Verneuil method

Last updated
Crystallization
Process-of-Crystallization-200px.png
Fundamentals
Concepts
Methods and technology

The Verneuil method (or Verneuil process or Verneuil technique), also called flame fusion, was the first commercially successful method of manufacturing synthetic gemstones, developed in the late 1883 [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, strontium titanate and spinel. 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. [2] [3]

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. In the 19th century, significant advances were achieved, with the first ruby formed by melting two smaller rubies together in 1817, and the first microscopic crystals created from alumina (aluminium oxide) in a laboratory in 1837. By 1877, chemist Edmond Frémy had devised an effective method for commercial ruby manufacture by using molten baths of alumina, yielding the first gemstone-quality synthetic stones. The Parisian chemist Auguste Verneuil collaborated with Frémy on developing the method, but soon went on to independently develop the flame fusion process, which would eventually come to bear his name.

One of Verneuil's sources of inspiration for developing his own method was the appearance of synthetic rubies sold by an unknown Genevan merchant in 1880. These "Geneva rubies" were dismissed as artificial at the time, but are now believed to be the first rubies produced by flame fusion, predating Verneuil's work on the process by 20 years. After examining the "Geneva rubies", Verneuil came to the conclusion that it was possible to recrystallise finely ground aluminium oxide into a large gemstone. This realisation, along with the availability of the recently developed oxyhydrogen torch and growing demand for synthetic rubies, led him to design the Verneuil furnace, where finely ground purified alumina and chromium oxide were melted by a flame of at least 2,000 °C (3,630 °F), and recrystallised on a support below the flame, creating a large crystal. He announced his work in 1902, publishing details outlining the process in 1904.

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 such as for timepieces.

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 owing 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. [4] 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. [4] But because the bauxite from which alumina is obtained is most likely by way of the Bayer process (the first stage of which introduces caustic soda in order to separate the Al2O3) particular attention must be paid to the feedstock. [5]

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. [6]

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. A telltale characteristic is the Verneuil crystal is curved growth lines (curved striae) form, as the cylindrical boule grows upwards in an environment with a high thermal gradient, while 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. [6]

See also

Related Research Articles

<span class="mw-page-title-main">Corundum</span> 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 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.

<span class="mw-page-title-main">Gemstone</span> Piece of mineral crystal used to make jewelry

A gemstone is a piece of mineral crystal which, when cut or polished, is used to make jewelry or other adornments. Certain rocks and occasionally organic materials that are not minerals may also be used for jewelry and are therefore often considered to be gemstones as well. Most gemstones are hard, but some softer minerals such as brazilianite may be used in jewelry because of their color or luster or other physical properties that have aesthetic value. However, generally speaking, soft minerals are not typically used as gemstones by virtue of their brittleness and lack of durability.

<span class="mw-page-title-main">Sapphire</span> Gem variety of corundum

Sapphire is a precious gemstone, a variety of the mineral corundum, consisting of aluminium oxide (α-Al2O3) with trace amounts of elements such as iron, titanium, cobalt, lead, chromium, vanadium, magnesium, boron, and silicon. The name sapphire is derived from the Latin word sapphirus, itself from the Greek word sappheiros (σάπφειρος), which referred to lapis lazuli. It is typically blue, but natural "fancy" sapphires also occur in yellow, purple, orange, and green colors; "parti sapphires" show two or more colors. Red corundum stones also occur, but are called rubies rather than sapphires. Pink-colored corundum may be classified either 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. Sapphire is the birthstone for September and the gem of the 45th anniversary. A sapphire jubilee occurs after 65 years.

<span class="mw-page-title-main">Ruby</span> Variety of corundum, mineral, gemstone

A ruby is a pinkish red to blood-red colored gemstone, a variety of the mineral corundum. Ruby is one of the most popular traditional jewelry gems and is very durable. Other varieties of gem-quality corundum are called sapphires. Ruby is one of the traditional cardinal gems, alongside 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.

<span class="mw-page-title-main">Chrysoberyl</span> Mineral or gemstone of beryllium aluminate

The mineral or gemstone chrysoberyl is an aluminate of beryllium with the formula BeAl2O4. The name chrysoberyl is derived from the Greek words χρυσός chrysos and βήρυλλος beryllos, meaning "a gold-white spar". Despite the similarity of their names, chrysoberyl and beryl are two completely different gemstones, although they both contain beryllium. Chrysoberyl is the third-hardest frequently encountered natural gemstone and lies at 8.5 on the Mohs scale of mineral hardness, between corundum (9) and topaz (8).

<span class="mw-page-title-main">Gemology</span> Science dealing with natural and artificial gemstone materials

Gemology or gemmology is the science dealing with natural and artificial gemstone materials. It is a geoscience and a branch of mineralogy. Some jewelers are academically trained gemologists and are qualified to identify and evaluate gems.

