M A TE RI A L S CH A RACT ER IZ A TI O N 59 ( 20 0 8 ) 5 8 7 –5 9 1

The spinodal decomposition in 17-4PH stainless steel

subjected to long-term aging at 350 °C

Jun Wang a,b,⁎, Hong Zou b , Cong Li b , Shaoyu Qiu b , Baoluo Shen a
a
School of Manufacturing Science and Engineering, Sichuan University, Chengdu, 610065, PR China
b
National Key Laboratory for Nuclear Fuel and Materials, Nuclear Power Institute of China, P.O. Box 436, Chengdu, 610041, PR China

AR TIC LE D ATA ABSTR ACT

Article history: The influence of aging time on the microstructure evolution of 17-4 PH martensitic stainless
Received 20 April 2006 steel was studied by transmission electron microscopy (TEM). Results showed that the
Received in revised form martensite decomposed by a spinodal decomposition mechanism after the alloy was
23 April 2007 subjected to long-term aging at 350 °C. The fine scale spinodal decomposition of α-ferrite
Accepted 30 April 2007 brought about a Cr-enriched bright stripe and a Fe-enriched dark stripe, i.e., α' and α phases,
separately, which were perpendicular to the grain boundary. The spinodal decomposition
Keywords: started at the grain boundary. Then with prolonged aging time, the decomposition
17-4 PH stainless steel microstructure expanded from the grain boundary to interior. The wavelength of the
Spinodal decomposition spinodally decomposed microstructure changed little with extended aging time.
Isothermal aging © 2007 Elsevier Inc. All rights reserved.
350 °C

1. Introduction
The type 17-4 precipitation hardening (17-4 PH) stainless steel
is widely used as structural materials for chemical and power
plants, such as light water reactors (LWRs) and pressurized
water reactors (PWRs) [1–4] due to its high strength, high
fracture toughness, good weldability and ease of machinabil-
ity. As an age hardenable stainless steel, the high strength and
toughness can be obtained after solution-annealing (SA) and
tempering [2–4]. The coherent copper-rich particles in matrix
can be found in the over-aged condition (H1100, which means
the 17-4 PH stainless steel temper treated at 1100 °F after SA
treatment) and the particles can enhance the alloy strength
significantly [1–6].
According to the Fe–Cr binary phase diagram [8,9], the Cr
concentration in the 17-4 PH stainless steel is within the
spinodal line, in which the phase decomposition of the
martensite into a Cr-enriched BCC phase (α′) and a Fe-
enriched BCC phase (α), is expected on aging below 450 °C
[8–11]. Considerable work has been carried out and showed
that the stainless steel was embrittlement when the α′ phase
was precipitated by spinodal decomposition during long-term
aging at intermediate temperature [5,7–13]. However, earlier
investigations using transmission electron microscopy (TEM)
have failed to reveal the detailed fine spinodal decomposition
structure of stainless steels. Recently, with atom probe (AP)
and atom probe field ion microscopy (APFIM), Danoix and
other researchers have revealed the phase separation due to
the spinodal decomposition into an ultrafine mixture of a Cr-
rich α′ phase and a Fe-rich α phase [5,7–9]. And more recently,
M. Murayama has shown the direct evidence of spinodal
decomposition of 17-4 PH SS after 5000 h at 400 °C employing
the three-dimension atom probe (3DAP), but failed to resolve
the finer scale of the microstructure [11].
These materials used in power plants are required to
remain in service for very long periods of time; hence,
understanding the microstructural evolution at the service
temperature is very important. Typical service temperatures

⁎ Corresponding author. School of Manufacturing Science and Engineering, Sichuan University, Chengdu, 610065, PR China. Tel./fax: +86 28
8541 8244.
E-mail address: srwangjun@163.com (J. Wang).

