Journal of Alloys and Compounds 938 (2023) 168684

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Microstructure and hydrogen transport properties of (V90Cr5Al5)90Cu10

alloy membranes ]]
]]]]]]
]]

⁎ ⁎
Xiao Liang a, Feifei Huang b, Songsong Xu a, , Jingjie Guo b, Dongmei Liu c, Xinzhong Li a,
a
School of Iron and Steel, Soochow University, 215000, PR China
b
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, PR China
c
Otto Schott Institute of Materials Research, Friedrich-Schiller-Universität, Jena 07743, Germany

a r t i cl e i nfo a bstr ac t

Article history: Our newly developed V90Cr5Al5 hydrogen permeable alloy has been extended to enhance malleability by Cu
Received 26 October 2022 alloying. The resulting (V90Cr5Al5)90Cu10 consists of bcc-(V) and fcc-(Cu) phases and can be cold rolled into a
Received in revised form 15 December 2022 thin membrane with a thickness of 0.1 mm due to the introduction of the ductile copper phase. After rolling
Accepted 29 December 2022
and annealing, (V90Cr5Al5)90Cu10 contains finer grains and a higher percentage of special grain boundaries
Available online 30 December 2022
compared to the as-cast case. The rolled/annealed (V90Cr5Al5)90Cu10 exhibits a lower hydrogen diffusivity
than the as-cast one, but a significantly improved hydrogen permeation flux due to the reduced membrane
Keywords:
Microstructure thickness and the inverse relationship of flux and thickness. Typically, a pronounced high hydrogen flux of
Hydrogen permeation ∼72 cc H2 cm−2min−1 was achieved at a hydrogen pressure difference of 0.6 MPa at 673 K. In comparison
(V90Cr5Al5)90Cu10 with V90Cr5Al5, Cu alloyed membranes exhibit enhanced resistance against hydrogen embrittlement and
enhanced long-term hydrogen permeation stability at 673 K.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction
The requirement for high purity hydrogen is growing rapidly in
the field of semiconductors, optical fiber, LED, clean energy, etc.
[1–4]. The purity of hydrogen acquired from most of the mass hy­
drogen production methods based on gasification and gas reforming
is insufficient for industrial application [5]. Hydrogen separation
with dense metal membranes is an efficient, economical, and en­
vironment-friendly choice for hydrogen purification. There are many
research development on metallic hydrogen permeable membranes
including Pd and its alloys [5–8], alloys of Group 5B (V, Nb, Ta)
[1,9–12], Mg-Ni alloys [13,14], etc. But the scarcity of Pd resources,
extremely high prices and harsh working conditions limit the large-
scale application of Pd and its alloys and seeking a substitute for Pd
is vital for the mass production of high purity hydrogen.
The high hydrogen permeability and low cost of the group 5B
metals make them promising candidates as substitutes for Pd.
However, the application of group 5B is limited by their faint re­
sistance against hydrogen embrittlement (HE) due to their high
hydrogen solubility. Selective alloying is a promising method for
limiting the HE by reducing the hydrogen solubility of the alloy. A
⁎
Corresponding authors.
E-mail addresses: ssxu@suda.edu.cn (S. Xu), Lixz@suda.edu.cn (X. Li).
series of alloys have been developed with the goal of achieving high
hydrogen permeability and low hydrogen solubility, including V-Ni
[15–17], V-Al [18,19], V-Pd [20,21], V-Cr [22], Nb-Mo-Co [23], Nb-W-
Mo [24], Ta-W [25], etc. Since the reduction of hydrogen solubility
has the adverse effect on hydrogen permeability, the combination of
hydrogen permeability and HE needs to be taken into consideration
during the development of hydrogen permeable alloys. According to
the previous work of our group, V90Cr5Al5 alloy has extremely high
hydrogen permeability (30.53 × 10−8 mol H2 m−1s−1Pa−0.5 at 673 K),
which is ∼19 times that of Pd, with an acceptable resistance to
HE [26].
Other than enhancing the permeability of the alloys, reducing the
thickness of the membranes is also an effective way to acquire ab­
normal hydrogen flux. However, the thickness of the V90Cr5Al5
membrane is difficult to reduce due to the solid solution strength­
ening of Cr and Al into the bcc-(V) lattice. The microhardness of
V90Cr5Al5 alloy is ∼255 HV, which is ∼2.5 times that of pure V [26].
Forming a dual-phase structure by alloying with Cu is an efficient
method to improve the malleability of an alloy, according to the
work on (V90Fe5Al5)90Cu10 [27].
In the present work, the hydrogen permeability and stability of
the dual-phase (V90Cr5Al5)90Cu10 alloy were studied. Firstly, the
microstructure of as-cast (AC) and rolled/annealed (RA)
(V90Cr5Al5)90Cu10 is characterized. Secondly, the hydrogen transfer
performance of the AC and RA-(V90Cr5Al5)90Cu10 membranes is

