Tuneable micro- and nano-periodic structures in a free-standing flexible urethane/urea elastomer film

We have studied the control and manipulation of tuneable equilibrium structures in a free-standing urethane/urea elastomer film by means of atomic force microscopy, small-angle light scattering and polarising optical microscopy. The urethane/urea elastomer was prepared by reacting a poly(propyleneoxide)-based triisocyanate-terminated prepolymer (PU) with poly(butadienediol) (PBDO), with a weight ratio of 60% PU/40% PBDO. An elastomer film was shear-cast onto a glass plate and allowed to cure, first in an oven, then in air. Latent micro- and nano-periodic patterns are induced by ultra-violet (UV) irradiation of the film and can be “developed” by applying a plane uniaxial stress or by immersing the elastomer in an appropriate solvent and then drying it. For this elastomer we describe six pattern states, how they are related and how they can be manipulated. The morphological features of the UV-exposed film surface can be tuned, reproducibly and reversibly, by switching the direction of the applied mechanical field. Elastomers extracted in toluene exhibit different surface patterns depending upon the state in which they were developed. Stress-strain data collected for the films before and after UV irradiation reveal anisotropy induced by the shear-casting conditions and enhanced by the mechanical field. We have interpreted our results by assuming the film to consist of a thin, stiff surface layer (“skin”) lying atop a thicker, softer substrate (“bulk”). The skin's higher stiffness is hypothesised to be due to the more extensive cross-linking of chains located near the surface by the UV radiation. Patterns would thus arise as a competition between the effects of bending the skin and stretching/compressing the bulk, as in the work of Cerda and Mahadevan (Phys. Rev. Lett. 90, 074302 (2003)). We present some preliminary results of a simulation of this model using the Finite Element package ABAQUS.     

Molecular mobility of confined phases in model mesoporous (MCM-41) and microporous (AlPO4-5 zeolite) host materials

This paper discusses the self-assembly of block copolymers into vesicular morphology. After a brief state of art of the field, a system based on an amphiphilic poly(butadiene)-b-poly(-L-glutamic acid) (PB-b-PGA) diblock copolymer in aqueous solution is discussed in detail. The aggregation behavior of this block copolymer has been investigated by means of fluorescence spectroscopy, dynamic (DLS) and static (SLS) light scattering as well as transmission electron microscopy (TEM). The diblock copolymer was found to form well-defined vesicles in water. The size of these so-called polymersomes or peptosomes could be reversibly manipulated as a function of both pH and ion strength. Depending on the pH of the aqueous solution, the hydrodynamic radii of these vesicles were found to vary from 100 nm to 150 nm. By cross-linking the 1,2-vinyl double bonds present in the polybutadiene block, the ability to transform a transient supramolecular self-organized aggregate into a permanent “shape-persistent stimuli-responsive nanoparticle” has been demonstrated. Received 25 June 2002 and Received in final form 22 October 2002 Published online: 11 March 2003     

What can polymer crystal structure tell about polymer crystallization processes?

Contrary to most or all other materials, crystallization of chiral but racemic polymers such as isotactic polypropylene is accompanied by a conformational rearrangement which leads to helical geometries: the building units of the crystal are helical stems, -20nm long, which can be either right-handed or left-handed. Helical hand cannot be reversed within the crystal structure: it is therefore a permanent marker and an indicator of molecular processes (in particular segregation/selection of helical hands) which take place during crystal growth, and more precisely during the crucial step of “efficient” helical stem deposition. The issue of proper helical hand selection during polymer crystal growth is mainly illustrated with isotactic polypropylene. Its various crystalline polymorphs (, , and smectic) display virtually all possible combinations of helical hands, azimuthal settings and even non-parallel orientation of helix axes in space. Furthermore, a specific homoepitaxy which generates a lamellar branching in the phase “quadrites” and composite structures makes it possible a) to determine the helical hand and associated azimuthal setting of every stem in the crystalline entities and b) to determine the impact on the crystal structure and morphology of “mistakes” in helical hand of the depositing stem. Analysis of these morphologies demonstrates that the crystallization of isotactic polypropylene (and by implication of other achiral, helical polymers) is a highly sequential and “substrate-determined” process, i.e. that the depositing stem probes the topography of the growth face prior to attachment. These observations appear difficult to reconcile with crystallization schemes in which molecules (helical segments) are prearranged in a kind of pseudo-crystalline bundle (and as such, are not subjected to the high constraints of crystal symmetry) before deposition as a preassembled entity on the substrate. Received: 5 May 2000     

