Journal of Membrane Science 415–416 (2012) 320–327

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Journal of Membrane Science

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

The effect of Ti on the microstructure, hydrogen absorption and diffusivity

of V–Ni alloy membranes
M.D. Dolan a,n, G. Song b, K.G. McLennan a, M.E. Kellam b, D. Liang b
a
CSIRO, Energy Technology, Pullenvale, QLD 4069, Australia
b
CSIRO, Process Science and Engineering, Clayton, VIC 3168, Australia

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

Article history: Vanadium is highly permeable to hydrogen which makes it one of the leading alternatives to Pd alloys
Received 29 February 2012 for hydrogen-selective alloy membrane applications. The tendency of vanadium to embrittle can be
Received in revised form reduced through alloying, thereby enabling V-based membranes to be developed for specific operating
13 April 2012
regimes. Foremost amongst these alloying additives are Ni and Ti. Ni is known to form V–Ni solid
Accepted 6 May 2012
solutions with decreased hydrogen absorption and diffusivity compared to V. The influence of Ti is
Available online 14 May 2012
more complex due to phase segregation, and this work focuses the influence of Ti on the micro-
Keywords: structural and chemical properties of hydrogenated vanadium–nickel solid solution alloys. Alloy
Hydrogen membranes of the compositions V90  xTixNi10 (where 2 rx r 10) were prepared by the sectioning
Membrane
arc-melted ingots and the deposition of a Pd dissociation/recombination catalyst at each surface.
Alloy
Hydrogen permeation measurements were undertaken using the constant pressure method, with feed
Vanadium
Nickel pressures ranging from 1 to 10 bar, permeate pressures o0.05 bar via use of a sweep gas, and
Titanium temperatures of 350 and 400 1C. Hydrogen absorption of these same alloys was measured under
corresponding conditions using the Sieverts’ method. The microstructures featured a dendritic
(branched) body-centred cubic vanadium solid solution matrix with interdendritic Ni–Ti compounds.
The Ti content in the matrix increased, while the Ni content decreased, with increasing bulk Ti content.
Hydrogen diffusivity increased with increasing bulk Ti content and increasing dissolved hydrogen
concentration. The Ni–Ti compounds, known for being weakly hydrogen absorbing, also scavenge
oxygen from the vanadium matrix, both of which are important in enhancing the embrittlement
resistance of these alloys. This work has shown that Ti is a favourable additive for vanadium–nickel
alloy membranes when added in the amount of  10 at%, with a hydrogen diffusivity (DH) equal to
4.2  10  8 m2 s  1 and hydrogen permeability of 1.2  10  7 mol  1 s  1 Pa  0.5 corresponding to a feed
pressure of 10 bar and temperature of 400 1C.
& 2012 Published by Elsevier B.V.

1. Introduction alloy membrane. A membrane reactor can, in a single stage,

The production of H2 from hydrocarbon-based feedstocks also
produces CO2 as a by-product, and the H2/CO2 mixture must be
separated to purify the H2 fuel and enable pre-combustion CO2
capture. As a consequence, the continued uptake of H2 as an
energy carrier is limited by the state-of-the-art in H2/CO2 separa-
tion technology. H2-selective membranes which offer continuous,
high-temperature separation are one of the prospective technol-
ogies presently under development in response to this need.
One of the targeted applications of H2-selective membrane
technology is the water–gas-shift (WGS) membrane reactor, a
device which couples a WGS catalyst with a hydrogen-selective
n
Corresponding author. Tel.: þ61 7 3327 4126.
E-mail address: michael.dolan@csiro.au (M.D. Dolan).
convert the CO component of a synthesis gas (derived from coal,
methane or other suitable hydrocarbon) to CO2 þH2 via reaction
with steam, simultaneously extract H2 and contain the CO2 at high
pressure in the raffinate [1–3]. Compared to separate shift and
separation processes, the membrane reactor offers the advantages
of process intensification and an artificially-high equilibrium con-
version brought about by the continuous depletion of the H2
reaction product from the reactor.
Of the various classes of H2-selective membrane, alloy mem-
branes are well suited to synthesis gas (syngas) conversion
processes as they can operate at compatible temperatures, and
are reasonably resistant to syngas and its impurities. Palladium
alloys are the accepted benchmark material for alloy membranes,
but the high price of palladium is driving the development of less-
expensive alternatives, especially in light of cost targets set by the
US Department of Energy [4].

