Nuclear Materials and Energy 25 (2020) 100798

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Nuclear Materials and Energy

journal homepage: www.elsevier.com/locate/nme

Development of nano-oxide particles dispersed alumina scale formed on

Zr-added FeCrAl ODS ferritic alloys
Hao Yu a, *, Sosuke Kondo a, Ryuta Kasada a, Naoko Oono b, Shigenari Hayashi b, Shigeharu Ukai b
a
Institute of Materials Research, Tohoku University, Sendai 980-8577, Japan
b
Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: In order to develop a robust alumina scale dispersed with nano-oxide particles for FeCrAl oxide dispersion
FeCrAl ferrite strengthened (ODS) ferritic alloys, the oxidation behavior of FeCrAl ODS ferritic alloys with zirconium and
ODS excessive oxygen (Ex. O) additions was investigated at 900 ◦ C in air. Zirconia incorporation into alumina scale
Oxidation
was not observed in the Ex. O-added FeCrAl ODS alloys at 900 ◦ C, instead of this, a distribution with dense Y-Zr
Alumina
oxide particles inside the alumina scale was found, which is expected to enhance the stability of the alumina scale
during service at elevated temperatures in nuclear applications. Preexisting large Zr-enriched precipitates formed
during the alloy fabrication process are incorporated into the alumina scales during oxidation, which would
increase the oxidation rate via providing a short-circuit paths for oxygen inward diffusion by themselves and
associated porosity. In addition to a traditional spherical shape, a unique tadpole-like shape of the fine Y-Zr oxide
particles in alumina was also observed, which is considered to be related to those incorporated coarse Zr-Y oxide
inclusions in alumina scale.

1. Introduction
Alumina-forming FeCrAl ODS ferritic alloys have been considered
key structural materials for fission and fusion reactors of the next gen­
eration due to their excellent performance against high-temperature
creep, irradiation and oxidation [1–5]. The tolerance against creep
deformation and neutron irradiation can be further improved by the
addition of small amounts of Zr, which is attributed to the formation of
fine Y-Zr oxide particles with a high number density [6]. However, at
high temperatures, the Zr also could play a detrimental role via forming
a ZrO2 inside the alumina scale. The formed ZrO2 will act as a rapid
oxygen inward diffusion pathway, thus weakening the oxidation resis­
tance of the alumina scale [7]. Such an unbeneficial effect of Zr is
associated with the Zr distribution type in matrix. Since the solubility of
Zr in the bcc Fe is negligibly small, the Zr atoms may segregate at grain
boundary or particle/matrix interface. If Zr was preferentially consumed
by an internal oxidation of the matrix during the fabrication process, the
activity of Zr to form ZrO2 precipitation in the alumina scale during the
subsequent environmental oxidation exposure will be significantly
reduced. The preferential oxidation is directly related on the oxygen
content in matrix. Even the oxygen solubility in ferritic Fe is very
limited, it was claimed that the oxygen can be forcibly dissolved into
matrix by the unique fabrication process of ODS alloys via mechanical
alloying (MA), which makes it possible to adjust the oxygen content in
FeCrAl ODS alloys [8]. The addition of Fe2O3 powder during MA process
is one of most used methods to introduce the oxygen into the matrix of
FeCrAl ODS alloys [9]. Besides, it is inevitable that the oxygen
contamination may happen during the whole fabrication process of ODS
alloys, such as MA and hot-extrusion, which would also introduce a
certain amount of oxygen into the alloys. In order to accurately quantify
the introduced oxygen content in the matrix of FeCrAl ODS alloys, the
concept of excessive oxygen (Ex. O) is put forward, which represents the
oxygen in the FeCrAl ODS alloys caused by the Fe2O3 powder addition
and the oxygen contamination. The Ex. O will consume the Zr in the
alloy by forming Y-Zr oxides during the alloy fabrication process, which
may prevent the formation of ZrO2 inside external alumina scale after­
ward. The authors investigated the oxidation behavior of the Zr-added
FeCrAl ferritic alloys at ultra-high temperatures from 1200 ◦ C to
1500 ◦ C and demonstrated that the Ex. O addition higher than 0.2 wt%
can effectively suppress the ZrO2 formation inside the alumina scale
[10].
In addition, an interesting point is that the alumina scale formed on

