Journal of Nuclear Materials 452 (2014) 235–240

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Journal of Nuclear Materials

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

Effects of thermal aging on microstructure and hardness of stainless

steel weld-overlay claddings of nuclear reactor pressure vessels
T. Takeuchi a,⇑, Y. Kakubo b, Y. Matsukawa b, Y. Nozawa b, T. Toyama b, Y. Nagai b, Y. Nishiyama c,
J. Katsuyama c, Y. Yamaguchi c, K. Onizawa c, M. Suzuki a
a
Japan Atomic Energy Agency, Oarai, Ibaraki 311-1393, Japan
b
The Oarai Center, Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313, Japan
c
Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The effects of thermal aging of stainless steel weld-overlay claddings of nuclear reactor pressure vessels
Received 11 June 2013 on the microstructure and hardness of the claddings were investigated using atom probe tomography
Accepted 4 April 2014 and nanoindentation testing. The claddings were aged at 400 °C for periods of 100–10,000 h. The fluctu-
Available online 17 May 2014
ation in Cr concentration in the d-ferrite phase, which was caused by spinodal decomposition, progressed
rapidly after aging for 100 h, and gradually for aging durations greater than 1000 h. On the other hand,
NiSiMn clusters, initially formed after aging for less than 1000 h, had the highest number density after
aging for 2000 h, and coarsened after aging for 10,000 h. The hardness of the d-ferrite phase also
increased rapidly for short period of aging, and saturated after aging for longer than 1000 h. This trend
was similar to the observed Cr fluctuation concentration, but different from the trend seen in the forma-
tion of the NiSiMn clusters. These results strongly suggest that the primary factor responsible for the
hardening of the d-ferrite phase owing to thermal aging is Cr spinodal decomposition.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction In duplex stainless steels, fluctuations in the Cr concentration

Weld overlay claddings made of stainless steel are used on the
inner surfaces of commercial water-cooled reactor pressure vessels
(RPVs) as protective barriers against corrosion. These claddings are
subjected to both neutron irradiation and prolonged thermal aging
at a service temperature of about 300 °C. The thermal and irradia-
tion environments may cause microstructural changes in the
claddings, resulting in the degradation of their mechanical proper-
ties and corrosion behavior. Thus, a detailed analysis of the
microstructural evolution of these claddings is necessary for
ensuring the integrity of RPVs.
The claddings are of the duplex type, consisting of two phases. It
is composed of approximately 90% austenite and 10% d-ferrite hav-
ing net-like structures [1]. The presence of the d-ferrite and austen-
itic phases is responsible for the claddings exhibiting enhanced
corrosion resistance [2]. However, it is known that the d-ferrite
phase undergoes significant hardening during thermal aging,
resulting in an increase in its ductile-brittle transition temperature
(DBTT), and a decrease in its upper shelf energy [3–5].
⇑ Corresponding author. Tel.: +81 29 266 7032; fax: +81 29 266 7071.
E-mail address: takeuchi.tomoaki@jaea.go.jp (T. Takeuchi).
owing to spinodal decomposition and the formation of a G phase
are considered to play a key role in the hardening of the d-ferrite
phase [6,7]. We had previously investigated the microstructural
changes in claddings aged at 400 °C for 10,000 h via three-dimen-
sional atom probe tomography (APT) [8,9]. In the as-received
materials subjected to post-welding heat treatment (PWHT) with
subsequent furnace cooling, a slight fluctuation of the Cr concen-
tration was observed due to spinodal decomposition in the d-fer-
rite phase, but not in the austenitic phase. The thermal aging
caused not only an increase in the degree of spinodal decomposi-
tion, but also the precipitation of G phases in the d-ferrite phase
with the composition ratio Ni/Si/Mn being 16:7:6.
Danoix et al. [10] have found that, in the case of cast duplex
stainless steels, the hardening at the d-ferrite phase in fully
annealed samples is associated with spinodal decomposition but
not with G-phase precipitation. On the other hand, Yamada et al.
[11] found that the G phase significantly contributed to the hard-
ening in similar annealing recovery tests. Hence, the effect that
the G phase has on hardening is still not clear.
In the case of the claddings, the effects of the duration of aging
on the microstructure and the relationship between the micro-
structure and the hardness of the claddings have not yet been
determined because an accurate estimation of the hardness of

