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BMM 1523 ENGINEERING MATERIAL



MUHAMAD MAT NOOR


MUHAMAD@ump.edu.my

JUL 2007

FACULTY OF MECHANICAL ENGINEERING
UNIVERSITI MALAYSIA PAHANG
Group Presentation (A, M05, M06)
No. Topics Group When
1
Materials Structure and Bonding
1
2
Properties of Materials
3
3
Metal Alloy
10
4
Ferrous Metals
5
5
Non-ferrous Metals
6
6
Polymer : Thermoplastic 9
7
Polymer : Thermosetting
4
8
Polymer : Elastomer
8
9
Ceramics
7
10
Composites 2
W14
W14
W14
W14
W14
W14
W14
W14
W15
W15
Group Presentation (B)
No. Topics Group When
1
Materials Structure and Bonding
20
2
Properties of Materials
11
3
Metal Alloy
19
4
Ferrous Metals
12
5
Non-ferrous Metals
18
6
Polymer : Thermoplastic 17
7
Polymer : Thermosetting
14
8
Polymer : Elastomer
15
9
Ceramics
16
10
Composites
13
W14
W14
W14
W14
W14
W14
W14
W14
W15
W15
Group Presentation (C)
No. Topics Group When
1
Materials Structure and Bonding
2
Properties of Materials
3
Metal Alloy
4
Ferrous Metals
5
Non-ferrous Metals
6
Polymer : Thermoplastic
7
Polymer : Thermosetting
8
Polymer : Elastomer
9
Ceramics
10
Composites
28
23
22
26
21
29
30
24
27
25
W14
W14
W14
W14
W14
W14
W14
W14
W15
W15
ENGINEERING MATERIALS
BMM1523
POLYMERS
CHAPTER 7
Polymeric Materials
Lecture Grp B(M03) 26Sept
Lecture Grp A(M05) 26Sept
Polymer
ME 355 W. Li
Polymerization Reactions
Chain polymerization,
also called addition
polymerization, with
the aid of initiators, to
form Paraffin or
Benzene.
Step reaction, also
called condensation,
dissimilar monomers
joined into short
groups that gradually
grow with by-product
released.
Timeline
Major Polymer Processes
Extrusion
Injection Molding
Blow Molding
Thermoforming
Recycling

Polymer Processes
Extrusion
ME 355 W. Li
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.
Injection Molding
ME 355 W. Li
Injection Molding Product Examples
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.
Injection Compression Molding
Injection Molding of Thermosets
Plastics set when they cool
Mold temperature will be set to allow full cavity fill, while increasing
production rate
Thermosets undergo a chemical crosslinking that produces
the solid structure
Mold temperature will be hotter usually set to allow full cavity fill,
while accelerating the chemical reaction to cure.
Often called Reaction Injection Molding (RIM)


Blow Molding Example Products
Blow Molding Processes
Injection Blow Molding Extrusion 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:
Stable supply of materials with
reliable collection and sorting
Economical, proven and
environmentally sound recycling
process
End use applications for the
recycled material

Challenges
10-12 main polymer types
Thousands of blends
Additives
Impurities in supply (labels, glass,
dirt, etc)
Recycling of Polymers
PET (polyethylene
terphthalate) beverage
containers, boil-in food pouches,
processed meat packages
HDPE (high density
polyethylene) milk bottles,
detergent bottles, oil bottles,
toys, plastic bags
PVC (polyvinyl chloride) food
wrap, vegetable oil bottles,
blister packaging
LDPE (low density
polyethylene) shrink-wrap,
plastic bags, garment bags

