Sunday, June 11, 2017

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Saturday, June 10, 2017

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Sunday, March 26, 2017

Synthetic Diamond

A synthetic diamond (also known as an artificial diamond, cultured diamond, or cultivated diamond) is diamond produced in an artificial process, as opposed to natural diamonds, which are created by geological processes. Synthetic diamond is also widely known as HPHT diamond or CVD diamond after the two common production methods (referring to the high-pressure high-temperature and chemical vapor deposition crystal formation methods, respectively). While the term synthetic is associated by consumers with imitation products, artificial diamonds are made of the same material (pure carbon, crystallized in isotropic 3D form). In the U.S., the Federal Trade Commission has indicated that the alternative terms laboratory-grown, laboratory-created, and [manufacturer-name]-created "would more clearly communicate the nature of the stone".

Numerous claims of diamond synthesis were documented between 1879 and 1928; most of those attempts were carefully analyzed but none were confirmed. In the 1940s, systematic research began in the United States, Sweden and the Soviet Union to grow diamonds using CVD and HPHT processes. The first reproducible synthesis was reported around 1953. Those two processes still dominate the production of synthetic diamond. A third method, known as detonation synthesis, entered the diamond market in the late 1990s. In this process, nanometer-sized diamond grains are created in a detonation of carbon-containing explosives. A fourth method, treating graphite with high-power ultrasound, has been demonstrated in the laboratory, but currently has no commercial application.

The properties of synthetic diamond depend on the details of the manufacturing processes; however, some synthetic diamonds (whether formed by HPHT or CVD) have properties such as hardness, thermal conductivity and electron mobility that are superior to those of most naturally formed diamonds. Synthetic diamond is widely used in abrasives, in cutting and polishing tools and in heat sinks. Electronic applications of synthetic diamond are being developed, including high-power switches at power stations, high-frequency field-effect transistors and light-emitting diodes. Synthetic diamond detectors of ultraviolet (UV) light or high-energy particles are used at high-energy research facilities and are available commercially. Because of its unique combination of thermal and chemical stability, low thermal expansion and high optical transparency in a wide spectral range, synthetic diamond is becoming the most popular material for optical windows in high-power CO2 lasers and gyrotrons. It is estimated that 98% of industrial grade diamond demand is supplied with synthetic diamonds.

Both CVD and HPHT diamonds can be cut into gems and various colors can be produced: clear white, yellow, brown, blue, green and orange. The appearance of synthetic gems on the market created major concerns in the diamond trading business, as a result of which special spectroscopic devices and techniques have been developed to distinguish synthetic and natural diamonds.


History

Moissan trying to create synthetic diamonds using an electric arc furnace
After the 1797 discovery that diamond was pure carbon, many attempts were made to convert various cheap forms of carbon into diamond. The earliest successes were reported by James Ballantyne Hannay in 1879 and by Ferdinand Frédéric Henri Moissan in 1893. Their method involved heating charcoal at up to 3500 °C with iron inside a carbon crucible in a furnace. Whereas Hannay used a flame-heated tube, Moissan applied his newly developed electric arc 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. Otto Ruff claimed in 1917 to have produced diamonds up to 7 mm in diameter, but later retracted his statement. In 1926, Dr. J Willard Hershey of McPherson College replicated Moissan's and Ruff's experiments, producing a synthetic diamond; that specimen is on display at the McPherson Museum in Kansas. Despite the claims of Moissan, Ruff, and Hershey, other experimenters were unable to reproduce their synthesis.

The most definitive replication attempts were performed by Sir Charles Algernon Parsons. A prominent scientist and engineer known for his invention of the steam turbine, he spent about 40 years (1882–1922) and a considerable part of his fortune trying to reproduce the experiments of Moissan and Hannay, but also adapted processes of his own. Parsons was known for his painstakingly accurate approach and methodical record keeping; all his resulting samples were preserved for further analysis by an independent party. He wrote a number of articles—some of the earliest on HPHT diamond—in which he claimed to have produced small diamonds. However, in 1928, he authorized Dr. C.H. Desch to publish an article[19] in which he stated his belief that no synthetic diamonds (including those of Moissan and others) had been produced up to that date. He suggested that most diamonds that had been produced up to that point were likely synthetic spinel.

GE diamond project
A 3-meter tall press
A belt press produced in the 1980s by KOBELCO
In 1941, an agreement was made between the General Electric (GE), Norton and Carborundum companies to further develop diamond synthesis. They were able to heat carbon to about 3,000 °C (5,430 °F) under a pressure of 3.5 gigapascals (510,000 psi) for a few seconds. Soon thereafter, the Second World War interrupted the project. It was resumed in 1951 at the Schenectady Laboratories of GE, and a high-pressure diamond group was formed with Francis P. Bundy and H.M. Strong. Tracy Hall and others joined this project shortly thereafter.

The Schenectady 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, then more were made by Hall. The GE team used tungsten carbide anvils within a hydraulic press to squeeze the carbonaceous sample held in a catlinite container, the finished grit being squeezed out of the container into a gasket. The team recorded diamond synthesis on one occasion, but the experiment could not be reproduced because of uncertain synthesis conditions, and the diamond was later shown to have been a natural diamond used as a seed.

Hall achieved the first commercially successful synthesis of diamond on December 16, 1954, and this was announced on February 15, 1955. His breakthrough was using a "belt" press, which was capable of producing pressures above 10 GPa (1,500,000 psi) and temperatures above 2,000 °C (3,630 °F). The press used a pyrophyllite container in which graphite was dissolved within molten nickel, cobalt or iron. Those metals acted as a "solvent-catalyst", which both dissolved carbon and accelerated its conversion into diamond. The largest diamond he produced was 0.15 mm (0.0059 in) across; it was too small and visually imperfect for jewelry, but usable in industrial abrasives. Hall's co-workers were able to replicate his work, and the discovery was published in the major journal Nature.He was the first person to grow a synthetic diamond with a reproducible, verifiable and well-documented process. He left GE in 1955, and three years later developed a new apparatus for the synthesis of diamond—a tetrahedral press with four anvils—to avoid violating a U.S. Department of Commerce secrecy order on the GE patent applications. Hall received the American Chemical Society Award for Creative Invention for his work in diamond synthesis.

Later developments
An independent diamond synthesis was achieved on February 16, 1953 in Stockholm by the ASEA (Allmänna Svenska Elektriska Aktiebolaget), one of Sweden's major electrical manufacturing companies. Starting in 1949, ASEA employed a team of five scientists and engineers as part of a top-secret diamond-making project code-named QUINTUS. The team used a bulky split-sphere apparatus designed by Baltzar von Platen and Anders Kämpe. Pressure was maintained within the device at an estimated 8.4 GPa for an hour. A few small diamonds 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, a company named Iljin Diamond; it was followed by hundreds of Chinese enterprises. Iljin Diamond allegedly accomplished diamond synthesis in 1988 by misappropriating trade secrets from GE via a Korean former GE employee.

A diamond scalpel consisting of a yellow diamond blade attached to a pen-shaped holder
A scalpel with single-crystal synthetic diamond blade
Synthetic gem-quality diamond crystals were first produced in 1970 by GE, then reported in 1971. The first successes used a pyrophyllite tube seeded at each end with thin pieces of diamond. The graphite feed material was placed in the center and the metal solvent (nickel) between the graphite and the seeds. The container was heated and the pressure was raised to about 5.5 GPa. The crystals grow as they flow from the center to the ends of the tube, and extending the length of the process produces larger crystals. Initially, a week-long growth process produced gem-quality stones of around 5 mm (1 carat or 0.2 g), and the process conditions had to be as stable as possible. The graphite feed was soon replaced by diamond grit because that allowed much better control of the shape of the final crystal.

The first gem-quality stones were always yellow to brown in color because of contamination with nitrogen. Inclusions were common, especially "plate-like" ones from the nickel. Removing all nitrogen from the process by adding aluminium or titanium produced colorless "white" stones, and removing the nitrogen and adding boron produced blue ones. Removing nitrogen also slowed the growth process and reduced the crystalline quality, so the process was normally run with nitrogen present.

Although the GE stones and natural diamonds were chemically identical, their physical properties were not the same. The colorless stones produced strong fluorescence and phosphorescence under short-wavelength ultraviolet light, but were inert under long-wave UV. Among natural diamonds, only the rarer blue gems exhibit these properties. Unlike natural diamonds, all the GE stones showed strong yellow fluorescence under X-rays. The De Beers Diamond Research Laboratory has grown stones of up to 25 carats (5.0 g) for research purposes. Stable HPHT conditions were kept for six weeks to grow high-quality diamonds of this size. For economic reasons, the growth of most synthetic diamonds is terminated when they reach a mass of 1 carat (200 mg) to 1.5 carats (300 mg).

