Hostname: page-component-8448b6f56d-wq2xx Total loading time: 0 Render date: 2024-04-19T21:16:21.670Z Has data issue: false hasContentIssue false

Soft X-Ray and Cathodoluminescence Examination of a Tanzanian Graphite Deposit

Published online by Cambridge University Press:  06 April 2020

Colin M. MacRae*
Affiliation:
CSIRO Mineral Resources, Microbeam Laboratory, Clayton, VIC, Australia
Mark A. Pearce
Affiliation:
CSIRO Mineral Resources, Australian Resources Research Centre, Kensington, WA, Australia
Nicholas C. Wilson
Affiliation:
CSIRO Mineral Resources, Microbeam Laboratory, Clayton, VIC, Australia
Aaron Torpy
Affiliation:
CSIRO Mineral Resources, Microbeam Laboratory, Clayton, VIC, Australia
Matthew A. Glenn
Affiliation:
CSIRO Mineral Resources, Microbeam Laboratory, Clayton, VIC, Australia
Salvy P. Russo
Affiliation:
ARC Centre of Excellence in Exciton Science, School of Science, RMIT University, Melbourne3000, VIC, Australia
*
*Author for correspondence: Colin M. MacRae, E-mail: colin.macrae@csiro.au
Get access

Abstract

Hyperspectral soft X-ray emission (SXE) and cathodoluminescence (CL) spectrometry have been used to investigate a carbonaceous-rich geological deposit to understand the crystallinity and morphology of the carbon and the associated quartz. Panchromatic CL maps show both the growth of the quartz and the evidence of recrystallization. A fitted CL map reveals the distribution of Ti4+ within the grains and shows subtle growth zoning, together with radiation halos from 238U decay. The sensitivity of the SXE spectrometer to carbon, together with the anisotropic X-ray emission from highly orientated pyrolytic graphite, has enabled the C Kα peak shape to be used to measure the crystal orientation of individual graphite regions. Mapping has revealed that most grains are predominantly of a single orientation, and a number of graphite grains have been investigated to demonstrate the application of this new SXE technique. A peak fitting approach to analyzing the SXE spectra was developed to project the C Kα 2pz and 2p(x+y) orbital components of the graphite. The shape of these two end-member components is comparable to those produced by electron density of states calculations. The angular sensitivity of the SXE spectrometer has been shown to be comparable to that of electron backscatter diffraction.

Type
Australian Microbeam Analysis Society Special Section AMAS XV 2019
Copyright
Copyright © Microscopy Society of America 2020

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.)

