POLYMERS

Polymers
• Polymers are a special kind of macromolecule.
• Most polymers are organic in origin, i.e. hydrocarbons. The intramolecular bonds
are covalent.
• Word polymer comes from the Greek words “poly” meaning “many”, and “meres”
meaning “parts or repeating units”
• Polymer consists of a large chain of repeating molecules (monomers) that are
attached in an end to end fashion. Individual chains interact to form a stronger
overall substance through entanglements and cross-links
• Polymer chains are flexible, and usually “clump” together into a smaller shape. This
enables the individual chains to interact and become entangled and give a polymer
its strength and flexibility
• Hydrocarbon compounds with the same composition may have different atomic
arrangements, a phenomenon called Isomerism. Physical properties of
hydrocarbons depend on the isomeric state.
Example: Two isomers for butane are normal
butane and isobutane. Boiling Temperatures
for normal butane and isobutane are 0.50 C
and 12.30 C respectively
Repeat units for 10 common Polymeric Materials
 Polymer Chemistry
• A polymer chain is built on a Carbon
• Monomer unit consists of a small carbon chain attached to a
specific type of functional group
• Functional group is what gives each polymer chain its individual
characteristics
• Polymer chains interact with one another, becoming entangled
• Polymer chains form cross-links with adjacent chains, which
allows the polymer to hold its shape and gives added strength
 Types / Groups of Polymers
• Two main types of polymers are:
– Natural (cotton, silk, wood, leather…)
– Synthetic (plastics, nylon, latex…)
• Polymer is a generic term that covers a wide variety and large
number of plastics, elastomers and adhesives.
• Main groups of polymers are thermoplastics polymers,
thermoset polymers, elastomers and adhesives.
– Term ‘plastic’ is used to describe both thermoplastics and thermosets,
although there are differences between the two.
– Elastomers are commonly called ‘rubbers’.
– Adhesives are an important sub-group of polymers, and can be
thermoplastic, thermoset or elastomer.

