1 s2.0 S0360319922062103 Main

international journal of hydrogen energy xxx (xxxx) xxx
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Phase-structural transformation of erbium

trihydride studied by thermal desorption
spectroscopy
Mingwang Ma, Lei Wang, Ruiyun Wan, Binghua Tang, Xiaohua Tan*
Institute of Electronic Engineering, China Academy of Engineering Physics, Mianyang 621999, China
highlights
Phase transformation sequence of ErH2.7 decomposition was b þ g./ b / a þ b / a.

Oxygen concentration increased after thermal decomposition due to the oxidation of Er.
Hydrogen atoms in the tetrahedral sites of b phase were more stable than these of octahedral.
Equilibrium H2 pressures were related to peaks of thermal desorption spectra.
article info abstract
Article history: Thermal desorption behaviours of erbium trihydride (ErH3) powders were studied using
Received 15 October 2022 simultaneous thermogravimetry and thermal desorption spectroscopy (TG-TDS) method.
Received in revised form The crystal structures and chemical compositions of the samples were investigated by X-
13 December 2022 ray diffraction analysis (XRD) and X-ray photoelectron spectroscopy (XPS), respectively.
Accepted 28 December 2022 Two-peak structures were observed in the hydrogen desorption spectra and the corre-
Available online xxx sponding activation energies were determined to be 160.7 and 212.3 kJ/mol, respectively.
The phase transformation sequences during thermal desorption process were established
Keywords: by combining the changing trends in the temperature/hydrogen content with the EreH
Erbium hydride phase diagram. It was established that the low-temperature and high-temperature peaks
Thermal desorption spectroscopy were related to the b þ g / b and a þ b / a phase transformation steps, respectively. The
Phase transformation origins of the observed TDS peaks and shoulders were attributed to the equilibrium
Hydrogen desorption hydrogen pressures of the phase regions that the decomposition reaction passed through.
Phase diagram © 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
two erbium hydride phases with distinctly different lattice

Introduction structures [8,9]. The thermodynamically-stable b-ErH2 has a
face-centered cubic (fcc) lattice of Er atoms with hydrogen
Rare earth (RE) metals have attracted much attention in the occupying the tetrahedral sites [10]. The trihydride, g-ErH3,
last decades for various technological applications as poten- has a hexagonal close-packed (hcp) Er sub-structure with
tial hydrogen storage materials [1,2], switchable mirrors [3,4], hydrogen situated in positions that are slightly displaced from
metal hydride battery anodes [5] and catalyst [6,7]. Erbium is tetrahedral and octahedral interstitial sites [11].
typical heavy RE metal, which reacts with hydrogen to form
* Corresponding author.
E-mail address: caepiee@163.com (X. Tan).
https://doi.org/10.1016/j.ijhydene.2022.12.328
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Ma M et al., Phase-structural transformation of erbium trihydride studied by thermal desorption spectroscopy,
International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2022.12.328
2 international journal of hydrogen energy xxx (xxxx) xxx
Hydrogen desorption kinetics are important for under-

