Journal of Nuclear Materials 417 (2011) 176179

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Journal of Nuclear Materials

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Development of Al added high-Cr ODS steels for fuel cladding of next generation nuclear systems
A. Kimura a,, R. Kasada a, N. Iwata a, H. Kishimoto a, C.H. Zhang a, J. Isselin a, P. Dou a, J.H. Lee a, N. Muthukumar a, T. Okuda b, M. Inoue c, S. Ukai d, S. Ohnuki d, T. Fujisawa e, T.F. Abe f
a

Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan Kobelco Research Institute, Inc., Takatsukadai 1-5-5, Nishi-ku, Kobe 651-2271, Japan Advanced Nuclear System R&D Directorate, Japan Atomic Energy Agency, Narita 4002, Oarai, Higashi-ibaraki, Ibaraki 311-1393, Japan d Graduate School of Engineering, Hokkaido University, N13, W8, Kita-ku, Sapporo 060-8628, Japan e EcoTopia Science Institute, Nagoya University, Furo, Chikusa-ku, Nagoya 464-8603, Japan f Structural Metals Center, National Institute for Materials Science, Sengen 1-2-1, Tsukuba, Ibaraki 305-0047, Japan
b c

a r t i c l e

i n f o

a b s t r a c t
A successful example of high-Cr oxide dispersion strengthened (ODS) steels development is introduced with showing key technologies to overcome the issues to meet material requirements for next generation nuclear systems as well as fusion blanket systems. Corrosion issue requires Cr concentration more than 14 wt.%, but aging embrittlement issue requires it less than 16 wt.%. An addition of 4 wt.%Al is effective to improve corrosion resistance of 16 wt.%Cr-ODS steel in supercritical water (SCW) and leadbismuth eutectics (LBE), while it is detrimental to high-temperature strength. An addition of small amount of Zr or Hf results in a signicant increase in creep strength at 973 K in Al-added ODS steels. Feasibility of high-Cr ODS steel without Al addition is assessed for fusion application in terms of corrosion resistance in SCW. 2011 Elsevier B.V. All rights reserved.

Article history: Available online 1 January 2011

1. Introduction Cladding materials development is a key issue to achieve high burn-up operation of Generation IV nuclear energy systems such as supercritical pressurized water reactor (SCPWR), sodium-cooled fast reactor (SFR), and lead bismuth-cooled fast reactor (LFR) and so on. The candidate cladding materials must have a high resistance to neutron irradiation embrittlement and void swelling as well as a good performance of mechanical properties at elevated temperatures. In addition, a good corrosion resistance of the claddings in the relevant environments has been certainly required for practical long term operation of the advanced ssion reactors [1,2]. Fusion blanket materials have been also required of high performances similar to the Generation IV nuclear systems, although there are characteristic issues for the fusion application, such as transmutation helium/hydrogen effects and material design towards low activation [3]. Oxide dispersion strengthened (ODS) ferritic/martensitic steels containing 912 wt.% chromium have been developed as the fuel cladding material of SFR because of their high creep strength at elevated temperatures and enough resistance to neutron irradiation embrittlement [4]. However, the (912)Cr-ODS ferritic/martensitic steels are not suitable for SCWR

owing to an insufcient corrosion resistance of the materials [57]. Corrosion resistance of iron based alloys is inuenced by chromium (Cr) and aluminum (Al). It is expected that an adequate combination of the contents will be available for Cr and Al in the steels for each blanket system. The Cr content can be balanced between a merit of corrosion resistance and a demerit of aging embrittlement with maintaining strength at elevated temperatures. The technology development for strengthening of the Al-added steel has been desired by controlling nano-scaled oxide dispersion morphology. Furthermore, low activation material scenario limits the use of Al as an alloy element of fusion materials. The feasibility check is also demanded for Al free 16Cr-ODS steels as a candidate material for fusion blanket structural material. In this work, alloy design methodology of high-Cr ODS steels is shown to improve corrosion resistance with maintaining high strength at elevated temperatures. The effects of Al addition on the high-Cr ODS steels are discussed to assess the feasibility of the Al free ODS steel to apply it to fusion blanket. 2. Alloy design 2.1. Chromium and aluminum 2.1.1. Corrosion properties Ukai et al. developed 9Cr-ODS martensitic steel as a cladding material for SFR. The application of 9Cr-ODS steel to the cladding

