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Production Of Fullerenes, Uses

As recently as 1984, carbon was thought to exist in only two solid forms. There was graphite, in which the carbon atoms arranged themselves as layered sheets of hexagonally bonded atoms, and there was diamond, in which the carbon atoms formed octahedral structures in which each carbon atom had four nearest neighbors.

Then, in 1985, chemists R. E. Smalley, R. F. Curl, J. R. Heath, and S. O'Brien at Rice University, and H. W. Kroto of the University of Sussex in England observed that a hollow truncated icosahedron, similar in shape to a soccer ball, and consisting of 60 carbon atoms, tends to form spontaneously when carbon vapor condenses. In 1990, physicists D. R. Huffman and L. Lamb of the University of Arizona, working with W. Kratschmer and K. Fostiropoulos of the Max Planck Institute in Germany, discovered a way to make bulk quantities of this C60 molecule, which investigations using high resolution electron microscopes have shown to have sizes of about one billionth of a meter.

As C60 has the same structure as the geodesic dome developed by American engineer and philosopher R. Buckminster Fuller, these molecules were christened buckminsterfullerenes by the group at Rice University. The Swiss mathematician Leonhard Euler had proved that a geodesic structure must contain 12 pentagons to close into a spheroid, although the number of hexagons may vary. Later research by Smalley and his colleagues showed that there should exist an entire family of these geodesic-dome-shaped carbon clusters. Thus, C60 has 20 hexagons; whereas its rugby-ball shaped cousin C70 has 25. Research has since shown that laser vaporization of graphite produces clusters of carbon atoms whose sizes range from two to thousands of atoms. These molecules are now known as fullerenes. All the even numbered species between C3and C600 are hollow fullerenes, but below C32, the fullerene cage is too brittle to remain stable. Helical microtubules of graphitic carbon have also been found.

Although many examples are known of five-membered carbon rings attached to six-membered rings in stable organic compounds (for example, the nucleic acids adenine and guanine), only a few occur whose two five-membered rings share an edge. The smallest fullerene in which the pentagons need not share an edge is C60; the next is C70. C72 and all larger fullerenes adopt structures in which the five-membered carbon rings are well separated, but the pentagons in these larger fullerenes occupy strained positions. This makes the carbon atoms at such sites particularly vulnerable to chemical attack. Thus, it turns out that the truncated icosahedral structure of C60 distributes the strain of closure equally, producing a molecule of great strength and stability. This molecule will, however, react with certain free radicals.

When compressed to 70% of its initial volume, the buckminsterfullerene is expected to become harder than diamond. After the pressure has been released, the molecule would be expected to take up its original volume. Experiments in which these molecules were thrown against steel surfaces at about 17,000 MPH (25,744 km/h) showed them to just bounce back.

Fullerenes are, in fact, the only pure, finite form of carbon. Diamond and graphite both form infinite networks of carbon atoms. Under normal circumstances, when a diamond is cut, the surfaces are instantly covered with hydrogen, which tie up the unattached surface bonds. The same is true of graphite. Because of their symmetry, fullerenes need no other atoms to satisfy their surface chemical bonding requirements.

The buckminsterfullerene seems to have an incredible range of electrical properties. It is currently thought that it may alternately exist in insulating, conducting, semiconducting, or superconducting forms.

Fullerenes with metal atoms trapped inside the carbon cage have also been studied. These are referred to as endohedral metallofullerenes. Reports of uranium, lanthanum, and yttrium metallofullerenes have appeared in the literature. It has been exceptionally difficult to isolate pure samples of these shrink-wrapped metal atoms, however.

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