"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

Diffusion dynamics of star-shaped macromolecules in dilute solutions

Polymer chains dissolved in a solvent take random conformations due to large internal degrees of freedom and are characterized geometrically by their average shape and size. The diffusive dynamics of such large macromolecules play an indispensable role in a plethora of engineering applications. The influence of the size of the polymer chain on its diffusion is well studied, whereas the same cannot be said for the shape of the polymer chain. In the present work, the influence of shape on the center-of-mass diffusion of the star-shaped chains in solution is investigated using Multi-particle Collision Dynamics. Star-shaped chains of varying degrees of functionality are modeled in a good solvent at infinite dilution. The radius of gyration($R_g$) of the star-shaped chains follows a functionality-independent scaling law with the chain length($N$), $R_g \sim N^{\nu}$, where $\nu \sim 0.627$. The shape of the polymer chains is calibrated by relative shape anisotropy. Highly anisotropic star-shaped polymer chains are found to have a faster rate of diffusion along the translational direction due to a slower rate of rotational diffusion when the radius of gyration of the polymer chains is maintained constant.Comment: 24 pages, 11 figure

The Hydrodynamic Interaction in Polymer Solutions Simulated with Dissipative Particle Dynamics

We analyzed extensively the dynamics of polymer chains in solutions simulated with dissipative particle dynamics (DPD), with a special focus on the potential influence of a low Schmidt number of a typical DPD fluid on the simulated polymer dynamics. It has been argued that a low Schmidt number in a DPD fluid can lead to underdevelopment of the hydrodynamic interaction in polymer solutions. Our analyses reveal that equilibrium polymer dynamics in dilute solution, under a typical DPD simulation conditions, obey the Zimm model very well. With a further reduction in the Schmidt number, a deviation from the Zimm model to the Rouse model is observed. This implies that the hydrodynamic interaction between monomers is reasonably developed under typical conditions of a DPD simulation. Only when the Schmidt number is further reduced, the hydrodynamic interaction within the chains becomes underdeveloped. The screening of the hydrodynamic interaction and the excluded volume interaction as the polymer volume fraction is increased are well reproduced by the DPD simulations. The use of soft interaction between polymer beads and a low Schmidt number do not produce noticeable problems for the simulated dynamics at high concentrations, except that the entanglement effect which is not captured in the simulations.Comment: 27 pages, 13 page

A finite excluded volume bond-fluctuation model: Static properties of dense polymer melts revisited

The classical bond-fluctuation model (BFM) is an efficient lattice Monte Carlo algorithm for coarse-grained polymer chains where each monomer occupies exclusively a certain number of lattice sites. In this paper we propose a generalization of the BFM where we relax this constraint and allow the overlap of monomers subject to a finite energy penalty \overlap. This is done to vary systematically the dimensionless compressibility $g$ of the solution in order to investigate the influence of density fluctuations in dense polymer melts on various s tatic properties at constant overall monomer density. The compressibility is obtained directly from the low-wavevector limit of the static structure fa ctor. We consider, e.g., the intrachain bond-bond correlation function, $P(s)$, of two bonds separated by $s$ monomers along the chain. It is shown that the excluded volume interactions are never fully screened for very long chains. If distances smaller than the thermal blob size are probed ($s \ll g$) the chains are swollen acc ording to the classical Fixman expansion where, e.g., $P(s) \sim g^{-1}s^{-1/2}$. More importantly, the polymers behave on larger distances ($s \gg g$) like swollen chains of incompressible blobs with P(s) \si m g^0s^{-3/2}.Comment: 46 pages, 12 figure