COMPOSITE MATERIALS

History

• The earliest man-made composite materials were straw and mud combined to
form bricks for building construction.

• Concrete is also a composite material, and is used more than any other man-
made material in the world. It consists of a binder (cement) and a
reinforcement (gravel).

• Composite materials occur in nature. Wood is a natural composite consisting

of cellulose as the fiber and lignin as the matrix. In bone, the collagen acts like
the resin and the mineral crystals act like the reinforcment.

• The first artificial fiber reinforced plastic was bakelite (thermosetting phenol
formaldehyde resin) which dates to 1907.
Most composites have two constituent materials:
- Matrix
- Reinforcement
 Composite Materials
Composite materials are made from two or more constituent materials with
significantly different physical or chemical properties, that when combined,
produce a material with characteristics different from the individual
components. The individual components remain separate and distinct
within the finished structure.

Most racquets are now made from composite

materials. The composite material is normally epoxy
resin reinforced with carbon fibers. The reinforcing
fibers in the matrix give the composite material even
more strength and stiffness and can withstand
impacts better than either the resin or the fibrous
material alone.
 Composites
Composites are combinations of two
materials in which one of the material is
called the reinforcing phase, is in the form of
fibers, sheets, or particles, and is embedded
in the other material called the matrix phase.

Components of composite materials

Reinforcement: Matrix materials Interface

fibers
Glass Polymers Bonding
Carbon Metals surface
Organic Ceramics
Boron
Ceramic
Metallic
7
Properties of Composite Materials
• In selecting a composite material, an optimum
combination of properties is usually sought,
rather than one particular property
– Example: fuselage and wings of an aircraft must be
lightweight and be strong, stiff, and tough
• Several fiber-reinforced polymers possess this
combination of properties
– Example: natural rubber alone is relatively weak
• Adding significant amounts of carbon black to NR
increases its strength dramatically
Why Composites are Important
• Composites can be very strong and stiff,
• very light in weight,
• Maintain strength up to high temperature
• Lower thermal expansion
• ratios of strength-to-weight and
stiffness-to-weight are several times
greater than steel or aluminum
• Fatigue properties are generally better than
for common engineering metals
Why Composites are Important
• Toughness is often greater too
• Composites have better corrosion and
oxidation resistance
• Possible to achieve combinations of
properties not attainable with metals,
ceramics, or polymers alone
Components in a Composite Material
• Nearly all composite materials consist of
two phases:
1. Primary phase - forms the matrix within
which the secondary phase is imbedded
2. Secondary phase - imbedded phase
sometimes referred to as a reinforcing agent,
because it usually serves to strengthen the
composite
• The reinforcing phase may be in the form of
fibers, particles, or various other geometries
1. Classification
 Properties are Determined by
Three Factors:
1. The materials used as component phases
in the composite
2. The geometric shapes of the constituents
and resulting structure of the composite
system
3. The manner in which the phases interact
with one another
 One Possible Classification of
Composite Materials
1. Traditional composites – composite materials
that occur in nature or have been produced
by civilizations for many years
– Examples: wood, concrete, asphalt
2. Synthetic composites - modern material
systems normally associated with the
manufacturing industries, in which the
components are first produced separately and
then combined in a controlled way to achieve
the desired structure, properties, and part
geometry
PHASES OF COMPOSITE
MATERIALS
 COMPOSITE MATERIALS
• Technology and Classification of Composite
Materials
• Metal Matrix Composites
• Ceramic Matrix Composites
• Polymer Matrix Composites
 Functions of the Matrix Material
(Primary Phase)

