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Quartz
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| Quartz | |
|---|---|
Quartz crystal cluster from Brazil | |
| General | |
| Category | Tectosilicate minerals, quartz group |
| Formula | SiO2 |
| IMA symbol | Qz[1] |
| Strunz classification | 4.DA.05 (oxides) |
| Dana classification | 75.01.03.01 (tectosilicates) |
| Crystal system | α-quartz: trigonal β-quartz: hexagonal |
| Crystal class | α-quartz: trapezohedral (class 3 2) β-quartz: trapezohedral (class 6 2 2)[2] |
| Space group | α-quartz: P3221 (no. 154)[3] β-quartz: P6222 (no. 180) or P6422 (no. 181)[4] |
| Unit cell | a = 4.9133 Å, c = 5.4053 Å; Z = 3 |
| Identification | |
| Formula mass | 60.083 g·mol−1 |
| Color | Colorless, pink, orange, white, green, yellow, blue, purple, dark brown, or black |
| Crystal habit | 6-sided prism ending in 6-sided pyramid (typical), drusy, fine-grained to microcrystalline, massive |
| Twinning | Common Dauphine law, Brazil law, and Japan law |
| Cleavage | none[5] |
| Fracture | Conchoidal |
| Tenacity | Brittle |
| Mohs scale hardness | 7 – lower in impure varieties (defining mineral) |
| Luster | Vitreous – waxy to dull when massive |
| Streak | White |
| Diaphaneity | Transparent to nearly opaque |
| Specific gravity | 2.65; variable 2.59–2.63 in impure varieties |
| Optical properties | Uniaxial (+) |
| Refractive index | nω = 1.543–1.545 nε = 1.552–1.554 |
| Birefringence | +0.009 (B-G interval) |
| Pleochroism | None |
| Melting point | 1670 °C (β tridymite); 1713 °C (β cristobalite)[2] |
| Solubility | Insoluble at STP; 1 ppmmass at 400 °C and 500 lb/in2 to 2600 ppmmass at 500 °C and 1500 lb/in2[2] |
| Other characteristics | Lattice: hexagonal, piezoelectric, may be triboluminescent, chiral (hence optically active if not racemic) |
| References | [6][7][8][9] |
Quartz is a hard 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 formula of SiO2. Quartz is, therefore, classified structurally as a framework silicate mineral and compositionally as an oxide mineral. Quartz is the second most abundant of the minerals and mineral groups that compose the Earth's lithosphere, with the feldspars making up 41% of the lithosphere by weight, followed by quartz making up 12%, and the pyroxenes at 11%.[10]
Quartz exists in two forms, the normal α-quartz and the high-temperature β-quartz, both of which are chiral. The transformation from α-quartz to β-quartz takes place abruptly at 573 °C (846 K; 1,063 °F). Since the transformation is accompanied by a significant change in volume, it can easily induce microfracturing of ceramics or rocks passing through this temperature threshold.
There are many different varieties of quartz, several of which are classified as gemstones. Since antiquity, varieties of quartz have been the most commonly used minerals in the making of jewelry and hardstone carvings, especially in Europe and Asia.
Quartz is the mineral defining the value of 7 on the Mohs scale of hardness, a qualitative scratch method for determining the hardness of a material to abrasion.
Etymology
[edit]The word "quartz" is derived from the German word Quarz,[11] which had the same form in the first half of the 14th century in Middle High German and in East Central German[12] and which came from the Polish dialect term kwardy, which corresponds to the Czech term tvrdý ("hard").[13] Some sources, however, attribute the word's origin to the Saxon word Querkluftertz, meaning cross-vein ore.[14][15]
The Ancient Greeks referred to quartz as κρύσταλλος (krustallos) derived from the Ancient Greek κρύος (kruos) meaning "icy cold", because some philosophers (including Theophrastus) believed the mineral to be a form of supercooled ice.[15] Today, the term rock crystal is sometimes used as an alternative name for transparent coarsely crystalline quartz.[16][17]: 205
Early studies
[edit]Roman naturalist Pliny the Elder believed quartz to be water ice, permanently frozen after great lengths of time.[18] He supported this idea by saying that quartz is found near glaciers in the Alps, but not on volcanic mountains, and that large quartz crystals were fashioned into spheres to cool the hands. This idea persisted until at least the 17th century. He also knew of the ability of quartz to split light into a spectrum.[19]
In the 17th century, Nicolas Steno's study of quartz paved the way for modern crystallography. He discovered that regardless of a quartz crystal's size or shape, its long prism faces always joined at a perfect 60° angle, thus discovering the law of constancy of interfacial angles.[20]
Crystal habit and structure
[edit]Quartz belongs to the trigonal crystal system at room temperature, and to the hexagonal crystal system above 573 °C (846 K; 1,063 °F). The former is called α-quartz; the latter is β-quartz. The ideal crystal shape is a six-sided prism terminating with six-sided pyramid-like rhombohedrons at each end. In nature, quartz crystals are often twinned (with twin right-handed and left-handed quartz crystals), distorted, or so intergrown with adjacent crystals of quartz or other minerals as to only show part of this shape, or to lack obvious crystal faces altogether and appear massive.[9][17]: 202–204
Well-formed crystals typically form as a druse (a layer of crystals lining a void), of which quartz geodes are particularly fine examples.[21] The crystals are attached at one end to the enclosing rock, and only one termination pyramid is present. However, doubly terminated crystals do occur where they develop freely without attachment, for instance, within gypsum.[22]
α-quartz crystallizes in the trigonal crystal system, space group P3121 or P3221 (space group 152 or 154 resp.) depending on the chirality. Above 573 °C (846 K; 1,063 °F), α-quartz in P3121 becomes the more symmetric hexagonal P6422 (space group 181), and α-quartz in P3221 goes to space group P6222 (no. 180).[23]
These space groups are truly chiral (they each belong to the 11 enantiomorphous pairs). Both α-quartz and β-quartz are examples of chiral crystal structures composed of achiral building blocks (SiO4 tetrahedra in the present case). The transformation between α- and β-quartz only involves a comparatively minor rotation of the tetrahedra with respect to one another, without a change in the way they are linked.[9][17]: 201 However, there is a significant change in volume during this transition,[24] and this can result in significant microfracturing in ceramics during firing,[25] in ornamental stone after a fire[26] and in rocks of the Earth's crust exposed to high temperatures,[27] thereby damaging materials containing quartz and degrading their physical and mechanical properties.
-
Common, prismatic quartz
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Sceptered quartz
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Sceptered quartz (as aggregates: "Elestial quartz")
-
Bipyramidal quartz
-
Tessin or tapered quartz
-
Twinned quartz (known as Japan law)
-
Dauphine quartz (single dominant face)
-
Druse quartz
-
Granular quartz
-
Massive quartz
Varieties (according to microstructure)
[edit]Although many of the varietal names historically arose from the color of the mineral, current scientific naming schemes refer primarily to the microstructure of the mineral. Color is a secondary identifier for the cryptocrystalline minerals, although it is a primary identifier for the macrocrystalline varieties.[28]
The most important microstructure difference between types of quartz is that of macrocrystalline quartz (individual crystals visible to the unaided eye) and the microcrystalline or cryptocrystalline varieties (aggregates of crystals visible only under high magnification). The cryptocrystalline varieties are either translucent or mostly opaque, while the macrocrystalline varieties tend to be more transparent. Chalcedony is a cryptocrystalline form of silica consisting of fine intergrowths of both quartz, and its monoclinic polymorph moganite.[29] Agate is a variety of chalcedony that is fibrous and distinctly banded with either concentric or horizontal bands.[30] While most agates are translucent, onyx is a variety of agate that is more opaque, featuring monochromatic bands that are typically black and white.[31] Carnelian or sard is a red-orange, translucent variety of chalcedony. Jasper is an opaque chert or impure chalcedony.[32]
| Type | Color and description | Transparency | Microstructure |
|---|---|---|---|
| Rock crystal | Colorless | Transparent | Macrocrystalline |
| Amethyst | Purple to violet colored quartz | Transparent | Macrocrystalline |
| Citrine | Yellow quartz ranging to reddish-orange or brown (Madeira citrine), and occasionally greenish yellow | Transparent | Macrocrystalline |
| Rose quartz | Pink, may display diasterism | Transparent | Macrocrystalline |
| Chalcedony | Fibrous, occurs in many varieties. The term is often used for white, cloudy, or lightly colored material intergrown with moganite. Otherwise more specific names are used. |
Translucent to opaque | Cryptocrystalline |
| Carnelian | Reddish orange chalcedony | Translucent | Cryptocrystalline |
| Aventurine | Quartz with tiny aligned inclusions (usually mica) that shimmer with aventurescence | Translucent to opaque | Macrocrystalline |
| Agate | Multi-colored, concentric or horizontal banded chalcedony | Semi-translucent to translucent | Cryptocrystalline |
| Onyx | Typically black-and-white-banded or monochromatic agate | Semi-translucent to opaque | Cryptocrystalline |
| Jasper | Impure chalcedony or chert, typically red to brown but the name is often used for other colors | Opaque | Cryptocrystalline or Microcrystalline |
| Milky quartz | White, may display diasterism | Translucent to opaque | Macrocrystalline |
| Smoky quartz | Light to dark gray, sometimes with a brownish hue | Translucent to opaque | Macrocrystalline |
| Tiger's eye | Fibrous gold, red-brown or bluish colored chalcedony, exhibiting chatoyancy. | Opaque | Cryptocrystalline |
| Prasiolite | Green | Transparent | Macrocrystalline |
| Rutilated quartz | Contains acicular (needle-like) inclusions of rutile | Transparent to translucent | Macrocrystalline |
| Dumortierite quartz | Contains large amounts of blue dumortierite crystals | Translucent | Macrocrystalline |
Varieties (according to color)
[edit]
Pure quartz, traditionally called rock crystal or clear quartz, is colorless and transparent or translucent and has often been used for hardstone carvings, such as the Lothair Crystal. Common colored varieties include citrine, rose quartz, amethyst, smoky quartz, milky quartz, and others.[33] These color differentiations arise from the presence of impurities which change the molecular orbitals, causing some electronic transitions to take place in the visible spectrum causing colors.
