Hostname: page-component-586b7cd67f-r5fsc Total loading time: 0 Render date: 2024-11-22T18:50:21.805Z Has data issue: false hasContentIssue false
  • English
  • Français

In Situ Observation of Electron Beam-Induced Phase Transformation of CaCO3 to CaO via ELNES at Low Electron Beam Energies

Published online by Cambridge University Press:  08 April 2014

Ute Golla-Schindler ,
Gerd Benner ,
Alexander Orchowski  and
Ute Kaiser
Ute Golla-Schindler*
Affiliation:
Group of Electron Microscopy of Material Science, University Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany
Gerd Benner
Affiliation:
Materials Division, Carl Zeiss Microscopy GmbH, Carl-Zeiss Str. 22, 73447 Oberkochen, Germany
Alexander Orchowski
Affiliation:
Materials Division, Carl Zeiss Microscopy GmbH, Carl-Zeiss Str. 22, 73447 Oberkochen, Germany
Ute Kaiser
Affiliation:
Group of Electron Microscopy of Material Science, University Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany
*
*Corresponding author. [email protected]
Get access

Abstract

It is demonstrated that energy-filtered transmission electron microscope enables following of in situ changes of the Ca-L2,3 edge which can originate from variations in both local symmetry and bond lengths. Low accelerating voltages of 20 and 40 kV slow down radiation damage effects and enable study of the start and finish of phase transformations. We observed electron beam-induced phase transformation of single crystalline calcite (CaCO3) to polycrystalline calcium oxide (CaO) which occurs in different stages. The coordination of Ca in calcite is close to an octahedral one streched along the <111> direction. Changes during phase transformation to an octahedral coordination of Ca in CaO go along with a bond length increase by 5 pm, where oxygen is preserved as a binding partner. Electron loss near-edge structure of the Ca-L2,3 edge show four separated peaks, which all shift toward lower energies during phase transformation at the same time the energy level splitting increases. We suggest that these changes can be mainly addressed to the change of the bond length on the order of picometers. An important pre-condition for such studies is stability of the energy drift in the range of meV over at least 1 h, which is achieved with the sub-Ångström low-voltage transmission electron microscope I prototype microscope.

Keywords

ELNESlow kV TEMSALVECaCO3 (calcite)radiation damage
Type
EDGE Special Issue
Information
Microscopy and Microanalysis , Volume 20 , Issue 3 , June 2014 , pp. 715 - 722
Copyright
© Microscopy Society of America 2014 

