Fibre Chemistry, Vol. 39, No.

1, 2007

METHODS OF CONTROLLING CURING

KINETICS IN POLYMER COATINGS

G. P. Andrianova and S. G. Dolgalev UDC 621.838.3:66.095.9

Traditional methods have limitations for controlling curing of polymers in a coating. The promise of using
the method of dielectric spectroscopy for studying the kinetics of curing of the binder in polymer coatings is
demonstrated.

Environmentally clean and zero-waste technologies for manufacturing high-quality decorative and protective polymer
coatings are required in different branches of industry. Such coatings retain strength, rigidity, ensure processability of the
comparatively cheap nonferrous metals from which an article is made, and give it the specific properties of the polymeric
materials — anticorrosive, dielectric, antifrictional, etc.
One promising way of fabricating polymer coatings is to use powdered composites based on thermosetting binders.
These materials can be used to form quality, lasting coatings with elevated performance and decorative properties on the
surfaces of not only metals, but also glass, ceramics, and plastics.
The powdered materials are solid disperse composites containing film-forming substances (resins), curing agents,
fillers, pigments, and additives. Such materials were initially based on epoxy and polyester resins with a molecular weight
of Mw = 1500-3500 [1]. Epoxy-polyester (or hybrid) and polyurethane systems were developed later. Regardless of the
composition, the finished composite should be a free-flowing disperse powder and have homogeneity, physical and chemical
stability, and invariability of composition during storage and use.
The coating is formed and the binder is cured by heating the article with the powdered composite applied on it. The
binder is cured by a step polymerization or polycondensation mechanism. The performance properties of such coatings are a
function of the degree of curing of the binder during formation of the polymer film on the surface of the article. The degree of
curing of the polymer determines the weather resistance and chemical resistance of the coating.
Methods of investigating the kinetics of curing of binders in polymer coatings is reviewed and examples of promising
new methods that can be used for analyzing the processes that take place in formation of coatings from powdered polymer
composites are cited in the present publication.
The kinetics of curing of coating material are usually judged by the change in the viscosity of the polymer melt in
curing, the thermal effects of the curing reaction, or the change in the number of functional groups. The kinetics of
curing thermosetting plastics based on the change in the plastic-viscous properties of the material is studied according to
GOST 15882-84. This standard establishes the method of determining the duration of the plastic-viscous state, curing at a
given shear stress and complete curing of thermosetting plastics.
The reactivity of resins with respect to thermal effects is determined by differential scanning calorimetry. This method
allows recording the heat flux characterizing the changes that take place in a substance as a result of heating.
However, all of these methods do not take into account surface events on the coating—solid phase boundary because
weighed portions of the material are the samples in this case.
During hot drying, the entire layer of the powdered coating should be uniformly heated to the necessary temperature.
The melt of the powdered material can thus attain the viscosity minimum without the appearance of a pronounced impediment
to its uniform spreading over the surface in curing. However, all of the methods of heating articles with a polymer coating
on them create a temperature gradient both over the thickness of the coating and over the surface of the article. For this

Moscow State University of Design and Technology. Translated from Khimicheskie Volokna, No. 1, pp. 59-62, January—
February, 2007.

0015-0541/07/3901-0079 © 2007 Springer Science+Business Media, Inc. 79

 Fig. 1. Diagram of the dielectric sensor: 1) dielectric support;
2) first capacitor comb; 3) second capacitor comb; 4) bonding
pads; 5) polymer coating.