Amethyst
[edit]Amethyst is a form of quartz that ranges from a bright vivid violet to a dark or dull lavender shade. The world's largest deposits of amethysts can be found in Brazil, Mexico, Uruguay, Russia, France, Namibia, and Morocco. Amethyst derives its color from traces of iron in its structure.[34]
Ametrine
[edit]Ametrine, as its name suggests, is commonly believed to be a combination of citrine and amethyst in the same crystal; however, this may not be technically correct. Like amethyst, the yellow quartz component of ametrine is colored by iron oxide inclusions. Some, but not all, sources define citrine solely as quartz with its color originating from aluminum-based color centers.[35][36] Other sources do not make this distinction.[37] In the former case, the yellow quartz in ametrine is not considered true citrine. Regardless, most ametrine on the market is in fact partially heat- or radiation-treated amethyst.[37]
Blue quartz
[edit]Blue quartz contains inclusions of fibrous magnesio-riebeckite or crocidolite.[38]
Dumortierite quartz
[edit]Inclusions of the mineral dumortierite within quartz pieces often result in silky-appearing splotches with a blue hue. Shades of purple or gray sometimes also are present. "Dumortierite quartz" (sometimes called "blue quartz") will sometimes feature contrasting light and dark color zones across the material.[39][40] "Blue quartz" is a minor gemstone.[39][41]
Citrine
[edit]Citrine is a transparent, yellow variety of quartz. The cause of its color is not well agreed upon. Evidence suggests the color of citrine is linked to the presence of aluminum-based color centers in its crystal structure, similar to those of smoky quartz.[35] Alternatively, it has been suggested that the color of citrine may be due to trace amounts of iron.[42]
Natural citrine is rare; most commercial citrine is heat-treated amethyst or smoky quartz. Heat-treated amethyst is often a darker yellow or even brown, and consequently it is sometimes called "burnt amethyst".[43] Unlike natural citrine, the color of heat-treated amethyst comes from trace amounts of the iron oxide minerals hematite and goethite. Clear quartz with natural iron inclusions or limonite staining may also be mistaken for citrine.[35] Brazil is the leading producer of citrine, with much of its production coming from the state of Rio Grande do Sul.[42]
Milky quartz
[edit]Milk quartz or milky quartz is the most common variety of crystalline quartz. The white color is caused by minute fluid inclusions of gas, liquid, or both, trapped during crystal formation,[44] making it of little value for optical and quality gemstone applications.[45]
Rose quartz
[edit]Rose quartz is a type of quartz that exhibits a pale pink to rose red hue. The color is usually considered as due to trace amounts of titanium, iron, or manganese in the material. Some rose quartz contains microscopic rutile needles that produce asterism in transmitted light. Recent X-ray diffraction studies suggest that the color is due to thin microscopic fibers of possibly dumortierite within the quartz.[46]
Additionally, there is a rare type of pink quartz (also frequently called crystalline rose quartz) with color that is thought to be caused by trace amounts of phosphate or aluminium. The color in crystals is apparently photosensitive and subject to fading. The first crystals were found in a pegmatite found near Rumford, Maine, US, and in Minas Gerais, Brazil.[47] The crystals found are more transparent and euhedral, due to the impurities of phosphate and aluminium that formed crystalline rose quartz, unlike the iron and microscopic dumortierite fibers that formed rose quartz.[48]
Smoky quartz
[edit]Smoky quartz is a gray, translucent version of quartz. It ranges in clarity from almost complete transparency to a brownish-gray crystal that is almost opaque. Some can also be black. The translucency results from natural irradiation acting on minute traces of aluminum in the crystal structure.[49]
Prase
[edit]Prase is a leek-green variety of quartz that gets its color from inclusions of the amphibole actinolite.[50][51] However, the term has also variously been used for a type of quartzite, a microcrystalline variety of quartz or jasper, or any leek-green quartz.[51]
Prasiolite
[edit]Prasiolite, also known as vermarine, is a variety of quartz that is green in color.[52] The green is caused by iron ions.[50] It is a rare variety in nature and is typically found with amethyst; most "prasiolite" is not natural – it has been artificially produced by heating of amethyst.[52] Since 1950, almost all natural prasiolite has come from a small Brazilian mine, but it is also seen in Lower Silesia in Poland.[citation needed] Naturally occurring prasiolite is also found in the Thunder Bay area of Canada.[52]
Piezoelectricity
[edit]Quartz crystals have piezoelectric properties; they develop an electric potential upon the application of mechanical stress.[53] Quartz's piezoelectric properties were discovered by Jacques and Pierre Curie in 1880.[54][55]
Occurrence
[edit]
Quartz is a defining constituent of granite and other felsic igneous rocks. It is very common in sedimentary rocks such as sandstone and shale. It is a common constituent of schist, gneiss, quartzite and other metamorphic rocks.[9] Quartz has the lowest potential for weathering in the Goldich dissolution series and consequently it is very common as a residual mineral in stream sediments and residual soils. Generally a high presence of quartz suggests a "mature" rock, since it indicates the rock has been heavily reworked and quartz was the primary mineral that endured heavy weathering.[56]
While the majority of quartz crystallizes from molten magma, quartz also chemically precipitates from hot hydrothermal veins as gangue, sometimes with ore minerals such as gold, silver and copper. Large crystals of quartz are found in magmatic pegmatites.[9] Well-formed crystals may reach several meters in length and weigh hundreds of kilograms.[57]
The largest documented single crystal of quartz was found near Itapore, Goiaz, Brazil; it measured approximately 6.1 m × 1.5 m × 1.5 m (20 ft × 5 ft × 5 ft) and weighed over 39,900 kg (88,000 lb).[58]
Mining
[edit]Quartz is extracted from open pit mines. Miners occasionally use explosives to expose deep pockets of quartz. More frequently, bulldozers and backhoes are used to remove soil and clay and expose quartz veins, which are then worked using hand tools. Care must be taken to avoid sudden temperature changes that may damage the crystals.[59][60]
Related silica minerals
[edit]
Tridymite and cristobalite are high-temperature polymorphs of SiO2 that occur in high-silica volcanic rocks. Coesite is a denser polymorph of SiO2 found in some meteorite impact sites and in metamorphic rocks formed at pressures greater than those typical of the Earth's crust. Stishovite is a yet denser and higher-pressure polymorph of SiO2 found in some meteorite impact sites.[17]: 201–202 Moganite is a monoclinic polymorph. Lechatelierite is an amorphous silica glass SiO2 which is formed by lightning strikes in quartz sand.[62]
Safety
[edit]As quartz is a form of silica, it is a possible cause for concern in various workplaces. Cutting, grinding, chipping, sanding, drilling, and polishing natural and manufactured stone products can release hazardous levels of very small, crystalline silica dust particles into the air that workers breathe.[63] Crystalline silica of respirable size is a recognized human carcinogen and may lead to other diseases of the lungs such as silicosis and pulmonary fibrosis.[64][65]
Synthetic and artificial treatments
[edit]
Not all varieties of quartz are naturally occurring. Some clear quartz crystals can be treated using heat or gamma-irradiation to induce color where it would not otherwise have occurred naturally. Susceptibility to such treatments depends on the location from which the quartz was mined.[66]
Prasiolite, an olive colored material, is produced by heat treatment;[67] natural prasiolite has also been observed in Lower Silesia in Poland.[68] Although citrine occurs naturally, the majority is the result of heat-treating amethyst or smoky quartz.[67] Carnelian has been heat-treated to deepen its color since prehistoric times.[69]
Because natural quartz is often twinned, synthetic quartz is produced for use in industry. Large, flawless, single crystals are synthesized in an autoclave via the hydrothermal process.[70][9][71]
Like other crystals, quartz may be coated with metal vapors to give it an attractive sheen.[72][73]
Uses
[edit]Quartz is the most common material identified as the mystical substance maban in Australian Aboriginal mythology. It is found regularly in passage tomb cemeteries in Europe in a burial context, such as Newgrange or Carrowmore in Ireland. Quartz was also used in Prehistoric Ireland, as well as many other countries, for stone tools; both vein quartz and rock crystal were knapped as part of the lithic technology of the prehistoric peoples.[74]
While jade has been since earliest times the most prized semi-precious stone for carving in East Asia and Pre-Columbian America, in Europe and the Middle East the different varieties of quartz were the most commonly used for the various types of jewelry and hardstone carving, including engraved gems and cameo gems, rock crystal vases, and extravagant vessels. The tradition continued to produce objects that were very highly valued until the mid-19th century, when it largely fell from fashion except in jewelry. Cameo technique exploits the bands of color in onyx and other varieties.