• Polymers; plastics, elastomers and structural adhesives, all of these

lack stiffness & strength to be used on their own in aircraft structures.
• But Polymers are useful when used in combination with other materials
such as fibre–polymer composites.
 Plastics
• Response of a polymer to mechanical forces at elevated temperatures is related
to its molecular structure. One classification scheme according to behavior with
rising temperature is as below.
• Thermoplastics polymers soften when heated (and eventually liquefy) and
harden when cooled—processes that are totally reversible and may be
repeated. Most linear polymers and those having some branched structures
with flexible chains are thermoplastic.
• Examples: include polyethylene, polystyrene, poly(ethylene terephthalate), and
poly(vinyl chloride).
• Thermosetting polymers become permanently hard during their formation and
do not soften upon heating. Network polymers have covalent crosslinks
between adjacent molecular chains. Heating to excessive temperatures will
cause severance of these crosslink bonds and polymer degradation.
• Thermoset polymers are generally harder and stronger than thermoplastics and
have better dimensional stability.
• Examples: include vulcanized rubbers, epoxies, phenolics and some polyester
resins
 Aerospace applications of polymers
• Most common use for polymers is the matrix phase of fibre composites.
• Polymers are the ‘glue’ used to hold together the high-stiffness, high-
strength fibres in fibre–polymer composites
• Another important use of polymers is as an adhesive for joining aircraft
components to produce high strength, durable joints using polymer
adhesives without the need for fasteners such as rivets and screws.
• Adhesives are used to join metal-to-metal, composite-to-composite and
metal-to-composite components. For example, adhesives are used to bond
ribs, spars and stringers to the skins of structural panels used throughout the
airframe.
• Adhesives are also used to bond face sheets to the core of sandwich
composite materials and to bond repairs to composite and metal
components damaged during service.
• Thin layers of adhesive are used to bond together Aluminium and fibre–
polymer composite sheets that produce the fibre–metal laminate called
GLARE, used in Airbus 380 fuselage.
• Elastomers are not suitable for use in aircraft structures because they lack
stiffness and strength.
• But elastomers do have exceptionally high elasticity with elongation values
between one hundred and several thousand percent, making elastomers
suitable when low stiffness and high elasticity is required, such as aircraft
tyres, seals and gaskets.
 Thermosetting - Epoxy resin
• Epoxy resin is the most common thermosetting polymer used in aircraft
structures.
• Epoxy resin is used as matrix phase in carbon-fibre composites for aircraft
structures and as an adhesive in aircraft structural joints and repairs.
• There are many types of epoxy resins. The cure reaction for certain types of
epoxy resins occurs rapidly at room temperature, although many of the
high-strength epoxies used in aircraft need to be cured at an elevated
temperature (120–180 °C).
• Epoxy resins are the polymer of choice in many aircraft applications
because of their low shrinkage and low release of volatiles during curing,
high strength, and good durability in hot and moist environments.
• Epoxy resin is used extensively in aircraft composite structures, but cannot
be safely used inside cabins because of its poor fire performance.
• Most epoxy resins easily ignite when exposed to fire, and release copious
amounts of heat, smoke and fumes.
 Thermosetting - Phenolic resin
• Federal Aviation Administration (FAA) regulations specify the maximum
limits on heat release and smoke produced by cabin materials in the event
of fire, and most structural-grade epoxy resins fail to meet the
specifications.
• Phenolic resins meet the fire regulations, and most of the internal fittings,
components and furniture in passenger aircraft are made of fibreglass–
phenolic composite and moulded phenolic resin.
 Thermosetting –
Polyimide, Bismaleimide and Cyanate
• Thermosetting polyimides, bismaleimides and cyanate esters polymers are
used in aircraft composite structures required to operate at temperatures
above the performance limit of epoxy resin, ~ upper range of 160–180 °C.
• Polyimides can operate continuously at temperatures up to 175 °C and
operating limit of ~ 300 °C. Polyimide called PMR-15 is the most common
matrix phase of CFRP composites, used in high-speed military aircraft and
jet engine components. The down-side of using polyimides is high cost.
• Bismaleimide (BMI) is used in fiber composites required to operate at
high temperature, upper limit ~ 200 °C. Carbon–BMI composites are used
in the F-35 Lightning II fighter along with carbon–epoxy materials.
• Cyanate resins, which are also known as cyanate esters, cyanic esters or
triazine resins, have good strength and toughness at high temperature,
and their maximum operating temperature is ~ 200 °C. Cyanate resins
pose a safety risk because they produce poisonous hydrogen cyanide
during cure reaction process.
 Thermoplastics
• Use of thermoplastics in aircraft, whether as matrix phase of fibre–polymer
composites or as a structural adhesive, is small compared with thermosets.
• Thermoplastics provide several important advantages over thermosets when
used in composite materials, most notably better impact damage resistance,
higher fracture toughness and higher operating temperatures.
• However, thermoplastics must be processed at high temperature, making it
expensive to manufacture into aircraft composite components.
• Thermoplastics used in aircraft composite structures are polyketones. It
include polyether ketone (PEK), polyether ketone ketone (PEKK) and the most
common polyether ether ketone (PEEK).
• Several types of thermoplastics are transparent, tough and impact resistant
which makes them well suited for aircraft windows and canopies.
• Thermoplastics most often used in aircraft windows are acrylic plastics and
polycarbonates.
• Acrylic plastic used in aircraft windows is polymethyl methacrylate (PMMA),
commercial called Plexiglas and Perspex. Acrylic plastics are lighter, stronger
and tougher than window glass.
• Polycarbonates are stronger and tougher than acrylic plastics and are used
when high-impact resistance is needed, such as cockpit windows and
canopies. In these applications, the material must have high impact
resistance because of the risk of collision with birds or hail storm.
 Mechanical properties of Polymers
• Mechanical properties / parameters of polymers are mostly the same as are
used for metals—i.e. modulus of elasticity, yield and tensile strengths.
• Mechanical characteristics of polymers are highly sensitive to strain rate,
temperature, and chemical nature of the environment (the presence of
water, oxygen, organic solvents, etc.)

Figure 15.1 Stress–strain behavior for brittle (curve A), Figure 15.2 Stress–strain curve for a
plastic (curve B), and highly elastic (elastomeric) (curve plastic polymer showing how yield &
C) polymers. tensile strengths are determined.
Mechanical properties of Polymers
 Mechanical properties of Polymers
• Polymers in many respects, mechanically dissimilar to metals.
• For example, modulus for highly elastic polymeric materials may be as low as
7 MPa, but may run as high as 4 GPa for some very stiff polymers; modulus
values for metals are much larger and range between 48 and 410 GPa
• Maximum tensile strengths for polymers are about 100 MPa and for some
metal alloys ~2400 MPa
• Metals rarely elongate plastically to more than 100%, some highly elastic
polymers may experience elongations to greater than 1000%.
• Mechanical characteristics of polymers are more sensitive to temperature.
• Influence of strain rate on mechanical behavior is also important.
– In general, decreasing the rate of deformation has the same influence on
stress–strain characteristics as increasing the temperature; i.e. the
material becomes softer and more ductile.
 Mechanical properties of Polymers
• Consider stress—strain
behavior for poly methyl
methacrylate (Plexiglas)
between 4 and 60 0C.
• Increasing the temperature
produces:
• a decrease in elastic
modulus,
• a reduction in tensile
strength, and
• an enhancement of ductility
• at 4 0C the material is totally
brittle, whereas there is
considerable plastic deformation
at both 50 and 60 0C