https://doi.org/10.1016/j.jallcom.2022.168684
0925-8388/© 2022 Elsevier B.V. All rights reserved.
X. Liang, F. Huang, S. Xu et al.
characterized, including the hydrogen solubility, the hydrogen per­
meability, and the hydrogen diffusivity. Thirdly, the stability of
(V90Cr5Al5)90Cu10 membranes is characterized by slow cooling per­
meation tests and long-term permeation tests, which are operated to
reveal the hydrogen embrittlement and endurance of the mem­
branes, respectively. Finally, the correlations between the hydrogen
transport properties and the introduced fcc-(Cu) phase are clarified.
2. Experiments
2.1. Sample preparations
V90Cr5Al5 and (V90Cr5Al5)90Cu10 ingots were prepared by arc
melting in the atmosphere of pure Ar. For each ingot, the remelt
procedure was conducted for 6 times, which included melting, so­
lidification and turning over of the ingot. The purity of the elemental
V, Cr, Al and Cu used for melting is higher than 99.95 %. The ingots
(30 g), were melted and solidified in the water-cooled copper cru­
cibles, which can provide a fast cooling rate during the solidification.
The as-cast (AC) disk samples of 12 mm in diameter used for hy­
drogen transfer performance characterization were cut from the
ingots with a spark erosion wire-cutting methine. All the surfaces of
the disk samples were ground and polished and the thickness of the
disks was controlled to be 0.6 mm.
For the rolling procedure, the rectangular samples
(25 mm × 18 mm × 7 mm) were cut from the ingots. The rolling
procedure was carried out at room temperature, and the rolling rate
was controlled to be 0.2 m/s. The deformation of each pass of the
samples was 0.2 mm. The final thicknesses of the rolled sheets were
less than 0.15 mm and the total deformation was more than 97.8 %.
More details of the rolling procedure can be found in Refs. [22,28].
Before annealing, the rolled sheets were ground and polished,
and sealed in quartz tubes filled with high purity Ar. The annealing
treatment was carried out at 1173 K for 168 h. The rolled/annealed
(RA) disk samples of 12 mm in diameter were cut from the sheets
after annealing. The final thickness (d) of the RA disk samples was
controlled as 0.1 mm due to the surface process.
2.2. Microstructure characterization
The crystallographic structure of V90Cr5Al5 and (V90Cr5Al5)90Cu10
was characterized by X-ray diffraction (XRD - Bruker D8 - 16 KW, Cu
- Kα) analysis. The microstructure and chemical composition were
analyzed by back-scattered electron (BSE), energy dispersive X-ray
(EDX), and electron back-scattered diffraction (EBSD) analysis using
scanning electron microscopy (SEM) (SEM - FEI Quanta 600FEG). The
microstructure of the bcc-(V) phase was characterized by trans­
mission electron microscopy (TEM) analysis. The samples for TEM
analysis were prepared in the following procedure. Thin samples of
thicknesses of 0.2 mm were cut from the as-cast ingot with wire-
cutting. The final thicknesses of the as-cast and the rolled/annealed
foil samples were controlled to be ∼ 0.1 mm by grinding and pol­
ishing. Round plate samples of 3 mm in diameter were punched
from the foil samples. After ion milling (GATAN695), the foil samples
were performed using transmission electron microscopy (TEM - JEM
3010, JEOL). The TEM tests were operated at 300 kV with a LaB6
cathode multiscan 1 k × 1 k CCD camera and EDX.
2.3. Hydrogen transfer performance characterization
After grinding and polishing, both surfaces of the disk samples
were coated with Pd of ∼ 600 nm in thickness for hydrogen dis­
sociation/association during the hydrogen permeation. The coating
procedure was performed using a radio frequency (RF) magnetron
sputtering machine (ZC-1000). The pressure-composition-tempera­
ture (PCT) curves were plotted at the pressure range of 0.01 ∼
2
Journal of Alloys and Compounds 938 (2023) 168684
0.8 MPa and the temperature range of 523 ∼ 673 K with a self-de­
signed Sieverts-type setup. The hydrogen solubility can be calculated
based on the pressure drop in the sample chamber during the tests.
The hydrogen permeability of the samples was measured using a
gas permeation apparatus, and the details of the apparatus can be
found in Refs. [29,30]. The Pd-coated disk membranes were sealed in
the apparatus by clamping between copper gaskets. The leakage
checks were carried out by introducing pure Ar at 0.7 MPa and
0.1 MPa to the upstream and downstream sides of the membranes
after the entire apparatus was evacuated. Then, the membrane
chamber was heated up and maintained at a certain temperature
range of 523 ∼ 673 K for 15 mins in vacuum. Pure hydrogen (5 N) at
0.15 MPa was introduced to the upstream side of the membranes to
initialize the permeation. The pressure of the upstream side (Pu) was
increased to 0.7 MPa by 0.05 MPa for each step, and the pressure of
the downstream side (Pd) was kept at 0.1 MPa. The hydrogen per­
meability can be calculated with the steady-state hydrogen flux at
each flux (J) and the hydrogen pressure.
The hydrogen permeation stability of the membranes was carried
out by analyzing the hydrogen flux at a fixed cooling rate. For each
membrane, the hydrogen pressure was maintained at 0.7 MPa on the
upstream side (Pu) and 0.1 MPa on the downstream side (Pd) during
the tests. After permeation at 673 K for 15 mins to ensure a steady-
state hydrogen flux, the membranes were cooled down to room
temperature at a controlled cooling rate of 2 K/min. The tests ended
when there was an abrupt increase in hydrogen flux during the
cooling procedure, which indicated the failure of the membrane due
to HE.
The endurance, another aspect of the stability of membranes, was
characterized by measuring the degradation of hydrogen flux in the
long-term hydrogen permeation tests for 240 h at a certain tem­
perature range of 523 ∼ 673 K. The Pu and Pd were kept at 0.7 and
0.1 MPa during the tests. After the long-term tests, SEM-EDS line
scans across the interfaces of the Pd layer and the substrate of the
membranes were carried out to characterize the interdiffusion at the
interfaces.
3. Results and discussion
3.1. Microstructure
The microstructure and XRD patterns of as-cast (V90Cr5Al5)90Cu10
and V90Cr5Al5 are shown in Fig. 1. It is obvious that V90Cr5Al5 only
consists of bcc-(V) solid solution, and the two phases of
Fig. 1. BSE images and XRD patterns of as-cast V90Cr5Al5 and (V90Cr5Al5)90Cu10.
X. Liang, F. Huang, S. Xu et al. Journal of Alloys and Compounds 938 (2023) 168684