0376-7388/$ - see front matter & 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.memsci.2012.05.012
 M.D. Dolan et al. / Journal of Membrane Science 415–416 (2012) 320–327
The most promising alternative, non-Pd alloy membrane
materials are those based on Group IVb and Vb in the periodic
table (Ti, V, Zr, Nb, Ta), particularly those with body-centred cubic
(BCC) or amorphous structures. The high permeability of BCC
metals and alloys has been known for some time [5], and several
groups have examined V [6–9], Nb [10–13] and Ta [14,15] alloys
for their applicability to hydrogen separation membranes. These
metals exhibit several major shortcomings which have limited
their industrial deployment [16]. Of most concern is their exces-
sive hydrogen absorption which can lead to brittle failure due to
decohesion or hydride precipitation.
These absorption-related deficiencies have driven the develop-
ment of alloys with reduced hydrogen absorption. The V–Ni alloys
[6,17,18] are the best example of this approach, with the addition of
Ni reducing hydrogen absorption to levels where mechanical stabi-
lity is greatly improved. Hydrogen permeability can be approxi-
mated as the product of absorption and diffusivity, and as a
consequence, any reduction in absorption to minimise embrittle-
ment-related issues will also reduce membrane permeability.
A strategy is required, therefore, to develop an alloy which max-
imises the diffusivity of hydrogen while minimising embrittlement
through (i) controlling absorption in the BCC phase, and/or (ii)
tailoring the microstructure to enhance embrittlement resistance.
Microstructures comprising a permeable phase combined with
a stabilizing phase is one possible route to creating a durable alloy
membrane. Previous investigations by the present authors [19] and
other [20,21] groups showed that addition of Ti to V–Ni BCC solid
solutions resulted in formation of a multi-phase microstructure
containing a primary BCC solid solution and weakly-absorbing
compounds based on NiTi and NiTi2 which are thought to stabilise
the structure against brittle failure during permeation. For amor-
phous alloys, partial devitrification could yield a similar result, and
Brinkman et al. [22] and Yamaura et al. [23] on Fe–Ni–B–Mo and Ni–
Nb–Zr glasses respectively have explored microstructure–permeation
relationships.
The main potential drawback of this approach is the creation of
diffusion barriers. In V–Ni–Ti alloys the Ni–Ti phases can act as
barriers to hydrogen diffusion [19], thereby dramatically decreasing
the hydrogen diffusivity through the bulk alloy. This can be
compensated by tailoring the alloy content to increase the hydrogen
absorption, but given the negative effect of hydrogen absorption on
the mechanical properties of alloys, this approach cannot be applied
indiscriminately. The ideal approach is to maintain the interconnect-
ing BCC structure while still precipitating sufficient Ni–Ti com-
pounds to provide enhanced mechanical properties.
The present research will examine the role of Ti on the
microstructure, hydrogen absorption and diffusivity in a compo-
sitional range which does not lead to formation of an intercon-
necting Ni–Ti microstructure. The previous study by this group
focused on alloys in the V85  xTixNi15 series, where Ti was-
r30 at%. In this series, alloys with TiZ15 at% formed the inter-
connecting dendritic microstructure which inhibited the
diffusivity of hydrogen. In addition, it is known that Ni reduces
both hydrogen absorption and diffusivity [18], so any reduction in
Ni content will significantly enhance permeability. Consequently,
the present study focuses on alloys in the V90  xTixNi10 series,
where Ti is between 2 and 10 at%. The V90Ni10 (i.e., Ti¼0) alloy
