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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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4

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Non-isothermal kinetics and in situ SR XRD studies

of hydrogen desorption from dihydrides of binary
TieV alloys

S. Suwarno a,*, J.K. Solberg a, J.P. Mæhlen b, R.V. Denys b, B. Krogh c,

E. Ochoa-Fernández c, B.T. Børresen c, E. Rytter c, I.E. Gabis d,
V.A. Yartys a,b,**
a
Department of Materials Science and Engineering, NTNU, NO-7491 Trondheim, Norway
b
Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway
c
Statoil ASA Research Centre, Rotvoll, NO-7005 Trondheim, Norway
d
Department of Physics, Saint-Petersburg State University, St. Petersburg, Russia

article info abstract

Article history: Phase transformations during dynamic dehydrogenation of Ti1
xVxH2 (x ¼ 0.1; 0.2; 0.3) were
Received 5 July 2013 studied using in situ Synchrotron X-Ray Diffraction (SR XRD) and non-isothermal kinetics
Received in revised form experiments. The main dehydrogenation path for g-Ti1
xVxH2 was found to be
21 August 2013 g / d / b / balloy. Body-centred tetragonal d-hydride was found to be an intermediate
Accepted 23 August 2013 phase of the g / b transformation in Ti0.8e0.9V0.1e0.2H2. TDS, in situ SR XRD and iso-
Available online 1 October 2013 conversional kinetics studies showed that hydrogen desorption from Ti1
xVxH2 is
composed of simultaneous reactions taking place between 300 and 600  C. The effective
Keywords: activation energy of hydrogen desorption depends on the vanadium contents and the re-
Titanium action pathway, increasing from 21 kJ/mol H2 (g / d) to 60e110 kJ/mol H2 (d / b).
Vanadium Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Metal hydride reserved.
In situ synchrotron X-ray diffraction
Thermal desorption spectroscopy
Isoconversional kinetics

1. Introduction 150 kg H/m3) [2]. Ti1
xVx alloys form a variety of hydrides

Titanium and vanadium form disordered BCC-type solid so-
lution alloys existing in a broad range of vanadium content
between 2.7 at.% to 80 at.% V [1]. TieV-based hydrides are able
to reach high densities of hydrogen (w4 wt.% H or about
containing up to 2 at. H/Me. Their crystal structures depend on
the alloy composition and the amount of absorbed hydrogen.
Hagi et al. [3] have shown that at low hydrogen content, TieV
alloys form a monohydride with a BCC crystal structure, b-
Ti1
xVxHy, y ¼ 0 to w1.4. Its lattice parameter increases

* Corresponding author. Present address: Uttrecht University, 3511 AC Utrecht, Netherlands. Tel.: þ31 649290657.
** Corresponding author. Department of Materials Science and Engineering, NTNU, NO-7491 Trondheim, Norway. Tel.: þ47 63 80 64 53;
fax: þ47 63 81 29 05.
E-mail addresses: S.Suwarno@uu.nl, warnoise@yahoo.com (S. Suwarno), volodymyr.yartys@ife.no (V.A. Yartys).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.08.103
 Author's personal copy
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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4
linearly with the hydrogen content [3]. At high hydrogen
densities (H/M ¼ 1.45e2), the crystal structure of the formed g-
dihydride is of the CaF2 type. There have been several studies
on the properties of titanium vanadium hydrides including an
X-ray structural study [4], studies of hydrogen diffusion [5e7]
and thermodynamics [6]. However, much less attention has
been addressing studies of the mechanisms of the hydroge-
nation and dehydrogenation processes [8,9]. Such studies are
important as Ti-rich TieV alloys are relevant for hydrogen
storage and show a potential in applications for hydrogen
storage and separation from gaseous mixtures at medium to
high temperatures [10].
In the present work, we used in situ synchrotron X-ray
diffraction (SR-XRD) and thermal desorption spectroscopy
experiments to study hydrogen desorption from Ti1
xVxH2,
x ¼ 0.1e0.3. Correlations between the hydrogen desorption
behaviour during thermal desorption spectroscopy studies
and the structural transformations observed by SR XRD are
reported and discussed.
2. Materials and experimental methods
Titanium sponge (99.7%) and vanadium turning (99.7% metal
basis) were melted together in argon environment using an
Edmund Bühler arc melter. Melting and remelting were done
at least three times to ensure chemical homogeneity. During
the melting, zirconium was used as a getter material to
reduce oxygen contamination during the alloy synthesis.
Then the alloy buttons were cut into pieces for the hydroge-
nation process. The alloy microstructure and chemical
composition were examined using a Leica MeF4 light optical
microscope and a JEOL JXA-8500F electron probe micro-
analyzer (EPMA).
Hydrogenation was done in a Sievert’s-type thermal
desorption spectroscopy (TDS) setup. Approximately 3e4 g of
alloy pieces were placed in an autoclave connected to a vac-
uum pump. When the pressure reached w5$10
5 mbar, the
autoclave was placed into a furnace. The sample was heated
to 600  C with a heating rate of 20 K/min and held at 600  C for
30 min. The furnace was then switched off, de-attached and
the autoclave was cooled down in air. When the sample
temperature reached 500  C, 20 bar of hydrogen gas was
introduced into the autoclave for hydrogenation. This process
was repeated two times to get fully hydrogenated samples.
Thermal desorption spectroscopy studies were done in vac-
uum, w1  10
5 mbar, at 2, 5 or 10 K/min heating rates; the
experiments span from room temperature to 800  C.
Hydrogen desorption experiments were also performed in
a differential scanning calorimeter coupled with thermal
gravimetric analysis (DSC/TGA) and in a temperature pro-
grammed reaction (TPR) experiment. During the DSC/TGA
experiment, 30 ml/min argon flow was used during the heat-
ing at a rate of 5 K/min from room temperature to 800  C.
During the TPR measurements the flow rate was 400 ml/min,
and the heating rate was 5 K/min. A Thermostar Mass Spec-
trometer (MS) from Pfeiffer Vacuum GmbH was connected to
the TPR outgoing gas flow for measuring the gas composition.
The MS was calibrated to determine concentrations of H2 in
the outgoing gas.
14705
In-situ Synchrotron X-ray diffraction (SR XRD) experiments
were done in an experimental setup identical to that used in
the work by Denys et al. [11]. A fine powder sample was put
into a double capillary arrangement, including a 0.5 mm
diameter quartz glass capillary of 0.01 mm wall thickness
placed inside a 0.7 mm diameter capillary of 0.02 mm wall
thickness. The capillary setup was attached to a goniometer
head and was connected to a vacuum pump with flexible
tubing that allowed the sample to wobble during the X-ray
exposure. Data was collected using a MAR2300 image plate
detector with a sample to detector distance of 199.54 mm. The
General Structure Analysis System (GSAS) [12] software was
used for Rietveld refinement of the powder patterns [13] using
profiles of the pseudo-Voigt function [14,15]. In situ SR-XRD
studies were performed with a synchrotron radiation wave-
length of 0.72085  A at a station BM01A, SwisseNorwegian
Beam Lines (SNBL), at the European Synchrotron Radiation
Facility (ESRF), Grenoble, France.
3. Results
3.1. Alloy microstructure and compositions
The microstructure of all Ti1
xVx alloys showed the presence
of very large grains, w200e800 mm, as observed in the light
optical microscope studies. Quantitative chemical composi-
tion analyses were performed by EPMA. Point by point mea-
surement was done along a line with a step length of 1 mm. A
statistical average was calculated from 20 points. The Ti and V
contents in the Ti0.7V0.3 sample was 71  1.5 at.% and
29  1 at.%, respectively. The Ti0.8V0.2 alloy was composed of
79  2 at.% Ti and 20  2 at.% V. For Ti0.9V0.1, the composition
was 89  2 at.% Ti and 10  0.5 at.% V, respectively. Thus, the
prepared samples of Ti1
xVx were chemically homogenous
alloys well within the nominal composition.
3.2. Thermal desorption spectroscopy
A fully hydrogenated sample Ti1
xVxH2 containing about
3.9 wt.% H was used in each TDS measurement. Fig. 1a shows
hydrogen desorption spectra during dehydrogenation of
Ti1
xVxH2. The hydrogen desorption traces of TiH1.9 are
included for comparison. The hydrogen desorption spectra of
Ti1
xVxH2 showed that desorption started at w100  C and that
the hydrogen flow rate increased as the sample temperature
increased. Further heating led to a maximum hydrogen flow
rate reached at a certain temperature (the TDS main peak
temperature). At a later stage, the hydrogen flow rate
decreased down to almost zero at 800  C, which indicates that
hydrogen was completely desorbed from the sample at that
temperature. The TDS main peak temperature was a unique
characteristic for each alloy composition, with the most stable
alloy hydride having the highest TDS temperature. Therefore,
the TDS main peak temperature was used as a measure of the
thermal stability of the hydrides.
The amount of desorbed hydrogen during the dehydroge-
nation was calculated by integrating the hydrogen flow rate
over the desorption time, Fig. 1b. Based on the integrated TDS
graphs, hydrogen desorption from the TieV hydrides could be
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14706 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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4

