Journal of Crystal Growth 249 (2003) 381387

HRTEM Study of yttrium oxide particles in ODS steels for fusion reactor application
. M. Klimiankou*, R. Lindau, A. Moslang
Institut fur . Materialforschung I, Forschungszentrum Karlsruhe GmbH, Postfach 3640, 76021 Karlsruhe, Germany Received 21 October 2002; accepted 5 November 2002 Communicated by R. Kern

Abstract An oxide dispersion strengthened ferritic-martensitic steel with yttrium oxide (Y2O3) was produced by mechanical alloying and hot isostatic pressing techniques for high-performance structures of fusion energy devices. The structure of the nanometer-sized Y2O3 particles analysed by HRTEM shows a strong correlation of its crystallographic orientation %1 % YO 81 1 % 0FeCr were found. The strong with the alloy lattice. The orientation correlations [1 1 0]YO8[1 1 1]FeCr and 1 1 orientation correlation appears during HIPing processes around 10501C, which is signicantly lower than the melting temperature of Y2O3 that amounts to 25001C. r 2002 Elsevier Science B.V. All rights reserved.
Keywords: A1. Crystal structure; A1. Directional solidication; A1. Nanostructures; B1. Metals; B1. Oxide dispersion strengthened steel; B1. Oxides

1. Introduction In the past few years, oxide dispersion strengthened (ODS) steels produced by mechanical alloying techniques have become increasingly interesting for structural applications in nuclear ssion and fusion power plants. The use of ODS alloys instead of the presently considered conventionally produced reduced-activation ferriticmartensitic (RAFM) steels would allow to improve creep resistance at high temperatures and consequently increase the operating temperature
*Corresponding author. Tel.: +49-7247-82-2903; fax: +497247-82-4567. E-mail address: mikhail.klimiankou@imf.fzk.de (M. Klimiankou).

of blanket structures in future fusion power reactors by 100 K to approximately 6501C or more. The attractiveness of high-strength, nanocomposed RAFM steels is not only due to favourable radiological properties but also due to a unique combination of small average grain sizes, high dislocation densities, and nanoclusters composed of YO solute atoms. As a rst step in the development of dispersion strengthened RAFM steels, two ODS alloys containing 0.5 and 0.3 wt% Y2O3, respectively, have been produced on the basis of a 9% CrWVTa RAFM European reference steel, called EUROFER97 [1]. The production process of the EUROFER-ODS alloys included mechanical alloying (MA) of inert-gas-atomised steel and yttria powder, followed by hot isostatic pressing (HIP) as an

0022-0248/03/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 2 - 0 2 4 8 ( 0 2 ) 0 2 1 3 4 - 6

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appropriate consolidation process of the MA powder. Although relevant mechanical properties, e.g. tensile strength, toughness, fatigue, and creep rupture of the alloy were screened very recently within a wide temperature range [2], detailed information concerning the crystalline structure of the ODS particles and its orientation with respect to the alloy matrix is still lacking. This information is important for improving RAFMODS alloys by means of targeted nanostructural tailoring. The knowledge about ODS particles and their interaction with the matrix would also help to prove nanoscale theory and modelling with simulation approaches that will be designed specically to address material structures and properties in the nanoscale regime. The experience shows that lattice coherency of the particles with surrounded matrix is of importance for strengthening mechanisms [3]. A correlation of the crystallographic orientation of a metallic matrix and oxide, carbide, nitride or Mn-metal precipitates was already observed and described in literature [47]. In these systems, however, orientation correlation was due to growth of precipitates during HIPing [57] or melting [4] processes and did not appear between already existing ODS nanoparticles and the host matrix. Appearance of orientation correlation in the cited papers is caused by the interchange of precipitate lattices with the matrix during the growth or solidication processes. In the present investigation, however, a correlation is most surprising, since the production process would not allow any orientation correlation to be expected. HRTEM investigations of ODS alloys were recently reported for NiAl compositions with various Ni/Al ratios [8], FeAl [9], NiCr [10,11], and FeCr [7] steels. The HRTEM studies showed lattice continuity between oxide and matrix [10,11]. Unfortunately, these publications did not present any detailed crystallographic consideration of lattice continuity nor was its origin discussed. Faceted oxide (Y2O3 or Al2O3) particles with preferred orientation to the matrix in an NiAl or Fe(2739)Al matrix were dealt with in Ref. [8]. Crystallographic analyses concerning an orientation correlation of Y2O3 particles with

