Materials Characterization 139 (2018) 311–318

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

Creep-induced microstructural evolution in a nickel-based superalloy T

designed for advanced ultra-supercritical boilers
⁎
Qingshuang Xua, Tieshan Caoa, Fei Yea, Fanghong Xub, Huifang Lia, Xudong Fangb, Jie Zhaoa,
a
School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
b
State Key Laboratory of Advanced Stainless Steel, Taiyuan Iron and Steel Group Company Limited, Taiyuan 030003, China

A R T I C LE I N FO A B S T R A C T

Keywords: Long-term microstructural stability is a major concern for candidate materials used in advanced ultra-super-
Ni-based superalloy critical (A-USC) power plants. In the present work, precipitation behavior of a nickel based superalloy designed
Precipitates for A-USC boilers, with a base composition of Ni-25Cr-20Co, was investigated during long-term thermal ex-
Grain boundary posure under different stresses at 1043 K. The results showed that the coarsening of γ′ precipitates in the grain
Creep
interior had occurred during thermal exposure in the presence and absence of stress. The microstructure around
Advanced ultra-supercritical
grain boundary was altered remarkably under stress. The precipitate-free zones (PFZs) commonly existed near
the grain boundary in the gauge sections of specimens after long-term creep. Coarsened and elongated particles
in the PFZs were identified as γ′-Ni3 (Ti, Al) precipitates by chemical composition analysis and diffraction
pattern. Furthermore, the morphology and distribution of MC-type carbides have no significant changes ob-
served due to their good stability, but discontinuous M23C6 appeared under stress, due to formation of PFZs
resulting in dissolution of the adjacent M23C6. Besides, the creep-rupture mechanism was discussed to explore a
potential approach for improving creep properties.

1. Introduction
To achieve high thermal efficiency of coal-fired power plants and
reduce carbon dioxides (CO2) emissions, it is imperative to develop
700 °C advanced ultra-supercritical (A-USC) power plants [1]. The
material of high temperature components of A-USC steam boilers is a
key to operating safely and improving efficiency. The material requires
high stress-rupture strength (100,000 h creep strength > 100 MPa at
750 °C) and high oxidation/corrosion resistance (< 2 mm cross-section
loss in 200,000 h), which are greatly beyond the capacity of current
ferritic or austenitic heat resistant steels [2,3]. Therefore, Ni-based
superalloys becomes a major class of candidate materials for the 700 °C
A-USC boilers due to their high creep strength and corrosion resistance.
Some Ni-based superalloys, for example, Haynes 282 [4], Inconel
617/617B [5–7], Nimonic 263 [8] and Inconel 740/740H [2,9,10],
have an increasingly wide utilization in a number of critical technolo-
gical areas, such as jet-engine turbines and power plants. Inconel 740H
has the highest rupture strength at 700 °C with rupture life of 105 h
among these alloys mentioned above [11]. 740H is a precipitation-
hardenable Ni-25Cr-20Co nickel-based superalloy used to manu-
factured superheater tubes and header pipes [11]. 740H is ameliorated
based on Inconel 740, since microstructural stability of latter is not
satisfying during aging and creep [9,12,13]. Precipitates are the main
contributor to high temperature strength in Ni-based superalloys, and
their morphology, size and chemical composition are of importance in
the investigation of 740H and other similar alloys. TG700A is a 740H-
type nickel-based superalloy designed and produced by Taiyuan Iron
and Steel Co., Ltd. The chemical composition of this alloy is similar to
740H alloy. TG700A mainly contains several kinds of precipitates such
as γ′, M23C6 and MC, similar to 740H [12]. Currently, microstructural
evolution and mechanical properties of the 740H-type alloys during
aging have been investigated [10,14,15]. Since the 740H-type alloys
including the TG700A, have recently been developed, few studies
concerning the microstructural evolution during long-term creep have
been carried out on these alloys.
In this work, precipitation behavior of TG700A alloy at 1043 K
(770 °C) under various stresses was investigated during long term
thermal exposure up to 12,694 h. Furthermore, some factors influen-
cing observed changes of precipitates were discussed. In the absence of
long-term creep data for the 740H-type alloy, the results provided a
unique opportunity to study microstructural evolution especially grain
boundary precipitates, so that its stability can be understood better.

