Taking account of the effect ale heteroatoms iq backbone, this article dealt with the mean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebra in accordance with the rotational isomeric st...Taking account of the effect ale heteroatoms iq backbone, this article dealt with the mean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebra in accordance with the rotational isomeric state model, Numerical calculation with the parameters available in the literatures indicated that the dependence of [S-2] on the molecular weight can be expressed by the general formula: [S-2]=aM(b).展开更多
Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechan...Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.展开更多
The mean-square radius of gyration <S^2>,the mean-square dipole moment <D^2>,the mean-square end-to-end distance <R^2> and their temperature coefficients of unsymmetrical disubstituted poly(methylphe...The mean-square radius of gyration <S^2>,the mean-square dipole moment <D^2>,the mean-square end-to-end distance <R^2> and their temperature coefficients of unsymmetrical disubstituted poly(methylphenylsiloxane) (PMPS) chains, as a function of stereochemical structure,confomational energies and length of polymers,were studied by using an improved configurational-confomational statistical method based on the rotational-isomeric-state theory.It is found that the increase in isotacticity of P...展开更多
An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side group...An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side groups is considered. The deduced formulas, based on the rotational isomer state theory, are used to investigate the configuration-dependent properties of the atactic polymer chain, and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated. For the fraction of meso dyads Wm= 0.4, the dependence of the radius of gyration Rg and the intrinsic viscosity [η] on the molecule mass M are Rg = 2.63×10^-2 M^0.50 nm and [η] = 7.36 × 10^-2 M^0.497, respectively, which are in agreement with the previous experimental data for the PαMS samples. A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains. The Rg increases linearly with the temperature T, and the effects of the chain length and the tacticity on the temperature coefficient are remarkable. These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.展开更多
The unperturbed dimension and temperature character of poly(dibenzyl itaconate)s (PDBzI) are studied by a revised rotational isomeric state (RIS) method. The improved formulas of the mean-square radius of gyration, de...The unperturbed dimension and temperature character of poly(dibenzyl itaconate)s (PDBzI) are studied by a revised rotational isomeric state (RIS) method. The improved formulas of the mean-square radius of gyration, deduced by the pseudo-stereochemical equilibrium approach, may be used to investigate the configurational-conformational properties of atactic polymers with large side groups [poly(itaconates) for instance]. The calculated results showed that poly(itaconates) have larger dimension of the molecule than other vinyl polymers. Comparison of the dimension between considering and without considering side groups showed that the effect of large side groups on the unperturbed dimension for short-chain polymers is more obvious than that of long-chain polymers and, if the dimension of side groups increases, the effect also increases. The dimension differences of PDBzI between short-chain and long-chain polymers are investigated by the relation of characteristic ratios and temperature coefficients with temperature. Moreover, the dependence between the temperature coefficients and the tacticity of chains shows that the temperature characters of the isotactic, syndiotactic and atactic PDBzI chains have remarkable difference.展开更多
The refractive index increment, dynamic and static laser light scattering, intrinsic viscosity [η] and Huggins constant （KH） of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60℃. Th...The refractive index increment, dynamic and static laser light scattering, intrinsic viscosity [η] and Huggins constant （KH） of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60℃. The intrinsic viscosity, Rn, Rg, A2, and （〈 S 〉2）^1/2 （calculated from viscosity data） and ＂a＂ values of nylon 12 are found to be higher in m-cresol than in sulphuric acid. All these parameters decrease with the increase in water contents in sulphuric acid. The refractive index increment, KH and activation energy show an opposite trend to that of [η]. The intrinsic viscosity, RH, Rg, A2, and （〈 S 〉2）^1/2 have maximum values around 30-40℃ in sulphuric acid/water system, whereas in m-cresol they fall at about 20℃. It has been concluded that the variation in size, interaction parameter （second virial coefficient）, [η] and KH of the polymer solutions with the alteration in solvent composition and temperature are the out come of change in thermodynamic quality of solvents, selective adsorption, hydrogen bonding and conformational transitions. It has also been concluded that the increase in temperature first enhances the quality of the solvent, encourages hydrogen bonding and specific adsorption, and then deteriorates, bringing conformational transitions in the polymer molecules. However, the addition of water to sulphuric acid continuously deteriorates the solvent quality. This characteristic of the solvent system brings conformational changes in the polymer especially at low temperatures.展开更多