http://dx.doi.org/10.1016/j.jnucmat.2014.04.003
0022-3115/Ó 2014 Elsevier B.V. All rights reserved.
236 T. Takeuchi et al. / Journal of Nuclear Materials 452 (2014) 235–240
Table 1
Chemical composition of the claddings.
C Si Mn P S Ni
wt.% 0.022 0.530 1.34 0.010 0.005 11.79
at.% 0.102 1.054 1.36 0.018 0.009 11.22
the d-ferrite phase has not yet been achieved, since the d-ferrite
phase is typically less than 5 lm in width.
The objective of this study was to investigate the effect of ther-
mal aging on the microstructure and hardness of claddings sub-
jected to thermal aging at 400 °C for periods of 100–10,000 h,
using APT and nanoindentation testing, to determine the mecha-
nism responsible for the hardening of the claddings.
2. Experimental
The claddings used were fabricated using the electroslag weld
overlay method. The chemical composition of the claddings is
listed in Table 1. The as-welded sample was subjected to a PWHT
at 615 °C for 7 h and subsequent furnace cooling (this sample is
referred to as the as-received sample). This sample consisted of
approximately 8% d-ferrite having net-like structures in an austen-
ite matrix. The width of the d-ferrite phase was a few micrometers.
Cladding samples were then thermally aged at 400 °C for 100,
1000, 2000, and 10,000 h, respectively. The samples for the APT
were first lifted via the lift-out method using a dual-beam focused
ion beam/scanning electron microscopy (FIB/SEM) ion milling
system [12]. They were then sharpened and either the austenite
phase or the d-ferrite phase was selected at the tips of the nee-
dle-like specimens. In order to analyze gallium-free specimens,
the damage caused by gallium implantation during fabrication
via FIB was minimized by using low-energy ions in the final pro-
cess. Only the gallium-free regions were used for the analyses.
An ultraviolet laser-pulse APT system (Cameca Instruments
LEAP 4000X-HR) equipped with an energy-compensating reflec-
tion lens [13–15] was used to analyze the microstructures. The
measurements were performed at a laser pulse energy of 60 pJ
Fig. 1. (a) SEM images of indentations made with loads of 1 mN, 2 mN, 3 mN, 5 mN, and 7 mN, and (b) the nanoindentation hardness at the d-ferrite phase of the trial cladding
material with indentation load.
and a repetition rate of 200 kHz at approximately 60 K. A high
direct current bias in the range of 3–10 kV was typically used.
Cr Approximately a few tens of millions of atoms were typically col-
22.34 lected during each measurement.
23.99 The surfaces of the samples for the nanoindentation tests were
treated using the following procedure. The samples were mounted
on an epoxy resin base, and were then mechanically polished with
sandpaper, followed by electrochemical polish at 8 °C in an ethanol
solution containing 5% perchloric acid. Finally, they were chemi-
cally polished using nitro-hydrochloric acid (aqua regia).
The nanoindentation tests to determine the hardness were per-
formed using a nanoindenter (ENT-1100a, Elionix Inc.). Since the
width of the net-like d-ferrite phase was only a few micrometers
as mentioned above, the size of the indentations needed to be less
than a few hundreds of nanometers so that they were not influ-
enced by the surrounding austenite phase. However, if the inden-
tations were too shallow, they would be affected by the surfaces
of the samples. Thus, in order to determine the optimal indentation
load, we used loads of 1, 2, 3, 5, and 7 mN and observed the indents
formed using SEM. The nanoindentation hardness of the cladding
material with indentation load and the SEM images of the indenta-
tions are shown in Fig. 1(a) and (b), respectively. The indentation
depth with 1 mN, where the SEM image of the indentation is no
longer clear, was estimated less than 100 nm where surface effects
could exist. On the other hand, the measurement values with more
than 3 mN, which partly include the hardness of austenite, scatter
and the distributions tend to shift toward lower range with the
load. On the basis of these results, an indentation load of 2 mN
was used in this study.
3. Results
3.1. APT observation
Three-dimensional maps showing the elemental concentrations
of Fe, Cr, Ni, Mn, and Si in the d-ferrite phases of the as-received
samples as well as those thermally aged at 400 °C for 100–
10,000 h are shown in Fig. 2. These elemental maps were con-
structed using 20-nm-thick slices to clearly illustrate in detail
 T. Takeuchi et al. / Journal of Nuclear Materials 452 (2014) 235–240 237

