How do we calculate the amount of amine hardener require to cure epoxy resin?

Epoxy resins:

The most common matrix for advanced composites and for a variety of demanding
applications is epoxy. Epoxies have taken this major role because of their:

 Excellent adhesion,
 Good strength,
 Low shrinkage,
 Good corrosion resistance,
 Processing versatility,
 Many other properties.

Epoxies may be more expensive than polyesters and may not perform as well in high
temperature applications as polyimides, but overall their properties are excellent.
Generally epoxies do a fine job in transferring loads to the reinforcement and in
protecting the reinforcement from adverse environmental effects.

Epoxy chemical structure and polymer formation:

Epoxies are characterized by the presence of an epoxy group-a three-membered ring with
two carbons and oxygen as shown in Figure 1. This epoxy group is the site of the
crosslinking reaction in roughly the same way as the carbon-carbon double bond in the
site of polyesters, although the crosslinking reactions are quite different.

The properties of the crosslinked polymer are more dependent upon the choice of curing
systems in epoxies than in polyesters, so both the nature of the epoxy and of the curing
system must be understood. Many epoxies use the slightly modified epoxy group with
one additional carbon. This group is called the glycidyl group and is illustrated in Figures
1 and 2.

In addition for being the site that is used for crosslinking, the epoxy group provides for
good adhesion with the reinforcement or with the “surface” of another material.

The aromatic (benzene) groups provide the stiffness, temperature stability and other
physical properties characteristic of epoxies.

Dyglycidyl ether of bisphenol A (DGEBPA):

The most common of the epoxy resin systems is based upon the condensation polymer
formed from epichlorohydrin and bisphenol A and is called diglycidyl ether of bisphenol
A (DGEBPA) (see Figures). The reaction to form the resin from the reactants is as
follows:

1
 GROUPS CH CH CH CH CH2
O O
Epoxy Group Glycidyl

REACTANTS
CH3

CH2 CH CH2 Cl + H O OH
O
CH3
Epichlorohydrin Bisphenol-A

EPOXY PRODUCT
CH3

CH2 CH CH2 O O CH2 CH CH2

O O
CH3

CH3

CH2 CH CH2 Cl + H O OH
O
CH3
Epichlorohydrin Bisphenol-A

CH3

CH2 CH CH2 O O H
O
CH3
Add another epichlohydrin

CH2 CH CH2 Cl Epichlorohydrin

O

CH3 CH3

HO OH CH2 CH CH2 O O CH2 CH CH2

O O
CH3 CH3
Above is the basic unit of DGEBPA

Add another Bisphenol A:

2
 CH3

HO OH Bisphenol-A

CH3

CH3 CH3

CH2 CH CH2 O O CH2 CH CH2 O OH

O OH
CH3 CH3

Add another Epichlohydrin:

CH2 CH CH2 Cl Epichlorohydrin

O

CH3 CH3

CH2 CH CH2 O O CH2 CH CH2 O O CH2 CH CH2

O O
CH3 OH CH3

Figure 1. Epoxy groups and reactants for epoxy polymers.

This resin is available at various chain lengths depending upon the amounts of reactants
present and other reaction conditions.

Specialty epoxy resins:

The other epoxies listed in Figure 2 are generally used for special property consideration
where DGEBPA is not appropriate. For instance:

 The epoxidized phenolic novolacs react more rapidly than do DGEBPA systems and
added strength and chemical resistance at high temperatures. Example: DOW DEN
438.
 The tetraglycidyl ether of tetrakis (hydroxyphenyl) ether has excellent adhesive
properties and greater strength, rigidity, resistance to moisture and improved electrical
properties at elevated temperatures. Example SHELL EPON 103
 Tetraglycidylmethylene dianiline (TGMDA) also exhibits improved properties at
elevated temperatures. Example: CIBA My-720.

3
 CH3 CH3

CH2 CH CH2 O O CH2 CH CH2 O O CH2 CH CH2

O n O
CH3 OH CH3
Diglycidyl Ether of Bisphenol A (DGEBPA)

CH2 CH2 CH2

O O O
CH CH CH
CH2 CH2 CH2
O O O
CH2 CH2
n

Epoxy Novolac (Epoxidized Phenolic Resin)

Example: DOW DEN 438

CH2 CH CH2 O C O CH2 CH CH2

O O

CH2 CH CH2 O C O CH2 CH CH2

O O
H
Tetraglycidylether of Tetrakis (Hydroxyphenyl) Ether
Example: SHELL EPON 103

O O
CH2 CH CH2 CH2 CH CH2
N CH2 N
CH2 CH CH2 CH2 CH CH2
O O
Tetraglycidylmethylene Dianiline (TGMDA)
Example: CIBA MY-720

Figure 2. Major epoxy resin systems

Curing systems for epoxies (hardeners):

Three cure systems are of primary importance for epoxies: amines, anhydrides and Lewis
acids (or catalytic curing).

Amines:

4
The most common curing system is the amine, in which one of the amine hydrogen reacts
with the epoxy ring to form a hydroxyl group which can then react with another group to
crosslink the chains. These reactions are addition reactions, and, therefore, no byproduct
is formed as would be formed in a condensation reaction. Primary amines (RNH2), which
contain two active amine hydrogens, are therefore capable of reacting with two epoxy
groups and achieving a greater crosslink density (number of crosslinks per polymer) than
single functional hardeners. This greater crosslink density generally improves physical
properties, although at the expense of flexibility. If the amine is aromatic, the overall
stiffness, low shrinkage, and temperature capability is improved, although toughness is
sacrificed.