6
Experimental data
Fitted data
5
Individual peaks fitting

H flow (cm3/g.mim)
2
3

2
3
1
1

100 200 300 400 500 600 700

o
Temperature ( C)

Fig. 2 e Hydrogen desorption spectrum of Ti0.8V0.2H2

during the heating (heating rate 2 K/min) in vacuum at
temperatures from 30  C to 800  C. The hydrogen
desorption spectrum consists of 3 curves related to three
individual hydride phase transformations during the
dehydrogenation.

The amount of hydrogen desorbed during the second step was

1.55 wt.%, or 0.77 H/M. The estimated amount of desorbed
hydrogen in the remaining hydride (the 3rd step) was 1.3 wt.%,
H/M ¼ 0.67.

3.3. Kinetic analysis

Fig. 1 e Thermal desorption spectra of Ti1LxVxH2: (a)
Hydrogen flow rate during non-isothermal
dehydrogenation at 1 3 10L5 mbar. The thermal stability
characterized by main peak temperature depends on the V
contents; (b) Integrated amounts of hydrogen desorbed.
Three segments can be identified and related to the
dehydrogenation steps.
divided into 3 segments. As can be seen from Fig. 1b, the 1st
segment correlated with the first step of dehydrogenation, i.e.
low temperature hydrogen desorption from the FCC g-hydride.
The hydrogen desorption mode then changed, starting at
about 300e400  C depending on the alloy composition. This
second mode of hydrogen desorption (the 2nd segment) was
the fastest one (large curve gradients). In agreement with the
TDS experiments, results from DSC/TGA as well as from the
TPR experiments showed that hydrogen desorption of
Ti0.8V0.2H2 was composed of three steps (see Supplementary
information, Fig. S1).
To further analyse the dehydrogenation steps of g-
T1
xVxH2, the hydrogen desorption spectrum curve from g-
T0.8V0.2H2 was deconvoluted into three individuals curves,
marked 1e3 in Fig. 2 using the pseudo-Voigt function. A
Pearson correlation coefficient, R2, of 0.99 indicated a good
quality of the fit. By simple calculations of the areas under the
curves, the amount of desorbed hydrogen in each step was
estimated. The amount of desorbed hydrogen during the 1st
step (1st curve) was calculated to be 1.1 wt.% or H/M ¼ 0.55.
The kinetics of a phase transformation can be expressed by an
equation describing the reaction rate. In case of reactions
involving solid and gas phases, it can be presented as [16]
dx
¼ KT f ðxÞKP ðPÞ (1)
dt
where x is the extent of conversion, i.e. the fraction of con-
verted phase at time t, KT and Kp are temperature and
pressure dependent kinetic rate constants, respectively, and
f(x) is a reaction model equation describing the trans-
formation reaction mechanism. KT can be expressed using
an Arrhenius relation, i.e. KT ¼ A exp (
E/RT), where A is a
pre-exponential factor, E is the activation energy, and T is
the temperature. For desorption, Kp is approximately equal
to 1
P/Peq where P is the partial pressure of the hydrogen
product during reactions, and Peq is the equilibrium pressure
of the hydrides. When the experiment is performed in vac-
uum, the pressure dependency can be eliminated since the
partial pressures of gas as a reaction product is very low and
assumed to be negligible. Thus, for the non-isothermal case
with a linear heating rate b ¼ dT/dt, by setting Kp ¼ 1 and by
replacing KT with the Arrhenius term, equation (1) can be
written as
dx A
¼ expð
E=RTÞf ðxÞ (2)
dT b
By rearranging equation (2) and by integrating over the
transformation process, the reaction model, g(x) can be

