A neutron reflectometry study of polystyrene network interfaces

We have used neutron reflectometry to measure interfacial widths between two polystyrene films, where either one or both films are crosslinked. The observed interfacial width between two networks is larger than the size expected for “dangling ends”, which suggests motion of heterogeneous regions of the networks. In the case when one of the networks is replaced by a linear polymer, the interfacial profile can be asymmetric with a diffusion “front” of linear polymer penetrating the network to a length scale of up to 200 ?. In the case of a more densely crosslinked network and a high molecular weight linear polymer the interface is symmetric implying negligible penetration. Received: 4 December 1996 / Revised: 13 October 1997 / Accepted: 23 December 1997     

Dynamics of strongly entangled polymer systems: activated reptation

The effect of excluded-volume interactions on the reptation dynamics of long polymer chains is considered theoretically. It is shown that interactions give rise to an exponential increase of the reptation time, , if polymer chains are long enough: , where is the number of monomers per entanglement. We propose a novel dynamical mechanism of activated reptation implying that neighboring chains exchange conformations of their terminal fragments. It is shown that the exchange mechanism is compatible with the equilibrium polymer chain statistics and that it provides a bridge between the previous theories. Received: 25 July 1997 / Accepted: 8 October 1997     

Polymer adsorption on heterogeneous surfaces

The adsorption of a single ideal polymer chain on energetically heterogeneous and rough surfaces is investigated using a variational procedure introduced by Garel and Orland (Phys. Rev. B 55, 226 (1997)). The mean polymer size is calculated perpendicular and parallel to the surface and is compared to the Gaussian conformation and to the results for polymers at flat and energetically homogeneous surfaces. The disorder-induced enhancement of adsorption is confirmed and is shown to be much more significant for a heterogeneous interaction strength than for spatial roughness. This difference also applies to the localization transition, where the polymer size becomes independent of the chain length. The localization criterion can be quantified, depending on an effective interaction strength and the length of the polymer chain. Received: 29 October 1997 / Revised: 19 December 1997 / Accepted: 6 March 1998     

Deformation of a tethered polymer in uniform flow

Static properties of a single polymer fixed at one end and subjected to a uniform flow field are investigated for several polymer models: the Gaussian chain, the freely jointed chain, and the FENE (Finitely Extensible Nonlinear Elastic) chain. By taking into account first the excluded-volume interaction and subsequently also the hydrodynamic interaction, the polymer models are gradually completed and the relevance of each effect for the polymer deformation can be identified. Results from computer simulations of these bead spring chains are compared with analytical calculations using either the conformational distribution function or blob models. To this end, in contrast to the blob model with non-draining blobs introduced for a tethered polymer by Brochard-Wyart, we here develop also a model with free-draining blobs. It turns out that a limited extensibility of the polymer – described by nonlinear spring forces in the model – leads to a flow velocity dependence of the end-to-end distance, segment density, etc. which agrees with the power law predictions of the blob model only for very long chains and in a narrow range of flow velocities. This result is important for comparison with recent experiments on DNA molecules which turn out to be still rather short in this respect. The relative importance of finite extensibility, the excluded-volume effect, and hydrodynamic interactions for polymers in flow is not fully understood at present. The simulation of reasonably long chains becomes possible even when fluctuating hydrodynamic interactions are taken into account without employing averaging procedures by introducing efficient numerical approximation schemes. At medium velocity of the uniform flow the polymer is partially uncoiled and simulations show that the effects of excluded-volume and hydrodynamic interactions are position-dependent. Both are stronger near the free end than near the tethered end of the polymer. A crossover from a nearly non-draining polymer at small flow velocities to a free-draining almost uncoiled chain at large velocities is found in the simulations. Accordingly, models assuming the polymer to be composed of either free- or non-draining subunits, like the two blob models, cannot correctly describe the extension and shape of a tethered polymer in flow, and simple power laws for the polymer extension, etc. cannot be expected. Received 21 June 1999     

Constrained fluctuation theories of rubber elasticity: General results and an exactly solvable model