* Corresponding author.
E-mail address: qqyu1111@163.com (H. Yu).

https://doi.org/10.1016/j.nme.2020.100798
Received 1 February 2020; Received in revised form 21 August 2020; Accepted 11 September 2020
Available online 21 September 2020
2352-1791/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
H. Yu et al.
the FeCrAl ODS ferrites is possible to be dispersed with Y-Zr oxide
particles based on other studies on alumina-forming ODS superalloys
[11], which is expected to mitigate irradiation defects formed in the
alumina scale and keep the alumina scale stable during nuclear irradi­
ation [12,13]. Conventional ODS steels are generally pre-oxidized to
form a passive chromium oxide film and a small amount of iron oxide to
protect the steels during practical application as a tritium breeder
blanket material in fusion reactor [14,15]. In contrast, the alumina-
forming FeCrAl ferritic ODS alloys is more competitive to act as the
materials and it would be very exciting if the formed single alumina
scale could be dispersed with dense nano-oxide particles during the pre-
oxidation. However, B.A. Pint [16] reported that the dynamic-
segregation of reactive-elements (RE) such as Y, Zr and Ti would
happen with a RE outward diffusion from the metal substrate to the gas
interface of alumina scale during high temperature oxidation. The
dynamic-segregation is sensitively dependent on the temperatures, i.e.,
high temperatures above 1000 ◦ C accelerate the RE outward diffusion
and induce RE-rich particles ripening and coarsening near the alumina
scale surface. Thus, a relatively low temperature below 900 ◦ C is more
suitable for developing the Y-Zr-O particles with a small size and high
number density inside the alumina scale for the Zr-added FeCrAl ODS
alloys. The fine Y-Zr oxide particles with high number density inside
alumina scale are expected to improve irradiation resistance of the
alumina scale by capturing defects and reducing irradiation swelling
[12].
In the present work, aimed at developing a superior alumina scale in
which the ZrO2 formation is eliminated and dense Y-Zr oxide particles
are dispersed, relatively high Ex. O contents of 0.2 wt% and 0.3 wt%
were added to suppress the ZrO2 formation inside the alumina scale
based on previous study [10]. Besides, 900 ◦ C in air was chosen to
conduct the oxidation since the relatively lower temperature is consid­
ered to be beneficial for the fine Y-Zr oxide particles formation in
alumina scale. In order to characterize the effect of Zr addition on the
oxidation properties, the FeCrAl ODS ferritic alloys without Zr addition
were prepared to act as comparison tests.
2. Experimental
Table 1 lists the actual chemical compositions of all the used samples
in this study, in which corresponding abbreviations are used to name the
samples. All alloys were subjected to MA process and then consolidated
with a hot-extrusion at 1150 ◦ C. The introduced Ex. O content into the
Zr-added ODS alloys was controlled via adjusting the Fe2O3 powder
amount during MA process. Specimens at as-extruded condition were
cut into a dimension of 10 × 6 × 2 mm for the oxidation test, and all the
surfaces were wet ground using SiC paper up to 4000-grit, and then
polished with 3 μm-diamond paste. After confirming that no residual
scratches remain on the surfaces by an optical microscopy, the samples
were ultrasonically cleaned in alcohol, and dried in hot air. Isothermal
oxidation test at 900 ◦ C was carried out inside a muffle furnace in air and
then subsequently air cooled to room temperature. In order to determine
the oxidation kinetics, the oxidation weight gains in different exposure
durations (1, 4, 9, 16, 25, 49, 64, 81, 100, 196, 225 h) were measured at
room temperature via a Sartorius precision electronic balance with a
resolution of 1 μg.
The crystalline structure of oxidized samples was detected using X-
ray diffraction (XRD, RIGAKU Ultima IV/SG operated at 40 kV/40 mA
Table 1
Actual compositions of the investigated alloys (in wt.%) and utilized
abbreviations.
No. Fe Cr Al Y2O3 Ti Zr Ex. O
0Zr Bal. 14.2 6.4 0.5 0.5 0 0.1
