Materials Characterization 130 (2017) 156–172

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Microstructure and texture study on an advanced heat-resistant alloy during MARK

creep
Yu Zhanga,b, Hongyang Jinga,b, Lianyong Xua,b,⁎, Lei Zhaoa,b, Yongdian Hana,b, Jun Liangc
a
School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
b
Tianjin Key Laboratory of Advanced Joining Technology, Tianjin 300350, China
c
Center for Minimally Invasive Life Assessment of High Temperature Materials, Shenhua Guohua (Beijin) Electric Power Research Institute Company, Beijing 100025,
China

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

Keywords: In the present work, creep deformation and fracture behaviours of Sanicro 25 alloy were obtained based on long-
Creep fracture term creep-strain tests. The multiscale precipitation behaviours were calculated thermodynamically and in-
Precipitation spected by examination of the microstructure of the as-crept alloy. Creep cavitation nucleation near the M23C6
Creep cavitation precipitates and an increase in amount of Laves phase with increased creep time were observed. The nanoscale
Dislocation substructure
MX-type and Cu-rich phases were found distributed evenly within the as-crept alloy, which leads to the high
EBSD
creep resistance of Sanicro 25 at elevated temperatures. The dislocation substructure evolution was surveyed,
and dislocation cells were discovered in abundance of the alloy during creep. The grain orientation transfor-
mation of the alloy before and after creep were analysed, and 〈111〉//RD and 〈001〉//RD were detected as
the preferred orientations during creep. The number of low-misorientation angles grain boundaries increased in
as-crept alloy due to the presence of grain rotation and dislocation cells.

1. Introduction
By increasing operating temperatures to approximately 700–760 °C
and steam pressures to > 35 MPa, advanced ultra-supercritical (A-USC)
technology has been on the cutting edge of research in high-efficiency
power generation technology aimed at promoting thermal efficiency
and reducing carbon emission by 40–50% as compared to current
generation boilers [1–3]. The materials used in A-USC superheaters and
re-heaters, however, are primarily Ni-based alloys coupled with striking
costs, which appears to be expensive and thus may not meet the eco-
nomic requirements. Thus, heat-resistant steels have attracted the at-
tention of electric power industry because they are relatively less ex-
pensive [4–6]. The advanced austenitic material Sanicro 25 (UNS
S31035) is thought to be a potential candidate for super/re-heaters of
A-USC plants, with high creep strength, great resistance to corrosive
media and excellent weldability [7–9]. Sanicro 25 exhibits the highest
creep strength among the commercially available heat resistant steels
due to solid-solution strengthening by W and N and the precipitation-
hardening mechanism derived from nanoscale Nb(C, N) and a Cu-rich
phase. The uniform distribution of nano-sized dispersed particles sig-
nificantly increase creep strength of the alloy [10].
Past researches have reported the observation of precipitation
behaviours during creep in some other Cu-bearing alloys such as Super
304H [4,11,12], 23Cr25NiWCuCo [7], 15%Cr super martensitic stain-
less steel [13], 316L-Cu [14], and 316L-Cu [15]. However, it has been
rarely reported on the multiscale precipitation behaviours of Sanicro 25
as for long-term creep process, especially on structures of nano-sized
particles dispersed within the alloy. Meanwhile, the detailed dislocation
development and grain transformation of the alloy during creep have
not yet clearly understood. In this study, we investigated the pre-
cipitation behaviours and dislocation sub-structure development in
Sanicro 25 based on long-term creep tests. Furthermore, the variation of
grain size and misorientation angles of the alloy before and after creep
were systematically analysed via electron backscatter diffraction tech-
nology.
2. Material and Methods
2.1. Material and Experiment Procedures
The as-received Sanicro 25 alloy used in the present investigation
was cold pilgered and solution annealed (1417–1523 K) in a seamless
tube. The ASME and measured chemical compositions of Sanicro 25 are
shown in Table 1. It is clear that Ni, N, and Mn stabilise the austenite

⁎
Corresponding author at: 31-171, No.135 Yaguan Road, Haihe Education Park, Tianjin 300350, China.
E-mail addresses: tdhjzy@tju.edu.cn (Y. Zhang), hjing@tju.edu.cn (H. Jing), xulianyong@tju.edu.cn (L. Xu), zhaolei85@tju.edu.cn (L. Zhao), hanyongdian@tju.edu.cn (Y. Han),
liangjun2266@sina.com (J. Liang).

http://dx.doi.org/10.1016/j.matchar.2017.05.037
Received 4 April 2017; Received in revised form 14 May 2017; Accepted 30 May 2017
Available online 31 May 2017
1044-5803/ © 2017 Elsevier Inc. All rights reserved.
Y. Zhang et al. Materials Characterization 130 (2017) 156–172

Table 1
The ASME and measured chemical composition of Sanicro 25 alloy.