Corresponding author. Tel.: +81 774 38 3476; fax: +81 774 38 3479.
E-mail address: kimura@iae.kyoto-u.ac.jp (A. Kimura). 0022-3115/$ - see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.jnucmat.2010.12.300

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of SCWR and LFR is limited because of insufcient corrosion resistance of the steel [1,2]. Corrosion test results in supercritical pressurized water (SCW) and leadbismuth eutectics (LBE) were referred to determine Cr and Al content. LBE has high solubility of nickel, iron and chromium, which are most important alloy elements in austenitic stainless steels, which is the reason of the difculty to use nickel super alloys and iron-based austenitic stainless steels as the structural materials for LBE cooled systems, especially at temperatures higher than 773 K [812]. Ferritic steels that contain only a small amount of nickel have been considered to be more adequate for LBE application. Above 873 K, however, the solubility of iron and chromium in LBE also becomes signicantly larger. In order to prevent material from dissolving into LBE, alumina coating was often conceived. Without alumina coating, however, it is also considered that alumina lm, which is spontaneously formed on the surface of the steel containing Al in solution, may suppress dissolution. Fig. 1 shows the appearance of ODS steel specimens after corrosion test in LBE with 106 wt.%O2 in solution for 10k h at 923 K. The Al free 19 wt.%Cr-ODS steel dissolved into LBE markedly, while those of ODS specimens containing 4 wt.%Al almost completely kept the specimen shape, indicating much higher resistance to LBE corrosion. It is worth to noting that the corrosion resistance in LBE is independent of Cr concentration from 13 to 19 wt.% in Al-added ODS steels. The addition of Al is considered to be inevitable for structural materials to apply to LBE nuclear systems especially above 773 K. As for the corrosion resistance in SCPW, the previous surveillance test results showed that nickel super alloys were preferable [13]. However, nickel alloys are rather susceptible to irradiation embrittlement as well as helium embrittlement [14]. Fig. 2 shows the weight gain after corrosion tests in SCPW (773 K, 25 MPa) up to 1800 h. The weight gain of 9Cr-ODS steel is much larger than 16Cr-ODS steel, indicating that 9Cr-ODS steel is not adequate for application to SCWR. An EPMA and XRD analysis revealed that a thick Fe3O4 lm was formed on the surface of 9Cr-ODS steel but

Fig. 2. Weight gain after corrosion tests in SCPW (783 K, 25 MPa) up to 1800 h.

not detected in the high-Cr ODS steels. It should be noted that the weight gain is much larger in SUS430 (16Cr) than in 16Cr-ODS steel. This clearly indicates that the oxide particles dispersion plays an effective role in the high corrosion resistance of ODS steels, since the corrosion resistance in water environment is mainly controlled by Cr concentration. The corrosion resistance of ODS steels increases with chromium concentration. The effect of Al on corrosion resistance depends on Cr concentration. In 19Cr-ODS steel, the addition of 4 wt.%Al did not remarkably inuence the corrosion resistance [2]. However, in 16Cr-ODS steel, the addition of Al improved corrosion resistance. The suppression of corrosion by Al addition in 16Cr-ODS steel is due to formation of very thin alumina lm on the surface. In 19Cr-ODS steel, rather dense chromia lm was observed on the specimen surface [5]. It is considered that 16 wt.%Cr is not large enough to form homogeneous and stable chromia on the whole specimen surface, while very thin alumina lm covers the whole specimen surface of the ODS steel added with 4 wt.%Al. Thus, an addition of Al is effective to improve corrosion resistance of 16Cr-ODS steel but not in 19Cr-ODS steel. 2.1.2. A trade-off issue: thermal aging embrittlement Although an increase in Cr concentration results in an improvement of corrosion properties, it also often increases susceptibility to aging embrittlement through the formation of Cr-rich secondary phases. A trade-off between corrosion resistance and aging embrittlement caused by increasing Cr content is one of the critical issues for high-Cr ODS steels [15]. Aging effects were investigated for ODS steels with different Cr content by measuring impact fracture energy at RT after aging at 773 K up to 10k h [16]. The Charpy V-notch specimen measures 1.5 mm square rod with 20 mm length. As shown in Fig. 3, the fracture energy at RT decreases with increasing Cr content before aging. Aging causes the reduction of the fracture energy. The ODS steels with Cr content higher than 18 wt.% showed a signicant reduction of fracture energy after the aging for 100 h. In contrast to this, 16Cr4Al ODS steel showed very small reduction of the fracture energy even after aging for 10k h. Microstructure observation by TEM revealed that ne secondary phases were formed in high density after aging for 1k h at 773 K even in 16Cr ODS steels. The secondary phases are considered to be Cr-rich phases. The effects of aging on tensile behavior are interesting. After the aging at 773 K for 1k h, Cr-rich secondary phases were formed in 16Cr-ODS steels, and caused a small reduction of the fracture energy at RT as shown in Fig. 3. However, the reduction of tensile elongation was almost negligible, but some hardening was observed at RT. This

