ENGR322 Spring 2008

Lecture Notes for Polymers and Composites

June 2-6, 2008

POLYMERIC MATERIALS
Part of the reason for continual change and rapid growth of the polymer materials industry has to do with the polymer
chemistry (polymer comes from "poly" [many] + "mer" [parts]). Starting with the mers or monomers, chemists build up
the polymers. Simplest chemistry of ADDITION and CONDENSATION polymerization produces single polymer chains
of varying length. These polymers are relatively easy to describe. What makes the area complex is when the chemists
start combining polymers of different types in COPOLYMERS and POLYMER BLENDS. This infinite variety of
polymers really begs for some kind of standard classification scheme to organize our discussion of these materials.
POLYMER CLASSIFICATIONS
Good news - ASTM D4000 has a complete and thorough standard classification system for polymers, copolymers,
blends, and composites. It is somewhat complex though; e.g. here is a polymer identification:

ASTM D4000-95A PA120G33A53380 GA140

Bad news - None of the polymer producers want to use the standard, preferring to keep their formulations "proprietary"
and stick to trade name identifications. But, to make sense of polymeric materials, you need to use the generic names as
much as possible.
Good news - there are only a few polymer families you need to be familiar with (see Budinski Figure 4.1).
Budinski categorizes the main polymer types as

THERMOPLASTICS (TP) which may be repeatedly softened for flow processing or recycling by heating.
These are generally tough, low strength and low cost materials.
THERMOSETS (TS) in which heating leads to chemical reactions (cross-linking) that is irreversible. These are
generally hard, brittle, and more thermally, chemically, and dimensionally stable than TP.
ELASTOMERS (EL) which have a specific definition:
o 1. at room temperature, stretch to more than 100% length,
o 2. hold for 5 minutes,
o 3. retracts to within 10% of original length within 5 minutes.

Budinski also makes separate categories for adhesives, coatings and fibers, but these are just different shapes and
applications of the main three groups.

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GENERIC POLYMER PROPERTIES

Atomic Bonding Review:
IONIC

METALLIC

COVALENT

NaCl

Any pure metal

diamond, graphite, Si-C, polymers.

Which has the highest strength?

Why are plastics so weak? The interaction between the polymer chains is weak (van der Waals bonding) and the density
is low. Compare hardness from Budinski (figure 6-8).
What can we do to increase the strength of polymers? There are five features we should keep in mind when trying to
characterize polymer materials.

1. Chemistry of the monomer, or repeating group:

Since the ultimate strength of the a polymer will depend on the strength of the bonds inn the backbone, the monomer
chemistry is critical.
EXAMPLE: Polyethylene (PE) versus Polyphenylene Sulfide (PPS)

PE relies on C-C bonds, while PPS relies of S-C bonds (not to mention that double C-C in the benzene ring). PPS is a
higher strength, higher use temperature material than PE.
[NOTE: the source of most monomers is either natural gas (acetals) or crude oil (everything else), which implies a
flammability issue.]

2. Molecular weight of the chain (the "n"):

Of course this is a statistically determined number for a given batch of polymer, but commonly is in the 106 range. It is
measured using a viscosity test (e.g. ASTM D-1238).
Since the long chains act like tangled spaghetti, the longer the chain (higher MW), the higher the strength: UHMWPE is
stronger than LLDPE.

3. Presence of side groups:

The monomer chemistry is such that we can fiddle with the properties of the polymer a lot by removing a H atom and
adding on a different side group.
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EXAMPLE: Polyethylene (PE) versus Polypropylene (PP)

PP is quite a bit stronger (about 5X) than PE because the larger methyl side-group (CH3) makes it harder for the
backbone to twist and untangle from the other polymer chains (chain stiffening).

4. Shape of the backbone:

The chemistry of the addition or condensation polymerization can be changed so that either LINEAR or BRANCHED CC backbones are produced (Budinski figures 3.5 and 3.6). Generally, increased branching leads to higher strengths and
use temperatures (because its harder to untangle) and lower densities.

