Core/shell structures of oxygen-rich nanofeatures in oxide-dispersion strengthened FeCr alloys

Emmanuelle A. Marquis Citation: Appl. Phys. Lett. 93, 181904 (2008); doi: 10.1063/1.3000965 View online: http://dx.doi.org/10.1063/1.3000965 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v93/i18 Published by the AIP Publishing LLC.

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APPLIED PHYSICS LETTERS 93, 181904 2008

Core/shell structures of oxygen-rich nanofeatures in oxide-dispersion strengthened FeCr alloys

Emmanuelle A. Marquisa
Department of Materials, University of Oxford, Oxford OX1 3PH, United Kingdom

Received 13 September 2008; accepted 24 September 2008; published online 4 November 2008 With the signicant improvement in high temperature creep properties and resistance to radiation damage by addition of nanoscale oxide features, oxide-dispersion strengthened ODS ferritic/ martensitic alloys are potential candidates for structural applications in nuclear fusion reactors. The structure of the oxygen-rich nanofeatures was analyzed by atom-probe tomography in three ODS alloys: MA957, ODS Fe 12 wt % Cr, and ODS Eurofer-97. Although eld evaporation and reconstruction of the precipitates suffer from artefacts, a core/shell structure is found even for very small precipitates. Precipitate cores are Y rich while shell regions are enriched in Ti, Cr, or V depending on alloy composition. 2008 American Institute of Physics. DOI: 10.1063/1.3000965 In the search for structural materials for fusion power plants, oxide-dispersion-strengthened ODS reduced activation ferritic/martensitic steels appear as potential candidates for blanket structures. The nanosized oxygen-rich structures stabilize grain boundaries, improve creep resistance, and provide a high density of trapping sites for helium,1 thereby increasing the possible operating temperature of these alloys to relevant values for the current design of nuclear plants, i.e., 650 C and higher.2 The superiority of ODS steel over their non-ODS counterpart is well understood and large efforts in Europe, USA, and Japan have been undertaken to establish the relationship between microstructure, mechanical properties, and irradiation behavior.1 Although the oxide nanofeatures NFs appear as the major component improving the overall material behavior, detailed knowledge of their internal structure and behavior is yet to be gained.1 Atom-probe tomography APT has been previously used to analyze NFs, principally in ODS Ti-containing steels. Larson et al.3 followed by Miller et al.47 found ne dispersions of Y-, O-, and Ti-rich precipitates with sizes between 3 and 5 nm in various alloys. Their results, particularly on NF chemical compositions, illustrate the complexity of analyzing ODS alloys. Indeed, particle compositions are highly sensitive to alloy chemistry, processing conditions, and choice of atom-probe tomography analysis parameters. More recent analytical transmission electron microscopy TEM measurements8 as well as APT observations9 in an ODS Eurofer-97 alloy revealed that 10 nm diameter NFs have core-shell structures with Y-rich cores and V- and Crenriched shells. The current work presents detailed APT analysis of the internal structure and composition of nanoscale oxygen-rich features in three different ODS FeCr based alloys. Particular emphasis is placed on analyzing the effects of evaporation artifacts affecting data interpretation. After thermomechanical processing, an ODS martensitic Eurofer-97 alloy of nominal composition 9Cr, 1.5W, 0.4Mn, 0.2V, 0.11C, and 0.3Y2O3 in wt % and described in Ref. 10 was annealed at 1050 C for 30 min, air cooled and tempered at 750 C for 2 h.11 An ODS ferritic/martensitic
a

