Beruflich Dokumente
Kultur Dokumente
1
MECH 221 PM Wood-Adams fall 2008
Introduction to Polymers
styrofoam cups
COMMERCIAL Polymers: used in
contact lenses large quantities for their lightweight,
rubber tires corrosion-resistance, and good
telephone housings formability.
epoxies - usually low strength and stiffness
sandwich bags
soda bottles ENGINEERING Polymers:
rubber bands improved strength and better
computer keyboard keys elevated temperature properties.
cables … etc
in fact, just look around your, house, dorm or apartment room and you’ll
likely find plenty of examples of polymeric materials.
Polymers:
THERMOPLASTICS, THERMOSETS AND ELASTOMERS 2
MECH 221 PM Wood-Adams fall 2008
Different aspects of polymer science
• Polymer synthesis
• Polymer characterization
• Polymer physical chemistry
– Paul J. Flory, Nobel prize for chemistry, 1974
• Polymer physics
– Pierre de Gennes, Nobel prize for physics, 1991
• Polymer engineering
– PP
– PVC
– PET
5
MECH 221 PM Wood-Adams fall 2008
Classification of polymers
• Thermosets: cannot be melted or dissolved
to be processed: chemical decomposition
occurs before softening
– Formation of a 3D network
– Example: epoxy (resin and hardener)
6
MECH 221 PM Wood-Adams fall 2008
Vulcanization of rubber
Sulphur reacts with
chain at the double bond
This kind of
materials are
referred to as
elastomers
7
MECH 221 PM Wood-Adams fall 2008
Molecular forces in polymers
• Intramolecular forces: generally covalent bonds
(strong)
(forces between atoms in one chain)
… --X--X--X--X--X--X--X--X--X--X--X--X--…
where each “X” represents a “mer.”
9
MECH 221 PM Wood-Adams fall 2008
Homopolymers and co-polymers
Homopolymers vs. co-polymers:
-If only one type of repeat unit is present, the polymer is called
a homopolymer.
-If a second monomer is also present in the chain, the resulting
material is called a co-polymer.
14
MECH 221 PM Wood-Adams fall 2008
Structure of Polymers
15
MECH 221 PM Wood-Adams fall 2008
Molecular weight
• Since not all chains in a sample of material are the same
length, and so there is a distribution of molecular weights
number average, M n = ∑ xi M i
weight average, M w = ∑ wi M i
molecular weight
Very large molecular weights are common for polymers
16
MECH 221 PM Wood-Adams fall 2008
Molecular weight
Alternative way to express average polymer chain size is degree
of polymerization - the average number of mer units in a chain:
17
MECH 221 PM Wood-Adams fall 2008
Molecular shape
• If the form of the molecule was strictly determined,
polymers would be straight
– in fact, the 109° bond angle in polyethylene gives a
cone of rotation around which the bond lies
109°
18
MECH 221 PM Wood-Adams fall 2008
Molecular shape
19
MECH 221 PM Wood-Adams fall 2008
Molecular structure
• Linear polymers
– long, flexible chains (with only 2 ends) with some van der
Waals or hydrogen bonding between chains
• Branched polymers
Chain packing efficiency is reduced compared
to linear polymers (lower density)
• Crosslinked polymers
– cross linkage happens either during synthesis or in a separate
process, typically involving addition of impurities which bond
covalently
– this is termed vulcanisation in rubber
20
MECH 221 PM Wood-Adams fall 2008
Molecular structure
21
MECH 221 PM Wood-Adams fall 2008
• Covalent chain configurations and strength:
secondary
bonding
22
MECH 221 PM Wood-Adams fall 2008
Crystallinity in polymers
• Although it may at first seem surprising, Polymers can form crystal
structures (all we need is a repeating unit, which can be based on
molecular chains rather than individual atoms)
• Some parts of structure align during cooling to form crystalline regions.
(Not like FCC + BCC metals - chains align alongside each other.)
• Around CRYSTALLITES get AMORPHOUS regions.