Fig. 2. Three-dimensional maps showing the elemental concentrations of Fe, Cr, Ni, Mn, and Si in the d-ferrite phase of the (a) as-received sample and those thermally aged at
400 °C for (b) 100 h, (c) 1000 h, (d) 2000 h, and (e) 10,000 h.

80 80 80 80 80
Cr Concentration [at.%]

(a) (b) (c) (d) (e)

60 60 60 60 60

40 40 40 40 40

20 20 20 20 20

0 0 0 0 0
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
Distance [nm] Distance [nm] Distance [nm] Distance [nm] Distance [nm]

Fig. 3. One-dimensional Cr concentration profiles in the d-ferrite phase of the (a) as-received sample and those thermally aged at 400 °C for (b)100 h, (c) 1000 h, (d) 2000 h,
and (e) 10,000 h. The concentrations were estimated in every 0.5 nm in sampling thickness and 3  3 nm2 in cross section.

the fluctuations in the chemical compositions of the tested sam-
ples. It was found that the concentration of Cr fluctuated rapidly
after thermal aging for 100 h but changed gradually when the
aging duration was longer than 1000 h. On the other hand, the for-
mation of NiSiMn clusters incubated for the aging shorter than
1000 h, increased in number density at 2000 and 10,000 h.
Fig. 3 shows the Cr concentration profile in a cuboid which has
the cross section area of 3  3 nm2. The concentrations were esti-
mated in every 0.5 nm step. In this case, the uncertainties on the
calculated compositions were 10% at most for 2 sigma. The mean
peak-to-peak amplitude of the concentration fluctuation seemed
to increase with increasing aging duration. Fig. 4 shows the
238 T. Takeuchi et al. / Journal of Nuclear Materials 452 (2014) 235–240

0.1 0.1 0.1 0.1 0.1

(a) (b) (c) (d) (e)
Fraction

0 0 0 0 0

-0.1 -0.1 -0.1 -0.1 -0.1

0 20 40 60 80 0 20 40 60 80 0 20 40 60 80 0 20 40 60 80 0 20 40 60 80

Number of Cr atoms Number of Cr atoms Number of Cr atoms Number of Cr atoms Number of Cr atoms
in 100 atoms in 100 atoms in 100 atoms in 100 atoms in 100 atoms

Fig. 4. The corresponding frequency distributions of Cr atom numbers per 100 atoms in the d-ferrite phase of the (a) as-received sample and those thermally aged at 400 °C
for (b)100 h, (c) 1000 h, (d) 2000 h, and (e) 10,000 h.

have been similar to the random one. However, as can be seen from
1.5
the images, none of the distributions was similar to a binominal
distribution in shape, as shown by the broken curve. The degrees
of the Cr concentration fluctuations were quantified using a scalar
parameter (V) defined as follows:
V

1 X
100
V¼ jOðiÞ  BðiÞj; ð1Þ
i¼0
as-received
where i is the number of atoms of the element per 100 atoms, and
O(i) and B(i) are the observed and binominal distributions of the
0.5
0 5000 10000 mean concentration of the element, respectively [16,17]. The value
Aging time [h]
of the parameter V in the case of the as-received sample increased
rapidly after the sample had been thermally aged for 100 h and then
Fig. 5. Relationship between aging time and values of the parameter V. the rate of increase in V is significantly less after 1000 h, as shown in
Fig. 5. On the other hand, the characteristic wave length of the con-
corresponding frequency distributions of the Cr atoms per 100 centration modulation was not obtained even by auto-correlation
atoms of the tested samples. In the case of a random spatial distri- function although the distance between the peaks of the concentra-
bution of Cr atoms, the experimental distribution curve should tion seemed to broaden with aging duration.

