9

Thermal Analysis
for Coatings
Characterizations

William S. Gilman
Gilman & Associates

9.1 Introduction ........................................................................9-1

9.2 Characteristics .....................................................................9-1
9.3 Techniques ...........................................................................9-1
9.4 Applications .........................................................................9-2
Bibliography ...................................................................................9-3

9.1 Introduction
The evaluation of substances and finished materials by thermal analysis will be discussed as a tool that
the paint chemist can use to help evaluate coating properties. These properties are those that change as
a function of temperature.

9.2 Characteristics
Substances change in a characteristic manner as they are heated. Thermal analysis (TA) monitors these
changes. TA procedures are generally used to characterize various substances and materials that change
chemically or physically as they are heated. These changes in properties as a function of temperature
have been used to help characterize the interrelationship of a coatings composition and performance.
TA methods or techniques measure changes in properties of materials as they are heated or at times cooled.
A TA evaluation entails subjecting a small sample of from a few milligrams to 100 mg to a programmed
change in temperature. The resulting change in property is detected, attenuated, plotted, and measured
by a recording device.
The instrumentation consists of an analysis module, a heating or cooling source, a measuring device,
and a system for reporting the results, usually as an XY plot. A computer is used to program and control
the procedure and analyze and store the results.

9.3 Techniques
The techniques of prime importance in coatings characterization and analysis include differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermogravimetric analysis (TGA), thermomechanical analysis (TMA), and dynamic mechanical analysis (DMA). Each of these will be discussed,
with examples of the information derivable from each procedure.

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9-2

Coatings Technology: Fundamentals, Testing, and Processing Techniques

DSC measures the heat flow and temperature associated with chemical transitions and reactions. The
difference in heat flow between a sample and a reference material is measured under precisely controlled
conditions. It measures heat flow into or out of a sample as an exothermic or endothermic change in
energy. Generally, the temperature range of use is 180C to +725C.
DTA has been replaced by DSC. However, DTA data also address changes in heat flow and measure
the evolution or absorbance of energy in relation to an inert reference. The temperature detection is
somewhat less accurate than DSC, and hence, it was replaced by DSC where better data are obtainable.
It also measures the temperature excursions of a sample in the range of 180C to +1600C.
TGA measures the change in mass as a function of temperature, time, and atmosphere. Thus, this
procedure is limited to applications where a change in mass occurs. Since only information concerning
the changes in mass is collected, nothing is revealed about the nature of the transitions. The energy
involved, or whether it is absorbed or released, is not detected or indicated. TGA measures only changes
in mass, usually in the temperature range of ambient to 1200C.
TMA measures dimensional changes as a function of temperature and time in materials. Both linear
and volumetric changes can be determined. TMA measures sample dimensional changes, generally, in
the range of 160C to +1200C.
Last, DMA is a thermal analysis technique that measures the properties of materials as they are
deformed under periodic stress. DMA employs a variable sinusoidal stress application, and the resultant
sinusoidal strain is measured. Or, stated differently, DMA is a technique that measures the modulus
(stiffness) and damping (energy dissipation) properties of materials as they are deformed under periodic
oscillatory stress. DMA detects sample modulus and damping changes in the temperature range of 150C
to +500C.

9.4 Applications
The practical applications associated with each technique are numerous, and it would be impractical
even to attempt to list or describe them. Therefore, for each technique of TA that we have mentioned, a
brief overview will be made with some specific applications of potential interest to the coating chemist.
The information that can be obtained from DTA and DSC is approximately the same, with the
exception that DSC gives quantitative as well as qualitative information. DSC and DTA have been
extensively used to study the temperatures and nature of transitions in materials heated under different
atmospheres. Oxidation stability of various substances is easily characterized. Evaluations of polymer
flammability and analysis of subambient phase transition are often conducted.
Coatings generally possess characteristic transitions, including glass transition (a transition related to
changes in specific heat), exothermic reactions caused by physical or chemical reactions such as crystallization or cross-linking reactions, melting, volatilization, dissociation, a phase change, and oxidation or
thermal decomposition. DSC with its ability to yield quantitative heats of reaction facilitates the determination of the relative heats of combustion for flame-retardant and untreated materials. The effectiveness of the flame retardant can also be assessed.
Reaction kinetic parameters of chemical reactions are derived from DSC data. Studies by isothermal
techniques as well as rising temperature methods are used. These methods use the rate of heat evolution
as the measured parameter. The classic epoxyamine reaction helps model production methods to
minimize raw materials and reaction times to obtain a quality product through first determining reaction
kinetics. In addition, because aging or oxidation is an exothermic reaction, this technique has been used
to study long-term stability of coatings.
The applications of TGA as an analytical tool center around determining changes in sample mass as
a function of time and temperature. Both isothermal and nonisothermal methods are used. For coatings
analysis, nonvolatiles and thermal stability determinations are usually conducted. However, as in DSC,
decomposition kinetics, accelerated aging, and oxidation stability can be conducted.
Unlike DSC, in which heating is done by conduction, TGA heats by convection and irradiation. Therefore, the temperature sensor is located in the vicinity of the sample to obtain a true temperature reading.