In the 1950s, research started in the Soviet Union and the US on the growth of diamond by pyrolysis of hydrocarbon gases at the relatively low temperature of 800 °C. This low-pressure process is known as chemical vapor deposition (CVD). William G. Eversole reportedly achieved vapor deposition of diamond over diamond substrate in 1953, but it was not reported until 1962. Diamond film deposition was independently reproduced by Angus and coworkers in 1968 and by Deryagin and Fedoseev in 1970. Whereas Eversole and Angus used large, expensive, single-crystal diamonds as substrates, Deryagin and Fedoseev succeeded in making diamond films on non-diamond materials (silicon and metals), which led to massive research on inexpensive diamond coatings in the 1980s.

In recent years, there has been a rise in cases of undisclosed synthetic diamond melee being found in set jewelry and within diamond parcels sold in the trade. Due to the relatively inexpensive cost of diamond melee, as well as relative lack of universal knowledge for identifying large quantities of melee efficiently, not all dealers have made an effort to test diamond melee to correctly identify whether it is of natural or man-made origin. However, international laboratories are now beginning to tackle the issue head-on, with significant improvements in synthetic melee identification being made.

Manufacturing technologies
There are several methods used to produce synthetic diamond. The original method uses high pressure and high temperature (HPHT) and is still widely used because of its relatively low cost. The process involves large presses that can weigh hundreds of tons to produce a pressure of 5 GPa at 1500 °C. The second method, using chemical vapor deposition (CVD), creates a carbon plasma over a substrate onto which the carbon atoms deposit to form diamond. Other methods include explosive formation (forming detonation nanodiamonds) and sonication of graphite solutions.

High pressure, high temperature
A schematic drawing of a vertical cross section through a press setup. The drawing illustrates how the central unit, held by dies on its sides, is vertically compressed by two anvils
Schematic of a belt press
In the HPHT method, there are three main press designs used to supply the pressure and temperature necessary to produce synthetic diamond: the belt press, the cubic press and the split-sphere (BARS) press. Diamond seeds are placed at the bottom of the press. The internal part of press is heated above 1400 °C and melts the solvent metal. The molten metal dissolves the high purity carbon source, which is then transported to the small diamond seeds and precipitates, forming a large synthetic diamond.

The original GE invention by Tracy Hall uses the belt press wherein the upper and lower anvils supply the pressure load to a cylindrical inner cell. This internal pressure is confined radially by a belt of pre-stressed steel bands. The anvils also serve as electrodes providing electric current to the compressed cell. A variation of the belt press uses hydraulic pressure, rather than steel belts, to confine the internal pressure. Belt presses are still used today, but they are built on a much larger scale than those of the original design.

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 a tetrahedral press, using four anvils to converge upon a tetrahedron-shaped volume. The cubic press was created shortly thereafter to increase the volume to which pressure could be applied. A cubic press is typically smaller than a belt press and can more rapidly achieve the pressure and temperature necessary to create synthetic diamond. However, cubic presses cannot be easily scaled up to larger volumes: the pressurized volume can be increased by using larger anvils, but this also increases the amount of force needed on the anvils to achieve the same pressure. An alternative is to decrease the surface area to volume ratio of the pressurized volume, by using more anvils to converge upon a higher-order platonic solid, such as a dodecahedron. However, such a press would be complex and difficult to manufacture.

A schematic drawing of a vertical cross-section through a BARS press: the synthesis capsule is surrounded by four tungsten carbide inner anvils. Those inner anvils are compressed by four outer steel anvils. The outer anvils are held a disk barrel and are immersed in oil. A rubber diaphragm is placed between the disk barrel and the outer anvils to prevent oil from leaking
Schematic of a BARS system
The BARS apparatus is the most compact, efficient, and economical of all the diamond-producing presses. In the center of a BARS device, there is a ceramic cylindrical "synthesis capsule" of about 2 cm3 in size. The cell is placed into a cube of pressure-transmitting material, such as pyrophyllite ceramics, which is pressed by inner anvils made from cemented carbide (e.g., tungsten carbide or VK10 hard alloy). The outer octahedral cavity is pressed by 8 steel outer anvils. After mounting, the whole assembly is locked in a disc-type barrel with a diameter about 1 meter. The barrel is filled with oil, which pressurizes upon heating, and the oil pressure is transferred to the central cell. The synthesis capsule is heated up by a coaxial graphite heater and the temperature is measured with a thermocouple.

Chemical vapor deposition
Chemical vapor deposition is a method by which diamond can be grown from a hydrocarbon gas mixture. Since the early 1980s, this method has been the subject of intensive worldwide research. Whereas the mass-production of high-quality diamond crystals make the HPHT process the more suitable choice for industrial applications, the flexibility and simplicity of CVD setups explain the popularity of CVD growth in laboratory research. The advantages of CVD diamond growth include the ability to grow diamond over large areas and on various substrates, and the fine control over the chemical impurities and thus properties of the diamond produced. Unlike HPHT, CVD process does not require high pressures, as the growth typically occurs at pressures under 27 kPa.

The CVD growth involves substrate preparation, feeding varying amounts of gases into a chamber and energizing them. The substrate preparation includes choosing an appropriate material and its crystallographic orientation; cleaning it, often with a diamond powder to abrade a non-diamond substrate; and optimizing the substrate temperature (about 800 °C) during the growth through a series of test runs. The gases always include a carbon source, typically methane, and hydrogen with a typical ratio of 1:99. Hydrogen is essential because it selectively etches off non-diamond carbon. The gases are ionized into chemically active radicals in the growth chamber using microwave power, a hot filament, an arc discharge, a welding torch, a laser, an electron beam, or other means.

During the growth, the chamber materials are etched off by the plasma and can incorporate into the growing diamond. In particular, CVD diamond is often contaminated by silicon originating from the silica windows of the growth chamber or from the silicon substrate. Therefore, silica windows are either avoided or moved away from the substrate. Boron-containing species in the chamber, even at very low trace levels, also make it unsuitable for the growth of pure diamond.

Detonation of explosives
An image resembling a cluster of grape where the cluster consists of nearly spherical particles of 5-nm diameter
Electron micrograph (TEM) of detonation nanodiamond

Diamond nanocrystals (5 nm in diameter) can be formed by detonating certain carbon-containing explosives in a metal chamber. These nanocrystals are called "detonation nanodiamond". During the explosion, the pressure and temperature in the chamber become high enough to convert the carbon of the explosives into diamond. Being immersed in water, the chamber cools rapidly after the explosion, suppressing conversion of newly produced diamond into more stable graphite. In a variation of this technique, a metal tube filled with graphite powder is placed in the detonation chamber. The explosion heats and compresses the graphite to an extent sufficient for its conversion into diamond. The product is always rich in graphite and other non-diamond carbon forms and requires prolonged boiling in hot nitric acid (about 1 day at 250 °C) to dissolve them. The recovered nanodiamond powder is used primarily in polishing applications. It is mainly produced in China, Russia and Belarus and started reaching the market in bulk quantities by the early 2000s.

Ultrasound cavitation
Micron-sized diamond crystals can be synthesized from a suspension of graphite in organic liquid at atmospheric pressure and room temperature using ultrasonic cavitation. The diamond yield is about 10% of the initial graphite weight. The estimated cost of diamond produced by this method is comparable to that of the HPHT method; the crystalline perfection of the product is significantly worse for the ultrasonic synthesis. This technique requires relatively simple equipment and procedures, but it has only been reported by two research groups, and has no industrial use as of 2012. Numerous process parameters, such as preparation of the initial graphite powder, the choice of ultrasonic power, synthesis time and the solvent, are not yet optimized, leaving a window for potential improvement of the efficiency and reduction of the cost of the ultrasonic synthesis.

Properties
Traditionally, the absence of crystal flaws is considered to be the most important quality of a diamond. Purity and high crystalline perfection make diamonds transparent and clear, whereas its hardness, optical dispersion (luster) and chemical stability (combined with marketing), make it a popular gemstone. High thermal conductivity is also important for technical applications. Whereas high optical dispersion is an intrinsic property of all diamonds, their other properties vary depending on how the diamond was created.

Crystallinity
Diamond can be one single, continuous crystal or it can be made up of many smaller crystals (polycrystal). Large, clear and transparent single-crystal diamonds are typically used in gemstones. Polycrystalline diamond (PCD) consists of numerous small grains, which are easily seen by the naked eye through strong light absorption and scattering; it is unsuitable for gems and is used for industrial applications such as mining and cutting tools. Polycrystalline diamond is often described by the average size (or grain size) of the crystals that make it up. Grain sizes range from nanometers to hundreds of micrometers, usually referred to as "nanocrystalline" and "microcrystalline" diamond, respectively.

