Polymeric and Composite Materials

POLYMERS AND
COMPOSITE MATERIALS
1. Fundamentals of Polymer Technology
2. Thermoplastic Polymers
3. Thermosetting Polymers
4. Elastomers
5. Composites--Technology and Classification
6. Composite Materials
7. Guide to the Processing of Polymers and Composite Materials
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
 Thermoplastic Polymers -
Thermoplastics
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
• Symbolized by TP
 Thermosetting Polymers -
Thermosets
• Cannot tolerate repeated heating cycles as thermoplastics can
• When initially heated, they soften and flow for molding
• Elevated temperatures also produce a chemical reaction that hardens the
material into an infusible solid
• If reheated, thermosets degrade and char rather than soften
• Symbolized by TS
 Elastomers (Rubbers)
Polymers that exhibit extreme elastic extensibility when subjected to
relatively low mechanical stress
• 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
• About 70% of the tonnage of all synthetic polymers produced
• Thermosets and elastomers share the remaining 30%
• On a volumetric basis, the current annual usage of polymers exceeds that of
metals
 Examples of Polymers
• Thermoplastics:
• Polyethylene, polyvinylchloride, polypropylene, polystyrene, and nylon
• Thermosets:
• Phenolics, epoxies, and certain polyesters
• Elastomers:
• Natural rubber (vulcanized)
• Synthetic rubbers, which exceed the tonnage of natural rubber
 Reasons Why Polymers are
Important
• Plastics can be molded into intricate part shapes, usually with no
further processing
• Very compatible with net shape processing
• On a volumetric basis, polymers:
• Are cost competitive with metals
• Generally, require less energy to produce than metals
• Certain plastics are 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
• 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 C2H4
Polyethylene

• Synthesis of polyethylene from ethylene

monomers: (1) n ethylene monomers, (2a)
polyethylene of chain length n; (2b) concise
notation for depicting polymer structure of chain
length n
 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
 Addition Polymerization
• In this process, the double bonds between carbon atoms in the
ethylene monomers are induced to open up so they can join with
other monomer molecules
• The connections occur on both ends of the expanding
macromolecule, developing long chains of repeating mers
• It is initiated using a chemical catalyst to open the carbon double
bond in some of the monomers
 Addition Polymerization
• Model of addition (chain) polymerization: (1) initiation, (2) rapid
addition of monomers, and (3) resulting long chain polymer molecule
with n mers at termination of reaction
 Step Polymerization
• In this form of polymerization, two reacting monomers are brought
together to form a new molecule of the desired compound
• As reaction continues, more reactant molecules combine with the
molecules first synthesized to form polymers of length n = 2, then
length n = 3, and so on
• In addition, polymers of length n1 and n2 also combine to form
molecules of length n = n1 + n2, so that two types of reactions are
proceeding simultaneously
 Step Polymerization
• Model of step polymerization showing the two types of reactions
occurring: (left) n-mer attaching a single monomer to form a
(n+1)-mer; and (right) n1-mer combining with n2-mer to form a
(n1+n2)-mer.
 Some Examples
• Polymers produced by addition polymerization:
• Polyethylene, polypropylene, polyvinylchloride, polyisoprene
• Polymers produced by step polymerization:
• Nylon, polycarbonate, phenol formaldehyde
Degree of Polymerization
• Since molecules in a given batch of polymerized
material vary in length, n for the batch is an average
• The mean value of n is called the degree of
polymerization (DP) for the batch
• DP affects the properties of the polymer
• Higher DP increases mechanical strength but also
increases viscosity in the fluid state, which makes
processing more difficult
 Molecular Weight
• The sum of the molecular weights of the monomers in the molecule
• MW = n times the molecular weight of each repeating unit
• Since n varies for different molecules in a batch, the molecular weight
must be interpreted as an average
Typical Values of DP and MW

