Orienting Ion-Containing Block Copolymers Using AC Electric Field

We consider orientation mechanisms for block copolymers in an electric field. Theoretical and experimental studies have shown that nonuniformity of the dielectric constant gives rise to a preferred orientation of the melt with respect to the applied field. We show that the presence of ions, as found in anionically prepared copolymers, may increase the alignment effect markedly. Time-varying (ac) and static (dc) fields are considered within a unified framework. We find that orientation of block copolymers can in principle be achieved without a dielectric contrast if there is a mobility contrast. The presence of ions is especially important at small field frequencies, as is in most experiments. Unlike the no-ions case, it is found that orienting forces depend on the polymer chain lengths. The mobile-ions mechanism suggested here can be used to reduce the magnitude of orienting fields as well as to discriminate between block copolymers of different lengths.Comment: 8 pages, 2 figure

Random Hydrophilic-Hydrophobic Copolymers

We study a single statistical amphiphilic copolymer chain AB in a selective solvent (e.g.water). Two situations are considered. In the annealed case, hydrophilic (A) and hydrophobic (B) monomers are at local chemical equilibrium and both the fraction of A monomers and their location along the chain can vary, whereas in the quenched case (which is relevant to proteins), the chemical sequence along the chain is fixed by synthesis. In both cases, the physical behaviour depends on the average hydrophobicity of the polymer chain. For a strongly hydrophobic chain (large fraction of B), we find an ordinary continuous $\theta$ collapse, with a large conformational entropy in the collapsed phase. For a weakly hydrophobic, or a hydrophilic chain, there is an unusual first-order collapse transition. In particular, for the case of Gaussian disorder, this discontinuous transition is driven by a change of sign of the third virial coefficient. The entropy of this collapsed phase is strongly reduced with respect to the $\theta$ collapsed phase. Email contact: [email protected]: Saclay-T94/077 Email: [email protected]

Interdigitation between surface-anchored polymer chains and an elastomer : consequences for adhesion promotion

We study the adhesion between a cross-linked elastomer and a flat solid surface where polymer chains have been end-grafted. To understand the adhesive feature of such a system, one has to study both the origin of the grafted layer interdigitation with the network, and the end-grafted chains extraction out of the elastomer when it comes unstuck from the solid surface. We shall tackle here the first aspect for which we develop a partial interdigitation model that lets us analytically predict a critical surface grafting density $\sigma^{*} \simeq P^{{1/10}}N^{-{3/5}}$ beyond which the layer no longer interdigitates with the elastomer. We then relate this result with recent adhesion measurements

History Memorized and Recalled upon Glass Transition

The memory effect upon glassification is studied in the glass to rubber transition of vulcanized rubber with the strain as a controlling parameter. A phenomenological model is proposed taking the history of the temperature and the strain into account, by which the experimental results are interpreted. The data and the model demonstrate that the glassy state memorizes the time-course of strain upon glassification, not as a single parameter but as the history itself. The data also show that the effect of irreversible deformation in the glassy state is beyond the scope of the present model. Authors' remark: The title of the paper in the accepted version is above. The title appeared in PRL is the one changed by a Senior Assistant Editor after acceptance of the paper. The recovery of the title was rejected in the correction process.Comment: 4 pages, 4 figure

Design of Copolymeric Materials

We devise a method for designing materials that will have some desired structural characteristics. We apply it to multiblock copolymers that have two different types of monomers, A and B. We show how to determine what sequence of A's and B's should be synthesised in order to give a particular structure and morphology. %For example in a melt of such %polymers, one may wish to engineer a body-centered %cubic structure. Using this method in conjunction with the theory of microphase separation developed by Leibler, we show it is possible to efficiently search for a desired morphology. The method is quite general and can be extended to design isolated heteropolymers, such as proteins, with desired structural characteristics. We show that by making certain approximations to the exact algorithm, a method recently proposed by Shakhnovich and Gutin is obtained. The problems with this method are discussed and we propose an improved approximate algorithm that is computationally efficient.Comment: 15 pages latex 2.09 and psfig, 1 postscript figure

"Wet-to-Dry" Conformational Transition of Polymer Layers Grafted to Nanoparticles in Nanocomposite