The method of synchrotron radiation small-angle X-ray scattering (SR-SAXS) has been used to obtain structural information on the system of bis (2-ethylhexyl) sulfosuccinate (AOT)/H2O/isooctane. By using the Guinier pl...The method of synchrotron radiation small-angle X-ray scattering (SR-SAXS) has been used to obtain structural information on the system of bis (2-ethylhexyl) sulfosuccinate (AOT)/H2O/isooctane. By using the Guinier plot (Ln I (q) versus q(2)) on the data sets in a defined small q range (0.03-0.06 Angstrom (-1)), the gyration radius at different water/surfactant molar ratio, W-0, was obtained. With the increase of W-0, the gyration radius (R-g) increased at the range of 23.2 similar to 52.7 Angstrom.展开更多
The analysis of animal movement patterns can provide important information on animals’ responses to habitat features. In this study, the movement paths of eastern chipmunks (<em>Tamias striatus</em>) were...The analysis of animal movement patterns can provide important information on animals’ responses to habitat features. In this study, the movement paths of eastern chipmunks (<em>Tamias striatus</em>) were examined in four landscapes, with different levels of habitat fragmentation, using either fluorescent powdering or spool-and-line tracking. Descriptions of the tree and ground vegetation communities were performed in the vicinity of the trail to obtain information on habitat use and habitat selection. Several key movement variables were calculated, including the total path length, net distance, fractal dimension, and radius of gyration. Despite statistically significant differences in some of the movement metrics between the four landscapes, the overall movement patterns were generically the same for all of chipmunk paths examined in this study. The data were compared to trends expected based on random or correlated random walks, as well as Lévy-walk models. The mean squared net displacement did not support the correlated random walk predictions, except at smaller spatial scales, but overall demonstrated Lévy-like super diffusive behaviour. Lévy-like patterns were also confirmed from the move-length distributions that demonstrated truncated-tail power-law behaviour. Although this would suggest invariance of the movement patterns at all spatial scales studied, fractal analysis revealed at least two transitions in movement patterns at scales of around 2 and 5 m. The transition point at 2 m was negatively correlated with the density of small trees, while the transition at ~5 m was positively correlated with the spatial distribution of large trees. As the habitat-preference data showed that small trees are among the least preferred habitat component, while large trees were among the most preferred habitat, chipmunks are likely to alter their movement behaviour to avoid small trees, and attracted towards large trees possibly to avoid predators. Overall, we determined three principal domains of movement: at smaller spatio-temporal scales, foraging activities dominate and the movement is highly correlated but also random;at intermediate spatial scales, chipmunks may be moving to avoid predators, using different environmental cues, and the movement is more directed (but still influenced by vegetation patterns at intermediate scales);at larger spatio-temporal scales, the movement is dominated by long-range/long-term memory and homing to burrows and other key habitat features, such as food caches, drives more directed movement. The fact that scale-dependent movement mechanisms could give rise to LW patterns is consistent with recent studies.展开更多
This work deals with the dependence of the z-average mean-square radius of gyration (<R 2> z) on the degree of branching(DB) for highly branched copolymers made from the one-pot cocondensation of AB 2 and AB mon...This work deals with the dependence of the z-average mean-square radius of gyration (<R 2> z) on the degree of branching(DB) for highly branched copolymers made from the one-pot cocondensation of AB 2 and AB monomers. A new expression of the degree of branching has been derived. The DB monotonously increases with increasing A group conversion and the fraction of AB 2 monomers. The value of DB calculated in accordance with our formula is lower than that given by Frey and coworkers. Howerver, when the reaction approaches completion, our expression of the degree of branching degenerates into the equation reported by Frey. Furthermore, the z-average mean-square of gyration of the resulting copolymer in the Θ state has been derived on the basis of the classical work developed by Stockmayer, Gordon, Li and Ba. The relationship between DB and <R 2> z is illustrated by numerical results. The z-average mean-square radius of gyration of the copolymer with a certain weight-average molecular weight monotonously decreases with increasing the degree of branching.展开更多
基金This work was supported by the National Natural Science Foundation of China
文摘Taking account of the effect ale heteroatoms iq backbone, this article dealt with the mean-square radii of gyration of polyalkyleneoxides by the approach of matrix algebra in accordance with the rotational isomeric state model, Numerical calculation with the parameters available in the literatures indicated that the dependence of [S-2] on the molecular weight can be expressed by the general formula: [S-2]=aM(b).