References

Becke, AD (1993). Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98(7), 56485652.Google Scholar
Botis, S, Pan, YM, Bonli, T, Xu, YK, Zhang, AM, Nokhrin, S & Sopuck, V (2006). Natural radiation-induced damage in quartz. II. Distribution and implications for uranium mineralization in the Athabasca basin, Saskatchewan, Canada. Can Mineral 44(6), 13871402.CrossRefGoogle Scholar
Britton, TB & Hickey, JLR (2018). Understanding deformation with high angular resolution electron backscatter diffraction (HR-EBSD). IOP Conference Series: Materials Science and Engineering, vol. 304, 012003. EMAS 2017 Workshop - 15th European Workshop on Modern Developments and Applications in Microbeam Analysis & IUMAS-7 Meeting - 7th Meeting of the International union of Microbeam Analysis Societies 7–11 May 2017, Konstanz, Germany.Google Scholar
Deer, WA, Howie, RA & Zussman, J (1992). An Introduction to the Rock-Forming Minerals, 2nd ed. Essex, England: Pearson Education limited.Google Scholar
Dovesi, R, Orlando, R, Erba, A, Zicovich-Wilson, CM, Civalleri, B, Casassa, S, Maschio, L, Ferrabone, M, De La Pierre, M, D'Arco, P, Noël, Y, Causà, M, Rérat, M & Kirtman, B (2014). CRYSTAL14: A program for the ab initio investigation of crystalline solids. Int J Quantum Chem 114(19), 12871317.CrossRefGoogle Scholar
Fritz, H, Abdelsalam, M, Ali, KA, Bingen, B, Collins, AS, Fowler, AR, Ghebreab, W, Hauzenberger, CA, Johnson, PR, Kusky, TM, Macey, P, Muhongo, S, Stern, RJ & Viola, G (2013). Orogen styles in the East African Orogen: A review of the Neoproterozoic to Cambrian tectonic evolution. J Afr Earth Sci 86, 65106.CrossRefGoogle ScholarPubMed
Götze, J, Plötze, M & Habermann, D (2001). Origin, spectral characteristics and practical applications of the cathodoluminescence (CL) of quartz – A review. Mineral Petrol 71(3), 225250.Google Scholar
Harrowfield, IR, MacRae, CM & Wilson, NC (1993). Chemical imaging on electron microprobes. Microbeam Anal 2(Suppl), 547548.Google Scholar
Holliday, JE (1968). Soft X-ray emission bands and bonding for transition metals, solutions and compounds. In Soft X-ray Band Spectra, Fabian, DJ (Ed.), pp. 101132. London and New York: Academic Press.Google Scholar
Ishii, S, Terauchi, M, Sato, Y, Tamura, N, Aono, M & Abe, H (2018). Soft X-ray emission spectroscopy study of characteristic bonding states and its distribution of amorphous carbon-nitride (a-CNx) films. Microscopy (Oxf). 67(4), 244249.CrossRefGoogle Scholar
Jara, AD, Betemariam, A, Woldetinsae, G & Kim, JY (2019). Purification, application and current market trend of natural graphite: A review. Int J Min Sci Technol 29(5), 671689.CrossRefGoogle Scholar
Kalceff, MA & Phillips, MR (1995). Cathodoluminescence microcharacterization of the defect structure of quartz. Phys Rev B Condens Matter 52(5), 31223134.CrossRefGoogle ScholarPubMed
Kalceff, MAS (2009). Cathodoluminescence microcharacterization of point defects in α-quartz. Mineral Mag 73(4), 585605.CrossRefGoogle Scholar
Kalceff, MAS, Phillips, MR, Moon, AR & Kalceff, W (2000). Cathodoluminescence microcharacterisation of silicon dioxide polymorphs. In Cathodoluminescence in Geosciences, Pagel, M, Barbin, V, Blanc, P & Ohnenstetter, D (Eds.), pp. 193224. Berlin, Heidelberg: Springer Berlin Heidelberg.CrossRefGoogle Scholar
Kaneyoshi, T, Kowada, Y, Tanaka, T, Kawai, J & Motoyama, M (1999). Molecular orbital calculation of graphite K-V X-ray emission spectra. Spectrochim Acta B 54(1), 189196.CrossRefGoogle Scholar
Leeman, WP, MacRae, CM, Wilson, NC, Torpy, A, Lee, C-TA, Student, JJ, Thomas, JB & Vicenzi, EP (2012). A study of cathodoluminescence and trace element compositional zoning in natural quartz from volcanic rocks: Mapping titanium content in quartz. Microsc Microanal 18(06), 13221341.CrossRefGoogle ScholarPubMed
MacRae, C, Wilson, N & Torpy, A (2013). Hyperspectral cathodoluminescence. Mineral Petrol 107(3), 429440.CrossRefGoogle Scholar
MacRae, CM, Pearce, MA, Wilson, NC & Torpy, A (2018 a). Crystallographic orientation information by soft X-ray spectroscopy. Microsc Microanal 24(S1), 20202021.CrossRefGoogle Scholar
