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    States of Order in Polymers

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    MianHusnain Iqbal
    The document discusses the various states of order that polymers can exist in, including solid, liquid, and crystalline states, and how factors like temperature, chain structure, and molecular weight affect the shape and properties of macromolecules in different environments like solutions, melts, and solids. It also covers topics like glass transition temperatures, crystallization, and the different physical forms polymers can take like amorphous, elastomeric, and semicrystalline.

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    © All Rights Reserved
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    States of Order in Polymers

    Uploaded by

    MianHusnain Iqbal
    42 views28 pages
    The document discusses the various states of order that polymers can exist in, including solid, liquid, and crystalline states, and how factors like temperature, chain structure, and molecular weight affect the shape and properties of macromolecules in different environments like solutions, melts, and solids. It also covers topics like glass transition temperatures, crystallization, and the different physical forms polymers can take like amorphous, elastomeric, and semicrystalline.

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    Amorphous and crystalline Polymers

    Original Title

    1. States of Order in Polymers

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    The document discusses the various states of order that polymers can exist in, including solid, liquid, and crystalline states, and how factors like temperature, chain structure, and molecular weight affect the shape and properties of macromolecules in different environments like solutions, melts, and solids. It also covers topics like glass transition temperatures, crystallization, and the different physical forms polymers can take like amorphous, elastomeric, and semicrystalline.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    42 views28 pages

    States of Order in Polymers

    Uploaded by

    MianHusnain Iqbal
    The document discusses the various states of order that polymers can exist in, including solid, liquid, and crystalline states, and how factors like temperature, chain structure, and molecular weight affect the shape and properties of macromolecules in different environments like solutions, melts, and solids. It also covers topics like glass transition temperatures, crystallization, and the different physical forms polymers can take like amorphous, elastomeric, and semicrystalline.

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    States of order in polymers

    States of Order in Polymers


    Configuration and conformation
    Polymer chain shape

    Macromolecules in:
    Solution
    Molten state
    Solid state
    Solid State Properties of Polymers

    PPE-206 Polymer Structure and Synthesis


    Polymer Phases

    Viscous Liquid

    Polydimethylsiloxane Tg = -123°C; Tm = -40 °C


    Elastomeric
    Polyisoprene Tg = -73 °C Semi-Crystalline
    Polybutadiene, Tg = -85 °C
    Polychloroprene, Tg = -50 °C Nylon 6,6, Tg = 50 °C; Tm = 265 °C
    Polyisobutylene, Tg = -70 °C Poly ethylene terephthalate, Tg = 65 °C; Tm =270 °C

    Glassy
    Polystyrene Tg = 100 °C
    Polymethyl methacrylate, Tg = 105 °C
    Glass-rubber-liquid
    Amorphous plastics have a complex
    thermal profile with 3 typical states:
    Glass phase (hard plastic) Polystyrene
    9

    8
    Leathery phase Tygon (plasticized PVC)
    Log(stiffness) 7
    Pa 6 Rubber phase (elastomer)
    5 polyisobutylene
    Tg
    4
    Liquid PDMS
    3

    Temperature
    Physical States of Polymers

     Liquids
     Silicon oils
     Specialty rubbers

    Solids
     Elastomers
     Amorphous
     Semicrystalline
    Macromolecules in Solution

    Importance of polymer solutions


     Polymer syntheses

    Molecular characterization

    Polymers processing to fibers
     Preparation of polymer blends, coatings and adhesives
     Polymer solutions (thickeners)
     Polymer mixtures/blends

    Polymer solutions are important because many polymer
    syntheses as well as most procedures for their molecular
    characterization are carried out in solution. Polymer solutions
    are furthermore essential in the processing of some polymers to
    fibers, preparation of polymer blends, coatings, and adhesives.
    Moreover, polymer solutions are applied because of their high
    viscosity (thickeners).
    Factors affecting properties of
    macromolecules
    Chemical composition
    Chain length
    Conformation
    Configuration

    Shape of isolated macromolecules:


    х compact sphere
    х extended rigid chain
     Loose coil shape
    Factors affecting coil shape

     Fixed bond angles


     Restricted rotation about the bonds
     Branching
     Incorporation of rigid chain components

    Aromatic rings

    Heterocyclic rings
     Intermolecular/intramolecular interactions

    H-bridges

    Electrostatic forces

     Fixed bond angles and restricted rotation about the bonds affect
    the shape of the coil. Branching and incorporation of rigid chain
    components (aromatic rings, heterocyclic rings) also influence the
    coil form. Finally, the shape of the coil is determined by
    intermolecular or intramolecular interactions, such as H-bridges or
    electrostatic forces
    Macromolecules in Solution
    Dilute polymer solution vs. low
    molecular weight compounds solution

    Swollen state (viscous effect)
     Polydispersity
     Coil shape
     Methods of the property measurement
    Solvents and Solubility

    Poor solvents (unperturbed coils)
     Good solvents (perturbed coils, swelling)
    Concentrated solution

    Critical concentration c*
    Macromolecules in Solution

    Molecular colloids

    Coil volume of macromolecules in solution
     20-1000 times larger than chain volume itself
     Swollen gel particle may consist of more than
    99% solvent

