'Silicon carbide' () is a
ceramic compound of
silicon and
carbon that is manufactured on a large scale for use mainly as an abrasive but also occurs in nature as the extremely rare mineral
moissanite.
Production
Due to the rarity of natural moissanite, silicon carbide is typically man-made. Most often it is used as an
abrasive where it is often known by the trademark 'carborundum', and more recently as a
semiconductor and
diamond simulant of gem quality. The simplest manufacturing process is to combine
silica sand and
carbon at a high temperature, between 1600 and 2500 °C. Th natural forms of carborundum in the form of saphires or rubys for example are simply too valuable to use as an industrial abrasive/
The material formed in the Acheson furnace varies in purity, according to its distance from the
graphite resistor heat source. Clear, pale yellow and green crystals have the highest purity and are found closest to the resistor. The color changes to blue and black at greater distance from the resistor, and these darker crystals are less pure and usually doped with
aluminium or
iron, which increases the
electrical conductivity of these samples.
Purer silicon carbide can be made by the more expensive process of
chemical vapor deposition (CVD). Commercial large
single crystal silicon carbide is grown using a
physical vapor transport method commonly known as modified
Lely method.
Purer silicon carbide can also be prepared by the
thermal decomposition of a polymer,
poly(methylsilyne), under an
inert atmosphere at low temperatures. Relative to the CVD process, the pyrolysis method is advantagous because the polymer can be formed into various shapes prior to thermalization into the ceramic.
Discovery
The material was manufactured by
Edward Goodrich Acheson around 1893, and he not only developed the electric batch
furnace by which SiC is still made today but also formed The Carborundum Company to manufacture it in bulk, initially for use as an abrasive. It is said that Acheson was trying to dissolve carbon in molten
corundum (
alumina) and discovered the presence of hard, blue-black crystals which he believed to be a compound of carbon and corundum: hence carborundum. Or, he named the material "carborundum" by analogy to
corundum, which is another very hard substance (9 on the
Mohs scale).
In nature
Naturally occurring 'moissanite' is found only in minute quantities in certain types of meteorite and in
corundum deposits and
kimberlite. Virtually all of the silicon carbide sold in the world, including moissanite jewels, is
synthetic. Natural moissanite was first found in
1893 as a small component of the
Canyon Diablo meteorite in
Arizona by Dr.
Ferdinand Henri Moissan, after whom the material was named in
1905. Moissan's discovery of naturally occurring SiC was initially disputed because his sample may have been contaminated by silicon carbide
saw blades that were already on the market at that time.
Analysis of SiC grains found in the Murchison carbonaceous chondrite meteorite has revealed anomalous isotopic ratios of carbon and silicon, indicating an origin from outside the solar system and closer to the galactic centre.
[1]
Properties
Silicon carbide exists in at least 70 crystalline forms. Alpha silicon carbide (α-SiC) is the most commonly encountered
polymorph; it is formed at temperatures greater than 2000 °C and has a
hexagonal crystal structure (similar to
Wurtzite). The beta modification (β-SiC), with a
face-centered cubic crystal structure (similar to
diamond and
zincblende or
sphalerite), is formed at temperatures below 2000 °C and is shown in the structure at the top of the page. Until recently, the beta form has had relatively few commercial uses, although there is now increasing interest in its use as a support for heterogeneous catalysts, owing to its higher surface area compared to the alpha form.
Silicon carbide has a specific gravity of 3.2, and its high sublimation temperature (approximately 2700 °C) makes it useful for
bearings and furnace parts. Silicon carbide does not melt at any known pressure. It is also highly inert chemically. There is currently much interest in its use as a
semiconductor material in electronics, where its high
thermal conductivity, high
electric field breakdown strength and high maximum
current density make it more promising than silicon for high-powered devices. In addition, it has strong coupling to
microwave radiation, which together with its high melting point, permits practical use in heating and casting metals. SiC also has a very low
coefficient of thermal expansion and experiences no
phase transitions that would cause discontinuities in thermal expansion.
Pure SiC is clear. The brown to black color of industrial product results from
iron impurities. The rainbow-like lustre of the crystals is caused by a
passivation layer of
silicon dioxide that forms on the surface.
Uses
Semiconductor
Pure α-SiC is an
intrinsic semiconductor with
band gaps of 3.28 eV (4H) and 3.03 eV (6H) respectively.
Possibly the earliest electrical application of SiC was in
lightning arresters in electric power systems. These devices must exhibit high
resistance until the
voltage across them reaches a certain threshold V
T, at which point their resistance must drop to a lower level and maintain this until the applied voltage drops below V
T.