Wt% C Si Mn S P Cr Ni Nb N W Co Cu

ASME 0.04–0.1 < 0.4 < 0.6 < 0.015 < 0.025 21.5–23.5 23.5–26.5 0.40–0.60 0.20–0.30 3.0–4.0 1.0–2.0 2.5–3.5
Measured 0.069 0.17 0.54 0.006 0.032 23.7 25.7 0.56 0.23 3.10 1.57 3.06

Fig. 1. (a) Creep deformation curves of Sanicro 25 and creep rate curve at 973 K; (b) high-temperature tensile tests results; (c) Creep rupture time vs. the reciprocal of temperature
multiplied by 10,000 at 973 K, 998 K, and 1023 K.

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Y. Zhang et al.
Table 2
List of creep test condition and the corresponding ruptured time.
Creep Ruptured Creep Ruptured
temperature–creep time, tr temperature–creep time, tr
stress stress
1023 K–180 MPa 264.6 h 998 K–220 MPa 370.7 h
1023 K–200 MPa 149.4 h 998 K–240 MPa 201.2 h
1023 K–220 MPa 73.9 h 973 K–180 MPa 3553.2 h
1023 K–240 MPa 52.5 h 973 K–200 MPa 1831.1 h
998 K–180 MPa 1154.9 h 973 K–220 MPa 1142.7 h
998 K–200 MPa 609.6 h 973 K–240 MPa 570.1 h
structure of Sanicro 25 and that a moderate amount of Cr forms tough
oxide scales capable of resisting environmental corrosion. The addition
of Nb inhibits intergranular corrosion by a strong carbide-forming re-
action and produces complex niobides that precipitate at high tem-
peratures.
Standard round creep-strain specimens (gauge length: 50 mm) and
high-temperature tensile specimens (gauge length: 25 mm) were
wrought parallel to the rolling direction of the Sanicro 25 tube. The
creep and high-temperature tensile tests were conducted in a leveraged
creep machine (CRIMS RDL50) with a high-temperature furnace. For
creep-strain and high-temperature tensile experiment, the specimen
was attached to three K-type thermocouples for monitoring tempera-
ture. The double LVDT (linear variable displacement transducer) ex-
tensometers were used to measure the gage length displacement and
record the cumulative strain for each specimen. The resolutions of
furnace temperature and LVDT extensometers were 0.1 K and
0.001 mm, respectively. High-temperature tensile tests were conducted
at 973, 998, and 1023 K at a crosshead speed of 0.1 mm/min. Creep
tests were conducted at temperatures of 973, 998, and 1023 K with the
stress levels of 180, 200, 220, and 240 MPa in an atmospheric en-
vironment.
2.2. Material Characterisation and Thermodynamic Simulation
The microstructures of the multiscale secondary phases in Sanicro
25 before and after creep were observed by scanning electron micro-
scopy (SEM, ZEISS EVO 18 and FEI Nova Nanosem 430) with energy
dispersive spectroscopy (EDS). Furthermore, finer precipitates were
clarified by transmission electron microscopy (TEM, Tecnai G2 F30)
with energy dispersive X-ray detector (EDX). High-resolution trans-
mission electron microscopy (HRTEM) and selected area electron dif-
fraction (SAED) patterns analysis were used to ascertain the lattice
structure of each phase. Grain size and orientation information were
measured by electron backscatter diffraction (EBSD). The Channel 5
software was used to analyse the EBSD results and display final data.
The samples for SEM observation were embedded and ground under
flowing water using 280, 400, 600, 800, 1000, 1500, and 2000 grit
successively. The samples were then polished, followed by etching in a
solution of HCL acid (20 mL), ethanol (20 mL), and CuSo4 (5 g). The
EBSD samples were ground and electrolytic polished in an alcohol so-
lution of 4% perchloric acid. TEM samples were prepared as thin foil
with a thickness of ~50 mm by mechanical polishing with silicon
carbide paper, followed by electrolytic double-jet thinning in a 20%
perchloric acid and ethanol solution. JmatPro® software can simulate a
wide range of material properties, including stable/metastable phase
equilibria and solidification behaviour. In this study, by importing the
measured chemical composition of Sanicro 25 into JmatPro software
(version 7.0), we calculated the proportions of various stable phases at
the experiment temperatures and the elementary compositions of theses
phases at 998 K.
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Materials Characterization 130 (2017) 156–172
3. Results and Discussion