    Dependence of solutions properties


     Solvent
     Temperature
     Molecular weight of the chain molecules
    Macromolecules in Solution

    Swelling

    Limited swelling (marked by volume increase)
     Unlimited swelling (complete dissolution)
     Crosslinked polymers: measure of degree of
    crosslinking
    Macromolecules in Solution

    Incompatibility of mixtures of polymer


    solutions
     10% solutions of polystyrene and poly(vinyl
    acetate), each in benzene
    Factors

    Structure of the macromolecule

    Molecular weight

    Mixing ratio

    overall polymer concentration
     Temperature
    Macromolecules in Solution

    Polyelectrolytes

    Polymers that fall apart into charged
    polyions and many oppositely charged
    counterions

    Solution expands, becomes thick and
    syrupy
    Macromolecules in Molten State

     Coiled chain conformation


    Types of motion
     Micro-Brownian (near Tg)
     Macro-Brownian (reptation) (in Tg range)

     Deformation under external forces


     Entropy-elasticity
    Macromolecules in Elastomeric State

     Non-crosslinked rubbers: do not return completely


    to their original length after stretching
     Elastomeric networks: return completely to their
    original length after stretching

     Correlation between degree of crosslinking, elasticity


    and elastic modulus
    Macromolecules in Amorphous (Glassy) State

    Noncrystalline amorphous phases are


    obtained below Tg
    Glasses are formed best when
    macromolecular chains are:

    Irregular in structure (atactic, branched,
    crosslinked)
     Regular (isotactic, syndiotactic unbranched) if
    cooled down suddenly
    Macromolecules in Amorphous (Glassy) State
    Ordered orientation of the macromolecular
    coils can also occur by:

    stretching
     casting films from solution during the drying
    stage of the film as a result of shrinkage

    pulling thin film away from the support

    Orientation causes anisotropy of various


    physical properties (light scattering)
    Macromolecules in Amorphous (Glassy) State
    Characteristics of amorphous polymers:

    transparent
     very often soluble in common organic
    solvents at room temperature

    Important amorphous polymers:


     Poly(vinyl chloride) 
    Cycloolefine

    Polystyrene copolymers

    Poly(methyl methacrylate)

    Polysulfone
     ABS-polymers

    Poly(ether sulfone)

    Polycarbonate

    Poly(ether imide)
    Macromolecules in the Crystalline State

    Formation

    Slow cooling of solutions/melts of
    macromolecules having:
     no branching
     no copolymers
     regular substitution pattern
     highly iso- or syndiotactic
    Macromolecules in the Crystalline State

    Degree of crystallinity

    fraction of semi crystalline material is termed
    as degree of crystallinity.

    Reason of reduced crystallinity


     Difficulty in changing their shape from the
    coiled state in the melt into the ordered one
    necessary for their incorporation in a crystal
    Macromolecules in the Crystalline State
    Models of crystallization process
     Fringed micelle model (Natural polymers)
     Cellulose and proteins (collagen, silk)
     Folded lamella model (Synthetic polymers)
     Polyethylene and polypropylene
    Macromolecules in the Crystalline State
    Folded lamella model
     Growth of single crystals

    Lamellae thickness (10-1000 micro meter)
     Role of tie molecules
    Macromolecules in the Crystalline State
    Conformation of folded lamella
     Planar zigzag
     Crystalline polyethylene
     Helix (3-, 4-, or 5-fold)
     Polypropylene
     Polyoxymethylene
     3-fold helix of isotactic PP

    A = carbon chain

    B = cross-section

    C = position of H atoms

    Polymorphism
    Macromolecules in the Crystalline State

     Effect of elongational flow on crystallization


    from solution

    Fibrils: fibrillar crystals

     Crystallization from melt



    Spherulites: containing both amorphous and crystalline
    regions
     Recognizable under microscope (diameter: micro meters)

     Chain folding is not as regular as in single crystals


    Macromolecules in the Crystalline State

    Factors affecting structure (morphology) of


    spherulites
     Radial disposition
     Longitudinal extension
     Temperature
     External conditions

    Pressure

    Orientation
     Number of nuclei
    Macromolecules in the Crystalline State

    Factors affecting degree of crystallization


    1. Structure(banda kesa he)
    2. Branching (khaandan kesa he)
    3. Polar groups(dost keese hain)
    4. Annealing: long heating at a certain temperature(terbiat)
    5. Slow cooling of the molten polymer(mizaj kesa he)
    6. Contact with a suitable swelling agent(bahair kese jaye ga)
    7. Symmetry along the main chain(zindgi me tawwazan)
    8. Number and length of side chains(talaqat)
    9. Nucleating
    Macromolecules in the Crystalline State

    Basic properties of crystalline polymers


     Opaque
     Soluble in few organic solvents at elevated
    temperature

    Technical important crystalline polymers


    • Polyethylene • Aliphatic/aromatic polyesters
    • Polypropylene • Aliphatic/aromatic polyamides
    • Aliphatic polyamides • Polytetrafluoroethylene
    • Polyoxymethylene • Poly(phenylene sulfide)
    • Poly(arylene ether ketone)s

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