Zr0.2Ex. O Bal. 14.8 6.4 0.5 0.5 0.4 0.2
Zr0.3Ex. O Bal. 15.1 7.0 0.5 0.5 0.4 0.3
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Nuclear Materials and Energy 25 (2020) 100798
with Cu-Kα). In order to analyze cross sections of the oxidized samples,
the oxidized samples were mounted in resins and then kept in grinding
until using 1 μm-diamond paste. Backscattered electron (BSE) pattern of
an electron probe micro-analyzer (EPMA, JEOL JXA-8530F) was utilized
to observe the polished cross sections. Corresponding elemental distri­
bution was also detected with a wavelength dispersive X-ray spectros­
copy (WDS) elemental mapping. Grain size of substrates in the cross
sections were observed by electron back-scattered diffraction (EBSD)
jointed in the EPMA. In order to investigate the oxide particles distri­
bution in the formed oxide scales, transmission electron microscopy
(TEM, JEOL ARM-200F) observation was carried out to further inves­
tigate the oxide scale by using scanning transmission electron micro­
scopy (STEM) imaging and X-ray energy dispersive spectroscopy (EDS)
elemental mapping. Focused ion beam (FIB, HITACHI, FB2200) was
used to prepare the TEM samples. Before FIB milling, carbon and
tungsten coatings were successively overlaid on the surface of oxidized
samples to maintain the integrity of the alumina scale.
3. Results
3.1. Weight gain by isothermal oxidation
Fig. 1 shows the weight gain per unit surface area as a function of
exposure time for all the FeCrAl ODS ferritic alloys at 900 ◦ C. It can be
confirmed that all specimens showed an approximate mass gain during
the initial stage of exposure (− 81 h). However, with increasing exposure
time, 0Zr specimens showed the smallest increase in weight in the later
stage (81–225 h), implying that Zr addition accelerated the oxidation
rate at longer exposure times even though with high Ex. O additions.
Besides, it seems that two Ex. O added samples exhibited similar
oxidation kinetics at 900 ◦ C, in spite of different Ex. O contents with 0.2
wt% and 0.3 wt%. Assuming that all oxidation rates follow classical
parabolic scale-growth kinetics [17], the oxidation rate constant kp
could be derived as follows,
ΔW2
kp = (1)
t
in which ΔW is the specific weight change of oxidized samples and t
is the oxidation time during exposure. Fig. 2 is the re-arranged oxidation
kinetics figure derived from mass gains as a function of square root of
time. In order to figure out the kp value, several straight lines were tried
to make to link all the dots in the Fig. 2. Interestingly, in contrast to a
straight line running through the results of 0Zr, the oxidation process of
both the two Zr-added specimens seems can be separated into two parts.
i.e., initial stage (− 81 h) and later stage (81–225 h). Table 2 lists the kp
values of each specimens, which are calculated from the squares of the
corresponding gradients in Fig. 2.
3.2. Microstructure of the oxide scales
Fig. 3 shows the XRD patterns for all the FeCrAl ferritic ODS alloys
oxidized at 900 ◦ C with various exposure times of 4 h, 9 h, 25 h, 49 h,
100 h and 225 h, in which (a), (b) and (c) represents the results of 0Zr,
Zr0.2Ex. O and Zr0.3Ex. O, respectively. In accordance with noticeable
characteristic peaks of Al2O3, it is confirmed that alumina formation
dominates all the oxide scales during overall exposure at 900 ◦ C in 225
h.
In order to investigate the distribution of elements in the oxidized
scales, cross sections of all samples oxidized within 225 h were prepared
and analyzed by EPMA. Based on BSE images, a single-layered oxide
scale with dark contrast could be found on the surfaces of all specimens,
as shown in Fig. 4, in which (a), (b) and (c) represents the cross section
obtained from 0Zr, Zr0.2Ex. O, Zr0.3Ex. O specimens, respectively.
Although a general trend indicated that the thickness of all the scales
formed in the three alloys is not homogeneous, it is apparent that the Zr-
free specimen possesses the thinnest oxide layer, which agrees well with
H. Yu et al. Nuclear Materials and Energy 25 (2020) 100798