⁎
Corresponding author at: School of Materials Science and Engineering, Dalian University of Technology, No.2 Linggong Road, Ganjingzi District, Dalian 116024, China.
E-mail address: jiezhao@dlut.edu.cn (J. Zhao).

https://doi.org/10.1016/j.matchar.2018.03.008
Received 14 November 2017; Received in revised form 5 March 2018; Accepted 7 March 2018
Available online 08 March 2018
1044-5803/ © 2018 Elsevier Inc. All rights reserved.
Q. Xu et al.
2. Materials and Methods
TG700A tubes in the present study were produced by Taiyuan Iron
and Steel Co., Ltd., with the chemical composition of Ni-25.44Cr-
20.55Co-1.43Al-1.35Ti-1.42Nb-0.49Mo-0.02Mn-0.24Fe-0.029 W-
0.07Si-0.03Cu-0.03C wt%. The as-received tube was first processed by
solution treatment at 1150 °C for 1 h and water quenching. Then, aging
heat treatment conducted at 820 °C for 5 h to set the γ′ structure.
Creep rupture test was carried out on smooth bar specimens fabri-
cated from the tubes in accordance with ASTM E139 at 1043 K under
stresses ranging from 260 to 160 MPa, with rupture lives ranging from
956 to 12,694 h. The grip and gauge sections of specimens after creep
were cross-sectioned using wire electrical discharge machining for
analysis. Characterization of microstructure after creep test involved
analysis of stressed and unstressed sections from the gauge and grip
areas of each specimen, respectively. Though, the grip section of the
specimen was lightly affected by plastic deformation, it could be con-
sidered to be under a simple stress-free state.
The specimens were ground and polished following standard me-
tallographical methods and then chemically etched in a fresh solution
of HCl, HNO3 and H2O volume proportions of 10: 1: 10 at 323 K (50 °C)
for 3 min. Subsequently, the microstructure was characterized by Leica
MEF4 optical microscope (OM) and Zeiss supra 5 Field Emission Gun
Scanning Electron Microscope (FE-SEM) equipped with an energy dis-
persive spectroscopy (EDS) microanalysis using an acceleration voltage
of 15 kV. Electron probe microanalyser (EPMA) (EPMA-1600) was used
to examine the local chemical composition of the specimens. After SEM
characterization, a coarsened zone was chosen for extraction and
thinning to electron transparency using focused ion beam (FIB, FEI
Helios Nanolab G3 CX) techniques. After FIB thinning, microstructural
analysis of the thinned specimen was carried out in the high-resolution
transmission electron microscopy (HRTEM, FEI Talos F200).
3. Results
3.1. Initial Microstructure
TG700A alloy mainly contains several kinds of precipitates such as
γ′, M23C6 and MC, which formed either during solidification, the final
normalizing and tempering heat treatment or during subsequent aging,
the same as 740H alloy [12]. Representative images of specimens be-
fore creep are shown in Fig. 1. The OM image of TG700A as-received
indicates an equiaxed microstructure, containing numerous annealing
twins which are beneficial to the strength. There are some blocky
particles about 1 μm in diameter string-like distributed in the grain
interior and at the grain boundaries, according to Fig. 1(b). This is as a
result of extrusion and rolling in the process of manufacturing as-re-
ceived TG700A tube samples. The MC carbides rich in Nb and Ti by EDS
(Fig. 1(c)) formed during solidification and were crushed into strings
along the hot rolling direction and remained in subsequent solution
treatment. At high magnification, an amount of spheroidal γ′ pre-
cipitates about 32 nm are found in the as-received specimen, mean-
while, M23C6 carbides rich in Cr precipitated along the grain boundary,
see Fig. 1(b) inset and (d).
3.2. Precipitate Changes in the Grain Interiors
Changes of γ′ precipitates in the grain interior in the grip and gauge
sections of creep-rupture specimens at 1043 K are shown in Fig. 2.
