Graphite () is a Crystallinity allotrope (form) of the element carbon. It consists of many stacked layers of graphene, typically in excess of hundreds of layers. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on a large scale (1.3million metric tons per year in 2022) for uses in many critical industries including refractories (50%), lithium-ion batteries (18%), foundries (10%), and lubricants (5%), among others (17%). Graphite converts to diamond under extremely high pressure and temperature. Graphite's low cost, thermal and chemical inertness and characteristic conductivity of heat and electricity finds numerous applications in high energy and high temperature processes.
In , graphite occurs with troilite and . Small graphitic crystals in meteoritic iron are called cliftonite. Some microscopic grains have distinctive Isotope compositions, indicating that they were formed before the Solar System.
There are two allotropic forms called alpha (hexagonal) and beta (rhombohedral), differing in terms of the stacking of the graphene layers: stacking in alpha graphite is ABA, as opposed to ABC stacking in the energetically less stable beta graphite. Rhombohedral graphite cannot occur in pure form. Natural graphite, or commercial natural graphite, contains 5 to 15% rhombohedral graphite and this may be due to intensive milling. The alpha form can be converted to the beta form through shear forces, and the beta form reverts to the alpha form when it is heated to 1300 °C for four hours.
Graphite is an electrical conductor, hence useful in such applications as arc lamp . 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 allow its use as pressure sensor in carbon microphones.
Graphite and graphite powder are valued in industrial applications for their self-lubricating and dry lubricant properties. However, the use of graphite is limited by its tendency to facilitate pitting corrosion in some stainless steel, Galvanic Corrosion . keytometals.com 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,Jones, Rick (USAF-Retired) Better Lubricants than Graphite. graflex.org and discouraged its use in aluminium-containing automatic weapons. Even graphite pencil marks on aluminium parts may facilitate corrosion. Another high-temperature lubricant, 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 its 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.
For a long time graphite has been considered to be hydrophobic. However, recent studies using highly ordered pyrolytic graphite have shown that freshly clean graphite is hydrophilic (contact angle of 70° approximately), and it becomes hydrophobic (contact angle of 95° approximately) due to airborne pollutants (hydrocarbons) present in the atmosphere. Those contaminants also alter the electric equipotential surface of graphite by creating domains with potential differences of up to 200 mV as measured with kelvin probe force microscopy. Such contaminants can be desorbed by increasing the temperature of graphite to approximately 50 °C or higher.
Natural and crystalline graphites are not often used in pure form as structural materials, due to their shear-planes, brittleness, and inconsistent mechanical properties.
Sometime 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, Cumbria, England, which the locals found useful for marking sheep. During the reign of Elizabeth I (1558–1603), Borrowdale graphite was used as a refractory material to line molds for cannonballs, resulting in rounder, smoother balls that could be fired farther, contributing to the strength of the English navy. This particular deposit of graphite was extremely pure and soft, and could easily be cut into sticks. Because of its military importance, this unique mine and its production were strictly controlled by the Crown.
During the 19th century, graphite's uses greatly expanded to include stove polish, lubricants, paints, crucibles, foundry facings, and , a major factor in the expansion of educational tools during the first great rise of education for the masses. The British Empire controlled most of the world's production (especially from Ceylon), but production from Austrian, German, and American deposits expanded by mid-century. For example, the Dixon Crucible Company of Jersey City, New Jersey, founded by Joseph Dixon and partner Orestes Cleveland in 1845, opened mines in the Lake Ticonderoga district of New York, built a processing plant there, and a factory to manufacture pencils, crucibles and other products in New Jersey, described in the Engineering & Mining Journal 21 December 1878. The Dixon pencil is still in production.
The beginnings of the revolutionary froth flotation process are associated with graphite mining. Included in the E&MJ article on the Dixon Crucible Company is a sketch of the "floating tanks" used in the age-old process of extracting graphite. Because graphite is so light, the mix of graphite and waste was sent through a final series of water tanks where a cleaner graphite "floated" off, which left waste to drop out. In an 1877 patent, the two brothers Bessel (Adolph and August) of Dresden, Germany, took this "floating" process a step further and added a small amount of oil to the tanks and boiled the mix – an agitation or frothing step – to collect the graphite, the first steps toward the future flotation process. Adolph Bessel received the Wohler Medal for the patented process that upgraded the recovery of graphite to 90% from the German deposit. In 1977, the German Society of Mining Engineers and Metallurgists organized a special symposium dedicated to their discovery and, thus, the 100th anniversary of flotation.