3.1. Creep Behaviours and Fracture Analysis of Sanicro 25
Creep deformation curves at 973 K, 998 K, and 1023 K of the pre-
sent tests are given in Fig. 1(a), demonstrating that Sanicro 25 alloy
exhibits typical creep behaviours with creep life extended as test tem-
peratures and applied stress levels decreased. The variation between
creep rate and creep time of alloy crept at 973 K under 180–240 MPa
are shown in Fig. 1(a) as well, form which the initial creep rate and
minimum creep rate were found evidently declining by around an order
of magnitude as applied stress decreased from 240 MPa to 180 MPa due
to the changes in microstructure [10]. The high-temperature tensile
tests results are shown in Fig. 1(b) as the form of engineering strain-
engineering stress, where it can be seen that the yield strength and
tensile strength all drop along with the test temperature, which is
caused by the weakening of precipitate strengthening [16]. It is noted
that the yield strength results of high-temperature tensile tests at 998 K
and 1023 K are close and both lower than yield strength at 973 K. This
was caused by the distinction in types of nanosized precipitation at
different temperatures, which is discussed in Section 3.1.2. The creep
test conditions and the corresponding creep rupture hours of the pre-
sent investigation are listed in Table 2. The creep rupture life (tr, h) with
applied stress (σa, MPa) and test temperature (T, K) can be expressed as
tr = Aσa− n exp (Qc/RT) [17], where A and n are creep constant and
exponent, respectively, R is gas constant, and Qc is the apparent acti-
vation energy for creep rupture life calculated by deducing the slope of
Arrhenius plot (ln tr vs. 1/T) shown in Fig. 1(c). The value of activation
energy for creep rupture was found slightly higher than that for creep
deformation, which is in line with the most common heat-resistant al-
loys including grade 92 [17] and Super 304H [18].
The typical fracture faces of specimens ruptured at 973 K, 998 K,
and 1023 K under 180–240 MPa are shown in Fig. 2 (a). The fracture
mode can be distinguished by the presence of rock-candy-like feature
(intergranular fracture, IF) and dimples feature (transgranular fracture,
TF). In the present study, Sanicro 25 alloy exhibits IF at 973 K under
stress level 180–240 MPa, and 998 K under 180–200 MPa, while the
transgranular fracture occurs at 1023 K under 200–240 MPa. It is worth
noting that combined fracture mode of IF and TF can be observed at
998 K under applied stress 220 MPa and 240 MPa and at 1023 K under
180 MPa. Furthermore, to check the fracture mode of the creep rup-
tured specimens, etched metallographs of the fracture frontier of spe-
cimens after creep at different conditions are displayed in Fig. 2(b)–(e).
As Fig. 2(b) and (c) shown, intergranular cracks appear in the alloy
ruptured after creep at 973 K under 180 MPa and 240 MPa, respec-
tively, which leads to an IF resulted from the microcracks initiating
along the grain boundaries. Plus, grains in fracture surfaces of these
specimens displayed the similar grain size (50–70 μm on average) with
the microstructure shown in Fig. 2(b) and (c). Transgranular cracks
were observed in the ruptured specimen after creep at 1023 K and
240 MPa (Fig. 2(d)), in accordance with the presence of dimples in a TF
mode. However, mixed fracture mode of IF and TF were detected when
transgranular and intergranular cracks appear simultaneously in the
microstructure of alloy crept at 973 K under 220 MPa and 240 MPa,
shown in Fig. 2(e).
3.2. Multiscale Precipitates Observation
3.2.1. As-Received Sanicro 25
The as-received Sanicro 25 comprised homogeneous austenite con-
taining many twinned structures and dispersed particles, as shown in
the SEM image in Fig. 3(a). TEM observation showed that these parti-
cles were approximately 200–300 nm (Fig. 3(b)) and 1–2 μm (Fig. 3(c))
in size. The EDS analysis in Fig. 3(b) showed they were undissolved
primary Nb-rich precipitates. Undissolved precipitation tends to be
remnant of the steel production process occurred in alloys containing
Y. Zhang et al. Materials Characterization 130 (2017) 156–172

