MM – 525

ADVANCED POLYMER
COMPOSITES
Lecture no. 2 : Matrices & Reinforcing Material
Major constituents of a composite material

• the matrix
• the reinforcing material

Other constituents
• coupling agents
• coatings, and
• fillers.
 THE MATRIX PHASE
The matrix phase may be a metal, ceramic, or polymer.
Carbon is also used as a matrix material with carbon fibers in
a class of composites known as carbon – carbon composite

In general, metals and polymers are used as matrix materials

because some ductility is desirable.

For CMC, the reinforcing component is added to improve

fracture toughness.
 THE MATRIX PHASE
 Metallic
Aluminum and its alloys, titanium alloys, magnesium alloys, copper-
based alloys, nickel-based super alloys, stainless steel : suitable for
high temperature applications (300 - 500°C)

 Ceramic
Aluminum oxide (Al2O3), carbon, silicon carbide, silicon nitride (Si3N4) :
suitable for high temperature applications

Metallic and ceramic matrices ― for high temperature applications.

 Polymeric
Thermoset polymers (resins)
Epoxies : principally used in aerospace and aircraft applications
Polyester, vinyl esters : commonly used in automotive, marine, chemical,
and electrical applications
Phenolics : used in bulk moulding compounds
Polyimides : for high temperature aerospace applications (250 - 400°C)

Thermoplastic polymers
Nylons, thermoplastic polyesters (eg., PET, PBT), polycarbonate,
polyacetals : used with discontinuous fibers in injection moulded articles
Polyamide-imide (PAI), polyether-ether ketone (PEEK), polysulfone,
polyphenylene sulfide : suitable for moderately high temperature
applications with continuous fibers
Functions of Fibers and Matrix
To develop a good understanding of composite behavior, one
should have a good knowledge of the roles of fibers and
matrix materials in a composite.

 The reinforcing fiber or fabric provides strength and stiffness

 The matrix gives rigidity and environmental resistance.

Fibers themselves are of little use without the presence of a
matrix material or binder.

A matrix material fulfills several functions in a composite

structure, most of which are vital to the satisfactory
performance of the structure.
Important functions of a matrix material:

 Binds the fibers together. Transmits load to the fibers.

 Isolates the fibers. This stops or slows the propagation
of brittle cracks from fiber to fiber.
 Provides protection to reinforcing fibers against chemical
attack and mechanical damage (wear).
 Provides a good surface finish quality (rigidity and shape
to the structure).
 Determines the maximum service temperature.
 The matrix material should be ductile. A ductile matrix will
increase the toughness of the structure.
• For higher toughness requirements, thermoplastic-based
composite are selected.

• Exception to ductile matrix is ceramic matrix.

 The failure mode is strongly affected by the type of matrix

material used in the composite as well as its compatibility
with the fiber.
The matrix plays a minor role in the tensile load –carrying.

Major influence on the compressive, inter laminar shear as

well as in-plane shear properties of the composite material.

Provides lateral support against the possibility of fiber buckling

under compressive loading , thus influencing to a large extent ,
the compressive strength of the composite material.
Selection of Matrix
Matrix selection is based on:
• chemical
• thermal
• electrical
• flammability
• environmental
• cost
• performance
• service operating temperature
• processing parameters for part manufacturing.
Polymer Matrices
The most common resin materials used in thermoset
composites are epoxy, polyester, vinylester, phenolics,
cyanate esters, bismaleimides, and polyimides.
Some of the basic properties of selected thermoset resins are
shown below:
Resin Material Density Tensile Modulus Tensile Strength
g/cm3 GPa MPa

Epoxy 1.2–1.4 2.5 – 5.0 50 – 110

Phenolic 1.2–1.4 2.7 – 4.1 35 – 60
Polyester 1.1–1.4 1.6 – 4.1 35 – 95
Epoxy

A very versatile resin system : broad range of properties and

processing capabilities
• low shrinkage
• excellent adhesion to a wide variety of substrate materials
• good chemical and environmental resistance,
• good mechanical properties, and
• good electrical insulating properties.
Starting materials for epoxy matrix are low-molecular weight
organic liquid resins containing a number of epoxide groups:

Common material : Diglycidyl ether of bisphenol A (DGEBA),

which contains two epoxide groups, one at each end of the
molecule
Reactive curing agent (amines, anhydrides, phenols,
carboxylic acids, alcohols etc.) added just before
incorporating fibers into the liquid mix which transforms the
liquid resin to the solid state.

One such curing agent is diethylene triamine (DETA).

Hydrogen atoms in the amine (NH2) groups of a DETA molecule
react with the epoxide groups of DGEBA molecules
As the reaction continues, DGEBA molecules form cross-links
with each other and a three-dimensional network structure is
slowly formed resulting in a solid epoxy polymer.
Curing time (pot life) and temperature depend on the type and
amount of curing agent.

• Some curing agents work at room temperature

• Some work at elevated temperatures

Accelerators are sometimes added to speed up the curing.

Other ingredients are:

Diluents ─ to reduce its viscosity and
Flexibilizers ─ to improve the impact strength of the cured
epoxy matrix.
Cross-link density affects the properties of the cured resin.
 Tensile modulus, Tg, thermal stability and chemical resistance
are improved with increasing cross-link density.
 But the strain to- failure and fracture toughness are reduced.

Factors that control the crosslink density are :

• the chemical structure of the starting liquid resin
• functionality of the curing agent
• the reaction conditions
The continuous use temperature for DGEBA-based epoxies
is ≤ 150°C.

Higher heat resistance (up to 250°C) can be obtained with

epoxies based on novolac and cycloaliphatics.