6.7
Relative dielectric constant

6.2

5.7

5.2

4.7

4.2
4 5 6 7 8 9 10 11 12 13
Time, min (logarihmic scale)

Fig. 2. Change in the dielectric constant of a compose based on

ED-20 epoxy resin at a frequency of 1 kHz.

reason, the methods of monitoring curing must make it possible to track this process at different points of the coating
applied on the article.
A thermostating instrument, a “polymerization plate,” and a timer which shows the time in seconds, are used to measure
the duration of gelation of polymer coatings in industrial conditions. The powdered coating is applied on the metal surface
heated to 180-200°C. The duration of gelation of the composite is established based on the time the powder melt loses fluidity.
The method of testing the coating for resistance to solvents is used to estimate completion of curing of the binder. This
test is frequently used as a fast method for estimating the completeness of curing of the coating by immersing the plate with the
applied coating in a solvent, acetone, for example. The uncured coatings are distinguished by low resistance to solvents.
Another method of testing coatings for resistance to solvents consists of dripping methyl ethyl ketone or a mixture of
methyl ethyl ketone and xylene on the surface of the cured coating. As a function of the type of initial powdered composite, the
finished coatings can have very different resistance to solvents. For this reason, the results must be compared with the standard
for a similar well-cured coating.
Indirect methods of determining the degree of curing of the polymer binder are also used. They include methods of
evaluating the physicomechanical properties of the polymer coating — the flexibility of the sample with the coating, the impact
strength, and the shearing resistance. Uncured coatings are brittle and crack when a mechanical load is applied.
The flexibility test allows determining the ability of the coating to withstand bending of the support. The flexibility is
tested by bending a tin plate with the coating around a conical mandrel. The smallest diameter at which cracking does not
occur is the flexibility index for a coating of determined thickness. The length of the crack formed when the conical mandrel
is changed can be another index.
The impact strength characterizes the ability of the coating to withstand impacts. Impact from the coating side is
evaluated as direct, and from the support side, as reverse. Both methods are used for evaluating the impact strength of coatings.

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The thickness and elasticity of the support are important factors in this test, and for this reason, they must be monitored to
obtain reliable results.
The shearing strength also characterizes the ability of a coating to withstand destruction on impact by some object.
Despite the fact that the shearing strength can be correlated with the impact strength, good impact strength does not mean that
the shearing strength will obligatorily be high. The impact test implies not only the impact effect but also deformation of the
coating with the support. In testing for shearing strength, the support is not deformed and only the coating is affected by the
impact. Gravel of different size, lead pellets, or other hard materials are most frequently used in shearing strength tests. The
test method in which gravel moved by high pressure hits the cold coating is typical. The shearing strength is judged by the mass
of the polymeric material split from the support.
However, all of these methods do not allow describing the kinetics of curing of the coating material completely enough.
The method of dielectric spectroscopy can be considered a new method of investigating the kinetics of curing of the binder in
the coating formed on the surface of an article. High sensitivity to the processes that take place in the material, simplicity of the
equipment, and compactness of the sensors are the advantages of dielectric methods of investigating polymers.
The change in the dielectric properties of a polymeric material (dielectric constant ε and dielectric loss tangent tan δ)
can indicate gelation, relaxation transitions in the polymer, or its reaction with the environment (adsorption of low-molecular-
weight polar substances by the surface of the polymer and diffusion into its bulk). For this reason, dielectric methods make it
possible to obtain information on the processes that take place in a polymer system both in formation and during use of the
coating.
The studies of curing of polymers by dielectric spectroscopy are based on the appearance of a sharp decrease in ion
mobility at the time of formation of a gel fraction in the polymer system, which alters its dielectric properties. The simplest
case is when the change in ionic conductivity is only due to a change in the mobility and not to a change in the charge or
concentration of the ions. As a function of the composition of the polymer and the electric field frequency in recording during
curing, the ratio of the ionic and dipole conductivities can vary strongly. In interpreting such data, it is important to reliably
distinguish the regions of ionic conductivity and dipole relaxation [2, 3].
A change in ion mobility will alter the dielectric parameters of the polymer system. To determine the dielectric constant
of a polymer composite, it is placed between the capacitor plates and the capacitance (C) is measured. The dielectric constant
ε is calculated with the equation:
d
ε=k C,
S
where k is the proportionality factor; d is the thickness of the dielectric sample; S is the area of its lateral face.
The dielectric sensor used to measure the electric capacitance of the polymer system can be a flat capacitor consisting
of two mutually penetrating but not intersecting combs (Fig. 1) made of a corrosion-resistant metal applied on a dielectric
support.
The polymer coating layer is formed by applying the dissolved polymer on the surface of the sensor. Since the metallization
layer is approximately 1 μm thick, the kinetics of spreading of the polymer solution can be regarded as spreading of a viscous
fluid over the smooth surface of a solid. Centrifugation is used to obtain especially thin polyimide coatings on the surface of
microelectronic devices from solution [4].
Special templates for forming a coating layer of defined thickness are used for applying coatings of powdered polymer
composites to the surface of the sensor [1]. Using such a sensor, we obtained the values of the relative dielectric constant
during curing of ED-20 resin in isothermal conditions (at 20°C). The curve of the change in the dielectric constant is shown in
Fig. 2.
The same shape of the curves of the change in the dielectric constant for curing the ED-20 epoxy—amine system at 140
and 160°C is reported in [5]. These curves were verified by differential scanning calorimetry. A comparison of the curves
demonstrated the possibility and effectiveness of using the capacitor dielectric sensor for studying the change in the properties
of the epoxy-amine composite during curing [5].
The results of a study of curing of several polymer systems based on bisphenol-A diglycidyl ether (BADGE) in isothermal
conditions (at 70°C) were presented as examples of the study of curing processes in [2]. The 50 Hz-10kHz frequency interval
was selected for the studies. The important decrease in the effect of the different electrode effects and the relative simplicity of
the experimental technique are an attractive property of this range.

