Crystal

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A crystal of amethyst quartz Amethystemadagascar2.jpg
A crystal of amethyst quartz
Microscopically, a single crystal has atoms in a near-perfect periodic arrangement; a polycrystal is composed of many microscopic crystals (called "crystallites" or "grains"); and an amorphous solid (such as glass) has no periodic arrangement even microscopically. Crystalline polycrystalline amorphous2.svg
Microscopically, a single crystal has atoms in a near-perfect periodic arrangement; a polycrystal is composed of many microscopic crystals (called "crystallites" or "grains"); and an amorphous solid (such as glass) has no periodic arrangement even microscopically.

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.

Contents

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. Examples of 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 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]

Crystal structure (microscopic)

Halite (table salt, NaCl): Microscopic and macroscopic
Sodium-chloride-3D-ionic.png
Microscopic structure of a Halite (mineral) crystal. (Purple is sodium ion, green is chlorine ion). There is cubic symmetry in the atoms' arrangement
Selpologne.jpg
Macroscopic (~16cm) halite crystal. The right-angles between crystal faces are due to the cubic symmetry of the atoms' arrangement

The scientific definition of a "crystal" is based on the microscopic arrangement of atoms inside it, called the crystal structure. A crystal is a solid where the atoms form a periodic arrangement. (Quasicrystals are an exception, see below).

Not all solids are crystals. For example, when liquid water starts freezing, the phase change begins with small ice crystals that grow until they fuse, forming a polycrystalline structure. In the final block of ice, each of the small crystals (called "crystallites" or "grains") is a true crystal with a periodic arrangement of atoms, but the whole polycrystal does not have a periodic arrangement of atoms, because the periodic pattern is broken at the grain boundaries. Most macroscopic inorganic solids are polycrystalline, including almost all metals, ceramics, ice, rocks, etc. Solids that are neither crystalline nor polycrystalline, such as glass, are called amorphous solids , also called glassy, vitreous, or noncrystalline. These have no periodic order, even microscopically. There are distinct differences between crystalline solids and amorphous solids: most notably, the process of forming a glass does not release the latent heat of fusion, but forming a crystal does.

A crystal structure (an arrangement of atoms in a crystal) is characterized by its unit cell, a small imaginary box containing one or more atoms in a specific spatial arrangement. The unit cells are stacked in three-dimensional space to form the crystal.

The symmetry of a crystal is constrained by the requirement that the unit cells stack perfectly with no gaps. There are 219 possible crystal symmetries, called crystallographic space groups. These are grouped into 7 crystal systems, such as cubic crystal system (where the crystals may form cubes or rectangular boxes, such as Halite (mineral) shown at right) or hexagonal crystal system (where the crystals may form hexagons, such as ordinary water ice).

Crystal faces and shapes

As a Halite (mineral) crystal is growing, new atoms can very easily attach to the parts of the surface with rough atomic-scale structure and many dangling bonds. Therefore, these parts of the crystal grow out very quickly (yellow arrows). Eventually, the whole surface consists of smooth, stable faces, where new atoms cannot as easily attach themselves. Crystal facet formation.svg
As a Halite (mineral) crystal is growing, new atoms can very easily attach to the parts of the surface with rough atomic-scale structure and many dangling bonds. Therefore, these parts of the crystal grow out very quickly (yellow arrows). Eventually, the whole surface consists of smooth, stable faces, where new atoms cannot as easily attach themselves.

Crystals are commonly recognized by their shape, consisting of flat faces with sharp angles. These shape characteristics are not necessary for a crystal—a crystal is scientifically defined by its microscopic atomic arrangement, not its macroscopic shape—but the characteristic macroscopic shape is often present and easy to see.

Euhedral crystals are those with obvious, well-formed flat faces. Anhedral crystals do not, usually because the crystal is one grain in a polycrystalline solid.

The flat faces (also called facets) of a euhedral crystal are oriented in a specific way relative to the underlying atomic arrangement of the crystal: they are planes of relatively low Miller index. [9] This occurs because some surface orientations are more stable than others (lower surface energy). As a crystal grows, new atoms attach easily to the rougher and less stable parts of the surface, but less easily to the flat, stable surfaces. Therefore, the flat surfaces tend to grow larger and smoother, until the whole crystal surface consists of these plane surfaces. (See diagram on right.)

One of the oldest techniques in the science of crystallography consists of measuring the three-dimensional orientations of the faces of a crystal, and using them to infer the underlying crystal symmetry.

A crystal's habit is its visible external shape. This is determined by the crystal structure (which restricts the possible facet orientations), the specific crystal chemistry and bonding (which may favor some facet types over others), and the conditions under which the crystal formed.

Occurrence in nature

Ice crystals Ice crystals.jpg
Ice crystals
Fossil shell with calcite crystals CalciteEchinosphaerites.jpg
Fossil shell with calcite crystals

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). [10]

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. [11]

Other rock crystals have formed out of precipitation from fluids, commonly water, to form druses or quartz veins. Evaporites such as Halite (mineral), 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. [12] A single snowflake is a single crystal or a collection of crystals, [13] while an ice cube is a polycrystal. [14]

Organigenic crystals

Many living organisms are able to produce crystals, for example calcite and aragonite in the case of most molluscs or hydroxylapatite in the case of vertebrates.