In the United States, in 1885, Hezekiah Bradford of Philadelphia patented a similar process, but it is uncertain if his process was used successfully in the nearby graphite deposits of Chester County, Pennsylvania, a major producer by the 1890s. The Bessel process was limited in use, primarily because of the abundant cleaner deposits found around the globe, which needed not much more than hand-sorting to gather the pure graphite. The state of the art, , is described in the Canadian Department of Mines report on graphite mines and mining when Canadian deposits began to become important producers of graphite.
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 these were 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.
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 where the high thermal conductivity of the graphite is critical to ensuring adequate cooling of the bottom and hearth of the furnace. 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.
Graphite is the "predominant anode material used today in lithium-ion batteries". Electric-vehicle (EV) batteries contain four basic components: anode, cathode, electrolyte, and separator. While there is much focus on the cathode materialslithium, nickel, cobalt, manganese, etc., the anode material used in virtually all EV batteries is graphite.
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 and . , , tablet computer, 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 removed from nuclear reactors has been investigated as a source of electricity for low-power applications. This waste is rich in carbon-14, which emits electrons through beta decay, so it could potentially be used as the basis for a betavoltaic device. This concept is known as the diamond battery.
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. 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. Low-quality amorphous graphite is used and sourced mainly from China.
In art, graphite is typically used to create detailed and precise drawings, as it allows for a wide range of values (light to dark) to be achieved. It can also be used to create softer, more subtle lines and shading. Graphite is popular among artists because it is easy to control, easy to erase, and produces a clean, professional look. It is also relatively inexpensive and widely available. Many artists use graphite in conjunction with other media, such as charcoal or ink, to create a range of effects and textures in their work. Graphite of various hardness or softness results in different qualities and tones when used as an artistic medium.
In milling, the incoming graphite products and concentrates can be ground before being classified (sized or screened), with the coarser flake size fractions (below 8 mesh, 8–20 mesh, 20–50 mesh) carefully preserved, and then the carbon contents are determined. Some standard blends can be prepared from the different fractions, each with a certain flake size distribution and carbon content. Custom blends can also be made for individual customers who want a certain flake size distribution and carbon content. If flake size is unimportant, the concentrate can be ground more freely. Typical end products include a fine powder for use as a slurry in oil drilling and coatings for foundry molds, carbon raiser in the steel industry (Synthetic graphite powder and powdered petroleum coke can also be used as carbon raiser). Environmental impacts from graphite mills consist of air pollution including fine particulate exposure of workers and also soil contamination from powder spillages leading to Heavy metals contamination of soil.
According to the United States Geological Survey (USGS), world production of natural graphite in 2016 was 1,200,000 , of which the following major exporters are: China (780,000 t), India (170,000 t), Brazil (80,000 t), Turkey (32,000 t) and North Korea (6,000 t). Graphite is not currently mined in the United States, but there are many historical mine sites including ones in Alabama, Montana, and in the Adirondacks of NY. Westwater Resources is in the development stages of creating a pilot plant for their Coosa Graphite Mine near Sylacauga, Alabama. U.S. production of synthetic graphite in 2010 was 134,000 t valued at $1.07 billion.
Graphite-containing Refractory are sometimes also recycled, but often are not due to their low graphite content: the largest-volume items, such as carbon-magnesite bricks that contain only 15–25% graphite, usually contain too little graphite to be worthwhile to recycle. However, some recycled carbon–magnesite brick is used as the basis for furnace-repair materials, and also crushed carbon–magnesite brick is used in slag conditioners.
While have a high graphite content, the volume of crucibles used and then recycled is very small.
A high-quality flake graphite product that closely resembles natural flake graphite can be made from steelmaking kish. Kish is a large-volume near-molten waste skimmed from the molten iron feed to a basic oxygen furnace and consists of a mix of graphite (precipitated out of the supersaturated iron), lime-rich slag, and some iron. The iron is recycled on-site, leaving a mixture of graphite and slag. The best recovery process uses hydraulic classification (which utilizes a flow of water to separate minerals by specific gravity: graphite is light and settles nearly last) to get a 70% graphite rough concentrate. Leaching this concentrate with hydrochloric acid gives a 95% graphite product with a flake size ranging from 10 mesh (2 mm) down.
