the assumption that the coarsening mode could decrease the interface tension more quickly.展开更多
The mechanism of phase inversion emulsification process (PIE) was studied for waterborne dispersion of highly viscous epoxy resin using non-ionic polymeric surfactants. Drop deformation and breakup, Theological proper...The mechanism of phase inversion emulsification process (PIE) was studied for waterborne dispersion of highly viscous epoxy resin using non-ionic polymeric surfactants. Drop deformation and breakup, Theological properties, conductivity, and particle size measurements reveal the micro-structural transition amid emulsification. It is revealed that strong flow causes water drop to burst with the formation of droplets and huge interface. Phase inversion corresponds to an abrupt rheological transition from a type of viscous melt with weak elasticity to a highly elastic type of aqueous gel. This implies that the phase inversion equivalent to a curvature inversion. Based on this, a geometric model is postulated to correlate process variables to the particle size. The coverage and conformation of the surfactant plays key role for the particle size of the final emulsion. The interactions of thermodynamic and hydrodynamic effects are also discussed. It is concluded that the thermodynamics control the PIE while the hydrodynamics drives the creation of interface and involves every step of PIE.展开更多
Acceptance ratio method, which has been used to calculate the depletion potential in binary hard-sphere mixtures, is extended to the computation of the depletion potential of non-rigid particle systems. The repulsive ...Acceptance ratio method, which has been used to calculate the depletion potential in binary hard-sphere mixtures, is extended to the computation of the depletion potential of non-rigid particle systems. The repulsive part of the Lennard-Jones pair potential is used as the direct pair potential between the non-rigid particles. The depletion potential between two big spheres immersed in a suspension of small spheres is determined with the acceptance ratio method through the application of Monte Carlo simulation. In order to check the validity of this method, our results are compared with those obtained by the Asakura-Oosawa approximation, and by Varial expansion approach, and by molecular dynamics simulation. The total effective potential and the depth of its potential well are computed for various softness parameters of the direct pair potential.展开更多
The self-consistent field theory (SCFT) based upon coarse-grained model is especially suitable for investigating thermodynamic equilibrium morphology and the phase diagram of inhomo-geneous polymer systems subjected t...The self-consistent field theory (SCFT) based upon coarse-grained model is especially suitable for investigating thermodynamic equilibrium morphology and the phase diagram of inhomo-geneous polymer systems subjected to phase separation. The advantage of this model is that the details of the chain such as the architecture of the chain and the sequence of blocks can be consid-ered. We present here an overview of SCFT approach and its applications in polymeric systems. In particular, we wish to focus on our group’s achievements in applications of SCFT in such fields: simulation of microphase separation morphologies of multiblock copolymers with a complex molecular architecture, interactions between brush-coated sheets in a polymer matrix, mixtures of flexible poly-mers and small molecular liquid crystals at the interface, shapes of polymer-chain-anchored fluid vesicles, self-assembled morphologies of block copolymers in dilute solution, and so on. Finally, the further developments as well as the perspective applications of SCFT are discussed.展开更多
Much attention has been paid to the natural mechanism of silkworm spinning due to the impressive me-chanical properties of the natural fibers. In this work, we studied the effect of Cu(II) ions on the secondary struct...Much attention has been paid to the natural mechanism of silkworm spinning due to the impressive me-chanical properties of the natural fibers. In this work, we studied the effect of Cu(II) ions on the secondary structure of Bombyx mori regenerated silk fibroin (SF) in dilute solution by circular dichroism (CD). The results indicate that a given amount of Cu(II) induces the SF conformational transition from random coil to β-sheet, however, further addition of Cu(II) is unfavorable for this conversion. Meanwhile, the conformational changes induced by Cu(II) follow a nuclea-tion-dependent aggregation mechanism, which is similar to that found in Prion protein (PrP) denaturation and Aβ-pep- tide aggregations, leading to the neurodegenerative disease. This work would help one understand further the natural spinning process of silkworm. Additionally, it would be sig-nificant for the study of the nervous system diseases, because silk fibroin, extracted in large amounts from Bombyx mori silkworm gland, could be a proper model to study PrP dena-turation and Aβ-peptide aggregations.展开更多
The cure-induced phase separation processes of various thermoplastics(TP)-modified thermosetting systems which show upper critical solution temperature(UCST)or lower critical solution temperature(LCST)were studied wit...The cure-induced phase separation processes of various thermoplastics(TP)-modified thermosetting systems which show upper critical solution temperature(UCST)or lower critical solution temperature(LCST)were studied with emphasis on the temperature dependency of the phase separation time and its potential application in the cure time-temperature processing window.We found that the phase separation time/temperature relationship follows the simple Arrhenius equation.The cure-induced phase separation activation energy E_(a)(ps)generated from the linear fitting of the Arrhenius equation is irrelevant to the detection means of phase separation time.We also found that E_(a)(ps)is insensitive to TP content,TP molecular weight and curing rate,but it changes with the cure reaction kinetics and the chemical environment of the systems.With the established phase separation time-temperature dependence relation,we can easily establish the whole cure time-temperature transformation(TTT)diagram with morphology information which is a useful map for the TP/TS composites processing industry.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant Nos 20403010 and 10335070) and the Science and Technology Commission of Shanghai Municipality (Grant Nos 0352nm116 and 0452nm007).