Polymorphism 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 Ih, but can also exist as the cubic Ice Ic, 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 known 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 wildly different properties. For example, diamond is among the hardest substances known, while graphite is so soft that it is used as a lubricant.

Polyamorphism is a similar phenomenon where the same atoms can exist in more than one amorphous solid form.

Crystallization

Vertical cooling crystallizer in a beet sugar factory. 1-cooling-crystallizer-schladen.JPG
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 thin-film deposition and epitaxy.)

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 meters are found in the Cave of the Crystals in Naica, Mexico. [15] 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

Two types of crystallographic defects.
Top right:
edge dislocation.
Bottom right:
screw dislocation. Vector de Burgers.PNG
Two types of crystallographic defects. Top right: edge dislocation. Bottom right: screw dislocation.

An ideal crystal has every atom in a perfect, exactly repeating pattern. [16] 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.

Twinned pyrite crystal group. Pyrite 60608.jpg
Twinned pyrite crystal group.

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 is supposed to consist 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 are almost always polycrystalline, though there are exceptions like amorphous metal and single-crystal metals. The latter are grown synthetically. (A microscopically-small piece of metal may naturally form into a single crystal, but larger pieces generally do not.) Ionic compound 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. Covalently bonded solids (sometimes called covalent network solids) are also very common, notable examples being diamond and quartz. Weak van der Waals forces also help hold together certain crystals, such as crystalline molecular solids, as well as the interlayer bonding in graphite. Polymer materials generally will form crystalline regions, but the lengths of the molecules usually prevent complete crystallization—and sometimes polymers are completely amorphous.

Quasicrystals

The material holmium-magnesium-zinc (Ho-Mg-Zn) forms quasicrystals, which can take on the macroscopic shape of a pentagonal dodecahedron. Only quasicrystals can take this 5-fold symmetry. The edges are 2 mm long. Ho-Mg-ZnQuasicrystal.jpg
The material holmium–magnesium–zinc (Ho–Mg–Zn) forms quasicrystals, which can take on the macroscopic shape of a pentagonal dodecahedron. Only quasicrystals can take this 5-fold symmetry. The edges are 2 mm long.

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" [17] ).

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. [18] The 2011 Nobel Prize in Chemistry was awarded to Dan Shechtman for the discovery of quasicrystals. [19]

Special properties from anisotropy

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

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.

See also

Related Research Articles

Crystallography scientific study of crystal structure

Crystallography is the experimental science of determining the arrangement of atoms in crystalline solids. The word "crystallography" is derived from the Greek words crystallon "cold drop, frozen drop", with its meaning extending to all solids with some degree of transparency, and graphein "to write". In July 2012, the United Nations recognised the importance of the science of crystallography by proclaiming that 2014 would be the International Year of Crystallography.

Crystallographic defect disruption of the periodicity of a crystal lattice

Crystallographic defects are interruptions of regular patterns in crystalline solids. They are common because positions of atoms or molecules at repeating fixed distances determined by the unit cell parameters in crystals, which exhibit a periodic crystal structure, are usually imperfect.

Materials science Interdisciplinary field which deals with discovery and design of new materials, primarily of physical and chemical properties of solids

The interdisciplinary field of materials science, also commonly termed materials science and engineering, is the design and discovery of new materials, particularly solids. The intellectual origins of materials science stem from the Enlightenment, when researchers began to use analytical thinking from chemistry, physics, and engineering to understand ancient, phenomenological observations in metallurgy and mineralogy. Materials science still incorporates elements of physics, chemistry, and engineering. As such, the field was long considered by academic institutions as a sub-field of these related fields. Beginning in the 1940s, materials science began to be more widely recognized as a specific and distinct field of science and engineering, and major technical universities around the world created dedicated schools for its study.

Mineralogy Scientific study of minerals and mineralised artifacts

Mineralogy is a subject of geology specializing in the scientific study of the chemistry, crystal structure, and physical properties of minerals and mineralized artifacts. Specific studies within mineralogy include the processes of mineral origin and formation, classification of minerals, their geographical distribution, as well as their utilization.

Quasicrystal Chemical structure

A quasiperiodic crystal, or quasicrystal, is a structure that is ordered but not periodic. A quasicrystalline pattern can continuously fill all available space, but it lacks translational symmetry. While crystals, according to the classical crystallographic restriction theorem, can possess only two-, three-, four-, and six-fold rotational symmetries, the Bragg diffraction pattern of quasicrystals shows sharp peaks with other symmetry orders—for instance, five-fold.

X-ray crystallography Technique used in studying crystal structure

X-ray crystallography (XRC) is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional picture of the density of electrons within the crystal. From this electron density, the mean positions of the atoms in the crystal can be determined, as well as their chemical bonds, their crystallographic disorder, and various other information.

Crystal structure Ordered arrangement of atoms, ions, or molecules in a crystalline material

In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns that repeat along the principal directions of three-dimensional space in matter.

