Balcerzak 2017

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
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Structure and hydrogen storage properties of

mechanically alloyed Ti-V alloys
M. Balcerzak*
University of Technology, Institute of Materials Science and Engineering, Jana Pawła II No 24, 61-138
Poznan
, Poland
Poznan
article info abstract
Article history: Ti-V alloys are potential candidates for hydrogen storage materials. In this study, me-
Received 14 November 2016 chanical alloying under an argon atmosphere was used to produce Ti2xVx nanocrystalline
Received in revised form alloys (x ¼ 0.5, 0.75, 1, 1.25, 1.5). Shaker type ball mill was used. An objective of the present
29 March 2017 study was to investigate an influence of chemical composition and method of production
Accepted 30 March 2017 on hydrogenation and dehydrogenation properties of Ti-V alloys. X-ray diffraction analyses
Available online xxx revealed formation of BCC solid solution after 14 h of milling. It is the first time of obtaining
this phase directly from mechanical alloying method. HRTEM images confirmed formation
Keywords: of nanocrystalline materials. Synthesized materials were studied by a conventional Sie-
Ti-V alloys vert's type apparatus at 303 K. It was observed that the maximum hydrogen storage ca-
Metal hydrides pacity is increased with increased Ti content in the alloy. Ti1.5V0.5 alloy showed high
Mechanical alloying hydrogen storage capacity at room temperature, which reached about 3.67 wt.%. Simul-
Thermodynamic properties taneously, it was noticed that Ti-rich alloys form more stable hydride phases than V-rich
DSC alloys. Observed properties resulted mainly from structure of studied materials.
X-ray diffraction © 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Conventionally, Ti-V based alloys have been prepared by

Introduction arc or induction melting e methods producing microcrystal-
line materials [1,4e6]. However, for some of alloys the desired
Recently, V-based hydrogen absorbing alloys with body- composition is difficult to obtain by using these techniques. It
centered cubic (BCC) structure showed good gravimetric and is due to different melting temperatures of constituting ele-
volumetric capacities compared to rare earth-based storage ments. Moreover, poor absorption-desorption kinetics in
materials [1]. It is due to the relatively low atomic mass of addition to a complicated activation procedure have limited
vanadium. Conventional metal hydrides are characterized by the practical use of these materials [1].
weight capacities less than 1.8 wt.%, while Ti-V based solid Substantial improvement of the hydridingedehydriding
solutions exhibit a hydrogen storage capacity close to 4 wt.% properties of metal hydrides could be achieved by the for-
[2]. This capacity is connected to the BCC structure which is a mation of nanocrystalline structure by non-equilibrium pro-
coarse packing structure and has more interstitial sites than cessing techniques such as mechanical alloying (MA) [1].
face-centered cubic (FCC) or hexagonal close-packed struc- Moreover, in MA there is no limitation on the number and
tures [3]. For this reason, BCC Ti-V alloys are attractive can- nature of the raw elements used.
didates as possible interstitial hydrogen storage materials.
* Fax: þ48 61 665 3576.

E-mail address: mateusz.balcerzak@put.poznan.pl.
http://dx.doi.org/10.1016/j.ijhydene.2017.03.224
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Balcerzak M, Structure and hydrogen storage properties of mechanically alloyed Ti-V alloys, Inter-
national Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.03.224
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
In the past, TiV alloy was MA in hydrogen and nitrogen

atmosphere to form amorphous materials [7]. In recent Experimental details
years, just a few papers were published on Ti-V based ma-
terials partially produced by MA method for hydrogen Chemicals
storage applications [8,9]. Ball-milling was also used as a
method for surface modification of Ti-V-Cr and Ti-V-Cr-Mn Used commercial powders: Titanium powder (Alfa Aesar,
alloys [6,10]. Published results are very promising. However, 325 mesh, 99.5%), Vanadium powder (Alfa Aesar, 325 mesh,
still little information can be found on Ti-V hydrogen stor- 99.5%).
age alloys produced by MA. Moreover, there is no paper on
preparation nanocrystalline Ti-V alloys directly from MA
Preparation of experimental materials
process.
Ti2xVx alloys powders (x ¼ 0.5, 0.75, 1, 1.25, 1.5) were prepared
For this reason, in this work, structural and hydrogen
by MA process. A shaker type ball mill (SPEX 8000 Mixer Mill)
storage properties of MA Ti-V alloys were studied.
was used. A composition of a starting materials mixture was
corresponding to a stoichiometry of an “ideal” reaction. The
ball to powder weight ratio was around 6.5:1. Stainless steel
balls were used. MA process lasted 14 h and was carried out in
argon atmosphere. MA was stopped every 1 h to dissipate a
heat and to reduce an excessive rise in temperature. These
breaks in MA process were done also to crush bulk materials
in vials as well as to scrape powder adhered to balls and walls.
Table 1 e Structural parameters obtained from the

