Chapter 10: Polymers Structure and Processing

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 1

 General Properties of Polymers

General Properties
• high strength-weight ratio
• high design capabilities (colors/transparency)
• ease of manufacture
• good resistance to chemicals
• high coefficient of thermal expansion
• low dimensional stability
• low material cost
• low density applications
• low strength/stiffness
• low electrical/thermal conductivity
• low temperature applications (up to 350C)

Plastics ~ Plastikos (Greek origin which means can be molded and shaped)

Polymer ~ Poly-Mer (multiple units): [C-H]+Cl, F, S, Si, N, O

Polymers can be natural (animal and vegetable organic products) or synthetic (petroleum)

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 2

 Mechanical Properties

TABLE 10.1 Approximate range of mechanical properties for various engineering

plastics at room temperature.

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 Polymer Molecular Structure

Polymers are made of multiple units, called “monomers”, combined

in a chemical process, called “polymerization” to form polymer
chains.
The chemical composition of the monomers determines the type of
the polymer, whereas, the chains structure resulting from the
polymerization process determines its properties.
Monomers are attached together during polymerization through
strong covalent bonds between carbon atoms. The double covalent
bond between the carbon atoms in a monomer (also called
molecule) opens up and forms a new covalent bond with an adjacent
monomer, thus forming a polymer chain.
The number of monomers (molecules) attached together in a chain
is called the degree of polymerization. The higher the degree of
polymerization, the longer the chains will be, which results in a
higher chain molecular weight (Pros: stronger, Cons.: harder to
process)
Polymer chains may attach to each other strongly through covalent
bonds (called cross linking) or loosely through weak secondary
bonds; such as van-der-waals or hydrogen bonds. Cross linking
produces stronger polymers (cons: harder to process)

FIGURE 10.1 Basic structure of some polymer molecules: (a) ethylene molecule; (b) polyethylene, a linear chain of many ethylene molecules; (c)
molecular structure of various polymers. These molecules are examples of the basic building blocks for plastics.

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 Effect of Molecular Weight
The higher the degree of polymerization the higher the molecular
weight of the polymer:
MW (polymer) = MW (monomer) * Degree of Polymerization
Where the degree of polymerization is equal to the number of
monomers attached to form a polymer chain.
Since not all the polymer chains have the same length, we use the
average length of the chains to calculate an average molecular
weight.
The higher the molecular weight make the polymer slower to flow;
i.e., higher viscosity.
Higher viscosity of the polymer requires higher forces and energy to
process the polymer.
However, higher molecular weight results in better mechanical
properties.

Figure 10.2 shows that as the molecular weight increases (x-axis),

the viscosity and strength increases. HOWEVER, after a certain
level of molecular weight, the improvement in mechanical strength
reaches a plateau, which means there is no gain in strength with
FIGURE 10.2 Effect of molecular weight and degree of increasing molecular weight. The molecular weight at the point
polymerization on the strength and viscosity of polymers. should become our maximum limit.

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 Polymer Chains
During polymerization process, monomers join together to form chains. Furthermore,
these chains may attach to each other loosely (secondary bonds) or strongly (cross
linking). As a result, there are four basic structures that can result from a
polymerization process:
(a) Linear: monomers attach covalently to form chains, weak secondary bonds form
between the chains (similar to the stickiness between noodles strands in a noodles
bowl). This the weakest structure amongst all. Thermoplastics such as acrylics, nylons,
polyethylene, and polyvinyl chloride exhibit this type of structure. They can be
softened by applying heat which makes them easy to process and reprocess.
(b) Branched: similar to linear structure, except that some monomers start to form
branches off the main chains. Chain-to-Chain bonds are still weak secondary bonds.
Thermoplastics with higher resistance to deformation, increased strength, lower
density; such as in polyethylene, exhibit this structure.
(c) Cross-linked: similar to the branched structure except that the branches form
covalent bonds with other branches or chains to form a three dimensional structure.
Chain-chain bond is covalent. Many rubbers and elastomers have this structure.
Vulcanization of rubber produces this structure. Higher in strength, hardness, stiffness,
brittleness, and dimensional stability
(d) Network: similar to cross linked structure except with a much shorter chains and
higher degree of cross linking. Three dimensional covalent bonds between monomers.
FIGURE 10.3 Schematic illustration of polymer chains. Examples include thermosetting plastics, such as epoxies and phenolics greatest
strength.