standing how processing steps effect the final state of erbium Experimental
hydride. However, despite the thermodynamic, optical, elec-
tronic and magnetic properties of erbium hydride have been Commercial erbium trihydride powder (99% pure) was used in
studied extensively [12,13], there are few reports on their this study and characterized by scanning electron microscope
thermal decomposition properties in the literature. It has been (ProX, Phenom, Netherlands) for its morphology, and energy
concluded that the change of hydrogen concentration affects dispersive spectroscopy (EDS) for its element content. The
thermal properties of the RE hydrides. The b-ErH2 is among particle size distribution of the as-received powder was
the most stable of the rare-earth hydrides [14], while the g- characterized by a laser particle size analyser (1064 L, CILAS,
ErH3 is chemically unstable and samples should be main- France).
tained in an overpressure of hydrogen with no air contact The decomposition of as-received powder was conducted
whatsoever during the desired measurements [15]. Lundin by TG-TDS (IGA-003, Hiden, UK). An ultra-sensitive microbal-
[16] has obtained the pressure-composition-temperature data ance of resolution 0.2 mg was mounted in the thermostated
for the EreH system and found the trihydride to decompose to heatsink with high precision temperature control. The sam-
the dihydride above 383 C at 1 atm pressure. Grimshaw et al. ples were loaded in a quartz sample container and suspended
[14] found that the trihydride component disappeared when from the hangdown quartz hook connected to the microbal-
heated above 400 C in vacuum. ance. Before measurements, the quartz reactor tube was
Thermal desorption spectroscopy (TDS), a technique evacuated up to 105 Pa and then pure argon gas (99.999%)
initially developed for the study of the kinetics of gas-solid was used as carrier gas at the pressure of 1 atm with a flow
surface interactions, has been commonly used to identify rate of 50 ml/min. The experimental apparatus and proced-
the rate-controlling step of H2 evolution and obtain the kinetic ures were described in detail in previous publications [29e31].
parameters for many metal hydrides [17e19]. In most cases, The samples with a weight of approximately 10 mg were
the information obtained from TDS spectra of metal hydrides heated up to 980 C with a linear temperature ramp of 2.5, 5, 10
is difficult to interpret because it should take into account and 20 C/min, respectively. The evolved H2 was measured
several processes, e.g. surface processes, bulk processes and using a quadrupole mass spectrometer (QMS) connected to
different thermodynamic phases [20e23]. Notwithstanding IGA-003 through a thin capillary tube. According to the mass
the difference in peak positions, both Gabis et al. [24] and loss after thermal decomposition, the as-received samples
Suwarno et al. [25] recorded a two-peak structure of thermal were intended to be trihydride with an H/Er ratio near 2.7.
desorption spectrum of ErH3. Qualitatively, the low- The phase structures were identified by XRD (Rigaku D/
temperature and high-temperature desorption peaks were Max-2400) using Cu-Ka radiation, at a scanning rate of 4 /
related to the thermal decompositions of erbium trihydride min with a generator voltage of 40 kV and current of 150 mA.
and erbium dihydride, respectively [24,25]. Nevertheless, the The phase compositions were determined on the basis of
origins of the desorption peaks and the corresponding phase JCPDS files provided by the International Center for Diffraction
transformation sequences during the entire thermal decom- Data. Lattice parameters were determined by Rietveld refine-
position process of erbium trihydride have not been well un- ment method [32]. The surface characterizations were ana-
derstood at present. lysed using X-ray photoelectron spectroscopy (XPS, AXIS Ultra
The simultaneous use of both thermogravimetry (TG) and DLD, Kratos) with a monochromatic Al Ka (1486.6 eV) line of an
thermal desorption spectroscopy (TDS) techniques provides X-ray source. XPS depth profiles were determined using an
the possibility of obtaining complete information on the argon sputtering gun. A rough sputtering rate was estimated
thermodynamics and kinetic properties of metal hydrides to be 0.21 nm/s on a Ta2O5 standard. The photoelectron peaks
[26e28]. Structural transformations can easily be distin- were fitted using a mix of Gaussian and Lorentzian forms, and
guished for the reason that the information of the conversion the background was determined by the Shirley method [33].
of the solid state decomposition and the hydrogen gas evo-
lution are obtained in the same temperature interval, which
allows to accurately determine the phase transformation Results and discussion
steps of the TDS spectra peaks [29e31]. Unfortunately, such
studies have not been performed for the erbium trihydride Sample characteristics
yet. Therefore, it is extraordinarily important to investigate
the hydrogen desorption characteristics of erbium trihydride As shown in Fig. 1(a), the morphology of as-received ErH3
by using simultaneous TG-TDS method, which is essential for powder is represented by irregular polyhedrons with sharp
improving the known applications of erbium hydride and to edges and cleavage planes. Fig. 1(b) presents the chemical
develop new applications. composition of the powder by EDS, which indicates that
This work is focused on the studies of the kinetics and erbium is the predominant element at the surface and some
mechanism of hydrogen desorption from erbium trihydride. impurities are revealed due to surface oxidation and
We present the TG-TDS results coupled with surface charac- contamination. Fig. 2 shows the particle size distribution of
terization techniques, aiming at determining the phase the as-received powder, which shows that the mean size of
transformation sequences and the corresponding kinetic pa- the powder is approximately 15 mm.
rameters during thermal decomposition. This study is Fig. 3 shows the XRD patterns of ErH3 powders before and
essential as allowing identifying the origins of TDS spectra after thermal decomposition. The original erbium hydride
peaks for erbium trihydride. containing nearly 2.7 H/Er ratio shows the co-existence of g-
international journal of hydrogen energy xxx (xxxx) xxx 3
Fig. 2 e Particle size distribution of as-received ErH3

