Cristobalite
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Cristobalite is a
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
polymorph of
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is ...
that is formed at very high temperatures. It has the same chemical formula as
quartz Quartz is a hard, crystalline mineral composed of silica ( silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical f ...
, SiO2, but a distinct crystal structure. Both quartz and cristobalite are polymorphs with all the members of the quartz group, which also include
coesite Coesite is a form ( polymorph) of silicon dioxide Si O2 that is formed when very high pressure (2–3 gigapascals), and moderately high temperature (), are applied to quartz. Coesite was first synthesized by Loring Coes Jr., a chemist at the ...
,
tridymite Tridymite is a high-temperature polymorph of silica and usually occurs as minute tabular white or colorless pseudo-hexagonal crystals, or scales, in cavities in felsic volcanic rocks. Its chemical formula is Si O2. Tridymite was first describe ...
and
stishovite Stishovite is an extremely hard, dense tetragonal form ( polymorph) of silicon dioxide. It is very rare on the Earth's surface; however, it may be a predominant form of silicon dioxide in the Earth, especially in the lower mantle. Stishovite ...
. It is named after Cerro San Cristóbal in Pachuca Municipality,
Hidalgo Hidalgo may refer to: People * Hidalgo (nobility), members of the Spanish nobility * Hidalgo (surname) Places Mexico * Hidalgo (state), in central Mexico * Hidalgo, Coahuila, a town in the north Mexican state of Coahuila * Hidalgo, Nuevo Leà ...
,
Mexico Mexico (Spanish language, Spanish: México), officially the United Mexican States, is a List of sovereign states, country in the southern portion of North America. It is borders of Mexico, bordered to the north by the United States; to the so ...
. It is used in dentistry as a component of
alginate Alginic acid, also called algin, is a naturally occurring, edible polysaccharide found in brown algae. It is hydrophilic and forms a viscous gum when hydrated. With metals such as sodium and calcium, its salts are known as alginates. Its colour ...
impression materials as well as for making models of teeth.


Properties


Metastability

Cristobalite is stable only above 1470 Â°C, but can crystallize and persist metastably at lower temperatures. The persistence of cristobalite outside its thermodynamic stability range occurs because the transition from cristobalite to
quartz Quartz is a hard, crystalline mineral composed of silica ( silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical f ...
or
tridymite Tridymite is a high-temperature polymorph of silica and usually occurs as minute tabular white or colorless pseudo-hexagonal crystals, or scales, in cavities in felsic volcanic rocks. Its chemical formula is Si O2. Tridymite was first describe ...
is "reconstructive", requiring the breaking up and reforming of the
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is ...
framework. These frameworks are composed of Si O4
tetrahedra In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all th ...
in which every oxygen atom is shared with a neighbouring tetrahedron, so that the
chemical formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...
of silica is Si O2. The breaking of these bonds, required to convert cristobalite to tridymite and quartz, requires considerable
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules p ...
and may not happen on a human time frame at room temperature. Framework silicates are also known as
tectosilicates Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust. In mineralogy, silica (silicon dioxide, ) is usually co ...
. When devitrifying silica, cristobalite is usually the first phase to form, even when well outside its thermodynamic stability range. This is an example of Ostwald's step rule. The dynamically disordered nature of the β phase is partly responsible for the low enthalpy of fusion of silica.


