AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

ADVANCED POLYMER COMPOSITES: PROPERTIES,

DEGRADATION AND DAMAGE MECHANISMS
AC Niranjanappa
Centre for Air Borne Systems, Bangalore

INTRODUCTION
Composite materials are of great interest due to
their light weight, high specific strength, high specific
modulus, directional properties and a wide variety
of possible applications. Of all the types of
composite materials, polymer matrix composites
(PMC) are very popular and are extensively used
in aerospace applications like aircraft wing,
fuselage, helicopter body, rotors, radomes, etc. The
polymer composites used in aerospace are generally
referred as advanced polymer composites due to
their high specific strength and high specific
modulus, as compared to other general purpose
polymer composites that are referred to as simply
Fibre Reinforced Plastics (FRP).
Among the polymer composites, the carbon
fibre, glass fibre, and aramid fibre reinforced with
thermoset resins like epoxy and polyester are well
known. These materials contribute to high
performance due to their basic structure and also
due to the strong bond formed at the fibre/matrix
interface. Thus, their properties and strength can
be attributed to these factors. Because of their
strong structural characteristics and combined with
their low specific gravities (of the order of 1.5 to
2.5), they have very high specific strengths as
compared to conventional structural materials like
wood, steel and aluminum.
Though polymer composites offer many
advantages with respect to specific strength and
modulus, they are not free from problems. Polymers
are known to degrade under service environments.
Especially the combined effect of moisture and

temperature (called the hypothermal condition) is

the most severe of all, which plasticises the resin
and reduces the strength of the composite material.
Other degradation effects include photo-oxidation
(heat plus ultraviolet radiation, cause polymer chain
scission), thermal cycling (changes in the
operational temperatures), etc., which also cause
reduction in the strength and the performance of
composites.
Unlike metals, which are homogeneous
structures, polymer composites are heterogeneous
and have complex damage mechanisms. In metals
the process of crack initiation, crack growth and
failure process is fairly well established and
understood, whereas in polymer composites, it is
an unfinished area and efforts are being made world
wide to study the damage mechanisms. This paper
will highlight some aspects of polymer composites,
their properties, degradation, and damage
mechanisms at the basic level.
Composites in the field of Materials

Man has always been using one or the kind of

material in his life from the ancient times. Materials
have been one of the important contributors in the
evolution of life and growth of technology. In fact,
the human civilization is designated on the basis of
materials used like the Stone Age, Bronze Age,
Iron Age, and Synthetic Age. The twentieth century
was the Synthetic Age, which began with the
introduction of plastics, later with the development
of composite materials and ended with the smart
materials and structures (Fig. 1). Also in the later
part of 20 th century there was a tremendous

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National Science Day Orations 2003

phase). Out of these two, the matrix is the weakest part, while reinforcement is the strongest part,
but as a composite system, the material will attain

CIVILISATION
STONE AGE

C om posite

BRONZE AGE
R einforcem e nt

Stress

IRON AGE
SYNTHETIC AGE

M atrix

PLASTICS

SMART

COMPOSITES

Fig. 1

Strain

Materials Classification

Fig. 3

As we all know, at the element level materials are

classified as metals (Al, Cu, Ag, etc.), non-materials (As, Ge etc.) and intermediates (Si, As, Ge,
etc.). Since the composition of most polymeric
composites is made up of carbon, nitrogen, oxygen, hydrogen etc. obviously they are non-metallic in nature. Based on the atomic structure, earlier materials were classified as metals, ceramics,
and polymers. Later, the other classes were included as electronic materials and composite materials (see Fig. 2).
MATERIALS

METALS

CERAMICS

ELECTRONIC
MATERIALS

Origin of Composite Materials

Composite materials are not new inventions. In

fact, composite materials existed in nature itself.
Thus nature is the origin of these materials. Most
living organisms have composite structures that
make them function efficiently and for a longer
life. For example, the microstructure of wood and
bone. Tree is a natural composite, which comprises
the cellulose, the fibrous material that acts as the
reinforcement and lignin, a natural polymer that
acts as the matrix. These two constituents together
form the cell walls in the wood and its structure
(Fig. 4a & b).

POLYMERS

COMPOSITE
MATERIALS

Fig. 2

What are Composite Materials?

Composite materials are basically heterogeneous

materials, having two or more physically distinct
components, when combined together they become
stronger and stiffer and perform superior to each
of the distinct components. In general, a composite material consists of a matrix (the continuous
phase) and a reinforcement (the intermittent

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Fig. 4

Bone, the framework of the living beings is another natural composite. The human bone is made
of collagen, the organic fibrous material (about
35% by weight), that acts as the reinforcement
and the bone tissue is a mineral, containing mostly
calcium, phosphate and carbonate, that acts as the
matrix (about 65% by weight). We all know that
this combination of collagen and mineral is strong
and durable.

AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

Composites in Ancient Times

Mankind has been exploiting the concept of composite materials since the ancient times. During
1500 BC, Egyptians used bamboo shoots as reinforcement to construct strong mud walls. Israelites were manufacturing bricks reinforced with
straw. They were constructing boats by embedding papyrus reeds in bitumen. People built powerful bows using wood, animal tendons, silk and
suitable adhesives. Japanese made composite
swords (popularly known as Samurai) using alternate laminated layers of steel and iron.
Growth of Composites in the 20th Century

The growth of modern composites started in the

early 1900s with the invention of various resins.
The first thermoset resin introduced in 1909 was
the phenolic. However, it did not become a popular matrix material as it was a hot cure type, involved complex processing and also it was expensive. Gradually the easy to process and economical polyester and epoxy resins were developed and
introduced in USA and Europe (between 1909 and
1947). In fact, in the early 1940s, the real growth
of structural composite began under the pressure
of World War II. In 1940, the complete aircraft
fuselage of Spitfire aircraft was built using flax
fibers (natural plant fibre) and phenolic resin in
UK. In 1942, USA constructed antenna radomes
for aircraft using glass fibre and polyester resin.
In the 1950s, the term Fibre Reinforced Plastic
(FRP), became well known and grew as a technology. It was used to build boat hulls, car bodies,
tanks, helmets, and containers for chemical industries. Gradually, many cold cure thermoset resins
were introduced, which made the fabrication and
processing easier. Though, the thermoplastics were
available and resolution used the modern world with
various plastic products, they were not suitable as
the matrix material in composites due to their low
strength, low thermal stability, and high processing
costs (now PEEK - Polyetheretherketone - an
advanced thermoplastic is used as a matrix material in some advanced composites).
Among the fibres, though the technology of
glass fibres existed for long, the fibres suitable for
structural components were introduced in 1937 by

Owens-Corning. In 1966, the boron fibre, the strongest of all fibres, was introduced. However, it was
very expensive, not suitable with general resins
available. In 1968, the carbon fibres suitable for
structural composites were introduced and later in
1972 aramid fibres developed by M/s Du Pont were
introduced for use. The aramid fibre of Du-Port is
known by popular trade name Kevlar and is widely
used in armour and aircraft.
Classification of Composites

Composite materials are classified based on the

type of matrix and on the type of reinforcements.
Based on the matrix, composites are classified as
Polymer Matrix Composites (PMC), Metal Matrix Composites (MMC) and Ceramic Matrix Composites (CMC). This classification along with the
type of matrix materials/fibres used is illustrated
in Fig. 5.
COM POSITE MATERIALS

Polym er Matrix
Com posites (PMC)

Glass, Carbon, Kevlar /

Epoxy, polyester, PEEK

Metal M atrix
Com posites (MM C)

Carbon, SiC, W, TiC /

Copper, Al, Iron

Ceram ic Matrix
Com posites (CM C)

Carbon, SiC, / Alumina,

calcium alumino silicate

Fig. 5

Based on the type of reinforcement, the composites are classified into three types - particulate
composites, fibrous composites and structural composites. Further, the particulate composites can be
either dispersion strengthened or large particle type;
the fibrous composites can be either short fibre or
long/continuous fibre type and the structural composites can be either laminar or sandwich composites.
In fact, the laminar and sandwich composites,
made using polymeric composite materials can be
considered as a subsection of continuous fibre composites (Fig. 6).
In this paper we will discuss only on the polymer matrix laminar composites. The schematic representation of fibrous, laminar and sandwich com

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National Science Day Orations 2003

COMPOSITE MATERIALS

Particulate

Dispersion
Strengthened
Large particle

Fibrous

Long / continuous fibre

Short fibre

Structural

Laminar
composites
Sandwich

Fig. 6

(a) Fibrous

(b) Laminar

(c) Sandwich
Fig. 7

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AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

Laminar composites are made by laying a number

of lamina one above the other, consolidating and
then curing. Sandwich composites are made by
incorporating a core (either honeycomb of foam)
between two thin laminates, called face sheets.
Metals Versus Composites

Before we understand the structures and properties of composite materials, let us briefly look into
the structures and formation of metals, so that we
can compare composites with them.
Formation of Metals and Alloys