Fig. 2. (a) Typical fracture morphologies of Sanicro 25; metallographs of fracture frontier in specimen after creep at (b) 973 K and 180 MPa, (c) 973 K and 240 MPa, (d) 998 K and
240 MPa, (e) 1023 K and 240 MPa.

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Y. Zhang et al.
Fig. 2. (continued)
microalloying elements such as Nb or Ti [20–23]. Fig. 3(d) depicts the
vicinity of a grain boundary junction, confirming that there was no
apparent precipitation on the grain boundaries before creep. Fig. 3(d)
also shows some irregularly arranged dislocations, which may have
been introduced during the steel-forming procedures or the preparation
of the samples. Fig. 3(e) shows the typical twinned structure of the as-
received Sanicro 25 alloy, which is common for austenite steel. The
Laue diffraction speckles of the twinned structure are displayed in
Fig. 3(e) as well.
3.2.2. As-Crept Sanicro 25 Alloy
A three-dimensional histogram of phase weight fraction versus
temperature of Sanicro 25 is shown in Fig. 4(a), which reveals that
Sanicro 25 alloy exhibits complicated precipitation behaviour during
high-temperature isothermal treatment, including Z, M23C6, Laves,
sigma, pi and Cu-rich phases. The weight percentage of the austenite
phase increased with increasing temperature, whereas that of the sigma
phase is decreased, which is caused by the lever principle according to
the binary iron-chromium equilibrium diagram [24]. The weight per-
centage of the Cu-rich phase decreased with increasing temperature
because the solubility of Cu in γ-Fe decreased from 3% (1108 K) to
0.32% (973 K) [25]. Fig. 4(b) depicts the elemental composition of the
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Materials Characterization 130 (2017) 156–172
different phases at 998 K, from which we can generally predict the
composition of the different precipitation products of the alloy. Because
of the inaccuracy of the thermodynamic software and limitations to
characterising the microstructure to some extent, the MX-type phase
was not worked out in the present simulation and the pi phase was not
found in these observations. However, the information obtained on the
proportions and elementary compositions of the second phases is ade-
quate for facilitating the subsequent analysis in the present work.
The Z phase (a Nb-rich CrN precipitation) with relatively large size
(1–2 μm) was mainly observed in the grain interior. Fig. 5 shows the
microstructure of a vicinity of triple boundaries in the specimen after
creep at 998 K and 180 MPa and the element distribution mapping of
Nb, Cr, Ni, and Fe, respectively. The areas rich in Nb indicate the sites
of the Z-phase. The concentration of Cr and the sparseness of Fe and Ni
simultaneously indicate the locations of Z phase and carbides. The EDS
results in Fig. 5 support the conclusion that the Z phase is a CrNbN
compound, which is found frequently in austenite alloys [26,27].
However, CrNbN has a negative effect on the creep strength due to the
consumption of Nb (the metallic element of a nanosized precipitation-
hardening phase) during the nucleation and growth of CrNbN [28]. In
Fig. 5, not only the Z-phase but also intergranular carbides are dis-
covered evidently. The TEM characterisation in Fig. 6(a) and (b) further
Y. Zhang et al. Materials Characterization 130 (2017) 156–172

Fig. 3. (a) Microstructure of the as-received alloy observed by SEM; TEM images of primary MX type precipitates with a mean diameter of (b) 200–300 nm and (c) 1–2 μm; (d) The
vicinity of grain boundaries junctions; (f) twinning structure.

