Graphite

The principal types of natural graphite, each occurring in different types of ore deposits, are

• Crystalline small flakes of graphite (or flake graphite) occurs as isolated, flat, plate-like particles with hexagonal edges if unbroken. When broken the edges can be irregular or angular;
• Amorphous graphite: very fine flake graphite is sometimes called amorphous;[7]
• Lump graphite (or 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.[8]
• Highly ordered pyrolytic graphite refers to graphite with an angular spread between the graphite sheets of less than 1°.[9]
• The name "graphite fiber" is sometimes used to refer to carbon fibers or carbon fiber-reinforced polymer.

Graphite consists of sheets of trigonal planar carbon.[14][15] The individual layers are called graphene. In each layer, the carbon atoms are arranged in a honeycomb lattice with a bond length of 0.142 nm, and the distance between planes is 0.335 nm.[16] Bonding between layers is relatively weak van der Waals bonds and are often occupied by gases, which allows the graphene-like layers to be easily separated and to glide past each other.[17]

Electrical conductivity perpendicular to the layers is consequently about 1000 times lower.[18]

The two forms of graphite are called alpha (hexagonal) and beta (rhombohedral). Their properties are very similar. They differ in terms of the stacking of the graphene layers: stacking in alpha graphite is ABA, as opposed to ABC stacking in energetically less stable and less common beta graphite.[19] 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.[20]

• 
  Scanning tunneling microscope image of graphite surface
• 
  Side view of ABA layer stacking
• 
  Plane view of layer stacking
• 
  Alpha graphite's unit cell

Theoretically predicted phase diagram of carbon

The equilibrium pressure and temperature conditions for a transition between graphite and diamond is well established theoretically and experimentally. The pressure changes linearly between 1.7 GPa at 0 K and 12 GPa at 5000 K (the diamond/graphite/liquid triple point).[21][22] However, the phases have a wide region about this line where they can coexist. At normal temperature and pressure, 20 °C (293 K) and 1 standard atmosphere (0.10 MPa), the stable phase of carbon is graphite, but diamond is metastable and its rate of conversion to graphite is negligible.[23] However, at temperatures above about 4500 K, diamond rapidly converts to graphite. Rapid conversion of graphite to diamond requires pressures well above the equilibrium line: at 2000 K, a pressure of 35 GPa is needed.[21]

Molar volume against pressure at room temperature

The acoustic and thermal properties of graphite are highly anisotropic, since phonons propagate quickly along the tightly bound planes, but are slower to travel from one plane to another. Graphite's high thermal stability and electrical and thermal conductivity facilitate its widespread use as electrodes and refractories in high temperature material processing applications. However, in oxygen-containing atmospheres graphite readily oxidizes to form carbon dioxide at temperatures of 700 °C and above.[24]

Graphite is an electrical conductor, hence useful in such applications as arc lamp electrodes. It 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 primarily conducted within the plane of the layers. The conductive properties of powdered graphite[25] allow its use as pressure sensor in carbon microphones.

Graphite and graphite powder are valued in industrial applications for their 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.[26] However, it has been shown that in a vacuum environment (such as in technologies for use in space), graphite degrades as a lubricant, due to the hypoxic conditions.[27] This observation led to the hypothesis 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 hypothesis has been refuted by studies showing that air and water are not absorbed.[28] 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,[29][30] and to promote galvanic corrosion between dissimilar metals (due to its electrical conductivity). It is also corrosive to aluminium in the presence of moisture. For this reason, the US Air Force banned its use as a lubricant in aluminium aircraft,[31] and discouraged its use in aluminium-containing automatic weapons.[32] Even graphite pencil marks on aluminium parts may facilitate corrosion.[33] 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 graphite. It is also highly anisotropic, and diamagnetic, thus it will float in mid-air above a strong magnet. If it is made in a fluidized bed at 1000–1300 °C then it is isotropic turbostratic, and is used in blood-contacting devices like mechanical heart valves and is called pyrolytic carbon, and is not diamagnetic. Pyrolytic graphite and pyrolytic carbon are often confused but are very different materials.[34]

Natural and crystalline graphites are not often used in pure form as structural materials, due to their shear-planes, brittleness, and inconsistent mechanical properties.