ρc ( ρ s − ρa )
% crystallinity = x100
ρ s ( ρc − ρa )
Where:
ρs = Density of sample
ρa = Density of the completely
amorphous polymer
ρc = Density of the completely
crystalline polymer
23
MECH 221 PM Wood-Adams fall 2008
Crystallinity in polymers
25
MECH 221 PM Wood-Adams fall 2008
Spherulites
When polymers are
crystallized they form
spherical structures
called spherulites
Crystalline structure of
polylactide crystallized from
bulk. 50x50 μm scan
MASc thesis of Yury Yuryev, Concordia U., 2006
26
MECH 221 PM Wood-Adams fall 2008
Mechanical properties of polymers
- There are three typical classes of polymer stress-strain characteristic
stress (MPa)
6 brittle
4 plastic
0 strain
0 2 4 6 8
27
MECH 221 PM Wood-Adams fall 2008
Mechanical properties of polymers
• Modulus of Elasticity
– may be as low as 7 MPa or has high as 4x103 MPa
(compare to 48-410 x 103 MPa for metals)
– TS polymers 100 MPa (metals up to 4100MPa)
• Elongation
– Often elongate plastically as much as 1000% (compare
to metals - rarely over 100%)
• Temperature Dependence
– Mechanical properties are very T dependent - even close
to room T
• Strain Rate Dependence
– same behavior as raising temperature
28
MECH 221 PM Wood-Adams fall 2008
Mechanical Properties of Polymers
29
MECH 221 PM Wood-Adams fall 2008
Mechanical Properties of Polymers
• Decreasing T...
--increases E
--increases TS
--decreases %EL
• Chain folded
model: crystals
are actually
small platelets
of interwoven
polymer chains
32
MECH 221 PM Wood-Adams fall 2008
Mechanisms of Plastic Deformation
- Semicrystalline Polymers
Unlike metals, TS is
not where neck forms
Because deformation
continues outside of
neck. Neck region is
actually strengthened
yield
35
MECH 221 PM Wood-Adams fall 2008
TENSILE RESPONSE: ELASTOMER
CASE
σ(MPa)
60 xbrittle failure
plastic failure
40 x
20 x
elastomer
final: chains
0
0 2 4 6 ε 8
are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, heavily cross-linked. is reversible!
0
ε
0 2 4 6 8
aligned,networked
cross- case
linked
case
37
MECH 221 PM Wood-Adams fall 2008
Strength in Polymers
• Major factors affect strength are temperature and strain rate:
– In general, decreasing the strain rate has the effect similar
to increasing the temperature.
39
MECH 221 PM Wood-Adams fall 2008
Melting and Glass Transition Temperature
For amorphous and semicrystalline polymers, this is a critical
aspect of designing with polymers.
40
MECH 221 PM Wood-Adams fall 2008
Melting and Glass Transition Temperature
• Melting of a crystalline polymer
– transforming solid with an ordered structure to a viscous
liquid with a highly random structure
• Amorphous glass transitions
– transformation from a rigid material to one that has rubber-
like characteristics
– temperature has large effect on chain flexibility
• Below glass transition temperature, Tg, polymers are usually
brittle and glass-like in mechanical behavior.
• Above glass transition, Tg, polymers are usually more elastic.
Why is That?
Bond rotations are “freezing” which means chains can’t slip past
each other so polymer becomes brittle, (no plastic deformation)
41
MECH 221 PM Wood-Adams fall 2008
Polymers and Spaghetti
• Amorphous polymers….hot, fresh spaghetti with not “clumps”
• Semicrystalline polymers….hot fresh spaghetti with some “clumps”
• Crystalline polymers….spaghetti the way my friend made it, mostly
“clumps” with some free strands
• …Glassy…Polymer below Tg, three day old spaghetti- left in the
sun!
Tg is low for
simple linear
polymers
Tg and Tm
increase with
mer complexity
42
MECH 221 PM Wood-Adams fall 2008
Effect of temp. on tensile response of thermoplastics
45
MECH 221 PM Wood-Adams fall 2008
Thermosets
• Crosslinking prevents melting and viscous flow
• Hot working, such as extrusion is not possible
• At high temperatures they decompose rather than melt
– although they can be used at higher temperatures than thermoplastics
and are more chemically inert
• Fabrication of thermosetting polymers is usually a two stage process
– In the first stage a linear polymer, with a low molecular weight is
prepared
– The second “curing” stage is carried out in a mould having the desired
shape during the addition of:
• heat and/or catalysts
• pressure
• During the cure, chemical and structural changes take place at a
molecular level
– crosslinked or network polymer formed
– this is dimensionally stable and can be removed from the mould while
hot 46
MECH 221 PM Wood-Adams fall 2008
Compression Moulding