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Hydrothermal synthesis

Hydrothermal synthesis

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Hydrothermal synthesis includes the various techniques of crystallizing substances from high-temperature aqueous solution
Aqueous solution
An aqueous solution is a solution in which the solvent is water. It is usually shown in chemical equations by appending aq to the relevant formula, such as NaCl. The word aqueous means pertaining to, related to, similar to, or dissolved in water...

s at high vapor pressure
Vapor pressure
Vapor pressure or equilibrium vapor pressure is the pressure of a vapor in thermodynamic equilibrium with its condensed phases in a closed system. All liquids have a tendency to evaporate, and some solids can sublimate into a gaseous form...

s; also termed "hydrothermal method". The term "hydrothermal" is of geologic
Geology
Geology is the science comprising the study of solid Earth, the rocks of which it is composed, and the processes by which it evolves. Geology gives insight into the history of the Earth, as it provides the primary evidence for plate tectonics, the evolutionary history of life, and past climates...

 origin. Geochemists
Geochemistry
The field of geochemistry involves study of the chemical composition of the Earth and other planets, chemical processes and reactions that govern the composition of rocks, water, and soils, and the cycles of matter and energy that transport the Earth's chemical components in time and space, and...

 and mineralogists have studied hydrothermal phase equilibria since the beginning of the twentieth century. George W. Morey at the Carnegie Institution and later, Percy W. Bridgman at Harvard University
Harvard University
Harvard University is a private Ivy League university located in Cambridge, Massachusetts, United States, established in 1636 by the Massachusetts legislature. Harvard is the oldest institution of higher learning in the United States and the first corporation chartered in the country...

 did much of the work to lay the foundations necessary to containment of reactive media in the temperature and pressure range where most of the hydrothermal work is conducted.

Hydrothermal synthesis can be defined as a method of synthesis of single crystal
Single crystal
A single crystal or monocrystalline solid is a material in which the crystal lattice of the entire sample is continuous and unbroken to the edges of the sample, with no grain boundaries...

s that depends on the solubility of minerals in hot water under high pressure. The crystal growth
Crystal growth
A crystal is a solid material whose constituent atoms, molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. Crystal growth is a major stage of a crystallization process, and consists in the addition of new atoms, ions, or polymer strings into...

 is performed in an apparatus consisting of a steel pressure vessel called autoclave
Autoclave
An autoclave is an instrument used to sterilize equipment and supplies by subjecting them to high pressure saturated steam at 121 °C for around 15–20 minutes depending on the size of the load and the contents. It was invented by Charles Chamberland in 1879, although a precursor known as the...

, in which a nutrient is supplied along with water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...

. A gradient of temperature is maintained at the opposite ends of the growth chamber so that the hotter end dissolves the nutrient and the cooler end causes seeds to take additional growth.

Possible advantages of the hydrothermal method over other types of crystal growth include the ability to create crystalline phases which are not stable at the melting point. Also, materials which have a high vapour pressure near their melting points can also be grown by the hydrothermal method. The method is also particularly suitable for the growth of large good-quality crystals while maintaining good control over their composition. Disadvantages of the method include the need of expensive autoclaves, and the impossibility of observing the crystal as it grows.

History


In 1839, the German chemist Robert Bunsen
Robert Bunsen
Robert Wilhelm Eberhard Bunsen was a German chemist. He investigated emission spectra of heated elements, and discovered caesium and rubidium with Gustav Kirchhoff. Bunsen developed several gas-analytical methods, was a pioneer in photochemistry, and did early work in the field of organoarsenic...

 contained aqueous solutions in thick-walled glass tubes at temperatures above 200 °C and at pressures above 100 bars
Bar (unit)
The bar is a unit of pressure equal to 100 kilopascals, and roughly equal to the atmospheric pressure on Earth at sea level. Other units derived from the bar are the megabar , kilobar , decibar , centibar , and millibar...

. The crystals of barium carbonate
Barium carbonate
Barium carbonate , also known as witherite, is a chemical compound used in rat poison, bricks, ceramic glazes and cement.Witherite crystallizes in the orthorhombic system...

 and strontium carbonate
Strontium carbonate
Strontium carbonate is the carbonate salt of strontium that has the appearance of a white or grey powder. It occurs in nature as the mineral strontianite.- Chemical properties :...

 that he grew under these conditions mark the first use of hydrothermal aqueous solvents as media. Other early reports of the hydrothermal growth of crystals were by Schafhäult in 1845 and by de Sénarmont in 1851, who produced only microscopic crystals. Later G. Spezzia (1905) published reports on the growth of macroscopic crystals. He used solutions of sodium silicate
Sodium silicate
Sodium silicate is the common name for a compound sodium metasilicate, Na2SiO3, also known as water glass or liquid glass. It is available in aqueous solution and in solid form and is used in cements, passive fire protection, refractories, textile and lumber processing, and automobiles...

