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The flux method is a crystal growth method where starting materials are dissolved in a solvent (flux), and are precipitated out to form crystals of a desired compound. The flux lowers the melting point of the desired compound, analogous to a wet chemistry recrystallization. [1] The flux is molten in a highly stable crucible that does not react with the flux. Metal crucibles, such as platinum, titanium, and niobium are used for the growth of oxide crystals. Ceramic crucibles, such as alumina, zirconia, and boron nitride are used for the growth of metallic crystals. [2] For air-sensitive growths, contents are sealed in ampoules or placed in atmosphere controlled furnaces.
Oxide fluxes are often combined to reduce volatility, viscosity, and reactivity towards the crucibles. Metallic fluxes aren't typically combined, [3] as they do not suffer from the same volatility, viscosity, and reactivity issues. An ideal flux should have the following properties: [2]
Metallic Flux | Oxide Flux | ||||
---|---|---|---|---|---|
Flux | Melting Point (°C) | Boiling Point (°C) | Flux | Melting Point (°C) | Boiling Point (°C) |
Aluminum | 660 | 2470 | Lead(II) Oxide | 888 | 1477 |
Bismuth | 271 | 1564 | Lead(II) Fluoride | 824 | 1293 |
Gallium | 30 | 2400 | Bismuth (III) Oxide | 817 | 1890 |
Indium | 157 | 2072 | Lithium Oxide | 1438 | 2600 |
Tin | 232 | 2602 | Molybdenum Trioxide | 802 | 1152 |
Lead | 328 | 1749 | Potassium Fluoride | 858 | 1502 |
The growth (starting materials, flux, and crucible) are heated to form a complete liquid solution. The growth is cooled to a temperature where the solution is fully saturated. Further cooling causes crystals to precipitate from the solution, lowering the concentration of starting materials in solution, and lowering the temperature where the solution is fully saturated. The process is repeated, decreasing temperature and precipitating more crystals. The process is then stopped at a desired temperature, and the growth is removed from the furnace. Practically, the flux method is done by placing the growth into a programmable furnace:[ citation needed ]
Additional steps may be added to this basic temperature profile, such as additional dwells or different cooling rates over different points of the cool. Crystallization can occur through spontaneous nucleation, encouragement with a seed, or through mechanical stress.[ citation needed ]
The growth of intermetallic compounds are air-sensitive.[ citation needed ] Oxygen in air reacts with heated metals to form metal oxides. Less commonly, nitrogen in the air can react with heated metals to form metal nitrides. Intermetallic growths are sealed under vacuum or inert-atmosphere ampoules to prevent oxidation. These ampoules are made out of quartz glass. The ampoules limits the maximum temperature of the growth to the melting point of the specific quartz glass, since it's typically lower than the melting point of the crucible or starting materials. One method of ampoule preparation is as follows:[ citation needed ]
After crystallization, often some solidified flux remains on the surface or inside the desired crystal. This flux may cause defects in the crystal due to the different thermal expansivities of the flux and crystal. [4] A solvent (typically an acid or a base) can dissolve the flux, but it's difficult to find a solvent that doesn't also dissolve the crystal. The flux can be removed mechanically using a blade or drill. If the crystal and flux have significantly different boiling points, the flux may be removed with evaporation. Flux can also be removed through recrystallization through use of a seed in the liquid phase, leaving the flux behind as the crystals accumulate.
The removal of excess flux is important to assess a crystals properties, as the flux can affect measurements. For example, tin and lead super conduct at low temperatures, [5] if a sample has tin or lead flux superconductivity can be observed even if the desired crystal is not a superconductor.
An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, opacity, and luster, but may have properties that differ from those of the pure metals, such as increased strength or hardness. In some cases, an alloy may reduce the overall cost of the material while preserving important properties. In other cases, the mixture imparts synergistic properties to the constituent metal elements such as corrosion resistance or mechanical strength.
Solder is a fusible metal alloy used to create a permanent bond between metal workpieces. Solder is melted in order to wet the parts of the joint, where it adheres to and connects the pieces after cooling. Metals or alloys suitable for use as solder should have a lower melting point than the pieces to be joined. The solder should also be resistant to oxidative and corrosive effects that would degrade the joint over time. Solder used in making electrical connections also needs to have favorable electrical characteristics.
Cubic zirconia (abbreviated CZ) is the cubic crystalline form of zirconium dioxide (ZrO2). The synthesized material is hard and usually colorless, but may be made in a variety of different colors. It should not be confused with zircon, which is a zirconium silicate (ZrSiO4). It is sometimes erroneously called cubic zirconium.
Solid-state chemistry, also sometimes referred as materials chemistry, is the study of the synthesis, structure, and properties of solid phase materials. It therefore has a strong overlap with solid-state physics, mineralogy, crystallography, ceramics, metallurgy, thermodynamics, materials science and electronics with a focus on the synthesis of novel materials and their characterization. A diverse range of synthetic techniques, such as the ceramic method and chemical vapour depostion, make solid-state materials. Solids can be classified as crystalline or amorphous on basis of the nature of order present in the arrangement of their constituent particles. Their elemental compositions, microstructures, and physical properties can be characterized through a variety of analytical methods.
Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment. Generally, the temperature program for a DSC analysis is designed such that the sample holder temperature increases linearly as a function of time. The reference sample should have a well-defined heat capacity over the range of temperatures to be scanned. Additionally, the reference sample must be stable, of high purity, and must not experience much change across the temperature scan. Typically, reference standards have been metals such as indium, tin, bismuth, and lead, but other standards such as polyethylene and fatty acids have been proposed to study polymers and organic compounds, respectively.
Heat treating is a group of industrial, thermal and metalworking processes used to alter the physical, and sometimes chemical, properties of a material. The most common application is metallurgical. Heat treatments are also used in the manufacture of many other materials, such as glass. Heat treatment involves the use of heating or chilling, normally to extreme temperatures, to achieve the desired result such as hardening or softening of a material. Heat treatment techniques include annealing, case hardening, precipitation strengthening, tempering, carburizing, normalizing and quenching. Although the term heat treatment applies only to processes where the heating and cooling are done for the specific purpose of altering properties intentionally, heating and cooling often occur incidentally during other manufacturing processes such as hot forming or welding.
A crucible is a ceramic or metal container in which metals or other substances may be melted or subjected to very high temperatures. Although crucibles have historically tended to be made out of clay, they can be made from any material that withstands temperatures high enough to melt or otherwise alter its contents.
In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a supersaturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading to precipitation, the chemical reagent causing the solid to form is called the precipitant.
Brazing is a metal-joining process in which two or more metal items are joined by melting and flowing a filler metal into the joint, with the filler metal having a lower melting point than the adjoining metal.
In metallurgy, a flux is a chemical cleaning agent, flowing agent, or purifying agent. Fluxes may have more than one function at a time. They are used in both extractive metallurgy and metal joining.
In materials science, a refractory is a material that is resistant to decomposition by heat or chemical attack that retains its strength and rigidity at high temperatures. They are inorganic, non-metallic compounds that may be porous or non-porous, and their crystallinity varies widely: they may be crystalline, polycrystalline, amorphous, or composite. They are typically composed of oxides, carbides or nitrides of the following elements: silicon, aluminium, magnesium, calcium, boron, chromium and zirconium. Many refractories are ceramics, but some such as graphite are not, and some ceramics such as clay pottery are not considered refractory. Refractories are distinguished from the refractory metals, which are elemental metals and their alloys that have high melting temperatures.
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.
Crystallization is the process by which solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some ways by which crystals form are precipitating from a solution, freezing, or more rarely deposition directly from a gas. Attributes of the resulting crystal depend largely on factors such as temperature, air pressure, and in the case of liquid crystals, time of fluid evaporation.
A superalloy, or high-performance alloy, is an alloy with the ability to operate at a high fraction of its melting point. Key characteristics of a superalloy include mechanical strength, thermal creep deformation resistance, surface stability, and corrosion and oxidation resistance.
A foundry is a factory that produces metal castings. Metals are cast into shapes by melting them into a liquid, pouring the metal into a mold, and removing the mold material after the metal has solidified as it cools. The most common metals processed are aluminum and cast iron. However, other metals, such as bronze, brass, steel, magnesium, and zinc, are also used to produce castings in foundries. In this process, parts of desired shapes and sizes can be formed.
A vacuum furnace is a type of furnace in which the product in the furnace is surrounded by a vacuum during processing. The absence of air or other gases prevents oxidation, heat loss from the product through convection, and removes a source of contamination. This enables the furnace to heat materials to temperatures as high as 3,000 °C (5,432 °F) with select materials. Maximum furnace temperatures and vacuum levels depend on melting points and vapor pressures of heated materials. Vacuum furnaces are used to carry out processes such as annealing, brazing, sintering and heat treatment with high consistency and low contamination.
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 equilibria since the beginning of the twentieth century. George W. Morey at the Carnegie Institution and later, Percy W. Bridgman at Harvard University 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.
Forest glass is late medieval glass produced in northwestern and central Europe from approximately 1000–1700 AD using wood ash and sand as the main raw materials and made in factories known as glasshouses in forest areas. It is characterized by a variety of greenish-yellow colors, the earlier products often being of crude design and poor quality, and was used mainly for everyday vessels and increasingly for ecclesiastical stained glass windows. Its composition and manufacture contrast sharply with Roman and pre-Roman glassmaking centered on the Mediterranean and contemporaneous Byzantine and Islamic glass making to the east.
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.
In chemistry, recrystallization is a technique used to purify chemicals. By dissolving a mixture of a compound and impurities in an appropriate solvent, either the desired compound or impurities can be removed from the solution, leaving the other behind. It is named for the crystals often formed when the compound precipitates out. Alternatively, recrystallization can refer to the natural growth of larger ice crystals at the expense of smaller ones.
Components of the gem materials desired in a single crystal form are dissolved in a flux (solvent).