- Hydrothermal synthesis
Hydrothermal synthesis includes the various techniques of crystallizing substances from high-temperature
aqueous solutions at high vapor pressures; also termed "hydrothermal method". The term " hydrothermal" is of geologic origin. Geochemists and mineralogists have studied hydrothermal phase equilibriasince the turn of the century. George W. Morey at the Carnegie Institutionand later, Percy W. Bridgmanat Harvard Universitydid 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 crystals which depends on the solubility of minerals in hot water under high pressure. The crystal growthis performed in an apparatus consisting of a steel pressure vessel called autoclave, in which a nutrient is supplied along with water. 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, good quality seeds of a fair size and the impossibility of observing the crystal as it grows [cite book
last = O'Donoghue
first = M.
year = 1983
title = A guide to Man-made Gemstones
publisher = Van Nostrand Reinhold Company
location = Great Britain
language = english
ISBN = 0-442-27253-7 ] .
In 1839, the German chemist
Robert Bunsencontained aqueous solutions in thick-walled glass tubes at temperatures above 200°C and at pressures above 100 bars. [cite journal
last = Laudise
first = R.A.
year = 1987
title = Hydrothermal Synthesis of Crystals
journal = C&EN
volume = September 28
pages = 30–43
accessdate = ] The crystals of
barium carbonateand strontiumcarbonate 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 [cite web
url = http://www.roditi.com/SingleCrystal/Quartz/Hydrothermal_Growth.html
title = Hydrothermal Crystal Growth - Quartz
accessdate = 2006-11-17
publisher = Roditi International] . Later G. Spezzia (1905) published reports on the growth of macroscopic crystals [cite journal
last = Spezzia
first = G.
year = 1905
journal = Accad. Sci. Torino Atti
volume = 40
pages = 254
accessdate = ] . He used solutions of
sodium silicate, 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) [cite book
last = Laudise
first = R.A.
title = Growth and perfection of crystals
language = english
pages =458–463 ] .
A large number of compounds belonging to practically all classes have been synthesized under hydrothermal conditions: elements, simple and complex
oxides, tungstates, molybdates, carbonates, silicates, germanates etc. Hydrothermal synthesis is commonly used to grow synthetic quartz, gems and other single crystals with commercial value. Some of the crystals which have been efficiently grown are emeralds, rubies, quartz, alexandriteand 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
autoclaves. 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. The closure is the most important element of the autoclave. Many designs have been developed for seals, the most famous being the Bridgman seal. In most cases steel-corroding solutions are used in hydrothermal experiments. To prevent corrosionof 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, copper, silver, gold, platinum, titanium, glassor quartz, Teflon, depending on the temperature and solution used.
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.
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.
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 which are thermodinamically 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.
Chemical vapor deposition
* [http://www.autoclaveengineers.com/ Hydrothermal crystal growth equipment producer]
* [http://www.roditi.com/SingleCrystal/Quartz/Hydrothermal_Growth.html Hydrothermal crystal growth of Quartz]
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