It was recognized early on that SiC had such a voltage-dependent resistance, and so columns of SiC pellets were connected between high-voltage
power lines and the earth. When a
lightning strike to the line raises the line voltage sufficiently, the SiC column will conduct, allowing the worst of the stroke to pass harmlessly to the earth instead of along the power line. Unfortunately, such SiC columns proved to conduct significantly at normal power-line operating voltages and thus had to be placed
in series with a
spark gap. This spark gap is
ionized and rendered conductive when lightning raises the voltage of the power line conductor, thus effectively connecting the SiC column between the power conductor and the earth, where it then operates as before.
The trouble here is that spark gaps used in lightning arrestors are notoriously unreliable: they either fail to strike an arc when needed or fail to turn off afterwards: this last is due to material failure or contamination by dust or salt. In fact, the whole idea of using the SiC column was to eliminate the need for the spark gap in a lightning arrester.
But with some intensive engineering, the gapped SiC lightning arrester proved to be a reasonably good lightning-protection tool for many years. There were several brand names;
GE and
Westinghouse made them, among others. The gapped SiC arrester has been largely displaced by no-gap arresters that use columns of
zinc oxide pellets.
Silicon carbide is used for blue
LEDs, ultrafast, high-voltage
Schottky diodes,
MOSFETs and high temperature
thyristors for high power switching. A famous paper by Jayan Baliga
[2] shows enormous potential of SiC as a power device material. However, some problems with the interface of SiC with
silicon dioxide has hampered the development of SiC based power MOSFET and IGBTs. Extensive research is going on to solve the problem.
Due to its high
thermal conductivity, SiC is also used as substrate for other semiconductor materials such as
gallium nitride.
[http://www.qinetiq.com/home/commercial/information_communication_and_electronics/Electronics/optronics/quantum_electronics.html] Due to its wide
band gap, SiC-based parts are capable of operating at high temperature (over 350 °C), which together with good
thermal conductivity of SiC reduces problems with cooling of power parts. They also possess increased tolerance to
radiation damage, making it a material desired for defense and aerospace applications. Its main competitor is
gallium nitride. Although
diamond has an even higher band gap, SiC-based devices are easier to manufacture due to the fact that it is more convenient to grow an insulating layer of
silicon dioxide on the surface of a silicon carbide wafer than it is with diamond.
Pure SiC is a poor
electrical conductor. Addition of suitable
dopants significantly enhances its conductivity. Typically, such material has a negative temperature coefficient between room temperature and about 900 °C, and
positive temperature coefficient at higher temperatures, making it suitable material for high temperature
heating elements.
Silicon carbide is also used as an
ultraviolet detector.
Nikola Tesla, around the turn of the 20th century, performed a variety of experiments with carborundum.
Electroluminescence of silicon carbide was observed by Captain
Henry Joseph Round in
1907 and by
O. V. Losev in the
Soviet Union in
1923.
[http://www.indiana.edu/~hightech/fpd/papers/ELDs.html]
Structural material
In the
1980s and
1990s, silicon carbide was studied on several research programs for high-temperature gas turbines in the
United States,
Japan, and
Europe. The components were intended to replace
nickel superalloy turbine blades or nozzle vanes. However, none of these projects resulted in a production quantity, mainly because of its low impact resistance and its low fracture
toughness.
Astronomy
Silicon carbide's hardness and rigidity make it a desirable
mirror material for
astronomical work, although its properties also make manufacturing and designing such mirrors quite difficult.
Silicon carbide may be a major component of the mantles of as-yet hypothetical
carbon planets.
Grit
Silicon carbide is a popular product in modern
lapidary due to the durablility and low cost of the material. It is also used in coarse to fine
grit sandpapers and as a grip tape in
skateboards.
Disc brake
Silicon-infiltrated
carbon-carbon composite is used for high performance
brake discs as it is able to withstand extreme temperatures. The silicon reacts with the graphite in the carbon-carbon composite to become silicon carbide. These discs are used on some sports cars, including the
Porsche Carrera GT.
Clutch
The Porsche Carrera GT has two plates made of silicon carbide as well.
Diesel particulate filter
Silicon carbide is used in a
sintered form for
diesel particulate filters.
Thin filament pyrometry
Silicon carbide fibers are used to measure gas temperatures in a diagnostic technique called
thin filament pyrometry.
Ceramic membrane
Silicon carbide is used for producing ceramic membranes for industrial processes, yielding high fluxes due to the sintering process.