In general, the heat resistance of an epoxy is improved if it

contains more aromatic rings in its basic
molecular chain.
Typical Properties of Cast Epoxy Resin (at 23°C)

Density 1.2–1.3 g/cm3

Tensile strength 55–130 MPa
Tensile modulus 2.75–4.10 GPa
Poisson’s ratio 0.2–0.33
Coefficient of thermal expansion 50–80 x 10-6 m/m per °C
Cure shrinkage 1–5 %
Epoxy matrix has the following advantages over other thermoset matrices :

1. Wide variety of properties, since a large number of starting materials,

curing agents , and modifiers are available
2. Absence of volatile matters during cure hence low shrinkage during cure
3. Excellent adhesion to a wide variety of fillers, fibers, and other substrates
4. Excellent resistance to chemicals and solvents
5. Good mechanical properties
6. Good electrical insulating properties

There are varying grades of epoxies with varying levels of performance

to meet different application needs.
The principal disadvantages are its relatively high cost and long cure time.
Other drawbacks are:
 High moisture absorption: reduces its glass transition temperature as
well as its modulus and other mechanical properties.
This can be reduced by changing the resin chemistry.

 Brittleness or low strain-to-failure: inherent problem of any highly cross-

linked resin which is detrimental for damage-tolerant composite
laminates.
For epoxy resins, this can be reduced by adding a small amount of
highly reactive carboxyl-terminated butadiene–acrylonitrile (CTBN) liquid
elastomer, which forms a second phase in the cured matrix and
impedes its microcracking.
Unsaturated Polyester
Polyester resins (thermosetting) are the most commonly used
matrices for fiberglass-base composites.
• Low cost,
• Low viscosity
• Fast cure time
• Versatility in many processes, and
• Good property performance.

Glass fibers + unsaturated polyesters → cross-linked to form

high-strength reinforced composite materials.
E.g., ethylene glycol or propylene glycol can be reacted with
maleic anhydride to form a linear unsaturated polyester that
has reactive C ═ C double bonds which can be cross-linked to
form thermosetting materials.

O
styrene t-butyl perbenzoate molecule (tBPB)
 Unsaturated PE are usually cross-linked with vinyl-type molecules such
as styrene in the presence of a free radical curing agent (eg. methyl
ethyl ketone (MEK) peroxide or t-butyl perbenzoate (tBPB) etc.) at
107°C –163°C. Styrene also reduces its viscosity and makes it easier
to handle.

O The reaction is accelerated with a small

t-butyl perbenzoate molecule (tBPB) amount of cobalt naphthenate.
Trace amounts of an inhibitor, such as hydroquinone or
benzoquinone, are added to the liquid mix to prevent premature
polymerization during storage.
Structure and Properties
Properties depend strongly on the cross-link density. The modulus,
Tg, and thermal stability of cured polyester resins are improved by
increasing the cross-link density, but the strain-to-failure and
impact energy are reduced.

Cross-link density is influenced by the number of unsaturation

points in an uncured polyester molecule.

Varying the weight ratio of saturated acids (isophthalic acid) and

unsaturated acids (maleic anhydride) modify the chemical
structure between the cross-linking sites.
The type of ingredients also influences the properties and
processing characteristics of polyester resins.
• Terephthalic acid ― higher HDT than either isophthalic or
orthophthalic acid, but it has the slowest reactivity of the three
phthalic acids.
• Adipic acid ― lowers the stiffness of polyester molecules.
Can be used as a flexibilizer for polyester resins.
• Diethylene glycol can also lower the stiffness . Propylene glycol,
on the other hand, makes the polyester resin more rigid, since
the pendant methyl groups in its structure restrict the rotation of
polyester molecules.
The amount and type of diluent are also important factors in
controlling the properties and processing characteristics of
polyester resins.

Styrene is the most widely used diluent because it has low

viscosity, high solvency, and low cost.

Drawbacks : flammability and potential (carcinogenic) health

hazard due to excessive emissions.
Higher styrene content

• reduces the modulus of the cured PE resin

• increases the total amount of unsaturation,

consequently, the curing time is increased
• tends to promote self-polymerization
(polystyrene-like properties to
dominate the cured polyester resin)
Polyester resins can be formulated in a variety of properties
ranging from hard and brittle to soft and flexible.

Typical Properties of Cast Thermoset Polyester Resins (at 23ºC)

Density 1.1–1.43 g/cm3

Tensile strength 34.5–103.5 MPa
Tensile modulus 2.1–3.45 Gpa
Elongation 1–5 %
HDT 60–205 ºC
Cure shrinkage 5–12 %
Low-viscosity materials ― can be mixed with high amounts of
fillers and reinforcements (e.g. 80% by weight of glass-fiber)

GFRP have outstanding strength (174 to 344 Mpa) and good

impact and chemical resistance.

The principal disadvantage of polyesters over epoxies is their

high volumetric shrinkage.

Although this allows easier release of parts from the mold, the
difference in shrinkage between the resin and fibers results in
uneven depressions (called sink marks) on the molded surface.
The sink marks are undesirable for exterior surfaces requiring
high gloss and good appearance
Applications

 Glass-reinforced unsaturated polyesters are used for

making automobile panels and body parts.

 Also used for small-boat hulls and in the construction

industry for building panels and bathrooms components.

 Other uses : pipes,tanks, and ducts where good corrosion

resistance is required.
VINYL ESTER (unsaturated vinyl ester resin)
The starting material is produced by the reaction of an unsaturated carboxylic
acid, such as methacrylic or acrylic acid, and an epoxy.

H2

The asterisk denotes

unsaturation points H2 H2
(reactive sites).
Unsaturated vinyl ester resins are dissolved in styrene monomer
(35 – 45 wt %), which reduces their viscosity and form cross-links
between the unsaturation points in adjacent vinyl ester molecules.
The curing reaction is similar to that for unsaturated polyesters.
Structure and Properties
The C ═ C double bonds (unsaturation points) occur only at the ends of
a vinyl ester molecule, and therefore, crosslinking can take place only at
the ends.
• Because of fewer cross-links, a cured vinyl ester resin is more
flexible and has higher fracture toughness than a cured polyester
resin.
• A unique characteristic of a vinyl ester molecule is that it contains a
number of OH (hydroxyl) groups along its length. These OH groups
can form hydrogen bonds with similar groups on a glass fiber surface
resulting in excellent wet-out and good adhesion with glass fibers.
Vinyl ester resins possess some good characteristics of both epoxy and of
unsaturated polyester resins, e.g.
 Excellent chemical resistance and tensile strength (like epoxy)
 Low viscosity and fast curing (like unsaturated polyester)

Volumetric shrinkage (5%–10%) is higher than epoxy resins.

