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Minerals/Metals/Body-centered cubics

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Metals in general fall into two groups of close-packing structures: face-centered cubic (fcc) and hexagonal close-packed (hcp). These two are the most efficient way to pack a bunch of hard marbles into the smallest space.

A face-centered cubic close-packed unit cell structure is outlined in red. Credit: Owen Graham.
This is a stick and ball model of a fcc unit cell. Credit: Baszoetekouw.
These models compare a fcc unit cell with hexagonal close-packing (hcp). Credit: Twisp.

An fcc structure differs from a hcp in the number of distinct close-packed layers: hcp has two, symbolized with A below B, and fcc which has three with A below B, but C above B before A again.

Body-centered cubics

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Main resources: Chemicals/Materials/Body-centered cubics and Body-centered cubics
 
This is a body-centered cubic unit cell. Credit: Baszoetekouw.

The body-centered cubic (bcc) metals have a structure for their unit cells shown in the diagram on the left. This is not a close-packed structure. As such it is expected to occur in close-packed structures at higher temperatures.

Many pure element metals occur in a bcc structure:

  1. α-Cr,
  2. α-Fe and δ-Fe,
  3. β-Hf,
  4. α-Li,
  5. α-Mn and δ-Mn,
  6. α-Mo,
  7. α-Nb,
  8. α-Ta,
  9. β-Ti,
  10. α-V,
  11. α-W, and
  12. β-Zr.

The minerals that are or contain these metals that crystallize in a bcc lattice: titanium (Ti) through chromium (Cr), zirconium (Zr) through molybdenum (Mo), and hafnium (Hf) through tungsten (W) are studied here.

Titanium minerals

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File:Iron-titanium phase diagram.png
This is an iron-titanium phase diagram. Credit: Hirokai.

"Microbeam analysis of eclogites from the ultrahigh-pressure metamorphic belt in Dabieshan, China has revealed native titanium inclusions in garnets of coesite eclogite. The inclusions are about 10 μm in size, have a submetallic luster from the thin oxidation film on the surface, and are brown under reflected light."[1]

Titanium "undergoes a phase transformation (hcp to bcc) at 882 °C [5]."[2]

As the phase diagram on the left indicates, there is a miscibility gap between bcc iron (α-Fe) and hcp (α-Ti) up to about 800°C.

Vanadium minerals

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File:Native vanadium crystals.png
In this backscattered electron micrograph on the left, the native vanadium crystals have been colorized in red. Credit: MikhailI Ostrooumov and Yuri Taran.
File:Fe-V Phase Diagram.gif
This Fe-V phase diagram shows which phases are to be expected at equilibrium for different combinations of vanadium content and temperature. Credit: Computational Thermodynamics Inc..

"[N]ative vanadium [occurs] in natural fumarolic incrustations and in the mineral assemblage precipitated in silica tubes inserted into high-temperature (750-830°C) fumaroles of Colima volcano – the most active volcano of Mexico, and one of the most active in the Americas. [...] The new mineral and its name (“vanadium”) have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (Williams et al., 2013; IMA # 2012- 021a). The holotype material has been deposited in the Geological Museum of National Mexican University (New mineral collection of Mexican Mineralogical Society with cataloged under FIM 12/01)."[3]

In the image on the right, the backscattered electron micrograph on the left side, has the native vanadium crystals colorized in red. The energy dispersive X-ray spectroscopy (EDS) spectrum on the right shows the vanadium peaks plus small amounts of Fe and S.[3]

As the phase diagram on the left indicates vanadium is bcc down to lower temperatures from its melting point.

Chromium minerals

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File:Native chromium.jpg
This is a native chromium nugget. Credit: Neal Ekengren.
File:Fe-Cr Phase Diagram.gif
Fe-Cr phase diagram shows which phases are to be expected at equilibrium for different combinations of chromium content and temperature. Credit: Computational Thermodynamics Inc.

Native chromium such as the nugget in the image on the right is very rare. It is also a hard mineral, probably because of an oxide coating giving it a slight bluish cast.

"An unusual mineral association (diamond, SiC, graphite, native chromium, Ni-Fe alloy, Cr2+-bearing chromite), indicating a high-pressure, reducing environment, occurs in both the peridotites and chromitites."[4]

As the phase diagram for the Fe-Cr system on the left shows, chromium is bcc from 600°C on up to melting. Chromium is also bcc at room temperature and pressure.

Zirconium minerals

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A lustrous crystal of zircon is perched on a tan matrix of calcite from the Gilgit District of Pakistan Credit: Robert M. Lavinsky.{{free media}}
File:Fe-Zr phase diagram.gif
This is a binary phase diagram of the iron-zirconum system. Credit: D. Arias and J.P. Abriata.{{fairuse}}
 
Hand-polished blue zircon from Cambodia is 3.36 carats. Credit: DonGuennie.{{free media}}

As the Fe-Zr phase diagram on the left demonstrates, zirconium has a hcp structure (α-Zr) at lower temperatures, including room temperature, and a bcc structure (β-Zr) at higher temperatures up to melting.

