Synthetic diamond

From Wikipedia, the free encyclopedia

Jump to: navigation, search
A collection of colorless cultured diamonds grown by Apollo Diamond, Inc. via chemical vapour deposition

Synthetic diamond (also known variously as HPHT diamond, CVD diamond, lab-created, manufactured, lab-grown or cultured diamond) is a term used to describe diamond crystals produced in a technological process, as opposed to natural diamond, which is produced by geological processes.

Synthetic diamond is not the same as diamond-like carbon, DLC, which is amorphous hard carbon, or as diamond simulants, which are made of other materials such as cubic zirconia or silicon carbide. The properties of synthetic diamond depend on the manufacturing process used to produce it, and can be inferior, similar or superior to those of natural diamond.[1]


[edit] History

Experimental set-up of Willard Hershey

The idea of making less expensive, gem-quality diamonds synthetically is not a new one. H. G. Wells described the concept in his short story "The Diamond Maker," published in 1911 [2]. In Capital Karl Marx commented, "If we could succeed, at a small expenditure of labour, in converting carbon into diamonds, their value might fall below that of bricks".[3]

After the 1797 discovery that diamond was pure carbon, many attempts were made to alter the cheaper forms of carbon — generally with little success. One of the early successes reported in the field was by Ferdinand Frédéric Henri Moissan in 1893. His method involved heating charcoal at up to 4000 °C with iron in a carbon crucible in an electric furnace, in which an electric arc was struck between carbon rods inside blocks of lime. The molten iron was then rapidly cooled by immersion in water. The contraction generated by the cooling supposedly produced the high pressure required to transform graphite into diamond. Moissan published his work in a series of articles in the 1890s.

Many other scientists tried to replicate his experiments. Sir William Crookes claimed success in 1909. Ruff claimed in 1917 to have reproduced diamonds up to 7 mm in diameter, but later retracted his claims. [4] In 1926, Dr. Willard Hershey of McPherson College read journal articles about Moissan's and Ruff's experiments and replicated their work, producing a synthetic diamond. That diamond is on display today in Kansas at the McPherson Museum. [5] Despite the claims of Moissan, Ruff, and Hershey, many other experimenters had enormous difficulty in creating the required temperatures and pressure with similar equipment, leading some to contend that the early successes were the result of seeding by good-willed co-workers. [6]

The most definitive duplication attempts [4] were performed by Sir Charles Algernon Parsons. He devoted 30 years and a considerable part of his fortune to reproduce many of the experiments of Moissan as well as those of Hannay but also adapted processes of his own. He wrote a number of articles — one of the earliest on high-pressure/high-temperature (HPHT) diamonds — in which he claimed to have produced small diamonds. [7]. However in 1928 he authorized C.H Desch to publish an article in which he stated his belief that no synthetic diamonds (including those of Moissan and others) had been produced up to that date. In fact he found that most diamonds produced so far were more likely than not synthetic spinel. [4]

[edit] GE diamond project

In 1941 an agreement was made between General Electric, Norton and Carborundum to further develop diamond synthesis. They were able to heat carbon to about 3000 °C (5432 °F) under a pressure of half a million psi, for a few seconds.[4] The Second World War ended this project soon thereafter. It was resumed in 1951 at the Schenectady Laboratories of GE and a high pressure diamond group was formed with F.P. Bundy and H.M. Strong. Shortly afterwards Tracy Hall and others joined it.

The group improved on the anvils designed by Percy Bridgman, who received a Nobel prize for his work in 1946. Bundy and Strong made the first improvements and more were made later by Hall. The GE team used a tungsten carbide anvil within a hydraulic press to squeeze the carbonaceous sample held in a catlinite container, the finished grit being squeezed out of the container through a gasket. It was believed that on one occasion a diamond was produced, but since experiments could not be reproduced such claims could not be maintained. [4]

Hall achieved the first commercially successful synthesis of diamond on December 16, 1954 (announced on February 15, 1955). His breakthrough was using an elegant "belt" press apparatus which raised the achievable pressure from 6 to 18 GPa and the temperature to 5000 °C, using a pyrophyllite container, and having the graphite dissolved within molten nickel, cobalt or iron, a "solvent-catalyst". The largest diamond he produced was 150 micrometres across, clearly unsuitable for jewelry but very useful in industrial abrasives.[4] Hall was able to have co-workers replicate his work and the discovery was published in Nature. He was the first person to grow a synthetic diamond according to a reproducible, verifiable and witnessed process and received a gold medal of the American Chemical Society in 1972 for his work.[4] Hall left GE in 1955, and three years later developed a completely independent apparatus for the synthesis of diamond, the tetrahedral press with four anvils, thus avoiding infringement of his previous patent, which was still assigned to GE.

