Acta Materialia 188 (2020) 1
15

Contents lists available at ScienceDirect

Acta Materialia
journal homepage: www.elsevier.com/locate/actamat

Full length article

Structural damage and phase stability of Al0.3CoCrFeNi high entropy alloy

under high temperature ion irradiation
Tengfei Yanga,b,*, Wei Guoc, Jonathan D. Poplawskyc, Dongyue Lid, Ling Wange, Yao Lib,
Wangyu Hua, Miguel L. Crespilloe, Zhanfeng Yanf, Yong Zhangd, Yugang Wangf,
Steven J. Zinkleb,e,**
a
College of Materials Science and Engineering, Hunan University, Changsha 410082, China
b
Department of Nuclear Engineering, University of Tennessee, Knoxville, TN 37996, United States
c
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United States
d
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China
e
Department of Materials Science & Engineering, University of Tennessee, Knoxville, TN 37996, United States
f
State Key Laboratory of Nuclear Physics and Technology, Center for Applied Physics and Technology, Peking University, Beijing 100871, China

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

Article History: An initially single phase high entropy alloy (HEA) Al0.3CoCrFeNi was irradiated by 3 MeV Au ions to a fluence
Received 5 November 2019 of 6 £ 1015 cm
2 (»31 dpa at damage peak) at four different temperatures ranging from 250 °C to 650 °C.
Revised 25 January 2020 Transmission electron microscopy (TEM) and Atom probe tomography (APT) were employed to study the
Accepted 30 January 2020
evolution of structural damage and phase stability with irradiation temperature. Al0.3CoCrFeNi exhibited a
Available online 5 February 2020
similar evolution of irradiation-induced defects with temperature as compared with conventional FCC alloys.
Keywords: At 250 °C and 350 °C, most of the visible irradiation-induced defects were faulted 1/3h111i dislocation loops.
High entropy alloy As the irradiation temperature increased to 500 °C, perfect 1/2h110i dislocation loops were observed along
Irradiation effect with the faulted loops. At the highest irradiation temperature 650 °C, only dislocation lines and networks
Structural damage could be observed. Regarding phase stability, the 3 MeV Au irradiation was observed to suppress the precipi-
Phase stability tation of (Ni, Al)-enriched nano clusters and the L12 ordered structure at irradiation temperatures 250 °C to
500 °C whereas precipitation of the B2 ordered structure was accelerated at 650 °C. This resulted in qualita-
tively opposite precipitation behavior between the ion irradiated damage region and unirradiated region at
500 °C and 650 °C. The opposite phase stability of the ion-irradiated damage region and unirradiated region
at different temperatures is attributed to the competing effects of ballistic dissolution vs irradiation enhanced
diffusion on precipitation.
© 2020 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction temperatures, chemically reactive environments and large time-

varying stresses [1
3]. The high dose neutron irradiation in aggres-
Advanced nuclear energy systems, including next generation fis- sive environments can cause serious structural damage in materials,
sion reactors and proposed fusion energy reactors, will operate in resulting in the degradation of mechanical properties, such as hard-
harsh environments involving intense neutron irradiation, high ening, creep, volume swelling, etc. [4]. Therefore, a daunting and
important challenge in the development of advanced nuclear energy
systems is the exploration of advanced structural materials with
This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-
higher performance that can endure high dose neutron irradiation
00OR22725 with the U.S. Department of Energy. The United States Government retains
and the publisher, by accepting the article for publication, acknowledges that the under extreme environments [5,6].
United States Government retains a non-exclusive, paid-up, irrevocable, world-wide Recently, high-entropy alloys (HEAs) have attracted tremendous
license to publish or reproduce the published form of this manuscript, or allow others attention because of their unique compositions, microstructures and
to do so, for United States Government purposes. The Department of Energy will pro- favorable mechanical properties [7]. HEAs are generally defined as a
vide public access to these results of federally sponsored research in accordance with
multi-element solid solution composed of five or more principal ele-
the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).
* Corresponding author at: College of Materials Science and Engineering, Hunan ments in equimolar or near-equimolar ratios [8]. Due to the high con-
University, Changsha 410082, China. figurational entropy and/or other factors, the formation of
** Corresponding author at: Department of Nuclear Engineering, University of Ten- intermetallic phases may be restrained and HEAs tend to form simple
nessee, Knoxville, TN 37996, USA.
structures like FCC (face-centered cubic) and BCC (body-centered
E-mail addresses: tyang7@utk.edu (T. Yang), szinkle@utk.edu (S.J. Zinkle).

https://doi.org/10.1016/j.actamat.2020.01.060
1359-6454/© 2020 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
2 T. Yang et al. / Acta Materialia 188 (2020) 1
15

cubic) lattices. This suppresses some of the phase instability disad- atomic radius of Al. In the current study, the structural damage and
vantages of conventional multi-component concentrated alloys, and phase stability of initially single phase Al0.3CoCrFeNi irradiated with
therefore HEAs can exhibit many attractive mechanical properties, heavy ions to a peak dose of »31 dpa at elevated temperatures
such as excellent low temperature fracture-resistance [9,10], strong (250
650 °C) were studied. Al0.3CoCrFeNi was chosen because (i) it is
resistance to softening (high strength and low plasticity) at high tem- in the compositional boundary region between single phase and
peratures [11,12], high hardness [13], encouraging fatigue resistance multi-phase in the phase diagram, thereby serving as a good model
[14] and wear resistance [15]. Furthermore, HEAs encompass a large system to study the phase stability of HEAs under irradiation; (ii) it
family of alloys, and thus a wide range of microstructures and has very good mechanical properties [29
34], in particular good duc-
mechanical properties can be achieved by adjusting the compositions tility at room temperature and high strength at high temperatures
of HEAs, which substantially extends the potential applications of [35], which are important for applications in advanced nuclear
HEAs. energy systems. The irradiation effects were characterized by trans-
Due to their unique structures and excellent mechanical proper- mission electron microscopy (TEM) and atom probe tomography
ties, HEAs have been proposed as promising candidates for structural (APT), focusing on the evolution of irradiation-induced defects with
applications in advanced nuclear energy systems [6]. Many investiga- temperature and phase stability of Al0.3CoCrFeNi under high temper-
tions have studied the irradiation responses of HEAs [16]. Recent ature irradiations.
work has shown that the accumulation of irradiation-induced struc-
tural damage at room temperature can be suppressed with increasing 2. Experimental
principal elements [17]. Furthermore, Jin et al. [18] compared the vol-
ume swelling of Ni-containing equiatomic alloys under high temper- The Al0.3CoCrFeNi alloy was prepared by vacuum-levitation, melt-
ature ion irradiation (500 °C), and found that the volume swelling ing a mixture of pure metals Al, Co, Cr, Fe and Ni in a high-purity
can be decreased by controlling the number and the type of alloying argon atmosphere. The source materials had a purity level higher
elements. FeCoCrMnNi HEA showed the lowest volume swelling than 99.0 wt percent (wt.%). The ingots were remelted at least three
(<0.2%) after irradiation to »53 displacement per atom (dpa) at 500 ° times in order to promote chemical homogeneity. The as-fabricated
C, which was 30 times lower than Ni (»6.7%) [18]. These results are Al0.3CoCrFeNi samples were characterized by X-ray diffraction (XRD),
highly encouraging indications that HEAs may be good candidates for scanning electron microscopy (SEM) equipped with an electron back-
nuclear energy systems. Generally, the improved irradiation resis- scattered diffraction (EBSD) detector, APT and TEM.
tance of HEAs is attributed to the high-level lattice distortions and All samples were mechanically polished using fine metallographic
compositional complexities [17
20]. abrasive paper and diamond paste. The polished samples were irradi-
The defect behavior of as-irradiated HEAs has been investigated to ated with 3 MeV Au ions to a fluence of 6 £ 1015 cm
2 (»31 dpa at
unveil the fundamental controlling mechanisms on irradiation toler- damage peak) at four different temperatures: 250 °C, 350 °C, 500 °C
ance of HEAs. He et al. studied the defect structure of FeCoCrNi irradi- and 650 °C [36,37]. The corresponding defect production and stop-
ated with high energy electrons at 400 °C and found that irradiation- ping range in samples were calculated using SRIM 2013 assuming a
induced defects included elliptical Frank (faulted) loops and polygo- displacement threshold energy of 40 eV in the quick Kinchin-Pease
nal perfect loops [21,22]. Both dislocation loops were interstitial-type option [38]. The damage (dpa) and implanted ion concentration pro-
and the growth of dislocation loops in FeCoCrNi was 40 times slower files are shown in Fig. S1 in the Supplementary Information.
than that in pure Ni. Lu et al. compared the irradiation-induced Cross-sectional TEM samples were all prepared by mechanical
defects in NiFe, NiCoFe, NiCoFeCr and NiCoFeCrMn at 500 °C and also polishing, followed by ion milling to form a wedge with sufficient
observed faulted 1/3h111i loops and perfect 1/2h110i loops in the as- electron transparency. TEM observations were conducted using a
irradiated alloys [23]. The relative percentage of irradiation-induced 300 keV, Tecnai F30 microscope. The foil thickness was measured by
faulted loops was found to increase with the number of components, an electron energy loss spectroscopy (EELS) system equipped on the
which indicated the evolution and growth of dislocation loops could TEM. APT measurements were conducted using a local electrode
be suppressed by increasing the compositional complexity. Kiran atom probe (CAMECA LEAP 4000X HR) with a 50 pJ laser energy, a
Kumar et al. studied the microstructure of a Co-free HEA FeNiMnCr pulse repetition rate of 200 kHz, a 30 K base temperature, and a 0.5%
under high temperature ion irradiation and found that the FeNiMnCr detection rate. A dual beam FIB-SEM system (FEI Nova 200) was used
exhibited a smaller defect cluster size and higher cluster density, as to prepare the needle-shaped APT tips following procedures
compared with conventional ion-irradiated Fe
Cr
Ni alloys at described elsewhere [39,40]. A Ni film with thickness of »60 nm was
400
700 °C [24]. These experimental results suggest that the evolu- deposited on all samples using a South Bay Technologies Ion Beam
tion of irradiation-induced defects can be restrained and delayed by Deposition system (IBSe) to protect the surface before sample prepa-
increasing the number of components (compositional complexity) in ration.
concentrated solid solution alloys, resulting in the good irradiation
tolerance of HEAs. 3. Results
Although the irradiation responses and defect behavior of HEAs
have been preliminarily studied, most investigations were focused 3.1. Microstructure of as-fabricated Al0.3CoCrFeNi sample
on several model HEAs and single-phase concentrated solid-solution
alloy (SP-CSA) systems, such as FeCoCrMnNi, FeCoCrNi, NiCoCr, etc., Fig. 1(a) shows the representative EBSD image of an as-fabricated
to explore the fundamental mechanisms influencing the defect Al0.3CoCrFeNi sample. Several large grains (with some embedded
behavior and irradiation tolerance of HEAs. The irradiation responses twins) are visible with grain sizes ranging from hundreds of mm to a
of many newly emerging HEAs with attractive mechanical properties millimeter. All the diffraction peaks in the XRD spectrum of the as-
have not yet been studied. Moreover, many previous studies were fabricated alloy (as shown in Fig. 1(b)) can be indexed as a FCC crystal

