Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium
Sorption properties and kinetic parameters of hydrogenating and dehydrogenating processes of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ eutectic alloy, in which partial substitution of each of its component with 2% and 5% of vanadium is performed, are investigated by Sieverts’ method. As determined, the introduction of va...
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Інститут металофізики ім. Г.В. Курдюмова НАН України
2015
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| Цитувати: | Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium / V. G. Ivanchenko, V. A. Dekhtyarenko, T. V. Pryadko // Металлофизика и новейшие технологии. — 2015. — Т. 37, № 4. — С. 521-530. — Бібліогр.: 16 назв. — рос. |
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irk-123456789-1118912017-01-16T03:03:37Z Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium Ivanchenko, V.G. Dekhtyarenko, V.A. Pryadko, T.V. Дефекты кристаллической решётки Sorption properties and kinetic parameters of hydrogenating and dehydrogenating processes of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ eutectic alloy, in which partial substitution of each of its component with 2% and 5% of vanadium is performed, are investigated by Sieverts’ method. As determined, the introduction of vanadium within the specified limits results in decrease of the temperature of the start of intensive hydrogen absorption, decrease of the duration of hydrogenating process, and also in substantial increase of sorption capacity (up to 2.85% wt.). As shown, the alloys, which are subjected to the sorption—desorption cycling, possess as much activated surface that behave themselves with regard to hydrogen similar to intermetallic compounds and can absorb hydrogen at the room temperature and the pressure of 0.23 MPa from the first seconds of the contact of the specimen with the hydrogen-containing medium with the average rate of (2—4)∙10³ wt.%/s. Сівертсовою методою досліджено сорбційні властивості і кінетичні параметри процесів гідрування і дегідрування виливаного евтектичного стопу Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅, в якому було виконано часткову заміну кожного з його компонентів на 2% і 5% Ванадію. Встановлено, що введення Ванадію в зазначених межах приводить до зниження температури початку інтенсивного вбирання Гідроґену, зменшення тривалости процесу гідрування, а також до істотного збільшення сорбційної місткости (до 2,85% мас.). Показано, що стопи, які пройшли циклування сорбція—десорбція, мають настільки активовану поверхню, що ведуть себе щодо водню неначе інтерметаліди і здатні вбирати Гідроґен за кімнатної температури і тиску у 0,23 МПа з перших секунд контакту зразка з водневим середовищем із середньою швидкістю у (2—4)∙10³ мас.%/с. Методом Сивертса исследованы сорбционные свойства и кинетические параметры процессов гидрирования и дегидрирования литого эвтектического сплава Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅, в котором была произведена частичная замена каждого из его компонентов на 2% и 5% ванадия. Установлено, что введение ванадия в указанных пределах приводит к понижению температуры начала интенсивного поглощения водорода, снижению продолжительности процесса гидрирования, а также к существенному увеличению сорбционной ёмкости (до 2,85% масс.). Показано, что сплавы, прошедшие циклирование сорбция—десорбция, обладают настолько активированной поверхностью, что ведут себя по отношению к водороду подобно интерметаллидам и способны поглощать водород при комнатной температуре и давлении 0,23 МПа с первых секунд контакта образца с водородсодержащей средой со средней скоростью (2—4)∙10³ масс.%/с. 2015 Article Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium / V. G. Ivanchenko, V. A. Dekhtyarenko, T. V. Pryadko // Металлофизика и новейшие технологии. — 2015. — Т. 37, № 4. — С. 521-530. — Бібліогр.: 16 назв. — рос. PACS: 61.66.Dk, 64.75.Bc, 68.43.Nr, 81.70.Jb, 81.70.Pg, 82.80.Ms, 88.30.rd http://dspace.nbuv.gov.ua/handle/123456789/111891 en Металлофизика и новейшие технологии Інститут металофізики ім. Г.В. Курдюмова НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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English |
| topic |
Дефекты кристаллической решётки Дефекты кристаллической решётки |
| spellingShingle |
Дефекты кристаллической решётки Дефекты кристаллической решётки Ivanchenko, V.G. Dekhtyarenko, V.A. Pryadko, T.V. Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium Металлофизика и новейшие технологии |