Rietveld refinement of Ti-V X-ray diffraction data.
Sample Phase Fraction a ( A) V ( A3) Rwp Final
(%) reduced
chi2
Ti1.5V0.5 Ti-V 92.6 3.239 33.98 5.7 1.8
V 7.4
Ti1.25V0.75 Ti-V 90.8 3.207 32.98 5.2 2.1
V 9.2
TiV Ti-V 97.6 3.156 31.43 5.0 2.2
V 2.4
Ti0.75V1.25 Ti-V 90.7 3.135 30,81 7.9 2.0
V 9.3
Ti0.5V1.5 Ti-V 93.8 3.101 29.82 5.8 1.3
V 6.2
Rwp-final weighted average Bragg R-factor.
Fig. 2 e Lattice parameter as a function of x in Ti2¡xVx. Ti

and V lattice parameters are marked by red squares (values
from literature) [17,18]. The x values are calculated from
EDS data. (For interpretation of the references to colour in
Fig. 1 e XRD spectra of Ti-V alloys after 14 h of mechanical this figure legend, the reader is referred to the web version
alloying. of this article.)
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 3
To avoid oxide phase formation, all these operations were Panalytical Empyrean powder diffractometer (Cu Ka radi-
performed in a purified Ar-filled glove box. The reason for use ation, l ¼ 1.54056
A) was used to investigate the structure of
of 14 h MA process was described in supplementary material materials during and after MA process. X-ray diffraction (XRD)
to this article. measurements were done at room temperature. Moreover,
XRD studies were also done on fully hydrogenated alloys in
Structural and morphology characterization order to understand the dehydrogenation properties of each
alloy. A voltage and anode current were 45 kV and 40 mA,
Structural characterization of obtained Ti-V alloys was done respectively.
to seek correlation with observed hydrogenation and dehy- The XRD profiles were refined with the Rietveld method
drogenation characteristics. using the Match software. XRD data were also used to calcu-
late average crystallite size and lattice strain by using Scherrer
equation and Williamson-Hall style plot. For these calcula-
tions shape factor for cubic symmetry analysis was selected.
All computations, based on XRD data, were made after sub-
tracting of background and peak fitting.
Microstructure, morphology of crystallites agglomerates
and elements composition of obtained MA powders were
determined by scanning electron microscopy (SEM) and by
energy dispersive spectroscopy (EDS) e Tescan digital micro-
scopy imaging VEGA TS5135. Based on SEM pictures, particle
size dimension distribution histograms were made. Each of
histogram was made by counting about thousand of particles.
Moreover, the detailed microstructure of MA Ti-V alloys
were investigated using transmission electron microscope e
TEM (Philips CM 20 Super Twin TEM microscope) and high
resolution TEM e HRTEM (Joel ARM 200F microscope).
Pressure-Composition-Isotherm (PCI) tests
Ti-V alloys were studied by a conventional Sievert's type PCI

apparatus, Particulate Systems, HPVA-200 with vacuum pump.
Hydrogen content in hydrides was measured by changes of
Table 2 e Average particle size, crystallites size and

lattice strain of obtained alloys.
Sample Average particle Crystallites Lattice
size (mm) size (nm) strain (%)
Ti1.5V0.5 90.8 8.8 0.015
Ti1.25V0.75 60.7 9.1 0.014
TiV 52.8 8.7 0.014
Ti0.75V1.25 19.8 7.6 0.016
Ti0.5V1.5 14.6 8.5 0.014
Table 3 e Chemical composition of samples determined