Efforts to synthesize quartz began in the mid-nineteenth century as scientists attempted to create minerals under laboratory conditions that mimicked the conditions in which the minerals formed in nature: German geologist Karl Emil von Schafhäutl (1803–1890) was the first person to synthesize quartz when in 1845 he created microscopic quartz crystals in a pressure cooker.[75] However, the quality and size of the crystals that were produced by these early efforts were poor.[76]
Elemental impurity incorporation strongly influences the ability to process and utilize quartz. Naturally occurring quartz crystals of extremely high purity, necessary for the crucibles and other equipment used for growing perfect large silicon boules to be sliced into silicon wafers in the semiconductor industry, are expensive and rare. These high-purity quartz are defined as containing less than 50 ppm of impurity elements.[77] A major mining location for high purity quartz is the Spruce Pine Mining District in Spruce Pine, North Carolina, United States.[78] Quartz may also be found in Caldoveiro Peak, in Asturias, Spain.[79]
By the 1930s, the electronics industry had become dependent on quartz crystals. The only source of suitable crystals was Brazil; however, World War II disrupted the supplies from Brazil, so nations attempted to synthesize quartz on a commercial scale. German mineralogist Richard Nacken (1884–1971) achieved some success during the 1930s and 1940s.[80] After the war, many laboratories attempted to grow large quartz crystals. In the United States, the U.S. Army Signal Corps contracted with Bell Laboratories and with the Brush Development Company of Cleveland, Ohio to synthesize crystals following Nacken's lead.[81][82] (Prior to World War II, Brush Development produced piezoelectric crystals for record players.) By 1948, Brush Development had grown crystals that were 1.5 inches (3.8 cm) in diameter, the largest at that time.[83][84] By the 1950s, hydrothermal synthesis techniques were producing synthetic quartz crystals on an industrial scale, and today virtually all the quartz crystal used in the modern electronics industry is synthetic.[71]
An early use of the piezoelectricity of quartz crystals was in phonograph pickups. One of the most common piezoelectric uses of quartz today is as a crystal oscillator. Also called a quartz oscillator or resonator, it was first developed by Walter Guyton Cady in 1921.[85][86] George Washington Pierce designed and patented quartz crystal oscillators in 1923.[87][88][89] The quartz clock is a familiar device using the mineral; it is simply a clock that uses a quartz oscillator as its time reference. Warren Marrison created the first quartz oscillator clock based on the work of Cady and Pierce in 1927.[90] The resonant frequency of a quartz crystal oscillator is changed by mechanically loading it, and this principle is used for very accurate measurements of very small mass changes in the quartz crystal microbalance and in thin-film thickness monitors.[91]
-
Rock crystal jug with cut festoon decoration by Milan workshop from the second half of the 16th century, National Museum in Warsaw. The city of Milan, apart from Prague and Florence, was the main Renaissance centre for crystal cutting.[92]
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Synthetic quartz crystals produced in the autoclave shown in Western Electric's pilot hydrothermal quartz plant in 1959
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Fatimid ewer in carved rock crystal (clear quartz) with gold lid, c. 1000
Almost all the industrial demand for quartz crystal (used primarily in electronics) is met with synthetic quartz produced by the hydrothermal process. However, synthetic crystals are less prized for use as gemstones.[93] The popularity of crystal healing has increased the demand for natural quartz crystals, which are now often mined in developing countries using primitive mining methods, sometimes involving child labor.[94]
See also
[edit]References
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- ^ Curie, Jacques; Curie, Pierre (1880). "Développement par compression de l'électricité polaire dans les cristaux hémièdres à faces inclinées" [Development, via compression, of electric polarization in hemihedral crystals with inclined faces]. Bulletin de la Société minéralogique de France. 3 (4): 90–93. doi:10.3406/bulmi.1880.1564.. Reprinted in: Curie, Jacques; Curie, Pierre (1880). "Développement, par pression, de l'électricité polaire dans les cristaux hémièdres à faces inclinées". Comptes rendus. 91: 294–295. Archived from the original on 5 December 2012. Retrieved 17 December 2013.
- ^ Curie, Jacques; Curie, Pierre (1880). "Sur l'électricité polaire dans les cristaux hémièdres à faces inclinées" [On electric polarization in hemihedral crystals with inclined faces]. Comptes rendus. 91: 383–386. Archived from the original on 5 December 2012. Retrieved 17 December 2013.
- ^ Boggs, Sam (2006). Principles of sedimentology and stratigraphy (4th ed.). Upper Saddle River, N.J.: Pearson Prentice Hall. p. 130. ISBN 0131547283.
- ^ Jahns, Richard H. (1953). "The genesis of pegmatites: I. Occurrence and origin of giant crystals". American Mineralogist. 38 (7–8): 563–598. Retrieved 7 April 2021.
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- ^ Arsenic, Metals, Fibres and Dusts. A Review of Human Carcinogens (PDF) (100C ed.). International Agency for Research on Cancer. 2012. pp. 355–397. ISBN 978-92-832-1320-8. Retrieved 27 November 2019.
- ^ Liccini, Mark, Treating Quartz to Create Color Archived 23 December 2014 at the Wayback Machine, International Gem Society website. Retrieved 22 December 2014
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- ^ Platonov, Alexej N.; Szuszkiewicz, Adam (1 June 2015). "Green to blue-green quartz from Rakowice Wielkie (Sudetes, south-western Poland) – a re-examination of prasiolite-related color varieties of quartz". Mineralogia. 46 (1–2): 19–28. Bibcode:2015Miner..46...19P. doi:10.1515/mipo-2016-0004.
- ^ Groman-Yaroslavski, Iris; Bar-Yosef Mayer, Daniella E. (June 2015). "Lapidary technology revealed by functional analysis of carnelian beads from the early Neolithic site of Nahal Hemar Cave, southern Levant". Journal of Archaeological Science. 58: 77–88. Bibcode:2015JArSc..58...77G. doi:10.1016/j.jas.2015.03.030.
- ^ Walker, A. C. (August 1953). "Hydrothermal Synthesis of Quartz Crystals". Journal of the American Ceramic Society. 36 (8): 250–256. doi:10.1111/j.1151-2916.1953.tb12877.x.
- ^ a b Buisson, X.; Arnaud, R. (February 1994). "Hydrothermal growth of quartz crystals in industry. Present status and evolution" (PDF). Le Journal de Physique IV. 04 (C2): C2–25–C2-32. doi:10.1051/jp4:1994204. S2CID 9636198.
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- ^ von Schafhäutl, Karl Emil (10 April 1845). "Die neuesten geologischen Hypothesen und ihr Verhältniß zur Naturwissenschaft überhaupt (Fortsetzung)" [The latest geological hypotheses and their relation to science in general (continuation)]. Gelehrte Anzeigen. 20 (72). München: im Verlage der königlichen Akademie der Wissenschaften, in Commission der Franz'schen Buchhandlung: 577–584. OCLC 1478717. From page 578: 5) Bildeten sich aus Wasser, in welchen ich im Papinianischen Topfe frisch gefällte Kieselsäure aufgelöst hatte, beym Verdampfen schon nach 8 Tagen Krystalle, die zwar mikroscopisch, aber sehr wohl erkenntlich aus sechseitigen Prismen mit derselben gewöhnlichen Pyramide bestanden. ( 5) There formed from water in which I had dissolved freshly precipitated silicic acid in a Papin pot [i.e., pressure cooker], after just 8 days of evaporating, crystals, which albeit were microscopic but consisted of very easily recognizable six-sided prisms with their usual pyramids.)