There is a homogeneous distribution of γ′ precipitates within γ grain
interior in the grip and gauge sections. It is clear that γ′ particle size in
the grip sections increased with creep time and the transition occurred
from the approximately spherical to rounded cubic in shape, as shown
in Fig. 2(a–c). Also, the density of γ′ precipitates decreases with in-
creasing creep time in the grip and gauge sections. Furthermore, the
microstructures in the gauge sections after creep are shown in
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Materials Characterization 139 (2018) 311–318
Fig. 2(d–f). Compared with the corresponding grip sections respec-
tively, morphology of γ′ precipitates in the grain interior had minor
change that γ′ particles were coalesced or elongated slightly in some
directions.
The change of γ′ particles in the grain interior is indicated quanti-
tatively in Fig. 3. As shown in scatter plot of Fig. 3, the determined
mean diameters of γ′ particles in the grip areas after creep for 956, 4329
and 12,694 h were about 88, 146 and 176 nm, respectively. Also, in the
corresponding gauge areas, the mean diameters of γ′ particles were 89,
148, 178 nm. The statistical result indicates that average sizes of γ′
precipitates between the grip and gauge areas have little difference. A
column chart of Fig. 3 reveals all of the average length-width ratios of
the γ′ particles in the gauge areas became larger than that of corre-
sponding grip areas, which is in accordance with the mentioned change
in the morphology of γ′ particles. It indicates that coalescence and
elongation of γ′ particles are mainly as a result of the presence of stress
during thermal exposure. However, the length-width ratios in the pre-
sence or absence of stress have no significant increase with creep time,
though different stresses.
3.3. Precipitate Changes at Grain Boundary
The representative SEM images of precipitates at grain boundary in
the grip and gauge sections of creep-rupture specimens at 1043 K are
shown in Fig. 4. MC carbides are still blocky and distributed randomly
in the grain interior and at the grain boundary after creep (indicated by
arrows in Fig. 4). The morphology and distribution of MC carbides have
no significant changes observed in all specimens after creep, which is in
accordance with the study of Yan et al. [10]. It illustrates MC carbides
have good stability during long-term creep at 1043 K. In the grip sec-
tions, the M23C6 carbides have almost completely occupied most of
grain boundary and twin boundary (indicated by arrows in Fig. 4(a-
c)).The diffusion of Cr from matrix to carbides along the grain bound-
aries is much faster and therefore the M23C6 carbides grow much more
quickly. As shown, the morphology and distribution of M23C6 carbides
have no remarkable difference. The formation of M23C6 was found to
occur after just a short time, and the amount of M23C6 carbides first
increases and then almost remains in the microstructure even after
long-term thermal exposure [16,17]. It can be deduced that the pre-
cipitation and growth of M23C6 carbides almost achieves thermo-
dynamic stability after some thermal exposure time in the absence of
applied stress.
In contrast, precipitates near the grain boundary were altered re-
markably after creep. Some regions are devoid of the fine γ′ precipitates
but containing coarsened, typically elongated second phase particles
near the grain boundary in the gauge section of creep-rupture speci-
mens as shown arrowed in Fig. 4(e–f). Grain boundary regions of si-
milar morphology have been identified in the literature as precipitate-
free zones (PFZs) [18–20]. However, PFZs used to specifically distin-
guish the grain boundary features are often not truly free of second
phases. So it is also called as precipitate denuded regions or coarsened
zones [21]. In the PFZs, the particles not only were coarsened and
elongated in some directions, but also visibly decreased.
Fig. 5 exhibits the micrographs and elemental mappings for a PFZ in
the specimen after creep for 12,694 h investigated by SEM and EPMA.