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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4
expressed in terms of temperature, activation energy and
heating rate, as follows:
Zx ZT
dx A at high x values as compared to the graphs for Ti0.8V0.2 and
gðxÞ ¼ ¼ expð
E=RTÞdT
f ðxÞ b
0 0
The integral on the right hand side of equation (3) is
generally called the temperature integral and can be solved by
using approximations or by numerical integration. Such so-
lutions are the so-called isoconversional methods [16,17]. One
solution of equation (3) is the following expression proposed
by Kissinger, Akira, Sunose (KAS) [18,19]:
bi Ex
ln ¼ CK ðxÞ

T2xi RTxi
where C is a constant, and the index i identifies an experiment
done at a heating rate i. Therefore, by performing a series of
non-isothermal experiments at different linear heating rates,
one can find the dependency of the activation energy on
temperature or on extent of conversion. This procedure is the
so-called model-free method by which one can find the acti-
vation energy without previous knowledge of the reaction
model [20,21].
In the present work, a series of non-isothermal dehydro-
genation tests were performed for each Ti1
xVxH2 alloy using
linear heating rates of 2, 5, and 10 K/min. By employing the
KAS relation, Ex versus x during the transformation g
(hydride) / BCC (metal) was obtained as shown in Fig. 3. It can
be seen that Ex changed with the extent of conversion. Also
from Fig. 1b, it can be deduced that the Ex dependency on x can
be divided into 3 segments; the 1st segment is for x < x1, the
2nd segment is for x1 < x < x2, and the 3rd segment is for x > x2.
It is worth noticing that the heating rates at the beginning of
experiment were not stable so that reliable Ex was not ach-
ieved for x < x1. Thus, only Ex values obtained for x > x1 will be
discussed further.
As can be seen from Fig. 3, in the 2nd segment, Ex decreased
for Ti0.8V0.2, but fluctuated for Ti0.7V0.3 and Ti0.9V0.1. This
behaviour was different in the 3rd segment within which Ex
increased as the transformation progressed. Furthermore, the
values of x for which the Ex graph changes depend on
segment 1: < 1
175 segment 2: 1< < 2 Ti0.8V0.2H2
segment 3: > 2
150 1
E (kJ/mol)
1
125
100
1
2 nuclei growth model for the 2nd segment and the three-
75
0.2 0.4 0.6
Fig. 3 e Dependency of the activation energy, Ex on the
extent of conversion for the binary TieV hydrides.
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14707
composition, indicating H content-related changes in the
desorption mechanism during the dehydrogenation process.
For Ti0.9V0.1H2 the Ex graph followed a slightly different trend
(3)
Ti0.7V0.3 indicating that the last step of hydrogen desorption
from the Ti0.9V0.1Hx might follow a different path and possibly
occurs by a different mechanism than in the other two cases.
During the determination of Ex by the isoconversional
method, a particular reaction model f(x) was not adopted, but
even though the values of the activation energy might be used
to predict a reaction mechanism. A phase transformation can
be assumed to follow a single reaction model when Ex remains
relatively constant at increasing extent of conversion [16].
(4) Thus, by observing Fig. 3, it can be seen that reaction mech-
anisms of hydrogen desorption within each segment for all
hydrides studied were composed of more than a single pro-
cess, except for Ti0.9V0.1Hx within the 3rd segment. In other
words, only for x > x2 the dehydrogenation of Ti0.9V0.1Hx
occurred by a single reaction mechanism.
To determine possible reaction mechanisms, model fitting
has been performed within each segment for every deconvo-
luted hydrogen spectrum. The extent of conversion value was
inserted into the reaction model, and a plot of g(x) versus x was
obtained for the various reaction models (Supplementary
information, Table S1). By using equation (3) these g(x)
graphs were fitted under the condition that the activation
energy value (E) should converge towards the values obtained
by the isoconversional method. This means that the activa-
tion energy value obtained from the KAS methods will not
always be the same as that obtained from the fitting since a
single reaction mechanism was assumed even though two or
more mechanisms may have operated. The integral temper-
ature was estimated using an approximation by Gorbachev
[22], i.e.
ZT    

E RT2
E
exp dT ¼ exp (5)
RT E þ 2RT RT
0
Fig. 4 shows plots of the reaction models g(x) for different re-
action mechanisms. As shown in Fig. 4, for Ti0.8V0.2Hx the re-
action mechanism within the 2nd segment was best fitted with
the Avrami-Erofeev nuclei growth model A1, [
ln(1
x)]2/3.
However, the numerical value of the activation energy received
Ti0.9V0.1H2 during the fitting, 80 kJ/mol H2, is lower than the average value
obtained by the isoconversional method. Thus, we assume that
simultaneous reactions must be occurring within the 2nd
Ti0.7V0.3H2
segment. In contrast, for Ti0.8V0.2Hx within the 3rd segment of
the desorption traces, the experimental data fitted well with the
2 three-dimensional contracting volume model with decelerated
interface D4 (see Supplementary information, Fig. S2a) with an
activation energy of desorption of 102 kJ/mol H2.
2 Fitting of the experimental data for Ti0.7V0.3Hx (not shown)
yielded similar reaction mechanisms, i.e. the Avrami-Erofeev
dimensional contracting volume model for 3rd segment. As
also shown in Fig. 4, the 2nd segment for Ti0.9V0.1Hx is well
0.8
described by the three-dimensional contracting volume
model with decelerated interface D4, g(1
2/3x)
(1
x)2/3.
The 3rd segment of Ti0.9V0.1Hx also follows the D4 model (see
Supplementary information, Fig. S2b). However, the fitted Ex
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14708 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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4

