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Polymers:
Definition
Engineered materials
characterized by large molecules
that are built up by the joining
together of smaller molecules
Polymers:
Polymers:
Advantages:
Lightweight
Specific gravity 1.1-1.6 compared to Mg
1.75
Ease of fabrication
Can be molded, extruded, cast, made into
thin films, & applied as coatings
Can often produce products in a single
operation
Excellent as-formed surfaces (low
finishing cost)
Low fabrication and tooling cost
Design versatility
Polymers: (Advantages
continued)
Good corrosion resistance
Electrical & thermal insulator
Integral color
Can be transparent
Polymers:
Limitations
Classification of Polymers:
Polymerization Mechanism:
Addition
Condensation
Polymer Structure
Linear, Chain, or Fiber
Network, Framework
Polymer Behavior
Thermoplastic
Thermosetting
Elastomer
Polymerization Mechanisms:
Addition
Monomers link together to form a
polymer with a repeated unit, known
as a mer
Activators or catalysts initiate and
terminate the chain
Relative amounts determine the average
length of the chain or degree of
polymerization (# of repeated units in the
chain)
Degree of polymerization can range from
75-750
Addition mechanism
The unsaturated double bond in the
monomer is broken to produce active
sites, which then attract additional
repeat units to either end to produce
a chain
Initiation and
Termination
Initiation of a
polyethylene chain by
chain-growth may
involve:
(a) producing free
radicals from
initiators such as
benzoyl peroxide,
(b) attachment of a
polyethylene repeat
unit to one of the
initiator radicals, and
(c) attachment of
additional repeat
units to propagate
the chain.
Polymerization Mechanisms:
Copolymers
Two different types of mers are combined
into the same addition chain
Copolymers often have more desirable
physical and mechanical properties
Properties can be altered by changing
proportions of the mers
Example: Vinyl chloride C2H3Cl plus
Vinylidine chloride C2H2Cl2
Resultant copolymer is saran
Addition Terminology:
Functionality: The number of sites
on a monomer where
polymerization links can form.
F = 1 no polymerization
F = 2 linear polymers
F = 3 or more network polymers
Polymerization Mechanisms:
Condensation Polymerization
Reactive molecules combine with one
another to produce a polymer plus a
small by-product molecule
Heat, pressure, or catalysts may be
required to drive the reaction
Example:
Phenol + formaldehyde Bakelite
+ H2O
Condensation
Mechanism
Structure Classification:
Linear:
C, O, or Si chains with H, Cl, F or
benzene ring pendants
All bonds within the molecule are
strong primary bonds
Intermolecular attraction is by weaker
Van der Waals forces
Also mechanical tangling of the fibers
Mechanical model: the cottonball
Structure Classification:
Framework
All atoms are connected to one
another by strong covalent bonds to
form a strong 3-dimensional network
Structure
Classification:
(a) Linear. Many van der Waals bonding between the chains hold it together. Examples of linear polymers are
polyethylene, polyvinyl chloride, polystyrene, nylon and the fluorocarbons.
(b) Branched. Side-branch chains connect to the main ones during synthesis of the polymer. These reduces
the packing efficiency, so lower density.
