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钙矾石
钙矾石, 3.3×2.6×2.5 cm. 产自南非北开普省卡拉哈里锰田
基本资料
类别硫酸盐
化学式Ca
6
Al
2
(SO
4
)
3
(OH)
12
·26H
2
O
施特龙茨分类7.DG.15
晶体分类Ditrigonal pyramidal (3m)
赫尔曼–莫甘记号: (3m)
晶体空间群P31c
晶胞a = 11.23, c = 21.44 [Å]; Z = 2
性质
颜色无色、淡黄色或乳白色
晶体惯态针状生长、棱纹状晶体; 纤维状至棉絮状
晶系六方晶系
解理{1010} 完全
莫氏硬度2-2.5
光泽玻璃光泽
条痕白色
透明性透明至不透明
比重1.77
光学性质单轴 (-)
折射率nω = 1.491, nε = 1.470
双折射δ = 0.021
发光性无荧光性
溶解度部分溶于水
可转变为在空气中部分脱水,变得不透明
参考文献[1][2][3]

钙矾石 是一种含水的钙铝硫酸盐矿物,其化学式为Ca
6
Al
2
(SO
4
)
3
(OH)
12
·26H
2
O
。它呈无色到黄色,晶系为三方晶系。其柱状晶体通常情况下无色,部分脱水后显白色。[2][3]钙矾石类矿物包括硅灰石膏和钙铬矾。[4]


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Discovery and occurrence

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Ettringite, 6.5×3.2 cm. N'Chwaning Mines, Kalahari manganese fields, Northern Cape Province, South Africa

Ettringite was first described in 1874 by J.Lehmann,[5] for an occurrence near the Ettringer Bellerberg volcano, Ettringen, Rheinland-Pfalz, Germany.[2][3] It occurs within metamorphically altered limestone adjacent to igneous intrusive rocks or within xenoliths. It also occurs as weathering crusts on larnite in the Hatrurim Formation of Israel.[2] It occurs associated with portlandite, afwillite and hydrocalumite at Scawt Hill, Ireland and with afwillite, hydrocalumite, mayenite and gypsum in the Hatrurim Formation.[2] It has also been reported from the Zeilberg quarry, Maroldsweisach, Bavaria; at Boisséjour, near Clermont-Ferrand, Puy-de-Dôme, Auvergne, France; the N’Chwaning mine, Kuruman district, Cape Province, South Africa; in the US, occurrences were found in spurrite-merwinite-gehlenite skarn at the 910 level of the Commercial quarry, Crestmore, Riverside County, California[6] and in the Lucky Cuss mine, Tombstone, Cochise County, Arizona.[2][3]

Occurrence in cement

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SEM image of fractured hardened cement paste, showing plates of calcium hydroxide and needles of ettringite (micron scale)

In concrete chemistry ettringite is a hexacalcium aluminate trisulfate hydrate, of general formula:

(CaO)6(Al2O3)(SO3)3·32H2O

or

(CaO)3(Al2O3)(CaSO4)3·32H2O.

Ettringite is formed in hydrated Portland cement system as a result of the reaction of calcium aluminate with calcium sulfate, both present in Portland cement.[7] Ettringite, the more prominent representative of AFt phases or (Al2O3-Fe2O3-tri), can also be synthesized in the laboratory by reacting stoichiometric amounts of calcium, aluminium and sulfate in water.

C3A + 3 CaSO4 → ettringite

In the cement system, the presence of ettringite depends on the ratio of calcium sulfate to tri-calcium aluminate (C3A); when this ratio is low, ettringite forms during early hydration and then converts to the calcium aluminate monosulfate (AFm phase or (Al2O3-Fe2O3-mono)). When the ratio is intermediate, only a portion of the ettringite converts to AFm and both can coexist, while ettringite is unlikely to convert to AFm at high ratios.

The following characters designate standard notations:[8]

C = CaO
S = SiO2
A = Al2O3
F = Fe2O3
S̅ = SO3
H = H2O
K = K2O
N = Na2O
m = mono
t = tri

AFt and AFm phases

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  • AFt: abbreviation for "alumina, ferric oxide, tri-sulfate" or (Al2O3 – Fe2O3 – tri). It represents a group of calcium sulfoaluminate hydrates. AFt has the general formula [Ca3(Al,Fe)(OH)6·12 H2O]2·X3·nH2O where X represents a doubly charged anion or, sometimes, two singly charged anions. Ettringite is the most common and important member of the AFt group (X in this case denoting sulfate).
  • AFm: abbreviation for "alumina, ferric oxide, mono-sulfate" or (Al2O3 – Fe2O3 – mono). It represents another group of calcium aluminate hydrates with general formula [Ca2(Al,Fe)(OH)6)]·X·nH2O where X represents a singly charged anion or 'half' a doubly charged anion. X may be one of many anions. The most important anions involved in Portland cement hydration are hydroxyl, sulfate and carbonate.