Cutting tools
In 1982 at the
Oak Ridge National Laboratories,
George Wei,
Terry Tiegs, and
Paul Becher discovered a composite of
aluminium oxide and silicon carbide
whiskers. This material proved to be exceptionally strong. Development of this laboratory-produced composite to a commercial product took only three years. In 1985, the first commercial cutting tools made from this alumina and silicon carbide whisker-reinforced composite were introduced by the Advanced Composite Materials Corporation (ACMC) and Greenleaf Corporation.
Heating element
References to silicon carbide
heating elements exist from the early 20th century when they were produced by Acheson's Carborundum Co. in the USA and EKL in Berlin. Silicon carbide offered increased operating temperatures compared with metallic heaters, although the operating temperature was limited initially by the water-cooled terminals, which brought the electric current to the silicon carbide hot zone. The terminals were not attached to the hot zone, but were held in place by weights, or springs. Operating temperature and efficiency was later increased by the use of separate low resistance silicon carbide "cold ends", usually of a larger diameter than the hot zone, but still held in place only by mechanical pressure. The development of reaction-bonding techniques led to the introduction of jointed elements. Initially, these featured larger diameter cold ends, but by the 1940s, equal diameter elements were being produced. From the 1960s onwards, one-piece elements were produced, with cold ends created by filling the pore volume with a silicon alloy. Another one-piece technique is to cut a spiral slot in a homogeneous tube where the hot section is desired. Further developments have included the production of multi-leg elements, where two or more legs are joined to a common bridge, and the production of high density, reaction-bonded elements, which provide additional resistance to
oxidation and chemical attack.
Silicon carbide elements are used today in the melting of non-ferrous metals and glasses,
heat treatment of metals,
float glass production, production of ceramics and electronics components, etc.
Nuclear Fuel
Silicon carbide is often used as a layer of the
TRISO coating for the
nuclear fuel elements of
high temperature gas cooled reactors or
very high temperature reactors such as the
Pebble Bed Reactor.
Jewel
As a
jewel used in
jewelry, silicon carbide is called 'Moissanite' for the jewel's discoverer Dr.
Henri Moissan [Moissanite Education]. Moissanite is somewhat similar to
diamond in several important respects: it is transparent and hard (9, although a patent states 8.5-9.0,
[3] - on the
Mohs scale compared to 10 for diamond), with a
refractive index between 2.65 and 2.69 (compared to 2.42 for diamond). Moissanite is somewhat harder than common
cubic zirconia. Unlike diamond, Moissanite is strongly
birefringent. This quality is desirable in some optical applications, but not in gemstones. For this reason, Moissanite jewels are cut along the
optic axis of the crystal to minimize birefringent effects. It is lighter (density 3.22 vs. 3.56), and much more resistant to heat. This results in a stone of higher
lustre, sharper facets and good resilience. Loose moissanite stones may be placed directly into ring moulds; unlike diamond, which burns at 800 °C, moissanite remains undamaged by temperatures up to twice the 900 °C melting point of
18k gold.
In 1998, Charles & Colvard introduced jewel-quality synthetic silicon carbide to the market under the name "moissanite". This gemstone possesses superior fire and brilliance to diamonds. Upon introduction, some jewelers misidentified moissanite as diamond. Moissanite's
thermal conductivity is very close to that of diamond, rendering useless the older thermal testers that they relied upon. Moissanite has a slightly higher
index of refraction (brilliance) and much greater
dispersion (fire) than diamond, as it shows many more "flashes" of color than a diamond. Unlike cubic zirconia and other diamond simulants, moissanite does not cloud over time, and is extremely durable.
Once its properties are known, moissanite is easy to distinguish from diamond, as it is
doubly refractive and has a very slight green, yellow, or gray fluorescence under ultraviolet light. Because the brilliance of the moissanite helps to cancel the perceived color, cuts with higher brilliance tend to have a much "whiter appearance" (i.e., round brilliant, square brilliant, and cushion cut) versus cuts that have a lower refractive index such as the marquise, radiant and especially the pear-shaped cut. The color is often defined as "near colorless" which on the diamond color scale ranges from G through J.
Charles & Colvard markets moissanite primarily to self-purchasing women. However, moissanite engagement rings, eternity bands and circle pendants have become popular among value-conscious consumers. For example, a 1-carat (200 mg) moissanite gem sells for about $500 (2007 USD), while a diamond of similar size and color typically sells for $4500 or more. Moissanite jewelry is sold at a wide variety of internet and retail outlets.
