Polymers

You may think of polymers as being a relatively modern invention

however naturally occurring polymers have been used for thousands of years wood, rubber, cotton, wool, leather, silk,.. etc

Artificial polymers are, indeed, relatively recent and mostly date from after WWII
in many cases, the artificial material is both better and cheaper than the natural alternative

MECH 221

PM Wood-Adams

fall 2008

Introduction to Polymers
styrofoam cups contact lenses rubber tires telephone housings epoxies sandwich bags soda bottles rubber bands computer keyboard keys cables etc
COMMERCIAL Polymers: used in large quantities for their lightweight, corrosion-resistance, and good formability. - usually low strength and stiffness

ENGINEERING Polymers: improved strength and better elevated temperature properties.

in fact, just look around your, house, dorm or apartment room and youll likely find plenty of examples of polymeric materials.

Polymers:
THERMOPLASTICS, THERMOSETS AND ELASTOMERS
MECH 221 PM Wood-Adams fall 2008
2

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 Each of these aspects has considerable industrial and research significance. The successful polymer scientist has some understanding of all of these areas.
MECH 221 PM Wood-Adams fall 2008
3

Definitions

Indicates a chain of n units

Polymer: long molecule made up by the repetition of small units Synonym: macromolecule High molecular weight (M) Ex. polystyrene (PS)

Monomer: molecule that combines with others (identical or different) to form a polymer Ex. ethylene (PE polyethylene) Oligomer: low molecular weight polymer, constituted of at least two monomers
MECH 221 PM Wood-Adams fall 2008
4

Classification of polymers
Thermoplastics: can be processed by melting (several cycles of heating and cooling are possible for thermally stabilized polymers) PS, PE PP PVC

PET
MECH 221 PM Wood-Adams fall 2008
5

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)

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

MECH 221

PM Wood-Adams

fall 2008

Molecular forces in polymers

Intramolecular forces: generally covalent bonds (strong)
(forces between atoms in one chain)

Intermolecular forces: Van der Waals forces (PE), hydrogen bridges (PS) (stronger). Can become very strong as M
(forces between two chains)

Entanglements (physical)
In the crystalline state the van der Waals bonds are very important. In the rubbery amorphous state the entanglements are very important.
MECH 221 PM Wood-Adams fall 2008

Basic Polymer Structure

Suppose our repeat unit is an X. Then, a linear polymer based on X would look like the following: --X--X--X--X--X--X--X--X--X--X--X--X-- where each X represents a mer. Sometimes, polymers contain functional side groups, called pendant groups: We call the primary linear chain the backbone
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. Model for a homopolymer: --X--X--X--X--X--X--X--X--X--X--XX Model for an alternating co-polymer: --X--W--X--W--X--W--X--W--X--W--XW Model for a random co-polymer: --X--X--X--W--X--W--X--X--W--X--WW Model for a block co-polymer: --X--X--X--X--X--X--X--X--W--W--W--W--W--W-MECH 221 PM Wood-Adams fall 2008
10

Other Copolymers
Graft: a polymer is grafted to another preformed macromolecule Ex. Impact resistant PS: PS branches on polybutadiene (rubber) Also, ABS branches of SAN on polybutadiene

Block : long sequences of different repeating units A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-A-A-A

MECH 221 PM Wood-Adams fall 2008
11

Hydrocarbon molecules
Hydrocarbons hydrogen and carbon, bonded covalently Simplest are methane, ethane, propane, butane CnH2n+2, the paraffin family where each carbon shares an electron either with another carbon or with a hydrogen Alternatively, a carbon can share two electrons with H H another carbon atom | | a double bond C= C | | hence ethylene, C2H4 H H And triple bonds are also possible e.g. acetylene, C2H2 HCCH Polymers are composed of hydrocarbon basic units (mers).
MECH 221 PM Wood-Adams fall 2008
12

Structure of Polymers
Examples of real monomers and their resulting polymers:

Polyethylene: (the mer unit is C2H4) ethylene

Polyethylene is used for flexible bottles, toys, battery parts, ice trays, and film wrapping and other packaging materials. It is tough but possesses low strength. Trade names: Ethron, Fortiflex, Hi-fax, Rigidex, Zendel.