Adhesive strength is low compared to epoxy resins.

The tensile and flexural properties of cured vinyl ester resins do not vary
appreciably with the molecular weight and type of epoxy resin or other
coreactants.

HDT and thermal stability can be improved by using heat-resistant epoxy

resins, such as phenolic-novolac types.
Typical Properties of Cast Vinyl Ester Resins (at 23°C)

Density (g/cm3) 1.12–1.32

Tensile strength, MPa 73–81
Tensile modulus, GPa 3–3.5
Elongation, % 3.5–5.5
HDT, °C 93–135
Cure shrinkage, % 5.4–10.3
Resin Viscosity ~ 200 cps
lower than polyester (~ 500cps) and
epoxy (~ 900cps).
Applications
• Alternative to polyester and epoxy materials in matrix
or composite materials, where its characteristics, strengths, and
bulk cost intermediate between polyester and epoxy.

• In homebuilt airplanes, the Glasair and Glastar kit planes made

extensive use of vinylester-reinforced fiberglass structures.

• A common resin in the marine industry due to its increased

corrosion resistance and ability to withstand water absorption.

• Extensively used to manufacture FRP tanks and vessels

Phenolics
First major plastic.
1909 - L.H. Baekland - patent Bakelite by reaction of phenol with
formaldehyde.

Phenolics are low in cost and have good electrical and heat
insulating properties along with good mechanical properties. Also
good high-temperature and moisture-resistant.

They are easily molded but limited in color (black or brown).

To obtain light-colored products, urea formaldehyde and melamine

formaldehyde are used.
Chemistry
Condensation polymerization of phenol and formaldehyde, with water
as a by-product. However, almost any reactive phenol or aldehyde
can be used to obtain different properties.
Two-stage (novolac) phenolic resins are commonly produced
for convenience for molding.

• First stage : a brittle thermoplastic resin is produced which

can be melted but which will not crosslink to
form a network solid.

• Second stage: A basic catalyst hexamethylenetetramine

(hexa) is added to the first- stage
phenolic resin.
On application of heat and pressure
hexa decomposes producing
ammonia which provides methylene
cross-linkages to form a network
structure.
Cross-linking (curing) temperature
ranges from 120 to 177ºC.
Their cure characteristics are different than other thermosetting resins
such as epoxies. Water is generated during cure reaction which is
removed during processing.

In the compression molding process, water can be removed by bumping

the press.
Properties of Phenol-Formaldehyde

• Relative Density 1.69-2.0

• Water Absorption 24h(%) 0.03-1.2
• Shrinkage 0.001-0.004
• Tensile Strength 48 – 124 MPa
• Compressive Strength 110 - 480 MPa
• Flexural Strength 82 - 410 MPa
• Izod Impact(ft-lb/in) 0.5-18.0
• Hardness Rockwell E 54-101
• Flammability V-0

High-Strength Glass Fiber Reinforced

Applications
Phenolic resins are used where following properties are important :
• Flame-resistance
• High temperature resistance
• Electrical properties
• Wear resistance
• Good chemical resistance and dimensional stability
Used for various composite manufacturing processes such as
filament winding, RTM, injection molding, and compression molding.

Phenolics provide easy processability, tight tolerances, reduced

machining, and high strength.

Because of high temperature resistance, phenolics are used in

exhaust components, missile parts, manifold spacers, commutators,
disc-brakes and transmission parts.

Also used for aircraft interiors.

Thermoplastic polymer
Advantages:

1. High impact strength and fracture resistance , which means excellent

damage tolerance.
2. Unlimited storage (shelf) life at room temperature
3. Shorter fabrication time
4. Postformability (e.g., by thermoforming)
5. Ease of joining and repair by welding, solvent bonding, and so on
6. Ease of handling (no tackiness)
7. Can be reprocessed and recycled
Disadvantages:

• High melt or solution viscosities – incorporation of continuous fibers

into a thermoplastic matrix is difficult.
• Lower creep resistance and lower – Nylons and PC are of very limited
thermal stability interest in structural applications
• Lower stiffness and strength
• More susceptible to solvents
Choice of a reinforced thermoplastic depends on
 the nature of the application
 the service environment and
 costs
In many cases conventional thermoplastic processing techniques can
be used to produce moulded articles
Mechanical properties of Selected Thermoplastic Matrix Resins (at 23°C)
considered suitable for high-performance composite application
Property PEEK PPS PSUL PEI PAI K-III LARC- TPI
Density (g/cm3) 1.30–1.32 1.36 1.24 1.27 1.40 1.31 1.37
Yield (Y) or Tensile (T) 100 82.7 70.3 105 185.5 102 138
strength, (MPa) (Y) (T) (Y) (Y) (T) (T) (T)
Tensile modulus, (GPa) 3.24 3.3 2.48 3 3.03 3.76 3.45

Elongation-at-break (%) 50 4 75 60 12 14 5

Poisson’s ratio 0.4 — 0.37 — — 0.365 0.36

Flexural strength, (MPa) 170 152 106.2 150 212 — —

Flexural modulus, 4.1 3 .45 2.69 3.3 4.55 — —

GPa
Fracture energy 6.6 — 3.4 3.7 3.9 1.9 —
kJ/m2
HDT, 8C (at 1.82 MPa) 4.7 4.9 5.6 5.6 3.6 — 3.5
CLTE, 10-5/°C
Nylons (Polyamides)
• Nylons provide a good surface appearance and good lubricity.
• Absorb moisture ─ Important design consideration. Affects the
properties and dimensional stability of the part.

Glass reinforcement minimizes this problem and produces a strong,

impact-resistant material. Impact resistance of long glass-filled nylon
is higher than aluminim and magnesium

• Glass-filled and carbon-filled nylons in pellet form are available for

injection molding purposes.
• Available as prepregs with various reinforcements.
• Also used for various pultruded components.
Polypropylene (PP)

Low-cost, low-density, versatile plastic. Also available as a co-

polymer (ethylene/propylene).