We present a new model of rubber elasticity where linear forces act to constrain the fluctuations of the eigenmodes of the phantom model. The model allows us to treat the constrained junction and the tube model within the same, transparent formalism, does not require any further approximations, and is particularly suited for the analysis of simulation data for (strained) model polymer networks. As an interesting side result we show that in order for the model to be consistent, the constraints (but not the mean polymer conformations!) have to deform affinely, a severe restriction that might also apply to other models. Complementary, we prove in analogy to the derivation of the virial theorem that introducing constraints into the phantom network Hamiltonian leads to extra terms in addition to the usual Doi-Edwards formulas for the polymer contribution to the stress tensor which vanish only for affinely deforming constraints. Received: 28 November 1997 / Received in final form and accepted: 31 March 1998     

On the number of intersections of self-repelling polymer chains

We give a detailed analysis of the intersection properties of polymers. Using the renormalization group we provide a full crossover function for the dependence of the number of intersections in a single polymer on chain length and excluded volume strength. We compare our results with Monte-Carlo data and with exact calculations for a random walk, finding good agreement in all respects. Restricting to the vicinity of the eight ternary fixed points we also calculate the number of intersections between two chains placed at a fixed distance, including the two halves of a block-copolymer. The analysis of these systems confirms the interpretation of the different contributions to the number of intersections in a single chain. Due to the highly nontrivial character of the correlations in a polymer chain the correction exponents in both cases however are different. None of the results can be extracted from any Flory-type estimate. Received: 1 April 1997 / Revised: 24 October 1997 / Accepted: 29 January 1998     

Change of the scaling behavior of the end-to-end square distance in a two-dimensional polydisperse system

The simulation of a two-dimensional, broadly polydisperse, living polymers system at high concentration reveals an unusual conformational behaviour for the longer chains. Unlike in three dimensions, the longer chains are not swollen but are squeezed by the smaller chains. This observation is discussed in terms of a two dimensional solvent- polymer mixture whose solvent particules are larger than the polymer monomers. Received: 13 December 1996 / Revised: 16 March 1998 / Accepted: 27 March 1998     

Microgels and fractal structures at interfaces and surfaces

The behavior of microgels near surfaces and their adsorption is studied by simple scaling theory. Two different types of microgels can be studied, i.e., fractal type microgels and randomly crosslinked polymer chains. In the first case the gel can be described mainly by introducing a spectral dimension. The second type requires more attention and uses the number of crosslinks as parameter. The main result is that soft gels with weakly coupled crosslinks and a low number of crosslinks adsorb much better than hard gels, with many crosslinks. Similar results for fractal gels and branched polymer are presented. Fractal gels with low connectivity adsorb easier than gels with a large connectivity dimension. We discuss also consequences on surface protection by microgels. Received: 11 August 1997 / Received in final form: 20 November 1997 / Accepted 22 January 1998     

Adsorption and spreading of polymers at plane interfaces; theory and molecular dynamics simulations

Nonequilibrium processes play a key role in the adsorption kinetics of macromolecules. It is expected that the competition between transport of polymer towards an interface and its subsequent spreading has a significant influence on the adsorbed amount. An increase of the transport rate can lead to an increase of the adsorbed amount, especially when the polymer has too little time to spread at the interface. In this study we present both molecular dynamics simulations and analytical calculations to describe some aspects of the adsorption kinetics. From MD simulations on a poly(ethylene oxide) chain in vacuum near a graphite surface, we conclude that the spreading process can, in first approximation, be described by either a simple exponential function or by first-order reaction kinetics. Combining these spreading models with the transport equations for two different geometries (stagnation-point flow and overflowing cylinder) we are able to derive analytical equations for the adsorption kinetics of polymers at solid-liquid and at liquid-fluid interfaces. Received: 18 July 1997 / Received in final form: 27 October 1997 / Accepted: 6 November 1997     

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t _r. The conformation can be described with two parameters only: , the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: is always smaller than (the deformation ratio of the whole sample). In the isotropic phase, has a constant value, while pincreases as tr. This latter behavior is not that expected for non-entangled chains, in which p varies as t _r ^1/2 (Rouse model). In the nematic phase, decreases as a stretched exponential function of t _r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain. Received 5 May 1999 and Received in final form 18 October 1999     

Two-dimensional polymer networks at a mixed boundary: Surface and wedge exponents

We provide general formulae for the configurational exponents of an arbitrary polymer network connected to the surface of an arbitrary wedge of the two-dimensional plane, where the surface is allowed to assume a general mixture of boundary conditions on either side of the wedge. We report on a comprehensive study of a linear chain by exact enumeration, with various attachments of the walk's ends to the surface, in wedges of angles and , with general mixed boundary conditions. Received: 20 October 1997 / Accepted: 13 May 1998     

