We considered two model systems of star-branched polymers near an impenetrable surface. The model chains were constructed on a simple cubic lattice. Each star polymer consisted of f = 3 arms of equal length and the total number of segments was up to 799. The excluded volume effect was included into these models only and therefore the system was studied at good solvent conditions. In the first model system polymer chain was terminally attached with one arm to the surface. The grafted arm could slide along the surface. In the second system the star-branched chain was adsorbed on the surface and the strength of adsorption was were varied. The simulations were performed using the dynamic Monte Carlo method with local changes of chain conformations. The internal and local structures of a polymer layer were determined. The lateral diffusion and internal mobility of star-branched chains were studied as a function of strength of adsorption and the chain length. The lateral diffusion and internal mobility of star-branched chains were studied as a function of strength of adsorption and the chain length. It was shown that the behavior of grafted and weakly adsorbed chains was similar to that of a free three-dimensional polymer, while the strongly adsorbed chains behave as a two-dimensional system. 相似文献
A model polymer network was constructed from branched chains. Each chain was built on a simple cubic lattice forming a star-branched polymer consisting of f = 3 arms of equal lengths. The fragment of network under consideration consisted of 1, 2 and 3 star polymers with different topology of connections. The only potential used was excluded volume (athermal chains). The properties of the network were determined by the means of computer simulations using the classical Metropolis sampling algorithm (local micromodifications of chain conformation). The behaviour of linear chains of the same molecular weight was also studied as a state of reference. The influence of attaching the next star-branched chain to the network on its static and dynamic properties was studied. The short-time dynamic behaviour of chain fragments was determined and discussed. 相似文献
Monte Carlo simulations of simple models of star-branched polymers were carried out. The model chains were confined to simple cubic lattice and consisted of f = 3 branches of equal length and the total number of polymer segments as well as the density of grafted chains on the surface were varied. The chains have had one arm end attached to an impenetrable plate. The simulations were performed by employing the set of local micromodifications of the chain conformations. The model chains were athermal, i.e. good solvent conditions were modeled, the excluded volume effect was present at the model. The density of grafted chains on the surface was varied from a single chain up to 0.3. The static and dynamic properties of the system were studied. The influence of polymer concentration as well as the polymer length on static and dynamic properties of the system studied was shown. The relation between the structure and short-time dynamics (relaxation times) was discussed. 相似文献
We show that Shaffer's version of the bond fluctuation model can be used to simulate three‐arm star polymers. We report a simulation study of both single stars and melts of star polymers with arm lengths up to 90 monomer units (approximately twice the entanglement crossover length for linear chains). Center‐of‐mass self‐diffusion of single stars is Rouse‐like (D ˜ N–1). Due to a limited range of molecular weights we cannot distinguish between a power‐law and an exponential dependence of the star‐melt self‐diffusion coefficient on arm length. 相似文献
A coarse-grained model of star-branched polymer chains confined in a slit was studied. The slit was formed by two parallel impenetrable surfaces, which were attractive for polymer beads. The polymer chains were flexible homopolymers built of identical united atoms whose positions in space were restricted to the vertices of a simple cubic lattice. The chains were regular star polymers consisted of f = 3 branches of equal length. The chains were modeled in good solvent conditions and, thus, there were no long-range specific interactions between the polymer beads-only the excluded volume was present. Monte Carlo simulations were carried out using the algorithm based on a chain's local changes of conformation. The influence of the chain length, the distances between the confining surfaces, and the strength of the adsorption on the properties of the star-branched polymers was studied. It was shown that the universal behavior found previously for the dimension of chains was not valid for some dynamic properties. The strongly adsorbed chains can change their position so that they swap between both surfaces with frequency depending on the size of the slit and on the temperature only. 相似文献