Offers good strength, stiffness, chemical resistance, and fatigue

resistance.

PP is used for machine parts, car components (fans, fascia

panels, etc.), and other household items, and has also been
pultruded with various reinforcements.
POLYETHER ETHER KETONE
Polyether ether ketone (PEEK) is a linear aromatic thermoplastic
(semicrystalline)

Repeating unit :

Max. crystallinity : 48% when cooled slowly

30% to 35% at normal cooling rates
Amorphous : if the melt is quenched

The presence of fibers in PEEK composites tends to increase the crystallinity

to a higher level, since the fibers act as nucleation sites for crystal formation.

Crystallinity increases both modulus and yield strength of PEEK, but reduces
its strain-to-failure
Tg = 143°C
MP = 335°C
Maximum continuous
use temperature = 250°C.

Melt processing = 370°C – 400°C for autoclave, hot press, and

diaphragm molding processes
> 500°C for tape winding operation for better
interply consolidation.
PEEK is a new-generation thermoplastic with some very good properties:

• High fracture toughness ─ 50–100 times higher than that of epoxies

• Low water absorption ─ Less than 0.5% at 23°C compared with
4% – 5% for aerospace-grade epoxies
• high service temperatures
• greater damage tolerance
• better solvent resistance

As it is semicrystalline, it does not dissolve in common solvents.

However, it may absorb some of the solvents like methylene chloride.
The amount of solvent absorption decreases with increasing crystallinity.
Carbon-reinforced PEEK composites (APC-2) have demonstrated
their usefulness
 in fuselage
 satellite parts, and other aerospace structures

The drawback of PEEK-based composites is that the materials

cost is very high.
POLYPHENYLENE SULFIDE
A semicrystalline ( max. 65%) polymer with the following repeating unit :

Glass transition temperature = 85°C

Crystalline melting point = 285°C
Melt processing = 300°C–345°C
Continuous use temperature = 240°C
It has excellent chemical resistance.
The relatively low Tg of PPS is due to the flexible sulfide linkage between
the aromatic rings. Its relatively high crystallinity is attributed to the chain
flexibility and structural regularity of its molecules.
Prepreg tape of PPS with several reinforcements is available.

The trade names of PPS-based prepreg systems are Ryton and

Techtron.

PPS-based composites are used for applications where great

strength and chemical resistance are required at elevated
temperature.
POLYSULFONE
Polysulfone is transparent, tough, strong, heat-resistant, high-
performance amorphous thermoplastic.

Repeating unit :

Glass transition temperature = 185°C

Crystalline melting point = 285°C
Melt processing = 310°C–410°C
Continuous use temperature = 160°C
Properties of polysulfone of special significance to the design engineer :

• High heat-deflection temperature of 174ºC.

• High tensile strength (for thermoplastics) of 70MPa.

• A relatively low tendency to creep.
• High tensile strain-to-failure (50%–100%)
• Resist hydrolysis in aqueous acid and alkaline environments
• Resistant to oxidizing agents, surfactants and hydrocarbon oils

Not resistant to low-polar organic solvents (eg. ketones and

chlorinated hydrocarbons), and aromatic hydrocarbons
Mechanically, polysulfone has high compaction resistance,
recommending its use under high pressures.

Polysulfone has the highest service temperature of all melt-

processable thermoplastics.

Polysulfone can be reinforced with glass fibers. The resulting

composite material has twice the tensile strength and three time
increase of its modulus.
Metal Matrices
Three main metals:

• Aluminum • Magnesium • Titanium

 Normally alloyed with other elements to improve their physical

and mechanical properties.

 Final properties strongly influenced by thermal and

mechanical treatments – microstructures

 Ductile and isotropic

• Not much increase in stiffness

• Important improvements
- wear characteristics
- creep performance
- resistance to thermal distortion

All three metals are reactive and a strong affinity for oxygen

Troublesome for production of composites – chemical reaction at

the interface between the matrix and the reinforcements
(especially troublesome for Ti)
Ceramic Matrices
Four main classes

• Glass ceramics

• Conventional ceramics (SiC, Si3N4, AL2O3, ZrO2)

• Cement & Concrete

• Carbon / Carbon
Glass ceramics
Complex glasss forming oxides e.g., borosilicates and aluminosilicates
– heat treated – crystalline phase precipitates to form a fine
dispersion in the glassy phase.

• Lower softening temperatures than crystalline ceramics

• Easier to fabricate
Conventional ceramics (SiC, Si3N4, AL2O3, ZrO2)

• Fully crystalline – crystalline grains randomly oriented

• Interest in layered ceramic structures in which sheets produced by a

powder route are separated by thin weak interlayers such as graphite.

• No fibres involved classification as composite marginal.

• Main attraction – relative ease of processing

Cement & Concrete

• Usually short fiber added for reinforcement in such a way that

moulding capabilities are not severly impaired.

Carbon / Carbon

Specialised advanced composites

Produced by vapor infiltration of an array of carbon fibers or by carbon

fibers in polymer matris – pyrolysed and densified
The reinforcing material
Engineer’s problem – Materials are never as strong as expected.

Reason: All materials contain defects of various kinds.

Glass & ceramic – strong covalent and ionic bonds but many tiny
pores or sharp cracks either on the surface or in the interior.
The most highly polished and dense ceramic – very rarely exceeds
1000th of the theoretical predicted strength.

Metals – faults in stacking of atoms in their crystalline array –

dislocations – shear strength 1000th or less of the theoretical value
Strength of any sample is actually determined by the size of the
largest crack.

2𝐸γ
Griffith σmax = where E is Young’s modulus, γ is
π𝑎
surface energy and 𝑎 is the flaw size

By reducing flaw size strength of the material can be raised.

Example:

Glass fibre – molten glass drawn to fine filament (10 μm) – free of
macroscopic defects + fibre too fine to contain defects of the size
found in bulk glass.

Freshly drawn glass fibre strength – 5 Gpa

Bulk glass strength – 100 Mpa

Need protection from abrasion and corrosion by moisture.
Other examples are Carbon fiber, SiC, aromatic polyamide, etc.