[edit] Later developments

Another successful diamond synthesis was produced on February 16, 1953 in Stockholm, Sweden by the QUINTUS project of ASEA (Allemanna Svenska Elektriska Aktiebolaget), Sweden's major electrical manufacturing company using a bulky split sphere apparatus designed by Baltzar von Platen and the young engineer Anders Kämpe (1928–1984). Pressure was maintained within the device at an estimated 83,000 atmospheres (8.4 GPa) for an hour. A few small crystals were produced, but not of gem quality or size. The work was not reported until the 1980s.

During the 1980s a new competitor emerged in Korea named Iljin Diamond, followed later by hundreds of Chinese entrants. Iljin Diamond allegedly accomplished this by misappropriating trade secrets from GE via a Korean former GE employee in 1988.[8]

Synthetic gem-quality diamond crystals were first produced in 1970 (reported in 1971) again by GE. Large crystals need to grow very slowly under extremely tightly controlled conditions. The first successes used a pyrophyllite tube seeded at each end with thin pieces of diamond and with the graphite feed material placed in the centre, the metal solvent, nickel, was placed between the graphite and the seeds. The container was heated and the pressure raised to around 55,000 atmospheres. The crystals grow as they flow from the centre to the ends of the tube, the longer the process is extended the larger the crystals - initially a week-long growth process produced gem-quality stones of around 5 mm and 1 carat (200 mg). The graphite feed was soon replaced by diamond grit, as there was almost no change in material volume so the process was easier to control.

The first gem-quality stones were predominantly cubic and octahedral in form and, due to contamination with nitrogen, always yellow to brown in color. Inclusions were common, especially "plate-like" ones from the nickel. Removing all nitrogen from the process by adding aluminium or titantium produced a colourless 'white' stone, while removing the nitrogen and adding boron produced a blue. However removing nitrogen slows the growth process and reduces the quality of the crystals, so the process is normally run with nitrogen present. In terms of physical properties the GE stones were not quite identical to natural stones. The colourless stones fluoresced and phosphoresced strongly under short-wave ultraviolet radiation but were inert under long-wave UV - in nature only blue stones should do this. All the GE stones also showed a strong yellow fluorescence under X-rays. De Beers Diamond Research Laboratory has since grown stones of up to 11 carats (2.2 g), but most stones are around 1 carat (200 mg) to 1.5 carats (300 mg) for economic reasons, especially with the spread of the Russian BARS apparatus since the 1980s.

In the 1950s, research has started in the US and Soviet Union on growth of diamond by pyrolysis of hydrocarbon gases, at relatively low temperatures of ~800 °C, in a low-pressure process called chemical vapor deposition (CVD). Eversole reportedly achieved vapour deposition of diamond over diamond substrate in 1953, but it was not reported until 1962[9]. Diamond film deposition was confirmed by Angus and coworkers in 1968[10] and by Deryagin and Fedoseev in 1970 [11]. The russian team succeded in growing diamond films on non-diamond (silicon) substrates that initiated massive research of growing "cheap diamond" in the 1980ies.

[edit] Properties

The gem diamond is just one of many different forms that diamond can take. Natural gem diamond is a single crystal diamond with low levels of impurities. This homogeneity is what allows it to be clear, while its material properties and hardness are what make it a popular gemstone. Most natural diamond removed from the earth's crust does not have the high purity or high crystallinity necessary to be a quality gemstone. Following are some important properties by which various types of diamond are described.