from materials weighted before synthesis and from EDS
measurements.
Sample Element Weight Weight Formula
before based on obtained
synthesis (%) EDS (%) from EDS
Ti1.5V0.5 Ti 73.85 75.01 Ti1.5V0.47
V 26.15 24.99
Ti1.25V0.75 Ti 61.07 62.34 Ti1.25V0.71
V 38.93 37.66
TiV Ti 48.44 49.40 TiV0.96
V 51.56 50.60
Ti0.75V1.25 Ti 36.09 37.31 Ti0.75V1.19
V 63.91 62.69
Fig. 3 e SEM micrograph of TiV alloy (a) and corresponding Ti0.5V1.5 Ti 23.88 24.87 Ti0.5V1.42
V 76.12 75.13
EDS element maps of Ti Ka1 (b) and V Ka1 (c).
Fig. 5 e Particle size dimension distribution histograms of

Fig. 4 e SEM micrograph of Ti-V alloys.
Ti-V alloys.
measuring chamber, which did not change more than 200 Pa

within 5 min. The mass of the sample for every measurement
run was around 1 g. Before hydrogen sorption-desortption
measurements no activation method was used. All alloys
have been only evacuated at 303 K for 1 h before tests.
Firstly, three cycles of hydrogen absorption kinetics studies
were done under 3 MPa hydrogen pressure at 303 K. These
measurements also provided information on activation
properties of these alloys. Between each cycle, materials were
degassed at 673 K (it is the highest possible to set at this device
degassing temperature). After kinetic/activation measure-
ments, degassed samples were tested to obtain Pressure-
Composition-Isotherm curves of Ti-V alloys (at 303 K and
under a hydrogen pressure range up to about 7 MPa).
DSC measurements
All of Ti-V alloys after hydrogenation were tested by differ-

ential scanning calorimeter (DSC) e TA DSC Q20. The tests
were performed up to 873 K, with heating rate of 10 K/min in
an argon atmosphere.
Results and discussion
Phase composition, structure and morphology
Fig. 1 shows XRD spectra of Ti-V alloys after 14 h of MA pro-

cess. It is evident that all samples are composed of BCC Ti-V
main phase and pure V minor phase. The ratio of Ti-V phase
to V phase weight fraction is changing from about 91:9 to 98:2
for different chemical compositions (Table 1). Obtained BCC
structure crystallizes in a Im-3m space group. This is the same
space group as of pure V and Ti-b. Ti-V based alloys, consisting
of two BCC structure phases were also obtained by Tsukahara
Fig. 6 e TEM image (a) and HRTEM image (b) of TiV alloy. et al. for arc melted Ti-V-Ni materials [11]. Apart from peak
broadening due to the reduction of crystallite size, the pat-
pressure in the system. Collection of data was fully automated terns of MA alloys have the same relative intensities as the as-
to assure high quality and high reproducibility of obtained cast Ti-V-Mn sample [3]. Moreover, it is important to note that
data. Condition for obtaining each equilibrium hydrogen this is the first time of obtaining BCC phase directly from MA
pressure was determined as constant, stable pressure in process e without any heat treatment process. According to
Table 4 e Summarized data from PCI and DSC measurements analyses on Ti-V alloys.
Sample Kinetic measurements RH/DH (%) TH-des (K)
Acycles H (wt%) T95 (min)
1 cycle 2 cycle 3 cycle 1 cycle 2 cycle 3 cycle
Ti1.5V0.5 2 0.02 3.67 3.09 e 32 35 2 855.1
Ti1.25V0.75 2 0.02 3.54 3.15 e 32 38 2 777.5
TiV 2 0.01 3.42 3.19 e 26 28 3 764.2
Ti0.75V1.25 2 0.02 3.22 3.13 e 35 31 8 742.3
Ti0.5V1.5 2 0.02 2.75 2.72 e 61 79 11 532.2
631.2
716.4
Acycles e number of activation cycles needed to obtain best kinetic properties.