Comparing with steel (piano wire) – these fibrous materials are

very appealing to engineers particularly on a strength/ density
or stiffness/density basis.

Since it is the reinforcing fibres that provide high strength and

stiffness combined with low density it is worthwhile to examine
them in a little more detail.
Functions of Reinforcements
Reinforcements are important constituents of a composite material.
Its main functions in a composite are:

• To carry the load. In a structural composite, 70 to 90% of the

load is carried by fibres.

• To provide stiffness, strength, thermal stability, and other

structural properties in the composites.

• To provide electrical conductivity or insulation, depending on the

type of fibre used.
 Some of the common types of reinforcements include:
• Continuous fibres (carbon tow, glass roving, aramid yarn)
• Discontinuous chopped fibres
• Woven fabric
• Multidirectional fabric (stitch bonded for three-dimensional properties)
• Stapled
• Woven or knitted three-dimensional preforms

The properties strongly depend on the way the fibers are laid in the
composites. All of the above combinations or only one form can be used in a
composite.
 Forms of Fibre Reinforcement in Composites

Depending on the type of application (structural or nonstructural)

and manufacturing method, the fiber form is selected.

 For structural applications, continuous fibers or long fibers are

recommended.
 For nonstructural applications, short fibers are recommended.
 Injection and compression molding utilize short fibers.
 Filament winding, pultrusion, and roll wrapping use
continuous fibers.
Long continuous fibers in the
direction of the load result in a
composite with properties far
exceeding the matrix resin
itself.
The same material chopped
into short lengths yields lower
properties than continuous (c)
(a) (b)
fibers.
(a) continuous and aligned, (b) discontinuous
and aligned, and
(c) discontinuous and randomly oriented
Even though reinforcement efficiency is lower for
discontinuous than for continuous fibers, discontinuous
(short length) fiber composites are becoming important in
the commercial market because of lower processing costs.

Chopped glass fibers are used extensively in polyester

matrices.

Tensile strengths of these short fiber composites can

approach 50% of their continuous fiber counterparts.
The most common reinforcing fibers are of glass, carbon, aramid and boron.

These are thin rodlike structures.

Typical fiber diameters range from 5 μm to 20 μm. The diameter of a glass

fiber is in the range of 5 to 25 μm, a carbon fiber is 5 to 8 μm, an aramid fiber
is 12.5 μm, and a boron fiber is 100 μm.

Such small sizes are difficult to handle.

Useful form of commercial fibers is a bundle produced by gathering a large
number of continuous filaments either in untwisted or twisted form.

Because of the thin diameter, the fiber is flexible and easily conforms to
various shapes.
Fibers are made into:
• strands ─ untwisted form for glass and Kevlar fibers
(for weaving or winding operations)
• tow ─ an untwisted bundle of carbon fibers
Rovings
• roving ─ collected and wound around a bobbin
(for delivery purpose)
• yarn ─ twisted form

Yarns

Twisted fiber bundle Untwisted bundle of Group of untwisted

(yarn) carbon fibers (tow) parallel strands
Fibers are the principal constituents in a fibre-reinforced composite material
and occupy the largest volume fraction in a composite laminate.

Fibers share the major portion of the load acting on a composite structure.
Proper selection of the fiber type, fiber volume fraction, fiber length, and
fiber orientation is very important, since it influences the following
characteristics of a composite laminate:
1. Density
2. Tensile strength and modulus
3. Compressive strength and modulus
4. Fatigue strength as well as fatigue failure mechanisms
5. Electrical and thermal conductivities
6. Cost
Glass Fibers
Glass is widely used as a material for reinforcing fibers due to its
following properties:

• Readily available and inexpensive material

• Simple and inexpensive technology of preparation of continuous
fibers from molten glass
• High tensile strength, which may reach 4100 MPa
• High corrosion resistance.
The types of glass used for fiberglasses are as follows:

E-Glass – the most popular and inexpensive glass fibers. Excellent insulator.
Composition : 52-56% SiO2, 12-16% Al2O3, 16-25% CaO, and 8-13% B2O3

S-Glass – stronger than E-Glass fibers. Used in military applications and in

aerospace. It consists of silica (SiO2), magnesia (MgO), alumina (Al2O3).

S+R-Glass – the strongest and most expensive glass fibers of low diameter
(half of that of E-Glass fibers).

C-Glass – corrosion and chemical resistant glass fibers. Used for

manufacturing storage tanks, pipes and other chemical resistant equipment.
 Glass Fibers

Glass fibers are produced by

 drawing monofilaments of glass
from a furnace containing molten
glass,
 coating the monofilaments with a
polymer to "dull" any surface
cracking, and
 gathering a large number of these
filaments to form a strand of glass
fibers.
The strands then are used to make glass fiber yarns, or rovings that
consist of a collection of bundles of continuous filaments.

Twisted fiber bundle

(yarn)
Continuous strand roving

Glass fibres are first wound into spools or bobbins after which they
can be either used in traditional textile processes such as weaving
or transformed into other forms.
Continuous glass fibres can
be woven with a variety of
different weaves to produce a
cloth which then can be
impregnated with a resin and
placed in a mould to form the
composite.
Long glass fibres can also be
randomly laid out to make a
non-woven mat. The size on
the fibres is used to hold them
together before the mat is
impregnated with the resin.
The glass fibres can be
chopped into lengths generally
between 5 and 75 mm in
length and used to produce
chopped strand mat or sheet
moulded compound. The size
on the fibres is used to hold
them together.
Glass fibres can be extruded in
a continuous form together with
a thermoplastic such as
polyamide and then chopped to
lengths of around 20 mm to be
used in injection moulding.
The most popular matrix materials for manufacturing fiberglasses are
thermosets such as unsaturated polyesters (UP), epoxies (EP) and
thermoplastics such as nylon (polyamide), polycarbonate (PC), polystyrene
(PS), polyvinylchloride (PVC).

Concentration of glass fibers in fiberglass is normally about 40% - 70%.