the NiAl matrix were presented in Ref. [9]. The authors suppose that the orientation correlation emerges during the mechanical alloying process. However, from the present understanding, it seems to be rather unlikely that the MA process, which includes repeated cold welding and fracture of powder particles at ambient or slightly elevated temperature, should somehow inuence the crystallographic orientation of the 520 nm sized particles inside the metallic matrix. The objective of the present work is to verify the existence of an unexpectedly strong orientation correlation between Y2O3 particles and the surrounding alloy matrix and to clarify whether it arises during MA or during HIPing. A further objective is a detailed investigation of the Y2O3 orientation from a crystallographic point of view by means of HRTEM.

2. Experimental The two EUROFER97-ODS alloys were produced by mechanical alloying of inert-gas-atomised master 9% CrWVTa steel (EUROFER97) together with 0.3 and 0.5 wt% yttria powder, respectively. Repeated impacts of energetic balls during mechanical alloying reduced the originally coarse Y2O3 particles of typically 1030 mm diameter by three orders of magnitude, thus leading to a remarkable solid-state mixing with a fairly homogeneous distribution of nano-sized Y2O3 particles. In a second step, the MA powders were consolidated around 10501C by hot isostatic pressing (HIPing). Both production processes, MA and HIPing, were performed by experienced industrial manufacturers. From the nal product form, i.e. from bars of 60 and 300 mm length, discs of 0.1 mm thickness were cut. Finally, TEM samples of 3 mm diameter were punched from these discs and electropolished in a TENUPOL device using H2SO4+80% CH3OH as electrolyte. For the TEM investigations of the matrix, grains with an orientation not far away from the low index orientation were chosen. Afterwards, the grains were exactly oriented using a double tilt holder.

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For the TEM investigation of the EUROFER97-ODS powder after mechanical alloying, a carbon lm on a cooper grid was used. The powder was pinched between two grids in order to prevent displacement of the single particles inside the magnetic pole shoes of the microscope. All samples were investigated in a Phillips 30CM microscope (accelerating voltage of 300 kV and ultimate lattice resolution of 0.144 nm). A double tilt specimen holder was used for the exact orientation of the grains relative to the incident electron beam. The evaluation of high-resolution TEM (HRTEM) images was performed by means of fast Fourier transformation (FFT) of the images.

3. Results and discussion In the as-received state, i.e. without any further heat treatment, the grains of EUROFER97-ODS material have a typical size of 25 mm [12]. They mostly consist of ferrite and, consequently, do not exhibit lath formations that are typical of martensitic steels. These features are in contrast with the transformation behaviour of conventionally fabricated ferritic-martensitic steels that have been analysed in a comprehensive R&D programme based on 62 different grades of steel and heats [13]. EUROFER97, for instance, is fully martensitic in the as-received state. After the reference heat treatment (90010501C/30 min+7501C/2 h), it exhibits a grain size of 1121 mm (ASTM 10.5-8) with typical martensitic laths inside the grain. Its microstructure is stable against long-term ageing up to 6501C [13]. As for EUROFER97, a preferable crystallographic orientation of grains with respect to each other was not found in EUROFER-ODS [12]. This nding was expected, as HIPing and not hot extrusion had been selected as the nal fabrication process. HIPing is the reason for the completely isotropic mechanical properties that do not favour one grain orientation at the expense of all other directions. The crystallographic lattice of the EUROFER97-ODS matrix corresponds to a-Fe with a BCC structure and a lattice constant of