The chemical structures, and viscosities of the commonly used amine curing agents are
shown in Table 1.

Table 1. Structures and Characteristics of Commonly Used Amine Curing Agents

AMINE HYDROGEN VISCOSITY @

AMINE CURING AGENTS EQUIVALENT 25°C (77°F), COMMENTS
WEIGHT - AHEW (g/eq) Pa.sec (cP)
Available from Dow
Diethylenetriamine (DETA) 0.0055- Chemical Company as
H2N CH2 CH2 NH CH2 CH2 NH2 20 0.0085 DEH 20 and also from
(5.5-8.5) Union Carbide
Corporation.
Available from Dow
Triethylenetetramine (TETA) Chemical Company as
0.020-0.023
H2N ((CH2)2 NH)2 CH2 CH2 NH2 24 DEH 24 and also from
(20-23)
Union Carbide
Corporation.
Diethylaminepropylamine
(DEAPA)
CH3 CH2 Available from Union
65  5.0
N CH2 NH2
Carbide Corporation.
3
CH3 CH2
Lewis base used as the sole
2-Ethyl-4-methylimidazole (EMI) curing agent in small
N C CH3
nonstoichiometric amount
Liquid at 25oC
(77°F)
to provide long pot life and
C CH 110 4-8 Pa.sec, good elevated-temperature
(4000-8000) properties. Available from
CH3 CH2
N Houdry Process &
H
Chemical Company as
EMI-24

5
An amine is a substance that contains nitrogen. There are three types of amines. When a
molecule containing a reactive group consisting of nitrogen is attached to two hydrogens,
this is called primary amine. When the reactive group consists of nitrogen attached to one
hydrogen, this is called secondary amine. When there is no hydrogen attached to the
nitrogen, this is called tertiary amine.

It can be seen that many of the structures given in Table 1 include reactive groups at each
end. These permit the formation of crosslinks between epoxy molecules. For example, an
amine end group with two hydrogens on the nitrogen (a primary amine) reacts with the
epoxy molecule as follows:

OH

NH2 NH2 + CH2 CH NH2 NH CH2 CH

O

When another amine hydrogen combines with a second epoxy molecule, a crosslink is
formed. The curing agents in Table 1 that contain secondary amine end groups (one
hydrogen on the nitrogen) react in much the same way.

OH
OH

+ CH2 CH NH2 N CH2 CH

NH2 NH CH2 CH
O
CH2

CH OH

For thorough crosslinking, the hydrogens of the primary and secondary amines should be
matched 1:1 with the epoxy groups. The amounts of curing agent and epoxy resin needed
in order to obtain the 1:1 stoichiometric quantity are calculated as follows:

Molecular weight of amine

Parts by weight of amine to be Number of available hydrogens per molecule
used with 100 parts by weight = X 100
of epoxy resin (phr) Epoxy equivalent weight

Tertiary amines (no hydrogen on the nitrogen) are Lewis bases that cure epoxy resins in
an entirely different manner than the aromatic and the aliphatic amines. They are added to
an epoxy resin in small nonstoichiometric amounts that have been empirically determined

6
to give the best properties. The curing agent operates as a true catalyst by initiating a self
perpetuating anionic polymerization.
+
R3 N + CH2 CH CH2 R R3 N CH2 CH CH2 R
O
O

+ +
R3 N CH2 CH CH2 R + CH2 CH CH2 R' R3 N CH2 CH CH2 R
O O
O
CH2 CH CH2 R'
O
CH2 CH CH2R''
O
and so on.

This homopolymerisation of epoxy molecule to epoxy molecule results in a polyether.

The ether linkages (C-O-C) are fairly stable against most acids (both organic and
inorganic) and alkalis. Further, like ester linkages, they are more thermally stable than the
carbon-nitrogen linkages formed by an amine cure. Of the Lewis bases listed in Table 1,
EMI is the most efficient, that is, it produces the highest degree of crosslinking and the
highest heat distortion temperature.

Example:

Question:

It is desired to cross link a DGEBPA epoxy resin using an amine curing agent called
DETA. The formula for the two materials are as shown below. How many grams of
DETA should be used if 100g of the epoxy resin is used.

Solution:

The epoxy formula has 21 carbon atoms, 24 Hydrogen atoms, and 4 oxygen atoms. The
mass of the epoxy unit is therefore:

m1 = 21 (12) + 24 (1) + 4 (16) = 340 g/mole

The DETA formula has 3 Nitrogen atoms and 13 Hydrogen atoms. The mass of DETA is:

m2 = 3 (14) + 13 (1) =55 g/mole.

In the epoxy molecule, there are two epoxy groups, the epoxy equivalent weight is
therefore:

7
m3 = 340/2 = 170 g/mole.

There are 4 available hydrogens in the amine molecule. The value of molecular weight of
amine over the number of available hydrogens per molecule is:

m4 = 55/4 = 13.75 g/mole

Parts by weight of amine to be used with 100 parts by weight of epoxy resin are:

% = 13.75/170 x 100 = 8.1%

For 100g of epoxy, the amount of amine curing agent to be used is: 8.1 g.