, natural crystals as seeds and supply, and a silver-lined vessel. By heating the supply end of his vessel to 320-350 °C, and the other end to 165-180 °C, he obtained about 15 mm of new growth over a 200 day period. Unlike modern practice, the hotter part of the vessel was at the top. Other notable contributions have been made by Nacken (1946), Hale (1948), Brown (1951), Walker (1950) and Kohman (1955).

Uses


A large number of compounds belonging to practically all classes have been synthesized under hydrothermal conditions: elements, simple and complex oxides, tungstate
Tungstate
In chemistry a tungstate is a compound that contains an oxoanion of tungsten or is a mixed oxide containing tungsten. The simplest tungstate ion is WO42−, "orthotungstate"...

s, molybdate
Molybdate
In chemistry a molybdate is a compound containing an oxoanion with molybdenum in its highest oxidation state of 6. Molybdenum can form a very large range of such oxoanions which can be discrete structures or polymeric extended structures, although the latter are only found in the solid state.The...

s, carbonates, silicate
Silicate
A silicate is a compound containing a silicon bearing anion. The great majority of silicates are oxides, but hexafluorosilicate and other anions are also included. This article focuses mainly on the Si-O anions. Silicates comprise the majority of the earth's crust, as well as the other...

s, germanates etc. Hydrothermal synthesis is commonly used to grow synthetic quartz
Quartz
Quartz is the second-most-abundant mineral in the Earth's continental crust, after feldspar. It is made up of a continuous framework of SiO4 silicon–oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall formula SiO2. There are many different varieties of quartz,...

, gems
Gemstone
A gemstone or gem is a piece of mineral, which, in cut and polished form, is used to make jewelry or other adornments...

 and other single crystals with commercial value. Some of the crystals that have been efficiently grown are emerald
Emerald
Emerald is a variety of the mineral beryl colored green by trace amounts of chromium and sometimes vanadium. Beryl has a hardness of 7.5–8 on the 10 point Mohs scale of mineral hardness...

s, rubies
Ruby
A ruby is a pink to blood-red colored gemstone, a variety of the mineral corundum . The red color is caused mainly by the presence of the element chromium. Its name comes from ruber, Latin for red. Other varieties of gem-quality corundum are called sapphires...

, quartz, alexandrite and others. The method has proved to be extremely efficient both in the search for new compounds with specific physical properties and in the systematic physicochemical investigation of intricate multicomponent systems at elevated temperatures and pressures.

Equipment for hydrothermal crystal growth


The crystallization vessels used are autoclave
Autoclave
An autoclave is an instrument used to sterilize equipment and supplies by subjecting them to high pressure saturated steam at 121 °C for around 15–20 minutes depending on the size of the load and the contents. It was invented by Charles Chamberland in 1879, although a precursor known as the...

s. These are usually thick-walled steel cylinders with a hermetic seal which must withstand high temperatures and pressures for prolonged periods of time. Furthermore, the autoclave material must be inert with respect to the solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...

. The closure is the most important element of the autoclave. Many designs have been developed for seals, the most famous being the Bridgman seal
Bridgman seal
A Bridgman seal, named after Percy Williams Bridgman, seals a high pressure volume by the use of a three part mechanism. A viscous material such as rubber, copper or soap stone is set so that it stretches longitudinally against a hard steel ring, followed by a softer steel ring and horizontally...

. In most cases steel
Steel
Steel is an alloy that consists mostly of iron and has a carbon content between 0.2% and 2.1% by weight, depending on the grade. Carbon is the most common alloying material for iron, but various other alloying elements are used, such as manganese, chromium, vanadium, and tungsten...

-corroding solutions are used in hydrothermal experiments. To prevent corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

 of the internal cavity of the autoclave, protective inserts are generally used. These may have the same shape of the autoclave and fit in the internal cavity (contact-type insert) or be a "floating" type insert which occupies only part of the autoclave interior. Inserts may be made of carbon-free iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

, copper
Copper
Copper is a chemical element with the symbol Cu and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is soft and malleable; an exposed surface has a reddish-orange tarnish...