5. Inter-chain interaction:
There are two main effects here. First, if we increase the attractive interaction between the side groups in a chain, we can
get the chains to fold back on themselves and order in a "CRYSTALLINE" polymer.
PE, PP, PET, and most nylons are crystalline polymers, as well as the aromatic polyamides, such as Nomex and Kevlar.
The effect of crystallization is to increase the strength (and decrease the toughness and processability).
Second, if the interaction between the side groups gets large enough for a chemical reaction to occur, then the chains
become "CROSS-LINKED", and the van der Waals bonding is replaced by a covalent bond, with a large increase in
strength. This is what happens in most TS and EL polymers. Often the cross-linking occurs because of a catalyst (in the
epoxies, for example).
With these five physical processes in mind, we should be able to at least compare the relative properties of polymers,
even if we don't know the specific property values.

POLYMER PROPERTIES

First Stop: Ashby

Second Stop: International Plastics Selector, or similar handbook
Third Stop: Manufacturer

In all cases, be sure you know how the property was measured (which ASTM standard was used?)

POLYMER PROCESSING
Clearly, whether the polymer is a TP or a TS has a big effect on the processing possibilities.
TP: heated to lower the viscosity and allow to flow, cooled in the mold, low processing temperatures,
fast turnaround time.
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TS: heated t flow, mixed with fillers, etc., heated in the mold until cross-linking has occurred, higher
processing temperatures than TP.
The most important processing approaches are (see Budinski for description)

Injection Molding
Compression Molding
Blow Molding, Rotational Molding (for hollow shapes)
Extrusion
Thermoforming
Reaction Injection Molding (RIM) (for foamed parts)

GENERAL WORDS
Temperature Dependence: this is very large for polymers, several orders of magnitude change in mechanical behavior
over a few tens of degrees temperature change is common.
Creep is a significant problem, especially in designs that require long time static loading.
Dimensional Stability: thermal, moisture stability is much worse for polymers than for metals.
Additives: properties can be dramatically changed by mixing in FILLERS (now we're talking composites or polymer
blends), or chemical modifiers such as PLASTICIZERS. In general, chemical add-ins should be avoided because of the
potential for aging effects.
Corrosion: in polymers usually means degradation due to chemical breakdown of the polymer chain backbone. UV is
particularly good at breaking bonds, as is some chemical attack.

COMPOSITE MATERIALS

I. INTRODUCTION
A very broad range of materials fit the definition: a material composed of two or more different materials (or phases).
The main idea behind composites is that the properties of composites will be determined, at least to first order, by the
simple RULE OF MIXTURES:
P(composite) = P(rein) V(rein) + P(matrix) V(matrix)
The attractiveness comes in that you can use very high performance fibers (in terms of mechanical strength) in a lower
strength matrix phase.

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There are three implications from the rule of mixtures:

1. INHOMOGENEITY: Because the composites are mixtures of two different phases or materials,
they are by nature inhomogeneous. This becomes an important consideration in corrosion couples, and
chemical reactivity.
2. ANISOTROPY: Because of the geometry of the reinforcement, you can have a wide variety in the
materials properties in different directions in the composite. There are three main types of symmetry:
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ISOTROPIC: in which all the properties are the same in all directions. An example
would be a composite with spherical reinforcements.
ORTHOTROPIC: with three orthogonal symmetry planes, for example, in a uniaxial
continuous fiber reinforcement, or laminated sheet reinforcement.
ANISOTROPIC: in which there is no symmetry, and the properties are different in
every direction. This is hard to do, but with Aramid fibers in a thermoplastic matrix,
the Aramid fibers are curled and knotted from the processing, and make for an
anisotropic composite.
3. The properties vary monotonically with the volume fraction of the reinforcement, but the
PERFORMANCE peaks in the middle.

Composites usually contain 20-50% reinforcement by volume.