was studied previously and will not be considered here.
2. Experimental
2.1. Membrane preparation
Alloy ingots were formed from high purity (99.99%) vanadium,
titanium and nickel pellets which were melted several times until
321
homogeneous on a water-cooled copper hearth using a vacuum/
argon arc melter. The arc-melted ingots were sectioned into
1000 mm-thick wafers using electrical discharge machining (EDM),
and the surfaces were mechanically polished and chemically
cleaned. Finally, each surface was sputter coated with a 500 nm-
thick Pd dissociation/recombination catalyst.
2.2. Microstructural analysis
Metallographic observation of the alloy microstructures was
carried out on polished samples in back-scattered electron (BSE)
mode using a Quanta 400 FEG-SEM. Phase quantification was
achieved using Image-Pro Plus 5.1 software.
X-ray diffraction (XRD) measurements were made with a
Bruker D8 advance X-ray diffractometer with Cu Ka radiation
(40 kV, 40 mA). The samples were scanned over the 2-theta range
20–1301 with a step size of 0.021 and a count time of 4 s. Analyses
were performed on the collected X-ray diffraction data using the
Bruker XRD search match programme EVA. Crystalline phases
were identified from the ICDD-JCPDS powder diffraction database.
Lattice parameters of the V-solid solution present in each alloy
were determined using the Pawley method [24] through the
Bruker TOPAS V4.2 program.
Quantitative composition analysis was performed on the BCC
V-solid solution and minor compounds using a JEOL 8500F electron
microprobe. The intensity measurements were conducted at 12 kV
accelerating voltage and a beam current of 30 nA. Oxygen quanti-
fication was carried out under the above conditions by measuring
the O Ka line. The oxygen detection limit for the instrument was
1 wt% due to partial overlap of the V and O emission spectra.
Electron back-scatter diffraction (EBSD) technique was used
for phase analysis of intermetallic compounds in the multi-phase
alloys. A JEOL 7001F field emission gun scanning electron micro-
scope (FEG-SEM) was used to collect Kikuchi patterns under
specimen inclination of 701 and operating at 20 kV. The acquired
EBSD patterns were indexed for phase determination using
Oxford Instruments Channel 5 HKL software.
O, N and C quantification was performed on bulk samples
(  9  3  3 mm3) of pure starting materials and the V80Ni10Ti10
alloy using a LECO elemental analyser.
2.3. Permeation testing
Hydrogen flux was measured at 350 and 400 1C in a custom-
designed apparatus using the constant pressure method [18].
A feed mixture of 90% H2 þ10% CO2 was passed over the feed
surface at pressures ranging from 1 to 10 bar (a), at one bar
intervals and at rates sufficient to prevent concentration polarisa-
tion. H2 permeated across the membrane where it was removed
from the reactor by a stream of Ar at ambient pressure. A gas
chromatograph, calibrated against standard gas mixtures, was
used to determine the resulting H2 concentration in the Ar
stream. The Ar flow rates were varied to maintain the H2 content
at o2%. Detection of CO2 in the Ar stream was used to indicate to
detect the presence of defects in the membrane. The resulting
concentration of H2 in the Ar stream was used to calculate the H2
flux across the membrane.
2.4. Absorption measurements
Hydrogen absorption was measured using the Sieverts’ tech-
nique in a custom-built apparatus [18]. Multiple desorption
isotherms were measured for each condition until duplicate
measurements were achieved. Measurements were performed
on alloy samples after previous permeation testing up to a
pressure of 15 bar (a) and at temperatures of 350 and 400 1C.
322 M.D. Dolan et al. / Journal of Membrane Science 415–416 (2012) 320–327