- ^ Byrappa, K. and Yoshimura, Masahiro (2001) Handbook of Hydrothermal Technology. Norwich, New York: Noyes Publications. ISBN 008094681X. Chapter 2: History of Hydrothermal Technology.
- ^ Götze, Jens; Pan, Yuanming; Müller, Axel (October 2021). "Mineralogy and mineral chemistry of quartz: A review". Mineralogical Magazine. 85 (5): 639–664. Bibcode:2021MinM...85..639G. doi:10.1180/mgm.2021.72. ISSN 0026-461X. S2CID 243849577.
- ^ Nelson, Sue (2 August 2009). "Silicon Valley's secret recipe". BBC News. Archived from the original on 5 August 2009. Retrieved 16 September 2009.
- ^ "Caldoveiro Mine, Tameza, Asturias, Spain". mindat.org. Archived from the original on 12 February 2018. Retrieved 15 February 2018.
- ^ Nacken, R. (1950) "Hydrothermal Synthese als Grundlage für Züchtung von Quarz-Kristallen" (Hydrothermal synthesis as a basis for the production of quartz crystals), Chemiker Zeitung, 74 : 745–749.
- ^ Hale, D. R. (1948). "The Laboratory Growing of Quartz". Science. 107 (2781): 393–394. Bibcode:1948Sci...107..393H. doi:10.1126/science.107.2781.393. PMID 17783928.
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- ^ Brush Development's team of scientists included: Danforth R. Hale, Andrew R. Sobek, and Charles Baldwin Sawyer (1895–1964). The company's U.S. patents included:
- Sobek, Andrew R. "Apparatus for growing single crystals of quartz", U.S. patent 2,674,520; filed: 11 April 1950; issued: 6 April 1954.
- Sobek, Andrew R. and Hale, Danforth R. "Method and apparatus for growing single crystals of quartz", U.S. patent 2,675,303; filed: 11 April 1950; issued: 13 April 1954.
- Sawyer, Charles B. "Production of artificial crystals", U.S. patent 3,013,867; filed: 27 March 1959; issued: 19 December 1961. (This patent was assigned to Sawyer Research Products of Eastlake, Ohio.)
- ^ Cady, W. G. (1921). "The piezoelectric resonator". Physical Review. 17: 531–533. doi:10.1103/PhysRev.17.508.
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- ^ Pierce, G. W. (1923). "Piezoelectric crystal resonators and crystal oscillators applied to the precision calibration of wavemeters". Proceedings of the American Academy of Arts and Sciences. 59 (4): 81–106. doi:10.2307/20026061. hdl:2027/inu.30000089308260. JSTOR 20026061.
- ^ Pierce, George W. "Electrical system", U.S. patent 2,133,642, filed: 25 February 1924; issued: 18 October 1938.
- ^ "The Quartz Watch – George Washington Pierce". The Lemelson Center, National Museum of American History, Smithsonian Institution. Archived from the original on 4 January 2009.
- ^ "The Quartz Watch – Warren Marrison". The Lemelson Center, National Museum of American History, Smithsonian Institution. Archived from the original on 25 January 2009.
- ^ Sauerbrey, Günter Hans (April 1959) [1959-02-21]. "Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung" (PDF). Zeitschrift für Physik (in German). 155 (2). Springer-Verlag: 206–222. Bibcode:1959ZPhy..155..206S. doi:10.1007/BF01337937. ISSN 0044-3328. S2CID 122855173. Archived (PDF) from the original on 26 February 2019. Retrieved 26 February 2019. (NB. This was partially presented at Physikertagung in Heidelberg in October 1957.)
- ^ The International Antiques Yearbook. Studio Vista Limited. 1972. p. 78.
Apart from Prague and Florence, the main Renaissance centre for crystal cutting was Milan.
- ^ "Hydrothermal Quartz". Gem Select. GemSelect.com. Retrieved 28 November 2020.
- ^ McClure, Tess (17 September 2019). "Dark crystals: the brutal reality behind a booming wellness craze". The Guardian. ISSN 0261-3077. Retrieved 25 September 2019.
External links
[edit]- Quartz varieties, properties, crystal morphology. Photos and illustrations
- Gilbert Hart, "Nomenclature of Silica", American Mineralogist, Volume 12, pp. 383–395. 1927
- "The Quartz Watch – Inventors". The Lemelson Center, National Museum of American History, Smithsonian Institution. Archived from the original on 7 January 2009.
- Terminology used to describe the characteristics of quartz crystals when used as oscillators
- Quartz use as prehistoric stone tool raw material
Quartz
View on GrokipediaHistory and Etymology
Etymology
The term "quartz" derives from the German word Quarz, first attested in printed sources in the early 16th century, which itself originates from Middle High German quarc or twarc, borrowed from West Slavic languages such as Polish twardy or Czech tvrdý, ultimately from Proto-Slavic *tvrdъ meaning "hard."[7][8] This etymology reflects the mineral's notable hardness, rated at 7 on the Mohs scale, distinguishing it from softer rocks encountered in mining contexts.[4] In historical usage, the Latin form quartzum appears in the works of the German scholar Georgius Agricola (1494–1555), who employed it in his 1530 treatise Bermannus and subsequent writings on mining and minerals, latinizing a Central European vernacular term to describe hard, vein-filling silica deposits.[9] Agricola's adoption helped standardize the nomenclature amid the era's burgeoning mineralogical studies, though he also used terms like crystallum and silicum interchangeably for similar materials.[4] Ancient Greek references to quartz-like minerals predate this Germanic-Slavic lineage, with clear varieties known as krystallos (κρύσταλλος), meaning "ice," due to their transparency and the belief that they were eternally frozen water formed by the gods.[10] This term influenced the modern word "crystal" and underscores early misconceptions about the mineral's nature in classical antiquity. From the 17th century onward, the terminology evolved in European mineralogy as scholars built on Agricola's classifications, refining "quartz" to encompass a broader range of silica polymorphs while distinguishing it from other gemstones and ores, a process that connected linguistic roots to systematic scientific description in early geological texts.[9]Early Studies
Ancient civilizations recognized quartz, particularly in its transparent form known as rock crystal, for both practical and ornamental purposes. In ancient Egypt, quartz was utilized from the Predynastic period through the Ptolemaic era, primarily as rock crystal for crafting beads, cosmetic vessels, and amulets, with its availability sourced from the Eastern Desert.[11] Additionally, crushed quartz sand served as an abrasive in stone-working tools, facilitating the shaping of harder materials like granite and diorite during the New Kingdom, as evidenced by residue in drill holes from sites such as Amarna.[12] The Greeks, through Theophrastus in his treatise On Stones (c. 315 BCE), described rock crystal as a form of ice eternally frozen by extreme cold, marking an early observational classification that influenced later natural histories.[13] Romans extended these uses, fashioning rock crystal into luxury vessels, jewelry, and even polyhedral dice for gaming or divination, valuing its clarity and perceived purity as hardened ice, with examples like undecorated ewers highlighting its aesthetic appeal in imperial artifacts.[14] During the Renaissance, systematic documentation of quartz advanced through scholarly compilations and empirical testing. Conrad Gesner, in his 1565 work De Rerum Fossilium, Lapidum et Gemmarum, provided one of the earliest illustrated descriptions of minerals and gems, including rock crystal as a distinct variety, emphasizing its forms and similarities to other fossils to aid naturalists and physicians in identification.[15] In the 17th century, Robert Boyle contributed experimental insights into mineral properties, including quartz's notable hardness, through assays detailed in his 1672 An Essay about the Origine & Virtues of Gems, where he tested durability against other substances and refuted ancient myths of its icy origin by demonstrating its resistance to melting and chemical behaviors under heat and acids.[16] The 18th and 19th centuries saw foundational theoretical advancements in quartz's classification via crystallography. René Just Haüy, in his seminal 1801 Traité de Minéralogie, proposed a theory of crystal structure based on stacked integral polyhedral molecules, applying it to quartz by analyzing cleavage planes and forms to explain its geometric diversity as variations of a primitive lattice, laying the groundwork for modern mineral systematics.[17] Building on this, the Curie brothers—Pierre and Jacques—observed in 1880 the piezoelectric effect in quartz during compression experiments, noting the generation of electric charges on crystal faces, as reported in their paper "Développement par pression de l'électricité polaire dans les cristaux hémiedres à faces inclinées," which linked mechanical stress to electrical polarity in asymmetric crystals like quartz.[18]Chemical Composition and Crystal Structure
Chemical Composition
Quartz is a mineral composed primarily of silicon dioxide, with the chemical formula SiO₂. This formula unit consists of one silicon atom bonded to two oxygen atoms, forming a tetrahedral structure that repeats in the mineral's lattice. By weight, pure quartz contains approximately 46.74% silicon and 53.26% oxygen.[19] In natural occurrences, quartz often incorporates trace impurities that substitute for silicon or occupy interstitial sites in the lattice, typically amounting to less than 1% by weight in high-purity forms. Common impurities include aluminum (Al), iron (Fe), and lithium (Li), which can replace silicon or form defect sites; these elements influence the mineral's optical properties, such as coloration in varieties like amethyst (Fe) or citrine (Fe). Other frequent trace elements are potassium (K), calcium (Ca), and sodium (Na), often derived from associated minerals or hydrothermal fluids during formation.[20][21] Isotopic variations in quartz, particularly oxygen isotopes (¹⁶O and ¹⁸O), provide insights into formation conditions and are widely used in geothermometry to estimate crystallization temperatures. The oxygen isotope ratio (δ¹⁸O) in quartz reflects equilibrium fractionation with coexisting fluids or minerals, with values typically ranging from -5% to +20% relative to standard mean ocean water (SMOW), depending on the depositional environment. Silicon isotopes (²⁸Si, ²⁹Si, ³⁰Si) also vary slightly, aiding in tracing magma sources or diagenetic processes. These isotopic signatures arise during the mineral's crystallization and contribute to its role in forming the tetrahedral framework of the crystal structure.[22][23]Crystal Structure
