Verneuil process

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Crystallization
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Concepts
Crystallization  · Crystal growth
Recrystallization  · Seed crystal
Protocrystalline  · Single crystal
Methods and technology
Boules
Bridgman–Stockbarger technique
Crystal bar process
Czochralski process
Epitaxy
Flux method
Fractional crystallization
Fractional freezing
Hydrothermal synthesis
Kyropoulos process
Laser-heated pedestal growth
Micro-pulling-down
Shaping processes in crystal growth
Skull crucible
Verneuil process
Zone melting
Fundamentals
Nucleation  · Crystal
Crystal structure  · Solid

The Verneuil process, also called flame fusion, was the first commercially successful method of manufacturing synthetic gemstones, developed in the late 1800s [1] by the French chemist Auguste Verneuil. It is primarily used to produce the ruby, sapphire and padparadscha varieties of corundum, as well as the diamond simulants rutile and strontium titanate. The principle of the process involves melting a finely powdered substance using an oxyhydrogen flame, and crystallising the melted droplets into a boule. The process is considered to be the founding step of modern industrial crystal growth technology, and remains in wide use to this day.

Contents

History

A sketch of an early furnace used by Verneuil to synthesise rubies using the Verneuil process. Verneuil torch sketch.png
A sketch of an early furnace used by Verneuil to synthesise rubies using the Verneuil process.

Since the study of alchemy began, there have been attempts to synthetically produce precious stones, and ruby, being one of the prized cardinal gems, has long been a prime candidate.

The first fusion of ruby was achieved by Antoine Lavoisie r in 1782, by melting three small rubies together under an oxygen blowpipe. [2] The first ruby to be fused from its chemical constituents was produced by Marc Gaudin in 1834 - though his stones were not transparent. [3] Jacques-Joseph Ébelmen was the first to synthesize transparent rubies in 1847. [4] Ébelmen's rubies were crystallised from a solution rather than through flame fusion. [4] But whilst Ébelmen's rubies were transparent, they were also microscopic. [4] Edmond Frémy would later improve the crystallisation of ruby from a solution to grow larger crystals: first alongside the industrial glass-maker Charles Feil, and latterly alongside his student Auguste Verneuil. [5] By this point Verneuil was already developing the process of flame fusion that would later bear his name.

Verneuil's work on the flame fusion of ruby became apparent in 1886 following the appearance of "Geneva Rubies". [6] These were the first synthetic rubies to be both large and transparent, and the first to be produced on a commercial basis. [6] However, the identity of their inventor, as well as the raw materials used in their initial production, remain matters of debate. [6] Shortly after the appearance of Geneva Rubies, Verneuil and his colleague Auguste Terreil were consulted on their manufacture and were immediately able to demonstrate the production of a flame fusion ruby. [6] By 1892 Verneuil had perfected a more efficient method of flame fusion. In his 'Verneuil furnace' finely ground particles of alumina and chromium oxide were melted by an oxyhydrogen flame of at least 2,000 °C (3,630 °F), and crystallised on a mobile support below the flame, creating a large crystal. Details of this new method were not published by Verneuil until 1902.

By 1910, Verneuil's laboratory had expanded into a 30-furnace production facility, with annual gemstone production by the Verneuil process having reached 1,000 kg (2,200 lb) in 1907. By 1912, production reached 3,200 kg (7,100 lb), and would go on to reach 200,000 kg (440,000 lb) in 1980 and 250,000 kg (550,000 lb) in 2000, led by Hrand Djevahirdjian's factory in Monthey, Switzerland, founded in 1914. The most notable improvements in the process were made in 1932, by S. K. Popov, who helped establish the capability for producing high-quality sapphires in the Soviet Union through the next 20 years. A large production capability was also established in the United States during World War II, when European sources were not available, and jewels were in high demand for their military applications.

The process was designed primarily for the synthesis of rubies, which became the first gemstone to be produced on an industrial scale. However, the Verneuil process could also be used for the production of other stones, including blue sapphire, which required oxides of iron and titanium to be used in place of chromium oxide, as well as more elaborate ones, such as star sapphires, where titania (titanium dioxide) was added and the boule was kept in the heat longer, allowing needles of rutile to crystallise within it. In 1947, the Linde Air Products division of Union Carbide pioneered the use of the Verneuil process for creating such star sapphires, until production was discontinued in 1974 due to overseas competition.