| description |
Sorption properties and kinetic parameters of hydrogenating and dehydrogenating processes of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ eutectic alloy, in which partial substitution of each of its component with 2% and 5% of vanadium is performed, are investigated by Sieverts’ method. As determined, the introduction of vanadium within the specified limits results in decrease of the temperature of the start of intensive hydrogen absorption, decrease of the duration of hydrogenating process, and also in substantial increase of sorption capacity (up to 2.85% wt.). As shown, the alloys, which are subjected to the sorption—desorption cycling, possess as much activated surface that behave themselves with regard to hydrogen similar to intermetallic compounds and can absorb hydrogen at the room temperature and the pressure of 0.23 MPa from the first seconds of the contact of the specimen with the hydrogen-containing medium with the average rate of (2—4)∙10³ wt.%/s. |
| format |
Article |
| author |
Ivanchenko, V.G. Dekhtyarenko, V.A. Pryadko, T.V. |
| author_facet |
Ivanchenko, V.G. Dekhtyarenko, V.A. Pryadko, T.V. |
| author_sort |
Ivanchenko, V.G. |
| title |
Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium |
| title_short |
Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium |
| title_full |
Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium |
| title_fullStr |
Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium |
| title_full_unstemmed |
Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium |
| title_sort |
hydrogen sorption properties of ti₀,₄₇₅zr₀,₃mn₀,₂₂₅ eutectic alloy alloyed with 2 at.% and 5 at.% of vanadium |
| publisher |
Інститут металофізики ім. Г.В. Курдюмова НАН України |
| publishDate |
2015 |
| topic_facet |
Дефекты кристаллической решётки |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/111891 |
| citation_txt |
Hydrogen Sorption Properties of Ti₀,₄₇₅Zr₀,₃Mn₀,₂₂₅ Eutectic Alloy Alloyed with 2 at.% and 5 at.% of Vanadium / V. G. Ivanchenko, V. A. Dekhtyarenko, T. V. Pryadko // Металлофизика и новейшие технологии. — 2015. — Т. 37, № 4. — С. 521-530. — Бібліогр.: 16 назв. — рос. |
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Металлофизика и новейшие технологии |
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521
CRYSTAL-LATTICE DEFECTS
PACS numbers:61.66.Dk, 64.75.Bc,68.43.Nr,81.70.Jb,81.70.Pg,82.80.Ms, 88.30.rd
Hydrogen Sorption Properties of Ti0.475Zr0.3Mn0.225 Eutectic Alloy
Alloyed with 2 at.% and 5 at.% of Vanadium
V. G. Ivanchenko, V. A. Dekhtyarenko, and T. V. Pryadko
G. V. Kurdyumov Institute for Metal Physics, N.A.S. of Ukraine,
36 Academician Vernadsky Blvd.,
UA-03680 Kyiv, Ukraine
Sorption properties and kinetic parameters of hydrogenating and dehydro-
genating processes of Ti0.475Zr0.3Mn0.225 eutectic alloy, in which partial substi-
tution of each of its component with 2% and 5% of vanadium is performed,
are investigated by Sieverts’ method. As determined, the introduction of va-
nadium within the specified limits results in decrease of the temperature of
the start of intensive hydrogen absorption, decrease of the duration of hy-
drogenating process, and also in substantial increase of sorption capacity (up
to 2.85% wt.). As shown, the alloys, which are subjected to the sorption—
desorption cycling, possess as much activated surface that behave themselves
with regard to hydrogen similar to intermetallic compounds and can absorb
hydrogen at the room temperature and the pressure of 0.23 MPa from the
first seconds of the contact of the specimen with the hydrogen-containing
medium with the average rate of (2—4)10
3
wt.%/s.
Сівертсовою методою досліджено сорбційні властивості і кінетичні пара-
метри процесів гідрування і дегідрування виливаного евтектичного стопу
Ti0,475Zr0,3Mn0,225, в якому було виконано часткову заміну кожного з його
компонентів на 2% і 5% Ванадію. Встановлено, що введення Ванадію в
зазначених межах приводить до зниження температури початку інтенси-
вного вбирання Гідроґену, зменшення тривалости процесу гідрування, а
також до істотного збільшення сорбційної місткости (до 2,85% мас.). По-
казано, що стопи, які пройшли циклування сорбція—десорбція, мають
настільки активовану поверхню, що ведуть себе щодо водню неначе інте-
рметаліди і здатні вбирати Гідроґен за кімнатної температури і тиску у
0,23 МПа з перших секунд контакту зразка з водневим середовищем із
середньою швидкістю у (2—4)10
3
мас.%/с.