Hardness
Synthetic diamond is the hardest known material, where hardness is defined as resistance to indentation. The hardness of synthetic diamond depends on its purity, crystalline perfection and orientation: hardness is higher for flawless, pure crystals oriented to the  direction (along the longest diagonal of the cubic diamond lattice). Nanocrystalline diamond produced through CVD diamond growth can have a hardness ranging from 30% to 75% of that of single crystal diamond, and the hardness can be controlled for specific applications. Some synthetic single-crystal diamonds and HPHT nanocrystalline diamonds (see hyperdiamond) are harder than any known natural diamond.

Impurities and inclusions

Every diamond contains atoms other than carbon in concentrations detectable by analytical techniques. Those atoms can aggregate into macroscopic phases called inclusions. Impurities are generally avoided, but can be introduced intentionally as a way to control certain properties of the diamond. Growth processes of synthetic diamond, using solvent-catalysts, generally lead to formation of a number of impurity-related complex centers, involving transition metal atoms (such as nickel, cobalt or iron), which affect the electronic properties of the material.

For instance, pure diamond is an electrical insulator, but diamond with boron added is an electrical conductor (and, in some cases, a superconductor), allowing it to be used in electronic applications. Nitrogen impurities hinder movement of lattice dislocations (defects within the crystal structure) and put the lattice under compressive stress, thereby increasing hardness and toughness.

Thermal conductivity
Unlike most electrical insulators, pure diamond is a good conductor of heat because of the strong covalent bonding within the crystal. The thermal conductivity of pure diamond is the highest of any known solid. Single crystals of synthetic diamond enriched in 12
C
 (99.9%), isotopically pure diamond, have the highest thermal conductivity of any material, 30 W/cm·K at room temperature, 7.5 times higher than copper. Natural diamond's conductivity is reduced by 1.1% by the 13
C
 naturally present, which acts as an inhomogeneity in the lattice.

Diamond's thermal conductivity is made use of by jewelers and gemologists who may employ an electronic thermal probe to separate diamonds from their imitations. These probes consist of a pair of battery-powered thermistors mounted in a fine copper tip. One thermistor functions as a heating device while the other measures the temperature of the copper tip: if the stone being tested is a diamond, it will conduct the tip's thermal energy rapidly enough to produce a measurable temperature drop. This test takes about 2–3 seconds.

Applications
Machining and cutting tools
A polished metal slab embedded with small diamonds
Diamonds in an angle grinder blade
Most industrial applications of synthetic diamond have long been associated with their hardness; this property makes diamond the ideal material for machine tools and cutting tools. As the hardest known naturally occurring material, diamond can be used to polish, cut, or wear away any material, including other diamonds. Common industrial applications of this ability include diamond-tipped drill bits and saws, and the use of diamond powder as an abrasive. These are by far the largest industrial applications of synthetic diamond. While natural diamond is also used for these purposes, synthetic HPHT diamond is more popular, mostly because of better reproducibility of its mechanical properties. Diamond is not suitable for machining ferrous alloys at high speeds, as carbon is soluble in iron at the high temperatures created by high-speed machining, leading to greatly increased wear on diamond tools compared to alternatives.

The usual form of diamond in cutting tools is micrometer-sized grains dispersed in a metal matrix (usually cobalt) sintered onto the tool. This is typically referred to in industry as polycrystalline diamond (PCD). PCD-tipped tools can be found in mining and cutting applications. For the past fifteen years, work has been done to coat metallic tools with CVD diamond, and though the work still shows promise it has not significantly replaced traditional PCD tools.

Thermal conductor
Most materials with high thermal conductivity are also electrically conductive, such as metals. In contrast, pure synthetic diamond has high thermal conductivity, but negligible electrical conductivity. This combination is invaluable for electronics where diamond is used as a heat sink for high-power laser diodes, laser arrays and high-power transistors. Efficient heat dissipation prolongs the lifetime of those electronic devices, and the devices' high replacement costs justify the use of efficient, though relatively expensive, diamond heat sinks. In semiconductor technology, synthetic diamond heat spreaders prevent silicon and other semiconducting materials from overheating.

Optical material
Diamond is hard, chemically inert, and has high thermal conductivity and a low coefficient of thermal expansion. These properties make diamond superior to any other existing window material used for transmitting infrared and microwave radiation. Therefore, synthetic diamond is starting to replace zinc selenide as the output window of high-power CO2 lasers and gyrotrons. Those synthetic polycrystalline diamond windows are shaped as disks of large diameters (about 10 cm for gyrotrons) and small thicknesses (to reduce absorption) and can only be produced with the CVD technique.Single crystal slabs of dimensions of length up to approximately 10 mm are becoming increasingly important in several areas of optics including heatspreaders inside laser cavities, diffractive optics and as the optical gain medium in Raman lasers. Recent advances in the HPHT and CVD synthesis techniques have improved the purity and crystallographic structure perfection of single-crystalline diamond enough to replace silicon as a diffraction grating and window material in high-power radiation sources, such as synchrotrons.[79][80] Both the CVD and HPHT processes are also used to create designer optically transparent diamond anvils as a tool for measuring electric and magnetic properties of materials at ultra high pressures using a diamond anvil cell.[81]

Electronics
Synthetic diamond has potential uses as a semiconductor, because it can be doped with impurities like boron and phosphorus. Since these elements contain one more or one less valence electron than carbon, they turn synthetic diamond into p-type or n-type semiconductor. Making a p–n junction by sequential doping of synthetic diamond with boron and phosphorus produces light-emitting diodes (LEDs) producing UV light of 235 nm.[ Another useful property of synthetic diamond for electronics is high carrier mobility, which reaches 4500 cm2/(V·s) for electrons in single-crystal CVD diamond.[84] High mobility is favourable for high-frequency operation and field-effect transistors made from diamond have already demonstrated promising high-frequency performance above 50 GHz. The wide band gap of diamond (5.5 eV) gives it excellent dielectric properties. Combined with the high mechanical stability of diamond, those properties are being used in prototype high-power switches for power stations.

Synthetic diamond transistors have been produced in the laboratory. They are functional at much higher temperatures than silicon devices, and are resistant to chemical and radiation damage. While no diamond transistors have yet been successfully integrated into commercial electronics, they are promising for use in exceptionally high-power situations and hostile non-oxidizing environments.

Synthetic diamond is already used as radiation detection device. It is radiation hard and has a wide bandgap of 5.5 eV (at room temperature). Diamond is also distinguished from most other semiconductors by the lack of a stable native oxide. This makes it difficult to fabricate surface MOS devices, but it does create the potential for UV radiation to gain access to the active semiconductor without absorption in a surface layer. Because of these properties, it is employed in applications such as the BaBar detector at the Stanford Linear Accelerator and BOLD (Blind to the Optical Light Detectors for VUV solar observations). A diamond VUV detector recently was used in the European LYRA program.

Conductive CVD diamond is a useful electrode under many circumstances. Photochemical methods have been developed for covalently linking DNA to the surface of polycrystalline diamond films produced through CVD. Such DNA modified films can be used for detecting various biomolecules, which would interact with DNA thereby changing electrical conductivity of the diamond film. In addition, diamonds can be used to detect redox reactions that cannot ordinarily be studied and in some cases degrade redox-reactive organic contaminants in water supplies. Because diamond is mechanically and chemically stable, it can be used as an electrode under conditions that would destroy traditional materials. As an electrode, synthetic diamond can be used in waste water treatment of organic effluents and the production of strong oxidants.

Gemstones
A colorless faceted gem
Colorless gem cut from diamond grown by chemical vapor deposition
Synthetic diamonds for use as gemstones are grown by HPHT or CVD methods, and currently represent approximately 2% of the gem-quality diamond market. However, there are indications that the market share of synthetic jewelry-quality diamonds may grow as advances in technology allows for larger higher-quality synthetic production on a more economic scale. They are available in yellow and blue, 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. Several companies also offer memorial diamonds grown using cremated remains.

Gem-quality diamonds grown in a lab can be chemically, physically and optically identical (and sometimes superior) to naturally occurring ones. The mined diamond industry has undertaken legal, marketing and distribution countermeasures to protect its market from the emerging presence of synthetic diamonds. Synthetic diamonds can be distinguished by spectroscopy in the infrared, ultraviolet, or X-ray wavelengths. The DiamondView tester from De Beers uses UV fluorescence to detect trace impurities of nitrogen, nickel or other metals in HPHT or CVD diamonds.

At least one maker of laboratory-grown diamonds has made public statements about being "committed to disclosure" of the nature of its diamonds, and laser-inscribes serial numbers on all of its gemstones. The company web site shows an example of the lettering of one of its laser inscriptions, which includes both the words "Gemesis created" and the serial number prefix "LG" (laboratory grown).

