Hostname: page-component-586b7cd67f-r5fsc Total loading time: 0 Render date: 2024-11-23T23:39:04.841Z Has data issue: false hasContentIssue false
  • English
  • Français

Beryllium incorporation in corundum

Published online by Cambridge University Press:  13 July 2022

Michael C. Jollands  and
Etienne Balan
Michael C. Jollands*
Affiliation:
Gemological Institute of America, 50 W. 47th Street, New York, NY 10036, United States of America
Etienne Balan
Affiliation:
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu, 75005 Paris, France
*
*Author for correspondence: Michael C. Jollands, Email: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

The structure of corundum is not amenable to accommodating beryllium, yet Be is commonly added to corundum for purposes of colour modification. Where the main sites in corundum are octahedrally coordinated, Be is tetrahedrally coordinated in all known Be minerals. To attempt to explain this discrepancy, the configurations of Be in the Be–Al–O±H system were determined using density functional theory (DFT). In the Be–Al–O system, the most likely Be configuration is in triangular coordination, replacing Al and bonded to three oxygen on the basal plane (large triangle) of the Al-vacant octahedral site. When H is added, OH groups form at the opposite face of the same octahedron, pointing either into or out of the site. Be–H (beryllium hydride) defects are also stable at the DFT level, with Be bonded to three O and one H. As some defects contain O–H or Be–H bonds, the DFT calculations can be corroborated by FTIR spectroscopy. Spectra recorded from 1000 corundum crystals with elevated Be confirm that bands centred at 3062 and 2490 cm–1 correspond to Be-associated defects. Polarised spectra show that the band at 2490 cm–1 resolves into two, one centred at 2491 cm–1, with a shoulder at 2523 cm–1, one of which is probably associated with a Be–H bond. The 3062 cm–1 band resolves into at least three, including a major band at 3058 cm–1, a shoulder at 3140 cm–1 and a small, sharp band at 3082 cm–1. Whilst there are caveats relating to curve fitting and baseline subtraction, the 3058 cm–1 band can probably be attributed to the defect where H points into the Al-vacant octahedral site, and the 3140 cm–1 band to the defect where the H points out. To our knowledge, this is the first occurrence of Be in triangular coordination proposed for a naturally occurring mineral. This substitution mechanism may also explain the high diffusivity of Be, as Be is effectively associated with its own Al vacancy.

Keywords

berylliumcorundumhydrogendensity functional theoryinfrared spectroscopydiffusion
Type
Article
Information
Mineralogical Magazine , Volume 86 , Issue 5 , October 2022 , pp. 758 - 766
Copyright
Copyright © The Author(s), 2022. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

