Graphite
Graphite | ||
---|---|---|
Specific gravity 1.9–2.3 | | |
Density | 2.09–2.23 g/cm3 | |
Optical properties | Uniaxial (−) | |
Pleochroism | Strong | |
Solubility | Soluble in molten nickel, warm chlorosulfuric acid[2] | |
Other characteristics | strongly anisotropic, conducts electricity, greasy feel, readily marks | |
References | [3][4][5] |
Graphite (
Types and varieties
Natural 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 hexagonaledges if unbroken. When broken, the edges can be irregular or angular;
- Amorphous graphite: very fine flake graphite is sometimes called amorphous;[8]
- Lump graphite (or vein graphite) occurs in fissure fractures and appears as massive platy intergrowths of fibrous or acicular crystalline aggregates, and is probably hydrothermal in origin.[9]
- Highly ordered pyrolytic graphite refers to graphite with an angular spread between the graphite sheets of less than 1°.[10]
- The name "graphite fiber" is sometimes used to refer to carbon fiber-reinforced polymer.
Synthetic graphite
Synthetic graphite (or artificial graphite) is a material consisting of graphitic carbon which has been obtained by graphitizing of non-graphitic carbon, by chemical vapor deposition from hydrocarbons at temperatures above 2,500 K (2,230 °C), by decomposition of thermally unstable carbides or by crystallizing from metal melts supersaturated with carbon.[11]
Biographite
Biographite is a commercial product proposal for reducing the carbon footprint of lithium, iron, phosphate (LEP) batteries. It is produced from forestry waste and similar byproducts by a company in New Zealand using a novel process called thermo-catalytic graphitisation which project is supported by grants from interested parties including a forestry company in Finland and a battery maker in Hong Kong[12][13]
Natural graphite
Occurrence
Graphite occurs in metamorphic rocks as a result of the reduction of sedimentary carbon compounds during metamorphism. It also occurs in igneous rocks and in meteorites.[5] Minerals associated with graphite include quartz, calcite, micas and tourmaline. The principal export sources of mined graphite are in order of tonnage: China, Mexico, Canada, Brazil, and Madagascar.[14]
In
Structure
Graphite consists of sheets of trigonal planar carbon.
Electrical conductivity perpendicular to the layers is consequently about 1000 times lower.[22]
There are two allotropic forms called alpha (
-
Scanning tunneling microscope image of graphite surface
-
Side view of ABA layer stacking
-
Plane view of layer stacking
-
Alpha graphite's unit cell
Thermodynamics
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).[26][27] However, the phases have a wide region about this line where they can coexist. At
Other properties
The
Graphite is an
Graphite and graphite powder are valued in industrial applications for their self-lubricating and dry
The use of graphite is limited by its tendency to facilitate
When a large number of crystallographic defects bind these planes together, graphite loses its lubrication properties and becomes what is known as
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 of natural graphite use
In the 4th millennium
Sometime before 1565 (some sources say as early as 1500), an enormous deposit of graphite was discovered on the approach to
During the 19th century, graphite's uses greatly expanded to include stove polish, lubricants, paints, crucibles, foundry facings, and pencils, 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.[44]
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.[45]
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, c. 1900, is described in the Canadian Department of Mines report on graphite mines and mining when Canadian deposits began to become important producers of graphite.[45][46]
Other names
Historically, graphite was called black lead or plumbago.
The term black lead usually refers to a powdered or processed graphite, matte black in color.
Uses of natural graphite
Natural graphite is mostly used for refractories, batteries, steelmaking, expanded graphite, brake linings, foundry facings, and lubricants.[51]
Refractories
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[update] 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[52] where the high thermal conductivity of the graphite is critical to ensuring adequate cooling of the bottom and hearth of the furnace.[53] 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
According to the USGS, US natural graphite consumption in refractories comprised 12,500 tonnes in 2010.[51]
Batteries
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.[54]
The demand for batteries, primarily
Radioactive graphite from old nuclear reactors is being researched as fuel.[citation needed] Nuclear diamond battery[clarification needed] has the potential for long duration energy supply for electronics and the internet of things.[55]
Graphite Anode Materials
Graphite is 'predominant anode material used today in lithium-ion batteries'[56] EV batteries contain four basic components: anode, cathode, electrolyte, and separator. While there is much focus on the cathode materials – lithium, nickel, cobalt, manganese, etc. – the predominant anode material used in virtually all EV batteries is graphite.[57]
Steelmaking
Natural graphite in
Brake linings
Natural amorphous and fine flake graphite are used in brake linings or
Foundry facings and lubricants
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
Everyday use
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.[9][59]
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.[60][61] 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.[62] Low-quality amorphous graphite is used and sourced mainly from China.[51]
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.
Pinewood derby
Graphite is probably the most-used lubricant in pinewood derbies.[65]
Other uses
Natural graphite has found uses in zinc-carbon batteries, electric motor brushes, and various specialized applications. 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.[66] The Scope soldering iron uses a graphite tip as its heating element.