One reason that the composites work so well is

I.A. PLASTIC CONSTRAINT.

Example: a weak layer of material surrounded by strong,
stiff layers. When put into tension normal to the interfaces,
the "weakest link" would be expected to fail first. But if the
weak layer is thin enough, it is constrained from plastically
flowing by the stiff material and can perform mechanically
nearly as well as the strong material.
An important consideration in all the composites is the strength of the INTERFACE between the matrix and the
reinforcement. The primary purpose of the interface is to transfer the load from the matrix into the reinforcement, so the
shear strength of the interfacial bond has to be strong enough to do this.

I.B. INTERFACIAL FRACTURE: Thinking about the fracture and failure process of composite materials, as the
strength increases, the composites generally become more brittle. According to the Cook-Gordon mechanism, to prevent
a fracture crack from propagating through the composite, we want to have a WEAK interface:

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If the bond strength is > 1/5 of the materials strength, then the crack crosses the reinforcement and failure occurs. If the
bond strength is < 1/5 of the material strength, the interface fails. This means that more energy has to be expended to fail
the composite, and you have an opportunity to find and repair (replace) the part before it completely fails.

If the interface is too weak, though, you get a fiber pull-out effect that limits the fracture toughness, plus you don't get
the load to transfer into the fiber to begin with.
Other important design properties of composites are the minimum reinforcement volume fraction, and the minimum
reinforcement length.

II. CLASSIFICATION OF COMPOSITES

In trying to classify composites, there are several approaches one might use: by matrix, reinforcement, reinforcement
shape, reinforcement orientation, volume fraction, etc. Let's go through a couple of these.
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II.A. CLASSIFICATION BY MATRIX MATERIAL

The reason for classifying composites by the matrix material is that it determines what kind of processing you can use,
what kind of reinforcement is possible, etc.

II.A.1. POLYMER MATRIX

The most common are thermosetting. Why?
1. The low viscosity in the components helps in wetting and filling the reinforcement.
2. The extensive cross-linking makes the matrix a high-performing mechanical structure as well.
3. The possibility of low temperature (room temperature) curing helps with the interfacial chemistry.
The most common TS matrices are:

II.A.1.a. PHENOLICS
Examples we've already covered; Bakelite, Formica, micarta, plywood. Typically filled with wood fibers, glass fibers,
paper, and cotton sheet.

II.A.1.b. EPOXIES
Probably the most important polymer matrix, due to the low viscosity, room temperature curing (with the appropriate
catalyst), and the low dimensional change on cross-linking (since there are no reaction by-products).

II.A.1.c. POLYESTERS
Low viscosity during the cross-linking process for a long time allows use on large structures.

II.A.1.d. SILICONES
As discussed previously, these are another entire class of materials, but are characterized by their high temperature
strength

II.A.1.e. THERMOPLASTIC MATRICES

The main problem with using thermoplastics as composite matrices is that, even at very high temperatures, the viscosity
never gets that low. This makes it hard to use for continuous fiber reinforcements because of the difficulty in flowing
around the fibers and wetting them. Generally need to use chopped/discontinuous fibers. Common matrices are PSU,
PES, PPS, PAI, polyetherimide, and polyetheretherketone (PEEK).
A fairly new approach to using the thermoplastics is to lay continuous fibers on sheets of thermoplastic, wrap it around
the mold, and heat to flow. Possibly will become important in the auto industry.

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II.A.2. METAL MATRIX MATERIALS

These composite materials are known as Metal Matrix Composite (or MMCs). About the only use so far has been with
discontinuous reinforcements, because of the flow and wetting problems. One way around the flow problems is
SQUEEZE CASTING, in which a fibrous preform is placed in an injection molding mold, and the liquid metal forced
into the mold under pressure. The high pressure must be maintained during the cool-down in order to prevent thermal
contraction voids forming. Because of the high temperatures, the reinforcements must be either other metals, or
ceramics.
Other approaches to MMCs are powder metallurgy techniques (e.g. SiC powders in Al matrix), or co-deformation if both
materials are ductile (e.g. Nb-Ti superconductors, Nb-Cu ).