A new simulation method for the determination of forces in polymer/colloid systems

We introduce a new simulation method, which we call the contact-distribution method, for the determination of the Helmholtz potential for polymer/colloid systems from lattice Monte-Carlo simulations. This method allows one to obtain forces between finite or semi-infinite objects of any arbitrary shape and dimensions in the presence of polymer chains in solution or physisorbed or chemisorbed at interfaces. We illustrate the application of the method using two examples: (i) the interaction between the tip of an atomic force microscope (AFM) and a single, end-grafted polymer chain and (ii) the interaction between an AFM tip and a polymer brush. Numerical results for the first two cases illustrate how the method can be used to confirm and extend scaling laws for forces and Helmholtz potentials, to examine the effects of the shapes and sizes of the objects and to examine conformational transitions in the polymer chains. Received: 15 May 1998 / Revised: 11 June 1998 / Accepted: 12 June 1998     

Energy-transfer and quantum trajectories in quasi-molecular networks

Continuous measurement models are conveniently based on master equations specified by the respective Hamiltonian and appropriate environment operators. As demonstrated by stochastic unraveling, the latter specify the dynamical process rather than static detection modes. We show that certain environment operators acting on a simple system may, in fact, require extended networks for implementation: Their Hamilton parameters re-appear in the effective environment operators of the reduced model. The resulting quantum trajectories typically involve competing paths, which may give rise to different fluctuation and noise properties even when the corresponding ensemble behavior is practically the same. Received: 21 July 1997 / Received in final form: 10 November 1997 / Accepted: 27 October 1997     

Calculation of scattering from stretched copolymers using the tube model: a generalisation of the RPA

There are many experimental situations in which polymer chains are constrained or localised into a small region of space (e.g. melt chains confined to a “tube”, network chains pinned by crosslinks). We show that detailed consideration of the quenched variables is vital in these experiments. This paper provides a crucial link between microscopic models with localising constraints and scattering patterns by a generalisation of the Random Phase Approximation (RPA) which allows for quenched translational variables. A method is developed which deals with correlations between the quenched variables brought about by incompressiblity (for example, in a polymer melt there are correlations between tubes because of the interaction between chains). As an example, the generalised RPA is applied to models based on the Warner-Edwards picture of the tube. Theoretical results for a melt of H-shaped copolymers are compared with experimental scattering. Early results suggest that to fit the scattering we may be forced to relax one of the central assumptions of the tube model; that the tube deforms affinely, that all chains retract by the same amount or that the tube diameter does not couple to the strain. Received 26 October 1998 and Received in final form 19 March 1999     

Charge density wave transport in submicron antidot arrays in NbSe3

We demonstrate for the first time that a periodic array of submicrometer holes (antidots) can be patterned into thin single NbSe₃ crystals. We report on the study of Charge Density Wave (CDW) transport of the network of mesoscopic units between antidots. Size of the elementary unit can be as small as 0.5 μm along the chain axis and in cross-section. We observe size effects for Ohmic residual resistance and in CDW transport current-voltage characteristics in submicronic networks. Received: 25 November 1997 / Received in final form: 30 March 1998 / Accepted: 6 April 1998     

On the scattering properties of a weakly charged polymer gel

A phenomenological model is presented to describe weakly charged polymer gels based on the classical elasticity theory. The structure factor of the gel is calculated considering both thermal and frozen concentration fluctuations as well as the screened Coulomb interaction. In agreement with the recent experimental finding the result shows anomalous crosslink-density dependence of the scattering profiles. Received: 28 March 1997 / Revised: 4 September 1997 / Accepted: 23 October 1997     

Field-induced winding of chiral polymers

We propose a microscopic model of a chiral polymer chain with permanent transverse dipoles interacting with an external electric field. Its behaviour has been investigated by computer simulation in the limit of weak chirality. Large-scale (tertiary) helical winding induced along the field direction has been found above a threshold field E_c, and the helix parameters have been calculated as functions of the field strength. Below E_c there is no coherent helical structure of the chain conformation. We find a characteristic scaling of the threshold and the winding radius a with the chain bending modulus , and . Received: 15 November 1997 / Accepted: 16 February 1998