Copolymer at a selective interface and two-dimensional wetting: a grand canonical approach

We consider two different problems involving the localization of a single polymer chain: (i) a periodic AB copolymer at a selective fluid-fluid interface, with the upper (resp. lower) fluid attracting A (resp. B) monomers (ii) a homopolymer chain attracted to a hard wall (wetting). Self avoidance is neglected in both models, which enables us to study their localization transition in a grand canonical approach. We recover the results obtained in previous studies via transfer matrix methods. Moreover, we calculate in this way the loop length distribution functions in the localized phase. Some finite size effects are also determined and tested numerically. Received 13 April 2000     

The segregation of poly(styrene-b-isoprene) diblock copolymers to the surface of a polystyrene melt: the effect of the ratio of block lengths

The effect of the ratio of block lengths on the interfacial partitioning of poly(styrene-block-1,4 isoprene) diblock copolymers from their mixtures with polystyrene homopolymer melt is investigated utilizing a series of copolymers with almost constant molecular weight but different compositions. The concentration profile of the copolymer is measured directly using the nuclear reaction analysis technique; a segregation of the diblock is found at both the air/polymer surface, due to the lower surface energy of polyisoprene, and at the substrate/polymer interface. No significant effect of the block length ratio on the free-surface excess was observed. The block molecular weights have apparently led to dangling chain conformations in the non-overlapping mushroom and in the overlapping mushroom regimes whereas the brush regime was not accessible; no indications of a real border between the two former regimes was found. Received: 20 July 1998 / Received in final form and Accepted: 11 September 1998     

Monolayers of diblock copolymer at the air-water interface: the attractive monomer-surface case

We have studied both experimentally and theoretically the surface pressure isotherms of copolymers of polystyrene-polyethyleneoxide (PS-PEO) at the air-water interface. The SCMF (single chain mean-field) theory provides a very good agreement with the experiments for the entire range of surface densities and is consistent with the experiments if an adsorption energy per PEO monomer at the air-water interface of about one k_{B T} is taken. In addition, the chain density profile has been calculated for a variety of surface densities, from the dilute to the very dense ones. The SCMF approach has been complemented by a mean-field approach in the low density regime, where the PEO chains act as a two-dimensional layer. Both theoretical calculations agree with the experiments in this region. Received: 19 June 1997 / Revised: 2 February 1998 / Accepted: 11 February 1998     

Adsorption of a random heteropolymer with random self-interactions onto an interface

We consider the adsorption of a random heteropolymer onto an interface within the model of Garel et al. [#!gareletal89!#] by taking into account random self-interactions and ternary repulsive interactions between the monomers. Within the replica trick and by using a self-consistent preaveraging procedure we map the adsorption problem onto the problem of binding state of a quantum mechanical Hamiltonian. The analysis of the latter is treated within the variational method based on the 2nd Legendre transform. Our study reveals a complex behaviour of the localization of the heteropolymer. In particular, we predict a reentrant localization transition for moderate values of the asymmetry of the distribution function of the monomer sequences along the heteropolymer. Received 9 October 2001 and Received in final form 27 February 2002 Published online 6 June 2002     

Diffusion of adsorbates on random alloy surfaces

In this work the diffusion of non-interacting adsorbates on a random AB alloy surface is considered. For this purpose a simple cubic (sc), body-centered cubic (bcc) or face-centered cubic (fcc) auxiliary metal lattice is introduced. The auxiliary lattice is truncated parallel to its (100) plane in such a way that the fourfold hollow positions of the metal surface form a regular net of adsorption sites with square symmetry. The adsorption energy of each adsorption site is determined by its own environment, i.e. by the numbers of direct A or B neighbors. The Monte-Carlo method has been utilized to simulate surface diffusion of adsorbates on such energetically heterogeneous alloy surfaces and to calculate the tracer, jump and chemical diffusion coefficients. The chemical diffusion coefficient was calculated via two different approaches: the fluctuation and the Kubo-Green method. The influence of energetical heterogeneities on the surface diffusion is largely pronounced at low temperatures and low surface coverages, where most of the adatoms are trapped by deep adsorption sites. It was found that at low temperatures the sequential occupation of the different types of adsorption sites can be observed. Received: 24 October 1997 / Accepted: 17 December 1997     

