1.

1 OBJECTIVES

1. To understand the process of curing in forming thermosetting resins.

2. To determine the gel time for different ratio of epoxy/amine system.
3. To determine the gel time for the same pair of epoxy-amine at different temperature.
4. To see the effect on gel time for different ratio of epoxy and amine at the same
temperature.
5. To see the effect on gel time for different temperature of epoxy and amine at the same
epoxy/amine ratio.
6. To determine the theoretical amount (% mol) of epoxy that has reacted at gel point.
7. To determine the activation energy, Ea for epoxy polymer using the data (gel time)
obtained at a particular temperature.

1.2 THEORY

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Epoxy or epoxide resins are those resins or polymers which are produced by condensation
reactions using an epoxy compound as an ingredient in the monomeric reactant mixture. The
curing or cross-linkage agents commonly in use are diamines. With amines, the reaction
involves through opening of the epoxide rings giving ß-hydroxy amino. Amines are fast
curing agent even at room temperature, they can react with epoxide groups and form a good
chemical resistance material but they are toxic and skin-sensitive.

Figure 1: epoxy monomer

Figure 2: diamine

Gel Point

Gel time is the time required for a liquid material to form gel under specified conditions of
temperature. The detail procedure to determine gel time should be referred to ASTM D2471-
94.

Activation Energy

The reaction kinetics of epoxy resins can be studied using differential scanning calorimeter
(DSC). The basic assumption in the kinetic study using DSC is the heat flow relative to the
instrumental base line is proportional to the reaction rate. It is also assumed that the
temperature gradient through the sample and the temperature difference between the sample
and reference are small.

. The degree of conversion, p at any time (t) during isothermal reaction is given by the
following equation:

2
 (1)
∆H t
p=
∆H c

Where ∆ Ht is the heat of reaction after time t, during each isothermal experiment and Hc
is the heat of complete reaction obtained from dynamic curing (temperature-scan mode). By
integrating equation (1) the rate of reaction, r is defined as:

(2)
dp 1  dH t 
r= =  
dt ∆H c  dt 

Calculation of Activation Energy, Ea from the Isothermal Reaction Kinetics of epoxy resin.

Without knowing the exact reaction mechanism, it is assumed that the reaction rate, dp/dt at
a given temperature is only dependent on the degree of conversion, ƒ(p).

The basic equation for the kinetic study can be written as:

(3)
dp
= kf ( p)
dt

where k is the Arrhenius rate constant. In this approach the reaction mechanism does not
change during the reaction process and equation (3) has the same form, for the same degree
of conversion, regardless of temperature. By integrating equation (3) from a reaction time of t
= 0 where p = 0 to a reaction time t with a conversion p, then equation (3) is reduced to:

=
t p
dp
∫ kdt
0
∫ f ( p)
0

For a given p, ∫ dp / f(p) is a constant (C) at any given temperature.

Therefore,

kt = C (4)
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Equation (4) shows that the rate constant k is inversely proportional to time for a given p
regardless of the f(p) at a given temperature.

The dependency of the reaction constant on temperature follows the Arrhenius law:

(5)
− Ea
k = k 0 e RT

By substituting equation (5) in equation (4) and taking logarithms on both sides, yields the
following

(6)
Ea
ln t = +A
RT

where Ea is the activation energy (kJ mol-1), A is a constant that is the sum of the logarithm of
the constant C of equation (4) and the logarithm of the frequency factor k0, and R is the gas
constant, 8.315 J K-1 mol-1. From equation (6), a plot of the logarithm of the time needed to
reach a conversion p versus the inverse of reaction temperature, 1/Tc will be linear with a
slope Ea/R. This equation was used to follow the activation energy during the reaction of the
unmodified and modified epoxy systems.

The above equation (6), can be used to calculate the activation energy, Ea for epoxy polymer
or any polymer system by measuring the time taken, t, for the sample to gel at a particular
temperature, T.

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2.1 RESULT

Below is the result obtained from the experiment mixing epoxy and amine at different mass
and temperature.

Mass Ratio Temperature Time (s)

Epoxy/Amine 20 g Epoxy6.4 g Room Temperature 1992 sec

Amine (25 ̊ C)

Epoxy/Amine 20 g Epoxy6.4 g 35 ̊ C 1697 sec

Amine

Epoxy/Amine 20 g Epoxy6.4 g 50 ̊ C 1366 sec

Amine

Epoxy/Amine 20 g Epoxy8 g 50 ̊ C 1214 sec

Amine

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2.2 DISCUSSION

ASTM D2741 is a standard test method for gel time and peak exothermic temperature of
reacting thermosetting resins. Hence, detail procedure in conducting the experiment is based
on the ASTM 2471 which the test method covers the determination of time where the initial
mixing of the reactants of a thermosetting plastic composition to the time when solidification
commences under condition approximating the conditions of use. Effects on gel time at
different ratio of epoxy and amine and temperature are monitored in this experiment. Epoxy
with molecular weight EPOLAM 50, 700g/mol and diamine with molecular weight 448g/mol
are used. ASTM 2741 is limited to reacting mixtures exhibiting gel times greater than 5
minutes which is also applied to the experimental condition as shown in the results.

