Materials 2

Lecture 6

Dr Philip Harrison
Outline of Current Lecture Polymers

• Examples of Common Polymers: Compositions and

Applications

• Molecular Weight

2
Recycling Polymers
• Recycling symbols – often printed on product

3
Polymer Composition
and Applications

4
Molecular Shape Polymers
• Single chain or ‘linear’ molecules can adopt a long
tangled structure
• The end-to-end distance is denoted as r – much
shorter than the total length of the chain

Random thermal motion causes

random path of chain

Mechanical and thermal properties

depend of rotational ability of chain -
depends on mer structure and
composition

e.g. stronger secondary bonds create

stronger inter-molecular interactions,
double bond is rotationally rigid and
side groups restrict mobility 5
Polymer Structure Polymers
• Repeat Units for 10 Common Polymers

6
Molecular Structure Polymers
• Look at the bonds both inside (intra) and between
(inter) polyethylene molecules
• Recall electronegativities of
H and C are 2.1 and 2.4

• Just polar covalent bonds

(small dipole)

• C atoms become slightly

negative, H slightly positive

• H atoms rotate away from

each other to minimise
electrostatic potential of
molecular configuration 7
Molecular Structure Polymers
• The dipoles between H-C atoms results in
secondary bonds between chains

• Positive charge on the

hydrogen atoms on one
chain are attracted to
negative charge on carbon
atom and visa versa

• Secondary bonds not very

strong for PE

8
Applications and Properties Polymers
• Polyethylene (flexible bottles, film wrapping
materials, plastic bags – LDPE, HDPE)
Good toughness, chemically resistance and
electrical insulation but has low strength

9
Molecular Structure Polymers
• Start with tetrafluroethylene, C2F4, synthesise
polytetrafluroethylene

F F F F

C C (C C )n
n

F F F F
Applications and Properties Polymers
• Fluorocarbons – e.g. PTFE (Telfon) (anti-
adhesive coatings such as non-stick pans,
anticorrosive seals and valves)
low coefficient of friction, high melt temperature,
chemically inert, excellent electrical properties,

11
Molecular Structure Polymers
• Start with vinyl chloride monomer, C2H3Cl, synthesise
polyvinylchloride

H H H H

C C (C C )n
n

H Cl H Cl

12
Molecular Structure Polymers
• Look at the bonds both inside (intra) and between
(inter) polyvinylchloride molecules

• Recall electronegativities of
H, C and Cl are 2.1, 2.4 and
2.9

• H-C are just polar covalent

bonds (small dipole), Cl-C is
slightly more polar covalent
but points in the opposite
direction

• Makes secondary
interactions stronger – stiffer
13
polymer
Applications and Properties Polymers
• Vinyls (pipe, garden hose, clothes)
low-cost, ordinarily rigid but can be made
flexible with plasticizers, susceptible to heat
distortion

14
Polymer Structure Polymers
• Repeat Units for 10 Common Polymers

15
Applications and Properties Polymers
• Polypropylene (Sterilizable bottles, packaging film,
TV cabinets, luggage, sports wear)
resistant to heat distortion, excellent chemical
properties and fatigue strength, chemically inert,
relatively inexpensive, poor resitance to UV light

16
Polymer Structure Polymers
• Repeat Units for 10 Common Polymers

17
Aromatic Ring Polymers
• The symbol:

indicates an aromatic ring, equivalent to:

H H

C C

C C

C C

H H 18
Molecular Structure Polymers
• Comparison of polyethylene and polystyrene chains

19
Applications and Properties Polymers
• Polystyrene (Foam, packaging)
excellent electrical properties & optical clarity,
relatively inexpensive

20
Applications and Properties Polymers
• Acrylics (polymethylmethacrylate) (Lenses,
outdoor signs, transparent aircraft enclosures)
outstanding light transmission & resistance to
weathering, only fair mechanical properties

21
Polymer Structure Polymers
• Repeat Units for 10 Common Polymers

22
Applications and Properties Polymers
• Polyamides (nylons) (Bearings, gears, jacketing
for cables and wires, stockings, clothing)
good mechanical strength, abrasion resistance
and toughness, low coefficient of friction,
absorbs water

23
Polymer Structure Polymers
• Repeat Units for 10 Common Polymers

24
Molecular Structure Polymers
• Look at the composition and shape of a couple of
mer units of polycarbonate

• Straight covalent bonds

along the polymer backbone
constrain chain rotations

• Strong inter-chain dipole

interactions restrict relative
sliding between chains

25
Applications and Properties Polymers
• Polycarbonate (Safety helmets, lenses, roofs)
dimensionally stable, low water absorption, very
good impact resistance and ductility, chemical
resistance average

26
Applications and Properties Polymers
• Polyester (PET) (Polyester fabric, Drinks bottles)
one of toughest plastic films, excellent fatigue
and tear strength, resistance to humidity, acids,
solvents

27
Polymer Structure Polymers
• Repeat Units for 10 Common Polymers

28
Molecular Structure Polymers
• Look at the composition and shape of a couple of
mer units of Bakelite

• The trifunctional repeat mer

unit creates a molecular
network in 3-D space

29
Applications and Properties Polymers
• Phenol-formaldehyde (Bakelite) (Motor housings,
telephones, electrical plugs)
excellent thermal stability to over 150oC, may
be compounded with large number of resins and
fillers, inexpensive, retro-appeal!!