Steel
Piece of silicon carbide used in steel making
Silicon carbide dissolved in a
basic oxygen furnace used for making
steel acts as a
fuel and provides energy which increases the scrap to hot metal ratio.
[http://www.millerandco.com/products/briquettes_steel/] It can also be used to raise tap temperatures and adjust the carbon content.
90% silicon carbide is used by the steel industry as a
ladle deoxidizer,
a source of
silicon and
carbon in the
ladle, an
electric furnace slag deoxidizer, and as a synthetic slag additive.
[http://www.millerandco.com/products/briquettes_steel/specifications/briq90.htm] According to Miller and Company,
[ Miller and Company] it costs less than
ferrosilicon and
carbon combination, produces cleaner steel due to low level of
trace elements, it has a low gas content, it does not lower the temperature of steel, and it has an abundant world wide supply. The silicon carbide used as a steel additive or fuel comes as a granular product in either bulk and bags.
50% and 65% silicon carbide are used in the
steel industry for processing steel and iron scrap. Typically supplied as
blocks and made from silicon carbide crucible scrap, it helps extend the hot metal supply and raises the tap temperature.
[http://www.millerandco.com/products/briquettes_steel/specifications/briq65.htm] The
blocks are typically made using an automated
concrete block making machine, and utilize
water and
limestone cement as a binder.
Armour
Like some other hard ceramics (namely
alumina and
boron carbide), silicon carbide is used in
composite armour (eg.
Chobham armour), and in
ceramic plates in
bulletproof vests.
Catalyst Support
The natural resistance to oxidation exhibited by silicon carbide, as well as the discovery of new ways to synthesize the higher surface area beta form, has led to significant interest in its use as a heterogeneous catalyst support. The beta cubic form has already been employed for several years as a catalyst support for the oxidation of C4 hydrocarbons, such as n-butane, to maleic anhydride.
In popular culture
★ In
Edgar Rice Burroughs'
Barsoom series, "carborundum" is used as building material for city walls.
★ In and the related series of books and movies (by
Arthur C. Clarke and
Stanley Kubrick, among others) the
monoliths (or at least their exteriors) were made of silicon carbide
★ In the ''
Discworld'' novel ''
Monstrous Regiment'': Carborundum is the name of the Troll that enlists.
★ In the movie
Snatch, a pawn shop employee (Sol) determines a diamond is actually Moissanite, much to the dismay of the thief (Bad Boy Lincoln) who stole the ring.
★ The name of the material is part of the pun "
Illegitimi non carborundum" (
Dog Latin for "don't let the bastards grind you down"), which figures into a football fight song of
Harvard University among other things.
★ In the BBC television show ''
Top Gear'', host
Jeremy Clarkson expresses excitement over the mere mention of silicon carbide used in the brakes and clutch of the Porsche Carrera GT.
Patents and trademarks
Edward Goodrich Acheson (1856–1931) patented the method for making silicon carbide powder on
February 28,
1893. On
May 19,
1896, he was also issued a patent for an electrical furnace used to produce silicon carbide.
[4] Carborundum is a trademark of
Saint-Gobain Abrasives.
See also
★
Diamond simulant.
★
Illegitimi non carborundum, mock-Latin using the trademark Carborundum as if it were a
Latin verb
gerund.
References
1. http://img.chem.ucl.ac.uk/www/kelly/history.htm
2. Comparison of 6H-SiC, 3C-SiC, and Si for power devices, Bhatnagar, M., Baliga, B.J., IEEE Transactions on Electron Devices, March 1993
3. Patent #5,762,896 Espacenet record
4. -- ''Production of artificial crystalline carbonaceous material''
Notes
Most in the jewelry industry may not recognize the 1/4 fractional intervals on the Mohs scale (a relative scale), and it is technically not correct since the Mohs scale only contains whole and half numbers. But the issuers of the patent use it in showing exactly where certain minerals are in relation to each other. On the original Mohs scale diamond was listed as a 10 and sapphire is listed as a 9. On an absolute scale, a diamonds hardness is between 5700–10400 on the Knoop scale, while a sapphire's hardness is 2000. The Knoop hardness of moissanite is 3000. This puts the Mohs hardness of moissanite around 8.5–9.25—as stated here, 9 1/4 may not be recognized, but 8.5–9.25 is the number used in the patents.
External links
★
A Brief History of Silicon Carbide J F Kelly, University of London
★
Material Safety Data Sheet for Silicon Carbide
★
Mindat.org
★
discovery of Moissanite by Moissan Moissan studied Meteorites. George Frederick Kunz describes this discovery in USGS annual report.
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