Mesoscopic and macroscopic dipole clusters: Structure and phase transitions

A two dimensional (2D) classical system of dipole particles confined by a quadratic potential is studied. This system can be used as a model for rare electrons in semiconductor structures near a metal electrode, indirect excitons in coupled quantum dots etc. For clusters of N ≤ 80 particles ground state configurations and appropriate eigenfrequencies and eigenvectors for the normal modes are found. Monte-Carlo and molecular dynamic methods are used to study the order-disorder transition (the “melting” of clusters). In mesoscopic clusters (N < 37) there is a hierarchy of transitions: at lower temperatures an intershell orientational disordering of pairs of shells takes place; at higher temperatures the intershell diffusion sets in and the shell structure disappears. In “macroscopic” clusters (N > 37) an orientational “melting” of only the outer shell is possible. The most stable clusters (having both maximal lowest nonzero eigenfrequencies and maximal temperatures of total melting) are those of completed crystal shells which are concentric groups of nodes of 2D hexagonal lattice with a number of nodes placed in the center of them. The picture of disordering in clusters is compared with that in an infinite 2D dipole system. The study of the radial diffusion constant, the structure factor, the local minima distribution and other quantities shows that the melting temperature is a nonmonotonic function of the number of particles in the system. The dynamical equilibrium between “solid-like” and “orientationally disordered” forms of clusters is considered.     

Deformed foam structure and transitions in a tube

The “staircase” (2,1,1) foam structure in an ordered foam under expansion in a cylindrical tube and the structural transition to the “bamboo” (1,1,0) structure are studied experimentally, analytically, and numerically using the Surface Evolver minimization program. An analytical expression of the oblique interface in the (2,1,1) structure, a minimal surface, but curved by stretching of the foam, is given as a classic example of singular perturbation (boundary layer) theory. The structural transition from staircase structure to bamboo structure takes place at a considerable dilation. The transition is not due to an edge length tending to zero continuously with dilation, but results from the equilibrium (2,1,1) solution losing its stability due to a saddle node bifurcation. Received 3 August 2000     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

Phase behavior and structure of an ABC triblock copolymer dissolved in selective solvent

A mean-field lattice theory is applied to predict the self-assembly into ordered structures of an ABC triblock copolymer in selective solvent. More specifically, the composition-temperature phase diagram has been constructed for the system (C)₁₄(PO)₁₂(EO)₁₇/water, where C stands for methylene, PO for propylene oxide and EO for ethylene oxide. The model predicts thermotropic phase transitions between the ordered hexagonal, lamellar, reverse hexagonal, and reverse cubic phases, as well as the disordered phase. The thermotropic behavior is a result of the temperature dependence of water interaction with EO- and PO-segments. The lyotropic effect (caused by changing the solvent concentration) on the formation of different structures has been found weak. The structure in the ordered phases is described by analyzing the species volume fraction profiles and the end segment and junction distributions. A “triple-layer” structure has been found for each of the ordered phases, with each layer rich in C-, PO-, and EO-segments, respectively. The blocks forming the layers are not stretched. The dependence of the domain spacing on polymer volume fraction and temperature is also considered. Received 17 April 2002 Published online: 21 January 2003     

Stimuli-responsive poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) triblock copolymers and complexation with poly(acrylic acid) at low pH

The self-organization of the double hydrophilic triblock copolymer poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide), PEO-b-P2VP-b-PEO, was investigated in dilute aqueous solution under several experimental conditions using turbidimetry, as well as static and dynamic light scattering. As a result of the temperature-sensitive properties of the end PEO blocks and the p H-responsive properties of the middle P2VP block, the formation of large star-like micellar nanostructures is observed at high p H, while at low p H, but in the presence of salt and at high temperature, flower-like micelles are formed. Moreover, the viscosimetric and dynamic light scattering studies at low p H revealed that micelle-like nanostructures are formed upon mixing the triblock copolymer with poly(acrylic acid), PAA, due to hydrogen bonding interpolymer complexation.     