The present communication reports the first direct measurement of the conformation of a polymer corona grafted around silica nano-particles dispersed inside a nanocomposite, a matrix of the same polymer. This measurement constitutes an experimental breakthrough based on a refined combination of chemical synthesis, which permits to match the contribution of the neutron silica signal inside the composite, and the use of complementary scattering methods SANS and SAXS to extract the grafted polymer layer form factor from the inter-particles silica structure factor. The modelization of the signal of the grafted polymer on nanoparticles inside the matrix and the direct comparison with the form factor of the same particles in solution show a clear-cut change of the polymer conformation from bulk to the nanocomposite: a transition from a stretched and swollen form in solution to a Gaussian conformation in the matrix followed with a compression of a factor two of the grafted corona. In the probed range, increasing the interactions between the grafted particles (by increasing the particle volume fraction) or between the grafted and the free matrix chains (decreasing the grafted-free chain length ratio) does not influence the amplitude of the grafted brush compression. This is the first direct observation of the wet-to-dry conformational transition theoretically expected to minimize the free energy of swelling of grafted chains in interaction with free matrix chains, illustrating the competition between the mixing entropy of grafted and free chains, and the elastic deformation of the grafted chains. In addition to the experimental validation of the theoretical prediction, this result constitutes a new insight for the nderstanding of the general problem of dispersion of nanoparticles inside a polymer matrix for the design of new nanocomposites materials

Interfaces of Modulated Phases

Numerically minimizing a continuous free-energy functional which yields several modulated phases, we obtain the order-parameter profiles and interfacial free energies of symmetric and non-symmetric tilt boundaries within the lamellar phase, and of interfaces between coexisting lamellar, hexagonal, and disordered phases. Our findings agree well with chevron, omega, and T-junction tilt-boundary morphologies observed in diblock copolymers and magnetic garnet films.Comment: 4 page

Statics of polymer droplets on deformable surfaces

The equilibrium properties of polymer droplets on a soft deformable surface are investigated by molecular dynamics simulations of a bead-spring model. The surface consists of a polymer brush with irreversibly end-tethered linear homopolymer chains onto a flat solid substrate. We tune the softness of the surface by varying the grafting density. Droplets are comprised of bead-spring polymers of various chain lengths. First, both systems, brush and polymer liquid, are studied independently in order to determine their static and dynamic properties. In particular, using a numerical implementation of an AFM experiment, we measure the shear modulus of the brush surface and compare the results to theoretical predictions. Then, we study the wetting behavior of polymer droplets with different contact angles and on substrates that differ in softness. Density profiles reveal, under certain conditions, the formation of a wetting ridge beneath the three-phase contact line. Cap-shaped droplets and cylindrical droplets are also compared to estimate the effect of the line tension with respect to the droplet size. Finally, the results of the simulations are compared to a phenomenological free-energy calculation that accounts for the surface tensions and the compliance of the soft substrate. Depending on the surface/drop compatibility, surface softness and drop size, a transition between two regimes is observed: from one where the drop surface energy balances the adhesion with the surface, which is the classical Young-Dupr\'e wetting regime, to another one where a coupling occurs between adhesion, droplet and surface elastic energies.Comment: 13 pages, 11 figure

Shear induced grain boundary motion for lamellar phases in the weakly nonlinear regime

We study the effect of an externally imposed oscillatory shear on the motion of a grain boundary that separates differently oriented domains of the lamellar phase of a diblock copolymer. A direct numerical solution of the Swift-Hohenberg equation in shear flow is used for the case of a transverse/parallel grain boundary in the limits of weak nonlinearity and low shear frequency. We focus on the region of parameters in which both transverse and parallel lamellae are linearly stable. Shearing leads to excess free energy in the transverse region relative to the parallel region, which is in turn dissipated by net motion of the boundary toward the transverse region. The observed boundary motion is a combination of rigid advection by the flow and order parameter diffusion. The latter includes break up and reconnection of lamellae, as well as a weak Eckhaus instability in the boundary region for sufficiently large strain amplitude that leads to slow wavenumber readjustment. The net average velocity is seen to increase with frequency and strain amplitude, and can be obtained by a multiple scale expansion of the governing equations