结构

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The mineral ettringite has a structure that runs parallel to the c axis -the needle axis-; in the middle of these two lie the sulfate ions and H2O molecules, the space group is P31c. Ettringite crystal system is trigonal, crystals are elongated and in a needle like shape, occurrence of disorder or twining is common, which affects the intercolumn material.[9] The first X-ray study was done by Bannister, Hey & Bernal (1936), which found that the crystal unit cell is of a hexagonal form with a=11.26 and c=21.48 with space group P63/mmcand Z=2. From observations on dehydration and chemical formulas there were suggestions of the structure being composed of Ca2+ and Al(OH)63−, were between them lie SO42− ions and H2O molecules. Further X-ray studies ensued; namely Wellin (1956) which determined the crystal structure of thaumasite, and Besjak & Jelenic (1966) which gave affirmation of the structure nature of ettringite.[9]

An ettringite sample extracted from Scawt Hill was analysed by C. E. Tilley, the crystal was 1.1 x 0.8 0.5 mm, with specific gravity of 1.772±0.002, the density was determined by immersing the sample in a solution of carbon tetrachloride mixed with bromoform. The crystal showed five prism faces of the form m {1010} and a small face a{1120}, with no pyramidal or basal faces, upon x-ray diffraction a Lauer gram along the c-axis revealed a hexagonal axis with vertical planes of symmetry, this study showed that the structure has a hexagonal and not a rhombohedral lattice.[10] further studies conducted on synthetic ettringite by use of x-ray and powder diffraction confirmed earlier assumptions and analyses.[11]

Upon analyzing the structure of both ettringite and thaumasite, it was deduced that both minerals have hexagonal structures, but different space groups. Ettringite crystals have a P31c with a=11.224 Å, c= 21,108 Å, while thaumasite crystals fall into space group P63 with a= 11.04 Å, c= 10.39 Å. While these two minerals form a solid solution, the difference in space groups lead to discontinuities in unit cell parameters. Differences between structures of ettringite and thaumasite arise from the columns of cations and anions: Ettringite cation columns are composed of Ca3[Al(OH)6·12H2O]3+, which run parallel to the c axis, and the other columns of sulfate anions and water molecules in channels parallel to these columns. In contrast, thaumasite consists of a cylindrical column of Ca3[Si(OH)6·12H2O]3+ in the c axis, with sulfate and carbonate anions in channels between these columns which contain water molecules as well.[12]

Further research

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Ongoing research on ettringite and cement phase minerals is in general to find ways to immobilize wastes and heavy metals from soils and the environment; this can be done by use of the proper cement phase forming mineral by use of lattice to extract according elements. For example, it is reported that copper immobilization at high pH can be achieved through formation of CSH/CAH and ettringite.[13] It is suggested that the crystal morphology of ettringite Ca6Al2(SO4)3(OH)12·26H2O can incorporate a variety of divalent ions: Cu2+, Pb2+, Cd2+ and Zn2+, which can substitute for the Ca2+ by incorporating these ions into the lattice.[13]

参见

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参考文献

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  1. ^ Ettringite data, Webmineral
  2. ^ 2.0 2.1 2.2 2.3 2.4 2.5 Ettringite in Handbook of Mineralogy
  3. ^ 3.0 3.1 3.2 3.3 Ettringite. Mindat.org
  4. ^ Ettringite-group.
  5. ^ Lehmann, J. (1874): Über den Ettringit, ein neues Mineral in Kalkeinschlüssen der Lava von Ettringen (Laacher Gebiet). N. Jb. Mineral. Geol. Paläont., 273-275
  6. ^ Carpenter, A.B. (1963): Oriented overgrowths of thaumasite on ettringite. Am. Mineral. 48
  7. ^ Merlini, Marco; Artioli, Gilberto; Cerulli, Tiziano; Cella, Fiorenza; Bravo, Anna. Tricalcium aluminate hydration in additivated systems. A crystallographic study by SR-XRPD. Cement and Concrete Research (Elsevier). 2008, 38 (4): 477–486. doi:10.1016/j.cemconres.2007.11.011. 
  8. ^ Bazant, Z.P.; Wittmann F.H. Creep and shrinkage in concrete structures. John Wiley and Sons. 1982. ISBN 0-471-10409-4. 
  9. ^ 9.0 9.1 Moore A E , Taylor H F W (1970), Crystal structure of ettringit, Acta Crystallographica Section B , 26 p.386-393
  10. ^ Bannister, M.A. (1935): Ettringite from Scawt Hill, Co. Antrim. Mineralogical Magazine, 24, 324-329
  11. ^ Goetz-Neunhoeffer, F. and Neubauer, J. (2006): Refined ettringite (Ca6Al2(SO4)3(OH)12·26H2O) structure for quantitative X-ray diffraction analysis. Powder Diffr. 21, 4-11.
  12. ^ Rachel L. Norman a,b, Sandra E. Dann a, Simon C. Hogg c, Caroline A. Kirk. (2013): Synthesis and structural characterisation of new ettringite and thaumasite type phases: Ca6[Ga(OH)6.12H2O]2(SO4)3.2H2O and Ca6[M(OH)6.12H2O]2(SO4)2(CO3)2, M = Mn, Sn, Solid State Sciences 25.
  13. ^ 13.0 13.1 Moon DH, Park JW, Cheong KH, Hyun S, Koutsospyros A, Park JH, Ok YS. (2013): Stabilization of lead and copper contaminated firing range soil using calcined oyster shells and fly ash, Environ Geochem Health 35