Polymeric compositions and their method of manufacture

Filled polymer compositions are made by dissolving the polymer binder in a suitable sublimable solvent, mixing the filler material with the polymer and its solvent, freezing the resultant mixture, and subliming the frozen solvent from the mixture from which it is then removed. The remaining composition is suitable for conventional processing such as compression molding or extruding. A particular feature of the method of manufacture is pouring the mixed solution slowly in a continuous stream into a cryogenic bath wherein frozen particles of the mixture result. The frozen individual particles are then subjected to the sublimation

Colloid-Induced Polymer Compression

We consider a model mixture of hard colloidal spheres and non-adsorbing polymer chains in a theta solvent. The polymer component is modelled as a polydisperse mixture of effective spheres, mutually noninteracting but excluded from the colloids, with radii that are free to adjust to allow for colloid-induced compression. We investigate the bulk fluid demixing behaviour of this model system using a geometry-based density-functional theory that includes the polymer size polydispersity and configurational free energy, obtained from the exact radius-of-gyration distribution for an ideal (random-walk) chain. Free energies are computed by minimizing the free energy functional with respect to the polymer size distribution. With increasing colloid concentration and polymer-to-colloid size ratio, colloidal confinement is found to increasingly compress the polymers. Correspondingly, the demixing fluid binodal shifts, compared to the incompressible-polymer binodal, to higher polymer densities on the colloid-rich branch, stabilizing the mixed phase.Comment: 14 pages, 4 figure

Phase diagram for a mixture of colloids and polymers with equal size

We present the phase diagram of a colloid-polymer mixture in which the radius a of the colloidal spheres is approximately the same as the radius R of a polymer coil (q=R/a1). A three-phase coexistence region is experimentally observed, previously only reported for colloid-polymer mixtures with smaller polymer chains (q0.6). A recently developed generalized free-volume theory (GFVT) for mixtures of hard spheres and non-adsorbing excluded-volume polymer chains gives a quantitative description of the phase diagram. Monte Carlo simulations also agree well with experimen

Demixing of colloid-polymer mixtures in poor solvents

The influence of poor solvent quality on fluid demixing of a model mixture of colloids and nonadsorbing polymers is investigated using density functional theory. The colloidal particles are modelled as hard spheres and the polymer coils as effective interpenetrating spheres that have hard interactions with the colloids. The solvent is modelled as a two-component mixture of a primary solvent, regarded as a background theta-solvent for the polymer, and a cosolvent of point particles that are excluded from both colloids and polymers. Cosolvent exclusion favors overlap of polymers, mimicking the effect of a poor solvent by inducing an effective attraction between polymers. For this model, a geometry-based density functional theory is derived and applied to bulk fluid phase behavior. With increasing cosolvent concentration (worsening solvent quality), the predicted colloid-polymer binodal shifts to lower colloid concentrations, promoting demixing. For sufficiently poor solvent, a reentrant demixing transition is predicted at low colloid concentrations.Comment: 6 pages, 3 figure

Soft core fluid in a quenched matrix of soft core particles: A mobile mixture in a model gel

We present a density-functional study of a binary phase-separating mixture of soft core particles immersed in a random matrix of quenched soft core particles of larger size. This is a model for a binary polymer mixture immersed in a crosslinked rigid polymer network. Using the replica `trick' for quenched-annealed mixtures we derive an explicit density functional theory that treats the quenched species on the level of its one-body density distribution. The relation to a set of effective external potentials acting on the annealed components is discussed. We relate matrix-induced condensation in bulk to the behaviour of the mixture around a single large particle. The interfacial properties of the binary mixture at a surface of the quenched matrix display a rich interplay between capillary condensation inside the bulk matrix and wetting phenomena at the matrix surface.Comment: 20 pages, 5 figures. Accepted for Phys. Rev.

Chains in critical fluids and nanopores

The conformational behavior of a polymer in a critical binary solvent confined in a porous medium is studied. The size of the polymer in bulk, which is mainly governed by the correlation length of the solvent density fluctuations, depends on the proximity to the critical point of the binary mixture. We find that in contrast to the bulk behavior, the conformational properties of the polymer in a porous medium depends strongly on the pore size. The latter controls the correlation length of the solvent density fluctuations and thus determines the polymer size.Comment: 6 page

Accurate description of bulk and interfacial properties in colloid-polymer mixtures

Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points in the phase-coexistence region, without the use of any fit parametersComment: 4 pages, 4 figure

Critical behavior of colloid-polymer mixtures in random porous media

We show that the critical behavior of a colloid-polymer mixture inside a random porous matrix of quenched hard spheres belongs to the universality class of the random-field Ising model. We also demonstrate that random-field effects in colloid-polymer mixtures are surprisingly strong. This makes these systems attractive candidates to study random-field behavior experimentally.Comment: 4 pages, 3 figures, to appear in Phys. Rev. Let

Formation and kinetics of transient metastable states in mixtures under coupled phase ordering and chemical demixing

We present theory and simulation of simultaneous chemical demixing and phase ordering in a polymer-liquid crystal mixture in conditions where isotropic- isotropic phase separation is metastable with respect to isotropic-nematic phase transition. It is found that mesophase formation proceeds by a transient metastable phase that surround the ordered phase, and whose lifetime is a function of the ratio of diffusional to orientational mobilities. It is shown that kinetic phase ordering in polymer-mesogen mixtures is analogous to kinetic crystallization in polymer solutions.Comment: 17 pages, 5 figures accepted for publication in EP

Colloids, polymers, and needles: Demixing phase behavior

We consider a ternary mixture of hard colloidal spheres, ideal polymer spheres, and rigid vanishingly thin needles, which model stretched polymers or colloidal rods. For this model we develop a geometry-based density functional theory, apply it to bulk fluid phases, and predict demixing phase behavior. In the case of no polymer-needle interactions, two-phase coexistence between colloid-rich and -poor phases is found. For hard needle-polymer interactions we predict rich phase diagrams, exhibiting three-phase coexistence, and reentrant demixing behavior.Comment: 9 pages, 15 figure