Методом Сивертса исследованы сорбционные свойства и кинетические
параметры процессов гидрирования и дегидрирования литого эвтектиче-
ского сплава Ti45,5Zr30Mn22,5, в котором была произведена частичная заме-
на каждого из его компонентов на 2% и 5% ванадия. Установлено, что
Металлофиз. новейшие технол. / Metallofiz. Noveishie Tekhnol.
2015, т. 37, № 4, сс. 521—530
Оттиски доступны непосредственно от издателя
Фотокопирование разрешено только
в соответствии с лицензией
2015 ИМФ (Институт металлофизики
им. Г. В. Курдюмова НАН Украины)
Напечатано в Украине.
522 V. G. IVANCHENKO, V. A. DEKHTYARENKO, and T. V. PRYADKO
введение ванадия в указанных пределах приводит к понижению темпера-
туры начала интенсивного поглощения водорода, снижению продолжи-
тельности процесса гидрирования, а также к существенному увеличению
сорбционной ёмкости (до 2,85% масс.). Показано, что сплавы, прошед-
шие циклирование сорбция—десорбция, обладают настолько активиро-
ванной поверхностью, что ведут себя по отношению к водороду подобно
интерметаллидам и способны поглощать водород при комнатной темпера-
туре и давлении 0,23 МПа с первых секунд контакта образца с водородсо-
держащей средой со средней скоростью (2—4)10
3
масс.%/с.
Key words: hydrogenating, dehydrogenating, hydrogen capacity, eutectic
alloys, intermetallide, solid solution.
(Received October 1, 2014; in final version, October 28, 2014)
1. INTRODUCTION
Modern investigations allow one to select quite certain materials with
the prescribed properties, such as the temperature and pressure of
formation and decomposition of hydrides, thermodynamic and kinetic
characteristics of the hydride formation processes [1]. Currently, both
LaNi5 and the alloys based on it are such the most required compounds.
However, the heavy weight of this class of materials makes problemat-
ic the issue of their use at development of automobile power sources. In
connection with this, the search of new effective metal compositions
for hydrogen accumulators, which use the elements lighter than REM,
acquires a special applicability. АВ2 intermetallic systems with Laves’
phase structure possess higher potential for changing of АВ2 com-
pounds in the capacity of hydrogen absorptive materials. For example,
Ti—Zr—Mn compounds absorb significant amount of hydrogen ( 1.8—
2.0% wt.) without the preliminary heat treatment [2, 3]. Maximal
sorption capacity is inherent to the alloys, which are located on the
lower boundary of homogeneity range. For this reason, optimal rela-
tionship of titanium and zirconium, as well as minimal content of
manganese in the intermetallic, makes possible to obtain the absorp-
tion capacity of 2.28% wt. [6].
For TiMn2 intermetallic compounds, introduction of vanadium re-
sults in the substantial increase of the nonstoichiometry range from
АВ1.4 to АВ2.8 for Ti—V—Mn system and from АВ1.2 to АВ3.5 for (Ti, Zr)—
V—Mn system as contrasted with (АВ1.5—АВ2.1) binary system [2]. The
results of Ref. [7] demonstrate that hydrogenating rate of (Ti, Zr)—V—
Mn exceeds the hydrogenating rate of LaNi5 by 20—50%.
Enhancement of the parameters listed above is possible not only due
to the account of alloying or optimization of the alloy mixture ratio.
Using of eutectic Ti—Zr—Mn-system-based alloys in the capacity of hy-
drogen accumulators also results in substantial increase of sorption
H SORPTION PROPERTIES OF Ti0.475Zr0.3Mn0.225 EUTECTIC ALLOY ALLOYED WITH V 523
capacity and enhancement of kinetic parameters of hydrogenating and
dehydrogenating processes due to combination of advantages of each
phase [8, 9]. These alloys typically consist of b.c.c. solid solution (Ti,
Zr, Mn) with high hydrogen capacity and Laves phases (Тi, Zr)Mn2х
with operation temperatures acceptable for exploitation and easiness
of the surface activation.
Manufacturing four-component eutectic (Ti, Zr)—(Mn, V), one can
expect the substantial increase of their sorption capacity and en-
hancement of the kinetic parameters of hydrogenating and dehydro-
genating processes.
