Nonlinear Rheology of Unentangled Polymer Melts Reinforced with High Concentration of Rigid Nanoparticles

A scaling model is presented to analyze the nonlinear rheology of unentangled polymer melts filled with high concentration of small spherical particles. Assuming the majority of chains to be reversibly adsorbed to the surface of the particles, we show that the emergence of nonlinearity in the viscoelastic response of the composite system subjected to a 2D shear flow results from stretching of the adsorbed chains and increasing desorption rate of the adsorbed segments due to the imposed deformation. The steady-state shear viscosity of the mixture in nonlinear shear thinning regime follows the power lawwhereis the applied shear rate. At large strain amplitude γ 0, the storage and loss moduli in strain sweep tests scale asandrespectively

Unveiling thermal transitions of polymers in subnanometre pores

The thermal transitions of confined polymers are important for the application of polymers in molecular scale devices and advanced nanotechnology. However, thermal transitions of ultrathin polymer assemblies confined in subnanometre spaces are poorly understood. In this study, we show that incorporation of polyethylene glycol (PEG) into nanochannels of porous coordination polymers (PCPs) enabled observation of thermal transitions of the chain assemblies by differential scanning calorimetry. The pore size and surface functionality of PCPs can be tailored to study the transition behaviour of confined polymers. The transition temperature of PEG in PCPs was determined by manipulating the pore size and the pore–polymer interactions. It is also striking that the transition temperature of the confined PEG decreased as the molecular weight of PEG increased

Radiation-induced melting in coherent X-ray diffractive imaging at the nanoscale

Coherent X-ray diffraction techniques play an increasingly significant role in imaging nanoscale structures which range from metallic and semiconductor samples to biological objects. The conventional knowledge about radiation damage effects caused by ever higher brilliance X-ray sources has to be critically revised while studying nanostructured materials

Fluorescence studies of confinement in polymer films and nanocomposites: Glass transition temperature, plasticizer effects, and sensitivity to stress relaxation and local polarity

Confinement effects in polystyrene and poly(methyl methacrylate) films and nanocomposites are studied by fluorescence. The ability to employ an intensive measurable, the excited-state fluorescence lifetime, in defining the glass transition temperature, Tg, of polymers is demonstrated and compared to the use of an extensive measurable, fluorescence intensity. In addition, intrinsic fluorescence from the phenyl groups in polystyrene is used to determine the Tg-confinement effect in films as thin as ~15 nm. The decrease in Tg with decreasing film thickness (below ∼60 nm) agrees well with results obtained by extrinsic pyrene fluorescence. Dye label fluorescence is used to quantify the enhancement in Tg observed with decreasing thickness (below ~90 nm) in poly(methyl methacrylate) films; addition of 2–4 wt% dioctyl phthalate plasticizer reduces or eliminates the Tg-confinement effect in films down to 20 nm thickness. Intrinsic polystyrene fluorescence, which is sensitive to local conformation, is used to quantify the time scales (some tens of minutes) associated with stress relaxation in thin and ultrathin spin-coated films at Tg + 10 K. Finally, the shape of the fluorescence spectrum of pyrene doped at trace levels in polystyrene films and polystyrene-silica nanocomposites is used to determine effects of confinement on microenvironment polarity