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,Acheson, E. G. "Manufacture of Graphite", , issued September 29, 1896. and in 1897 started commercial production. The Acheson Graphite Co. was formed in 1899.
Synthetic graphite can also be prepared from polyimide and then commercialized.
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 for .
It is possible to create battery-grade graphite by recycling the numerous fines from battery production. The process involves spray drying the fines over petroleum pitch with a binder and cross-linking agent, then drying them.
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.
Glassworking tools are often made from graphite since it will not stick to hot molten glass, unlike metal tools and moulds which require coatings or lubricants, which are themselves often graphite-based. Glass production machines make significant use of graphite for handling the molten glass and freshly formed items.
Among the different graphite sources, flake graphite has the highest number of patent families, with more than 5,600 filed worldwide from 2012 to 2021. Supported by active research from its commercial entities and research institutions, China is the country most actively exploiting flake graphite and has contributed to 85 percent of global patent filings in this area.
At the same time, innovations exploring new synthesis methods and uses for artificial graphite are gaining interest worldwide, as countries seek to exploit the superior material qualities associated with this man-made substance and reduce reliance on the natural material. Patenting activity is strongly led by commercial entities, particularly world-renowned battery manufacturers and anode material suppliers, with patenting interest focused on Electric battery anode applications.
The exfoliation process for bulk graphite, which involves separating the carbon layers within graphite, has been extensively studied between 2012 and 2021. Specifically, ultrasonic and thermal exfoliation have been the two most popular approaches worldwide, with 4,267 and 2,579 patent families, respectively, significantly more than for either the chemical or electrochemical alternatives.
Global patenting activity relating to ultrasonic exfoliation has decreased over the years, indicating that this low-cost technique has become well established. Thermal exfoliation is a more recent process. Compared to ultrasonic exfoliation, this fast and solvent-free thermal approach has attracted greater commercial interest.
As the most widespread anode material for lithium-ion batteries, graphite has drawn significant attention worldwide for use in Electric battery applications. With over 8,000 patent families filed from 2012 to 2021, battery applications were a key driver of global graphite-related inventions. Innovations in this area are led by battery manufacturers or anode suppliers who have amassed sizable patent portfolios focused strongly on battery performance improvements based on graphite anode innovation. Besides industry players, academia and research institutions have been an essential source of innovation in graphite anode technologies.
Graphite for polymer applications was an innovation hot topic from 2012 to 2021, with over 8,000 patent families recorded worldwide. However, in recent years, in the top countries of applicant origin in this area, including China, Japan and the United States of America (US), patent filings have decreased.
Graphite for manufacturing ceramics represents another area of intensive research, with over 6,000 patent families registered in the last decade alone. Specifically, graphite for refractory accounted for over one-third of ceramics-related graphite patent families in China and about one-fifth in the rest of the world. Other important graphite applications include high-value ceramic materials such as for specific industries, ranging from electrical and electronics, aerospace and precision engineering to military and Nuclear graphite.
Carbon brushes represent a long-explored graphite application area. There have been few inventions in this area over the last decade, with less than 300 patent families filed from 2012 to 2021, very significantly less than between 1992 and 2011.
Biomedicine, sensor, and conductive ink are emerging application areas for graphite that have attracted interest from both academia and commercial entities, including renowned universities and multinational corporations. Typically for an emerging technology area, related patent families were filed by various organizations without any players dominating. As a result, the top applicants have a small number of inventions, unlike in well-explored areas, where they will have strong technology accumulation and large patent portfolios. The innovation focus of these three emerging areas is highly scattered and can be diverse, even for a single applicant. However, recent inventions are seen to leverage the development of graphite nanomaterials, particularly graphite and graphene.
Structure
Thermodynamics
Other properties
History of use
Other names
Uses
Refractories
Batteries
Steelmaking
Brake linings
Foundry facings and lubricants
Everyday use
Pencils
Pinewood derby
Other uses
Expanded graphite
Intercalated graphite
Mining, beneficiation, and milling
Occupational safety
United States
Recycling
History of synthetic graphite
Invention of a production process
Scientific research
Electrodes
Powder and scrap
Neutron moderator
Other uses
Research and innovation
See also
Sources
Further reading
External links
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