Fig. 1. The appearance of ODS steel specimens after corrosion test in LBE solved with 106 wt.%O2 for 1 104 h at 923 K.

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0.8

Absorbed Energy at RT, J

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 12 14

1,000h

Aged at 500C
As-Received

4,300h 10,000h 100h

16

18

20

22

Cr concentration, wt%
Fig. 3. The dependence of the absorbed energy at RT on the Cr concentration of the ODS steel after aging at 773 K for different period up to 10,000 h. Fig. 4. The tensile strength of 19Cr-ODS steels with and without addition of Al as well as JLF-1 steel.

behavior was very similar to that of ODS steels after neutron irradiation that caused a hardening without a signicant reduction of total elongation at RT. Since the thickness of fuel cladding is around 0.5 mm, the ductile-to-brittle transition temperature (DBTT) shift by aging is considered to be much smaller than those obtained for thicker specimen (1.5 mm thickness) for evaluation of the DBTT of the ODS steels in this work. Fracture toughness high enough to coldwork piping is required for the fabrication of cladding. Finally, in order to reduce the susceptibility to aging embrittlement, it is recommended that the Cr content is lower than 16 wt.%. 2.2. Tungsten and titanium The addition of W or Ti inuences on high-temperature strength. According to the R&D of reduced activation ferritic steels for fusion blanket application, the addition of W to 9Cr martensitic steel is effective to increase creep rupture time at 873 K [17]. Although W is ferrite former, martensite is still stable when W content is less than 2 wt.% [17]. Previous works on chemical compositions of oxide particles in high Cr-ODS ferritic steel and 9Cr-ODS martensitic steel showed that the addition of small amount of Ti resulted in decreasing oxide particles size and increasing their number density, and consequently increasing strength at elevated temperatures [4]. The microstructural examinations of the oxide particles by TEM-EDS and 3D-AP suggested that the ne oxide particles were pyrochlore, Y2Ti2O5 [15]. Although Al addition may convert the crystal structure and chemical compositions of the oxide particles, Ti was necessary to keep the size of the oxide particles being smaller. 2.3. Minor alloying element 2.3.1. Reduction of strength by Al addition Most serious problem of Al addition is a loss of strength. Fig. 4 shows the effects of Al addition on the tensile strength of the 19CrODS steel, which clearly indicates that the Al addition signicantly reduces the tensile strength, although the tensile strength of 19Cr 4Al-ODS steel is still much higher than a reduced activation ferritic steel, JLF-1. In order to investigate the mechanism of this reduction of strength by Al addition, TEM observations were performed, and it was revealed that the structure and dispersion morphology of the oxide particles were different between the steels with and without Al addition [18]. In the Al-added steel, the average

