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Correlative Atom Probe Tomography and Transmission Electron Microscopy Analysis of Grain Boundaries in Thermally Grown Alumina Scale

  • Ivan Povstugar (a1), Juliane Weber (a2) (a3), Dmitry Naumenko (a4), Taihong Huang (a4) (a5), Martina Klinkenberg (a2) and Willem J. Quadakkers (a4)...


We employed correlative atom probe tomography (APT) and transmission electron microscopy (TEM) to analyze the alumina scale thermally grown on the oxide dispersion-strengthened alloy MA956. Segregation of Ti and Y and associated variation in metal/oxygen stoichiometry at the grain boundaries and triple junctions of alumina were quantified and discussed with respect to the oxidation behavior of the alloy, in particular, to the formation of cation vacancies. Correlative TEM analysis was helpful to avoid building pragmatically well-looking but substantially incorrect APT reconstructions, which can result in erroneous quantification of segregating species, and highlights the need to consider ionic volumes and detection efficiency in the reconstruction routine. We also demonstrate a cost-efficient, robust, and easy-handling setup for correlative analysis based solely on commercially available components, which can be used with all conventional TEM tools without the need to modify the specimen holder assembly.


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*Author for correspondence: Ivan Povstugar, E-mail:


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Aguiar, JA, Stokes, A, Jiang, C-S, Aoki, T, Kotula, PG, Patel, MK, Gorman, B & Al-Jassim, M (2016). Revealing surface modifications of potassium-fluoride-treated Cu(In,Ga)Se2: A study of material structure, chemistry, and photovoltaic performance. Adv Mater Interfaces 3, 1600013.
Arslan, I, Marquis, EA, Homer, M, Hekmaty, MA & Bartelt, NC (2008). Towards better 3-D reconstructions by combining electron tomography and atom-probe tomography. Ultramicroscopy 108, 15791585.
Baik, S-I, Yin, X & Seidman, DN (2013). Correlative atom-probe tomography and transmission electron microscope study of a chemical transition in a spinel on an oxidized nickel-based superalloy. Scr Mater 68, 909912.
Bale, CW, Bélisle, E, Chartrand, P, Decterov, SA, Eriksson, G, Gheribi, AE, Hack, K, Jung, I-H, Kang, Y-B, Melançon, J, Pelton, AD, Petersen, S, Robelin, C, Sangster, J, Spencer, P & Van Ende, M-A (2016). Factsage thermochemical software and databases, 2010–2016. Calphad 54, 3553.
Bas, P, Bostel, A, Deconihout, B & Blavette, D (1995). A general protocol for the reconstruction of 3D atom probe data. Appl Surf Sci 87–88, 298304.
Birks, N, Meier, GH & Pettit, FS (2006). Introduction to the High-Temperature Oxidation of Metals. Cambridge, UK: Cambridge University Press.
Boll, T, Unocic, KA, Pint, BA & Stiller, K (2017). Interfaces in oxides formed on NiAlCr doped with Y, Hf, Ti, and B. Microsc Microanal 23, 396403.
Chen, Y, Reed, RC & Marquis, EA (2014). Interfacial solute segregation in the thermally grown oxide of thermal barrier coating structures. Oxid Met 82, 457467.
Chen, Y, Rice, KP, Prosa, TJ, Marquis, EA & Reed, RC (2015). Integrated APT/t-EBSD for grain boundary analysis of thermally grown oxide on a Ni-based superalloy. Microsc Microanal 21, 687688.
Chen, YM, Ohkubo, T, Kodzuka, M, Morita, K & Hono, K (2009). Laser-assisted atom probe analysis of zirconia/spinel nanocomposite ceramics. Scr Mater 61, 693696.
Clemens, D, Bongartz, K, Speier, W, Hussey, RJ & Quadakkers, WJ (1993). Analysis and modelling of transport processes in alumina scales on high temperature alloys. Fresenius J Anal Chem 346, 318322.
Cojocaru-Mirédin, O, Schwarz, T & Abou-Ras, D (2018). Assessment of elemental distributions at line and planar defects in Cu(In,Ga)Se2 thin films by atom probe tomography. Scr Mater 148, 106114.
Devaraj, 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, 993998.
Diercks, DR, Gorman, BP, Manerbino, A & Coors, G (2014). Atom probe tomography of yttrium-doped barium-cerium-zirconium oxide with NiO addition Salvador, P. (Ed.). J Am Ceram Soc 97, 33013306.
Diercks, DR, Tong, J, Zhu, H, Kee, R, Baure, G, Nino, JC, O'Hayre, R & Gorman, BP (2016). Three-dimensional quantification of composition and electrostatic potential at individual grain boundaries in doped ceria. J Mater Chem A 4, 51675175.