In May 2015, a record was set for an HPHT colorless diamond at 10.02 carats. The faceted jewel was cut from a 32.2-carat stone that was grown within 300 hours.

Traditional diamond mining has led to human-rights abuses in Africa and elsewhere. The 2006 Hollywood movie Blood Diamond helped to publicize the situation. Consumer demand for synthetic diamonds is increasing, albeit from a small base, as customers look for stones which are ethically sound, and are cheaper.

According to a report from the Gem & Jewellery Export Promotional Council, synthetic diamonds accounted for 0.28% of diamond produced for use as gem stones in 2014. Lab diamond jewellery is sold in the United States by brands including Pure Grown Diamonds (formerly known as Gemesis) and Lab Diamonds Direct; and in the UK by Nightingale online jewellers.

Synthetic diamonds sold as jewelry typically sell for 15–20% less than natural equivalents, but the relative price is expected to decline further as production economics improve.

Diamond Enhancement

Diamond enhancements are specific treatments, performed on natural diamonds (usually those already cut and polished into gems), which are designed to improve the visual gemological characteristics of the diamond in one or more ways. These include clarity treatments such as laser drilling to remove black carbon inclusions, fracture filling to make small internal cracks less visible, color irradiation and annealing treatments to make yellow and brown diamonds a vibrant fancy color such as vivid yellow, blue, or pink.

The CIBJO and government agencies such as the United States Federal Trade Commission explicitly require the disclosure of all diamond treatments at the time of sale. Some treatments, particularly those applied to clarity, remain highly controversial within the industry—this arises from the traditional notion that diamonds hold a unique or "sacred" place among the gemstones, and should not be treated too radically, if for no other reason than a fear of damaging consumer confidence.

Clarity and color enhanced diamonds sell at lower price points when compared to similar, untreated diamonds. This is because enhanced diamonds are originally lower quality before the enhancement is performed, and therefore are priced at a substandard level. After enhancement, the diamonds may visually appear as good as their non-enhanced counterparts. Therefore, treated diamonds appear to have a greater value than they would before treatment, but whether this is in fact the case is questionable.

Clarity enhancements


The clarity, or purity, of a diamond refers to internal inclusions of the diamond, and is one of the 4-C's in determining a diamonds' value. Common inclusions that appear inside diamonds are black carbon spots and small cracks, commonly referred to as fractures or "feathers", due to their feathery whitish appearance when viewed from above or through the side. Diamonds may also have other inclusions such as air bubbles and mineral deposits such as iron or garnet. The size, color, and position of the inclusions are factors in determining the value of a diamond, especially when the other gemological characteristics are of a higher standard.

Laser drilling
The development of laser drilling techniques have increased the ability to selectively target, remove and significantly reduce the visibility of black carbon inclusions on a microscopic scale. Diamonds containing hematite inclusions have been laser-drilled since the late 1960s, a technique credited to Louis Perlman that did a successful test a year after General Electric had made a similar one with a diamond for industrial use in 1962.

The laser drilling process involves the use of an infrared laser (of surgical grade at a wavelength about 1064 nm) to bore very fine holes (less than 0.2 millimeters or 0.005 inches in diameter) into a diamond to create a route of access to a black carbon crystal inclusion. Because diamond is transparent to the wavelength of the laser beam, a coating of amorphous carbon or other energy-absorbent substance is applied to the surface of the diamond to initiate the drilling process. The laser then burns a narrow tube or channel to the inclusion. Once the location of included black carbon crystal has been reached by the drill channel, the diamond is soaked in sulfuric acid to dissolve the black carbon crystal. After soaking in sulfuric acid the black carbon crystal will dissolve and become transparent (colorless) and sometimes slightly whitish opaque. Under microscopic inspection the fine drill or bore holes can be seen, but are not distracting and do not affect sparkle or brilliance of the diamond. While the channels are usually straight in direction, from an entry point on the surface, some drilling techniques are drilled from within, using naturally occurring fractures inside the stone to reach the inclusion in a way that mimics organic "feathers" (This method is sometimes referred to as KM drilling which stands for special drilling in Hebrew). The channels are microscopic so that dirt or debris cannot travel down the channel. The surface-reaching holes can only be seen by reflecting light off of the surface of the diamond during microscopic viewing such as a jeweler's 10x magnifying lens or loupe and are invisible to the naked eye.

Fracture filling


While fracture filling as a method to enhance gems has been found in gems over 2,500 years old,the diamond's unique refractive index required a more advanced solution than simple wax and oil treatments. This technology became available roughly 20 years after the time the laser drilling technique was developed. Simply put, "fracture filling" makes tiny natural fractures inside diamonds less visible to the naked eye or even under magnification. Fractures are very common inside diamonds and are created during the diamond's creation in the earth's crust. As the rough diamond travels up from the earth's crust through volcanic pipes it comes under extreme stresses and pressures, and during this travel tiny fractures can form inside the diamond. If these fractures are visible and damaging to the beauty of the diamond, it will have much lower demand and won't be as salable to jewelers and the general public, making them candidates for fracture filling and thus visually improve the appearance of the diamond.

The fracture filling of diamond is often the last step in the process of diamond enhancement, following laser drilling and acid-etching of inclusions, though if the fractures are surface-reaching, no drilling may be required. This process, which involves the use of specially-formulated solutions with a refractive index approximating that of diamond, was pioneered by Zvi Yehuda of Ramat Gan, Israel. Yehuda is now used as a brand name applied to diamonds treated in this manner. Koss & Schechter, another Israel-based firm, attempted to modify Yehuda's process in the 1990s by using halogen-based glasses, but this was unsuccessful. The details behind the Yehuda process have been kept secret, but the filler used is reported to be lead oxychloride glass, which has a fairly low melting point. The New York-based Dialase also treats diamonds via a Yehuda-based process, which is believed to use lead-bismuth oxychloride glass, but research into creating better, more durable, less traceable solutions is still being done, creating more silicone based solutions for the fracture filling process.

The solution present in fracture-filled diamonds can usually be detected by a trained gemologist under the microscope: while each diamond gets a treatment that fits its unique shape, state and fracture status, there may be traces of surface-reaching bore holes and fractures associated with drilled diamonds, air bubbles and flow lines within the glass, which are features never seen in untreated diamond. More dramatic is the so-called "flash effect", which refers to the bright flashes of color seen when a fracture-filled diamond is rotated; the color of these flashes ranges from an electric blue or purple to an orange or yellow, depending on lighting conditions (light field and dark field, respectively). The flashes are best seen with the field of view nearly parallel to the filled fracture's plane (although specific fractures in untreated diamonds may cause similar "flash effect"). In strongly colored diamonds the flash effect may be missed if examination is less than thorough, as the stone's body color will conceal one or more of the flash colors. For example, in brown-tinted "champagne" diamonds, the orange-yellow flashes are concealed, leaving only the blue-purple flashes to be seen. One last but important feature of fracture-filled diamonds is the color of the solution itself: it is sometimes a yellowish to brownish, and along with being visible in transmitted light, it can affect the overall color of the diamond, making the diamond fall an entire color grade after fracture-filling. For this reason fracture-filling is normally only applied to stones whose size is large enough to justify the treatment: however, stones as small as 0.02 carats (4 mg) have been fracture-filled.

The fracture-filling of diamond is a controversial treatment within the industry—and increasingly among the public as well—because some companies do not disclose this process when selling these stones. It is important to note that while fracture filling is a durable process, some solutions are damaged and may even melt at certain temperatures (1,400 °C or 1,670 K), causing the diamond to "sweats" the solution under the heat of a jeweler's torch; thus routine jewelry repair can lead to degradation of clarity caused by the loss of the solution used to fill the cracks, especially if the jeweler is not aware of the treatment.

Positions on certification of enhanced diamonds are polarized. On one hand some gemological laboratories, including that of the influential Gemological Institute of America, refuse to issue certificates for fracture-filled diamonds. Conversely others including EGL (European Gemological Laboratories) & GGL (Global Gem Labs) will certify such diamonds to their achieved clarity level while also stating on the certificate that the diamond is clarity enhanced.

A third type of labs may certify these diamonds to the original clarity level. This rends any treatment benefit moot by disregarding apparent clarity and instead assigning the diamond a grade reflecting its original, pre-treatment clarity. This has raised quite a commotion, as this puts fracture-filled diamonds outside of the traditional realm of diamond certification, damaging their legitimacy as mostly natural diamonds. This demand for clarity enhanced diamond grading has caused the creation of new labs or an update to existing lab procedures to include remarks regarding any clarity enhancements procedures (drilling, fracture filling) into their regular reports, boosting the validity of this trade.

