Elastic property of bilayer membrane in copolymer-homopolymer mixtures

We study the domain morphology in a phase separated state of diblock copolymer-homopolymer mixtures. In the situation that one of the blocks of copolymers is incompatible with homopolymers, formation of a bilayer membrane of block copolymers is shown to be possible in the matrix of homopolymers. Starting with the free energy functional in terms of the local volume fractions of each monomer, we derive the bending and curvature rigidities in the Helfrich free energy for a membrane. It is found that the curvature modulus is negative only in a limited region of the parameters, where a closed shape of a membrane like a vesicle is possibly formed. We establish a method to calculate the rigidities without a molecular picture in a consistent way with the field theoretic model free energy. Stability of a bilayer membrane compared with micelles is also investigated. Received: 22 July 1997 / Received in final form: 1 December 1997 / Accepted: 22 January 1998     

Phase behavior of binary blends of symmetric polystyrene-polybutadiene diblock copolymers studied using SANS

Binary blends of compositionally symmetric diblock copolymers are investigated using small-angle neutron scattering. The study focuses on the miscibility of blends of polystyrene-polybutadiene diblock copolymers as a function of chain length ratio and blend composition, and the results are related to the theoretical phase diagram put forward by M.W. Matsen (J. Chem. Phys. 103, 3268 (1995)). Three different low molar mass copolymers were blended with a high molar mass copolymer. We find very good coincidence with the theoretical phase diagram obtained. Only for blends having a chain length ratio of 0.06, theory predicts that a larger amount of short copolymers can be dissolved in the matrix of long copolymers, and vice versa. With the latter blends and volume fractions of short chains between 0.11 and 0.70, the second-order Bragg-peaks do not vanish, which indicates that the lamellae are asymmetric. Received: 9 February 1998 / Revised: 20 April 1998 / Accepted: 24 April 1998     

Chain segment ordering in lamellar sublayers of block copolymers: A NMR study

The chain segment dynamics in the bulk lamellar phase of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers has been probed by NMR. The experiments were performed on a PS-PDMS diblock and on a PS-PDMS-PS triblock with twice the molecular weight. In the diblock, at room temperature, the PDMS block segments undergo uniaxial reorientations around the normal to the lamellae. In the triblock, the reorientational motions exhibit a lower degree of symmetry: deviations from a uniaxial dynamics are observed. Such a behaviour originates in the anchorage of both PDMS chain ends into the PS glassy layers. Received 27 September 2001 and Received in final form 18 January 2002     

Structural properties of charged diblock copolymer solutions

Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene) PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water. The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor (), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found to be weak. Received: 19 June 1997 / Received in final form: 4 September 1997 / Accepted: 9 October 1997     

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     

Formation of ordered micro-porous membranes

Regular micro-porous polymeric membranes have recently been discovered by rapidly evaporating a solution of CS₂ containing poly(p-phenylene)-block-polystyrene [#!ref1!#]. 1,2-dichloroethane (a chlorated solvent in which polystyrene gel phase has never been observed) is also found to produce ordered structures, which definitively excludes eventual effect of the gelation process during the membrane formation. The observation of the solution surface during the solvent evaporation reveals the growing of micron-sized water droplets trapped at the surface and forming compact aggregates. The study of the solution/water interface shows that the water droplets profile is in agreement with the pore shape observed in the membranes. Moreover, the copolymer was found to precipitate at the interface, forming a layer encapsulating the droplets and preventing their coalescence. In that way, the final structure results from the droplets stacking under the action of large surface currents. Finally, we argue that the decisive element in the formation of ordered structures is the ability of the polymer to precipitate at the solution/water interface, which seems to be related the star-polymer microstructure. Received: 18 August 1998     

Polyelectrolytes tethered to a free surface

Several attempts have been already carried out in order to tether charged chains by an end at a free fluctuating surface. We review here most of these attempts and focus on how close the physics of charged brushes can be investigated by such an approach. We first describe results about films of charged-neutral diblock copolymers spread at the surface of water. Results can be mostly rationalized in terms of charged brushes although additional structurations and fluctuations of the interface can be observed. The latter deformations are also observed when adsorbed layers of charged-neutral diblock copolymers are considered. At last, we examine how free suspended films of charged-neutral diblock copolymers can be viewed as two opposing charged brushes, both in terms of thickness and pressure. Received 9 May 2000     

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     

Chain radius dependence on concentration in a 2D living polymer system

A living polymer system is used to study the effect of concentration on a broad, polydisperse two-dimensional polymer system. It is found that the mean squared end-to-end radius of a chain of L monomers does not decrease by following a simple power law of the concentration but by a function of the form . An origin for such a behaviour is proposed. Received: 21 November 1997 / Received in final form: 21 April 1998 / Accepted: 24 April 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     

Random copolymers at a selective interface: Many chains with excluded volume interactions

We investigate numerically, using the bond-fluctuation model, the adsorption of many random AB-copolymers with excluded volume interactions at the interface between two solvents. We find two regimes, controlled by the total number of polymers. In the first (dilute) regime, the copolymers near the interface extend parallel to it, while in the second regime they extend perpendicular to it. The density at the interface and the density in the bulk depend differently on the total number of copolymers: In the first regime the density at the interface increases more rapidly than in the bulk, whereas the opposite is true in the second regime. Received 4 March 1998 and Received in final form 22 September 1998     

Polyelectrolyte brushes with specific charge distribution: Mean-field lattice theory

A novel polymer system containing charged diblock polymers grafted onto a planar surface, simple salt and solvent has been considered in the framework of a mean-field lattice theory. On the basis of predicted volume fraction profiles of polymer segments, free ends, block junctions, and small ions, a detailed picture of the system has emerged. It is found that the structure of the polymer brush is decisively dependent of the relative charge of the blocks. For certain conditions, bimodal profiles appear which demonstrate the simultaneous presence of two types of chain conformations, one coiled and one stretched. Received 30 August 2000     