Fig. 1. Weight gain curves for the FeCrAl ODS ferritic alloys oxidized at 900 ◦ C in air for 225 h.

Fig. 2. The fitted parabolic curves for the FeCrAl ODS ferritic alloys oxidized at 900 ◦ C in air for 225 h.

the mass gain exhibited in Fig. 1. With regard to the Zr-added specimens,
even different Ex. O contents with 0.2 wt% and 0.3 wt% were added, it is
difficult to obtain a significant scale thickness difference from the BSE
images in the Fig. 4 (b) and (c).
Fig. 5 shows corresponding EPMA elemental maps of the cross sec­
tions, in which (a), (b) and (c) belong to the 0Zr, Zr0.2Ex. O and Zr0.3Ex.
O, respectively. According to the enrichment of only aluminum and
oxygen elements at the outer dark layer and the alumina diffraction
peaks obtained from the XRD results in Fig. 3, the oxide scales formed on
all the tested FeCrAl ODS ferritic alloys at 900 ◦ C in air were confirmed
to be single-layered alumina scales. Besides, spot-like enrichments of Zr
and Ti inside the substrate also can be observed, which demonstrates the
existence of Zr-rich precipitates in the matrix of Zr-added alloys.
The grain of substrates in the cross sections was observed with EBSD.

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H. Yu et al. Nuclear Materials and Energy 25 (2020) 100798

Table 2
Parabolic rate constants of the FeCrAl ODS ferritic alloys oxidized at 900 ◦ C in
air for 225 h.
Superalloys Parabolic rate constant, kp (g2⋅cm¡4⋅s¡1)
14
0Zr 2.39 × 10−
14
Zr0.2Ex. O 2.89 × 10− (~81 h)
14
6.42 × 10− (81 ~ 225 h)
14
Zr0.3Ex. O 2.86 × 10− (~81 h)
14
6.19 × 10− (81 ~ 225 h)

Fig. 4. The cross-section morphologies of oxidized samples at 900 ◦ C in 225 h,

(a), (b) and (c) represents the 0Zr, Zr0.2Ex. O and Zr0.3Ex. O samples,
respectively.

Fig. 3. XRD results obtained from the 0Zr (a), Zr0.2Ex. O (b), Zr0.3Ex. O (c)
alloys oxidized at 900 ◦ C in 4, 9, 25, 49, 100 and 225 h, respectively, in which
the alloys prior to oxidation also have been tested.
According to the image quality (IQ) maps in Fig. 6, the grain size ranges
in 0Zr, Zr0.2Ex. O and Zr0.3Ex. O alloys were measured to be 0.53–7.89
μm, 0.27–6.54 μm and 0.28–4.64 μm, respectively. It is noticeable that
the average grain size in the 0Zr specimen is larger than that in the two
Zr-added samples.
In order to obtain a more detailed microstructure information in the
formed single-layered alumina scale, TEM observation on the Zr 0.2Ex.

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H. Yu et al. Nuclear Materials and Energy 25 (2020) 100798

Fig. 5. EPMA elemental maps obtained from 0Zr (a), Zr0.2Ex. O (b) and Zr0.3Ex. O samples oxidized at 900 ◦ C for 225 h.