Color enhancements

Generally there are three major methods to artificially alter the color of a diamond: irradiation with high-energy subatomic particles; the application of thin films or coatings; and the combined application of high pressure and high temperature (HPHT). However, there is recent evidence that fracture filling is not only used to improve clarity, but that it can be used for the sole purpose to change the color into a more desirable color as well.

The first two methods can only modify color, usually to turn an off-color Cape series stone (see Material properties of diamond: Composition and color) into a more desirable fancy-colored stone. Because some irradiation methods produce only a thin "skin" of color, they are applied to diamonds that are already cut and polished. Conversely, HPHT treatment is used to modify and remove color from either rough or cut diamonds—but only certain diamonds are treatable in this manner. Irradiation and HPHT treatments are usually permanent insofar as they will not be reversed under normal conditions of jewelry use, whereas thin films are impermanent.

Irradiation


Pure diamonds, before and after irradiation and annealing. Clockwise from left bottom: 1) Initial (2×2 mm) 2-4) Irradiated by different doses of 2-MeV electrons 5-6) Irradiated by different doses and annealed at 800 °C.


Sir William Crookes, a gem connoisseur as well as a chemist and physicist, was the first to discover radiation's effects on diamond color when in 1904 he conducted a series of experiments using radium salts. Diamonds enveloped in radium salt slowly turned a dark green; this color was found to be localized in blotchy patches, and it did not penetrate past the surface of the stone. The emission of alpha particles by the radium was responsible. Unfortunately radium treatment also left the diamond strongly radioactive, to the point of being unwearable. A diamond octahedron so treated was donated by Crookes to the British Museum in 1914, where it remains today: it has lost neither its color nor radioactivity.

Presently diamonds are safely irradiated in four ways: proton and deuteron bombardment via cyclotrons; gamma ray bombardment via exposure to cobalt-60; neutron bombardment via the piles of nuclear reactors; and electron bombardment via Van de Graaff generators. These high-energy particles physically alter the diamond's crystal lattice, knocking carbon atoms out of place and producing color centers. Irradiated diamonds are all some shade of green, black, or blue after treatment, but most are annealed to further modify their color into bright shades of yellow, orange, brown, or pink. The annealing process increases the mobility of individual carbon atoms, allowing some of the lattice defects created during irradiation to be corrected. The final color is dependent on the diamond's composition and the temperature and length of annealing.

Cyclotroned diamonds have a green to blue-green color confined to the surface layer: they are later annealed to 800 °C to produce a yellow or orange color. They remain radioactive for only a few hours after treatment, and due to the directional nature of the treatment and the cut of the stones, the color is imparted in discrete zones. If the stone was cyclotroned through the pavilion (back), a characteristic "umbrella" of darker color will be seen through the crown (top) of the stone. If the stone was cyclotroned through the crown, a dark ring is seen around the girdle (rim). Stones treated from the side will have one half colored deeper than the other. Cyclotron treatment is now uncommon.

Gamma ray treatment is also uncommon, because although it is the safest and cheapest irradiation method, successful treatment can take several months. The color produced is a blue to blue-green which penetrates the whole stone. Such diamonds are not annealed. The blue color can sometimes approach that of natural Type IIb diamonds, but the two are distinguished by the latter's semiconductive properties. As with most irradiated diamonds, most gamma ray-treated diamonds were originally tinted yellow; the blue is usually modified by this tint, resulting in a perceptible greenish cast.

The two most common irradiation methods are neutron and electron bombardment. The former treatment produces a green to black color that penetrates the whole stone, while the latter treatment produces a blue, blue-green, or green color that only penetrates about 1 millimeter deep. Annealing of these stones (from 500–900 °C for neutron-bombarded stones and from 500–1200 °C for electron-bombarded stones) produces orange, yellow, brown, or pink. Blue to blue-green stones that are not annealed are separated from natural stones in the same manner as gamma ray-treated stones.

Prior to annealing, nearly all irradiated diamonds possess a characteristic absorption spectrum consisting of a fine line in the far red, at 741 nm—this is known as the GR1 line and is usually considered a strong indication of treatment. Subsequent annealing usually destroys this line, but creates several new ones; the most persistent of these is at 595 nm.

It should be noted that some irradiated diamonds are completely natural. One famous example is the Dresden Green Diamond. In these natural stones the color is imparted by "radiation burns" in the form of small patches, usually only skin deep, as is the case in radium-treated diamonds. Naturally irradiated diamonds also possess the GR1 line. The largest known irradiated diamond is the Deepdene.

Coatings
The application of colored tinfoil to the pavilion (back) surfaces of gemstones was common practice during the Georgian and Victorian era; this was the first treatment—aside from cutting and polishing—applied to diamond. Foiled diamonds are mounted in closed-back jewelry settings, which may make their detection problematic. Under magnification, areas where the foil has flaked or lifted away are often seen; moisture that has entered between the stone and foil will also cause degradation and uneven color. Because of its antique status, the presence of foiled diamonds in older jewelry will not detract from its value.

In modern times, more sophisticated surface coatings have been developed; these include violet-blue dyes and vacuum-sputtered films resembling the magnesium fluoride coating on camera lenses. These coatings effectively whiten the apparent color of a yellow-tinted diamond, because the two colors are complementary and act to cancel each other out. Usually only applied to the pavilion or girdle region of a diamond, these coatings are among the hardest treatments to detect—while the dyes may be removed in hot water or alcohol with ease, the vacuum-sputtered films require a dip in sulfuric acid to remove. The films can be detected under high magnification by the presence of raised areas where air bubbles are trapped, and by worn areas where the coating has been scratched off. These treatments are considered fraudulent unless disclosed.

Another coating treatment applies a thin film of synthetic diamond to the surface of a diamond simulant. This gives the simulated diamond certain characteristics of real diamond, including higher resistance to wear and scratching, higher thermal conductivity, and lower electrical conductivity. While resistance to wear is a legitimate goal of this technique, some employ it in order to make diamond simulants more difficult to detect through conventional means, which may be fraudulent if they are attempting to represent a simulated diamond as real.

High-pressure high-temperature treatment
A small number of otherwise gem-quality stones that possess a brown body color can have their color significantly lightened or altogether removed by HPHT treatment, or, depending on the type of diamond, improve existing color to a more desirable saturation. The process was introduced by General Electric in 1999. Diamonds treated to become colorless are all Type IIa and owe their marring color to structural defects that arose during crystal growth, known as plastic deformations, rather than to interstitial nitrogen impurities as is the case in most diamonds with brown color. HPHT treatment is believed to repair these deformations, and thus whiten the stone. (This is probably an incorrect conclusion, the whitening due to destruction of stable vacancy clusters according to one of the researchers). Type Ia diamonds, which have nitrogen impurities present in clusters that do not normally affect body color, can also have their color altered by HPHT. Some synthetic diamonds have also been given HPHT treatment to alter their optical properties and thus make them harder to differentiate from natural diamonds. Pressures of up to 70,000 atmospheres and temperatures of up to 2,000 °C (3,632 °F) are used in HPHT procedure.

Also in 1999, Novatek, a Provo, UT manufacturer of industrial diamonds known for its advancements in diamond synthesis, accidentally discovered that the color of diamonds could be changed by the HPHT process. The company formed NovaDiamond, Inc. to market the process. By applying heat and pressure to natural stones, NovaDiamond could turn brown Type I diamonds light yellow, greenish yellow, or yellowish green; improve Type IIa diamonds by several color grades, even to white; intensify the color of yellow Type I diamonds; and make some bluish gray Type I and Type IIb colorless (although in some cases natural bluish gray diamonds are more valuable left alone, as blue is a highly desired hue). In 2001, however, NovaDiamond quit the HPHT gem business because of what the company's leader, David Hall, characterized as the underhanded practices of dealers. Apparently, dealers were passing off NovaDiamond enhanced gems as naturally colored, and the company refused to be party to this deception.

Definitive identification of HPHT stones is left to well-equipped gemological laboratories, where Fourier transform spectroscopy (FTIR) and Raman spectroscopy are used to analyze the visible and infrared absorption of suspect diamonds to detect characteristic absorption lines, such as those indicative of exposure to high temperatures. Indicative features seen under the microscope include: internal graining (Type IIa); partially healed feathers; a hazy appearance; black cracks surrounding inclusions; and a beaded or frosted girdle. Diamonds treated to remove their color by General Electric are given laser inscriptions on their girdles: these inscriptions read "GE POL", with "POL" standing for Pegasus Overseas Ltd, a partnered firm. It is possible to polish this inscription away, so its absence cannot be a trusted sign of natural color. Although it is permanent, HPHT treatment should be disclosed to the buyer at the time of sale.

