Resin Systems for Use in Fibre-Reinforced Composite Materials

Resin Systems for Use in Fibre-Reinforced

Composite Materials

Topics Covered
Resin Types
Polyester Resins
Vinyl Ester Resin
Epoxy Resins
Resin Comparison Summary

Resin Types
The resins that are used in fibre-reinforced composites are sometimes 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. Manmade 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 fibres such as
glass.

Thermosetting materials, or ‘thermosets’, are formed from a chemical reaction in situ, where the resin and
hardener or resin and catalyst are mixed and then undergo a non-reversible chemical reaction to form a hard,
infusible product. In some thermosets, such as phenolic resins, volatile substances are produced as by-products
(a ‘condensation’ reaction). Other thermosetting resins such as polyester and epoxy cure by mechanisms that do
not produce any volatile by products and thus are much easier to process (‘addition’ reactions). Once cured,
thermosets will not become liquid again if heated, although above a certain temperature their mechanical
properties 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 thermoset 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 (stiffness) drop sharply, and as a result the compressive and shear strength of the
composite does too. Other properties such as water resistance and colour stability also reduce markedly above
the resin’s 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.

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 resins such as these are of the ‘unsaturated’ type. Unsaturated polyester resin is a thermoset, capable
of being cured from a liquid or solid state when subject to the right conditions. Unsaturated polyester differs from
saturated polyester such as Terylene™, which cannot be cured in this way. It is usual, however, to refer to
unsaturated polyester resins as ‘polyester resins’, or simply as ‘polyesters’. In chemistry the reaction of a base
with an acid produces a salt. Similarly, in organic chemistry the reaction of an alcohol with an organic acid
produces an ester and water.

By using special alcohols, such as a glycol, in a reaction with di-basic acids, a polyester and water will be
produced. This reaction, together with the addition of compounds such as saturated di-basic acids and
cross-linking monomers, forms the basic process of polyester manufacture. As a result there is a whole range of

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polyesters made from different acids, glycols and monomers, all having varying properties.

There are two principle types of polyester resin used as standard laminating systems in the composites industry.
Orthophthalic polyester resin is the standard economic resin used by many people. Isophthalic polyester resin is
now becoming the preferred material in industries such as the marine industry where its superior water resistance
is desirable. Figure 1 shows the idealised chemical structure of a typical polyester. Note the positions of the ester
groups (CO - O - C) and the reactive sites (C* = C*) within the molecular chain.

Figure 1. Idealised chemical structure of a typical isophthalic polyester.

Most polyester resins are viscous, pale coloured liquids consisting of a solution of polyester in a monomer, which
is usually styrene. The addition of styrene in amounts of up to 50% helps to make the resin easier to handle by
reducing its viscosity. The styrene also performs the vital function of enabling the resin to cure from a liquid to a
solid by ‘cross-linking’ the molecular chains of the polyester, without the evolution of any by-products. These
resins can therefore be moulded without the use of pressure and are called ‘contact’ or ‘low pressure’ resins.
Polyester resins have a limited storage life as they will set or ‘gel’ on their own over a long period of time. Often
small quantities of inhibitor are added during the resin manufacture to slow this gelling action. For use in
moulding, a polyester resin requires the addition of several ancillary products.

These products are generally:

• Catalyst

• Accelerator

 Additives: Thixotropic

Pigment
Filler
Chemical/fire resistance

A manufacturer may supply the resin in its basic form or with any of the above additives already included. Resins
can be formulated to the moulders requirements ready simply for the addition of the catalyst prior to moulding.
As has been mentioned, given enough time an unsaturated polyester resin will set by itself. This rate of
polymerisation is too slow for practical purposes and therefore catalysts and accelerators are used to achieve the
polymerisation of the resin within a practical time period. Catalysts are added to the resin system shortly before
use to initiate the polymerisation reaction. The catalyst does not take part in the chemical reaction but simply
activates the process. An accelerator is added to the catalysed resin to enable the reaction to proceed at
workshop temperature and/or at a greater rate. Since accelerators have little influence on the resin in the
absence of a catalyst they are sometimes added to the resin by the polyester manufacturer to create a
‘pre-accelerated’ resin. The molecular chains of the polyester can be represented as follows (Figure 2), where ‘B’
indicates the reactive sites in the molecule.

Figure 2. Schematic representation of polyester resin (uncured).

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With the addition of styrene ‘S’, and in the presence of a catalyst, the styrene cross links the polymer chains at
each of the reactive sites to form a highly complex three-dimensional network as represented in Figure 3.

Figure 3. Schematic representation of polyester resin (cured).

The polyester resin is then said to be ‘cured’. It is now a chemically resistant (and usually) hard solid. The
cross-linking or curing process is called ‘polymerisation’. It is a non-reversible chemical reaction. The
‘side-by-side’ nature of this cross-linking of the molecular chains tends to mean that the polyester laminates
suffer from brittleness when shock loadings are applied.

Great care is needed in the preparation of the resin mix prior to moulding. The resin and any additives must be
carefully stirred to disperse all the components evenly before the catalyst is added. This stirring must be thorough
and careful as any air introduced into the resin mix affects the quality of the final moulding. This is especially so
when laminating with layers of reinforcing materials as air bubbles can be formed within the resultant laminate,
which can weaken the structure. It is also important to add the accelerator and catalyst in carefully measured
amounts to control the polymerisation reaction to give the best material properties. Too much catalyst will cause
too rapid a gelation time, whereas too little catalyst will result in under-cure. Colouring of the resin mix can be
carried out with pigments. The choice of a suitable pigment material, even though only added at about 3% resin
weight, must be carefully considered, as it is easy to affect the curing reaction and degrade the final laminate by
use of unsuitable pigments.

