ENGINEERING MATERIALS
BMM1523
CHAPTER 8
POLYMERS
Polymeric Materials
Polymer
Major Polymer Processes
Extrusion
Injection Molding
Blow Molding
Thermoforming
Recycling
Polymer Processes
Extrusion
Extrusion Product Examples
ME 355 W. Li
Extrusion Characteristics
The extrusion machine forms the basis of
nearly all other polymer processes.
Basically involves melting polymer pellets
and extruding them out through a two
dimensional die.
Produces long, thin products
Coating for electrical wire
Fishing Line
Tubes, etc.
ME 355 W. Li
Injection Molding
Injection Molding Product Examples
ME 355 W. Li
Injection Molding Machine Basics
Injection Molding Process Control
Very similar to die
casting
Must control heat
transfer and fluid flow
Do that by controlling
temperature and
pressure
Gas Assist Injection Molding
– Applicable to hollow parts without interior control.
Blow Molding Example Products
Blow Molding Processes
Extrusion Blow Molding Injection Blow Molding
Stretch Blow Molding
Thermoforming
(a) Vacuum, (b) Pressure, (c) Drape-vacuum,
(d) Plug-assist, (e) Pressure-bubble plug assist
Thermoforming Products
Polymer Recycling
1998 – Approximately 20% of plastic waste is
recycled (optimistic estimate)
1998 – Polymers account for approximately
18% by volume of material to landfills
Needs vs. Challenges
Needs for a viable program: Challenges
Stable supply of materials with 10-12 main polymer types
reliable collection and sorting
Thousands of blends
Economical, proven and
environmentally sound Additives
recycling process Impurities in supply (labels,
End use applications for the glass, dirt, etc)
recycled material
Recycling of Polymers
• PET (polyethylene • PP (polypropylene) margarine
terphthalate) beverage and yogurt containers, caps for
containers, boil-in food pouches, containers, wrapping to replace
processed meat packages cellophane
• HDPE (high density • PS (polystyrene) egg cartons,
polyethylene) milk bottles, fast food trays, disposable
detergent bottles, oil bottles, plastic silverware
toys, plastic bags
• Other multi-resin containers
• PVC (polyvinyl chloride) food
wrap, vegetable oil bottles,
blister packaging
• LDPE (low density
polyethylene) shrink-wrap,
plastic bags, garment bags
Polymer
A compound consisting of long‑chain
molecules, each molecule made up of
repeating units connected together
There may be thousands, even millions of units in a
single polymer molecule
The word polymer is derived from the Greek words
poly, meaning many, and meros (reduced to mer),
meaning part
Most polymers are based on carbon and are
therefore considered organic chemicals
Types of Polymers
Polymers can be separated into plastics and
rubbers
As engineering materials, it is appropriate to
divide them into the following three
categories:
1. Thermoplastic polymers
2. Thermosetting polymers
3. Elastomers
where (1) and (2) are plastics and (3) are rubbers
Plastics
Plastics are:
●
A large and varied group of synthetic materials
●
Produced through forming and molding processes
●
Classified as either thermoplastic or thermosetting.
N
Thermoplastic Polymers -
Thermoplastics (TP)
Solid materials at room temperature but
viscous liquids when heated to
temperatures of only a few hundred
degrees
This characteristic allows them to be easily
and economically shaped into products
They can be subjected to heating and
cooling cycles repeatedly without
significant degradation
Thermoplastics Products
N
Thermosets
THERMOSETS are distinguished by their highly
cross‑linked three‑dimensional,
covalently‑bonded structure within the
molecule
Chemical reactions associated with
cross‑linking are called curing or setting
In effect, the formed part (e.g., pot handle,
electrical switch cover, etc.) becomes one large
macromolecule
Always amorphous and exhibits no glass
transition temperature
Cannot tolerate repeated heating cycles as
thermoplastics can
When initially heated, they soften and flow for
molding
But elevated temperatures also produce a
chemical reaction that hardens the material into
an infusible solid
If reheated, thermosets degrade and char rather
than soften
Mechanical Properties of Thermosets
Rigid - modulus of elasticity is two to three times
greater than thermoplastics
Brittle, virtually no ductility
Less soluble than thermoplastics in common
solvents
Capable of higher service temperatures than
thermoplastics
Strength and hardness not effected by
temperature or rate deformation. If temperature
raise sufficiently, it will burn up, degrade.