, silver
Silver
Silver is a metallic chemical element with the chemical symbol Ag and atomic number 47. A soft, white, lustrous transition metal, it has the highest electrical conductivity of any element and the highest thermal conductivity of any metal...

, gold
Gold
Gold is a chemical element with the symbol Au and an atomic number of 79. Gold is a dense, soft, shiny, malleable and ductile metal. Pure gold has a bright yellow color and luster traditionally considered attractive, which it maintains without oxidizing in air or water. Chemically, gold is a...

, platinum
Platinum
Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is a dense, malleable, ductile, precious, gray-white transition metal...

, titanium
Titanium
Titanium is a chemical element with the symbol Ti and atomic number 22. It has a low density and is a strong, lustrous, corrosion-resistant transition metal with a silver color....

, glass
Glass
Glass is an amorphous solid material. Glasses are typically brittle and optically transparent.The most familiar type of glass, used for centuries in windows and drinking vessels, is soda-lime glass, composed of about 75% silica plus Na2O, CaO, and several minor additives...

 (or quartz
Quartz
Quartz is the second-most-abundant mineral in the Earth's continental crust, after feldspar. It is made up of a continuous framework of SiO4 silicon–oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall formula SiO2. There are many different varieties of quartz,...

), or Teflon, depending on the temperature and solution used.catalyst materials prepared by hydrothermal methods.

Temperature-difference method


The most extensively used method in hydrothermal synthesis and crystal growing. The supersaturation is achieved by reducing the temperature in the crystal growth zone. The nutrient is placed in the lower part of the autoclave filled with a specific amount of solvent. The autoclave is heated in order to create two temperature zones. The nutrient dissolves in the hotter zone and the saturated aqueous solution in the lower part is transported to the upper part by convective motion of the solution. The cooler and denser solution in the upper part of the autoclave descends while the counterflow of solution ascends. The solution becomes supersaturated in the upper part as the result of the reduction in temperature and crystallization sets in.

Temperature-reduction technique


In this technique crystallization takes place without a temperature gradient between the growth and dissolution zones. The supersaturation is achieved by a gradual reduction in temperature of the solution in the autoclave. The disadvantage of this technique is the difficulty in controlling the growth process and introducing seed crystals. For these reasons, this technique is very seldom used.

Metastable-phase technique


This technique is based on the difference in solubility between the phase to be grown and that serving as the starting material.
The nutrient consists of compounds that are thermodynamically unstable under the growth conditions. The solubility of the metastable phase exceeds that of the stable phase, and the latter crystallize due to the dissolution of the metastable phase. This technique is usually combined with one of the other two techniques above.

See also


  • Crystallography
    Crystallography
    Crystallography is the experimental science of the arrangement of atoms in solids. The word "crystallography" derives from the Greek words crystallon = cold drop / frozen drop, with its meaning extending to all solids with some degree of transparency, and grapho = write.Before the development of...

  • Verneuil Process
    Verneuil process
    The Verneuil process, also called flame fusion, was the first commercially successful method of manufacturing synthetic gemstones, developed in 1902 by the French chemist Auguste Verneuil. It is primarily used to produce the ruby and sapphire varieties of corundum, as well as the diamond simulants...

  • Czochralski
  • Epitaxy
    Epitaxy
    Epitaxy refers to the deposition of a crystalline overlayer on a crystalline substrate, where the overlayer is in registry with the substrate. In other words, there must be one or more preferred orientations of the overlayer with respect to the substrate for this to be termed epitaxial growth. The...

  • Crystal growth
    Crystal growth
    A crystal is a solid material whose constituent atoms, molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. Crystal growth is a major stage of a crystallization process, and consists in the addition of new atoms, ions, or polymer strings into...

  • Chemical vapor deposition
    Chemical vapor deposition
    Chemical vapor deposition is a chemical process used to produce high-purity, high-performance solid materials. The process is often used in the semiconductor industry to produce thin films. In a typical CVD process, the wafer is exposed to one or more volatile precursors, which react and/or...

  • Flux method
    Flux method
    Flux method is a method of crystal growth where the components of the desired substance are dissolved in a solvent . The method is particularly suitable for crystals needing to be free from thermal strain and it takes place in a crucible made of non-reactive metal such as platinum, tantalum,...



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