161
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displays the detailed microstructure of this precipitation in the same
specimen. As shown in Fig. 6(b), the EDX result of spectrum 3 shows a
very high Cr content (over 70%), and the SAED analysis confirmed that
the precipitation with a size of 200–300 nm is Cr23C6 with space group
of Fn-3m, which was also reported by Stojan et al. in a microstructure
study for Sanicro 25 after heat treatment [29]. Cr23C6 is known as a
carbide with significantly high coarsening rate during high-temperature
exposing [30–32]. However, the coarsened Cr23C6 precipitation on the
grain boundaries is the vital site for the initiation of creep cavities. As
shown in Fig. 6(c), microscale creep cavitation was found around
Cr23C6 precipitates in the specimen after creep at 973 K and 200 MPa.
The nature of the nucleation and growth of creep cavities in a Ni-18Cr-
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Materials Characterization 130 (2017) 156–172
Fig. 4. (a) 3-Dimensional histogram of phase weight friction vs.
temperature of Sanicro 25. (b) The variation in the elemental com-
position of different phases at 998 K.
18Fe alloy were examined in literature [33], where cavities were nu-
cleated at the intergranular coarse second-phase carbides, following the
ripening behaviour of the carbides, and cavities tended to growth
principally in the grain (on one side of the grain boundary), in which
the matrix-carbide interface was incoherent and therefore the binding
force between matrix and carbides is weak. In addition, coarsening
carbides result in stress concentrations due to its obstruction effect of
grain boundary slide upon application of a stress [34]. Also, coarse
Cr23C6 increase cavity nucleation at a grain boundary through vacancy
condensation by increasing the grain boundary free energy. As shown
in Fig. 6(d), a ~5 μm-long crack was observed in the specimen after
creep at 973 K and 180 MPa. According to elements scanning line, the
Y. Zhang et al.
Cr-rich areas show the presence of Cr23C6, which demonstrates that
creep cavitation connected into cracks and led to the eventual fracture.
Furthermore, the scanning line of element tungsten in Fig. 6(d)
fluctuated evidently, alluding to the fact that W-rich phase formed
during creep. Fig. 7(a) shows a backscattered electron (BSE) image and
the element distribution maps of precipitates of the specimen after
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Materials Characterization 130 (2017) 156–172
Fig. 5. Z phase and its EDS results in the specimen crept after 998 K
and 180 MPa and the distribution mapping of Nb, Cr, Ni, and Fe,
respectively.
creep at 973 K and 180 MPa. The aggregation of Nb and lack of Fe
confirmed that the phase in a large size located in the middle of the
Fig. 7(a) was CrNbN phase as per the analysis of Fig. 5. The Cr-rich
areas symbolised the presence of Cr23C6. However, the W-rich pre-
cipitates extensively distributed all over the field of view were identi-
fied as Laves phase according to the composition calculation in
Y. Zhang et al.
Fig. 6. (a) The chain-like M23C6 phase of specimen after creep at 998 K and 180 MPa and (b) the detailed microstructure of M23C6 with its SAED and EDAX results; (c) Creep cavitation
around M23C6 precipitates of the specimen ruptured after creep at 973 K and 200 MPa; (d) A ~ 5 μm-long crack observed in the specimen after creep at 973 K and 180 MPa.
Fig. 4(b). TEM was used to look further into these phase. Fig. 7(b)
displays the precipitates of the specimen after creep 998 K and
180 MPa. The EDX results of spectrums 4 and 5 demonstrate the pre-
sence of Laves and sigma phases. As shown in Fig. 7(b), Laves is a W-
rich Fe-compound and the sigma phase has a typical composition of Fe,
Cr, and Ni, which is in line with the calculation results shown in
Fig. 4(b). Laves precipitation is a strengthening phase widely used in
most commercial austenitic steels [35]; however, its use decrease the
toughness of the steel [36]. The Fe-Cr intermetallic sigma phase is one
of the main reasons for the decreased toughness and elongation of the
steels [37]. The Laves phase precipitating in Sanicro 25 is approxi-
mately 100–200 nm, which has been reported in the literature [36],
where Laves phase precipitates in the Fe-20Cr-30Ni-2Nb-5Al alloy were
205 nm in diameter after 24 h aging, and they showed a slight increase
in diameter to 301 nm after aging for 1325 h. Fig. 7(c) shows TEM
observation of a succession of precipitates in the specimen after creep at
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Materials Characterization 130 (2017) 156–172
1023 K and 180 MPa. Higher-magnification images in Fig. 7(c) illus-
trate that the Laves phase has a lobate shape, whereas the sigma phase
has relatively square edges. The SAED images of the two types of pre-
cipitation in Fig. 7(c) show that the structures of Laves and sigma
phases are Fe2W (space group Fm-3m) and FeCrNi (space group lm-3m),
respectively. Fig. 7(d) display the precipitates distribution in the spe-
cimen after creep at 973 K and 180 MPa. Increase in the quantity of
Laves phase from 1023 K (Fig. 7(d)) to 973 K (Fig. 7(c)) is quite sig-
nificant under the same observation scale. Fig. 7 (e) represents the
other areas of the same specimen as an evidence for the phenomenon
above. The longer creep rupture time (264.6 h at 1023 K and 3553 h at
973 K, both under 180 MPa) may well contribute to the increase in the
amount of Laves phase [38].
Nanoscale precipitation was also observed distinctly in Fig. 7(e).
Nano-sized MX (M is normally a carbide- or nitride-forming transition
metallic element like Ti, Nb, V, Hf and X is C or N) phase with diameter
Y. Zhang et al. Materials Characterization 130 (2017) 156–172