Structures

There is more than one form of the cristobalite framework. At high temperatures, the structure is called β-cristobalite. It is in the
cubic crystal system In crystallography, the cubic (or isometric) crystal system is a crystal system where the unit cell is in the shape of a cube. This is one of the most common and simplest shapes found in crystals and minerals. There are three main varieties ...
,
space group In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it uncha ...
Fdm (No. 227,
Pearson symbol The Pearson symbol, or Pearson notation, is used in crystallography as a means of describing a crystal structure, and was originated by W. B. Pearson. The symbol is made up of two letters followed by a number. For example: * Diamond structure ...
''cF104''). It has the diamond structure but with linked tetrahedra of silicon and oxygen where the carbon atoms are in diamond. A
chiral Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from i ...
tetragonal In crystallography, the tetragonal crystal system is one of the 7 crystal systems. Tetragonal crystal lattices result from stretching a cubic lattice along one of its lattice vectors, so that the cube becomes a rectangular prism with a squar ...
form called α-cristobalite (space group either P41212, No. 92, or P43212, No. 96, at random) occurs on cooling below about 250 Â°C at ambient pressure and is related to the cubic form by static tilting of the silica tetrahedra in the framework. This transition is variously called the low-high or \alpha\beta transition. It may be termed "displacive"; i.e., it is not generally possible to prevent the cubic β form from becoming tetragonal by rapid cooling. Under rare circumstances the cubic form may be preserved if the crystal grain is pinned in a matrix that does not allow for the considerable spontaneous strain that is involved in the transition, which causes a change in shape of the crystal. This transition is highly discontinuous. Going from the α form to the β form causes an increase in volume of 3 or 4 percent. The exact transition temperature depends on the crystallinity of the cristobalite sample, which itself depends on factors such as how long it has been annealed at a particular temperature. The cubic β phase consists of dynamically disordered silica tetrahedra. The tetrahedra remain fairly regular and are displaced from their ideal static orientations due to the action of a class of low-frequency
phonons In physics, a phonon is a collective excitation in a periodic, elastic arrangement of atoms or molecules in condensed matter, specifically in solids and some liquids. A type of quasiparticle, a phonon is an excited state in the quantum mechanic ...
called rigid unit modes. It is the "freezing" of one of these rigid unit modes that is the soft mode for the α–β transition. In β-cristobalite, there are right-handed and left-handed helices of tetrahedra (or of silicon atoms) parallel to all three axes. In the α–β phase transition, however, only the right-handed or the left-handed helix in one direction is preserved (the other becoming a two-fold screw axis), so only one of the three degenerate cubic crystallographic axes retains a fourfold rotational axis (actually a
screw axis A screw axis (helical axis or twist axis) is a line that is simultaneously the axis of rotation and the line along which translation of a body occurs. Chasles' theorem shows that each Euclidean displacement in three-dimensional space has a scr ...
) in the tetragonal form. (That axis becomes the "c" axis, and the new "a" axes are rotated 45° compared to the other two old axes. The new "a" lattice parameter is shorter by approximately the square root of 2, so the α unit cell contains only 4 silicon atoms rather than 8.) The choice of axis is arbitrary, so that various
twins Twins are two offspring produced by the same pregnancy.MedicineNet > Definition of TwinLast Editorial Review: 19 June 2000 Twins can be either ''monozygotic'' ('identical'), meaning that they develop from one zygote, which splits and forms two em ...
can form within the same grain. These different twin orientations coupled with the discontinuous nature of the transition (volume and slight shape change) can cause considerable mechanical damage to materials in which cristobalite is present and that pass repeatedly through the transition temperature, such as refractory bricks. File:B-cristobal1.png, An idealized model of β-cristobalite, showing corner-bonded Si O4 tetrahedra. There is a right-handed four-fold screw axis at the centre of half the white squares, and a left-handed one at the centre of the others. In this projection we see glide planes parallel to the axes and mirrors on the diagonals. In reality the tetrahedra are constantly wobbling. File:B-cristobal2.png, β-cristobalite viewed along the 101 direction. File:A-cristobal.png, The crumpled framework of α-cristobalite, related to the β form by static tilting of the tetrahedra. This view corresponds to the view along the 101 direction of the previous illustration, except that the "b" axis of that picture is now horizontal. The two-fold screw axes appear here as two-fold axes of rotation going through the middle of the white areas and between the pairs of almost superimposed oxygen atoms. File:Α-Cristobalite.svg, Unit cell of α-cristobalite; red spheres are oxygen atoms. We see here five silicon atoms in a helix (the first and the last are equivalent atoms in the lattice) going in the "c" direction (into the page). The horizontal and vertical axes are the "a" axes. File:Β-Cristobalite.svg, Unit cell of β-cristobalite; red spheres are oxygen atoms.


Occurrence

Cristobalite occurs as white octahedra or
spherulite In petrology, spherulites () are small, rounded bodies that commonly occur in vitreous igneous rocks. They are often visible in specimens of obsidian, pitchstone, and rhyolite as globules about the size of millet seed or rice grain, with a dul ...
s in acidic volcanic rocks and in converted diatomaceous deposits in the
Monterey Formation The Monterey Formation is an extensive Miocene oil-rich geological sedimentary formation in California, with outcrops of the formation in parts of the California Coast Ranges, Peninsular Ranges, and on some of California's off-shore isla ...
of the US state of California and similar areas. The micrometre-scale spheres that make up precious
opal Opal is a hydrated amorphous form of silica (SiO2·''n''H2O); its water content may range from 3 to 21% by weight, but is usually between 6 and 10%. Due to its amorphous property, it is classified as a mineraloid, unlike crystalline form ...
exhibit some X-ray diffraction patterns that are similar to that of cristobalite, but lack any long-range order so they are not considered true cristobalite. In addition, the presence of structural water in opal makes it doubtful that opal consists of cristobalite.


References


Further reading

* ''American Geological Institute Dictionary of Geological Terms''. * Durham, D. L., "Monterey Formation: Diagenesis". in: ''Uranium in the Monterey Formation of California''. US Geological Survey Bulletin 1581-A, 1987. * ''Reviews in Mineralogy and Geochemistry'', vol. 29., ''Silica: behavior, geochemistry and physical applications''. Mineralogical Society of America, 1994. * R. B. Sosman, ''The Phases of Silica''. (Rutgers University Press, 1965)


External links

* {{Silica minerals Polymorphism (materials science) Tetragonal minerals Minerals in space group 92 Minerals in space group 96 Silica polymorphs Silicon compounds Silicon dioxide Minerals in space group 227