Cairo University

Faculty of Engineering
Mining, Petroleum and Metallurgy Department
4th Year Metallurgy

Elective Course (2) -

Composite Materials
MET 443
LECTURE 5
By Dr. Ahmed Hatem Al-Khoribi
• Types of resins
• Epoxy

• Epoxy resins have been in the industry

for several decades. They were first
commercialized in 1946. Nowadays they
are widely used in industry as protective
coatings and for engineering applications
such as laminates and panels, tooling,
molding, bonding and adhesives, and
others.
• Epoxy resin is a very common matrix used in
the processing of FRP composites, especially
CFRP composites, owing to its superior fatigue,
bonding strength, and toughness when
compared to other resin systems such as
polyester and vinyl ester resins.

• These superior properties can be attributed to

the aromatic groups (benzene rings) that are
present in the epoxy resin, making it stronger
and more thermo-stable than other resins. In
addition, epoxy resin possesses much greater
water resistance than both resins.
• Epoxies have also been used extensively for
several applications due to their excellent
properties such as excellent adhesion, high
specific strength, good corrosion resistance, high
dimensional stability (i.e. high resistance to
thermal influences), low shrinkage upon curing
(as compared to polyester resin), and good
electrical insulating properties and processing
versatility.

• In addition, the processing of epoxy resins does

not involve toxic gases. On the other hand, epoxies
are more expensive than polyesters and have
higher viscosities than polyesters and are usually
more brittle.
• The most important epoxy resins used in the
construction, aerospace, and automotive
industries are oligomers (low-molecular weight
polymers), produced from the condensation
polymerization reaction of bisphenol A and
epichlorohydrin forming a resin called
diglycidyl ether of bisphenol A (DGEBA) as
shown in Figure.
• This condensation polymerization reaction
provides an excellent balance between
physical, chemical and electrical properties.
• HCl is produced as a by-product during this
reaction.
• The figure below shows the condensation
polymerization reaction of bisphenol A and
epichlorohydrin forming epoxy resin DGEBA.
• The figure below shows the structural formula
of a basic epoxy molecule with two epoxy
groups (an epoxy group, also called epoxide
ring, is a three-membered ring with two
carbons atoms and an oxygen atom) at two
ends.
• The most common curing agents that are used to
form cross-linked network between the linear
molecular chains of epoxy resin are: amines and
anhydrides.

• However, the curing (cross-linking) reaction is

addition polymerization reaction where the epoxy
group (ring) opens and reacts with the curing
agent without the formation of by-products.

• Note: Anhydride is a type of chemical compound

derived by the removal of water molecules from
an acid. An amine is a substance that contains
nitrogen.
• The figure below shows the structure of a cured
epoxy glue. The triamine hardener is shown in red,
the resin in black. The resin's epoxide groups have
reacted with the hardener and are not present
anymore. The material is highly cross-linked and
contains many OH groups, which allow adhesive
properties.
• There are several reasons why epoxy resins out-
perform other resins such as vinyl ester and
polyester resins.
• Among these reasons are their enhanced
impermeability to water (i.e. high water
resistance), and the high bonding qualities they
posses. The ability to adhere to aramid (Kevlar),
carbon, and glass fibers as well as the ability to
bond to most materials very well has allowed the
use of epoxy resins for repairing structures and
columns.
• Another reason why epoxy resins are the first
choice in repairing is their extremely durability.
Epoxy resins also do not change weight
throughout their lifetime.
• Note: In condensation polymerization, each step of
the process is accompanied by formation of low
molecular weight by-products (for example, water,
alcohols, and hydrogen halides).

• Note: In addition polymerization, monomers react to

form a polymer without the formation of by-
products.
• Polyester

• Polyester-based matrix is the most frequently

used matrix since polyester resin is very cheap
when compared to other resins.
• Polyester resins are low-viscosity liquids based on
unsaturated polyesters.
• The unsaturation arises from the C=C double
bond which survived the polymerization reaction
(that formed the linear molecular chains of
unsaturated polyesters) and is contained in every
repeating unit of the polymer.
• This double bond is very important since it is
where the cross-linking (curing) occurs.
• The unsaturated polyesters are dissolved in a
reactive curing agent such as styrene to form
cross-links.
• However, for the cross-linking reaction (which is
addition polymerization reaction) to initiate, a
free radical initiator must be added to the
unsaturated polyester and styrene in order to
break the C=C double bond allowing styrene to
form cross-links between the linear molecular
chains.
• The addition of heat and a free radical initiator,
such as organic peroxide, results in a cross-linking
reaction, converting the low-viscosity solution
into a three-dimensional thermosetting matrix.
Cross-linking can also be accomplished at room
temperature using peroxides.
• The figure below shows a styrene molecule
and a polyester molecule.
• Basically, the cross-linking reaction is initiated
by a molecule that readily produces free
radicals (a chemical species with unpaired
electrons).
• The most common group of such free radical
initiator molecules is the organic peroxides.
Organic peroxides are useful as initiators or
cross-linking agents because of the thermally
unstable O–O bond which decomposes to
form free radicals. Basically, organic peroxides
can be viewed as derivatives of hydrogen
peroxides in which one or both hydrogen
atoms are replaced by organic radicals.
• Polyester resins can also be formulated to have good
UV resistance and to be used in outdoor
applications. The linear molecular chains of
unsaturated polyesters are formed by the
condensation polymerization of a diacid and a
dialcohol (a diacid means two organic acid groups
are present in a molecule, and a dialcohol,
sometimes called a diol, has two alcohol groups in
the molecule). H2O is produced as a by-product
during this reaction.
• Vinyl ester

• Vinyl ester resins are produced by the addition of

unsaturated carboxylic acids (methacrylic or
acrylic acid) (these molecules have the COOH
termination) to an epoxy resin that contains
epoxide rings (DGEBA).
• The reaction of acid addition to the epoxide ring
(esterification) is exothermic and produces a
hydroxyl group without the formation of by-
products (e.g. water).
• As such, the production of the vinyl ester resins
by addition polymerization is less chaotic and
messy than the production of polyester resins
where condensation polymerization occurs.
• Since vinyl esters are unsaturated esters of epoxy
resins, they have mechanical and in-service
properties similar to those of epoxy resins but,
because their processing and curing techniques
are similar to those of the polyesters, they are
sometimes identified as a class of unsaturated
polyester.
• Like unsaturated polyesters, vinyl esters contain
double bonds that can react and form cross-links
if they are broken, i.e. if transformed into free
radicals. For that reason, a free radical initiator
must be added. Typical free radical initiators for
vinyl ester resins are organic peroxides.
• Owing to their chemical structure, vinyl ester resins
have fewer cross-links than polyesters.
• They also are more flexible and have higher toughness
than polyesters. Also, they have very good wet-out and
good adhesion when reinforced with glass fibers.
• The properties of vinyl ester resins are a good
combination of those of epoxy and polyester resins
making them the preferred choice for manufacturing
glass fiber reinforced composites.
• They exhibit some of the beneficial properties of
epoxies such as tensile strength and chemical resistance
as well as those of polyesters such as viscosity and fast
curing.
• However, their volumetric shrinkage is greater than that
of epoxy and their adhesive strength is moderate
compared to that of epoxy resins.
• Phenol

• Phenol resins are used when there are

requirements for high fire resistance,
temperature resistance, low smoke
generation, and flame retardation when
subjected to fire.

• In general, all types of resins are sensitive to

UV radiation. Therefore, they require an
appropriate protection by means of special
additives.