We know that metals are crystalline in nature. The

structure of a metal forms at the atomic level. The
atoms occupy a fixed position to give a definite
crystal structure like Face Centre Cubic (FCC),
Body Centre Cubic (BCC), Close Packed Hexagonal (HCP) etc. The basic crystal structure is
termed a unit cell. When the metal is in a liquid
state, no such crystal structure exists. When the
molten metal cools down to the freezing point, the
atoms at some points arrange themselves to the
unit cell shape (called nucleation), and then the
structure starts growing around such base units in
three dimension and become grains. When the
crystals meet each other they form the grain boundary.
In the case of alloys, solute atoms (alloying
elements) either occupy the intermediate positions
between the solvent (base element) atoms (called
interstitial) or replace the solvent atoms in the crystal structure (called substitutional). In such a case,
the unit cell itself may get changed (for example
the occupation of an intermediate position by the
carbon atom in a BCC cell of iron changes it into a
tetragonal structure). The type of alloy formation
depends on the sizes of the solute and solvent atoms. When the liquid alloy is cooled down, the process of nucleation and grain growth takes place
similar to metals.
Formation of Polymers

Polymer matrix composites are heterogeneous

materials, made up of amorphous polymers and
fibres (certain fibres like carbon/graphite are

crystalline). In the case of polymers, they are made

of macromolecules of hydrocarbons; each made
of a combination of elements like H, C, N, O, etc.
Hence, the macromolecule becomes the base unit
(mer unit) in the formation of the polymer. In each
of these mer units, the atoms are bound together
by strong covalent bonds. Each of these mer units
are held together in the form of long and flexible
chains, for which a string of carbon atoms
becomes the backbone. Polymers may have
molecular structures with long continuous chains,
branched chains, or cross-linked network. The type
of molecular structure decides the strength and
stiffness of the polymers. Polymers, which have
only long continuous and branched chains are
generally weak and are termed as thermoplastics.
The polymers with cross-linked structures are
strong and are termed as thermosets. A typical
mer unit of a polymer and the different chain
structures are schematically illustrated in Fig. 8.
Formation of Composites

When the fibres are embedded in a polymer matrix

and cured, the matrix undergoes polymerisation (a
chemical reaction), by which the linear/branched/
cross-linked chains are formed, and the composite
becomes a strong structure. The fibres and the
matrix will form a strong interface and become
the source of strength. Due to this heterogeneity
composites offer anisotropic and directional
properties, unlike metals and alloys that are
homogeneous and offer isotropic properties.
Advantages of Composites

Some of the advantages of polymer composites

are briefly out lined below:

They are light in weight, about 2 to 5 times lighter as

compared to conventional structural materials like

aluminum and steel.
They give high specific strength (i.e. strength to
weight ratio), which is about 4 to 6 times as
compared to aluminum and steel.
Their specific stiffness is much higher, about 3 to 5
times that of aluminum and steel.
They have good chemical resistance and durability.
Compared to metals, polymer composites are known
to have a longer fatigue life.
Polymer composites are suitable to fabricate complex
shapes and in many instances it is possible to

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National Science Day Orations 2003

a) Mer unit

b) Linar

d) Cross-linked

c) Branched

e) Cross linked (3d network)

Fig. 8

obtain near net shape of the component.

Most polymer matrices along with glass and aramid

fibres are transparent to electromagnetic waves.
Hence, they are suitable as radome materials.

fields are mentioned as follows:

General: The most familiar use of polymer composite

Drawbacks of Polymer Composites

Composite materials are not without problems.

Some of their drawbacks are as follows:

Most composite materials are very expensive, they

require special machinery for fabrication. Also, the

processes cannot be automated, unlike in metals.
The inspection/testing of polymer composites is a
difficult area. They require special techniques and
equipment.
Since polymer composites are bad electrical
conductors, they generally require lightning
protection, especially when used in aircraft
applications and in radomes.
Most polymers are vulnerable to environmental
degradation. The most affecting features are the
hygrothermal conditions and degradation by
photo-oxidation of polymers.
As compared to metals, polymer matrices are brittle,
do not undergo plastic deformation and hence have
a low damage tolerance.

Application of polymer Composites

Polymer composite materials are being used in all

parts of life. Some common examples in various

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is helmet, used to protect the head from injuries,

while driving or in factories, and mines. Helmets
are made of glass fibres and polyester resins. Many
garden tools are made of carbon-epoxy composites
as they very light, strong and durable. PMCs are
being used for making furniture also.
Transportation: Varieties of polymer composites
(both monolithic and sandwiches) are used in
automotive bodies, railway bogies, ships, boats
etc.
Civil Construction: In civil engineering, polymer
composites are used for the manufacture of doors,
window shutters, roof sheets, bridges etc.
Biomedical: Some special polymer composites are
finding applications in biomedical field like in the
manufacture of dentures, artificial limbs and human
organs like heart valves, etc.
Sports: In this area, tennis rackets, cycles, skis etc.
are made using carbon/epoxy composites.
Aerospace Industry: This is the field, which exploited
the composite materials extensively. Both military
and civil aircrafts use varying range of polymer
composites for primary and secondary structural
members. The modern fighter planes use about 4050% of composites by weight. In space
applications, rockets, space shuttles, satellites all
use composites.