focused on the effects of compositional complexity on the defect structure with a lattice constant of 3.585 A. Bright field (BF) TEM
behavior of HEAs at a single irradiation temperature; only a limited imaging and corresponding selected area electron diffraction (SAED)
number of investigations have examined effects of temperature on analysis (as shown in Fig. 1(c) and 1(d)) confirmed the as-fabricated
irradiation-induced defects. Al0.3CoCrFeNi to be single FCC phase with a large grain size, and no
AlxCoCrFeNi is a well-studied HEA system [25
29]; the micro- observable precipitates.
structure and mechanical properties of AlxCoCrFeNi can be signifi- The composition and elemental solute spatial distributions in the
cantly modified by varying the Al concentration due to the large as-fabricated sample were characterized by APT, as shown in Fig. 2.
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 3

Fig. 1. Microstructure of as-fabricated Al0.3CoCrFeNi sample; (a) EBSD image; (b) XRD pattern; (c) BF TEM image; and (d) selected area electron diffraction pattern (SAED) taken
from the [100] direction.

The measured composition (at.%) was Al: »7.0; Co: »22.4; Cr: »22.5; and b)). This intersection angle and orientation with respect to the
Fe: »23.3; Ni: »24.3, and the elemental distributions homogeneity crystal direction are consistent with {111} habit planes. The average
was tested using a frequency distribution analysis (FDA). A FDA was sizes of dislocation loops in the samples irradiated at 250 °C and
performed on a 15 nm £ 15 nm £ 15 nm volume away from poles in 350 °C are similar, with diameters of 12.8 nm and 14.1 nm, respec-
the atom probe dataset (as shown in Fig. 2(b
e)), which found no tively (as shown in Fig. 5(a)), and the corresponding loop densities
evidence of possible local chemical ordering for Al, Fe, Co and Cr; are 1.8 £ 1022 m
3 and 1.6 £ 1022 m
3, respectively (as shown in
however, Ni showed a slightly heterogeneous behavior. Ni clustering Fig. 5(b)). Besides the dislocation loops, some small defect clusters
or precipitation was unable to be visually distinguished in the atom and small dislocation segments were also observed in the highly
maps or with isoconcentration surfaces, but there was some hetero- damaged region and near surface region, respectively. Most of these
geneity associated with the poles. small defect clusters appeared as black dots smaller than »5 nm.
Based on previous results of irradiation-induced structural damage in
3.2. TEM results of Al0.3CoCrFeNi irradiated at elevated temperatures SP-CSAs [17,41,42] and high magnification observations reported
later in this paper, these defects are predominantly small stacking-
Fig. 3 shows the BF TEM cross section images of Al0.3CoCrFeNi irra- fault tetrahedra (SFTs).
diated at four different temperatures, with the original surface As the irradiation temperature increased to 500 °C (as shown in
located at the top of each image. All BF images in Fig. 3 were taken Fig. 3(c)), the highly damaged region disappeared. Instead, a moder-
under two-beam BF conditions using a diffraction vector g = (022) ate density of large and isolated defect clusters was observed in this
near the [211] zone axis. The irradiation-induced structural damage region. The average size of dislocation loops increased to 32.7 nm
and its evolution with temperature can be clearly observed. At lower (as shown in Fig. 5(a)), while the loop density decreased to
temperatures (250 °C and 350 °C), a highly damaged region contain- 3.0 £ 1021 m
3 (as shown in Fig. 5(b)).
ing a high density of small defect clusters was present over the depth Weak beam dark field (WBDF) imaging and the “g ¢ b” method
range of 300
700 nm (as shown in Fig. 3(a and b)). Detailed charac- were employed to obtain a more detailed characterization of the dis-
terization using a diffraction vector g = (002) near the [110] zone axis location loops in the 500 °C irradiated sample. Figs. 6 and 7 exhibit
revealed two groups of edge-on dislocation loops with an intersec- the WBDF images of nearly edge-on (Fig. 6) and nearly face-on dislo-
tion angle of 71° in the highly damaged region (as shown in Fig. 4(a cation loops (Fig. 7), which were taken with g = (002) and g = (002)
4 T. Yang et al. / Acta Materialia 188 (2020) 1
15

Fig. 2. (a) The atom maps of Al, Fe, Co, Cr, Ni for as-fabricated Al0.3CoCrFeNi sample; (b)
(f) the frequency distribution analyses of the atom probe dataset.

near the [110] zone axis, respectively. The fringes inside the loop observed in the near surface region (0
400 nm, as shown in
periphery, which are characteristic of faulted dislocation loops for Fig. 9); the corresponding density and percentage of perfect loops
this diffraction vector, can be clearly observed, demonstrating that is »1.5 £ 1021 m
3 and »50% over the entire irradiated region. Lu
many of these defects are faulted loops. The “g ¢ b” analysis revealed et al. [23] studied the fraction of faulted loops in ion irradiated
(as shown in Fig. S2 in Supplementary Information) the Burgers vec- NiFe, NiCoFe, NiCoFeCr and NiCoFeCrMn (3 MeV Ni, 5 £ 1016 cm
2,
tors of the five nearly face-on dislocation loops visible in Fig. 7 were 500 °C), and found the fraction of faulted loops in NiCoFeCr and
b = §1/3 [111]. Based on characterization results of WBDF imaging NiCoFeCrMn were »65% and »50%, which are basically consistent
and dislocation loop observation of ion-irradiated FCC alloys [23,43], with current study if different irradiation ions and fluences are
these defects, including nearly edge-on and face-on dislocation loops, considered. It should be noted that the observed depth range of
were determined to be faulted 1/3h111i edge-type dislocation loops irradiation-induced structural damage at 250
500 °C (»700 nm)
lying on {111} habit planes. The edge-on dislocation loops were exceeded the depth range predicted by SRIM (»500 nm, Fig. S1 in
located on (111) and (111) planes, indicated by red arrows and blue the Supplementary Information). A similar observation of dis-
arrows in Fig. 6(a and b), respectively; while the face-on dislocation placement damage beyond the SRIM predicted damage depths has
loops were located on (111) plane. The relative orientations of elec- been reported in other ion-irradiated materials, such as Ni, NiFe
tron beam, g vectors and habit planes of faulted loops are illustrated and NiCo, and has been attributed to mobile defect diffusion
in Figs. 6(c and d) and 7(c), respectively. beyond the irradiated region [20].
Based on the conventional inside-outside method using §g (as At the highest irradiation temperature of 650 °C, BF imaging (as
shown in Figs. 6 and 7), it was found that the faulted dislocation loops shown in Fig. 3(d)) shows a dramatic decrease in the defect cluster
in the 500 °C irradiated specimen were all interstitial-type. Since density; only long dislocation lines and networks were observed. No
the defect distribution and morphologies are qualitatively similar for faulted loops could be found in the TEM image using a diffraction vec-
the lower irradiation temperatures, it is reasonable to believe tor g = (002) near the [110] zone axis (as shown in Fig. 4(d)), which
that the dislocation loops formed at 250 °C and 350 °C are also suggests that the dislocation loops have grown and intersected each
interstitial-type 1/3h111i faulted loops. other to produce a network dislocation structure, as is commonly
Near the peak damage region (400
700 nm) of the 500 °C irra- observed in conventional FCC materials at elevated irradiation tem-
diated specimen, most of irradiation-induced defects are faulted peratures [43
45]. From similar irradiation studies on other FCC
1/3 h111i loops, as shown in Fig. 4(c), and Fig. S3
S4 in Supple- materials, the small vacancy-type defect clusters were expected to
mentary Information. Some triangle-shaped SFTs were also become thermally unstable at high temperatures such 650 °C and
observed in this region, as shown in the inset of Fig. 4(c) and might dissociate or transform to other defects. As compared to lower
Fig. 8. Numerous dislocation segments and perfect loops were temperatures (250
500 °C), the 650 °C damaged region containing
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 5