Despite some improvements in the method, the Verneuil process remains virtually unchanged to this day, while maintaining a leading position in the manufacture of synthetic corundum and spinel gemstones. Its most significant setback came in 1917, when Jan Czochralski introduced the Czochralski process, which has found numerous applications in the semiconductor industry, where a much higher quality of crystals is required than the Verneuil process can produce. Other alternatives to the process emerged in 1957, when Bell Labs introduced the hydrothermal process, and in 1958, when Carroll Chatham introduced the flux method. In 1989 Larry P Kelley of ICT, Inc. also developed a variant of the Czochralski process where natural ruby is used as the 'feed' material.

Process

A simplified diagram of the Verneuil process Verneuil process diagram.svg
A simplified diagram of the Verneuil process
A small ruby boule, still attached to the rod, produced by the Verneuil process Flame fusion of corundum.jpg
A small ruby boule, still attached to the rod, produced by the Verneuil process

One of the most crucial factors in successfully crystallising an artificial gemstone is obtaining highly pure starting material, with at least 99.9995% purity. In the case of manufacturing rubies, sapphires or padparadscha, this material is alumina. The presence of sodium impurities is especially undesirable, as it makes the crystal opaque. Depending on the desired colouration of the crystal, small quantities of various oxides are added, such as chromium oxide for a red ruby, or ferric oxide and titania for a blue sapphire. Other starting materials include titania for producing rutile, or titanyl double oxalate for producing strontium titanate. Alternatively, small, valueless crystals of the desired product can be used.

This starting material is finely powdered, and placed in a container within a Verneuil furnace, with an opening at the bottom through which the powder can escape when the container is vibrated. While the powder is being released, oxygen is supplied into the furnace, and travels with the powder down a narrow tube. This tube is located within a larger tube, into which hydrogen is supplied. At the point where the narrow tube opens into the larger one, combustion occurs, with a flame of at least 2,000 °C (3,630 °F) at its core. As the powder passes through the flame, it melts into small droplets, which fall onto an earthen support rod placed below. The droplets gradually form a sinter cone on the rod, the tip of which is close enough to the core to remain liquid. It is at that tip that the seed crystal eventually forms. As more droplets fall onto the tip, a single crystal, called a boule , starts to form, and the support is slowly moved downward, allowing the base of the boule to crystallise, while its cap always remains liquid. The boule is formed in the shape of a tapered cylinder, with a diameter broadening away from the base and eventually remaining more or less constant. With a constant supply of powder and withdrawal of the support, very long cylindrical boules can be obtained. Once removed from the furnace and allowed to cool, the boule is split along its vertical axis to relieve internal pressure, otherwise the crystal will be prone to fracture when the stalk is broken due to a vertical parting plane.

When initially outlining the process, Verneuil specified a number of conditions crucial for good results. These include: a flame temperature that is not higher than necessary for fusion; always keeping the melted product in the same part of the oxyhydrogen flame; and reducing the point of contact between the melted product and support to as small an area as possible. The average commercially produced boule using the process is 13 mm (0.51 in) in diameter and 25 to 50 mm (0.98 to 1.97 in) long, weighing about 125 carats (25.0 g). The process can also be performed with a custom-oriented seed crystal to achieve a specific desired crystallographic orientation.

Synthetic Corundum SynthKorVerneuil.png
Synthetic Corundum

Crystals produced by the Verneuil process are chemically and physically equivalent to their naturally occurring counterparts, and strong magnification is usually required to distinguish between the two. One of the telltale characteristics of a Verneuil crystal is curved growth lines (curved striae) formed as the cylindrical boule grows upwards in an environment with a high thermal gradient; the equivalent lines in natural crystals are straight. Another distinguishing feature is the common presence of microscopic gas bubbles formed due to an excess of oxygen in the furnace; imperfections in natural crystals are usually solid impurities.