• It is a continuous phase which acts as a

binder.
• Holds the imbedded phase in place
• FUNCTIONS
 2. Functions of the Matrix Material
(Primary Phase)
• Protect dispersed phases from environment
• Transfer Stresses to phases
• Holds the imbedded phase in place
• When a load is applied, the matrix shares
the load with the secondary phase, in some
cases deforming so that the stress is
essentially born by the reinforcing agent
 The Reinforcing Phase
(Secondary Phase)
• Function is to reinforce the primary phase
• Imbedded phase is most commonly one of
the following shapes:
– Fibers
– Particles
– Flakes
Figure 9.1 - Possible physical shapes of imbedded phases in composite
materials: (a) fiber, (b) particle, and (c) flake
 Particles and Flakes
• A second common shape of imbedded phase
is particulate, ranging in size from microscopic
to macroscopic
• Flakes are basically two-dimensional
particles - small flat platelets
• The distribution of particles in the composite
matrix is random, and therefore strength and
other properties of the composite material are
usually isotropic
• Strengthening mechanism depends on particle
size
 Fibers
Filaments of reinforcing material, usually
circular in cross-section
• Filaments provide greatest opportunity for
strength enhancement of composites
– The filament form of most materials is
significantly stronger than the bulk form
 Reinforcement
• Fiber Type
• Fiberglass
• Carbon
• Aramid
• Textile Structure
– Unidirectional
– Woven
– Braid
 Fiberglass
• E-glass:Alumina-calcium-borosilicate
glass (electrical applications)

• Glass offers good mechanical,

electrical, and thermal properties at
a relatively low cost(reinforcements
 Carbon Fiber

• PAN: Fiber made from

Polyacrylonitrile precursor
fiber

• High strength and stiffness

 Aramid
• Kevlar™
• Para aramid fiber characterized by
high tensile strength and modulus

• Excellent Impact Resistance

• Good Temperature Resistance

 Fabric Structures
• Woven: Series of Interlaced yarns at 90° to each
other
•
• Knit: Series of Interlooped Yarns
•
• Braided: Series of Intertwined, Spiral Yarns
•
• Nonwoven: Oriented fibers either
mechanically, chemically, or thermally bonded
Continuous vs. Discontinuous Fibers
• Continuous fibers - very long; in theory,
they offer a continuous path by which a
load can be carried by the composite part
• Discontinuous fibers (chopped sections of
continuous fibers) - short lengths (L/D =
roughly 100)
– Important type of discontinuous fiber are
whiskers - hair-like single crystals with
diameters down to about 0.001 mm (0.00004
in.) with very high strength
Fiber Orientation – Three Cases
• One-dimensional reinforcement, in which
maximum strength and stiffness are
obtained in the direction of the fiber
• Planar reinforcement, in some cases in the
form of a two-dimensional woven fabric
• Random or three-dimensional in which the
composite material tends to possess
isotropic properties
 Figure 9.3 - Fiber orientation in composite materials:
(a) one-dimensional, continuous fibers; (b) planar, continuous fibers in the
form of a woven fabric; and (c) random, discontinuous fibers
 Materials for Fibers
• Fiber materials in fiber-reinforced composites:
– Glass – most widely used filament
– Carbon – high elastic modulus
– Boron – very high elastic modulus
– Polymers - Kevlar
– Ceramics – SiC and Al2O3
– Metals - steel
• The most important commercial use of fibers
is in polymer composites
 FRP Properties
• High strength-to-weight and modulus-to-weight
ratios
• Low specific gravity - a typical FRP weighs only
about 1/5 as much as steel; yet, strength and
modulus are comparable in fiber direction
• Good fatigue strength
• Good corrosion resistance, although polymers are
soluble in various chemicals
• Low thermal expansion - for many FRPs, leading to
good dimensional stability
• Significant anisotropy in properties
 FRP Applications
• Aerospace – much of the structural weight of
todays airplanes and helicopters consist of
advanced FRPs
• Automotive – somebody panels for cars and
truck cabs
– Continued use of low-carbon sheet steel in cars is
evidence of its low cost and ease of processing
• Sports and recreation
– Fiberglass reinforced plastic has been used for
boat hulls since the 1940s
– Fishing rods, tennis rackets, golf club shafts,
helmets, skis, bows and arrows.
 The Interface
• There is always an interface between constituent
phases in a composite material
• For the composite to operate effectively, the phases
must bond where they join at the interface

