Quartz
Quartz | |
---|---|
General | |
Category | Silicate mineral[1] |
Formula (repeating unit) | SiO2 |
IMA symbol | Qz[2] |
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)[3] |
Space group | α-quartz:P3221(no. 154)[4] β-quartz:P6222(no. 180) orP6422(no. 181)[5] |
Unit cell | a = 4.9133Å,c = 5.4053 Å; Z = 3 |
Identification | |
Formula mass | 60.083g·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 | {0110} Indistinct |
Fracture | Conchoidal |
Tenacity | Brittle |
Mohs scalehardness | 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 (βtridymite); 1713 °C (βcristobalite)[3] |
Solubility | Insoluble atSTP;1 ppmmassat 400 °C and 500 lb/in2to 2600 ppmmassat 500 °C and 1500 lb/in2[3] |
Other characteristics | Lattice:hexagonal,piezoelectric,may betriboluminescent,chiral(hence optically active if notracemic) |
References | [6][7][8][9] |
Quartzis a hard,crystallinemineralcomposed of silica (silicon dioxide). The atoms are linked in a continuous framework of SiO4silicon–oxygentetrahedra,with each oxygen being shared between two tetrahedra, giving an overallchemical formulaofSiO2.Quartz is, therefore, classified structurally as aframework silicate mineraland compositionally as anoxide mineral.Quartz is the second most abundantmineralinEarth'scontinental crust,behindfeldspar.[10]
Quartz exists in two forms, the normal α-quartz and the high-temperature β-quartz, both of which arechiral.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 asgemstones.Since antiquity, varieties of quartz have been the most commonly used minerals in the making ofjewelryandhardstone carvings,especially in Europe and Asia.
Quartz is themineraldefining the value of 7 on theMohs scale of hardness,a qualitativescratchmethod for determining the hardness of a material to abrasion.
Etymology
[edit]The word"quartz"is derived from theGermanwordQuarz,[11]which had the same form in the first half of the 14th century inMiddle High Germanand inEast Central German[12]and which came from thePolishdialect termtwardy,which corresponds to theCzechtermtvrdý( "hard" ).[13]Some sources, however, attribute the word's origin to theSaxonwordQuerkluftertz,meaningcross-vein ore.[14][15]
TheAncient Greeksreferred to quartz asκρύσταλλος(krustallos) derived from theAncient Greekκρύος(kruos) meaning "icy cold", because somephilosophers(includingTheophrastus) understood the mineral to be a form ofsupercooledice.[16]Today, the termrock crystalis sometimes used as an alternative name for transparent coarsely crystalline quartz.[17][18]
Early studies
[edit]Roman naturalistPliny the Elderbelieved quartz to be waterice,permanently frozen after great lengths of time.[19]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 aspectrum.[20]
In the 17th century,Nicolas Steno's study of quartz paved the way for moderncrystallography.He discovered that regardless of a quartz crystal's size or shape, its long prism faces always joined at a perfect 60° angle.[21]
Crystal habit and structure
[edit]Quartz belongs to thetrigonal crystal systemat room temperature, and to thehexagonal crystal systemabove 573 °C (846 K; 1,063 °F). Theideal crystal shapeis a six-sidedprismterminating with six-sided pyramid-likerhombohedronsat each end. In nature, quartz crystals are oftentwinned(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 appearmassive.[22][23]
Well-formed crystals typically form as adruse(a layer of crystals lining a void), of which quartzgeodesare particularly fine examples.[24]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, withingypsum.[25]
α-quartz crystallizes in the trigonal crystal system,space groupP3121 orP3221 (space group 152 or 154 resp.) depending on the chirality. Above 573 °C (846 K; 1,063 °F), α-quartz inP3121 becomes the more symmetric hexagonalP6422 (space group 181), and α-quartz inP3221 goes to space groupP6222 (no. 180).[26]
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 (SiO4tetrahedra 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.[22][27]However, there is a significant change in volume during this transition,[28]and this can result in significant microfracturing in ceramics during firing,[29]in ornamental stone after a fire[30]and in rocks of the Earth's crust exposed to high temperatures,[31]thereby damaging materials containing quartz and degrading their physical and mechanical properties.
