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Polymers: - You May Think of Polymers As Being A Relatively Modern Invention
Polymers: - You May Think of Polymers As Being A Relatively Modern Invention
Polymers: - You May Think of Polymers As Being A Relatively Modern Invention
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
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
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Definitions
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
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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
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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
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Vulcanization of rubber
Sulphur reacts with chain at the double bond
MECH 221
PM Wood-Adams
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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
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
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MECH 221
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fall 2008
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
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).
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Structure of Polymers
Examples of real monomers and their resulting polymers:
This is an example of a linear chain homopolymer, where the X in our model is replaced with the ethylene group.
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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.
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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.
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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
Molecular weight
Alternative way to express average polymer chain size is degree of polymerization - the average number of mer units in a chain:
m = f jm j
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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
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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:
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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
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Molecular structure
Network polymers: 3D networks made from trifunctional mers. Examples: epoxies, phenolformaldehyde. These are thermosetting materials!
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secondary
bonding
Linear
Branched
Cross-Linked
Network
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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
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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
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Polymer Crystals
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Spherulites
When polymers are crystallized they form spherical structures called spherulites
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0 0 2 4 6 8
strain
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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
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.
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Decreasing T...
--increases E --increases TS --decreases %EL
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.
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stable conformation
stressed conformation
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Two adjacent chain folded lamellae and interlamellar amorphous material before deformation
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Tilting of Separation of lamellar chain crystalline folds block segments Orientation of block segments and tie chains with tensile axis 33
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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)
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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.
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plastic failure
elastomer
Deformation is reversible!
(MPa)
xbrittle failure 60 40
onset of necking
plastic failure
Initial
20 0 0 2 4 6 8
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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
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Strength in Polymers
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Tg is low for simple linear polymers Tg and Tm increase with mer complexity
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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
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
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PM Wood-Adams
fall 2008
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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
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this is dimensionally stable and can be removed from the mould while hot 46
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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
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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
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Thermoplastic Extrusion
Blow Moulding
The parison is a hollow tube of softened plastic Its shape is determined by the screw speed and/or the die opening
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