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  • American Institute of Physics (AIP)  (4)
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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5291-5306 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effects of polydispersity on the linear viscoelastic properties of concentrated polymer solutions and melts are analyzed. Existing theories for the dynamics of linear polymers, based on the idea of each polymer confined in a fixed tube, are shown to be incapable of describing observed rheological response of polydisperse polymers. A model is proposed which, in a self-consistent manner, solves the many chain problem given the solution to the single chain problem. Two types of polymer relaxation are incorporated in the model. The first type is escape of a polymer from its tube by motion of the polymer itself. It includes all dynamic modes available to the single chain in a tube—those due to its reptation—as well as other modes, such as fluctuations in tube length. The second type is relaxation of a polymer chain by the motions of the surrounding polymers forming its tube (constraint release). The relaxation modulus is then the product of two functions μ(t) and R(t). μ(t) is the fraction of tube occupied at time t=0 that has not been evacuated at time t, thereby representing escape of the polymer from its tube (solution to the single chain problem). R(t) represents relaxation by the constraint release process, which is modeled by a Rouse chain with random bead mobilities. The probability distribution of these mobilities is determined, in a self-consistent way, from the disentanglement rates due to the tube evacuation processes of the surrounding chains. Thus R(t) is calculated from the spectrum of relaxation rates of the μ(t) processes for the surrounding chains. The predictions of the model with some single chain solutions μ(t) from the literature are compared with oscillatory shear data for binary blends of nearly monodisperse polybutadiene, in which both components are well entangled.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 3777-3788 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The presence of two distinctly different local segmental mobilities found in the case of several phase mixed polymer blends by two-dimensional 2H-NMR, dielectric spectroscopy and depolarized dynamic light scattering is rationalized through a simple concentration fluctuation model. Our primary hypothesis is that, although the probability of the occurrence of concentration fluctuations is symmetric about the mean value in a given volume, the "cooperative volume'' over which a fluctuation must occur for it to be detected by a dynamic probe is not a constant, but rather depends on the composition of the cooperative volume. Consequently, we suggest that the cooperative volume associated with a concentration fluctuation be determined by the local composition in a self-consistent manner. In the case of systems with weak interactions and large Tg contrast, these ideas are shown to create a bimodal probability density function for dynamic concentration fluctuations, which has a local maximum corresponding to small cooperative volumes rich in the more mobile component, in addition to the bulk composition itself. We also predict the broadening of both the segmental relaxation time spectrum and the single calorimetric glass transition of the blends with increasing concentration of the slow component. Comparisons of the predictions are made for two experimental systems with different thermodynamic and kinetic effects to illustrate the present approach. Further, we predict the effects of concentration fluctuations in the case of three other blends whose segmental dynamics have not been examined experimentally to date. We predict that the dynamics of the two components approximately follow time–temperature superposition either in the case of strongly interacting blends or for systems that have closely matched Tg values and Williams–Landel–Ferry (WLF) coefficients. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 6121-6128 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We recently proposed a concentration fluctuation model to describe the segmental dynamics of miscible polymer blends [Kumar et al., J. Chem. Phys. 105, 3777 (1996)]. This model assumes the existence of a cooperative volume, similar to that in the Adam-Gibbs picture of the glass transition, over which segments have to reorganize in a concerted fashion to facilitate stress relaxation. No molecular theory exists for the cooperative volume. Consequently, here we critically compare two alternative functional dependences for this quantity in the context of the segmental dynamics of the most extensively studied miscible polymer blend, 1,4-polyisoprene (PI) and polyvinylethylene (PVE): (a) The Donth model, which assumes the Vogel form for the temperature dependence of relaxation processes, with a relaxation time that diverges at the Vogel temperature, roughly 50 K below the glass transition, and (b) a more recent dynamic scaling model that predicts the relaxation time diverges algebraically, only about 10 K below the glass transition. We find that the dynamic scaling model provides a near-quantitative description of the segmental relaxation in PI/PVE blends. In contrast, the Donth model predicts that the relaxation time spectrum for PI, the faster relaxing component, is bimodal, in qualitative disagreement with NMR experiments and our dielectric measurements reported here. Our results therefore emphasize two findings. First, our model can describe the segmental relaxations of the components of a polymer blend in a near-quantitative manner. Second, and more fundamentally, it appears that the dynamic scaling model describes segmental dynamics of polymers near their glass transition. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 865-868 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We examine the thermodynamics of supercooled liquids focusing on the immediate vicinity of an onset temperature, TA, where system dynamics just begin to experience caging effects. Simulation data from a polymer model and from small molecule mixtures show, in agreement with experiment, that the configurational entropy becomes strongly temperature dependent below TA. Since the diffusion coefficient follows the Adam-Gibbs relationship, our results clearly establish a thermodynamic connection to the localized dynamics of glass-forming liquids. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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