This is an example of a linear chain homopolymer, where the X in our model is replaced with the ethylene group.
MECH 221 PM Wood-Adams fall 2008

13

Structure of Polymers Polypropylene: (the mer unit is now C3H6) propylene

Polypropylene is used for such items as bottles, TV cabinets, luggage. It tends to be relatively strong and resistant to heat. It has the trade names Herculon, Meraklon, and Profax.
MECH 221 PM Wood-Adams fall 2008
14

Structure of Polymers Polyvinyl chloride: (the mer unit is C2H3Cl)

Polyvinyl chloride is a very popular, low cost rigid material It can be made flexible by adding plasticizers. It is used as floor coverings, pipe, garden hose, electrical wire insulation, and (at one time) phonograph records. Tradenames: PVC, Saran, Tygon, Darvic, Geon.
MECH 221 PM Wood-Adams fall 2008
15

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
Mi is mean weight in size range, i xi is the fraction of total number of chains in size range, i wi is the fraction of total weight in size range, i weight average, M w

amount of polymer

= wi M i

molecular weight

Very large molecular weights are common for polymers

MECH 221 PM Wood-Adams fall 2008
16

Molecular weight
Alternative way to express average polymer chain size is degree of polymerization - the average number of mer units in a chain:

The mer molecular weight for a co-polymer can be determined by:

m = f jm j

fj chain fraction of mer j mj molecular weight of mer j

MECH 221

PM Wood-Adams

fall 2008

17

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

MECH 221

PM Wood-Adams

fall 2008

18

Molecular shape
Hence the polymer chain can bend, twist, and kink into many shapes adjacent molecules can intertwine leading to the highly elastic nature of many polymers, such as rubber

Random kinks and coils lead to entanglement, like in the spaghetti structure:
MECH 221 PM Wood-Adams fall 2008
19

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
MECH 221 PM Wood-Adams fall 2008
20

Molecular structure
Network polymers: 3D networks made from trifunctional mers. Examples: epoxies, phenolformaldehyde. These are thermosetting materials!

MECH 221

PM Wood-Adams

fall 2008

21

 Covalent chain configurations and strength:

secondary

bonding

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

MECH 221

PM Wood-Adams

fall 2008

22

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.

% crystallinity =

c ( s a ) x100 s ( c a )

Where: s = Density of sample a = Density of the completely amorphous polymer c = Density of the completely crystalline polymer
MECH 221 PM Wood-Adams fall 2008
23

Crystallinity in polymers
Most real polymers contain both amorphous and crystalline regions, as shown here.

% crystallinity depends on several factors: Rate of cooling (faster cooling less crystallinity) Type of polymer (simple structures more crystallinity) (Copolymers less crystallinity) Linear polymers more easily form crystals - Degree of Crystallinity ranges from 5 - 95% - The higher % Crystallinity higher strength
MECH 221 PM Wood-Adams fall 2008
24

Polymer Crystals

MECH 221

PM Wood-Adams

fall 2008

25

Spherulites
When polymers are crystallized they form spherical structures called spherulites

Crystalline structure of polylactide crystallized from bulk. 50x50 m scan

MASc thesis of Yury Yuryev, Concordia U., 2006

MECH 221

PM Wood-Adams

fall 2008

26

Mechanical properties of polymers

- There are three typical classes of polymer stress-strain characteristic
stress (MPa) 6 brittle

plastic highly elastic elastomeric

0 0 2 4 6 8

strain

MECH 221

PM Wood-Adams

fall 2008

27

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
MECH 221 PM Wood-Adams fall 2008
28

Mechanical Properties of Polymers

Elastic modulus is very much lower than for metals or ceramics Beyond the yield point sample deforms plastically. Tensile stress (TS) is the stress at fracture TS may be less or greater than the yield strength.
Schematic stressstrain curve for a plastic polymer showing how yield and tensile strengths are determined.
29

MECH 221

PM Wood-Adams

fall 2008

Mechanical Properties of Polymers

Decreasing T...
--increases E --increases TS --decreases %EL

Effect of temperature on stress-strain behavior of PMMA (left).

Increasing strain rate causes the same effects as decreasing T.

MECH 221 PM Wood-Adams fall 2008
30

Molecular Structure: Polymer Crystal Models

Chain folded model: crystals are actually small platelets of interwoven polymer chains In many bulk polymers crystallized from the melt, these platelets often arrange themselves in radiating patterns to form spherulites.
MECH 221 PM Wood-Adams fall 2008
31

Mechanisms of Elastic Deformation, in Amorphous & Semicrystalline Polymers

Elastic deformation takes place due to the elongation of chain molecules by bond stretching (all regions) and bond rotation (amorphous region), along the direction of the applied stress. Bonds do not break and chains do not slip past each other. If either of these happen yielding occurs. Inter-molecular bonding (Van der Waals) is much weaker than other types, hence the low yield strengths of polymers compared to metals or ceramics.
MECH 221 PM Wood-Adams

stable conformation

bond stretched and rotated

stressed conformation
32

fall 2008

Mechanisms of Plastic Deformation - Semicrystalline Polymers

Two adjacent chain folded lamellae and interlamellar amorphous material before deformation

Elongation of amorphous tie chains

MECH 221

PM Wood-Adams

Tilting of Separation of lamellar chain crystalline folds block segments Orientation of block segments and tie chains with tensile axis 33
fall 2008

Plastic Deformation - Semicrystalline Polymers

Unlike metals, TS is not where neck forms Because deformation continues outside of neck. Neck region is actually strengthened

yield

Mechanism - chains slip past each other (bonds rotate to allow this), some inter-molecular van der Waals bond breaking. - Result is a highly oriented structure in the neck region of our tensile specimen)
MECH 221 PM Wood-Adams fall 2008
34

PREDEFORMATION BY DRAWING
Drawing...
--stretches the polymer prior to use --aligns chains to the stretching direction Results of drawing: --increases the elastic modulus (E) in the stretching dir. --increases the tensile strength (TS) in the stretching dir. --decreases ductility (%EL) Annealing after drawing... --decreases alignment --reverses effects of drawing.