Fig. 3. BF images of Al0.3CoCrFeNi irradiated with 3 MeV Au ions to 6 £ 1015 cm
2 at (a) 250 °C; (b) 350 °C; (c) 500 °C; and (d) 650 °C, respectively. Note that the depth range of (d) is
larger than that of others. All BF images were taken under two-beam BF conditions using a diffraction vector g = (022) near the [211] zone axis.

long dislocation segments extended toward deeper regions as far as regions for Al0.3CoCrFeNi irradiated at 250
650 °C. It can be seen that
»1 mm from the surface. the Al0.3CoCrFeNi FCC solid solution phase was stable for tempera-
tures below 500 °C in both irradiated and unirradiated regions. Only
3.3. Phase stability of Al0.3CoCrFeNi irradiated at elevated temperatures diffraction spots belonging to the FCC phase were observed in both
the irradiated region and unirradiated region (Fig. 10(a and b) and (e
The as-fabricated alloy consists of a homogeneous elemental dis- and f)), and no precipitates were observable in the HRTEM images (as
tribution as shown by the TEM and APT results in Figs. 1 and 2. To shown in Fig. 11(a and b) and (e and f)).
study the phase stability of Al0.3CoCrFeNi under high temperature However, the unirradiated region and irradiated region exhibited
ion irradiations, including the possible compositional fluctuation, opposite precipitation behavior at 500 °C and 650 °C. Coherent super-
precipitation, decomposition and phase transformation, the micro- lattice diffractions spots associated with the L12 precipitate structure
structures of the irradiated region were characterized by APT and were present in the SAED patterns of the unirradiated region at 500 °C,
TEM. The underlying unirradiated region (which experienced the as shown in Fig. 10(c). The FFT of the HRTEM image also confirmed the
same heating process as the irradiated regions without any irradia- formation of coherent L12 precipitates in the unirradiated region (as
tion), was also characterized to clarify the effects of thermal anneal- shown in the inset of Fig. 11(c)), and the inverse FFT image (Fig. 12(a))
ing at various temperatures. revealed the average size of the L12 precipitates to be about 2
5 nm.
Figs. 10 and 11 show the SAED patterns and high-resolution TEM When the irradiation temperature was further increased to 650 °C, the
(HRTEM) images combined with the Fast Fourier Transformation superlattice spots of L12 became nearly invisible in the SAED pattern
(FFT) images, respectively, of the unirradiated region and irradiated of the unirradiated region, indicating the L12 structure was thermally
6 T. Yang et al. / Acta Materialia 188 (2020) 1
15

Fig. 4. BF TEM images taken with a diffraction vector g = (002) near the [110] zone axis showing the defect structures of Al0.3CoCrFeNi irradiated at (a) 250 °C; (b) 350 °C; (c) 500 °C
and (d) 650 °C. Edge-on dislocation loops on {111} habit planes can be observed at 250 °C, 350 °C and 500 °C. The inset of (c) shows a typical stacking-fault tetrahedron (indicated
by the red circle). Note that the scale bars are different due to the different defect sizes. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

unstable at 650 °C. In contrast to the unirradiated region, the SAED pat- enhanced or -induced precipitation in Al0.3CoCrFeNi at 500 °C. Con-
terns and HRTEM images show that the irradiated region maintained versely, weak but distinct superlattice diffraction spots of B2 structure
the single FCC phase with no evidence of precipitates for an irradiation were observed in the SAED pattern of the irradiated region at 650 °C,
temperature of 500 °C (as shown in Figs. 10(g) and 11(g)). This indi- as shown in Fig. 10(h). The FFT of the HRTEM image also confirmed
cates that irradiation with 3 MeV Au ions can suppress the thermally- the formation of B2 structure precipitates (as shown in the inset of

Fig. 5. (a) Average size and (b) density of dislocation loops for Al0.3CoCrFeNi irradiated at different temperatures.
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 7

Fig. 8. (a) (g, 3 g) WBDF TEM image with g = § [002] near [110] zone axis and (b) high
resolution TEM image of Al0.3CoCrFeNi irradiated with 3 MeV Au ions at 500 °C. Several
defects with the characteristic triangle shape of SFTs are indicated by red circles in (a)
and (b). (For interpretation of the references to colour in this figure legend, the reader
is referred to the web version of this article.)

Ni and Al in the precipitates increased from »41 at.% and »10 at.%
to »55 at.% and »25 at.%, respectively, when the temperature
increased from 250 °C to 500 °C. Note that the precipitates for the
500 °C sample were larger than those in the 250 °C sample. Local
magnification effects during an APT experiment, due to differences
in evaporation fields between the precipitates and matrix causes
ion mixing at the precipitate/matrix interfaces. This effect will cause
the precipitate and matrix compositions to mix for smaller precipi-
tates, with the severity of mixing dependent on the precipitate size.
Therefore, the real difference of precipitate compositions between
different temperatures may be smaller than the measured results.
Fig. 6. (a) and (b) exhibit the (g, 3 g) WBDF images of four representative dislocation
Compared to unirradiated regions, the irradiated regions have a
loops on (111) and (111) planes, respectively, which were taken with (a) g = (002) and
(b) g = (002) near [110] zone axis; (c) and (d) illustrate the orientations of dislocation much lower concentration of detectable precipitation for irradiation
loops and directions of g vectors and electron beam, respectively. temperatures of 250
500 °C. Only a few nano precipitates enriched
with Ni and Al were observed in the Al0.3CoCrFeNi irradiated at 350 °
Fig. 11(h)), and the inverse FFT image in Fig. 12(b) revealed the average C and 500 °C. This is consistent with the TEM results (Figs. 10 and 11)
size of the B2 precipitates was 6
10 nm, which was larger than that of that ion irradiation can suppress the precipitation in Al0.3CoCrFeNi
the L12 precipitates formed in the unirradiated region at 500 °C. for temperatures below 650 °C. In contrast, several larger precipitates
Since Ni and Al can form several intermetallic compounds with enriched with Ni and Al were present in the irradiated region at 650 °
L12 and B2 structures, it was expected that these precipitates might C, while the unirradiated region was nearly precipitate-free (as
be enriched with Ni and Al. Fig. 13 shows APT reconstructions with shown in Fig. 13(d)). The concentrations of Ni and Al solute in
Au ions (yellow) and 29 at.% Ni isoconcentration surfaces (green sur- detected precipitates were highest (»60 at.% and »28 at.%, respec-
faces) of Al0.3CoCrFeNi irradiated at different temperatures. The APT tively) for the 650 °C irradiated specimen.
results revealed that a large number of nano precipitates were APT results confirmed the contrasting precipitation behavior of
homogeneously present in the unirradiated regions (> 500 nm the unirradiated and ion-irradiated regions of Al0.3CoCrFeNi for the
depth) and the precipitate density and size were obviously four different irradiation temperatures. Furthermore, irradiation-
increased with increasing irradiation temperature from 250 °C to induced segregation at defects was not observed in the irradiated
500 °C. Conversely, Ni-rich precipitates were not observed in the Al0.3CoCrFeNi at any temperature, which is different from the irradia-
unirradiated regions at 650 °C. The proximity histograms of concen- tion responses of Al0.1CoCrFeNi at elevated temperatures [46]. It
tration profiles from the matrix to the precipitates are given in should be noted that a few Ni-enriched precipitates were observed
Fig. 14. These histograms confirmed that the precipitates were by APT in the unirradiated regions of Al0.3CoCrFeNi irradiated at 250 °
enriched with Ni, Al and depleted in Fe, Co, Cr. The compositional C and 350 °C; however, these small precipitates were not detected by
segregation increased with temperature, and the concentrations of TEM characterization. This was probably attributed to the low density

