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Wollastonite

Single chain calcium inosilicate (CaSiO<sub>3</sub>)

Wollastonite

Single chain calcium inosilicate (CaSiO<sub>3</sub>)

FieldValue
nameWollastonite
categoryInosilicate mineral
imageWollastoniteUSGOV.jpg
formulaCalcium metasilicate, CaSiO3
IMAsymbolWo
molweight116.159g/mol
strunz9.DG.05
systemTriclinic
Monoclinic polytype exists
classPinacoidal ()
(same H-M symbol)
symmetry*P* (Triclinic)
unit cella = 7.925 Å, b = 7.32 Å,
c = 7.065 Å; α = 90.055°,
β = 95.217°, γ = 103.42°; Z = 6
colorWhite, colorless or gray
habitRare as tabular crystals—commonly massive in lamellar, radiating, compact and fibrous aggregates.
twinningCommon
cleavagePerfect in two directions at near 90°
fractureSplintery to uneven
mohs4.5 to 5.0
lusterVitreous or dull to pearly on cleavage surfaces
refractivenα = 1.616–1.640
nβ = 1.628–1.650
nγ = 1.631–1.653
opticalpropBiaxial (−)
birefringenceδ = 0.015 max
2VMeasured: 36° to 60°
streakWhite
gravity2.86–3.09
otherHeat of formation (@298): −89.61kJ
melt1540 °C
solubilitySoluble in HCl, insoluble in water
diaphaneityTransparent to translucent
references

Monoclinic polytype exists (same H-M symbol)

P21/a (Monoclinic) c = 7.065 Å; α = 90.055°, β = 95.217°, γ = 103.42°; Z = 6 nβ = 1.628–1.650 nγ = 1.631–1.653

Gibbs free energy: 41.78kJ Wollastonite is a calcium inosilicate mineral (CaSiO3) that may contain small amounts of iron, magnesium, and manganese substituting for calcium. It is usually white. It forms when impure limestone or dolomite is subjected to high temperature and pressure, which sometimes occurs in the presence of silica-bearing fluids as in skarns or in contact with metamorphic rocks. Associated minerals include garnets, vesuvianite, diopside, tremolite, epidote, plagioclase feldspar, pyroxene and calcite. It is named after the English chemist and mineralogist William Hyde Wollaston (1766–1828).

Despite its chemical similarity to the compositional spectrum of the pyroxene group of minerals—where magnesium (Mg) and iron (Fe) substitution for calcium ends with diopside and hedenbergite respectively—it is structurally very different, with a third tetrahedron in the linked chain (as opposed to two in the pyroxenes).

Uses

Wollastonite is among the fastest reacting silicates, but may have high costs associated with carbon storage. Addition of wollastonite to soil stimulates organic carbon mineralization.

Ceramics

Wollastonite has industrial importance in ceramics manufacturing as an additive.

In ceramics, wollastonite decreases shrinkage and gas evolution during firing, increases green and fired strength, maintains brightness during firing, permits fast firing, and reduces crazing, cracking, and glaze defects.

Construction

Wollastonite can serve as a substitute for asbestos in floor tiles, friction products, insulating board and panels, paint, plastics, and roofing products. Similar to asbestos, wollastonite is resistant to chemical attack, stable at high temperatures, and improves flexural and tensile strength in composites. In some industries, wollastonite is used in different percentages of impurities, such as its use as a fabricator of mineral wool insulation, or as an ornamental building material. Wollastonite is used in a cement announced in 2019 which "reduces the overall carbon footprint in precast concrete by 70%."

Wollastonite has been studied for carbon mineralization for storage of carbon dioxide (CO2) according to the following reaction: :

Metallurgy

In metallurgical applications, wollastonite serves as a flux for welding, a source for calcium oxide, a slag conditioner, and to protect the surface of molten metal during the continuous casting of steel.

Paint

As an additive in paint, wollastonite improves the durability of the paint film, acts as a pH buffer, improves its resistance to weathering, reduces gloss, reduces pigment consumption, and acts as a flatting and suspending agent.

Plastic

In plastics, wollastonite improves tensile and flexural strength, reduces resin consumption, and improves thermal and dimensional stability at elevated temperatures. Surface treatments are used to improve the adhesion between the wollastonite and the polymers to which it is added.

Plastics and rubber applications were estimated to account for 25% to 35% of U.S. sales in 2009, followed by ceramics with 20% to 25%; paint, 10% to 15%; metallurgical applications, 10% to 15%; friction products, 10% to 15%; and miscellaneous, 10% to 15%. Ceramic applications probably account for 30% to 40% of wollastonite sales worldwide, followed by polymers (plastics and rubber) with 30% to 35% of sales, and paint with 10% to 15% of sales. The remaining sales were for construction, friction products, and metallurgical applications.

Substitutes

White acicular crystals of wollastonite (field of view 8 mm) from the Central Bohemia Region, Czech Republic

The acicular nature of many wollastonite products allows it to compete with other acicular materials, such as ceramic fiber, glass fiber, steel fiber, and several organic fibers, such as aramid, polyethylene, polypropylene, and polytetrafluoroethylene in products where improvements in dimensional stability, flexural modulus, and heat deflection are sought.

Wollastonite also competes with several nonfibrous minerals or rocks, such as kaolin, mica, and talc, which are added to plastics to increase flexural strength, and such minerals as barite, calcium carbonate, gypsum, and talc, which impart dimensional stability to plastics.