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Thermal Analysis for Coatings Characterizations

9-3

Applications involving estimating polymer decomposition, polymer lifetime, distinguishing flameretardant polymer from nontreated polymer of the same type, and kinetics of drying, have been reported.
For coatings analysis, compositional analysis may assist in determining why performance properties
changes have occurred. For example, weight loss curves for materials ostensibly of exactly the composition
with identical weight losses behaved differently in a formulation. Upon further examination, it was
observed that the weight loss of one occurred at slightly different temperatures and in different modes,
indicating differences in materials.
With ever-increasing control on organic volatiles in coatings, TGA can be used for volatile organic
content determination.
As with DSC, thermal or long-term degradation stability of coatings based on one resin or another
can be conducted as a formulation tool.
Applications of TMA are related to a samples dimensions as a function of time and temperature.
Information, such as the compatibility of coating and substrate, performance of an elastomer in a harsh
environment, and the adhesion of one material to another, such as multilayered wrapper or baked on
coating on a metal substrate, can be obtained.
The direct application of TMA in coatings technology is found in dilatometry, or the determination
of the coefficient of thermal expansion. It is particularly useful in determining if two dissimilar coatings
can adhere to each other.
The applications of DMA provide information about transition temperatures, curing phenomena, and
mechanical properties. These properties include impact resistance and even sound absorption. The
technique measures the properties of materials as they are deformed under periodic stress. Another way
to state DMA testing is that it measures the viscoelastic response of a material under periodic load.
Applications range from viscoelastic measurements to kinetics of cross-linking. Modulus values, such
as flex, Youngs, and shear provide information on a materials stiffness, while mechanical damping
correlates with the amount of energy dissipated as heat during deformation.
In coating technology, DMA is applicable in the study of film properties, such as the cure process and
film formation. Various properties around the glass transition point may be studied. For example, in
thermoplastic materials, increasing rubbery state modulus usually means increasing molecular weight.
In thermosets, increasing rubbery state modulus values indicate higher cross-link density.
TA is constantly undergoing improvements in order to obtain faster, more reliable, and new information. For example, in most TGA decomposition measurements, the heating rate is maintained constant
over the decomposition range, self-compensating for internal cooling. Devices are available that will
detect both TGA and DSC data on the same sample simultaneously.
Maximum resolution TGA by rate adjustment addresses weight losses occurring in overlapping temperature regions. The overlapping can be seen using the first derivative of the TGA signal.
TA, such as the techniques already mentioned, can be coupled to a mass spectrometer or infrared
spectrometer to analyze the effluent output of the TA instrument.
Modulated DSC is an innovation with increased sensitivity, higher resolution, more complete analysis,
and easy data interpretation.
DMA is now available with multiple modes of degradation, including single and dual cantilever, threepoint bend, shear sandwich, compression, and tension. Frequency multiplexing of 0.01 to 200 Hz is provided.
We have attempted to describe the vast capabilities of TA. This technology is at its best when more
then one instrument is used on a research or production problem. In combination, these devices can
supply insight into relationships between formulations, processing, and performance of coatings.

Bibliography
Blain, Roger, A faster approach to obtaining kinetic parameters, American Laboratory, January 1998, p.
21.
Cassel, Bruce, et al., Rapid DSC determination of polymer crystallinity, American Laboratory, January
1998, p. 24.

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Coatings Technology: Fundamentals, Testing, and Processing Techniques

Colborn, Robert, Modern Science and Technology. Princeton, NJ: Van Nostrand, 1965.
Foreman, Jon, Dynamic mechanical analysis of polymers, American Laboratory, January 1997, p. 21.
Hassel, Robert L., Evaluation of polymer flammability by thermal analysis, American Laboratory, January
1997.
Hassel, Robert L., Using Temperature to Control Quality, Second Quarter 1991 P1 Quality. Hitchcock,
1991.
Hassel, Robert L., Thermomechanical analysis instrumentation for characterization of materials, American Laboratory, January 1991.
Kelsey, Mark, et al., Complete thermogravimetric analysis, American Laboratory, January 1997, p. 17.
Neag, C. Michael, Coatings Characterizations by Thermal Analyses. ASTM Manual 17. West Conshohocken, PA: American Society for Testing and Materials, 1995.
Park, Chang-Hwan, et al., Syntheses and characterizations of two component polyurethane flame retardant coatings using 2,4dichlor modified polyester, J. Coat. Technol., December 1997, p. 21.
Reading, Micheal, et al., Thermal analysis for the 21st century, American Laboratory, January 1998, p. 13.
Riesen, Rudolf, Maximum resolution in TGA by rate adjustment, American Laboratory, January 1998,
p. 18.
TA Instruments Company, Thermal Analysis Application briefs available from TA Instruments Company,
New Castle, Delaware: TA-8A, Thermal Solutions Long Term Stability Testing of Printing Inks
by DSC; TA-73, A Review of DSC Kinetics Methods; TA-75, Decomposition Kinetics Using TGA;
TA-121, Oxidation Stability of Polyethylene Terephthalate; TA-123, Determination of Polymer
Crystallinity by DSC; TA-125, Estimation of Polymer Lifetime by TGA Decomposition Kinetics;
TA-134, Kinetics of Drying by TGA; and TA-135, Use of TGA to Distinguish Flame-Retardant
Polymers from Standard Polymers.

2007 by Taylor & Francis Group, LLC