Figure 9.4 - Interfaces between phases in a composite material:

(a) direct bonding between primary and secondary phases
 Interphase
• In some cases, a third ingredient must be added to
achieve bonding of primary and secondary phases
• Called an interphase, this third ingredient can be
thought of as an adhesive

Figure 9.4 - Interfaces between phases: (b) addition of a third

ingredient to bond the primary phases and form an interphase
 Other Composite Structures
• Laminar composite structure –
conventional
• Sandwich structure
• Honeycomb sandwich structure
 Laminar Composite Structure
Two or more layers bonded together in an integral
piece
• Example: plywood in which layers are the same
wood, but grains are oriented differently to increase
overall strength of the laminated piece

Figure 9.7 - Laminar composite structures: (a)

conventional laminar structure
 Sandwich Structure – Foam Core
Consists of a relatively thick core of low density
foam bonded on both faces to thin sheets of a
different material

Figure 9.7 - Laminar

composite structures: (b)
sandwich structure using foam
core
 Sandwich Structure – Honeycomb Core
• An alternative to foam core
• Either foam or honeycomb achieves high
strength-to-weight and stiffness-to-weight ratios

Figure 9.7 - Laminar

composite structures: (c)
sandwich structure using
honeycomb core
Other Laminar Composite Structures
• Automotive tires - consists of multiple layers
bonded together
• FRPs - multi-layered fiber-reinforced plastic panels
for aircraft, automobile body panels, boat hulls
• Printed circuit boards - layers of reinforced plastic
and copper for electrical conductivity and insulation
• Snow skis - composite structures consisting of layers
of metals, particle board, and phenolic plastic
• Windshield glass - two layers of glass on either side
of a sheet of tough plastic
 Disadvantages of Composites
In November 1999, America’s Cup boat “Young America” broke in
two due to debonding face/core in the sandwich structure.

50
Metal Matrix Composites (MMCs)
A metal matrix reinforced by a second phase
• Reinforcing phases:
1. Particles of ceramic (these MMCs are
commonly called cermets)
2. Fibers of various materials: other metals,
ceramics, carbon, and boron
 Cermets
MMC with ceramic contained in a metallic matrix
• The ceramic often dominates the mixture,
sometimes up to 96% by volume
• Bonding can be enhanced by slight solubility
between phases at elevated temperatures
used in processing
• Cermets can be subdivided into
1. Cemented carbides – most common
2. Oxide-based cermets – less common
 Cemented Carbides
One or more carbide compounds bonded in a metallic
matrix
• The term cermet is not used for all of these
materials, even though it is technically correct
• Common cemented carbides are based on tungsten
carbide (WC), titanium carbide (TiC), and chromium
carbide (Cr3C2)
• Tantalum carbide (TaC) and others are less common
• Metallic binders: usually cobalt (Co) or nickel (Ni)
Figure 9.11 - Composite materials in the Boeing 757
(courtesy of Boeing Commercial Airplane Group)
 Application of Composites

Lance Armstrong’s 2-
lb. Trek bike, 2004
Tour de France

Pedestrian bridge in
Denmark, 130 feet
long (1997)

Swedish Navy, Stealth

(2005)

57
Application of Composites in
Aircraft Industry

20% more fuel

efficiency and 35,000
lbs. lighter
58
 Reinforcements

The role of reinforcement in composite materials is primarily to add

mechanical properties to the material such as strength and stiffness

Reinforcements basically come in three forms:

•particulate
•discontinuous fiber
•continuous fiber

Reinforcements become fibers when one dimension becomes long

compared to others. Discontinuous reinforcements (chopped fibers, milled
fibers) vary in length from a few millimeters to a few centimeters.
 Matrix Materials
Polymer matrix composites are the most commonly used type of composite material

Matrix material;
• Holds the fibers together, thus transferring the load between fibers and
between the composite and the supports,
• Protects the fibers from environment and mechanical abrasion
• Carries some of the loads particularly transverse stress and interlaminar shear stress.
(Some properties of the composite such as transverse stifness and strength are matrix
dominated. Matrix dominated properties depend strongly on the operating temperature)

The matrix of PMCs is a polymer that can be either:

•Thermoset
•Thermoplastic
 Matrix

The role of the matrix is to bind the reinforcement together so that the applied
stress is distributed among the reinforcement and to protect the surface of the
reinforcement from being damaged.