The timescale of spinodal dewetting at a polymer/polymer interface

We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate) (PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface. Received 25 June 2001 and Received in final form 5 December 2001     

Operadic deformations as a tool for cogravity

The deformation equation and its integrability condition (Bianchi identity) of a non-(co)associative deformation in operad algebra are found. Based on physical analogies, two ideas ofcogravity equations are proposed. Presented at the 11th Colloquium “Quantum Groups and Integrable Systems”, Prague, 20–22 June 2002.     

Growth kinetics of polymer crystals in bulk

Temperature-dependent measurements of spherulite growth rates carried out for i-polystyrene, poly(ε -caprolactone) and linear polyethylene show that the controlling activation barrier diverges at a temperature which is 14K, 22K and 12K, respectively, below the equilibrium melting points. We discuss the existence of such a “zero growth temperature” T _zg in the framework of a recently introduced thermodynamic multiphase scheme and identify T _zg with the temperature of a (hidden) transition between the melt and a mesomorphic phase which mediates the crystal growth. The rate-determining step in our model of crystal growth is the attachment of chain sequences from the melt onto the lateral face of a mesomorphic layer at the growth front. The necessary straightening of the sequence prior to an attachment is the cause of the activation barrier. A theory based on this view describes correctly the observations. With a knowledge of T _zg it is possible to fully establish the nanophase diagram describing the stability ranges of crystalline and mesomorphic layers in a melt. An evaluation of data from small-angle X-ray scattering, calorimetry and optical growth rate measurements yields heats of transition and surface free energies of crystals and mesophase layers, as well as the activation barrier per monomer associated with the chain stretching. According to the theory, the temperature dependence of the crystallization rate is determined by both the activation energy per monomer and the surface free energy of the preceding mesomorphic layer. Data indicate that the easiness of crystallization in polyethylene is first of all due to a particularly low surface free energy of the mesomorphic layer.     

Comment on “The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films” by J.S. Sharp,J.H. Teichroeb and J.A. Forrest

Sharp, Teichroeb and Forrest [J.S. Sharp, J.H. Teichroeb, J.A. Forrest, Eur. Phys. J. E 15, 473 (2004)] recently published a viscoelastic contact mechanics analysis of the embedment of gold nanospheres into a polystyrene (PS) surface. In the present comment, we investigate the viscoelastic response of the surface and conclude that the embedment experiments do not support the hypothesis of a liquid surface layer of sufficiently reduced “rheological temperature” to explain reports of very large reductions in the glass temperature of freely standing ultrathin polystyrene films. We also report some errors and discrepancies in the paper under comment that resulted in an inability to reproduce the reported calculations. We present our findings of error in a spirit of clarifying the problem of embedment of spheres into surfaces and in order that others can understand why they may not reproduce the results reported by Sharp, Teichroeb and Forrest. In the comment, we also examine the effects of the magnitude of the forces that result from the polymer surface-nanosphere particle interactions on the viscoelastic properties deduced from the embedment data and we provide a comparison of apparent surface or “rheological” temperature vs. experimental temperature that indicates further work needs to be performed to fully understand the surface embedment experiments. Finally, we comment that the nanosphere embedment measurements have potential as a powerful tool to determine surface viscoelastic properties.     

The bulk dynamics of a compositionally asymmetric diblock copolymer studied using dynamic light scattering

We have studied the bulk dynamics of a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) (PEP-PDMS) diblock copolymer in a large temperature range both in the ordered and in the disordered state. The volume fraction of the PEP block is 0.22. Apart from the disordered state, the sample shows three ordered morphologies. Using dynamic light scattering, we have investigated the dynamics in all four phases and combined these results with those obtained using pulsed field gradient NMR. In the disordered state, we find--apart from the slow cluster mode--the heterogeneity mode related to the self-diffusion of single chains. The relaxation time of this mode, reduced by temperature and the zero-shear viscosity , , increases with temperature. In the cubic phase right below the ODT temperature, we observe two diffusive processes, and we attribute the faster one to the mutual diffusion of micelles and block copolymers not bound to micelles (“free chains”) through the PDMS matrix. The slower mode may either be due to the mutual diffusion of free chains and chains bound to PEP micelles or to the cooperative diffusion of micellar aggregates. In the non-cubic ordered state at intermediate temperatures, an additional weak diffusive mode is observed. The low-temperature ordered state is body-centered cubic, and here, only the mutual diffusion of micelles and free chains lies in our experimental time window. Received 19 March 1999 and Received in final form 25 August 1999     