with H/M  2 crystallize with an FCC CaF2 type crystal struc-

Fig. 4 e Fitting of the experimental data of segment 2 for
Ti0.8V0.2Hx and Ti0.9V0.1Hx using various reaction models.
The heating rate of the TDS experiment was 5 K/min.
A1 [ Avrami-Erofeev one-dimensional nuclei growth;
A2 [ Avrami-Erofeev two-dimensional nuclei growth;
A3 [ Avrami-Erofeev three-dimensional nuclei growth;
CV1 [ One-dimensional contracting volume; CV2 [ Two-
dimensional contracting volume; CV3 [ Three-
dimensional contracting volume; D1 [ One-dimensional
diffusion controlled; D2 [ Two-dimensional diffusion
controlled; D3 [ Three-dimensional diffusion controlled;
D4 [ Three-dimensional contracting volume with
decelerated interface.
values of 112 kJ/mol H2 within 2nd segment and 118 kJ/mol H2
within the 3rd segment are both higher for the last sample
with the highest Ti content. The activation energy within 3rd
segment was equal to the value obtained from the iso-
conversion method of KAS that showed that a single reaction
mechanism had been operating.
3.4. Phase-structural composition
The alloys Ti1
xVx (x > 0.1) have a BCC structure, space
groupIm3m [1]. The corresponding hydrides of these alloys
ture, space groupFm3m, and are called g hydrides. After
completion of the TDS process, the dehydrogenated powders
contain only a BCC phase, except of richest with titanium
Ti0.9V0.1, which contained a mixture of BCC and HCP a-phase,
space group P63/mmc.
Table 1 gives the crystallographic data of the fully hydro-
genated alloys, the g hydrides, and the corresponding dehy-
drogenated alloys. g-Ti0.9V0.1H2 was fitted with a single g-
Ti0.9V0.1H2 phase even though the hydride powder could be
composed of two types of g-(TieV)H2. For Ti0.8V0.2 and Ti0.7V0.3,
it is observed that the unit cell lattice parameter depend on
the vanadium contents: it decreases as the vanadium content
increases. The unit cell volume expansion per dissolved
hydrogen atom (DnH) is equal to the unit cell volume of the
metal hydride subtracted by the unit cell volume of the
metallic phase (same crystal structure) divided by the number
of hydrogen atoms in the unit cell. Since there exist no stable
FCC TieV alloys, the unit cell volume is calculated based on
electronic structure calculations by Wolverton [23]. The re-
sults are given in Table 1, which shows that the obtained
values are close to the typical value observed for the metal
hydrides (according to Fukai, i.e. 2.8  A3/at.H [24]), which is
consistent with occupancy of the tetrahedral sites.
3.5. In situ SR-XRD study of Ti0.8V0.2H2
A g-Ti0.8V0.2H2 powder sample containing 3.96 wt.% H was
used in the in situ experiment. The phase evolution during the
hydrogen desorption from g-Ti0.8V0.2H2 while the sample was
heated in vacuum at 3 K/min is shown in Fig. 5. The diffraction
pattern at each time-step was fitted using Rietveld refinement
methods in the GSAS. During the fitting, Rwp and Rp were in
the ranges of 4.6e11.7% and 3.4e9.7%, respectively. Selected
results of the Rietveld refinements are given in Table 2. It can
be seen that at 40  C the powder was composed of nearly
100 wt.% g with a unit cell lattice parameter of 4.4332(5)  A.
Diffraction patterns above 320  C were fitted as two-phase
hydride samples, i.e. g FCC and d BCT (base centred tetrag-
onal) structure type, space group I4/mmm. A strong indication
that the sample was composed of a mixture of g and d can be
seen by observing the progress of the overlapping peaks of g-
(111) and d-(101) from 450  C to 497  C, as shown in the inset in
Fig. 5. Asymmetric profiles were also observed for the (200),

Table 1 e Crystallographic data for the BCC Ti1LxVx alloys and their corresponding hydrides.
x Ti1
xVx g-(Ti1
xVx)Hw2 DnH (
A3/at.H) Comments

a (
A) V (
A3) 
A V (
A3)

0.1 3.20770(2) 33.005(5) 4.4390(7) 87.47(4) e Two phase alloy

a ¼ 2.94272(2) 35.097(5)
c ¼ 4.6798(4)
0.2 3.2322(2) 33.76(1) 4.4341(5) 87.17(9) 2.81 This work
0.3 3.2113(3) 33.11(6) 4.40168(5) 85.28(9) 2.74 This work
0 a ¼ 2.95111 35.33 4.454 88.35 2.62 [2,25] a
c ¼ 4.68433
a
1 3.03 27.8 4.27 77.5 2.93 [26]
a
Calculated from crystal structure data given in the references.
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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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4 14709

Fig. 5 e Phase evolution during in-situ SR-XRD of g-Ti0.8V0.2H2. The figure inset shows overlapping g-(111) and d-(101) peaks.
Small fraction (w0.5 wt.%) of stable g hydride was observed up to 580  C. The experiment was performed by increasing
temperature from 30  C to 800  C in vacuum.

(220), and (311) g peaks. Such asymmetric profiles are an
indication that the sample has been partly transformed to a
tetragonally deformed BCT structure. Some fitted SR-XRD
spectra at high temperatures are given in Supplementary
information (Fig S3).
Fig. 6 shows the phase fraction changes derived from the
Rietveld refinements. As can be seen from the figure, at low
temperatures the powder was composed of g-Ti0.8V0.2H2 and
this phase was preserved up to 320  C. Above 320  C, some g
hydride transformed to d-Ti0.8V0.2H1.5. The fraction of g
decreased very fast in the temperature range 320  Ce390  C.
As a result, the d-Ti0.8V0.2Hw1.5 fraction increased fast, and it
reached a maximum of 55 wt.% at 390  C. The d phase fraction
decreased above 390  C because d readily transformed to the b

Table 2 e Crystallographic data at selected temperatures during the dehydrogenation of g-Ti0.8V0.2H2.

Temperature ( C) Phase-space group Unit cell lattice Abundance (wt.%) Rietveld refinements parameter
parameter ( A)
Rwp (%) Rp (%)
a
40 g-Ti0.8V0.2H2(Fm3m) a ¼ 4.4332(5) 100 6 5.3
310 g-Ti0.8V0.2H2(Fm3m) a ¼ 4.4478(5) 100a 5.8 4.7
360 g-Ti0.8V0.2H1.8(Fm3m) a ¼ 4.415(1) 52(1) 9.1 7.2
d-Ti0.8V0.2H1.4(I4/mmm) a ¼ 3.161(1) 47(1)
c ¼ 4.308(1)
420 g-Ti0.8V0.2H1.6(Fm3m) a ¼ 4.394(1) 36(1) 11.7 9.7
d-Ti0.8V0.2H1.2(I4/mmm) a ¼ 3.152(1) 27(1)
c ¼ 4.282(2)
b-Ti0.8V0.2H0.7(Im3m) a ¼ 3.381(1) 35.8(7)
530 g-Ti0.8V0.2H1.7(Fm3m) a ¼ 4.410(1) 5.9(3) 5.2 3.4
b-Ti0.8V0.2H0.4(Im3m) a ¼ 3.3467(3) 94.07(4)
780 b-Ti0.8V0.2H0.02(Im3m) a ¼ 3.28189(7) 100a 4.6 3.8
800 b-Ti0.8þxV0.2
x(Im3m) a ¼ 3.27738(1) 98.8(1) 8.4 6.2
a-Ti(V)-(P63/mmc) a ¼ 2.995(1) 1.1(2)
c ¼ 4.823(3)
a
Phase fraction parameter was not refined during Rietveld refinements.
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14710 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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4