Composites are classified according to their matrix phase:

•Polymer matrix composites (PMC's)
•Ceramic matrix composites (CMC's)
•Metal matrix composites (MMC's)
 Advantages of Polymer Matrix Composites

Polymer composites are lightweight materials providing an advantage

for;
• aircraft hulls (gövde), bicycle bodywork,
• military and heavy goods vehicles use composites in both bodywork and
engine and transmission systems.
• mass transit systems in trains, subways and buses use composites for
ceilings, walls, floors and seating.

Polymer composites have a high resistance to chemical corrosion and

scratching. Their resilience to seawater and rust is an advantage when
used in boats or other marine craft manufacture.

Easy to fabricate of very complex parts with

low tooling cost.
 Disadvantages of Polymer Matrix Composites

• Because the matrix decomposes at high temperatures, current PMCs are

limited to service temperatures below about 300° C.

• Experience over the past 15 years with advanced composite structures in

military aircraft indicates that reliable PMC structures can be fabricated.
However, their high cost remains a major barrier to more widespread use in
commercial applications.

• Most advanced PMCs today are fabricated by a laborious process called lay-
up. Although automation is beginning to speed up this process, production
rates are still too slow to be suitable for high-volume, low-cost industrial
applications such as automotive production lines. New fabrication methods
that are much faster and cheaper will be required before PMCs can
successfully compete with metals in these applications.
 Composite products
Composite products range from skateboards to components of the space shuttle.
The industry can be generally divided into two basic segments:
• industrial composites
• advanced composites

The distinction is based on the level of mechanical properties. Materials within

these categories are often called "advanced" if they combine the properties of
high strength and high stiffness, low weight and corrosion resistance.

Industrial Composites. The industrial composites

industry has been in place for over 40 years in the
world. This large industry utilizes various resin
systems including polyester, epoxy, and other
specialty resins. These materials, along with a catalyst
or curing agent and some type of fiber reinforcement
(typically glass fibers) are used in the production of a
wide spectrum of industrial components and
consumer goods: boats, piping, auto bodies, and a
variety of other parts and components.
Advanced Composites : Advanced composites industry is
characterized by the use of expensive, high-performance resin systems
and high-strength, high-stiffness fiber reinforcement. The aerospace
industry, including military and commercial aircraft is the major
customer for advanced composites. These materials have also been
adopted for use by the sporting goods suppliers who sell high-
performance equipment to the golf, tennis, fishing, and archery
markets.

While aerospace is the predominant market for advanced composites

today, the industrial and automotive markets will increasingly see the
use of advanced composites.

Surfboard with carbon nanotube

reinforced epoxies
 • Also BMW goes for composites. The BMW M6 has an overall
weight of only 1710 kg. The composite roof is 6 kg lighter than a
conventional steel roof.

• In the BMW M3 model, the aluminium bumper beam has been

replaced by a glass/polyamide bumper beam. A weight reduction
from 7 kg to 3.1 kg was realized, and its crash performance was
three to four times better than the metal beam.

BMW M6 with carbon fibre roof Glass/polyamide bumper beam for BMW M3
http://www.hsc.csu.edu.au/engineering_studies/focus/aero/2579/polymer_composites.html
transverse tensile failure shear failure

yellow part: matrix

black part: long fiber
 Thermoset Matrices

A thermoset matrix is formed by the irriversible chemical transformation of a resin

system into an amorphous cross-linked polymer matrix.

The polymer is called resin system during processing and matrix after the polymer
has cured.

Thermosetting resins have low viscosity which allows for excellent impregnation of
the fiber reinforcement and high processing speeds.