See also

Related Research Articles

Corundum Oxide mineral

Corundum is a crystalline form of aluminium oxide typically containing traces of iron, titanium, vanadium and chromium. It is a rock-forming mineral. It is also a naturally transparent material, but can have different colors depending on the presence of transition metal impurities in its crystalline structure. Corundum has two primary gem varieties: ruby and sapphire. Rubies are red due to the presence of chromium, and sapphires exhibit a range of colors depending on what transition metal is present. A rare type of sapphire, padparadscha sapphire, is pink-orange.

Gemstone Piece of mineral crystal used to make jewelry

A gemstone is a piece of mineral crystal which, in cut and polished form, is used to make jewelry or other adornments. However, certain rocks and occasionally organic materials that are not minerals are also used for jewelry and are therefore often considered to be gemstones as well. Most gemstones are hard, but some soft minerals are used in jewelry because of their luster or other physical properties that have aesthetic value. Rarity is another characteristic that lends value to a gemstone.

Sapphire gem variety of corundum

Sapphire is a precious gemstone, a variety of the mineral corundum, consisting of aluminum oxide (α-Al2O3) with trace amounts of elements such as iron, titanium, chromium, vanadium, or magnesium. It is typically blue, but natural "fancy" sapphires also occur in yellow, purple, orange, and green colors; "parti sapphires" show two or more colors. The only color corundum stone that the term sapphire is not used for is red, which is called a ruby. Pink colored corundum may be either classified as ruby or sapphire depending on locale. Commonly, natural sapphires are cut and polished into gemstones and worn in jewelry. They also may be created synthetically in laboratories for industrial or decorative purposes in large crystal boules. Because of the remarkable hardness of sapphires – 9 on the Mohs scale (the third hardest mineral, after diamond at 10 and moissanite at 9.5) – sapphires are also used in some non-ornamental applications, such as infrared optical components, high-durability windows, wristwatch crystals and movement bearings, and very thin electronic wafers, which are used as the insulating substrates of special-purpose solid-state electronics such as integrated circuits and GaN-based blue LEDs.

Ruby Variety of corundum, mineral, gemstone

A ruby is a pink to blood-red colored gemstone, a variety of the mineral corundum. Other varieties of gem-quality corundum are called sapphires. Ruby is one of the traditional cardinal gems, together with amethyst, sapphire, emerald, and diamond. The word ruby comes from ruber, Latin for red. The color of a ruby is due to the element chromium.

Strontium titanate chemical compound

Strontium titanate is an oxide of strontium and titanium with the chemical formula SrTiO3. At room temperature, it is a centrosymmetric paraelectric material with a perovskite structure. At low temperatures it approaches a ferroelectric phase transition with a very large dielectric constant ~104 but remains paraelectric down to the lowest temperatures measured as a result of quantum fluctuations, making it a quantum paraelectric. It was long thought to be a wholly artificial material, until 1982 when its natural counterpart—discovered in Siberia and named tausonite—was recognised by the IMA. Tausonite remains an extremely rare mineral in nature, occurring as very tiny crystals. Its most important application has been in its synthesized form wherein it is occasionally encountered as a diamond simulant, in precision optics, in varistors, and in advanced ceramics.

Asterism (gemology) ornamental stones that exhibit a luminous star when cut en cabochon

Asterism, the property of a star stone (asteria), is the phenomenon of gemstones exhibiting a star-like concentration of reflected or refracted light when cut en cabochon.

Boule (crystal) Synthetic ingot of crystal

A boule is a single crystal ingot produced by synthetic means.

Bridgman–Stockbarger technique

The Bridgman–Stockbarger technique is named after Harvard physicist Percy Williams Bridgman (1882-1961) and MIT physicist Donald C. Stockbarger (1895–1952). The technique includes two similar but distinct methods primarily used for growing boules, but which can be used for solidifying polycrystalline ingots as well.

Diamond simulant diamond-like object which is not a diamond

A diamond simulant, diamond imitation or imitation diamond is an object or material with gemological characteristics similar to those of a diamond. Simulants are distinct from synthetic diamonds, which are actual diamonds having the same material properties as natural diamonds. Enhanced diamonds are also excluded from this definition. A diamond simulant may be artificial, natural, or in some cases a combination thereof. While their material properties depart markedly from those of diamond, simulants have certain desired characteristics—such as dispersion and hardness—which lend themselves to imitation. Trained gemologists with appropriate equipment are able to distinguish natural and synthetic diamonds from all diamond simulants, primarily by visual inspection.