diameter of the oxide particles was about 7 nm but less than 3 nm in the Al free ODS steel. The number density of the oxide particles was reduced by almost one order of magnitude. The crystal structure of the oxide particle was also changed by the Al addition. As mentioned before, the ne oxide particles in the steel without Al addition were mainly pyrochlore [19], while those in the steel with Al addition were mostly rather larger yttrium aluminum perovskites (YAP) and yttrium aluminum hexagonal (YAH) [20]. 2.3.2. Strengthening by oxide particles modication Yttriumaluminum oxide particles are not adequate for strengthening of ODS ferritic steels, while yttriumtitanium pyrochlore is effective for strengthening. Although alumina and yttria are well known as thermally stable oxides, the possible other sort of ne oxide particles are searched for their application to strengthening of the ODS steels with Al and Y. There are many stable oxide former elements, such as Y, Al, Ti, V, Ta, Nb, Hf, Zr, and so on. Table 1 shows the oxide formation energies of each alloy element at 1500 K. Among them yttria is familiar for ODS alloy production. The oxide formation energy is ranging widely from 520 for Nb to 995 kJ/mol O2 for Y at 1500 K. Since the formation energy of yttria and alumina is 995 and 800 kJ/mol O2, respectively, Hf and Zr may inuence on the characteristics of oxide particles [21]. The effects of a small addition of Hf and Zr on the strengthening were investigated for 16Cr4AlY2O3-ODS steel. Fig. 5 shows the
Table 1 The oxide formation energies of each alloy element at 1500 K [18]. Family Elements Atomic# Oxide Formation energy 3A Sc 21 Sc2O3 990 Y Atomic# Oxide Formation energy 39 Y2 O3 995 La Atomic# Oxide Formation energy 57 La2O3 4A Ti 22 TiO2 770 Zr 40 ZrO2 800 Hf 72 HfO2 900 5A V 23 V2 O5 570 Nb 41 Nb2O 500 Ta 73 Ta2O5 570 3B Al 13 Al2O3 800 4B Si 14 SiO2

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As for the corrosion resistance in LBE, it is considerably improved by Al addition that causes the formation of thin alumina on the specimen surface. In the case of Al free ODS steels, the dissolution of Fe and Cr increases considerably at elevated temperatures higher than 773 K, which may limit the operation window of the LBE cooled system [24]. 4. Concluding remarks (1) Corrosion issue requires Cr concentration more than 14 wt.%, but aging embrittlement issue requires it less than 16 wt.%. An addition of 4 wt.%Al is effective to improve corrosion resistance of 16 wt.%Cr-ODS steel in SCW and LBE, while it is detrimental to high-temperature strength. (2) An addition of small amount of Zr or Hf results in a signicant increase in creep strength at 973 K in Al-added ODS steels. (3) The Al free 16Cr-ODS steel has an enough corrosion resistance in SCPW (873 K, 25 MPa, C(O) = 8 ppm), although the corrosion rate of the Al free 16Cr-ODS steel is about 3.5 times higher than that of the Al-added 16Cr-ODS steel.

Fig. 5. Effects of extrusion temperature and addition of minor elements on the ultimate tensile stress (UTS) of 16Cr4Al ODS steel at 973 K.

Table 2 Creep test results at 973 K of each candidate ODS steel. Materials 16Cr-ODS 16Cr4Al-ODS 16Cr4Al-ODS-Zr 16Cr4Al-ODS-Hf Creep strength (973 K, 10 k h) (MPa) 100 60 120 110

