ENB 331, week 10

Maksym Rybachuk
Refs: §14 “Materials Sci & Eng: an Introduction” by W. Callister, Jr., §7 “Eng. Materials: Properties & Selection” by K.G. Budinski et al.


The word polymer is derived from the Greek words πολύ - poly meaning "many”, and µέρος - meros meaning "part". the term was coined in 1833 by Jöns Jacob Berzelius, although his definition of a polymer was quite different from the one used at present time.

A polymer is a large molecule (macromolecule) composed of repeating structural units (monomers) Plastics, rubbers and fiber materials are typically polymers of high molecular mass Monomers of these materials are either natural or synthetic organic compounds note: WWII provided for the initial growth of polymer industry

addition polymerisation 2.Polymers: bonding There are 2 ways the molecules can attach to each other 1.e.e. by chemical reaction i. ‘link’ to each other i. condensation polymerisation .

Polymers: chemical bonding Chemical bonding types: –  metallic –  ionic –  H –  Van de Waals –  covalent polymers are covalently bonded (i. electron pair share) in a long chains of repeating molecules .e.

Polymers: molecules ‘Most’ polymers are hydrocarbon polymers – hydrocarbons with H and C atoms covalently bonded together ‘essentially all’ molecules in polymers are saturated e. for ethylene C2H4 for acetylene C2H2 molecules with = and ! bonds are termed unsaturated 7 .g.

Polymers: molecules .

g.Polymers: molecules Isomers are hydrocarbon compounds with the same composition BUT with different atomic arrangements e.0.3 C) .5 C) isobutane (. ‘normal’ butane (.12.

Polymers: backbone Molecules in polymers are gigantic. often referred as macromolecules basic backbone structure .

Polymers: CH groups .

e. ethylene is converted to polyethylene PE (under P. often at a presence of a appropriate catalyst) i.Polymers: chemistry Molecules are ‘joined’ together in a polymerisation reaction (i. T) .e.

Polymers: chemistry The polymer chain forms by sequential addition of PE monomer units to an active initiator-mer center. .

Polymers: chemistry If H atoms in PE are replaced by F poly-tetra-fluoro-ethylene (PTFE) Cl poly-vinyl chloride (PVC) CH3 (methyl group) poly-propylene (PP) .

Polymers: chemistry .

Mi is the mean (middle) molecular weight of size range i xi is the fraction of the total number of chains within the corresponding size range .Polymers: molecular weight Polymers with long chains have large molecular weights (mass) Number-average molecular weight M n = ! xi M i where.

Polymers: molecular weight Polymers with long chains have large molecular weights (mass) Weight-average molecular weight M n = !wi M i where. Mi is the mean (middle) molecular weight of size range i wi is the weight fraction of the molecules within the same size interval .

n (average number of mer units in a chain) Number average degree of polymerisation Mn nn = m where. M n is the number average molecular weight m is the mer molecular weight .Polymers: molecular weight Average chain size of a polymer can be expressed using the degree of polymerisation.

M w is the weight average molecular weight m is the mer molecular weight . n (average number of mer units in a chain) Weight .Polymers: molecular weight Average chain size of a polymer can be expressed using the degree of polymerisation.average degree of polymerisation Mw nw = m where.

Polymers: molecular weight For a copolymer (a polymer with 2 or more molecular units). m can be determined from m = ! fjmj where. fj is the chain fraction mj is the molecular weight of mer j .

resins solid polymers . gases short chain polymers with < 100g/mol short-medium chain polymers with < 1000g/mol medium-long chain polymers 10.Polymers: molecular weight Molecular weight awards determines properties of polymers liquids.000 – few Ms g/mol waxy solids.

Polymers: molecular weight .

Polymers: molecular structure Molecular structure (along with molecular weight and shape) determines physical properties of a polymer Linear Branched PE. bakelite . PMMA LDPE Cross-linked rubbers Network epoxies. PVC.