Fe 12 wt % Cr model alloy containing 0.25 wt % Y2O3 was annealed at 750 C for 4 h following hot-isostatic pressing at 1100 C.12 The third alloy, a commercial vendor MA957 with nominal composition 14Cr, 0.9Ti, 0.3Mo, and 0.25Y2O3, was hot extruded at 1150 C. APT samples were prepared by electropolishing using a solution of 2% percholoric acid in 2-butoxyethanol. Field ion imaging FIM was performed on a 3DAP microscope with samples maintained at 50 K in 105 torr of helium. Analyses were performed using a LEAP-3000XSI or a LEAP-3000HR microscope. During analysis, samples were maintained between 30 and 40 K and either voltage pulsing 20% pulse fraction, 200 kHz repetition rate or laser pulsing wavelength of 532 nm, pulse width of 10 ps, repetition rate of 200 kHz, energy of 0.4 nJ and spot size 5 m was used for eld evaporation. In the three alloys, the oxide NFs appear as dark regions during FIM imaging arrowed in Fig. 1, suggesting that a lower evaporation eld than that of the surrounding matrix is required to evaporate these oxygen-rich phases.13 In such a case, a precipitate appearing at the surface of the specimen will momentarily evaporate at a faster rate than the surrounding matrix until a lower local of curvature is reached, the eld is decreased at the precipitate, and an equiprobability of eld ionization is established over the emitter surface. The dimple thereby created at the surface of the evaporating precipitate creates a focusing effect for the ions originating from the precipitates and from the nearby surrounding matrix13 and, indeed, the detected atomic density at the particles in the three alloys is up to four times higher than in the surrounding matrix. Although focusing of the ion trajectories implies that the particles should also appear compressed in

Author to whom correspondence should be addressed. Tel.: 44 1865 273711. FAX: 44 1865 273789. Electronic mail: emmanuelle.marquis@ materials.ox.ac.uk.

FIG. 1. FIM images of a ODS Fe-12Cr alloy, b MA957, and c ODS Eurofer 97 alloy. 2008 American Institute of Physics

0003-6951/2008/9318/181904/3/$23.00

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Emmanuelle A. Marquis

Appl. Phys. Lett. 93, 181904 2008

FIG. 2. Color online Slices though 3D reconstructions showing the evaporation structures of small oxide NFs and proles in a MA957 in voltage mode, b ODS Fe-12Cr alloy in voltage mode, and c ODS Eurofer 97 alloy in laser mode.

the lateral dimensions, the oxygen atoms are detected over a wider lateral extent than the metal ions present in the precipitates. This effect is visible in both voltage and laser pulsing modes and particularly noticeable in Fig. 3c as indicated by the black arrows. Similar observations on the evaporation behavior of O from NFs have been reported previously.47 It is possible that chromatic aberrations whereby ion trajectory depends on atom type such as described in Ref. 14 may take place. Another specic characteristic of the reconstructed particles is the systematic presence of a solute-rich area underneath in the evaporation sequence each Y-rich cloud, as shown in Figs. 2a2c. Concentration proles calculated along 2 nm diameter cylinders intercepting the particles and oriented parallel to the specimen axis, reveal not only a Ti, Cr, or V rich area underneath the particles but a similar and smaller region above the particles as well Figs. 2a2c. Since the crystallographic orientation of the APT samples prepared from bulk materials is random, this systematic evaporation sequence is interpreted as being an evaporation artifact due to trajectory aberrations and evaporation eld variations as explained above. Moreover, the feature geometry leading to such evaporation patterns is that of a coreshell structure, with the shell region and possibly the core region requiring a lower evaporation eld than the matrix. In the ODS Fe12Cr alloy, a Cr rich shell is observed that extends slightly further in the depth direction than the O atoms. In the ODS Eurofer-97 alloy, V and O are present in the shell and a Cr enhancement is also observed in the shell and core

FIG. 3. Color online Slices though 3D reconstructions showing the evaporation structures of larger oxide NFs and proles in a MA957, b ODS Fe-12Cr alloy, and c ODS Eurofer 97 alloy. All samples were analyzed in laser pulsing mode.