H e hydrogen concentration from kinetic measurements.
T95 e time needed to reach 95% of maximum hydrogen capacity.
RH/DH e Reversibility of hydriding-dehydriding process (PCT tests).
TH-des (oC) e Hydrogen desorption peak temperature.
phase diagram, Ti-V solid solution exists above 1123 K for TiV
composition [12]. However, BCC phase alloys were directly
synthesized in the past by other preparation methods like arc
melting or magnetic levitation melting [11,13e16].
The main e BCC phase peaks shifted to lower angles with
increasing of Ti content (Fig. 1). It indicates that the unit cell
increased. On the Fig. 2 a lattice parameter as a function of
composition of MA Ti-V alloys was shown. The x values are
calculated from data obtained from EDS measurements
(shown below). The lattice parameters were determined with
Rietveld refinement method (values are listed in Table 1).
Moreover, the values of pure Ti and V lattice parameter are
(marked by red squares) also presented. It can be seen that a
decrease in the lattice parameter with increase V content is in
a good linearity with Vegard's law. Such evolution was ex-
pected as vanadium has a smaller atom radius than titanium
has (0.134 nm and 0.147 nm respectively).
Based on XRD data, crystallite size and lattice strain were
calculated. Both of them did not change with changes of
chemical composition. The crystallite size is about 8e9 nm in
all cases (Table 2).
Fig. 3 shows SEM micrograph of TiV alloy and corre-
sponding to this area EDS elements maps. It can be seen that
Ti and V elements are distributed uniformly almost over the
entire area of the alloy. Similar results were also obtained for
all alloys (not shown here).
Table 3 presents a chemical compositions of samples
determined from materials weighted before synthesis and
from EDS measurements. It can be noticed that these compo-
sitions differs between each other. However, the difference is
so small that can be connected to accuracy of EDS method. For
this reason it can be considered that obtained materials are
characterized by the chemical composition close to assumed.
SEM micrographs of all synthesized Ti-V alloys are shown
on Fig. 4. All of materials are characterized by cleavage, frac-
tured and porous morphology which is typical for mechani-
cally alloyed materials. Moreover, all of them are composed of
irregular particles. Two samples with the highest V content
are also characterized by bimodal particle size distribution. It
can be seen that about 50 mm particles are formed by much
smaller agglomerated grains (around 1 mm).
On Fig. 5 presented are particle size dimension distribution
histograms of Ti-V alloys. It can be seen that size of particles is
reduced with increased V content in Ti-V alloy. The average
particle sizes of Ti-V alloys are listed in Table 2. The size is
reduced from 90.8 mm for Ti-rich alloy to 14.6 mm for V-rich alloy.
The detailed morphology of TiV alloy is shown on Fig. 6.
Fig. 6a presents a TEM micrograph of morphology of fine
particle. Moreover, HRTEM image (Fig. 6b) shows multi-
crystalline structure. Nanocrystals with different orientations
are agglomerated in bigger forms. The size of crystallites is of
the same order of magnitude as the value obtained from the
Scherrer equation. Moreover, the values of d(100) and d(200)
spacings correspond to values obtained from Rietveld refine-
ment (are also indicated in Fig. 6b).
Hydrogen absorptionedesorption properties
The most important data from hydrogen absorption- Fig. 7 e Time-capacity curves of Ti-V alloys in activation/
desorption measurements are summarized in Table 4. These kinetic measurements.
measurements were done without any activation procedure.