O specimen after exposure at 900 ◦ C for 225 h was conducted. Based on
the low-angle annular dark-field (LAADF) STEM images in Fig. 7, it is
apparent that the thickness of the alumina scale is heterogeneous, which
is consistent with the BSE image observed in the Fig. 4 (b). Underneath a
thin alumina layer, some large grains with an average size of 1.01 μm
can be observed in substrate, as marked with orange broken lines in
Fig. 7 (a). Remarkably, in the thickest alumina layer, in addition to small
grains of the substrate with a mean size of 0.61 μm, a coarse precipitate
with an approximate diameter of 0.43 μm could be observed inside the
alumina scale. In the magnified LAADF-STEM image of Fig. 7 (b), pores
around the coarse precipitate were also observed, as marked with yellow
arrows. Besides, a large number of fine particles could be observed

5
H. Yu et al.
Fig. 6. EBSD IQ maps obtained from substrates of 0Zr (a), Zr0.2Ex. O (b), Zr0.3Ex. O (c) alloys.
Fig. 7. TEM LAADF images obtained from the Zr0.2Ex. O specimen oxidized at 900 ◦ C for 225 h.
inside the alumina scale. An interesting point should be noted is that the
shape of the particles near the coarse precipitate and / or the pores, i.e.,
in contrast to a common spherical shape in other areas, tadpole-like
particles were found in there, as marked with red arrows in Fig. 7 (b),
which seem to point towards the direction of the coarse precipitate and /
or the pores with their heads. EDS analysis on the coarse precipitate and
fine particles were conducted. As shown in Fig. 8 (a), the coarse pre­
cipitate possesses a relatively high Zr concentration in addition to being
enriched in Y and O, which is named coarse Zr-Y oxide inclusions
hereafter. In respect of the fine particles, based on corresponding EDS
maps in Fig. 8 (b), an enrichment of Y and Zr elements can be observed
in it, which are considered to be Y-Zr oxide particles in accordance with
the references [18,19]. In addition, some slightly larger Y-Zr oxide
particles marked with green arrows also can be observed in the Fig. 8
(b).
4. Discussion
4.1. ZrO2 elimination in alumina scale
The present results confirm that all the FeCrAl ODS ferritic alloys
with and without Zr addition are capable of forming a stable alumina
scale at 900 ◦ C. Ex. O additions with 0.2 wt% and 0.3 wt% make the Zr-
added alloys possess a comparable oxidation resistance with Zr-free
samples. It is noticeable that no ZrO2 precipitates were observed in
the alumina scale formed on Zr-added samples with 0.2 wt% and 0.3 wt
% Ex. O additions. The incorporation of ZrO2 in alumina is directly
determined by the Zr reservoir in alloys [20]. It was claimed that the Zr
activity in the alloy matrix decreased significantly through adding Ex. O
to promote the formation of stable Y-Zr compound oxide particles during
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Nuclear Materials and Energy 25 (2020) 100798
the consolidation of FeCrAl ODS alloys [10]. Thus, during the oxidation
process at 900 ◦ C, it is reasonable to suppose that the reservoir of Zr in
the alloy is quite limited since the Zr was considerably consumed by the
pre-formed fine Y-Zr compound oxide particles, as demonstrated by
previous TEM works [9].
4.2. Oxidation kinetics
In terms of oxidation rates, both Ex. O added samples are slightly
faster than that of the 0Zr alloys in the initial stage (− 81 h), which may
be caused by a smaller average grain size in the substrate of Zr-added
samples, as shown in Fig. 6, because a fast cation and anion ions diffu­
sion via grain boundary could be expected in the small substrate grain.
Dense distribution of fine Y-Zr oxide particles in the Zr-added FeCrAl
ODS alloys is responsible for the smaller average grain size, which
provides a strong pinning effect to inhibit the substrate grain growth
[21,22]. Besides, the grain size in the substrates of all FeCrAl ODS alloys
(Fig. 6) is inhomogeneous, which derived from the heterogeneous dis­