Quartz crystallizes in the trigonal crystal system, belonging to the chiral space groups P3₁21 (No. 152) or P3₂21 (No. 154), depending on the handedness of the structure.[24] The atomic arrangement consists of corner-sharing SiO₄ tetrahedra that form continuous helical chains parallel to the c-axis, with each silicon atom tetrahedrally coordinated to four oxygen atoms and each oxygen bridging two silicon atoms. This helical configuration imparts chirality to the crystal lattice, resulting in enantiomorphic forms that are mirror images but non-superimposable. The unit cell of α-quartz is hexagonal in appearance due to the trigonal symmetry, with lattice parameters Å, Å, and angles , , containing three formula units (Z = 3).[24] Within this cell, the SiO₄ tetrahedra are slightly distorted, with Si–O bond lengths varying between approximately 1.60 Å and 1.61 Å, and Si–O–Si bridging angles around 144°.[25] These distortions contribute to the stability of the low-temperature phase and differentiate quartz from other silica polymorphs. At ambient pressure, quartz undergoes a reversible phase transition from the low-temperature α-form to the high-temperature β-form at 573°C, classified as a displacive, second-order transition driven by a soft phonon mode at the zone-boundary T-point.[26] During this inversion, the crystal symmetry increases from trigonal (P3₁21 or P3₂21) to hexagonal (P6₂22 or P6₄22), accompanied by a small volume expansion of about 0.8% and a rotation of the SiO₄ tetrahedra toward more regular geometries without breaking bonds.[27] The transition involves coherent atomic displacements along a single order parameter related to the tetrahedral tilt angle, maintaining the helical chain motif but altering its pitch.[27]Crystal Habit
Quartz crystals most commonly display a prismatic habit, characterized by elongated six-sided prisms with rhombohedral terminations, often featuring horizontal striations on the prism faces.[28] This form arises from the mineral's underlying trigonal symmetry and is prevalent in hydrothermal vein deposits.[29] Pyramidal habits occur when the rhombohedral faces dominate, resulting in shorter, more pointed crystals, while drusy habits manifest as encrustations of fine, closely spaced crystals covering a surface.[30] Massive habits, lacking distinct crystal faces, appear in dense, intergrown aggregates, particularly in metamorphic or sedimentary contexts.[28] Twinning is a prominent feature in quartz, occurring primarily under two laws: the Dauphiné law and the Brazil law.[31] Dauphiné twinning involves a 180° rotation around the c-axis (), producing penetration twins of the same handedness, often induced by cooling through the α-β inversion at 573°C or by applied pressure.[32] Brazil law twinning, in contrast, results from reflection across {10\overline{1}1} planes, creating penetration twins of opposite handedness with the twin components reoriented at approximately 60° relative to each other.[33] These twins are common in natural quartz and can form during temperature decreases or stress events in geological settings.[31] The external habit of quartz is influenced by environmental factors during growth, such as temperature and pressure, which affect crystal face development and overall morphology.[34] For instance, higher temperatures near the β-quartz stability field promote more equant or stubby prisms, while lower temperatures and varying pressures in hydrothermal systems lead to elongated prisms or irregular habits due to fluctuating solution chemistry and space availability.[31] Pressure-induced deformation can also enhance twinning, altering the apparent habit in tectonically active regions.[32]Physical and Optical Properties
Mechanical and Thermal Properties
Quartz possesses a Mohs hardness of 7, which positions it as a relatively hard mineral capable of scratching materials like steel but being scratched by topaz or corundum.[35] This hardness arises from the strong Si-O covalent bonds in its SiO₂ tetrahedral framework, contributing to its durability in geological environments and industrial applications.[35] Its specific gravity is 2.65 g/cm³, reflecting a moderate density that distinguishes it from denser silicates like feldspar while aligning with its composition as a pure silica polymorph.[36] Quartz exhibits no cleavage, lacking preferred planes of weakness in its crystal lattice, which results in a conchoidal fracture pattern characterized by smooth, shell-like curved surfaces when broken.[35] This fracture type is typical of brittle, amorphous-like breaks in crystalline materials without internal planar defects.[35] Under applied stress, quartz demonstrates brittle behavior, preferentially fracturing rather than undergoing ductile deformation, a trait that limits its plasticity at ambient conditions but enhances its resistance to abrasion.[37] The thermal properties of quartz are marked by anisotropy due to its trigonal crystal symmetry, with differing expansion rates along principal axes. The linear thermal expansion coefficient perpendicular to the c-axis () is , while parallel to the c-axis () it is , leading to dimensional changes that vary directionally with temperature. This anisotropy influences quartz's stability in thermal gradients, such as in geological settings or precision oscillators, where uneven expansion can induce internal stresses if not accounted for.Optical Properties
Quartz exhibits a wide range of transparency, from opaque milky varieties due to internal scattering by microscopic inclusions or defects to highly transparent gem-quality crystals that allow clear transmission of light. In its purest form, quartz is transparent across the ultraviolet (UV), visible, and near-infrared (IR) spectra, with transmission typically extending from approximately 0.18 μm in the UV to beyond 3.5 μm in the IR, though absorption bands may appear due to impurities or structural defects.[38][39] As a uniaxial positive crystal, quartz has ordinary and extraordinary refractive indices of and , respectively, measured at the sodium D line (589 nm). This results in a low birefringence of , which produces subtle interference colors in thin sections under polarized light, often appearing as first-order gray. The low birefringence contributes to quartz's minimal optical distortion in most applications.[29] Quartz displays low dispersion of 0.013, accounting for the separation of wavelengths and contributing to its subdued fire compared to high-dispersion gems like diamond. In colored varieties, weak pleochroism may be observed, where the intensity or slight hue variation depends on the orientation relative to the optic axis, often linked to trace impurities creating color centers as referenced in its chemical composition.[40][41] Quartz is optically active, exhibiting the rotation of the plane of polarization of light passing through it due to its chiral crystal structure. This property arises from the helical arrangement of its tetrahedra and exists in two enantiomorphic forms: left-handed (laevo-rotatory) and right-handed (dextro-rotatory). The specific rotation is approximately ±21.7° per mm of thickness at 589 nm wavelength.[42]Electrical Properties
Quartz exhibits the piezoelectric effect, a phenomenon arising from its asymmetric trigonal crystal structure that lacks a center of inversion, allowing mechanical stress to generate an electric charge.[43] In the direct piezoelectric effect, applied stress along the X-axis produces a voltage proportional to the stress, characterized by the strain coefficient pC/N.[44] The inverse (converse) piezoelectric effect occurs when an applied electric field deforms the crystal, enabling applications such as actuators where precise mechanical motion is induced by voltage.[45] Alpha-quartz also demonstrates pyroelectricity through a secondary mechanism, where changes in temperature produce electric charge via coupling between thermal expansion and the piezoelectric response, rather than primary spontaneous polarization.[46] This effect generates a polarization change with a reported pyroelectric coefficient on the order of C/m²K, reflecting the material's sensitivity to thermal variations in non-polar piezoelectric crystals like quartz.[47] The dielectric constant of alpha-quartz is approximately at low frequencies, indicating its ability to store electrical energy effectively, which underpins its utility in frequency control devices such as oscillators (detailed in Technological Uses).[48] This value varies slightly with orientation, being higher parallel to the c-axis () than perpendicular ().[48]Varieties
Microcrystalline and Cryptocrystalline Varieties