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Common, prismatic quartz
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Sceptered quartz
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Sceptered quartz (as aggregates: "Elestial quartz" )
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Bipyramidal quartz
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Tessin or tapered quartz
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Twinned quartz (known as Japan law)
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Dauphine quartz (single dominant face)
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Druse quartz
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Granular quartz
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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.[32]
Type | Color and description | Transparency |
---|---|---|
Herkimer diamond | Colorless | Transparent |
Rock crystal | Colorless | Transparent |
Amethyst | Purple to violet colored quartz | Transparent |
Citrine | Yellow quartz ranging to reddish-orange or brown (Madeira citrine), and occasionally greenish yellow | Transparent |
Ametrine | A mix of amethyst and citrine with hues of purple/violet and yellow or orange/brown | Transparent |
Rose quartz | Pink, may displaydiasterism | Transparent |
Chalcedony | Fibrous, variously translucent, cryptocrystalline quartz occurring in many varieties. The term is often used for white, cloudy, or lightly colored material intergrown withmoganite. Otherwise more specific names are used. |
|
Carnelian | Reddish orange chalcedony | Translucent |
Aventurine | Quartz with tiny aligned inclusions (usuallymica) that shimmer withaventurescence | Translucent to opaque |
Agate | Multi-colored, curved or concentric banded chalcedony (cf. Onyx) | Semi-translucent to translucent |
Onyx | Multi-colored, straight banded chalcedony orchert(cf. Agate) | Semi-translucent to opaque |
Jasper | Opaque cryptocrystalline quartz, typically red to brown but often used for other colors | Opaque |
Milky quartz | White, may displaydiasterism | Translucent to opaque |
Smoky quartz | Light to dark gray, sometimes with a brownish hue | Translucent to opaque |
Tiger's eye | Fibrous gold, red-brown or bluish colored chalcedony, exhibitingchatoyancy. | |
Prasiolite | Green | Transparent |
Rutilated quartz | Containsacicular(needle-like)inclusionsofrutile | |
Dumortierite quartz | Contains large amounts of bluedumortieritecrystals | Translucent |
Prase | Green | Translucent |
Varieties (according to color)
[edit]Pure quartz, traditionally called rock crystal or clear quartz, is colorless andtransparentor translucent and has often been used forhardstone carvings,such as theLothair 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.
The most important distinction between types of quartz is that ofmacrocrystalline(individual crystals visible to the unaided eye) and themicrocrystallineorcryptocrystallinevarieties (aggregatesof crystals visible only under high magnification). The cryptocrystalline varieties are either translucent or mostly opaque, while the transparent varieties tend to be macrocrystalline.Chalcedonyis a cryptocrystalline form ofsilicaconsisting of fine intergrowths of both quartz, and itsmonoclinicpolymorphmoganite.[34]Other opaque gemstone varieties of quartz, or mixed rocks including quartz, often including contrasting bands or patterns of color, areagate,carnelianor sard,onyx,heliotrope,andjasper.[22]
Amethyst
[edit]Amethystis 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. Sometimes amethyst and citrine are found growing in the same crystal. It is then referred to asametrine.Amethyst derives its color from traces of iron in its structure.[35]
Blue quartz
[edit]Blue quartz contains inclusions of fibrousmagnesio-riebeckiteorcrocidolite.[36]
Dumortierite quartz
[edit]Inclusions of the mineraldumortieritewithin 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.[37][38]"Blue quartz" is a minor gemstone.[37][39]
Citrine
[edit]Citrine is a variety of quartz whose color ranges from pale yellow to brown due to a submicroscopic distribution of colloidalferrichydroxide impurities.[40]Natural citrines are rare; most commercial citrines are heat-treatedamethystsorsmoky quartzes.However, a heat-treated amethyst will have small lines in the crystal, as opposed to a natural citrine's cloudy or smoky appearance. It is nearly impossible to differentiate between cut citrine and yellowtopazvisually, but they differ inhardness.Brazil is the leading producer of citrine, with much of its production coming from the state ofRio Grande do Sul.The name is derived from the Latin wordcitrinawhich means "yellow" and is also the origin of the word "citron".Sometimes citrine and amethyst can be found together in the same crystal, which is then referred to asametrine.[41]Citrine has been referred to as the "merchant's stone" or "money stone", due to a superstition that it would bring prosperity.[42]