Zircon has the ideal chemical formula of ZrSiO
4, is a nesosilicate, and has a unit cell of a = 6.607(1), c = 5.982(1) [Å]; Z = 4. Crystals shocked by meteorite impact show polysynthetic twins on {112}.

Radiometric dating

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Zircons contain trace amounts of uranium and thorium (from 10 ppm up to 1 wt%) and can be dated using several modern analytical techniques. Because zircons can survive geologic processes like erosion, transport, even high-grade metamorphism, they contain a rich and varied record of geological processes. Zircons are usually dated by uranium-lead (U-Pb), fission track, cathodoluminescence, and U+Th/He techniques.

Imaging the cathodoluminescence emission from fast electrons can be used as a pre-screening tool for high-resolution secondary-ion-mass spectrometry (SIMS) to image the zonation pattern and identify regions of interest for isotope analysis. This is done using an integrated cathodoluminescence and scanning electron microscope.[5]

Detrital zircon geochronology, i.e., zircons in sedimentary rock can identify the sediment source.

Zircons from Jack Hills in the Narryer Gneiss Terrane, Yilgarn Craton, Western Australia, have yielded U-Pb ages up to 4.404 billion years,[6] interpreted to be the age of crystallization, making them the oldest minerals so far dated on Earth.

The oxygen isotopic compositions of some of these zircons have been interpreted to indicate that more than 4.4 billion years ago there was already water on the surface of the Earth.[6][7] This interpretation is supported by additional trace element data,[8][9] but is also the subject of debate.[10][11] In 2015, "remains of biotic life" were found in 4.1 billion-year-old rocks in the Jack Hills of Western Australia.[12][13] According to one of the researchers, "If life arose relatively quickly on Earth ... then it could be common in the universe."[12]

Niobium minerals

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File:Iron-niobium phase diagram.png
This is an iron-niobium phase diagram. Credit: E. Paul and L.J. Swartendruber.

As can be seen in the iron-niobium phase diagram on the left, niobium is single phase (α-Nb) up to its melting temperature. This is a bcc structure.

It appears to be the case that native niobium does not occur in the surface rocks on Earth.

Molybdenum minerals

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File:Native molybdenum Luna 24 landing site.jpg
This is a scanning electron micrograph of native molybdenum particles in lunar regolith. Credit: A. V. Mokhov and P. M. Kartashov.
File:Fe-Mo Phase Diagram.gif
This is a calculated iron-molybdenum phase diagram. Credit: Computational Thermodynamics Inc.

The electron micrograph on the right shows a couple of pieces of native molybdenum found in lunar regolith at the Luna 24 landing site after transport back to Earth and analysis.

The phase diagram for the iron-molybdenum system demonstrates that molybdenum is bcc (α-Mo) for its intermediate and higher temperatures. It's also bcc at room temperature.

Hafnium minerals

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File:Fe-Hf phase diagram.gif
This is an iron-hafnium phase diagram. Credit: H. Okamoto.{{fairuse}}

Note in the iron-hafnium phase diagram on the left that hafnium occurs in two phases: hcp (α-Hf) at lower temperatures and bcc (β-Hf) at higher temperatures up to melting.

Tantalum minerals

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File:Native tantalum from Greenland.jpg
This is a piece of native tantalum from Kvanefjeld Mountain, Kuannersuit Plateau, Ilímaussaq complex, Narsaq, Kujalleq, Greenland. Credit: V.V. Seredin.
File:Iron-Tantalum phase diagram.png
This is a National Bureau of Standards phase diagram for Fe-Ta. Credit: L.J. Swartzendruber and E. Paul.

On the right is a scanning electron micrograph of a piece of native tantalum from Kvanefjeld Mountain, Kuannersuit Plateau, Ilímaussaq complex, Narsaq, Kujalleq, Greenland.

The iron-tantalum phase diagram on the left shows the bcc (α-Ta) phase from lower temperatures through and up to melting.

Tungsten minerals

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File:Native tungsten Luna 24 landing site.jpg
The small, bright crystalline mass on the right of this electron micrograph is native tungsten. Credit: Andrei V. Mokhov.
File:Fe-W-phase-diagram.jpg
This is an iron-tungsten phase diagram. Credit: Satyendra.

In the scanning electron micrograph on the right is a bright grain, or crystalline mass, of native tungsten. The sample is a fragment of lunar silicate glass from the Luna 24 landing site, Mare Crisium, The Moon. The fragment is bright in backscattered electrons.

The iron-tungsten phase diagram on the left shows that the bcc phase of tungsten (α-W) occurs from lower temperatures on up to the melting temperature.

