JOURNAL OF MATERIALS SCIENCE LETTERS 14 (1995) 1600 1603

Dispersion behaviour of oxide particles in mechanically alloyed ODS steel

T. O K U D A , M. F U J I W A R A

Chofu-ldta Plant, Kobe Steel, Ltd., 2222-1, Ikeda, Onoe-cho, Kakogawa, Hyogo 675, Japan

Yttrium oxide (Y203; yttria) is one of the most thermodynamically stable materials, so that it is generally used as a dispersoid in many kinds of dispersion strengthened alloys. In previous studies [1, 2] of oxide dispersion strengthened (ODS) ferritic steels developed for fuel cladding tubes in fast breeder reactors, we found a configuration change of Y203 particles by a addition of a small amount of titanium in 12% Cr base ferritic steels. Titanium addition was very beneficial in producing finer oxide particles, and therefore creep rupture strength of Ticontaining ODS ferritic steel was particularly improved. In this study, we examined the mechanisms of size change of oxide particles during mechanical alloying (MA) and heat treating after MA. Table I shows the chemical composition of the tested oxide dispersion strengthened steels. The alloy in this smdy contains about 10 times the 51203 and Ti as a practical one in order to increase the volume fraction of oxides and make clear the size change of oxide particles. Master alloy powders were argon gas atomized 13% Cr based ferritic steel with an average size of 70/xm; oxide powders were pure Y203 oxide powders with mean diameter 20 nm. The alloy and oxide powders were mechanically alloyed in a high energy attrition ball mill. The mill charge consisted of about 1 kg weight of alloying powder with 15 kg weight of hard steel balls of 9.5 mm diameter. The powders were agitated for up to 48 h in an argon gas atmosphere at a rotational speed of 290 rpm. The asatomized metal powders with spherical equiaxed grains become multi-layered flaky shape by kneading during MA. Part of the mechanically alloyed powders was annealed in vacuum and the other powders were packed in mild steel cans followed by degassing at 673 K in 1.33 10 .2 Pa vacuum for 2 h, and hotextruded to bar at 1423 K and 1123 K. As-MA and annealed powders were pressed into discs and examined by X-ray diffraction, small angle X-ray scattring (SAXS) and transmission electron microscopy (TEM). Thin foils for TEM specimens were electropolished directly from the disc. A conventional X-ray diffraction method was utilized with CuK radiation operating at 200 mA, 40 kV.

SAXS [3] using MoK was obtained from a rotating anode generator operating at 240 mA, 50 kV. The dispersoid size distributions in MA powders were determined by a calculation of log-normal distribution parameters from the SAXS spectra. Fig. 1 shows X-ray diffraction patterns of MA powders milled for 48 h and powders after MA amlealed at temperatures from 1173 K to 1573 K for 1 h. Every diffraction peak of as-MA powders was identified with the peaks of b.c.c, iron. Peaks of Y203 or any other kind of oxide were not detected. This means Y203 would be decomposed to yttrium and oxygen atoms during the MA process and dissolved in the 13% Cr ferritic steel. It is well known that carbide, nitride or intermetallic compound can dissolve in metal during MA b y force. It is known that oxides such as Y203, which do not have any solubility limit, can dissolve in metal during a MA process. The pattern of the annealed powders at 1173 K after MA was the same as that of as-MA powders. On the other hand new peaks were observed in the patterns of powders annealed at 1273 K. These new peaks were consistent with yttrium and titanium bioxides and titanium oxides. The bi-oxides were identified with Y2TiO5 and Y2Ti207. In an annealing process above 1273 K , dissolved oxygen in the MA process would be bonded with Y and Ti to make more stable bi-oxide than simple Y203 mono-oxide. Y-Tl bi-oxides have two types of combination of Y203 +TiO2, i.e. Y2TiO5 and Y203 + 2 T i O i.e. Y2Ti207 . Both bi-oxides are thermodynamically

TAB LE I Chemicalcompositionof ODS ferriticsteelsamples(wt%) Alloy 3%Ti-3%Y~O3 Practical

1600

10

20

Fe Bal. Bal.

Cr

Ti

Y203 2.85 0.3

O 0.18

40 60 2e (degrees)

80

13.56 2.91 13 0.3

Figure 1 X-raydiffraction patternof MApowders:(a) as-MA;andheat treated (b) 1173K/1 la; (c) 1273K/1 h; (d) 1373K/1 h; (e) 1473K/1 la; (f) 1573K/1 h.

0261-8028 1995 Chapman & Hall

stable at elevated temperature, even above 2273 K [4]. Residual titanium oxides, other than those consumed for Y-Ti bi-oxides, were not rutile type TiO2, but non-stoichiometric TiOl.. Fig. 2 shows transmission electron micrographs of thin foils of MA powders. Even when the dislocation density was extremely high, no precipitates or oxides

were observed in the matrix. Also, no carbides (M23C6, TiC) or nitrides (TiN) were observed. Solubility limits of the interstitial atoms (C, N) in the ferritic steel are enlarged by MA [5], We found that oxide like Y203, which had no solubility limit originally even at high temperatures near the melting point of the alloy, could have some solubility by MA.