powders. The histogram indicates the amount of the
particle at the size and read from left vertical axis. The red
line indicates the total amount of the particle up to the size
and read from right vertical axis. (For interpretation of the
references to color/colour in this figure legend, the reader is
referred to the Web version of this article.)
Fig. 1 e SEM image of as-received ErH3 powder (a) and its

typical EDS spectrum (b).
Fig. 3 e XRD patterns of ErH3 powders before and after TDS
measurement.
ErH3 (a ¼ 0.6263 nm, c ¼ 0.6519 nm), b-ErH2 (a ¼ 0.5118 nm) and
Er2O3 (a ¼ 1.0508 nm). According to the EreH phase diagram
[34], the as-received powder is located at b þ g two-phase re- crystal structures of Er2O3 have been reported in the literature,
gion. As explained in the introduction, the g phase has a hcp including the hexagonal (A-type, space group: P 3 m1),
metal lattice (space group: P 3 c1) with hydrogen occupying the monoclinic (B-type, space group: C2/m) and cubic (C-type,
positions that are slightly displaced from tetrahedral and space group: Ia 3) structures [38]. Among these sesquioxide
octahedral interstitial sites [11]. The b phase having a fluorite structures, the cubic structure is the most commonly
structure (space group: Fm 3 m) forms over a small range of observed. In particular, the phase transformation from the
compositions between ErH1.8 to ErH2.2. For ErH1.8 to ErH2.0 cubic to monoclinic occurs under ion irradiation or high
hydrogen atoms are located at tetrahedral sites while for pressure conditions [38,39]. In this study, only the cubic Er2O3
ErH2.0 to ErH2.2 additional hydrogen atoms will occupy the less is found since it is the most stable form of erbium sesquioxide
favorable octahedral positions [35]. The presence of Er2O3 is at low (<300 K) and high (>973 K) temperatures [40].
associated the so-called air-formed oxide film of as-received After thermal decomposition measurement, the main
ErH3. For erbium and many RE metals, oxygen is a major phase constituent has the structure of Er (a ¼ 0.3566 nm,
contaminant which would contribute to a stoichiometric c ¼ 0.5594 nm) and Er2O3 (a ¼ 1.0560 nm), indicating that the
deficiency [36,37]. The Er metal most assuredly contains an decomposition has been finished. Pure Er has a hcp crystal
oxide passivation layer due to exposure to air. Three main structure. The increased intensities of Er2O3 phase than as-
received powder can be explained by considering the exis- coefficient on the RE, leading to the formation of hydroxide
tence of residual oxygen in the experimental apparatus [44]. The presence of hydrated oxide has also been found in
because Er readily forms a very stable sesquioxide. A trace air-exposed thin Er films by others [15,42,43]. It is possible that
amount of ErH2 is detected in the XRD pattern, meaning that in spite of the high vacuum before argon flow was introduced
ErH2 has a high thermal stability. in the TG-TDS measurements, hydroxide could arise from
The surface chemical compositions of the ErH3 powders water contamination since water could desorb from those
before and after TDS measurement were analysed using XPS sections of the gas inlet system that can not be baked.
depth profile measurements. Fig. 4 shows the evolutions of By resolving all the sputtering levels of the Er 4d peaks, the
the Er 4d and O 1s core level spectra of the ErH3 powders before relatively concentration (atomic percent) of each component
and after TDS measurement as a function of sputtering time. vs. sputtering time can be obtained, as shown in Fig. 5. The
From the Er 4d spectra in Fig. 4(a) and (c), it can be seen that Er reference binding energies used in resolving the Er 4d peak are
4d region exhibits complex multiplet splitting, with many 167.6 eV for metallic Er [15,41e43], 169.4 eV for Er2O3 [15,42],
satellite features as indicated by the numerals 1 and 2. The and 171.5 eV for ErOx. ErOx is taken to be representative of
wide spread multiplet structure in the 4d XPS spectrum has oxidized erbium as reported by Brumbach et al. [43], since the
been measured experimentally for many RE metals and background is mostly devoid of spectral intensity from
compounds. It is believed that the multiple splitting is domi- metallic erbium. These binding energies vary slightly for the
nated by the 4d-4f exchange interaction [41]. However, the Er samples at different sputtering levels. It should be noted that
4d peak and its nearest satellite have not been well resolved. erbium has only one oxidation state, the peak indicated as
One broad peak appears at binding energy (BE) of ~169.5 eV ErOx can not be attributed to a second oxide as in the case of
prior to sputtering for all the samples, which is similar to pure multiple oxidation state. In other words, both the components
Er2O3 in shape and peak position [15]. As the sputtering pro- of Er2O3 and ErOx contribute the concentration of erbium
gresses, a doublet starts to appear in the Er 4d line shape. A oxide. All the samples show Er2O3 is the main erbium chem-
component at 167.6 eV corresponding to metallic Er 4d 5/2 ical compound with tiny evidence for the presence of ErOx.
[15,41e43] grows in intensity with continued sputtering, The contributions due to metallic Er increase while these of
indicating that the oxide layer is partially removed and the Er2O3 and ErOx decrease with the increase in sputtering time.
metallic erbium is exposed. The powder after TDS measurement shows a relatively lower
The O 1s spectra show two peaks (Fig. 4(b) and (d)) prior to metallic Er concentration than the as-received powder, indi-
sputtering in the ErH3 powders before and after TDS mea- cating an increase of oxide components after TDS.
surement. One peak at 530.7 eV is attributed to Er2O3 and the Fig. 6 shows the relative content of oxygen (O/(O þ Er)) as a
other at 532.9 eV is attributed to the hydroxide [42], the in- function of the sputtering time. The relative content profiles
tensity of which decreases with the increase in sputtering were obtained by integrating the intensities between 150 and
time. It has been reported that H2O has a high adhesion 220 eV for Er 4d and 526e538 eV for O 1s after subtracting the
Fig. 4 e Evolutions of the Er 4d and O 1s core level spectra of as-received ErH3 powders ((a) and (b)) and ErH3 powders after
TDS measurement ((c) and (d)) as a function of sputtering time.
received sample in the entire depth range, indicating that