da-Fe 0:287 nm [14]. Because of the extinction conditions, it was only possible to resolve atomic planes of /1 1 0S type by means of HRTEM. Resolution of atomic planes of /2 0 0S type is possible in theory, but extraordinarily difcult in practice, as the plane is close to the resolution limit of the microscope. Another reason is the magnetic nature of the EUROFER 97-ODS material. The Y2O3 powder material has a crystalline BCC structure with a 1.06 nm lattice constant [14]. The HRTEM investigations conrm this crystallographic structure also for the ODS particles embedded in the alloy. In the HIPed EUROFER-ODS alloy, the TEM investigations showed the presence of Y2O3 particles inside each grain. The distribution of particles varied between different grains as well as inside individual grains [1,12]. The particle size varied in the range from 3 to 45 nm with a statistical average size of 12 nm. Usually, the particles appeared to have a spherical shape (Fig. 1a). The particles with a diameter larger than 12 nm tended to have a well-established faceted surface (Fig. 1b). The faceted particles are marked with an arrow in Fig. 1. The matrix grain is here oriented along the [1 0 0] FeCr zone axis. Because of this exact orientation, the Y2O3 particles are not clearly visible in the image. The TEM image in Fig. 1a was taken from another grain with the zone axis indicated using higher Miller indexes, which will be discussed below. The high-resolution TEM (HRTEM) images of the particles shown in Fig. 1a are presented in Fig. 2a and b. The particles with numbers 3, 4, and 5 have the same orientation with the [0 1 1] zone axis. The FFT images taken from these three particles (Fig. 2c) demonstrate that these particles also have the same orientation in the image plane. Reexes of the /2 2 2S type are marked with lines. The difference in the orientation of the particles with respect to each other is less than 0.51the detection limit estimated for this method. Fig. 2b shows the particles numbered 2 and 3. It seems that the particles have a different orientation in the image plane. The FFT image presented in Fig. 2d, however, reveals that both particles are oriented along the [1 1 0] zone axis and they can be attributed to one equally oriented plane of the

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Fig. 1. TEM micrographs of the Y2O3 particles with different grains. The numbered particles on part (a) have the spherical shape whereas the particles marked with an arrow on part (b) show the faceted shape.

Fig. 2. HRTEM micrographs of the particles presented in Fig. 1a with the corresponding numbering are presented on the picture parts (a) and (b). FFT of parts (a) and (b) are presented on parts (c) and (d), respectively.

/2 2 2S type. The reexes of particle no. 2 are marked by the dashed lines. Indication of the % 2YO indexes coincident atomic planes with the 2 2 %1 % as it was done in Fig. 2d requires to take the 0 1 direction for the zone axis of particle no. 2. Particle no. 1 (Fig. 1a) has the same orientation as the particle no. 2. Such orientation relation between the particles can be dened as the mirror % 2YO symmetry of the whole crystal using the 2 2 axis.

Interaction between particles and FeCr lattices is the driving force for the orientation correlation between the particles. To characterise this interaction, the next step was to nd the orientation correlation between Y2O3 particles and the FeCr matrix. Fig. 3 shows the HRTEM image taken from an ODS particle which is surrounded by the matrix (M) lattice. This image was taken from the grain oriented with [1 1 1]M zone axis to the electron beam. The FFT of the image shows the

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Fig. 3. HRTEM micrograph of the Y2O3 particle with surrounded matrix (a) and with FFT of the micrograph (b).

matrix lattice as a hexagonal pattern with reexes of the /1 1 0S type and d110 =0.203 nm distance. The zone axis of the Y2O3 (YO) particle is oriented along the [1 1 0] zone axis and, consequently, [1 1 0]YO8[1 1 1]M. In the FFT image, the Y2O3 lattice is rectangular with reexes of the /1 1 1S type. The orientation correlation of both lattices in %1 % YO 81 1 % 0M : The angle the image plane is 1 1 % 1YO and 0 1 % 1M is 10.51. between 1 1 Such orientation correlation to the matrix is exhibited by numerous, but not by all particles in the grain. This also applies to the grain presented in Figs. 1a and 2 discussed above. The reason why not all Y2O3 particles have the same orientation is that they choose one of the four directions of the /1 1 1SM type. Consequently, 4 (four) equally valid crystallographic orientations of both lattices {1 1 0}YO8{1 1 1}M exist. Each of these orientation possibilities will exhibit its own diffraction pattern at different matrix orientations. The atomic planes of the matrix are not presented in Fig. 2a and b, because the matrix is probably oriented in 20 14 11M direction. It is located under an angle of 70.51 to the [1 1 0] direction. The calculated orientation requirements [1 1 0]YO8[1 1 1]M and %1 % YO 81 1 % 0M remain valid in this case. This 1 1 is also the reason why the electron diffraction would be less suitable for the determination of orientation correlation. The grain, the orientation