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 The results obtained by the dielectric method are in satisfactory agreement with the data obtained by viscometry and the
torsion pendulum method for all polymer systems investigated, and the results of the extrapolation were not a function of the
electric field frequency within the limits of the errors of the experiment and calculation [2].
The dielectric method can also be used for monitoring the change in the properties of a polymer as a result of exposure
to environmental conditions. The study of sorption of water by a polyimide coating by the dielectric method could be an
example of this application [6]. The dependence of the kinetics of sorption of moisture by a polyimide coating on the temperature
of heat treatment of the polyimide in formation of the coating was investigated.
Sensor samples with a thermoplastic polyimide coating 3 μm thick were placed in a desiccator in which 90% humidity
was maintained. The diffusion coefficient of the moisture into the coating was calculated with the Fick equation. Sorption of
water vapors was determined by the change in the electric capacitance of the sensor. The electric capacitance of the comb
capacitor was measured with a E8-4 meter at a frequency of 1 kHz.
The dielectric method of determining the diffusion coefficient is based on the fact that the capacitance of the dielectric
sensor with the polymer coating varies with diffusion of a polar low-molecular-weight substance into the coating. This is
because the concentration of dipoles increases in the substance of the coating. The change in the concentration of dipoles, and
thus the low-molecular-weight substance in the polymer coating of the sensor can be evaluated by the change in the dielectric
properties of this sensor in time.
As a consequence, both the kinetics of curing of the binder in thin polymer coatings and the change in the properties of
the coating material during use can be investigated with the method of dielectric spectroscopy.

REFERENCES

1. Powdered Paints. Coatings Technology [Russian translation], Khimiya, St. Petersburg (2001).
2. G. F. Novikov, T. L. Elizarova, and A. V. Chukalin, “Study of relaxation processes in cured epoxy-amine model systems
by dielectrometry,” Proceedings of the VI All-Russian Conference on the Structure and Dynamics of Molecular Systems
[in Russian], Butlerovskie Soobshcheniya, No. 2 (1999).
3. G. F. Novikov et al., Vysokomolek. Soedin., No. 42(7), 1228-1237 (2000).
4. T. S. Goncharova, Zarubezhn. Elektron. Tekh., No. 8, 53-82 (1989).
5. N. A. Kozlov, Doctoral Dissertation, Moscow Aviation Engineering Institute, Moscow (2003).
6. P. G. Babaevskii, N. A. Kozlov, et al., Plast. Massy, No. 9, 31-35 (2003).

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