  • Crystallinity
A mass of diamond may be one single, continuous crystal or it may be made up of many smaller crystals ("polycrystalline"). Single crystal diamond is typically used in gemstones, while polycrystalline diamond is commonly used in industrial applications such as mining and cutting tools. Within polycrystalline diamond the diamond is often described by the average size of the crystals that make it up, called the "grain size." Grain sizes range from nanometers to hundreds of micrometers, usually referred to as "nanocrystalline" and "microcrystalline" diamond, respectively.
  • Hardness
A diamond's hardness can vary depending on its impurities and crystallinity. Nanocrystalline diamond produced through CVD diamond growth, for instance, can have a wide range of hardness from 30% to 75% of single crystal diamond, and the hardness can be controlled to be used in specific applications. Some single crystal diamonds grown through chemical vapor deposition have been shown to be harder than any known natural diamond.
  • Impurities and inclusions
No crystal is absolutely pure. Any substance other than carbon found in a diamond is an impurity, and may also be called an inclusion, due to the way these impurities fall in the crystal lattice. While inclusions can be unwanted, they can also be introduced on purpose to control the properties of the diamond. For instance, while pure diamond is an electrical insulator, diamond with small amounts of boron added is an electrical conductor, possibly allowing it to be used in new technological applications. Nitrogen impurities hinder movement of dislocations and put the lattice under compressive stress, increasing hardness and toughness.[12] Diamond color may also be tuned using different impurities.

Gem-quality diamonds grown in a lab can be chemically, physically and optically identical to naturally occurring ones although they can be distinguished by spectroscopy in infrared, ultraviolet, or X-ray wavelengths. The DiamondView tester from De Beers uses UV fluorescence to detect trace impurities of nickel or other metals in HPHT diamonds, or hydrogen in some LP CVD diamonds.

[edit] Manufacturing technologies

There are several methods used to produce synthetic diamonds. The original method is High Pressure High Temperature (HPHT) and is still widely used because of its relative low cost. It uses large presses that can weigh a couple of hundred tons to produce a pressure of 5 GPa at 1,500 degrees Celsius to reproduce the conditions that create natural diamond inside the Earth. A second method, using chemical vapor deposition or CVD, was invented in the 1980s, and is basically a method creating a carbon plasma on top of a substrate onto which the carbon atoms deposit to form diamond. Other methods are explosive formation (detonation nanodiamond) and ultrasound sonication of solutions of graphite.

[edit] High pressure, high temperature

The GE method is called HPHT (High Pressure, High Temperature). There are two main press designs used to supply the pressure and temperature necessary to produce synthetic diamond. These basic designs are the belt press and the cubic press. There are a number of other designs, but only belt press and cubic press are used for industrial scale manufacturing.

The original GE invention by Tracy Hall, uses the belt press, wherein upper and lower anvils supply the pressure load and heating current to a cylindrical volume. This internal pressure is confined radially by a belt of pre-stressed steel bands. A variation of the belt press uses hydraulic pressure to confine the internal pressure, rather than steel belts. Belt presses are still used today by the major manufacturers at a much larger scale than the original designs.

The second type of press design is the cubic press. A cubic press has six anvils which provide pressure simultaneously onto all faces of a cube-shaped volume. The first multi-anvil press design was actually a tetrahedral press, using only four anvils to converge upon a tetrahedron-shaped volume. The cubic press was created shortly thereafter to increase the pressurized volume. A cubic press is typically smaller than a belt press and can achieve the pressure and temperature necessary to create synthetic diamond faster. However, cubic presses cannot be easily scaled up to larger volumes. To illustrate, one could increase the pressurized volume by either increasing the size of the anvils, thereby increasing by a great factor the amount of force needed on the anvils to achieve a similar pressurization, or by decreasing the surface area to volume ratio of the pressurized volume by using more anvils to converge upon a different platonic solid (such as a dodecahedron), but such a press would be unnecessarily complex and not easily manufacturable.

[edit] Chemical vapor deposition

Chemical vapor deposition of diamond is a method of growing diamond by creating the environment and circumstances necessary for carbon atoms in a gas to settle on a diamond substrate in diamond crystalline form. This method of diamond growth has been the subject of a great deal of research since the early 1980s, especially due to its potential applications in the cutting tool, semiconductor and diamond gem industries.