Note: As branching and cross linking increases (a) to (d), mechanical properties
increase, chemical resistance increases, thermal resistance and dimensional stability
increase.
- Thermoplastics exhibit structures similar to (a) and (b). (can be cross linked too)
- Thermosets exhibit structures similar to (c) and (d).

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 Polymers Viscoelasticity and Glass-Transition Temperature
The combined elastic and viscous behavior of polymers is known as “viscoelasticity”.
Increasing cross linking of polymers increases its Elastic Modulus (E) and reduces the softening (drop in stiffness) at higher temperatures
(i.e. improves heat resistance). The same behavior is observed with increasing crystallinity (defined in the next slide) .
Polymers states can be classified as: glassy (highest stiffness), leathery (soft), rubbery (softer), and viscous (melt). As the temperature
increases, stiffness decreases, thus the polymer transforms from glassy state to leathery state.
The temperature at which the transformation takes place is called: glass transition temperature (Tg).
The temperature at which the polymer becomes viscous is called: melting temperature (Tm).

TABLE 10.2 Glass-Transition and Melting

Temperatures of Selected Polymers

FIGURE 10.4 Behavior of polymers as a function of temperature and (a)

degree of crystallinity and (b) cross-linking.

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 Crystallinity
During polymerization, polymer chains and molecules can form an orderly
arrangement of molecules known as crystalline structure (crystallite), or a
disorderly arrangement known as amorphous structure.
Often, the polymerization process results in a combination of both structures
in the bulk matrix. The percentage of crystalline structure in the bulk is
known as “degree of crystallinity”, which can range from 0% (perfect
amorphous) to 100% (perfect crystalline).
The degree of crystallinity can be controlled by adjusting the polymerization
process parameters; such as lower temperature, or by using certain additives
which promotes crystallinity (also known as catalysts).
As crystallinity increases, hardness, stiffness, brittleness, density, and heat
resistance will increase

Amorphous polymers, such as acrylic and polycarbonate, have a glass-

transition temperature Tg, but do not have a specific melting point Tm,
therefore: amorphous polymers have a melting range[Tg –Tm] whereas
FIGURE 10.5 Amorphous and crystalline regions in a crystalline polymers have a melting point [Tm]. Partly crystalline polymers,
polymer. Note that the crystalline region (crystallite) has such as polyethylene and nylons, contract sharply at their melting points
an orderly arrangement of molecules. The higher the during cooling.
crystallinity, the harder, stiffer, and less ductile is the The three main structures are:
polymer.
Amorphous: polymer chains exist without long-range order (ex.
Polycarbonate, polystyrene)
Crystalline: long polymer molecules arranged in order
Semi-Crystalline: mixture of amorphous and crystalline

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 Deformation of Polymers

FIGURE 10.7 Various deformation modes for polymers.: (a) elastic; (b) FIGURE 10.8 General terminology describing the behavior of three
viscous; (c) viscoelastic (Maxwell model); and (d) viscoelastic (Voigt or types of plastics. PTFE is polytetrafluoroethylene (Teflon, a trade
Kelvin model). In all cases, an instantaneously applied load occurs at name). Source: After R.L.E. Brown.
time to, resulting in the strain paths shown.

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 Temperature Effect on Mechanical Properties

FIGURE 10.9 Effect of temperature on the stress- FIGURE 10.10 Effect of temperature on the
strain curve for cellulose acetate, a thermoplastic. impact strength of various plastics. Note that
Note the large drop in strength and increase in small changes in temperature can have a
ductility with a relatively small increase in significant effect on impact strength. Source: P.C.
temperature. Source: After T.S. Carswell and H.K. Powell.
Nason.
Also, note that different polymers have different
response to increasing temperature.

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 Polymer Behavior in Tension

FIGURE 10.14 Typical load-elongation

curve for elastomers. The area within
the clockwise loop, indicating loading
and unloading paths, is the hysteresis
loss. Hysteresis gives rubbers the
capacity to dissipate energy, damp
vibration, and absorb shock loading, as
in automobile tires and vibration
FIGURE 10.13 (a) Load-elongation curve for polycarbonate, a thermoplastic. Source: After R.P.
dampeners for machinery.
Kambour and R.E. Robertson. (b) High-density polyethylene tension-test specimen, showing
uniform elongation (the long, narrow region in the specimen).