The scatters of Ni, Cr, Co, Al, Ti, Nb and C elements for the specimen are
shown in Fig. 5(b) respectively. The mappings indicate that Ni, Al, Ti
and Nb are enriched in the second phase particles of the PFZ. Finally, it
can be concluded that the coarsened or elongated second phases were
identified as γ′ precipitates, main chemical composition of which is Ni3
(Al, Ti, Nb) in Ni-based superalloys. Furthermore, Cr and C enriched on
the edge of the PFZ, see Fig. 5(b). It suggests M23C6 carbides discretely
distributed on the side of the PFZ. In the gauge area, the different
distribution of M23C6 carbides exists in the same specimen. There are
only continuous M23C6 carbides at the grain boundary without PFZ, as
shown in Fig. 5(a). It can be deduced that PFZs influenced the
Q. Xu et al.
Fig. 1. Microstructural characteristics of TG700A before creep: (a) OM image of microstructure; (b) SEM image showing the presence of MC carbides and inset image showing γ′
precipitates and M23C6; (c), (d) EDS analysis of (Nb, Ti)C and Cr-rich M23C6.
distribution of M23C6 carbides around.
Fig. 6(a) shows the dark-field and high-angle annular detector dark-
field (HAADF) microscopy images around the grain boundary in the
TG700A alloy after creep for 12,694 h. Corresponding results of map-
ping studies portray the coexistence of Ni, Al, Ti, Nb, Cr and Co ele-
ments, as shown in Fig. 6(b–h). The elements segregate differently in
the phases at the grain boundary, leading to a varying contrast ob-
served. As shown in the elemental maps, the distribution of all the
elements in the γ matrix is homogeneous, but Ni, Al, Ti and Nb mainly
partition into the γ′ phases, while Cr and C mainly partition into the
M23C6 carbides, being consistent with the results obtained from the
EPMA study. Differing from M23C6 carbides distributed along grain
boundaries in the grip section, it is noteworthy that granular M23C6
carbides are actually not close to the grain boundary.
The microstructure at the grain boundary was also examined by
HRTEM. All the images in Fig. 7 were obtained in a 〈111〉 γ zone axis. It
presents the high-resolution TEM image (Fig. 7(b)) of the interface
between the elongated particle and matrix, marked by the solid line
frame region I in the TEM dark field image (Fig. 7(a)). As seen from
Fig. 7b, diffraction patterns of the elongated precipitate and matrix (as
indicated by regions II and III in the Fig. 7(b), respectively), were ob-
tained by a fast Fourier transformation (FFT) and are shown insets. It
indicated an array of hexagonal symmetry dots and revealed the crys-
talline nature of the particle, being consistent with an ordered face-
centered cubic L12 structure γ′-Ni3(Al, Ti) phase. As shown in Fig. 7(c)
and (d), the lattice fringes of region II and region III in (b) were con-
structed by an inverse FFT (IFFT) using the diffraction spots (indicated
by the black circles), respectively. The regular behavior of the lattice
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Materials Characterization 139 (2018) 311–318
fringes indicates almost free of obvious defects inside the γ′ particle. By
contrast, an amount of lattice distortion occurred in the γ matrix, due to
dislocations accumulation controlled by Orowan looping mechanism.
Dislocation could not shear large γ′ precipitates during creep.
4. Discussion
TG700A alloy is a γ′-strengthened, precipitation-hardenable super-
alloy with excellent microstructural stability like 740H. Its precipitates
mainly are γ′, MC and M23C6 before and after creep test. Compared with
Inconel 740, no η phase precipitation was observed even though after
creep up to 12,694 h due to lower Ti/Al ratio. Microstructural evolution
during thermal exposure and the corresponding rupture behavior are
discussed systematically on the basis of the characterization of micro-
structures.
4.1. Coarsening Behavior of γ′ Precipitates
The average diameter of γ′ particles in the TG700A alloy is about
32 nm before creep test. The γ′ particle size increases with creep time
during thermal exposure. The statistical result indicates that average
sizes of γ′ precipitates have little difference in the absence and presence
of stress (Fig. 3). It suggests that coarsening process of γ′ precipitates in
the grain interiors is not dominated by applied stress but the thermal
exposure time. Several previous studies [22–27] have concluded that
coarsening behavior of γ′ precipitates proposed in some Ni-based and
Ni-Fe-based superalloys commonly follows the Lifshitz–Slyozov-Wagner
(LSW) growth kinetics model diffusion-controlled [28]. It has been
Q. Xu et al.
Fig. 2. Typical changes of γ′ precipitates in the grain interior in the grip and gauge sections after creep: (a) 956 h/0 MPa, (b) 4329 h/0 MPa, (c) 12,694 h/0 MPa, (d) 956 h/260 MPa, (e)
4329 h/200 MPa, (f) 12,694 h/160 MPa.