Advert for Crane's Black Lead, c. 1905

Historically, graphite was called black lead or plumbago.[8][42] Plumbago was commonly used in its massive mineral form. Both of these names arise from confusion with the similar-appearing lead ores, particularly galena. The Latin word for lead, plumbum, gave its name to the English term for this grey metallic-sheened mineral and even to the leadworts or plumbagos, plants with flowers that resemble this colour.

The term black lead usually refers to a powdered or processed graphite, matte black in color.

Abraham Gottlob Werner coined the name graphite ("writing stone") in 1789. He attempted to clear up the confusion between molybdena, plumbago and black lead after Carl Wilhelm Scheele in 1778 proved that there are at least three different minerals. Scheele's analysis showed that the chemical compounds molybdenum sulfide (molybdenite), lead(II) sulfide (galena) and graphite were three different soft black minerals.[43][44][45]

The use of graphite as a refractory (heat-resistant) material began before 1900 with graphite crucibles 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. As of 2017 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 bricks requiring not quite so large flake graphite; for these and others there is now much more flexibility in the 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 mold, 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[47] where the high thermal conductivity of the graphite is critical to ensuring adequate cooling of the bottom and hearth of the furnace.[48] High-purity monolithics are often used as a continuous furnace lining instead of 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 closures. Many of the plant closures resulted from the acquisition of Harbison-Walker Refractories by RHI AG and some plants had their equipment auctioned off. Since much of the lost capacity was for carbon-magnesite brick, graphite consumption within the refractories area moved towards alumina-graphite shapes and Monolithics, and away from the brick. The major source of carbon-magnesite brick is now 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 comprised 12,500 tonnes in 2010.[46]

The use of graphite in batteries has increased since the 1970s. Natural and synthetic graphite are used as an anode material to construct electrodes in major battery technologies.[49]

The demand for batteries, primarily nickel–metal hydride and lithium-ion batteries, caused a growth in demand for graphite in the late 1980s and early 1990s – a growth driven by portable electronics, such as portable CD players and power tools. Laptops, mobile phones, tablets, and smartphone products have increased the demand for batteries. Electric-vehicle batteries are anticipated to increase graphite demand. As an example, a lithium-ion battery in a fully electric Nissan Leaf contains nearly 40 kg of graphite.

Radioactive graphite from old nuclear reactors is being researched as fuel. Nuclear diamond battery has the potential for long duration energy supply for electronics and the internet of things.[50]

Natural graphite in steelmaking mostly goes into raising the carbon content in molten steel; it can also serve to lubricate the dies used to extrude hot steel. Carbon additives face competitive 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 a specified level. An estimate based on USGS's graphite consumption statistics indicates that steelmakers in the US used 10,500 tonnes in this fashion in 2005.[46]

Natural amorphous and fine flake graphite are used in brake linings or brake shoes for heavier (nonautomotive) vehicles, and became important with the need to substitute for asbestos. This use has been important for quite some time, but nonasbestos organic (NAO) compositions are beginning to reduce graphite's market share. A brake-lining industry shake-out with some plant closures has not been beneficial, nor has an indifferent automotive market. According to the USGS, US natural graphite consumption in brake linings was 6,510 tonnes in 2005.[46]

A foundry-facing mold wash is a water-based paint of amorphous or fine flake graphite. Painting the inside of a mold with it and letting it dry leaves a fine graphite coat that will ease the separation of the object cast after the hot metal has cooled. Graphite lubricants are specialty items for use at very high or very low temperatures, as forging die lubricant, an antiseize agent, a gear lubricant for mining machinery, and to lubricate locks. Having low-grit graphite, or even better, no-grit graphite (ultra high purity), is highly desirable. It can be used as a dry powder, in water or oil, or as colloidal graphite (a permanent suspension in a liquid). An estimate based on USGS graphite consumption statistics indicates that 2,200 tonnes were used in this fashion in 2005.[46] Metal can also be impregnated into graphite to create a self-lubricating alloy for application in extreme conditions, such as bearings for machines exposed to high or low temperatures.[51]

Graphite pencils

The ability to leave marks on paper and other objects gave graphite its name, given in 1789 by German mineralogist Abraham Gottlob Werner. It stems from γράφειν ("graphein"), meaning to write or draw in Ancient Greek.[8][52]

From the 16th century, all pencils were made with leads of English natural graphite, but modern pencil lead is most commonly a mix of powdered graphite and clay; it was invented by Nicolas-Jacques Conté in 1795.[53][54] It is chemically unrelated to the metal lead, whose ores had a similar appearance, hence the continuation of the name. Plumbago is another older term for natural graphite used for drawing, typically as a lump of the mineral without a wood casing. The term plumbago drawing is normally restricted to 17th and 18th-century works, mostly portraits.

