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    Polymers & Elastomers: Concepts: Glass Transition Temperature Natural Rubber, Vulcanisation

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    1. Polymers exhibit different behaviors depending on temperature, especially around the glass transition temperature (Tg). Below Tg they are rigid and brittle, above they are rubbery. 2. Natural rubber is a polymer of the monomer isoprene. It is liquid and not very useful. Vulcanization crosslinks the polymer chains using sulfur, making it a solid elastic material. 3. Elastomers have mobile polymer chains that allow large, reversible deformations when stretched. They contract when heated due to decreasing entropy of the stretched state.

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    Polymers & Elastomers: Concepts: Glass Transition Temperature Natural Rubber, Vulcanisation

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    navish
    31 views27 pages
    1. Polymers exhibit different behaviors depending on temperature, especially around the glass transition temperature (Tg). Below Tg they are rigid and brittle, above they are rubbery. 2. Natural rubber is a polymer of the monomer isoprene. It is liquid and not very useful. Vulcanization crosslinks the polymer chains using sulfur, making it a solid elastic material. 3. Elastomers have mobile polymer chains that allow large, reversible deformations when stretched. They contract when heated due to decreasing entropy of the stretched state.

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    APL

    Original Title

    Lecture 13 23Aug17

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    1. Polymers exhibit different behaviors depending on temperature, especially around the glass transition temperature (Tg). Below Tg they are rigid and brittle, above they are rubbery. 2. Natural rubber is a polymer of the monomer isoprene. It is liquid and not very useful. Vulcanization crosslinks the polymer chains using sulfur, making it a solid elastic material. 3. Elastomers have mobile polymer chains that allow large, reversible deformations when stretched. They contract when heated due to decreasing entropy of the stretched state.

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    31 views27 pages

    Polymers & Elastomers: Concepts: Glass Transition Temperature Natural Rubber, Vulcanisation

    Uploaded by

    navish
    1. Polymers exhibit different behaviors depending on temperature, especially around the glass transition temperature (Tg). Below Tg they are rigid and brittle, above they are rubbery. 2. Natural rubber is a polymer of the monomer isoprene. It is liquid and not very useful. Vulcanization crosslinks the polymer chains using sulfur, making it a solid elastic material. 3. Elastomers have mobile polymer chains that allow large, reversible deformations when stretched. They contract when heated due to decreasing entropy of the stretched state.

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    of 27

    IIT Delhi

    APL 102

    Polymers & Elastomers


    Concepts: Glass transition temperature; natural rubber, vulcanisation,

    Lecture 13
    Recap
    IIT Delhi Poly (many) mer (unit)

    Crystallinity:
    % of material that is crystalline

    Polymer classification
    (based on arrangement of monomers)
     Linear/chain polymer &
     Network polymers

    - Long chain polymer


    Degree of Polymerization:
    Plastics Fibres Elastomer No. of repeating monomers in a chain
    Classification of Polymers
    IIT Delhi

    Based on the behaviour with temperature

    Thermoplastics

    Thermosets
    Thermoplastics vs Thermosets
    IIT Delhi

     Thermoplastics:
    -- little cross linking
    -- ductile
    -- soften w/heating and harden on cooling
    -- polyethylene (PE), polypropylene (PP)
    polycarbonate, PVC, PMMA, polystyrene

     Thermosets:
    -- more cross linking (10 to 50 % of mers)
    -- hard and brittle
    -- do NOT soften w/heating
    -- vulcanized rubber, epoxies, bakelite (switches)
    polyester resin, phenolic resin

    (F.W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)
    IIT Delhi
    Question for thought?

    What is the important characteristic behavior that polymers


    exhibit as f(T)?

    Glass transition
    T
    IIT Delhi

    Callister,
    rubber
    viscous
    Fig. 16.9
    mobile liquid Tm
    liquid tough
    plastic
    Tg

    partially
    crystalline
    crystalline
    solid
    solid

    Molecular weight

    (F.W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)
    Glass Transition Temperature
    IIT Delhi

    The temperature at which the polymer experiences the transition from


    rubbery to rigid state is termed the glass transition temperature, Tg

    Tm

    Rubbery
    T
    Tg

    Rigid solid

    Typically Tg is 0.4 – 0.75 Tm


    Elastic deformation of Polymers
    IIT Delhi

     In metals/ceramics Young's modulus (E) generally decrease with


    increase in temperature

     The change in modulus is not that significant in these materials as


    compared to polymers

    For polymers, however, a temperature change of 30 °C may change the


    elastic modulus by a factor of 1,000
    Effect of T on Polymer Stiffness
    IIT Delhi