基金supported by the National Natural Science of Foundation of China(NSFC)(Nos.20674014, 20425415,20274010,50103003,20221402)
文摘The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns(2D TRLS) has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in which the secondary phase separation takes place.The results of the 2D TRLS provided more detailed information that was not readily observed in the 1D TRLS patterns.(i) During the first process of phase separation,the sequential order of coarsening in size of the domains among the larger and smaller ones has been reversed between the diffusion regime and the hydrodynamic regime. (ii) The change of the larger domains in size,due to the hydrodynamic flow in the late stage of the first phase separation process,keeps on taking place earlier than that of the new domains appeared in the secondary phase separation process. (iii) During the secondary phase separation process the size growth of the smaller domains takes place earlier than that of the larger ones,probably due to the assumption that the coarsening mode could decrease the interface tension more quickly.
基金This project was supported by the National Natural Science Foundation of China (No. 20490220)Major State Basic Research Projects (No. 2003CB615604), Shengli Oilfield, SINOPEC.
文摘The mechanism of phase inversion emulsification process (PIE) was studied for waterborne dispersion of highly viscous epoxy resin using non-ionic polymeric surfactants. Drop deformation and breakup, Theological properties, conductivity, and particle size measurements reveal the micro-structural transition amid emulsification. It is revealed that strong flow causes water drop to burst with the formation of droplets and huge interface. Phase inversion corresponds to an abrupt rheological transition from a type of viscous melt with weak elasticity to a highly elastic type of aqueous gel. This implies that the phase inversion equivalent to a curvature inversion. Based on this, a geometric model is postulated to correlate process variables to the particle size. The coverage and conformation of the surfactant plays key role for the particle size of the final emulsion. The interactions of thermodynamic and hydrodynamic effects are also discussed. It is concluded that the thermodynamics control the PIE while the hydrodynamics drives the creation of interface and involves every step of PIE.
基金Project supported by the National Natural Science Foundation of China (Grant No. 20974026)the Shanghai Pujiang Program of China (Grant No. 08PJ1402000)the Shanghai Educational Development Foundation of China (Grant No. 2008CG02)
文摘Acceptance ratio method, which has been used to calculate the depletion potential in binary hard-sphere mixtures, is extended to the computation of the depletion potential of non-rigid particle systems. The repulsive part of the Lennard-Jones pair potential is used as the direct pair potential between the non-rigid particles. The depletion potential between two big spheres immersed in a suspension of small spheres is determined with the acceptance ratio method through the application of Monte Carlo simulation. In order to check the validity of this method, our results are compared with those obtained by the Asakura-Oosawa approximation, and by Varial expansion approach, and by molecular dynamics simulation. The total effective potential and the depth of its potential well are computed for various softness parameters of the direct pair potential.
基金This work was supported by the National Basic Research Program of China (Grant No. 2005CB623800) the National Natural Science Foundation of China (Grant Nos. 20474012, 20374016 & 20104002)This review was recommended by Prof.Li Lemin,member of editorial of Science in China.
文摘The self-consistent field theory (SCFT) based upon coarse-grained model is especially suitable for investigating thermodynamic equilibrium morphology and the phase diagram of inhomo-geneous polymer systems subjected to phase separation. The advantage of this model is that the details of the chain such as the architecture of the chain and the sequence of blocks can be consid-ered. We present here an overview of SCFT approach and its applications in polymeric systems. In particular, we wish to focus on our group’s achievements in applications of SCFT in such fields: simulation of microphase separation morphologies of multiblock copolymers with a complex molecular architecture, interactions between brush-coated sheets in a polymer matrix, mixtures of flexible poly-mers and small molecular liquid crystals at the interface, shapes of polymer-chain-anchored fluid vesicles, self-assembled morphologies of block copolymers in dilute solution, and so on. Finally, the further developments as well as the perspective applications of SCFT are discussed.
文摘Much attention has been paid to the natural mechanism of silkworm spinning due to the impressive me-chanical properties of the natural fibers. In this work, we studied the effect of Cu(II) ions on the secondary structure of Bombyx mori regenerated silk fibroin (SF) in dilute solution by circular dichroism (CD). The results indicate that a given amount of Cu(II) induces the SF conformational transition from random coil to β-sheet, however, further addition of Cu(II) is unfavorable for this conversion. Meanwhile, the conformational changes induced by Cu(II) follow a nuclea-tion-dependent aggregation mechanism, which is similar to that found in Prion protein (PrP) denaturation and Aβ-pep- tide aggregations, leading to the neurodegenerative disease. This work would help one understand further the natural spinning process of silkworm. Additionally, it would be sig-nificant for the study of the nervous system diseases, because silk fibroin, extracted in large amounts from Bombyx mori silkworm gland, could be a proper model to study PrP dena-turation and Aβ-peptide aggregations.
文摘The cure-induced phase separation processes of various thermoplastics(TP)-modified thermosetting systems which show upper critical solution temperature(UCST)or lower critical solution temperature(LCST)were studied with emphasis on the temperature dependency of the phase separation time and its potential application in the cure time-temperature processing window.We found that the phase separation time/temperature relationship follows the simple Arrhenius equation.The cure-induced phase separation activation energy E_(a)(ps)generated from the linear fitting of the Arrhenius equation is irrelevant to the detection means of phase separation time.We also found that E_(a)(ps)is insensitive to TP content,TP molecular weight and curing rate,but it changes with the cure reaction kinetics and the chemical environment of the systems.With the established phase separation time-temperature dependence relation,we can easily establish the whole cure time-temperature transformation(TTT)diagram with morphology information which is a useful map for the TP/TS composites processing industry.