1044-5803/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2007.04.018
588 MA TE RI A L S CH A R A CT ER IZ A TI O N 59 ( 20 0 8 ) 5 8 7–5 9 1

Table 1 – Composition of the type 17-4 PH stainless steel (weight %)

Elements C Si Mn P S Cr Ni Cu Nb Fe

Weight % 0.04 0.6 0.3 0.023 0.013 16.39 4.32 3.4 0.36 Bal.

in power plant applications are about 300 °C [7]. The spinodal
decomposition in stainless steel plays an important role in the
degradation of mechanical properties during long-term aged
at intermediate temperature [10,11].
The aim of the present work is try to investigate and
characterize the spinodally decomposed behavior in 17-4 PH
stainless steel aged more than 10,000 h at 350 °C, which is
slightly above the service temperature, in order to enhance the
microstructural evolution. The transmission electron micro-
scope was used to examine and elucidate the microstructural
development.
2. Experimental Procedure
Chemical composition of 17-4 PH stainless steel (SS) is given in
Table 1.
The initial material as delivered for manufacturing test
specimens was hot rolled to 20 mm thickness in an L-T
(longitudinal-transverse) orientation and subsequently cut
into specimens.
Heat treatment included two steps:
(1) Solution treatment for half an hour at 1040 °C and then
oil quench;
(2) Temper (precipitation) treatment for 4 h at 595 °C and
then air cool.
The tempering treated alloy specimen was held in oven
type furnace at 350 °C for more than 10,000 h and then
subjected to microstructural analyses. Specimens for TEM
observation were prepared by standard methods involving
mechanical grinding, polishing and dimpling followed by ion
milling of foils to perforation on a liquid nitrogen-cooled
specimen stage to eliminate further aging during the thin-
ning period. Microstructural studies were performed in a
Philips TECNAI 20 TEM operating at an accelerating voltage of
200 kV.

Fig. 1 – The morphology (a) of the 17-4 PH SS after quenching Fig. 2 – The morphology (a) of the spinodal decomposition
and tempering treatment at 595 °C × 4 h and SADP (b) from 17-4 PH SS after 4320 h aging at 350 °C and SADP (b) from [100]
[113¯] diffraction axis. diffraction axis.
 M A TE RI A L S CH A RACT ER IZ A TI O N 59 ( 20 0 8 ) 5 8 7 –5 9 1 589

3. Results and Discussion

The martensite transformation start (Ms) of this stainless steel

is around 105 °C [1]. Hence, the microstructures of martensite
could be obtained easily in 17-4 PH stainless steel after
solution treatment. The transmission electron micrograph at
a low magnification, as shown in Fig. 1, was obtained from the
precipitation-temper-treated specimen. The corresponding
microstructure is composed basically of lath martensite.
There are numerous dispersing fine precipitates in the
martensite lath after tempering-treatment. Associating the
selected area electron diffraction (SADP), those precipitates
identify as ε-copper with the K–S (Kurdjumov–Sachs) orienta-
tion relationship with martensite matrix, which is consistent
with others reports [10,11,14].The coherent ε-copper particles
have the dispersion hardening effect of the alloy.
Fig. 2 is the TEM photograph of the microstructure of the
alloy after aging 4200 h (about 6 months) at 350 °C. With the
corresponding EDX, the fine scale spinodally decomposed
microstructure was identified. Evidence of spinodal decom-
position of the martensite phase is seen in Fig. 2 in the form of
fine-scale decomposition of the α-ferrite to produce Cr-rich α′-
phase (bright image domains) and Fe-rich α-phase (dark image
domains), which is consistence with Weng's report [13]. The α

Fig. 4 – The morphology (a) of the spinodally decomposed

microstructure (white arrowed) and secondary carbide, M23C6
(black arrowed) of 17-4 PH SS after aging 11,000 h at 350 °C,
and SADP (b) from [01¯1] diffraction axis.