Fig. 7. (a) BSE image and the corresponding element mappings of precipitation in specimen after creep at 973 K and 180 MPa; (b) Laves and sigma phases observed by TEM, and the EDS spectra
of the specimen crept after 998 K and 180 MPa; TEM images of precipitates of Laves and sigma phases in the specimen after creep (c) at 1023 K and 180 MP and at (d, e) 973 K and 180 MPa.

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Fig. 8. Nano-MX precipitates of specimens after creep

under 180 MPa at (a) 973 K, (b) 998 K, and (c) 1023 K,
respectively; (d) HRTEM micrograph of an MX precipitate
in specimen after creep at 973 K and 220 MPa and its
corresponding SAED pattern; Interactions between dis-
locations and MX of specimen after creep under 180 MPa
at (e, f) 1023 K and (g, h) 973 K.

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Fig. 9. Nano-Cu phase of the specimen after creep at 973 K under (a–c) 220 MPa and (d) 180 MPa.
of 7–8 nm in the austenitic matrix is one of the decisive strengthening
precipitation for Sanicro 25, which was discovered in the alloy after
creep at all test temperatures. Fig. 8(a), (b) and (c) show the MX pre-
cipitates (dark apex) scattered uniformly in the specimens after creep at
973 K, 998 K, and 1023 K under 180 MPa, respectively. However,
negligible changes (< 2 nm) were observed in specimens after creep at
different conditions in the present investigation, demonstrating that the
nitride precipitation in Sanicro 25 is a coarsening-resistant phase with
little dependence on creep time or test temperatures. This is originated
from the significantly low solubility of MX phase in austenite reported
by V. T. Ha and W. S. Jung [39]. Fig. 8(d) presents the HRTEM mi-
crograph of the MX precipitate in the specimen after creep at 973 K and
220 MPa and the SAED image of MX region shows a NbN phase with the
space group of Fm-3m. Furthermore, interactions between dislocations
and precipitates in specimens after creep at 973 K (Fig. 8(e) and (f)) and
1023 K (Fig. 8(g) and (h)) under 180 MPa illustrate that nano-MX
precipitates militated against the dislocations moving by general
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Materials Characterization 130 (2017) 156–172
climbing up mechanism, which was in line with the high-angle annular
dark field (HAADF) images from literature [40]. Higher-magnification
TEM images of interactions between dislocations and MX precipitates
are shown in Fig. 8(e) and (h) for describing the interactions between
dislocations and precipitates in detail. The segments labelled (A) are
qualitatively consistent with what would be interpreted for a general
climb mechanism, where the whole dislocation line in the vicinity of a
precipitate climbs out of the glide plane to bypass the particle. Several
other noteworthy features can be observed in Fig. 8(e) and (h), in-
cluding: dislocation junctions (B) and particles (C) are labelled as well.
Nano-sized Cu-rich precipitates are expected to exist principally at
973 K in accordance with the phase thermodynamic calculation.
Fig. 9(a) shows the nanoscale phase dispersed among the matrix of the
specimen after creep at 973 K and 220 MPa, while such fine dispersion
was invisible at 998 K (Fig. 8(b)) and 1023 K (Fig. 8(c)) under the same
observation scale. HRTEM images of the alloy after creep at 973 K and
220 MPa are shown in Fig. 9(b) and (c), from which the precipitates
Y. Zhang et al. Materials Characterization 130 (2017) 156–172

Fig. 10. (a) Creep curve of the specimen crept at 1023 K and 180 MPa and (b–d) typical dislocation substructures.

