07/09/2023

220331 - Composite Materials

Master’s Degree in Aeronautical Engineering

Part 1. Composition, manufacturing and properties

Prof. Marcelo Antunes

[email protected]

Module 2: Raw materials for Dedication: 15 hours Large group: 4 hours

aerospace composites Small group: 2 hours
Autonomous learning: 9 hours

Description Reinforcements for aerospace composites. Fibres. Basic properties of

fibres and engineering materials. Fibre types. Fibre finishes. Fabrics.
Fabric types. Core materials for sandwich panels. Foam Cores.
Honeycombs. Design considerations. Polymer matrices.
Thermosetting polymer matrix. Types of resins. Gelation, curing and
post-curing. Thermoplastic polymer matrices. Engineering and high
performance thermoplastics. Comparison of resin properties.
Related activities - Theory and practical classes
- Laboratory session: Physical-chemical analysis of components of
composites.

1
 07/09/2023

Part 1. Composition, manufacturing and properties

Module 2b: Raw materials for aerospace composites:

Polymer matrices

2.4. Thermosetting polymer matrices.

2.4.1. Gelation, curing and post-curing.
2.4.2. Types of thermosetting resins.
2.5. Thermoplastic polymer matrices.
2.5.1. Engineering thermoplastic polymers.
2.5.2. High-performance thermoplastic polymers.
2.6. Comparison of properties.

Module 2b: Polymer matrices for composites

Polymer matrices play the following main roles in composites:

• Give shape to the composite part.

• Keep the fibres in place.
• Transfer stresses to the fibres.
• Protect the reinforcement from the environment, such as chemicals and moisture.
• Protect the surface of the fibres from mechanical degradation.
• Act as shielding from damage due to handling.

Although polymers have low mechanical properties compared to the fibres, the matrix influences
many mechanical properties of the composite. These properties include:

• Transverse modulus and strength.

• Shear modulus and strength.
• Compressive strength.
• Inter‐laminar shear strength.
• Thermal expansion coefficient.
• Thermal resistance.
• Fatigue strength.

Polymers used as matrix in fibre‐reinforced composites are generally called ‘resins’. Polymers can
be classified under two types: ‘thermosets’ and ‘thermoplastics’, according to the effect of heat on
their properties.
4

2
 07/09/2023

2.4. Thermosetting polymers

Thermosetting resins (‘thermosets’) are supplied as liquid chemicals (low MW, low viscosity) and
undergo an in‐situ non‐reversible chemical reaction that features polymerization and crosslinking,
to form a hard, infusible material. Consequently, thermosets become crosslinked during fabrication
and do not soften upon reheating.

Curing of a thermoset as heat is applied

The chains (molecules) are crosslinked (bonded) to each other to make a stiff 3D structure.
Difference with rubbers is that these involve crosslinking of already polymerized molecules to
stiffen the molecules together in the vulcanization process.
5

Heat is needed to cause polymerization, to increase MW and to cause ‘molecular stiffening’

through crosslinking. Heat reduces the viscosity of the chemicals until the reaction occurs and then
causes an important increase in viscosity during crosslinking.
Types of thermosets:

‐ Temperature‐activated
‐ Catalyst‐activated
‐ Mixing‐activated

Temperature‐activated:

All thermosets require heat to undergo chemical reaction.

• Low temperature thermosets (room temperature curing) react to a more rubbery polymer that
gets stiffer upon additional heat.
• Pot life: Time required for the thermoset to react and transform into a solid after mixing.
• Gel time: Time required for the thermoset to form a gel or skin (and stop flowing).

Several thermosets are supplied as powders or in granular form.

• Heat reduces the viscosity and melts the polymer to allow it to flow and be molded.
• Additional heat triggers the chemical reaction, which forms a crosslinked 3D structure.

Common temperature‐activated (≡ heat-activated) polymers: Formaldehyde (FOR), Phenoplasts

(PF), Aminoplasts (UF), Polyester, Vinyl ester, alkyd, allyl, furan, some epoxies, and polyimides.
6

3
 07/09/2023

Catalyst‐activated:

Some thermosets are supplied in a stable liquid form.