Fig. 7 shows timeecapacity curves of Ti-V alloys in activation
cycles/kinetic measurements. All of materials are in inactive
state in the first cycle of measurements. The best hydroge-
nation properties were obtained in the second cycle for all of
the materials. It means that studied alloys have to be acti-
vated. However, the activation procedure does not have to be
complicated (in this study, initial hydrogenation and degass-
ing at 673 K was only used). Mentioned above activation
properties are different from properties of Ti-V based mate-
rials synthesized in the past. For those materials addition of
3d elements was necessary to improve kinetic properties [1].
Moreover, described in the past method of Ti-V alloys acti-
vation seems more complicated [14].
The maximum hydrogen concentration value (obtained in
the second cycle) was reduced from 3.67 wt% for Ti-rich alloy
to 2.72 wt% for V-rich alloy (Table 4). The capacity obtained by
Ti-rich alloy is higher than obtained in the past for Ti-V-Cr-Mn
(prepared by magnetic levitation melting with/without me-
chanically pulverized) [4,6]. The difference between
maximum hydrogen concentration values in second and third
cycle (especially visible for Ti1.5V0.5, Ti1.25V0.75 and TiV alloys)
are due to the high stability of the hydride phases e it is dis-
cussed in the following part of the publication.
Almost all synthesized alloys absorbed 95% of maximum
hydrogen capacity within about 30 min. The only exception
was V-rich alloy which was characterized be the worst kinetic
properties. Although, all materials absorbed hydrogen
without any incubation time, it should be considered that
from practical point of view, Ti-V alloys are characterized by
poor kinetic properties. The kinetics of hydrogen sorption
process can be improved by changes in chemical composition.
For example, V-Ti-Cr-Fe alloys can reach the maximum ca-
pacity within 4 min [19].
Fig. 8 shows P-C isotherms at 303 K of Ti-V alloys. The
plateau pressures are very low for all compositions which
indicates the high stability of these hydrides. However, there
is a slight plateau pressure increase with increase of V content
in alloy. It caused less hydride stability and therefore easier
hydrogen desorption. The plateau pressure is correlated to the
alloy unit cell volume. Increase of V content leads to the
decrease of the unit cell volume. Therefore, the interstitial
sites for hydrogen become smaller and insertion of hydrogen
is harder so the plateau pressure increase. Moreover, the in-
crease of the V content, decrease the hydrogen storage ca-
pacity. A similar tendency was previously observed by J.
Matsuda et al. for arc melted Ti-V alloys [20].
Desorption properties of studied alloys were quantitatively
presented by reversibility of hydriding-dehydriding. All of al-
loys are characterized by low reversibility at 303 K (Table 4).
However, the reversibility is increased with increased V-con-
tent in the alloy. The shape of desorption curves suggests
existence of the plateau region during hydrogen desorption
process. Unfortunately, the pressure is several orders of
magnitude lower than atmospheric pressure. Study of
Fig. 8 e P-C Isotherms at 303 K of Ti-V alloys. Arrows

indicate direction of hydrogen concentration changes
(sorption/desorption).
hydrogen desorption plateau region at so low equilibrium

pressure unfortunately exceed the capabilities of measure-
ment equipment. For this reason, the plateau region of
hydrogen desorption process was not observed.
Fully hydrogenated samples have been subjected to the
XRD and DSC measurements. Fig. 9 shows XRD spectra of Ti-V
alloys after hydrogenation. All patterns show a two phases
structure, made of body-centered tetragonal (BCT) phase and
a FCC phase. This BCT phase crystallizing in a I4/mmm space
group, corresponds to a BCC structure elongated along the c
axis. It is a monohydride structure (hydrogen storage capacity:
1.5e1.9 wt%) [21]. The FCC phase crystallizing in a Fm-3m
space group, is a fully hydrogenated phase (hydrogen stor-
age capacity: 1.9e4 wt%) [21]. All of fully hydrogenated alloys
should be composed only of FCC structure. The presence of
BCT phase is probably related to the partial desorption of
hydrogen from materials during transferring from Sievert's
type device to XRD diffractometer. Transformation of FCC to
BCT structure is a first step of hydrogen desorption process in
these alloys.
One can notice that the BCT phase abundance tends to
increase as V content increases. This indicates the V-rich di-
hydride are less stable than Ti-rich di-hydride phase and it
fits well to the desorption part of P-C isotherms results. The
same tendency of hydrides stability changes was observed in
the past for arc melted Ti0.8V0.2 and Ti0.9V0.1 alloys [13].
Fig. 10 shows a DSC profile of the Ti-V alloys hydrides.
Typically, there should be two peaks: full hydride phase
transferring to the mono-hydride phase, mono-hydride phase
transferring to dehydrogenated BCC phase as in Ref. [6].
However, for almost all alloys, samples exhibit one clearly
visible endothermic peak of hydrogen desorption reaction.
The hydrogen desorption peak temperature is high which
proves that the hydride phases are rather stable in a gasesolid
reaction. The only exception is Ti0.5V1.5 alloy for which visible
are at least three peaks. It can be concluded that due to the
reduced hydride stability, desorption reaction is divided into
three steps: from FCC to BCT phase, from BCT to deformed
BCC phase (hydrogen storage capacity: 0e1.5 wt%) and from
deformed BCC phase to the BCC phase [21].
Hydrogen desorption peak temperatures are listed in
Table 4. It is easy to see that with increasing of V content, the
peak temperature decreased from 855.1 K to 716.4 K, which
proves that V addition reduces the temperature stability of
the FCC hydride phase. Such a high hydrogen desorption
temperature influenced the mentioned above results of
activation/kinetic measurements. For all studied alloys, this
temperature is higher than 673 K e the highest possible to set
at the Sievert's type device hydrogen degassing temperature.
It means that, not all of the hydrogen was desorbed from
materials during the degassing (between the second and
third cycle). Therefore, before third cycle, materials are
partially hydrogenated and the final obtained hydrogen
storage capacity is reduced. However, the difference between
the maximum hydrogen capacities obtained in second and
third cycle for studied materials is decreased with increased
V content in alloys (what is connected with reduced hydride
stability). Another reason for the decrease in hydrogen stor-
age capacity may be a degradation process. However, as Fig. 9 e XRD spectra of fully hydrogenated Ti-V alloys.
Conclusions
The hydrogen storage Ti2xVx alloys powders (x ¼ 0.5, 0.75, 1,

