Crystal
This article is about crystalline solids. For other uses, see Crystal (disambiguation). "Xtal" redirects here. For the Aphex Twin track, see Selected Ambient Works 85-92.
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions.[1][2] In addition, macroscopic single crystals are usually identifiable by their geometrical shape, consisting of flat faces with specific, characteristic orientations. The scientific study of crystals and crystal formation is known as crystallography. The process of crystal formation via mechanisms of crystal growth is called crystallization or solidification.
The word crystal derives from the Ancient Greek word κρύσταλλος (krustallos), meaning both "ice" and "rock crystal",[3] from κρύος (kruos), "icy cold, frost".[4][5]
Examples of large crystals include snowflakes, diamonds, and table salt.
Most inorganic solids are not crystals but polycrystals, i.e. many microscopic crystals fused together into a single solid. Polycrystals include most metals, rocks, ceramics, and ice. A third category of solids is amorphous solids, where the atoms have no periodic structure whatsoever. Examples of amorphous solids include glass, wax, and many plastics.
Despite the name, lead crystal, crystal glass, and related products are not crystals, but rather types of glass, i.e. amorphous solids.
Crystals, or crystalline solids, are often used in pseudoscientific practices such as crystal therapy, and, along with gemstones, are sometimes associated with spellwork in Wiccan beliefs and related religious movements.[6][7][8]
Rocks
By volume and weight, the largest concentrations of crystals in the Earth are part of its solid bedrock. Crystals found in rocks typically range in size from a fraction of a millimetre to several centimetres across, although exceptionally large crystals are occasionally found. As of 1999, the world's largest known naturally occurring crystal is a crystal of beryl from Malakialina, Madagascar, 18 m (59 ft) long and 3.5 m (11 ft) in diameter, and weighing 380,000 kg (840,000 lb).[12]
Some crystals have formed by magmatic and metamorphic processes, giving origin to large masses of crystalline rock. The vast majority of igneous rocks are formed from molten magma and the degree of crystallization depends primarily on the conditions under which they solidified. Such rocks as granite, which have cooled very slowly and under great pressures, have completely crystallized; but many kinds of lava were poured out at the surface and cooled very rapidly, and in this latter group a small amount of amorphous or glassy matter is common. Other crystalline rocks, the metamorphic rocks such as marbles, mica-schists and quartzites, are recrystallized. This means that they were at first fragmental rocks like limestone, shale and sandstone and have never been in a molten condition nor entirely in solution, but the high temperature and pressure conditions of metamorphism have acted on them by erasing their original structures and inducing recrystallization in the solid state.[13]
Other rock crystals have formed out of precipitation from fluids, commonly water, to form druses or quartz veins. Evaporites such as halite, gypsum and some limestones have been deposited from aqueous solution, mostly owing to evaporation in arid climates.
Ice
Water-based ice in the form of snow, sea ice, and glaciers are common crystalline/polycrystalline structures on Earth and other planets.[14] A single snowflake is a single crystal or a collection of crystals,[15] while an ice cube is a polycrystal.[16] Ice crystals may form from cooling liquid water below its freezing point, such as ice cubes or a frozen lake. Frost, snowflakes, or small ice crystals suspended in the air (ice fog) more often grow from a supersaturated gaseous-solution of water vapor and air, when the temperature of the air drops below its dew point, without passing through a liquid state. Another unusual property of water is that it expands rather than contracts when it crystallizes.[17]
Organigenic crystals
Many living organisms are able to produce crystals grown from an aqueous solution, for example calcite and aragonite in the case of most molluscs or hydroxylapatite in the case of bones and teeth in vertebrates.
Polymorphism and allotropy
Main articles: Polymorphism (materials science) and Allotropy
The same group of atoms can often solidify in many different ways. Polymorphism is the ability of a solid to exist in more than one crystal form. For example, water ice is ordinarily found in the hexagonal form Ice I~h, but can also exist as the cubic Ice I~c, the rhombohedral ice II, and many other forms. The different polymorphs are usually called different phases.