Figure 2 TEM of thin foils of MA powder.

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Fig. 3 shows the size distribution of dispersoids, which is analysed by SAXS, in as-MA and the annealed powders. Although the average size of Y203 before MA was 20 nm, most of the dispersoids became smaller than 1 nm after MA. Because the lattice parameter of Y203 is 1.03 nm [5], the size of dispersoids in MA powder, which is equivalent to atomic state, practically corresponds to solid solution in the ferritic steel. Although Y203 originally has little solubility limit in solid steel, part of it can dissolve in liquid steel. A metastable condition such as liquid or amorphous, which can dissolve any oxide, would be produced not only by lattice defects generated by MA, but also by chemical reaction; for example, reduction of oxides and rapid diffusion of substitutional atoms. The size of dispersoids after annealing over 1273K is larger than in as-MA. This means precipitation of new dispersoids from the solid solution. The size distributions of annealed powders annealed at 1273 K and 1473 K are almost the same. These kinds of Y-Ti bi-oxides may be too stable to grow slowly even at high temperatures after nucleation of oxides. The size of dispersoids in titaniumfree 13Cr-3%7203 steel also reduces during the MA process, but the size is not so small as in titaniumadded steel. Titanium may promote dissolving reactions and may be able to reduce Y203 to yttrium and oxygen atoms under low oxygen environments as inside the ferritic steel. In the hot-extruded bar, almost the same results as for the annealed powder were obtained. The X-ray diffraction pattern of the bar extruded at 1123 K showed only peaks of the b.c.c, structure of fenitic steel, but the pattern of the bar extruded at 1423 K had Y-Ti bi-oxide and steel peaks. Fig. 4 shows thin foils of heat-treated bar extruded at 1423 K and cold rolled (60% reduction) and annealed at 1473 K for 1 h. A uniform dispersion of very fine oxides about 5 nm is observed. This microstructure is necessary to obtain high creep strength alloy for long-time service. Consequently it has been shown that Y203 particle size becomes smaller with MA processing time, and after 48 h MA, all the Y203 particles eventually disappeared. In MA powders annealed above 1273 K, precipitation of Y2Ti207 and Y2TiO5 complex fine oxide particles with an average diameter of about 5 nm were observed. These results show a solid
Lattice Parameter of Y203 (1.03 nm)

100

~ 8oiiii~i ,--+!-.]-!!!.!~ ......... +.~-i-~44.

so

ii'ii \
'

i iiii

=
rr

40

~ii / "

iilii
Figure 4 TEM of thin foils of heat-treated bar.

_~ 20 0 0.1 1 10 100 Diameter of dispersoid (nm)

Figure 3 Size distribution of dispersoids: 13Cr-3Ti-3Y203 [] as-MA (4811); O M A + 1273 K/1 h; A M A + 1473 K/1 h. 13Cr- 3Y203 as-MA (48 11). Y203 powder. 1602

solution of 7 2 0 3 oxide in the ferritic base matrix during the MA proeess, and in the following annealing process, a thermochemical reaction between Y203 and Ti occurred. This non-equilibrium

solid solution state of the oxide in a ferritic base matrix was maintained in a hot extmsion process at 1273 K. This process is considered to be effective for controlling microstructures [6] (recrystallization [7]) and for improving the mechanical properties of ODS steels at elevated temperatures.

References
1. T. O K U D A , S. N O M U R A , S. S I L L K A K U R A , K. A S A B E , S. T A N O U F and M. F U J I W A R A , in Proceedings of the International Conference on Solid state powder processing, Indianapolis, USA, edited by A. H, Clauer and J. J. de Barbadillo, The Minerals, Metals and Materials Society (TMS, USA, 1990) pp. 195-202.

S. N O M U R A and T. O K U D A , ibid. (TMS, USA, 1990) pp. 203~211. 3. J . J . S T E P H E N S and S. S P O O N E R , Aeta Metall. 34 (1986) 303-312. 4. R. S. R O T H , A. E. M c H A L E and R. S. R O T H , J. Am. Ceram. Soc., 69 (1986) 827. 5. M. R U H L E and Th. S T E F F E N S , Z Metallkd 83 ( 1 9 9 2 ) 4 3 6 440. 6. Th. K E H A G I A S , L. C O H E U R and P. D E L A V I G N E T T E , J. Mater. Sci. Lett. 12 (1993) 1059-1061. 7. A. A L A M O , H. REGLE, G. PONS and J. L. B E C H A D E , Mater. Sci. Forum 88-90 (1992) 183-190.

2.

Received 12 April and accepted 5 June 1995

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