Current Opinion in Solid State and Materials Science 22 (2018) 1–7

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Current Opinion in Solid State and Materials Science

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

Hydrogen embrittlement in compositionally complex FeNiCoCrMn FCC

solid solution alloy
K.E. Nygren a, K.M. Bertsch b,c, S. Wang a, H. Bei d, A. Nagao c,e, I.M. Robertson a,c,f,⇑
a
Department of Engineering Physics, University of Wisconsin-Madison, Madison, WI 53706, USA
b
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA
c
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, Fukuoka 819-0395, Japan
d
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
e
Material Surface & Interface Science Research Department, Steel Research Laboratory, JFE Steel Corporation, 1-1 Minamiwatarida-cho, Kawasaki-ku, Kawaksai, Kanagawa
210-0855, Japan
f
Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI 53706, USA

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

Article history: The influence of internal hydrogen on the tensile properties of an equi-molar FeNiCoCrMn alloy results in
Received 30 September 2017 a significant reduction of ductility, which is accompanied by a change in the fracture mode from ductile
Revised 6 November 2017 microvoid coalescence to intergranular failure. The introduction of 146.9 mass ppm of hydrogen reduced
Accepted 27 November 2017
the plastic strain to failure from 0.67 in the uncharged case to 0.34 and 0.51 in hydrogen-charged spec-
Available online 1 December 2017
imens. The reduction in ductility and the transition in failure mode are clear indications that this alloy
exhibits the classic signs of being susceptible to hydrogen embrittlement. The results are discussed in
Keywords:
terms of the hydrogen-enhanced plasticity mechanism and its influence on hydrogen-induced intergran-
High entropy alloy
Hydrogen embrittlement
ular failure. Furthermore, a new additional constraint that further promotes intergranular failure is intro-
Mechanical properties duced for the first time.
Grain boundaries Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Equi-molar and multi-element alloys, including the group of
five-element alloys referred to as high-entropy alloys, provide
the opportunity to tailor the properties of the system; see reviews
by Miracle and Senkov [1], Zhang et al. [2] and Diao et al. [3].
Single-phase FCC high-entropy alloys exhibit high thermal stability
[4], high malleability [5], slow diffusion [6], low yield strength,
high ductility [7], and high fracture toughness at cryogenic tem-
peratures [8]. The electronic, thermal and magnetic properties
are also modified by increasing the number of elements [9,10]. It
was predicted theoretically and shown experimentally that the
electrical and thermal conductivity is reduced significantly in
high-entropy alloys compared to other alloys, as is the electron
mean free path. These changes result in slower heat dissipation
from displacement cascades created by heavy-ion irradiation,
which results in a greater tolerance for the accumulation of radia-
tion damage [9–11]. However, it was found that the number of ele-
ments was not the dominating factor, as specific elements had a
different influence on the accumulation of the damage under both
⇑ Corresponding author.
E-mail address: irobertson@wisc.edu (I.M. Robertson).
ion [12] and electron irradiation [13]. These properties have been
explained by the combined influences of the high entropy (thermo-
dynamics), low diffusivity (kinetics), and lattice distortion (struc-
ture) of these alloys as well as the sensitivity of the properties to
alloy composition [14].
Recently, it has been reported that the five-element high-
entropy alloy FeNiCoCrMn was not susceptible to hydrogen
embrittlement, which would place it in a unique class of metals
and alloys [15,16]. Zhao et al. reported that the tensile properties
were similar in the uncharged and hydrogen-charged alloys, with
the hydrogen-charged alloy showing only a 5% decrease in ductility
[15]. The fracture surfaces of the uncharged and hydrogen-charged
specimens of the FeNiCoCrMn alloy were similar and consisted of
microvoids, which indicate a ductile failure mode in both cases.
Based on these observations, Zhao et al. concluded that this alloy
was not embrittled by hydrogen. However, hydrogen-induced duc-
tile failure by microvoid coalescence is common, although it is
often accompanied by a change in the characteristics of the dim-
ples in terms of size and depth [17]. Luo et al. used electrochemical
charging to introduce hydrogen into an alloy of the same composi-
tion and concluded that hydrogen, rather than being detrimental to
the mechanical properties as it is in most other alloys, was benefi-
cial [16]. Hydrogen was reported to enhance strengthening and