Fig. 6 e Evolution of phase composition calculated from

Fig. 7 e (a) Changes of the g and d hydride lattice
powder diffraction data of Ti0.8V0.2Hx by Rietveld
parameters of Ti0.8V0.2Hx during non-isothermal
refinement method with Rwp [ 3.76e10.28% and
transformation. The d lattice parameters are plotted in a
Rp [ 2.61e7.19%. d-hydride formed from g-hydride at
deformed FCC setting. The g lattice parameter increased up
320  C and existed up to about 500  C. The b hydride
to 320  C and started to decrease rapidly when the
appeared at about 390  C.
d hydride formed at 320  C. Above 450  C. The lattice
parameter of the remaining g hydride slightly increased.

hydride. The amount of b phase increased upon increasing

temperature. In other words, the transformation of g / d and
d / b occurred simultaneously at temperatures above 390  C.
Thus, there was a three-phase region g þ d þ b in the tem-
perature range 390  Ce500  C.
The co-existence of three phases during hydrogen trans-
formation has previously been observed in the AB5-H2 system
[27]. However, it can be observed in Fig. 6 that the direct
transformation of g / b also occurred at high temperatures
when the amount of remaining g hydride was about 10 wt.% or
less. Above 580  C, the hydride became a single phase b hy-
dride. At 790  C, small amounts of HCP a-Ti were observed and
reached maximum of 1.1 wt.% at 800  C (not shown in the
figure).
The changes of the unit cell lattice parameters during non-
isothermal dehydrogenation are shown in Fig. 7. It can be seen
that, when only the single g phase is present, the unit cell
lattice parameter increased with temperature. A decrease of
the g lattice parameter started at 310  C. At 320  C the decrease
in the g lattice parameter was significant and was accompa-
nied by a formation of the d hydride. The unit cell lattice
parameter of the remaining g hydride did not change signifi-
cantly from 390  C to 450  C. However, above 450  C, the lattice
0.94. The unit cell lattice parameter of the b hydride at 400  C
was 3.3796(2) 
A. Upon further heating, this unit cell parameter
linearly decreased as hydrogen was desorbed from the
sample.
Fig. 8 shows changes of the unit cell volume per metal atom
due to hydrogen desorption from the hydride,
DVH ¼ VMH
VM =nM , where VMH is the unit cell volume of the
hydride, VM is unit cell volume of the metal of the same crystal
structure, and nM is number of metal atoms in the unit cell. In
order to account for the thermal expansion effect, the unit cell
volume changes of the g and d hydrides were corrected by
linear extrapolation of the unit cell volume changes to the
temperatures below 100  C, where hydrogen desorption does
not occur. The effect of temperature on the unit cell volume
change for the b phase was corrected by the difference in b unit
cell volume at 850  C and at room temperature. As can be seen
5
4
VH/M (Å3)