Thermosets Applications
Thermoset products include countertops,
plywood adhesives, paints, molded parts,
printed circuit boards and other fiber
reinforced plastics.
Elastomers
Polymers that exhibit extreme elastic
extensibility when subjected to relatively low
mechanical stress
Also known as rubber
Some elastomers can be stretched by a factor
of 10 and yet completely recover to their
original shape
Although their properties are quite different
from thermosets, they share a similar
molecular structure that is different from the
thermoplastics
Types of Polymers
Polymer Family Tree
Thermoplastics Thermosets/Elastomers
90% of market 10% of market
Polyethylene Epoxy
33% Melamine Formaldehyde
Vinyls Phenolic
16% Polyester (unsaturated)
Polypropylene Polyimide
15% Silicone
PMMA Urea Formaldehyde
ABS
Nylon
Polycarbonate
Saturated Polyester
PEEK
PVC
Range of Mechanical Properties for
Various Engineering Plastics
TABLE 7.1
Elongation Poisson’s
Material UTS (MPa) E (GPa) (%) ratio ()
ABS 28–55 1.4–2.8 75–5 —
ABS, reinforced 100 7.5 — 0.35
Acetal 55–70 1.4–3.5 75–25 —
Acetal, reinforced 135 10 — 0.35–0.40
Acrylic 40–75 1.4–3.5 50–5 —
Cellulosic 10–48 0.4–1.4 100–5 —
Epoxy 35–140 3.5–17 10–1 —
Epoxy, reinforced 70–1400 21–52 4–2 —
Fluorocarbon 7–48 0.7–2 300–100 0.46–0.48
Nylon 55–83 1.4–2.8 200–60 0.32–0.40
Nylon, reinforced 70–210 2–10 10–1 —
Phenolic 28–70 2.8–21 2–0 —
Polycarbonate 55–70 2.5–3 125–10 0.38
Polycarbonate, reinforced 110 6 6–4 —
Polyester 55 2 300–5 0.38
Polyester, reinforced 110–160 8.3–12 3–1 —
Polyethylene 7–40 0.1–1.4 1000–15 0.46
Polypropylene 20–35 0.7–1.2 500–10 —
Polypropylene, reinforced 40–100 3.5–6 4–2 —
Polystyrene 14–83 1.4–4 60–1 0.35
Polyvinyl chloride 7–55 0.014–4 450–40 —
Reasons Why Polymers are Important:
Plastics can be formed by molding into intricate
part shapes, usually with no further processing
required
Very compatible with net shape processing
On a volumetric basis, polymers:
Cost competitive with metals
Generally require less energy to produce than metals
Certain plastics are translucent and/or
transparent, which makes them competitive
with glass in some applications
General Properties of Polymers
Low density relative to metals and ceramics
Good strength‑to‑weight ratios for certain (but
not all) polymers
High corrosion resistance
Low electrical and thermal conductivity
Limitations of Polymers as
Engineering Materials
Low strength relative to metals and ceramics
Low modulus of elasticity (stiffness)
Service temperatures are limited to only a few
hundred degrees
Viscoelastic properties, which can be a distinct
limitation in load bearing applications
Some polymers degrade when subjected to
sunlight and other forms of radiation
Molecular Weight
The molecular weight (MW) of a polymer is the
sum of the molecular weights of the mers in
the molecule;
MW = n times the molecular weight of each
repeating unit
Since n varies for different molecules in a batch, the
molecule weight must be interpreted as an average
Molecular Weight and Degree of
Polymerization
Figure 7.3 Effect of molecular weight and
degree of polymerization on the strength
and viscosity of polymers.
Typical Values of DP and MW
for Selected Polymers
Polymer DP(n) MW
Polyethylene 10,000 300,000
Polyvinylchloride 1,500 100,000
Nylon 120 15,000
Polycarbonate 200 40,000
Degree of Polymerization
Since molecules in a given batch of
polymerized material vary in length, n for the
batch is an average; its statistical distribution
is normal
The mean value of n is called the degree
of polymerization (DP) for the batch
DP affects properties of the polymer: higher
DP increases mechanical strength but also
increases viscosity in the fluid state, which
makes processing more difficult.