PP (polypropylene) margarine
and yogurt containers, caps for
containers, wrapping to replace
cellophane
PS (polystyrene) egg cartons,
fast food trays, disposable
plastic silverware
Other multi-resin containers
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
Thermosetting Polymers -
Thermosets (TS)
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
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
Market Shares
Thermoplastics are commercially the most
important of the three types, constituting around
70% of the tonnage of all synthetic polymers
produced.
Thermosets and elastomers share the
remaining 30% about evenly, with a slight edge
for the former.
On a volumetric basis, current annual usage of
polymers exceeds that of metals.
Polyethylene
33%
Vinyls
16%
Polypropylene
15%
PMMA
ABS
Nylon
Polycarbonate
Saturated Polyester
PEEK
PVC
90% of market
Thermoplastics
Epoxy
Melamine Formaldehyde
Phenolic
Polyester (unsaturated)
Polyimide
Silicone
Urea Formaldehyde
10% of market
Thermosets/Elastomers
Polymer Family Tree
Types of Polymers
Examples of Polymers
Thermoplastics:
ABS, Acetals, Acrylics, Cellulosics, Fluorocarbons,
Polyamides, Polycarbonates, Polyesters, Polyethylenes,
Polypropylenes, Polystyrenes, Polysulfones,
Polyurethanes, Polyvinyl Chlorides
Thermosets:
Alkyds Aminos. Epoxies.Phenolics.
Elastomers:
Magnetic Rubber. Natural Rubber. Cements. Latex.
Rubberized Fabrics. Vulcanized Rubber.
Range of Mechanical Properties for
Various Engineering Plastics
TABLE 7.1
Material UTS (MPa) E (GPa)
Elongation
(%)
Poissons
ratio ()
ABS
ABS, reinforced
Acetal
Acetal, reinforced
Acrylic
Cellulosic
Epoxy
Epoxy, reinforced
Fluorocarbon
Nylon
Nylon, reinforced
Phenolic
Polycarbonate
Polycarbonate, reinforced
Polyester
Polyester, reinforced
Polyethylene
Polypropylene
Polypropylene, reinforced
Polystyrene
Polyvinyl chloride
2855
100
5570
135
4075
1048
35140
701400
748
5583
70210
2870
5570
110
55
110160
740
2035
40100
1483
755
1.42.8
7.5
1.43.5
10
1.43.5
0.41.4
3.517
2152
0.72
1.42.8
210
2.821
2.53
6
2
8.312
0.11.4
0.71.2
3.56
1.44
0.0144
755

7525

505
1005
101
42
300100
20060
101
20
12510
64
3005
31
100015
50010
42
601
45040

0.35

0.350.40

0.460.48
0.320.40

0.38

0.38

0.46

0.35

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
Synthesis of Polymers
Nearly all polymers used in engineering are
synthetic
They are made by chemical processing
Polymers are synthesized by joining many small
molecules together into very large molecules, called
macromolecules, that possess a chain-like structure
The small units, called monomers, are generally
simple unsaturated organic molecules such as
ethylene C
2
H
4

Synthesis of polyethylene from ethylene monomers:
(1) n ethylene monomers yields (2a) polyethylene of
chain length n; (2b) concise notation for depicting the
polymer structure of chain length n
Structure
of
Polymer
Molecules
Figure 7.2 Basic structure of polymer molecules: (a) ethylene molecule; (b) polyethylene,
a linear chain of many ethylene molecules; molecular structure of various polymers.
These are examples of the basic building blocks for plastics
Polymerization
As a chemical process, the synthesis of polymers
can occur by either of two methods:
1. Addition polymerization
2. Step polymerization
Production of a given polymer is generally
associated with one method or the other
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
Polyethylene
Polyvinylchloride
Nylon
Polycarbonate
DP(n)
10,000
1,500
120
200
MW
300,000
100,000
15,000
40,000
Tutorial
What are some advantages and disadvantages of the injection-
molding process for molding thermoplastics?

Advantages :
Potential for creating high quality parts at a high production rate;
Low labor costs; good surface finishes;
Capability for a highly automated process;
Ease of producing intricate shapes.

The primary disadvantages:
The large initial investment required to purchase the machine
necessitates a large volume of production;
The process must be closely controlled to produce a high quality
part.
Tutorial
1. Define the following terms: chain polymerization, monomer, and
polymer.

Answer :
Chain polymerization is the process by which monomers are
chemically combined into long-chain molecular polymers.

A monomer is the simple molecule that is covalently bonded with
other monomers toform long molecular chains.

A polymer is the long-chain molecule formed from monomer units.
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.
Lecture Grp C(M01) 27Sept
Lecture Grp B(M03) 27Sept
Degree of Polymerization
Tutorial
Degree of Polymerization
Degree of Polymerization
Tutorial
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