parameter of g increased, which indicates that this g hydride 3

must be the Ti-rich g (TieV)Hx.
As can be seen in Fig. 7 where the changes in the lattice 2
parameters of the d hydride are plotted in a distorted FCC
setting (BCT unit cell). As the transformation proceeds, there 1
is an anisotropic contraction of the cubic unit cell, which
0
changes c/a from 1 to 0.96 in a deformed FCC (BCT) cell. Prior to
the formation of b phase, both the a- and the c-axes continu- 0 100 200 300 400 500 600 700 800 900
ously decreased upon the heating indicating that hydrogen Temperature ( C) o
was desorbed as d formed. This is in agreement with the phase
fraction evolution as discussed earlier. However, when the b Fig. 8 e Evolution of unit cell volume change per metal
phase formed, the a-axis of the d hydride increased while the atom due to hydrogen desorption from Ti0.8V0.2Hx. For FCC
c-axis continued to decrease so that c/a finally decreased to TieV, VM is based on the calculated value of 64.67 A3.
 Author's personal copy
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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4
from Fig. 8, the specific volume of the unit cell decreased lin-
early during the heating of the sample due to hydrogen
desorption. The linearly fitted lines in Fig. 8 indicate that the
rates of volume decrease of the g and d unit cell volumes are
equal, i.e. 0.0086 
A3/K, and are higher than that of the b-hy-
dride, being 0.0044 A3/K.
The slopes of the unit cell volume changes of the g and
d phases are similar, which indicates a tetragonal site occu-
pation. The slope of the unit cell volume changes of the b
hydride is approximately half of that for the g and d phases.
Considering that the stoichiometric concentration of H in the
dihydrides g and d are approximately 2 times higher than for
the monohydride b, the lattice volume changes due to a
desorption of one hydrogen atom must be approximately the
same, i.e. 0.004 A/K. This is not surprising since we assume
that H atoms fill similar interstitial sites in these structures.
Dividing DVH by DnH (the atomic volume of hydrogen given
in Table 1) gives the amount of desorbed hydrogen in unit H/M
during progress of dehydrogenation progress (not shown).
Such calculation was performed using DnH value of 2.82  A3 for
3
g and d and 2.17 A for b, taken from a previous investigation
[3]. At the beginning of the experiment, the g hydride con-
tained w2 H/M, and this amount decreased upon the heating.
The d hydride contained 1.58 H/M when it first formed at
320  C, and then this value continuously decreased to 1.15 H/M
before the hydride transformed to b. The first formed b (at
400  C) contained 0.78 H/M, and this value was reduced upon
further heating. Thus, the Ti0.8V0.2H1.99 transformation upon
dehydrogenation as observed by in situ SR-XRD is g-
Ti0.8V0.2H2 / d-Ti0.8V0.2H1.58 / b-Ti0.8V0.2H0.78 / BCC-
Ti0.8V0.2.
4. Discussion
The TDS, DSC/TGA and TPD hydrogen desorption spectra
presented above have shown that hydrogen desorption from
g-Ti1
xVxH2 dihydrides is composed of several stages.
Different steps of hydrogen desorption, corresponding to the
phase diagram of the system and in situ SR-XRD data, can be
identified as:
(1) nucleation of d hydride;
(2) nucleation of b hydride;
(3) complete decomposition of d hydride;
(4) complete decomposition of g hydride.
Because hydrogen evacuation rates are different for the SR
XRD and TDS experimental setups, some variation in the
temperature of the events was observed.
From the diagram shown in Fig. 6 we conclude that below
w320  C hydrogen evolution takes place from a single-phase
hydride. The hydride does not change its FCC CaF2 type of
crystal structure; however, the unit cell parameter slightly
increases during the H desorption (see Table 1). This means
that vacancies are formed in the lattice when the hydrogen
stoichiometry becomes lower than H/Ti0.8V0.2 ¼ 2.0. Hydrogen
desorption takes place from the surface of the hydride and is
related to the increase in concentration of the vacancies and
their diffusion from the surface to the core of the particles
14711
while hydrogen atoms diffuse in opposite direction, from the
bulk of the hydride to the surface of the particles. As the initial
hydride has metallic properties, we assume that desorption
takes place from the whole surface area of the powder
particles.
A simple mechanism of hydrogen desorption from a
single-phase hydride and a characteristic form of the initial
parts (1st segment) of the thermal desorption spectra makes
fitting of the experimental data possible. An Arrhenius type of
dependence dx=dt ¼ SC2 k0des expð
E=RTÞ with fitting parame-
ters A and E has been used during the fitting of the initial part
(red line in Fig. 9) of the TDS graphs for all samples, having
different content of vanadium. The rate of change of hydrogen
content in the samples can be presented as
dx
¼ SC2 k0des expð
E=RTÞ (6)
dT
where
S is the specific surface area of the hydride sample (we
assume that it does not change during the experiment),
C is the hydrogen content in the subsurface part of the
sample,
k0des is a desorption constant accounting for a shape factor,
E is the activation energy of hydrogen desorption.
An analysis of the expression above leads to the conclusion
that C remains practically constant during the first step of
hydrogen desorption when g-hydride starts to decompose. In
the last expression for the desorption flow the hydrogen
content C represents either “lattice” or “diffusion-active”
hydrogen. The very successful fitting and the fact that
“diffusion-active” hydrogen changes its concentration in a
broad interval are in favour of the first option, i.e. that the
hydrogen is present as “lattice” hydrogen. The fitting was
performed for curves obtained with the lowest heating rate, as
in their case influence of the diffusion-driven changes in the
Fig. 9 e Hydrogen vacuum desorption traces from
Ti0.8V0.2H2 at a heating rate of 2 K/min. Red line represents
calculated data. The numbers show different steps of the
desorption process and are used for description in the text.
(For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this
article.)
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14712 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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4
subsurface concentration should be maximum, and the con-
centration C should change within the narrow limits. For the
alloys Ti0.8V0.2 and Ti0.7V0.3 the heating rate was 2 K/min, and
for Ti0.9V0.1 is was 5 K/min. A good agreement between the
fitted and the experimental data is evident from Fig. 9. In the
initial part of hydrogen desorption spectra (1st segment), the
activation energy remains approximately the same for all
studied alloys, 21 kJ/mol H2. E has a rather small value, in
agreement with the data of the calorimetric study which
showed absence of significant heat effects at working tem-
peratures below 300  C (see Supplementary information,
Fig. S1a). A certain difference in the rate of hydrogen release
from the alloys containing different amounts of vanadium is
due to the differences in the values of A, which again result
from variations in the surface area, S.
An increase in temperature leads an increase the desorp-