The first ever use of polymer composites was

in 1940, by the Gorden Aerolite, UK. They used

AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

flax fibres (a natural plant fibre) with phenolic resin

and built the complete airframe for the aircraft
Spitfire. The untwisted flax fibre/phenolic composite
had a specific strength close to that of duraluminium
(about 170 GPa), which was the widely used
aluminium alloy for aircraft building in the early
twentieth century.
PROPERTIES
In this section let us see what are advanced
polymer matrix composites, their constituents,
types, their structures and properties.
What are Advanced Polymer Composites?

As mentioned polymer composites are those,

which have a polymer as the matrix with fibres as
the reinforcement. Among polymer composites,
there are two classes - Fibre Reinforced Plastics
(FRP) and the Advanced Polymer Composites.
FRP became a popular terminology in 1950s and
refers to general-purpose polymer composites.
They are characterised by low strength, short
fibres, low volume fraction (<50% fibres) and are
mostly made of short fibre glass with polyester or
epoxy resins. They find applications in the
manufacture of car bodies, roof sheets, doors,
boats, chemical containers, etc.
On the other hand, advanced polymer
composites are used in high performance
applications like in aerospace. They are
characterised by high volume fraction (60-65% of
fibres), continuous fibres, high fibre modules
(greater than 150 GPa) and may use glass, carbon,
aramid fibres with epoxy, polyester, phenolic resins.
The subsequent topics are mostly related to
advanced polymer composites, though some may
also be relevant to general composite materials.
Constituents of Polymer Composites

There are two primary constituents of an advanced

polymer composite - the reinforcement, generally
long continuous fibres and the matrix, some kind
of resins. In a composite material, the
reinforcement is the main load bearing member
(in tension) and it gives the necessary form and
shape to the component/structure. A matrix has

many functions, like it protects the fibre from the

environment, binds and holds the fibres together,
transfers the load between fibres and takes the
load in compression/ shear/ transverse directions.
Types of Matrices (Resins)

There are two types of polymer matrices, the

thermosets, and the thermoplastics.
Thermoset Matrices

These are highly viscous fluids, which are formed

to the required shape (mixing with the
reinforcement) and then cured. These can be either
room temperature or high temperature cured types,
depending upon their composition. These have high
strength and high temperature stability due to their
cross-linked structure (Fig. 9a). These are widely
used in both high performance and general FRP
composites. The commonly used thermoset resins
are epoxy, polyester, phenolic and bismaleimide
(BMI).

Fig. 9

Thermoplastic Matrices

These are generally solids, which are melted,

formed to the required shape, and then cooled.
Unlike the thermosets (which cannot be remelted
after curing), thermoplastics can be remelted and
reshaped. They have a long, linear chain structure
without any cross-linking (Fig. 9b). Hence, they
have low strength and suitable only for low
temperature applications.
They have better damage tolerance than
thermosets and generally used in thermosets to
enhance their damage tolerance. The important
thermoplastic resins are polyetheretherketone
(PEEK), , polyimide (PI), polyethersulfane (PES),
polyphenylsulfane (PPS), etc.

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National Science Day Orations 2003

Types of Fibres

Fibres are the reinforcement members used in

polymer composites. They have long axis and very
small diameter. There are three classes of fibres
whisker, fibres, and metallic wires. Whiskers
have small diameter (less than 10 mm) and are
about 1 to 10 mm long. The basic requirement of a
fibre to be referred as a whisker is that it must be
a single crystal, with high aspect ratio (length to
diameter). Since, whiskers are defect-free, they
are the strongest materials. They are very expensive and used in ceramic matrix composites.
Fibres are those, which are used in polymer
composites. They may be short or continuous in
form, having diameters ranging between 8 to 15
mm. They are either polycrystalline or amorphous
made of polymers/ceramics like glass, carbon and
aramid fibres.

Weave Patterns (Refer to Fig. 10)

In a woven fabric, the main or length direction (00)

is termed the warp along which the fibres run, while
the perpendicular or width direction (900) in which
the holding fibres run is termed the weft or fill.
Some of the different weave patterns are as
follows:

Plain Weave (linen weave): In this, one weft

fibre passes successively above and below
each warp fibre and inversely in the following
pass.

Twill Weave: In this, the warp and weft fibres

cross in a specific sequence/ frequency and
give a diagonal texture on the fabric. For
example in a 22 twill weave, each warp passes
above and below two weft fibres. This has a
better drape than the plain weave.

