We discuss the computation of the third virial coefficient in polymer systems, focusing on an additional contribution absent in the case of monoatomic fluids. We determine the interpenetration ratio and several quantities that involve the third virial coefficient for star polymers with 4 and 6 arms in the good-solvent regime, in the limit of a large degree of polymerization.
A simulation technique is described for quantifying the contribution of three-body interactions to the thermodynamical properties of coarse-grained representations of complex fluids. The method is based on comparing the third virial coefficient $B_3$ for a complex fluid with that of an approximate coarse-grained model described by a pair potential. To obtain $B_3$ we introduce a new technique which expresses its value in terms of the measured volume-dependent asymptote of a certain structural function. The strategy is applicable to both Molecular Dynamics and Monte Carlo simulation. Its utilit…
The effects of solvent quality and core wetting on the circularization of star polymers
Università di Trento（特伦托大学）；INFN-TIFPA, Trento Institute for Fundamental Physics and Applications（意大利国家核物理研究所-特伦托基础物理与应用研究所）；University of Padova（帕多瓦大学）；INFN, Sezione di Padova（意大利国家核物理研究所帕多瓦分部）
The problem of demixing in the Asakura-Oosawa colloid-polymer model is considered. The critical constants are computed using truncated virial expansions up to fifth order. While the exact analytical results for the second and third virial coefficients are known for any size ratio, analytical results for the fourth virial coefficient are provided here, and fifth virial coefficients are obtained numerically for particular size ratios using standard Monte Carlo techniques. We have computed the critical constants by successively considering the truncated virial series up to the second, third, four…
We experimentally measure the osmotic pressures of linear polymers and three-, four-, and eight-arm star polymers in a good solvent via membrane osmometry. These results reveal that the osmotic equations of state in the star polymer solutions are universally described by the same scaling function that describes linear polymer solutions. This universality is achieved by canceling increasing overlap concentrations and decreasing osmotic pressure, owing to the increased arm number. We further clarify the molar mass and arm number dependencies of the gyration radius and interpenetration factor, en…
Star polymer is a typical nonlinear macromolecule possessing special thermodynamic behaviors for the existence of a jointing point. The thermodynamic transitions of a single star polymer are systematically studied with bond fluctuation model using Wang-Landau sampling technique. A new analysis method applying the shape factor is proposed to determine coil-globule (CG) and liquid-crystal (LC) transitions, which shows higher efficiency and precision than canonical specific heat function. It is found that the LC transition of star polymer at lower temperature obeys the identical scaling law as li…
Capillary filling of star polymer melts in nanopores
South China University of Technology（华南理工大学）；Max Planck Institute for Polymer Research（马克斯·普朗克聚合物研究所）；University of Ioannina（约阿尼纳大学）；Institute of Materials Science and Computing, University Research Center of Ioannina (URCI)（约阿尼纳大学研究中心材料科学与计算研究所）
Large scale Monte Carlo simulations of dense layers of grafted polymer chains in good solvent conditions are used to explore the relaxation of a polymer brush. Monomer displacements are analyzed for the directions parallel and perpendicular to the grafting plane. Auto-correlation functions of individual segments or chain sections are monitored as function of time. We demonstrate that the terminal relaxation time $τ$ of grafted layers well in the brush regime grows exponentially with degree of polymerization $N$ of the chains, $τ\propto N^{3}\exp(N/N_{e})$, with $N_{e}$ the entanglement degree …
We investigate the efficiency of gelation and network formation in telechelic star polymer melt, where the tips of polymer arms are dipoles while rest of the monomers are uncharged. Our work is motivated by the experimental observations [A.Kulkarni et.al, Macromolecules, {\bf 48}, 6580 (2015)], in which rheological studies of telechelic star polymers of poly-(L-actide), a bio-degradable polymer, showed a drastic increase in elastic properties (up to $2000$ times) compared to corresponding star polymers without the telechelic arm ends. In contrast to previous studies, we avoid using effective a…
Star polymer undergoes a transformation from a group of loosely coupled chains at low number of arms to a dense hairy colloid at their high number. This change affects solubility, aggregation and rheological behavior and is of much practical interest. We study the range of size and shape properties of the star molecule and of its individual arms upon this transformation. Theoretical calculations are based on a continuous chain model and are performed in the first order in $ε=4-d$. Computer simulations are done by the dissipative particle dynamics and in part by Monte Carlo method and the resul…
The escape transition of a polymer "mushroom" (a flexible chain grafted to a flat non-adsorbing substrate surface in a good solvent) occurs when the polymer is compressed by a cylindrical piston of radius $R$, that by far exceeds the chain gyration radius. At this transition, the chain conformation abruptly changes from a two-dimensional self-avoiding walk of blobs (of diameter $H$, the height of the piston above the substrate) to a "flower conformation", i.e. stretched almost one-dimensional string of blobs (with end-to-end distance $\approx R$) and an "escaped" part of the chain, the "crown"…
We describe a general simulation scheme for assessing the thermodynamic consequences of neglecting many-body effects in coarse-grained models of complex fluids. The method exploits the fact that the asymptote of a simple-to-measure structural function provides direct estimates of virial coefficients. Comparing the virial coefficients of an atomistically detailed system with those of a coarse-grained version described by pair potentials, permits the role of many-body effects to be quantified. The approach is applied to two models: (i) a size-asymmetrical colloid-polymer mixture, and (ii) a solu…
