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Table A9.1.2 also demonstrates that at each gelatin concentration, the number of bonds per gelatin molecule is relatively constant. This number, of course, is the number of bonds taking part in three-dimensional network formation. Not all the gelatin chains are bound in a true tetrafunctionally crosslinked network. Many dangling chain ends exist at these low concentrations, and the network must be very imperfect. The gelation molecule is basically composed of short a-helical segments in the form of a triple helix with numerous intramolecular bonds at room temperature; see Section 9.13. The a-helical segments are interrupted by proline and hydroxy proline functional groups. These groups disrupt the helical structure, yielding intervening portions of chain that behave like random coils, and which may be relatively free to develop intermolecular bonds. The subject has been reviewed by Djabourov (A7) and Melnichenko et al. (A8). In this experiment the concentration of sugar was kept constant so as to minimize its effect on the modulus. In concluding, it must be pointed out that if sanitary measures are maintained, the nal product may be eaten at the end of the experiment. If gelation ve times normal or higher is included in the study, the student should be prepared for his or her jaws springing open after biting down!

A1. A. Veis, Macromolecular Chemistry of Gelatin, Academic Press, Orlando, 1964. A2. E. M. Marks, in Encyclopedia of Chemical Technology, Kirk-Othmer, Interscience, New York, 1966, Vol. 10, p. 499. A3. J. L. Laurent, P. A. Janmey, and J. D. Ferry, J. Rheol., 24, 87 (1980). A4. M. Miller, J. D. Ferry, F. W. Schremp, and J. E. Eldridge, J. Phys. Colloid Chem., 55, 1387 (1951). A5. J. D. Ferry, Viscoelastic Properties of Polymers, 3rd ed., Wiley, New York, 1980, pp. 529539. A6. L. H. Sperling, Interpenetrating Polymer Networks and Related Materials, Plenum Press, New York, 1981, p. 177. A7. M. Djabourov, Contemp. Phys., 29(3), 273 (1988). A8. Yu. Melnichenko, Yu. P. Gomza, V. V. Shilov, and S. I. Osipov, Polym. Intern. (Brit. Polym. J.), 25(3), 153 (1991).

APPENDIX 9.2 ELASTIC BEHAVIOR OF A RUBBER BAND Stretching a rubber band makes a good demonstration of the stressstrain relationships of cross-linked elastomers.The time required is about 30 minutes.

Reproduced in part from A. J. Etzel, S. J. Goldstein, H. J. Panabaker, D. G. Fradkin, and L. H. Sperling, J. Chem. Ed., 63, 731 (1986).



The equipment includes a large rubber band (Star band size 107, E. Faber, Inc., Wilkes-Barre, PA, is suitable), a set of weights up to 25 kg, and a meter stick. Also required are hooks to attach the weights and a high place from which to hang the rubber band. First, the rubber band is measured, both in length and cross section, and the hooks are weighed. Increasing weight is hung from the rubber band, its length being recorded at each step. When it nears its breaking length, caution is advised. A plot of stress (using initial cross-sectional area) as a function of a, Figure A9.2.1, demonstrates the nonlinearity of the stressstrain relationship. Initial values of the slope of the curve yield Youngs modulus, E. The sharp upturn of the experimental curve at high elongations is due to the limited extensibility of the chains themselves. The number of active network chains per unit volume can be calculated from equation (9.34) as 1.9 102 mol/m3. A MooneyRivlin plot according to equation (9.50) yields a curve that rapidly increases for values of 1/a greater than 0.25; see Figure 9.18. The constants 2C1 and 2C2 are calculated from the intercept and slope, respectively. Values of 2.3 105 Pa and 2.8 105 Pa were obtained, respectively.

Figure A9.2.1

Simple rubberelastic behavior of a rubber band under increasing load.