Glass fibers reinforced polymer matrix composites are manufactured by
open mold processes, closed mold processes and Pultrusion method.
Laminate structure
Fiberglass materials usually have laminate structure.
A large number of fibers are incorporated into a thin layer (0.1–1 mm) of
matrix (also containing coupling agent or fiber surface coating + fillers and
other additives) to form a lamina (ply).
Various glass fibers orientations result in anisotropy of the material
properties in the plane parallel to the laminates.

unidirectional orientation bidirectional orientation multidirectional orientation

The bi- or multidirectional orientation of fibers is obtained by weaving

or other processes used in the textile industry.
A lamina can also be constructed using discontinuous (short) fibers.

Unidirectional orientation Random orientation

Stacking several laminas in a specified sequence and then consolidating

them to form a laminate. Various laminas in a laminate may contain fibers
either all in one direction or in different directions.

Laminate (consolidated stack of many layers)

 Fiberglasses (Glass fibers reinforced polymer matrix composites)
are characterized by the following properties:
 High strength-to-weight ratio;
 High modulus of elasticity-to-weight ratio;
 Good corrosion resistance;
 Good insulating properties;
 Low thermal resistance (as compared to metals and ceramics).

Fiberglass materials are used for manufacturing: boat hulls and marine
structures, automobile and truck body panels, pressure vessels, aircraft
wings and fuselage sections, housings for radar systems, swimming
pools, welding helmets, roofs, pipes.
Carbon Fibers

 Carbon fibers are very expensive but they have a combination of

very high strength, low density, and high elastic modulus. These
properties make the use of carbon fiber-plastic composite
materials especially attractive for aerospace applications.

 The reinforcing dispersed phase may be in form of either

continuous or discontinuous carbon fibers of diameter about
0.0004” commonly woven into a cloth.
 Carbon fibers are produced mainly from two sources,
polyacrylonitrile (PAN) and pitch, which are called precursors.
 In general, carbon fibers are produced from PAN precursor
fibers by three processing stages:

(1) stabilization, (2) carbonization, and (3) graphitization.

1. Stabilization stage

The PAN fibers are first stretched to align the fibrillar

networks within each fiber parallel to the fiber axis.
Then they are oxidized in air at about 200-220°C while held
in tension in order to provide cross-linking between the
fibrils to avoid melting at the next stage.

Figure shows how the linear PAN molecule is converted to a

ladder structure by the introduction of oxygen.
2. Carbonization stage

The cross-linked fibrils are pyrolated

(heated) under a nitrogen atmosphere
which leads to the loss of the O and H
so that at 1000 °C only C and about
7wt% of N remain.
Carbonization stage contd.

Heating to above 1000 °C progressively eliminates the nitrogen

and around 1500—1600 °C a wholly carbon fibre is achieved.

During the carbonization process, graphite like fibrils, or

ribbons, are formed within each fiber and provide the great
increase in tensile strength observed.
A high strength carbon fibre with a diameter
of 7 μm made from a PAN precursor.
3. Graphitization stage

It involves complete conversion of the fiber to oriented

graphite crystal form by heating the fiber while under
tension to temperatures above 2000°C.

This graphitization procedure can raise the elastic

modulus to levels exceeding 250 GPa.
 High Tensile Strength Carbon Fibers

The graphitized filaments have high tensile modulus but

relatively low tensile strength.

Their tensile strength can be increased by hot stretching

them above 2000°C, during which the graphitic planes
align in the filament direction.
 5 min in N2 1 min in N2

2 – 3 hours

Fibrillar network aligned Crosslinked fibrils pyrolated. Complete conversion of the fiber
and crosslinked Graphite like fibrils formed. to oriented graphite crystal.
TS greatly increased. Modulus exceeds 250 GPa
 Carbon Fibers from pitch percursors

Pitch – a by-product of petroleum refining or

coal coking , lower cost than PAN

• Carbon atoms arranged in low mol wt aromatic

ring patterns.

• Heating above 300°C polymerizes – joins these

molecules in 2 dimensional, sheet like
structures. Highly viscous state – mesophase.

• Melt spinning mesophase. While passing

through spinneret, mesophase pitch molecules Alignment of mesophase
become aligned in the filament direction. pitch into a pitch filament
 Carbon Fibers from pitch percursors

• Filaments cooled to freeze the orientation

• Next heated between 250°C to 400°C in oxygen atmosphere to

stabilize them and to make them infusible.

• Filaments are carburized at around 2000°C.

Rest of the process is similar to that PAN percursors.

Multistage furnace High-temperature furnace
500 to 1500°C 1500 to 3000°C

↓
Carbon fibers are used for reinforcing polymer matrix due to their
following properties:

Very high modulus of elasticity (3.10 to 4.45 Gpa) exceeding that

of steel;
High tensile strength (3.10 to 4.45 Gpa) which may reach 7 GPa;
Low density: 1800 kg/m³;
High chemical inertness
fiber diameters of 7 µm to 10 µm

The main disadvantage of carbon (Graphite) fibers is catastrophic

mode of failure (carbon fibers are brittle).
The types of carbon fibers are as follows:
UHM (ultra high modulus). Modulus of elasticity > 450GPa
HM (high modulus). Modulus of elasticity is in the range 350-450GPa
IM (intermediate modulus). Modulus of elasticity is in the range 200-
350GPa
HT (high tensile, low modulus). Tensile strength > 3 GPa, modulus of
elasticity < 100 GPa
SHT (super high tensile). Tensile strength > 4.5GPa
The most popular matrix materials for manufacturing Carbon Fiber
Reinforced Polymers (CFRP) are thermosets such as epoxy, polyester
and thermoplastics such as nylon (polyamide).

CFRP materials usually have laminate structure, providing reinforcing

in two perpendicular directions.

CFRP are manufactured by open mold processes, closed mold

processes and Pultrusion method.