5 2.5
(a) (b)
Radius of clusters [nm]

4 2
clusters [×1023 m-3]
Number density of

3 1.5

2 1

1 0.5

0 0
0 5000 10000 0 5000 10000
Aging time [h] Aging time [h]

0.003 50
(c) (d) Ni
Concentration of Ni, Si, and
Volume fraction of clusters

Si
Mnin the clusters [at.%]

40
Mn
0.002
30

20
0.001

10

0 0
0 5000 10000 0 5000 10000
Aging time [h] Aging time [h]

Fig. 6. Change in the (a) number density, (b) radius of gyration, (c) volume fraction, and (d) composition of the clusters with the aging time.
 T. Takeuchi et al. / Journal of Nuclear Materials 452 (2014) 235–240 239

8.0 10.0
(a) (b)
8.0

7.0

H IT [GPa]
6.0

4.0
6.0

2.0

5.0 0
0 5000 10000 0 5000 10000

Aging time [h] Aging time [h]

Fig. 7. Relationship between the HIT of the (a) ferrite and (b) austenite (b) phases with the aging time.

vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uX
10
u n
u ðxi  xc Þ2 þ ðyi  yc Þ2 þ ðzi  zc Þ2
t
i¼1
9 lg ¼ ; ð2Þ
n
8 where xi, yi, and zi are the spatial coordinates of each atom; n rep-
HIT [GPa]

resents the number of atoms in the cluster; and xc, yc, and zc are
7 the coordinates for the center of mass of the atom in question. To
estimate the composition of the clusters, we used an algorithm that
6 took into consideration all the atoms within a distance, L, of
0.38 nm from the selected solute atom (these were assumed to be
5 the clustered atoms) and disregarded all the atoms within a dis-
tance, e, of 0.30 nm from the unselected matrix atoms [19,20].
4 Fig. 6 shows (a) the number density (Nd), (b) radius of gyration,
0.5 1 1.5 2
(c) volume fraction and (d) composition of the clusters as functions
V
of the aging time. The value of Nd remained low for aging durations
Fig. 8. Relationship between the values of HIT and those of the parameter V for the shorter than 1000 h but rapidly increased at the 2000 h aging, and
d-ferrite phase. then decreases at the 10,000 h aging. The radius of gyration almost
unchanged with the aging time. The volume fraction rapidly
increased by the 2000 h aging, and then decreases at the 10,000 h
aging. On the other hand, except for the as-received condition, the
Danoix et al. concentrations of Ni, Si, and Mn in the clusters increased rapidly
Pareige et al.
1000 after aging for less than 1000 h and then seemed to increase grad-
Present work
ually for longer aging periods.

3.2. Nanoindentation test

Hv

500
Fig. 7 shows the effect of the aging time on the nanohardness of
the d-ferrite and the austenite phases. In the case of the d-ferrite
phase, the nanohardness increased rapidly after aging for 100 h
and then almost plateaued at approximately 7 GPa after aging for
0 1000 h. This trend was similar to that noticed in the values of the
0 0.5 1.0 1.5
parameter V, which are shown in Fig. 4. On the other hand, in
V the case of the austenite phase, the hardness remained almost con-
stant, at 2.6 GPa, irrespective of the aging time.
Fig. 9. Relationship between the values of HV and those of the parameter V for the
d-ferrite phase.
4. Discussion