2. MATERIALS AND METHODS OF INVESTIGATION
Alloys are produced in a laboratory electric arc furnace with perma-
nent tungsten electrode on cooled copper furnace hearth by the way of
six-fold remelting in the atmosphere of the purified argon, using iodic
titanium with a purity of 99.95%, iodic zirconium with the purity of
99.975%, electrolytic vanadium–99.9%, and electrolytic manga-
nese–99.99% as primary components. Chemical composition of alloys
is determined by fluorescent X-ray analysis using VRA-40 spectrome-
ter. Coincidence with nominal composition is within an error of meas-
urement (0.03%).
Phase composition and lattice parameters are determined by the X-
ray phase analysis method using DRON-3M diffractometer with GUR-
8 standard goniometer in FeK radiation by the way of photography of
both plane monolithic and powder specimens. Lines of diffractograms
are identified using JCPDS (International Center for Diffraction Data)
database.
Interaction of alloys and hydrogen is studied by Sieverts’ method in
IVGM-2M installation [10] in the heating mode with the rate of
4C/min within the temperature range from room temperature to
500C and under isobaric-isothermal conditions under the pressure of
0.6 MPa. Hydrogen purified by sorption is introduced at room tem-
perature, when pressure in working reactor of the installation reaches
the value of 1.3310
6
MPa. During the hydrogenating process, the
time dependences
2H
( ),P T() are registered and all other parameters
are calculated proceeding from them. Amount of the absorbed hydro-
gen is determined by weighing with the accuracy of 1.510
5
g and is
calculated by the pressure change in the closed space.
Desorption of hydrogen from hydrogenation products is investigat-
ed using automated dilatometric complex (ADC) designed at the
G. V. Kurdyumov Institute for Metal Physics of N.A.S.U. for investi-
gation of physical processes, which proceed during the heating of pow-
der compacts [11].
The 47.5 Ti—30 Zr—22.5 Mn eutectic alloy is chosen as a based one
524 V. G. IVANCHENKO, V. A. DEKHTYARENKO, and T. V. PRYADKO
(hereinafter alloy compositions are presented in at.%). Alloying prin-
ciple consists in partial substitution of each from its components by
2% and 5% of vanadium (see Table 1).
3. RESULTS AND DISCUSSION
Information concerning the impact of V on the structure and phase
composition of 47.5 Ti—30 Zr—22.5 Mn eutectic alloy is presented in
Ref. [12]. Partial substitution of 2% and 5% of zirconium and 2% of
titanium by vanadium does not result in the structure change. The
substitution of 5% of Ti, as well as the substitution of 2% and 5% of
manganese by vanadium results in appearance of primary crystals of a
solid solution. In all cases, alloying results in the increase of the vol-
ume part of the -phase and is accompanied by the distribution of va-
nadium between -solid solution and intermetallide with the advantage
of the last one. In such a case, the Mn content in -phase decreases and
the boundary of homogeneity range shifts toward the solid solution.
In the case of investigation of the sorption properties of specified
alloys, the possibility of their hydrogenating at room temperature, as
well as in the case of the initial 47.5 Тi—30 Zr—22.5 Mn eutectics is
supposed. Alloys are held in the hydrogen atmosphere at the pressure
of 0.6 MPa during 24 hours. The specified hydrogenation mode does
not lead to the activation of specimens’ surface. Obviously, some criti-
cal volume fraction of intermetallide on the surface of the specimen is
necessary to initiate the process of the active hydrogen absorption at
room temperature. The change of the ratio of phases’ fractions due to
the vanadium alloying renders impossible the process of hydrogena-
tion at the specified parameters.
Intensive hydrogen absorption is detected during the heating pro-
cess and under conditions of isobaric and isothermal holding of alloys
at temperatures of 500C and the same pressure.
As in the case of the bearing 47.5 Тi—30 Zr—22.5 Mn eutectic alloy,
TABLE 1. Nominal composition of alloys.
Designation Alloy composition, at.%
Ti Zr Mn V
V Mn
V Mn 2
V Mn 5
47.5
47.5
30
30
20.5
17.5
2
5
V Zr
V Zr 2
V Zr 5
47.5
47.5
28
25
22.5
22.5
2
5
V Ti
V Ti 2
V Ti 5
45.5
42.5
30
30
22.5
22.5
2
5
H SORPTION PROPERTIES OF Ti0.475Zr0.3Mn0.225 EUTECTIC ALLOY ALLOYED WITH V 525
the process of doped alloys hydrogenation proceeds in two stages, rates
of which differ by order of magnitude ((2—3)10
4
wt.%/s for the first
and (5—7)10
3
wt.%/s for the second stage) (see Fig. 1, a). Duration of
the first stage at which drastic increase of the hydrogenating rate oc-
curs as well as the amount of absorbed hydrogen are in the direct de-
pendence on the ratio of fractions of phases presented in the alloys.