Shelf life: is the time the unmixed resin system can be stored without degredation.
(Refrigerated storage is usually recommended)

Pot life or gel time: is the time the mixed resin can be handled before the viscosity
grows to a point where processing is no longer possible.
 Curing can vary from minutes to hours (depending on the choice of the catalyst and
reactivity of the resin).

 The reactions are exothermic.

 Once cured, the mixture thickens, releases heat, solidifies and shrinks. The
volumetric shrinkage upon curing varies from 4% for epoxy to 8% for polyester. Since
the fiber reinforcement does not shrink, internal stress can be induced causing cracking,
fiber misalignment, dimensional inaccuracy and surface roughness.

Thermosets, because of their three-dimensional crosslinked structure, tend to have

high dimensional stability, high-temperature resistance, and good resistance to solvents.

 The most common thermoset resins are polyester, vinyl ester, epoxy and phenolics.
Thermosetting polyesters are commonly used in fiber-reinforced plastics, and epoxies
make up most of the current market for advanced composites resins.
 Polyester Resins

heat

free radical initiator

unsaturated polyester

* Cross linking can be accomplished at room temperature using suitable activators.

*Polyester resins can be used in many outdoor

applications. Superior durability, color retention
and resistance to fiber erosion can be obtained
when styrene-MMA monomer blends are used.

*MMA-polyesters have refractive index

matched to that of glass fibers allowing to
prepare transparent building panels.

*Polyester resins are considered low cost resins.

Applications include;
• transportation markets (large body parts for automobiles, trucks, trailers,
buses)
• marine (small and large boat hulls and other marine equipment)
• building (panels, bathtub and shower shells)
Traditional unsaturated polyesters are polycondensation products based on saturated and
unsaturated dicarboxylic acids and primary bivalent alcohols. Typically, these systems are
dissolved in styrene which reacts with and cross-links the unsaturated resin when a cobalt
salt and an organic peroxide, are used. The cobalt salt decomposes the peroxide to form
free radicals, R'·, which initiate the crosslinking of the system. This reaction mechanism is
described in Figure 1.

(Ref. Bayer Material Science)

 Vinyl Ester Resins
Vinyl ester resins have some
advantages over unsaturated
polyesters:
•They don't absorb as much water,
•They don't shrink nearly as much
when cured.
•They have very good chemical
resistance.
•Because of the hydroxyl groups, it
bonds well to glass.

It is a common resin in the marine

industry due to its increased
corrosion resistance and ability to
withstand water absorption.

* The cost of vinyl ester resins is between that of polyesters and epoxies.
 Epoxy Resins

•Because of all those hydroxyl groups, epoxy resins can bond well to glass fibers.
•Epoxies shrink less than other materials when they're cured (1.2-4% by volume).
•Epoxy resins are widely used because of their high mechanical properties and
high corrosion resistances.
•Epoxy systems are used in applications like aerospace, defense, marine, sports
equipment. They are also used as adhesives, body solders (lehim), sealant and
casting compounds. Besides, they have a wide range of uses in the electrical
business because of their excellent electrical insulation.,
 Phenolic Resins
• Phenolic resins have low flammability and low smoke production compared
with other low-cost resins.
• They have good dimensional stability under temperature fluctuations and
good adhesive properties.

Used as molded disc brake

cylinders, saucepan handles,
electrical plugs and switches,
parts for electrical irons and
interior construction materials of
aircraft and mass transit vehicles
where smoke production must be
extremely low.

*Cost of phenolic resins is competitive with polyesters. Disadvantages of these resins

include high curing temperatures and pressures, longer curing times than polyesters, and
limited color range.
 NOTE
 Temperature has a detrimental influence on modulus and strength for
polymers.

 Higher Tg results in a more brittle matrix with lower elongation and

mechanical properties. The operating temperature is always below the Tg,
which is high for brittle resins and lower for toughened resins. This means
there is always a trade-off between high temperature application and
mechanical properties.

 Moisture absorption is another consideration because of the detrimental

effects the moisture has on mechanical properties of the matrix and the
composite.