Diamond Color

A chemically pure and structurally perfect diamond is perfectly transparent with no hue, or color. However, in reality almost no gem-sized natural diamonds are absolutely perfect. The color of a diamond may be affected by chemical impurities and/or structural defects in the crystal lattice. Depending on the hue and intensity of a diamond's coloration, a diamond's color can either detract from or enhance its value. For example, most white diamonds are discounted in price when more yellow hue is detectable, while intense pink diamonds or blue diamonds (such as the Hope Diamond) can be dramatically more valuable. Of all colored diamonds, red diamonds are the rarest. The Aurora Pyramid of Hope displays a spectacular array of naturally colored diamonds, including red diamonds.


Possible colors


The Hope Diamond, 45.52 carats (9.104 g), dark grayish-blue

Jewellers diamonds in groups of similar colors. These from the National Museum of Natural History are a medium brown color.

The 296 gems of the Aurora Pyramid of Hope as exhibited in the Natural History Museum in London under natural light.
Diamonds occur in a variety of colors—steel gray, white, blue, yellow, orange, red, green, pink to purple, brown, and black.[1][2] Colored diamonds contain interstitial impurities or structural defects that cause the coloration, whilst pure diamonds are perfectly transparent and colorless. Diamonds are scientifically classed into two main types and several subtypes, according to the nature of impurities present and how these impurities affect light absorption:

Type I diamonds have nitrogen atoms as the main impurity, commonly at a concentration of 0.1%. If the nitrogen atoms are in pairs they do not affect the diamond's color; these are Type IaA. If the nitrogen atoms are in large even-numbered aggregates they impart a yellow to brown tint (Type IaB). About 98% of gem diamonds are type Ia, and most of these are a mixture of IaA and IaB material: these diamonds belong to the Cape series, named after the diamond-rich region formerly known as Cape Province in South Africa, whose deposits are largely Type Ia. If the nitrogen atoms are dispersed throughout the crystal in isolated sites (not paired or grouped), they give the stone an intense yellow or occasionally brown tint (Type Ib); the rare canary diamonds belong to this type, which represents only 0.1% of known natural diamonds. Synthetic diamond containing nitrogen is Type Ib. Type I diamonds absorb in both the infrared and ultraviolet region, from 320 nm (3.2×10−7 m). They also have a characteristic fluorescence and visible absorption spectrum (see Optical properties of diamond).[3]

Type II diamonds have no measurable nitrogen impurities. Type II diamonds absorb in a different region of the infrared, and transmit in the ultraviolet below 225 nm (2.25×10−7 m), unlike Type I diamonds. They also have differing fluorescence characteristics, but no discernible visible absorption spectrum. Type IIa diamond can be colored pink, red, or brown due to structural anomalies[4] arising through plastic deformation during crystal growth—these diamonds are rare (1.8% of gem diamonds), but constitute a large percentage of Australian production. Type IIb diamonds, which account for 0.1% of gem diamonds, are usually light blue due to scattered boron within the crystal matrix; these diamonds are also semiconductors, unlike other diamond types (see Electrical properties of diamond). However, a blue-grey color may also occur in Type Ia diamonds and be unrelated to boron.[5] Also not restricted to type are green diamonds, whose color is caused by GR1 color centers in the crystal lattice produced by exposure to varying quantities of radiation.[3]

Pink and red are caused by plastic deformation of the crystal lattice from temperature and pressure. Black diamonds are caused by microscopic black or gray inclusions of other materials such as graphite or sulfides and/or microscopic fractures. Opaque or opalescent white diamonds are also caused by microscopic inclusions.[6] Purple diamonds are caused by a combination of crystal lattice distortion and high hydrogen content.[7]

Grading white diamonds[edit]

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The majority of diamonds that are mined are in a range of pale yellow or brown color that is termed the normal color range. Diamonds that are of intense yellow or brown, or any other color are called fancy color diamonds. Diamonds that are of the very highest purity are totally colorless, and appear a bright white. The degree to which diamonds exhibit body color is one of the four value factors by which diamonds are assessed. Diamonds have a color grading system that refers to the absence of color. This system goes from D to Z.The more colorless a diamond is, the rarer and more valuable is because it appears white and brighter to the eye.[8]

History of color grading[edit]
Color grading of diamonds was performed as a step of sorting rough diamonds for sale by the London Diamond Syndicate.

As the diamond trade developed, early diamond grades were introduced by various parties in the diamond trade. Without any co-operative development these early grading systems lacked standard nomenclature, and consistency. Some early grading scales were; I, II, III; A, AA, AAA; A, B, C. Numerous terms developed to describe diamonds of particular colors: golconda, river, jagers, cape, blue white, fine white, and gem blue, "brown".

Grading the normal color range[edit]
Refers to a grading scale for diamonds in the normal color range used by internationally recognized laboratories (GIA & IGI for example). The scale ranges from D which is totally colorless to Z which is a pale yellow or brown color. Brown diamonds darker than K color are usually described using their letter grade, and a descriptive phrase, for example M Faint Brown. Diamonds with more depth of color than Z color fall into the fancy color diamond range.

Diamond color is graded by comparing a sample stone to a master stone set of diamonds. Each master stone is known to exhibit the very least amount of body color that a diamond in that color grade may exhibit. A trained diamond grader compares a diamond of unknown grade against the series of master stones, assessing where in the range of color the diamond resides. This process occurs in a lighting box, fitted with daylight equivalent lamps. Accurate color grading can only be performed with diamond unset, as the comparison with master stones is done with diamond placed on its table facet and pavilion side facing upwards. When color grading is done in the mounting, the grade is expressed as an estimated color grade and commonly as a range of color. Grading mounted diamonds involves holding the mounted diamonds table close to the table facet of the master stone and visually comparing the diamond color under the same color conditions as unmounted diamond grading. The resulting grade is typically less accurate, and is therefore expressed as a range of color. While a grading laboratory will possess a complete set of master stones representing every color grade, the independent grader working in a retail environment works with a smaller subset of master stones that covers only the typical grade range of color they expect to encounter while grading. A common subset of master stones would consist of five diamonds in two grade increments, such as an E, G, I, K, and M. The intermediate grades are assessed by the graders judgement.

Diamonds in the normal color range are graded loose (for example F–G).


Diamonds that rate toward the colorless end of the range are sometimes known as "high-color" diamonds, and those toward the other end, "low-color" diamonds.[citation needed] These terms refer to the relative desirability (as demonstrated by market prices) of color grades, not the intensity of the color itself.

Grading fancy color diamonds[edit]
Yellow or brown color diamonds having color more intense than "Z", as well as diamonds exhibiting color other than yellow or brown are considered fancy colored diamonds. These diamonds are graded using separate systems which indicate the characteristics of the color, and not just its presence. These color grading systems are more similar to those used for other colored gemstones, such as ruby, sapphire, or emerald, than they are to the system used for white diamonds.[14]

Colored diamond grading system[edit]

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Diamond colors more saturated than this scale are known as "fancy color" diamonds. Any light shade of diamond other than Light Yellow or Light Brown automatically falls out of the scale. For instance, a pale blue diamond won't get a "K", "N", or "S" color grade, it will get a Faint Blue, very Light Blue or Light Blue grade.

Laboratories use a list of 27 color hues that span the full spectrum for colored gems and diamonds (Red, Orangish-Red, Reddish-Orange, orange, Yellowish-Orange, Yellow-Orange, Orange-Yellow, Orangish-Yellow, Yellow, Greenish-Yellow, Green-Yellow, Yellow-Green, Yellowish-Green, Green, Bluish-Green, Blue-Green, Green-Blue, Greenish-Blue, Blue, Violetish-Blue, Bluish-Violet, Violet, Purple, Reddish-Purple, Red-Purple, Purple-Red, Purplish-Red). A modifying color combination can also be added (e.g., Olive or Brown-Olive) for stones without the purest hues. Additionally, for diamonds the following colors are used: White (which are milky), Black (which are opaque), Gray, Pink, Brown.

The saturation of these hues is then described with one of nine descriptors: Faint, Very Light, Light, Fancy Light, Fancy, Fancy Dark, Fancy Intense, Fancy Deep, Fancy Vivid.

The terms "Champagne", "Cognac" and "Coffee" refer to different types of brown diamonds. In the diamond processing/dealing industry, the word "Brown" is considered a killer as far as diamond value goes. Even though champagne is a light yellow color, champagne diamonds are Light Brown. Cognac is usually used to describe a diamond that is Orangish-Brown because cognac is a deep golden-orange color. Coffee is usually used to describe a diamond that is a Deep Brown or Vivid Brown color. Some grading agencies may also describe brown stones as Fancy Yellowish-Brown, Fancy Light Brown, Fancy Intense Brown, etc.