and α′ phases have different crystal structures. The morphol-

Fig. 3 – The morphology (a) of the spinodal decomposition in
17-4 PH SS after 11,000 h aging at 350 °C and SADP (b) from
[100] diffraction axis.
ogy of spinodal decomposition of ferrite is alternately parallel
stripe, generally along the grain boundary (GB). The electron
diffraction patterns of the two-phase modulated structure
taken from [100] crystal axis (Fig. 2b) shows only one set of BCC
diffraction spots and the image of the spinodal decomposition
microstructure is not clear, which maybe suggests that the
spinodal decomposition is just in the incipient stage. It is
apparent that the lattice mismatch between α′ and α phases
(αCr = 0.2885 nm, αFe = 0.2866 nm for the pure elements) is the
reason of the development the contrast, because the α′ phase
has a high level of Cr [13].
After aged at 350 °C for 11,000 h (about 15 months), the TEM
micrographs revealed a great deal of spinodally decomposed
microstructure (Fig. 3a). Fig. 3b shows the electron diffraction
pattern of the spinodally decomposed microstructure from
the [100] crystal axis. Comparing Figs. 2 and 3, it is clear that
the spinodal decomposition first takes place at the grain
boundary, and then the decomposition expands from grain
boundary to interior. This is because the atoms at the grain
boundaries have high mobility and the grain boundary has a
higher free energy. In the incipient stage of spinodal decom-
position, those atoms at the grain boundary will be inclined to
move to decrease the free energy. Atom migration leaves
590 MA TE RI A L S CH A R A CT ER IZ A TI O N 59 ( 20 0 8 ) 5 8 7–5 9 1
Table 2 – The spinodal decomposition wavelength of 17-4
PH stainless steel and CF8M duplex stainless steel under
various aging conditions (data of CF8M is from [5])
Aging condition 17-4 PH/nm CF8M/nm
Un-aged / /
10,000 h at 300 °C 3.4
4000 h at 350 °C 5.5 5.8
11,000 h at 350 °C 6 7.0
4000 h at 400 °C / 17
11,000 h at 400 °C / 15
behind a discontinuous (or cellular) microstructure consisting
of alternating lamellae of Fe-rich and Cr-rich regions. So the
decomposition starts by grain boundary enriching of Fe or Cr,
setting off a composition wave that produces alternating Fe
and Cr bands near the grain boundary [16].
Fig. 4 shows the decomposed microstructure in the 17-4 PH
stainless steel after aged at 350 °C for 11,000 h. This type of
discontinuous microscopic structure consisting of alternating
Fe-rich and Cr-rich stripe is consistent with Ramanarayan's
theory [16], but the alternating stripe microstructure has
different with the “basket-weave” or mottled appearance.
This has the appearance of an orange peel, and has been
reported in some aged duplex stainless steels [10,13]. This
maybe caused by the differences in the type of alloy and the
aging condition. The inherent anisotropy of the alloy is
another important explanation to the anisotropy of the
spinodal decomposition. So the spinodal decomposition will
be growing in the direction of lowest elastic modulo of the
alloy [13].
Table 2 is the change of the spinodal decomposition
wavelength (λ⁎) of the 17-4 PH stainless steel with extension
of aging time at 350 °C. It is obvious that with the prolonging
aging time from 4200 h to 11,000 h, the change of λ⁎ is small,
which is consistence with the reports of F. Danoix [5], S.B Ren
[15] and Ramanarayan [16]. From Table 2, a remarkable
conclusion can be made, the effect of aging temperature on
spinodal decomposition wavelength is more important than
the aging time.
Interestingly, under the various aging conditions, second-
ary carbides were observed near the spinodal decomposition
(black arrowed in Figs 3a and 4a). Based on SADP (Fig. 4b), the
secondary carbides are identified as M23C6. Habibi Bajguirani
[14] has observed similarly M23C6 in the intermediate tem-
perature aging condition of 15-5 PH stainless steel. So the
presumption that the precipitation of secondary carbide may
play a pole in the spinodal decomposition mechanism can be
proposed.
4. Conclusion
When the 17-4 PH stainless steel was subjected to long-term
aging at 350 °C, spinodal decomposition occurred. The spinodal