tion rate; at some moment, which decreases the content of
hydrogen in the subsurface layers, as the amount of hydrogen
coming via diffusion from the bulk does not compensate for
the desorbed H2. This leads to the bending of the TDS curve at
260  C. When the hydrogen content drops below the critical
value at 320  C (point 1 in the TDS traces), a phase transition
takes place. After nucleation of the d-hydride, during a modest
temperature increase from 320  C to 390  C, this hydride be-
comes a major component in the sample as its abundance
surpasses 55%. Thus, we assume that a thick shell of d-hydride
is formed which grows inside the particle leading to the
contraction of the central spherical core of the g-hydride. As d-
hydride is rather rich in hydrogen, a contribution of the ged
transformation to the overall desorption is rather limited.
Nucleation of the b-hydride taking place at 390  C (point 2
in the TDS traces) correlates with the maximum rates of
hydrogen desorption; thus, the hydrogen flow rate signifi-
cantly increases. According to the DSC data (Supplementary
information, Fig. S1a), hydrogen desorption at such a tem-
perature is accompanied by a significant heat effect. This
observation well agrees with a stronger metal-hydrogen bond
in the b-hydride compared to in the g-hydride. Decreasing
abundance of the d-hydride (taking place at temperatures
between 420 and 500  C) is accompanied by a decrease in the
hydrogen flow rate.
From Fig. 6 it is evident that both g and d hydrides are in
equilibrium with b-hydride in this three phase region. In other
words, in this region there are simultaneous transformations
g / d and d / b. It is worth mentioning that a similar
behaviour has also been observed in the AB5eH2 system [14].
The DSC traces (Supplementary information, Fig. S1a), how-
ever, show that the heat effect of the transformations reaches
maximum in the temperature interval 450e500  C, which in-
dicates that the energy level of hydrogen is higher in the d-
phase than in the b-hydride.
At the moment when the d-hydride vanishes (w500  Cdpoint
3), the remaining amount of g-hydride is rather low (see Fig. 6).
However, decomposition of the remaining g hydride in the
temperature range 500 < T < 580  C keeps the hydrogen
desorption flow at a rather high level. We believe that H2
desorption at these temperatures takes place from the surface of
the b-hydride, and that g-hydride exists as a contracting area
located inside the b-hydride. At T > 580  C (point 4) no further
hydrogen is available from the hydrogen-rich g-hydride, and
during the further stages hydrogen is released from the single-
phase b hydride, which is a solid solution of hydrogen in a
metal alloy. As the temperatures become higher, the hydrogen
diffusion coefficient increases i and despite of the presence of
rather large particles of the powdered hydride, it seems that
hydrogen diffusion is no longer a limiting step of hydrogen
desorption. Consequently, the rate of hydrogen transfer from
the alpha solid solution into the gaseous phase becomes pre-
dominant, pointing on a strong metal-hydrogen binding in the
solid solution.
Thus, from both TDS and in situ SR-XRD, the path of g-
Ti0.8V0.2H2.0 non-isothermal dehydrogenation can be proposed
as follows: g / d / b / balloy, noting that the transformations
g / d and d / b were simultaneously occurring within the
material. The direct transformation g / b also happened at
high temperatures above 500  C when the amount of g hydride
was about 10 wt.%. This direct transformation g / b origi-
nates from the Ti-rich phase having the higher thermal sta-
bility than the major (Ti,V)-based gamma hydride.
Simultaneous decomposition reactions were occurring
during hydrogen desorption. This is in agreement with in situ
SR-XRD results that showed that at intermediate tempera-
tures, reactions g / d and d / b took place in parallel during
the transformation of g-Ti0.8V0.2H2. At higher temperatures,
interaction between the transformations d / b and b / balloy
also took place during the dehydrogenation of the b-
Ti0.8V0.2H0.7. This indicates that, most likely the intermediate
phase d was participating in the transformation of g to b hy-
dride of Ti0.9V0.1Hx. For TiH2 a direct transformation of g to b
has been shown.
Based on the KAS method presented in the previous sec-
tion, the activation energy for the d / b transformation was
79 kJ/mol H2 for Ti0.8V0.2Hx and 60 kJ/mol H2, i.e. the slightly
lower, for Ti0.7V0.3Hx. During the dynamic transformation
d / b another reaction also proceeded, i.e. dehydrogenation of
the b hydride. The transformation g / b in the case of Ti0.9V0.1
was fitted to the three-dimensional contracting volume model
with a decelerated interface. The g / b transformation during
dehydrogenation of Ti0.9V0.1H2 followed the TiH2 trans-
formation during which a direct transformation of g to b was
observed [28]. The activation energy of the transformation
g / b was about 112 kJ/mol H2. The hydrogen desorption
mechanism from the g hydride of Ti0.9V0.1 is rather compa-
rable to the transformation of FCC to BCC hydrides of titanium
which is limited by the interface reaction [29]. The activation
energy of the FCC / BCC TiH2 transformation is in the range
of 123e137 kJ/mol H2 [29,30] which is significantly higher than
that of Ti0.9V0.1H2 due to the vanadium alloying in the latter.
The main difference is that for the in Ti0.9V0.1 hydride the
interface was decelerated upon the progress of dehydroge-
nation. The reason for a decelerated interface must be a
stronger hydrogen binding of hydrogen to Ti, or slow diffusion
of hydrogen within the transformed particle. Since the
hydrogen diffusion within b hydride is fast at high tempera-
tures, the first reason is probably the most reasonable one.
The high stability of the g hydride up to 580  C, is proposed
to be associated with the presence of a Ti-rich TieV hydride,
i.e. Ti0.8þxV0.2
xHy. As mentioned earlier, Ti and V form a
disordered BCC solid solution. Furthermore, TieV alloys have
a positive energy of mixing, so a miscibility gap exists in the
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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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4
phase diagram of the TieV system. Ti1
xVx alloys tend to form
clusters and other related types of short range ordering. The
occurrence of an a-Ti phase at about 790  C during the in situ
experiment therefore most likely originates from a Ti-rich
TieVeH phase. This separation of a Ti phase from the main
BCC hydride phase was not observed in the dehydrogenated
samples (ex-situ studies) of Ti0.7V0.3. This behaviour can also
be explained from the equilibrium TieV phase diagram. The
balloy / a þ balloy transformation temperature decreases with
increasing vanadium fraction. As a result, at lower vanadium
fractions, the temperature range for the a-Ti phase formation
is broad, so the driving force for the formation is also high. No
a-Ti (HCP) was observed in the dehydrogenated Ti0.7V0.3 alloys.
Therefore, it is evident that formation of a-Ti from the BCC
phase will be dominant in low vanadium alloys.
The existence of the Ti-rich TieVeH hydrides mentioned
above is also in agreement with the TDS result shown in Fig. 1,