of the precipitates. Although the extent of the shell is asymmetric in the three-dimensional 3D reconstruction with an apparent thicker layer underneath each precipitate, the actual thickness is expected to be on average uniform around the precipitates as shown previously by transmission electron microscopy.8 Similar reconstructed uneven shell thicknesses have been observed in larger precipitate structures in Al alloys.15,16 The stretching in depth is enhanced by the actual nonuniform evaporation sequence yielding the dimpled tip shape and the assumed uniform evaporation over a hemispherical tip shape used in the reconstruction algorithm. The evaporation sequence error displaces the low evaporation eld regions core and shell toward the apex of the tip. The presence of a shell is observed independently of the size of the nanofeatures. Figure 2 illustrates the case of small NFs with sizes less than 4 nm where the evaporation and reconstruction artifacts occur over distances as large as the NFs themselves and the internal structure is signicantly altered. Figure 3 illustrates the case for larger NFs 8 nm and larger where the shell structure is visible all around the core. As the size increases, the distinction between core and shell becomes clearer, i.e., the length scale of the nanoparticles become larger than that of trajectory aberrations. The exact compositions of the cores and shells are difcult to determine and require accurate understanding of the evaporation eld, evaporation sequence, and ion trajectories. An estimate of the combined concentrations can, however,

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Emmanuelle A. Marquis TABLE I. Measured concentrations in oxide core/shell NFs with sizes less than 5 nm. Alloy MA957 ODS Fe12Cr Eurofer O 42.8 3.6 36.9 3.5 35.9 4.2 Ti 37.9 3.0 Y 14.6 1.2 24.8 5.8 24.7 3 Cr 4.6 1.0 37.1 4.8 4.4 6.2 V

Appl. Phys. Lett. 93, 181904 2008

M:O 1.3 1.7 1.8

33.9 2.3

be obtained using a cluster search algorithm17 based on the evaporating species Y, YO plus TiO MA957 or CrO ODS Fe12Cr or CrO, and VO Eurofer with a separation distance of 0.9 1.1 nm depending on the alloy and dataset, a matrix inclusion distance of 0.5 0.6 nm and an erosion distance of 0.5 0.65 nm. Assuming that the presence of Fe inside the particles is strictly due to some matrix atoms being focused and their trajectories overlapping with that of the particles atoms, a subtraction of the matrix concentration based on the number of Fe atoms found in the precipitates is performed. The resulting concentrations are shown in Table I. Since the reconstructed oxygen atom distribution covers a wider volume than for the metal atoms, the concentration of this element in the particles may be underestimated. Note that the concentrations measured by the cylinder method are strongly affected by the choice of the cylinder diameter and the value of 2 nm was chosen as to avoid edge effects due to the small precipitate sizes. The depletion of Cr in Fig. 2a is not representative and a variety of behaviors is actually observed with an average Cr enrichment in the particles as found by a cluster search algorithm method Table I. The M:O ratio is comparable in all three alloys. In the three alloys as well, other solutes, Mn, Al, Si, and C also partition to some NFs and the overall concentrations are in general agreement with previous works.57 Separating shell and core atoms is difcult without assumptions on the particle or shell structures, or without further experimental observations using different techniques such as shell thickness from TEM observation. The similarities between the structure of the oxide nanoparticles in all three alloys, i.e., a Y-rich core and solute-rich shell, suggest that their structures may be governed by common fundamental thermodynamic properties, such as the interfacial energy between the oxide phases and the surrounding matrix. The Y2O3 oxide the most stable of the Cr, V, Ti, Y oxides with the highest free energy of formation18 may, however, have a high nucleation barrier and the presence of a shell would decrease the interfacial energy, favoring the nucleation of the oxide particles. This may account for the higher number density of oxide particles obtained with addition of Ti.4 Note that a similar mechanism was described for the formation of CuMnNi rich precipitates in RPV steels.19 Future work will involve characterizing the interfacial properties, quantifying the effect of precipitate size, irradiation, and thermal annealing on the development and stability of core/shell structures, as well as determining respective compositions and the role of solutes.