https://doi.org/10.1016/j.cossms.2017.11.002
1359-0286/Ó 2017 Elsevier Ltd. All rights reserved.
2 K.E. Nygren et al. / Current Opinion in Solid State and Materials Science 22 (2018) 1–7
toughening mechanisms. This was attributed to hydrogen reducing
the stacking-fault energy and therefore the phase stability of the
alloy.
In this paper, the tensile behavior of the five-element alloy
FeNiCoCrMn was studied in the absence and presence of hydrogen.
Gas-phase hydrogen charging at elevated temperature was used to
introduce hydrogen uniformly throughout the sample. It will be
demonstrated unequivocally that this alloy is susceptible to hydro-
gen embrittlement. It undergoes a significant decrease in the strain
to failure in the presence of hydrogen, which is accompanied by a
transition in the fracture mode from ductile microvoid coalescence
to a mixed failure mode that includes intergranular failure. This
reduction in ductility coupled with the transition in fracture mode
are classic characteristics of hydrogen embrittlement and are
explained in terms of the hydrogen enhanced localized plasticity
mechanism [18,19]. In addition, it will be proposed that the inabil-
ity of the grain boundaries to realign towards the tensile axis dur-
ing uniaxial loading in the hydrogen-charged alloy provides an
additional driving force for the hydrogen-induced transition in
the failure mode.
2. Experimental procedure
The near-equi-molar FeNiCoCrMn alloy was produced by arc
melting, rolling, and annealing. Electrical discharge machining
was used to cut flat dog-bone-type specimens with a gauge
length of 10 mm and cross-sectional dimensions of approximately
2 mm  2 mm from the cold-rolled sheets. The specimens were
cut such that the longitudinal axis was perpendicular to the roll-
ing direction. The specimens were annealed at 1200 °C for 24 h.
The resulting microstructure consisted of approximately equiaxed
grains with a mean grain size of 70 mm; annealing twin bound-
aries were frequently observed making the effective grain size
50 mm.
The samples were charged with hydrogen in an autoclave at a
hydrogen gas pressure of 120 MPa at 200 °C for 160 h. The total
time the samples were at room temperature was between 8 and
10 days for transportation to and from the hydrogen-charging
facility. At all other times they were stored in liquid nitrogen. Uni-
axial tensile tests were conducted at a constant displacement rate
of 1.7  10 5 mm s 1 (an initial strain rate of approximately
1.7  10 6 s 1) using a MTS QTest/5 tensile machine with a 5 kN
load cell. Two hydrogen-charged samples were tested and are
referred to as HC1 and HC2. HC1 was tested shortly after it was
removed from the liquid nitrogen storage vessel and brought to
room temperature, whereas HC2 was mechanically polished for
initial electron backscattering diffraction (EBSD) analysis before
testing. The polishing and EBSD analysis took approximately 10 h.
The hydrogen content of the uncharged and hydrogen-charged
samples was measured using gas chromatograph thermal desorp-
tion analysis after the tensile tests were complete. This ensured
that the 8 and 10 days the samples were at room temperature
did not result in loss of hydrogen. A ramp rate of 200 °C h 1 was
used in the thermal desorption test from room temperature to
800 °C.
The fracture surfaces and external surfaces were investigated
using scanning electron microcopy (SEM) with either a LEO
1530–1 FESEM or an FEI Helios G4 PFIB CXe with an ElstarTM
SEM column being used. Electron dispersive spectroscopy (EDS)
and EBSD measurements were performed using EDA TEAMTM
EDS software and instrumentation attached to the FEI Helios G4
PFIB. The EDS measurements were performed using an Octane Elite
silicon drift detector. EBSD measurements were performed using
an Hikari EBSD camera using a step size of 0.5 mm, accelerating
voltage of 30 kV, and current of 26 nA.
Samples for examination in a scanning/transmission electron
microscope were prepared by focused ion beam machining using
an FEI Helios G4 PFIB CXe. The electron microscopy was performed
in a Tecnai TF-30 S/TEM, which was operated at 300 keV.
3. Results
The thermal desorption analysis spectra for the uncharged and
hydrogen-charged alloy following the completion of the mechani-
cal property tests are shown in Fig. 1. The hydrogen concentration
of the uncharged sample is defined to be the total hydrogen des-
orbed from room temperature to 643 °C, and that of the HC1 sam-
ple from room temperature to 660 °C, which corresponds to the
first desorption peak. From Fig. 1, the hydrogen concentration