Figure 15.3 The influence of temperature on

stress–strain characteristics of poly methyl methacrylate.
 Macroscopic Deformation
• Tensile stress–strain curve for a semi-
crystalline material, which was initially
undeformed, is shown in Figure 15.4.
• Both upper & lower yield points are
evident, followed by a near horizontal
region.
• At upper yield point, a small neck forms
within the gauge section of the specimen.
• Within this neck, the chains become
oriented (i.e., chain axes become aligned
parallel to the elongation direction, a
condition that is represented schematically
in Figure 15.13d), which leads to localized
strengthening.
• It results in a resistance to continued
deformation at this point, and specimen Figure 15.4 Schematic tensile stress–strain curve
for a semi-crystalline polymer. Specimen contours
elongation proceeds by the propagation of at several stages of deformation are included.
this neck region along the gauge length;
the chain orientation phenomenon (Figure
15.13d) accompanies this neck extension.
 ANELASTICITY
• During study of behavior of metals, it was considered that elastic
deformation is time independent — that is, that an applied stress produces
an instantaneous elastic strain that remains constant over the period of
time the stress is maintained.
• Moreover, upon release of the load the strain is totally recovered — that is,
the strain immediately returns to zero.
• In most engineering materials, however, there will also exist a time-
dependent elastic strain component. That is, upon release of load elastic
deformation is recovered after lapse of some finite time.
• This time-dependent elastic behavior is known as Anelasticity, and it is due
to time-dependent microscopic & atomistic processes that causes
deformation.
• For metals, anelasticity is normally small and is often neglected.
• However, for some polymeric materials its magnitude is significant; in this
case it is termed Viscoelastic Behavior
 VISCOELASTIC DEFORMATION
• Amorphous polymer behave like a glass at low temperatures, a rubbery solid
at intermediate temperatures (above glass transition temperature), and a
viscous liquid as the temperature is further raised. For relatively small
deformations, mechanical behavior at low temperatures may be elastic.
• At the highest temperatures, viscous or liquid like behavior prevails. For
intermediate temperatures the polymer is a rubbery solid that exhibits the
combined mechanical characteristics of these two extremes; the condition is
termed viscoelasticity.
• Elastic deformation is instantaneous, i.e. strain occurs the instant the stress is
applied or released (strain is independent of time). In addition, upon release
of external stress, deformation is totally recovered (Figure 15.5b).
• For totally viscous behavior, deformation or strain is not instantaneous; i.e. in
response to applied stress, deformation is delayed or dependent on time.
This deformation is not reversible or completely recovered after stress is
released (Figure 15.5d)
• For intermediate viscoelastic behavior, imposition of a stress in the manner
of Figure 15.5a results in instantaneous elastic strain, followed by a viscous,
time-dependent strain, a form of anelasticity (Figure 15.5c)
 VISCOELASTIC DEFORMATION

Figure 15.5 (a) Load versus time, where load is applied instantaneously at time
ta and released at tr. For the load–time cycle in (a),
the strain-versus time responses are for totally elastic (b),
Viscoelastic (c), and viscous (d) behaviors.
 Viscoelastic Relaxation Modulus
• Viscoelastic behavior of polymeric materials is dependent on time and
temperature.
• Several experimental techniques may be used to measure and quantify this
behavior. Stress relaxation measurements represent one possibility.
• With these tests, a specimen is initially strained rapidly in tension to a
predetermined and relatively low strain level.
• The stress necessary to maintain this strain is measured as a function of
time, while temperature is held constant.
• Stress is found to decrease with time because of molecular relaxation
processes that take place within the polymer.
• Relaxation Modulus Er(t), a time-dependent elastic modulus for viscoelastic
polymers, is defined as:
,σ(t) is measured time-dependent stress and Є0 is the
strain level, which is maintained constant.
Glass Transition Temperature: Temperature at which a reversible change
occurs in a polymer when it is heated to a certain temperature and undergoes a
transition from a hard and glassy to a soft and ductile condition.
 Viscoelastic Relaxation Modulus