Today, pencils are still a small but significant market for natural graphite. Around 7% of the 1.1 million tonnes produced in 2011 was used to make pencils.[55] Low-quality amorphous graphite is used and sourced mainly from China.[46]

Graphite is probably the most used lubricant in Pinewood derbies.[56]

Graphene is used to make the 40mm acoustic drivers that deliver sound to the ear. The dynamic drivers, also known as moving coil drivers, employ an electrically charged voice coil to move a cone and produce sound waves. These drivers are made up of more than 95% graphene and preserve the majority of the material's mechanical qualities while being easier to shape and less expensive to manufacture. It is a lightweight, rigid, and low-density material that is perfect for loudspeaker membranes. The heavier a speaker's cone, the harder is to drive. Since graphene has such a high strength-to-weight ratio, graphene drivers can reduce the amount of power needed to move the coil back and forth, resulting in increased efficiency and better sound. As a result, earphones with graphene drivers are lighter and more compact.[57]

Natural graphite has found uses in zinc-carbon batteries, electric motor brushes, and various specialized applications. Graphite of various hardness or softness results in different qualities and tones when used as an artistic medium.[58] Railroads would often mix powdered graphite with waste oil or linseed oil to create a heat-resistant protective coating for the exposed portions of a steam locomotive's boiler, such as the smokebox or lower part of the firebox.[59] The Scope soldering iron uses a graphite tip as its heating element.

Expanded graphite is made by immersing natural flake graphite in a bath of chromic acid, then concentrated sulfuric acid, which forces the crystal lattice planes apart, thus expanding the graphite. The expanded graphite can be used to make graphite foil or used directly as a "hot top" compound to insulate molten metal in a ladle or red-hot steel ingots and decrease heat loss, or as firestops fitted around a fire door or in sheet metal collars surrounding plastic pipe (during a fire, the graphite expands and chars to resist fire penetration and spread), or to make high-performance gasket material for high-temperature use. After being made into graphite foil, the foil is machined and assembled into the bipolar plates in fuel cells. The foil is made into heat sinks for laptop computers which keeps them cool while saving weight, and is made into a foil laminate that can be used in valve packings or made into gaskets. Old-style packings are now a minor member of this grouping: fine flake graphite in oils or greases for uses requiring heat resistance. A GAN estimate of current US natural graphite consumption in this end-use is 7,500 tonnes.[46]

Structure of CaC₆

Graphite forms intercalation compounds with some metals and small molecules. In these compounds, the host molecule or atom gets "sandwiched" between the graphite layers, resulting in a type of compound with variable stoichiometry. A prominent example of an intercalation compound is potassium graphite, denoted by the formula KC₈. Some graphite intercalation compounds are superconductors. The highest transition temperature (by June 2009) T_c = 11.5 K is achieved in CaC₆, and it further increases under applied pressure (15.1 K at 8 GPa).[60] Graphite's ability to intercalate lithium ions without significant damage from swelling is what makes it the dominant anode material in lithium-ion batteries.

In 1893, Charles Street of Le Carbone discovered a process for making artificial graphite. In the mid-1890s, Edward Goodrich Acheson (1856–1931) accidentally invented another way to produce synthetic graphite after synthesizing carborundum (silicon carbide or SiC). He discovered that overheating carborundum, as opposed to pure carbon, produced almost pure graphite. While studying the effects of high temperature on carborundum, he had found that silicon vaporizes at about 4,150 °C (7,500 °F), leaving the carbon behind in graphitic carbon. This graphite became valuable as a lubricant.[8]

Acheson's technique for producing silicon carbide and graphite is named the Acheson process. In 1896, Acheson received a patent for his method of synthesizing graphite,[61] and in 1897 started commercial production.[8] The Acheson Graphite Co. was formed in 1899.

