::: Application Report

Thermal Curing of 1-Component Impregnating

Resins

Relevant for: DMTA reaction kinetics, curing resins Passendes Bild!

Natural and synthetic resins like the tree resin shown on the picture are
used for a broad range of applications, like for the production of varnishes
or adhesives. This report shows the thermal curing of a 1-component
impregnating resin measured on a rheometer. cc by: copyright/friscomix

1 Introduction • disposable aluminum plate(s) D-PP12

used for samples with G’ modulus not significantly
Impregnating resins are key components of modern above 150 MPa
production. The advantages are excellent protection from
• disposable aluminum plate(s) D-PP08
a wide variety of environmental factors as well as improved used for samples with G’ modulus not significantly
heat transfer and wire insulation. above 1500 MPa.

Conventional dip & bake technology is a time consuming

and energy intensive manufacturing process which
requires large-scale equipment. It also leads to high
emissions during the curing process and it requires
frequent cleaning.

To reduce costs and improve product quality, it is essential

to evaluate the material properties during the entire
production process.

Modern rheometers in combination with modular DMTA

accessories allow measurements from the liquid raw Fig. 1 Lower Peltier temperature control device with disposable
plates (upper and lower)
product to the finally cured solid.

2 Experimental Setup
2.1 Sample and Measuring Device
A 1-component impregnating resin was measured. MCR
series rheometers are suitable for this type of
measurement.
It is recommended to use the following plate(s):
• a special shaft D-CP/PP7
for holding the disposable measuring plates
• disposable aluminum plate(s) D-PP25
used for samples with G’ modulus not significantly
above 10 MPa
• disposable aluminum plate(s) D-PP15
used for samples with G’ modulus not significantly
above 60 MPa
2.2 Default
In most cases, a D-PP15 is a good compromise for a
reasonable measuring sensitivity from the liquid to the solid
form.
2.3 More Sensitivity until Reaching the Gel Point
For a better sensitivity at the lower end of the measuring
curve the diameter should be increased (25 mm or above)
with the disadvantage of measuring only relative
information of the solid material.
2.4 More Sensitivity Exceeding the Curing Point
Whenever the absolute modulus of the solid-like behavior
is of highest priority, a D-PP08 is the best choice.

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::: Application Report

2.5 Best Choice for Measuring on Pure Solids 2.8 Standards

(Bars)
An even more precise technique is offered by the solid
rectangular fixture SRF which allows high precision DMTA
measurements on solid bars. Disadvantage: the sample
must be cut into the right shape e.g. (10 x 2 x 50) mm
2.6 Temperature Control Device
A Peltier oven with a Peltier controlled lower plate
P-PTD 200 and an actively Peltier controlled upper hood
H-PTD 200 was used. The system ensures a virtually
gradient free measurement, offering rapid cooling and
heating based on the thermo-electrical effect of the Peltier
system (lower & upper one).
http://en.wikipedia.org/wiki/Thermoelectric_cooling
In order to protect the lower Peltier plate from destruction,
a special holder for disposable dishes was setup (see
figure 1).
2.7 Measuring Profile
In accordance to the processing conditions the following
measuring profile was designed.
All intervals:
normal force compensation 0 N
hysteresis ±0.5 N
oscillation with frequency 1 Hz
Interval 1 (3 minutes):
heating with 25 K/min from 20° C to 100 °C
strain = 5 %: low viscosity -> set high strain value
The rheometer in combination with the parallel plate
measuring system fulfils the following standards:
DIN53018, ISO6721-10
3 Results and Discussion
The kinetics of the reactive resin has been investigated by
presetting a temperature ramp followed by an isothermal
step at the curing temperature.
The 1-component impregnating resin presented in figure 3
was heated from 20 °C to 100 °C within 3 minutes. While
increasing the temperature the resin undergoes a viscosity
reduction.
3.1 Softening Point or Viscosity Minimum
From interval 2 onwards, the temperature is kept constant
and the viscosity reaches a minimum value which is the so
called softening point (red dot at 56 mPas appearing
6 minutes after the maximum temperature was reached).
Until reaching the softening point the sample is liquid like
and shows ideal dip-coating or leveling properties.
Due to the permanent exposure to a high temperature the
cross-linking reaction starts. With the occurrence of initial
cross-links the sample turns into a non-Newtonian liquid
and as a consequence, the viscosity increases by 7
decades in a logarithmically scaled diagram. The sample is
found to be solid at the end of the test.

Interval 2 (12 minutes):

isothermal 100 °C
simulation of oven temperature
strain reduced from 5 % to 0.1 %:
while sample becomes increasingly solid-like

Interval 3 (30 minutes):

isothermal 100 °C
simulation of oven temperature
strain=0.1 %:
sample is solid like -> low strain value

Interval 4: Setback to initial temperature 20 °C.

Fig. 3 Complex viscosity versus time of a 1- component curing
resin.

For any further investigations it is recommended to have a

closer look at the moduli (G', G'') versus time in order to
obtain significant changes of the mechanical material
Fig. 2 Measuring profile with 4 intervals properties.

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::: Application Report

3.2 Pot Life

With the occurrence of initial cross-links a storage modulus

G' can be measured.
At this point the end of the almost horizontal plateau with
its constant complex viscosity is reached (figure 3), and the
complex viscosity starts to increase. Until reaching its pot
life (blue dot) the sample is still soft and liquid-like.

3.3 Sol-Gel Point

The value of the cross-point of G' and G'' (figure 4)

indicates the sol-gel transition from where on the value of
the storage modulus predominates over the value of the
Fig. 5 Relative rate of cross-linking X(t) and storage modulus G'
loss modulus. At the sol-gel point (green dot), the resin
versus time in a linear scaled diagram
reaches a gel-like state with an increasing degree of
cross-linkage. During the long lasting after-curing period the sample
reaches its final rigidity and the rate of cross-linking
becomes constant showing the value of almost zero.

Table 1: Evaluated Points

Softening point (red) 9.0 min

Pot life (blue) 10.1 min

Sol-gel point (green) 10.8 min

Curing point (yellow) 18.0 min

Fig. 4 Storage modulus G' and loss modulus G'' versus time of a
1-component curing resin
3.4 Rate of Cross-LInkage
The slope X(t) of the storage modulus in the diagram
(linear scale) below (figure 5) is an indirect measure of the
rate of cross-linking.
3.5 Curing Point
The maximum slope X(18 min) is reached after about
18 min (yellow dot). From that point onwards the reaction
is slowing down. This maximum slope of G' (linear scale)
can also be interpreted as the curing point. While looking
at the logarithmically scaled diagram in figure 4 it is obvious
that the sample has almost reached its final material
properties after about 18 min.
4 Summary
It could be shown that the EC-Twist or MCR rheometers
can be used to characterize curing resins beginning from
the liquid state at ambient temperature until reaching the
solid state after curing finally.
The entire process of curing is measured with respect to
the sample's viscosity and other material properties. In
addition, some significant points can be analyzed such as
the softening point, the sol-gel point and the curing point.
Further, the rheometer software allows the calculation of
the relative rate of cross-linking based on the slope of G'(t).
One more benefit of this method is the ability of having a
simulation which almost meets the true processing
conditions with respect of time and temperature.
Text: Klaus Wollny
Contact: Anton Paar GmbH
Tel:+49 711 720 91 0
rheo-application@anton-paar.com
http://www.anton-paar.com

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