"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

Hybridized polymer matrix composite

Under certain conditions of combined fire and impact, graphite fibers are released to the atmosphere by graphite fiber composites. The retention of graphite fibers in these situations is investigated. Hybrid combinations of graphite tape and cloth, glass cloth, and resin additives are studied with resin systems. Polyimide resins form the most resistant composites and resins based on simple novolac epoxies the least resistant of those tested. Great improvement in the containment of the fibers is obtained in using graphite/glass hybrids, and nearly complete prevention of individual fiber release is made possible by the use of resin additives

Stimulus-responsive colloidal sensors with fast holographic readout

Colloidal spheres synthesized from polymer gels swell by absorbing molecules from solution. The resulting change in size can be monitored with nanometer precision using holographic video microscopy. When the absorbate is chemically similar to the polymer matrix, swelling is driven primarily by the entropy of mixing, and is limited by the surface tension of the swelling sphere and by the elastic energy of the polymer matrix. We demonstrate though a combination of optical micromanipulation and holographic particle characterization that the degree of swelling of a single polymer bead can be used to measure the monomer concentration in situ with spatial resolution comparable to the size of the sphere.Comment: 5 pages, 4 figure

High-temperature polymer matrix composites

Polymers research at the NASA Lewis Research Center has produced high-temperature, easily processable resin systems, such as PMR-15. In addition, the Polymers Branch has investigated ways to improve the mechanical properties of polymers and the microcracking resistance of polymer matrix composites in response to industry need for new and improved aeropropulsion materials. Current and future research in the Polymers Branch is aimed at advancing the upper use temperature of polymer matrix composites to 700 F and beyond by developing new resins, by examining the use of fiber reinforcements other than graphite, and by developing coatings for polymer matrix composites to increase their oxidation resistance

Double walled carbon nanotube/polymer composites via in-situ nitroxide mediated polymerisation of amphiphilic block copolymers

Because of their unique physical, chemical, and structural properties, carbon nanotubes (CNT) are playing an increasingly important role in the development of new engineering materials [1]. Across many different applications, CNT/polymer composites have been extensively studied [2] S.B. Sinnot and R. Andrews, Carbon nanotubes: synthesis, properties, and applications, Crit Rev Solid State Mater Sci 26 (2001), pp. 145–249.[2]. The key problem for CNT/polymer composite elaboration is the dispersion, compatibilization, and stabilization of the CNT in the polymer matrix. To solve this problem, a structure with di-block copolymers, one with a good affinity to CNT (monomer M1), the other being the matrix (monomer M2), is proposed in this study, as shown on the two steps mechanism of Fig. 1

Studies of fiber-matrix adhesion on compression strength

A study was initiated on the effect of the matrix polymer and the fiber matrix bond strength of carbon fiber polymer matrix composites. The work includes tests with micro-composites, single ply composites, laminates, and multi-axial loaded cylinders. The results obtained thus far indicate that weak fiber-matrix adhesion dramatically reduces 0 degree compression strength. Evidence is also presented that the flaws in the carbon fiber that govern compression strength differ from those that determine fiber tensile strength. Examination of post-failure damage in the single ply tests indicates kink banding at the crack tip

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.

Fluid-fluid demixing curves for colloid-polymer mixtures in a random colloidal matrix

We study fluid-fluid phase separation in a colloid-polymer mixture adsorbed in a colloidal porous matrix close to the \theta -point. For this purpose we consider the Asakura-Oosawa model in the presence of a quenched matrix of colloidal hard spheres. We study the dependence of the demixing curve on the parameters that characterize the quenched matrix, fixing the polymer-to-colloid size ratio to 0.8. We find that, to a large extent, demixing curves depend only on a single parameter f, which represents the volume fraction which is unavailable to the colloids. We perform Monte Carlo simulations for volume fractions f equal to 40% and 70%, finding that the binodal curves in the polymer and colloid packing-fraction plane have a small dependence on disorder. The critical point instead changes significantly: for instance, the colloid packing fraction at criticality increases with increasing f. Finally, we observe for some values of the parameters capillary condensation of the colloids: a bulk colloid-poor phase is in chemical equilibrium with a colloid-rich phase in the matrix.Comment: 26 pages, 8 figures. In publication in Molecular Physics, special volume dedicated to Luciano Reatto for his 70th birthda

Layer-by-layer polypyrrole coated graphite oxide and graphene nanosheets as catalyst support materials for fuel cells

For the production of advanced types of catalyst support materials, the distinguished properties of graphene nanosheets were combined with the structural properties of conducting polypyrrole by the incorporation of graphene nanosheets into a polymer matrix by the proposed simple and low-cost fabrication technique. A precise tuning of electrical conductivity and thermal stability was achieved by controlling the polymer thickness of randomly dispersed graphene nanosheets. Initially, graphene nanosheets were fabricated in large quantities via a mild chemical synthetic route involving graphite oxidation, ultrasonic treatment, and chemical reduction. Then, polypyrrole/graphene nanosheet composites with improved conductivity, thermal stability, and high surface area were synthesized by in situ polymerization with the different pyrrole feed ratios. Although graphite oxide sheets have electrically insulating property, partially oxidized graphite oxide was also utilized as conductive fillers in polymer matrix. However, polypyrrole/graphene nanosheet composites have better electrical conductivity than polypyrrole/graphite oxide composites