Fig. 8 shows the correlation between the values of the parame-

In the austenite phase, we found no microstructural changes, ter V and the nanohardness of the d-ferrite phase. The relationship
although the elemental maps for the austenite phases are not between them was quite linear. In order to compare the present
shown in this paper. results of nanoindentation hardness (HIT) to the previous results
The NiSiMn clusters were identified using the maximum sepa- of Vickers micro hardness (HV) testing [10,21], the values of the
ration algorithm, which is based on a friend-of-friends concept HIT obtained in this study were converted to equivalent HV using
[18]. The parameters used to characterize the morphology of the the following relationship that exists between them [22]:
NiSiMn clusters were the following: the maximum separation dis-
tance, dmax, which was 0.38 nm, and the minimum number of HV ¼ 0:0924  HIT : ð3Þ
atoms, Nmin, which were 30. The size of each precipitate, i.e., the Fig. 9 shows the relationship between the ‘‘converted’’HV values
radius of gyration (lg), was estimated from the position of the sol- and those of the parameter V for the d-ferrite phase. Previously
ute atoms in the precipitate using the following equation: reported values of HV[10,21] as functions of the parameter V are
240 T. Takeuchi et al. / Journal of Nuclear Materials 452 (2014) 235–240
also shown. The relationship between the ‘‘converted’’HV values
and those of the parameter V was also found to be linear, as was
the case with the previous results. Although the number density
of the NiSiMn clusters was high in the samples aged for 2000 h
and 10,000 h, even in the case of these samples, the relationship
between the two parameters did not deviate significantly from a
linear one. These results suggested that the primary cause of the
hardening of the d-ferrite phase were the fluctuations in the Cr
concentrations of the aged samples owing to spinodal decomposi-
tion, which are similar to what is reported in Refs. [10,21]. This
does not mean that the NiSiMn clusters did not contribute to the
hardening; only that spinodal decomposition contributed to a
greater degree to the hardening. To determine precisely the extents
to which the two factors contribute to the hardening, further stud-
ies involving annealing recovery tests are necessary.
The average value of the ratio of the concentrations of Ni, Si, and
Mn (Ni/Si/Mn) in the clusters was about 16:4:6 except for the as-
received condition, as shown in Fig. 6(c). In our previous studies
[8,9], we had observed precipitation in the d-ferrite phase of the
G phase in thermally aged claddings; the composition ratio Ni/Si/
Mn of the G phase was found to be 16:7:6. Hence, the NiSiMn clus-
ters observed in this study can be assumed to be precursors of the
G phase since the compositions of the two were only slightly dif-
ferent. As can be seen from Fig. 6(a) and (b), the NiSiMn clusters,
which started forming when the aging times were smaller than
1000 h, had the highest Nd in the case of aging for 2000 h. In addi-
tion, their radius of gyration almost unchanged with the aging
time.
5. Conclusion
The evolution of the microstructures of stainless steel claddings,
subjected to thermal aging at 400 °C for periods of 100–10,000 h,
and the correlation between the microstructures and the hardness
of the claddings were investigated using APT and nanoindentation
testing. The results of the microstructural observations showed
that the fluctuations in the Cr concentration increased rapidly after
aging for 100 h and gradually in the case of aging longer than
1000 h. The number density, Nd, of the NiSiMn clusters remained
low for aging durations shorter than 1000 h and increased rapidly