Fig. 2. BSE images of cold-rolled (a) and rolled/annealed (b) (V90Cr5Al5)90Cu10.

(V90Cr5Al5)90Cu10 are considered as bcc-(V) and fcc-(Cu). Based on Table 1

the V-Cu binary system [31], the (V) phase can only dissolve minor Grain boundary structure for AC, CR and RA-(V90Cr5Al5)90Cu10.
amounts of Cu at temperatures lower than 673 K. The Cu element Properties Criterion Samples
solidified as fcc-(Cu) at the grain boundaries of the bcc-(V) phase. AC CR RA
According to the XRD results, the locations of the bcc-(V) peaks of
Average grain size (μm) ∼320 ∼6 ∼15
the (V90Cr5Al5)90Cu10 and V90Cr5Al5 are identical to those of pure V.
Special boundary fraction (%) length 4 28.6 16.9
There is a minor change in the lattice parameter when dissolving Cu, Twin boundary fraction (%) length 1.9 15.1 12.3
Cr and Al into V. The atomic radius of Cr (128 pm) is smaller than V
(134 pm), and Al (143 pm) is larger than V. Apparently, co-alloying V
with a comparable amount of Cr and Al has little influence on the
lattice parameter of V. the rolled/annealed (RA) samples, the fractions slightly decreased
The microstructures of cold-rolled and rolled/annealed compared with the cold-rolled (CR) samples.
(V90Cr5Al5)90Cu10 are shown in Fig. 2. As shown in Fig. 2(a), the fcc- Fig. 4 shows the TEM results of the bcc-(V) phase of as-cast (AC)
(Cu) aligned along the rolling direction after cold rolling. After an­ and rolled/annealed (RA) (V90Cr5Al5)90Cu10. Cu-rich particles are
nealing at 1173 K for 168 h, the continuous fcc-(Cu) separated into observed inside the bcc-(V) grains of the AC and RA samples, as
particles due to the instability. There are also tiny fcc-(Cu) particles shown in the TEM bright-field images in Fig. 4(a, b). Compared with
precipitated from the bcc-(V) due to the low solubility of Cu in V at the AC sample, the Cu-rich particles of the RA sample are larger in
1173 K, shown in Fig. 2(b). average size and fewer in amount. The HRTEM images, as shown in
The microstructures of as-cast, cold-rolled and rolled/annealed Fig. 4(c, d), show the lattice spacing of the bcc-(V) phase decreased
(V90Cr5Al5)90Cu10 are illustrated by EBSD maps in Fig. 3. According to from 0.21 nm of the AC sample to 0.20 nm of the RA sample.
the statistical analysis, the average size of the randomly oriented
grains of the as-cast (AC) sample is ∼320 µm. After cold-rolling (CR), 3.2. Hydrogen transport performance
the average size of the crushed grains is ∼6 µm and increases to ∼
15 µm after annealing (RA). As shown in Table 1, the fractions of To enhance the malleability of V90Cr5Al5 alloy, the dual-phase
special and twin boundaries increased after cold-rolling (CR). As for microstructure is formed by introducing the fcc-(Cu) phase. Since

Fig. 3. EBSD maps of as-cast (a), cold-rolled (b) and rolled/annealed (c) (V90Cr5Al5)90Cu10.