3. Results and discussion
3.1. Microstructure
All alloys in this series solidify via a dendritic (branched)
primary vanadium solid solution (VSS) with inter-dendritic inter-
metallic compounds. The resulting multi-phase microstructures
are shown in Fig. 1. Irregular shrinkage pores are evident at the
grain boundaries and between dendrites, but these are discontin-
uous and do not allow leakage of gases across the membrane. The
differences in contrast in Fig. 1 reflect segregation between Ni and
V/Ti, and crystallographic orientation of the VSS grains [19,25,26].
The addition of Ti modifies the Ni-solute partitioning to allow
the formation of Ni–Ti compounds. The compositional data in
Table 1 shows that addition of Ti progressively reduces the Ni
content in the VSS, while the majority of Ti is retained in the VSS.

Fig. 1. Micrographs of (a) V88Ti2Ni10, (b) V86Ti4Ni10, (c) V84Ti6Ni10, (d) V82Ti8Ni10, (e) V80Ti10Ni10, showing the VSS phase (several grey shades), Ni–Ti compounds (white)
and voids (black).
 M.D. Dolan et al. / Journal of Membrane Science 415–416 (2012) 320–327 323

Table 1
Chemical and structural characteristics of V90  xTixNi10 alloys.

Alloy Lattice Composition Volume Phases present

parameter VSS of VSS (%) fraction of
phase (at%) VSS (Å)

V88Ti2Ni10 V90.9Ti1.4Ni7.7 3.0120 7 0.0005 99.2 VSS, s, NiTi, NiTi2

V86Ti4Ni10 V90.6Ti2.9Ni6.5 3.0180 7 0.0006 98.5 VSS, s, NiTi, NiTi2
V84Ti6Ni10 V89.9Ti4.0Ni6.2 3.0237 7 0.0003 96.1 VSS, s, NiTi, NiTi2
V82Ti8Ni10 V89.1Ti5.1Ni5.7 3.0312 7 0.0002 96.8 VSS, NiTi, NiTi2
V80Ti10Ni10 V87.7Ti6.5Ni5.8 3.0333 7 0.0001 96.3 VSS, NiTi, NiTi2

Table 2
Oxygen concentration determined by LECO and microprobe (n.d. denotes oxygen
was not detected).

Raw material Alloy Phase Fig. 2. XRD patterns of alloys in the V90  xTixNi10 series. Peak positions for Vss (J)
and NiTi2 (&) are shown. The concentration of other phases is below the
V Ni Ti V90Ni10 V80Ti10Ni10 VSS NiTi NiTi2 detection limit.