Edmond Frémy French chemist

Edmond Frémy was a French chemist. He is perhaps best known today for Frémy's salt, a strong oxidizing agent which he discovered in 1845. Fremy's salt is a long-lived free radical that finds use as a standard in electron paramagnetic resonance spectroscopy.

Auguste Victor Louis Verneuil French chemist

Auguste Victor Louis Verneuil was a French chemist best known for developing a more efficient form of flame fusion, and so enabling the industrial production of synthetic gemstones. Flame-fusion had previously been used by Antoine Lavoisier to synthesize the first corundum in 1782, by Marc Gaudin to produce the first synthetic ruby in 1834, and by the unknown inventor of Geneva Rubies to produce the first large and transparent rubies in around 1886. But Verneuil increased the efficiency of the process, known today as the Verneuil process, which remains in use as an inexpensive means of making synthetic corundum.

Synthetic alexandrite is an artificially-grown variety of chrysoberyl crystal, composed of beryllium aluminum oxide (BeAl2O4). The name is also often used erroneously to describe synthetically-grown corundum.

Tairus


Tairus is a synthetic gemstone manufacturer. It was formed in 1989 as part of Mikhail Gorbachev's perestroika initiative to establish a joint venture between the Russian Academy of Sciences and Tairus Created Gems Co Ltd. of Bangkok, Thailand. Today Tairus is a major supplier of hydrothermally grown gemstones to the jewellery industry. Later, Tairus became a privately held enterprise, operating out of its Bangkok distribution hub under the trade name Tairus, owned by Tairus Created Gems Co Ltd. of Bangkok, Thailand.

Marc Antoine Auguste Gaudin French chemist

Marc Antoine Auguste Gaudin (1804–1880) was a French chemist.

Jacques-Joseph Ebelmen French chemist

Jacques-Joseph Ébelmen was a French chemist.

Micro-pulling-down method of growing crystals

The micro-pulling-down (μ-PD) method is a crystal growth technique based on continuous transport of the melted substance through micro-channel(s) made in a crucible bottom. Continuous solidification of the melt is progressed on a liquid/solid interface positioned under the crucible. In a steady state, both the melt and the crystal are pulled-down with a constant velocity.

Shelby Gem Factory American artificial gemstone manufacturer

The Shelby Gem Factory, also known as ICT Incorporated, is a Michigan company that manufactures artificial gemstones through proprietary processes. The factory makes more varieties of man-made gemstones than any other in the world. It grows artificial gems and gem simulants, including synthetic ruby and sapphire and simulated diamonds, citrine, topaz, and other birthstone substitutes, and mounts them in gold or silver jewelry.

Golden sheen sapphire

Golden Sheen Sapphire, is a name that is known to be associated with golden sapphire. It typically shows a metallic golden colour with translucent material also possible. It has the same color, chemical properties and features as black star sapphire.

Kyropoulos process

The Kyropoulos process is a method of bulk crystal growth used to obtain single crystals. The process is named for Spyro Kyropoulos, who proposed the technique in 1926 as a method to grow brittle alkali halide and alkali earth metal crystals for precision optics.

References

  1. "The Chemical News and Journal of Physical Science". 1891.
  2. Evans, James (2020). The History of Synthetic Ruby. Lustre Gemmology. pp. 3–8. ISBN   1916165206.
  3. Evans, James (2020). The History of Synthetic Ruby. Lustre Gemmology. pp. 13–15. ISBN   1916165206.
  4. 1 2 3 Evans, James (2020). The History of Synthetic Ruby. Lustre Gemmology. p. 16. ISBN   1916165206.
  5. Evans, James (2020). The History of Synthetic Ruby. Lustre Gemmology. pp. 17–27. ISBN   1916165206.
  6. 1 2 3 4 Evans, James (2020). The History of Synthetic Ruby. Lustre Gemmology. pp. 28–36. ISBN   1916165206.