Fig. 3. Mean size and length-width ratio of γ′ precipitates at different creep time.
observed that generally the precipitates grow at an almost constant
volume fraction, following a power law expression:
rt3 − r03 = kt.
where rt, r0 are the mean sizes of the particle at time t and 0 respec-
tively, and k is the coarsening rate coefficient [23]. As shown in Fig. 8,
the coarsening behavior of γ′ precipitates in the alloy is consistent with
the mentioned studies, broadly according to the LSW theory. The
driving force for precipitate coarsening mostly comes from reduction of
the specific free energy at the precipitate/matrix interface [23]. Due to
the lattice misfit increasing with thermal exposure time, the interfacial
coherency was disrupted and the energy of the γ′/γ interface increased,
resulting in an enhanced driving force for γ′ coarsening [29]. Thus the
reduction in interfacial energy manifested as precipitates coarsened. It
is well known that a distribution of immobile γ′ particles in the γ matrix
tends to lower its interfacial energy by diffusion of γ′ forming elements
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Materials Characterization 139 (2018) 311–318
from the smaller to the larger members of the distribution, thereby
diminishing the total particle number but increasing the average par-
ticle size [23]. In other words, small γ′ particles dissolve and large ones
grow at the expense of smaller ones.
Besides, the transition of γ′ occurred from the approximately sphe-
rical to rounded cubic in shape during thermal exposure without stress
(Fig. 2(a–c)). It indicates the lattice misfit between γ′ phase and γ
matrix increased gradually. The morphology of γ′ precipitates mainly
depends on the balance between the surface (interfacial) energy and the
elastic strain energy, and the latter is closely associated with the γ-γ′
misfit [28]. When the lattice misfit is low, interfacial energy dominates
the morphology of precipitates and spherical γ′ particles are shown due
to their minimum surface area with the same volume. Inversely, with
lattice misfit increasing, the elastic strain energy induced by lattice
misfit takes an increasingly dominant role and cuboidal γ′ particles are
exhibited [30].
The average length-width ratio of the γ′ particles became slightly
larger in the presence than absence of stress (a column chart of Fig. 3).
It indicates that coalescence and elongation of γ′ particles are mainly as
a result of stress during long-term thermal exposure. However, the
length-width ratios have no significant increase with creep time, though
different stresses. This is a possible reason that deformation of poly-
crystalline specimen mainly occured at the grain boundary in the way
of sliding and migration, and slightly in the grains with dislocation
sliding. Substantially, the release of strain energy in the grain interiors
gave rise to coalescence and elongation of γ′ particles. Moreover, there
is no significant change in the strain energy in the grain interiors under
different stresses, even if long term thermal exposure.
4.2. Formation of PFZs
The precipitates near grain boundary were altered remarkably in
the presence of stress during long-term thermal exposure (Fig. 4). There
is a close relationship between formation of PFZs and precipitate
changes near the grain boundary. It can be concluded that the
Q. Xu et al.
Fig. 4. Typical changes of precipitates at the grain boundary in the grip and gauge sections after creep: (a) 956 h/0 MPa, (b) 4329 h/0 MPa, (c) 12,694 h/0 MPa, (d) 956 h/260 MPa, (e)
4329 h/200 MPa, (f) 12,694 h/160 MPa.
coarsened or elongated second phases were identified as γ′ precipitates,
through the chemical composition and crystallographic structure
(Fig. 5–7). This result is different from cellular precipitates identified as
M23C6 carbides and referred in the literature [15]. And Cr and C en-
riched on the edge of the PFZ in Fig. 5(b). It suggests M23C6 carbides
discretely distributed at the side of the PFZ. The M23C6 carbides con-
tinuously and discretely appeared at grain boundary where PFZs were
found ((Fig. 4(e) and 5(a)), while there are only continuous chain-like
M23C6 carbides at the grain boundary without PFZs (Fig. 4(f)). It can be
deduced that the distribution of M23C6 carbides is associated with the
formation of adjacent PFZs. It has been reported that M23C6 carbides
can suppress the formation and growth of PFZs [31].