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Fig. 11. Schematic diagram of samples used in EBSD examination.
were observed with a size of < 5 nm. Cu-rich particles and the γ-Fe
substrate share the same face-centred cubic (FCC) crystal structure and
consequently a full-coherent interface generates between Cu-rich phase
and substrate [11]. Nevertheless, the nano-sized phase surveyed by
HRTEM shown in Fig. 9(c), where “0.2088 nm” is identified as the in-
terplanar spacing of crystal plane (111) of copper phase. Also, as shown
in Fig. 9(d), the nano-Cu phase was observed not coarsen after creep
over 3500 h at 973 K and 180 MPa, which means that the nanoscale Cu-
rich phase indeed contributes to the creep-resistance performance due
to its uniform dispersion and high coarsen-resistance.
3.3. Dislocation Substructure Development
The creep behaviour of pure metals and alloys is known to be par-
titioned into three regimes that are notably impacted by dislocation
substructure variation at elevated temperatures [41]. The primary
Fig. 12. The grain orientation maps (RD, TD, and ND) and IPFs of the as-received alloy.
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Materials Characterization 130 (2017) 156–172
creep regime (regime I), secondary creep regime (regime II), and ter-
tiary creep regime (regime III) of deformation curve (creep strain vs.
creep time normalized by creep life) of Sanicro 25 alloy crept at 1023 K
and 180 MPa are depicted in Fig. 10(a). In regime I, the creep rate
decreases significantly under high temperature. The creep rate then
reaches a minimum value, followed by a shorter steady state creep
stage. Fast creep deformation occurs in regime III up to the time of
ultimate fracture. It should be emphasised that the creep rate decreases
as the creep strain increases in regime I due to work hardening caused
by the multiplication and interactions of dislocation in plastic de-
formation. A steady creep rate appears in the secondary creep regime,
where the effects of work hardening and recovery are balanced by
processes such as dislocation annihilation and rearrangement. Rapid
growth of the creep rate in regime III may well be attributed to creep
recovery and the growth of creep cavities [42].
For comprehending the dislocation substructures development, the
interrupted creep tests of Sanicro 25 at 1023 K and 180 MPa were
performed by rapid cooling specimen under constant load, which
maintains the dislocation substructures well. TEM micrographs in
Fig. 10(b)–(f) show the typical dislocation substructures of specimens
after creep 30 h (Fig. 10(b)), 80 h (Fig. 10(c)), and 200 h (Fig. 10(d))
at1023 K and 180 MPa. As shown in Fig. 10(b), at the inception of creep
deformation, dislocations soon tangled with each other and trans-
formed into dislocation walls (Fig. 10(c)) accompanied by a surge in
dislocation density. However, as shown in Fig. 10(d), dislocation cells
formed in large quantities during creep regimes II and III, inside which
the dislocation density is fairly lower and misorientation angle between
dislocation cells is considered low [41]. Fig. 10(e) and (f) show the
dislocation substructures of specimens after creep at 973 K and
180 MPa, which confirms the occurrence of dislocation cells in sub-
stantially larger portions.
3.4. Texture Analysis Before and After Creep
To better understand the creep behaviour of the alloy at high
Y. Zhang et al.
Fig. 13. (a) Grain orientation maps (RD) of microstructures of the specimen after creep at different creep condition and (b) the IPFs (RD) of the same areas.
temperatures, EBSD was used to investigate the grain orientation and
size of the alloy before and after creep under different conditions. As
shown in Fig. 11, the observation plane of the samples for EBSD char-
acterisation was taken parallel to the rolling direction (RD) of the as-
received tube and also parallel to the creep direction of the as-crept
specimen. The transversal direction (TD) and normal direction (ND) are
also labelled in the Fig. 11. Fig. 12 presents the grain orientation maps
(RD, TD, and ND) of the as-received alloy. No remarkable texture
component features were observed in the alloy before creep from the
inverse polar figures (IPFs), which was in accordance with most aus-
tenite alloys [43]. However, strong changes in the texture component
occurred in the alloy after creep. Fig. 13(a) depicts the grain orientation
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Materials Characterization 130 (2017) 156–172
maps (RD) of microstructures of specimens ruptured under different