• Small amount of liquid (catalyst) is added, starting the cure reaction to form a 3D structure.
• Chemical type and amount of catalyst controls the extent and speed of reaction.
• Many systems can set at room temperature.
• Useful for casting resins and for glass fibre‐reinforced composites.

A common polymer is unsaturated polyester resin (UP).

Mixing‐activated:

Some thermosets are supplied as two stable liquids.

• When the two are added together, a chemical reaction starts and forms a 3D structure.
• Ratio of the two chemicals and temperature controls the extent of reaction and the speed of
polymerization.
• Many systems can set at room temperature.
• Useful for casting resins and for glass fibre‐reinforced composites.

Common polymers are polyurethane and epoxies. Polyurethane can be mixed at high speeds using
a Reaction Injection Molding (RIM) process.

Gelation, curing and post‐curing.

In some thermosets, such as phenolic resins, volatile substances are produced as by‐products
(‘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
and its degree of cure. Above the Tg, the molecular structure of the thermoset changes from a rigid
state to a more flexible one. 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.
8

4
 07/09/2023

The majority of structural parts are made with three main types: polyester, vinylester and epoxy.

On addition of the catalyst or hardener a resin becomes more viscous until it reaches a state when
it is no longer a liquid and has lost its ability to flow. This is the ‘gel point’. The resin will continue to
harden until it reaches its maximum hardness and properties. The curing reaction is exothermal.

The speed of cure is controlled by the amount of accelerator in a polyester or vinylester resin and
by varying the type, not the quantity, of hardener in an epoxy resin. Generally, polyester resins
produce a more severe exotherm and a faster development of initial mechanical properties than
epoxies for a similar working time.

As curing is exothermal, it is possible to accelerate it by applying heat to the system (the higher the
temperature the faster the final hardening). This can be most useful when curing would otherwise
take several hours or even days at room temperature.
9

A quick rule of thumb for accelerating the effect of heat on a resin is that a 10 °C increase in
temperature will roughly double the reaction rate.

Therefore, if a resin gels in a laminate in 25 minutes at 20 °C it will gel in about 12 minutes at 30 °C,
providing no extra exotherm occurs.

• Curing at elevated temperatures has the added

advantage that it actually increases the end
mechanical properties of the material, and many
resin systems will not reach their ultimate
mechanical properties unless the resin is given
this ‘postcure’.

• The postcure involves augmenting the laminate

temperature after the initial room temperature
cure, increasing the amount of molecular
crosslinking.

To some degree this postcure will occur naturally at warm room temperatures, but higher
properties and shorter postcure times will be obtained if elevated temperatures are used. This is
particularly true for the material’s softening point or Tg, which, up to a point, increases with
increasing postcure temperature.

10

5
 07/09/2023

Types of thermosetting resins

Polyester resins
Polyester resins (UP) are the most widely used resin systems, particularly in the marine industry. UP
resin is capable of being cured from a liquid or solid state when subjected to the right conditions.
By using di‐alcohols (glycols) in reaction with di‐acids or anhydrides, unsaturated polyesters are
produced. At least some of the acid (or anhydride) features C=C double bonds for unsaturation. This
reaction, together with the addition of crosslinking monomers, is the basic process of UP resin
synthesis. Varying properties result for UP resins by using different acids, glycols and monomers.
There are two main types of polyester resins used as standard laminating systems in the
composites industry. Orthophthalic polyester resin is the standard economic resin used by many
people. Nevertheless, isophthalic polyester resin is now becoming the preferred material in
industries such as marine, where its superior water resistance is desirable.

The idealized 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.
11

Most polyester resins are viscous, pale coloured liquids consisting of a solution of a polyester in a
monomer which is usually styrene. The addition of styrene in amounts of 30% 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 ‘crosslinking’ the molecular chains
of the polyester without the evolution of any by‐products.

With the addition of styrene, and in the presence of a catalyst, the styrene crosslinks the polymer
chains at each of the reactive sites to form a highly complex three‐dimensional network:

The UP resin is then said to be

‘cured’. It is now a chemically
resistant hard solid. The cross‐
linking or cure reaction is also
called ‘polymerization’. It is a non‐
reversible chemical reaction.