Associate Editor: Andrew G Christy

References

Abduriyim, A. and Kitawaki, H. (2006) Applications of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to gemology. Gems and Gemology, 42, 98.CrossRefGoogle Scholar
Abduriyim, A., Kitawaki, H. and Shida, J. (2004) A New Technique for the Analysis of Corundum Using Laser Ablation ICP-MS. Technical Note, Agilent Technologies Inc., Santa Clara, California, USA.Google Scholar
Ando, K. (1987) Magnesium-impurity diffusion in Al2O3 single crystals. Pp. 149–158 in: Nonstoichiometric Compounds (Catlow, C.R.A. and Mackrodt, W.C., editors). Vol. 23. The American Ceramic Society, Westerville, Ohio, USA.Google Scholar
Apostolopoulos, V., Hickey, L.M.B., Sager, D.A. and Wilkinson, J.S. (2006) Diffusion of gallium in sapphire. Journal of the European Ceramic Society, 26, 2695–2698.CrossRefGoogle Scholar
Balan, E. (2020) Theoretical infrared spectra of OH defects in corundum (α-Al2O3). European Journal of Mineralogy, 32, 457–467.CrossRefGoogle Scholar
Balmer, W.A. and Krzemnicki, M.S. (2015) Be-detection by FTIR on Corundum: A Preliminary Report. IGC, Vilnius, Lithuania.Google Scholar
Baroni, S., De Gironcoli, S., Dal Corso, A. and Giannozzi, P. (2001) Phonons and related crystal properties from density-functional perturbation theory. Reviews of Modern Physics, 73, 515.CrossRefGoogle Scholar
Belonoshko, A.B., Rosengren, A., Dong, Q., Hultquist, G. and Leygraf, C. (2004) First-principles study of hydrogen diffusion in α-Al2O3 and liquid alumina. Physical Review B, 69, 24302–24302.CrossRefGoogle Scholar
El-Aiat, M.M. and Kröger, F.A. (1982) Hydrogen donors in α-Al2O3. Journal of Applied Physics, 53, 3658–3667.CrossRefGoogle Scholar
Emmett, J.L., Scarratt, K., McClure, S.F., Moses, T., Douthit, T.R., Hughes, R., Novak, S., Shigley, J.E., Wang, W. and Bordelon, O. (2003) Beryllium diffusion of ruby and sapphire. Gems & Gemology, 39, 84–135.CrossRefGoogle Scholar
Fielitz, P., Ganschow, S., Kelm, K. and Borchardt, G. (2020) Aluminium self-diffusion in high-purity α- Al2O3: Comparison of Ti-doped and undoped single crystals. Acta Materialia, 195, 416–424.CrossRefGoogle Scholar
Galakhov, F.Y. (1957) Studies of the aluminous region of ternary aluminosilicate systems 2. The system BeO–Al2O3–SiO2. Bulletin of the Academy of Sciences of the USSR, Division of chemical science, 6, 1062–1067.CrossRefGoogle Scholar
Giannozzi, P., Baroni, S., Bonini, N., Calandra, M., Car, R., Cavazzoni, C., Ceresoli, D., Chiarotti, G.L., Cococcioni, M. and Dabo, I. (2009) Quantum espresso: A modular and open-source software project for quantum simulations of materials. Journal of physics: Condensed Matter, 21, 395502.Google ScholarPubMed
Gontier-Moya, E.G., Bernardini, J. and Moya, F. (2001) Silver and platinum diffusion in alumina single crystals. Acta Materialia, 49, 637–644.CrossRefGoogle Scholar
Gonze, X. and Lee, C. (1997) Dynamical matrices, born effective charges, dielectric permittivity tensors, and interatomic force constants from density-functional perturbation theory. Physical Review B, 55, 10355–10368.CrossRefGoogle Scholar
Hamann, D.R. (2013) Optimized norm-conserving vanderbilt pseudopotentials. Physical Review B, 88, 085117.CrossRefGoogle Scholar
Haneda, H. and Monty, C. (1989) Oxygen self-diffusion in magnesium- or titanium-doped alumina single crystals. Journal of the American Ceramic Society, 72, 1153–1157.CrossRefGoogle Scholar
Hänni, H. and Pettke, T. (2002) Eine neue diffusionsbehandlung liefert orangefarbene und gelbe saphire. Zeitschrift der Deutschen Gemmologischen Gesellschaft, 51, 137–152.Google Scholar