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

Burns, R.G. (1993). Mineralogical Applications of Crystal Field Theory. Cambridge, New York: Cambridge University Press. pp. 30–36.CrossRefGoogle Scholar
Cater, D.E. & Buseck, P.R. (1985). Mechanism of decomposition of dolomite Ca0.5Mg0.5CO3, in the electron microscope. Ultramicroscopy 18, 241–252.CrossRefGoogle Scholar
deGroot, F.M.F., Grioni, M. & Fuggle, J.C. (1989). Oxygen 1s x-ray-absorption edges of transition-metal oxides. Phys Rev B 40, 5715–5723.CrossRefGoogle Scholar
Egerton, R.F. (2012). Mechanism of radiation damage in beam-sensitive specimens, for TEM accelerating voltages between 10 kV and 300 kV. Microsc Res Tech 75, 1550–1556.CrossRefGoogle Scholar
Fiquet, G., Richet, P. & Montagnac, G. (1999). High-temperature thermal expansion of lime, periclase, corundum and spinel. Phys Chem Minerals 27, 103–111.CrossRefGoogle Scholar
Garvie, L.A.J., Craven, A.J. & Brydson, R. (1994). Use of electron-energy loss near-edge fine structure in the study of minerals. Am Mineralogist 79, 411–425.Google Scholar
Golla, U., Schindler, B. & Reimer, L. (1994). Contrast in the transmission mode of a low-voltage scanning electron microscope. J Microsc 173, 219–225.CrossRefGoogle Scholar
Golla-Schindler, U., Schweigert, W., Benner, G., Orchowski, A. & Kaiser, U. (2013). Quantitative study of electron radiation damage by in situ observation of the phase transformation from CaCO3 to CaO with high and Low kV transmission electron microscopy. Microsc Microanal 19(Suppl 2), 1214–1215.CrossRefGoogle Scholar
Graf, D.L. (1961). Crystallographic tables for the rhombohedral carbonates. Am Mineralogist 46, 1283–1316.Google Scholar
Hofer, F. & Golob, P. (1987). New examples for near-edge fine structures in electron energy loss spectroscopy. Ultramicroscopy 21, 379–384.CrossRefGoogle Scholar
Kahl, F. & Rose, H. (2000). Design of a monochromator for electron sources. Proc 11th Eur Cong Electr Micr 1, 1459–1460.Google Scholar
Kaiser, U., Biskupek, J., Meyer, J.C., Leschner, J., Lechner, L., Rose, H., Stoger-Pollach, M., Khlobystov, A.N., Hartel, P., Muller, H., Haider, M., Eyhusen, S. & Benner, G. (2011). Transmission electron microscopy at 20 kV for imaging and spectroscopy. Ultramicroscopy 111, 1239–1246.CrossRefGoogle Scholar
Klein, C. & Hurlbut, C.S. Jr. (1993). Metamict minerals. In Manual of Mineralogy (after James D. Dana), 21st ed. Klein C. & Hurlbut C.S. Jr (Eds.), pp. 159–160. New York: Wiley.Google Scholar
Krivanek, O.L. & Paterson, J.H. (1990). ELNES of 3d transition-metal oxides. Ultramicroscopy 32, 313–318.CrossRefGoogle Scholar
Lanio, S., Rose, H. & Krahl, D. (1986). Test and improvement design of a corrected imaging magnetic energy filter. Optik 73, 56–68.Google Scholar
Meyer, J.C., Eder, F., Kurasch, S., Skakalova, V., Kotakoski, J., Park, H.-J., Roth, S., Chuvilin, A., Eyhusen, S., Benner, G., Krasheninnikov, A.V. & Kaiser, U. (2012). Accurate measurement of electron beam induced displacement cross sections for single-layer graphene. Phys Rev Lett 108, 196102–196108.CrossRefGoogle ScholarPubMed
MkHoyan, K.A., Silcox, J., McGuire, M.A. & Disalvo, F.J. (2006). Radiolytic purification of CaO by electron beams. Philosophical Mag 86, 2907–2917.CrossRefGoogle Scholar
Muller, D. (1999). Why changes in bond length and cohesion lead to core-level shifts in metals, and consequences for the spatial difference method. Ultramicroscopy 78, 163–174.CrossRefGoogle Scholar
Murooka, Y. & Walls, M.G. (1991). Beam damage on anisotropic material (CaCO3) in STEM. EMAG 91. Inst Phys Conf Ser 119, 337–340.Google Scholar
Reimer, L. (1997). Transmission Electron Microscopy, 4th ed. Berlin, Heidelberg, New York: Springer Verlag.CrossRefGoogle Scholar
Rez, P. & Blackwell, A. (2011). Ca L23 spectrum in amorphous and crystalline phases of calcium carbonate. J Phys Chem B 115, 11193–11198.CrossRefGoogle ScholarPubMed
Rose, H. (1990). Outline of a spherically corrected semi-aplanatic medium-voltage TEM. Optik 85, 19–24.Google Scholar
Tietz, H., Ghadimi, R. & Daberkow, I. (2012). Single electron events in TEM. Imag Microsc 14, 46–48.Google Scholar
Towe, K.M. (1978). Ultrastructure of clacite decomposition in vacuo. Nature 274, 239– 240.CrossRefGoogle Scholar
Uhlemann, S., Haider, M. & Rose, H. (1994). Procedures for adjusting and controlling the alignment of a spherically corrected electron microscope. In ProcICEM-13 Paris, B. Jouffrey (Ed.), et al., pp. 193–194. Paris I: Les Editions de Physique.Google Scholar
Uhlemann, S. & Haider, M. (2002). Experimental set-up of a fully electrostatic monochromator for a 200 kV TEM. Proc 15th Int Cong Electr Micr 3, 327–328.Google Scholar
Walls, M.G. & Tence, M. (1989). EELS study of beam-induced decomposition of calcite in STEM. EMAG-MICRO 89. Inst Phys Conf Ser 98, 255–258.Google Scholar