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8.3

METHODS OF MEASURING TRANSITIONS IN POLYMERS

The glass transition and other transitions in polymers can be observed experimentally by measuring any one of several basic thermodynamic, physical, mechanical, or electrical properties as a function of temperature. Recall that in rst-order transitions such as melting and boiling, there is a discontinuity in the volumetemperature plot. For second-order transitions such as the glass transition, a change in slope occurs, as illustrated in Figure 8.5 (9). The volumetric coefcient of expansion, a, is dened as a= 1 V V T p (8.18)

where V is the volume of the material, and a has the units K-1. While this quantity increases as the temperature increases through Tg, it usually changes over a range of 1030C. The elbow shown in Figure 8.5a is not sharp. Similar changes occur in the enthalpy, H, and the heat capacity at constant pressure, Cp (Figure 8.5b and e, respectively). 8.3.1 Dilatometry Studies

There are two ways of characterizing polymers via dilatometry. The most obvious is volumetemperature measurements (24), where the polymer is conned by a liquid and the change in volume is recorded as the temperature is raised (see Figure 8.8). The usual conning liquid is mercury, since it does not swell organic polymers and has no transition of its own through most of the temperature range of interest. In an apparatus such as is shown in Figure 8.8, outgassing is required. The results may be plotted as specic volume versus temperature (see Figure 8.9) (24). Since the elbow in volumetemperature studies is not sharp (all measurements of Tg show a dispersion of some 2030C), the two straight lines below and above the transition are extrapolated until they meet; that point is usually taken as Tg. Dilatometric and other methods of measuring Tg are summarized in Table 8.5. The straight lines above and below Tg in Figure 8.9, of course, yield the volumetric coefcient of expansion, a. The linear coefcient of expansion, b, can also be employed (25). Note that a = 3b. Dilatometric data agree well with modulustemperature studies, especially if the heating rates and/or length of times between measurements are controlled. (Raising the temperature 1C/min roughly corresponds to a 10 s mechanical measurement.) Besides being a direct measure of Tg, dilatometric studies provide free volume information, of use in theoretical studies of the glass transition phenomenon (see Section 8.6.1).

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Figure 8.8 A mercury-based dilatometer (24). Bulb A contains the polymer (about 1 g), capillary B is for recording volume changes (Hg + polymer), G is a capillary for calibration, sealed at point F. After packing bulb A, the inlet is constricted at E, C contains weighed mercury to ll all dead space, and D is a second constriction.

Figure 8.9

Dilatometric studies on branched poly(vinyl acetate) (24).

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Table 8.5

Methods of measuring the glass transition and thermal properties

Method Dilatometry Volume-temperature Linear expansivity Thermal DSC DTA Calorimetric, Cp Mechanical Static Dynamic Torsional braid analysis Dielectric and magnetic Dielectric loss Broad-line NMR Melt viscosity TGA

Representative Instrumentation Polymer conned by mercury (home made) TMS + computer Modulated DSC 2920 (TA Instruments) DuPont 900 Perkin-Elmer modulated DSC, Pyris 1 Gehman, Clash-Berg Rheometrics RDA2 (Rheometrics Scientic) TBA (Plastics Analysis Instruments) DuPont Dielectric Analyzer, DEA 2920 Joel JNH 3H60 Spectrometer Weissenberg Rheogoniometer HiRes TGA 2950 (TA Instruments)

8.3.2

Thermal Methods

Two closely related methods dominate the eldthe older method, differential thermal analysis (DTA), and the newer method, differential scanning calorimetry (DSC). Both methods yield peaks relating to endothermic and exothermic transitions and show changes in heat capacity. The DSC method also yields quantitative information relating to the enthalpic changes in the polymer (2628) (see Table 8.5). The DSC method uses a servo system to supply energy at a varying rate to the sample and the reference, so that the temperatures of the two stay equal. The DSC output plots energy supplied against average temperature. By this improved method, the areas under the peaks can be directly related to the enthalpic changes quantitatively. As illustrated by Figure 8.10 (29), Tg can be taken as the temperature at which one-half of the increase in the heat capacity, DCp, has occurred. The increase in DCp is associated with the increased molecular motion of the polymer. Figure 8.10 shows a hysteresis peak associated with the glass transition. Such hysteresis peaks appear frequently, but not all the time. They are most often associated with some physical relaxation, such as residual orientation. On repeated measurement, the hysteresis peak usually disappears. An improved method of separating a transient phenomenon such as the hysteresis peak from the reproducible result of the change in heat capacity is obtained via the use of modulated DSC (25,26); see Table 8.5. Here, a sine wave is imposed on the temperature ramp. A real-time computer analysis