Polymers: molecular structure degree of crystallinity vs T crosslinking vs T .

Polymers: molecular configuration Stereomeric polymers are those with atoms linked together in the same order (head to tail) but differ in their spatial arrangement iso-tactic configuration syndio-tactic configuration atactic configuration .

Thermoplastic vs thermosetting Polymers ‘behave’ differently with rising temperature. phenolics.g. epoxy. polyurethanes . PS. The response of a polymer to mechanical forces at high T is related to its dominant molecular structure There are: thermoplastic polymers (liquefy at high T. PVC thermosetting polymers (become hard at high T. process reversible) e. PE. PP.g. do not soften) e.

Polymers: thermoplastic A commodity Thermoplastics are used in low or no stress applications to replace wood. polyamides (nylons).g. polyesters. polyolefins. polycarbonates. fluoroplastics. etc note: engineering thermoplastics are developed with mechanical properties to compete with metals acetals (polyoxym ethylene). acrylics. These provide: high strength and stiffness good fatigue life dimensional stability chemically inert good friction and wear resistanc . etc. vinyls. styrenes. glass and papers e.

alloys and steel These provide: higher dimensional stability greater resistance to creep high thermal stability high rigidity and hardness Thermosetting polymers consist of: a) a resin + curing agents b) a filler and reinforcement . composite materials.Polymers: thermosets Thermosets are used in high stress applications to replace ceramics.

Polymers: copolymers A polymer composed of 2 or more mer units a)  random b)  alternating c)  block d)  graft .

Polymers: copolymers .

Polymers: copolymers Effect of additional groups on the properties of copolymers CH2 CH C=O O CH3 CH3 Polymethylacrylate (PMA) soft and rubbery (T = 10 C) CH2 C C=O O CH3 Polymethylmethacrylat (PMMA) hard plastic (T = 105 °C) .

Polymers: copolymers Effect of free volume on the properties of copolymers CH3 CH2 C C=O O CH3 CH3 CH2 C C=O O CH2 CH3 CH2 C CH3 CH2 C CH3 C=O O CH2 CH2 CH2 CH3 C=O O CH2 CH2 CH3 Polymethyl methacrylate 105 °C Polyethyl methacrylate 65 °C Polypropyl methacrylate 35 °C Polybutyl methacrylate 20 °C 32 .

e. impact resistant PS (grey) added to rubber (white particles) 33 . mechanically) This is to: mix ‘compatibiliser’ compounds to prevent separation of constituents produce a product with a single or several glass transition temperature e.Polymers: copolymers Copolymers are often alloyed and blended (i.g.

Polymers: crystallinity Polymer crystallinity is defined as the packing of molecular chains so as to produce an ordered atomic array PE crystalline structure .

% where.Polymers: crystallinity The degree of crystallinity. ρs is the density of a specimen for which the % crystallinity is to be determined ρa is the density of a totally amorphous polymer ρc is the density of a perfectly crystalline polymer .

Polymers: melting Polymers in the solid state have either a predominantly amorphous or a semi-crystalline state Melting temperature. Tm. marks the behavior between these states .

Tg Tg is associated with the viscosity increasing at higher rate than the rate of structural rearrangement .Polymers: Tm and Tg Another parameter is glass transition temperature.

Polymers: mechanical behavior Work hardening of linear polymers (e.g. nylon) can increase strength and Y .

Polymers: mechanical behavior Time-dependent load response of polymeric materials elastic visco-elastic viscous .

Polymers: mechanical behavior .

Polymers: mechanical behavior .

Polymers: craze formation .

cracks) Crazes are capable of supporting some reduced stress relative to the un-crazed material. Typically < 5mm in size Growth is determined by: a) chain slippage b) rupture of primary bonds within molecular entanglements c) detachment at the craze-matrix interface. .e.Polymers: craze formation Crazes occur owing to local orientation of molecules and tend to grow along planes normal to tensile stress (i.

Polymers: craze patterns Patch Mackerel Hackle .