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Rubber Elastomer

Rubber Elastomer

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Published by: bthong3977 on Mar 03, 2012
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07/21/2013

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 59
Chapter 3. Rubber elasticity
3.1. IntroductionNatural rubber is obtained by coagulation of a latex from a tree called
 Hevea Brasiliensis.
It consists predominantly of 
cis
-1,4-polyisoprene. Fossilised naturalrubber discovered in Germany in 1924 stems back about 50 million years. Columbuslearned during his second voyage to America about a game played by the natives of Haiti in which balls of an elastic ‘tree-resin’ were used. The word ‘rubber’
 
is derivedfrom the ability of this material to remove (rub off) marks from paper, which wasnoted by Joseph Priestley in 1770. Rubber materials are not restricted to naturalrubber. They include a great variety of synthetic polymers of similar properties. An
elastomer
 
is a polymer that exhibits rubber elastic properties, i.e. a material that canbe stretched to several times its original length without breaking and which, uponrelease of the stress, immediately returns to its original length. Rubbers are almostelastic materials, i.e. their deformation is instantaneous and they show almost nocreep.The unique character of rubber was discovered in 1305 by John Gough whodescribed his experiments and findings as follows:‘Hold one end of the slip of rubber …. between the thumb and forefinger of eachhand; bring the middle of the piece into slight contact with the lips; …. extend theslip suddenly; and you will immediately perceive a sensation of warmth in that partof the mouth that touches it … For this resin evidently grows warmer the further itis extended; and the edges of the lips possess a higher degree of sensibility, whichenables them to discover these changes with greater facility than other parts of thebody. The increase in temperature, which is perceived upon extending a piece of Caoutchouc, may be destroyed in an instant, by permitting the slip to contractagain; which it will do quickly by virtue of its own spring, as oft as the stretchingforce ceases to act as soon as it has been fully exerted.’ Gough made the followingcomment about a second experiment: ‘If one end of a slip of Caoutchouc befastened to a rod of metal or wood, and a weight be fixed at the other extremity….; the thong will be found to become shorter with heat and longer with cold.’To convince yourself, please make the experiment. You will only need a strip of rubber, a weight and a hair-dryer. Gough presented no good explanation to theunexpected findings, i.e. that the stiffness increases with increasing temperature andthat heat is evolved during stretching. It took almost 50 years before thethermodynamics of the rubber elasticity was formulated.
 
 60
Figure 3.1. Entropy-driven elasticity of rubber materials
Rubbers exhibit predominantly
entropy-driven
 
elasticity. This was concludedalready by William Thomson (Lord Kelvin) (1857) and James Prescott Joule (1859)through measurements of force and specimen length at different temperatures. Theydiscovered the thermo-elastic effects: (a) a stretched rubber sample subjected to aconstant uniaxial load contracts reversibly on heating; (b) A rubber sample gives outheat reversibly when stretched. These observations were consistent with the view thatthe entropy of the rubber decreased on stretching. The molecular picture of theentropic force originates from theoretical work during the 1930’s. It was suggestedthat the covalently bonded polymer chains were oriented during extension. Furthertheoretical development occurred during the 1940's and the stress-strain behaviourwas traced back to the conformational entropy. The view that the long chainmolecules are stretched to statistically less favourable states still prevails (Fig. 3.1).You can make a very simple demonstration with a piece of rope, which will act as amodel of the polymer chain. Take the ends of the rope with your two hands. If youkeep your hands close, the rope can take many different shapes. If you separate theends of the rope, fewer shapes are possible. Hence, the number of shapes the rope cantake decreases with the displacement of the ends. The force acting on the polymermolecule is equal to the slope of the free energy vs. displacement curve (Fig. 3.1). Theinstantaneous deformation occurring in rubbers is due to the high segmental mobilityand thus to the rapid changes in chain conformation of the molecules. The energybarriers between different conformational states must therefore be small compared tothe thermal energy (
 RT 
).The reversible character of the deformation is a consequence of the fact thatrubbers are lightly
crosslinked
(Fig. 3.2). The crosslinks prevent the chains fromslipping past each other. The chains between adjacent crosslinks contain typically
 
 61several hundred main chain atoms. The crosslinks are covalent bonds in conventionalrubbers.
Figure 3.2. Crosslinked rubber. The crosslinks are indicated by filled circles
From a historical perspective, the accomplishment by Charles Nelson Goodyear in1839 of a method to
vulcanize
natural rubber with sulphur was a crucialbreakthrough. Sulphur links attached to the
cis
-1,4-polyisoprene molecules formed thenetwork structure which is a prerequisite for obtaining elastic properties (Fig. 3.3).Goodyear got the idea from Nathaniel Hayward, who found that natural rubberbecame less sticky by mixing it with sulphur. Goodyear found accidentally thatnatural rubber and sulphur reacted at elevated temperatures: a coated piece of fabricwith rubber, sulphur and a few other ingredients was hang close to a stove and the partin direct contact with the stove had greatly changed its properties. Goodyearunderstood the importance of his finding and continued the experimenting. Thediscovery of vulcanization led to a large increase in production of natural rubber from750 tons at 1850 to 6000 tons in 1860. Scotland’s John Dunlop made use of Goodyear’s discovery in1888 by placing an air-filled rubber tube on his son’s bicycle.It worked and was the start of a new era.
Figure 3.3. Sulphur bridges invulcanized cis-1,4 -polyisopreneFigure 3.4. Structure of thermoplastic elastomers

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