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CHAPTER-4
THERIOTICAL ANALYSIS OF FRP MATERIAL
4.1 Matrix materials
Polymers are the most used for matrix than metal or ceramics. They are very poor
inductors of heat and electricity and are generally more resistant to ceramicals than
metals. Polymers are giant chain like structures of molecules with conveniently bonded
carbon atom forming the backbone of chain. The process of making large molecules
(polymers) from small ones (monometers) is called polymerization.

4.1.1 Functions of the matrix phase

1) It binds the fibers together and acts as a medium by which an externally applied
stress is transmitted and distributed to the fibers; only a very small proportion of
an applied load is sustained by the matrix phase.
2) The matrix material should be ductile.
3) The matrix should protect the individual fibers from fiber damage as a result of
mechanical abrasion and chemical corrosion with environment.
4) The matrix separates the fiber layers and by the virtue of its relative softness,

prevents crack propagation from fiber which otherwise may lead to premature
failure of the composite. The adhesive bonding force between the fiber pullout and
adequate bonding is essential for the effective transmittance of stress from weak
matrix to the strong reinforcement.

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4.2 Catalyst and Accelerators

Catalysts are materials, which initiate the chemical reaction that cause the resin to
undergo phase transformation from liquid to solid. Accelerator increases the speed of the
catalytic action. The pot life and gel time depends upon the quantity of accelerator and
catalyst taken.
A wide range of catalysts, accelerators, systems are available for use with
polymers resin. The selection of proper catalyst and amount to use for applications
depends on the resin, the curing temperature, required working or pot life and the gel
time.
The most commonly catalyst is benzoyl peroxide, which is efficient, easy to
handle, readily soluble in monomeric styrene storable for long periods of the time without
the loss of activity and stable at room temperature. Cobalt naphtha late is used as
accelerator.

4.3 Resin systems

Any resin system for use in a composite material will require the following
properties
1) Good mechanical properties.
2) Good adhesive properties.
3) Good toughness properties.
4) Good resistance to environmental degradation.

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4.3.1 Mechanical properties of the resin system

Figure 4.1: Stress-strain curve for an ideal resin system

The figure below shows the stress / strain curve for an ideal resin system.
The curve for this resin shows high ultimate strength, high stiffness and a high strain
to failure. This means that the resin is initially stiff but at the same time will not suffer
from brittle failure.
It should also be noted that when a composite is loaded in tension, for the full
mechanical properties of the fiber component to be achieved, the resin must be able to
deform to at least the same extent as the fiber. The figure below gives the strain to
failure for e-glass, s-glass, aramid and high-strength grade carbon fibers on their own.
Here it can be seen that, for example, the s-glass fiber, with an elongation to break of
5.3%, will require a resin with an elongation to break of at least this value to achieve
maximum tensile properties.

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Figure 4.2: Selection criteria for the ideal resin system for a fiber

4.3.2 Adhesive properties of the resin system

High adhesion between resin and reinforcement fibers is necessary for any resin
system. This will ensure that the loads are transferred efficiently and will prevent
cracking or fiber / resin debonding when stressed.

4.3.3 Toughness properties of the resin system

Toughness is a measure of a materials resistance to crack propagation, but in a
composite this can be hard to measure accurately. However, the stress /strain curve of the
resin system on its own provides some indication of the materials toughness. Generally
the more deformation the resin will accept before failure the tougher and more crackresistant the material will be. Conversely, a resin system with a low strain to failure will
tend to create a brittle composite, which cracks easily. it is important to match this
property to the elongation of the fiber reinforcement.

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4.3.4 Environmental properties of the resin system

Good resistance to the environment, water and other aggressive substances,
together with an ability to withstand constant stress cycling, are properties essential to
any resin system. These properties are particularly important for use in a marine
environment.