Polymer DP(n) MW
Polyethylene 10,000 300,000
Polyvinylchloride 1,500 100,000
Nylon 120 15,000
Polycarbonate 200 40,000
Polymer Molecular Structures
• 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, characteristic of elastomers
• Tightly cross-linked, characteristic of thermosets
Polymer Molecular Structures

Linear
Branched

Loosely cross-linked Tightly cross-linked

 Effect of Branching on Properties
• Thermoplastic polymers always possess linear or branched structures
or a mixture of the two
• Branches increases entanglement among the molecules, which makes
the polymer
• Stronger in the solid state
• More viscous at a given temperature in the plastic or liquid state
 Effect of Cross-Linking on
Properties
• Thermosets possess a high degree of cross-linking; elastomers
possess a low degree of cross-linking
• Thermosets are hard and brittle, while elastomers are elastic and
resilient
• Cross-linking causes the polymer to become chemically set
• The reaction cannot be reversed
• The polymer structure is permanently changed; if heated, it degrades or
burns rather than melt
 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%
 Crystalline Polymer Structure
• 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 & 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 115C 135C
(239F) (275F)
Some Observations About
Crystallization
• Linear polymers consist of long molecules with
thousands of repeated mers
• Crystallization involves folding back and forth of the long
chains upon themselves
• The crystallized regions are called crystallites
• Crystallites take the form of lamellae randomly mixed
in with amorphous material
• A crystallized polymer is a two-phase system
• Crystallites interspersed in an amorphous matrix
 Factors for Crystallization
• Slower cooling promotes crystal formation and growth
• Mechanical deformation, as in the stretching of a heated
thermoplastic, tends to align the structure and increase crystallization
• Plasticizers (chemicals added to a polymer to soften it) reduce
crystallinity
Thermal Behavior of Polymers

• Specific volume
(density)-1 as a
function of
temperature
 Additives
• Properties of a polymer can often be beneficially changed by
combining it with additives
• Additives either alter the molecular structure or
• Add a second phase, in effect transforming the polymer into a composite
material
 Types of Additives by Function
• Fillers – strengthen polymer or reduce cost
• Plasticizers – soften polymer and improve flow
• Colorants – pigments or dyes
• Lubricants – reduce friction and improve flow
• Flame retardents – reduce flammability of polymer
• Cross-linking agents – for thermosets and elastomers
• Ultraviolet light absorbers – reduce degradation from sunlight
• Antioxidants – reduce oxidation damage
Thermoplastic Polymers (TP)
• Thermoplastic polymers can be heated from solid
state to viscous liquid and then cooled back down to
solid
• Heating and cooling can be repeated many times without
degrading the polymer
• Reason: TP polymers consist of linear and/or branched
macromolecules that do not cross-link upon heating
• Thermosets and elastomers change chemically when
heated, which cross-links their molecules and
permanently sets these polymers
 Mechanical Properties of
Thermoplastics
• Low modulus of elasticity (stiffness)
• E is much lower than metals and ceramics
• Low tensile strength
• TS is about 10% of 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
Strength vs. Temperature