In their pioneering work in the area, the Japanese passed a mixture of carbon-containing gas (methane in their case) and hydrogen into a quartz tube at a pressure of 0.05 atmospheres. Using microwaves the mixture was heated to 800 °C, disassociating both the methane and hydrogen into elemental forms. The carbon is deposited on a substrate, the majority as graphite but a very small proportion as diamond crystal. The graphite is 'removed' by the hydrogen leaving a thin layer of diamond; initially the layer was around 25 μm in thickness.

[edit] Explosive detonation

Diamond nanocrystals can be formed from the detonation of certain explosives, resulting in the formation of detonation nanodiamond. These nanodiamonds are only now beginning to reach the market in bulk quantities, principally from Russia and China.[citation needed]

[edit] Ultrasound cavitation

Diamond nanocrystals can be synthesized from a suspension of graphite in organic liquid at atmospheric pressure and room temperature using ultrasonic cavitation. The yield is approximately 10%. Cost of nanodiamonds produced by this method are estimated to be competitive with the HPHT process. [13]

[edit] Applications

Given the extraordinary set of physical properties diamond exhibits, diamond has and could have a wide-ranging impact in many fields.

[edit] Machining and cutting tools

Diamonds have long been used in machine tools, especially when machining non-ferrous alloys, as carbon dissolves in iron at the high temperatures created by high-speed machining. While natural diamond is certainly still used for this, the amount of synthetic diamond is far greater. The most common usage of diamond in cutting tools is done by distributing micrometer-sized diamond grains in a metal matrix (usually cobalt), hardening it and then sintering it onto the tool. This is typically referred to in industry as poly-crystalline diamond (PCD). PCD tipped tools are often used in mining and in the automotive aluminium cutting industry.

Diamond tools have been developed for stone, construction, etc for easy cutting, demolition of structures[14]

For the past fifteen years work has also been done in the hope of using CVD diamond growth to coat tools with diamond,[15] and though the work still shows promise it has not significantly displaced traditional PCD tools.

[edit] Electronics

CVD diamond also has applications in electronics. Conductive diamond is a useful electrode under many circumstances.[16] Photochemical methods have been developed for covalently linking DNA to the surface of polycrystalline diamond films produced through CVD. In addition, the diamonds can detect redox reactions that cannot ordinarily be studied and in some cases degrade redox-reactive organic contaminants in water supplies. Because diamond is almost completely chemically inert it can be used as an electrode under conditions that would destroy traditional materials. For such reasons waste water treatment of organic effluents,[17] as well as production of strong oxidants, have been published.[18] A number of companies produce diamond electrodes.

Diamond shows great promise as a potential radiation detection device. Diamond has a similar density to that of soft tissue, is radiation hard and has a wide bandgap. It is employed in applications such as the BABAR detector at Stanford.[19]

Diamond also has potential uses as a semiconductor.[20] This is because the diamonds can be "doped" with impurities like boron and phosphorus. Since these elements contain one more or one less valence electron than carbon, they turn the diamonds into p-type or n-type semiconductors. Diamond transistors are functional to temperatures many times that of silicon and are resistant to chemical and radioactive damage. While no diamond transistors have yet been successfully integrated into commercial electronics, they show promise for use in exceptionally high power situations and hostile environments.

CVD diamond growth has also been used in conjunction with lithographic techniques to encase microcircuits inside diamond. CVD process is also used to create designer diamond anvils as a novel probe for measuring electric and magnetic properties of materials at ultra high pressures using a diamond anvil cell.[21]

HPHT "type IIa" diamonds are, as of 2007, approaching the very high purity and crystallographic structure perfection required to replace silicon in applications like X-ray tomographic imaging at synchrotrons;[22] they will be able to sustain the increased intensities of next generation light sources.[23]

[edit] Gemstones

Diamonds for use as gemstones are grown by high-pressure, high-temperature (HPHT)[24] and by chemical vapor deposition (CVD) methods. They are available in fancy yellow or blue colors, and to a lesser extent colorless (or 'white'). The yellow color comes from nitrogen impurities in the manufacturing process while the blue color comes from boron. Other colors such as pink or green are achievable after synthesis using irradiation. Gem-quality diamonds are currently produced by:

Company Method Optical property
Apollo Diamond CVD colorless
Chatham HPHT
D.NEA yellow
Gemesis yellow

Several companies also offer memorial diamonds grown using cremated remains.