Illustrate the following types of copolymers by using filled and
open circles for their mers: (a) random, (b) alternating, (c)
block, and (d) graft.
Tutorial
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
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
(20,000 lb/in
2
)
700 MPa
(100,000 lb/in
2
)
Melting temperature 115C
(239F)
135C
(275F)
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
N
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
N
Thermoplastic Polymers (TP)
A thermoplastic polymer can be heated from a solid
state to a viscous liquid state and then cooled back
down to solid
This heating and cooling cycle can be repeated
multiple times without degrading the polymer
The reason is that TP polymers consist of linear
(and/or branched) macromolecules that do not
cross-link upon heating
By contrast, thermosets and elastomers change
chemically when heated, which cross-links their
molecules and permanently sets these polymers
General Properties and Characteristics
of Thermosets
Rigid - modulus of elasticity is two to three times
greater than TP
Brittle, virtually no ductility
Less soluble than TP in common solvents
Capable of higher service temperatures than TP
Cannot be remelted - instead they degrade or burn
Elastomers
Polymers capable of large elastic deformation
when subjected to relatively low stresses
Some can be extended 500% or more and still
return to their original shape
Two categories:
1. Natural rubber - derived from biological plants
2. Synthetic polymers - produced by polymerization
processes similar to those used for thermoplastic and
thermosetting polymers
Model of long elastomer molecules, with low degree
of cross-linking: (a) unstretched, and (b) under
tensile stress
Vulcanization
Curing to cross-link most elastomers
Vulcanization = the term for curing in the context of
natural rubber (and certain synthetic rubbers)
Typical cross-linking in rubber is one to ten links per
hundred carbon atoms in the linear polymer chain,
depending on degree of stiffness desired
Considerable less than cross-linking in thermosets
Increase in stiffness as a function of strain for three
grades of rubber: natural rubber, vulcanized rubber, and
hard rubber
Natural Rubber (NR)
NR consists primarily of polyisoprene, a high molecular-weight
polymer of isoprene (C
5
H
8
)
It is derived from latex, a milky substance produced by various
plants, most important of which is the rubber tree that grows in
tropical climates
Latex is a water emulsion of polyisoprene (about 1/3 by
weight), plus various other ingredients
Rubber is extracted from latex by various methods that
remove the water
Properties: Good resistance to abrasion and fatigue,
high frictional properties, but has low resistance to oil,
heat, ozone and sunlight.
Natural Rubber Products
Largest single market for NR is automotive tires
Other products: shoe soles, bushings, seals, and shock
absorbing components
In tires, carbon black is an important additive; it
reinforces the rubber, serving to increase tensile strength
and resistance to tear and abrasion
Other additives: clay, kaolin, silica, talc, and calcium
carbonate, as well as chemicals that accelerate and
promote vulcanization
Synthetic Rubbers
Today, the tonnage of synthetic rubbers is more
than three times that of NR
Development of synthetic rubbers was
motivated largely by world wars when NR
was difficult to obtain
The most important synthetic is styrene-butadiene
rubber (SBR), a copolymer of butadiene (C
4
H
6
) and
styrene (C
8
H
8
)
As with most other polymers, the main raw material
for synthetic rubbers is petroleum
Thermoplastic Elastomers (TPE)
A thermoplastic that behaves like an elastomer
Elastomeric properties not from chemical
cross-links, but from physical connections between
soft and hard phases in material
Cannot match conventional elastomers in elevated
temperature strength and creep resistance
Products: footwear; rubber bands; extruded tubing,
wire coating; molded automotive parts, but no tires
Mechanical Properties of Thermoplastics
Low modulus of elasticity (stiffness)
E is two or three orders of magnitude lower than
metals and ceramics
Low tensile strength
TS is about 10% of the metal
Much lower hardness than metals or ceramics
Greater ductility on average
Tremendous range of values, from 1% elongation for
polystyrene to 500% or more for polypropylene
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
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.
Tutorial
1. What are some of the advantages of plastics for use in
mechanical engineering designs?

Answer : The incorporation of plastics in engineering
designs often allows for the elimination of many parts and
finishing operations, the reduction of weight and noise, and
the simplification of assembly processes. In some cases,
plastics eliminate the need for
lubrication of parts.
Tutorial
1. What are some of the advantages of plastics for use in electrical
engineering designs?

Answer : Plastics are used extensively in electrical designs primarily
because of their outstanding insulating properties and low cost.
However, their low density and facilitation of
assembly processes are also important to electronic applications.
2. What are some of the advantages of plastics for use in chemical
engineering designs?

Answer : Chemical engineering designs take advantage of the
corrosion resistant and thermal
insulating properties of plastics.
Biodegradable Plastics
Most plastics are renewable, not biodegradable and
difficult to recycle.