In the first paper of the series, a statistical model for star-branched polycondenzation of AB type monomers in the presence of a polyfunctional agent RAf was completely developed. The analytical expressions obtained for the number-average (D̄P̄n̄) and weight-average (D̄P̄w̄) degree of polymerization, and the dispersion index (D) for whole polymer species, linear and star macromolecular chains, are now derived as function of the feed and of end-group analysis. Also the important molecular parameter, mole fraction of star-branched polymer, can be evaluated. Some numerical examples are presented. It is illustrated that the molecular weight properties of the linear and star-branched polymers in the mixture of the products, very important factors for the application of this kind of polymeric materials, can be determined starting from the feed and terminal group analysis. Polymerization and oligomerization of 6-aminocaproic acid were carried out in the presence of trimesic (T3) acid and 2,2,6,6-tetra(β-carboxyethyl)cyclohexanone (T4) and EDTA as tri- and terra-functional agents. The molecular weights calculated are in good agreement with those obtained by Size Exclusion Chromatography (SEC), end group analysis and NMR spectra. 相似文献
The simple cubic‐lattice model of polymer chains was used to study the dynamic properties of adsorbed, branched polymers. The model star‐branched chains consisted of f = 3 arms of equal lengths. The chain was modeled with excluded volume, that is, in good solvent conditions. The only interaction assumed was a contact potential between polymer segments and an impenetrable surface. This potential was varied to cover both weak and strong adsorption regimes. The classical Metropolis sampling algorithm was used for models of star‐branched polymers in order to calculate the dynamic properties of adsorbed chains. It was shown that long‐time dynamics (diffusion constant) and short‐time dynamics (the longest relaxation time) were different for weak and strong adsorption. The diffusion of weakly adsorbed chains was found to be qualitatively the same as for free nonadsorbed chains, whereas strongly adsorbed chains behaved like two‐dimensional polymers. The time‐dependent properties of structural elements such as tails, loops, and trains were also determined.
The mean lifetimes of tails, loops, and trains versus the bead number for the chain with N = 799 beads for the case of the weak adsorption εa = −0.3. 相似文献
A simple model of branched polymers in confined space is developed. Star‐branched polymer molecules are built on a simple cubic lattice with excluded volume and no attractive interactions (good solvent conditions). A single star molecule is trapped in a network of linear polymer chains of restricted mobility. The simulations are carried out using the classical Metropolis algorithm. Static and dynamic properties of the star‐branched polymer are determined using various networks. The dependence of the longest relaxation time and the self‐diffusion coefficient on chain length and network properties are discussed and the proper scaling laws formulated. The possible mechanism of motion is discussed. The differences between the motion of star‐branched polymers in such a network are compared with the cases of a dense matrix of linear chains and regular rod‐like obstacles. 相似文献
We studied the properties of simple models of linear and star-branched polymer chains confined in a slit. The polymer chains were built of united atoms and were restricted to a simple cubic lattice. Two macromolecular architectures of the chain linear and star-branched with three branches (of equal length) were studied. The excluded volume was the only potential introduced into the model and thus, the system was athermal. The chains were put between two parallel and impenetrable surfaces. Monte Carlo simulations with a sampling algorithm based on chain’s local changes of conformation were carried out. The differences and similarities in the global size and the structure and of linear and star-branched chains were shown and discussed. 相似文献
A uniform star-branched polymer model with f = 3 arms based on a simple cubic lattice was studied by means of the dynamic Monte Carlo method. The model chain is athermal with excluded-volume interactions and it is flexible. A new type of local micromodification was introduced to make the branching point movable. Static properties of the star polymer are in accordance with other theoretical predictions and experimental evidence. Scaling of the self diffusion constant and the terminal relaxation times is close to those of the Rouse theory and to simulation results of linear chains. 相似文献
Simulations of simple models of polymer chains were carried out by the means of the dynamic Monte Carlo method. The model chains were confined to a simple cubic lattice. Three different chain architectures were studied: linear, star‐branched and ring chains. The polymer model chain interacted with an impenetrable surface with a simple contact attractive potential. It was found that size parameters of all these polymers obey scaling laws. The temperatures of the transitions from weakly to strongly adsorbed chain were determined. It was shown for weakly adsorbed chains that ring polymers are always ca. 50% more adsorbed than linear and star‐branched ones. The properties of adsorbed linear and star‐branched polymers are very similar in the length of chain and the strength of adsorption studied. Strongly adsorbed ring polymers are still more adsorbed but differences between all kinds of chains become less pronounced. 相似文献