In contrast to grain interiors, the γ′ precipitates in the PFZs coar-
sened markedly and elongated in certain directions, which have no
clear relationship with loading direction (vertical, as indicated in
Fig. 4). Interestingly, this is different from rafting in superalloys, which
direction is vertical or parallel to the applied stress axis [32,33]. A point
is for certain, that the formation of PFZs can be bound up with stress or
strain, due to different stresses and deformation degrees in the gauge
and grip sections (Fig. 4). The average area fractions of PFZs were
maintained respectively from 20 SEM images of the different positions
at the distance of about 2 mm from the fracture surfaces, as shown in
Fig. 5. The micrographs and elemental mapping for specimen after creep for 12,694 h observed by SEM (a) and EPMA (b).
315
Materials Characterization 139 (2018) 311–318
Fig. 9. The semi-quantitative result indicates the area fraction of PFZs
increases with creep time. This reveals the formation of PFZs is essen-
tially a solid atom diffusion-controlled process, no matter what me-
chanism. However, the bulk diffusion mechanism probably is not the
only mechanism in this case due to morphology of γ′ in the PFZs ob-
viously different from grain interior, and boundary and pipe diffusion
may play an important role on the formation of PFZs [19].
It was observed that the PFZs had the same crystallographic or-
ientation with an adjacent high dislocation density grain [31]. Then, a
mechanism is proposed in the literature that the small γ′ particles dis-
solved on strain-induced grain boundary migration (SIBM), and re-
precipitated and coarsened when γ′ forming elements were over-
saturated. What's more, several mechanisms of PFZ formation, such as
Nabarro–Herring creep, Grain boundary carbide formation and Grain
boundary sliding/migration, were discussed detailedly in Ref. [21]. The
primary mechanism applicable to alloy 740H is discontinuous coar-
sening reactions (DC) [21,34]. Both SIBM and DC mechanisms depend
on the enhanced diffusivity at a moving grain boundary that acts as the
reaction front providing a conduit for faster mass transport, and cata-
lyzes PFZ formation including coarsening and elongation of γ′ particles.
The initial γ′ particles dissolved with SIBM due to the moving
boundary with high free energy. Meanwhile, the moving boundary
Q. Xu et al.
Fig. 6. Images of microstructure near the grain boundary after creep rupture test at 770 °C/160 MPa: (a) high-angle annular detector dark-field (HAADF) image; (b)–(h) elemental maps of
Ni, Cr, Co, Nb, Al, Ti and C respectively.
provided a short circuit path of diffusion of γ′ forming elements, re-
sulting in inhomogeneous distribution of alloying elements and mi-
crosegregation in local regions. The γ′ particles re-precipitated and
coarsened at a migrating reaction front as a result of solute super-
saturation. Discontinuous coarsening of γ′ precipitates occurred,
leading to the formation of PFZ adjacent to the grain boundary [35].
Simultaneously, the corresponding error bars increases with creep time
in Fig. 9. It is likely as a result that asynchronous boundary movement
influences on diffusion process, i.e. a fast solute transport across reac-
tion front accompanying with some new moving boundaries starting
up. Furthermore, the moving boundary with high free energy can result
in dissolution of precipitates (γ′ or M23C6) around, though the pre-
cipitates may hinder boundary movement, especially M23C6. So dis-
continuous, granular and smaller size M23C6 carbides formed around
the PFZ.
4.3. Precipitates and Creep Fracture
In order to clarify the relationship between precipitates and fracture
in the alloy studied during long-term creep, microstructure character-
istics of fracture surface longitudinal section near the fracture surface in
the gauge of creep-ruptured specimens after 12,694 h were in-
vestigated, as shown in Fig. 10. It indicates that the fractural mode is
generally an intergranular mode (Fig. 10 (a)), but fracture surface of
grains is not smooth in the presence of networks (Fig. 10 (b)). It can be
seen that many microcracks occurred by the growth and coalescence of
the microvoids mainly formed at the grain boundary during creep and
microcracks didn't propagate straightly along the grain boundary due to
PFZ, as shown in Fig. 10(c).
