Polymers

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.

Polymers

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

Polymers
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

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

Polymers: chemical bonding

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

Polymers: molecules
Most polymers are hydrocarbon polymers hydrocarbons with H and C atoms covalently bonded together essentially all molecules in polymers are saturated

e.g. for ethylene C2H4

for acetylene C2H2 molecules with = and

bonds are termed unsaturated

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Polymers: molecules

Polymers: molecules
Isomers are hydrocarbon compounds with the same composition BUT with different atomic arrangements

e.g. normal butane (- 0.5 C)

isobutane (- 12.3 C)

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

Polymers: CH groups

Polymers: chemistry
Molecules are joined together in a polymerisation reaction (i.e. often at a presence of a appropriate catalyst) i.e. ethylene is converted to polyethylene PE (under P, T)

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

Polymers: molecular weight

Polymers with long chains have large molecular weights (mass) Number-average molecular weight

M n = ! xi M i
where, 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) 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

Polymers: molecular weight

Average chain size of a polymer can be expressed using the degree of polymerisation, 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, n (average number of mer units in a chain) Weight - average degree of polymerisation

Mw nw = m
where, M w is the weight average molecular weight m is the mer molecular weight

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

Polymers: molecular weight

Molecular weight awards determines properties of polymers liquids, gases short chain polymers with < 100g/mol short-medium chain polymers with < 1000g/mol medium-long chain polymers 10.000 few Ms g/mol

waxy solids, resins

solid polymers

Polymers: molecular weight

Polymers: molecular structure

Molecular structure (along with molecular weight and shape) determines physical properties of a polymer Linear Branched PE, PVC, PMMA LDPE

Cross-linked

rubbers

Network

epoxies, bakelite

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. 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, process reversible) e.g. PE, PP, PS, PVC

thermosetting polymers (become hard at high T, do not soften) e.g. epoxy, phenolics, polyurethanes

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

Polymers: thermosets
Thermosets are used in high stress applications to replace ceramics, composite materials, 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

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

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Polymers: copolymers
Copolymers are often alloyed and blended (i.e. mechanically) This is to: mix compatibiliser compounds to prevent separation of constituents produce a product with a single or several glass transition temperature

e.g. impact resistant PS (grey) added to rubber (white particles)

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

PE crystalline structure

Polymers: crystallinity
The degree of crystallinity, %

where, s is the density of a specimen for which the % crystallinity is to be determined a is the density of a totally amorphous polymer c 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

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

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

Polymers: craze formation

Crazes occur owing to local orientation of molecules and tend to grow along planes normal to tensile stress (i.e. 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.

Polymers: craze patterns

Patch Mackerel Hackle