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Quantitative Analysis of Nitrogen by Atom Probe Tomography Using Stoichiometric γ′-Fe4N Consisting of 15N Isotope

Published online by Cambridge University Press:  26 November 2021

Jun Takahashi Open the ORCID record for Jun Takahashi [Opens in a new window] ,
Kazuto Kawakami ,
Koyo Miura ,
Mitsuhiro Hirano  and
Naofumi Ohtsu
Jun Takahashi*
Affiliation:
Advanced Technology Research Laboratories, Nippon Steel Corporation, 20-1 Shintomi, Futtsu, Chiba293-8511, Japan
Kazuto Kawakami
Affiliation:
Resource and Process Solution Dev., Nippon Steel Technology Co. Ltd., 20-1 Shintomi, Futtsu, Chiba293-0011, Japan
Koyo Miura
Affiliation:
School of Earth, Energy and Environmental Engineering, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido090-8507, Japan
Mitsuhiro Hirano
Affiliation:
School of Earth, Energy and Environmental Engineering, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido090-8507, Japan
Naofumi Ohtsu
Affiliation:
School of Earth, Energy and Environmental Engineering, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido090-8507, Japan
*
*Corresponding author: Jun Takahashi, E-mail: takahashi.3ct.jun@jp.nipponsteel.com
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Abstract

The nitrogen deficiency in steels measured by atom probe tomography (APT) is considered to arise from the obscurement of singly charged dimer nitrogen ions (N2+) by the iron-dominant peak (56Fe2+) at 28 Da. To verify this by quantifying the amount of N2+ ions, γ′-Fe4N consisting of the 15N isotope was prepared on iron substrates by plasma nitriding using a nitrogen isotopic gas (15N2). Although considerable amounts of 15N2+ were observed at 30 Da without overlap with any iron peak, the observed nitrogen concentrations of γ′-Fe4N were clearly lower than the stoichiometric composition (19–20 at%), using both pulsed voltage and pulsed laser atom probes. The origin of the missing nitrogen, excluding nitrogen obscured by other ion species, was predicted to be the occurrence of neutral nitrogen or nitrogen gas molecules in field evaporation. The generation rate of iron nitride ions (FeN2+) for 15N was significantly lower than that for 14N in γ′-Fe4N, which affected the amount of the missing nitrogen. The isotope effect suggests that the isotopic ratio cannot always be determined from only one ion species among the multiple species observed in the APT analysis. We discuss the mechanism of the isotope effect in FeN2+ formation by field evaporation.

Keywords

atom probeγ′-Fe4Nisotope effectnitrogen deficiencynitrogen isotope
Type
Materials Science Applications
Information
Microscopy and Microanalysis , Volume 28 , Issue 1 , February 2022 , pp. 42 - 52
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Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of the Microscopy Society of America