Frustrated Blume-Emery-Griffiths model

A generalised integer S Ising spin glass model is analysed using the replica formalism. The bilinear couplings are assumed to have a Gaussian distribution with ferromagnetic mean . Incorporation of a quadrupolar interaction term and a chemical potential leads to a richer phase diagram with transitions of first and second order. The first order transition may be interpreted as a phase separation, and contrary to what has been argued previously, it persists in the presence of disorder. Finally, the stability of the replica symmetric solution with respect to fluctuations in replica space is analysed, and the transition lines are obtained both analytically and numerically. Received 13 January 1997     

An auger investigation of oxygen-enhanced tin segregation on a liquid Pb−Sn alloy

Summary Auger measurements of the surface composition have been performed on solid and molten Pb-5at%Sn alloys. They confirm the theoretical predictions that, in the absence of oxygen, liquid or solid alloys exhibit no significant surface segregation. On the contrary, surface composition measurements and simultaneous surface tension measurements clearly show that oxygen adsorption strongly affects the segregation of tin at the liquid-vapour interface. This surface enrichment is driven by the contribution of the reaction free energy and of the products surface tension.     

Effects of finite thickness on interfacial widths in confined thin films of coexisting phases

The capillary broadening of a 2-phase interface is investigated both experimentally and theoretically. When a binary mixture in a thin film with thickness D segregates into two coexisting phases the interface between the two phases may form parallel to the substrate due to preferential surface attraction of one of the components. We show that the interfacial profile (of intrinsic width w₀) is broadened due to capillary waves, which lead to fluctuations, of correlation length of the local interface positions in the directions parallel to the confining walls. We postulate that acts as an upper cutoff for the spectrum of capillary waves on the interface, so that the effective mean square interfacial width w varies as . In the limit of large D this yields or respectively for the case of short- or long-range forces between walls and the interface. We used the Nuclear Reaction Analysis depth profiling technique, to investigate this broadening effect directly in two binary polymer mixtures. Our results reveal that the interfacial width indeed increases with film thickness D, though the observed interfacial width is lower than the predicted w. This is probably due to surface tension effects imposed by the confining surfaces which are not taken into account in our model. Received: 19 February 1998 / Received in final form: 2 September 1998 / Accepted: 8 September 1998     

Bending of charged flexible membranes due to the presence of macroions

We investigate the bending of flexible charged membranes due to the presence of rigid rodlike macroions in the framework of the Debye-Hückel approximation. When the macroions are fixed in space at some distance from the bilayer the membrane bends towards them; we calculate the exact deformation profile. On the other hand a macroion which is adsorbed on the membrane causes a deflection of the bilayer. Finally, we consider swollen lamellar polyanion/charged-lipid complexes where the macroions are intercalated between charged lipid bilayers. We predict the occurrence of a double adsorption (pinching effect) of the macroion for sufficiently flexible membranes. Received: 9 February 1998 / Revised: 9 June 1998 / Accepted: 2 July 1998     

Adsorption of hydrophobic polyelectrolytes at the air/water interface: Conformational effect and history dependence

We present an experimental study of the adsorption of hydrophobic highly charged polyelectrolytes on a neutral and hydrophobic surface, the air/water interface. The polymer was a randomly sulphonated polystyrene with charge fractions between 0.3 and 0.9 and the adsorbed layers were characterised by Langmuir through measurements, ellipsometry and X-ray reflectivity. The adsorption rate is always very slow and the resulting layers are very thin (< 3 nm). A maximum of adsorption with the charge fraction is observed which we relate to the conformation of the chains in solution. We show that adsorption is partially irreversible, strongly hysteretic and that the state of an adsorbed layer depends on its history. Received 16 June 2000     

Why one needs a functional renormalization group to survive in a disordered world

In this paper, we discuss why functional renormalization is an essential tool to treat strongly disordered systems. More specifically, we treat elastic manifolds in a disordered environment. These are governed by a disorder distribution, which after a finite renormalization becomes non-analytic, thus overcoming the predictions of the seemingly exact dimensional reduction. We discuss how a renormalizable field theory can be constructed even beyond 2-loop order. We then consider an elastic manifold embedded inN dimensions, and give the exact solution forN →ɛ This is compared to predictions of the Gaussian replica variational ansatz, using replica symmetry breaking. Finally, the effective action at order 1/N is reported.     