1.25, 1.5) were prepared by MA process. The structural and
hydrogen storage properties of these alloys have been inves-
tigated systematically in this paper. XRD analysis revealed
that all materials are composed of two phases: main Ti-V BCC
solid solution and pure V phase. It is the first time of obtaining
BCC main phase material directly from MA process (without
heat treatment). HRTEM studies revealed formation of parti-
cles of agglomerated nanocrystals after MA process. Struc-
tural and PCI measurements indicate that the hydrogen
storage properties are directly connected with lattice param-
eters. The hydrogen storage capacity of Ti-rich alloys is larger
than of V-rich alloys because of larger lattice parameter of Ti-
rich alloys than V-rich ones. However, V-rich alloys hydrides
are less stable than Ti-rich ones. For this reason the selection
of the most suitable material for hydrogen storage properties
is not easy. Moreover, it is important to note that the price of V
is about eight times higher than the price of Ti.
In summary, it was shown in this work that MA Ti-V alloys
can actively absorb hydrogen at room temperature (up to
3.67 wt%). The hydrogen desorption properties still need to be
improved.
Acknowledgement
Financial assistance from National Science Centre, Poland

(no. 2015/17/N/ST8/00271).
Appendix A. Supplementary data
Supplementary data related to this article can be found at

http://dx.doi.org/10.1016/j.ijhydene.2017.03.224.
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

Available online at www.sciencedirect.com

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

Structure and hydrogen storage properties of

article info abstract

Conventionally, Ti-V based alloys have been prepared by

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In the past, TiV alloy was MA in hydrogen and nitrogen

Table 1 e Structural parameters obtained from the

Rwp-final weighted average Bragg R-factor.

Fig. 2 e Lattice parameter as a function of x in Ti2¡xVx. Ti

Pressure-Composition-Isotherm (PCI) tests

Ti-V alloys were studied by a conventional Sievert's type PCI

Table 2 e Average particle size, crystallites size and

Table 3 e Chemical composition of samples determined

Fig. 5 e Particle size dimension distribution histograms of

measuring chamber, which did not change more than 200 Pa

All of Ti-V alloys after hydrogenation were tested by differ-

Results and discussion

Phase composition, structure and morphology

Fig. 1 shows XRD spectra of Ti-V alloys after 14 h of MA pro-

Acycles e number of activation cycles needed to obtain best kinetic properties.

Hydrogen absorptionedesorption properties

measurements were done without any activation procedure.

Fig. 8 e P-C Isotherms at 303 K of Ti-V alloys. Arrows

hydrogen desorption plateau region at so low equilibrium

The hydrogen storage Ti2xVx alloys powders (x ¼ 0.5, 0.75, 1,

Financial assistance from National Science Centre, Poland

Appendix A. Supplementary data

Supplementary data related to this article can be found at

[1] Bibienne T, Tousignant M, Bobet J-L, Huot J. Int J Alloys

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