Citrine was first appreciated as a golden-yellow gemstone in Greece between 300 and 150 BC, during theHellenistic Age.Yellow quartz was used prior to that to decorate jewelry and tools but it was not highly sought after.[43]
Milky quartz
[edit]Milk quartz or milky quartz is the most common variety of crystalline quartz. The white color is caused by minutefluid inclusionsof 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 oftitanium,iron,ormanganesein the material. Some rose quartz contains microscopicrutileneedles that produceasterismin transmitted light. RecentX-ray diffractionstudies suggest that the color is due to thin microscopic fibers of possiblydumortieritewithin 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 ofphosphateoraluminium.The color in crystals is apparently photosensitive and subject to fading. The first crystals were found in apegmatitefound nearRumford,Maine,US, and inMinas 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 theironand microscopicdumortieritefibers that formed rose quartz.[48]
Smoky quartz
[edit]Smoky quartzis 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 green variety of quartz.[50]The green color is caused by inclusions ofamphibole.[51]
Prasiolite
[edit]Prasiolite,also known asvermarine,is a variety of quartz that is green in color.[52]The green is caused by iron ions.[51]It is a rare mineral in nature and is typically found with amethyst; most "prasiolite" is not natural – it has been artificially produced by heating of amethyst.Since 1950[citation needed],almost all natural prasiolite has come from a smallBrazilianmine, but it is also seen inLower SilesiainPoland.Naturally occurring prasiolite is also found in theThunder Bayarea ofCanada.[52]
Piezoelectricity
[edit]Quartz crystals havepiezoelectricproperties; they develop anelectric potentialupon the application ofmechanical stress.[53]Quartz's piezoelectric properties were discovered byJacquesandPierre Curiein 1880.[54][55]
Occurrence
[edit]Quartz is a defining constituent ofgraniteand otherfelsicigneous rocks.It is very common insedimentary rockssuch assandstoneandshale.It is a common constituent ofschist,gneiss,quartziteand othermetamorphic rocks.[22]Quartz has the lowest potential forweatheringin theGoldich dissolution seriesand consequently it is very common as a residual mineral in stream sediments and residualsoils.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 moltenmagma,quartz also chemically precipitates from hothydrothermalveinsasgangue,sometimes withoreminerals like gold, silver and copper. Large crystals of quartz are found in magmaticpegmatites.[22]Well-formed crystals may reach several meters in length andweighhundreds of kilograms.[57]
The largest documented single crystal of quartz was found nearItapore,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 fromopen pit mines.Miners occasionally use explosives to expose deep pockets of quartz. More frequently,bulldozersandbackhoesare 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]Tridymiteandcristobaliteare high-temperaturepolymorphsof SiO2that occur in high-silicavolcanicrocks.Coesiteis a denser polymorph of SiO2found in some meteorite impact sites and in metamorphic rocks formed at pressures greater than those typical of the Earth's crust.Stishoviteis a yet denser and higher-pressure polymorph of SiO2found in some meteorite impact sites.[62]Moganiteis a monoclinic polymorph.Lechatelieriteis anamorphoussilicaglassSiO2which is formed bylightningstrikes in quartzsand.[63]
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.[64]Crystalline silica of respirable size is a recognized humancarcinogenand may lead to other diseases of the lungs such assilicosisandpulmonary fibrosis.[65][66]
Synthetic and artificial treatments
[edit]Not all varieties of quartz are naturally occurring. Some clear quartz crystals can be treated using heat orgamma-irradiationto induce color where it would not otherwise have occurred naturally. Susceptibility to such treatments depends on the location from which the quartz was mined.[67]