LECO 0.36 o 0.006 0.09 0.61 0.52

(wt%)
Probe n.d.
(wt%) (i.e.,o1)
This is also evidenced by the expansion of the VSS lattice with
increasing bulk Ti content, since Ti is larger than Ni [27]. The VSS
volume fraction decreases as the bulk Ti concentration increases,
but this BCC phase still accounted for 96% of the total alloy
volume in the in the highest-Ti alloy, greater than the 94% at
which hydrogen diffusion is blocked [19] (Table 2).
Different types of intermetallic compounds precipitate in the
interdendritic regions after formation of the vanadium solid solu-
tion. These phases are the s-phase, formed through peritectic
reaction (between the solid and liquid phases) and with a compo-
sition of V66.7Ti5.8Ni27.5 or (V,Ti)72.5Ni27.5 [28], as well as NiTi and
NiTi2 compounds (with partial V dissolution) which were identified
previously. The relative amounts of these compounds are depen-
dent on bulk Ti content. The s-phase only forms where Tir6%, and
at higher Ti contents the Ni–Ti precipitates become larger and
more populous. Even at the highest Ti content the VSS remains
continuous and consequently there are no barriers to hydrogen
diffusion as observed with higher-Ti alloys.
Fig. 2 shows XRD patterns for each alloy in the series. The
content of NiTi2 clearly increases with increasing Ti content, but
other compounds are present at levels below the detection limit.
The figure also clearly shows the increase in VSS lattice parameter
with increasing bulk Ti content, as evidenced by the shift to lower
2-theta angles.
3.2. Distribution of O, N and C
Chemical analysis showed that the total weight per cent of
CþN in the arc-cast alloys was between 0.01 and 0.03 wt%, which
is almost same as that of the starting material. This content
of these trace elements is not considered to be significant.
The content of oxygen in the arc-cast alloys V90Ni10 and
V80Ni10Ti10 was calculated to be 0.31 and 0.29 wt% respectively.
The comparison between the calculated and measured values
indicates the extra oxygen is introduced during the arc-melting
process.
Microprobe measurements were carried out on the VSS matrix
regions of V90Ni10, and the VSS, NiTi and NiTi2 regions in V80Ni10Ti10.
The O concentrations measured in each VSS matrix in each alloy
were below the detection limit of the spectrometer used. The
1.22 3.83
highest oxygen content was found in the NiTi2 compound which
supports the hypothesis that Ti acts to scavenge oxygen from the
VSS matrix. Amano et al. [29] showed that removal of oxygen from
the VSS phase enhances diffusivity, so the role of Ti in scavenging
oxygen should be beneficial. This analysis was hindered somewhat
by the poor sensitivity of the instrumentation due to overlap
between the O Ka and V b emission lines, but despite this, the role
of the Ti in scavenging oxygen is clear, and supported by the
relative positions of V, Ni and Ti on an Ellingham diagram for oxide
formation. Aluminium, another previously-reported alloying addi-
tion for V-based alloy membranes [30], would demonstrate a
similar oxygen scavenging effect.
3.3. Hydrogen absorption
Hydrogen absorption isotherms for each alloy are shown in
Fig. 3. As with other alloys in the V–Ni [18] and Pd–Ag [31]
systems reported previously, Sieverts’ law (i.e., concentration is
proportional to p0.5) is not followed at high H/M loadings, with
the Sieverts’ exponent (n) decreasing with increasing hydrogen
concentration. Given the high hydrogen concentrations involved,
there are fundamental changes in the physical and electronic
properties of the host alloy and as a consequence, an alternative
interpretation is that the Sieverts’ constant is actually a function
of dissolved hydrogen concentration.
In amorphous alloys, deviation from Sieverts’ behaviour is
attributed to a distribution of site energies in the host metal, with
favourable sites filling first (at low pressure), and less-favourable
sites filling progressively as pressure increases [32]. In crystalline
alloys the distribution of site energies are almost discrete (allow-
ing for defects formed during casting). The observed behaviour is
more likely a function of the expansion of the host lattice which
accompanies hydrogen uptake.
In each case, the dissolved hydrogen concentration (r, expressed
as hydrogen/metal atom ratio) is greater at 350 1C than 400 1C, as
expected. There is also a trend at 400 1C of increasing absorption
with increasing Ti content, whereas at 350 1C the isotherms show a
much smaller Ti dependence.
3.4. Hydrogen flux
The measured H2 flux for each alloy at 400 and 350 1C are
shown in Fig. 4. Flux increases with increasing temperature,
324 M.D. Dolan et al. / Journal of Membrane Science 415–416 (2012) 320–327
Fig. 3. Variation in dissolved hydrogen concentration (r) with the square root of
hydrogen pressure (p0.5) at 400 1C (top) and 350 1C (bottom).
increasing feed-side partial hydrogen pressure (p1) and with
increasing Ti content. The equivalent permeability of the alloy
with the highest flux (V80Ti10Ni10) at 400 1C is approximately
1.2  10  7 mol m  1 s  1 Pa  0.5 at 400 1C, and 1.4  10  7 at
350 1C, significantly greater than alloys in the previous V85 x
TixNi15 series [19], as expected from the reduced Ni concentration.
3.5. Hydrogen diffusivity
In a non-dilute system, hydrogen diffusivity can be expressed as
 
