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...wondered Andrew.
Well, some types w e get from a tree, and good old Charles made it more useful
...answered Lucy.
1.1 Natural rubber
There is much discussion about natural products which may yet be discovered in the fast
disappearing rain forests, indeed a significant portion of pharmaceutical organic chemicals
attribute their origin to the vast diversity of plant life found there. Even though alchemy
has been left far behind there is a long way to go before all the elegant pathways which
nature uses to synthesize her molecules are discovered. In the meantime we often rely on
her to do it for us.
This book will focus on materials which owe their historical origin to a single chemical
called polyisoprene, found in the sap of a tree named Hevea braziliensis (see Figure 1.1)
found growing originally in the jungles of Brazil, and is also found in the milky latex of
the humble milkweed (Asclepias spp.) and dandelion (Taraxacum spp.).
Polyisoprene, especially when chemically modified by vulcanization, has the remarkable
ability to substantially return to its originaI shape after being stretched considerably.
Any material which fulfills this requirement, is entitled to be called rubber. ASTM D
1566 gives a more detailed definition of rubber [l]. Polyisoprene extracted from Hevea
braziliensis is called natural rubber (NR). This elastic property, as Suzuki points out,
eventually led to a multi-billion dollar industry, and has affected the lives of the vast
majority of the people on this planet [2].
Early rubber technologists were found among the Aztecs and Mayas of South America,
who used rubber for shoe soles, coated fabrics, and playballs, well over 2,000 years ago.
An MRPRA (Malaysian Rubber Producers Research Association) article [3] mentions
that the Aztec king, Montezuma was paid tribute by the lowland tribes in the form of
16,000 rubber balls, and that ball courts have been excavated in Snaketown in the southwestern United States dating back to AD 600-900.
3
Figure 1.1 Leaf and seed from the Heveu bruziliensis tree
Subramaniam, in the late Maurice Mortons book Rubber Technology [4], attributes
Christopher Columbus as the first European to discover NR, in the early 1490s, when he
found natives in Haiti playing ball with an extract from a tree. The book goes on to
describe how, by the 18th century, uses for NR were well established in Europe, where
the English chemist J. B. Priestley gave it its name since it rubbed out pencil marks.
Stern [ 5 ] mentions the Scotsman Macintosh who in 1823 used the solvent naphtha to
dissolve rubber and applied the resulting solution to textiles to produce rainproof clothing.
Rubber at that time was supplied in hard blocks. Stern [SI notes that Thomas Hancock
in London in 1830 used what can be described as the first internal mixing machine (see
section 4.3), which mechanically worked the rubber, making it softer and therefore more
easily processable. Stern mentions that Hancock moved on to two roll mills (see section
4.2), and that it took a hundred years before the internal mixer re-appeared, becoming a
key element in the industry. Buist [6]says that Hancocks internal mixer was invented in
1820, and mentions that Hancock called it a pickle, as Buist puts it to confuse his
competitors. He also mentions that Hancocks company, James Lyne Hancock Ltd., in
London was the first British Rubber company, founded in 1820.
Rubber products, up to the 19th century, had a major flaw, they were sticky on hot days,
and very stiff when cold. This doesnt seem like much of a problem until you sit down in
your sticky rubber raincoat on a hot day and lift up the chair with you when you stand.
This problem was solved by a major discovery attributed to Charles Goodyear of Woburn,
Massachusetts, USA in 1839. Duerden [7]writes that Goodyear accidentally visited the
4
History
rubber goods store of the Roxbury Company in New York, around 1832, and as a result
became obsessed with the problems of rubber manufacture, to the extent of financial crisis,
resulting in frequent visits to the pawnbrokers shop. Duerden comments that, in his search
to modify rubber to make it more useful, Goodyear purchased the claim of combining
sulfur with India Rubber from Nathaniel Hayward. Goodyear was then awarded a contract
from the US Government to manufacture mail bags. These bags were made from rubber
containing sulfur and white lead. Before long the mail bags started to decompose. Instead
of leading him to riches, Duerden mentions that it brought Goodyear and his large family
to poverty. He must have been close to giving up when a momentous discovery took place.
By chance he heated the raw rubber-sulfur-lead combination, and found that the material
charred like leather, and vulcanized rubber, as we know it, was born. The resulting
composition was a much stronger material and was no longer sticky at higher temperatures.
Duerden writes that Goodyear took out a US patent for this momentous discovery in 1841
but that he profited little from it.
Later, in 1843, Hancock was also combining sulfur with rubber and using heat. Stern [8]
states that an artist friend of Hancock, coined the term vulcanization for this process,
after Vulcan, the god of fire. In this book, the words vulcanize, cure, and cross-linking
will be used synonymously. This discovery expanded significantly the number of uses for
rubber, since it achieved far more than just making a non-sticky material. In fact the vast
majority of rubber products today, owe their existence to vulcanization. A relative
newcomer on the scene, thermoplastic elastomers, do not need curing.
As time went on, the quantity of rubber consumed continuously increased. This created
an intense demand from the jungles of Brazil, and the dark side of our human nature
appeared in all its ugliness. Suzuki [l]mentions that the native people of the Amazon
were ruthlessly exploited, and that a rubber tapper could be killed, simply for not bringing
in the required quantity of rubber from the surrounding trees. Supply and transportation
problems began to occur in the Amazon basin, which was the only known source of raw
rubber at that time. White 191 describes how, in 1876, seeds were taken out of Brazil and
grown into seedlings at Kew Gardens in England. They were then shipped to the Far
East. Suzuki comments that virtually all of the supply of natural rubber today comes
from millions of trees which owe their heritage to those few seedlings. This is food for
thought, when the topic of preserving genetic diversity, in this case, the rainforest, arises.
In 1889 John Dunlop in England invented the first commercially successful pneumatic
tire, which was at that time used for bicycles [lo]. Dunlop produced his first vehicle
pneumatic tire in 1906 [ l l ] . An interesting observation by Stern, is that in 1904, in
England, it was found that a powder called carbon black (see section 3.3.7), blended
into rubber, significantly increased a number of its mechanical properties [12]. It seems
surprising that this major discovery was then left on the shelf for about eight years. By
History
addition to the armory of the rubber industry is a class of materials called thermoplastic
elastomers which are gaining increasing prominence in the marketplace. They behave
like rubber at room temperature but soften like plastic when heated. When cooled
down, they return to their rubbery state.
The rubber that started it all, NR, has survived the onslaught of the synthetic rubbers
exceptionally well and today still represents nearly one-third of all rubber in the
marketplace. The new awareness of our environment gives N R the added advantage of
being seen as a renewable resource, because most synthetic elastomers are derived from
petroleum oil based starting materials.
References
1.
ASTM D 1566-98
Standard Terminology Relating to Rubber.
2.
3.
4.
5.
6.
7.
8.
9.
History
16. D. L. Hertz, Jr., in Handbook of Elastomers, Ed., A. K. Bhowmick and H. L.
Stephens, Marcel Dekker Inc., New York, USA, 1988, p.464.
17. C. L. Bryant, Acrylonitrile-Butadiene (Nitrile) Rubbers, in Rubber Technology
and Manufacture, Ed., C. M. Blow, Newnes-Butterworths, London, 1977, p.119120.
18. W. Hofmann, Rubber Technology Handbook, Hanser Publishers, Munich,
Germany, 1989, p.2.