MEAN-SQUARE RADIUS OF GYRATION AND DIPOLE MOMENT OF POLY(METHYLPHENYLSILOXANE) CHAINS

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...

STUDY ON MEAN-SQUARE RADIUS OF GYRATION FOR POLYALKYLENEOXIDES

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).

ROLE AND IMPORTANCE OF RADIUS OF GYRATION OF CHAINS IN THE MELT IN THE CRYSTALIZATION OF POLY(1-BUTENE)

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.

DIMENSIONS OF ATACTIC POLY(α-METHYLSTYRENE)CHAINS WITH SIDE GROUPS

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.

SOLVENT QUALITY AND SOLUTION BEHAVIOR OF NYLON 12

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.

Movement Patterns of the Eastern Chipmunk (<i>Tamias striatus</i>) in Four Fragmented Landscapes of Prince Edward Island, Canada

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 (Tamias striatus) 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.

THE PROPERTIES OF A SINGLE POLYMER CHAIN IN SOLVENT CONFINED IN A SLIT: A MOLECULAR DYNAMICS SIMULATION

A single polymer chain in solvent confined in a slit formed by two parallel plates is studied by using molecular dynamics simulation method. The square radii of gyration and diffusion behaviors of polymers are greatly affected by the distance between the two plates, but they do not follow the same way. The chain size decays drastically with increasing h （h is the distance between two plates）, until a basin occurs, and a universal h/（Rg）o dependence for polymer chains with different degrees of polymerization can be obtained. While, for the chain＇s diffusion coefficient, it decays monotonously and there is no such basin-like behavior. Furthermore, we studied the radial distribution function of confined polymer chains to explain the reason why there is a difference for the decay behaviors between dynamic properties and static properties. Besides, we also give the degree of confinement dependence of the static scaling exponent for a single polymer chain. Our work provides an efficient way to estimate the dynamics and static properties of confined polymer chains, and also helps us to understand the behavior of polymer chains under confinement.

Theoretical Interpretation of Conformation Variations of Polydimethylsiloxane Induced by Nanoparticles

There has been controversy as to whether the addition of nanoparticles to a polymer melt causes perturbed chain structure of polymers. In this work, the chain conformations of polydimethylsiloxane（PDMS） with addition of polyhedral oligomeric silsesquioxane（POSS） nanoparticles have been studied using a classical density functional approach. Under the strong interactions of POSS-PDMS, the radius of gyration of PDMS in the nanocomposites can either increase or decline depending on particle loading. After adding nanoparticles with larger size or weaker interactions, both the increasing and the declining amplitudes can be largely suppressed. The results provide a deep understanding of chain conformation in polymer nanocomposites.

Molecular size characterization of heavy oil fractions in vacuum and solution by molecular dynamic simulation

Two kinds of heavy oils were fractionated into eight fractions by Liquid-Solid Adsorption Chromatography,respectively,and samples were collected to measure properties.According to the elemental analysis,molecular weight and 1H-NMR data,average molecular structures of polycyclic aromatic and heavy resin were constructed with improved Brown-Ladner(B-L)method and several corrections.And then,the most stable conformations of polycyclic aromatic and heavy resin in vacuum and toluene solution were obtained by molecular dynamic simulation,and the molecular size was gotten via the radius of gyration analysis.The results showed that the radius of gyration of polycyclic aromatic and heavy resin was 0.55-0.70 nm in vacuum and 0.60-0.90 nm in toluene solution.With molecular weight increasing,the molecular size in vacuum and toluene solution also increased.Due to the swelling behavior of solvent,the alkyl side chains of heavy oil molecule in solution were more stretched.Thus,the molecular size in toluene solution was larger than that in vacuum.