Polymers

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

Possible ease of assembly

Snap fits and self tapping fasteners

Polymers:

Limitations

Low strength (but may be okay in

strength to weight ratio)
Low rigidity
Not suitable for elevated temp
500F is considered upper limit

Poor wear resistance

Poor dimensional stability
High thermal expansion
Sensitive to moisture and radiation

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

Example: Ethylene Polyethylene

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

Degree of Polymerization: The

average number of mers in each
polymer chain
D.P. = Molecular Weight of Polymer
Molecular Weight of Mer

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

Thermoplastics Altering Properties

Increase the degree of
polymerization
Longer chains are stronger

Use nonsymmetrical monomers

Larger side structures (bumps)
EX: Cl in PVC (polyvinylchloride)
EX: Benzene groups in polystyrene

Cross-link adjacent chains

Promote crystallization
The parallel alignment of chains
enhances vanderWaals bonding

Type of monomer

Crystallization
1) easiest in simple monomers
2) most likely for slow cooling
3) can occur as a result of
deformation

Thermoplastics Altering Properties

Branching
Branching generally weakens due to
lower density and greater chain
separation

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

Easily molded when hot and soft

Mold must be cooled to induce hardening
Production is slowed by heating and cooling
of the mold

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

Typical forming processes for thermoplastic:

(a) extrusion, (b) blow molding, (c) injection
molding, (d) thermoforming, (e) calendaring,
and (f) spinning.

Behavior Classification:
Thermosets:
3-D Framework or Highly cross-linked
High strength, stiffness and hardness
No chains to slide

Elevated temperature promotes an

irreversible setting reaction
Subsequent heating results in burning
or charring
Cannot be recycled (burned as fuel!)
http://youtu.be/pHCF1kmlW0U

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

Examples: epoxies, melamine,

polyester, phenolics

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

Typical forming processes for thermosetting

polymers: (a) compression molding and (b)
transfer molding.

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

Tailoring Properties Through

Additives:
Additive agents, such as fillers,
plasticizers, lubricants, coloring agents,
stabilizers, antioxidants, antistatic
agents, flame retardants, and
reinforcement can be incorporated into
polymers to:

Improve properties
Reduce costextenders
Improve moldability
Impart color
Prevent deterioration in various
environments

 Property comparison:
Polymers versus Metals
Material

Condition

TS (ksi) E(106psi) Elo

Polyethylene

Branched

0.025

90-650

Polyethylene

Crystallized

0.100

50-800

Polyvinyl chloride Cl-sides

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

Thermoset two-part epoxies

Elastomer silicone bath-tub caulk

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.

Some of the common types of adhesives include:

1. Epoxies: These may be single component resins that
cure with heat or two component mixtures that utilize some
form of curing agent.
2. Cyanoacrylates: These are liquid monomers that
polymerize when spread into a thin film and are in the
presence of moisture. The commercial super glues are in
this family. Curing is at room temperature.
3. Anaerobics: These are one component materials that
polymerize when shut off from oxygen in the presence of a
metal catalyst. Some of these adhesives can even bond
through oil films.
4. Acrylics: One possibility here is to apply adhesive to
one surface and catalyst to another. These can be stored
for some time, but will bond at room temperature upon
contact.
5. Urethanes: Permit large degree of elastic strain.

Some other common types of adhesives include:

6. Silicones: Cure from the moisture in the air to form a
very flexible, low-strength seal.
7. High-temperature adhesives: Designed for use under
elevated temperature service conditions.
8. Hot-melt adhesives: These are thermoplastics which
soften or liquify when heated and reharden upon cooling.
9. Evaporative: Water or a solvent evaporates to leave a
solid resin. Examples: Duco-cement, model glues.
10.Pressure sensitive: Such as rubber cement, Post-it
Notes, etc.

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).

Advantages of Adhesives - continued

7. The material is a thermal and electrical insulator.
8. The adhesive also acts as a noise, shock and vibration
damper. This can serve to enhance the fatigue life of the
assembly.
9. The adhesive provides a corrosion barrier. Being a
nonconductor, it breaks galvanic cells.
10. The adhesive also serves to seal the joint against
penetration by moisture, gases, and fluids.
11. There is usually little surface preparation required. It is
possible to bond directly to oxides, and rough surfaces are
actually beneficial, since they provide enhanced gripping.
12. Less precision is required in joint fit-up. The adhesive fills
the variable gaps.

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.

Some other significant limitations are:

5. Assembly operations make take more time
due to the curing operation.
6. Some of the adhesives contain objectionable
chemicals or solvents.
7. There is no provision for easy disassembly
and reassembly, as with screws or other
fasteners.