Apparent slip at a polymer-polymer interface

We consider a planar interface between strongly-segregated homopolymers subjected to steady shear in the plane of the interface. We develop a constitutive equation for stress relaxation in an inhomogeneous system for chains obeying Rouse dynamics. Using this equation, the interfacial viscosity for a symmetric blend is found to be in agreement with a scaling prediction due to de Gennes, where is the bead friction coefficient, b is the segment length, is the segment volume and is the Flory-Huggins interaction parameter driving the phase separation. We generalize our results to asymmetric blends and describe a phenomenological extension to entangled melts. Received: 18 August 1997 / Received in final form: 1 December 1997 / Accepted: 2 December 1997     

Polymer adsorption

We consider the adsorption of linear polymer and copolymer chains at surfaces and interfaces. We first remind de Gennes' theory for homopolymers, made of a single monomer species. Then we turn to multi block and random copolymers. In the latter case, we consider both cases when the A and B monomer species are distributed along the chain in a noncorrelated and correlated way, respectively. For each case, we discuss single chain adsorption and the saturation of the surface. Various measurable quantities are evaluated.     

Loss of Ergodicity in the Transition from Annealed to Quenched Disorder in a Finite Kinetic Ising Model

We consider a kinetic Ising model which represents a generic agent-based model for various types of socio-economic systems. We study the case of a finite (and not necessarily large) number of agents N as well as the asymptotic case when the number of agents tends to infinity. The main ingredient are individual decision thresholds which are either fixed over time (corresponding to quenched disorder in the Ising model, leading to nonlinear deterministic dynamics which are generically non-ergodic) or which may change randomly over time (corresponding to annealed disorder, leading to ergodic dynamics). We address the question how increasing the strength of annealed disorder relative to quenched disorder drives the system from non-ergodic behavior to ergodicity. Mathematically rigorous analysis provides an explicit and detailed picture for arbitrary realizations of the quenched initial thresholds, revealing an intriguing “jumpy” transition from non-ergodicity with many absorbing sets to ergodicity. For large N we find a critical strength of annealed randomness, above which the system becomes asymptotically ergodic. Our theoretical results suggests how to drive a system from an undesired socio-economic equilibrium (e.g. high level of corruption) to a desirable one (low level of corruption).     

Dynamical linked cluster expansions with applications to disordered systems

Dynamical linked cluster expansions are linked cluster expansions with hopping parameter terms endowed with their own dynamics. We discuss physical applications to systems with annealed and quenched disorder. Examples are the bond-diluted Ising model and the Sherrington-Kirkpatrick spin glass. We derive the rules and identify the full set of graphs that contribute to the series in the quenched case. This way it becomes possible to avoid the vague extrapolation from positive integer n to n = 0, that usually goes along with an application of the replica trick. Received 13 December 2001 Published online 25 June 2002     

Exact results for the adsorption of a semiflexible copolymer chain in three dimensions

Lattice model of directed self-avoiding walk has been solved analytically to investigate adsorption–desorption phase transition behaviour of a semiflexible sequential copolymer chain on a two-dimensional impenetrable surface perpendicular to the preferred direction of the walk of the copolymer chain in three dimensions. The stiffness of the chain has been accounted by introducing an energy barrier for each bend in the walk of the copolymer chain. Exact value of adsorption–desorption transition points have been determined using the generating function method for the cases in which one type of monomer is having interaction with the surface, namely (i) no interaction (ii) attractive interaction and (iii) repulsive interaction. Results obtained in each of the case show that for stiffer copolymer chain adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.     

Phase diagram of randomly polymerized membrane

Using a replica formalism, a generalization of a recent mean field model corresponding to the observed wrinkling transition in randomly polymerized membranes is presented. In this model we study the effects of global fluctuations of the surface normals to the flat membrane, which can be introduced by a random local field. In absence of these global fluctuations, we show that, the model exhibits both continuous and discontinuous transitions between flat and wrinkled phases, contrary to what has been predicted by Bensimon et al. and Attal et al. Phase diagrams both in replica symmetry and in breaking of replica symmetry in sense of Almeida and Thouless are given. We have also investigated the effects of global fluctuations on the replica symmetry phase diagram. We show that, the wrinkled phase is favored and the flat phase is unstable. For large global fluctuations, the transition between wrinkled and flat phases becomes first order. Received: 3 December 1997 / Revised: 31 March 1998 / Accepted: 3 August 1998