Expanded graphite
Expanded graphite is made by immersing natural flake graphite in a bath of
Intercalated graphite
Graphite forms
History of synthetic graphite
Invention of a process to produce synthetic graphite
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 (also called silicon carbide). 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.[9]
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,[68] and in 1897 started commercial production.[9] The Acheson Graphite Co. was formed in 1899.
Synthetic graphite can also be prepared from polyimide and then commercialized.[69][70]
Scientific research
Electrodes
Graphite
Electrolytic
Powder and scrap
The powder is made by heating powdered
Neutron moderator
Special grades of synthetic graphite, such as Gilsocarbon,
Other uses
Modern
Graphite has been used in at least three
Graphite composites are used as absorber for high-energy particles, for example in the Large Hadron Collider beam dump.[78]
Graphite rods when filed into shape are used as a tool in glassworking to manipulate hot molten glass.[79]
Graphite mining, beneficiation, and milling
Graphite is mined by both
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
According to the
Occupational safety
Potential health effects include:
- Inhalation: No inhalation hazard in manufactured and shipped state. Dust and fumes generated from the material can enter the body by inhalation. High concentrations of dust and fumes may irritate the throat and respiratory system and cause coughing. Frequent inhalation of fume/dust over a long period of time increases the risk of developing lung diseases. Prolonged and repeated overexposure to dust can lead to pneumoconiosis. Pre-existing pulmonary disorders, such as emphysema, may possibly be aggravated by prolonged exposure to high concentrations of graphite dusts.
- Eye contact: Dust in the eyes will cause irritation. Exposed may experience eye tearing, redness, and discomfort.
- Skin contact: Under normal conditions of intended use, this material does not pose a risk to health. Dust may irritate skin.
- Ingestion: Not relevant, due to the form of the product in its manufactured and shipped state. However, ingestion of dusts generated during working operations may cause nausea and vomiting.
- Potential physical / chemical effects: Bulk material is non-combustible. The material may form dust and can accumulate electrostatic charges, which may cause an electrical spark (ignition source). High dust levels may create potential for explosion.
United States
The
Graphite recycling
The most common way of recycling graphite occurs when synthetic graphite electrodes are either manufactured and pieces are cut off or lathe turnings are discarded for reuse, or the electrode (or other materials) are used all the way down to the electrode holder. A new electrode replaces the old one, but a sizeable piece of the old electrode remains. This is crushed and sized, and the resulting graphite powder is mostly used to raise the carbon content of molten steel.
Graphite-containing refractories 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 crucibles 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.
Research and innovation in graphite technologies
Globally, over 60,000 patent families in graphite technologies were filed from 2012 to 2021. Patents were filed by applicants from over 60 countries and regions. However, graphite-related patent families originated predominantly from just a few countries. China was the top contributor with more than 47,000 patent families, accounting for four in every five graphite patent families filed worldwide in the last decade. Among other leading countries were Japan, the Republic of Korea, the United States and the Russian Federation. Together, these top five countries of applicant origin accounted for 95 percent of global patenting output related to graphite.[84]
Among the different graphite sources,
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 battery anode applications.[84]
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.[84]
As the most widespread anode material for lithium-ion batteries, graphite has drawn significant attention worldwide for use in 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 – Chinese universities, in particular – 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.[84]
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 carbides for specific industries, ranging from electrical and electronics, aerospace and precision engineering to military and nuclear applications.
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.
See also
- Carbon fiber
- Carbon nanotube
- Exfoliated graphite nano-platelets
- Fullerene
- Graphene
- Graphitizing and non-graphitizing carbons
- Intumescent
- Lonsdaleite
- Passive fire protection
- Pyrolytic carbon
Sources
This article incorporates text from a free content work. Licensed under CC-BY. Text taken from Patent Landscape Report - Graphite and its applications, WIPO.
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Further reading
- Lipson, H.; Stokes, A. R. (1942). "A New Structure of Carbon". Nature. 149 (3777): 328. S2CID 36502694.
- C.Michael Hogan; Marc Papineau; et al. (December 18, 1989). Phase I Environmental Site Assessment, Asbury Graphite Mill, 2426–2500 Kirkham Street, Oakland, California, Earth Metrics report 10292.001 (Report).
- Klein, Cornelis; Cornelius S. Hurlbut, Jr. (1985). Manual of Mineralogy: after Dana (20th ed.). Wiley. ISBN 978-0-471-80580-9.
- Taylor, Harold A. (2000). Graphite. Financial Times Executive Commodity Reports. London: Mining Journal Books. ISBN 978-1-84083-332-4.
- Taylor, Harold A. (2005). Graphite. Industrial Minerals and Rocks (7th ed.). Littleton, CO: AIME-Society of Mining Engineers. ISBN 978-0-87335-233-8.
External links
- Battery Grade Graphite
- Graphite at Minerals.net
- Mineral galleries
- Mineral & Exploration – Map of World Graphite Mines and Producers 2012
- Mindat w/ locations
- giant covalent structures
- The Graphite Page
- Video lecture on the properties of graphite by M. Heggie, University of Sussex
- CDC – NIOSH Pocket Guide to Chemical Hazards