Microcrystalline quartz refers to varieties where the crystal grains are too small to be resolved by the naked eye or even a standard optical microscope, typically forming fibrous or granular aggregates. Chalcedony is the primary example of a microcrystalline quartz aggregate, characterized by its waxy luster and fine-grained texture resulting from elongated quartz crystallites arranged in parallel fibers.[49] These fibers have diameters ranging from 50 to 100 nanometers, which is less than 1 micrometer, contributing to the material's uniform appearance and translucency in some forms.[49] Chalcedony often exhibits intergrowths with moganite, a polymorph of SiO₂ that shares the same chemical composition as quartz but features a distinct monoclinic crystal structure with alternating silicon-oxygen tetrahedra.[50] This moganite component, identified through techniques like Raman spectroscopy, can constitute up to significant portions of the structure, influencing the material's optical and mechanical properties.[51] Subtypes of chalcedony include agate and jasper, which share the same microcrystalline foundation but differ in internal patterning. Agate forms as banded chalcedony, with layers of varying composition that result from sequential deposition in cavities, creating concentric or parallel bands visible under magnification.[52] Jasper, in contrast, is a more granular or massive subtype of chalcedony, often denser due to tighter intergrowths of the quartz-moganite matrix.[53] Cryptocrystalline quartz varieties, such as flint and chert, represent even finer-grained forms where individual crystals are submicroscopic and indistinguishable without advanced microscopy, forming dense, homogeneous masses. These occur predominantly as nodules or beds in sedimentary environments, precipitated from silica-rich groundwater percolating through limestones, chalks, or other porous sediments.[54] Flint typically develops as dark, nodular concretions within limestone and chalk formations, while chert forms broader layers or irregular masses in various sedimentary rocks, both deriving from the diagenetic recrystallization of biogenic or inorganic silica sources.[55] The cryptocrystalline texture arises from the aggregation of nano-scale quartz particles, often with minor moganite inclusions, during low-temperature sedimentary processes.[56]Macrocrystalline Varieties
Macrocrystalline quartz varieties are characterized by their coarse-grained texture, where individual crystals are visible to the naked eye, distinguishing them from finer-grained forms. These varieties typically form in igneous, metamorphic, or hydrothermal environments, exhibiting euhedral to subhedral habits that highlight the hexagonal symmetry of the quartz structure.[4][1] Rock crystal represents the purest form of macrocrystalline quartz, consisting of clear, colorless single crystals that are transparent and free of significant pigmentation or inclusions. These crystals often develop in prismatic or pyramidal habits, growing to impressive sizes in vugs or veins, such as those in pegmatites or alpine clefts. Notable growth forms include gwindel habits, where multiple quartz individuals stack with a twisted, rotational alignment due to successive nucleation on rotating platforms during formation in alpine fissures, and sceptre habits, featuring a larger, bulbous termination overgrowing a narrower stem, commonly observed in basaltic geodes.[57][58][59] Milky quartz arises from the same macrocrystalline framework but appears white and turbid due to abundant microscopic inclusions of fluids or gases trapped during crystallization. These inclusions, often comprising up to 10% of the crystal volume, scatter light to produce translucency ranging from semi-transparent to nearly opaque, with a waxy to vitreous luster. Common in hydrothermal veins, milky quartz frequently exhibits distorted or twinned forms, such as artichoke-like aggregates, and may contain minor impurities like chlorite or iron oxides that subtly alter its shade.[60][4] Aventurine quartz displays a sparkling effect known as aventurescence, resulting from oriented platy inclusions embedded within the macrocrystalline matrix. The green variety typically features fuchsite, a chromium-rich muscovite mica, which reflects light to create a shimmering, metallic luster, while iron oxide variants, such as those with hematite platelets, yield orange to red hues through similar specular reflections. This phenomenon enhances the gemological appeal of aventurine, formed in metamorphic quartzites where inclusions align parallel to crystal planes.[61][62]Color Varieties
Quartz exhibits a wide range of colors due to trace impurities, inclusions, and structural defects induced by natural processes such as irradiation. These color varieties are primarily macrocrystalline forms, where pigmentation arises from specific chemical substitutions or embedded materials within the crystal lattice. While colorless rock crystal is the base form, colored variants like amethyst and citrine result from iron incorporation, whereas smoky and rose quartz involve aluminum or fibrous inclusions interacting with radiation or light scattering. Amethyst, the violet to purple variety, derives its color from trace amounts of ferric iron (Fe³⁺) ions substituting for silicon in the lattice, activated by natural irradiation that creates charge-transfer absorption bands around 530 nm.[63] This coloration often displays zoning, with color intensity varying in concentric bands due to fluctuating iron concentrations during growth.[64] Heating amethyst above 400°C irreversibly transforms it to yellow citrine by reducing Fe³⁺ to Fe²⁺ or altering defect centers, a process mimicking natural thermal events.[64] Citrine, ranging from pale yellow to deep orange, occurs naturally through the incorporation of ferric iron (Fe³⁺) impurities, which produce broad absorption in the violet-blue spectrum, resulting in complementary warm hues.[65] Unlike the more abundant heated amethyst variant, genuine natural citrine forms under oxidizing conditions with iron oxide traces, such as goethite, and is rarer, often sourced from hydrothermal veins.[66] Smoky quartz, characterized by brown to gray tones, results from natural radiation interacting with trace aluminum (Al³⁺) substituting for silicon, forming hole-trapping color centers that absorb visible light.[67] The intensity depends on radiation dose from nearby radioactive elements like uranium; extreme cases yield the nearly black morion variety.[63] Heating above 200–300°C bleaches smoky quartz by annealing these defects, reversible via re-irradiation.[68] Rose quartz, prized for its soft pink shade, achieves coloration through microscopic fibrous inclusions of dumortierite-like minerals or titanium dioxide (TiO₂) needles, which cause diffuse light scattering similar to Rayleigh effects.[69] The star rose subtype exhibits asterism, a six-rayed star effect from aligned rutile or similar inclusions reflecting light.[70] These massive, rarely prismatic crystals fade under prolonged UV exposure due to instability in the inclusion network.[71] Other notable color varieties include blue quartz, tinted by inclusions of riebeckite, crocidolite, or tourmaline fibers that scatter blue wavelengths; green prase from actinolite inclusions or prasiolite via irradiation-induced Fe²⁺ centers in heated amethyst; and milky quartz, appearing white from dense gas or fluid inclusions trapping light.[72][73][74] These hues enhance quartz's versatility in gemology while highlighting its responsiveness to geological impurities and energies.Formation and Occurrence
Geological Formation
Quartz, the most abundant and widely distributed silicate mineral in the Earth's crust, forms through diverse geological processes primarily involving the crystallization of silica (SiO₂) under varying temperature, pressure, and chemical conditions. Its formation is governed by the solubility and precipitation behavior of silica in natural fluids and melts, leading to its occurrence in igneous, metamorphic, and sedimentary rocks. In igneous settings, quartz primarily originates from the crystallization of silica-rich magmas. During the cooling of felsic magmas, such as those composing granites, quartz is typically the last mineral to crystallize due to its high silica content requirement and lower melting point compared to earlier-forming feldspars and mafic minerals.[75] This process occurs in plutonic environments where magma solidifies slowly at depth, allowing for the development of coarse-grained quartz crystals within granite and related rocks.[76] Additionally, quartz forms in hydrothermal veins through the precipitation from hot, silica-saturated fluids derived from cooling magmas; these fluids migrate through fractures in surrounding rocks, depositing quartz as temperatures drop below silica's solubility threshold, often in association with ore minerals.[77] Such vein systems highlight quartz's role in the magmatic-hydrothermal transition, where it nucleates along interfaces between melt and host rock.[78] Metamorphic formation of quartz involves the recrystallization of pre-existing silica-rich rocks under elevated heat and pressure, without melting. In regional or contact metamorphism, quartz grains in protoliths like sandstones undergo solid-state recrystallization, enlarging and interlocking to form quartzite—a nearly pure quartz rock with enhanced hardness and density.[79] This process obliterates the original sedimentary texture as quartz grains adjust to minimize internal energy, typically at temperatures exceeding 300–500°C and pressures of 1–10 kbar, preserving quartz's hexagonal crystal structure due to its thermodynamic stability in these conditions.[80] The resulting quartzite often retains faint vestiges of bedding from the parent sandstone, illustrating the role of directed stress in promoting grain boundary migration and polygonal fabric development. Sedimentary processes contribute to quartz formation through the precipitation of silica from aqueous solutions and the diagenetic transformation of biogenic silica. In marine or lacustrine environments, amorphous silica (opal) from dissolved siliceous organisms, such as diatoms and radiolaria, accumulates as siliceous ooze; during burial and diagenesis, this biogenic silica undergoes progressive crystallization, first to opal-CT and then to microcrystalline quartz, forming bedded cherts.[81] This transformation is driven by increasing temperature and pressure in the sediment column, which enhances silica solubility and reprecipitation, often resulting in dense, finely crystalline chert layers that resist compaction due to early quartz cementation.[82] Inorganic precipitation also occurs in silica-supersaturated waters, such as those influenced by hydrothermal activity or weathering of siliceous rocks, directly forming nodular or bedded cherts through episodic silica gel deposition and subsequent dehydration.[83] Quartz's persistence in these low-temperature regimes underscores its low solubility in neutral pH fluids at surface conditions, facilitating its accumulation in sedimentary sequences.Natural Occurrence