Harris, L.A. and Yakel, H.L. (1966) The crystal structure of calcium beryllate, Ca12Be17O29. Acta Crystallographica, 20, 295–301.CrossRefGoogle Scholar
Harris, L.A. and Yakel, H.L. (1967) The crystal structure of Y2BeO4. Acta Crystallographica, 22, 354–360.CrossRefGoogle Scholar
Hauffe, K. and Hoeffgen, D. (1970) Zum mechanismus der umladung von kobaltionen im saphir. Berichte der Bunsengesellschaft für physikalische Chemie, 74, 537–546.Google Scholar
Hawthorne, F.C. and Huminicki, D.M.C. (2002) The crystal chemistry of beryllium. Pp. 333–403 in: Beryllium: Mineralogy, Petrology, and Geochemistry (Grew, Ed, editor). Reviews in Mineralogy and Geochemistry, 50. Mineralogical Society of America, Washington DC.CrossRefGoogle Scholar
Hickey, L.M.B., Martins, E., Román, J.E., Brocklesby, W.S. and Wilkinson, J.S. (1996) Fluorescence of Ti3+ ions thermally diffused into sapphire. Optics Letters, 21, 597–599.CrossRefGoogle Scholar
Jollands, M.C., Burnham, A.D., O'Neill, H.S.C., Hermann, J. and Qian, Q. (2016) Beryllium diffusion in olivine: A new tool to investigate timescales of magmatic processes. Earth and Planetary Science Letters, 450, 71–82.CrossRefGoogle Scholar
Jollands, M.C., Blanchard, M. and Balan, E. (2020) Structure and theoretical infrared spectra of OH defects in quartz. European Journal of Mineralogy, 32, 311–323.CrossRefGoogle Scholar
Kronenberg, A.K., Castaing, J., Mitchell, T.E. and Kirby, S.H. (2000) Hydrogen defects in α- Al2O3 and water weakening of sapphire and alumina ceramics between 600 and 1000°C-I. Infrared characterization of defects. Acta Materialia, 48, 1481–1494.CrossRefGoogle Scholar
Krzemnicki, M.S., Hänni, H.A. and Walters, R.A. (2004) A new method for detecting be diffusion-treated sapphires: Laser-induced breakdown spectroscopy (LIBS). Gems & Gemology, 40, 314–322.CrossRefGoogle Scholar
Le Gall, M., Lesage, B. and Bernardini, J. (1994) Self-diffusion in α- Al2O3 I. Aluminium diffusion in single crystals. Philosophical Magazine A, 70, 761–773.CrossRefGoogle Scholar
Legros, C., Lesage, B., Borchardt, G., Kilo, M. and Jomard, F. (2005) Lanthanide diffusion in single crystalline and polycrystalline pure or yttrium doped alpha-alumina. Defect and Diffusion Forum, 237–240, 432–437.CrossRefGoogle Scholar
Lesage, B., Huntz, A.M. and Petot-ervas, G. (1983) Transport phenomena in undoped and chromium or yttrium doped-alumina. Radiation Effects, 75, 283–299.CrossRefGoogle Scholar
Libowitzky, E. and Beran, A. (2006) The structure of hydrous species in nominally anhydrous minerals: Information from polarized IR spectroscopy. Pp. 29–52 in: Water in Nominally Anhydrous Minerals (Keppler, Hans and Smyth, Joseph R., editors). Reviews in Mineralogy and Geochemistry, 62,. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.CrossRefGoogle Scholar
Mao, W., Chikada, T., Shimura, K., Suzuki, A. and Terai, T. (2013) Energetics and diffusion of hydrogen in α- Al2O3 and Er2O3. Fusion Engineering and Design, 88, 2646–2649.CrossRefGoogle Scholar
Moya, F., Moya, E.G., Juvé, D., Tréheux, D., Grattepain, C. and Aucouturier, M. (1993) SIMS study of copper diffusion into bulk alumina. Scripta Metallurgica et Materialia, 28, 343–348.CrossRefGoogle Scholar
Moya, E.G., Moya, F., Sami, A., Juvé, D., Tréheux, D. and Grattepain, C. (1995) Diffusion of chromium in alumina single crystals. Philosophical Magazine A, 72, 861–870.CrossRefGoogle Scholar
Moya, E.G., Moya, F., Lesage, B., Loudjani, M.K. and Grattepain, C. (1998) Yttrium diffusion in α-alumina single crystal. Journal of the European Ceramic Society, 18, 591–594.CrossRefGoogle Scholar