3
X. Liang, F. Huang, S. Xu et al.
Fig. 4. TEM bright-field and HRTEM images of as-cast (a), (c) and rolled/annealed (b), (d) (V90Cr5Al5)90Cu10.
the hydrogen permeability of the fcc-(Cu) phase is much lower than
that of the bcc-(V) phase, the hydrogen permeability decrease is
inevitable. Other than malleability and hydrogen permeability, the
resistance to hydrogen embrittlement (HE) and the sustainability
during long-term permeation are also important criteria for hy­
drogen permeable membranes. In the following, the hydrogen
transport performance of (V90Cr5Al5)90Cu10 alloy will be discussed.
3.2.1. Hydrogen solubility
The PCT curves for AC and RA-(V90Cr5Al5)90Cu10 samples at the
temperatures of 523 ∼ 673 K are plotted in the form of Sieverts’ law,
as shown in Fig. 5. At a given hydrogen pressure, with increasing
temperature, the hydrogen solubility decreases. The PCT curves for
the AC and RA samples are approximately the same. The hydrogen
concentrations (r) of AC and RA samples at 673 K in the hydrogen
atmosphere of 0.8 MPa are 0.282 and 0.285 in the form of atomic
hydrogen/metal ratio (H/M). This indicated that the hydrogen solu­
bility of the as-cast (V90Cr5Al5)90Cu10 does not change much after
cold rolling and annealing.
3.2.2. Hydrogen permeability
The steady-state hydrogen flux (J) of AC and RA-(V90Cr5Al5)90Cu10
membranes, plotted against the upstream hydrogen pressure (Pu), is
4
Journal of Alloys and Compounds 938 (2023) 168684
shown in Fig. 6(a). The downstream hydrogen pressure (Pd) was
0.1 MPa. The hydrogen flux (J) of the RA sample is much higher than
that of the AC sample under the same condition. The permeability
(Φ) of the AC and RA-(V90Cr5Al5)90Cu10 membranes, compared with
V90Cr5Al5, pure V and pure Pd, is shown in Fig. 6(b). The hydrogen
permeability (Φ) of the V90Cr5Al5 is higher than that of the
(V90Cr5Al5)90Cu10 membranes, which implies that fcc-(Cu) is a bar­
rier for hydrogen permeation. Between the (V90Cr5Al5)90Cu10 mem­
branes, the RA membrane exhibits lower permeability (Φ), which
indicates the hydrogen diffusivity (D) decreases after the rolling and
annealing, since the hydrogen solubility (K) of the alloys are merely
the same, on the basis of Φ = D×K.
The hydrogen flux (J) of AC and RA-(V90Cr5Al5)90Cu10 membranes
at Pu of 0.7 MPa and Pd of 0.1 MPa at 673 K, compared with V90Cr5Al5,
(V90Fe5Al5)90Cu10, V90Fe5Al5, and pure Pd, is shown in Fig. 7 [27,29].
The RA-(V90Cr5Al5)90Cu10 membrane exhibits a pronounced high
hydrogen flux (J) of ∼0.48 mol H2 m−2s−1 (64 cc H2 cm−2min−1),
which is ∼4.7 times that of the AC-(V90Cr5Al5)90Cu10 membrane, ∼4
times that of pure Pd (fabricated by magnetron sputtering at the
thickness of 0.07 mm) [27,29]. Due to its better malleability, the RA-
(V90Cr5Al5)90Cu10 can achieve a much lower thickness than the AC-
(V90Cr5Al5)90Cu10 during the cold rolling procedure, which leads to a
higher hydrogen flux (J), although the RA membrane has a lower
X. Liang, F. Huang, S. Xu et al. Journal of Alloys and Compounds 938 (2023) 168684

Fig. 5. PCT curves for as-cast (AC) (a) and rolled/annealed (RA) (b) (V90Cr5Al5)90Cu10 membranes.

Fig. 6. Steady-state hydrogen flux (J) plotted against upstream hydrogen pressure (Pu) for different as-cast (AC) and rolled/annealed (RA) (V90Cr5Al5)90Cu10 membranes (a);
hydrogen permeability (Φ) of pure V, Pd and different V-based membranes (b).