Fig. 7. (g, 3 g) WBDF images of five nearly face-on dislocation loops on the (111) plane, which were taken with (a) g = (002) and (b) g = (002) near [110] zone axis; (c) exhibits the
orientations of dislocation loops and directions of g vectors and electron beam, respectively.
8 T. Yang et al. / Acta Materialia 188 (2020) 1
15

temperature generally can be divided into five stages according to the

defect behavior [43,47,48]. In recovery stage I, only interstitials are
capable of long range migration. With increasing temperature, small
interstitial clusters and interstitial-impurity complexes start to migrate,
corresponding to stage II. In stage III, vacancy motion initiates. Stage IV
and V correspond to the migration of vacancy clusters (including
vacancy-impurity clusters) and thermal dissociation of sessile vacancy
clusters, respectively [43]. When temperature is lower than stage I,
defect migration does not occur and the accumulation of irradiation-
induced structural damage is typically proportional to the dose until
saturation [49]. When the temperature is higher than stage V, irradia-
tion-induced defects typically consists of dislocation loops, network
dislocations and voids. SFTs are not stable in this temperature range.
Al0.3CoCrFeNi showed a typical temperature-dependent evolution
of irradiation-induced defects for FCC metals. As irradiation tempera-
ture increased, the defect size increased while the defect density
decreased due to the increasing defect mobility and dissociation of
small defect clusters. The loop growth and interaction between indi-
vidual dislocations and loops resulted in the loop unfaulting and for-
mation of perfect 1/2 h110i loops at 500 °C and the dislocation
networks at 650 °C. Similar temperature-dependent effects on the irra-
diation-induced defects have been observed in many conventional FCC
alloys [44
46,48,50
53]. Based on the observed effects of tempera-
Fig. 9. (g, 3 g) WBDF TEM images of Al0.3CoCrFeNi irradiated with 3 MeV Au ions at ture on the irradiated microstructure, the four temperatures in the cur-
500 °C. Both images were taken with g = § [002] near a [110] zone axis. Several nearly rent study correspond to near or above defect recovery stage III (onset
edge-on faulted loops and nearly face-on faulted loops in (a) are indicated by red
of vacancy migration) to above stage V (thermal dissolution of SFTs
arrows and blue arrows, respectively; the perfect loops are marked by white rectangles
and the direction toward surface is also indicated. (b) shows several large perfect loops and other small vacancy clusters) for Al0.3CoCrFeNi [54].
(outlined by white rectangles) in the near surface region. (For interpretation of the At 250 °C and 350 °C, numerous interstitial-type dislocation loops
references to colour in this figure legend, the reader is referred to the web version of can be found up to »200 nm beyond the damaged region calculated
this article.) by SRIM, which demonstrates that the interstitial-type defects are
mobile and can diffuse beyond the irradiation region. On the other
and small size of the precipitates. These precipitates were probably in hand, visible vacancy-type defect clusters only include very tiny SFTs.
the incubation period due to the low temperature, and therefore the This suggests that both the temperatures 250 °C and 350 °C lie within
L12 structure was not completely formed. defect recovery Stage III to IV for Al0.3CoCrFeNi, wherein interstitials
and interstitial-type defect clusters have sufficient mobility to
4. Discussion migrate and form dislocation loops whereas the irradiation-induced
vacancies are predominantly tied up in sessile SFT vacancy clusters
4.1. Irradiation-induced defect evolution at elevated temperatures that are thermally stable [54]. Similar to prior work on conventional
FCC metals [43], recent MD simulations and Cs-corrected STEM indi-
Temperature plays an important role in the irradiation-induced cate that SFTs with sizes of several nm can directly form by the aggre-
structural damage, and the microstructural evolution with irradiation gation of vacancies during the picosecond-scale formation and

Fig. 10. SAED patterns of (a)
(d) unirradiated region and (e)
(h) irradiated region of Al0.3CoCrFeNi at different temperatures. The corresponding irradiation temperatures are 250 °
C (a and e), 350 °C (b and f), 500 °C (c and g), 650 °C (d and h), respectively.
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 9

Fig. 11. HRTEM images and corresponding FFTs of (a)
(d) unirradiated region and (e)
(h) irradiated region of Al0.3CoCrFeNi at different temperatures. The corresponding irradia-
tion temperatures are 250 °C (a and e), 350 °C (b and f), 500 °C (c and g), 650 °C (d and h), respectively. The superlattice reflections belonging to L12 and B2 in (c) and (h) are marked
by red circles in the inset diffraction patterns. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

quenching of displacement cascades in SP-CSAs [19,20,55]. Therefore, larger SFTs. This suggests that 500 °C approximately corresponds to
most of vacancy-type defects are tiny vacancy clusters and SFTs in recovery stage IV, where the mobility of interstitial clusters is further
this temperature regime, and most of the interstitial-type defects are enhanced and vacancies are highly mobile [43]. In this stage, most of
larger faulted 1/3h111i dislocation loops on {111} habit planes. vacancies are still tied up in the SFTs formed in the displacement cas-
As the irradiation temperature increased to 500 °C, observed irra- cades. Considering the possibility of moderate coarsening of the SFT
diation-induced defects became more diverse, including the faulted population during extended irradiation, larger SFTs can be observed
1/3h111i loops, perfect 1/2h110i loops, dislocation segments and compared to the lower irradiation temperatures. Faulted 1/3h111i

Fig. 12. Inverse FFT images of (a) the unirradiated region of Al0.3CoCrFeNi at 500 °C and (b) irradiated region of Al0.3CoCrFeNi at 650 °C. The FFT images were acquired by masking (a)
the (010) and (011) reflections of L12 structure and (b) (011) reflections of B2 structure, respectively. Several precipitates with ordered structure are indicated by blue circles. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
10 T. Yang et al. / Acta Materialia 188 (2020) 1
15

Fig. 13. 29 at.% Ni isoconcentration surfaces of Al0.3CoCrFeNi irradiated at (a) 250 °C, (b) 350 °C, (c) 500 °C and (d) 650 °C. The deposited Au ions are indicated by yellow color. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

loops are nucleated at a lower density and thereby become relatively with increasing compositional complexity/number of constituent ele-
larger compared to lower temperature irradiation by absorbing irra- ments. MD simulations also found that smaller-sized and higher
diation-produced interstitials. Some loops can unfault according to number densities of clusters were formed with increasing composi-
the well-known reaction in FCC metals (Eq. (1)), resulting in the for- tional complexity [19,41], consistent with TEM and Rutherford back-
mation of perfect 1/2 h110i loops. scattering and channeling (RBS/C) results. These evolutions of defect
density and morphology with decreasing compositional complexity
1=3 h 111 i þ 1=6 h 112 i ¼ 1=2 h 110 i ð1Þ
are qualitatively similar to the evolution of defects in Al0.3CoCrFeNi
At 650 °C, only long dislocation segments and dislocation net- with increasing irradiation temperature in the current study (as
works were present, indicating the vacancy-type SFTs were thermally shown in Fig. 15). The evolution of the defect microstructure in
unstable at this temperature and that the perfect interstitial-type dis- Al0.3CoCrFeNi with increasing irradiation temperature can be attrib-
location loops have grown and interacted to produce a dislocation uted to increased defect mobility, along the reduced thermal stability
network, as is commonly observed in conventional FCC alloys [44]. of vacancy clusters. The corresponding mechanisms of the effects of
This corresponds to temperatures above recovery stage V, where the compositional complexity on irradiated microstructure evolution in
irradiation-induced defects generally only include network disloca- SP-CSAs have similarly been attributed to the modulation of defect
tions, cavities and a few dislocation loops. Thermal dissociation of migration, which can significantly delay or reduce the formation of
small defect clusters causes the defect density to be significantly large dislocation loops and voids [23,56].
decreased while the defect mobility is greatly enhanced. The mobile Furthermore, Zaddach et al. studied and compared the stacking
defects can migrate a long distance before being absorbed by other fault energies of Ni, FeNi, FeCrNi, FeCoCrNi and FeCoCrMnNi and
defect clusters. Therefore, the depth region of irradiation-induced found that stacking fault energies decrease with the number of com-
defects was dramatically increased compared with that at lower tem- ponents [57]. This suggests a low stacking fault energy may occur in
peratures. at least some HEAs, which has been also pointed out by many other
It is very interesting to note that Lu et al. [23] compared the struc- studies [58
60]. The energetics analysis of interstitial loops in HEAs
tural defects in various Ni-based SP-CSAs irradiated at 500 °C and was also carried out by Wang et al. [61]. They also found that the
found that the defect size decreased and the defect density increased stacking fault energy decreases with increasing compositional
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 11

Fig. 14. Proximity histograms showing the spatial variations in composition from matrix into precipitates for Al0.3CoCrFeNi irradiated at (a) 250 °C, (b) 350 °C, (c) 500 °C and (d)
650 °C.

