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2 THERMAL ANALYSIS GENERAL PRINCIPLES OF OPERATION Thermal analysis refers to a variety of techniques in which a property of a sample is continuously measured as the sample is programmed through a predetermined temperature profile. Among the most common techni- ques are thermal gravimetric analysis (TA) and differential scanning calorimetry @SC). In TA the mass loss versus increasing temperature of the sample is recorded. The basic instrumental requirements are simple: a precision balance, a programmable furnace, and a recorder (Figure 1). Modern instruments, however, tend to be automated and include software for data reduction. In addition, provisions are made for surrounding the sample with an air, nitrogen, or an oxygen atmosphere. In a DSC experiment the difference in energy input to a sample and a reference material is measured while the sample and reference are subjected to a controlled temperature program. DSC requires two cells equipped with thermocouples in addition to a programmable furnace, recorder, and gas controller. Automation is even more extensive than in TA due to the more complicated nature of the instrumentation and calculations. A thermal analysis curve is interpreted by relating the measured property versus temperature data to chemical and physical events occurring in the sample. It is frequently a qualitative or comparative technique. In TA the mass loss can be due to such events as the volatilization of liquids and the decomposition and evolution of gases from solids. The onset of volatilization is proportional to the boiling point of the liquid. The residue remaining at high temperature represents the percent ash content of the sample. Figure 2 shows the TA spectrum of calcium oxalate as an example. 17 18 Polymer Characterization Figure 1. Typical components of a TA instrument. Figure 2. Shows the TA spectrum of calcium oxalate. Atmosphere Control Sample Holder Recorder Furnace Balance Control Recording Balance Furnace Temperature Programmer Temperature Sensor joe sulton Thermal Analysis 19 In DSC the measured energy differential corresponds to the heat content (enthalpy) or the specific heat of the sample. DSC is often used in conjunction with TA to determine if a reaction is endothermic, such as melting, vaporization and sublimation, or exothermic, such as oxidative degradation. It is also used to determine the glass transition temperature of polymers. Liquids and solids can be analyzed by both methods of thermal analysis. The sample size is usually limited to lo- 20 mg. Thermal analysis can be used to characterize the physical and chemical properties of a system under conditions that simulate real world applications. It is not simply a sample composition technique. Much of the data interpretation is empirical in nature and more than one thermal method may be required to fully understand the chemical and physical reactions occurring in a sample. Condensation of volatile reaction products on the sample support system of a TA can give rise to anomalous weight changes. THERMAL ANALYSIS OF POLYMERS A simple example of the relationship between “structure” and “properties” is the effect of increasing molecular weight of a polymer on its physical (mechanical) state; a progression from an oily liquid, to a soft viscoelastic solid, to a hard, glassy elastic solid. Even seemingly minor rearrangements of atomic structure can have dramatic effects as, for example, the atactic and syndiotactic stereoisomers of polypropylene-- the first being a viscoelastic amorphous polymer at room temperature while the second is a strong, fairly rigid plastic with a melting point above 160°C. At high thermal energies conformational changes via bond rotations are frequent on the time scale of typical processing operations and the polymer behaves as a liquid (melt). At lower temperatures the chains solidifies by either of two mechanisms: by ordered molecular packing in a crystal lattice, crystdization, or by a gradual freezing out of long range molecular motions, vitrification. These transformations, which define the principal rheological regimes of mechanical behavior: the melt, the rubbery state, and the semicrystalline and glassy amorphous solids, are accompanied by transitions in thermodynamic properties at the glass transition temperature, the crystalline melting, and the crystalli- zation temperatures. 20 Polymer Characterization Thermal analysis techniques are designed to measure the above mentioned transitions both by measurements of heat capacity and mechanical moduhrs (stiffness). Differential Scanning Calorimetry @SC) The DSC measures the power (heat energy per unit time) differential between a small weighed sample of polymer (ea. 10 mg) in a sealed aluminum pan referenced to an empty pan in order to maintain a zero temperature differential between them during programmed heating and cooling temperature scans. The technique is most often used for characterizing the T,, T,, T,, and heat of fusion of polymers (Figure 3). The technique can also be used for studying the kinetics of chemical reactions, e.g., oxidation and decomposition. The conversion of a measured heat of fusion can be converted to a % crystallinity provided, of course, the heat of fusion for the 100% crystalline polymer is known. Thermogravimetric Analysis (TGA) TGA makes a continuous weighing of a small sample (ca 10 mg) in a controlled atmosphere (e.g., air or nitrogen) as the temperature is increased at a programmed linear rate. The thermogram shown in Figure 4 illustrates weight losses due to desorption of gases (e.g., moisture) or decomposition (e.g., HBr loss from halobutyl, CO, from calcium carbonate filler). TA is a very simple technique for quan- titatively analyzing for filler content of a polymer compound (e.g., carbon black decomposed in air but not nitrogen). While oil can be readily detected in the thermogram it almost always overlaps with the temperature range of hydrocarbon polymer degradation. The curves cannot be reliably deconvoluted since the actual decomposition range of a polymer in a polymer blend can be affected by the sample morphology. Thermomechanical Analysis (TMA) TMA consists of a quartz probe which rests on top of a flat sample (a few mms square) in a temperature controlled chamber. When setup in neutral buoyancy (with ‘flat probe’) then as the temperature is increased the probe rises in direct response to the expansion of the sample yielding I AH/At glass transition crystallization \ (onset) I area = crystalline melting oxidation/ onset + Heating scan (typically 2OWmin) c exo / - - Cooling scan TEMPERATURE II + i l Important characteristics: Ts , T,,, , heat of fusion on heating; Tc on cooling E 2 v1’ Figure 3. Illustrates typical polymer DSC thermograms. z Thermal Analysis 23 thermal expansion coefficient versus temperature scans. Alternatively, with the ‘penetration probe’ under dead loading a thermal softening profile is obtained (penetration distance versus temperature). Although this is a simple and versatile experiment, it gives only a semi-quantitative indication of mechanical modulus versus temperature. The DMTA, described below, gives an absolute modulus measurement. Dynamic Mechanical Thermal Analysis (DMTA) DMTA is a measurement of the dynamic moduli (in-phase and out-of- phase) in an oscillatory mechanical deformation experiment during a programmed temperature scan at controlled frequency. Thermograms are usually plotted to show elastic modulus, E, and tan 6 versus temperature (Figure 5). The peak of the tan 6 is a particularly discriminatorymeasure of T,, although this is the center of the relaxation whereas in the DSC experiment the onset temperature of the T, relaxation is usually reported. In such a case the DSC T, will be lower than that for DMTA by an amount that varies with the specific polymer. There is, in addition, a frequency effect which puts the mechanical (ca. 1 Hz) T, about 17°C higher than that for a DSC measurement (ca. O.OOOlHz) for an assumed activation energy of 400 Id/mole (typical for polymer TJ. The DMTA has a frequency multiplexing capability which can be used for calculating activation energies using time-temperature superposition software. The temperature range of the DMTA is from -150°C to 300°C and frequencies from 0.033 to 90 Hz. The sample size for the usual flexural test mode is 1 mm x 10 mm x 40 mm; slightly less sample is required in the parallel plate shear mode. 24 Polymer Characterization cJr1ve Shaft (selected amDlltude) Drive shaft (selected amplitude) clamps (a) Flexure mode (TV) Shear mode
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