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References

Angseryd, J, Liu, F, Andrén, H-O, Gerstl, SSA & Thuvender, M (2011). Quantitative APT analysis of Ti(C,N). Ultramicroscopy 111, 609–614.CrossRefGoogle Scholar
Baldwin, JE, Gallagher, SS, Leber, PA, Raghavan, AS & Shukia, R (2004). Deuterium kinetic isotope effects and mechanism of the thermal isomerization of bicyclo[4.2.0]oct-7-ene to 1,3-cyclooctadiene. J Org Chem 69, 7212–7219.CrossRefGoogle ScholarPubMed
Cheng, L, Stark, I, Korevaar, BM, Mittemeijer, EJ & Smith, GDM (1988). The initial stage of aging iron-nitrogen martensite. In Proc Int Cof High Nitrogen Steels. pp. 97–101. London: The Institute of Metals.Google Scholar
de Laeter, JR, Böhlke, JK, Bièvre, PD, Hidaka, H, Peiser, HS, Rosman, KJR & Taylor, PDP (2003). Atomic weights of the elements: Review 2000. Pure Appl Chem 75, 683–800.CrossRefGoogle Scholar
Devataj, A, Colby, R, Hess, WP, Perea, DE & Thevuthasan, S (2013). Role of photoexcitation and field ionization in the measurement of accurate oxide stoichiometry by laser-assisted atom probe tomography. J Phys Chem Lett 4, 993–998.CrossRefGoogle Scholar
Diercks, DR, Gorman, BP, Kirchhofer, R, Sanford, N, Bertness, K & Brubaker, M (2013). Atom probe tomography evaporation behavior of c-axis GaN nanowires: Crystallographic, stoichiometric, and detection efficiency aspects. J Appl Phys 114, 184903.CrossRefGoogle Scholar
Gault, B, Moody, MP, Cairney, JM & Ringer, SP (2012). Springer Series in Materials Science, Atom Probe Microscopy. New York: Springer.CrossRefGoogle Scholar
Gault, B, Saxey, DW, Ashton, MW, Sinnott, SB, Chiaramonti, AN, Moody, MP & Schreiber, DK (2016). Behavior of molecules and molecular ions near a field emitter. New J Phys 18, 033031.CrossRefGoogle Scholar
Göhring, H, Fabrichnaya, O, Leineweber, A & Mittemeijer, EJ (2016). Thermodynamics of the Fe-N and Fe-N-C systems: The Fe-N and Fe-N-C phase diagrams revisited. Metall Mater Trans A 47A, 6173–6186.CrossRefGoogle Scholar
Haydock, R & Kingham, DR (1980). Post-ionization of field-evaporation ions. Phys Rev Lett 44, 1520–1523.CrossRefGoogle Scholar
Hirano, M, Yamane, M & Ohtsu, N (2015). Surface characteristics and cell-adhesion performance of titanium treated with direct-current gas plasma comprising nitrogen and oxygen. Appl Surf Sci 354, 161–167.CrossRefGoogle Scholar
Jiang, S, Xu, H, Sun, Y & Song, T (2019). Performance analysis of Fe-N compounds based on valence electron structure. J Alloy Compounds 779, 427–432.CrossRefGoogle Scholar
Kingham, DR (1982). The post-ionization of field evaporated ions: A theoretical explanation of multiple charge state. Sur Sci 116, 271–301.CrossRefGoogle Scholar
Kinno, T, Kitamoto, K, Takeno, S & Tomita, M (2015). Laser-assisted atom probe tomography of 15N-enriched nitride thin films for analysis of nitrogen distribution in silicon-based structure. Appl Surf Sci 349, 89–92.CrossRefGoogle Scholar
Kitaguchi, HS, Lozano-Peres, S & Moody, MP (2014). Quantitative analysis of carbon in cementite using pulsed laser atom probe. Ultramicroscopy 147, 51–60.CrossRefGoogle ScholarPubMed
Kobayashi, Y, Takahashi, J & Kawakami, K (2011). Anomalous distribution in atom map of solute carbon in steel. Ultramicroscopy 111, 600–603.CrossRefGoogle ScholarPubMed
Langelier, B, Van Landeghem, HP, Botton, GA & Zurob, HS (2017). Interface segregation and nitrogen measurement in Fe-Mn-N steel by atom probe tomography. Microsc Microana 23, 385–395.CrossRefGoogle ScholarPubMed
Leslie, WC (1981). The Physical Metallurgy of Steels. New York: MacGrill-Hill.Google Scholar
Menand, A & Kingham, DR (1984). Isotropic variations in field evaporation charge-state of boron ions. J Phys D: Appl Phys 17, 203–208.CrossRefGoogle Scholar
Miller, MK (2000). Atom Probe Tomography: Analysis at the Atomic Level. New York: Kluwer Academic/Plenum Publishers.CrossRefGoogle Scholar
Miyamoto, G, Shinbo, K & Furuhara, T (2012). Quantitative measurement of carbon content in Fe-C binary alloys by atom probe tomography. Scripta Mater 67, 999–1002.CrossRefGoogle Scholar
Miyamoto, G, Suetsugu, S, Shinbo, K & Furuhara, T (2015). Surface hardening and nitride precipitation in the nitriding of Fe-M1-M2 ternary alloys containing Al, V, or Cr. Metall Mater Trans A 46A, 5011–5020.CrossRefGoogle Scholar
Ohtsu, N, Kozuka, T, Shibata, Y & Yamane, M (2017). Effect of plasma nitriding on the structural stability and hydrogen absorption capability of Pd-coated Nb during thermal treatment. Appl Surf Sci 423, 980–685.CrossRefGoogle Scholar
Russo, ED, Blum, I, Houard, IJ, Gilbert, M, de Costa, G, Blavette, D & Rigutti, L (2018). Compositional accuracy of atom probe tomography measurements in GaN: Impact of experimental parameters and multiple evaporation events. Ultramicroscopy 187, 126–134.CrossRefGoogle ScholarPubMed
Santhanagopalan, D, Schreeiber, DK, Perea, DE, Martens, RL, Janssen, Y, Khalifah, P & Mend, YS (2015). Effect of laser energy and wavelength on the analysis of LiFePO4 using laser assisted atom probe tomography. Ultramicroscopy 148, 57–64.CrossRefGoogle Scholar
Saxey, DW (2011). Correlated ion analysis and the interpretation of atom probe mass spectra. Ultramicroscopy 111, 473–479.CrossRefGoogle ScholarPubMed
Sha, W, Chang, L, Smith, GDW, Cheng, L & Mittemeijer, EJ (1992). Some aspects of atom-probe analysis of F-C and F-N systems. Surf Sci 266, 416–423.CrossRefGoogle Scholar
Takahashi, J, Kawakami, K & Kobayashi, Y (2011). Quantitative analysis of carbon content in cementite in steel by atom probe tomography. Ultramicroscopy 111, 1233–1283.CrossRefGoogle ScholarPubMed
Takahashi, J, Kawakami, K & Kobayashi, Y (2020). Study on quantitative analysis of carbon and nitrogen in stoichiometric θ-Fe3C and γ′-Fe4N by atom probe tomography. Micros Microanal 26, 185–193.CrossRefGoogle Scholar
Takahashi, J, Kawakami, K & Raabe, D (2017). Comparison of the quantitative analysis performance between pulsed voltage atom probe and pulsed laser atom probe. Ultramicroscopy 175, 105–110.CrossRefGoogle ScholarPubMed
Takahashi, J, Kawakami, K, Yamaguchi, Y & Sugiyama, M (2007). Development of atom probe specimen preparation techniques for specific regions in steel materials. Ultramicroscopy 107, 744–749.CrossRefGoogle ScholarPubMed
Wiberg, KB (1955). The deuterium isotope effect. Chem Rev 55, 713–743.CrossRefGoogle Scholar
Yamaguchi, Y, Takahashi, J & Kawakami, K (2009). The study of quantitativeness in atom probe analysis of alloying elements in steel. Ultramicroscopy 109, 541–544.CrossRefGoogle Scholar