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 Types of Plastics
Thermoplastics
- Polymers that soften at temperatures higher than their Tg (which makes them easier to form) and hardens when cooled down (reversible process).
Multiple heating and cooling cycles do not degrade the polymer.
- Linear and branched polymers joined with weak secondary bonds
- Strength and hardness are affected by heat and rate of deformation
- Examples: acrylics, nylons, polyethelenes, polyvinyl chloride (PVC)

Elastomers (rubbers)
- Can be natural or synthetic
- Elastic-mers forming extra long, folded, chains with few cross links between the chains.
- Amorphous structure with low transition temperatures Tg. Stretching elastomers improves the orderly arrangement of the chains (i.e. crytallinity)
- Low elastic modulus, soft
- Can be cross-linked for higher stiffness and hardness (a process known as volcanization with sulfur), once volcanized can not be reshaped (e.g., tires)

Thermosets
- Molecules cross-linked in a three-dimensional arrangement forming a giant molecule with strong covalent bonds. The cross linking process is irreversible.
- The cross-linking reaction during polymerization (curing) is irreversible
- Do not have a sharply defined Tg
- Strength and hardness are not affected by heat or rate of deformation
- Better mechanical, thermal, and chemical properties, electrical resistance, and dimensional stability than thermoplastics
- Burns up and degrade at higher temperatures
- Examples: epoxies, polyester, urethane, phenolic

Polymers Blends:
1. Homopolymers: one type of monomers in the matrix
2. Copolymers: two types of monomers to improve strength, toughness, and formability (ex. Styrene-Butadiene)
3. Terpolymers: three types of monomers (ex. ABS: Acrylonitrile-Butediene-Styrene)

Polyblends: mixing amorphous and crystalline polymers to improve mechanical behavior (ductility).

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 12

 Plastics Processes

TABLE 10.6 Characteristics of processing plastics and reinforced plastics.

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 [1] Extrusion Process

Principle: melting polymer pellets (or powder) inside a barrel with a rotating screw and forcing the melt through an extrusion die having
the desired orifice shape. Most of the energy used in the process is generated by shearing the polymer resin between the screw and barrel
walls. External heaters on the barrel wall help to maintain the generated heat inside the barrel. The size and shape of the screw determines
the heat profile and residence time of the melt inside the barrel (selected based on the type of the extruded polymer. A breaker plate (1)
helps trap inclusions that may be present in the melt, (2) build higher pressure inside the barrel which increases the generated heat, and
(3) provide homogenous mixing to the melt before exiting through the die orifice.

FIGURE 10.22 Schematic illustration of a typical extruder.

Consists of: Process Characteristics:

- melting and mixing polymer resin with additives - simple
- consolidating the melted pellets into a homogenous melt pool - high production rate
- forcing the melt through an extrusion die - use of recycled/scrap material
- cooling in a water tank or atmosphere - fully automated
- cutting the parts into the required lengths - adaptability to different materials

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 Examples: Blown-Film and Pipe Extrusion

FIGURE 10.25 (a) Schematic illustration of production of thin film

and plastic bags from a tube produced by an extruder, and then
blown by air. (b) A blown-film operation.
FIGURE 10.26 Extrusion of plastic tubes. (a) Extrusion using
a spider die (see also Fig.6.59) and pressurized air; (b)
coextrusion of tube for producing a bottle.

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 [2] Injection Molding Process
Principle: melting polymer pellets in a barrel (similar to extrusion) and injecting the melt
into a die cavity (mold) having the desired shape.

Consists of:
- melting polymer pellets
- consolidating the polymer melt into a homogenous melt pool
- forcing the melt into a mold cavity under high pressure
- allowing the polymer to solidify in the cool mold cavity
- extracting the finished part

Process Characteristics:
- simple
- high production rate
- use of recycled/scrap material
- fully automated
- adaptability to different materials
Injection Molding Cycle
FIGURE 10.27 Injection molding with (a) a plunger and (b)
1. Plastication: plastic pellets are melted in a steel barrel with an internal reciprocating screw.
Energy is supplied by the shearing of highly viscous polymer and the heaters mounted on the a reciprocating rotating screw.
machine barrel.