These resins can therefore be molded without the use of pressure and are called ‘contact’ or ‘low
pressure’ resins. UP 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 (hydroquinone, tertiary butyl catechol).
12

6
 07/09/2023

Heat or radiation can trigger the crosslinking reaction. However, the rate of cure is too slow for
practical purposes and hence catalysts are used. For use in molding, a UP resin requires the
addition of auxiliary products. These are generally:

■ Catalyst (“iniciador”). Starts or activates the crosslinking reaction (also called initiator). Methyl
ethyl ketone (MEK) peroxide, benzoyl peroxide, cumene hydroperoxide, etc.

■ Accelerator (“catalizador”). Accelerates the decomposition of the organic peroxide initiators and
thus promotes crosslinking. It is retrieved at the end of the reaction. Cobalt octoate, etc. The
accelerator is added to the catalyzed 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.

■ Additives: Thixotropic agents, pigments, fillers, flame retardants, etc.

13

Great care is needed in the preparation of the resin mix prior to molding:

• The resin and any additives must be carefully stirred to evenly disperse all the components
before the catalyst is added.

• Stirring must be thorough and careful as any air introduced into the resin mix affects the quality
of the final molding. This is especially so when laminating with layers of reinforcing materials as air
bubbles can weaken the structure.

• It is also important to add the accelerator and catalyst in carefully measured amounts to control
the polymerization reaction to give the best material properties. Too much catalyst will cause a too
fast gelation time, whereas too little catalyst will result in under‐cure.

• Colouring of the resin mix can be carried out with pigments. It is easy to affect the curing reaction
and degrade the final laminate by use of excess and/or unsuitable pigments.

• Filler materials are used extensively with polyester resins to reduce the cost of the part, to
facilitate molding or to impart specific properties, among others.

• Fillers are often added in quantities up to 50% of the resin weight. Such addition levels will affect
the flexural and tensile strength of the laminate.

• The use of fillers can be beneficial when laminating or casting thick components, where
otherwise considerable exothermic heating can occur. Addition of certain fillers can also contribute
to increase the fire resistance of the laminate.
14

7
 07/09/2023

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.

Vinyl ester resins are 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. Vinyl toluene is sometimes used instead of styrene as crosslinking agent.

The vinyl ester molecule 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.

The idealized chemical structures of typical vinyl ester

and unsaturated polyester molecules.
15

Epoxy resins

The large family of epoxy resins represent some of the highest performance resins of those
available at this time. They are usually identifiable by their characteristic amber or brown color.

The simplest epoxy (ethylene oxide) group is a three‐member ring structure known as ‘alpha‐
epoxy’ or ‘1,2‐epoxy’. Epoxy resins are easily and quickly cured from 5°C to 150°C, depending on
the choice of curing agent.

Epoxies generally out‐perform most other resins in terms of mechanical properties and resistance
to environmental degradation, which leads to their almost exclusive use in aircraft components.

Epoxy resins have a number of useful properties. Both the liquid resin and the curing agents form
low viscosity easily processed systems. 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 primary construction material for high‐performance boats
or as secondary application to sheath hulls or replace water‐degraded polyester resins and gel
coats. Epoxies find uses as adhesives, caulking and casting compounds, sealants, varnishes and
paints, as well as laminating resins for a wide variety of industrial applications.

One of the most advantageous properties of epoxies is their low shrinkage during curing, which
minimizes fabric ‘print‐through’ and internal stresses. High adhesive strength and high mechanical
properties are also enhanced by high electrical insulation and good chemical resistance.
16

8
 07/09/2023

Epoxy resins are formed from a molecular structure similar to vinylester with reactive sites at either
end. The absence of ester groups means that the epoxy resin has particularly good water resistance.
When the epoxy molecule contains aromatic groups, the resin has a very good stiffness, toughness
and heat resistant properties.
Epoxy resins:

Diglycidyl ether of bisphenol A (DGEBRA)

Tetraglycidyl methylene dianiline (TGMD)
Epoxy phenol cresol novolac
Cycloaliphatic epoxies (CA)
Idealized chemical structure of a typical Epoxy (Diglycidyl Ether of Bisphenol‐A)

Epoxies differ from polyester resins in that they are cured

by a ‘hardener’ rather than a catalyst. The hardener
(amines or anhydrides) has active hydrogens that react
with epoxy groups by an ‘addition reaction’. Often an
amine (DETA, TETA, hexamethylene tetramine) is used to
cure the epoxy, with two epoxy sites binding to each amine
site (i.e., primary amine).