4.4 Resin types

The resins that are used in the fiber-reinforced composites can also be referred to
as polymers. All polymers exhibit an important common property in that they are
composed of long chain like molecules consisting of many simple repeating units .man
made polymers are generally called synthetic resins or simply resins. Polymers can be
classified under two types thermoplastic and thermosetting according to the effect of heat
on their properties.
Thermoplastics, like metals, soften with heating and eventually melt, hardening
again with cooling. This process of crossing the softening or melting point on the
temperature scale can be repeated as often as desired without any appreciable effect on
the material properties in either state. Typical thermoplastics include nylon,
polypropylene and abs, and these can be reinforced, although usually only with short,
chopped fibers such as glass.
Thermosetting materials, or, thermo sets, are formed from a chemical reaction in
situ, where the resin and hardener or resin and catalyst are mixed and then undergo a nonreversible chemical reaction to form a hard, infusible product. In some thermo sets, such
as phenolic resins, volatile substances are produced as by-products. Other thermosetting
resins such as polyester and epoxy, by mechanisms that do not produce any volatile by
products and thus are much easier to process. Once cured, thermo sets will not become
liquid again if heated, although above a certain temperature their mechanical properties

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will change significantly. This temperature is known as the glass transition temperature
(Tg), and varies widely according to the particular resin system used, its degree of cure
and whether it was mixed correctly. Above the Tg, the molecular structure of the thermo
set changes from that of a rigid crystalline polymer to a more flexible, amorphous
polymer. This change is reversible on cooling back below the Tg. Above the Tg
properties such as resin modulus drop sharply, and as a result the compressive and shear
strength of the composite does too. Other properties such as water resistance and color
stability also reduce markedly above the resins Tg.
Although there are many different types of resin in use in the composite industry,
the majority of structural parts are made with three main types, namely polyester, vinyl
ester and epoxy.

4.4.1 Polyester resins

Polyester resins are the most widely used resin systems, particularly in the marine
industry. By far the majority of dinghies, yachts and workboats built in composites make
use of this resin system. Polyester resin is the preferred material in marine industries
marine due to its superior. Polyester resin is the preferred material in marine industries
marine due to its superior water resistance.
Polyester resins are of the unsaturated type. Unsaturated polyester resin is a
thermo set, capable of being cured from a liquid or solid state when subject to the right
conditions. It is usual to refer to unsaturated polyester resins as polyester resins, or
simply as polyesters. There is a whole range of polyesters made from different acids,
glycols and monomers, all having varying properties. For use in molding polyester resin
requires the addition of several ancillary products. These products are generally a
catalyst, an accelerator and additives such as pigments and fillers.

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4.4.2 Epoxy resins

The large family of epoxy resins represents some of the highest performance
resins of those available at this time. Epoxies generally out-perform most other resin
types in terms of mechanical properties and resistance to environmental degradation,
which leads to their almost exclusive use in aircraft components. As a laminating resins
their increased adhesive properties and resistance to water degradation make these resins
ideal for use in applications such as boat building. Here epoxies are widely used as a
primary construction material for high-performance boats or as a secondary application to
sheath a hull or replace water-degraded polyester resins and gel coats.
The term epoxy refers to a chemical group consisting of an oxygen atom bonded
to two carbon atoms that are already bonded in some way. the simplest epoxy is a threemember ring structure known by the term alpha-epoxy or 1,2-epoxy. The idealized
chemical structure is shown in the figure below and is the most easily identified
characteristic of any more complex epoxy molecule.

Figure 4.3: Idealized chemical structure of a simple epoxy (ethylene oxide)

Usually identifiable by their characteristic amber or brown coloring, epoxy resins

have a number of useful properties. Both the liquid resin and the curing agents form low
viscosity easily processed systems. Epoxy resins are easily and quickly cured at any
temperature from 5c to 150c, depending on the choice of curing agent. One of the most
advantageous properties of epoxies is their low shrinkage during cure, which minimizes
fabric print-through, and internal stresses. High adhesive strength and high mechanical

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properties are also enhanced by high electrical insulation and good chemical rsistance.
Epoxies find uses as adhesives, caulking compounds, casting compounds, sealants,
varnishes and paints, as well as laminating resins for a variety of industrial applications.
Epoxy resins are formed from a long chain molecular structure similar to vinyl
ester with reactive sites at either end. In the epoxy resin, however, epoxy groups instead
of ester groups form these reactive sites. The absence of ester groups means that the
epoxy resin has particularly good water resistance. The epoxy molecule also contains two
ring groups at its center which are able to absorb both mechanical and thermal stresses
better than linear groups and therefore give the epoxy resin very good stiffness, toughness
and heat resistant properties.