hydrogen permeability (Φ). Due to the higher hydrogen permeability
(Φ) of the V90Cr5Al5 than V90Fe5Al5 and lower thickness, The hy­
drogen flux (J) of RA-(V90Cr5Al5)90Cu10 is ∼1.9 times higher than that
of the RA-(V90Fe5Al5)90Cu10.
3.2.3. Hydrogen diffusivity
According to Fisk’s first law, the hydrogen diffusivity coefficients
(D) of AC and RA-(V90Cr5Al5)90Cu10 can be calculated by D=J×d/ΔC, as
shown in Fig. 8. The ΔC is the hydrogen concentration difference
between the upstream and the downstream surfaces of the mem­
brane, which can be acquired from the hydrogen solubility results
(PCT curve). It is worth noticing that the D value increases with the
average hydrogen concentration ((ru+ rd)/2), due to the potential
barrier for the hydrogen atom to hop between interstitial sites de­
creasing with the increasing hydrogen solubility [32,33]. After
rolling and annealing, the recrystallized fcc-(Cu) particles dis­
tributed along the rolling direction and the nanoscale fcc-(Cu) par­
ticles precipitated from the bcc-(V) matrix are hindered for
hydrogen transportation, shown in Fig. 2 and Fig. 4, which lead to a
lower hydrogen diffusivity.
3.3. Hydrogen permeation stability
The stability during the hydrogen permeation contains the sen­
sitivity to hydrogen embrittlement (HE) and the degradation of hy­
drogen flux during long-term application. The HE of the membranes

5
X. Liang, F. Huang, S. Xu et al.
Fig. 7. Steady-state hydrogen flux (J) at 673 K for as-cast (AC) and rolled/annealed
(RA) membranes of (V90Cr5Al5)90Cu10, V90Cr5Al5, (V90Fe5Al5)90Cu10, V90Fe5Al5 and
Pure Pd. [27,29].
Fig. 8. Apparent hydrogen diffusion coefficients (D) against hydrogen concentration
((ru+ rd)/2) at 523∼673 K of as-cast (AC) (a) and rolled/annealed (RA) (b)
(V90Cr5Al5)90Cu10 membranes.
is characterized by analyzing the hydrogen permeation flux under
controlled cooling rates of 2 K/min, as shown in Fig. 9. The hydrogen
flux decreases with decreasing temperature. The abrupt increase in
the hydrogen flux that occurs during the cooling indicates that the
integrity of the membrane is undermined. The failure of membranes
was observed only on the AC samples. For (V90Cr5Al5)90Cu10, the
temperature of HE failure is a bit lower than V90Cr5Al5, which in­
dicated that the inserting of fcc-(Cu) slightly enhanced the me­
chanical stability of V90Cr5Al5 [26]. There is no abrupt increase in the
hydrogen flux observed in the hydrogen permeation flux curve of the
RA-(V90Cr5Al5)90Cu10, showing the outstanding resistance to HE of
the RA sample. Since the hydrogen solubility of the AC and RA
6
Journal of Alloys and Compounds 938 (2023) 168684
Fig. 9. Hydrogen permeation flux during cooling from 673 K at a cooling rate of 2 K/
min for as-cast (AC) and rolled/annealed (RA) membranes of (V90Cr5Al5)90Cu10 and
V90Cr5Al5. [26].
samples are almost the same, the resistance of HE for the RA samples
is attributed to the even distribution of the fine fcc-(Cu) phase in the
bcc-(V) matrix and the smaller grain size of the bcc-(V) (Fig. 3).
The degradation of hydrogen flux during long-term permea­
tion is commonly observed in V-based hydrogen permeable
membranes. The results of the long-term permeation tests of the
RA-(V90Cr5Al5)90Cu10 membranes are shown in Fig. 10. For each
temperature, the hydrogen flux decreases during the long-term
tests, but the decreasing rate gets slower along with time. After
hydrogen permeation for 240 h at 673 K, the relative hydrogen flux
(J/J0) of RA-(V90Cr5Al5)90Cu10 membranes dropped to 90.5 %. As
the temperature decrease, the relative hydrogen flux after 240 h is
90.9 % at 623 K, 91.6 % at 573 K, and 98.2 % at 523 K. According to
Fig. 10(b), during the long-term tests, the AC-(V90Cr5Al5)90Cu10
membrane exhibits a higher hydrogen permeation flux than that
of the V90Cr5Al5, which indicates that the fcc-(Cu) phase enhanced
the hydrogen permeation stability of the V-based alloy. The RA-
(V90Cr5Al5)90Cu10 membrane shows the highest stability during
hydrogen permeation.
According to our previous research, the degradation of hy­
drogen flux during the long-term test is related to the aggregation
of the Pd layer, and the interdiffusion between the Pd coating
layer and the V-based substrate [34]. The composition profiles
across the interface of the AC and RA membranes after long-term
tests are analyzed, as shown in Fig. 11. The concentration of Pd
slowly decreases from the surface to the substrate of the mem­
branes, indicating that the interdiffusion between the Pd layer and
the substrate occurs after the long-term tests. The thickness of the
interdiffusion layer is ∼1 µm after the 240 h permeation test at
673 K for the AC membrane. As for the RA sample, the thickness of
the interdiffusion layer is ∼0.5 µm after the long-term test. There
are pin holes on the surface of the Pd layer of both the AC and RA
membranes. According to our previous work, the evenly dis­
tributed pin holes will not change the hydrogen flux [34]. There­
fore, the permeation stability during the long-term tests of the
RA-(V90Cr5Al5)90Cu10 membranes is enhanced due to the re­
sistance of interdiffusion between the Pd layer and the RA sub­
strate. The resistance to interdiffusion can be attributed to the
parallel structure of the matrix caused by cold rolling.
X. Liang, F. Huang, S. Xu et al. Journal of Alloys and Compounds 938 (2023) 168684