Filler materials are used extensively with polyester resins for a variety of reasons including:

• To reduce the cost of the moulding

• To facilitate the moulding process

• To impart specific properties to the moulding

Fillers are often added in quantities up to 50% of the resin weight although such addition levels will affect the
flexural and tensile strength of the laminate. The use of fillers can be beneficial in the laminating or casting of
thick components where otherwise considerable exothermic heating can occur. Addition of certain fillers can also
contribute to increasing the fire-resistance of the laminate.

Vinyl Ester Resins

Vinyl ester 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 vinyl ester resins tougher and more resilient
than polyesters.

The vinyl ester molecule also features fewer ester groups. These ester groups are susceptible to water
degradation by hydrolysis which means that vinyl esters 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.

Figure 4 below shows the idealised chemical structure of a typical vinyl ester. Note the positions of the ester
groups and the reactive sites (C* = C*) within the molecular chain.

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Figure 4. Idealised chemical structure of a typical epoxy based vinyl ester.

The molecular chains of vinyl ester, represented in Figure 5 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:

Figure 5. Schematic representation of vinyl ester resin (uncured).

With the reduced number of ester groups in a vinyl ester 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 vinyl ester
(Figure 6) 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 post cure.

Figure 6. Schematic representation of vinyl ester resin (cured).

Epoxy Resins
The large family of epoxy resins represent 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
resin 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 three-member ring structure known by the term
‘alpha-epoxy’ or ‘1,2-epoxy’. The idealised chemical structure is shown in Figure 7 below and is the most easily
identified characteristic of any more complex epoxy molecule.

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Figure 7. Idealised chemical structure of a simple epoxy (ethylene oxide).

Usually identifiable by their characteristic amber or brown colouring, 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 5°C to 150°C, depending on the choice of curing agent. One
of the most advantageous properties of epoxies is their low shrinkage during cure, which minimises fabric
‘print-through’, and internal stresses. High electrical insulation and good chemical resistance also enhance high
adhesive strength and high mechanical properties. Epoxies find uses as adhesives, caulking compounds, casting
com pounds, 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 centre 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. Figure 8
below shows the idealised chemical structure of a typical epoxy. Note the absence of the ester groups within the
molecular chain.

Figure 8. Idealised chemical structure of a typical epoxy (diglycidyl ether of bisphenol-A).

Epoxies differ from polyester resins in that a ‘hardener’ rather than a catalyst cures them. The hardener, often an
amine, is used to cure the epoxy by an ‘addition reaction’ where both materials take place in the chemical
reaction. The chemistry of this reaction means that there are usually two epoxy sites binding to each amine site.
This forms a complex three-dimensional molecular structure, which is illustrated in Figure 9.

Figure 9. Schematic representation of epoxy resin (cured 3-d structure)

Since the amine molecules ‘co-react’ with the epoxy molecules in a fixed ratio, it is essential that the correct mix
ratio is obtained between resin and hardener to ensure that a complete reaction takes place. If amine and epoxy
are not mixed in the correct ratios, unreacted resin or hardener will remain within the matrix, which will affect the
final properties after cure. To assist with the accurate mixing of the resin and hardener, manufacturers usually

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formulate the components to give a simple mix ratio that is easily achieved by measuring out by weight or
volume.

Resin Comparison Summary

The polyesters, vinyl esters and epoxies discussed here probably account for some 90% of all thermosetting resin
systems used in structural composites. In summary the main advantages and disadvantages of each of these
types are summarised in Table 1

Table 1. Advantages and Disadvantages of Common Thermosetting Resins Used in Structural Composites.

POLYESTER: Advantages Disadvantages

• Easy to use • Only moderate mechanical properties

• Lowest cost of resins available • High styrene emissions in open moulds

• High cure shrinkage

• Limited range of working times

VINYL ESTER: Advantages Disadvantages
• Very high chemical/environmental resistance • Post cure generally required for high
properties
• Higher mechanical properties than polyesters
• High styrene content

• Higher cost than polyesters

• High cure shrinkage

EPOXIES: Advantages Disadvantages
• High mechanical and thermal properties • More expensive than vinyl esters

• High water resistance • Critical mixing

• Long working times available • Corrosive handling

• Temperature resistance can be up to 140°C wet and 220°C dry

• Low cure shrinkage

Source: SP Systems

For more information on this source please visit SP Systems

Date Added: Oct 25, 2001

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Gurit (UK)

Gurit (UK)
St Cross Business Park
Newport
Isle of Wight, PO30 5WU
United Kingdom
PH: 44 (1983) 828 100
Fax: 44 (1983) 828100
Email: [email protected]
Visit Gurit (UK) Website

Primary Activity
Material Manufacturer
Service Provider

Company Background
With years of experience and expertise in composite materials and technologies, we offer a comprehensive range of
solutions for customers around the globe. High performance and cost-effectiveness are our drivers for satisfying
demanding requirements in markets such as wind energy, marine and automotive.

With headquarters in the UK, and further operations in North America, Spain and Australia, our product range
includes heavyweight structural prepregs, liquid epoxies for resin infusion and laminating, structural adhesives, dry
reinforcements, core materials and structural design and process engineering services.

Number of Employees
700

Territories Serviced
Global

Services
• Supply of composite materials
• Engineering and design consultancy

Trade Names
SPRINT(TM)

Sales Contact
Mr Adrian Williams
Sales Manager

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