Satin Weave: In this each warp fibre passes

over three or more wefts and then under one.
When a warp passes continuously over four
wefts and below in the fifth weft, it is termed
five-harness satin weave. Satin weave is used
for fabrics that require improved formability.

Triaxial Weave (Doweave): In this each warp

will pass above and below wefts that are
diagonal (at about 600) to each other. These
are very stable, resist tearing, and offer
isotropic properties in the plane.

Unidirectional (Non-woven) Fabric: In this, the

fibres run mainly in the warp direction and it
has a least number of weft fibres to support
the warp fibres. Unidirectional fabrics offer the
highest advantage of formability and
directional properties. Most aerospace
applications use unidirectional fabrics to
achieve the required strength and stiffness.

3-D Fabrics: In this, in addition to the warp

and weft, a third fibre runs in the z-direction
(thickness). Thus it is suitable for thick fabrics
and used in preforms of certain shapes. The
fibre in the third direction gives higher strength
to the fabric and improves its damage tolerance.

Metallic wires (having diameters 0.5 to 1 mm)

made of steel, molybdenum and tungsten are used
in automotive tyres, high pressure hoses and rocket
motor casings.
Fabrics and Reinforcement Forms

Before we understand the fabric and reinforcement

forms, let us understand some fundamental
terminology used.

Fibre: It is a general term used to refer to a material

that has long fibre axis.

Filament: It represents one single fibre.

Strand: It is a collection of a number of filaments,
without any count.

Tow: It is also a collection of a number of filaments,

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but has a definite number, say about 5000 filaments

and it is not twisted.
Yarn: It can be considered as a twisted tow. It will
have about 40 turns per meter.
Roving: It is the bundled strands and generally
wound around a cylindrical holder for convenience
of handling.
Woven Roving: It is a two dimensional arrangement
of tows or yarns made using different weave
patterns.

AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

Fig. 10

Prepregs

When we use a fabric for the fabrication of a

component, we have to lay the fabric, apply the
required resin, consolidate by pressing with a roller,
then lay the fabric plus resin again, and continue
these steps. In such a case it is more laborious
and the resin control may not be good. For
aerospace applications, generally fabrics
preimpregnated with required amount resin, called
prepregs are used. Prepregs are manufactured
by dipping the fabric in a fluid resin, controlling the
resin quantity and then curing it partially to B-stage
(the viscous resin in uncured form is said to be in
A-stage, partially cured in B-stage and fully cured
in C-stage). In fabrication, since the prepregs have
the required amount of resin (60-65%), there is no
need to apply any resin. The laid prepregs can be
compacted and cured.
The advantage is the ease of processing and
uniform resin control throughout the component.
Prepregs are protected with thin plastic sheets and
rolled as tapes on a roller. Prepregs when stored
at 18C will retain their properties for about one
year (shelf life).
Hybrid Reinforcements for Composites

Hybrid composites can be obtained by combining

two or more kinds of fibres. These can be formed
at three levels yarn, lamina and laminate. In a
hybrid yarn, different types of filaments (say glass
and carbon) are bundled together. In a hybrid lamina,

the warp can be of one fibre, while the weft can

be of different fibre. The third type of hybrid is in
the laminate, in which the alternate layers of lamina
of different fibres are laid. Hybrid laminates are
used for better properties like strength, stiffness
and damage tolerance.
Mechanical Properties of Composites

Since polymer composite materials are

heterogeneous, have a fibre and matrix, they exhibit
anisotropic properties. That means, their strength
properties are different in different directions. If
we consider a composite lamina (Fig. 11), the
composite is very strong in the longitudinal direction
(i.e. along the fibres) and the tensile strength is
mainly dependent on the fibre strength. Hence this
tensile strength becomes a fibre-dominated
property.
The composites are generally weak in the
transverse direction (perpendicular to the
longitudinal direction in the same plane) and in this
case the composite strength is dependent on the
matrix strength. This is true in the case of
composites using unidirectional fabrics. With the
use of unidirectional fabrics, the strengths in the
transverse direction can be improved for a
laminate. Generally the transverse strength,
compressive strength, shear strength and the
interlaminar shear strengths depend on the matrix
strength and are referred to as matrix dominated
properties.