@ ln p1=2
DH ¼ DnH ¼ DnH f ðrÞ ð1Þ
@ ln r T
where DH is the concentration-dependent diffusion coefficient, and
DnH is the concentration-independent diffusion coefficient. The
thermodynamic factor f(r) can be calculated from the absorption
isotherms shown in Fig. 3 using the approach described previously
[18].
The concentration-dependent diffusion coefficients can be cal-
culated from each flux measurement and the dissolved hydrogen
concentration (r) corresponding to the feed-side (p1) and perme-
ate-side (p2) hydrogen partial pressures. These DH values are
shown in Fig. 5, plotted against the average dissolved hydrogen
Fig. 4. Variation in measured H2 flux with feed pressure at 400 1C (top) and 350 1C
(bottom).
content in the alloy, (r1 þr2)/2. Since the permeate-side concentra-
tion is close to zero, the average is taken to be half of the feed-side
concentration, r1/2.
Fig. 5 shows several clear trends. As expected, diffusivity
increases with temperature, and with increasing dissolved hydro-
gen concentration. This latter effect is consistent with our
previous observations of V–Ni alloys. The data also shows an
increase in diffusivity (for a given H/M) with increasing Ti content
(illustrated most clearly at 350 1C). Previously it was observed
that Ni decreased hydrogen diffusivity (and absorption). This
suggests a given solute has a similar influence on both hydrogen
absorption and diffusivity.
Fig. 6 shows values for the concentration-independent diffu-
sion coefficient, DnH . These values should be independent of
dissolved hydrogen concentration, but they show a small inflec-
tion to higher values as r increases. The DnH values do not show the
consistent Ti concentration dependence as the DH values.
For this discussion the role of the Ni–Ti compounds can be
ignored as (i) they are present in low concentrations, (ii) they
form discrete inclusions within the VSS matrix, and (iii) they make
a minimal contribution to hydrogen transport through the mem-
brane [19]. The most important considerations are therefore the
Ni and Ti contents in the VSS matrix.
 M.D. Dolan et al. / Journal of Membrane Science 415–416 (2012) 320–327
Fig. 5. Variation in DH with average dissolved hydrogen concentration (r1/2)
at 400 1C (top) and 350 1C (bottom).
The bulk of the literature concerning hydrogen diffusivity
through vanadium alloys is focused on low temperatures in order
to simulate the long-term exposure to hydrogen-releasing envir-
onments, for example, in fusion reactors. The addition of Ti to V
has been shown in several publications to reduce hydrogen
diffusivity at low temperatures. At o480 K and H/Mo0.1, dif-
fusivity in V–Ti alloys was found to decrease with increasing r and
Ti content [33–35], the reverse of that which has been observed
here. The influence of Ti was also found [35] to be dramatic, with
addition of 8 at% Ti to V decreasing DH by one order of magnitude.
Several groups [35,36] also found that, like Ti, Cr reduces DH in the
temperature range 340–480 K. This is unexpected because V lies
intermediate to Ti and Cr on the periodic table.
In the above cases, a trapping effect of substitutional atoms
was used to describe the reduction in DH. A rule of thumb
proposed by Shirley and Hall [37] states that elements to the left
of the host (in this case, V) trap hydrogen, and those to the right
do not, because the elastic interaction is attractive at the first and
second neighbouring sites if the solute causes the V lattice to
expand. Ti (with an atomic radius of 0.1462 nm [27]) should
therefore trap H in V-based (0.1316 nm) alloys.
It is questionable whether this applies to the present study for
several key reasons. Firstly, this study was undertaken at much
325
Fig. 6. Variation in DnH with average dissolved hydrogen concentration (r1/2) at
400 1C (top) and 350 1C (bottom).
higher temperatures (623–673 K) where the influence of trapping
on hydrogen diffusion will be reduced. Furthermore, the much
higher H/M values examined here (0.2–0.5 at the feed surface)
means the concentration of dissolved hydrogen far exceeds that