oxygen has been driven into the inner of the powder during
the dehydrogenation reaction.
Despite the differences in detection limit and detection
depth, both the XPS and XRD measurements show a higher
concentration of Er2O3 for the sample after thermal dehy-
drogenation. The main reason may be attributed to the
oxidation of Er during the dehydrogenation process. As
mentioned earlier, the Er metal readily forms a very stable
sesquioxide passivation layer due to exposure to air. After Er is
precipitated, it would be oxidized by the little residual oxygen
in the apparatus, thereby leading to the increase of oxygen
concentration. The formation of oxides may be determined by
both the oxygen solubility in the original particle and the
adsorption of oxygen at the surface during heat treatment and
subsequent air exposure.
Thermal desorption properties
Fig. 7 shows the TDS spectra of the total ErH3 decomposition at

different heating rates. It can be seen that prominent H2
release accompanied by mass loss starts at approximately
300 C. The TDS spectrum consists of two peaks, which are
denoted as Peak I and Peak II, respectively. With the increase
of heating rate, the two peaks shift to high temperature.
Two-peak structures of TDS spectra of erbium trihydride
Fig. 5 e The concentration profiles (at.%) of different have been found by Gabis et al. [24] and Suwarno et al. [25]
chemical state of Er for ErH3 powders before and after under continuous vacuum conditions. They related the low-
dehydrogenation. temperature and high-temperature peaks to ErH3 / ErH2
and ErH2 / Er transformations, respectively [24,25]. However,
the peak temperatures obtained by Gabis et al. [24] and
Suwarno et al. [25] were lower than the results in this study. A
possible explanation is that the hydrogen pressure in the
background of TDS apparatus has a significant impact on the
desorption kinetics [48,49]. In continuous vacuum conditions,
hydrogen pressure is almost nil and gas-phase effect is
removed, leading to a lower desorption temperature. For the
case of TDS measurements in flowing argon carrier as shown
in this study, the gas-phase effect should not be neglected due
to the residual hydrogen pressure inside the apparatus. On the
other hand, XRD and XPS analyses have revealed that an oxide
Fig. 6 e XPS depth profiles of relative oxygen

