APPENDIX 9.

1 GELATIN AS A PHYSICALLY CROSS-LINKED ELASTOMER

497

sample was then released and cooled. In terms of a, to what extent will the sample remain stretched? 18. You are shipwrecked on a desert island. You nd some bushes that have a sticky sap. You also nd the island has all kinds of minerals. How do you get off the island?

APPENDIX 9.1 GELATIN AS A PHYSICALLY CROSS-LINKED ELASTOMER Introduction Ordinary gelatin is made from the skins of animals by a partial hydrolysis of their collagen, an important type of protein (A1,A2). At home, a crude type of gelatin can be prepared from the broth of cooked meats and fowl; this material also frequently gels on cooling. When dissolved in hot water, the gelatin protein has a random coil type of conformation. On cooling, a conformational change takes place to a partial helical arrangement. At the same time, intermolecular hydrogen bonds form, probably involving the NH linkage. On long standing, such gels may also crystallize locally. The bonds that form in gelatin are known not to be permanent, but rather they relax in the time frame of 103 to 106 s (A3A5). The amount of bonding also decreases as the temperature is raised. The purpose of this appendix is to demonstrate the counting of these bonds via modulus measurements. Theory By observing the depth of indentation of a sphere into the surface of gelatin, indentation modulus is easily determined. The indentation modulus yields its close relative, Youngs modulus. The cross-link density and thus the number of hydrogen bonds (simple physical cross-links) are readily determined by treating the gelatin as a hydrogen-bonded elastomer. Youngs modulus may be determined by indentation using the Hertz (A6) equation: E= 3(1 - v 2 )F 4 h3 2 r 1 2 (A9.1.1)

where F represents the force of sphere against the gelatin surface = mg (dynes), h represents the depth of indentation of sphere (cm), r is the radius of sphere (cm), g represents the gravity constant, and v is Poissons ratio.
Reproduced in part from the G. V. Henderson, D. O. Cambell, V. Kuzmicz, and L. H. Sperling, J. Chem. Ed., 62, 269 (1985).

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CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

The ball indentation experiment is the scientic analogue of pressing on an object with ones thumb to determine hardness. The less the indentation, the higher the modulus. Youngs modulus is related to the cross-link density through rubber elasticity theory; see equation (9.36): E = 3nRT (A9.1.2)

Assuming a tetrafunctional cross-linking mode (four chain segments emanating from the locus of the hydrogen bond): E = 6 mRT (A9.1.3)

where n represents the number of active chain segments in network and m is the cross-link density (moles of cross-links per unit volume). For this experiment, the gelatin was at 278.0 K, the temperature of the refrigerator employed.

Experimental Time: About 30 minutes, the gelatin prepared previously. Principles Illustrated: 1. Helix formation and physical cross-linking in gelatin. 2. Rubber elasticity in elastomers. 3. Physical behavior of proteins. Equipment and Supplies: Five 150 75 mm Pyrex crystallizing dishes or soup dishes Five 2-cup packets of avored Jello brand gelatin (8 g protein per packet) Eighteen 2-cup packets of unavored Knox brand gelatin (6 g protein per packet) One metric ruler One steel bearing (1.5-in. diameter and 0.226 kgor any similar spherical object) One lab bench One knife Five different concentrations (see Table A9.1.1) of gelatin were prepared, each in 600 ml of water, and allowed to set overnight in a refrigerator at 5.0C. Then indentation measurements were made by placing the steel bearing in the center of the gelatin samples and measuring the depth of indentation, h (see Figure A9.1.1). As it is difcult to see through the gelatin to observe this depth,

APPENDIX 9.1

GELATIN AS A PHYSICALLY CROSS-LINKED ELASTOMER

499

Table A9.1.1 Gelatin concentrations

Dish Concentration Jellob Gelatinc

a

1
a

2 2.0 1 5

3 1.0 1 2

4 0.75 1 1.25

5 0.50 1 0.5

3.0 1 8

Concentration = number of times the normal gelatin concentration (each dish contains 600 ml of water). b Jello = number of 2-cup packets of Jello brand black raspberry avored gelatin. c Gelatin = number of 2-cup packets of Knox brand unavored gelatin.

Figure A9.1.1 gelatin.

Schematic of experiment, measuring the indentations of the heavy ball in the

it is desirable to measure the height of the bearing from the level surface of the gelatin and subtract this quantity from the diameter of the bearing (Figure A9.1.1). The measured depth of indentation, the radius of the bearing, and the force due to the bearing are algebraically substituted into equation (A9.1.1). This value of Youngs modulus is substituted into equation (A9.1.3) to yield hydrogen bond cross-link density. Results A plot of E as a function of gelatin concentration (Figure A9.1.2) demonstrates a linear increase in Youngs modulus at low concentrations. The slight upward curvature at high concentrations is caused by the increasing efciency of the network. However, the line should go through the origin. Physical cross-link concentrations were determined using equation (A9.1.3), and the results are shown in Table A9.1.2. Assuming a molecular weight of about 65,000 g/mol for the gelatin, there is about 1.2 physical bonds per molecule (see Table A9.1.2). Using gelatin as a model cross-linked elastomer, its rubber elasticity can also be demonstrated by a simple stretching experiment. Thin slices of the

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Figure A9.1.2 Modulus of gelatin samples versus concentration. By comparison, a rubber band has a Youngs modulus of about 1 106 pascals (1 pascal = 10 dynes/cm2).

Table A9.1.2 Gelatin indentations yield bond numbers

Concentration 0.5 0.75 1.0 2.0 3.0

h (cm) 1.50 1.30 1.20 0.80 0.40

m (mol/cm3) 3.5 10 4.4 10-7 5.0 10-7 9.1 10-7 2.6 10-6
-7

N 1.20 1.00 1.00 0.86 1.70

Key: h, indentation measured at gelatin temperature of 5C; Cx, number of hydrogen bonds; N, number of bonds per molecule.

more concentrated gelatin samples were cut and stretched by hand. On release from stretches up to about 50%, the sample snaps back, illustrating the rubberlike elasticity of these materials. At greater elongation the sample breaks, however. The material is weak because the gelatin protein chains are much diluted with water. Discussion For rubbery materials, Youngs modulus is related to the number of cross-links in the system. In this case the cross-links are of a physical nature, caused by hydrogen bonding. Measurement of the modulus via ball indentation techniques allows a rapid, inexpensive method of counting these bonds. Table A9.1.2 shows that the number of these bonds is of the order of 10-7 mol/cm3. The number of these bonds also was shown to increase linearly with concentration, except at the highest concentrations.

APPENDIX 9.2

ELASTIC BEHAVIOR OF A RUBBER BAND

501

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!

REFERENCES
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).