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    Polymeric Liquid Behavior in Oscillatory Shear Flow

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    Kanso, Mona
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    Abstract
    One of the great challenges in chemical engineering is to predict physical

    properties from molecular structure. Predicting transport properties presents

    special challenges, especially for macromolecular structures. This thesis focuses

    on the properties governing momentum transport in polymeric liquids, and

    specifically those properties conferring elasticity to such liquids.

    In the first part of this thesis, we examine the second order orientation tensor

    for the simplest molecular model relevant to a polymeric liquid in largeamplitude

    oscillatory shear flow (LAOS), the rigid dumbbell suspension. From

    the second invariant of the order parameter tensor, we calculate the scalar, the

    nematic order, and examine its evolution for a polymeric liquid in LAOS. We

    find this nematic order, our main result, to be even. We use Lissajous figures to

    illustrate the roles of the Weissenberg and Deborah numbers on the evolving

    order in LAOS. We use the low frequency limit of our main result to arrive at an

    expression for the nematic order in steady shear flow. This work gives a first

    glimpse into macromolecular order in LAOS.

    In the second part of this thesis, we explore general rigid bead-rod theory, which

    explains polymer viscoelasticity from macromolecular orientation. By means of

    general rigid bead-rod theory, we relate the complex viscosity of polymeric liquids

    to the architecture of axisymmetric macromolecules. In this work, we explore the

    zero-shear and complex viscosities of 24 different axisymmetric polymer

    configurations. When non-dimensionalized with the zero-shear viscosity, the

    complex viscosity depends on the dimensionless frequency and the sole

    dimensionless architectural parameter, the macromolecular lopsidedness. In this work,

    in this way, we compare and contrast the elastic and viscous components of the

    iii

    complex viscosities of macromolecular chains that are straight, branched, ringed, or

    star-branched. We explore the effects of branch position along a straight chain,

    branched-chain backbone length, branched-chain branch-functionality, branch

    spacing along a straight chain (including pom-poms), the number of branches along

    a straight chain, ringed polymer perimeter, branch-functionality in planar stars, and

    branch dimensionality. In addition, we study diblock copolymers by exploring the

    effects of linear density, macromolecular length, and bead number ratio on

    relaxation time.
    URI for this record
    http://hdl.handle.net/1974/26437
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