In addition, the same atoms may be able to form noncrystalline phases. For example, water can also form amorphous ice, while SiO2 can form both fused silica (an amorphous glass) and quartz (a crystal). Likewise, if a substance can form crystals, it can also form polycrystals.
For pure chemical elements, polymorphism is referred to as allotropy. For example, diamond and graphite are two crystalline forms of carbon, while amorphous carbon is a noncrystalline form. Polymorphs, despite having the same atoms, may have very different properties. For example, diamond is the hardest substance known, while graphite is so soft that it is used as a lubricant. Chocolate can form six different types of crystals, but only one has the suitable hardness and melting point for candy bars and confections. Polymorphism in steel is responsible for its ability to be heat treated, giving it a wide range of properties.
Polyamorphism is a similar phenomenon where the same atoms can exist in more than one amorphous solid form.
Crystallization
Main articles: Crystallization and Crystal growth
Vertical cooling crystallizer in a beet sugar factory.
Crystallization is the process of forming a crystalline structure from a fluid or from materials dissolved in a fluid. (More rarely, crystals may be deposited directly from gas; see: epitaxy and frost.)
Crystallization is a complex and extensively-studied field, because depending on the conditions, a single fluid can solidify into many different possible forms. It can form a single crystal, perhaps with various possible phases, stoichiometries, impurities, defects, and habits. Or, it can form a polycrystal, with various possibilities for the size, arrangement, orientation, and phase of its grains. The final form of the solid is determined by the conditions under which the fluid is being solidified, such as the chemistry of the fluid, the ambient pressure, the temperature, and the speed with which all these parameters are changing.
Specific industrial techniques to produce large single crystals (called boules) include the Czochralski process and the Bridgman technique. Other less exotic methods of crystallization may be used, depending on the physical properties of the substance, including hydrothermal synthesis, sublimation, or simply solvent-based crystallization.
Large single crystals can be created by geological processes. For example, selenite crystals in excess of 10 m are found in the Cave of the Crystals in Naica, Mexico.[18] For more details on geological crystal formation, see above.
Crystals can also be formed by biological processes, see above. Conversely, some organisms have special techniques to prevent crystallization from occurring, such as antifreeze proteins.
Defects, impurities, and twinning
Main articles: Crystallographic defect, Impurity, Crystal twinning, and Mosaicity
An ideal crystal has every atom in a perfect, exactly repeating pattern.[19] However, in reality, most crystalline materials have a variety of crystallographic defects: places where the crystal's pattern is interrupted. The types and structures of these defects may have a profound effect on the properties of the materials.
A few examples of crystallographic defects include vacancy defects (an empty space where an atom should fit), interstitial defects (an extra atom squeezed in where it does not fit), and dislocations (see figure at right). Dislocations are especially important in materials science, because they help determine the mechanical strength of materials.
Another common type of crystallographic defect is an impurity, meaning that the "wrong" type of atom is present in a crystal. For example, a perfect crystal of diamond would only contain carbon atoms, but a real crystal might perhaps contain a few boron atoms as well. These boron impurities change the diamond's color to slightly blue. Likewise, the only difference between ruby and sapphire is the type of impurities present in a corundum crystal.
In semiconductors, a special type of impurity, called a dopant, drastically changes the crystal's electrical properties. Semiconductor devices, such as transistors, are made possible largely by putting different semiconductor dopants into different places, in specific patterns.
Twinning is a phenomenon somewhere between a crystallographic defect and a grain boundary. Like a grain boundary, a twin boundary has different crystal orientations on its two sides. But unlike a grain boundary, the orientations are not random, but related in a specific, mirror-image way.
Mosaicity is a spread of crystal plane orientations. A mosaic crystal consists of smaller crystalline units that are somewhat misaligned with respect to each other.