Tutorial
Degree of Polymerization
Tutorial
Degree of Polymerization
Linear, Branched, and Cross-
linked Polymers
Linear structure – chain-like structure
Characteristic of thermoplastic polymers
Branched structure – chain-like but with side
branches
Also found in thermoplastic polymers
Cross-linked structure
Loosely cross-linked, as in an elastomer
Tightly cross-linked, as in a thermoset
Polymer Chains
Figure 7.4 Schematic illustration
of polymer chains. (a) Linear
structure--thermoplastics such as
acrylics, nylons, polyethylene, and
polyvinyl chloride have linear
structures. (b) Branched structure,
such as in polyethylene. (c) Cross-
linked structure--many rubbers or
elastomers have this structure, and
the vulcanization of rubber
produces this structure. (d)
Network structure, which is
basically highly cross-linked--
examples are thermosetting
plastics, such as epoxies and
phenolics.
Linear structure of a thermoplastic polymer
Various structures of polymer molecules: (a) linear,
characteristic of thermoplastics
Branched structure that includes side
branches along the chain
Various structures of polymer molecules: (b) branched
Cross-linked polymers, in which primary
bonding occurs between branches and other
molecules at certain connection points
Various structures of polymer molecules:
(c) loosely cross‑linked as in an elastomer
Tightly cross-linked or network structure - in
effect, the entire mass is one gigantic macromolecule
Various structures of polymer molecules:
(d) tightly cross‑ linked or networked structure as in a thermoset
Copolymers – A polymer which has two types of mer in the same molecule.
Eg: styrene-butadiene, which is used widely for automobile tires.
Terpolymers – Contains three types of mer. Eg: ABS (acrylonitrile-butadiene-
styrene), which is used for helmets, telephones and refrigerator liners
• Terpolymers- in effect, the entire mass is one
gigantic macromolecule
Crystallinity in Polymers
Both amorphous and crystalline structures are
possible, although the tendency to crystallize
is much less than for metals or non‑glass
ceramics
Not all polymers can form crystals
For those that can, the degree of crystallinity
(the proportion of crystallized material in the
mass) is always less than 100%
Crystallinity
Figure 7.6 Amorphous and
crystalline regions in a
polymer. The crystalline
region (crystallite) has an
orderly arrangement of
molecules. The higher the
crystallinity, the harder,
stiffer, and less ductile the
polymer.
Crystallized regions in a polymer: (a) long
molecules forming crystals randomly mixed in with
the amorphous material; and (b) folded chain
lamella, the typical form of a crystallized region
Have you ever left a plastic bucket or some other plastic object outside during the
winter, and found that it cracks or breaks more easily than it would in the summer
time? What you experienced was the phenomenon known as the glass transition.
This transition is something that only happens to polymers, and is one of the things
that make polymers unique. The glass transition is pretty much what it sounds like.
There is a certain temperature(different for each polymer) called the glass transition
temperature, or Tg for short. When the polymer is cooled below this temperature, it
becomes hard and brittle, like glass. Some polymers are used above their glass
transition temperatures, and some are used below. Hard plastics like polystyrene and
poly(methyl methacrylate), are used below their glass transition temperatures; that is
in their glassy state. Their Tg's are well above room temperature, both at around 100
o
C. Rubber elastomers like polyisoprene and polyisobutylene, are used above their
Tg's, that is, in the rubbery state, where they are soft and flexible. Amorphous and
Crystalline Polymers
Crystallinity and Properties
As crystallinity is increased in a polymer:
Density increases
Stiffness, strength, and toughness increases
Heat resistance increases
If the polymer is transparent in the amorphous
state, it becomes opaque when partially crystallized
Low Density vs. High Density
Polyethylene
Polyethylene type Low density High density
Degree of crystallinity 55% 92%
Specific gravity 0.92 0.96
Modulus of elasticity 140 MPa 700 MPa
(20,000 lb/in2) (100,000 lb/in2)
Melting temperature 115C 135C
(239F) (275F)