Temperatures of the start of the intensive absorption, amount of oc-
cluded hydrogen at the temperature of isothermal holding and at room
temperature, as well as the duration of the hydrogenating process are
determined from the kinetic dependences (see Fig. 1, b and Table 2).
It is established that alloying with vanadium results in the decrease
of the temperature of intensive absorption start (see Table 2) (for the
initial alloy it is 540C [8]). During avalanche-type absorption (the sec-
ond stage), the drastic increase of the reactor temperature by 1012C
per one gram of the formed hydride is detected, i.e., the absorption pro-
cess proceeds with heat release. Duration of the hydrogenation process
hyd increases from 10—15 min for the alloys with vanadium content of
2% to 40—50 min for alloys with vanadium content of 5%.
Taking into account the temperature of the start of the active ab-
sorption and the rate of hydrogen adsorption on both stages, one can
state that the hydration process begins from the solid solution (Ti,
Zr, Mn, V) [13], and cracks formation, which accompanies this process
in material with the surface free of an oxide film, facilitates the pro-
cess of the intermetallide activation and promotes its lightning-like
saturation. Typical deviation of the dependence of change of pressure
on temperature during cooling from the linear law, inherent to all al-
loys, attests to renewal of hydrogenating process with decrease of tem-
perature to 250—300C.
a b
Fig. 1. Changes in temperature and pressure of hydrogen with time (a) and
dependence of pressure (MPa) on temperature (b) at hydrogenation of 47.5 Тi—
30 Zr—17.5 Mn—5 V alloy.
526 V. G. IVANCHENKO, V. A. DEKHTYARENKO, and T. V. PRYADKO
Using X-ray phase analysis, it is established that the end product of
hydrogenation of all alloys consists of hydrides, which are formed on
the base of initial phases only:
- -hydride based on (Ti, Zr, V, Mn)Н2х solid solution with face can-
tered cubic arrangement of CaF2-type;
- -hydride based on (Ti, Zr, V, Mn)Н2х solid solution with tetrago-
nal arrangement of ThH2-type;
- -hydride based on (Ti, Zr)(V, Mn)2хH1х Laves phase with crystal-
line structure of MnZn2-type.
Lattice parameters of products of alloys hydrogenation are present-
ed in Table 3.
These results demonstrate that decomposition of phases during hy-
drogenation of the specified alloys does not take place.
It is assumed that the presence of two hydrides based on -solid solu-
tion with cubic and tetragonal lattices is connected with impossibility
of achievement of maximal hydrogen capacity of alloys under the spec-
ified modes of hydrogenation. This fact allows using not only alloying,
but also optimization of parameters of hydrogenation processes of pro-
duced alloys for the increase of sorption capacity.
For separate estimations of the hydrogen capacity of -solid solution
and Laves phase, the ratio of their molar fractions by Rietveld refine-
ment is performed. As far as phase decomposition does not take place
at hydrogenation, it should come as no surprise that ratio of molar
fractions of hydrides, produced based on each of phases, remains equal
to the relationship of molar fractions in initial conditions.
Amount of hydrogen in the hydride based on the Laves phase is cal-
culated in accordance with [14], hereunder the increase of the lattice
cell volume comprises 2.910
3
nm3
per unit of Н/М, where M is a
number of metal atoms in the lattice cell (Pearson’s symbol for the
structure of the MgZn2 type–hP12 type ). Measured increment of the
TABLE 2. Kinetic parameters of the process of alloys hydrogenation.