concentrations for ErH3 powders before and after
dehydrogenation.
Shirley background for every sputtering level. The sensitivity

factors are 2.0 and 0.67 for the Er 4d and O 1s lines, respectively
[45]. With an increase in the sputtering time, the relative ox-
ygen concentrations decrease gradually for all samples. The
continuous decreasing oxygen concentration has also been
revealed by Auger electron spectroscopy (AES) [15], Nuclear
reaction analysis (NRA) [46] and Ion beam analysis (IBA) [47] Fig. 7 e TDS spectra of as-received ErH3 powders at
methods. The sample of pure Er after complete dehydroge- different heating rates. Inset shows the Kissinger plots for
nation shows relatively higher oxygen content than the as- the two peaks of TDS spectra.
layer forms on ErH3 particle. It is important thus to take into curve. As the trajectory indicates, multiple phases or two-
account the influence of this surface layer on hydrogen phase coexistences in the EreH system are involved in the
desorption kinetics. It is known from literature [50] that oxy- decomposition. The points where the trajectory intersects the
gen atoms occupy the tetrahedral interstitial sites in the phase boundaries represent the positions where phase
erbium lattice. Obviously, the presence of oxygen on the transformations happen. The phase transformation sequence
tetrahedral sites affects the state and configuration of the for the decomposition of ErH3 can be schematized as: b þ g/ b
neighboring hydrogen atoms. Furthermore, it can be expected / a þ b / a.
that the presence of oxygen decreases the randomness of the The entire thermal decomposition process is divided into
distribution of hydrogen atoms due to repulsion. In fact, four steps, as shown in Fig. 8(b).The downward dashed lines
erbium oxide coatings has been developed as tritium perme- show the points where the TG curve intersects the phase
ation barriers (TPB) in fusion blanket systems due to its high boundaries obtained from Fig. 8(a). Before heating, the sample
permeation reduction factor [51]. Therefore, the erbium oxide is located in b þ g two-phase region. As it was mentioned
acts as an effective hydrogen diffusion barrier due to the lower earlier, the g phase has a hcp metal lattice with hydrogen
diffusivity of H through erbium oxide compared with hydride situated in positions that are slightly displaced from the
phase [52] and is beneficial to delay the release of hydrogen. In tetrahedral and octahedral interstitial sites [11]. Compared to
view of this, we suggest that the hydrogen transport through the high thermal stable b phase the g phase is chemically
the surface oxide film would be the rate-limiting step for the g unstable. Therefore, Peak I is related to the vanishing of g
phase region, which is consistent with the propositions of phase, namely b þ g/ b step. We have suggested that the
other researchers [53]. equilibrium hydrogen pressure (Peq) of each single-phase or
The activation energy for each peak was determined ac- two-phase coexistence is related to the corresponding peak or
cording to Kissinger relation [54], as shown in the inset of shoulder of TDS spectrum [31]. The ascending edge of the low-
Fig. 7. The values of activation energies derived from this plot temperature peak (Peak I) may be attributed to the Peq of b þ g
are 160.7 and 212.3 kJ/mol for Peak I and Peak II, respectively. two-phase that is a function of temperature only. The Peq
Peak I is associated with lower activation energy, meaning reaches 104 Pa [16] that would be distinctly detected using
that the corresponding phase transformation step needs QMS system at the temperature of 300 C, thereby leading the
adsorbing less heats. It has been found that the dihydride has sharp increase of H2 signal (Fig. 8 (b)) accompanied by mass
much higher enthalpy of formation than the trihydride due to loss (Fig. 8 (a)). The g phase is totally decomposed at 360 C, in
the higher stability of the dihydride [52]. Lundin [16] has also agreement with the observation by Grimshaw et al. [14] who
obtained the enthalpies of formation of ErH3 and ErH2 derived found that the trihydride component disappeared when
from the Van't Hoff plots as 82.9 and 220.2 kJ/mol, respectively. heated above 400 C in vacuum.
The activation energy for ErH2 decomposition (Peak II) pre- The second step is related to the hydrogen evolution from