4.4.3 Vinyl Ester Resins

Vinylester resins are similar in their molecular structure to polyesters, but differ
primarily in the location of their reactive sites, these being positioned only at the ends of
the molecular chains. As the whole length of the molecular chain is available to absorb
shock loadings this makes vinylester resins tougher and more resilient than polyesters.
The vinylester molecule also features fewer ester groups. These ester groups are
susceptible to water degradation by hydrolysis which means that vinylesters exhibit better
resistance to water and many other chemicals than their polyester counterparts, and are
frequently found in applications such as pipelines and chemical storage tanks.
The figure below shows the idealised chemical structure of a typical vinylester.
Note the positions of the ester groups and the reactive sites (C* = C*) within the
molecular chain.

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Figure 4.4: Idealized chemical structure of vinylester

The molecular chains of vinylester, represented below, can be compared to the

schematic representation of polyester shown previously where the difference in the
location of the reactive sites can be clearly seen:

With the reduced number of ester groups in a vinylester when compared to a

polyester, the resin is less prone to damage by hydrolysis. The material is therefore
sometimes used as a barrier or 'skin' coat for a polyester laminate that is to be immersed
in water, such as in a boat hull. The cured molecular structure of the vinylester also
means that it tends to be tougher than a polyester, although to really achieve these
properties the resin usually needs to have an elevated temperature postcure.

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Vinyl esters provide excellent resistance to water, organic solvents and alkalis, but
less resistance to acids than polyesters. Vinyl esters are stronger than polyesters and more
resilient than epoxies. Molding conditions for vinyl esters are similar to those for
polyesters.

Best Processes
Open Molding (Hand Lay-up/Spray-up), SMC/BMC, RTM. The best process for
your product is a function of your tooling budget, part specification (such as dimensional
tolerance and physical properties) and production volume.

Technical Details
Surface quality is not as good as with polyesters. The built-in toughness of vinyl esters
makes smooth surfaces hard to accomplish. The double bonded nature creates shrinkage,
which has a negative impact on surface quality.
The double bonded vinyl groups give the entire matrix a toughness that exceeds
polyesters by about 2X depending on the test used. For example, typical tensile properties
in SMC start at approximately 15,000psi and flexural properties exceed 30,000psi when
using 28% glass reinforcement. As with polyesters, vinyl esters are not practical without
additives, reinforcements and fillers. The next step up for toughness would be
polyurethanes or epoxies.
Modulus (stiffness) is on a par - slightly less - than polyesters because of the toughness
built in to the backbone of the ester linkage. Normal viscosity for vinyl esters is less than
polyester, about 500 centipoise when cut in styrene monomer. Both polyester and vinyl
ester resins will react and build in molecular weight to a solid waxy resin and be mostly
unusable in that waxy state. Consequently, they are generally cut in styrene monomer for
management as a liquid resin.

Typical structural matrix resins

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Tensile
strength
(Mpa)

Tensile
modulus
(Mpa)

Tg
(k)

Epoxy

103.4

4.1

463

Bismaleimide

82.7

4.1

547

Polyamide

137.9

4.8

630

Polynylene

65.5

4.3

366

Polyetheretherketon

70.3

1.1

400

Resin
Thermo sets

Thermoplastic

Table 4.1: Typical structural matrix resins

4.5 Core Materials

4.5.1 Balsa

End grain balsa's closed-cell structure consists of elongated, prismatic cells

with a length (grain direction) that is approximately sixteen times the diameter (see
Figure 2-7). In densities between 6 and 16 pounds ft3 (0.1 and 0.25 gms/cm3), the
material exhibits excellent stiffness and bond strength. Stiffness and strength
characteristics are much like aerospace honeycomb cores Although the static strength of
balsa panels will generally be higher than the PVC foams, impact energy absorption is
lower. Local impact resistance is very good because

stress

is

efficiently

transmitted between sandwich skins. End-grain balsa is available in sheet form for
flat panel construction or in a scrim-backed block arrangement that conforms to
complex curves.

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Figure 4.5:
Balsa Cell Geometry with A = Average Cell Length = .025"; B = Average Cell Diameter = .
00126"; C = Average Cell Wall Thickness = .00006" [Baltek Corporation]

4.5.2 Thermoset Foam

Foamed plastics such as cellular cellulose acetate (CCA), polystyrene, and

polyurethane are very light (about 2 lbs/ft3) and resist water, fungi and decay.
These materials have very low mechanical properties and polystyrene will be
attacked by polyester resin. These foams will not conform to complex curves. Use
is generally limited to buoyancy rather than structural applications. Polyurethane is
often foamed in-place when used as a buoyancy material

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Figure 4.6: Hexagonal Honeycomb Ge- ometry