The cavities initiate at the interface between carbides (M23C6 or
MC) at the grain boundary and PFZ. In general, this interface can hinder
the movement of dislocation. Meanwhile, it also leads to localized stress
concentration because of existence of hard and brittle phase (carbides).
Some studies [20,36,37] have proved PFZs have low creep strength, on
account of absence of γ′ precipitates preventing the movement of dis-
location, as main contributors to high temperature strength in Ni-based
superalloys. In this alloy, an amount of lattice distortion occurred in the
γ matrix (Fig. 7(d)) rather than the γ′ particle interior (Fig. 7(c)), due to
316
Materials Characterization 139 (2018) 311–318
dislocations accumulation controlled by Orowan looping mechanism.
Dislocation could not shear large size γ′ precipitates during creep. In
addition, the stress concentration around carbides is enough to form
cavity when it becomes large. Therefore, the M23C6 or MC carbides
become the crack initiation due to the growth of M23C6 carbides or
presence of large MC carbides at the grain boundary [38]. In contrast,
no cavities form in the PFZ interiors or initiate at the interface between
coarsened or elongated γ′ precipitates and PFZs. There are two main
reasons for it, one is relatively lower stress concentration not enough to
form cavities around the interface, and the other is γ′ precipitates im-
proving the strength of PFZs by precipitation strengthening. Ductility is
as important as creep strength at elevated temperature, and a small
amount of PFZs can improve the elongation [31]. The creep properties
can be improved by controlling the size of carbides and PFZs near the
grain boundary properly.
5. Conclusions
In the present study, precipitation behavior of a nickel based su-
peralloy with a base composition of Ni-25Cr-20Co was investigated
during long-term creep at 1043 K, focusing on the changes of pre-
cipitates in the grain interior and at the grain boundary under the
combined influence of time and stress. Based on the results presented in
this studied, the following conclusions can be made:
1. The coarsening of γ′ particles in the grain interior basically follows
LSW theory in the presence and absence of stress. Morphology of γ′
particles transformed from the approximately spherical to rounded
cubic in the absence of stress, while slight coalescence and elonga-
tion of γ′ particles occurred under stress during long-term thermal
exposure.
2. The precipitates near the grain boundary were altered remarkably
under stress, precipitate-free zones (PFZs), coarsened and elongated
particles, and discrete M23C6 carbides arising compared to stress-
free grip section.
3. Coarsened and elongated particles in the PFZs have been identified
as γ′ precipitates by chemical composition and diffraction pattern.
The primary mechanism of PFZ formation is likely discontinuous
Q. Xu et al. Materials Characterization 139 (2018) 311–318

Fig. 7. (a) TEM dark field image of microstructure at the grain boundary. (b) HRTEM image of the interface between the elongated particle and matrix (region I in the (a)).The black
broken line in (b) indicates the interface. (c) and (d) IFFT images constructed using the diffraction spots (indicated by the black circles) respectively in region II and region III in (b), and
dislocations are marked with “T”. The inset images in (b) are the corresponding FFT patterns of the rectangular regions, 〈111〉 beam direction in the γ matrix.

Fig. 8. A plot of γ′ size versus thermal exposure time in LWS model.

coarsening reactions of γ′ precipitates, due to diffusion resulting in
inhomogeneous distribution of alloying elements and micro-
segregation in local regions. Furthermore, PFZ may influence dis-
tribution and size of the adjacent M23C6 carbides at the grain
boundary.
Fig. 9. Mean area fractions of PFZs at the distance of about 2 mm from the fracture
surfaces at different creep time.
4. The interfaces between large carbides at the grain boundary and
PFZs are the crack initiation sites due to high localized stress con-
centration and low strength PFZs.

317
Q. Xu et al.
Fig. 10. Microstructure characteristics of fracture surface (a, b) and longitudinal section(c) near the fracture surface after creep for 12,694 h.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant number: U1610256) and the National
High-tech Research and Development Project of China
(2015AA034402).
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