Figure 15.6 Schematic plot of logarithm of

relaxation modulus versus logarithm of time for a
viscoelastic polymer; isothermal curves are
Figure 15.7 Logarithm of the relaxation modulus versus
generated at temperatures T1 through T7.
temperature for amorphous polystyrene, showing the five
Temperature dependence of the relaxation modulus
different regions of viscoelastic behavior.
is represented as log Er(t1) versus temperature.
 Viscoelastic Creep
• Polymeric materials are susceptible to time-dependent deformation when
stress level is maintained constant; such deformation is termed viscoelastic
creep.
• Viscoelastic creep may be significant even at room temperature and under
modest stresses that lie below the yield strength of the material.
• Example: automobile tires may develop flat spots on their contact surfaces
when the automobile is parked for prolonged time periods.
• Creep tests on polymers are conducted in the same manner as for metals; i.e.
a stress (normally tensile) is applied instantaneously and is maintained at a
constant level while strain is measured as a function of time. Creep tests are
performed under isothermal conditions.
• Creep results are represented as a time-dependent Creep Modulus Ec(t),
,σ0 is constant applied stress and Є(t) is time-dependent strain.

• Creep modulus is also temperature sensitive and diminishes with increasing

temperature.
 Fracture of Polymers
• Fracture strengths of polymeric materials are low relative to metals/ceramics.
• Mode of fracture in thermosetting polymers (heavily cross-linked networks) is
brittle. In simple terms, during the fracture process, cracks form at regions of
localized stress concentration (scratches, notches, sharp flaws).
• As with metals, the stress is amplified at tips of these cracks, leading to crack
propagation and fracture. Covalent bonds in the network or cross- linked
structure are severed during fracture.
• For thermoplastic polymers, both ductile and brittle modes are possible, and
many of these materials are capable of experiencing a DBT transition.
• Factors that favor brittle fracture are reduction in temperature, increase in strain
rate, presence of a sharp notch, increased specimen thickness, and any
modification of polymer structure that raises Tg.
• Susceptibility of polymers to fracture when a crack is present may be expressed
in terms of the plane strain fracture toughness, KIc which depend on
characteristics of the polymer (molecular weight, percent crystallinity, etc.) as
well as temperature, strain rate, and the external environment.
 Fracture of Polymers

Figure 15.9 Schematic drawings of

(a) a craze showing microvoids and fibrillar bridges, and
(b) a craze followed by a crack.

Crazing frequently precedes fracture in some thermoplastic polymers. Associated

with crazes are regions of very localized plastic deformation, which lead to formation
of small and interconnected micro voids. Fibrillar bridges form between these
micro voids wherein molecular chains become oriented as in Fig 15.13d.
 Miscellaneous Applications
Adhesives – already discussed
Coatings
• Coatings are applied to the surface of materials for following functions:
– to protect the item from the environment that may produce corrosive or
deteriorative reactions;
– to improve the item’s appearance; and
– to provide electrical insulation.
• Many ingredients in coating materials are organic in origin and fall into different
classifications: paint, varnish, enamel, lacquer, and shellac.
• Many common coatings are latexes. A latex is a stable suspension of small insoluble
polymer particles dispersed in water.
Foams
• Foams are plastic materials that contain relatively high volume percentage of small
pores and trapped gas bubbles.
• Both thermoplastic and thermosetting materials are used as foams; include
polyurethane, rubber, polystyrene, and poly vinyl chloride.
 Miscellaneous Applications
Films
• Polymeric materials have found widespread use in the form of thin films having
thicknesses between 0.025 and 0.125 mm.
• Films are used extensively as bags for packaging food products and other
merchandise, as textile products, etc.
• Some of the polymers manufactured in film form are polyethylene, polypropylene,
cellophane, and cellulose acetate
Fibers
• The fiber polymers are capable of being drawn into long filaments having at least a
100:1 length-to-diameter ratio.
• Most commercial fiber polymers are used in textile industry, being woven or knit
into cloth or fabric.
• The rapid growth in use of fibre–polymer composites in aircraft and helicopters
since the mid-1990s has led to its use as the most commonly used structural
materials (generally as replacement of Alunimum).
• Aerospace grade fibers of Carbon, Aramid, Glass, Boron, etc along with epoxy
resin or as pre-impregnated material, are used extensively on aerial platforms.