complexity and the low stacking fault energy provides the energetic changing the compositional complexity of SP-CSAs and HEAs in order
driving force for the formation of faulted loops in HEAs [61]. There- to avoid the serious hardening or volume swelling for a certain irradi-
fore the low stacking fault energy stabilizes the faulted dislocation ation temperature, this will greatly enhance the flexibility of SP-CSAs
loops and restrains the transformation from faulted loops to perfect and HEAs for use in advanced nuclear energy systems.
loops. This is consistent with our experiment results (Al0.3CoCrFeNi Furthermore, a recent study has reported that the stacking fault
exhibited a similar but much slower defect evolution with tempera- energy of AlxCoCrFeNi is increased with increasing Al concentration
ture, as compared with conventional FCC alloys) and other studies, [63]. Because the evolution of irradiation-induced defects is related
such as Lu et al. [23], in which they found that a higher fraction of to stacking fault energy, the properties of irradiation-induced defects
faulted loops exists in the more compositionally complex alloys, at different temperatures and the microstructural evolution of Alx-
which indicate that increasing compositional complexity can extend CoCrFeNi can potentially be tailored by changing the Al content. This
the incubation period and delay loop growth. Therefore, the composi- provides a strategy to modify the irradiation responses of AlxCoCr-
tional complexity may also restrain the transformation from faulted FeNi, which can promote the application of AlxCoCrFeNi in advanced
loops to perfect loops and slow the defect evolution due to a reduc- nuclear energy systems. However, further investigation is required to
tion in stacking fault energy. further clarify the effects of Al.
Based on the qualitatively similar evolution of irradiation-induced It should be noted that no voids were observed in the Al0.3CoCr-
defects with temperature and with compositional complexity, an FeNi irradiated with 3 MeV Au ions at four different temperatures
intriguing possibility is that the compositional complexity of multi- ranging from 250 °C to 650 °C. However, voids were observed in
component miscible alloy systems can be adjusted to make them many other ion irradiated HEAs and SP-CSAs (500 °C, 3 MeV/1.5 MeV
favorable for operation in a certain irradiation temperature (tailored Ni), including FeCoCrMnNi, FeCoCrNi, etc. [18,56]. The different
irradiation microstructure). Since the defect mobility is low at low response to void swelling might be attributed to the effects of depos-
temperature, irradiation can produce pronounced hardening due to ited ions. It has been pointed out that implanted ions can suppress
the formation of a high density of small defect clusters, which serve the formation of voids in numerous metals [64
67]. The maximum
as obstacles to dislocation motion. In contrast, irradiation induced depth range of irradiation-induced structural damage of 3 MeV Au
volume swelling and precipitation/segregation will become signifi- ions was predicted by SRIM calculation to be »500 nm, while the Au
cant at higher temperature due to the high defect mobility induced- concentration peak of »0.4 at.% occurred at »300 nm with a FWHM
agglomeration of vacancies and solutes [4]. Nuclear materials are of »200 nm (as shown in Fig. S1 in the Supplementary Information).
generally used in a temperature window range in which degradation Therefore the implanted ion effects on void swelling suppression
of mechanical properties induced by various deleterious effects is were expected to be significant for 3 MeV Au ions. In contrast, the
acceptable [62]. Therefore, if we can control the defect mobility by damage depths of 3 MeV and 1.5 MeV Ni ions were larger, which
12 T. Yang et al. / Acta Materialia 188 (2020) 1
15

Fig. 15. The evolution of irradiation-induced defects with compositional complexity (Ni-based SP-CSAs, 3 MeV Ni, 500 °C) [23] and temperature (Al0.3CoCrFeNi, 3 MeV Au,
250
650 °C), which are outlined by a dashed blue rectangle and red rectangle, respectively. The blue arrow indicates that the defect mobility is increased with increasing tempera-
ture and decreasing compositional complexity. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

could reach »2 mm and »1.2 mm, respectively. Thus there was a Gwalani et al. studied the phase stability of Al0.3CoCrFeNi and
wider safe analysis region [58] for 3 MeV and 1.5 MeV Ni ions, where found the formation of (Ni, Al) enriched L12 precipitates after
artifacts associated with effects of the surface and implanted ions annealing at 550 °C for 150 h [69]. The L12 precipitates were unsta-
were less pronounced. Follow-on ion irradiation studies of the cur- ble and replaced by lath-like B2 precipitates after annealing at 700 °
rent Al0.3CoCrFeNi HEA using higher energy and/or lower mass bom- C for 50 h and the average size of B2 precipitates (longitudinal axis
barding ions would be useful to confirm the void swelling resistance » 175 nm) was much larger than that of L12 precipitates (»5 nm)
observed in the current investigation. [69]. These prior results on high temperature annealing of Al0.3CoCr-
FeNi [69] are essentially consistent with the structural evolution of
the unirradiated regions at different temperatures in the current
4.2. Phase stability of Al0.3CoCrFeNi irradiated at elevated temperatures study. Numerous small L12 precipitates enriched with Ni and Al
were observed in the unirradiated region at 500 °C. When the tem-
In our previous work, we studied the phase stabilities of Al-con- perature increased to 650 °C, the small L12 precipitates became
taining HEAs with a stable single phase microstructure (Al0.1CoCrFeNi) unstable and thus the structure nearly became a homogeneous solid
and multi-phase microstructure (Al0.75CoCrFeNi and Al1.5CoCrFeNi) solution again. However, no B2 precipitate was found in unirradi-
and found that the HEA with a stable single phase microstructure ated region at 650 °C, which might be a result of the lower tempera-
(Al0.1CoCrFeNi) still retained a homogeneous solid solution structure ture (650 °C vs 700 °C) and shorter heating time (»3.5 h vs 50 h) in
under irradiation from room temperature to 650 °C [46], but irradia- the current study compared to ref. [69]. B2 precipitates were gener-
tion resulted in the further phase separation for initially multi-phase ally formed in Al0.3CoCrFeNi at longer annealing times or/and higher
HEAs even at room temperature [68]. In this work, the phase stability annealing temperatures [70,71].
of Al0.3CoCrFeNi under irradiation was different from stable single Our TEM and APT results revealed that the effects of 3 MeV Au ion
phase HEA and multi-phase HEAs, which was found to depend on tem- irradiation on the precipitation behavior of Al0.3CoCrFeNi varied with
perature (as shown in Fig. 10). The ion irradiated damage and unirradi- increasing temperature. At 500 °C, the irradiation suppressed precipi-
ated regions also showed opposite precipitation behaviors that tation of the L12 ordered phase. In contrast, precipitation of the B2
changed with increasing irradiation temperature (as shown in Fig. 13). ordered phase was enhanced by irradiation when the temperature
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 13