tribution of oxide particles, i.e., dense oxide particles were dispersed in
finer grains, while sparse oxide particles were dispersed in larger grains
[23]. The distribution of oxide particles is closely related to the growth
of oxide scales. Stringer et al. [24] claimed that the dispersed Y2O3
particles in the matrix of the post-oxidized materials could act as het­
erogeneous nucleation sites for Cr2O3 grains on the materials surface
and allow a rapid formation of the Cr2O3 scale with a finer Cr2O3 grain
size. The dispersed oxide particles in the three FeCrAl ODS specimens
are also deemed to have the similar effect on the formation of alumina
scale. Alumina scales grow inward since its growth is governed by the
inward diffusion of oxygen [25]. The dense oxide particles in small
substrate grains would provide more nucleation sites for Al2O3 grains for
H. Yu et al.
Fig. 8. STEM elemental maps obtained from Zr0.2Ex. O samples oxidized at 900 ◦ C for 225 h.
the inward growth of alumina scales. As a result, alumina scales with
smaller grain sizes would form near the small substrate grains and then
exhibit faster growth rates due to an accelerated oxygen grain boundary
inward diffusion [26,27], which is corresponding to the heterogeneous
thickness of the formed alumina scales in the Fig. 7 (a).
However, with longer exposure time, the oxidation of Zr-added
samples increased significantly and was apparently faster than the 0Zr
samples in the later stage (81–225 h), as shown in Fig. 2. The accelerated
oxidation rates of Zr0.2Ex. O and Zr0.3Ex. O are attributed to the exis­
tence of the coarse Zr-Y oxide inclusions in the alumina scale. As shown
in the LAADF-STEM images in Fig. 7, a most thick alumina scale can be
observed in the same vertical line with the coarse Zr-Y oxide inclusions.
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Nuclear Materials and Energy 25 (2020) 100798
Even a rapid growth rate of alumina could be expected on the substrate
with a small grain size, it is obvious that the thickness grows drastically
once the coarse Zr-Y oxide inclusions appeared. The formation of coarse
Zr-Y oxide inclusions is related to the large Zr-enriched precipitates
originally existed in the ODS alloys, which were formed during the hot-
extrusion consolidation and were incorporated into the alumina scale
during the oxide scale growth. In order to demonstrate the presence of
the Zr-enriched precipitates in the matrix of hot-extruded alloys, EPMA
observation was conducted for the samples in prior to oxidation testing.
In contrast to the spot-like enrichment of Ti in the 0Zr specimen in Fig. 9
(a), a significant Zr/Zr-Y enrichment was able to be observed in the
matrix of Zr 0.2Ex. O specimen in Fig. 9 (b). The oxide particles
H. Yu et al.
Fig. 9. EPMA elemental maps obtained from 0Zr (a) and Zr0.2Ex. O (b) samples in prior to the oxidation testing.
dispersed in ODS alloys are formed by decomposition of Y2O3 during MA
process and its re-precipitation with the added solutes such as Zr/Ti
during subsequent consolidation [19]. A lower formation energy of Zr/
Zr-Y oxides than that of Ti/Ti-Y oxides is responsible for the occurrence
of the Zr-enriched precipitates in the Zr-added alloys during the
consolidation of hot-extrusion [10,28]. Currently, even the EPMA did
not carry out for the Zr0.3Ex. O sample, it is reasonable to assume that
the large Zr-enriched precipitates also appeared after hot-extrusion
process in the Zr0.3Ex. O sample. As demonstrated in the EPMA maps
of oxidized samples in Fig. 5 (b) and (c), obvious Zr-enriched pre­
cipitates with a considerably large size could be found in both the sub­
strates of 2.0 wt% and 3.0 wt% Ex. O samples. The large Zr-enriched
precipitates located near the surface at the as-extruded condition
would be embedded in the external alumina scale and then promote the
growth of the oxide in both the Zr0.2Ex. O and Zr0.3Ex. O samples.
A detailed stoichiometric ratio of the coarse Zr-Y oxide inclusions has