decomposition occurred firstly at the grain boundary. The fine
scale spinodal decomposition of martensite brings about Cr-
rich bright image lamellae and Fe-rich dark image lamellae, i.e.,
α′ and α phases, respectively. The alternated lamellae image of
the α′ and α phase are perpendicular to the grain boundary.
After aged at 350 °C for 4200 h, the spinodal decomposition is
just in the incipient stage. Then with prolonged aging time, the
decomposition microstructure expanded from grain boundary
to interior. The wavelength of the spinodal decomposition
microstructure changed little with extended aging time. The
effect of aging temperature on spinodal decomposition wave-
length is greater than the effect of aging time.
Acknowledgements
This work was carried out with the financial support from The
Key Nuclear Fuel and Nuclear Materials Laboratory of China, PR
China, under grant Contract No.51481080104ZS8501. The
authors would like to thank Prof. Zuo Rulin of Chongqi Uni-
versity, PR China, and Prof. Gao Shengji of Sichuan University,
PR China, for their generous help and invaluable discussion
during the course of the research.
REFERENCES
[1] Hsiao CN, Chiou CS, Yong JR. Aging reactions in a 17-4 PH
stainless steel. Mater Chem Phys 2002;74:132–42.
[2] Wang Jun, Zou Hong, Wu Xiaoyon, Li Cong, Qiu Shaoyu, Shen
Baoluo. The effect of long-term isothermal aging on dynamic
fracture toughness of type17-4 PH SS at 350 °C. Mater Trans
2005;46:846–51.
[3] Wang Jun, Zou Hong, Li Cong, Qiu Shao-Yu, Shen Bao-Luo.
The effect of microstructural evolution on hardening
behavior of type 17-4 PH stainless steel in long-term aging at
350 °C. Mater Charact 2006;57:274–80.
[4] Wu Jui-Hung, Lin Chih-Kuang. Tensile and fatigue properties
of 17-4 PH stainless steel at high temperatures. Metall Mater
Trans, A Phys Metall Mater Sci 2002;3:1715–24.
[5] Danoix F, Auger P. Atom probe studies of the Fe–Cr system
and stainless steels aged at intermediate temperature: a
review. Mater Charact 2000;44:177–201.
[6] Wu Jui-Hung, Lin Chih-Kuang. Effect of strain rate on
high-temperature low-cycle fatigue of 17-4 PH stainless
steels. Mater Sci Eng, A Struct Mater: Prop Microstruct Process
2005;390:291–8.
[7] Chung HM. Aging and life prediction of cast duplex stainless
steel components. Int J Press Vessels Piping 1992;50:179–213.
[8] Shiao JJ, Tsai CH, Kai JJ, Huang JH. Aging embrittlement and
lattice image analysis in a Fe–Cr–Ni duplex stainless steel
aged at 400 °C. J Nucl Mater 1994;217:269–78.
[9] Miller MK, Hyde JM, Hetherington MG, Cerezo A, Smith GDW,
Elliott CM. Spinodal decomposition in Fe–Cr alloys:
experimental study at the atomic level and comparison with
computer models — I. Introduction and methodology. Acta
Metall Mater 1995;43:3385–401.
[10] Shek CH, Shao YZ, Wong KW, Lai JKL. Spatial fractal
characteristic of spinodal decomposition in Fe–Cr–Ni duplex
stainless steel. Scr Mater 1997;37:529–33.
[11] Murayama M, Katayama Y, Hono K. Microstructural evolution
in a 17-4 PH stainless steel after aging at 400 °C. Metall Mater
Trans, A Phys Metall Mater Sci 1999;30:345–53.
[12] Seiichi Kawaguchi, Naruo Sakamoto, Genta Takano, Fukuhisa
Matsuda, Yasushi Kikuchi, L'Ubos Mraz. Microstructural
changes and fracture behavior of CF8M duplex stainless
steels after long-term aging. Nucl Eng Des 1997;174:273–85.
[13] Weng KL, Chen HR, Yang JR. The low-temperature aging
embrittlement in a 2205 duplex stainless steel. Mater Sci Eng,
A Struct Mater: Prop Microstruct Process 2004;379:119–32.
 M A TE RI A L S CH A RACT ER IZ A TI O N 59 ( 20 0 8 ) 5 8 7 –5 9 1 591

[14] Bajguirani HR Habibi. The effect of aging upon the
microstructure and mechanical properties of type 15-5 PH
stainless steel. Mater Sci Eng, A Struct Mater: Prop Microstruct
Process 2002;338:142–59.
[15] Ren SB, Tadaki T, Shimizu K, Wang XT. Electron diffraction
study of aging processes in Fe-1.83 wt pct C martensite at
room temperature. Metall Mater Trans, A Phys Metall Mater
Sci 1995;26:2001–5.
[16] Ramanarayan H, Abinandanan TA. Grain boundary effects on
spinodal decomposition II. Discontinuous microstructures.
Acta Mater 2004;52:921–30.