of Ti. Cannelli suggested that each Ti trapped a single H atom [38],
which in the context of the present work means up to 90% of the
dissolved H will be in non-trapping sites. Our observations
support those of Eguchi and Morozumi, who showed in their
high-temperature study that Ti increases hydrogen diffusivity in
vanadium [39].
The desired effect of any alloying addition to V is a reduction in
hydrogen absorption and an increase in DH (so as to improve
mechanical properties with minimal flux penalty). It was seen
previously that Ni does indeed reduce absorption, but also
decreases DH significantly [18,29]. The present study shows that
Ti in the presence of Ni increases DH, as is desirable, but also
increases absorption.
These findings suggest that alloying V with a larger atom
which also reduces absorption will result in an improved mem-
brane by allowing absorption to be controlled without incurring a
large diffusivity penalty. Candidate elements which meet these
criteria include Al (0.1432 nm, previously examined by Zhang
et al.) [30], Ag (0.1445 nm, but immiscible in V) [9], Pd (0.1375 nm)
326 M.D. Dolan et al. / Journal of Membrane Science 415–416 (2012) 320–327
[8], Zn (0.1395 nm, but forming a V4Zn5 compound instead of a VSS)
[40], Au (0.1442 nm, but like Pd, prohibitively expensive) and Sn
(0.1620 nm, soluble in V up to 10 at%) [41].
4. Conclusions
The early work of Steward to calculate theoretical permeabil-
ity of Group IV and V metals promoted interest in these metals for
hydrogen separation applications. Among these metals, vanadium
has received continued attention due to its promising combina-
tion of high permeability and wide solubility range for additive
metals which can improve embrittlement resistance. Foremost
amongst these additives are Ni and Ti. In an extension of previous
work which showed Ni to decrease both hydrogen absorption
and diffusivity in V, the present work studied the influence of Ti
on the microstructural and chemical properties of hydrogenated
vanadium–nickel solid solution alloys.
The addition of Ti leads to the formation of NiTi and NiTi2
compounds (both with partial V dissolution) with weak hydrogen
absorption and low permeability, and with Ti r10 at%, these
compounds are discontinuous and have no negative impact on
diffusivity, unlike the higher-Ti alloys examined previously. Ele-
mental analysis shows these Ni–Ti compounds to scavenge
oxygen from the VSS phase which is important as oxygen is
known to accelerate embrittlement in these alloys.
Increasing the Ti content in the bulk alloy increases the VSS
lattice parameter via an increase in Ti content and decrease in Ni
content, whereas the VSS volume fraction is decreased due to
Ni–Ti compound formation. The change in VSS composition is
accompanied by a favourable increase in hydrogen diffusivity
through the bulk alloy which can be attributed partly to the effect
of Ti addition and partly to the effect of decreased Ni. Hydrogen
diffusivity through alloys in this series shows strong hydrogen
concentration dependence. Whereas any increase in hydrogen
diffusivity across the membrane is favourable because of its direct
relationship with hydrogen flux, this must be balanced against
the requirement for embrittlement resistance under industrially
relevant H2 separation conditions. This work has shown that Ti is
a favourable additive for vanadium–nickel alloy membranes, and
the V80Ti10Ni10 alloy exhibits a promising combination of hydro-
gen absorption and diffusivity, as well as a microstructure which
contains 4% of stabilizing Ni–Ti compounds in a form which does
not inhibit hydrogen diffusion.
Further work is required to quantify the mechanical properties
of these alloys under realistic operating conditions and geome-
tries, and to develop mass transfer models to guide the develop-
ment of optimised microstructures.
Acknowledgements
This research was funded by the CSIRO Advanced Materials
Transformational Capability Platform, and CSIRO Advanced Coal
Technology.
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