Quartz ranks as the second most abundant mineral in the Earth's crust after feldspars, constituting approximately 12% of its mass.[84] This widespread presence stems from quartz's stability under surface conditions, allowing it to persist through geological processes.[85] It is a dominant constituent in various rock types, particularly in the continental crust where it contributes significantly to the overall mineralogy.[86] Significant quartz deposits occur in diverse geological settings worldwide. Hydrothermal veins, formed by mineral-rich fluids circulating through fractures, host notable occurrences, such as those in the Ouachita Mountains near Hot Springs, Arkansas, USA, where clear quartz crystals are prevalent.[87] Pegmatites, coarse-grained igneous rocks, yield gem-quality varieties like amethyst, with major deposits in Minas Gerais, Brazil, including areas around Conselheiro Pena and Itambacuri.[88] In sedimentary environments, quartz dominates desert sands, as seen in the Sahara and Arabian deserts, where wind and water sorting concentrate resistant quartz grains into vast dune fields.[89] Quartz commonly associates with other minerals in igneous and secondary deposits. In granitic rocks, it intergrows with feldspars and micas, forming essential components of the matrix in plutonic intrusions.[90] It also lines cavities as drusy coatings or fills geodes, where crystals grow inward from the walls of hollows in volcanic or sedimentary hosts, such as those found in Brazilian basalts or Midwestern U.S. limestones. These associations highlight quartz's role in both primary igneous assemblages and secondary cavity infills.[91]Extraction and Processing
Mining Methods
Quartz mining primarily targets natural deposits found in veins and pegmatites, employing methods suited to the scale and purity requirements of the material. For industrial-grade massive quartz, open-pit mining is the predominant technique, involving the removal of overburden soil and rock to access shallow deposits, followed by excavation using heavy machinery. This method is cost-effective for large-volume extraction but can lead to significant surface disturbance. Underground mining is utilized for deeper or more concentrated deposits, where tunnels and shafts are driven into the earth to reach quartz veins, minimizing surface impact at the expense of higher operational costs and safety challenges.[92][93] Vein extraction, common in both open-pit and underground operations, focuses on quartz occurring in fractures within host rock, often requiring drilling to create access points and controlled blasting to fracture the surrounding material without damaging the quartz crystals. Blasting uses explosives to expose and loosen the veins, while subsequent drilling and wedging allow for precise removal of blocks or crystals. These techniques are essential for high-purity quartz used in electronics and optics, as they enable selective recovery from mineralized zones.[93] For gem varieties such as amethyst, mining emphasizes selective and manual methods to preserve the integrity of geodes and crystals. In Brazil's Rio Grande do Sul region and Pará state, miners employ hand tools like picks, chisels, hammers, and jackhammers to carefully extract intact amethyst geodes from basalt host rock in open pits or shallow tunnels, often reaching depths of up to 60 meters. Similar artisanal approaches are used in Uruguay's Artigas region, where hand chiseling targets volcanic basalt formations containing large geodes, prioritizing quality over volume to avoid fracturing delicate structures.[94] Following extraction, quartz undergoes processing to enhance purity and usability. Initial crushing reduces large rocks to manageable sizes using jaw or cone crushers, followed by screening to separate particles by size. Washing with water removes surface dirt, clay, and soluble impurities through scrubbing and desliming, while sorting—often manual or via optical and magnetic separators—grades the material based on color, clarity, and contamination levels. These steps typically increase silica content to over 99% for high-value applications.[95][96] Environmental impacts of quartz mining include the generation of silica dust from crushing and blasting, which poses respiratory health risks such as silicosis to workers through inhalation of fine crystalline silica particles. Dust control measures, such as water spraying for humidification during processing, ventilation systems in underground operations, and personal protective equipment, are implemented to mitigate airborne particles and limit exposure. Reuse of mining waste, like tailings in construction aggregates, further reduces dust dispersion from storage piles.[97]Synthetic Production
Synthetic quartz is primarily produced through the hydrothermal method, which replicates the high-temperature, high-pressure conditions found in natural geological veins. This technique involves dissolving silica in an alkaline aqueous solution within a sealed autoclave, where a temperature gradient promotes the precipitation and growth of quartz crystals on seed plates. The process was first successfully demonstrated for macroscopic crystals by Italian mineralogist Giorgio Spezia between 1898 and 1908, using sodium silicate solutions and natural quartz seeds at temperatures below 300°C.[98] Commercial-scale development accelerated in the 1940s through U.S. government-funded research at Bell Laboratories, leading to industrial production by the 1950s to meet demands for piezoelectric devices during and after World War II.[99] Typical hydrothermal synthesis occurs at temperatures of 300–500°C and pressures of 100–200 MPa (1,000–2,000 bar), using sodium hydroxide or carbonate as the solvent in vertical or horizontal autoclaves that can exceed 10 meters in length. Nutrient material, often crushed natural quartz, is placed in a warmer zone to dissolve slowly, while cooler seed crystals (cut from high-quality quartz) are positioned in the precipitation zone to ensure controlled, oriented growth. This seed crystal technique yields large, low-defect boules up to 50 cm in diameter and several meters long, optimized for piezoelectric applications in electronics, such as oscillators and frequency controls. The resulting synthetic quartz exhibits identical structure and properties to natural quartz, including the α-quartz trigonal crystal system, but with superior purity and consistency due to controlled impurities.[100][99] Global annual production of synthetic quartz reached approximately 20,000 metric tons in the 2020s, predominantly for high-tech sectors, with major producers including companies in the United States, Japan, and China operating large autoclave facilities. Growth cycles last 30–60 days per run, enabling high-volume output while minimizing defects like inclusions or twinning through precise pH and nutrient management.[101] In addition to full synthesis, natural quartz crystals undergo artificial treatments to enhance color and appearance for gemological purposes. Smoky quartz is commonly produced by irradiating colorless or pale quartz containing trace aluminum impurities with gamma rays or electrons, creating color centers that yield the characteristic brown to black hues; this process mimics natural radiation exposure but accelerates it in controlled facilities. Citrine, a yellow-to-orange variety, is typically obtained by heating amethyst at 400–500°C, which oxidizes iron impurities to produce the desired color, often resulting in reddish undertones if heated longer; reversal by reheating can occur, distinguishing treated from natural stones. Coatings, such as thin metal oxide layers applied via vacuum deposition, enhance luster and iridescence on quartz surfaces, though these are disclosed as surface treatments to prevent confusion with natural phenomena like aventurescence.Applications and Uses
Industrial Uses
Quartz, primarily in the form of high-purity silica sand, serves as a fundamental raw material in glass manufacturing, where it provides the primary source of silicon dioxide essential for forming the glass matrix.[102] For this application, the sand typically requires a minimum purity of 95% SiO₂ to ensure clarity, strength, and chemical stability in the final product, with lower iron oxide content to prevent discoloration.[103] This high-grade quartz sand is processed to uniform grain sizes, facilitating melting and fusion with other ingredients like soda ash and limestone during production.[104] High-purity quartz sand, known as frac sand, is also extensively used as a proppant in hydraulic fracturing operations for petroleum extraction. The sand's high sphericity, roundness, and purity (typically >99% SiO₂) allow it to prop open fractures in rock formations, enabling hydrocarbon flow while withstanding high pressures and temperatures. Sizes ranging from 20/40 to 100 mesh are common, with global demand exceeding 50 million tons annually as of 2023.[105] In foundry operations and ceramics, quartz sand and powder are widely employed for creating molds, cores, and refractory linings due to their thermal stability and refractoriness.[106] Quartz-based sands are mixed with binders to form precise casting molds for metal alloys, offering high permeability and resistance to high temperatures during pouring.[107] In ceramics, finely ground quartz acts as a non-plastic filler in glazes and clay bodies, enhancing structural integrity and reducing shrinkage while contributing to vitrification at firing temperatures.[108] The hardness of quartz, rated at 7 on the Mohs scale, makes it an effective abrasive material in industrial processes such as sandblasting and the production of grinding wheels.[106] Quartz powder or sand is propelled in sandblasting to clean and etch surfaces like metal and stone, exploiting its angular grains for efficient material removal without excessive embedding.[109] In grinding wheels, quartz aggregates or powders are incorporated into bonded abrasives to provide cutting action on hard substrates, leveraging the mineral's durability for prolonged use.[110] As a versatile filler, quartz powder is added to concrete mixtures to improve compressive strength and durability, typically at 10-20% replacement levels for cement, enhancing the matrix's density and resistance to cracking.[111] In paints and coatings, it functions as an extender, increasing opacity, abrasion resistance, and weatherability while reducing formulation costs.[112] Additionally, quartz serves as the primary feedstock for silicon metal production through carbothermic reduction, where silica reacts with carbon in an electric arc furnace according to the equation SiO₂ + 2C → Si + 2CO, yielding metallurgical-grade silicon for further industrial applications.[113][104]Gemological and Decorative Uses