not yet determined, but it is not difficult to estimate the oxygen diffusion
coefficient in the coarse Zr-Y oxide inclusions at 900 ◦ C in air is near 7.0
× 10− 13 m2 s− 1 in terms of the studies about the oxygen diffusion co­
efficient of yttria stabilized zirconia (YSZ) [29]. It is known that the
oxygen diffusion coefficient in Al2O3 can be calculated to be 5.5 × 10− 31
m2 s− 1 at 900 ◦ C [30], which is much smaller than that in the Zr-Y in­
clusions. Thus, the coarse Zr-Y oxide inclusions are able to provide short-
circuit paths for oxygen inward diffusion and then increase the oxidation
8
Nuclear Materials and Energy 25 (2020) 100798
rate once it was incorporated in alumina scale. Besides, STEM image of
Fig. 7 (b) proved that pores were formed near the large Zr-Y inclusions.
Undoubtedly, the porosity could also act as significant short-circuit
paths for oxygen transport in the form of molecular gas diffusion. D.
Naumenko et al. [20] also observed a porosity which prefers to form
near zirconia inclusions in alumina scales of Zr-added FeCrAlY alloys,
and proposed it is attributed to the phase transformations of the zirconia
incorporation caused. In this study, even zirconia precipitates are not
found in alumina scale, it is supposed that the coarse Zr-Y oxide in­
clusions can also act as a similar effect for the formation of the porosity,
since both of them possess a rapid oxygen diffusion coefficient. Besides,
unlike the alumina with a large columnar grain structure in other areas,
the alumina beneath the coarse Zr-Y oxide inclusions shows a smaller
alumina grain size. As mentioned above, the smaller alumina grains are
due to the fact that the coarse Zr-Y oxides inclusions provide more
nucleation sites for the formation of new alumina grains. Therefore, the
coarse Zr-Y oxide inclusions, including associated porosity and the
smaller alumina grain size, are responsible to the increase of oxidation
rate in the Zr0.2Ex. O sample. The detrimental effect begins with the
incorporation of the coarse Zr-Y oxide inclusions inside alumina scale
during long exposure period, which is corresponding to the increased kp
values in later stage (81–225 h) in the Table 2.
H. Yu et al.
4.3. Nano-oxide particles distribution in alumina scale
The oxygen partial pressure in the coarse Zr-Y oxide inclusions /
pores regions would be increased [20,31], which contributes the dis­
tribution of Y-Zr oxide particles in alumina scale, especially for the
formation of the unique tadpole-like Y-Zr-O particles. It is known that
the alumina has a very limited solubility for most cations, such as Y
solubility in the alumina is less than 10 ppm even near to the melting
point of alumina. Thus, RE elements would be forced to disperse mainly
at alumina grain boundaries or become precipitates [32–35]. In the case
of Zr-added FeCrAl ODS alloys, fine Y-Zr oxide particles are dispersed
inside matrix prior to oxidation, which would be incorporated along
grain boundaries as well as in the interior of alumina grains as the grains
continue to grow [33]. The Y-Zr oxide particle/alumina interface in the
alumina grains is also expected to act as a preferential site for the
segregation of RE elements, similar to the role of grain boundaries. Thus,
a coarsening and/or coalescence of those Y-Zr oxide particles inside
alumina scale must happened, which is quite consistent with the slightly
larger size of the Y-Zr oxide particles in the STEM image of Fig. 8 (b). In
the case of Zr-Y inclusions incorporated, a tadpole-like shape of the Y-Zr
oxide particles would be formed. B. A. Pint [16] proposed that RE ions
tend to diffuse from the metal substrate to the gas interface of the scale,
in which the driving force for this outward diffusion is the oxygen po­
tential gradient across the scale. Therefore, the locally increased oxygen
partial pressure in the large Zr-Y inclusions and associated pores should
induce the onset of a similar dynamic-segregation. Even segregation of