Fig. 10. Sustainable hydrogen permeability of rolled/annealed (RA) (V90Cr5Al5)90Cu10 alloy at different temperatures (a) and comparison of the degradation in normalized
hydrogen permeation flux between as-cast (AC) and rolled/annealed (RA) (V90Cr5Al5)90Cu10 membranes (b).

Fig. 11. Composition profiles across the interface and the SEM results of the Pd layer for different as-cast (AC) (a) and rolled/annealed (RA) (b) (V90Cr5Al5)90Cu10 membranes after
hydrogen permeation for 240 h at 673 K.

4. Conclusions Resources. Dongmei Liu: Conceptualization, Supervision, Writing –

review & editing. Xinzhong Li: Conceptualization, Funding ccquisi­
Dual-phase (V90Cr5Al5)90Cu10 malleable alloy has been developed tion, Resources, Supervision, Writing – review & editing, Project
by introducing the fcc-(Cu) phase into the V90Cr5Al5 hydrogen administration.
permeable alloy. The hydrogen permeability and stability of the
(V90Cr5Al5)90Cu10 membranes were investigated experimentally. By
cold-rolling, the thickness of the membrane reaches 0.1 mm due to Data Availability
the malleability enhancement of the fcc-(Cu) phase. After rolling and
annealing, the hydrogen solubility has little change. The hydrogen No data was used for the research described in the article.
permeation flux of the RA-(V90Cr5Al5)90Cu10 membrane has reached
0.48 mol H2 m−2s−1 at 673 K (∼64 cc H2 cm−2min−1), which is ∼4.7
times that of the AC membrane, although the RA membrane is lower Declaration of Competing Interest
on hydrogen diffusivity. The RA membranes exhibit higher stability
against hydrogen embrittlement at low temperatures attributed to The authors declare that they have no known competing fi­
the even distribution of the fcc-(Cu) phase and the smaller size of nancial interests or personal relationships that could have appeared
the bcc-(V) grains. The introduction of fine fcc-(Cu) particles also to influence the work reported in this paper.
hinders the interdiffusion between the Pd layer and the substrate
alloy, which enhances the stability of the (V90Cr5Al5)90Cu10 mem­
branes during long-term permeation. Acknowledgments

CRediT authorship contribution statement
Xiao Liang: Investigation, Data curation, Methodology, Writing –
original draft. Feifei Huang: Investigation, Methodology. Songsong
Xu: Data curation, Writing – review & editing. Jingjie Guo:
This project was supported by the National Natural Science
Foundation of China (Grant Nos. 52171043 and 52101148), the
Natural Science Foundation of Jiangsu Province (Grant No.
BK20210725) and the Major Science and Technology R & D Projects
in Shunyi District, Beijing.