Hypotheses

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Main resource: Hypotheses
  1. Taking on a bcc structure to defer melting to a higher temperature came before a fcc or hcp structure.

See also

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References

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  1. ↑ Jing Chen, Jiliang Li, and Jun Wu (30 April 2000). "Native titanium inclusions in the coesite eclogites from Dabieshan, China". Earth and Planetary Science Letters 177 (3-4): 237-40. doi:10.1016/S0012-821X(00)00057-1. http://www.sciencedirect.com/science/article/pii/S0012821X00000571. Retrieved 2015-08-19. 
  2. ↑ B.B. Panigrahi, M.M. Godkhindi , K. Das, P.G. Mukunda, and P. Ramakrishnan (15 April 2005). "Sintering kinetics of micrometric titanium powder". Materials Science and Engineering: A 396 (1-2): 255-62. doi:10.1016/j.msea.2005.01.016. http://www.sciencedirect.com/science/article/pii/S0921509305000778. Retrieved 2015-08-19. 
  3. ↑ 3.0 3.1 MikhailI Ostrooumov and Yuri Taran (20 May 2015). "Discovery of Native Vanadium, a New Mineral from the Colima Volcano, State of Colima (Mexico)". Revista de la Sociedad Española de Mineralogía: 109-10. http://www.uhu.es/fexp/sem2015/arc/macla/macla_20_109-110.pdf. Retrieved 2015-08-19. 
  4. ↑ Wen-Ji Bai, Mei-Fu Zhou, and Paul T. Robinson (August 1993). "Possibly diamond-bearing mantle peridotites and podiform chromitites in the Luobusa and Donqiao ophiolites, Tibet". Canadian Journal of Earth Sciences 30 (8): 1650-9. doi:10.1139/e93-143. http://www.nrcresearchpress.com/doi/abs/10.1139/e93-143. Retrieved 2015-08-19. 
  5. ↑ BV, DELMIC. "Zircons - Application Note | DELMIC". request.delmic.com. Retrieved 2017-02-10.
  6. ↑ 6.0 6.1 Wilde S.A., Valley J.W., Peck W.H. and Graham C.M. (2001). "Evidence from detrital zircons for the existence of continental crust and oceans on the Earth 4.4 Gyr ago". Nature 409 (6817): 175–8. doi:10.1038/35051550. PMID 11196637. http://www.geology.wisc.edu/%7Evalley/zircons/Wilde2001Nature.pdf. 
  7. ↑ Mojzsis, S.J., Harrison, T.M., Pidgeon, R.T.; Harrison; Pidgeon (2001). "Oxygen-isotope evidence from ancient zircons for liquid water at the Earth's surface 4300 Myr ago". Nature 409 (6817): 178–181. doi:10.1038/35051557. PMID 11196638. 
  8. ↑ Ushikubo, T., Kita, N.T., Cavosie, A.J., Wilde, S.A. Rudnick, R.L. and Valley, J.W. (2008). "Lithium in Jack Hills zircons: Evidence for extensive weathering of Earth's earliest crust". Earth and Planetary Science Letters 272 (3–4): 666–676. doi:10.1016/j.epsl.2008.05.032. 
  9. ↑ "Ancient mineral shows early Earth climate tough on continents". Physorg.com. June 13, 2008.
  10. ↑ Nemchin, A.A., Pidgeon, R.T., Whitehouse, M.J.; Pidgeon; Whitehouse (2006). "Re-evaluation of the origin and evolution of >4.2 Ga zircons from the Jack Hills metasedimentary rocks". Earth and Planetary Science Letters 244: 218–233. doi:10.1016/j.epsl.2006.01.054. 
  11. ↑ Cavosie, A.J., Valley, J.W., Wilde, S.A., E.I.M.F.; Valley; Wilde; e.i.m.f. (2005). "Magmatic δ18O in 4400–3900 Ma detrital zircons: a record of the alteration and recycling of crust in the Early Archean". Earth and Planetary Science Letters 235 (3–4): 663–681. doi:10.1016/j.epsl.2005.04.028. 
  12. ↑ 12.0 12.1 Borenstein, Seth (19 October 2015). "Hints of life on what was thought to be desolate early Earth". Yonkers, NY: Mindspark Interactive Network. Retrieved 8 October 2018.
  13. ↑ Bell, Elizabeth A.; Boehnike, Patrick; Harrison, T. Mark et al. (19 October 2015). "Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon". Proc. Natl. Acad. Sci. U.S.A. (Washington, D.C.: National Academy of Sciences) 112: 14518–21. doi:10.1073/pnas.1517557112. ISSN 1091-6490. PMID 26483481. PMC 4664351. http://www.pnas.org/content/early/2015/10/14/1517557112.full.pdf. Retrieved 2015-10-20. 
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