CFRP are used for manufacturing: automotive marine and aerospace

parts, sport goods (golf clubs, skis, tennis racquets, fishing rods),
bicycle frames.
CFRP are characterized by the following properties:
Light weight;
High strength-to-weight ratio;
Very High modulus elasticity-to-weight ratio;
High Fatigue strength;
Good corrosion resistance;
Very low coefficient of thermal expansion;
Low impact resistance;
High electric conductivity;
High cost.
Aramid Fibers

Originally developed as a replacement of steel in automotive

tires.
Aramid fibers ( Kevlar ) is a low-density, high-strength fiber
(T.S. = 3620 Mpa) designed for such applications as ropes,
cables, and even ballistic armor.

The properties of Kevlar 49 make it useful as reinforcement

for plastics in composites for the aerospace, marine, and
automotive industries as well as many other applications.
 chemical repeating unit of Kevlar

Kevlar polymer chain

Extrusion imparts anisotropy to the filaments.

Strength is increased in the lengthwise direction.
During drawing molecules are oriented.
The aromatic ring structure gives high rigidity to the polymer
chains, causing them to have a rodlike structure.
Strong covalent bonding in the polymer chains provides the
strength and high elastic modulus character.
Kevlar aramid is used for high-performance composite applications
where light weight, high strength, stiffness, impact and fatigue
resistance are important.
Kevlar fibers possess the following properties:
 High tensile strength (five times stronger per weight unit than steel);
 High modulus of elasticity;
 Very low elongation up to breaking point;
 Low weight;
 High chemical inertness;
 Very low coefficient of thermal expansion;
 High Fracture Toughness (impact resistance);
 High cut resistance;
 Textile processibility;
 Flame resistance.
The disadvantages of Kevlar are:
• ability to absorb moisture
• difficulties in cutting and machining
• low compressive strength
Kevlar may protect carbon fibers and improve their
properties: hybrid fabric (Kevlar + Carbon fibers) combines
very high tensile strength with high impact and abrasion
resistance.

The most popular matrix materials for manufacturing Aramid

Fiber Reinforced Polymers are Thermosets such as Epoxies
(EP), Vinylester and Phenolics (PF).

Kevlar Fiber Reinforced Polymers are manufactured by open

mold processes, closed mold processes and Pultrusion
method.
SIC Fibers

The most important nonoxide ceramic fiber.

• It has rough surface – good for fibre/matrix adhesion but

somewhat reactive towards oxygen.
• Well wetted by molten metals.
• Reasonably stable as a reinforcement for MMCs based
on Al & Cu.

Major application in metal – and ceramic – matrix composites

CVD process of making fibers are:
• A coating is deposited on a fibrous substrate
resulting in a large dia sheath with a core, i.e., the
fiber itself is a composite.
• No stretching or drawing. Lateral growth by
thickening occurs.
• Final dia of the fiber ~ 10 times that of the starting
fiber substrate.
Ex: B(W) — Boron on a tungsten substrate
and SiC(C) — SiC on a carbon substrate
Boron on a carbon substrate is also possible.
Boron Fibers
The boron is chemically vapor deposited onto a moving
tungsten filament to provide a continuous boron fiber.

Typical boron fiber dia : 75, 100, 140, 200 pm, with 100 pm being
the most common.

Boron has high strength and high stiffness.

B(W) fibers find applications mostly in aerospace and the

sporting goods industry.
The SiC barrier layer is vapor deposited
onto the boron to prevent any adverse
reaction between B and the matrix, such
as Al or Ti, at high temperatures.

Major drawbacks of most CVD produced

fibers are there large diameter (which
makes them less flexible) and high cost.
 Fiber Surface Treatments

During production the fibrers are treated with a fluid.

• It improves the surface wettability with the matrix

• Create a strong bond at the fiber-matrix interface

Both are essential for effective reinforcement.

Glass Fibre Finishes
Sizing
Glass fibre rovings that are to be used in direct fibre processes are
treated with a 'dual-function' finish at the point of fibre manufacture.
This finish performs several functions.

(a) it facilitates the production of strands from individual fibres

(b) it reduces damage to fibres during mechanical handling and
(c) it acts as a process aid during moulding.
(d) it improves bonding between fibers and the matrix
This treatment is known as sizing.
The size is a mixture of
• lubricants → prevents abrasion between the filaments
• antistatic agents → reduce antistatic friction between the filaments
• binder → packs the filaments together into a strand

May also contain small percentage of a coupling agent that promotes

adhesion between the matrix and the fibers.
Surface treatment for Glass fibers

Chemical coupling agents are used for the surface treatment of glass
fibers

(1) to improve the fiber/matrix interfacial strength and

(2) to protect the fiber surface from moisture and reactive fluids.

Before treating glass fiber with a coupling agent, its surface must be
cleaned from the size (which is often starch based) at the time of
forming.
It is done either by heating the fiber in an air circulating oven at 340 C
for 15 – 20 h or with chemicals.
The scoured glass fibers or woven fabric is then immersed into the
aqueous solution of a silane.

R’ – Si(OR)3 + 3H2O R’ – Si(OH)3 + 3HOR

Chemical bonds (Si – O – Si) as well as physical bonds (hydrogen

bonds) are established between OH groups on the glass fiber surface
(hygroscopic) and R’ – Si(OH)3 molecules.
When treated glass fibers are incorporated into a resin matrix, the
functional group R’ in the silane film reacts with the resin to form a
coupling between fiber and matrix.
Fiber–matrix coupling effect :
Fracture surfaces of uncoupled (Fig. a) and coupled
(Fig. b), fiber-reinforced epoxies are compared.

In the uncoupled system the interfacial failure is

characterized by clean fiber surfaces, thin cracks
(debonding) between fibers and matrix, and clear (a)
impressions in the matrix from which the fibers have
pulled out or separated.

In the coupled system strong interfacial strength is

characterized by fiber surfaces coated with thin layers
of matrix and the absence of fiber–matrix debonding
as well as absence of clear fiber surface impressions
in the matrix. Cohesive failure in the matrix.
(b)
 SEM micrograph of Injection moulded PP with short glass fibres

Without coupling agent With coupling agent

Hull & Clyne

The interfacial bond created by silanes or other coupling agents allows
a better load stress transfer between fibers and matrix, which in turn
improves the tensile strength as well as the interlaminar shear strength
of the composite.
However, the extent of strength improvement depends on the
compatibility of the coupling agent with the matrix resin.
Although a strong interface produces higher strength, a relatively
weaker interface may contribute to higher energy dissipation through
debonding at the fiber–matrix interface, which may be beneficial for
attaining higher fracture toughness.
Carbon Fibre Finishes

Carbon fiber surfaces are chemically inactive and must be treated to

form surface functional groups that promote good chemical bonding
with the polymer matrix.