of which is described by high indexes, produces a low contrast in the TEM images. The HRTEM image of the Y2O3 particles, hence, has a much better quality than at the low-index orientation. For example, the contrasts in Fig. 1a and b may be compared. During the TEM investigations, several highresolution images were taken with the grains oriented along /1 0 0SM or /1 1 0SM zone axis (for example, Fig. 1b, where crystallographic faceting is evident). But only the grains with a /1 1 1SM zone axis orientation were used for the determination of lattices correlation. Using the images having an orientation other than /1 1 1SM, it is difcult to determine the correlation of the lattices, as the Y2O3 particles are oriented along the high-index zone axis. At best, the Y2O3 particles are oriented such that only one atomic plane can be resolved using HRTEM. In this case, it is impossible to determine the exact particle orientation. Mirror symmetry makes the problem even more complicated. Very few scientic publications exist with regard to the orientation of ODS particles with a metallic matrix [9,10]. In both cases, the ODS alloy was prepared using MA and hot extrusion. The orientation relationship was found as [0 1 0]Fe8[1 1 0]Y2O3 and (0 0 1)Fe8(1 0 0)Y2O3. This orientation differs by 10.41 to our result

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discussed above. However, if the lattice of the Y2O3 particle is rotated around the [1 0 2] axis, the new [0 1 0]Y2O3 vector will be coincident with % 12 1Y2 O3 which is parallel to the the old 2 [0 1 0]Fe direction. This difference is probably due to the different alloy matrix, although the lattice constant differences between FeAl (dFeAl 0:291 nm) and FeCr amount to 1% only. Following the addition of the Y2O3 powder to the EUROFER 97 powder, the preparation was performed in two steps. First, the particles were added and incorporated into the matrix by mechanical alloying. The second preparation step was the HIP process, in which the material was HIPed at 10501C. The orientation correlation is supposed to emerge during one of these two steps. For example, it was supposed that the orientation correlation emerges during the mechanical alloying process [9]. Detailed investigation of the preparation steps strongly suggests that orientation correlation appears after the HIP process, although this is hardly deemed possible at rst view. The Y2O3 particles remain in the solid state during HIP processes, because the melting point of Y2O3 amounts to 25001C. The effect of the reduced melting point with a reduction of the particle size is not strong enough to suggest that the particles are in the liquid state during the processes. According to theoretical calculations, the melting point is reduced by 310%, if the particle size is 8 15 nm [15]. Although the Y2O3 particles remain in the solid state during the HIPing process, it seems possible that they may change their crystallographic orientation. This is supported by experimental facts and results published concerning Y2O3 properties. It is known [16,17] that in Y2O3 powder with a particle size of 25 mm sintering starts at 9009501C. This implies the beginning of surface diffusion on the powder particles well below the melting temperature. This diffusion process could also lead to a change of the particle shape and original crystallographic orientation. As the ODS particles here have a size that is smaller by more than three orders of magnitude, the time needed to change the crystallographic orientation by diffusion can be signicantly lower. Fig. 4 shows the Y2O3

Fig. 4. TEM micrograph of the material after MA.

particles incorporated in a at EUROFER 97 grain by MA before the HIPing process. Almost all Y2O3 particles have a non-spherical shape. On the other hand, numerous TEM images taken from the alloy after the HIPing process reveal that all small Y2O3 particles possess a spherical shape (Fig. 1a). Only the relatively large particles >15 nm may have a faceted one (Fig. 1b). This suggests that the particles denitely change their shape during the HIPing process. Surface diffusion leads to the minimisation of surface energy and the formation of spherical or faceted particles. These considerations and the experimental ndings suggest that the orientation correlation of ODS particles and the matrix most likely evolves during the HIPing process. This well-dened orientation correlation is due to an interchange between the matrix and the Y2O3 lattices. The calculation of the lattice mist shows that 3dFe110 2dY2 O3 111 E0:5%: 2dY2 O3 111 1