 Unreinforced polymers provide unlimited freedom for aesthetic design, they

suffer from creep problems. Reinforcing plastics with fibers virtually
eliminates the creep problem and opens unlimited variation of mechanical
properties under the designer’s control.
 Thermoplastic Matrices
• Unlike the curing process of thermosetting resins, the processing of
thermoplastics is reversible, and, by simply reheating to the process
temperature, the resin can be formed into another shape if desired.
• Thermoplastics have high viscosity at processing temperatures, which makes
them more difficult to process. The high shear stresses needed to make
thermoplastic flow cause damage to the fibers resulting in a reduction of fiber
length. Since, impregnation is impaired by high viscosity, special care must be
taken to assure contact between the fibers and the polymer.
• Thermoplastics do not require refrigerated storage.
• Have unlimited shelf or pot life.
• Thermoplastics, although generally inferior to thermosets in high-temperature
strength and chemical stability, are more resistant to cracking and impact
damage. However, it should be noted that recently developed high-performance
thermoplastics or engineering thermoplastics, such as PEEK, exhibit excellent
high temperature strength and solvent resistance.
Engineering Thermoplastics / High Performance Thermoplastics

Poly ether etherketone (PEEK)

• The most common thermoplastic matrix for high performance applications.

• Have a semicrystalline microstructure with very low water absorption (0.5% by
weight) at room temperature, much lower than for most epoxies.
• PEEK has a glass transition temperature of around 143°C and melts around 343°C.
The operating temperature is around 250°C (operating temperature for brittle
epoxies is ̴250°C and toughened epoxies between 75-185°C).
• CF/PEEK is shown to be more than 10 times tougher than CF/epoxy*.

*Ahmed Khairy Noor, Samuel L. Venneri, Future Aeronautical and Space Systems, ISBN:1563471884, 1997
Polysulfones • Amorphous thermoplastic.
• Excellent stability under hot and
wet conditions.
• Their high hydrolysis stability allows
their use in medical applications
requiring autoclave and steam
sterilization.
• They rated as self-extinguishing,
with low smoke and toxic fume
generation.
• PS has a glass transition
temperature of around 185°C and
the operating temperature is
around 165°C.
• Due to the high cost of raw
materials and processing,
polysulfones are used in specialty
applications.
• Not UV-stable 
 Polyimides

• Amorphous thermoplastics with

high glass transition temperatures.

•Polyamide-imides have
exceptional mechanical, thermal
and chemical resistant properties.
These properties put polyamide-
imides at the top of the price and
performance pyramid.

•PAI has low processability .

http://www.dupont.com/products-and-services/membranes-films/polyimide-
films/brands/kapton-polyimide-film/videos/video-kapton-unlock-your-imgination.html
You should consider TPI Blends if
you are looking for an easy-to-
process high heat material
providing superior part reliability
through:
•Great dimensional stability under
high heat conditions
•Higher retention of mechanical
properties under high continuous
/ peak temperature (up to 300°C
with TPI!)
•Better infrared heat resistance
and improved surface reflection
(i.e. metalized surfaces) through
excellent light transmission
properties
•Continuity of part performance
in harsh environments through
excellent chemical resistance (i.e.
Oil & Gas Industry, Aerospace,
Under-the-hood in Automotive
etc...)
 Thermoplastics offer great promise for the future from a manufacturing point
of view, because;

it is easier and faster to heat and cool a material than it is to cure it

This makes thermoplastic matrices attractive to high-volume industries such

as the automotive industry. Currently, thermoplastics are used primarily with
discontinuous fiber reinforcements such as chopped glass or
carbon/graphite. However, there is great potential for high-performance
thermoplastics reinforced with continuous fibers. For example,
thermoplastics could be used in place of epoxies in the composite structure
of the next generation of fighter aircraft*.

*Barbero E. J. Introduction to Composite Materials Design , Taylor and Francis, 1999.

 1. Classification
Primary Phase, Matrix

Secondary Phase,
Reinforcement