Since the hardener ‘co‐reacts’ with the epoxy molecules in

a fixed ratio, it is essential to use a correct mix ratio
between resin and hardener to ensure complete reaction.
If amine and epoxy are not mixed in the correct ratios,
unreacted resin or hardener will remain within the matrix,
affecting the final properties after curing.
17

Other resins used in composites

Besides polyesters, vinylesters and epoxies, there are a number of other specialized resin systems
that are used where their unique properties are required:

Phenolic resins

Primarily used where high fire‐resistance is required, phenolics also retain their properties at
elevated temperatures. Typical cost: £2‐4/kg.

Formed by reaction between phenol and formaldehyde. Condensation reaction releases water as a
by‐product. The condensation nature of their curing process releases water as a by‐product tending
to lead to the inclusion of voids and surface defects, and the resins tend to be brittle and do not
have high mechanical properties.

Initial low molecular weight, soluble and fusible, is called A‐Stage resin. Condensation reaction
involves more and more phenol molecules that causes the resin to pass through a rubbery,
thermoplastic state that is partially soluble phase, B‐stage. Fully cured crosslinked resin ‐ C‐ Stage.

18

9
 07/09/2023

If phenol/formaldehyde reaction is carried out in excess formaldehyde and base catalyst is called
resole at low molecular weight stage. Requires just heat to convert to C‐stage.

If phenol/formaldehyde reaction is carried out in excess phenol with an acid catalyst is called
novolac. Requires addition of a hardener (hexamethylene tetramine) to achieve C‐Stage.
Reinforcements are commonly mixed with novolacs for producing composites.

Phenolic is an old thermoset resin (Bakelite) used for general purpose parts: electrical switches,
junction boxes, automotive molded parts, consumer appliance parts, handles, abrasive binder for
grinding wheels and brakes, billiard balls. Fillers (cellulosic fibres like wood flour, minerals like
talc, or carbon black) are usually required due to high shrinkage and brittleness.

Fibre‐reinforced phenolics have aerospace applications:

• Rocket nozzles.
• Nose cones due to ablative nature (pass from solid to gas during burning).
• High temperature aircraft ducts.
• Wings and fins.
• Mufflers.
• Repair kits.
• Fire resistant rigid foams.

Aminoplasts (amino resins)

• Similar to phenol, formaldehyde can also react with melamine or urea to form a 3D molecular
network through condensation reaction involving the oxygen and two hydrogens from two different
molecules.
• Resins can be cured from both one or two stage systems (resol or novolac prepolymers).
• Supplied as powder, granule form or pills (compacted preforms). Can be made translucent or in
light colors for aesthetics. Molding temperatures (125‐200 °C) and molding pressures of 130‐550
bar for compression molding and 1200 bar for injection‐molding.

o Urea‐formaldehyde resins are used for many of the same applications as phenolics. Moldable
foam system is used for home insulation.

o Melamine‐formaldehyde resins noted for their excellent water resistance. Form surface layers for
decorative laminates (Formica). Also usually used as adhesives for water resistant plywood.

20

10
 07/09/2023

Furan resins

• Furan resins are thermoset condensation bio‐based resins derived from renewable sources.
Produced from pentose sugars (from the hemicellulosic part of agricultural wastes), furfuryl alcohol
or its prepolymers make up the raw materials of furan thermosets.

• Current advances (http://www.jeccomposites.com/news/composites‐news/application‐novel‐furan‐resins‐

composites) render furan resins appropriate to produce natural fibre‐reinforced composites
(NFRC) as those for automotive interior trim parts.

• The high intrinsic fire resistance of furan resins renders these composite materials applicable for
fireproof purposes in public transport, construction, etc.

• Combined with formaldehyde‐based thermosets is used as binder for sand in foundry work,
abrasive particles in grinding wheels, or as adhesives and matrix for reinforced plastics where
corrosion resistance is important.
21

Polyurethanes (PUR)
• High toughness materials, sometimes hybridized with other resins, due to relatively low laminate
mechanical properties under compression. Typical cost: £2‐8/kg.
• Reaction between isocyanate (R‐N=C=O) and alcohol (polyol). Crosslinking occurs between
isocyanate groups (‐NCO) and the polyol’s hydroxyl end groups (‐OH). Catalysts are used to initiate
the reaction.
• Ratio between the two gives a range of properties between a flexible foam (some crosslinking) to
a rigid urethane (high crosslinking degree). Density can range from 15 kg/m3 to as high as 1100
kg/m3.
• PUR foams are produced by chemical blowing agents.
• RIM process is used to produce automobile parts, as fenders and bumper covers. Structural RIM
produces fibre‐reinforced PUR parts.

