Gruneisen parameters of bead-spring chains: MD simulation and theory.

Molecular Dynamics (MD) simulations were carried out in a microcanonical ensemble to compute the Gruneisen parameter (denoted as γ) of a liquid of bead-spring chains having 10 beads/chain. γ was studied over a wide range of temperatures below and above the glass transition temperature. We found that the Gruneisen parameter varied in the range of 2.1-3.1 and was significantly higher than typically observed experimentally in real polymers. In the glass, a theory was developed for γ using a cell model in which the beads are harmonically bound to their respective cell centers. The resulting Gruneisen parameter is predicted to increase slightly with temperature. Above the glass transition temperature, we employed the generalized Flory dimer equation-of-state and the polymer reference interaction model theory to calculate γ. In these calculations, we found that γ decreased with temperature in the liquid. The theoretical predictions for γ were found to be in good qualitative agreement with our MD simulations, without any adjustable parameters, both above and below Tg. In experiments on real polymers, γ undergoes a sharp discontinuity at the glass transition. By contrast, in our MD simulations, γ varies smoothly over a broad transition region.

The glass transition temperature of thin films: A molecular dynamics study for a bead-spring model.

Molecular dynamics simulations were carried out on free-standing liquid films of different thicknesses h using a bead-spring model of 10 beads per chain. The glass transition temperatures, Tg, of the various films were determined from plots of the internal energy versus temperature. We used these simulations to test the validity of our earlier conjecture that the glass transition of a confined liquid could be approximated by pre-averaging over the non-uniform density profile of the film. Using the density profiles from our simulations, we computed the average density of the free-standing films as a function of temperature. In all our film simulations we found, within the error of the simulation, that Tg of the film occurred at the same density (or packing fraction) as the bulk system at the bulk glass transition temperature TgB. By equating these densities at their respective glass transition temperatures, as suggested by the simulations, we deduced that Tg/TgB is proportional to h0/h. This is consistent with previous simulations and experimental data. Moreover, the parameter h0 is determinable in our model from the density profile of the films.

Understanding the force-vs-distance profiles of terminally attached poly(N-isopropyl acrylamide) thin films.

In this work, we examine the interaction between thin films composed of terminally anchored poly(N-isopropyl acrylamide) (PNIPAAm) immersed in water and test surfaces. Understanding this force of interaction can be important when using PNIPAAm surfaces in biotechnological applications such as biological cell cultures. The two novel contributions that are presented here are (1) the use of a recently developed self-consistent field (SCF) theory to predict the force-vs-distance profiles, and (2) the use of a modified polymer scaling theory to estimate the wet film thickness from experimental force-vs-distance profiles. SCF theory was employed to model the equilibrium structure of the uncompressed PNIPAAm chains, and the force between a compressed polymer film and a test surface as a function of wall separation distance. The parameters that were varied include temperature, polymer molecular weight, and surface coverage. The force-vs-distance profiles obtained at low and high temperatures with the SCF theory were in qualitative agreement with the experimentally measured profiles reported in the literature. We also compared the results of our SCF theory to the Alexander de Gennes scaling theory and found agreement at large separation distance. We also propose a method to estimate the wet polymer film thickness from a force-vs-distance profile obtained from an atomic force microscope measurement. The main novelties of this approach are that we employed a density functional theory corrected version of scaling theory proposed by McCoy et al. [McCoy, J. D.; Curro, J. G. J. Chem. Phys. 2005, 122, 164905], and we provide equations to account for various geometries of AFM tips.

Van der Waals model for phase transitions in thermoresponsive surface films.

Phase transitions in polymeric surface films are studied with a simple model based on the van der Waals equation of state. Each chain is modeled by a single bead attached to the surface by an entropic-Hooke's law spring. The surface coverage is controlled by adjusting the chemical potential, and the equilibrium density profile is calculated with density functional theory. The interesting feature of this model is the multivalued nature of the density profile seen at low temperature. This van der Waals loop behavior is resolved with a Maxwell construction between a high-density phase near the wall and a low-density phase in a "vertical" phase transition. Signatures of the phase transition in experimentally measurable quantities are then found. Numerical calculations are presented for isotherms of surface pressure, for the Poisson ratio, and for the swelling ratio.