was increased to 650 °C. It should be noted that the precipitation sup- Second, the L12 precipitates in the unirradiated region showed a
pression effects of irradiation were also observed at 250 °C and 350 °C homogeneous distribution. In contrast, the B2 precipitates in the
(as shown in Fig. 13(a and b)) although only segregation of Ni and Al irradiated region at 650 °C exhibited a heterogeneous distribution.
occurred and the ordered L12 precipitate phase was not fully formed The 29 at.% Ni isoconcentration surfaces (green surfaces) of
in the unirradiated regions at either temperature. Al0.3CoCrFeNi irradiated at 650 °C were carefully checked in differ-
The phase stability of metastable alloys under ion irradiation has ent directions, as shown in Fig. S5 in the Supplementary Informa-
been widely studied by theoretical and experimental methods, espe- tion. Combined with the defect morphology revealed by TEM
cially for immiscible binary alloys [72
80]. Generally, the microstruc- characterization, we speculate the B2 precipitates produced in the
tural evolution depends on the relative importance of two competing 650 °C irradiated region were preferentially formed at dislocation
dynamical interactions [73]. First, energetic irradiation-induced dis- lines. Three groups of precipitates which might be located at differ-
placement cascades can induce atomic mixing, resulting in ballistic ent dislocation lines were identified in Fig. S5 in the Supplementary
dissolution of precipitates and the formation of homogeneous solid Information. The dislocation lines became nucleation centers, facili-
solution structures. On the other hand, irradiation-enhanced and tating the formation of B2 precipitates. In contrast, very few disloca-
thermally driven atomic diffusion tends to enhance the nucleation tions were present in the unirradiated region so heterogeneous
and growth of precipitates if the thermodynamic equilibrium state is nucleation of the B2 phase at 650 °C was suppressed. Moreover the
a two-phase or multi-phase regime, resulting in the enhanced forma- atomic diffusion along dislocation lines was enhanced [87
89],
tion of precipitates in the system. The observed phase stability which could also facilitate the precipitation.
depends on various factors, including dose rate [75], cascade size,
temperature [72], thermodynamic property of alloy system [81],
compositional effects [75] and possible coupled solute-defect irradia- 5. Conclusions
tion induced solute segregation phenomena. Three different steady-
state microstructures can be formed [73], including homogeneous This work studied the irradiation responses of Al0.3CoCrFeNi at
solid solution, compositional patterning and macroscopic phase sepa- elevated temperatures, focusing on the irradiation-induced defects
ration, which correspond to an irradiation-induced mixing-dominant and phase stability. The average size of defect clusters increased
system, comparable influences of mixing and diffusion, and thermo- while the density decreased with increasing irradiation temperature,
dynamic diffusion-dominant system, respectively. and the irradiation-induced dislocation loops transformed from pre-
It can be expected that the irradiation-induced mixing is dominant dominantly faulted 1/3h111i dislocation loops at 250 °C and 350 °C to
in the low temperature region because the thermally driven-atomic dif- a mixture of faulted 1/3h111i dislocation loops and perfect loops at
fusion is restrained. Therefore, it is assumed that the irradiation-induced 500 °C. At the highest irradiation temperature of 650 °C, the stable
mixing was dominant for Al0.3CoCrFeNi irradiated with 3 MeV Au ions defects only include long dislocation segments and network disloca-
when the temperature was less than or equal to 500 °C, resulting in a tions. The evolution of irradiation-induced defects with temperature
homogeneous supersaturated solid solution structure in the irradiated is similar with many other conventional FCC alloys and can be inter-
region. It should be noted that although the defect distributions preted by the effects of temperature on the mobilities and thermal
extended to a depth of 700 nm due to defect diffusion, the observed stability of interstitials and vacancies and their clusters.
depth range of the solid solution microstructure was only 500 nm, Irradiation by 3 MeV Au ions produced competing effects (due to
which is consistent with the displacement cascade damaged region cal- ballistic mixing and irradiation-enhanced diffusion) on the phase sta-
culated by SRIM (as shown in Fig. S1 in the Supplementary Informa- bility at different temperatures. At low temperatures (500 °C), irra-
tion). This indicates that the precipitation was suppressed by the diation suppressed the precipitation of L12 phases due to the
irradiation induced displacement cascades, instead of subsequent dominant effect of irradiation-induced ballistic mixing at low tem-
migrating defects. Compared with other binary and ternary FCC alloys peratures. In contrast, irradiation enhanced the precipitation of B2
[82,83], the temperature range for a pronounced suppression effect of phases at 650 °C due to the irradiation-enhanced diffusion effects at
irradiation in Al0.3CoCrFeNi is dominant is very high (> 500 °C), which elevated temperatures. The precipitation of B2 phases was facilitated
may be caused by the large displacement cascade size of 3 MeV Au by RED and irradiation-induced dislocations, which increased the
ions and/or sluggish atom diffusion of HEAs [84]. atom mobility and served as nucleation centers for the precipitates,
When the irradiation temperature increased to 650 °C, the irradia- respectively.
tion by 3 MeV Au ions enhanced the formation and growth of B2 pre-
cipitates in the ion irradiated region. Two different mechanisms are Declaration of competing interest
proposed to interpret the precipitation enhancement induced by irra-
diation of 3 MeV Au ions at 650 °C. The authors declare that they have no known competing financial
First, the precipitation enhancement of Al0.3CoCrFeNi at 650 °C interests or personal relationships that could have appeared to influ-
was possibly induced by radiation enhanced diffusion (RED) [85]. A ence the work reported in this paper.
similar effect has been reported in the neutron irradiation embrittle-
ment of reactor pressure vessel (RPV) steel, which is mainly attrib-
uted to the irradiation-enhanced precipitation of solutes (Cu, Mn, Ni, Acknowledgements
Si, P) [86], as well as for numerous other alloy systems. In the current
study, it is assumed that the effect of irradiation-induced mixing was This work was financially supported in part by the Office of Fusion
less pronounced at 650 °C due to the high thermally driven atomic Energy, US Department of Energy (grant # DE-SC0006661 with the
diffusion and thermodynamic effects dominated the microstructural University of Tennessee), the National Magnetic Confinement Fusion
evolution of the system. Tang et al. [71] compared the annealing- Energy Research Project 2015GB113000 and the National Natural Sci-
induced phase transformation in nanocrystalline and coarse-grained ence Foundation of China (11905057, 11935004). YZ very much
Al0.3CoCrFeNi HEA and found that the B2 phase was formed in nano- appreciates the financial support from the National Natural Science
crystalline Al0.3CoCrFeNi HEA at a lower temperature, which was Foundation of China (Nos. 51671020), 111 Project (B07003), and the
attributed to the enhanced elemental diffusion along grain bound- Program for Chang-jiang Scholars and the Innovative Research Team
aries in nanocrystalline Al0.3CoCrFeNi. This demonstrates that the of the University. Atom probe tomography was conducted at ORNL’s
increase of atomic diffusion can decrease the threshold temperature Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE
of precipitation of B2 phase in Al0.3CoCrFeNi HEA. Office of Science User Facility.
14 T. Yang et al. / Acta Materialia 188 (2020) 1
15

