The mineral graphite is one of the allotropes of carbon. It was named by Abraham Gottlob Werner in 1789 from the Greek γραφειν (graphein): "to draw/write", for its use in pencils, where it is commonly called lead , as distinguished from the actual metallic element lead. Unlike diamond (another carbon allotrope), graphite is an electrical conductor, a semimetal, and can be used, for instance, in the electrodes of an arc lamp. Graphite holds the distinction of being the most stable form of carbon under standard conditions. Therefore, it is used in thermochemistry as the standard state for defining the heat of formation of carbon compounds. Graphite may be considered the highest grade of coal, just above anthracite and alternatively called meta-anthracite, although it is not normally used as fuel because it is hard to ignite.
There are three principal types of natural graphite, each occurring in different types of ore deposit:
- Crystalline flake graphite (or flake graphite for short) occurs as isolated, flat, plate-like particles with hexagonal edges if unbroken and when broken the edges can be irregular or angular;
- Amorphous graphite occurs as fine particles and is the result of thermal metamorphism of coal, the last stage of coalification, and is sometimes called meta-anthracite. Very fine flake graphite is sometimes called amorphous in the trade;
- Lump graphite (also called vein graphite) occurs in fissure veins or fractures and appears as massive platy intergrowths of fibrous or acicular crystalline aggregates, and is probably hydrothermal in origin.
Highly Ordered Pyrolytic Graphite or Highly Oriented Pyrolytic Graphite (HOPG) refers to graphite with an angular spread of the between the graphite sheets of less than 1°. This highest-quality synthetic form is used in scientific research. The name "graphite fiber" is also sometimes used to refer to carbon fiber or carbon fiber-reinforced polymer.
Occurrence
Minerals associated with graphite include quartz, calcite, micas, iron meteorites, and tourmalines. Graphite has various other characteristics. Thin flakes are flexible but inelastic, the mineral can leave black marks on hands and paper, it conducts electricity, and displays superlubricity. Its best field indicators are softness, luster, density and streak.
According to the United States Geological Survey (USGS), world production of natural graphite in 2008 was 1,110 thousand tonnes (kt), of which the following major exporters are: China (800 kt), India (130 kt), Brazil (76 kt), North Korea (30 kt) and Canada (28 kt). Graphite is not mined in US, but US production of synthetic graphite in 2007 was 198 kt valued at $1.18 billion. US graphite consumption was 42 kt and 200 kt for natural and synthetic graphite, respectively.
Properties
Graphite is a layered compound. In each layer, the carbon atoms are arranged in a hexagonal lattice with separation of 0.142 nm, and the distance between planes is 0.335 nm. The two known forms of graphite, alpha (hexagonal) and beta (rhombohedral), have very similar physical properties (except that the graphene layers stack slightly differently). The hexagonal graphite may be either flat or buckled. The alpha form can be converted to the beta form through mechanical treatment and the beta form reverts to the alpha form when it is heated above 1300 °C. The layering contributes to its lower density.
The acoustic and thermal properties of graphite are highly anisotropic, since phonons propagate very quickly along the tightly-bound planes, but are slower to travel from one plane to another.
Graphite can conduct electricity due to the vast electron delocalization within the carbon layers (a phenomenon called aromaticity). These valence electrons are free to move, so are able to conduct electricity. However, the electricity is only conducted within the plane of the layers.
Graphite and graphite powder are valued in industrial applications for its self-lubricating and dry lubricating properties. There is a common belief that graphite's lubricating properties are solely due to the loose interlamellar coupling between sheets in the structure. However, it has been shown that in a vacuum environment (such as in technologies for use in space), graphite is a very poor lubricant. This observation led to the discovery that the lubrication is due to the presence of fluids between the layers, such as air and water, which are naturally adsorbed from the environment. This molecular property is unlike other layered, dry lubricants such as molybdenum disulfide. Recent studies suggest that an effect called superlubricity can also account for graphite's lubricating properties. The use of graphite is limited by its tendency to facilitate pitting corrosion in some stainless steel, and to promote galvanic corrosion between dissimilar metals (due to its electrical conductivity). It is also corrosive to aluminium in presence of moisture. For this reason, the US Air Force banned its use as a lubricant in aluminium aircraft , and discouraged its use in aluminium-containing automatic weapons . Even graphite pencil marks on aluminium parts may facilitate corrosion . Another high-temperature lubricant, hexagonal boron nitride, has the same molecular structure as graphite. It is sometimes called white graphite , due to its similar properties.
