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Register a new userCoupling of nanoparticle dynamics to polymer center-of-mass motion in semidilute polymer solutions
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We investigate the dynamics of nanoparticles in semidilute polymer solutions when the nanoparticles are comparably sized to the polymer coils using explicit- and implicit-solvent simulation methods. The nanoparticle dynamics are subdiffusive on short time scales before transitioning to diffusive motion on long time scales. The long-time diffusivities scale according to theoretical predictions based on full dynamic coupling to the polymer segmental relaxations. In agreement with our recent experiments, however, we observe that the nanoparticle subdiffusive exponents are significantly larger than predicted by the coupling theory over a broad range of polymer concentrations. We attribute this discrepancy in the subdiffusive regime to the presence of an additional coupling mechanism between the nanoparticle dynamics and the polymer center-of-mass motion, which differs from the polymer relaxations that control the long-time diffusion. This coupling is retained even in the absence of many-body hydrodynamic interactions when the long-time dynamics of the colloids and polymers are matched.
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We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using x-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve as a function of normalized length scales. These results suggest that the soft interaction potential between polymer-grafted nanoparticles and free polymer allows polymer-grafted nanoparticles to diffuse faster than predicted based on bulk rheology and modifies the coupling between grafted particle dynamics and the relaxations of the surrounding free polymer.
In our previous publication (Ref. 1) we have shown that the data for the normalized diffusion coefficient of the polymers, $D_p/D_{p0}$, falls on a master curve when plotted as a function of $h/lambda_d$, where $h$ is the mean interparticle distance and $lambda_d$ is a dynamic length scale. In the present note we show that also the normalized diffusion coefficient of the nanoparticles, $D_N/D_{N0}$, collapses on a master curve when plotted as a function of $h/R_h$, where $R_h$ is the hydrodynamic radius of the nanoparticles.
The organization of nano-particles inside grafted polymer layers is governed by the interplay of polymer-induced entropic interactions and the action of externally applied fields. Earlier work had shown that strong external forces can drive the formation of colloidal structures in polymer brushes. Here we show that external fields are not essential to obtain such colloidal patterns: we report Monte Carlo and Molecular dynamics simulations that demonstrate that ordered structures can be achieved by compressing a `sandwich of two grafted polymer layers, or by squeezing a coated nanotube, with nano-particles in between. We show that the pattern formation can be efficiently controlled by the applied pressure, while the characteristic length--scale, i.e. the typical width of the patterns, is sensitive to the length of the polymers. Based on the results of the simulations, we derive an approximate equation of state for nano-sandwiches.
We present a comprehensive investigation of polymer diffusion in the semidilute regime by fluorescence correlation spectroscopy (FCS) and dynamic light scattering (DLS). Using single-labeled polystyrene chains, FCS leads to the self-diffusion coefficient while DLS gives the cooperative diffusion coefficient for exactly the same molecular weights and concentrations. Using FCS we observe a new fast mode in the semidilute entangled concentration regime beyond the slower mode which is due to self-diffusion. Comparison of FCS data with data obtained by DLS on the same polymers shows that the second mode observed in FCS is identical to the cooperative diffusion coefficient measured with DLS. An in-depth analysis and a comparison with current theoretical models demonstrates that the new cooperative mode observed in FCS is due to the effective long-range interaction of the chains through the transient entanglement network.
We present results of temperature dependent measurements of dynamics of micellar nanoparticle - polymer composites of fixed volume fraction and variable polymer chain grafting density. For nanoparticles with lower grafting density we observe dynamically arrested state at low temperatures corresponding to an attractive glass while at high temperature the same system shows relaxation typical of a repulsive glass. For higher grafting density, the low temperature dynamics resembles more of a gel which crosses over to a repulsive glass at high temperature. Possible reasons for such fascinating dynamical transitions is delineated.
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