II.A.3. CERAMIC MATRIX COMPOSITES

Here you must use powder metallurgy approaches, since you can't melt process the ceramics. Examples: transformation
toughening of Al2O3 using ZrO2, or Si3N4 matrices with SiC whiskers for fracture toughness.

II.B. CLASSIFICATION BY REINFORCEMENT MATERIAL

II.B.1. GLASS
Three main types of glass reinforcements:
E-glass (for "electrical"): developed to reduce the water vapor attack on the sodium atoms present in
ordinary glass. The attack produces atomic-sized stress raisers, and lowers the strength. Since cracks
start at the surface, sizing (protective coating) is very important. These are high strength materials
(UTS ~ 4500 MPa).
S-glass (for "strong"): higher strength glass than E-glass, UTS ~ 4750 MPa.
Microspheres: Used in syntactic foams to artificially foam non-foamable materials (principally
epoxies).

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II.B.2. POLYMER FIBERS

A common high strength fiber is Kevlar (an aramid), with a UTS of ~3100 MPa.
An older type of polymer fiber used in polymer matrix composites was polypropylene.
More recent idea: IPN (interpenetrating networks) in which a TS cross-linking polymer is used as a reinforcement in a
TP matrix. Especially useful in silicone TS to provide some degree of self lubrication.

II.B.3. BORON FIBERS

The UTS of born fibers can be as high as 3200 MPa , and it's main advantage over other reinforcements is the high
elastic modulus (380 GPa), high melting temperature (3800 C), and low density (2.5 g/cc). The disadvantage is that it's
not easy to make ($200/lb or so). Used in MMCs systems.

II.B.4. CARBON-GRAPHITE FIBERS

The UTS is as high as 5500 MPa, but is usually lower (~2500 MPa ). The modulus is also high, about 350 GPa (with a
record set at 758 GPa). Common production route is the controlled graphitization of polyacrylonitrile (PAN). Compared
to Boron fibers, it looks pretty good at about $10/lb.

II.B.5. METALS
Some people claim there's not much use for metal reinforcements, except for the matching of thermal expansion
coefficients, and modification of thermal conductivities. There is increasing interest in their use in smart materials as
SENSORS and as ACTUATORS.

II.C. CLASSIFICATION BY REINFORCEMENT SHAPE

This is important because the shape of the reinforcement affects the uniformity and directionality of the properties, as
well as the allowable processing techniques.
Some examples of different reinforcement shapes: spherical powders, whiskers, plates, discontinuous fibers, continuous
fibers, sheets (non-woven, woven, solid), three dimensional weaves.

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Silicon-carbide plates
Boron-carbide Fibers

Alpha SiC fibers.

Beta SiC Fibers

General Rules for optimum performance in reinforcement shape:

Ceramic matrices: discontinuous small fibers or whiskers, or small diameter plates.
Metal matrices: discontinuous small whiskers or thin platelets.
Polymer matrices: large diameter fibers and whiskers, large plates.

Typical Sizes:
SiC whiskers: 50-200 um long, 1-3 um diameter
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SiC plates: 120 um diameter, 5-20 um thick

Fiberglass (short) 180-200 um long, 5-25 um diameter
Fiberglass (long) 3000-4000 um long, 5-25 um diameter

III. COMPOSITE APPLICATIONS

Usually used in load bearing applications, but should also be considered for
Thermal Conductivity Modification
Thermal Expansion Matching
Specialized Chemical Applications

NEVER Abrasive Wear!

References
M. F. Ashby, MATERIALS SELECTION IN MECHANICAL DESIGN,
Third Edition
K. G. Budinski, M. K. Budinski, Engineering Materials: Properties and
Selection, 6th edition, Prentice Hall, 1999.
End of File.

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