Solid-state physics is the study of rigid matter, or solids, through methods such as quantum mechanics, crystallography, electromagnetism, and metallurgy. It is the largest branch of condensed matter physics. Solid-state physics studies how the large-scale properties of solid materials result from their atomic-scale properties. Thus, solid-state physics forms a theoretical basis of materials science. It also has direct applications, for example in the technology of transistors and semiconductors.

Neutron diffraction application of neutron scattering to the determination of the atomic and/or magnetic structure of a material

Neutron diffraction or elastic neutron scattering is the application of neutron scattering to the determination of the atomic and/or magnetic structure of a material. A sample to be examined is placed in a beam of thermal or cold neutrons to obtain a diffraction pattern that provides information of the structure of the material. The technique is similar to X-ray diffraction but due to their different scattering properties, neutrons and X-rays provide complementary information: X-Rays are suited for superficial analysis, strong x-rays from synchrotron radiation are suited for shallow depths or thin specimens, while neutrons having high penetration depth are suited for bulk samples.

Crystallite Tiny crystals which form as materials cool, affecting their physical properties

A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. The orientation of crystallites can be random with no preferred direction, called random texture, or directed, possibly due to growth and processing conditions. Fiber texture is an example of the latter. Crystallites are also referred to as grains. The areas where crystallites meet are known as grain boundaries. Polycrystalline materials, or polycrystals, are solids that are composed of many crystallites of varying size and orientation.

Epitaxy crystal growth process

Epitaxy refers to a type of crystal growth or material deposition in which new crystalline layers are formed with a well-defined orientation with respect to the crystalline substrate. The new layers formed are called the epitaxial film or epitaxial layer. The relative orientation of the epitaxial layer to the crystalline substrate is defined in terms of the orientation of the crystal lattice of each material. For epitaxial growth, the new layer will be crystalline and will all have a single orientation relative to the substrate; amorphous growth or multicrystalline growth with random crystal orientation does not meet this criterion.

In crystallography, a crystallographic point group is a set of symmetry operations, corresponding to one of the point groups in three dimensions, such that each operation would leave the structure of a crystal unchanged i.e. the same kinds of atoms would be placed in similar positions as before the transformation. For example, in a primitive cubic crystal system, a rotation of the unit cell by 90 degree around an axis that is perpendicular to two parallel faces of the cube, intersecting at its center, is a symmetry operation that projects each atom to the location of one of its neighbor leaving the overall structure of the crystal unaffected.

Crystallization process by which a solid forms, where the atoms or molecules are highly organized into a structure

Crystallization or crystallisation is the process by which a solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some of the 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.

Texture (crystalline) crystalline term

In materials science, texture is the distribution of crystallographic orientations of a polycrystalline sample. A sample in which these orientations are fully random is said to have no distinct texture. If the crystallographic orientations are not random, but have some preferred orientation, then the sample has a weak, moderate or strong texture. The degree is dependent on the percentage of crystals having the preferred orientation. Texture is seen in almost all engineered materials, and can have a great influence on materials properties. Also, geologic rocks show texture due to their thermo-mechanic history of formation processes.

Crystallinity refers to the degree of structural order in a solid. In a crystal, the atoms or molecules are arranged in a regular, periodic manner. The degree of crystallinity has a big influence on hardness, density, transparency and diffusion. In an ideal gas, the relative positions of the atoms or molecules are completely random. Amorphous materials, such as liquids and glasses, represent an intermediate case, having order over short distances but not over longer distances.

Single crystal material in which the crystal lattice of the entire sample is continuous and unbroken to the edges of the sample, with no grain boundaries

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. The absence of the defects associated with grain boundaries can give monocrystals unique properties, particularly mechanical, optical and electrical, which can also be anisotropic, depending on the type of crystallographic structure. These properties, in addition to making them precious in some gems, are industrially used in technological applications, especially in optics and electronics.

Selected area diffraction crystallographic experimental technique that can be performed inside a transmission electron microscope

Selected area (electron) diffraction, is a crystallographic experimental technique that can be performed inside a transmission electron microscope (TEM).

A crystallographic database is a database specifically designed to store information about the structure of molecules and crystals. Crystals are solids having, in all three dimensions of space, a regularly repeating arrangement of atoms, ions, or molecules. They are characterized by symmetry, morphology, and directionally dependent physical properties. A crystal structure describes the arrangement of atoms, ions, or molecules in a crystal.

Solid One of the four fundamental states of matter

Solid is one of the four fundamental states of matter. The atoms in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structural rigidity and resistance to a force applied to the surface. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire available volume like a gas. The atoms in a solid are bound to each other, either in a regular geometric lattice, or irregularly. Solids cannot be compressed with little pressure whereas gases can be compressed with little pressure because the molecules in a gas are loosely packed.

Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites. Polymers can crystallize upon cooling from melting, mechanical stretching or solvent evaporation. Crystallization affects optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is estimated by different analytical methods and it typically ranges between 10 and 80%, with crystallized polymers often called "semi-crystalline". The properties of semi-crystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains.

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Further reading