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Thermal Characterization of Polymers Josh Nunn, Leslie Sanders, Brent Beadles MSE 2410: The 241 Goons, Clemson

University Introduction: This lab introduces the principles and techniques of thermal characterization of polymers using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal characterization is a method to determine the properties of materials, including polymers, to help identify unknown materials and determine composition, determine processing parameters, and determine the thermal history. Even the crystallinity of the material can be effectively determined using calorimetric techniques. For this lab, we used the two most popular thermal analysis techniques, TGA and DSC. These two techniques are often used in combination to determine the properties of a material. TGA is used to determine how the mass of a sample varies with temperature by measuring the weight loss of the sample during a heating regime1. This technique measures reaction, decomposition, dehydration, evaporation, and degradation. It is used mostly to determine moisture/solvent content and to monitor degradation behavior. DSC is used to determine how heat flow through a sample varies with temperature by first scanning the temperature applied to the sample through a range, then comparing the temperature of the sample to a reference value, and finally, calculating the heat flow2. The result of this procedure is the heat flow, measured as enthalpy, required to maintain equal temperatures. DSC is well suited to the investigation of melting phenomena due to melting point and enthalpy of fusion being among the data obtained. This is helpful in determining the purity of materials and the degree of crystallinity of polymers. Results: Our groups data is listed in the following figures and graphs. Figure 1: TGA graph of Ethylene Vinyle Acetate (EVA) Table 1: Average and Standard Deviation for EVA EVA Value

Figure 3: DSC thermogram of PET

Once all groups had gathered their data, we analyzed and compared the results, taking the averages of all the data given and calculating the standard deviation. Group 1 did not take all of the data for the thermal gravimetric analysis of EVA, and analyzed the opposite first order reaction for the DSC analysis. This means that we were not able to take a fully accurate mean or standard deviation for several of the presented values. Our analysis and results are shown in the following tables.

Starting Mass (mg) % Acetic Acid Mass Acetic Acid (mg) % Polymer Backbone Mass Polymer Backbone (mg) Char Yield (%) Residue (mg)
Figure 2: TGA graph of Calcium Oxalate Monohydrate (Caox)

17.861 0.00205 29.897 0.10214 5.340 0.01858 69.79 0.02828 12.465 0.00707 0.255 0.00707 0.0455 0.00126

Table 2: Average and Standard Deviation for Caox Caox Value

Starting Mass (mg) % Water Mass Water (mg) % Carbon Monoxide Mass Carbon Monoxide (mg) % Carbon Dioxide

17.606 0.00046 12.377 0.00577 2.179 18.750 0.03464 3.301 0.00608 30.117 0.00577

Mass Carbon Dioxide (mg) Char Yield (%) Residue (mg)

5.302 0.00115 38.757 0.04163 6.823 0.00721

For the DSC thermograms, since group 1 analyzed a different 1st order transition, and almost all of the other teams values where identical to ours, the only value to report the average and standard deviation for was the Enthalpy of Transition. It is listed below: Table 3: Average and Standard Deviation for PET PET Value

seem odd. The graph shows the glass transition phase, which is a transition from solid to semi-liquid, occurring at a lower temperature than the crystallization transition. This is most likely due to the fact that the sample was quenched from melting, the quickness of the cooling causing the outer surface to stiffen, but the insides keeping it warm enough to warm back up with the addition of some outside heat, causing it to turn semi-solid before cooling down and crystallizing. After the crystallization transition, the sample is heated even more and has a melt transition towards the end, as expected. References: 1. Kreuer, K. D., E. Schnherr, and J. Maier. "Proton and oxygen diffusion in BaCeO< sub> 3</sub> based compounds: A combined thermal gravimetric analysis and conductivity study." Solid State Ionics 70 (1994): 278-284. Jelesarov, Ilian, and Hans Rudolf Bosshard. "Isothermal titration calorimetry and differential scanning calorimetry as complementary tools to investigate the energetics of biomolecular recognition." Journal of molecular recognition 12.1 (1999): 3-18.

Enthalpy of Transition (J/g)

44.535 0.07778

Discussion: As you can see from the figures above, each sample went through several different transitions during the analysis process. The graph of the TGA analysis of EVA has two distinct slopes. These mark two drastic weight losses in the material during the heating process. The first slope corresponds to the evaporation of acetic acid, and the second corresponds to the evaporation of various fragments of the polymer backbone. The graph produced by the TGA analysis of Caox has three different slopes. The first shows the mass lost from the evaporation of water, the second from the evaporation of carbon monoxide, and the third from the evaporation of carbon dioxide. This makes this test very valuable for monitoring the degradation behavior of materials, as well as discovering the operating temperature of polymers. The operating temperature of a polymer is extremely important. It is the temperature range in which the polymer in question does not degrade. Without knowing the range in which you can safely work with a polymer, it could fail at any time. The graph of the DSC analysis of a PET sample is quite different from those of the TGA analysis. This graph features sharp dips in both the positive and negative directions of the yaxis, forming steep hills and valleys. These sharp changes correspond to spikes in heat flow (either in or out of the system), signaling transition changes in the material. Our graph showed 3 such features, a slight drop towards the beginning, a steep peek around the middle, and a deep valley at the end. The shallow drop at the beginning corresponds to a second order transition because it shows very little enthalpy change, in this case, it is a glass transition. A glass transition is a transition occurring in some materials in which they shift from a hard, relatively brittle state to a slightly molten, rubberlike state3. The steep peak towards the middle represents a sharp jump in enthalpy, making it a first order reaction. This one is exothermic, making it a crystallization transition. Crystallization is when a material in liquid form starts to form back into a solid. Lastly, the deep valley at the end is also representative of a 1st order transition. This one however, is a melting transition. This is when the material changes from a solid to a liquid. Conclusion: All of our values for the TGA analysis make sense. They all seem to behave exactly like they would be expected to. However, the DSC analysis yielded results that

2.

3.

Gibbs, Julian H., and Edmund A. DiMarzio. "Nature of the glass transition and the glassy state." The Journal of Chemical Physics 28.3 (2004): 373-383.

Acknowledgements: I would like to thank both Benoit and Pavel for their helpful hints and guidance, as well as Dr. Blouin for his lecture on these analytical techniques before the lab started. I would also like to thank both of my team mates for their work in this lab.