Y/Zr elements on the Y-Zr particle/alumina interface also happened in
this case, it would be endowed with a certain direction towards to the
high oxygen potential, namely, towards the location of the coarse Zr-Y
oxide inclusions and associated pores. Besides, tails of the tadpole-like
Y-Zr particles seem longer near the substrate, which is attributed to
relatively abundant Zr/Y reservoirs near substrate. Some Y-Zr oxide
particles seem to be aligned inside alumina-scale, as shown in the STEM
image in Fig. 7 (b), which may be attributed to the same level of oxygen
partial pressure, since they maintain almost the same distance from the
coarse Zr-Y oxide inclusions and associated pores. The above two models
for the Y-Zr particles distribution in the alumina incorporated without
and with the large Zr-Y inclusions are shown in Fig. 10 (a) and (b).
Fig. 11 illustrates schematically the overall progress of alumina scale
formation in the Zr-0.2 Ex. O specimens oxidized at 900 ◦ C, in which the
relationship between the large Zr-Y inclusions and the distribution of Y-
Zr oxide particles inside alumina scale is exhibited.
Fig. 10. Proposed models for the Y-Zr oxide particles distribution in the alumina scale incorporated without (a) and with (b) the coarse Zr-Y oxide inclusions during
oxidation at 900 ◦ C in air.
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Nuclear Materials and Energy 25 (2020) 100798
5. Conclusions
In order to develop nano-oxide particles dispersed alumina scale for
Zr-added FeCrAl ODS ferritic alloys, oxidation behavior of FeCrAl ODS
ferritic alloys with zirconium and excessive oxygen additions at 900 ◦ C
in air has been investigated. Corresponding results could be summarized
as follows:
1. With the additions of 0.2 wt% and 0.3 wt% Ex. O, ZrO2 precipitates
inside the alumina scales of the Zr-added FeCrAl ODS ferritic alloys
were eliminated at 900 ◦ C, which is supposed to be resulted from a
consumed reservoir of Zr by the pre-formed Zr-Y compound oxide
particles in alloys via adding Ex. O. However, some of the pre-formed
Zr-Y precipitates with large size may deteriorate the stability of
alumina scale for long-term exposure at elevated temperatures.
2. Oxidation rate of Zr-added samples would be accelerated at long
exposure with incorporation of coarse Zr-Y oxide inclusions into
alumina scale, resulting from the short-circuit diffusion paths for
oxygen provided by themselves and associated porosity. Originally
formed Zr-enriched precipitates with relatively large size in alloys
during fabrication process are responsible to the formation of the
coarse Zr-Y oxide inclusions. In order to avoid the formation of large
Zr-Y precipitates, which would deteriorate the oxidation resistance
at 900 ◦ C, a relatively small amounts of Zr should be added to the
alloy.
3. Dense Y-Zr oxide particles dispersion inside alumina scale was ob­
tained in the oxidation of 0.2 wt% Ex. O added FeCrAl alloys at
900 ◦ C. In addition to a spherical shape of the Y-Zr-O particles, a kind
of unique tadpole-like shape was found in the alumina scale, which is
related to an accelerated dynamic-segregation of RE elements driven
by the oxygen potential gradient across the coarse Zr-Y oxide in­
clusions and associated pores in alumina scale.
CRediT authorship contribution statement
Hao Yu: Investigation, Writing - original draft. Sosuke Kondo:
Writing - review & editing. Ryuta Kasada: Writing - review & editing.
Naoko Oono: Writing - review & editing. Shigenari Hayashi: Writing -
review & editing. Shigehara Ukai: Conceptualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
H. Yu et al.
Fig. 11. Schematic illustration for the alumina formation of Zr0.2Ex. O and Zr0.3Ex. O samples during oxidation at 900 ◦ C in air.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work is supported by Grant-in-Aid for Research Activity start-up
(19K21029) and Cooperative Research and Development Center for
Advanced Materials, IMR (19G0413).
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