Felfer, P & Cairney, J (2011). New equipment for correlative FIB/TEM/atom probe and site-specific preparation using STEM live imaging. Microsc Microanal 17, 756757.
Gault, B, de Geuser, F, Stephenson, LT, Moody, MP, Muddle, BC & Ringer, SP (2008). Estimation of the reconstruction parameters for atom probe tomography. Microsc Microanal 14, 296305.
Gault, B, Loi, ST, Araullo-Peters, VJ, Stephenson, LT, Moody, MP, Shrestha, SL, Marceau, RKW, Yao, L, Cairney, JM & Ringer, SP (2011). Dynamic reconstruction for atom probe tomography. Ultramicroscopy 111, 16191624.
Gorman, BP, Diercks, DR, Salmon, D, Stach, E, Amador, G & Hartfield, C (2008a). Hardware and techniques for cross-correlative TEM and atom probe analysis. Micros Today 16, 4247.
Gorman, BP, Puthucode, A, Diercks, DR & Kaufman, MJ (2008b). Cross-correlative TEM and atom probe analysis of partial crystallisation in NiNbSn metallic glasses. Mater Sci Technol 24, 682688.
Gülgün, MA, Voytovych, R, Maclaren, I, Rühle, M & Cannon, RM (2002). Cation segregation in an oxide ceramic with low solubility: Yttrium doped α-alumina. Interface Sci 10, 99110.
Hellman, OC & Seidman, DN (2002). Measurement of the Gibbsian interfacial excess of solute at an interface of arbitrary geometry using three-dimensional atom probe microscopy. Mater Sci Eng A 327, 2428.
Herbig, M, Choi, P & Raabe, D (2015). Combining structural and chemical information at the nanometer scale by correlative transmission electron microscopy and atom probe tomography. Ultramicroscopy 153, 3239.
Herbig, M, Raabe, D, Li, YJ, Choi, P, Zaefferer, S & Goto, S (2014). Atomic-scale quantification of grain boundary segregation in nanocrystalline material. Phys Rev Lett 112, 126103.
Huang, T, Naumenko, D, Song, P, Lu, J & Quadakkers, WJ (2018). Effect of Titanium addition on alumina growth mechanism on yttria-containing FeCrAl-base alloy. Oxid Met 90, 671690.
Huczkowski, P, Gopalakrishnan, SG, Nowak, W, Hattendorf, H, Iskandar, R, Mayer, J & Quadakkers, WJ (2016). Effect of Zr content on the morphology and emissivity of surface oxide scales on FeCrAlY alloys. Adv Eng Mater 18, 711720.
Karahka, M, Xia, Y & Kreuzer, HJ (2015). The mystery of missing species in atom probe tomography of composite materials. Appl Phys Lett 107, 062105.
Kim, J-H, Kim, BK, Kim, D-I, Choi, P-P, Raabe, D & Yi, K-W (2015). The role of grain boundaries in the initial oxidation behavior of austenitic stainless steel containing alloyed Cu at 700°C for advanced thermal power plant applications. Corros Sci 96, 5266.
Kirchhofer, R, Diercks, DR & Gorman, BP (2015). Near atomic scale quantification of a diffusive phase transformation in (Zn, Mg)O/Al2O3 using dynamic atom probe tomography. J Mater Res 30, 11371147.
Kontis, P, Pedrazzini, S, Gong, Y, Bagot, PAJ, Moody, MP & Reed, RC (2017). The effect of boron on oxide scale formation in a new polycrystalline superalloy. Scr Mater 127, 156159.
La Fontaine, A, Yen, H-W, Felfer, PJ, Ringer, SP & Cairney, JM (2015). Atom probe study of chromium oxide spinels formed during intergranular corrosion. Scr Mater 99, 14.
Larson, DJ, Prosa, TJ, Ulfig, RM, Geiser, BP & Kelly, TF (2013). Local Electrode Atom Probe Tomography. New York, US: Springer New York.
Loi, ST, Gault, B, Ringer, SP, Larson, DJ & Geiser, BP (2013). Electrostatic simulations of a local electrode atom probe: The dependence of tomographic reconstruction parameters on specimen and microscope geometry. Ultramicroscopy 132, 107113.
London, AJ, Lozano-Perez, S, Moody, MP, Amirthapandian, S, Panigrahi, BK, Sundar, CS & Grovenor, CRM (2015). Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys. Ultramicroscopy 159, 360367.
Marquis, EA, Yahya, NA, Larson, DJ, Miller, MK & Todd, RI (2010). Probing the improbable: imaging C atoms in alumina. Mater Today 13, 3436.
Maugis, P & Hoummada, K (2016). A methodology for the measurement of the interfacial excess of solute at a grain boundary. Scr Mater 120, 9093.
Miller, MK & Hetherington, MG (1991). Local magnification effects in the atom probe. Surf Sci 246, 442449.