Dewetting on porous media with aspiration

We consider a porous solid covered with a water film (or with a drop) in situations where the liquid is pumped in, either spontaneously (if the porous medium is hydrophilic) or mechanically (by an external pump). The dynamics of dewetting is then strongly modified. We analyse a few major examples, a) horizontal films, which break at a certain critical thickness, b) the “modified Landau-Levich problem” where a porous plate moves up from a bath and carries a film: aspiration towards the plate limits the height H reached by the film, c) certain situation where the hysteresis of contact angles is important. Received 5 October 1999 and Received in final form 7 February 2000     

Impact of network activity on noise delayed spiking for a Hodgkin-Huxley model

In a Hodgkin-Huxley neuron model driven just above threshold, external noise can increase both jitter and latency of the first spike, an effect called “noise delayed decay” (NDD). This phenomenon is important when considering how neuronal information is represented, thus by the precise timing of spikes or by their rate. We examine how NDD can be affected by network activity by varying the model's membrane time constant, τ_m. We show that NDD is significant for small τ_m or high network activity, and decreases for large τ_m, or low network activity. Our results suggest that for inputs just above threshold, the activity of the network constrains the neuronal coding strategy due to, at least in part, the NDD effect.     

Recent trends in the tuning of polymersomes’ membrane properties

“Polymersomes” are vesicular structures made from the self-assembly of block copolymers. Such structures present outstanding interest for different applications such as micro- or nano-reactor, drug release or can simply be used as tool for understanding basic biological mechanisms. The use of polymersomes in such applications is strongly related to the way their membrane properties are controlled and tuned either by a precise molecular design of the constituting block or by addition of specific components inside the membrane (formulation approaches). Typical membrane properties of polymersomes obtained from the self-assembly of “coil coil” block copolymer since the end of the nineties will be first briefly reviewed and compared to those of their lipidic analogues, named liposomes. Therefore the different approaches able to modulate their permeability, mechanical properties or ability to release loaded drugs, using macromolecular engineering or formulations, are detailed. To conclude, the most recent advances to modulate the polymersomes’ properties and systems that appear very promising especially for biomedical application or for the development of complex and bio-mimetic structures are presented.     

Flory radius of polymers in a periodic field: An exact analytic theory

We found an exact expression for the Flory radius R _F of Gaussian polymers placed in an external periodic field. This solution is expressed in terms of the two parameters η and a that describe the reduced strength of an external field and the period of the field to the polymer gyration radius ratio, respectively. R _F is found to be a decaying function of η for any values of a . Provided that the gyration radius is of the order of the period of an external field or less, the ground-state (GS) approximation of the exact result for R _F is shown to give qualitatively incorrect results. In addition to the “ground-state” contribution, the exact solution for R _F contains an additional term that is overlooked by the GS approximation. This term gives rise to the fact that R _F as a function of η exhibits power law behavior (rather than exponential decay obtained from the GS result) once η exceeds the threshold value η_con .     

Preparation of poly (styrene)-b-poly (acrylic acid)/γ-Fe2O3 composites

The use of a block copolymer, poly (styrene)-b-poly (acrylic acid) (PS-b-PAA) to prepare a magnetic nanocomposite was investigated. Poly (styrene)-poly (t-butyl acrylate) block copolymer, being synthesized by atom transfer radical polymerization, was hydrolyzed with hydrochloric acid for obtaining PS-b-PAA. The obtained PS-b-PAA was then compounded with the modified γ-Fe₂O₃, and subsequently the magnetic nanocomposite was achieved. The products were characterized by ¹H NMR, FTIR, gel permeation chromatography, thermogravimetric analysis, transmission electron microscopy and vibrating sample magnetometer. The results showed that the nanocomposites exhibited soft magnetism, with the mean diameter of 100 nm approximately.     

Amphiphilic diblock copolymers with adhesive properties: I. Structure and swelling with water

We study asymmetric block copolymers with the simple diblock AB architecture, in the case where the longer block A is both hydrophobic and “soft”, whereas the shorter block B is hydrophilic and “hard”. Materials with such a particular combination of physico-chemical and mechanical properties have distinctive advantages, in particular for designing water-compatible adhesive materials. The phase diagram is established, combining NMR and SAXS characterisations of the materials. The swelling with water is monitored through gravimetry and “time-resolved” SAXS. Indications of maintained adhesive properties in a wet environment are given.