Biodegradability means the microbial species in the environment will
degrade a portion or entire polymeric material, under the right
environmental conditions and without producing toxic.

The end products of the degradation of the material are carbide and
water. There are 3 different biodegradable plastics:

1. Starch based, extracted from potatoes, wheat, rice, corn
2. Lactic based, fermenting feed stocks produce lactic acid, the
polymerize to form polyester resin.
3. Fermentation of sugar. Organics acids are added to sugar
feed stock. Resultant of highly crystalline and very stiff
polymer.
Biodegradable Plastic Bag
www.aichi-inst.jp/ ~mikawa/biodegrade/
Before buried in sand After buried in sand
www.biotech.wisc.edu/.../ Poster/feedstocks.html
N
Tutorial
What are some of the advantages of thermosetting plastics for
engineering design applications?
What is the major disadvantage of thermosets that thermoplastics do
not have?

Answer :
General advantages of thermosetting plastics include one or more of
the following: high thermal stability; high rigidity; high dimensional
stability; resistance to creep and deformation under load; light weight;
and high electrical and thermal insulating properties.
Tutorial
What are some of the advantages of epoxy thermoset resins? What
are some of their applications?

Answer :
Advantageous properties of epoxy resins include: good chemical and
environmental resistance, good mechanical properties, good
electrical insulating properties, low cure shrinkage, strong adhesive
properties and exceptional wetting characteristics.

This set of attributes makes epoxies a natural choice for a wide
variety of protective and decorative coatings, adhesives, fiber-
reinforced matrix materials, electrical potting and encapsulating
applications.
Tutorial
What are elastomers? What are some elastomeric materials?

Answer :
Elastomers (rubbers) are polymeric materials whose dimensions can
be significantly altered under stress yet return to nearly or exactly
their original dimensions once the stress is removed.

Examples of elastomeric materials include natural rubber, synthetic
polyisoprene, styrene-butadiene rubber, nitrile rubbers,
polychloroprene, and the silicones.
Tutorial
What is natural rubber latex?
Briefly describe how natural rubber is produced in the bulk form?

Answer :
Natural rubber latex is a milky liquid, collected from trees and diluted
to approximately 15 percent rubber content.

This mixture is coagulated with formic acid, and the material is then
compressed into sheets by rollers and dried.

Subsequently, milling between heavy rolls is performed to break up
some of the long polymer chains and thus reduce their average
molecular weight.
Tutorial
1. How does the average molecular mass of a thermoplastic affect its
strength?
2. How does the amount of crystallinity within a thermoplastic
material affect (a) its strength, (b) its tensile modulus of elasticity,
and (c) its density?
3. Explain why low-density polyethylene is weaker than high-density
polyethylene.
4. Explain why thermosetting plastics have in general high strengths
and low ductilities.

Also pls do some DP and MW calculation. Do remember some g/mol
Example
H=1g/mol
C=12, N=14, O=16

Tutorial (Answer)
1. How does the average molecular mass of a thermoplastic affect its strength?
The average molecular mass of a thermoplastic directly affects its strength as it is indicative of the degree of polymerization of the solid; the
plastic must attain a critical molecular mass to become a stable solid. However, increasing the mass beyond this minima does not
appreciably increase the thermoplastic.s strength.
2. How does the amount of crystallinity within a thermoplastic material affect (a) its
strength, (b) its tensile modulus of elasticity, and (c) its density?
(a) As the amount of crystallinity increases, the polymer chains become more tightly packed and the tensile strength increases.
(b) The tensile modulus of elasticity is also directly related to crystallinity; the modulus increases with increasing crystallinity.
(c) Increased crystallinity corresponds to an increase in density.
2. Explain why low-density polyethylene is weaker than high-density polyethylene.
Low-density polyethylene is weaker than high-density because the molecular chains are
more branched and farther apart from each other, causing weaker bonding forces and thus
lower strength.
2. Explain why thermosetting plastics have in general high strengths and low ductilities.
In general, thermosetting plastics have high strengths and low ductilities because their molecular structure is comprised of a covalently
bonded network produced by chemical reaction within the material after casting or during pressing under heat and pressure.

Also pls do some DP and MW calculation. Do remember some g/mol
Example
H=1g/mol
C=12, N=14, O=16

Thank You
Thank You
Extra Note for Polymer
Polymer and Polymer Processing
ME 355 W. Li
Polymer, Resin, and Plastics
A polymer is any substance made up of many of
repeating units, building blocks, called mers.
When in form ready for further working, they are
called resins.
Polymers are seldom used in their neat form, most
often compounded with various additives. The
resulting material is usually referred to as a plastic.
Frequently, polymers, resins, plastics are used
interchangeably.