2. Injection: hydraulic pressure moves the screw down the barrel, acting as a piston to force
the plastic through the nozzle and into the mold. Ram motion is controlled by the maximum
pressure limit or maximum flow rate limit.

3. Holding (Packing): holding pressure acts to pack more polymer into the mold as the plastic in
the cavity cools and shrinks. (~ 90% injection pressure). Switching to holding is initiated by the
ram distance or cavity pressure and it ends when the plastic in the gate freezes.

4. Cooling and Ejection: can be controlled by a preset time or using sensors.

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Injection Molding……continued

Injection molding cycle Machine Parameters (independent)

1. Resin pellets are fed to screw from the hopper - Barrel temperature
2. Resin is melted by mechanical shearing and heating - Mold temperature
3. Screw rotation pushes molten resin towards the nozzle while - Ram pressure
is the screw is moving backward.
4. Nozzle is brought forward into contact with the mold’s sprue - Ram velocity
bushing (only once) - Holding pressure
5. Mold is closed, clamp force is applied - Screw speed
6. Ram arms pushes the screw forward by hydraulic pressure, - Cooling time
thus forcing the molten resin into the mold cavity. A non- - Shot size
return valve prevents the melt from flowing backward.
7. Injection pressure is reduced to 90% to become a Holding
Pressure. It compensates for polymer shrinkage during Process Parameters (dependent)
cooling. - Melt temperature
8. The gate solidifies, no more poylemr gets in. - Cavity pressure
9. The mold is cooling down (water channels) - Melt velocity
10. Mold is opened - Cooling rate
11. Part is ejected - Melt viscosity
12. Screw starts rotating (back to step 3)
Part quality parameters
- Dimensions
- Mechanical properties
- Appearance

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 17

 [3] Reaction-Injection Molding

Principle: A multipart thermosetting polymer (e.g.

polyurethane) is mixed and injected into a mold. After
the part sets, the mold is opened, and the part is
removed. Post curing may be used. This process is similar
to using a two-part epoxy.

1. Very little energy is required, most energy is

provided by the chemical reaction.
2. Parts up to 100 lb can be produced.
3. Surfaces don't have flow lines found in
traditional injection molding.
4. RIM materials tend to be low weight,
corrosion resistant, and variable properties
can be obtained by additives and ratio
adjustment.
5. RIM machines use lower pressures, and are
therefore less expensive.
6. Typical parts are; bus bumpers, large
electronics cases, shoes, etc.
FIGURE 10.31 Schematic illustration of the reaction-injection-
molding process. 7. Fillers can be used to increase strength.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 18

 [4] Blow Molding
Principle:

(a) Extrusion blow molding: A tube is extruded and clamped into a

mold having a cavity of the shape of the bottle. The tube is then
blown outward to fill the mold cavity. Typical pressure is 350-700 kPa.

(b) Injection blow molding: A short tubular piece (parison) is inection-

molded and transferred to a a blow-molding die. Hot air is injected
into the parison to fill the mold cavity.

• Typical parts: plastic beverage bottles and hollow containers.

• Used with thermoplastics only.

FIGURE 10.32 Schematic illustrations of (a) the blow-molding

process for making plastic beverage bottles and (b) a three-station
injection-blow-molding machine.

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 [5] Rotational Molding

Principle: A premeasured quantity of powdered

thermosets/thermoplastics is placed thin-walled heated
metal mold.
• The mold is heated in a large oven and rotates around
two perpendicular axes.
• Heating fuses the thermoplastic powder without
melting it. Chemical cross linking agents are used with
thermosets.
• Can be used with thermoplastics or thermosets.
• Hollow parts such as: tanks, cans, buckets, toys, and
footballs.

FIGURE 10.33 The rotational molding (rotomolding or rotocasting) process. Trash cans, buckets,
carousel horses and plastic footballs can be made by this process.

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 [6] Thermoforming

Principle: Thermoplastic sheets/films are heated in an oven to the sag point (soft) and then placed over a mold, at room
temperature. Vacuum pressure (or a ram) forces the sheet against the mold.

• Commonly used in making advertising signs, cookie and candy trays, panels for shower stalls, and packaging.
• Used with thermoplastics only.