Surface treatments also increase the surface area by creating

micropores or surface pits on already porous carbon fiber surface.
Increase in surface area provides a larger number of contact points for
fiber–matrix bonding.
Treatments for carbon fibers are of two types, oxidative or nonoxidative

Concentration depend on the end use of the fibre.

• For weaving the size level is about 1-2% by weight

• For tape prepregging or filament winding (or similar single-fibre
processes), the size level is about 0.5-1%.

The chemistry and level of the size are important not only for protection and
matrix compatibility but also because they effect the degree of spread of the
fibre.

Unsized fibers will be prone to broken filaments caused by general handling.

Most carbon fibre suppliers offer 3-4 levels of size for each grade of fibre.
Aramid Fibre Finishes
Aramid fibres are treated with a finish at the point of manufacture
primarily for matrix compatibility. This is because aramid fibres require
far less protection from damage caused by fibre handling.

Two methods have been successful in improving the interfacial

adhesion of aramid fibers with epoxy resin :
1. Filament surface oxidation or plasma etching
2. Formation of reactive groups (amines (NH2), on the fiber surface
The main types of fibre treatment are:

• Composite finish
• Rubber compatible finish (belts and tyres) and
• Waterproof finish (ballistic soft armour)

Like the carbon fibre finishes, there are differing levels of

composite application finish depending on the type of process in
which the fibre will be used.
Interfacial properties and contribution to composite properties

Key questions for the developer of a sizing to ask are:

1. Which resin needs to be reinforced by the fiber?

2. Which process will be used to make a composite part with that

particular resin - reinforcement combination?

3. What requirements does the final composite part need to meet?

Styles of reinforcement
• Semi-continuous sheets of ‘prepregs’

• Woven fabrics

• Nonwoven (noncrimp) fabrics

• Chopped fibers aligned - in the form of prepregs, mats etc.

Prepregs

Single layers of fibre tows impregnated with the required matrix

resin and flattened between paper career sheets.

Stacked in different direction as per design requirement and hot

pressed to consolidate the laminate.
Woven fabrics
Used in trailers, containers, barge covers, and water tower blades, and in
other marine wet lay-up applications.
These fabrics are woven yarns, rovings, or tows in mat form in a single layer.

two sets of yarns interlaced at right angles

Unidirectional woven fabrics : Fibers in

0° are up to 95% of the total weight of
the fabric.
Plain-weave pattern : Fibers in 0° and Common weave styles
90° directions are equally distributed.
 carbon fabrics in a variety of weave styles Glass and carbon fibers

Hybrid fabrics in various combinations : glass/carbon and aramid/carbon

For lightning strike purposes : conductive wires are woven into fabric.

Woven fabrics are also used to make prepregs, as well as in RTM and SRIM
processes as feedstock.

Woven fabrics are inexpensive.

Noncrimp Fabrics
Yarns are placed parallel to each other and
then stitched together using polyester thread.

Warp unidirectional fabric is used when fibers are needed in one direction
only, for example, in stiffness-critical applications such as water ski
applications where the fabric is laid along the length of the ski to improve
resistance to bending.
Weft unidirectional fabrics, reinforcements are laid at 90°
(or weft direction) only.

Weft fabrics are typically used in filament wound

tubes and pipes and also pultruded components
where reinforcement in the weft direction is
necessary.

Warp triaxial (0°, ±45°) fabric : used to increase

longitudinal stiffness and torsional rigidity.
Weft triaxial (90°, ±45°) fabric : used to increase
transverse stiffness and torsional rigidity.
Noncrimp fabrics
• offer greater flexibility compared to woven fabrics.
• fibers can be laid at almost any angle from 0° to 90°, including 45°, 90°,
30°, 60°, and 22°, and then stitched to make multiaxial stitched plies.
• are available in a thick layer and thus an entire laminate could be
achieved in a single-layer fabric.
Woven fabrics : Made from rovings mostly on the 0° and 90° axes.
Noncrimp fabrics offer greater strength because fibers remain straight;
whereas in woven fabrics, fibers bend over each other.

This is useful in making thicker laminates such as boat hulls and reduces
the number of fabrication steps.
END
 Hydrolysis of organo silane to silanol

(b)

Hydrogen bonding between hydroxyl groups of the

silanol and those attached to the glass surface
 (c)

Polysiloxane bonded to the glass after condensation reactions during drying

(d)

Bonding between the functional group R and the polymer matrix

FILLERS AND OTHER ADDITIVES

Fillers are added to a polymer matrix for one or more of the

following reasons:
1. Reduce cost
2. Increase modulus
3. Reduce mold shrinkage
4. Control viscosity
5. Produce smoother surface
The most common filler for polyester and vinyl ester resins is calcium
carbon ate (CaCO3), which is used to reduce cost as well as mold
shrinkage. Examples of other fillers are clay, mica, and glass micro
spheres (solid as well as hollow ).
Although fillers increase the modulus of an unreinforced matrix, they
tend to reduce its strength and impact resistance .
Properties of Calcium Carbonate-Filled Polyester Resin
Property Unfilled Polyester Filled with 30 phr
Density, g/cm3 1.30 1.48
HDT, ⁰C 79 83
Flexural strength, MPa 121 62
Flexural modulus, GPa 4.34 7.1
Impact strength and crack resistance of brittle thermosetting polymers
can be improved by mixing them with small amounts of a liquid
elastomeric toughener, such as carboxyl-terminated polybutadiene
acrylonitrile (CTBN ).

In addition to fillers and tougheners, colorants, flame retardants, and

ultraviolet (UV) absorbers may also be added to the matrix resin