creep conditions (marked under each image), where crystal plane or-
ientations 〈111〉//RD and 〈001〉//RD were found to be the main
texture components compared to the as-received alloy. Moreover, as for
the detected region of specimens after creep at 973 K and 1023 K, the
area with 〈001〉//RD increased and the area with 〈111〉//RD de-
creased as the test stress level decreased. As shown in Fig. 13(b), IPFs of
the same areas as Fig. 13(a) further confirmed the preferred orientation
〈111〉//RD was detected in the specimens after creep at higher stress
levels (220 MPa and 200 MPa) at both 973 K and 1023 K. The {111}-
orientated plane is recognised as the slip plane for FCC metals [44].
However, the lower test stresses were applied to creep specimens, the
Y. Zhang et al.
Fig. 14. The variation of correlated frequency vs. misorientation angle.
more frequently the orientation 〈001〉//RD was detected in the as-
crept alloy. Zhang et al. [45] reported that {100}-oriented grains have
the lowest strain energy for all observed FCC metal including γ-Fe, Cu,
Al, Ag, Au, Ni, Pb and Th, and that the change in texture from {111} to
{100} can be driven by minimising strain energy under the lower stress.
The variation of correlated frequency vs. misorientation angle of
rolling plane (the same area as Fig. 13(a)) in as-received tube and as-
crept specimens under different test conditions is shown in Fig. 14(a).
The as-received microstructure shows both low-misorientation angle
grain boundaries (LABs) and high-misorientation angel grain bound-
aries (HABs). Nevertheless, the grain boundaries with the special mis-
orientation angle of 60° decreased dramatically after creep at all con-
dition, which was caused by the elimination of twins during creep
[43,46]. Fig. 15 shows the coincidence site lattice (CSL) maps (the same
areas as Fig. 13(a)) of as-received alloy and specimens after creep at
Fig. 15. CSL maps of as-received alloy and as-crept specimen.
Fig. 16. Grain boundaries maps of as-received alloy and as-crept specimen.
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Materials Characterization 130 (2017) 156–172
973 K and 1023 K, where the quantity of the twinned grain boundaries
(the Σ3 grain boundaries represented by the red segments) in the crept
alloy obviously decreased compared to the as-received alloy, which
confirms the conclusion above. Fig. 16 shows the maps (the same area
as Fig. 15) of grain boundaries types of as-received alloy and as-crept
specimen, where the black segments stand for HABs (misorientation
angle > 15°) and the red segments stand for LABs (misorientation angle
≤ 15°). The amount of LABs of crept microstructure in detected areas
were found notably higher than that of as-received alloy due to the
grain boundary deformation during creep process (GBS and GBM) [47].
Also, the presence of massive dislocation cells contributed to the sig-
nificant occurrence of LABs, which was in keeping with the TEM ob-
servations in Section 3.2. Moreover, the decrease in twins structure
(Fig. 15) and the increase in LABs (Fig. 16) with higher creep tem-
perature may be caused by stronger reaction of grain boundary de-
formation at a higher temperature [47].
4. Conclusion
The precipitation behaviours, dislocation substructure development
and grain transformation of the Sanicro 25 alloy after creep at 973 K,
998 K, and 1023 K over a stress range of 180–240 MPa were in-
vestigated. The following conclusions were drawn from the study.
i. The as-received Sanicro 25 alloy was with a homogeneous austenite
material containing a number of twinned structures and dispersed
particles.
ii. The Cr23C6 precipitates were considered to be the primary sites of
creep cavitation nucleation. The increase in the quantity of the
Laves phase can be attributed to the longer creep time.
iii. Nano-MX and Cu-rich precipitates in as-crept specimens were in-
vestigated by TEM. Climbing mechanism between nanoscale MX
precipitates and dislocations were observed.
iv. The amount of LABs of the alloy obviously increased because of the
grain boundary deformation and dislocation cells formed during
Y. Zhang et al.
creep.
v. 〈111〉//RD and 〈001〉//RD were found to be the main texture
components as compared to the as-received alloy.
Acknowledgement
The authors wish to acknowledge the financial support provided by
the Project of the National Natural Science Foundation of China (Grant
number 51475326) and the Distinguished-Reserved Academic Program
of Tianjin University.
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