基金This work was supported by the Deutsche Forschungsgemeinschall and der Chemischen Industrierate, Alexander von Humboldt Stiffeng and the China National Distinguished Young Investigator Fund (No. 29925413).
文摘Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.
基金supported by the National Basic Research Program (973) of China (No.10574109)the Zhejiang Provincial Science and Technology Department (No.2007G60G1120019)+1 种基金National Science Foundation of Zhejiang Province (No.Y604064)Zhejiang Gongshang University (No.08-13),China.
文摘The mean-square radius of gyration <S^2>,the mean-square dipole moment <D^2>,the mean-square end-to-end distance <R^2> and their temperature coefficients of unsymmetrical disubstituted poly(methylphenylsiloxane) (PMPS) chains, as a function of stereochemical structure,confomational energies and length of polymers,were studied by using an improved configurational-confomational statistical method based on the rotational-isomeric-state theory.It is found that the increase in isotacticity of P...
文摘An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly（α-methylstyrene）（PαMS） chains is studied, in which the effect of large side groups is considered. The deduced formulas, based on the rotational isomer state theory, are used to investigate the configuration-dependent properties of the atactic polymer chain, and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated. For the fraction of meso dyads Wm= 0.4, the dependence of the radius of gyration Rg and the intrinsic viscosity [η] on the molecule mass M are Rg = 2.63×10^-2 M^0.50 nm and [η] = 7.36 × 10^-2 M^0.497, respectively, which are in agreement with the previous experimental data for the PαMS samples. A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains. The Rg increases linearly with the temperature T, and the effects of the chain length and the tacticity on the temperature coefficient are remarkable. These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.
基金Project supported by the National Basic Research Program (973) of China (No. 10574109)the Zhejiang Provincial Science and Technology Department (No. 2005C24008)the Natural Science Foundation of Zhejiang Province (No. Y604064), China
文摘The unperturbed dimension and temperature character of poly(dibenzyl itaconate)s (PDBzI) are studied by a revised rotational isomeric state (RIS) method. The improved formulas of the mean-square radius of gyration, deduced by the pseudo-stereochemical equilibrium approach, may be used to investigate the configurational-conformational properties of atactic polymers with large side groups [poly(itaconates) for instance]. The calculated results showed that poly(itaconates) have larger dimension of the molecule than other vinyl polymers. Comparison of the dimension between considering and without considering side groups showed that the effect of large side groups on the unperturbed dimension for short-chain polymers is more obvious than that of long-chain polymers and, if the dimension of side groups increases, the effect also increases. The dimension differences of PDBzI between short-chain and long-chain polymers are investigated by the relation of characteristic ratios and temperature coefficients with temperature. Moreover, the dependence between the temperature coefficients and the tacticity of chains shows that the temperature characters of the isotactic, syndiotactic and atactic PDBzI chains have remarkable difference.