Supplementary materials [29] W.R. Wang, W.L. Wang, J.W. Yeh, Phases, microstructure and mechanical proper-
ties of AlxCoCrFeNi high-entropy alloys at elevated temperatures, J. Alloy Compd.
589 (2014) 143–152.
Supplementary material associated with this article can be found [30] D. Li, C. Li, T. Feng, Y. Zhang, G. Sha, J.J. Lewandowski, P.K. Liaw, Y. Zhang, High-
in the online version at doi:10.1016/j.actamat.2020.01.060. entropy Al0.3CoCrFeNi alloy fibers with high tensile strength and ductility at
ambient and cryogenic temperatures, Acta Mater. 123 (2017) 285–294.
[31] J.C. Rao, H.Y. Diao, V. Ocelík, D. Vainchtein, C. Zhang, C. Kuo, Z. Tang, W. Guo,
J.D. Poplawsky, Y. Zhou, P.K. Liaw, J.T.M. De Hosson, Secondary phases in AlxCoCr-
FeNi high-entropy alloys: an in-situ TEM heating study and thermodynamic
References appraisal, Acta Mater. 131 (2017) 206–220.
[32] H.-P. Chou, Y.-S. Chang, S.-K. Chen, J.-W. Yeh, Microstructure, thermophysical and
[1] S.J. Zinkle, J.T. Busby, Structural materials for fission & fusion energy, Mater. Today electrical properties in AlxCoCrFeNi (0x2) high-entropy alloys, Mater. Sci. Eng.
12 (11) (2009) 12–19. B 163 (3) (2009) 184–189.
[2] P. Yvon, F. Carre
, Structural materials challenges for advanced reactor systems, J. [33] Y.-F. Kao, T.-J. Chen, S.-K. Chen, J.-W. Yeh, Microstructure and mechanical prop-
Nucl. Mater. 385 (2) (2009) 217–222. erty of as-cast, -homogenized, and -deformed AlxCoCrFeNi (02x22) high-
[3] K.L. Murty, I. Charit, Structural materials for GEN-IV nuclear reactors: challenges entropy alloys, J. Alloy Compd. 488 (1) (2009) 57–64.
and opportunities, J. Nucl. Mater. 383 (1) (2008) 189–195. [34] P. Liaw, F. Zhang, C. Zhang, G. Wang, X. Xie, H. Diao, C.-H. Kuo, Z. An, M. Hemphill,
[4] S.J. Zinkle, G. Was, Materials challenges in nuclear energy, Acta Mater. 61 (3) Experimental and Computational Investigation of High Entropy Alloys for
(2013) 735–758. Elevated-Temperature Applications, Univ. of Tennessee, Knoxville, TN,United
[5] S.J. Zinkle, Advanced materials for fusion technology, Fusion Eng. Des 74 (1) States, 2016.
(2005) 31–40. [35] H.Y. Yasuda, H. Miyamoto, K. Cho, T. Nagase, Formation of ultrafine-grained
[6] S.J. Zinkle, L.L. Snead, Designing radiation resistance in materials for fusion microstructure in Al0.3CoCrFeNi high entropy alloys with grain boundary precipi-
energy, Annu. Rev. Mater. Res. 44 (2014) 241–267. tates, Mater. Lett. 199 (2017) 120–123.
[7] D.B. Miracle, O.N. Senkov, A critical review of high entropy alloys and related con- [36] Y. Zhang, M.L. Crespillo, H. Xue, K. Jin, C.H. Chen, C.L. Fontana, J.T. Graham,
cepts, Acta Mater. 122 (2017) 448–511. W.J. Weber, New ion beam materials laboratory for materials modification and
[8] J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau, S.Y. Chang, irradiation effects research, Nucl. Instrum. Meth. B 338 (2014) 19–30.
Nanostructured high-entropy alloys with multiple principal elements: novel alloy [37] M.L. Crespillo, J.T. Graham, Y. Zhang, W.J. Weber, Temperature measurements
design concepts and outcomes, Adv. Eng. Mater. 6 (5) (2004) 299–303. during high flux ion beam irradiations, Rev. Sci. Instrum. 87 (2) (2016) 024902.
[9] B. Gludovatz, A. Hohenwarter, D. Catoor, E.H. Chang, E.P. George, R.O. Ritchie, A [38] R.E. Stoller, M.B. Toloczko, G.S. Was, A.G. Certain, S. Dwaraknath, F.A. Garner, On
fracture-resistant high-entropy alloy for cryogenic applications, Science 345 the use of SRIM for computing radiation damage exposure, Nucl. Instrum. Meth. B
(6201) (2014) 1153–1158. 310 (2013) 75–80.
[10] B. Gludovatz, A. Hohenwarter, K.V. Thurston, H. Bei, Z. Wu, E.P. George, [39] Z. Jiao, G.S. Was, Novel features of radiation-induced segregation and radiation-
R.O. Ritchie, Exceptional damage-tolerance of a medium-entropy alloy CrCoNi at induced precipitation in austenitic stainless steels, Acta Mater. 59 (3) (2011)
cryogenic temperatures, Nat. Commun. 7 (2016) 10602. 1220–1238.
[11] O.N. Senkov, G.B. Wilks, D.B. Miracle, C.P. Chuang, P.K. Liaw, Refractory high- [40] M.K. Miller, K.F. Russell, K. Thompson, R. Alvis, D.J. Larson, Review of atom probe FIB-
entropy alloys, Intermetallics 18 (9) (2010) 1758–1765. Based specimen preparation methods, Microsc. Microanal. 13 (6) (2007) 428–436.
[12] O.N. Senkov, G.B. Wilks, J.M. Scott, D.B. Miracle, Mechanical properties of [41] F. Granberg, K. Nordlund, M.W. Ullah, K. Jin, C. Lu, H. Bei, L.M. Wang,
Nb25Mo25Ta25W25 and V20Nb20Mo20Ta20W20 refractory high entropy alloys, F. Djurabekova, W.J. Weber, Y. Zhang, Mechanism of radiation damage reduction
Intermetallics 19 (5) (2011) 698–706. in equiatomic multicomponent single phase alloys, Phys. Rev. Lett. 116 (13)
[13] P.K. Huang, J.W. Yeh, T.T. Shun, S.K. Chen, Multi-principal-element alloys with (2016) 135504.
improved oxidation and wear resistance for thermal spray coating, Adv. Eng. [42] K. Jin, W. Guo, C. Lu, M.W. Ullah, Y. Zhang, W.J. Weber, L. Wang, J.D. Poplawsky,
Mater. 6 (1/2) (2004) 74–78. H. Bei, Effects of Fe concentration on the ion-irradiation induced defect evolution
[14] M.A. Hemphill, T. Yuan, G.Y. Wang, J.W. Yeh, C.W. Tsai, A. Chuang, P.K. Liaw, and hardening in Ni-Fe solid solution alloys, Acta Mater. 121 (2016) 365–373.
Fatigue behavior of Al0.5CoCrCuFeNi high entropy alloys, Acta Mater. 60 (16) [43] S.J. Zinkle, 1.03-Radiation-Induced Effects on microstructure, Comprehensive
(2012) 5723–5734. Nuclear Materials. 1. Basic Aspects of Radiation Effects in Solids, Elsevier, Amster-
[15] M.-H. Chuang, M.-H. Tsai, W.-R. Wang, S.-J. Lin, J.-W. Yeh, Microstructure and dam, 2011, pp. 65–98.
wear behavior of AlxCo1.5CrFeNi1.5Tiy high-entropy alloys, Acta Mater. 59 (16) [44] B.L. Eyre, Transmission electron microscope studies of point defect clusters in fcc
(2011) 6308–6317. and bcc metals, J. Phys. F: Metal Phys. 3 (2) (1973) 422–470.
[16] T. Yang, C. Li, S.J. Zinkle, S. Zhao, H. Bei, Y. Zhang, Irradiation responses and defect [45] S.J. Zinkle, P.J. Maziasz, R.E. Stoller, Dose dependence of the microstructural evo-
behavior of single-phase concentrated solid solution alloys, J. Mater. Res. 33 lution in neutron-irradiated austenitic stainless steel, J. Nucl. Mater. 206 (2)
(2018) 3077–3091. (1993) 266–286.
[17] Y. Zhang, G.M. Stocks, K. Jin, C. Lu, H. Bei, B.C. Sales, L. Wang, L.K. Be
land, [46] T. Yang, S. Xia, W. Guo, R. Hu, J.D. Poplawsky, G. Sha, Y. Fang, Z. Yan, C. Wang, C. Li,
R.E. Stoller, G.D. Samolyuk, M. Caro, A. Caro, W.J. Weber, Influence of chemical Effects of temperature on the irradiation responses of Al0.1CoCrFeNi high entropy
disorder on energy dissipation and defect evolution in concentrated solid solution alloy, Scr. Mater. 144 (2018) 31–35.
alloys, Nat. Commun. 6 (2015) 8736. [47] S. Takaki, J. Fuss, H. Kuglers, U. Dedek, H. Schultz, The resistivity recovery of high
[18] K. Jin, C. Lu, L.M. Wang, J. Qu, W.J. Weber, Y. Zhang, H. Bei, Effects of compositional purity and carbon doped iron following low temperature electron irradiation,
complexity on the ion-irradiation induced swelling and hardening in Ni-contain- Radiat. Eff. 79 (1
4) (1983) 87–122.
ing equiatomic alloys, Scr. Mater 119 (2016) 65–70. [48] C.-C. Fu, J.D. Torre, F. Willaime, J.-L. Bocquet, A. Barbu, Multiscale modelling of
[19] D.S. Aidhy, C. Lu, K. Jin, H. Bei, Y. Zhang, L. Wang, W.J. Weber, Point defect evolu- defect kinetics in irradiated iron, Nat. Mater. 4 (1) (2005) 68–74.
tion in Ni, NiFe and NiCr alloys from atomistic simulations and irradiation experi- [49] M.J. Makin, F.J. Minter, Irradiation hardening in copper and nickel, Acta Metall. 8
ments, Acta Mater. 99 (2015) 69–76. (10) (1960) 691–699.
[20] C. Lu, K. Jin, L.K. Be
land, F. Zhang, T. Yang, L. Qiao, Y. Zhang, H. Bei, H.M. Christen, [50] B. Singh, A. Horsewell, P. Toft, D. Edwards, Temperature and dose dependencies of
R.E. Stoller, Direct observation of defect range and evolution in ion-irradiated sin- microstructure and hardness of neutron irradiated OFHC copper, J. Nucl. Mater.
gle crystalline ni and Ni binary alloys, Sci. Rep. 6 (2016) 19994. 224 (2) (1995) 131–140.
[21] M.-R. He, S. Wang, K. Jin, H. Bei, K. Yasuda, S. Matsumura, K. Higashida, [51] H.C. Liu, T.E. Mitchell, Defect aggregation in irradiated Ni3Al and NiAl, J. Nucl.
I.M. Robertson, Enhanced damage resistance and novel defect structure of CrFe- Mater. 107 (2/3) (1982) 318–326.
CoNi under in situ electron irradiation, Scr. Mater. 125 (2016) 5–9. [52] S. Fabritsiev, A. Pokrovsky, Effect of irradiation temperature on microstructure,
[22] M.-R. He, S. Wang, S. Shi, K. Jin, H. Bei, K. Yasuda, S. Matsumura, K. Higashida, radiation hardening and embrittlement of pure copper and copper-based alloy, J.
I.M. Robertson, Mechanisms of radiation-induced segregation in CrFeCoNi-based Nucl. Mater. 367 (2007) 977–983.
single-phase concentrated solid solution alloys, Acta Mater. 126 (2017) 182–193. [53] S. Zinkle, L. Snead, Microstructure of copper and nickel irradiated with fission
[23] C. Lu, T. Yang, K. Jin, N. Gao, P. Xiu, Y. Zhang, F. Gao, H. Bei, W.J. Weber, K. Sun, neutrons near 230 C, J. Nucl. Mater. 225 (1995) 123–131.
Y. Dong, L. Wang, Radiation-induced segregation on defect clusters in single- [54] M. Nastar, F. Soisson, Comprehensive Nuclear Materials. 1.Basic Aspects of Radia-
phase concentrated solid-solution alloys, Acta Mater. 127 (2017) 98–107. tion Effects in Solids, Elsevier, Amsterdam, 2011.
[55] L.K. Be
land, C. Lu, Y.N. Osetskiy, G.D. Samolyuk, A. Caro, L. Wang, R.E. Stoller, Fea-
[24] N.A.P.K. Kumar, C. Li, K.J. Leonard, H. Bei, S.J. Zinkle, Microstructural stability and
mechanical behavior of FeNiMnCr high entropy alloy under ion irradiation, Acta tures of primary damage by high energy displacement cascades in concentrated
Mater. 113 (2016) 230–244. Ni-based alloys, J. Appl. Phys. 119 (8) (2016) 085901.
[25] S. Gorsse, D.B. Miracle, O.N. Senkov, Mapping the world of complex concentrated [56] C. Lu, L. Niu, N. Chen, K. Jin, T. Yang, P. Xiu, Y. Zhang, F. Gao, H. Bei, S. Shi, Enhanc-
alloys, Acta Mater. 135 (2017) 177–187. ing radiation tolerance by controlling defect mobility and migration pathways in
[26] T. Yang, S. Xia, S. Liu, C. Wang, S. Liu, Y. Zhang, J. Xue, S. Yan, Y. Wang, Effects of Al multicomponent single-phase alloys, Nat. Commun. 7 (2016) 13564.
addition on microstructure and mechanical properties of AlxCoCrFeNi high- [57] A.J. Zaddach, C. Niu, C.C. Koch, D.L. Irving, Mechanical properties and stacking
entropy alloy, Mater. Sci. Eng. A 648 (2015) 15–22. fault energies of nifecrcomn high-entropy alloy, JOM 65 (12) (2013) 1780–1789.
[27] C. Li, J.C. Li, M. Zhao, Q. Jiang, Effect of aluminum contents on microstructure and [58] S. Huang, W. Li, S. Lu, F. Tian, J. Shen, E. Holmstro €m, L. Vitos, Temperature depen-
properties of AlxCoCrFeNi alloys, J. Alloy Compd. 504S (0) (2010) S515. dent stacking fault energy of FeCrCoNiMn high entropy alloy, Scr. Mater. 108
[28] W.-R. Wang, W.-L. Wang, S.-C. Wang, Y.-C. Tsai, C.-H. Lai, J.-W. Yeh, Effects of Al (2015) 44–47.
addition on the microstructure and mechanical property of AlxCoCrFeNi high- [59] A.J. Zaddach, R.O. Scattergood, C.C. Koch, Tensile properties of low-stacking fault
entropy alloys, Intermetallics 26 (0) (2012) 44–51. energy high-entropy alloys, Mater. Sci. Eng. A 636 (2015) 373–378.
 T. Yang et al. / Acta Materialia 188 (2020) 1
15 15