ME 355 W. Li
Properties and Applications
Low density, high corrosion resistance, electrical
insulation.
Ease of manufacturing into complex shapes.
Widely used for consumer products.
Emerging as structural polymers (T<150-250C).
Sales of plastics, on a volume basis, has grown more
than double the steel production in the U.S.
ME 355 W. Li
Polymerization Reactions
Chain polymerization,
also called addition
polymerization, with
the aid of initiators, to
form Paraffin or
Benzene.
Step reaction, also
called condensation,
dissimilar monomers
joined into short
groups that gradually
grow with by-product
released.
ME 355 W. Li
Polyethylene
33%
Vinyls
16%
Polypropylene
15%
PMMA
ABS
Nylon
Polycarbonate
Saturated Polyester
PEEK
Polyurethane
Some are thermosets as well.
PVC
Not Cross-Linked
90% of market
Thermoplastics
Will reform when melted
Epoxy
Melamine Formaldehyde
Phenolic
Polyester (unsaturated)
Polyimide
Polyurethane
Some are thermoplastic as well.
Silicone
Urea Formaldehyde
Cross-linked
10% of market
Thermosets/Elastomers
Will not reform
Polymer Family Tree
Types of Polymers
ME 355 W. Li
Basic Concepts
Molecular weight (MW)
Degree of polymerization (DP)
Chain structures
Crystalline and amorphous polymers
Glass transition temperature (Tg) and melting
temperature (Tm)
Mechanical properties
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Source of Strength of Polymers
Primary Bond - Covalent
Bonding
Secondary Bonds
van der Waals
Dipole Bonds
Hydrogen Bonds

PE - mer

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Major Polymer Processes
Extrusion
Injection Molding
Blow Molding
Thermoforming

Recycling

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Polymer Processes
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Extrusion
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Extrusion Product Examples
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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.
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Injection Molding (See Video)
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Injection Molding Product Examples
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Injection Molding Machine Basics
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Injection Molding Process Control
Very similar to die casting
Must control heat transfer
and fluid flow
Do that by controlling
temperature and pressure

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Gas Assist Injection Molding
Applicable to hollow parts without interior control.
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Injection Compression Molding
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Injection Molding of Thermosets
Plastics set when they cool
Mold temperature will be set to allow full cavity fill, while increasing
production rate
Thermosets undergo a chemical crosslinking that produces
the solid structure
Mold temperature will be hotter usually set to allow full cavity fill,
while accelerating the chemical reaction to cure.
Often called Reaction Injection Molding (RIM)


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Blow Molding Example Products
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Blow Molding Processes (See Video)
Injection Blow Molding Extrusion Blow Molding
Stretch Blow Molding
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Thermoforming
(a) Vacuum, (b) Pressure, (c) Drape-vacuum,
(d) Plug-assist, (e) Pressure-bubble plug assist
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Thermoforming Products

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Polymer Recycling
1998 Approximately 20% of plastic waste is
recycled (optimistic estimate)
1998 Polymers account for approximately 18% by
volume of material to landfills
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Needs vs. Challenges
Needs for a viable program:
Stable supply of materials with
reliable collection and sorting
Economical, proven and
environmentally sound recycling
process
End use applications for the
recycled material

Challenges
10-12 main polymer types
Thousands of blends
Additives
Impurities in supply (labels, glass,
dirt, etc)
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Recycling of Polymers
PET (polyethylene
terphthalate) beverage
containers, boil-in food pouches,
processed meat packages
HDPE (high density
polyethylene) milk bottles,
detergent bottles, oil bottles,
toys, plastic bags
PVC (polyvinyl chloride) food
wrap, vegetable oil bottles,
blister packaging
LDPE (low density
polyethylene) shrink-wrap,
plastic bags, garment bags