7
X. Liang, F. Huang, S. Xu et al.
References
[1] M.D. Dolan, Non-Pd BCC alloy membranes for industrial hydrogen separation, J.
Membr. Sci. 362 (2010) 12–28, https://doi.org/10.1016/j.memsci.2010.06.068
[2] T. Sinigaglia, F. Lewiski, M.E.S. Martins, J.C.M. Siluk, Production, storage, fuel
stations of hydrogen and its utilization in automotive applications-a review, Int.
J. Hydrog. Energy 42 (2017) 24597–24611, https://doi.org/10.1016/j.ijhydene.
2017.08.063
[3] W. Liu, H. Zuo, J. Wang, Q. Xue, B. Ren, F. Yang, The production and application of
hydrogen in steel industry, Int. J. Hydrog. Energy 46 (2021) 10548–10569,
https://doi.org/10.1016/j.ijhydene.2020.12.123
[4] A.M. Oliveira, R.R. Beswick, Y. Yan, A green hydrogen economy for a renewable
energy society, Curr. Opin. Chem. Eng. 33 (2021) 100701, https://doi.org/10.1016/
j.coche.2021.100701
[5] F. Borgognoni, S. Tosti, M. Vadrucci, A. Santucci, Combined methane and ethanol
reforming for pure hydrogen production through Pd-based membranes, Int. J.
Hydrog. Energy 38 (2013) 1430–1438, https://doi.org/10.1016/j.ijhydene.2012.11.
036
[6] F. Gallucci, S. Tosti, A. Basile, Pd–Ag tubular membrane reactors for methane dry
reforming: A reactive method for CO2 consumption and H2 production, J. Membr.
Sci. 317 (2008) 96–105, https://doi.org/10.1016/j.memsci.2007.03.058
[7] Z. Yin, Z. Yang, M. Du, J. Mi, L. Hao, Y. Tong, Y. Feng, S. Li, Effect of annealing
process on the hydrogen permeation through Pd–Ru membrane, J. Membr. Sci.
654 (2022) 120572, https://doi.org/10.1016/j.memsci.2022.120572
[8] N.A. Al-Mufachi, S. Nayebossadri, J.D. Speight, W. Bujalski, R. Steinberger-
Wilckens, D. Book, Effects of thin film Pd deposition on the hydrogen perme­
ability of Pd60Cu40 wt% alloy membranes, J. Membr. Sci. 493 (2015) 580–588,
https://doi.org/10.1016/j.memsci.2015.07.015
[9] D.M. Viano, M.D. Dolan, F. Weiss, A. Adibhatla, Asymmetric layered vanadium
membranes for hydrogen separation, J. Membr. Sci. 487 (2015) 83–89, https://
doi.org/10.1016/j.memsci.2015.03.048
[10] Z.-j Xu, Z.-m Wang, J.-l Tang, J.-q Deng, Q.-r Yao, H.-y Zhou, Effects of Mo alloying
on the structure and hydrogen-permeation properties of Nb metal, J. Alloy.
Compd. 740 (2018) 810–815, https://doi.org/10.1016/j.jallcom.2018.01.076
[11] Y. Erhu, L. Wei, W. Hao, Z. Kexiang, G. Xiaoyu, H. Renjun, C. Jian, Z. Yongjin,
C. Hailiang, Z. Huanzhi, X. Fen, S. Lixian, Quaternary Nb-Hf-Co-Fe alloy with
superior hydrogen permeation properties over a wide temperature range, J.
Alloy. Compd. 912 (2022) 165232, https://doi.org/10.1016/j.jallcom.2022.165232
[12] H. Yukawa, A. Teshima, D. Yamashita, S. Ito, S. Yamaguchi, M. Morinaga, Alloying
effects on the hydriding properties of vanadium at low hydrogen pressures, J.
Alloy. Compd. 337 (2002) 264–268, https://doi.org/10.1016/S0925-8388(01)
01936-3
[13] H. Fu, W. Wu, Y. Dou, B. Liu, H. Li, Q. Peng, Hydrogen diffusion kinetics and
structural integrity of superhigh pressure Mg-5 wt%Ni alloys with dendrite in­
terface, J. Power Sources 320 (2016) 212–221, https://doi.org/10.1016/j.jpowsour.
2016.04.045
[14] X. Ding, R. Chen, Y. Jin, X. Chen, J. Guo, Y. Su, H. Ding, H. Fu, Activation mechanism
and dehydrogenation behavior in bulk hypo/hyper-eutectic Mg-Ni alloy, J. Power
Sources 374 (2018) 158–165, https://doi.org/10.1016/j.jpowsour.2017.11.034
[15] M.D. Dolan, G. Song, K.G. McLennan, M.E. Kellam, D. Liang, The effect of Ti on the
microstructure, hydrogen absorption and diffusivity of V–Ni alloy membranes, J.
Membr. Sci. 415–416 (2012) 320–327, https://doi.org/10.1016/j.memsci.2012.05.
012
[16] G. Song, M.E. Kellam, D. Liang, M.D. Dolan, Influence of processing conditions on
the microstructure and permeability of BCC V–Ni membranes, J. Membr. Sci. 363
(2010) 309–315, https://doi.org/10.1016/j.memsci.2010.07.051
[17] J.-Y. Oh, W.-S. Ko, J.-Y. Suh, Y.-S. Lee, B.-J. Lee, W.Y. Yoon, J.-H. Shim, Enhanced
high temperature hydrogen permeation characteristics of V–Ni alloy membranes
containing a trace amount of yttrium, Scr. Mater. 116 (2016) 122–126, https://doi.
org/10.1016/j.scriptamat.2016.02.003