30
Applications and Properties Polymers
• Elastomers (tyres, inner-tubes, seals, O-rings and gaskets, heels and
soles of shoes, diaphragms, oil, chemical and petrol hose)
Elastomers used for when flexibility or elasticity required, type of
elastomer will depend on factors such as chemical, abrasion, electrical
or temperature resistance

31
Polymer Structure Polymers
• When all the repeating units along chain are same,
polymer is a homopolymer

• However, chains may be composed of two or more

different mer units – copolymer

• Monomers like ethylene can each react with two

other monomers to build linear chain-like molecular
structure – bifunctional

• Others like phenol-formaldehyde have three active

bonds - trifunctional
32
Molecular Weight

33
Molecular Weight Polymers
• Not all polymer chains grow to same length – have
a distribution of lengths

Lower M

Higher M

Molecular weight, Mi: Mass of one mole of chains

(1 mole = 6.02x1023 molecules)
34
Molecular Weight Polymers
• Usually specify an average molecular weight –
two predominant methods of defining this average

Number average molecular weight

Weight average molecular weight

35
Number Average Molecular Weight Polymers
• Start by dividing chains into size ranges

• Determine fraction of chains within each size range

• Use

where Mi is the mean molecular weight of size range

i, and xi is the fraction of the total number of chains in
this range
36
Weight Average Molecular Weight Polymers
• Start by dividing chains into size ranges

• Determine fraction of the total weight of the chains

within each size range

• Use

where Mi is the mean molecular weight of size range

i, and wi is the weight fraction of the total weight of
chains in this range
37
Example 1 Polymers
• Use an extreme (and unrealistic) example, just to
illustrate the difference between the two methods

• Consider a sample of containing 100,000 chains

• 90,000 chains have a molecular weight of 1000

g/mol

• 10,000 chains have a molecular weight of 100,000

g/mol

38
Example of Number Average Polymers
• 90,000 chains have a molecular weight of 1000
g/mol, 10,000 chains of 100,000 g/mol

0.9
Number fraction

= 0.9x1000+0.1x100,000
= 10,900 g/mol
0.1
1000 100,000
Molecular weight (g/mol) Number average molecular
weight leans towards the
molecular weight of the more
numerous chains 39
Example of Weight Average Polymers
• Total weight = 90,000x1000+10,000x100,000 = 1090,000,000
• Weight fractions are: 90,000,000/1090,000,000 = 0.083 and
1000,000,000/1090,000,000 = 0.917

0.9
= 0.083x1000+0.917x100,000
Weight fraction

= 91,783 g/mol

Weight average molecular

0.1 weight leans towards the
1000 100000` molecular weight of the
Molecular weight (g/mol)
heavier molecules 40
Interactive Session Polymers
• Which polymer is used to make disposable shopping bags (used in
supermarkets)?
High density polyethylene
• Which polymer is often used to make sun-glasses and crash-
helmets?
Polycarbonate
• To which family of polymeric materials does Teflon belong?
Fluoro-carbons
• If all the repeat units along the polymer chain are the same, what
generic name do we give to this type of polymer?
Homopolymer
• What’s the difference between a bifunctional and a trifunctional
monomer?
Bifunctional has 2 active bonds, trifunctional has 3
41
Interactive Session Polymers
• Which tends to be highest, the weight average or number average
molecular weight?
Weight average
• Given that the chemical formula for the mer unit of
polytetrafluoroethylene is C2F4 and the atomic weight of fluorine
is 19, estimate it’s molecular weight
= 12x2+19x4 = 100 g/mol
• A copolymer is composed of 25% of monomer A with a molecular
weight of 50 g/mol and 75% of monomer B with a molecular
weight of 100 g/mol. What is the average mer molecular weight?
= 0.25x50 + 0.75x100 = 87.5 g/mol
• Name two causes for reduced polymer chain mobility
Main chain double bonds and large side groups

42
http://learning.sec.hccs.edu/members/anne.wahlborg/Graphics/electronegativity

43
Molecular Structure Polymers
• Properties also depend on molecular structure
Direction of increasing strength

secondary
bonding

Linear B ranched Cross-Linked Network

Extensive Van Branching Adjacent Trifunctional

der Waals and reduces chains are mer units form
hydrogen packing and bonded to each 3-dimensional
bonds between lowers density other, e.g. networks
chains, e.g. vulcanisation of
Polyethylene Polyethylene rubber
PVC PVC
Polystyrene Polystyrene 44
Nylon Nylon