MacRae, CM, Wilson, NC, Johnson, SA, Phillips, PL & Otsuki, M (2005). Hyperspectral mapping — Combining cathodoluminescence and X-ray collection in an electron microprobe. Microsc Res Tech 67(5), 271277.CrossRefGoogle Scholar
MacRae, CM, Wilson, NC, Torpy, A & Hughes, AE (2019). Fast hyperspectral soft X-ray mapping. Microsc Microanal 25(S2), 246247.CrossRefGoogle Scholar
MacRae, CM, Wilson, NC, Torpy, A & Piane, CD (2018 b). Soft X-ray and cathodoluminescence measurement, optimisation and analysis at liquid nitrogen temperatures. IOP Conference Series: Materials Science and Engineering, Vol. 304, 012010. EMAS 2017 Workshop - 15th European Workshop on Modern Developments and Applications in Microbeam Analysis & IUMAS-7 Meeting - 7th Meeting of the International union of Microbeam Analysis Societies 7–11 May 2017, Konstanz, Germany.Google Scholar
Meunier, JD, Sellier, E & Pagel, M (1990). Radiation-damage rims in quartz from uranium-bearing sandstones. J Sediment Res 60(1), 5358.Google Scholar
Monkhorst, HJ & Pack, JD (1976). Special points for Brillouin-zone integrations. Phys Rev B 13(12), 51885192.CrossRefGoogle Scholar
Nolze, G (2007). Image distortions in SEM and their influences on EBSD measurements. Ultramicroscopy 107(2–3), 172183.CrossRefGoogle ScholarPubMed
Owen, MR (1988). Radiation-damage halos in quartz. Geology 16(6), 529532.2.3.CO;2>CrossRefGoogle Scholar
Pownceby, MI & MacRae, CM (2010. Electron microbeam analysis techniques used for the characterization of industrial minerals. In Advances in the Characterization of Industrial Minerals, Mineralogical Society of Great Britain and Ireland, Christidus, GE (Ed.), pp. 227286. Budapest, Hungary: Eotvos University Press.CrossRefGoogle Scholar
Robinson, BW, Ware, NG & Smith, DGW (1998). Modern electron-microprobe trace-eleement analysis in mineralogy. In Modern Approaches to Ore and Environmental Mineralogy, Cabri, LJ & Vaughan, DJ (Eds.), pp. 153180. Ottawa, Canada: Mineralogical association of Canada.Google Scholar
Robinson, GR, Hammarstrom, JM & Olson, DW (2017). Graphite. U.S. Geological Survey Critical Mineral Resources of the United States—Economic and Environmental Geology and Prospects for Future Supply, J1-J24.Google Scholar
Srbinovsky, J, Wilson, NC, MacRae, CM & Russo, SP (2005). Ab initio modelling of Kα X-ray spectra in single walled carbon nanotubes. J Comput Theor Nanosci 2(2), 272276.CrossRefGoogle Scholar
Suess, MJ, Mueller, E & Wepf, R (2011). Minimization of amorphous layer in Ar+ ion milling for UHR-EM. Ultramicroscopy 111(8), 12241232.CrossRefGoogle ScholarPubMed
Terauchi, M, Koike, M, Fukushima, K & Kimura, A (2010). Development of wavelength-dispersive soft X-ray emission spectrometers for transmission electron microscopes – An introduction of valence electron spectroscopy for transmission electron microscopy. J Electron Microsc (Tokyo) 59(4), 251261.CrossRefGoogle ScholarPubMed
Teruachi, M, Takahashi, H, Takakura, M, Murano, T & Koshiya, S (2019). Handbook of Soft X-ray Emission Spectra. Japan: IMRAM, Tohoku University and JEOL Ltd.Google Scholar
Thomas, JB, Watson, BE, Spear, FS, Shemella, PT, Nayak, SK & Lanzirotti, A (2010). TitaniQ under pressure: The effect of pressure and temperature on the solubility of Ti in quartz. Contrib Mineral Petrol 160(5), 743759.CrossRefGoogle Scholar
Vasyukova, O, Goemann, K, Kamenetsky, V, MacRae, C & Wilson, N (2013). Cathodoluminescence properties of quartz eyes from porphyry-type deposits: Implications for the origin of quartz. Am Mineral 98(1), 98109.CrossRefGoogle Scholar
Wark, DA & Watson, EB (2006). TitaniQ: A titanium-in-quartz geothermometer. Contrib Mineral Petrol 152(6), 743754.CrossRefGoogle Scholar
Wilson, NC & MacRae, CM (2005). An automated hybrid clustering technique applied to spectral data sets. Microsc Microanal 11(Suppl), 434435.CrossRefGoogle Scholar
Wilson, NC, MacRae, CM, Torpy, A, Davidson, CJ & Vicenzi, EP (2012). Hyperspectral cathodoluminescence examination of defects in a carbonado diamond. Microsc Microanal 18(06), 13031312.CrossRefGoogle Scholar