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National Science Day Orations 2003

Type of Fibre/Matrix

In a composite, different types of fibre and matrix

materials are used. The strength of a composite
thus depends on the properties of the type of fibre
and the matrix. The commonly used fibres in
polymer composites are glass, carbon/graphite,
and aramid, along with polymer matrices like
epoxy, polyester, phenolic, etc. Among fibres,
carbon is the stiffest and strongest of all, next being
the aramid and glass fibres. Among matrices,
thermosets are stronger, durable, and stable at high
temperatures, while thermoplastics are weak and
are not suitable for aerospace applications.
Fig. 11

Structure of Fibres

In general, the overall strength and performance

of a composite depends on many factors, like:
-

Fibre size
Fibre/matrix type
Structure of fibre/matrix
Fibre/matrix interface bonding
Lay-up sequence

These are briefly discussed below:

Fibre Size/Diameter

We know that material strength is directly

proportional to the inherent properties. Also, with
reducing size of the material, the amount of flaws
are reduced, thereby making it more stronger.
Other benefits of smaller size are it will have a
higher flexibility and will have a large contact area
with the matrix, thereby having higher fibre/matrix
interface. The variation of strength of a typical
carbon fibre with respect to its diameter is
illustrated in Fig. 12.

Glass Fibre: Glass fibres have an amorphous

structure they consist of oxides of aluminum,
calcium, magnesium and sodium. The high strength
of the glass fibres is due to the 3-D structure of
the oxides, in which the Si and O are held by strong
covalent bonds. The fibre diameter is about 8 to
10 mm.
Glass fibres are used as structural members
in aerospace, either individually or in combination
with carbon fibres. Glass fibres along with epoxy
and polyester are widely used in radomes due to
their high EM transparency.
Carbon/Graphite Fibres: Graphite is a
crystalline form of carbon. The graphite crystal is
made up of layers comprising carbon atoms in a
hexagonal fashion (Fig. 13a) called basal planes.
The carbon atoms are held together by strong
covalent bonds, while these basal planes are
stacked one above the other and held together by
weak van der Waals Bonds (Fig. 13b). The basal
planes extend in the direction of fibre axis. Due to
this structure, carbon fibres are very strong along
their axis, both in tension and compression.
Most carbon fibres used in composites have
the structure of turbostratic graphite. This structure
is close to that of graphite, but with some
irregularities. Thus, the fibres are stretched to bring
in alignment of the structure while manufacturing.
The typical carbon fibre structure is shown in Fig.
14. The fibre diameter varies from 8 to 10 mm.

Fig. 12

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AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

Fig. 13

Fig. 14

Aramid Fibre

This is one of the most successful man made

organic fibres. Though there are many
manufacturers, having their own trademarks, the
Kevlar aramid fibre from M/s Du Pont is very

popular. In aramid fibres, the molecules are held

together in planar layers by strong covalent bonds,
along the fibre axis. In the transverse direction,
they are held by weak hydrogen bonds (Fig. 15a).
The layers are pleated axially and stacked radially
to give a 3-D structure (Fig. 15b).

Fig. 15

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Due to this, the aramid fibres are very strong

in the axial tensile direction and poor in axial
compressive direction, as the structure is
collapsible under compressive loads. However, the
structure has a high impact resistance, as it absorbs
more energy. The other beneficial property of
aramid fibre is that it has high temperature stability.
The drawback of aramid fibres is that they are
highly hygroscopic and absorb more amount of
moisture from the environment. Thus they are not
suitable for primary structures in aerospace
applications.
In Kevlar, three brands are widely used
kevlar-29, kevlar-49 and kevlar-149. Kevlar-29 is
a tough fibre used mainly as the armor material
(like bullet proof rests), ropes, cables and
reinforcement in tyres. Kevlar-49 and Kevlar-149
are used as secondary structures in aerospace like
engine cowlings, doors, etc. Since, kevlar has good
electromagnetic transparency, they are also used
in the radome manufacture.
Fibre-Matrix Interface

In a polymer matrix composite, a strong interface

is established between the fibre and the matrix.
Higher the interface strength, higher is the strength
of the composite. The response of a composite to
humid/corrosive environment depends on this
interface strength. Generally, weak fibre-matrix
interface results in low strength, but high fracture
toughness. On the other hand, a strong interface
results in high composite strength, but the material
exhibits a brittle behavior and hence a low fracture
resistance.
Though the fibre-matrix interface can be
established by various means like mechanical

bonding, molecular entanglement, electrostatic

forces, chemical bonding, etc., only the chemical
bonding gives the best results. To achieve this most
fibres surfaces are chemically treated and such
chemicals used are termed coupling agents. The
chemicals used are such that they are compatible
with both the fibres and the type of matrix used.
The coupling agents in the form of a chemical
coating, also help in protecting the brittle fibres from
damaging while handling, promote resin wetting
and bonding between the fibre/matrix.
Glass fibres are given a silane coating; carbon
fibres with oxidizing agents or a thin layer of epoxy
(only for use with epoxy matrix) and aramid fibres
are coated with polyvinyl alcohol or epoxy. When
the chemical on the fibres reacts with the matrix,
it forms a new interphase, which in turn will have
an interface each with the fibre and the matrix
Lay-up Sequence