for aging periods up to 2000 h. Finally, it decreased again in the
case of aging for 10,000 h. On the other hand, the radius of gyration
(lg) almost unchanged with increasing aging time. The NiSiMn clus-
ters were assumed to be precursors of the G phase because of the
similarity in the compositions of the two. The results of the hard-
ness tests showed that the relationship between the values of HV
and those of the parameter V (Cr concentration relative to a bino-
mial distribution) in the case of the d-ferrite phase was linear,
regardless of the number density of the NiSiMn clusters. This fact
suggested that the primary factor responsible for the hardening
of the d-ferrite phase in the claddings was the fluctuations in the
Cr concentration owing to spinodal decomposition in good agree-
ment with previous work in Refs. [10,21].
Acknowledgements
This study was carried out under the Cooperative Research
Program of the International Research Center for Nuclear Materials
Science, the Institute for Materials Research (IMR), Tohoku Univer-
sity. Some of the results discussed here are those from the ‘‘Study
of degradation mechanism of stainless steel weld-overlay cladding
of nuclear reactor pressure vessels,’’ sponsored by the Strategic
Promotion Program for Basic Nuclear Research of the Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan.
This study was partially supported by a Grant-in-Aid for Scientific
Research (A) (21246142) from MEXT and by the Budget for Nuclear
Research of MEXT, after screening and counseling by the Atomic
Energy Commission, Japan. The authors would like to thank
T. Kojima, H. Terashima, and M. Ono of JFE Techno-Research
Corporation for their fabrication of the claddings.
References
[1] J.A. Brooks, A.W. Thompson, Inter. Mater. Rev. 36 (1) (1991) 16.
[2] I. Alvarez-Armas, S. Degallaix-Moreuil, Duplex Stainless Steels, Wiley-ISTE,
New York, 2009.
[3] F.M. Haggag, S.K. Iskander, Nucl. Eng. Des. 118 (1990) 297.
[4] F.M. Haggag, W.R. Corwin, R.K. Nanstad, Nucl. Eng. Des. 124 (1990) 129.
[5] F.M. Haggag, R.K. Nanstad, NUREG/CR-6363 ORNL/TM-13047, 1997.
[6] N.M. Chung, O.K. Chopra, in: International Symposium on Environmental
Degradation of Materials in Nuclear Power Systems, Traverse City, MI, USA, 30
August, 1987.
[7] T. Hamaoka, A. Nomoto, K. Nishoda, K. Dohi, N. Soneda, Phil. Mag. 92 (2012)
4354.
[8] T. Takeuchi, J. Kameda, Y. Nagai, T. Toyama, Y. Nishiyama, K. Onizawa, J. Nucl.
Mat. 415 (2011) 198.
[9] T. Takeuchi, J. Kameda, Y. Nagai, T. Toyama, Y. Matsukawa, Y. Nishiyama, K.
Onizawa, J. Nucl. Mat. 425 (2012) 60.
[10] F. Danoix, P. Auger, D. Blavette, Microsc. Microanal. 10 (2004) 349.
[11] T. Yamada, S. Okano, H. Kuwano, J. Nucl. Mater. 350 (2006) 47.
[12] D.J. Larson, D.T. Foord, A.K. Petford-Long, H. Liew, M.G. Blamire, A. Cerezo,
G.D.W. Smith, Ultramicroscopy 79 (1999) 287.
[13] M.K. Miller, Atom Probe Tomography, Kulwar Academic/Plenum Publishing,
New York, NY, 2000.
[14] S.J. Sijbrandij, A. Cerezo, T.J. Godfrey, G.D.W. Smith, App. Surf. Sci. 94 (95)
(1996) 428.
[15] N.M. Chung, O.K. Chopra, International symposium on environmental
degradation of materials in nuclear power systems, Traverse City, MI, USA,
30 Aug 1987.
[16] D. Blavette, G. Grancher, A. Bostel, J. Phys. 49 (C6) (1988) 433.
[17] P. Auger, A. Menand, D. Blavette, J. Phys. 49 (C6) (1988) 439.
[18] J.M. Hyde, C.A. English, Mater. Res. Soc. Symp. 650 (2001) R661.
[19] D. Vaumousse, A. Cerezo, P.J. Warren, Ultramicroscopy 95 (2003) 215.
[20] A. Morley, G. Sha, S. Hirosawa, A. Cerezo, G.D.W. Smith, Ultramicroscopy 109
(2009) 535.
[21] C. Pareige, S. Novy, S. Saillet, P. Pareige, J. Nucl. Mat. 411 (2011) 90.
[22] ISO 14577:2002 Metallic materials – Instrumented indentation test for
hardness and materials parameters.