Value of colored diamonds[edit]

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Diamonds that enter the Gemological Institute of America's scale are valued according to their clarity and color. For example, a "D" or "E" rated diamond (both grades are considered colorless) is much more valuable than an "R" or "Y" rated diamond (light yellow or brown). This is due to two effects: high-color diamonds are rarer, limiting supply; and the bright white appearance of high-color diamonds is more desired by consumers, increasing demand. Poor color is usually not enough to eliminate the use of diamond as a gemstone: if other gemological characteristics of a stone are good, a low-color diamond can remain more valuable as a gem diamond than an industrial-use diamond, and can see use in diamond jewelry. Furthermore, it is much more cost effective to purchase a near-colorless grade diamond (e.g. "G" rated) instead of a colorless grade diamond (e.g. "D" rated), as they are nearly indistinguishable to the naked untrained eye, especially when mounted on a ring setting.[15]

Fancy diamonds are valued using different criteria than those used for regular diamonds. When the color is rare, the more intensely colored a diamond is, the more valuable it becomes. Another factor that affects the value of Fancy-Colored diamonds is fashion trends. For example, pink diamonds fetched higher prices after Jennifer Lopez received a pink diamond engagement ring.[citation needed] Traditional industrial use and low-grade quality has not stopped creative merchants, such as Le Vian, from marketing dark brown diamonds as so-called "chocolate diamonds".[16]

Fancy-colored diamonds such as the deep blue Hope Diamond are among the most valuable and sought-after diamonds in the world. In 2009 a 7-carat (1.4 g) blue diamond fetched the then highest price per carat ever paid for a diamond when it was sold at auction for 10.5 million Swiss francs (US$9.5 million at the time) which is in excess of US$1.3 million per carat.[17] This record was broken in 2013 when an orange diamond sold for US$35 million or US$2.4 million per carat.[18] It was again broken in 2016 when the Oppenheimer Blue, a 14.62-carat (2.924 g) vivid blue diamond became the most expensive jewel ever sold at auction.[19] It is the largest fancy vivid blue diamond classified by the Gemological Institute of America ever sold at auction; it sold at Christie's in Geneva in May 2016 for US$50.6 million (GBP 34.7m; 56.83m SFr).[20]

Diamond Clarity

Diamond clarity is a quality of diamonds relating to the existence and visual appearance of internal characteristics of a diamond called inclusions, and surface defects called blemishes. Clarity is one of the four Cs of diamond grading, the others being carat, color, and cut. Inclusions may be crystals of a foreign material or another diamond crystal, or structural imperfections such as tiny cracks that can appear whitish or cloudy. The number, size, color, relative location, orientation, and visibility of inclusions can all affect the relative clarity of a diamond. A clarity grade is assigned based on the overall appearance of the stone under ten times magnification.

Most inclusions present in gem-quality diamonds do not affect the diamonds' performance or structural integrity and are not visible to the naked eyes. However, large clouds can affect a diamond's ability to transmit and scatter light. Large cracks close to or breaking the surface may reduce a diamond's resistance to fracture.

Diamonds with higher clarity grades are more valued, with the exceedingly rare Flawless graded diamond fetching the highest price. Minor inclusions or blemishes are useful, as they can be used as unique identifying marks analogous to fingerprints. In addition, as synthetic diamond technology improves and distinguishing between natural and synthetic diamonds becomes more difficult, inclusions or blemishes can be used as proof of natural origin.


Inclusions and blemishes

There are several types of inclusions and blemishes, which affect a diamond's clarity to varying degrees. Features resulting from diamond enhancement procedures, such as laser lines, are also considered inclusions or blemishes.

Inclusions
Clouds
Feathers
Included crystals or minerals
Knots
Cavities
Cleavage
Bearding
Internal graining
Pinpoint
Laser lines
The diamond industry uses the term "internal characteristics" instead of "inclusions". For natural diamonds, the "internal characteristics" in the diamond are growth crystals that give the diamond its character and unique fingerprint. When diamonds are graded, they are magnified at 10x power.

Blemishes
Polish lines
Grain boundaries
Naturals
Scratches
Nicks
Pits
Chips
Breaks
Dark spots
Light spots
Clarity grading
Gemological Institute of America (GIA)

History
In 1952, Richard T. Liddicoat, along with Marquis Person, Joe Phillips, Robert Crowningshield and Bert Krashes began to work on a new diamond grading system which they called the "diamond grading and evaluation appraisal". In 1953, they released their new system which assessed three aspects of diamonds; make, color and clarity. They took terminology used in the industry at the time and refined the definitions to produce a clarity scale by which diamonds could be consistently graded. The system at that time contained nine grades: Flawless, VVS1, VVS2, VS1, VS2, SI1, SI2, I1, and I2. The 'I' of the I1, and I2 grades originally stood for "Imperfect".

During the 1970s, two changes were made to the system. Firstly, the Internally Flawless grade was added, as GIA noticed that many diamonds were being aggressively cut to remove any surface blemishes, and thereby reducing the cutting quality ("make") of the diamonds. The Internally Flawless grade gave diamond manufacturers a choice to leave blemishes on the surface of the stone, and achieve a grade higher than VVS1. The second change made to the grading system was the introduction of the I3 grade. This change was made in response to a growing number of diamonds of very low clarity being cut.

The last change to the clarity grading system took place in the 1990s when the term "imperfect" was changed to "included".

The GIA grading system today
GIA diamond clarity grading scale
Category Flawless Internally Flawless Very Very Slightly Included Very Slightly Included Slightly Included Included
Grade FL IF VVS1 VVS2 VS1 VS2 SI1 SI2 I1 I2 I3
The GIA diamond grading scale is divided into six categories and eleven grades. The clarity categories and grades are:

Flawless category (FL) diamonds have no inclusions or blemishes visible under 10x magnification.
Internally Flawless category (IF) diamonds have no inclusions visible under 10x magnification, only small blemishes on the diamond surface.
Very, Very Slightly Included category (VVS) diamonds have minute inclusions that are difficult for a skilled grader to see under 10x magnification. The VVS category is divided into two grades; VVS1 denotes a higher clarity grade than VVS2. Pinpoints and needles set the grade at VVS.
Very Slightly Included category (VS) diamonds have minor inclusions that are difficult to somewhat easy for a trained grader to see when viewed under 10x magnification. The VS category is divided into two grades; VS1 denotes a higher clarity grade than VS2. Typically the inclusions in VS diamonds are invisible without magnification; however, infrequently some VS2 inclusions may still be visible. An example would be on a large emerald cut diamond which has a small inclusion under the corner of the table.
Slightly Included category (SI) diamonds have noticeable inclusions that are easy to very easy for a trained grader to see when viewed under 10x magnification. The SI category is divided into two grades; SI1 denotes a higher clarity grade than SI2. These may or may not be noticeable to the naked eye.
Included category (I) diamonds have obvious inclusions that are clearly visible to a trained grader under 10x magnification. Included diamonds have inclusions that are usually visible without magnification or have inclusions that threaten the durability of the stone. The I category is divided into three grades; I1 denotes a higher clarity grade than I2, which in turn is higher than I3. Inclusions in I1 diamonds often are seen by the unaided eye. I2 inclusions are easily seen, while I3 diamonds have large and extremely easy to see inclusions that typically impact the brilliance of the diamond, as well as having inclusions that are often likely to threaten the structure of the diamond.
GIA clarity grading procedure
GIA clarity grading is performed under 10x magnification with darkfield illumination. The GIA Laboratory uses as standard equipment binocular stereo microscopes which are able to zoom to higher magnifications. These microscopes are equipped with darkfield illumination, as well as an ultraviolet filtered overhead light. When grading is performed using a 10x handheld loupe, darkfield illumination is more difficult to achieve. The grader must use a light source in such a way that the base of the stone is lit from the side, and the crown of the stone is shielded from the light.

After thoroughly cleaning the diamond, the diamond is picked up using tweezers in a girdle-to-girdle hold. The grader views the diamond for the first time through the table, studying the culet area of the stone for inclusions. The diamond is then set down and picked up with the tweezers in a table-to-culet hold. In this position, the diamond can be studied from the pavilion side, and the crown side, examining the diamond through each facet for inclusions. Once a sector of the diamond has been thoroughly examined, the grader rotates the diamond in the tweezer, so that the neighboring sector can be examined. The grader uses darkfield lighting to reveal characteristics, and alternates to reflected, overhead lighting to ascertain whether a characteristic lies within the stone, on the stones surface, or both. If the grader is using a stereo microscope, she may zoom in to a higher magnification to make closer observations of an inclusion, but then return to 10x magnification to make an assessment of its impact on the clarity grade.

If a stereo binocular microscope has been used, a final assessment using a 10x loupe is performed before the final judgment is made on the clarity of the stone. The grader first decides the clarity category of the diamond: none (FL, or IF for a blemish), minute (VVS), minor (VS), noticeable (SI), or obvious (I). The decision is then made on the grade of the diamond.