[60] J. Liu, C. Chen, Y. Xu, S. Wu, G. Wang, H. Wang, Y. Fang, L. Meng, Deformation [74] R.A. Enrique, P. Bellon, Phase stability under irradiation in alloys with a positive heat
twinning behaviors of the low stacking fault energy high-entropy alloy: an in- of mixing: effective thermodynamics description, Phys. Rev. B 60 (21) (1999) 14649.
situ TEM study, Scr. Mater. 137 (2017) 9–12. [75] S. Shu, N. Almirall, P.B. Wells, T. Yamamoto, G.R. Odette, D.D. Morgan, Precipita-
[61] X.-X. Wang, L.-L. Niu, S. Wang, Energetics analysis of interstitial loops in single- tion in Fe-Cu and Fe-Cu-Mn model alloys under irradiation: dose rate effects,
phase concentrated solid-solution alloys, J. Nucl. Mater. 501 (2018) 94–103. Acta Mater. 157 (2018) 72–82.
[62] S.J. Zinkle, N.M. Ghoniem, Operating temperature windows for fusion reactor [76] P. Krasnochtchekov, R. Averback, P. Bellon, Homogeneous phase separation in
structural materials, Fusion Eng. Des. 51/52 (2000) 55–71. binary alloys under ion irradiation conditions: role of interstitial atoms, Phys.
[63] Y.-C. Yang, C. Liu, C.-Y. Lin, Z. Xia, Core effect of local atomic configuration and design Rev. B 75 (14) (2007) 144107.
principles in AlxCoCrFeNi high-entropy alloys, Scr. Mater. 178 (2020) 181–186. [77] J. Ye, P. Bellon, Nanoscale patterning of chemical order induced by displacement
[64] S.J. Zinkle, L.L. Snead, Opportunities and limitations for ion beams in radiation cascades in irradiated alloys. I. A kinetic Monte Carlo study, Phys. Rev. B 70 (9)
effects studies: bridging critical gaps between charged particle and neutron irra- (2004) 094104.
diations, Scr. Mater. 143 (2018) 154–160. [78] J.M. Gonzalez-Miranda, P.L. Garido, J. Marro, J.L. Lebowitz, Nonequilibrium phase
[65] J.B. Whitley, G.L. Kulcinski, P. Wilkes, H.V. Smith, The depth dependent damage diagram of ISING model with competing dynamics, Phys. Rev. Lett. 59 (17) (1987)
profile in nickel irradiated with nickel or copper ions, J. Nucl. Mater. 79 (1) (1979) 1934–1937.
159–169. [79] G. Martin, Phase stability under irradiation: ballistic effects, Phys. Rev. B 30 (3)
[66] J.G. Gigax, T. Chen, H. Kim, J. Wang, L.M. Price, E. Aydogan, S.A. Maloy, (1984) 1424–1436.
D.K. Schreiber, M.B. Toloczko, F.A. Garner, L. Shao, Radiation response of alloy T91 [80] R.S. Nelson, J.A. Hudson, D.J. Mazey, The stability of precipitates in an irradiation
at damage levels up to 1000 peak dpa, J. Nucl. Mater. 482 (2016) 257–265. environment, J. Nucl. Mater. 44 (3) (1972) 318–330.
[67] T.-n. Yang, C. Lu, K. Jin, M.L. Crespillo, Y. Zhang, H. Bei, L. Wang, The effect of [81] M.H. Mathon, Y. de Carlan, G. Geoffroy, X. Averty, A. Alamo, C.H. de Novion, A
injected interstitials on void formation in self-ion irradiated nickel containing SANS investigation of the irradiation-enhanced a
a0 phases separation in 7
12
concentrated solid solution alloys, J. Nucl. Mater. 488 (2017) 328–337. Cr martensitic steels, J. Nucl. Mater. 312 (2/3) (2003) 236–248.
[68] T. Yang, S. Xia, S. Liu, C. Wang, S. Liu, Y. Fang, Y. Zhang, J. Xue, S. Yan, Y. Wang, Pre- [82] N.Q. Vo, S.W. Chee, D. Schwen, X. Zhang, P. Bellon, R.S. Averback, Microstructural
cipitation behavior of AlxCoCrFeNi high entropy alloys under ion irradiation, Sci. stability of nanostructured Cu alloys during high-temperature irradiation, Scr.
Rep. 6 (2016) 32146. Mater. 63 (9) (2010) 929–932.
[69] B. Gwalani, V. Soni, D. Choudhuri, M. Lee, J.Y. Hwang, S.J. Nam, H. Ryu, S.H. Hong, [83] R.A. Enrique, K. Nordlund, R.S. Averback, P. Bellon, Nonequilibrium self-organiza-
R. Banerjee, Stability of ordered L12 and B2 precipitates in face centered cubic tion in alloys under irradiation leading to the formation of nanocomposites, Nucl.
based high entropy alloys - Al0.3CoFeCrNi and Al0.3CuFeCrNi2, Scr. Mater. 123 Instrum. Meth. B 202 (2003) 206–216.
(2016) 130–134. [84] K.-Y. Tsai, M.-H. Tsai, J.-W. Yeh, Sluggish diffusion in Co-Cr-Fe-Mn-Ni high-
[70] T.-T. Shun, Y.-C. Du, Microstructure and tensile behaviors of FCC Al0.3CoCrFeNi entropy alloys, Acta Mater. 61 (13) (2013) 4887–4897.
high entropy alloy, J. Alloy Compd. 479 (2009) 157–160. [85] R. Sizmann, The effect of radiation upon diffusion in metals, J. Nucl. Mater. 69
[71] Q. Tang, Y. Huang, H. Cheng, X. Liao, T.G. Langdon, P. Dai, The effect of grain size (1978) 386–412.
on the annealing-induced phase transformation in an Al0.3CoCrFeNi high entropy [86] G. Odette, G. Lucas, Embrittlement of nuclear reactor pressure vessels, JOM 53 (7)
alloy, Mater. Des. 105 (2016) 381–385. (2001) 18–22.
[72] C. Abromeit, H. Wollenberger, S. Matsumura, C. Kinoshita, Stability of ordered [87] L.C. Luther, Diffusion along dislocations, J. Chem. Phys. 43 (7) (1965) 2213–2218.
phases under irradiation, J. Nucl. Mater. 276 (1) (2000) 104–113. [88] G. Williams Jr, L. Slifkin, Diffusion along dislocations, Phys. Rev. Lett. 1 (7) (1958) 243.
[73] R.A. Enrique, P. Bellon, Compositional patterning in systems driven by competing [89] V.E. Wood, M. Glasser, A. Austin, Diffusion along dislocations, J. Chem. Phys. 45 (3)
dynamics of different length scale, Phys. Rev. Lett. 84 (13) (2000) 2885. (1966) 1079–1080.