Prasiolite, an olive colored material, is produced by heat treatment;[68]natural prasiolite has also been observed in Lower Silesia in Poland.[69]Although citrine occurs naturally, the majority is the result of heat-treating amethyst or smoky quartz.[68]Carnelianhas been heat-treated to deepen its color since prehistoric times.[70]
Because natural quartz is oftentwinned,synthetic quartz is produced for use in industry. Large, flawless, single crystals are synthesized in anautoclavevia thehydrothermal process.[71][22][72]
Like other crystals, quartz may becoated with metal vaporsto give it an attractive sheen.[73][74]
Uses
[edit]Quartz is the most common material identified as the mystical substancemabaninAustralian Aboriginal mythology.It is found regularly in passage tomb cemeteries in Europe in a burial context, such asNewgrangeorCarrowmoreinIreland.Quartz was also used inPrehistoric Ireland,as well as many other countries, forstone tools;both vein quartz and rock crystal wereknappedas part of thelithic technologyof the prehistoric peoples.[75]
Whilejadehas been since earliest times the most prized semi-precious stone for carving inEast AsiaandPre-ColumbianAmerica, in Europe and the Middle East the different varieties of quartz were the most commonly used for the various types ofjewelryandhardstone carving,includingengraved gemsandcameo 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 geologistKarl Emil von Schafhäutl(1803–1890) was the first person to synthesize quartz when in 1845 he created microscopic quartz crystals in apressure cooker.[76]However, the quality and size of the crystals that were produced by these early efforts were poor.[77]
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 growingsiliconwafersin thesemiconductorindustry, are expensive and rare. These high-purity quartz are defined as containing less than 50 ppm of impurity elements.[78]A major mining location for high purity quartz is the Spruce Pine Gem Mine inSpruce Pine, North Carolina,United States.[79]Quartz may also be found inCaldoveiro Peak,inAsturias,Spain.[80]
By the 1930s, the electronics industry had become dependent on quartz crystals. The only source of suitable crystals was Brazil; however,World War IIdisrupted 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.[81]After the war, many laboratories attempted to grow large quartz crystals. In the United States, the U.S. Army Signal Corps contracted withBell Laboratoriesand with theBrush Development Companyof Cleveland, Ohio to synthesize crystals following Nacken's lead.[82][83](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.[84][85]By the 1950s,hydrothermal synthesistechniques were producing synthetic quartz crystals on an industrial scale, and today virtually all the quartz crystal used in the modern electronics industry is synthetic.[72]
An early use of the piezoelectricity of quartz crystals was inphonographpickups. One of the most common piezoelectric uses of quartz today is as acrystal oscillator.Thequartz oscillatoror resonator was first developed byWalter Guyton Cadyin 1921.[86][87]George Washington Piercedesigned and patentedquartz crystal oscillatorsin 1923.[88][89][90]Thequartz clockis a familiar device using the mineral. Warren Marrison created the first quartz oscillator clock based on the work of Cady and Pierce in 1927.[91]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 thequartz crystal microbalanceand inthin-film thickness monitors.[92]
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Rock crystal jug with cut festoon decoration byMilanworkshop from the second half of the 16th century,National MuseuminWarsaw.The city of Milan, apart fromPragueandFlorence,was the mainRenaissancecentre for crystal cutting.[93]
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Synthetic quartz crystals produced in the autoclave shown inWestern Electric's pilot hydrothermal quartz plant in 1959
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Fatimidewer 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.[94]The popularity ofcrystal healinghas increased the demand for natural quartz crystals, which are now often mined indeveloping countriesusing primitive mining methods, sometimes involvingchild labor.[95]
See also
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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 fromthe originalon 7 January 2009.
- Terminology used to describe the characteristics of quartz crystals when used as oscillators
- Quartz use as prehistoric stone tool raw material