FIGURE 10.35 Various thermoforming processes for thermoplastic sheet. These processes are commonly used in making
advertising signs, cookie and candy trays, panels for shower stalls, and packaging.

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 [7] Compression Molding
Principle: A preheated/premeasured charge of
polymer powder/liquid is placed into a heated
mold. Forming is done under pressure from a
plug or the die itself. Flash is trimmed or
machined.
• Used mainly with thermosets. Can be used
with thermoplastics or elastomers.
• Typical parts: dishes, pot handles, container
caps, and fittings.

FIGURE 10.35 Types of compression molding, a process similar to forging: (a) positive, (b) semipositive, and (c) flash.
The flash in part (c) is trimmed off. (d) Die design for making a compression-molded part with undercuts. Such designs
also are used in other molding and shaping operations.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 22

 [8] Transfer Molding
Principle: Uncured thermosetting material is placed in a heated transfer pot/chamber and injected into heated closed molds by a
ram/plunger/or rotating screw. Molds typically have multiple cavities with runners between them (similar to injection molding
molds).

• Molds are more expensive than compression molds.

• This process is particularly suitable for intricate parts with varying wall thickness.
• Typical parts: electrical and electronic parts, rubber and silicon parts.

FIGURE 10.36 Sequence of operations in transfer molding of thermosetting plastics. This process is particularly
suitable for making intricate parts with varying wall thicknesses.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 23

 [9] Casting, Potting, Encapsulation

Principle: Liquid resins are pourable plastics or elastomer compounds used to cast parts, make molds or form a
structure in place. The resins are mixed with a suitable hardener, catalyst or activator and then poured into an open
mold to cure (solidify).

FIGURE 10.37 Schematic illustration of (a) casting, (b) potting, and (c) encapsulation of plastics.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 24

 [10] Calendering

Principle: Calendering of thermoplastics is an operation for the production of continuous sheet or film of uniform thickness, by squeezing the
molten material between a pair of heated driven rolls. The molten material is fed to the calender rolls from a mixer and two-roll mill system, or from
a large extruder.
• The major plastic material that is calendered is PVC. Products range from wall covering and upholstery fabrics to reservoir linings and
agricultural mulching materials.
• Owing to the large separating forces developed in the calender gap, the rolls tend to bend. This may result in undesirable thickness variations in
the finished product.
• Compensations for roll deflections are provided by using crowned rolls having a larger diameter in the middle than at the ends or by roll
bending.

FIGURE 10.38 Schematic illustration of calendering. Sheets produced by

this process are subsequently used in processes such as thermoforming.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 25

 [11-1] Reinforced Prepregs

FIGURE 10.40 (a) Manufacturing process for

polymer-matrix composite. Source: After T.-
W. Chou, R.L. McCullough, and R.B. Pipes. (b)
Boron-epoxy prepreg tape. Source: Textron
Systems.

FIGURE 10.41 Manufacturing process for producing

reinforced-plastic sheets. The sheet is still viscous
at this stage and can later be shaped into various
products. Source: After T.-W. Chou, R. L.
McCullough, and R. B. Pipes.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 26

[11-2] Vacuum and Pressure Molding (Reinforced Plastics)

FIGURE 10.42 (a) Vacuum-bag forming. (b) Pressure-bag forming. Source: After T. H. Meister.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 27

[11-3] Open Mold Processing

FIGURE 10.43 Manual methods of

processing reinforced plastics: (a)
hand lay-up and (b) spray-up.
These methods are also called
open-mold processing. (c) A boat
hull made by these processes.
Source: Courtesy of Genmar
Holdings, Inc.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 28

 [11-4] Filament Winding

FIGURE 10.44 (a) Schematic illustration of the filament-winding process. (b) Fiberglass being wound over aluminum liners for
slide-raft inflation vessels for the Boeing 767 aircraft. Source: Advanced Technical Products Group, Inc., Lincoln Composites.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 29

 [11-5] Pultrusion

FIGURE 10.45 (a) Schematic illustration of the pultrusion process. (b) Examples of parts made by
pultrusion. Source: Courtesy of Strongwell Corporation.

CHAPTER 10: POLYMERS STRUCTURE AND PROCESSING 30