Acknowledgement Present study includes the result of Development of super ODS steels with high-resistance to corrosion towards highly efcient nuclear systems entrusted to Kyoto University by the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT). References
[1] A. Kimura, S. Ukai, M. Fujiwara, in: Proc. Int. Conf. On Grobal Environ. Adv. Nucl. Power Plants, (GENES4/ ANP2003), CD-ROM le, 2003, p. 1198, ISBN: 4901332-01-5. [2] A. Kimura, S. Ukai, M. Fujiwara, in: Proc. Int. Cong. Adv. Nucl. Power Plants, (ICAPP-2004), CD-ROM le, 2004, p. 2070, ISBN: 0-89448-680-2. [3] M.J. Alinger, G.R. Odette, D.T. Hoelzer, J. Nucl. Mater. 329333 (2004) 382387. [4] S. Ukai, T. Nishida, H. Okada, T. Okuda, M. Fujiwara, K. Asabe, J. Nucl. Sci. Technol. 34 (3) (1997) 256. [5] H.S. Cho, A. Kimura, S. Ukai, M. Fujiwara, J. Nucl. Mater. 329333 (2004) 387 391. [6] H.S. Cho, A. Kimura, J. ASTM Int. 2 (7) (2005) 194205. [7] A. Alamo, V. Lambard, X. Avelty, M.H. Maton, J. Nucl. Mater. 329333 (2004) 333338. [8] H.U. Borgstedt, G. Drechsler, G. Frees, Z. Peric, J. Nucl. Mater. 155157 (1988) 728731. [9] M. Broc, T. Flament, P. Fauvet, J. Sannier, J. Nucl. Mater. 155157 (1988) 710 714. [10] V. Coen, H. Kolbe, L. Orecchia, J. Nucl. Mater. 155157 (1988) 740743. [11] T. Sample, H. Kolbe, J. Nucl. Mater. 283287 (2000) 13361340. [12] G. Benamati, C. Fazio, I. Ricapito, J. Nucl. Mater. 307311 (2002) 13911395. [13] M. Harada, O. Kubota, H. Anada, Kobe Steel Eng. Rep. 53 (3) (2003) 9297. [14] M.R. James, S.A. Maloy, F.D. Gac, W.F. Sommer, J. Chen, H. Ullmaier, J. Nucl. Mater. 296 (2001) 139144. [15] T.R. Allen, C.L. Trybus, J.I. Cole, J. Nucl. Mater. 270 (1999) 290300. [16] R. Kasada, H.S. Cho, N. Okuda, A. Kimura, Mater. Sci. Forum 561565 (2007) 17731776. [17] A. Kimura, H. Kayano, T. Misawa, H. Matsui, J. Nucl. Mater. 212215 (1994) 690694. [18] P. Dou, R. Kasada, A. Kimura, T. Okuda, M. Inoue, S. Ukai, S. Ohnuki, T. Fujisawa, F. Abe, J. Nucl. Mater. 417 (2011) 166170. [19] S. Yamashita, S. Ohtsuka, N. Akasaka, S. Ukai, S. Ohnuki, Philos. Mag. Lett. 84 (8) (2004) 525. [20] P. Dou, A. Kimura, T. Okuda, M. Inoue, S. Ukai, S. Ohnuki, T. Fujisawa, F. Abe, Acta Mater., in press. [21] Metal Data Book, Jpn Inst. Metals, 1984, pp. 84. [22] A. Kimura, R. Kasada, N. Iwata, J. Isselin, P. Dou, J.H. Lee, T. Okuda, M. Inoue, S. Ukai, S. Ohnuki, T. Fujisawa, F. Abe, in: Proceedings of International Workshop on 2nd Structural Materials for Innovative Nuclear Systems, OECD Nuclear Energy Agency, J. Nucl. Mater. 417 (2011) 896899. [23] J.H. Lee, R. Kasada, A. Kimura, T. Okuda, M. Inoue, S. Ukai, S. Ohnuki, T. Fujisawa, T.F. Abe, J. Nucl. Mater. 417 (2011) 12251228. [24] S. Takaya, T. Furukawa, M. Inoue, T. Fujisawa, T. Okuda, F. Abe, S. Ohnuki, A. Kimura, J. Nucl. Mater. 398 (2010) 132138.

tensile strength at 973 K of each candidate ODS steel. 16Cr4Al is a standard candidate ODS steel whose chemical compositions are 16Cr4Al2W0.15Ti0.35Y2O3. 16Cr is 16Cr-ODS steel without Al addition, showing much higher strength than 16Cr4Al. The extrusion temperature was 1423 K except for the steels without notication in the gure. The addition of small amount of Hf and Zr is very effective to increase the strength at 973 K. TEM observation revealed that the addition of Hf and Zr reduced and increased the size and the number density of oxide particles, respectively. Furthermore, the number density of grain boundary precipitates, such as carbides and oxides were increased remarkably by addition of Hf or Zr. Grain boundary precipitates are well known as obstacles for grain boundary sliding that is a typical deformation mode at elevated temperatures [22]. This effect also resulted in a signicant increase in long term creep properties of the ODS alloy at 973 K, as summarized in Table 2. Thus, the positive effect of addition of Hf or Zr overcomes the negative effect of Al addition on high-temperature strength. The Zr addition is more recommended than Hf addition in terms of thermal neutron cross section area or neutron absorption. 3. Al free 16Cr-ODS steel for fusion application From a viewpoint of reduced activation, Al is not an adequate element for application to fusion blanket. The advantage of Al addition is signicant in corrosion resistance as mentioned above. The corrosion rate of Al free 16Cr-ODS steel in SCPW at 873 K is about 3.5 times higher than that of Al added 16Cr-ODS steel. Based on the corrosion test results, the corrosion depth of the Al free 16Cr-ODS steel is estimated to be 35 lm for 10 years in SCPW (25 MPa, 873 K, C(O) = 8 ppm and ow rate = 16.7 ml/min) [23]. Although the effect of ow rate of SCPW on the corrosion rate is necessary to assess the feasibility for fusion application, it can be concluded that the Al addition is not inevitable for 16Cr-ODS steel for the application to SCPW cooled blanket system for DEMO or beyond.