Alloy Тabs, Chyd, min
Hydrogen concentration
СН, wt.% Н/Ме (Н/Ме) (Н/Ме)
at Тroom, Рhyd at Тroom, Рatm
V Mn 2 495 10 2.68 2.71 1.72 1.45 1.97
V Mn 5 450 40 2.81 2.85 1.81 1.43 2.16
V Zr 2 395 15 2.62 2.66 1.67 1.41 1.97
V Zr 5 490 45 2.48 2.66 1.64 1.34 1.91
V Ti 2 490 15 2.36 2.58 1.58 1.41 1.91
V Ti 5 335 55 2.58 2.62 1.67 1.39 1.98
H SORPTION PROPERTIES OF Ti0.475Zr0.3Mn0.225 EUTECTIC ALLOY ALLOYED WITH V 527
lattice cell of the Laves phase per one metallic atom provides the possi-
bility to estimate the sorption capacity of intermetallide, and the rest
of the adsorbed hydrogen to charge to contribution of - and -hydrides
based on the solid solution (see Table 2).
The obtained data point at the fact that alloying with vanadium re-
sults in the substantial increase of the sorption capacity and enhance-
ment of kinetic and thermodynamic parameters of hydrating processes
due to combination of each phase advantages. It is specifically typical
to the alloys, in which hydride-nonforming Mn is substituted with the
hydride-forming V. In this case, the titanium-based solid solution ab-
sorbs hydrogen with the kinetics, similar to the kinetics of the hydro-
gen sorption by intermetallide and reaches the high level of hydrogen
capacity for the short time. This feature is conditioned by the high sur-
face area of the interphase boundaries, which is typical for the eutectic
structures, across which the diffusion coefficient is approximately 103
times higher than that in the bulk. In addition, high rate of hydrogen
absorption is in a greater part caused by the crystal b.c.c. structure of
-phase, in which the hydrogen diffusion coefficient is almost three
orders of magnitude higher than hydrogen diffusion coefficient in -
phase with h.c.p. lattice [15].
Hydride formation process proceeds in the form of an avalanche also
due to the brittleness of the Laves phase, resulting in quick cleaving of
TABLE 3. Results of X-ray phase analysis of the products of alloys hydro-
genation.
Alloy
Lattice parameters а (and с), 0.0009 nm
Initial phases Hydrogenated Dehydrogenated
-
phase
-
phase
-
hydride
-
hydride
-
hydride
-
phase
-
phase
-
phase
V
Mn 2
0.5195
(0.8430)
0.3347
0.5587
(0.9177)
0.4467
0.4553
(0.4700)
0.5189
(0.8523)
0.3380
0.3000
(0.4774)
V
Mn 5
0.5186
(0.8428)
0.3334
0.5574
(0.9155)
0.4438
0.4538
(0.4685)
0.5176
(0.8503)
0.3367
0.2985
(0.4750)
V
Zr 2
0.5199
(0.8449)
0.3362
0.5572
(0.9152)
0.4438
0.4534
(0.4681)
0.5187
(0.8520)
0.3382
0.2997
(0.4769)
V
Zr 5
0.5190
(0.8442)
0.3356
0.5548
(0.9113)
0.4420
0.4523
(0.4669)
0.5175
(0.8501)
0.3367
0.2965
(0.4718)
V
Ti 2
0.5203
(0.8439)
0.3375
0.5598
(0.9192)
0.4597
0.4534
(0.4680)
0.5203
(0.8546)
0.3386
0.2970
(0.4726)
V
Ti 5
0.5200
(0.8430)
0.3373
0.5569
(0.9148)
0.4433
0.4539
(0.4686)
0.5191
(0.8527)
0.3381
0.2985
(0.4750)
528 V. G. IVANCHENKO, V. A. DEKHTYARENKO, and T. V. PRYADKO
the forming hydride and formation of the clean surfaces, ready for the
hydrogen sorption.
Mass-spectrometric investigations of the products of hydrogenation
of the vanadium-doped alloys shows that the release of hydrogen at the
initial pressure in the chamber of 410
3
Pa begins at the temperature
of (55 5)C (see Fig. 2). It is lower by 25C than that of non-doped
eutectic alloy.
Integration of the surface area under each of peaks shows that in the
temperature range from 200C to 300C under the specified technolog-
ical conditions 50% of the absorbed hydrogen precipitate from 47.5
Тi—30 Zr—17.5 Mn—5 V alloy. Taking into account that 34% falls to
the share of intermetallide, the first peak with the maximum at the
temperature of 265C may be interpreted as simultaneous release of
hydrogen from the intermetallide-based hydride [6] and -hydride
based on -solid solution during its decomposition until -hydride.