N'Dah, E, Galerie, A, Wouters, Y, Goossens, D, Naumenko, D, Kochubey, V & Quadakkers, WJ (2005). Metastable alumina formation during oxidation of FeCrAl and its suppression by surface treatments. Mater Corros 56, 843847.
Naumenko, D, Gleeson, B, Wessel, E, Singheiser, L & Quadakkers, WJ (2007). Correlation between the microstructure, growth mechanism, and growth kinetics of alumina scales on a FeCrAlY alloy. Metall Mater Trans A 38, 29742983.
Nguyen, TD, La Fontaine, A, Yang, L, Cairney, JM, Zhang, J & Young, DJ (2018). Atom probe study of impurity segregation at grain boundaries in chromia scales grown in CO 2 gas. Corros Sci 132, 125135.
Nychka, JA & Clarke, DR (2005). Quantification of aluminum outward diffusion during oxidation of FeCrAl alloys. Oxid Met 63, 325352.
Pedrazzini, S, Child, DJ, West, G, Doak, SS, Hardy, MC, Moody, MP & Bagot, PAJ (2016). Oxidation behaviour of a next generation polycrystalline Mn containing Ni-based superalloy. Scr Mater 113, 5154.
Perea, DE, Arslan, I, Liu, J, Ristanović, Z, Kovarik, L, Arey, BW, Lercher, JA, Bare, SR & Weckhuysen, BM (2015). Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography. Nat Commun 6, 7589.
Pint, BA (1996). Experimental observations in support of the dynamic-segregation theory to explain the reactive-element effect. Oxid Met 45, 137.
Pint, BA (1997). On the formation of interfacial and internal voids in α-Al2O3 scales. Oxid Met 48, 303328.
Pint, BA (2003). Optimization of reactive-element additions to improve oxidation performance of alumina-forming alloys. J Am Ceram Soc 86, 686695.
Pint, BA, Garratt-Reed, AJ & Hobbs, LW (1995). The reactive element effect in commercial ODS FeCrAl alloys. Mater High Temp 13, 316.
Quadakkers, WJ, Elschner, A, Holzbrecher, H, Schmidt, K, Speier, W & Nickel, H (1992). Analysis of composition and growth mechanisms of oxide scales on high temperature alloys by SNMS, SIMS, and RBS. Mikrochim Acta 107, 197206.
Quadakkers, WJ, Holzbrecher, H, Briefs, KG & Beske, H (1989). Differences in growth mechanisms of oxide scales formed on ODS and conventional wrought alloys. Oxid Met 32, 6788.
Schreiber, DK, Olszta, MJ & Bruemmer, SM (2013). Directly correlated transmission electron microscopy and atom probe tomography of grain boundary oxidation in a Ni-Al binary alloy exposed to high-temperature water. Scr Mater 69, 509512.
Stiller, K, Viskari, L, Sundell, G, Liu, F, Thuvander, M, Andrén, H-O, Larson, DJ, Prosa, T & Reinhard, D (2013). Atom probe tomography of oxide scales. Oxid Met 79, 227238.
Sundell, G, Thuvander, M & Andrén, H-O (2012). Enrichment of Fe and Ni at metal and oxide grain boundaries in corroded Zircaloy-2. Corros Sci 65, 1012.
Thompson, K, Lawrence, D, Larson, DJ, Olson, JD, Kelly, TF & Gorman, B (2007). In situ site-specific specimen preparation for atom probe tomography. Ultramicroscopy 107, 131139.
Toji, Y, Matsuda, H, Herbig, M, Choi, P-P & Raabe, D (2014). Atomic-scale analysis of carbon partitioning between martensite and austenite by atom probe tomography and correlative transmission electron microscopy. Acta Mater 65, 215228.
Unocic, KA, Chen, Y, Shin, D, Pint, BA & Marquis, EA (2018). STEM and APT characterization of scale formation on a La,Hf,Ti-doped NiCrAl model alloy. Micron 109, 4152.
Unocic, KA, Essuman, E, Dryepondt, S & Pint, BA (2012). Effect of environment on the scale formed on oxide dispersion strengthened FeCrAl at 1050°C and 1100°C. Mater High Temp 29, 171180.
Yang, JC, Nadarzinski, K, Schumann, E & Rühle, M (1995). Electron microscopy studies of NiAl/γ-Al2O3 interfaces. Scr Metall Mater 33, 10431048.
Young, DJ (2016). High Temperature Oxidation and Corrosion of Metals. Amsterdam, Netherlands: Elsevier.
Young, DJ, Naumenko, D, Niewolak, L, Wessel, E, Singheiser, L & Quadakkers, WJ (2010). Oxidation kinetics of Y-doped FeCrAl-alloys in low and high pO2 gases. Mater Corros 61, 838844.
Zanuttini, D, Blum, I, Rigutti, L, Vurpillot, F, Douady, J, Jacquet, E, Anglade, P-M & Gervais, B (2017). Simulation of field-induced molecular dissociation in atom-probe tomography: Identification of a neutral emission channel. Phys Rev A 95, 061401.
Zhou, X, Yu, X, Kaub, T, Martens, RL & Thompson, GB (2016). Grain boundary specific segregation in nanocrystalline Fe(Cr). Sci Rep 6, 34642.



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