Grading systems by other organizations
The clarity grading system developed by the GIA has been used throughout the industry as well as by other diamond grading agencies including the American Gemological Society (AGS), and the International Gemological Institute (IGI). There are other smaller labs which use the GIA system as well. These grading agencies base their clarity grades on the characteristics of inclusions visible to a trained professional when a diamond is viewed from above under 10x magnification.

Confédération Internationale de la Bijouterie, Joaillerie, Orfèvrerie des Diamants, Perles et Pierres (CIBJO)
CIBJO diamond clarity grading scale
GIA all stones FL IF VVS1 VVS2 VS1 VS2 SI1 SI2 I1 I2 I3
CIBJO over 0.47ct Loupe clean VVS1 VVS2 VS1 VS2 SI1 SI2 PI PII PIII
CIBJO under 0.47ct Loupe clean VVS VS SI PI PII PIII
The CIBJO or the International Confederation of Jewellery, Silverware, Diamonds and Stones developed the International Clarity Scale for grading diamonds. This clarity scale mirrors the GIA grading scale, except nomenclature varies. The CIBJO system names these clarity grades; Loupe Clean, Very, very small inclusions (VVS1 and VVS2), Very small inclusions (VS1 and VS2), Small inclusions (SI1 and SI2), Pique (P1, P2, and P3).

Clarity grading by CIBJO standards is by examination using a 10x achromatic, aplanatic loupe in normal light.

American Gem Society
AGS diamond clarity grading scale
FL IF VVS1 VVS2 VS1 VS2 SI1 SI2 I1 I2 I3
AGS 0 1 2 3 4 5 6 7 8 9 10
The American Gem Society grades clarity on a number scale between 0 and 10. These numbers grades correlate almost exactly with the GIA system, but with some differences. The flawless and internally flawless (0) grades are grouped together with notation defining whether the stone is free from external blemishes, the VVS through SI grades are numbered 1 through 6, and then there are four grades 7 through 10 for the included category.

Clarity grading by AGS standards requires examination using a binocular stereo microscope equipped with adjustable zoom magnification and darkfield illumination.

International Diamond Council (IDC)
IDC diamond clarity grading scale
GIA FL IF VVS1 VVS2 VS1 VS2 SI1 SI2 I1 I2 I3
IDC Loupe clean VVS1 VVS2 VS1 VS2 SI1 SI2 PI PII PIII
The IDC or the International Diamond Council uses a very similar standard to CIBJO. IDC loupe clean stones that have external blemishes have notations made on the grading report. IDC clarity grading is by examination using a 10x achromatic, aplanatic loupe in normal light.

European Gemological Laboratory
EGL diamond clarity grading scales
GIA FL IF VVS1 VVS2 VS1 VS2 SI1 SI2 I1 I2 I3
EGL USA IF VVS1 VVS2 VS1 VS2 SI1 SI2 SI3[9] I1 I2 I3
EGL India FL IF VVS1 VVS2 VS1 VS2 SI1 SI2 SI3 P1 P2 P3
The European Gemological Laboratory (EGL) introduced the SI3 as a clarity grade. While intended as a range to include borderline SI2 / I1 stones, it is now commonly used to mean I1's which are "eye clean", that is, which have inclusions which are not obviously visible to the naked eye.

Clarity grading considerations
All grades reflect the appearance to an experienced grader when viewed from above at 10x magnification, though higher magnifications and viewing from other angles are used during the grading process. The grader studies the diamond for internal characteristics and judges them on the basis of five clarity factors: size, number, position, nature, and color or relief. The clarity grade is assessed on the basis of the most noticeable inclusions, the so-called "grade setting inclusions". Less significant inclusions are ignored for the purposes of setting the grade; however, they may still be plotted onto a diamond plot chart.

Accurate clarity grading as with other grading steps must be done with the diamond "loose" (not set into any mounting). Inclusions are often difficult to see from the crown side of the diamond, and may be concealed by the setting.

Size
The first clarity factor which is assessed is a clarity characteristic's size. Larger characteristics are typically more noticeable under magnification, thereby placing the diamond into a lower clarity grade.

Number
The second clarity factor which is assessed is the number of clarity characteristics. Generally, the more characteristics, the lower the clarity grade. This assessment is made by judging how readily they can be seen, not by the actual number of characteristics.

Position
The third clarity factor which is assessed is the characteristic's position. When an inclusion is directly under the table of the diamond it is most visible. An inclusion under the table and positioned close to a pavilion facet will reflect multiple times around the stone, giving this type of inclusion the name "reflector". Reflectors are graded as if each reflection were an inclusion (although in plotting the diamond it is only plotted once). For this reason, reflectors have a greater impact on the clarity grade. Inclusions become less visible when they are positioned under the crown facets, or near the girdle of the stone. These inclusions may often be more easily seen from the pavilion side of the diamond than from crown side of the diamond.

Additionally, the position of large feathers, knots and included crystals positioned where they extend to the girdle or crown of the stone affect the clarity grade. Diamonds worn in jewelry typically will withstand breakage, however inclusions of this nature and in these positions can pose a risk for further extension of the break in the structure of the diamond. Inclusions that are judged to pose at least a moderate risk of breakage to the stone are graded in the Included category.

Nature
The fourth clarity factor which is assessed is a characteristic's nature. The characteristic's nature determines whether it is internal (extending into the stone) or external (limited to the surface of the stone). Internal characteristics automatically exclude the diamond from the Flawless, and Internally Flawless categories. External characteristics exclude the diamond from the Flawless category.

An internal characteristic of a diamond may be classified as a(n): bruise, cavity, chip, cleavage, cloud, crystal, feather, grain center, indented natural, internal graining, knot, laser drill hole, needle, pinpoint, or twinning wisp.

An external characteristic of a diamond may be classified as a(n): abrasion, natural, nick, pit, polish lines, polish mark, scratch, surface graining, or extra facet.

The nature will also determine whether an inclusion poses a risk to the stone. An inclusion that may cause a break in the crystal structure (included crystal, feather, knot, and cleavage) may, depending on its position, pose a moderate level of risk for further breakage.

Color or relief
The fifth clarity factor which is assessed is the color and relief of clarity characteristics. Characteristics that contrast with the surrounding diamond are said to have "relief". The degree to which this color and relief is noticeable affects the clarity grade of the diamond. Colored inclusions invariably show contrast and are more easily seen. An exception is a black pinpoint inclusion, which is often more difficult to see than a white pinpoint.

Rarity and value
Diamonds become increasingly rare when considering higher clarity gradings. Only about 20% of all diamonds mined have a clarity rating high enough for the diamond to be considered appropriate for use as a gemstone; the other 80% are relegated to industrial use. Of that top 20%, a significant portion contains an inclusion or inclusions that are visible to the naked eye upon close inspection. Those that do not have a visible inclusion when the gem is examined approximately 6 inches from the naked eye are known as "eye-clean", although visible inclusions can sometimes be hidden under the setting in a piece of jewelry. The most expensive gem diamonds fall within the VS and SI grades with FL, IF, and even VVS stones commanding significant premiums. FL and IF stones are sometimes referred to as "museum quality" or "investment grade" to denote their rarity although the term "investment grade" is misleading as diamonds have historically been illiquid and questionable stores of value.

As many diamond purchases are infrequent, for example an engagement ring, there is a level of concern by end consumers having to pay large premiums for clarity grade differences that are important to the certificate or diamond industry but not to the buying public who cannot discern the difference with the naked eye.

Clarity enhancement

Laser "drilling" involves using a laser to burn a hole to a colored inclusion, followed by acid washing to remove the coloring agent. The clarity grade is the grade after the treatment. The treatment is considered permanent.

GIA, as a matter of policy, does not grade clarity-enhanced diamonds but it will grade laser-drilled diamonds since it considers the enhancement to be permanent in nature. If you see a GIA Diamond Report with the words "clarity enhanced" or "fracture-filled," it is surely a counterfeit report.

Clarity can also be "enhanced" by filling the fracture much like a car windshield crack can be treated. Such diamonds are sometimes called "fracture filled diamonds". Reputable vendors must disclose this filling and reputable filling companies use filling agents which show a flash of color, commonly orange or pink, when viewed closely. There is a significant price discount for fracture-filled diamonds. The GIA will not grade fracture-filled diamonds, in part because the treatment is not as permanent as the diamond itself. Reputable companies often provide for repeat treatments if heat causes damage to the filling. The heat required to cause damage is that of a blowtorch used to work on settings, and it is essential to inform anyone working on a setting if the diamond is fracture-filled, so they can apply cooling agents to the diamond and use greater care while working on it.