The mined diamond industry is evaluating marketing and distribution countermeasures to these less expensive alternatives. The three largest distributors have made public statements about selling their diamonds with full disclosure and have implemented measures to laser-inscribe serial numbers on their gemstones.[25]

[edit] See also

[edit] References

  1. ^ H. Sumiya, Rev. Sci. Instrum. 76 (2005), p. 026112
  2. ^ "The Diamond Maker", Project Gutenberg
  3. ^ Karl Marx (1867). Capital, Vol. 1. Wikisource. 
  4. ^ a b c d e f g Nassau, Kurt (1980). Gems made by Man. Chilton Book Co.. 
  5. ^ J. Willard Hershey Ph.D. (1940). Book of Diamonds. Heathside Press, New York. 
  6. ^ O'Donoghue, Michael (ed.) Gems, 6th edition, Elsevier, 2006, ISBN 10: 0-75-065856-8. p. 473
  7. ^ See Synthetic Diamond Section, Parson's articles of 1893 and those of others
  8. ^ General Electric v. Sung, 843 F. Supp. 776
  9. ^ W. G. Eversole Synthesis of diamond, US patent 3030187 and 3030188 (1962)
  10. ^ J. C. Angus et al. J. Appl. Phys. 39 (1968) 2915
  11. ^ B.V. Deryagin and D. V. Fedoseev Rus. Chem. Rev. 39 (1970) 783
  12. ^ Catledge, Shane A. (1999), "Effect of nitrogen addition on the microstructure and mechanical properties of diamond films grown using high-methane concentrations", Journal of Applied Physics 86: 698, doi:10.1063/1.370787 
  13. ^ Khachatryan et al. (2008) Graphite-to-diamond transformation induced by ultrasonic cavitation. Diamond and Related Materials 17(6), June, 931–936.
  14. ^ Diamond tools manufactured using synthetic diamonds and metal matrix images, applications videos
  15. ^ Ahmed et al. (2003) Diamond films grown on cemented WC–Co dental burs using an improved CVD method. Diamond and Related Materials 12(8), August, 1300–1306.
  16. ^ M. Panizza and G. Cerisola (2005) Application of diamond electrodes to electrochemical processes. Electrochimica Acta 51(2), October, 191–199.
  17. ^ D. Gandini, E. Mahé, P.A. Michaud, W. Haenni, A. Perret, Ch. Comninellis (2000) Oxidation of carbonylic acids at boron-doped diamond electrodes for wastewater treatment. Journal of Applied Electrochemistry 20;1345.
  18. ^ P.A. Michaud, E. Mahé, W. Haenni, A. Perret, Ch. Comninellis (2000) Preparation of peroxodisulfuric acid using Boron-Doped Diamond thin film electrodes. Electrochemical and Solid-State Letters 3(2), Letters online.
  19. ^ M. Bucciolini (2005) Diamond dosimetry: Outcomes of the CANDIDO and CONRADINFN projects. Nuclear Instruments and Methods in Physics Research A 552, 189–196.
  20. ^ A. Denisenko and E. Kohn (2005) Diamond power devices. Concepts and limits. Diamond and Related Materials 14(3-7), March-July, 491–498.
  21. ^ D.D. Jackson and C. Aracne-Ruddle and V. Malba and S.T. Weir and S.A. Catledge and Y.K. Vohra, Rev. Sci. Instrum., 74, 2467-2471 (2003)
  22. ^ J.Heartwig et al.. "Diamonds for Modern Synchrotron Radiation Sources". 
  23. ^ A. M. Khounsary et al. "Diamond Monochromator for High Heat Flux Synchrotron X-ray Beams". 
  24. ^ R. Abbaschian et al. "High pressure–high temperature growth of diamond crystals using split sphere apparatus" Diam. Rel. Mater. 14 (2005) 1916
  25. ^ Yarnell, Amanda (February 2, 2004). "The many facets of man-made diamonds". Chemical and Engineering News (American Chemical Society): pp. 26-31. Retrieved on 2007-10-19. 

[edit] Further reading

[edit] External links

Personal tools