It was mentioned earlier that laminar composites

can be made by laying a number of lamina one
above the other and then by consolidating and
curing. The laying up of laminae is not done
randomly, but in a definite orientation of each
lamina. The orientation of a lamina is with respect
to the direction of placement of the warp fibre.
For example, the warp in x-direction is taken as
0, then the orientation of a warp fibre in the ydirection is 90. This applies to unidirectional fabrics
also. Depending upon the number of lamina above
and below the plane of symmetry, the laminate can
be either symmetric or balanced or both.
Depending upon the orientation, the laminates are
either cross ply or quasi-isotropic. Some typical
lay-up sequences are schematically illustrated in
Fig. 16.

Fig. 16

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AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

When all the UD laminae are in the 0 direction, it

becomes a UD laminate. This will have maximum
strength in the 0 and least strength in the 90 direction. Cross-ply laminates will have equal strength
in both longitudinal and transverse directions.
Quasi-isotropic laminates will have similar in plane
properties in all the directions due to the lamina
orientation. The selection of type of lay-up orientation depends on the requirement of strengths in
different directions.
Strengths of Polymer Composite
Materials

The tensile strength and specific tensile strengths

of commonly used advanced polymer matrix composites are illustrated in Fig. 17 and Fig. 17. These
values are for uni-direction composites with 60%
fibre volume fraction, for comparison the strengths
of common structural materials wood, aluminum
and steel are also included.

of the material. The composite degradation may

take place at the surface level (i.e. matrix), fibre
level and at the fibre/matrix interface.
Chemical and Physical Degradation

As discussed earlier, the matrix solidifies and

becomes strong due to chemical reaction leading
to cross-linking of polymer chains. Also the fibre/
matrix interface is formed due to chemical action.
These are the sources of strength in the polymer
matrix composite material. When the composite
undergoes chemical degradation, the primary
(covalent) bonds in the matrix are broken and even
form some new chemical entities, thus reducing
the strength of the matrix. Similarly, the fibre/matrix
interface may also be damaged, thus reducing the
bond between the fibre and the matrix.
The chemical degradation of polymer composites
may be caused by various reasons like:
-

Strengths of Common Structural Materials

Tensile Strength (MPa)

2000

1500

1000
500
0
Wood

Al

Steel

Gl/Ep

Gr/Ep (HM)

Gr/Ep (HS)

Ke/Ep

Fig. 17

Sp. Strengths of Structural Materials

Hydrolysis: The action of water, acids and

alkalis with the material.
Oxidation: The action of air (oxygen), ozone,
liquid oxidizing agents (both salts and acids).
Corrosion: In the case of carbon fibres in
contact with conducting materials.
Leaching: Involving the dissolution of
polymers by solvents, which happens in
polymers that are not cross-linked (weakly
bonded).
Stress Corrosion: Due to load in acidic
environments
In physical degradation, there is no breakage of
chemical bonds. It is associated with physical
damage to the material like micro-cracks,
swelling, erosion etc.

Sp. Strength (MPa)

1200
1000
800
600
400
200
0
Wood

Al

Steel

Gl/Ep

Gr/Ep (HM)

Gr/Ep (HS)

Ke/Ep

Fig. 18

DEGRADATION OF POLYMER
COMPOSITES
In general, degradation refers to the reduction in
properties of fibre and matrix in a composite
material and hence reduction in the performance

Generally, the matrix material is most

vulnerable to both physical and chemical
degradation. Once the matrix is degraded at the
surface, the fibre/matrix interface gets degraded
and then the degradation of the fibre starts. Both
the physical and chemical degradation contribute
to the reduced strength and performance of the
composite material.
Environmental Factors Causing
Degradation

The degradation of polymeric composites is mostly

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National Science Day Orations 2003

due to the service environment. The environmental

factors that contribute to the degradation are as
below:

Moisture: The primary factor, which affects

the polymer composites is the moisture in the
service environment (in the form of humidity
in air or sea water in marine applications). Most
polymers are known to absorb moisture by
diffusion process. Thermosets absorb about
1 to 1.5% by weight, while thermoplastics
absorb about 0.1 to 0.3%. The absorbed
moisture plasticises the matrix and reduces the
matrix-dominated properties like compressive
and shear strengths. It has been shown that
the reduction tensile strength of composites
due to moisture absorption is negligible. Other
effect of absorbed moisture include the
reduction in glass transition temperature of
the matrix and hence reduction in its service
temperature.
Temperature: In thermoset polymers, a lower
temperature makes the composite brittle, while
a higher temperature makes it soft. The
brittleness induced by lower temperature
reduces the fatigue performance, while higher
temperature reduces the strength and stiffness
of the material. Higher temperatures are known
to cause and accelerate chemical degradation,
but in the presence of moisture and oxygen. It
may also induce micro-cracks in the matrix
material.
Hygrothermal Conditions: It is a combination
of humid and high temperature environment.
In fact the degradation due to moisture is more
severe under high temperature conditions and
lead to faster deterioration of the composite
properties and performance.