<span class="mw-page-title-main">Aluminium oxide</span> Chemical compound with formula Al2O3

Aluminium oxide (or aluminium(III) oxide) is a chemical compound of aluminium and oxygen with the chemical formula Al2O3. It is the most commonly occurring of several aluminium oxides, and specifically identified as aluminium oxide. It is commonly called alumina and may also be called aloxide, aloxite, or alundum in various forms and applications. It occurs naturally in its crystalline polymorphic phase α-Al2O3 as the mineral corundum, varieties of which form the precious gemstones ruby and sapphire. Al2O3 is significant in its use to produce aluminium metal, as an abrasive owing to its hardness, and as a refractory material owing to its high melting point.

<span class="mw-page-title-main">Strontium titanate</span> 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.

<span class="mw-page-title-main">Transparent ceramics</span> Ceramic materials that are optically transparent

Many ceramic materials, both glassy and crystalline, have found use as optically transparent materials in various forms from bulk solid-state components to high surface area forms such as thin films, coatings, and fibers. Such devices have found widespread use for various applications in the electro-optical field including: optical fibers for guided lightwave transmission, optical switches, laser amplifiers and lenses, hosts for solid-state lasers and optical window materials for gas lasers, and infrared (IR) heat seeking devices for missile guidance systems and IR night vision. In commercial and general knowledge domains, it is commonly accepted that transparent ceramics or ceramic glass are varieties of strengthened glass, such as those used for the screen glass on an iPhone.

<span class="mw-page-title-main">Asterism (gemology)</span>

An asterism is a star-shaped concentration of light reflected or refracted from a gemstone. It can appear when a suitable stone is cut en cabochon.

<span class="mw-page-title-main">Boule (crystal)</span> Synthetic ingot of crystal

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

<span class="mw-page-title-main">Bridgman–Stockbarger method</span> Method of crystallization

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

<span class="mw-page-title-main">Diamond simulant</span> 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 exhibiting 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.

<span class="mw-page-title-main">Auguste Victor Louis Verneuil</span> French chemist (1856–1913)

Auguste Victor Louis Verneuil was a French chemist who invented the first commercially viable process for the manufacture of synthetic gemstones. In 1902 he discovered the "flame fusion" process, called the Verneuil process, which is an inexpensive method of making artificial corundum, or rubies and sapphires.

Synthetic alexandrite is an artificially grown crystalline variety of chrysoberyl, composed of beryllium aluminum oxide (BeAl2O4).

<span class="mw-page-title-main">Oxyhydrogen</span> Explosive mixture of hydrogen and oxygen gases

Oxyhydrogen is a mixture of hydrogen (H2) and oxygen (O2) gases. This gaseous mixture is used for torches to process refractory materials and was the first gaseous mixture used for welding. Theoretically, a ratio of 2:1 hydrogen:oxygen is enough to achieve maximum efficiency; in practice a ratio 4:1 or 5:1 is needed to avoid an oxidizing flame.

<span class="mw-page-title-main">Micro-pulling-down</span> Crystal growth technique

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.

<span class="mw-page-title-main">Kyropoulos method</span> Method of bulk crystal growth used to obtain single crystals

The Kyropoulos method, also known as the KY method or Kyropoulos technique, is a method of bulk crystal growth used to obtain single crystals.

Carroll Chatham (1914–1983) was an American chemist who developed the flux method for synthesizing emeralds. He was the first person to develop a method for creating man-made emeralds that was able to make them commercially available. He founded the jewelry company Chatham which is still selling Chatham emeralds to this day.

References

  1. Verneuil, Auguste (20 February 1891). "The Chemical News and Journal of Physical Science" [translated from the French Revue Générale des Sciences Pures et Appliquées vol 2, number 1, 15 January 1891]: 96.{{cite journal}}: Cite journal requires |journal= (help)
  2. Dobrovinskaya, Elena R.; Lytvynov, Leonid A.; Pishchik, Valerian (2009). Sapphire: Material, Manufacturing, Applications. Springer Science & Business Media. ISBN   9780387856957.
  3. Pelleg, Joshua (2016). "Diffusion in Alumina Single Crystals". Diffusion in Ceramics (PDF). Solid Mechanics and Its Applications. Vol. 221. Springer Science & Business Media. pp. 113–177. doi:10.1007/978-3-319-18437-1_11. ISBN   978-3-319-18436-4.
  4. 1 2 Bhat, H.L. (2014). Introduction to Crystal Growth: Principles and Practice. CRC Press. p. 173. ISBN   9781439883303.
  5. Kelly, James Leslie (1962). "A Study of the Influences of Bayer Process Impurities on the Crystallization of Alumina Trihydrate". LSU Historical Dissertations and Theses. A Dissertation Submitted to the Graduate Facility of the Louisiana State University and Agricultural and Mechanical College In partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemical Engineering: Louisiana State University and Agricultural & Mechanical College. doi: 10.31390/gradschool_disstheses.761 . S2CID   103735465.
  6. 1 2 "Verneuil / Flame-Fusion Method". Gemstone Buzz. Archived from the original on 21 November 2008.