Thermal Analysis for Coatings Characterizations 9.1 Introduction 1 9.2 Characteristics 91 9.3 Techniques 91 William $. Gilman 9.4 Applications 92 Gilnan © Associates Bibliography 93 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 coating’s composition and performance. ‘TA methods or techniques measure changes in properties of materials as they are heated or at times cooled ATA evalu subjecting a small sample of froma 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 an is module, a heating or cooling source, a measuring device, and a system for reporting the results, usually as an X-¥ 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 scan ning calorimetry (DSC), differential thermal analysis (DTA), thermogravimetric analysis (TGA), ther: ‘momechanical analysis (TMA), and dynamic mechanical analysis (DMA). Each of these will be discussed, With examples of the information derivable from each proceduce. o92 Coatings Technology Handbook, Third Edition 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 measutes heat flow into oF out of a sample as an exothermic or endothermic change in energy. Generally the temperature range of use is -180°C to +725°C. DTA has been replaced by DSC.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 ~180°C to +1600°C, "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 itis absorbed of released, is not detected or indicated. TGA measures only changes in mass, usually in the temperature range of ambient to 1200°C. "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 ~160°C to +1200°C, Last, DMA is a thermal analysis technique that measures the properties of materials as they ate 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 (stillness) and damping (energy dissipation) properties of materials as they are deformed under periodic oscillatory stress. DMA detects sample modulus and damping changes inthe temperature range of -150°C. to 450°C. 9.4 Applications ‘The practical applications associated with each technique ate numerous, and it would be impractical even to attempt to list oF 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 Aammability 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 crystal: lization 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 deter- ‘mination ofthe relative heats of combustion for flame-retardant and untreated materials The effective- ness 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 a rising temperature methods are used. These methods use the rate of heat evolution as the measured parameter. The classic epoxy-amine reaction helps model production methods to nimize raw materials and reaction times to obtain a quality product through first determining reaction kinetics. In addition, because aging oF 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, There- fore, the temperature sensor is located in the vicinity ofthe sample to obtain a true temperature reading. ©2009 Tyr Ar Gap.‘Thermal Analysis for Coatings Characterizations 93 Applications involving estimating polymer decomposition, polymer lifetime, distinguishing flame- retardant polymer from nontreated polymer ofthe same type, and kinetics of drying, have been reported. For coatings analysis, compositional analysis may assist in determining why performance properties changeshave 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. Iti particularly useful in determining if wo 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, Young's, and shear provide information on a materials stifiness, 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 thermoset, increasing rubbery state modulus values indicate higher cross-link density. ‘TA is constantly undergoing improvements in order to obtain faster, more reliable, and new informa. tion, 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 tem- perature 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, three point 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 oF production problem. In combination, these devices can supply insight into relationships between formulations, processing, and performance of coatings. Bibliography Roger, “A faster approach to obtaining kinetic parameters” American Laboratory, January 1998, p. 21 Cassel, Bruce, et al. 1998, p. 24 pid DSC determination of polymer crystallinity.” American Laboratory, January ©2009 Tyr Ar Gap.9.4 Coatings Technology Handbook, Third Edition 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?” Amer- ican Laboratory, anuary 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 Consho- hocken, PA: American Society for Testing and Materials, 1995. Park, Chang-Hwan, et al,"“Syntheses and characterizations of two component polyurethane flame retar- dant coatings using 2,4dichlor modified polyester” J. Coat. Technol, December 1997, p. 21 Reading, Micheal, etal,“ Thermal analysis for the 21* century,” American Laboratory, January 1998, p. 13. Riesen, Rudolf, “Maximum resolution in TGA by rate adjustment” American Laboratory, January 1998, pls. ‘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 Caystallinity 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. ©2009 Tyr Ar Gap.