When a large number of crystallographic defects bind these planes together, graphite loses its lubrication properties and becomes what is known as pyrolytic carbon. This material is useful for blood-contacting implants such as artificial heart valves. It is also highly diamagnetic, thus it will float in mid-air above a strong magnet.
Natural and crystalline graphites are not often used in pure form as structural materials, due to their shear-planes, brittleness and inconsistent mechanical properties.
History
Graphite was used by the 4th millenium B.C. Marica culture to create a ceramic paint to decorate pottery during the Neolithic Age in southeastern Europe.
Some time before 1565 (some sources say as early as 1500), an enormous deposit of graphite was discovered on the approach to Grey Knotts from the hamlet of Seathwaite in Borrowdale parish, Cumbria, England, which the locals found very useful for marking sheep. This particular deposit of graphite was extremely pure and soft, and could easily be broken into sticks. This remains the only deposit of graphite found in this packed form.
Uses of natural graphite
Natural graphite is mostly consumed for refractories, steelmaking, expanded graphite, brake linings, and foundry facings-lubricants. Graphene, which occurs naturally in graphite, has unique physical properties and might be one of the strongest substances known; however, the process of separating it from graphite will require some technological development before it is economically feasible to use it in industrial processes.
Refractories
This end-use begins before 1900 with the graphite crucible used to hold molten metal; this is now a minor part of refractories. In the mid 1980s, the carbon-magnesite brick became important, and a bit later the alumina-graphite shape. Currently the order of importance is alumina-graphite shapes, carbon-magnesite brick, monolithics (gunning and ramming mixes), and then crucibles.
Crucibles began using very large flake graphite, and carbon-magnesite brick requiring not quite so large flake graphite; for these and others there is now much more flexibility in size of flake required, and amorphous graphite is no longer restricted to low-end refractories. Alumina-graphite shapes are used as continuous casting ware, such as nozzles and troughs, to convey the molten steel from ladle to mould, and carbon magnesite bricks line steel converters and electric arc furnaces to withstand extreme temperatures. Graphite Blocks are also used in parts of blast furnace linings where the high thermal conductivity of the graphite is critical. High-purity monolithics are often used as a continuous furnace lining instead of the carbon-magnesite bricks.
The US and European refractories industry had a crisis in 2000-2003, with an indifferent market for steel and a declining refractory consumption per tonne of steel underlying firm buyouts and many plant closings. Many of the plant closings resulted from the RHI acquisition of Harbison-Walker Refractories; some plants had their equipment auctioned off. Since much of the lost capacity was for carbon-magnesite brick, graphite consumption within refractories area moved towards alumina-graphite shapes and monolithics, and away from the brick.The major source of carbon-magnesite brick is now imports from China. Almost all of the above refractories are used to make steel and account for 75% of refractory consumption; the rest is used by a variety of industries, such as cement.
According to the USGS, US natural graphite consumption in refractories was 11,000 tonnes in 2006.
Steelmaking
Natural graphite in this end use mostly goes into carbon raising in molten steel, although it can be used to lubricate the dies used to extrude hot steel. Supplying carbon raisers is very competitive, therefore subject to cut-throat pricing from alternatives such as synthetic graphite powder, petroleum coke, and other forms of carbon. A carbon raiser is added to increase the carbon content of the steel to the specified level. A GAN consu
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Patent number: 4050932 Filing date: Aug 5, 1976 Issue date: Sep 27, 1977