In ceramics, wollastonite competes with carbonates, feldspar, lime, and silica as a source of calcium and silicon. Its use in ceramics depends on the formulation of the ceramic body and the firing method.

Composition

In a pure CaSiO3, each component forms nearly half of the mineral by weight: 48.3% of CaO and 51.7% of SiO2. In some cases, small amounts of iron (Fe), and manganese (Mn), and lesser amounts of magnesium (Mg) substitute for calcium (Ca) in the mineral formula (e.g., rhodonite). Wollastonite can form a series of solid solutions in the system CaSiO3-FeSiO3, or hydrothermal synthesis of phases in the system MnSiO3-CaSiO3.

Geologic occurrence

Wollastonite usually occurs as a common constituent of a thermally metamorphosed impure limestone, it also could occur when the silicon is due to metamorphism in contact altered calcareous sediments, or to contamination in the invading igneous rock. In most of these occurrences it is the result of the following reaction between calcite and silica with the loss of carbon dioxide:

:CaCO3 + SiO2 → CaSiO3 + CO2

Wollastonite may also be produced in a diffusion reaction in skarn, it develops when limestone within a sandstone is metamorphosed by a dike, which results in the formation of wollastonite in the sandstone as a result of outward migration of Ca.

Structure

Unit cell of triclinic wollastonite-1A
Tetrahedra arrangement within the chains in pyroxenes compared to wollastonite

Wollastonite crystallizes triclinically in space group P with the lattice constants a = 7.94 Å, b = 7.32 Å, c = 7.07 Å; α = 90,03°, β = 95,37°, γ = 103,43° and six formula units per unit cell. Wollastonite was once classed structurally among the pyroxene group, because both of these groups have a ratio of Si:O = 1:3. In 1931, Warren and Biscoe showed that the crystal structure of wollastonite differs from minerals of the pyroxene group, and they classified this mineral within a group known as the pyroxenoids. It has been shown that the pyroxenoid chains are more kinked than those of pyroxene group, and exhibit longer repeat distance. The structure of wollastonite contains infinite chains of [SiO4] tetrahedra sharing common vertices, running parallel to the b-axis. The chain motif in wollastonite repeats after three tetrahedra, whereas in pyroxenes only two are needed. The repeat distance in the wollastonite chains is 7.32 Å and equals the length of the crystallographic b-axis.

Molten CaSiO3 maintains a tetrahedral SiO4 local structure at temperatures up to 2000 °C. The nearest neighbor Ca-O coordination decreases from 6.0(2) in the room temperature glass to 5.0(2) in the 1700 °C liquid, coincident with an increasing number of longer Ca-O neighbors.

References

References

  1. Warr, L.N.. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine.
  2. [http://www.mindat.org/min-4323.html Wollastonite], Mindat
  3. [http://webmineral.com/data/Wollastonite-1A.shtml Wollastonite], Webmineral
  4. [http://rruff.geo.arizona.edu/doclib/hom/wollastonite.pdf Wollastonite], ''Handbook of Mineralogy''
  5. [http://www.minsocam.org/ammin/am79/am79_134.pdf American Mineralogist, V. 79, pp. 134-144, 1994]
  6. (January 27, 2015). "Mineral Resource of the Month: Wollastonite". American Geosciences Institute.
  7. (2020-10-18). "Magmatic and Metasomatic Effects of Magma–Carbonate Interaction Recorded in Calc-silicate Xenoliths from Merapi Volcano (Indonesia)". Journal of Petrology.
  8. (1992). "An introduction to the rock-forming minerals". Longman Scientific & Technical.
  9. [https://pubs.usgs.gov/periodicals/mcs2022/mcs2022-wollastonite.pdf Wollastonite], ''Mineral Commodity Summaries'' 2021
  10. Robert L. Virta [https://minerals.usgs.gov/minerals/pubs/commodity/wollastonite/myb1-2009-wolla.pdf Wollastonite], ''USGS 2009 Minerals Yearbook'' (October 2010)
  11. National Academies of Sciences, Engineering, and Medicine. (2019). "Negative Emissions Technologies and Reliable Sequestration: A Research Agenda". The National Academies Press.
  12. (2023). "Wollastonite addition stimulates soil organic carbon mineralization: Evidences from 12 land-use types in subtropical China". Catena.
  13. Deer, Howie and Zussman. ''Rock Forming Minerals; Single Chain Silicates'', Vol. 2A, Second Edition, London, The Geological Society, 1997.
  14. Andrews, R. W. (1970). ''Wollastonite''. London, Her Majesty's Stationery Office.
  15. Alter, Lloyd. (August 15, 2019). "LafargeHolcim is selling CO2-sucking cement for precast, reduces emissions by 70 percent".
  16. (January 2019). "Co-Benefits of Wollastonite Weathering in Agriculture: CO2 Sequestration and Promoted Plant Growth". ACS Omega.
  17. (1961). "The crystal structures of wollastonite and pectolite". Proceedings of the National Academy of Sciences.
  18. Benmore, C.J.. (2010). "Temperature-dependent structural heterogeneity in calcium silicate liquids". Phys. Rev. B.
  19. Skinner, L.B.. (2012). "Structure of molten CaSiO3: Neutron diffraction isotope substitution with aerodynamic levitation and molecular dynamics Study". J. Phys. Chem. B.
  20. Eckersley, M.C.. (1988). "Structural ordering in a calcium silicate glass". Nature.
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