Synthetic graphite can also be prepared from polyimide and commercialized.[62][63]

Highly oriented pyrolytic graphite (HOPG) is the highest-quality synthetic form of graphite. It is used in scientific research, in particular, as a length standard for scanner calibration of scanning probe microscope.[64][65]

Graphite electrodes carry the electricity that melts scrap iron and steel, and sometimes direct-reduced iron (DRI), in electric arc furnaces, which are the vast majority of steel furnaces. They are made from petroleum coke after it is mixed with coal tar pitch. They are then extruded and shaped, then baked to carbonize the binder (pitch), and finally graphitized by heating it to temperatures approaching 3000 °C, at which the carbon atoms arrange into graphite. They can vary in size up to 3.5 m (11 ft) long and 75 cm (30 in) in diameter. An increasing proportion of global steel is made using electric arc furnaces, and the electric arc furnace itself is becoming more efficient, making more steel per tonne of electrode. An estimate based on USGS data indicates that graphite electrode consumption was 197,000 tonnes in 2005.[46]

Electrolytic aluminium smelting also uses graphitic carbon electrodes. On a much smaller scale, synthetic graphite electrodes are used in electrical discharge machining (EDM), commonly to make injection molds for plastics.[66]

The powder is made by heating powdered petroleum coke above the temperature of graphitization, sometimes with minor modifications. The graphite scrap comes from pieces of unusable electrode material (in the manufacturing stage or after use) and lathe turnings, usually after crushing and sizing. Most synthetic graphite powder goes to carbon raising in steel (competing with natural graphite), with some used in batteries and brake linings. According to the USGS, US synthetic graphite powder and scrap production were 95,000 tonnes in 2001 (latest data).[46]

Special grades of synthetic graphite, such as Gilsocarbon,[67][68] also find use as a matrix and neutron moderator within nuclear reactors. Its low neutron cross-section also recommends it for use in proposed fusion reactors. Care must be taken that reactor-grade graphite is free of neutron absorbing materials such as boron, widely used as the seed electrode in commercial graphite deposition systems – this caused the failure of the Germans' World War II graphite-based nuclear reactors. Since they could not isolate the difficulty they were forced to use far more expensive heavy water moderators. Graphite used for nuclear reactors is often referred to as nuclear graphite. Herbert G. McPherson, a Berkeley trained physicist at National Carbon, a division of Union Carbide, was key in confirming a conjecture of Leo Szilard that boron impurities even in "pure" graphite were responsible for a neutron absorption cross-section in graphite that compromised U-235 chain reactions. McPherson was aware of the presence of impurities in graphite because, with the use of Technicolor in cinematography, the spectra of graphite electrode arcs used in movie projectors required impurities to enhance emission of light in the red region to display warmer skin tones on the screen. Thus, had it not been for color movies, chances are that the first sustained natural U chain reaction would have required a heavy water moderated reactor.[69]

Graphite (carbon) fiber and carbon nanotubes are also used in carbon fiber reinforced plastics, and in heat-resistant composites such as reinforced carbon-carbon (RCC). Commercial structures made from carbon fiber graphite composites include fishing rods, golf club shafts, bicycle frames, sports car body panels, the fuselage of the Boeing 787 Dreamliner and pool cue sticks and have been successfully employed in reinforced concrete. The mechanical properties of carbon fiber graphite-reinforced plastic composites and grey cast iron are strongly influenced by the role of graphite in these materials. In this context, the term "(100%) graphite" is often loosely used to refer to a pure mixture of carbon reinforcement and resin, while the term "composite" is used for composite materials with additional ingredients.[70]

Modern smokeless powder is coated in graphite to prevent the buildup of static charge.

Graphite has been used in at least three radar absorbent materials. It was mixed with rubber in Sumpf and Schornsteinfeger, which were used on U-boat snorkels to reduce their radar cross section. It was also used in tiles on early F-117 Nighthawk stealth strike fighters.

Graphite composites are used as absorber for high-energy particles, for example in the Large Hadron Collider beam dump.[71]

Graphite rods when filed into shape are used as a tool in glassworking to manipulate hot molten glass.[72]

People can be exposed to graphite in the workplace by breathing it in as well as through skin contact or eye contact.

The Occupational Safety and Health Administration (OSHA) has set the legal limit (permissible exposure limit) for graphite exposure in the workplace as a time weighted average (TWA) of 15 million particles per cubic foot (1.5 mg/m³) over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of TWA 2.5 mg/m³ respirable dust over an 8-hour workday. At levels of 1250 mg/m³, graphite is immediately dangerous to life and health.[75]