This is a very pronounced consistency agreement of the lattices in these directions. But the

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denition of atomic planes with interchange being the largest reorientation force is difcult and requires additional investigations. For example, the inuence of the temperature during the HIP processes on the orientation correlation or the interaction of dislocations with ODS particles which is relevant for the strengthening mechanism have not yet been investigated.

References
. [1] R. Lindau, A. Moslang, M. Schirra, P. Schlossmacher, M. Klimenkov, 10th International Conference on Fusion Reactor Materials (ICFRM-10), October 1419, 2001, Baden-Baden, Germany, J. Nucl. Mater. 306310 (2002) to be published. . [2] R. Lindau, A. Moslang, M. Klimiankou, IEA Workshop on Ferretic Martensitic Steels, on November 14, 2002, Garching, Germany, to be published in proceedings. [3] S.S. Campos, E.V. Morales, H.J. Kestenbach, Metall. Mater. Trans. A 32 (2001) 1245. [4] Z.Y. Chen, Y.Y. Chen, Q. Shu, G.Y. An, D. Li, D.S. Xu, Y.Y. Liu, J. Mater. Sci. 35 (2000) 5605. [5] D.V. Shtansky, K. Nakai, Y. Ohmori, Acta Mater. 48 (2000) 969. [6] P. Yang, O. Engler, H.-J. Klaar, J. Appl. Cryst. 32 (1999) 1105. [7] S. Kobayashi, K. Nakai, Y. Ohmori, Acta Mater. 49 (2001) 1891. [8] R. Behr, J. Mayer, E. Arzt, Interm. 7 (1999) 423. [9] B.J. Inkson, P.L. Threadgill, Mater. Res. Soc. Symp. Proc. 460 (1997) 767. [10] M. Mujahid, J.W. Martin, J. Mater. Sci. Lett. 13 (1994) 153. [11] M. Mujahid, C.A. Gater, J.W. Martin, J. Mater. Eng. Perform. 7 (4) (1998) 524532. . [12] M. Klimiankou, R. Lindau, A. Moslang, to be published. [13] M. Schirra, H. Finkler, Transformation behaviour of the ferritic-martensitic steels with 814% chromium, FZKA Report 6730, June 2002. [14] J.V. Smith, Powder Diffraction File, American Society for Testing Materials, Philadelphia, PA, 196265, Vol. 13, Inorganic. [15] K.F. Peters, J.B. Cohen, Y.-W. Chung, Phys. Rev. B 57 (1998) 13430. [16] Gmelin Handbook of Inorganic and Organometallic Chemistry, 8th Edition, Springer SE C1, Berlin u.a., p.182. [17] L.B. Borovkova, L.B. Lukin, E.S. Poluboyarinov, Tr. Mosk. Chimiko-Technol. Inst. imeni D. I. Mendileeva 68 (1971) 85.

4. Conclusion HRTEM investigations on oxide dispersion strengthened RAFN steel clearly revealed the existence and origin of an unexpectedly strong orientation correlation between Y2O3 particles and the surrounding alloy matrix. This orientation was also investigated in detail from the crystallographic point of view. The structure of the Y2O3 particles analysed by HRTEM shows the correlation of its crystallographic orientation with the FeCr matrix. The orientation correlation was %1 % YO 8 found to be [1 1 0]YO8[1 1 1]M and 1 1 % 1 1 0M : Analysis of the HRTEM images also demonstrates that particles exhibit symmetrical % 2 direction as the orientations using the 2 2 symmetry axis. The strong orientation correlation did not appear during mechanical alloying as was believed by some former researchers, but during the HIPing processes around 10501C, which is signicantly lower than the melting temperature of Y2O3, which amounts to 25001C. The interface between the Y2O3 particles and the steel matrix is clean and well bonded.