Chemistry of Diamond

Part 1: Carbon Chemistry & Diamond Crystal Structure

By Anne Marie Helmenstine, Ph.D., About.com Guide See More About:

diamonds carbon geochemistry gemstones crystals

Rough Octohedral Diamond Crystal

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Federal Steel Supply, IncCarbon and chrome-moly steel pipe Heavy wall tubular goods from stockwww.FedSteel.com Natural Colored DiamondsWholesale Natural Color Diamonds & JewelryAmgad.com The word 'diamond' derives from Greek adamao, meaning 'I tame' or 'I subdue' or the related word adamas, which means 'hardest steel' or 'hardest substance'. Everyone knows diamonds are hard and beautiful, but did you know a diamond could be the oldest material you might own? While the rock in which diamonds are found may be 50 to 1,600 million years old, the diamonds themselves are approximately 3.3 billion years old. This discrepancy is because the volcanic magma that solidifies into rock where diamonds are found did not create them, but only transported the diamonds from the Earth's mantle to the surface. Diamonds also may be formed under the high pressures and temperatures at the site of meteorite impacts. The diamonds formed during an impact may be relatively 'young', but some meteorites contain star dust, debris from the death of a star, which may include diamond crystals. One such meteorite is known to contain tiny diamonds over 5 billion years old. These diamonds are older than our solar system! Start with Carbon Understanding the chemistry of a diamond requires a basic knowledge of the element carbon. A neutral carbon atom has 6 protons and 6 neutrons in its nucleus, balanced by 6 electrons. The electron shell configuration of carbon is 1s22s22p2. Carbon has a valence of 4, since 4 electrons can be accepted to fill the 2p orbital. Diamond is made up of repeating units of carbon atoms joined to four other carbon atoms via the strongest chemical linkage, covalent bonds. Each carbon atom is in a rigid tetrahedral network where it is equidistant from its neighboring carbon atoms. The structural unit of diamond consists of 8 atoms, fundamentally arranged in a cube. This network is very stable and rigid, which is why diamonds are so very hard and have a high melting point. Virtually all carbon on Earth comes from the stars. Studying the isotopic ratio of the carbon in a diamond makes it possible to trace the history of the carbon. For example, at the earth's surface the ratio of isotopes carbon-12 and carbon-13 is slightly different from that of star dust. Also, certain biological processes actively sort carbon isotopes according to mass, so the isotopic ratio of carbon that has been in living things is different from that of the Earth or the stars. Thus it is known that the carbon for most natural diamonds comes most recently from the mantle, but the carbon for a few diamonds is recycled carbon of microorganisms, formed into diamonds by the earth's crust via plate tectonics. Some minute diamonds that are generated by meteorites are from carbon available at the site of impact; some diamond crystals within meteorites are still fresh from the stars. Crystal Structure