Compare to cold working in metals!

MECH 221

PM Wood-Adams

fall 2008

35

TENSILE RESPONSE: ELASTOMER CASE

(MPa)
60 xbrittle failure 40 20 0 0
initial: amorphous chains are kinked, heavily cross-linked.

plastic failure

elastomer

final: chains are straight, still cross-linked

Deformation is reversible!

Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked case) --plastic response (semi-crystalline case)
MECH 221 PM Wood-Adams fall 2008
36

TENSILE RESPONSE: BRITTLE vs PLASTIC

Near Failure

(MPa)
brittle failure x 60
onset of necking

40
Initial

plastic failure

20 0 0 2 4 6 8

aligned,networked crosscase linked case

MECH 221

PM Wood-Adams

fall 2008

37

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. Other Factors that influence strength Tensile strength increases with molecular weightmore entangled (short strings vs long) TS = TS - A/Mn Strength can be increased by increasing the degree of crosslinking (inhibits chain motion - makes it more brittle) Crystallinity increases strength by increasing intermolecular bonding Deforming a polymer can increase its strength - so that chains become oriented
MECH 221 PM Wood-Adams fall 2008
38

Strength in Polymers

Influence of degree of crystallinity and MW on strength

MECH 221

PM Wood-Adams

fall 2008

39

Melting and Glass Transition Temperature

For amorphous and semicrystalline polymers, this is a critical aspect of designing with polymers. Crystalline polymers: there is a discontinuous change in specific volume at Tm Amorphous polymer: continuous, no Tm - but there is an increase in slope at Tg, the glass transition temperature, Semicrystalline polymer: intermediate to crystalline and amorphous, show both transistions.
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 rubberlike 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 cant slip past each other so polymer becomes brittle, (no plastic deformation)
MECH 221 PM Wood-Adams fall 2008
41

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 GlassyPolymer below Tg, three day old spaghetti- left in the sun!

Tg is low for simple linear polymers Tg and Tm increase with mer complexity
MECH 221 PM Wood-Adams fall 2008
42

Effect of temp. on tensile response of thermoplastics

Stress strain behavior of PMMA Modulus of PS

MECH 221 PM Wood-Adams fall 2008
43

Polymer Additives
Mechanical, chemical, physical Properties can be modified by additives: Fillers
Improve tensile and compressive strengths, abrasion resistance, toughness, and thermal stability sand, glass, clay, talc (eg. carbon in tires) Particle sizes range from very small (10 nm) to large (mm)

Plasticizers: small molecules which occupy positions between polymer chains (increase distance and interactions between chains)
increases flexibility, ductility, and toughness reduces hardness and stiffness

Stabilizers
UV resistance of C-C bonds Oxidation resistance

Colorants and Flame Retardants

MECH 221 PM Wood-Adams fall 2008
44

Forming of Polymers

Polymeric materials are normally fabricated at elevated temperatures and often by application of pressure The technique used to form a particular polymer depends on whether it is thermoplastic or thermosetting the atmospheric stability of the material at which forming takes place the geometry and size of the final product If the polymer is thermoplastic, the temperature at which it softens will also dictate the process

MECH 221

PM Wood-Adams

fall 2008

45

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
MECH 221

this is dimensionally stable and can be removed from the mould while hot 46
PM Wood-Adams fall 2008

Compression Moulding
Both thermoplastics and thermosets can be formed by compression mould The polymer, or mixture of resin and hardener is heated and compressed between dies This method is well suited to forming of: thermoset casings for appliances thermoplastic car bumpers Since a thermoset can be removed when hot, cycle times can be as low as: 10 seconds for small components 10 minutes for large thick walled mouldings
MECH 221 PM Wood-Adams fall 2008

47

Injection Moulding

In injection moulding, polymer granules are compressed by a ram or a screw heated until molten injected into a cold, split mould under pressure The moulded polymer is cooled below Tg the mould opens and the product is ejected This process gives high precision mouldings because the polymer cools under pressure Cycle time is typically between 1 5minutes
MECH 221 PM Wood-Adams fall 2008

48

Thermoplastic Extrusion

It is a cheap continuous process for producing shapes of constant section

MECH 221 PM Wood-Adams fall 2008
49

Blow Moulding
The parison is a hollow tube of softened plastic Its shape is determined by the screw speed and/or the die opening

Eg. Container fabrication similar to glass bottle production

MECH 221 PM Wood-Adams fall 2008

50