Packing of poly(tetrafluoroethylene) in the liquid state: Molecular dynamics simulation and theory.

Molecular dynamics simulations and polymer reference interaction site model theory calculations were carried out on the C(48)F(98) oligomer of poly(tetrafluoroethylene) (PTFE) at 500 and 600 K. The exp-6 force field of Borodin, Smith, and Bedrov, was used in both the simulation and theory. The agreement between theory and simulation was equivalent to earlier studies on polyolefin melts. The intermolecular pair correlation functions of PTFE were shifted to larger distances relative to polyethylene (PE) due to the difference in the van der Waals radii of F and H atoms. A similar shift to lower wave vectors was found in the structure factor of PTFE relative to PE.

The colloidal force of bead-spring chains in a good solvent.

A recently developed density functional theory (DFT) for tethered bead-spring chains is used to investigate colloidal forces for the good solvent case. A planar surface of tethered chains is opposed to a bare, hard wall and the force exerted on the bare wall is calculated by way of the contact density. Previously, the case of large wall separation was investigated. The density profiles of the unperturbed chains, in that case, were found to be neither stepfunctions nor parabolas and were shown to accurately predict computer simulation results. In the present paper, the surface forces that result from the distortion of these density profiles at finite wall separation is studied. The resulting force function is analyzed for varying surface coverages, wall separations, and chain lengths. The results are found to be in near quantitative agreement with the scaling predictions of Alexander [S. Alexander, J. Phys. (Paris) 38, 983 (1977)] when the layer thickness is "correctly" defined. Finally, a hybrid Alexander-DFT theory is suggested for the analysis of experimental results.

Density functional theory of realistic models of polyethylene liquids in slit pores: comparison with monte carlo simulations.

Density functional theory is applied to study properties of fully detailed, realistic models of polyethylene liquids near surfaces and compared to results from Monte Carlo simulations. When the direct correlation functions from polymer reference interaction site model (PRISM) theory are used as input, the theory somewhat underpredicts the density oscillations near the surface. However, good agreement with simulation is obtained with empirical scaling of the PRISM-predicted direct correlation functions. Effects of attractive interactions are treated using the random-phase approximation. The results of theoretical predictions for the attractive system are also in reasonable agreement with simulation results. In general, the theory performs best when the wall-polymer interaction strength is comparable to polymer-polymer interactions.

Comparison of random-walk density functional theory to simulation for bead-spring homopolymer melts.

Density profiles for a homopolymer melt near a surface are calculated using a random-walk polymeric density functional theory, and compared to results from molecular dynamics simulations. All interactions are of a Lennard-Jones form, for both monomer-monomer interactions and surface-monomer interactions, rather than the hard core interactions which have been most investigated in the literature. For repulsive systems, the theory somewhat overpredicts the density oscillations near a surface. Nevertheless, near quantitative agreement with simulation can be obtained with an empirical scaling of the direct correlation function. Use of the random phase approximation to treat attractive interactions between polymer chains gives reasonable agreement with simulation of dense liquids near neutral and attractive surfaces.

Anomalous mixing behavior of polyisobutylene/polypropylene blends: molecular dynamics simulation study.

The unusual mixing behavior of polyisobutylene (PIB) with head-to-head (hhPP) and head-to-tail polypropylene (PP) is studied using large-scale molecular dynamics (MD). The heats of mixing and Flory chi parameters were computed from MD simulations of both blends using a united atom model. The chi parameters from the simulations were estimated from the structure factors using the random phase approximation in analogy with neutron scattering (SANS) experiments. MD simulations for syndiotactic hhPP/PIB predicted a lower critical solution temperature with a chi parameter in very good agreement with SANS experiments on the atactic hhPP/PIB blend. MD simulations also predicted that the isotactic PP/PIB blend was immiscible at high molecular weight in qualitative agreement with cloud point measurements on atactic PP/PIB.