remaining in the uncharged (open circles) and HC1 samples (filled
circles) was 1.4 mass ppm (76 at. ppm) and 146.9 mass ppm (8239
at. ppm), respectively. For comparison, the thermal desorption
analysis spectra for a 2.0 mm thick Ni sample (filled squares) fol-
lowing charging at 200 °C for a duration of 160 h under a gas pres-
sure of 120 MPa, and for 4.0 mm thick SUS316L austenitic stainless
steel (filled triangles) charged with hydrogen in a 120 MPa hydro-
gen gas environment at 280 °C for 400 h are included in Fig. 1. The
peak 1 hydrogen concentration in Ni and SUS316L were 42.5 mass
ppm (2492 at. ppm) and 104.2 mass ppm (5812 at. ppm), respec-
tively. The rate-determining step for the thermal desorption pro-
cess of these three materials is diffusion due to the low hydrogen
diffusivity [20]. The observation that the maximum in the desorp-
tion peak for the FeNiCoCrMn alloy and Ni occurs at 409 °C sug-
gests that the hydrogen diffusivity is similar in both materials
and lower than in stainless steels. The calculated initial hydrogen
concentration for the charging conditions used for Ni is 41.3 mass
ppm (2423 at. ppm) [21] and the thermal desorption analysis of Ni
presented in Fig. 1 was conducted after 11 days of storage at room
temperature. This result suggests that the outgassing of hydrogen
from Ni was negligible after 11 days at room temperature. The
hydrogen concentration in the FeNiCoCrMn alloy was measured
following a total time at room temperature of between 8 – 10 days,
by comparison with the Ni result it is reasonable to conclude that
the change in the hydrogen concentration due to the time at room
temperature was negligible. In comparing this hydrogen
Fig. 1. Thermal desorption analysis spectra of the uncharged and hydrogen-
charged FeNiCoCrMn alloy; heating rate = 200 °C/h. Data for Ni and SUS316L
austenitic stainless steel (heating rate = 200 °C/h) are included for comparison.
 HC1; s uncharged; N Ni; j SUS 316 L austenitic stainless steel.
 K.E. Nygren et al. / Current Opinion in Solid State and Materials Science 22 (2018) 1–7
concentration to that in Ni and SUS 316L austenitic stainless steel,
it is found that the concentration in the FeNiCoCrMn alloy is
greater. This suggests that the FeNiCoCrMn alloy has a higher sol-
ubility of hydrogen. Preliminary microstructural analysis showed
no evidence for the formation of hydrides in the hydrogen-
charged material, indicating that hydrogen is retained in the lattice
and in other traps such as dislocations, grain boundaries, and
precipitates.
The stress-strain curves for the uncharged and hydrogen-
charged samples are compared in Fig. 2. Both HC1 and HC2 exhib-
ited higher yield strengths than the uncharged material; the 0.2%
offset yield strengths were 152, 214, and 207 MPa in the
uncharged, HC1, and HC2 samples, respectively. The ultimate ten-
sile strengths were 507, 528, and 475 MPa in the uncharged, HC1,
and HC2 samples, respectively. Both hydrogen-charged samples
failed at a significantly lower strain than the uncharged sample.
The strain at failure was 67% in the uncharged sample, whereas
it was 51% and 34% for HC1 and HC2, respectively. It is noted that
Gludovatz et al. reported a range of failure strains for this alloy
composition in the absence of hydrogen, suggesting that variations
in internal defects, oxides, grain size or grain boundary misorienta-
tion distribution may be the root cause of the scatter in the failure
strains [8]. However, the difference of strain to failure between the
uncharged and hydrogen-charged materials in the current study is
statistically significant and indicates this material is embrittled by
hydrogen.
The fracture surfaces of the uncharged, HC1, and HC2 samples
are compared in the fractographs presented in Fig. 3. The
uncharged sample exhibited a ductile microvoid coalescence fail-
ure mode, Fig. 3(a), with precipitates evident in the microvoids,
see Fig. 3(d). EDS analysis of a precipitate within a void, the results
of which are presented in Fig. 4 as elemental maps, confirmed that
the precipitates were rich in Cr and Mn and deficient in Fe, Co and
Ni. In contrast, both hydrogen-charged samples exhibited predom-
inantly intergranular failure as evidenced by the fractographs pre-
sented in Fig. 3(b) and (c). However, there were subtle differences
between HC1 and HC2. HC1 showed extensive secondary cracking,
as well as dimples and ductile fracture features in multiple regions,
including on some surfaces that appeared macroscopically flat, see
Fig. 3(e). Similar ductile features were identified on the fracture
