POLYMER (2)

Polymer crystallinity

Deff Packing of molecular chains to produce an ordered atomic array Complexity of molecular structure large variety from well ordered crystalline-amorphous Density of crystalline polymer >amorphous one of the same material & MWin cryatalline the chain is more closely packed

Degree of cryatallinity by weight:

Density

s, c, a density of speciment to determine the % crystallineity, of perfectly crystalline polymer, of totally amorphous polymer

n = number of mers A= MW of mers Vc = unit cell volume Na= 6.023x1023 mers/mol

Degree of crytallinity depends on rate of cooling during solidification, chain configuration, molecular chemistry

Crystallization is not favored in polymers with chemically complex repeat unit but easily accomplished for linear polymer, even for very rapid cooling rates
Branches polymer rarely to be crystalline; any side branches interfere crystalization

Crosslink polymer almost totally amorphous; the crosslink prevent the chain from rearranging & aligning to crystalline structure

Bulkier side bond groups of atom less tendency for crystallization

General rule for cryatalllization the more irregular & random the repeat unit arrangement, the greater is the tendency for the development of noncrytallinity Random & graft copolymer amorphous Degree of crystallinity affects physical properties

Crystalline polymers are usually stronger & more resistant to dissolution & softening by heat

Melting

Tm Transformation of solid material (ordered structure) to viscous liquid (random structure) Occurs upon heating at Tm Melting takes place over a range of T Thicker the layer, higher Tm Impurities decrease Tm

Glass transition

Tg Temperature at which polymer transforms from rubbery to rigid upon cooling Affect on stiffness, heat capacity & coeff. of thermal expansion Occurs in amorphous & semi crytalline Lower T limit for application Due to a reduction in motion of large segment of molecule chain with changing T

Crystalline discontinue change in specific vol. at Tm

Polymer synthesis & processing

Polymer synthesis: 1)polymerisation 2)additive materials 3)finishing pieces POLYMERISATION monomers are linked together to generate long chains composed of repeat units raw material: derived from coal, natural gas, petroleum

1) Addition/chain reaction polymerization monomer units are attached one at a time in chainlike fashion to form a linear macromolecules synthesis of polyethylene, polypropylene, PVC 3 stages: initiation, propagation & termination affect MW

i) Initiation active centre capable of propagation is formed by reaction between an initiator (catalyst) species & monomer unit

ii) Propagation linear growth of polymer chain by sequential addition of monomer unit to the active growing chain molecule

1000 repeat units in 10-2 -10-3 s

iii) Termination a) active end of 2 propagation chain may link together form 1 molecule

b) two growing molecule that react to form two dead chains

2) Condensation (step reaction) polymerisation Stepwise intermolecular chemical reaction that may involve more than 1 monomer species By product: small MW (water) No reactant species has chemical formula in the repeat unit; intermolecular reaction occurs everytime a repeat unit is formed

Reaction times for condensation are generally longer than for addition polymerisation

POLYMER ADDITIVES Additives introduce to enhance/modify properties, thus more serviceable: plasticizers, stabilizers, colorants, flame retardants, fillers * Stabilizers - Additive to counteract deterioration in some polymers under normal environment expose to light-UV & oxidation - UV radiation interact with & cause severe in covalent bond & molecular chain

Approaches to UV stabilization: 1)Add UV absorbent material layer at surface; to block out the radiation before penetrating into & damage the polymer 2)Add materials that react with bond broken by radiation before they participate in other reactions lead more damage - Oxidation chemical interaction between oxygen (O2 or O3) with polymer; Stabilizer consume oxygen before it reaches polymer &/ prevent the oxidation reaction that would further damage - Prevent photochemical degradation C black

* Colorants - give color to polymer - added as dyes molecules dyes dissolve in polymer - added as pigment remain separate phase * Plasticizers - Improve flexibility, toughness; reduce hardness & stiffness - Used in brittle materials (Tr): PVC,

-small plasticizer molecules occupy position between large polymer chain * Flame retardants -Used in textile & toys -interfere the combustion process/initiating different combustion reaction generate less heat, reduce T slowing burning

Polymer type
Classification is based on end-use: plastics, elastomers, fibers, coating, adhesive, foams & films. Particular polymers may be used in more than 1 applications. PLASTICS materials that have structural rigidity under load & use for general purpose application Polyethylene, polypropylene, PVC, polystyrene, epoxies Some are very rigid, other are flexible, exhibite elastic & plastic deformation when stress, sometimes experiencing deformation before fracture Linear/branched must be used below glass transition T (if amorphous) or below melting T (semicryatalline)

ELASTOMERS (rubber)

To increase tensile strength, abrasion, tear resistance & stiffness additives (C black) Silicone material backbone chain Si & O

R, R= side bonded atom Crosslink structure

Silicon elastomers: have a high degree of flexibility at low T (to -90 C); stable at T as high as 250 C Resistant to weathering & lubricant oil (used in automobile engine compartement) Biocompatiility (blood tubing)

FIBERS long filament at least 100:1 length to diameter ratio high tensile range over wide T range high modulus elastisity abrasion resistance high MW to be a strong material; will not break during drawing high crystalline polymer; high tensile strength linear structure with regular order

*convenience in washing: fiber properties (melting & glass T) stable in various environments: acids, base, bleaches, dry cleaning solvent & sunlight

COATING Function: 1) Protect from corrosive/deteriorative reaction 2) Improve appearance 3) Provide electrical insulation paint, varnish, enamel Many coating are latex (stable suspension of small insoluble polymer particle disperse in water); less organic solvent, less VOC emission smog

ADHESIVES used to bond 2 surface of solid material together 2 type: mechanical & chemical *Mechanical: there is actual penetration of adhhesive into surface pores & crevices *Chemical involves intermolecular forces polyurethanes, polysiloxanes, epoxies acrylic

Factors to choose adhesive: 1. Materials & porosities to be bond 2. Requires adhesive properties 3. Exposure environment 4. Processing conditions

Adhesive advantage over other joining technologies: 1. join dissimilar materials & thin components 2. lighter weight 3. better fatigue resistance 4. lower manufacturing cost DrawbacksT limitation; maintain mechanical integrity only at low T, strength decreases with T Used in aerospace, automotive, construction etc

Films 0.025-0.125 mm thickness -low density, high flexibility, high tensile & tear strength, resistance to moisture & chemical, low -permeability to some gases (water vapor) -polytethylene, polypropylene, cellulose acetate

Foams -plastic material with high vol of small pores & trapped gas bubble -polyurethane, rubber, polystyrene -generated by dissolving an inert into molten polymer (high P); when P reduce rapidly, the gas comes out of solution & forms bubbles & pores that remain in the solid as it cools