22

11
 07/09/2023

23

Polyimides (PI), bismaleimides (BMI) and polybenzimidazole (PBI)

• Polyimides are stable up to 315 ºC. High cost (> £80/kg). Aerospace (missile, aero‐engine parts).

• PI are characterized by heterocyclic groups containing a nitrogen and two carbonyl groups.
Formed from two step condensation:

o First step: An aromatic dianhydride reacts with an aromatic diamine to form polyamic acid.
o Second step: Curing of the polyamic acid (formation of a 5‐member ring imide group;
condensation of solvent molecules ‐water, alcohol, solvents‐, chain extension and crosslinking.

High viscosities of polyamid acids require use of

prepregs in composites, impregnating the fibre mat
with solutions of monomers. Long times and gradual
increase in temperature are needed. Dupont’s Avimid
PI grades are marketed as prepregs.

• Polyimides tend to be difficult to process due to their condensation reaction emitting water
during curing, and are relatively brittle when cured.

• Linear polyimides are produced with a thermoplastic behavior.

24

12
 07/09/2023

Polybenzimidazoles (PBI) are characterized by a five member ring containing two nitrogen atoms
attached to a benzene ring.

Less prevalent, PBI have equivalent and sometimes superior physical and thermal properties than
polyimides. Both PI and PBI are structurally planar and very rigid. Large aromatic groups are
added into the polymer to make it stiffer.
The resin is expensive, difficult to process and toxic. It is a thermoplastic with a Tg over 427 ºC. It
does not burn, does not contribute as fuel to flames and does not produce smoke. Forms a tough
char.
Bismaleimides (BMI) are primarily used in aircraft composites where operation at high
temperatures (230 °C wet/250 °C dry) is required. Examples: engine inlets, high speed aircraft
flight surfaces. Typical cost: > £50/kg.

Advantages:
• Low processing temperature vs. polyimides (cured at 150 ºC). Standard epoxy processing
equipment can be used due to same T. Post‐curing at 245 ºC is required to complete the reaction.
• BMI are fully formed polyimides when reacted to form composite. Thus, no volatiles are
removed and no consolidation problems.
• Tack and drape are quite good because of the liquid component of the reactants.
25

26

13
 07/09/2023

Cyanate Esters

Primarily used in the aerospace industry. The material’s excellent dielectric properties makes it very
suitable for use with low dielectric fibres such as quartz for the manufacture of radomes. The
material also possesses a temperature stability up to around 200 °C wet. Typical cost: £40/kg.

Silicones

Synthetic resin using silicon as backbone rather than the carbon of organic polymers. Good fire‐
resistant properties and capacity to withstand elevated temperatures. High temperature for curing
is needed. Used in missile applications. Typical cost: > £15/kg.

27

2.6 Thermoplastic polymer matrices

Generally, thermoplastics are reinforced with glass and a few with carbon fibres.

• General advantages:
– Requires less processing time since it is heated and not cured.
– Thermoplastic pre‐pregs have infinite shelf life versus thermosets.
• General disadvantages:
– Have lower thermal resistance than most thermoset composites.
– Have lower strength and modulus than some thermoset composites.
– Have difficulty wetting out high fibre loading composites.

Three main groups of useful thermoplastic polymers:

• Commodity plastics: PP, PE, PVC, PS, etc. (< 2 €/kg)

• Engineering plastics: PC, PET, PBT, Nylon, ABS, etc. (2‐5 €/kg)
• High performance plastics: High cost (> 20 €/kg) and high thermal properties.
Polyether ether ketone (PEEK), polyether ketone (PEK), liquid crystalline polymers (LCP), poly(p‐
phenylene sulfide) (PPS), polyarylsulfones (PSU, PESU, PPSU), polyetherimides (PEI).

28

14