By use of the pivot algorithm, star-branched chains with F = 4, 8 and 12 arms of length n and linear chains (F = 2) are generated on a tetrahedral lattice (120 ≤ nF ≤ 3 840). By taking into account nearest neighbour interactions (each contact contributes an energy ϕ kT to the total energy of the configuration) a variation of the thermodynamic quality of the solvent is simulated by a variation of the energy parameter ϕ near the value of ϕθ = -0,475, characteristic of theta-conditions. For theta-conditions various quantities characteristic of the instantaneous shape of polymers exhibit similar values as found for nonreversal random walks; furthermore, while linear theta-chains are slightly less asymmetric than athermal ones, the opposite behaviour is found for star-branched polymers. Clearly, for all thermodynamic conditions the asymmetry of configurations decreases with increasing number of arms but remains appreciable even for F = 12. 相似文献
We apply the tube model to a specific problem in polymer melt dynamics - the rheology of star polymers as an additive to a monodisperse linear matrix. We find that the tube dilation picture of constraint release may be applied to the relaxation of the star fraction. There are four qualitatively different cases depending on the relative concentrations and relaxation times of the two fractions. Terminal relaxation times and relaxation spectra are calculated for each case and compared with available experimental data. The existence of a modified Rouse relaxation such that G(t)∼t−3/2 is argued. 相似文献
Cooperative motion algorithm (CMA) is applied to simulate properties of polymer stars in dense systems which are considered as representations of polymer melts. Effects of arm number and arm length of stars on static and dynamic properties of model systems are analysed. Static properties are characterised by star sizes and their spatial correlations. Dynamic properties describing arm orientation relaxation and translational motion of stars are presented. Results indicate strong ordering effects for multiarm stars in the melt and suggest that the terminal relaxation of star melts can alternatively be controlled by arm orientation relaxation or by cooperative star translations depending in the two parameters of star structure i.e. arm length and arm number. 相似文献
Molecular dynamics simulations (dissipative particle dynamics–DPD) were developed and used to quantify wall-normal migration of polymer chains in microchannel Poseuille flow. Crossflow migration due to viscous interaction with the walls results in lowered polymer concentration near the channel walls. A larger fraction of the total flow volume becomes depleted of polymer when the channel width h decreases into the submicron range, significantly reducing the effective viscosity. The effective viscosity was quantified in terms of channel width and Weissenberg number Wi, for 5% polymer volume fraction in water. Algebraic models for the depletion width δ(Wi, h) and effective viscosity μe(δ/h, Wi) were developed, based on the hydrodynamic theory of Ma and Graham and our simulation results. The depletion width model can be applied to longer polymer chains after a retuning of the polymer persistence length and the corresponding potential/thermal energy ratio. 相似文献
This paper presents a modeling-based approach to the prediction of the molar mass distribution of the various species in a star-branched polycondensation mixture. The interpretation of experimental SEC data of the mixture of linear, cyclic and star-branched molecules is not straightforward, because of the different sizes of those molecules (having the same molecular mass). Therefore we have opted to use SEC analysis with only a concentration detector and fit the experimental data to the theoretical mass distribution, corrected for the volume of the various molecules. This allows the relative fraction and the distribution of the various species in the mixture (linear, cyclic and star-branched) to be determined. To demonstrate this, the six-arm star-branched poly-epsilon-caprolactam based on the six-functional coupling molecule, hexa(6-caproic acid) melamine has been analyzed. Five polymer mixtures with different initial concentration of coupling molecule have been synthesized. As the initial concentration of coupling molecule increased, we found that the weight fraction of star-branched molecules increased, while the weight fraction of linear and cyclic molecules decreased. We also found that the weight-average molar mass and the arm length decrease as the initial fraction of the coupling molecule increases. 相似文献