in which one can observe that the stability of the TieV hydride
depends on the alloy composition, i.e. atomic ratio between Ti
and V. Thus, there must be an inhomogeneity in the sample of
g-Ti0.8V0.2H2.0.. This kind of inhomogeneity in the TieVeH2
system was suggested to be a result of a high-pressure syn-
thesis and also of hydrogenationedehydrogenation cycling.
Since our sample of g-Ti0.8V0.2H2.0 was prepared using 20 bar
hydrogenation pressure, such inhomogeneity is rather likely.
5. Conclusions
Hydrogen absorptionedesorption properties of Ti1
xVxH2
have been studied using thermal desorption spectroscopy and
in situ synchrotron X-ray diffraction studies. The following
conclusions can be drawn:
(a) The Ti1
xVx alloys form a saturated g-Ti1
xVxH2 dihydride
(sp.gr.Fm3m) upon hydrogenation. The changes in the
lattice parameters of the dihydrides correlate with the
trends observed for the lattice parameters of the initial
alloys.
(b) Isoconversional kinetics studies indicated that dynamic
dehydrogenation of Ti1
xVxH2 is composed of simulta-
neous reactions that are in agreement with TDS and in situ
SR XRD studies.
(c) The main dehydrogenation path of g-Ti1
xVxH2 is
g / (d) / b / balloy. The BCT hydride d (sp.gr. I4/mmm),
has been observed in hydride phases containing 20 and
30 at.% V. For 10 at.% V, transformation of g hydride to b
hydride follows a direct g / b route, which is similar to the
transformation of TiH2, i.e. without formation of d hydride
phase as an intermediate step.
(d) A simple model of hydrogen desorption from single phase
hydrides nicely describes its release from g-Ti1
xVxH2.
This allowed accurate determination of the activation
energy of hydrogen desorption for all the investigated
TieV hydrides.
(e) At high vanadium content, 20e30 at.% V, the kinetics of the
transformation of d to b hydride was well fitted by a one
dimensional Avrami-Erofeev nucleation and growth model,
while at high titanium/vanadium ratios hydride decompo-
sition is affected by formation of a Ti-rich hydride.
14713
Acknowledgements
The authors thank the Norwegian Research Council Norway
and Statoil for their financial support. We appreciate a skilful
assistance from the personnel of Swiss-Norwegian Beam
Lines during the SR XRD experiments.
Nomenclature
E activation energy, kJ/mol H2
A pre-exponential factor, 1/min
x extent of conversion
b heating rate, K/min
k kinetics constant, 1/min
C hydrogen content in the surface
S sample surface of hydride particle, cm2/g
VH unit cell volume of metal hydride, 
A3
g FCC hydride sp. gr. Fm3m
d BCT hydride sp. gr. I4/mmm
b BCC hydride sp. gr. Im3m
Appendix A. Supplementary data
Supplementary data related to this article can be found online
at http://dx.doi.org/10.1016/j.ijhydene.2013.08.103.
references
[1] Predel B. Ti-V (Titanium-vanadium). In: Madelung O, editor.
Springer Materials e the Landolt-Börnstein database (http://
www.springermaterials.com). http://dx.doi.org/10.1007/
10551312_2842.
[2] San-Martin A, Manchester F. The HeTi (hydrogenetitanium)
system. J Phase Equilib 1987;8:30e42.
[3] Hagi T, Sato Y, Yasuda M, Tanaka K. Structure and phase
diagram of TieVeH system at room temperature. Mater
Trans 1987;28:198e204.
[4] Hayashi S, Hayamizu K. X-ray diffraction and 1H and 51V
NMR study of the TieVeH system. J Less-Common Met
1990;161:61e75.
[5] Ueda T, Hayashi S, Hayamizu K. Hydrogen motion and local
structure of metals in Ti1
yVyHx as studied by 1H NMR. Phys
Rev B 1993;48:5837e43.
[6] Brouwer R, Rector J, Koeman N, Griessen R. Hydrogen as a
local probe: diffusion and short-range order in Ti1
yVy alloys.
Phys Rev B 1989;40:3546e59.
[7] Sevilla EH, Cotts RM. Hydrogen diffusion in bcc TiHx and
Ti1
yVyHx. Phys Rev B 1988;37:6813e20.
[8] Nowak B, Hayashi S, Hayamizu K, Yamamoto O. X-ray
diffraction and 1H and 51V NMR study of the structure of a
TieVeH alloy in relation to preparation conditions. J Less-
Common Met 1986;123:75e84.
[9] Ono S, Nomura K, Ikeda Y. The reaction of hydrogen with
alloys of vanadium and titanium. J Less-Common Met
1980;72:159e65.
[10] Suwarno S, Gosselin Y, Solberg JK, Maehlen JP, Williams M,
Krogh B, et al. Selective hydrogen absorption from gaseous
 Author's personal copy
14714 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 3 8 ( 2 0 1 3 ) 1 4 7 0 4 e1 4 7 1 4
mixtures by BCC TieV alloys. Int J Hydrogen Energy
2012;37:4127e38.
[11] Denys RV, Riabov AB, Maehlen JP, Lototsky MV, Solberg JK,
Yartys VA. In situ synchrotron X-ray diffraction studies of
hydrogen desorption and absorption properties of Mg and
MgeMmeNi after reactive ball milling in hydrogen. Acta
Mater 2009;57:3989e4000.
[12] Larson AC, Dreele RBV. Los Alamos National Laboratory
Report LAUR; 2004.
[13] Rietveld H. A profile refinement method for nuclear and
magnetic structures. J Appl Crystallogr 1969;2:65e71.
[14] Howard C. The approximation of asymmetric neutron
powder diffraction peaks by sums of Gaussians. J Appl
Crystallogr 1982;15:615e20.
[15] Thompson P, Cox DE, Hastings JB. Rietveld refinement of
DebyeeScherrer synchrotron X-ray data from Al2O3. J Appl
Crystallogr 1987;20:79e83.
[16] Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA,
Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee
recommendations for performing kinetic computations on
thermal analysis data. Thermochim Acta 2011;520:1e19.
[17] Vyazovkin S. Isoconversional kinetics. In: Michael EB,
Patrick KG, editors. Handbook of thermal analysis and
calorimetry. Elsevier Science B.V.; 2008. p. 503e38.
[18] Kissinger HE. Reaction kinetics in differential thermal
analysis. Anal Chem 1957;29:1702e6.
[19] Akahira T, Sunose T. Method of determining activation
deterioration constant of electrical insulating materials.
Research report. Chiba Inst Technol Sci 1971;16:22e31.
[20] Vyazovkin S, Wight CA. Model-free and model-fitting
approaches to kinetic analysis of isothermal and
nonisothermal data. Thermochim Acta 1999;340e341:53e68.
[21] Ortega A. The kinetics of solid-state reactions toward
consensus, part 2: fitting kinetics data in dynamic
conventional thermal analysis. Int J Chem Kinet
2002;34:193e208.
[22] Gorbachev VM. A solution of the exponential integral in the
non-isothermal kinetics for linear heating. J Therm Anal
1975;8:349e50.
[23] Wolverton C, Ceder G, de Fontaine D, Dreyssé H. Ab initio
determination of structural stability in fcc-based transition-
metal alloys. Phys Rev B 1993;48:726e47.
[24] Fukai Y. Site preference of interstitial hydrogen in metals. J
Less-Common Met 1984;101:1e16.
[25] Yakel Jr H. Thermocrystallography of higher hydrides of
titanium and zirconium. Acta Crystallogr 1958;11:46e51.
[26] Müller H, Weymann K. Investigation of the ternary systems
NbeVeH and TaeVeH. J Less-Common Met
1986;119:115e26.
[27] Riabov AB, Denys RV, Maehlen JP, Yartys VA. Synchrotron
diffraction studies and thermodynamics of hydrogen
absorption-desorption processes in La0.5Ce0.5Ni4Co. J Alloy
Compd 2011;509:S844e8.
[28] Borchers C, Khomenko TI, Leonov AV, Morozova OS.
Interrupted thermal desorption of TiH2. Thermochim Acta
2009;493:80e4.
[29] Liu H, He P, Feng JC, Cao J. Kinetic study on nonisothermal
dehydrogenation of TiH2 powders. Int J Hydrogen Energy
2009;34:3018e25.
[30] Evard EA, Gabis IE, Voyt AP. Study of the kinetics of hydrogen
sorption and desorption from titanium. J Alloy Compd
2005;404e406:335e8.