surface of the HC2 sample, although with a lower frequency. This
observation of a change in fracture mode is also consistent with
this material being susceptible to hydrogen embrittlement.
Fig. 2. Engineering stress-strain curves for uncharged, HC1, and HC2 specimens.
3
Closer inspection of the faceted surfaces of both HC1 and HC2
indicated that they were not flat but showed evidence of slip traces
or steps; these are common features on a hydrogen-induced inter-
granular facet [21,22]. On the same facet, these steps could lie in
three directions. On some surfaces these steps were curved signif-
icantly, which is an indication that a high degree of deformation
had occurred. These steps could result from the disruptions of
the grain boundaries caused by the intersection and transmission
of dislocation slip systems or deformation twins [23]. An example
of this structure is shown in the fractograph presented in Fig. 5.
The disruptions on the free surfaces caused by the intersections
of dislocation slip systems and deformation twins were examined
along the gauge length. For the uncharged sample, intersections on
the surface occurred in up to three different directions and the
steps were distinct and high. In contrast, in the hydrogen-
charged material, activity was observed on multiple slip systems
but in most grains the steps were less distinct and shallower in
appearance. An additional difference between the uncharged and
hydrogen-charged samples was the presence of microcracks along
the grain boundaries away from fracture surface in the hydrogen-
charged samples only. Examples of these microstructural features
are compared for the uncharged and hydrogen-charged samples
in Fig. 6(a) and (b), respectively. In Fig. 6, the images are not from
the same distance from the fracture surface; Fig. 6(a) is approxi-
mately 1.6 mm from the fracture surface in the uncharged sample
and Fig. 6(b) is approximately 300 lm from the fracture surface in
HC2. Examples of these traces and steps are indicated with arrows
in Fig. 6(a) and (b), and examples of microcracks with arrowheads
in Fig. 6(b). To confirm that these microcracks lie along grain
boundaries and the fracture mode is appropriately labelled inter-
granular, an EBSD map of the same area prior to loading is pre-
sented as Fig. 6(c). Superimposing the EBSD map on the
deformed image confirms the microcracks lie along the grain
boundaries; the locations of the microcracks are indicated by
arrowheads in Fig. 6(c). Another important feature revealed in
Fig. 6 is that the grains in the uncharged alloy rotate towards
and elongate in the direction of the tensile axis, which runs from
top to bottom in this figure. In contrast, the grains in the
hydrogen-charged alloy do not show the same rotation or elonga-
tion. This can be seen by comparing Fig. 6(b) and (c). This is the
first report of hydrogen having an influence of the shape of the
grain and restricting its ability to rotate and elongate in response
to the applied load.
To determine the deformation processes associated with the
change in the fracture mode, the microstructural state needs to
be assessed. Preliminary observations of the evolved microstruc-
ture in the uncharged and hydrogen-charged samples beneath
the fracture surfaces revealed that the deformation occurred by
dislocation slip and deformation twinning. Examples of the
deformed microstructure adjacent to the fracture surfaces of the
uncharged and hydrogen-charged samples are compared in
Fig. 7. The region beneath a microvoid in the uncharged specimen
and the faceted fracture surface of the HC1 sample are shown in
the STEM diffraction contrast images presented in Fig. 7(a) and
(b), respectively. Here it is important to remember that these frac-
ture surfaces are different and they were formed at different
strains, 67% and 51% for the uncharged and hydrogen-charged
samples, respectively. In the uncharged alloy, a region with sub-
grains elongated parallel to the void surface exists immediately
below the fracture surface; this region is indicated with an arrow-
head in Fig. 7(a). The presence of this sub-surface region is consis-
tent with observations made in other systems [24,25]. Beyond this
layer, the microstructure transitions into a dislocation cell struc-
ture on which deformation twins are superimposed; an example
of a deformation twin is indicated by the double arrow. Beneath
the intergranular facet in HC1, a dislocation cell structure exists
4 K.E. Nygren et al. / Current Opinion in Solid State and Materials Science 22 (2018) 1–7