The crystal structure of a diamond is a face-centered cubic or FCC lattice. Each carbon atom joins four other carbon atoms in regular tetrahedrons (triangular prisms). Based on the cubic form and its highly symmetrical arrangement of atoms, diamond crystals can develop into several different shapes, known as 'crystal habits'. The most common crystal habit is the eight-sided octahedron or diamond shape. Diamond crystals can also form cubes, dodecahedra, and combinations of these shapes. Except for two shape classes, these structures are manifestations of the cubic crystal system. One exception is the flat form called a macle, which is really a composite crystal, and the other exception is the class of etched crystals, which have rounded surfaces and may have elongated shapes. Real diamond crystals don't have completely smooth faces, but may have raised or indented triangular growths called 'trigons'. Diamonds have perfect cleavage in four different directions, meaning a diamond will separate neatly along these directions rather than break in a jagged manner. The lines of cleavage result from the diamond crystal having fewer chemical bonds along the plane of its octahedral face than in other directions. Diamond cutters take advantage of lines of cleavage to facet gemstones. Graphite is only a few electron volts more stable than diamond, but the activation barrier for conversion requires almost as much energy as destroying the entire lattice and rebuilding it. Therefore, once diamond is formed, it will not reconvert back to graphite because the barrier is too high. Diamonds are said to be metastable, since they are kinetically rather than thermodynamically stable. Under the high pressure and temperature conditions needed to form diamond its form is actually more stable than graphite, and so over millions of years carbonaceous deposits may slowly crystallize into diamond. Properties of Diamonds Diamond is the hardest natural material. The Mohs hardness scale, on which diamond is a '10' and corundum (sapphire) is a '9', doesn't adequately attest to this incredible hardness, as diamond is exponentially harder than corundum. Diamond is also the least compressible and stiffest substance. It is an exceptional thermal conductor - 4 times better than copper - which gives significance to diamonds being called 'ice'. Diamond has an extremely low thermal expansion, is chemically inert with respect to most acids and alkalis, is transparent from the far infrared through the deep ultraviolet, and is one of only a few materials with a negative work function (electron affinity). One consequence of the negative electron affinity is that diamonds repel water, but readily accept hydrocarbons such as wax or grease. Diamonds do not conduct electricity well, although some are semiconductors. Diamond can burn if subjected to a high temperature in the presence of oxygen. Diamond has a high specific gravity; it is amazingly dense given the low atomic weight of carbon. The brilliance and fire of a diamond are due to its high dispersion and high refractive index. Diamond has the highest reflectance and index of refraction of any transparent substances. Diamond gemstones are commonly clear or pale blue, but colored diamonds, called 'fancies', have been found in all the colors of the rainbow. Boron, which lends a bluish color, and nitrogen, which adds a yellow cast, are common trace impurities. Two volcanic rocks that may contain diamonds are kimberlite and lamproite. Diamond crystals frequently contain inclusions of other

minerals, such as garnet or chromite. Many diamonds fluoresce blue to violet, sometimes strongly enough to be seen in daylight. Some blue-fluorescing diamonds phosphoresce yellow (glow in the dark in an afterglow reaction). Type of Diamonds

Natural Diamonds Natural diamonds are classified by the type and quantity of impurities found within them. Type Ia - This is the most common type of natural diamond, containing up to 0.3% nitrogen. o Type Ib - Very few natural diamonds are this type (~0.1%), but nearly all synthetic industrial diamonds are. Type Ib diamonds contain up to 500 ppm nitrogen. o Type IIa - This type is very rare in nature. Type IIa diamonds contain so little nitrogen that it isn't readily detected using infrared or ultraviolet absorption methods. o Type IIb - This type is also very rare in nature. Type IIb diamonds contain so little nitrogen (even lower than type IIa) that the crystal is a p-type semiconductor. Synthetic Industrial Diamonds
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Synthetic industrial diamonds are produced the process of High Pressure High Temperature Synthesis (HPHT). In HPHT synthesis, graphite and a metallic catalyst are placed in a hydraulic press under high temperatures and pressures. Over the period of a few hours the graphite converts to diamond. The resulting diamonds are usually a few millimeters in size and too flawed for use as gemstones, but they are extremely useful as edges on cutting tools and drill-bits and for being compressed to generate very high pressures. (Interesting side note: Although used to cut, grind, and polish many materials, diamonds aren't used to machine alloys of iron because the diamond abrades very quickly, due to a high-temperature reaction between iron and carbon.)

Thin Film Diamonds A process called Chemical Vapor Deposition (CVD) may be used to deposit thin films of polycrystalline diamond. CVD technology makes it possible to put 'zero-wear' coatings on machine parts, use diamond coatings to draw the heat away from electronic components, fashion windows that are transparent over a broad wavelength range, and take advantage of other properties of diamonds.

Additional Reading

Diamond - Molecule of the Month - This site covers the properties of diamonds, the differences between diamond and graphite, classification of natural diamonds, manufacture of synthetic industrial diamond, and chemical vapor deposition of polycrystalline diamond. Links to Groups Studying CVD Diamond - The Bristol University chemical vapor deposition diamond group maintains this list of other groups engaged in similar research. The Chemistry of Carbon - This article provides an overview of basic chemistry associated with carbon, emphasizing the crystallographic difference between graphite and diamond. The Nature of Diamonds - The American Museum of Natural History offers this exceptional site, which includes a description of diamonds, discussion of origins and history, mining and distribution information, use in industry and technology, use in jewelry and gems, and bibliography.

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