(c) Crosslinked. Adjacent linear chains are actually connected - covalently bonding the chains. Many of the rubber
materials consist of polybutadiene crosslinked with S atoms, the process is called vulcanisation
(d) Network. Mer units with three active covalent bonds form 3D networks. e.g. epoxies
Behavior Classification:
Thermoplastics
For linear polymers, the mechanical
and physical properties are largely
determined by the Van der Waals
forces
These plastics soften with increasing
temperature and become harder and
stronger when cooled
The softening and hardening can be
repeated indefinitely, and no
chemical change occurs
Thermoplastics (continued)
Because the molecules have different
lengths, thermoplastics materials do
not have a definite melting point, but
soften over a range of temperature
As the temperature drops, transitions
occur
Liquidpour and cast, or injection mold
Rubberylarge amounts of plastic
deformation are possible, can mold or
extrude
Leatherystronger and stiffer
Crystalline or glassy
Thermoplastics (Continued)
Controlling or modifying properties
Model with cotton ball
Alter properties by interfering with
slippage between fibers
Type of monomer
Crystallization
1) easiest in simple monomers
2) most likely for slow cooling
3) can occur as a result of
deformation
Cold working
Brings chains into parallel alignment
Enhances vanderWaals interaction
Produce Copolymers
Deformation of
Thermoplastics
1) Stress initially straightens
out the individual chains
2) Continued stress then
causes the chains to slide
past each other (break Van
der Waals bonds)
Copolymers
Thermoplastics (Continued)
Processing a Thermoplastic
Recycling thermoplastics
If the various types of resins and additives
can be separated, many thermoplastics can
be recycled into useful productsusually
with some downgrading in use
EX: polyethylene (milk bottles) &
polypropylene
(two-liter soda bottles)
Forming of Thermoplastic
Polymers
Behavior Classification:
Thermosets:
3-D Framework or Highly cross-linked
High strength, stiffness and hardness
No chains to slide
Thermosets (Continued)
Since deformation requires breaking
of primary bonds
Strong, but brittle
Compared to thermoplastics,
thermosets are
Stronger
Stiffer
Lower in ductility
Poorer in impact
Thermosets (Continued)
Processing thermosets
Molds operate at constant elevated
temperature, but time is required for the
curing or setting reaction
Since the cured material has strength
and rigidity even when hot, product
removal from the mold is possible
without mold cooling
Forming of Thermosetting
Polymers
Behavior Classification:
Elastomers
A special class of linear polymers with
high elastic deformation, such as a
rubber band
Elasticity is not the stretching of
bonds, but the uncoiling of twisted or
curled molecules
Cross-linking can be used to restrict
viscous flow and tailor properties
Soft & flexible hard & brittle
Once cross-linked, cannot uncross-link
Example: Vulcanization of rubber by
sulfur
crosslinks
Elastomers
Improve properties
Reduce costextenders
Improve moldability
Impart color
Prevent deterioration in various
environments
Property comparison:
Polymers versus Metals
Material
Condition
Polyethylene
Branched
0.025
90-650
Polyethylene
Crystallized
0.100
50-800
0.375
2-40
Polystyrene
Benzene-sides
0.500
1-3
Bakelite
Framework
1.0
Aluminum
Annealed
13
10.0
15-30
1040 steel
Annealed
75
30.0
30
Structural Adhesives:
Polymers form the basis of the
structural adhesives and come from
all three behavior families:
Thermoplastic hot-melt glues
Structural Adhesives
Tremendous advances have been made recently in the development, use,
and reliability of structural (i.e. load-bearing) adhesives.
Use has increased rapidly, even in such quality- and durability-conscious
areas as the automotive and aircraft industries.
Both metals and nonmetals can be bonded, as well as the plastics and
composites.
Structural adhesives span the entire range of polymeric types and forms,
including thermoplastic resins (such as hot melt adhesives), thermosetting
resins (like the epoxies), and artificial elastomers (like silicones).
They can be applied in a variety of forms, including drops, beads, pellets,
tapes, and coatings, and are available in the form of liquids, pastes, gels,
and solids.
Curing is the process by which the properties of the adhesives are
changed, and may involve condensation reactions, polymerization, or
vulcanization.
Curing can be by means of heat, radiation or light, moisture, activators,
catalysts, multiple-component reactions, or combinations of these.
Advantages of Adhesives
Adhesives have a number of advantages, when compared to the
alternative methods of joining, such as welding, brazing, soldering,
mechanical joints, fasteners, spot welds, shrink fits, etc.
1. All materials or combinations of materials can be joined.
These materials can readily accommodate differences in
thermal expansion or contraction.
2. Joining can be performed at low temperatures. There is no
heat affected zone.
3. Thin or delicate materials can be joined.
4. The entire joint area can be bonded. This provides good
stress distribution over the entire joint area. The lower
strength of the adhesive is compensated by the increased
area of the bond (in contrast to spot welds or discrete
fasteners).
5. Inexpensive
6. Light weight joining (in contrast to welds or fasteners).
Limitations of Adhesives
Some of the significant limitations are:
1. The adhesives are generally not stable above 350F.
Therefore, they should not be used for conditions of
elevated temperature service.
2. The joints are difficult to inspect for quality. Few of the
standard nondestructive tests work for the polymericbased adhesives.
3. Consistent results require control of the surface
preparation, adhesive preparation, application and curing.
4. The life expectancy of the joints is hard to predict.