Müller, R. and Günthard, H.H. (1966) Spectroscopic study of the reduction of nickel and cobalt ions in sapphire. The Journal of Chemical Physics, 44, 365–373.CrossRefGoogle Scholar
Newnham, Ε.E. and De Haan, Υ.M. (1962) Refinement of the αAl2O3, Ti2O3, V2O3 and Cr2O3 structures. Zeitschrift für Kristallographie-Crystalline Materials, 117, 235–237.CrossRefGoogle Scholar
Oishi, Y. and Kingery, W.D. (1960) Self-diffusion of oxygen in single crystal and polycrystalline aluminum oxide. The Journal of Chemical Physics, 33, 480–486.CrossRefGoogle Scholar
Paladino, A.E.K. and Kingery, W.D. (1962) Aluminum ion diffusion in aluminum oxide. The Journal of Chemical Physics, 37, 957–962.CrossRefGoogle Scholar
Pan, X.-D., Xu, Y.-P., Lu, T., Lyu, Y.-M., Zhou, H.-S., Yang, Z.-S., Niu, G.-J., Li, X.-C., Gao, F. and Luo, G.-N. (2021) First-principles study on the dissolution and diffusion properties of hydrogen in α- Al2O3. Ceramics International, 47, 5699–5707.CrossRefGoogle Scholar
Perdew, J.P., Burke, K. and Ernzerhof, M. (1996) Generalized gradient approximation made simple. Physical Review Letters, 77, 3865–3868.CrossRefGoogle ScholarPubMed
Ramirez, R., Gonzalez, R., Colera, I. and Vila, R. (1997) Protons and deuterons in magnesium-doped sapphire crystals. Journal of the American Ceramic Society, 80, 847–850.CrossRefGoogle Scholar
Reddy, K.P.R. and Cooper, A.R. (1982) Oxygen diffusion in sapphire. Journal of the American Ceramic Society, 65, 634–638.CrossRefGoogle Scholar
Roberts, R.M., Elleman, T.S., Palmour III, H. and Verghese, K. (1979) Hydrogen permeability of sintered aluminum oxide. Journal of the American Ceramic Society, 62, 495–499.CrossRefGoogle Scholar
Schlipf, M. and Gygi, F. (2015) Optimization algorithm for the generation of ONCV pseudopotentials. Computer Physics Communications, 196, 36–44.CrossRefGoogle Scholar
Sérier, B., Berroug, A., Juvé, D., Tréheux, D. and Moya, E.G. (1993) Silver-alumina solid state bonding: Study of diffusion and toughness close to the interface. Journal of the European Ceramic Society, 12, 385–390.CrossRefGoogle Scholar
Shayesteh, A., Tereszchuk, K., Bernath, P.F. and Colin, R. (2003a) Infrared emission spectra of BeH2 and BeD2. The Journal of Chemical Physics, 118, 3622–3627.CrossRefGoogle Scholar
Shayesteh, A., Tereszchuk, K., Bernath, P.F. and Colin, R. (2003b) Infrared emission spectra of BeH and BeD. The Journal of Chemical Physics, 118, 1158–1161.CrossRefGoogle Scholar
Somjit, V. and Yildiz, B. (2019) Doping α-Al2O3 to reduce its hydrogen permeability: Thermodynamic assessment of hydrogen defects and solubility from first principles. Acta Materialia, 169, 172–183.CrossRefGoogle Scholar
Takahashi, N., Mizoguchi, T., Nakagawa, T., Tohei, T., Sakaguchi, I., Kuwabara, A., Shibata, N., Yamamoto, T., Ohashi, N. and Ikuhara, Y. (2010) Cr diffusion in Al2O3: Secondary ion mass spectroscopy and first-principles study. Physical Review B, 82, 174302.CrossRefGoogle Scholar
Wang, F., Lai, W., Li, R., He, B. and Li, S. (2016) Fast hydrogen diffusion along the σ7 grain boundary of α- Al2O3: A first-principles study. International Journal of Hydrogen Energy, 41, 22214–22220.CrossRefGoogle Scholar
Wang, H.A., Krzemnicki, M.S., Chalain, J.-P., Lefèvre, P., Zhou, W. and Cartier, L.E. (2016) Simultaneous high sensitivity trace-element and isotopic analysis of gemstones using laser ablation inductively coupled plasma time-of-flight mass spectrometry. Journal of Gemmology, 35.CrossRefGoogle Scholar
Supplementary material: File

Jollands and Balan supplementary material

Jollands and Balan supplementary material

Download Jollands and Balan supplementary material(File)
File 8.6 MB