Chemical bonds
In general, solids can be held together by various types of chemical bonds, such as metallic bonds, ionic bonds, covalent bonds, van der Waals bonds, and others. None of these are necessarily crystalline or non-crystalline. However, there are some general trends as follows:
Metals crystallize rapidly and are almost always polycrystalline, though there are exceptions like amorphous metal and single-crystal metals. The latter are grown synthetically, for example, fighter-jet turbines are typically made by first growing a single crystal of titanium alloy, increasing its strength and melting point over polycrystalline titanium. A small piece of metal may naturally form into a single crystal, such as Type 2 telluric iron, but larger pieces generally do not unless extremely slow cooling occurs. For example, iron meteorites are often composed of single crystal, or many large crystals that may be several meters in size, due to very slow cooling in the vacuum of space. The slow cooling may allow the precipitation of a separate phase within the crystal lattice, which form at specific angles determined by the lattice, called Widmanstatten patterns.[20]
Ionic compounds typically form when a metal reacts with a non-metal, such as sodium with chlorine. These often form substances called salts, such as sodium chloride (table salt) or potassium nitrate (saltpeter), with crystals that are often brittle and cleave relatively easily. Ionic materials are usually crystalline or polycrystalline. In practice, large salt crystals can be created by solidification of a molten fluid, or by crystallization out of a solution. Some ionic compounds can be very hard, such as oxides like aluminium oxide found in many gemstones such as ruby and synthetic sapphire.
Covalently bonded solids (sometimes called covalent network solids) are typically formed from one or more non-metals, such as carbon or silicon and oxygen, and are often very hard, rigid, and brittle. These are also very common, notable examples being diamond and quartz respectively.[21]
Weak van der Waals forces also help hold together certain crystals, such as crystalline molecular solids, as well as the interlayer bonding in graphite. Substances such as fats, lipids and wax form molecular bonds because the large molecules do not pack as tightly as atomic bonds. This leads to crystals that are much softer and more easily pulled apart or broken. Common examples include chocolates, candles, or viruses. Water ice and dry ice are examples of other materials with molecular bonding.[22]Polymer materials generally will form crystalline regions, but the lengths of the molecules usually prevent complete crystallization—and sometimes polymers are completely amorphous.
Quasicrystals
A quasicrystal consists of arrays of atoms that are ordered but not strictly periodic. They have many attributes in common with ordinary crystals, such as displaying a discrete pattern in x-ray diffraction, and the ability to form shapes with smooth, flat faces.
Quasicrystals are most famous for their ability to show five-fold symmetry, which is impossible for an ordinary periodic crystal (see crystallographic restriction theorem).
The International Union of Crystallography has redefined the term "crystal" to include both ordinary periodic crystals and quasicrystals ("any solid having an essentially discrete diffraction diagram"[23]).
Quasicrystals, first discovered in 1982, are quite rare in practice. Only about 100 solids are known to form quasicrystals, compared to about 400,000 periodic crystals known in 2004.[24] The 2011 Nobel Prize in Chemistry was awarded to Dan Shechtman for the discovery of quasicrystals.[25]
Special properties from anisotropy
See also: Crystal optics
Crystals can have certain special electrical, optical, and mechanical properties that glass and polycrystals normally cannot. These properties are related to the anisotropy of the crystal, i.e. the lack of rotational symmetry in its atomic arrangement. One such property is the piezoelectric effect, where a voltage across the crystal can shrink or stretch it. Another is birefringence, where a double image appears when looking through a crystal. Moreover, various properties of a crystal, including electrical conductivity, electrical permittivity, and Young's modulus, may be different in different directions in a crystal. For example, graphite crystals consist of a stack of sheets, and although each individual sheet is mechanically very strong, the sheets are rather loosely bound to each other. Therefore, the mechanical strength of the material is quite different depending on the direction of stress.
Not all crystals have all of these properties. Conversely, these properties are not quite exclusive to crystals. They can appear in glasses or polycrystals that have been made anisotropic by working or stress—for example, stress-induced birefringence.
Crystallography
Main article: Crystallography
Crystallography is the science of measuring the crystal structure (in other words, the atomic arrangement) of a crystal. One widely used crystallography technique is X-ray diffraction. Large numbers of known crystal structures are stored in crystallographic databases.
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