PP (polypropylene) margarine
and yogurt containers, caps for
containers, wrapping to replace
cellophane
PS (polystyrene) egg cartons,
fast food trays, disposable
plastic silverware
Other multi-resin containers
Processing of Polymer Composites
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What are Composites
Composites are often classified
by the type of matrix: polymer,
metal or ceramic
In addition, composites my be
classified by the type of
embedded material (a.k.a.,
reinforcement) fiber, particle,
whisker, flake, etc.
Rule of mixtures says that each
constituent contributes to the
properties of the composite in
proportion to its volume fraction

m f c
f f ) 1 (
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Fibers dominate composite properties
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Components of Polymer Composites
Polymer Resin
Usually a thermoset
Epoxy
Bismaleimide
Polyimide
Thermoplastics
Polyester
Vinylester
Reinforcing fiber
Fiberglass
Graphite (Carbon)
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Fabrication of Composites (See Video)
Fabrication of polymer-matrix composites
Open-mold processes
Pultrusion
Closed-mold processes (Matched-die molding)
Metal-matrix composites
Ceramic-matrix composites

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Open-Mold Processes
Shaping:
Male or female mold
Hand lay-up
Spry molding
Tape laying
Filament winding
Curing:
Open air
Vacuum bag
High pressure bag
Heated pressure vessel

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Filament Winding
Control the orientation of
the fiber using a relative
motion of rotation and
linear motion
Example Products:
Pressure Vessels
Fishing Poles
Light Poles

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Pultrusion
Fibers or cloth are pulled
through a resin bath
Heated in a die with a
shaped profile
Cured to shape
Cut to length
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Closed Molding
Can be done using Pre-preg
or wet layup
Process:
Resin impregnated fibers cut
to proper geometry
Heated Die sets close on part
Part is cured at temperature
Die opens and part is ejected
from mold
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Vent Injection Port
Gasket
Index
Receptacle
Index
Pin
Resin Transfer Molding (RTM)
Male
mold half
Female Mold Half
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The Resin Transfer
Molding Process:

Fiber reinforcement is placed in
the mold

The mold is closed and clamped

Resin is injected into the mold
cavity under pressure

The resin cures

The part is removed from the
mold

Pressurized
Resin
Air
Air
The RTM Process
Steps of RTM Process
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Open vs. Closed Molding
Open Molding
Only one sided mold
Limited temperature control
Lower capital cost for molds
Closed molding or
compression molding
Two sided mold part is
sandwiched between two
mold halves
Pressure applied
Improved material properties
(fewer voids)
Higher Capital cost
Definition
Plastic is broadly defined as
Any inherently formless material that can be molded
or modeled under heat or pressure
As early as
Go back as far as the Old Testament
References of:
Fillers
Adhesives
Coatings
Good Ol Enoch Noyes
1760
Opened business with the use of natural polymers
Made combs out of organic proteins (Keratin and
Albuminiod) derived from animal horns, hoofs, an
tortoise shells
In the beginning
Greek word plastikos
First natural plastics
Tortoise shell
Tree resins
Shellac
Insect secretion

Natural Rubber
Natural rubber: mainly
polyisopropene



Tends to be sticky when
hot, brittle when warm
Does not reform when
stretched
isoprene
n
polyisoprene
Natural Rubber
Natural rubber: mainly
polyisopropene



Tends to be sticky when
hot, brittle when warm
Does not reform when
stretched
isoprene
n
polyisoprene
S
S
S
S
S
S
Sulfur
crosslinking
Charles Goodyear, 1839
Oven cleaning
Ebonite bracelet from 1880
1851: Hard Rubber 20-30% Sulfur
Christian Schoenbine
Swiss Chemist
1840s
Developed Cellulose nitrate
Mix of cotton (wifes apron), nitric acid, and sulfuric
acid
Early Films
Highly flammable and explosive
Parkes Invents Celluloid
The first man-made plastic was unveiled by
Alexander Parkes at the 1862 Great International
Exhibition in London.
Parkesine- organic material derived from cellulose that
could be molded in heat and retain its shaped when cooled
Buttons
Combs
Pens
Alexander Parkes- 1855
Rights sold to Daniel Spill (1865)
Patented
Downfall- high cost of the raw materials needed in its
production.


John Wesley Hyatt
Billiard Co. in U.S.
Needed substitute for ivory in making balls
John Wesley Hyatt developed collodion
Upon spilling a bottle of collodion in his workshop, he
discovered that the material congealed into a tough,
flexible film
Camphor and cellulose nitrate
Occasional Explosion upon impact
H
3
C
H
2
C
CH
3
O
Bakelite
Dr. Leo Baekeland
First totally synthetic plastic (1907)
Didnt throw away his foul glassware
Patented in 1909
Thermoset resin
Replaced rubber for insulation in
electrics

Bakelite
OH
OH
O
H
+
: O : OH OH
:
OH
H+
OH OH
2
+
O OH OH OH
OH OH
HO
HO OH
OH
OH
Bakelite

Phenol-formaldehyde resins
which he called Bakelite.