Polymeric films with greater impact and ballistic resistance are highly desired for numerous applications, but molecular configurations that best address this need remain subject to debate. We study the resistance to ballistic impact of thin polymer films using coarse-grained molecular dynamics simulations, investigating melts of linear polymer chains and star polymers with varying number 2<=f<=16 and degree of polymerization 10<=M<=50 of the arms. We show that increasing the number of arms f or the length of the arms M both result in greater specific penetration energy within the parameter ra…
We study conformations and dynamics of active star polymers. The analysis shows that active star polymers stretching behaviour is quite different from that of active linear chains. The visual inspection of conformations and bond-bond correlations reveal a better coordination for the alignment and coordination of bonds for the star polymers than for the linear counterparts. The architecture substantially affects the chain extension transition at high values of active force. The scaling laws for the shape factor and the arm asphericity ratio established for the passive star polymers coincide wit…
The structural and dynamical properties of ultra-soft colloids - star polymers - exposed to a uniform external force field are analyzed applying the multiparticle collision dynamics approach, a hybrid coarse-grain mesoscale simulation approach, which captures thermal fluctuations and long-range hydrodynamic interactions. In the weak field limit, the structure of the star polymer is nearly unchanged, however in an intermediate regime, the radius of gyration decreases, in particular transverse to the sedimentation direction. In the limit of a strong field, the radius of gyration increases with f…
The dynamics of phantom bead-spring chains with the topology of a symmetric star with $f$ arms and tadpoles ($f=3$, a special case) is studied, in the overdamped limit. In the simplified case where the hydrodynamic radius of the central monomer is $f$ times as heavy as the other beads, we determine their dynamical eigenmodes exactly, along the lines of the Rouse modes for linear bead-spring chains. These eigenmodes allow full analytical calculations of virtually any dynamical quantity. As examples we determine the radius of gyration, the mean square displacement of a tagged monomer, and, for s…
Active embracement enables autonomous tweezing in active star polymers
Heinrich-Heine-Universität Düsseldorf（杜塞尔多夫海因里希·海涅大学）；Universita di Trento（特伦托大学）；INFN-TIFPA, Trento Institute for Fundamental Physics and Applications（意大利国家核物理研究所-特伦托基础物理与应用研究所）；University of Rome La Sapienza（罗马第一大学）
By means of multiscale molecular simulations, we show that telechelic-star polymers are a simple, robust and tunable system, which hierarchically self-assembles first into soft-patchy particles and then into targeted crystalline structures. The self-aggregating patchy behavior can be fully controlled by the number of arms per star and by the fraction of attractive monomeric units at the free ends of the arms. Such self-assembled soft-patchy particles while forming, upon augmenting density, gel-like percolating networks and stable ordered structures, preserve properties as particle size, number…
Conformational properties of regular dendrimers and more general hyperbranched polymer stars with Gaussian statistics for the spacer chains between branching points are revisited numerically. We investigate the scaling for asymptotically long chains especially for fractal dimensions $d_f = 3$ (marginally compact) and $d_f = 2.5$ (diffusion limited aggregation). Power-law stars obtained by imposing the number of additional arms per generation are compared to truly self-similar stars. We discuss effects of weak excluded volume interactions and sketch the regime where the Gaussian approximation s…
We present an analysis of the impact of structural disorder on the static scattering function of f-armed star branched polymers in d dimensions. To this end, we consider the model of a star polymer immersed in a good solvent in the presence of structural defects, correlated at large distances r according to a power law \sim r^{-a}. In particular, we are interested in the ratio g(f) of the radii of gyration of star and linear polymers of the same molecular weight, which is a universal experimentally measurable quantity. We apply a direct polymer renormalization approach and evaluate the results…
We investigate the effect of the number of arms (functionality f ) on the mobility of the branch point in symmetric star polymers. For this purpose we carry out large-scale molecular dynamics simulations of simple bead-spring stars and neutron spin echo (NSE) spectroscopy experiments on center labeled polyethylene stars. This labeling scheme unique to neutron scattering allows us to directly observe the branch point motion on the molecular scale by measuring the dynamic structure factor. We investigate the cases of different functionalities f = 3, 4 and 5 for different arm lengths. The analysi…
By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $\sim f^{1/4}$ and the effective interaction as $\sim f^{2}$, as opposed to $\sim f^{1/5}$ and $\sim f^{3/2}$, respectively, in three dimensions. Our results de…
Using the bond fluctuation model we study polymer networks obtained by endlinking of symmetric 4-arm star polymers. We consider two types of systems. Solutions of one type (A) of star polymers and solution of two types (A,B) of star polymer where A-type polymers can only crosslink with B-type polymers. We find that network defects in $A$ networks are dominated by short dangling loops close to overlap concentration $c^{*}$. $AB$ networks develop a more perfect network structure, since loop sizes involving an odd number of stars are impossible, and thus, the most frequent dangling loop with larg…
Coarse-graining to create minimalist models for dynamic, end-linked star-polymer networks
McKetta Department of Chemical Engineering, The University of Texas at Austin（德克萨斯大学奥斯汀分校麦凯塔化学工程系）；Department of Chemical Engineering, Auburn University（奥本大学化学工程系）；Department of Chemical Engineering and Biointerfaces Institute, University of Michigan（密歇根大学生物界面研究所化学工程系）；McKetta Department of Engineering, The University of Texas at Austin（德克萨斯大学奥斯汀分校麦凯塔工程学院）
Star polymers can exhibit a heterogeneous dynamical behavior due to their internal structure. In this work we employ atomistic molecular dynamics simulations to study translational motion in non-entangled polystyrene and poly(ethylene oxide) star-shaped melts. We focus on the local heterogeneous dynamics originating from the multi-arm star-like architecture and quantify the intramolecular dynamical gradient. By examining the translational motion at length scales of the order of the Kuhn length, we aim to find common features for both studied chemistries and to provide a critical and direct com…