• Deformation
resistance
(strength) of
polymers as a
function of
temperature
Physical Properties of
Thermoplastics
• Lower densities than metals or ceramics
• Typical specific gravity for polymers are 1.2 (compared
to ceramics (~ 2.5) and metals (~ 7)
• Much higher coefficient of thermal expansion
• Roughly five times the value for metals and 10 times the
value for ceramics
• Much lower melting temperatures
• Insulating electrical properties
 Commercial Thermoplastic
Products and Raw Materials
• Thermoplastic products include
• Molded and extruded items
• Fibers and filaments
• Films and sheets
• Packaging materials
• Paints and varnishes
• Starting plastic materials are normally supplied to the fabricator in
the form of powders or pellets in bags, drums, or larger loads by truck
or rail car
 Thermosetting Polymers (TS)
• TS polymers are distinguished by their highly cross-linked
three-dimensional, covalently-bonded structure
• Chemical reactions associated with cross-linking are called curing or
setting
• In effect, formed part (e.g., pot handle, electrical switch cover, etc.)
becomes a large macromolecule
• Always amorphous and exhibits no glass transition temperature
 General Properties of Thermosets
• Rigid - modulus of elasticity is two to three times greater than
thermoplastics
• Brittle, virtually no ductility
• Less soluble in common solvents than thermoplastics
• Capable of higher service temperatures than thermoplastics
• Cannot be remelted - instead they degrade or burn
 Cross-Linking in TS Polymers
• Three categories:
1. Temperature-activated systems
2. Catalyst-activated systems
3. Mixing-activated systems
• Curing is accomplished at the fabrication plants that make the parts
rather than the chemical plants that supply the starting materials to
the fabricator
 Temperature-Activated Systems
Curing caused by heat supplied during part shaping operation (e.g.,
molding)
• Starting material is a linear polymer in granular form supplied by the
chemical plant
• As heat is added, material softens for molding, but continued heating
causes cross-linking
• Most common TS systems
• The term “thermoset" applies best to these polymers
 Catalyst-Activated Systems
Cross-linking occurs when small amounts of a catalyst are added to the
polymer, which is in liquid form
• Without the catalyst, the polymer remains stable and liquid
• Once combined with the catalyst it cures and changes into solid form
 Mixing-Activated Systems
Mixing of two chemicals results in a reaction that forms a cross-linked
solid polymer
• Elevated temperatures are sometimes used to accelerate the
reactions
• Most epoxies are examples of these systems
 TS vs. TP Polymers
• TS plastics are not as widely used as the TP
• One reason is the added processing costs and complications involved in
curing
• Largest market share of TS = phenolic resins with  6% of the total
plastics market
• Compare polyethylene with  35% market share
• TS Products: countertops, plywood adhesives, paints, molded parts,
printed circuit boards and other fiber reinforced plastics
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 like those used for thermoplastic and
thermosetting polymers
 Characteristics of Elastomers
• Elastomers consist of long-chain molecules that are cross-linked (like
thermosetting polymers)
• They owe their impressive elastic properties to two features:
1. Molecules are tightly kinked when unstretched
2. Degree of cross-linking is substantially less than thermosets
 Elastomer Molecules
• Model of long elastomer molecules, with low degree of cross-linking:
(left) unstretched, and (right) under tensile stress
 Elastic Behavior of Elastomer
Molecule
• When stretched, the molecules are forced to uncoil and straighten
• Natural resistance to uncoiling provides the initial elastic modulus of
the aggregate material
• Under further strain, the covalent bonds of the cross-linked molecules
begin to play an increasing role in the modulus, and stiffness
increases
• With greater cross-linking, the elastomer becomes stiffer, and its
modulus of elasticity is more linear
 Stiffness of Rubber
• Increase in stiffness as a function of strain for three grades of rubber:
natural rubber, vulcanized rubber, and hard rubber
 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
• Considerably less than cross-linking in thermosets
 Natural Rubber (NR)
• NR = polyisoprene, a high molecular-weight polymer of isoprene
(C5H8)
• 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
Vulcanized Natural Rubber
• Properties: High tensile strength, tear strength,
resilience (capacity to recover shape), and
resistance to wear and fatigue
• Weaknesses: degrades when subjected to heat,
sunlight, oxygen, ozone, and oil
• Some of these limitations can be reduced by
additives
• Market share of NR  22% of total rubber volume
(natural plus synthetic)
 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
• Development of synthetic rubbers was motivated largely by world
wars when NR was difficult to obtain
• Tonnage of synthetic rubbers is now more than three times that of NR
• The most important synthetic rubber is styrene-butadiene rubber
(SBR), a copolymer of butadiene (C4H6) and styrene (C8H8)
• 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 the 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
 COMPOSITE MATERIALS
1. Technology and Classification of Composite Materials
2. Metal Matrix Composites
3. Ceramic Matrix Composites
4. Polymer Matrix Composites
5. Guide to Processing Composite Materials