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Figure 8.10 Example of differential scanning calorimetry trace of poly(ethylene terephthalatestat-p-oxbenzoate), quenched, reheated, and cooled at 0.5 K/min through the glass transition, and reheated for measurement at 10 K/min (29). Tg is taken at the temperature at which half the increase in heat capacity has occurred. The width of the glass transition is indicated by DT. Note that DHc and DHf are equal in magnitude but opposite in sign.

allows a plot of not only the whole data but also its transient and reproducible components. Figure 8.10 also illustrates the crystalline and melting behavior of this material. Due to the thermal treatment of the sample, it is amorphous before the last heating. Above the glass transition temperature, the increased molecular motion allows the sample to crystallize. At some higher temperature, the polymer melts. The heats of crystallization, DHc, and the heat of fusion, DHf, determined by the areas under the curves must be equal, of course. This type of difcultly crystallizable copolymer of poly(ethylene terephthalate), is widely used in todays two-liter soda pop bottles. At room temperature the polymer is in its glassy state, with some order but little actual cystallinity. Besides being transparent and mechanically tough, such copolymers have very low permeability to both oxygen and carbon dioxide; see Table 4.5. A related technique, thermogravimetric analysis (TGA), must be introduced at this point. In using TGA, the weight of the sample is recorded continuously as the temperature is raised. Volatilization, dehydration, oxidation, and other chemical reactions can easily be recorded, but the simple transitions are missed, as no weight changes occur. 8.3.3 Mechanical Methods

Since the very notion of the glassrubber transition stems from a softening behavior, the mechanical methods provide the most direct determination

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of the transition temperature. Two fundamental types of measurement prevailthe static or quasistatic methods, and the dynamic methods. Results of the static type of measurement have already been shown in Figure 8.2. For amorphous polymers and many types of semicrystalline polymers in which the crystallinity is not too high, stress relaxation, Gehman, and/or GlashBerg instrumentation provide rapid and inexpensive scans of the temperature behavior of new polymers before going on to more complex methods. Several instruments are employed to measure the dynamic mechanical spectroscopy (DMS) behavior (see Table 8.5). The Rheovibron (30) requires a sample that is self-supporting and that yields absolute values of the storage modulus and tan d. The value of E is calculated by equation (8.17). Typical data are shown in Figure 8.11 (31). Although the instrument operates at several xed frequencies, 110 Hz is most often employed. The sample size is about that of a paper match stick. This method provides excellent results with thermoplastics (30) and preformed polymer networks (31). An increasingly popular method for studying the mechanical spectra of all types of polymers, especially those that are not self-supporting, is torsional braid analysis (TBA). In this case the monomer, prepolymer, polymer solution, or melt is dipped onto a glass braid, which supports the sample. The braid is set into a torsional motion. The sinusoidal decay of the twisting action is recorded as a function of time as the temperature is changed (3235). Because the braid acts as a support medium, the absolute magnitudes of the transitions are not obtained; only their temperatures and relative intensities are recorded. The TBA method appears to have largely replaced the torsional pendulum (33). Figure 8.12 shows typical TBA data for cellulose triacetate. Also shown by way of comparison are DTA and TGA results. In Figure 8.12, p represents the

Figure 8.11 Dynamic mechanical spectroscopy on polystyrene cross-linked with 2% divinyl benzene. Data taken with a Rheovibron at 110 Hz. Note that the tan d peak occurs at a slightly higher temperature than the E peak (31). Experiment run by J. J. Fay, Lehigh University.

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Figure 8.12 Comparison of torsional braid analysis, differential thermal analysis, and thermogravimetric analysis data for cellulose triacetate. The bottom gure shows the twisting of the sample in the absence of oscillations as a result of expansion or contraction of the sample at Tg and Tf (35).

period of oscillationthat is, the inverse of the natural frequency of the sample, braid, and attachments. The quantity 1/p2 is a measure of the stiffness of the system, proportional to the modulus. Since the modulus of the glass braid stays nearly constant through the range of measurement, all changes are representative of the polymer. The quantity n represents the number of oscillations required to reduce the angular amplitude, A, by a xed ratio. In this case, Ai/Ai+n = 20 (34). By way of comparison, earlier measurements via

