Search

In polymer nanoparticle composites (PNCs) with attractive interactions between nanoparticles (NPs) and polymers, a bound layer of the polymer forms on the NP surface, with significant effects on the macroscopic properties of the PNCs. The adsorption and wetting behaviors of polymer solutions in the presence of a solid surface are critical to the fabrication process of PNCs. In this study, we use both classical density functional theory (cDFT) and molecular dynamics (MD) simulations to study dilute and semi-dilute solutions of short polymer chains near a solid surface. Using cDFT, we calculate the equilibrium properties of polymer solutions near a flat surface while varying the solvent quality, surface-fluid interactions, and the polymer chain lengths to investigate their effects on the polymer adsorption and wetting transitions. Using MD simulations, we simulate polymer solutions near solid surfaces with three different curvatures (a flat surface and NPs with two radii) to study the static conformation of the polymer bound layer near the surface and the dynamic chain adsorption process. We find that the bulk polymer concentration at which the wetting transition in the poor solvent system occurs is not affected by the difference in surface-fluid interactions; however, a threshold value of surface-fluid interaction is needed to observe the wetting transition. We also find that with good solvent, increasing the chain length or the difference in the surface-polymer interaction relative to the surface-solvent interaction increases the surface coverage of polymer segments and independent chains for all surface curvatures. Finally, we demonstrate that the polymer segmental adsorption times are heavily influenced only by the surface-fluid interactions, although polymers desorb more quickly from highly curved surfaces.

We performed microsecond-long, atomistic molecular dynamics simulations on a series of precise poly(ethylene-co-acrylic acid) ionomers neutralized with lithium, with three different spacer lengths between acid groups on the ionomers and at two temperatures. Ionic aggregates form in these systems with a variety of shapes ranging from isolated aggregates to percolated aggregates. At the lower temperature of 423 K, the ionic aggregate morphologies do not reach a steady-state distribution over the course of the simulations. At the higher temperature of 600 K, the aggregates are sufficiently mobile that they rearrange and reach steady state after hundreds of nanoseconds. For systems that are 100% neutralized with lithium, the ions form percolated aggregates that span the simulation box in three directions, for all three spacer lengths (9, 15, and 21). In the partially neutralized systems, the morphology includes lithium ion aggregates that may also include some unneutralized acid groups, along with a coexisting population of acid group aggregates that form through hydrogen bonding. In the lithium ion aggregates, unneutralized acid groups tend to be found on the ends or sides of the aggregates.

Fibers of single wall carbon nanotubes extruded from super-acid suspensions exhibit preferred orientation along their axes. We characterize the alignment by x-ray fiber diagrams and polarized Raman scattering, using a model which allows for a completely unaligned fraction. This fraction ranges from 0.17 to 0.05±0.02 for three fibers extruded under different conditions, with corresponding Gaussian full widths at half maximum (FWHM) from 64° to 44°±2°. FWHM, aligned fraction, electrical, and thermal transport all improve with decreasing extrusion orifice diameter. Resistivity, thermoelectric power, and resonant-enhanced Raman scattering indicate that the neat fibers are strongly p doped; the lowest observed ρ is 0.25 mΩ cm at 300 K. High temperature annealing increases ρ by more than 1 order of magnitude and restores the Raman resonance associated with low-energy van Hove transitions, without affecting the nanotube alignment.

Nanoparticle and polymer dynamics in nanocomposites containing spherical nanoparticles were investigated by means of molecular dynamics simulations. We show that the polymer diffusivity decreases with nanoparticle loading due to an increase of the interfacial area created by nanoparticles, in the polymer matrix. We show that small sized nanoparticles can diffuse much faster than that predicted from the Stokes-Einstein relation in the dilute regime. We show that the nanoparticle diffusivity decreases at higher nanoparticle loading due to nanoparticle-polymer interface. Increase of the nanoparticle radius slows the nanoparticle diffusion.

For single-wall carbon nanotube (SWNT) films deposited from suspension onto filter membranes, or by drop casting or spin coating onto flat substrates, the tube axes lie preferentially in the film plane. Using x-ray scattering and a two-dimensional detector, we show that this out-of-plane mosaic spread can be easily and accurately quantified. It varies significantly with deposition conditions, and the aligning effects of deposition and external force in the film plane (e.g., magnetic field) are additive. Films from well-dispersed tubes show better alignment than from poor dispersions. The finite out-of-plane mosaic in C60@SWNT films enables quantitative separation of one-dimensional diffraction (chains of C60 peas) from the 2D rope lattice diffraction.

Binary blends of a lamellar poly(styrene‐b‐isoprene) diblock copolymer and homopolystyrenes of various molecular weights self‐assembled into highly ordered morphologies upon solvent evaporation. The equilibrium blend morphologies were studied by transmission electron microscopy and small angle x‐ray scattering. The type of ordered morphology (lamellae, the ordered bicontinuous double diamond morphology, cylinders on a hexagonal lattice, and spheres on a cubic lattice) observed in each blend was generally dictated by the overall polystyrene volume fraction in the blend, i.e., the homopolymer concentration. The blend morphology also depended on the homopolymer molecular weight at a single fixed composition. The intermaterial dividing surface between the polystyrene and the polyisoprene microdomains was characterized by the interfacial mean curvature (H) and the average area per copolymer junction (σj). H and σj increased as the homopolymer concentration increased and/or as the homopolymer molecular weight d...

In this paper, we demonstrate reversible resistive switching in silver/polystyrene/silver nano-gap devices comprising Ag nano-strips separated by a nanoscale gap and encapsulated in polystyrene (PS). These devices show highly reversible switching behavior with high on-off ratios (>103) during cyclic switching tests over many cycles. We also observe evolution of the gap after extensive testing, which is consistent with metal filament formation as the switching mechanism in these Ag/PS/Ag nano-gap devices. The reversible electrical bistability demonstrated here was accomplished with an electrically inactive polymer, thereby extending the range of polymers suitable for organic digital memory applications.

We have designed, constructed, and evaluated an environmental chamber that has in situ dynamic control of temperature (25 to 90 °C) and relative humidity (0% to 95%). The compact specimen chamber is designed for x-ray scattering in transmission with an escape angle of 2θ = ±30°. The specimen chamber is compatible with a completely evacuated system such as the Rigaku PSAXS system, in which the specimen chamber is placed inside a larger evacuated chamber (flight path). It is also compatible with x-ray systems consisting of evacuated flight tubes separated by small air gaps for sample placement. When attached to a linear motor (vertical displacement), the environmental chamber can access multiple sample positions. The temperature and relative humidity inside the specimen chamber are controlled by passing a mixture of dry and saturated gas through the chamber and by heating the chamber walls. Alternatively, the chamber can be used to control the gaseous environment without humidity. To illustrate the value of this apparatus, we have probed morphology transformations in Nafion(®) membranes and a polymerized ionic liquid as a function of relative humidity in nitrogen.

The thermal conductivity of single-walled carbon nanotube (SWCNT)/polystyrene composites, prepared by a method known to produce a uniform distribution of SWCNT bundles on the micrometer length scale, was measured in the temperature range from approximately 140 to 360 K. The thermal conductivity enhancement (50% for 1 mass % at 300 K) is reasonably constant above room temperature but is reduced at the lower temperatures. This result is consistent with the expected, large contribution of interfacial thermal resistance in SWCNT/polymer composites. Enhancements in electrical conductivity show that 1 mass % loading is in the region of the electrical percolation threshold.