    An example of
    Polystyrene

    The drastic change is associated with the temperature being high enough to weaken the secondary
    bonds of the polymer allowing more chain movement and therefore decreasing the polymer stiffness.
    IIT Delhi

    Elastomers
    IIT Delhi
    Elastomers
     Exhibit rubber like elasticity
     Long chain molecules with some cross-link
     Crosslinks are present at a distance of few hundred monomers
     Natural tendency for bending and coiling
    Mobile segments

     Chain segments have translational mobility


    at room temperature

    Cross-link points
    IIT Delhi

    Liquid natural rubber (latex)


    being collected from the
    rubber tree

    Liquid state:
    Translation point confirmed
    IIT Delhi
    Isoprene molecule

    H H3C H
    C=C-C=C
    H H H
    commons.wikimedia.org
    IIT Delhi
    Question for thought?

    What should be done for repeating this monomer in a chain?


    IIT Delhi

    H CH3 H H H CH3 H
    C CC C CC CC
    H H H H H

    Isoprene Polymerization Polyisoprene


    molecule mer
    Liquid (Latex)

    Bigger side group requires more space, since rotational movement is difficult.
    Because of double bond it starts bending, this provides natural tendency of
    bending and coiling
    IIT Delhi
    Question for thought?

    Natural rubber (Liquid) is not so useful, it is subjected to some


    process to convert it to hard, soft rubber. What is that?
    Vulcanisation
    IIT Delhi

    Heat the liquid with Sulphur

    H H CH3 H
    CC CC
    H H
    + 2S
    H H
    CC CC
    H H CH3 H
    Vulcanisation
    IIT Delhi

    H H CH3 H
    CC CC


    Cross-links


    H H
    S S
    H H



    CC CC
    H H CH3 H

    Now this becomes solid mass!!


    IIT Delhi

    Here cross-linking happen


    through foreign atoms or
    molecules

    Ref: Wulff Series


    Effect of cross-linking on polyisoprene
    IIT Delhi

    Natural
    Elastomer Ebonite
    rubber
    liquid Elastic solid Hard &
    (soft rubber) brittle

    not lightly heavily


    cross (x)-linked x-linked x-linked
    Summary of key points
    IIT Delhi

    Plastics have non-directional property and changing the mer leads to


    various polymers

    Fibres have directional property

    Elastomers – rubber like behaviour with mobile segments

    Note that by playing with degree of the vulcanization one can


    generate various possibilities.

    After 100% crosslinking we call this as ebonite.

    Cross link after every few 100 monomers gives soft rubber.
    IIT Delhi
    Question for thought?

    How do the elastomer behave while mechanically loaded?


    Mechanical behavior of Elastomers
    IIT Delhi

    (Lab expt. after Minor 1)

    1. A few hundred percent of temporary (recoverable)


    deformation on stretching

    2. The deformation is non-linear, Stress  strain

    3. The stretched elastomers contracts on heating


    Elastomer Elastomer sample
    IIT Delhi sample under tension

    Tensile force heat

    straight
    Coiled chains chains

    Higher Lower
    entropy entropy Still lower
    entropy

    Contracts on
    heating
    F
    IIT Delhi

    Elastomers have ve thermal expansion coefficient,


    i.e., they CONTRACT on heating!!

    Lab expt. after Minor 1


    Section 10.3 of the textbook
     S 
    F  T  
    IIT Delhi

     Enthalpy change on
    stretching = 0
     L T
     I law of Thermodynamics  F → Force applied to stretch
     II law of Thermodynamics  T → Constant temperature
     L → Length of molecule
     S → Entropy

     Entropy change for stretch


    L0 → L  
     Change in number of S  S 0  k ln 
    configurations
    0 → 
     0 
    Announcement
    IIT Delhi

     Minor I exam details:

    Date: 31-Aug-17
    Venue: LH 121 & LH 308
    Time: 2:30 to 3:30 pm

     Minor I Syllabus: Topics covered till today (23rd Aug 17) lecture

     Tuesday (29th Aug) Lab is on this Saturday (26th Aug)

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