Buckling in a solid Langmuir monolayer: light scattering measurements and elastic model

Above a surface pressure threshold , we detect a buckled state in the low temperature solid phase of a phospholipid monolayer spread at the air-formamide interface. Stable ripples are observed with a Brewster angle microscope, and light scattering provides measurements mNm^-1, wavelength m and amplitude of a few nm for the deformation. A model, coupling the monolayer thickness and elongation, and consistent with the monolayer texture, is also presented. Received: 18 August 1997 / Revised: 9 December 1997 / Accepted: 29 January 1998     

Scaling approach of the convective drying of a porous medium

We propose a simplified, theoretical approach of the evolution of liquid distribution during the convective drying of a granular packing. In the absence of gravity effects three regimes are distinguished according to the relative importance of surface evaporation, capillarity or evaporation from the interior of the sample. The evolution of the drying rate as a function of the saturation can be inferred from the characteristic velocities associated to each of these effects. We also carried out drying experiments of bead packings saturated with ethanol, at four different velocities of the boundary convection current, and with bead size ranging from 4.5 to 100 μm. The drying curves exhibit different regimes with a scaling as a function of particle radius and current velocity as predicted by the theory. Received 7 June 1999 and Received in final form 25 October 1999     

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     

Surface tension effects in the zero gravity inflow of a drop into a fluid

As a drop of fluid is deposited on the surface of a miscible fluid (that we call the solvent), it undergoes a strong pulling due to its surface rupture and it acquires a kinetic energy independently of gravity. For the drop and the solvent being of the same fluid we observe a drop injection at an initial velocity which scales as the square root of the surface tension of the drop against air. Once injected, the drop develops a transverse instability giving rise to an expanding ring. Viscosity terminates the process and stops the ring. We show that the final ring height follows a scaling law whereas two asymptotical scaling regimes can be identified for the ring radius. Received 31 August 1999     

Extensive stretch of polysiloxane network chains with random- and super-coiled conformations

The stress-elongation relations at large deformations for the polymer network chains with randomcoiled and supercoiled conformations are investigated using the polysiloxane networks with high elongations at break far over 10. Supercoil is the conformation of network chains in deswollen polymer networks which are made by removing solvent from the networks crosslinked in solutions at low polymer concentrations. The validity of the scaling concept of Pincus blob for the mechanical response of a polymer chain is experimentally confirmed for the network composed of randomcoiled chains. The analysis of the stress- relations for the deswollen networks comprised of supercoiled chains on the basis of the Pincus blob concept suggests that supercoil is a much more contracted conformation relative to randomcoil. Received: 25 August 1997 / Received in final form: 13 October 1997 / Accepted: 22 January 1998     

Morphologies of diblock copolymer thin films before and after crystallization

Spin-coated thin films of about 100nm of low-molecular-weight hydrogenated poly(butadiene-b- ethyleneoxide) (PB_h-PEO) diblock copolymers have been crystallized at various constant temperatures. Crystallization has been observed in real time by light microscopy. Detailed structural information was obtained by atomic force microscopy, mainly enabled by the large viscoelastic contrast between amorphous and crystalline regions. The behavior in thin films is compared to the bulk properties of the polymer. Crystallization started from an annealed microphase separated melt where optical microscopy indicated a lamellar orientation parallel to the substrate. A small difference in the length of the crystallizable block produced significantly different crystallization behavior, both in the bulk and in thin films. For thin films of the shortest diblock copolymer (45% PEO content) and for an undercooling larger than about 10 degrees, crystallization created vertically oriented lamellae. These vertical lamellae could be preferentially aligned over several micrometers when crystallization occurred close to a three-phase contact line. Annealing at temperatures closer to the melting point or keeping the sample at room temperature for several months allowed the formation of a lamellar structure parallel to the substrate. A tentative interpretation based on kinetically caused chain folding and relaxation within the crystalline state, with implications on general aspects of polymer crystallization, is presented. Received 19 March 1999 and Received in final form 14 December 1999     

Tilt model of inverted amphiphilic mesophases

We present an alternative model of structure and energetics of the inverted amphiphilic mesophases. The previous studies of the inverted hexagonal, H_II, and inverted micellar cubic, Q_II, phases considered the amphiphilic monolayers to be homogeneously bent. In contrast, we assume a unit cell of an inverted mesophase to consist of flat fragments of monolayer. Hence, the unit cells of the H_II and Q_II phases are represented by a hexagonal rod and a polyhedron, respectively. Our model is motivated by Turner and Gruner's X-ray diffraction reconstruction of structure of the H_II phase. The only deformation of the amphiphilic monolayers we consider is tilt of the hydrocarbon chains with respect to the monolayer surface, determined by the packing constraints imposed in the mesophases. Applying our recent model for the elastic energy of tilt in liquid membranes [#!ref23!#], we show that: i) tilt accounts in a natural way for the frustration energy of mesophases resulting from filling by the hydrocarbon chains the corners of the unit cells, ii) the energy of tilt variation along the membrane surface is analogous to the bending energy. We compute the energetics of the H_II, Q_IIsc and Q_IIfcc phases and obtain a hypothetical phase diagram in terms of the elastic constants of monolayers. Moreover, we calculate the structural dimensions of the mesophases. We verify the model showing that the obtained phase diagram describes the recent data for the glycolipids/water systems; the predicted dimensions of the Q_II phase are in accord with the measured values; the model treats quantitatively the structural features observed for the H_II phase. Received: 9 February 1998 / Revised: 4 June 1998 / Accepted: 3 July 1998