Fig. 3. Fractographs of (a) uncharged, (b) HC1, and (c) HC2 with magnified views of the fracture surfaces (d) uncharged, (e) HC1, and (f) HC2.

Fig. 4. Elemental map showing the composition of the particle associated with the void in uncharged material. (a) SEM image of the void, (b) Co (c) Ni, (d) Fe, (e) Cr, and
(f) Mn.

as shown in Fig. 7(b). The presence of deformation twins was less

evident in the hydrogen-charged alloy. Despite the smaller strain
to failure, the dislocation cell size (300–500 nm) was similar to
that in the uncharged samples and the cell walls were thicker. This
type of dislocation cell structure has been observed beneath inter-
granular facets in other hydrogen embrittled systems [22,26]. The
observation of a comparable cell size and thicker cell walls despite
the differences in strain at failure are indicative of hydrogen having
enhanced the evolution of the microstructure through the HELP
mechanism [19].

4. Discussion

It is demonstrated for the first time that the FCC equi-molar,

Fig. 5. Fractograph of a facet in HC1.
single-phase FeNiCoCrMn alloy is susceptible to hydrogen embrit-
tlement. This embrittlement was accompanied by a change in frac-
ture mode from ductile microvoid coalescence to intergranular
failure. In this regard, this alloy behaves similar to Ni, which
undergoes a transition in the failure mode from transgranular to
intergranular with increasing hydrogen concentration [22]. A tran-
sition in failure mode also occurs in BCC Fe [26]. For both Ni [22]
and Fe [26], it has been proposed that the presence of hydrogen
on the grain boundary, while a necessary condition for the ultimate
 K.E. Nygren et al. / Current Opinion in Solid State and Materials Science 22 (2018) 1–7 5

Fig. 6. Deformation on the free surface (a) uncharged specimen (b) HC2. (c) EBSD of the free surface region shown in (b) prior to loading. Arrows indicate the traces and steps,
arrowheads microcracks. The tensile axis is vertical.

Fig. 7. Bright-field STEM diffraction contrast micrographs of the deformed microstructure beneath fracture surfaces of (a) the uncharged specimen and (b) HC1. Arrowhead
marks the near-surface region with subgrains and the double arrow marks the deformation twins.