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volumetemperature had placed Tg at 172C (36,37) and Tf at 307C (36), in good agreement with the TBA results in Figure 8.12. The DTA results in Figure 8.12 show Tf at 290C while the TBA shows rst an exothermic, then an endothermic decomposition at 356C and 400C, respectively, corresponding to the weight loss shown by the TGA study. Cellulose triacetate is known to have three second-order transitions (37); it is not clear whether the lower temperature transitions associated with the DTA plot represent these or other motions (38). 8.3.4 Dielectric and Magnetic Methods

As stated previously, part of the work performed on a sample will be converted irreversibly into random thermal motion by excitation of the appropriate molecular segments. In Section 8.3.3 the loss maxima so produced through mechanical means were used to characterize the glass transition. The two important electromagnetic methods for the characterization of transitions in polymers are dielectric loss (3) and broad-line nuclear magnetic resonance (NMR) (3941). The dielectric loss constant, e , or its associated tan d can be measured by placing the sample between parallel plate capacitors and alternating the electric eld. Polar groups on the polymer chain respond to the alternating eld. When the average frequency of molecular motion equals the electric eld frequency, absorption maxima will occur. If the dielectric measurements are carried out at the same frequency as the DMS measurements, the transitions will occur at the same temperatures (see Figure 8.13) (41). The glass transition for the polytriuorochloroethylene at

Figure 8.13 Mechanical and dielectric loss tangent tan d and NMR absorption line width dH (maximum slope, in gauss) of polytriuorochloroethylene (Kel-F) (41).

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52C shown is due to static measurements.The values at 100C shown are close to those reported for dynamic measurements (15). Broad-line NMR measurements depend on the fact that hydrogen nuclei, being simply protons, possess a magnetic moment and therefore precess about an imposed alternating magnetic eld, especially at radio frequencies. Stronger interactions exist between the magnetic dipoles of different hydrogen nuclei in polymers below the glass transition temperature, resulting in a broad signal. As the chain segments become more mobile with increasing temperature through Tg, the distribution of proton orientations around a given nucleus becomes increasingly random, and the signal sharpens. The behavior of NMR spectra below and above Tg is illustrated in Figure 8.14 (39). The narrowing of the line width through the glass transition for polytriuorochloroethylene is shown in the inset of Figure 8.13. A number of other methods of observing Tg are discussed by Boyer (9). 8.3.5 A Comparison of the Methods

All the methods of measuring Tg depend on either a basic property or some derived property. The principal ones have already been discussed.
Basic Property Volume Modulus Dielectric loss Derived Property Refractive index Penetrometry Resistivity

Figure 8.14 Broad-line NMR spectra of a cured epoxy resin. (a) Broad line at 291 K; (b) motionally narrowed line at 449 K (Tg + 39 K) (39).

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From a practical point of view, since the derived property frequently represents the quantity of interest, it is measured rather than the basic property. The methods most commonly used at the present time (9) include directrecording DSC units, the Rheometric Scientic ARES System, and the torsional braid. The special value of the mechanical units lies in the fact that loss and storage moduli are frequently of prime engineering value. Thus the instrument supplies basic scientic information about the transitions while giving information about the damping and stiffness characteristics. On the other hand, DSC supplies thermodynamic information about Tg. Of particular interest is the change in the heat capacity, which reects fundamental changes in molecular motion. Thus values of Cp are of broad theoretical signicance, as described in Section 8.6. 8.3.6 The ColeCole Plot

The ColeCole plot usually presents a loss term vs. a storage term as a function of frequency or time element (42). Figure 8.15 (43) illustrates a plot of Youngs loss modulus against Youngs storage modulus of an epoxy network as a function of frequency through the glass transition region. The epoxy was based on diglycidyl ether of bisphenol A and diaminodiphenyl methane, the latter serving as the cross-linker. Note the characteristic near-semicircular appearance of this plot. Although the ColeCole plot was rst introduced in the context of a dielectric relaxation spectrum, it helped discover that the molecular mechanism underlying both dielectric relaxation and stress relaxation are substantially identical (44). Figure 8.13 provides an illustration, with temperature instead of frequency. Specically, the same molecular motions that generate a frequency dependence for the dielectric spectrum are also responsible for the relaxation of orientation in polymers above Tg. Subsequently the ColeCole type of plot has been applied to the linear viscoelastic mechanical properties of polymers, especially in the vicinity of the glass transition, including the dynamic compliance and dynamic viscosity functions.

Figure 8.15 ColeCole plot for an epoxy network through the glass transition region. Usually, these plots illustrate dynamic mechanical behavior, where the storage quantity is plotted against the loss quantity. Inverted, nearly semicircular curves as shown are common.