Applications & Synthesis of Polymers

Crystallization
the process by which, upon cooling, an ordered (crystalline) solid phase is produced from a liquid melt with highly random molecular structure Stages: nucleation & growth process Upon cooling, through Tm, nuclei form wherein small regions of the tangled & random ordered & aligned in manner of chain-folded layers T>Tm nuclei are unstable because of thermal atomic vibrations that tend to disrupt the ordered arrangement crystallization growth stage nuclei grow by continue ordering & allignment of additional molecular chain; same thickness, increase in lateral

 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 tendency for crystallization

less

General rule for crystallization the more irregular & random the repeat unit arrangement, the greater is the tendency for the development of noncrystallinity 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) Reverse process of crystallization Occur when polymer heated, at Tm Melting takes place over a range of T (no single Tm) polymers compose of variety of MW; MW> Tm > During melting rearrangement of molecules from ordered to disordered Double bonds, bulky side restrict molecular rotation lower flexibility & increase Tm

Glass transition
Tg Temperature at which polymer transforms from liquid rubbery rigid upon cooling Retain disordered molecular of liquid state Affect on stiffness, heat capacity & coeff. of thermal expansion Occurs in amorphous & semi crystalline Due to a reduction in motion of large segment of molecule chain with changing T

 Upon heating through Tg, the amorphous solid transform from solid to rubbery < Tg molecules frozen > Tg molecules rotate & move Flexibility is diminished

Tg increases in case of: -MW -bulky side group reduce chain mobility -double bond & aromatic group stiffen polymer chain

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. 1) 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 exhibit 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)

2) Elastomers (rubber)
To increase tensile strength, abrasion, tear resistance & stiffness additives (C black) Synthetic elastomers SBR (styrene butadiene copolymers), reinforced with C back tyres Silicone rubber: backbone chain Si & O

R, R = side bonded atom Crosslink structure

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

 ELASTOMERS

3) Fibers
long filament (L/D)=100:1 Mostly used in textile industry; woven or knit Subjected to stretching, twisting, shearing & abrasion high tensile strength, 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 thermal properties melting & glass T stable in various environments: acids, base, bleaches, dry cleaning solvent & sunlight relative nonflammable and amenable to drying

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

2) ADHESIVES substances used to bond 2 surfaces of solid material (adherends) 2 types of bond: mechanical & chemical *Mechanical actual penetration of adhhesive into surface pores & crevices *Chemical intermolecular forces between adhesive & adherend Natural: casein, starch

Synthetic: polyurethanes, polysiloxanes, epoxies acrylic Factors to choose adhesive: 1. Materials & porosities to be bond 2. Requires adhesive properties 3. T exposure environment 4. Processing conditions

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

3) FILMS Thin layer 0.025-0.125 mm thickness Packaging, tape Characteristic: low density, high flexibility, high tensile & tear strength, resistance to moisture & chemical, low -permeability to some gases (water vapor) polytethylene, polypropylene, cellulose acetate

4) FOAMS

plastic material with high vol of small pores & trapped gas bubble Thermoplastic & thermosetting: polyurethane, rubber, polystyrene Cushion, thermal insulation Bubbles are 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

SYNTHETIS & PROCESSING

stages in 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 2 classifications according reaction mechanism: addition & condensation

1) Addition polymerization
Chain reaction polymerization monomer units are attached one at a time in chainlike fashion to form a linear macromolecules Result in exact multiple of original monomer synthesis of polyethylene, polypropylene, PVC 3 stages: initiation, propagation & termination affect MW Stages are controlled to ensure degree of polymerization of product

i)

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

active initiator;

unpaired electron

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 2 ways: a) combination active end of 2 propagation chain may link together form 1 molecule

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

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

 Stepwise process repeated produce a linear molecule

t condensation > t addition polymerisation Thermosetting polyester & phenolformaldehyde, nylons, polycarbonates

POLYMER ADDITIVES
Additives substances introduce to enhance/modify properties, thus more serviceable: plasticizers, stabilizers, colorants, flame retardants, fillers

FILLERS
# to improve tensile & compressive strength, abrasive resistance, toughness, dimensional, thermal stability etc # inexpensive materials that replace some vol of more expensive polymer reduce cost # wood flour (sawdust), silica flour, sand, glass, clay etc

Plasticizers
- Improve flexibility, toughness; reduce hardness & stiffness - Liquids having low vapor P & low MW - Small plasticizer molecules occupy positions between large polymer chain, increase interchain distance with reduction intermolecular bonding - Used in brittle materials (Tr): PVC - Lower Tg at Tr polymer may be used with some pliability & ductility - Application: thin sheet, film, tubing, raincoats

Stabilizers
- Additive to counteract deterioration in some polymers under normal environment expose to light-UV & oxidation # 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

interact with & cause severe in covalent bond & molecular chain - Approaches to UV stabilization: add UV absorbent & add material react with broken bond 1) Add UV absorbent material - layer at surface as sunscreen - 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

# UV radiation

Colorants
- give color to polymer - added as dyes - molecules dyes dissolve in polymer -added as pigment filler materials that do - not dissolve, remain separate phase - small size & refractive index near the parent polymers

Flame retardants
- Most all pure polymer are flammable - used in textile & toys - interfere the combustion process by initiating different combustion reaction generate less heat, reduce T slowing burning