The author acknowledges G.R. Odette University of California, Santa Barbara, USA for stimulating discussions and for providing the MA957, Professor A. Cerezo and Professor G.D.W. Smith University of Oxford for valuable support, the group of R. Pareja Universidad Carlos III, Madrid, Spain for supplying the ODS Fe-12Cr alloy, and R. Lindau Forschungszentrum Karlsruhe, Germany for the ODS Eurofer-97. This work was funded by Engineering and Physical Sciences Research Council EPSRC under Grant No. EP/077664.
G. R. Odette, M. L. Alinger, and B. D. Wirth, Annu. Rev. Mater. Res. 38, 471 2008. 2 R. Lasser, N. Baluc, J.-L. Boutard, E. Diegele, S. Dudarev, M. Gasparotto, A. Moslang, R. Pippan, B. Riccardi, and B. van der Schaaf, Fusion Eng. Des. 82, 511 2007. 3 D. J. Larson, P. J. Maziasz, I.-S. Kim, and K. Miyahara, Scr. Mater. 44, 359 2001. 4 M. K. Miller, E. A. Kenik, K. F. Russell, L. Heatherly, D. T. Hoelzer, and P. J. Maziasz, Mater. Sci. Eng., A 353, 140 2003. 5 M. K. Miller, D. T. Hoelzer, E. A. Kenik, and K. F. Russell, J. Nucl. Mater. 329, 338 2004. 6 M. K. Miller, D. T. Hoelzer, E. A. Kenik, and K. F. Russell, Intermetallics 13, 387 2005. 7 M. K. Miller, K. F. Russell, and D. T. Hoelzer, J. Nucl. Mater. 351, 261 2006. 8 M. Klimenkov, R. Lindau, and A. Moslang, New insights in the structure of ODS particles in ODS-Eurofer alloy, J. Nucl. Mater. to be published. 9 C. Williams, Part II thesis, University of Oxford, 2008. 10 R. Lindau, A. Moslang, M. Rieth, M. Klimiankou, E. Materna-Morris, A. Alamo, A. A. F. Tavassoli, C. Cayron, A. M. Lancha, P. Fernandez, N. Baluc, R. Schaublin, E. Diegele, G. Filacchioni, J. W. Rensman, B. van der Schaaf, E. Lucon, and W. Dietz, Fusion Eng. Des. 75, 989 2005. 11 Z. Lu, R. G. Faulkner, and N. Riddle, Proceedings of the 13th International Conference on Fusion Reactor Materials, 2007 unpublished, p. 105. 12 V. de Castro, T. Leguey, A. Muoz, M. A. Monge, R. Pareja, E. A. Marquis, S. Lozano-Perez, and M. L. Jenkins, Microstructural characterization of Y2O3 ODS-Fe-Cr model alloys, J. Nucl. Mater. to be published. 13 T. Sakurai, A. Sakai, and H. W. Pickering, Atom-Probe Field Ion Imaging and its Applications Academic, London, 1989, p. 9. 14 E. A. Marquis and F. Vurpillot, Chromatic aberrations in the eld evaporation behaviour of small precipitates, Microsc. Microanal. to be published. 15 T. Sakurai, A. Kobayashi, Y. Hasegawa, A. Sakai, and H. Pickering, Scr. Metall. 20, 1131 1986. 16 V. Radmilovic, A. Tolley, E. A. Marquis, M. D. Rossell, Z. Lee, and U. Dahmen, Scr. Mater. 58, 529 2008. 17 D. Vaumousse, A. Cerezo, and P. J. Warren, Ultramicroscopy 95, 215 2003. 18 D. R. Sigler, Oxid. Met. 32, 337 1989. 19 C. L. Liu, G. R. Odette, B. D. Wirth, and G. E. Lucas, Mater. Sci. Eng., A 238, 202 1997.
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