Other factors that cause degradation include

thermal spikes (sudden rise in temperature),
thermal cycling (variation from low to high, and
high to low temperatures), ultraviolet radiation
(photo-oxidation) and lightning strikes (causing
physical damage). The effects of these factors
include both physical and chemical degradation like
cracks, swelling, internal stresses, fibre/matrix
damage etc. All these lead to reduced strength
and performance of the composite material and
may lead to catastrophic failure of the structure.
Enough care has to be taken in the design and
manufacture to protect the composite materials
from these environmental factors. This may include

protecting/ conducting paints, UV absorbers,

conducting strips, etc., on the finished composite
part.
DAMAGE MECHANISMS
Damage in a composite material refers to the initiation of a failure. In a polymer composite, it may
include matrix cracking, debonding, delamination
and fibre fracture. The damage may be due to the
applied stress, fatigue, environmental degradation,
and/or impact. Thus damage may involve both
physical and chemical degradation. Any kind of
damage reduces the strength and performance of
a material. Damage resistance and damage tolerance are the two important terms relevant in this
study.
Damage resistance is the ability of materials
to resist the initiation of damage. That means a
material requires higher energy to undergo damage. Damage tolerance is the ability of materials
to delay the growth of damage once it is initiated.
It also indicates the ability of a material to perform
satisfactorily, in the presence of damage.

Damage/Failure Modes

Unlike the metals, the damage the mechanisms

are complex in polymer matrix composite materials.
The factors that make the damage mechanisms
complex include the fibre/matrix interface, the type
of fabric weaves, the lay-up sequence, loading
conditions etc. A typical damage/failure process
in tension in a fibre composite is illustrated in
Fig. 19.

Fig. 19

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AC Niranjanappa : Advanced Polymer Composites: Properties,

Degradation And Damage Mechanisms

When loaded in tension, the matrix being the

weakest, once the stress exceeds the matrix failure
stress, it cracks first and the crack propagates till
its comes across a fibre. Since there is a strong
bond between the fibre/matrix, under the applied
load, the energy is utilised in debonding of the fibre/
matrix interface. Then the crack propagates
further. As the matrix crack length increases and
a critical size, the load is fully taken by the fibres,
and when the stress exceeds the failure stress of
the fibres, the fibres fracture. As the crack grows
and widens, the fibres are pulled out of the matrix.
The reason why, the failure is gradual and not
catastrophic in fibre composites is due to the fact
that as some fibres fracture and the matrix crack
extends, some fibres ahead of the crack (not
fractured) still support the load (called fibre
bridging) while being debonded.
Damage/Failure in Fibres

In advanced polymer composites, mostly glass,

carbon and aramid fibres are used in thermoset
resin matrices. Hence, the damage modes related
to them are briefly discussed here.The glass and
carbon fibres are brittle in nature and hence
undergo brittle failure (in tension), without any yield
and reduction in cross-sectional area (Fig. 20a,b).

Fig. 21

impact damages, the composite fails with lower

energy. On the other hand, with a lower fibre/
matrix interface bond the composite will have lower
strength and stiffness, but a higher damage
tolerance.
Effect of Environmental Factors on the
Damages

The environmental factors like moisture and

temperature have a profound effect on the damage
modes of fibre reinforced polymer composites.
These factors, further complicate the damage
modes and some may aid or delay the failure
process. Extensive research is being carried-out
worldwide in these areas.
CONCLUSIONS
The polymer matrix composites have revolutionised
the field of materials. They are being used in all
parts of life. But these materials are not without
problems and we are yet to understand more about
these materials. In these materials, the degradation
and damage mechanisms are the critical issues,
which are being addressed throughout the world.
REFERENCES

Fig. 20

On the other hand, aramid fibres undergo ductile

failure, hence are associated with yielding and
reduction in cross-sectional area. Since, the
aramids have a complex, collapsible type of
structure, they undergo buckling with kink
formation when loaded in bending/compression and
form fibrils in tensile failure (Fig. 21a,b).
Effect of Fibre/Matrix Bond Strength on
Failure

A higher fibre/matrix interface bond makes the

composite strong and stiff, but it will have a lower
damage tolerance. That means when subjected to

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National Science Day Orations 2003

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