failure of the grain boundary, is by itself not sufficient. It was pro-
posed that the additional driving force was derived from the local
stresses associated with the work-hardening that occurred in the
grain interior and the changes in the grain boundary structure that
accompany the incorporation and emission of dislocations as strain
was transferred across the grain boundary in hydrogen. Support for
these additional mechanisms was found in the microstructure
beneath the intergranular facets in Ni and Fe, which was further
developed than suggested by the magnitude of the macroscopic
strain to failure [22,26]. The redistribution of hydrogen through
transport by glissile dislocations was considered to create a
dynamic exchange of hydrogen with the grain boundary and this
was considered to play an important role in establishing conditions
that promoted grain boundary decohesion. Initial evaluation of the
deformed microstructure in the hydrogen-charged FeNiCoCrMn
samples shows an extensive work-hardened microstructure
accompanying the intergranular fracture, Fig. 7.
For the first time it is reported that hydrogen influences the
ability of the grains to elongate and rotate in the direction of the
tensile axis. A similar observation has been made in hydrogen-
charged Ni following uniaxial loading [27]. These observations sug-
gest that an additional compatibility constraint will be established
6 K.E. Nygren et al. / Current Opinion in Solid State and Materials Science 22 (2018) 1–7
across the grain boundaries as the adjoining grains cannot rotate
and elongate in response to the deformation. This additional con-
straint would further favor failure of a grain boundary that has
been weakened by the presence of hydrogen.
These results are in marked contrast to those that have been
published [15,16]. Both previous studies claimed this alloy was
immune to hydrogen embrittlement, which would place it in a
unique group of metals that exhibit negligible hydrogen embrittle-
ment. Zhao et al. reported that the FeNiCoCrMn alloy, despite con-
taining a higher hydrogen concentration than 304 and 316L, was
more resistant to hydrogen embrittlement than these austenitic
stainless steels, and did not exhibit a transition in fracture mode
at a hydrogen concentration of 76.5 mass ppm [15]. Here it is
important to note several characteristics of hydrogen embrittle-
ment. It is well known that hydrogen embrittlement occurs within
a well-defined window of strain rate and temperature [28]. The
embrittling potency of hydrogen is generally greater for decreasing
strain rates [28]. Zhao et al. used a strain rate of 1.7  10 4 s 1
whereas an initial strain rate of 1.7  10 6 s 1 was used in this
study. Additionally, the hydrogen content in their alloy was 76.5
mass ppm compared to 146.9 mass ppm, which might not be suf-
ficient to cause a change in the fracture mode from transgranular
to intergranular. Such a dependence of the failure mode transition
on the hydrogen concentration has been reported in Ni [29]. Fur-
ther, the dichotomy presented by the observations by Luo et al.
[16] can be explained by the hydrogen-charging method
employed, the sluggish diffusion of hydrogen in this alloy, and
the use of a strain rate of 1.0  10 4 s 1. Electrochemical charging
conditions at room temperature can create a high surface concen-
tration of trapped hydrogen, which may include the formation of a
near-surface hydride. Luo et al. reported intergranular fracture in
the near-surface region and this may be explained by a locally high
hydrogen concentration. The proposal that the beneficial effects
are attributable to hydrogen reducing the stacking-fault energy
does not agree with observations of the impact of hydrogen on
the mechanical properties of other FCC alloys in which the magni-
tude of the reduction in the stacking-fault energy has been mea-
sured directly [30]. These alloys remained susceptible to
hydrogen embrittlement despite the reduction in the stacking-
fault energy. Finally, they proposed that hydrogen affected the
propensity for a system to deform by twinning. However, there
has been no evidence to support that a hydrogen-induced reduc-
tion in the stacking-fault energy results in an increased propensity
of the system to deform by twinning or that deformation twinning
is enhanced by hydrogen [31]. Indeed, initial assessment of the
evolved microstructure does not show hydrogen increasing the
propensity for deformation and if anything it may show the oppo-
site effect. However, additional analysis is needed to confirm this
statement. Nygren has reported deformation twinning in the near
fracture surface region of 316L. However, these twins were super-
imposed on a dislocation cell structure and it was shown that the
twins appeared only after the dislocation cell structure could not
continue to support the strain [32].
5. Conclusions
1. The high-entropy FCC alloy FeNiCoCrMn is embrittled in the
presence of hydrogen and this is accompanied by a change in
fracture mode from ductile microvoid coalescence to intergran-
ular failure.
2. The solubility of hydrogen in this alloy is higher than in other
FCC alloys such as types 304 and 316L austenitic stainless steels
or Ni.
3. The hydrogen diffusivity in this alloy appears to be similar to
that in Ni and lower than that in austenitic stainless steels.
4. To understand the influence of hydrogen on the mechanical
properties of this class of alloys, further assessment of the frac-
ture toughness and fatigue-crack growth as well as determina-
tion of fundamental properties such as the diffusivity,
permeability and solubility of hydrogen are required.
Acknowledgements
SW, KEN, KMB and IMR gratefully acknowledge the support of
the National Science Foundation through Award No. CMMI-
1406462. AN acknowledges the support from JFE Steel Corporation.
KB and KN acknowledge partial support from the World Premier
International Research Center Initiative (WPI), MEXT, Japan,
through the International Institute for Carbon-Neutral Energy
Research (I2CNER) of Kyushu University. HB was supported by
the US Department of Energy, Office of Science, Basic Energy
Sciences, Materials Sciences and Engineering Division. The electron
microscopy was carried out using facilities and instrumentation in
the Materials Science Center at the University of Wisconsin-
Madison, which is partially supported by NSF through the Materi-
als Research Science and Engineering Center (DMR-1121288). This
manuscript has been authored by UT-Battelle, LLC under Contract
No. DE-AC05-00OR22725 with the U.S. Department of Energy.
The United States Government retains and the publisher, by
accepting the article for publication, acknowledges that the United
States Government retains a non-exclusive, paid-up, irrevocable,
world-wide license to publish or reproduce the published form of
this manuscript, or allow others to do so, for United States Govern-
ment purposes. The Department of Energy will provide public
access to these results of federally sponsored research in accor-
dance with the DOE Public Access Plan (http://energy.gov/down-
loads/doe-public-access-plan).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.cossms.2017.11.002.
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