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    5 The Degree of Crystallinity

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    agooh92
    The document discusses the thermal properties and crystallization behavior of polymers. It explains that below the glass transition temperature, polymers are in a glassy state but become more mobile and able to crystallize above this point. The rate of cooling after processing impacts the degree of crystallinity, with slower cooling allowing more crystallization. Stretching polymers before cooling also increases crystallinity. Differential scanning calorimetry can determine the degree of crystallinity based on the heat of melting measured compared to fully crystalline samples.

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    5 The Degree of Crystallinity

    Uploaded by

    agooh92
    120 views6 pages
    The document discusses the thermal properties and crystallization behavior of polymers. It explains that below the glass transition temperature, polymers are in a glassy state but become more mobile and able to crystallize above this point. The rate of cooling after processing impacts the degree of crystallinity, with slower cooling allowing more crystallization. Stretching polymers before cooling also increases crystallinity. Differential scanning calorimetry can determine the degree of crystallinity based on the heat of melting measured compared to fully crystalline samples.

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    5 The degree of crystallinity

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    The document discusses the thermal properties and crystallization behavior of polymers. It explains that below the glass transition temperature, polymers are in a glassy state but become more mobile and able to crystallize above this point. The rate of cooling after processing impacts the degree of crystallinity, with slower cooling allowing more crystallization. Stretching polymers before cooling also increases crystallinity. Differential scanning calorimetry can determine the degree of crystallinity based on the heat of melting measured compared to fully crystalline samples.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    120 views6 pages

    5 The Degree of Crystallinity

    Uploaded by

    agooh92
    The document discusses the thermal properties and crystallization behavior of polymers. It explains that below the glass transition temperature, polymers are in a glassy state but become more mobile and able to crystallize above this point. The rate of cooling after processing impacts the degree of crystallinity, with slower cooling allowing more crystallization. Stretching polymers before cooling also increases crystallinity. Differential scanning calorimetry can determine the degree of crystallinity based on the heat of melting measured compared to fully crystalline samples.

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    of 6

    THERMAL PROPERITES OF

    POLYMERS
    Crstalline polymer

    Glassy Viscous
    Viscoelastic state
    state state
    TG TC TM

    Amorphous polymer
    Glassy Viscoelastic Viscous
    state state state
    TG

    TG - glass transition temperature


    TC - crystallization temperature
    TM - melting temperature
    CRYSTALLIZATION
    Below the glass transition, polymers are in a glassy state.
    They are stiff and hard.
    Their macrochains do not have much energy to move.
    The macrochains do not change their conformations.

    Above the glass transition, the polymers gain a lot of mobility.

    When the polymer is above the glass temperature (during heating and cooling as well), its
    macrochains have enough energy to crystallize (to move into ordered arrangements, called
    crystals).

    Each polymer has different degree of crystallinity. It depends on the polymer chemical structure.
    Some polymers do not have crystallinity at all – they are amorphous polymers.
    There are not 100% crystalline polymers.
    CRYSTALLIZATION
    In the industry, the processes of shaping particular products are
    based on the subsequent heating and cooling operations.
    The polymer in the form of granules is introduced into the machine,
    such as injection molding machine or extruder. It is melted inside.
    Than it leaves the machine and is cooled down in the mold or in the
    air or water bath.
    That cooling process is essential for the degree of crystallinity.
    If it is slow – the polymer macrochains have time to organize and
    form crystals.
    If it is fast – the polymer macrochains do not have time to organize
    and only small amounts of crystals are formed.
    If the degree of crystallinity is insufficient, the material will not have
    proper properties and will deform during use, because the polymer
    „remembers” its optimum degree of crystallinity and it tends to
    achieve this level of crystallinity. It is easy, if this polymer is at the
    temperature above Tg.
    Therefore, the degree of crystallinity has to be controlled. It can be
    done with the use of DSC.
    Stretch supported CRYSTALLIZATION
    In the industry, sometimes, products are stretched before cooling.
    Stretching increases the degree of crystallinity. As a result increases in mechanical properties are observed.
    Polymeric materials are stiffer, more durable, they have thinner walls and therefore they are lighter.
    Fibers, films and sometimes bottles are stretched.
    CRYSTALLIZATION
    When polymers crystallize, they give off heat (this is an
    exothermic process).
    Tc – crystallization
    This is seen as a big peak in the thermogram. temperature
    Its presence in the thermogram depends on the degree of
    crystallinity in the polymer, which was generated during previous
    cooling operation.
    If cooling was slow – that peak is not present in the thermogram.
    If the cooling was fast – that peak is present in the thermogram.

    Area of the peak –


    the latent energy of
    crystallization
    DEGREE OF POLYMER
    CRYSTALLINITY BY DSC
    H
    X cDSC = 100
    H100
    Xc DSC – the degree of crystallinity determined by DSC [%]
    H – the measured enthalpy of melting of the sample [J/g]
    H100 – the enthalpy of melting of a 100% pure crystalline sample of the same
    polymer [J/g]

    H100 for some polymers are available in the literature:

    [1] Mandelkern L., Crystallization of Polymers, McGraw-Hill, New York (1964).


    [2] METTLER TOLEDO Collected Applications TA, Mettler Toledo buletin

    H100=115 J/g for PET

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