4.5.3 Syntactic Foams

Syntactic foams are made by mixing hollow microspheres of glass, epoxy and
phenolic into fluid resin with additives and curing agents to form a moldable, curable,
lightweight fluid mass. Omega Chemical has introduced a sprayable syntactic core
material called SprayCoreTM. The company claims that thicknesses of 3 8" can
be achieved at densities between 30 and 43 lbs/ft3. The system is being marketed as a
replacement for core fabrics with superior physical properties. Material cost for a square
foot of 3 8" material is approximately $2.20
4.5.4 Cross Linked PVC Foams:
Polyvinyl foam cores are manufactured by combining a polyvinyl copolymer
with stabilizers,plasticizers, cross-linking compounds and blowing agents. The mixture
is heated under pressure to initiate the cross-linking reaction and then submerged in hot
water tanks to expand to the desired density. Cell diameters range from .0100 to .100
inches (as compared to .0013 inches for balsa). [2-2]

The resulting material is

thermoplastic, enabling the material to conform to compound curves of a hull.

PVC

foams have almost exclusively replaced urethane foams as a structural core material,
except in configurations where the foam is blown in place.

A number of

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manufacturers market cross-linked PVC products to the marine industry in sheet form
with densities ranging from 2 to 12 pounds per ft3.

As with the balsa products, solid

sheets or scrim backed block construction configurations are available.

Figure 4.7: Core Strengths and Moduli for Various Core Densities of Aramid Honeycomb

4.5.5 Linear PVC Foam:

Airex and Core-Cell are examples of linear PVC foam core produced for the
marine industry. Unique mechanical properties are a result of a non-connected molecular
structure, which allows significant displacements before failure. In comparison to the cross
linked (non-linear) PVCs, static properties will be less favorable and impact will be
better. For Airex, individual cell diameters range from .020 to .080 inches. [2-3] Table
2-8 shows some of the physical properties of the core materials presented here.

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4.5.6 FRP Planking:

Seemann Fiberglass, Inc. developed a product called C-Flex in 1973 to help
amateurs build a cost effective one-off hull. The planking consists of rigid fiberglass
rods held together with unsaturated strands of continuous fiberglass rovings and a
light fiberglass

cloth.

The self-supporting material will conform to compound

curves. Typical application involves a set of male frames as a form. The planking has
more rigidity than PVC foam sheets, which eliminates the need for extensive
longitudinal stringers on the male mold. A 18 inch variety of C-Flex weighs about
12 pound dry and costs about $2.00 per square foot.
4.5.7 Core Fabrics:
Various natural and synthetic materials are used to manufacture products to
build up laminate thickness economically. One such product that is popular in the
marine industry is Firet Core mat, a spun-bound polyester produced by Lantor.
Hoechst

Celanese

has

recently introduced a product called Trevira, which is a

continuous filament polyester. The continuous fibers seem to produce a fabric with
superior mechanical properties.
from inorganic vitreous fibers.

Ozite produces a core fabric called CompozitexTM

The manufacturer claims that a unique manufacturing

process creates a mechanical fiber lock within the fabric.

Although many manufacturers

have had much success with such materials in the center of the laminate, the use of a
Nonstructural thick ply near the laminate surface to eliminate print-through requires
engineering forethought.

The high modulus, low strength ply can produce premature

cosmetic failures. Other manufacturers have started to produce bulking products

that are primarily used to build up laminate thickness

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4.5.8 Plywood:
Plywood should also be mentioned as a structural core material, although
fiberglass is generally viewed as merely a sheathing when used in conjunction with
plywood.

Exceptions to this characterization include local reinforcements in way of

hardware installations where plywood replaces a lighter density core to improve

compression properties of the laminate.

Plywood is also sometimes used as a form

for longitudinals, especially in way of engine mounts.

Concern over the continued

propensity for wood to absorb moisture in a maritime environment, which can cause
swelling and subsequent delamination, has precipitated a decline in the use of wood in
conjunction with FRP. Better process control in the manufacture of newer marine grade
plywood should diminish this problem.
it a poor bonding surface.

The uneven surface of plywood can make

Also, the low strength and low strain characteristics of

plywood can lead to premature failures when used as a core with thin skins.
The technique of laminating numerous thin plies of wood developed by the
Gougeon Brothers and known as wood epoxy saturation technique (WEST System)
eliminates many of the shortcomings involved with using wood in composite structures.

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