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  • Polymer Bulk Morphology & Properties

    Încărcat de

    Soraya
    14 vizualizări41 pagini
    Polymer morphology and properties in the bulk state can be amorphous or semi-crystalline depending on the cooling process. Polymers transition between solid, molten, and glassy states depending on temperature, with characteristic melting and glass transition temperatures. Polymer chains reptate and crystallize through various cooling or solvent evaporation methods. Techniques like X-ray diffraction are used to characterize crystalline structure. The glass transition is influenced by factors like chain flexibility and tacticity. Viscoelastic behavior is studied through creep, stress relaxation, and dynamic mechanical analysis to understand both elastic and viscous responses over time.

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    Polymer bulk state

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    The Bulk State

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    Polymer morphology and properties in the bulk state can be amorphous or semi-crystalline depending on the cooling process. Polymers transition between solid, molten, and glassy states depending on temperature, with characteristic melting and glass transition temperatures. Polymer chains reptate and crystallize through various cooling or solvent evaporation methods. Techniques like X-ray diffraction are used to characterize crystalline structure. The glass transition is influenced by factors like chain flexibility and tacticity. Viscoelastic behavior is studied through creep, stress relaxation, and dynamic mechanical analysis to understand both elastic and viscous responses over time.

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    14 vizualizări41 pagini

    Polymer Bulk Morphology & Properties

    Încărcat de

    Soraya
    Polymer morphology and properties in the bulk state can be amorphous or semi-crystalline depending on the cooling process. Polymers transition between solid, molten, and glassy states depending on temperature, with characteristic melting and glass transition temperatures. Polymer chains reptate and crystallize through various cooling or solvent evaporation methods. Techniques like X-ray diffraction are used to characterize crystalline structure. The glass transition is influenced by factors like chain flexibility and tacticity. Viscoelastic behavior is studied through creep, stress relaxation, and dynamic mechanical analysis to understand both elastic and viscous responses over time.

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    Polymermorphologyandpropertiesinthebulkstate

    Polymersolids

    Amorphous

    Semicrystalline

    Polymermorphologyinthebulkstate

    Molten state
    cooling
    Crystalline structure

    Polymermorphologyinthebulkstate

    Melting

    Tm

    V
    Glasstransition

    Tg

    Polymermorphologyinthebulkstate

    Reptation is the snake-like thermal motion of very long linear,


    entangled macromolecules in polymer melts or concentrated
    polymer solutions

    Reptationofpolymerchains

    1
    D 2
    M

    Polymermorphologyinthebulkstate

    Polymermorphologyinthebulkstate

    Solvent evaporation

    From solution
    Solution cooling
    Crystallization
    Cooling the melt
    From the melt

    Heating the glassy phase

    Polymermorphologyinthebulkstate

    LDPE crystals precipitated from a xylene


    solution (lamellar shaped)

    LDPE spherulites (observed through CP)


    obtained on cooling from the melt

    Polymermorphologyinthebulkstate

    Fiber formation

    The system becomes anisotropic

    Polymermorphologyinthebulkstate

    Xray diffraction
    Monocromatic Xray
    beam

    Braggs law

    Polymermorphologyinthebulkstate

    Polymermorphologyinthebulkstate

    XRD pattern of isotactic PP

    Polymermorphologyinthebulkstate

    Polymermorphologyinthebulkstate

    Theories of Tg

    The Free-Volume theory

    Specific volume

    V V0 V f
    Vf

    V f K ( R G )(T Tg )

    K
    V0

    Tg

    Temperature

    Polymermorphologyinthebulkstate

    The Kinetic theory


    6-7oC shift in Tg per decade of time scale of the experiment

    Polymermorphologyinthebulkstate

    The Thermodynamic theory


    The glass transition is a true second order transition, which takes
    place at time scale infinitely long.

    Polymermorphologyinthebulkstate

    Physical aging

    Polymermorphologyinthebulkstate

    Factors which affect Tg:


    Chain flexibility

    Polyethylene Terephtalate
    Tg= -123oC

    Tg= +69oC

    Tg= +185oC

    Polymermorphologyinthebulkstate

    Presence of aliphatic side groups

    Polymermorphologyinthebulkstate

    Tacticity

    Tabla p. 409 Sperling

    Polymermorphologyinthebulkstate

    Presence of stiff, bulky side groups

    Polymermorphologyinthebulkstate

    Pressure

    Polymermorphologyinthebulkstate

    Molecular weight

    Polymermorphologyinthebulkstate

    Degree of crosslinking
    In thermosets, Tg increases as the molecular weight between crosslinks decreases

    TTT diagram

    Polymermorphologyinthebulkstate

    Increase in number of
    gell particles

    Polymer bulk

    First formation of infinite


    network, theoretical gel point

    Gel particles

    Molecular weight increase

    Polymermorphologyinthebulkstate

    Modification of Tg by means of plasticizers


    By copolymerization reactions or blending (internal plasticizesr)

    1
    w1 w2

    Tg Tg1 Tg 2

    Fox equation

    By adding low MW compounds (external plasticizers)

    Plasticizers must be:


    -Compatible
    -Miscible with the polymer
    -Permanent, that is they need to have low diffusion coefficient and low vapour
    pressure

    Polymerpropertiesinthebulkstate

    Polymer Viscoelasticity

    Polymerpropertiesinthebulkstate

    l l0
    l0

    stress

    A0

    = E
    Hookes law

    ElasticSolid

    deformation

    stress

    .
    =
    Newtons law

    ViscousFluid
    rateofdeformation

    Polymerpropertiesinthebulkstate

    Polymers are generally non-Newtonian, except over narrowly defined


    ranges of strain rate.

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    Three fundamental methods for characterizing the viscoelastic behavior of polymers:

    Creep
    Stress relaxation
    Dynamic-mechanical analysis

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    In an idealized creep curve, we can distinguish four regions:


    the initial elastic response region: Hookes law with zero-time modulus
    a transition region: nonlinear increase in strain
    an equilibrium region: strain increases linearly with time, characteristic of
    viscous flow
    And, on removal of the stress
    a recovery region, characterized by an initial elastic retraction followed
    by a strain decay.
    Strain asymptotically approaches a non-zero value: permanent set
    Data are generally reported as a time-dependent creep compliance:

    (t )
    J (t )

    Polymerpropertiesinthebulkstate

    In the stress relaxation test, viscoelastic materials respond


    with a stress which decays with time.

    Stress relaxation data are commonly reported as timedependent stress relaxation modulus:

    (t )
    E (t )

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    A typical stress-strain curve for a polymer

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    Necking: zone with a lower section, much more strained than


    the neighbouring regions, characterized by chain orientation

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    Polymerpropertiesinthebulkstate

    Measurement of resilience

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