The first three results in the table are for experimental of effects on gel time at
different temperature where as temperature increased, the gel time is decreased. As
mentioned in the theory, curing process is a chemical reaction in which the epoxide groups in
epoxy resin reacts with a curing agent to form a highly crosslinked network. Hence,
temperature influences the curing speed where higher temperature gives more heat which
then helps to fasten the reaction rate. The epoxy resins cure quickly and easily at any
temperature and, as proven the gel time decreased as temperature increased.

Amines on the other hand are the most commonly used curing agents for the epoxy
resin where it can react with the epoxide groups even at room temperature. The third and
fourth results in the table are meant to compare effects on the gel time at different ratio of
epoxy and amine at same temperature. With presence of more curing agents to react with the
epoxy resins, it reduce the time taken for the formation of gel which is being observed in this
experiment. Hence, with proven results the different ratio of epoxy and amine will also affect
the gel time in the curing process.

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 The theoretical amount of reacted epoxy can be calculated using equation below,

1
PC =
r ( f − 1)( g − 1)

Where,

Pc is the % mol epoxy that has reacted at gel point

r is mol ratio of epoxy and amine

f is number of hydrogen atom in epoxy which is 1

g is number of hydrogen atom in amine which is 4

MW Epoxy is molecular weight epoxy which is 700 g/mol

MW Amine is molecular weight amine which is 448 g/mol

Calculation result for % mol of epoxy that has reacted at gel point

Temperature Mass Mass Mol Mol Amine

̊
( C)
Epoxy Amine Epoxy (mol)
(g) (g)

25 20 6.8 0.02857142 0.01428571

9

35 20 6.8 0.02857142 0.01428571

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 9

50 20 6.8 0.02857142 0.01428571

9

50 20 8 0.02857142 0.01785714
9

Gel time-temperature profile can be calculated by plotting the equation below,

Ea
ln t gel = C +
RT

Where,

t gel is time taken for mixing epoxy and amine (sec)

Ea is activation energy (kJ/mol)

R is gas constant 8.314 J/mol K (1)

T is temperature in Kelvin

Time gel, t (sec) ln t Temperature ( ̊ C) Temperature (K) 1/T

1992 7.59689 25 298.15 0.003354016

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 1697 7.43661 30 308.15 0.003245173

1366 7.21964 50 323.15 0.003094538

From graph, we get the slope is 1453. Thus Activation energy can be calculated using
equation below,

Ea/R = 1453/K

Ea= 1453/K x 8.314 J/mol K

Ea = 12.0802 kJ/mol

Thus, Ea value is 12.0802 kJ/mol.

In processing point of view, longer gel point time is more preferable compare to short
gel point time. This is because, a long gel point time required less reactive catalyst and low
operating temperature. This also will lead to better cooling jacket operation since less heat
will be release from the equipment when applying longer gel point time (i.e low operating
temperature).

An example for chemical reaction that take place between epoxy and amine can be
seen as below:

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Besides amine, component that can be used as cross linker is Methylene Chloride.

Epoxy resins is widely use in paints and coating as well as in use in electrical systems
and electronic. Epoxy resin is preferred compared to other polymers because epoxy offers the
broadest range of performance parameter compare to any polymer. It can also be applied to a
process that required higher operating temperature and and more rapid manufacture process.
It can be use to produce various type of equipments compare to other polymers.

3.1 CONCLUSION

Through the experiment we learnt that in forming thermosetting resin, one of the processes is
crosslinking or curing reaction. In order to understand the process better, one parameter that
is, gel time is being tested in the experiment.

From the first part of the experiment, the mixing samples of epoxy and amine are tested in
different temperature. The result shows that higher temperature gave lower gel time.

For the second part of the experiment, affect on different ratio of epoxy and amine is being
tested where higher contains of amine in the ratio increase formation rate of gel, hence
decrease the gel time.

Therefore we could understand better on factors that might as well affecting formation of
thermosetting resins.

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REFERENCES

1. CAB 4023 Polymer Process Engineering Laboratory Manual, Universiti Teknologi

PETRONAS, Jan 2010
2. Kumar Anil, K.Gupta Rakesh; Fudamentals of Polymer, McGraw-Hill Internation
Editions, Singapore, 1998
3. N. G. McCrum, C. P. Buckley and C. B. Bucknall; Principles of Polymer
Engineering, Oxford University Press, New York, 1997
4. Websites:
• http://www.threebond.co.jp/en/technical/technicalnews/pdf/tech32.p
df
• http://www.epoxies.com/curing.htm
• http://sunilbhangale.tripod.com/epoxy.html
• http://pslc.ws/macrogcss/epoxy.html

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