sented in Fig. 7 is in good agreement with the value of 221.8 kJ/ the single b phase region. The Peq of single phase region is a
mol for the heat of formation for ErH2 [36] and Lundin's re- function of temperature as well as hydrogen content. As the
ported value of 220.2 kJ/mol [16]. The higher activation energy temperature increases while hydrogen content decreases, the
for ErH3 decomposition (Peak I) than the enthalpy of formation decrease of hydrogen content plays a leading role and therefore
of ErH3 may be due to the surface effect (i.e. surface oxide) as the Peq of b phase has the descending trend, leading to the
elucidated above. It is likely that the oxide layer impacts the formation of the descending edge of Peak I. Note that the H/Er
trihydride phase energy to some extent, while not impacting ratio maintains at 2.0 instead of decreasing continuously in the
the dihydride. One possible reason is that the surface oxide is temperature range of 435e485 C as indicated in Fig. 8(a), which
thermally reduced at high temperature [15]. It has been shown likely can be explained by the hydrogen site occupations in the
that the thermal annealing with higher temperature leads to a b phase. The b phase is stable over a relatively small region of H/
degradation of the passive oxide and permits the diffusion of Er ratio of approximately 1.8e2.2. When the H/Er ratio is less
hydrogen [43]. The mathematical modeling study of the ki- than 2.0, hydrogen will seek its ground state in the tetrahedral
netics of hydrogen desorption from ErH3 has also shown that sites and when the H/Er ratio exceeds 2.0, additional hydrogen
the low-temperature peak is controlled by surface processes, will occupy the octahedral positions [35]. It has been concluded
but diffusion is one of the limiting factors for the high- that the octahedral site is less stable with a lower migration
temperature peak [53]. Therefore, the activation energy for barrier energy of 0.62 eV using first principles calculations [50].
ErH3 decomposition is more sensitive to surface oxide than It is assumed that the hydrogen atoms in the octahedral sites
ErH2 decomposition during continuous heating of sample. have been evacuated completely at 435 C as indicated in
Fig. 8(b), where bOct and bTet denote the hydrogen site occupa-
Phase transformation sequences tions in octahedral and tetrahedral sites in the b phase,
respectively. In contrast, the tetrahedral sites maintain com-
The simultaneous knowledge of hydrogen content changing plete occupancy in the temperature range of 435e485 C and
and H2 desorption can be used to attribute the peaks of TDS the hydrogen atoms in the tetrahedral sites start to evolve
spectra to the corresponding phase transformation steps. above 485 C due to their high thermal stabilities. The
Fig. 8(a) shows the phase diagram of the EreH system [34] assumption is consistent with the fact that the H/Er ratio in
combined with the changing trend of temperature/hydrogen sputtered erbium hydride films decreased to approximately
content at a heating rate of 10 C/min. The H/Er atom ratio was 2.0 at a growth temperature of 460 C found by Adams et al. [11].
calculated from the TG curve. It can be seen that the decom- With the further increase of temperature, the H/Er ratio
position proceeds from right to left as indicated by the TG drops below 1.8 and the precipitation of a phase occurs (step
Fig. 8 e EreH system [34] combined with the changing trend of temperature/hydrogen content (a) and the phase
transformation steps of TDS spectrum (b) for the dehydrogenation of ErH3 at a heating rate of 10 C/min.
III). In the a phase, hydrogen is in solid solution with the Er rate from 2.5 to 20 C/min. The XRD and XPS depth profile
metal, up to an H/Er ratio of 0.2 [16]. Ab initio calculations [55] analysis showed that after thermal decomposition, the rela-
and experimental observations [56] have shown that the H tive oxygen concentration increased compared with that of
atoms introduced into the hcp Er are combined tightly with as-received ErH3 powder due to the oxidation of the precipi-
the neighboring host atoms and prefers the tetrahedral site tated Er metal.
rather than the octahedral site. The Peq of a þ b two-phase is a Two-peak structures were observed in the TDS spectra and
function of temperature only [16], leading the formation of the the corresponding activation energies were determined to be