文摘The refractive index increment, dynamic and static laser light scattering, intrinsic viscosity [η] and Huggins constant （KH） of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60℃. The intrinsic viscosity, Rn, Rg, A2, and （〈 S 〉2）^1/2 （calculated from viscosity data） and ＂a＂ values of nylon 12 are found to be higher in m-cresol than in sulphuric acid. All these parameters decrease with the increase in water contents in sulphuric acid. The refractive index increment, KH and activation energy show an opposite trend to that of [η]. The intrinsic viscosity, RH, Rg, A2, and （〈 S 〉2）^1/2 have maximum values around 30-40℃ in sulphuric acid/water system, whereas in m-cresol they fall at about 20℃. It has been concluded that the variation in size, interaction parameter （second virial coefficient）, [η] and KH of the polymer solutions with the alteration in solvent composition and temperature are the out come of change in thermodynamic quality of solvents, selective adsorption, hydrogen bonding and conformational transitions. It has also been concluded that the increase in temperature first enhances the quality of the solvent, encourages hydrogen bonding and specific adsorption, and then deteriorates, bringing conformational transitions in the polymer molecules. However, the addition of water to sulphuric acid continuously deteriorates the solvent quality. This characteristic of the solvent system brings conformational changes in the polymer especially at low temperatures.
文摘The method of synchrotron radiation small-angle X-ray scattering (SR-SAXS) has been used to obtain structural information on the system of bis (2-ethylhexyl) sulfosuccinate (AOT)/H2O/isooctane. By using the Guinier plot (Ln I (q) versus q(2)) on the data sets in a defined small q range (0.03-0.06 Angstrom (-1)), the gyration radius at different water/surfactant molar ratio, W-0, was obtained. With the increase of W-0, the gyration radius (R-g) increased at the range of 23.2 similar to 52.7 Angstrom.
文摘The analysis of animal movement patterns can provide important information on animals’ responses to habitat features. In this study, the movement paths of eastern chipmunks (<em>Tamias striatus</em>) were examined in four landscapes, with different levels of habitat fragmentation, using either fluorescent powdering or spool-and-line tracking. Descriptions of the tree and ground vegetation communities were performed in the vicinity of the trail to obtain information on habitat use and habitat selection. Several key movement variables were calculated, including the total path length, net distance, fractal dimension, and radius of gyration. Despite statistically significant differences in some of the movement metrics between the four landscapes, the overall movement patterns were generically the same for all of chipmunk paths examined in this study. The data were compared to trends expected based on random or correlated random walks, as well as Lévy-walk models. The mean squared net displacement did not support the correlated random walk predictions, except at smaller spatial scales, but overall demonstrated Lévy-like super diffusive behaviour. Lévy-like patterns were also confirmed from the move-length distributions that demonstrated truncated-tail power-law behaviour. Although this would suggest invariance of the movement patterns at all spatial scales studied, fractal analysis revealed at least two transitions in movement patterns at scales of around 2 and 5 m. The transition point at 2 m was negatively correlated with the density of small trees, while the transition at ~5 m was positively correlated with the spatial distribution of large trees. As the habitat-preference data showed that small trees are among the least preferred habitat component, while large trees were among the most preferred habitat, chipmunks are likely to alter their movement behaviour to avoid small trees, and attracted towards large trees possibly to avoid predators. Overall, we determined three principal domains of movement: at smaller spatio-temporal scales, foraging activities dominate and the movement is highly correlated but also random;at intermediate spatial scales, chipmunks may be moving to avoid predators, using different environmental cues, and the movement is more directed (but still influenced by vegetation patterns at intermediate scales);at larger spatio-temporal scales, the movement is dominated by long-range/long-term memory and homing to burrows and other key habitat features, such as food caches, drives more directed movement. The fact that scale-dependent movement mechanisms could give rise to LW patterns is consistent with recent studies.
文摘This work deals with the dependence of the z-average mean-square radius of gyration (<R 2> z) on the degree of branching(DB) for highly branched copolymers made from the one-pot cocondensation of AB 2 and AB monomers. A new expression of the degree of branching has been derived. The DB monotonously increases with increasing A group conversion and the fraction of AB 2 monomers. The value of DB calculated in accordance with our formula is lower than that given by Frey and coworkers. Howerver, when the reaction approaches completion, our expression of the degree of branching degenerates into the equation reported by Frey. Furthermore, the z-average mean-square of gyration of the resulting copolymer in the Θ state has been derived on the basis of the classical work developed by Stockmayer, Gordon, Li and Ba. The relationship between DB and <R 2> z is illustrated by numerical results. The z-average mean-square radius of gyration of the copolymer with a certain weight-average molecular weight monotonously decreases with increasing the degree of branching.