Polyvinyl Chloride (PVC)
PVC was first created by the
German chemist Eugen
Baumann in 1872.
Patented in 1913
Waldo L. Semon, invented a
way to make polyvinyl
chloride (PVC) useful
Polyvinyl Chloride (PVC)
Cl
Cl Cl Cl Cl Cl Cl
R
Cl
Cl
R
Cl Cl
sunlight
Baumann's 1872 experiment
sealed tube
R

Applications of PVC
Applications of PVC
O
O
O
O
plasticizers
Polymerization
In 1920, German Hermann
Staudinger published theories on
polyaddition
Nine year later published the
polymerization of polystyrene.
Ph Ph Ph Ph Ph
1%
+
Ph Ph Ph
Polystyrene
Dow Chemical brought
polystyrene to the U.S.
in 1937
Toy shark, in
Polystyrene, with
moving jaw, Made in
USA around 1950
Merrifield resins
Styrofoam
Foam egg cartons, burger containers, coffee cups ,
"peanuts" used in packing and the lightweight foam
pieces that cushion new appliances and electronics.
Gas is blown in during the polymerization-- 95 % of
styrofoam is air (try dissolving in acetone)
CFCs were used until the 80s: phased out and
replaced with pentane or CO2
Polystyrene up close
Dr. Wallace H. Carothers
1930s research on
polymer chains at
DuPont Chemical
Department
Invented Neoprene and
Nylon
Nylons
Condensates of aliphatic diacids with aliphatic
diamines
Introduced in the 1939 Worlds Fair
Nylonmania interrupted during WWII, but
resumed after the war (the infamous Nylon
riots of 1946)
O
OH
O
HO
H
2
N
NH
2
O
N
H
O
H
N
H
N
N
H
O
O
etc. . .
+
- H
2
O
Nylon 66
co-crystalline
Fibers are spun (showerhead)
Neoprene: The first Synthetic Rubber
Cl
R
Cl
R

Cl
Cl
R
Cl

etc
benzoyl peroxide
inititates free radical
polymerization
Synthetic Rubbers
Gasoline pump hoses,
Hoses for automobile engines
Styrene/Butadiene copolymer (SBR) is the most important synthetic rubber,
and was the first and most widely produced rubber of WWII
Plexiglass: anionic polymerization
Me CO
2
Me
Polymethylmethacrylate:
cat Nu

Me
CO
2
Me
Nu
Me CO
2
Me
Me CO
2
Me
MeO
2
C
Me
Windshields, plastic coatings, hard and soft contact lenses
Ok, but how can I make a leisure suit
Polyesters
O
OMe
MeO
O
OH
HO
O
O
O
O
O
O
O O O
O
O
O
Dacron
Teflon

Teflon
Polytetrafluoroethylene
(PTFE)
Dupont Chemical
Department
First used for artillery shell
covers
F F
F F
World War II
Polyethylene (1933)
Imperial Chemical Industries in England
E.W. Fawcett & R.O. Gibson
First used for underwater cable coatings and insulation
for radar
High density polyethylene
Ziegler-Natta catalysts
Low density polyethylene
1939
Polyethylene
1943 Karl Ziegler changed
polymerization of polyethylene
Use of catalysts
Now is most widely produced
and perhaps most versatile
plastic
Polypropylene
Guilio Natta continued Zieglers work
Created polypropylene in 1957
Substituted for polyethylene where high
temperatures were involved
Ex. Dishwasher safe dishes
Cars front bumper made of
polypropylene in 1978
Stereochemistry and Polymer Properties
isotactic
syndiotactic
atactic
Isotactic: fabrics for carpets, automobile parts, battery casings,
medicine bottles
Syndiotactic: new applications are emerging
Atactic: soft, and not very useful
Relevant Additional Links
History of Plastic and Leo Bakeland
inventors.about.com/library/inventors/blplastic.htm
History of Plastics
www.lle.mdx.ac.uk/site/docs/dt/Historyofplastics.html
About Plastics
www.americanplasticscouncil.org/benefits/about_plasti
cs/history.html
Thank You