ascending edge of the high-temperature peak (Peak II). 160.7 and 212.3 kJ/mol, respectively. The activation energy for
Peak II is formed when the vanishing of the b phase takes the high-temperature peak was in good agreement with the
place, namely a þ b / a step. At the end of the decomposition, value of the enthalpy of formation of ErH2. The higher acti-
the entire particle is transformed into a single a phase, meaning vation energy for the low-temperature peak than the enthalpy
that the high temperature shoulder of TDS spectrum is related of formation of ErH3 was associated with the gas-phase and
to the hydrogen release from this single phase region (step Ⅳ). surface (i.e. surface oxide) effects.
According to Sievert's law S¼KsP1/2, where S is the solubility of The phase transformation sequence for the decomposition
hydrogen in Er, Ks is Sievert's constant which obeys the of ErH3 can be schematized as: b þ g/ b / a þ b / a. The low-
Arrhenius' equation, and P is the pressure of hydrogen gas, the temperature and high-temperature peaks in the TDS spectra
hydrogen pressure of a phase is a function of the solubility of were related to the vanishing of the g and b phase, respec-
hydrogen in Er as well as the temperature. As the temperature tively. Heating b phase up to 435 C revealed removal of
increases while the solubility decreases, the hydrogen pressure hydrogen occupations in the octahedral sites with no reduc-
has a descending trend, thereby leading to the formation of the tion of tetrahedral sites. While the hydrogen atoms in the
high temperature shoulder of Peak II. tetrahedral sites started to evolve above 485 C due to their
higher thermal stabilities. The origins of the observed TDS
peaks and shoulders were attributed to the equilibrium
Conclusions hydrogen pressures of the phase regions that the decompo-
sition reaction passed through.
Thermal desorption behaviours of ErH3 powders were studied These results give insight into the trapping and diffusion of
using simultaneous TG-TDS measurements with the heating hydrogen atoms in erbium hydride by using simultaneous TG-
TDS method. This work is expected to provide the basis for a [14] Grimshaw JA, Spooner FJ, Wilson CG, McQuillan AD. The
fundamental understanding of hydrogen behaviours in RE growth of crystals of erbium hydride. J Mater Sci
metals and exploration of the technological applications of RE 1981;16:2855e9.
[15] Tewell CR, King SH. Observation of metastable erbium
metal hydrides.
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[16] Lundin CE. The erbium-hydrogen system. Trans Metall Soc
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Declaration of competing interest
[17] Lu X, Depover T, Johnsen R. Evaluation of hydrogen diffusion
and trapping in nickel Alloy 625 by thermal desorption
The authors declare that they have no known competing spectroscopy. Int J Hydrogen Energy 2022;47:31673e83.
financial interests or personal relationships that could have [18] Zaika YV, Sidorov NI, Fomkina OV. Identification of hydrogen
appeared to influence the work reported in this paper. permeability and thermal desorption parameters of
vanadium-based membrane. Int J Hydrogen Energy
2021;46:10789e800.
[19] Nechaev YS, Alexandrova NM, Cheretaeva AO,
Acknowledgment €
Kuznetsov VL, Ochsner A, Kostikova EK, et al. Studying the
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This work is supported by the PFCAEP project No. nanostructures and graphite. Int J Hydrogen Energy
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international journal of hydrogen energy xxx (xxxx) xxx

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Phase-structural transformation of erbium

Phase transformation sequence of ErH2.7 decomposition was b þ g./ b / a þ b / a.

article info abstract

two erbium hydride phases with distinctly different lattice

Hydrogen desorption kinetics are important for under-

Fig. 2 e Particle size distribution of as-received ErH3

Fig. 1 e SEM image of as-received ErH3 powder (a) and its

received sample in the entire depth range, indicating that

Thermal desorption properties

Fig. 7 shows the TDS spectra of the total ErH3 decomposition at

Fig. 6 e XPS depth profiles of relative oxygen

Shirley background for every sputtering level. The sensitivity

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