Journal of Alloys and Compounds 938 (2023) 168684
[18] S. Kumar, M. Taxak, N. Krishnamurthy, A.K. Suri, G.P. Tiwari, Terminal solid so­
lubility of hydrogen in V–Al solid solution, Int. J. Refract. Met. Hard Mater. 31
(2012) 76–81, https://doi.org/10.1016/j.ijrmhm.2011.09.009
[19] C. Nishimura, T. Ozaki, M. Komaki, Y. Zhang, Hydrogen permeation and trans­
mission electron microscope observations of V–Al alloys, J. Alloy. Compd.
356–357 (2003) 295–299, https://doi.org/10.1016/S0925-8388(02)01273-2
[20] V.N. Alimov, A.O. Busnyuk, M.E. Notkin, E.Y. Peredistov, A.I. Livshits,
Substitutional V–Pd alloys for the membranes permeable to hydrogen: hydrogen
solubility at 150–400 °C, Int. J. Hydrog. Energy 39 (2014) 19682–19690, https://
doi.org/10.1016/j.ijhydene.2014.09.122
[21] V.N. Alimov, I.V. Bobylev, A.O. Busnyuk, M.E. Notkin, E.Y. Peredistov, A.I. Livshits,
Hydrogen transport through the tubular membranes of V-Pd alloys: permeation,
diffusion, surface processes and WGS mixture test of membrane assembly, J.
Membr. Sci. 549 (2018) 428–437, https://doi.org/10.1016/j.memsci.2017.12.017
[22] X. Li, F. Huang, D. Liu, X. Liang, R. Chen, M. Rettenmayr, Y. Su, J. Guo, H. Fu, V-Cr-
Cu dual-phase alloy membranes for hydrogen separation: an excellent combi­
nation of ductility, hydrogen permeability and embrittlement resistance, J.
Membr. Sci. 524 (2017) 354–361, https://doi.org/10.1016/j.memsci.2016.11.020
[23] F. Liu, Z. Xu, Z. Wang, M. Dong, J. Deng, Q. Yao, H. Zhou, Y. Ma, J. Zhang, N. Wang,
Z. Guo, Structures and mechanical properties of Nb-Mo-Co(Ru) solid solutions
for hydrogen permeation, J. Alloy. Compd. 756 (2018) 26–32, https://doi.org/10.
1016/j.jallcom.2018.04.235
[24] Y. Awakura, T. Nambu, Y. Matsumoto, H. Yukawa, Hydrogen solubility and per­
meability of Nb–W–Mo alloy membrane, J. Alloy. Compd. 509 (2011) S877–S880,
https://doi.org/10.1016/j.jallcom.2010.10.133
[25] H. Yukawa, T. Nambu, Y. Matsumoto, Ta-W alloy for hydrogen permeable
membranes, Mater. Trans. (2011) 610–613.
[26] F. Huang, X. Li, X. Shan, J. Guo, F. Gallucci, M. van Sint Annaland, D. Liu, Hydrogen
transport through the V-Cr-Al alloys: hydrogen solution, permeation and
thermal-stability, Sep. Purif. Technol. 240 (2020) 116654, https://doi.org/10.
1016/j.seppur.2020.116654
[27] X. Li, F. Huang, Y. Su, J. Guo, M. Rettenmayr, D. Liu, Development of dual-phase
V90Fe5Al5/Cu alloys for enhanced malleability and sustainable hydrogen per­
meability, J. Membr. Sci. 591 (2019) 117325, https://doi.org/10.1016/j.memsci.
2019.117325
[28] X. Li, D. Liu, X. Liang, R. Chen, M. Rettenmayr, Y. Su, J. Guo, H. Fu, Hydrogen
transport behavior of as-cast, cold rolled and annealed Nb40Ti30Co30 alloy
membranes, J. Membr. Sci. 514 (2016) 294–304, https://doi.org/10.1016/j.
memsci.2016.04.055
[29] J.Y. Yang, C. Nishimura, M. Komaki, Effect of overlayer composition on hydrogen
permeation of Pd–Cu alloy coated V–15Ni composite membrane, J. Membr. Sci.
282 (2006) 337–341, https://doi.org/10.1016/j.memsci.2006.05.037
[30] J.Y. Yang, C. Nishimura, M. Komaki, Hydrogen permeation of Pd60Cu40 alloy
covered V–15Ni composite membrane in mixed gases containing H2S, J. Membr.
Sci. 309 (2008) 246–250, https://doi.org/10.1016/j.memsci.2007.10.036
[31] M. Hämäläinen, K. Jääskeläinen, R. Luoma, M. Nuotio, P. Taskinen, O. Teppo, A
thermodynamic analysis of the binary alloy systems Cu-Cr, Cu-Nb and Cu-V,
Calphad 14 (1990) 125–137, https://doi.org/10.1016/0364-5916(90)90014-Q
[32] J. Evtimova, E. Drioli, G. De Luca, A density functional theory study of hydrogen
occupation in VNiTi alloys used for dense metal membranes, J. Alloy. Compd.
665 (2016) 225–230, https://doi.org/10.1016/j.jallcom.2016.01.037
[33] D.S. Sholl, Using density functional theory to study hydrogen diffusion in metals:
a brief overview, J. Alloy. Compd. 446–447 (2007) 462–468, https://doi.org/10.
1016/j.jallcom.2006.10.136
[34] X. Liang, X. Li, H. Nagaumi, J. Guo, F. Gallucci, M. van Sint Annaland, D. Liu,
Degradation of Pd/Nb30Ti35Co35/Pd hydrogen permeable membrane: a numer­
ical description, J. Membr. Sci. 601 (2020) 117922, https://doi.org/10.1016/j.
memsci.2020.117922