Quartz varieties suitable for gemological use are primarily cut and polished to enhance their aesthetic qualities, with techniques varying based on transparency. Transparent forms, such as rock crystal and amethyst, are typically faceted to maximize light reflection and brilliance, often using brilliant or mixed cuts that create sparkle through precise angular facets.[114] Opaque or translucent varieties, including rose quartz, are more commonly shaped into cabochons, which feature a smooth, rounded dome to highlight color and subtle internal effects without the need for facets.[115] Amethyst, recognized as the birthstone for February, is frequently faceted into cuts like ovals or emeralds to preserve its purple hue while improving wearability in jewelry.[40] Historically, quartz has been employed in jewelry and carvings since at least 4,000 years ago, with ancient civilizations valuing its durability for decorative purposes. In ancient Egypt, clear quartz was carved into protective amulets and scarabs, symbolizing purity and eternity. Mesopotamian artisans around 4000 BCE fashioned quartz into beads and talismans, integrating it into necklaces and seals for both ornamental and ritualistic roles.[40] These early uses laid the foundation for quartz's enduring role in hardstone carving, where intricate designs in varieties like chalcedony showcased the mineral's workability. In modern decorative applications, quartz continues to be popular for its versatility in jewelry and ornamental objects, particularly through varieties like rose and smoky quartz. Rose quartz is often drilled into beads for necklaces and bracelets, leveraging its soft pink tones for romantic or healing-themed designs, while its Mohs hardness of 7 ensures durability in everyday wear.[116] Smoky quartz, with its earthy brown shades, is crafted into spheres and pendants, valued for grounding aesthetics in contemporary home decor and minimalist jewelry.[40] These forms emphasize the appeal of quartz color varieties, such as the gentle pastels of rose quartz that evoke emotional warmth. The value of quartz gems is determined by several key factors, including clarity, size, and color intensity, which directly influence market desirability. High-clarity specimens with minimal inclusions command premium prices, as eye-clean stones enhance visual appeal without distractions.[117] Larger sizes, particularly over 10 carats in transparent varieties, are rarer and thus more valuable, though common abundance keeps overall prices accessible compared to rarer gems.[117] Intense, even coloration—such as deep purple in amethyst or rich brown in smoky quartz—further elevates worth, with vivid tones fetching higher returns. In the gem trade, any treatments like heat application to produce citrine from amethyst or irradiation for smoky quartz must be disclosed to maintain transparency and ethical standards, as mandated by organizations like the GIA to inform buyers of potential durability impacts.[118][119]Technological Uses
Quartz crystals, leveraging their piezoelectric properties, are widely employed in precision timekeeping devices such as watches and clocks through AT-cut resonators that provide exceptional frequency stability over temperature variations.[120] These AT-cut crystals typically oscillate at a standard frequency of 32,768 Hz, which is divided down to generate one-second pulses for accurate timekeeping, enabling quartz-based clocks to maintain accuracies on the order of seconds per month.[121] This application dominates consumer electronics, where billions of such oscillators ensure reliable synchronization in devices ranging from smartphones to computers.[122] In optical technologies, quartz's low dispersion and high transparency in the ultraviolet to infrared spectrum make it ideal for components like lenses and prisms in lasers and spectrometers.[123] Fused quartz prisms, for instance, are used in pulse-shaping setups for ultrashort laser systems due to their ability to introduce controlled negative group-velocity dispersion without significant chromatic aberrations.[123] Similarly, high-purity synthetic quartz variants like Suprasil serve as lenses and windows in UV spectrometers, where minimal absorption and birefringence ensure precise wavelength separation and high-resolution spectral analysis.[124] For semiconductor and photovoltaic manufacturing, fused silica crucibles made from high-purity quartz sand are essential in the Czochralski process for growing high-purity silicon crystals, as their chemical inertness limits oxygen contamination to levels below 10^18 atoms/cm³ in the final ingots.[125][126] This enables the production of wafers for integrated circuits with defect densities suitable for advanced microelectronics.[127] High-purity quartz sand is also a primary upstream material for optical fiber production, serving as the basis for preforms in processes that yield low-loss silica fibers.[126] In emerging quantum technologies during the 2020s, quartz-based phononic crystal resonators have been integrated into hybrid acoustic systems, coupling superconducting qubits to mechanical modes for enhanced coherence times on the order of milliseconds (e.g., 1 ms at 8 K) in circuit quantum acoustodynamics platforms.[128]Related Minerals and Safety
Related Silica Minerals
Quartz is one of several polymorphs of silicon dioxide (SiO₂), each exhibiting distinct crystal structures and stability conditions despite sharing the same chemical composition.[129] Among the crystalline polymorphs, cristobalite adopts a cubic structure and is stable at high temperatures, typically forming above approximately 1470°C under atmospheric pressure, though it inverts to lower-temperature forms upon cooling.[129] Tridymite, with a hexagonal structure, occupies an intermediate stability field, crystallizing between about 870°C and 1470°C at 1 atm, and is commonly found in volcanic rocks.[129] In contrast, quartz itself is the low-temperature polymorph, with its α-form stable below 573°C at 1 atm, making it the most prevalent silica phase under surface conditions.[130] High-pressure polymorphs include coesite, which has a monoclinic structure and is stable above roughly 2 GPa at room temperature, often preserved in impact craters or deeply subducted rocks.[131] Stishovite, featuring a tetragonal rutile-type structure with octahedral coordination of silicon, requires even higher pressures—above about 10 GPa—and is rarer, typically associated with meteorite impacts.[129] Lechatelierite represents an amorphous form of silica, lacking long-range crystalline order, and occurs naturally in fused silica from lightning strikes (fulgurites) or volcanic activity.[132] Similarly, silica glass is a synthetic or natural non-crystalline variant with the same disordered tetrahedral network. Opal, while also amorphous, is distinguished by its hydrated composition (SiO₂·nH₂O), forming through precipitation from silica-rich waters and exhibiting play-of-color due to microstructural ordering.[132] Keatite, a rare tetragonal polymorph, is metastable and does not appear in standard phase diagrams; it has a density intermediate between that of α-cristobalite and β-quartz, and is infrequently observed in hydrothermal or synthetic contexts.[133] Keatite-like forms, including synthetic analogs, highlight the diversity of silica's structural possibilities under non-equilibrium conditions.[134]Health and Safety Considerations
Quartz, primarily composed of crystalline silica (SiO₂), poses significant health risks when its fine particles, known as respirable crystalline silica (RCS), become airborne during handling, processing, or use. Inhalation of RCS can lead to silicosis, a progressive and irreversible lung disease characterized by fibrosis and scarring of lung tissue, which impairs breathing and increases susceptibility to respiratory infections. Additionally, RCS is classified as a Group 1 carcinogen by the International Agency for Research on Cancer (IARC), with sufficient evidence linking chronic exposure to lung cancer. Regulatory bodies have established strict exposure limits to mitigate these risks. The Occupational Safety and Health Administration (OSHA) sets a permissible exposure limit (PEL) for RCS at 50 micrograms per cubic meter (µg/m³) as an 8-hour time-weighted average (TWA), requiring employers to implement engineering controls, work practices, and personal protective equipment to maintain levels below this threshold. Effective mitigation strategies include wet processing methods to suppress dust generation, local exhaust ventilation systems to capture airborne particles, and regular monitoring of exposure levels in high-risk environments such as stone fabrication or construction sites involving quartz materials. In gemological applications, handling quartz crystals or stones generally presents minimal health risks due to low dust production during normal wear or display. However, activities like cutting, grinding, or polishing can generate RCS dust, necessitating the use of dust control measures similar to industrial settings. Recent studies from the 2020s have highlighted potential toxicity from nano-sized silica particles derived from quartz processing, which may penetrate deeper into lung tissues and exacerbate inflammatory responses, though further research is ongoing to quantify these effects in occupational contexts.References
- https://en.wiktionary.org/wiki/quartz