Proceeding from the data of Ref. [16], the peak at the temperature of
390C corresponds to the -hydride decomposition. At the temperature
of 500C, the process of release of hydrogen terminates. Comparison of
the lattice parameters of the initial, hydrogenated, and dehydrogenat-
ed alloys testifies to practically 100% reverse capacity of alloys (see
Table 2).
Data of experiments on investigation of the influence of the sorp-
tion—desorption—sorption cycling on kinetic and sorption properties
shows that the alloys of the specified group possess as much activated
surface that the hydration begins at room temperature and the pres-
sure of 0.23 MPa from the first seconds of contact of the specimen with
Fig. 2. Change of the intensity of the hydrogen release (in arbitrary units)
during the heating of hydrogenating products of 47.5 Ti—30 Zr—17.5 Mn—5 V
alloy.
H SORPTION PROPERTIES OF Ti0.475Zr0.3Mn0.225 EUTECTIC ALLOY ALLOYED WITH V 529
hydrogen containing medium with an average rate of (2—4)10
3
wt.%/s.
Such an enhancement of the kinetic parameters can be explained by
the dispergation of the specimen during the sorption—desorption cycle
as well as by the decrease of the oxygen concentration on the surface
and in a bulk of particles because of its interaction with the releasing
atomic hydrogen. Hydrating temperature during the second cycle
points at the fact that in this case the absorption begins from interme-
tallide [6].
Kinetic parameters of sorption and desorption as well as sorption
capacity of alloys in succeeding cycles do not practically change. Insig-
nificant increase of the hydrogen adsorption rate is connected with the
increase of the reaction surface, caused by the disintegration of the
particles.
4. CONCLUSIONS
1. Partial substitution of the alloy components by vanadium results in
the substantial increase of the sorption capacity and the enhancement
of kinetic and thermodynamic parameters of the processes of hydro-
genation. In this case, the titanium-based solid solution absorbs the
hydrogen with kinetics, similar to the kinetics of the sorption of the
hydrogen by the intermetallide and reaches the high level of the hy-
drogen capacity during the short time.
2. Hydrogenation of the alloys activated by the sorption—desorption
cycle takes place at room temperature and significantly lower pressure
of 0.23 MPa. In this case, the sorption capacity remains unchanged,
and time during which it reaches its maximal value decreases signifi-
cantly.
REFERENCES
1. C. A. McAuliffe, Hydrogen and Energy (London: Gulf Publishing: 1980).
2. S. V. Mitrokhin, T. N. Bezuglaya, and V. N. Verbetsky, J. Alloys Compd.,
330—332: 146 (2002).
3. V. N. Verbetsky and S. V. Mitrokhin, International Scientific Journal for
Alternative Energy and Ecology ISJAEE, No. 10: 30 (2005).
4. S. Semboshi, N. Masahashi, and S. Hanada, J. Alloys Compd., 352: 210 (2003).
5. H. Taizhong, W. Zhu, Y. Xuebin, C. Jinshou, X. Baojia, H. Tiesheng, and
X. Naixin, Intermetallics, 12: 91 (2004).
6. V. G. Ivanchenko, V. A. Dekhtyarenko, and T. V. Pryadko, Poroshkovaya
Metallurgiya, Nos. 5/6: 129 (2013) (in Ukrainian).
7. Z. Dehouche, M. Savard, F. Laurencelle, and J. Goyette, J. Alloys Compd., 400:
276 (2005).
8. V. Ivanchenko, T. Pryadko, V. Dekhtyarenko, and T. Kosorukova, Chemistry of
530 V. G. IVANCHENKO, V. A. DEKHTYARENKO, and T. V. PRYADKO
Metals and Alloys, 1, No. 2: 133 (2008).
9. V. G. Ivanchenko, V. A. Dekhtyarenko, T. V. Pryadko, Metallofiz. Noveishie
Tekhnol., 33, Special Issue: 479 (2011) (in Russian).
10. G. F. Kobzenko and A. A. Shkola, Zavodskaya Laboratoriya, 7: 41 (1990) (in
Russian).
11. O. M. Ivasishin, V. T. Cherepin, V. N. Kolesnik, and M. M. Gumenyuk, Pribory i
Tekhnika Eksperimenta, 3: 147 (2010) (in Russian).
12. V. G. Ivanchenko, V. A. Dekhtyarenko, T. V. Pryadko, and V. I. Nychyporenko,
Metallofiz. Noveishie Tekhnol., 36, No. 6: 803 (2014) (in Russian).
13. V. G. Ivanchenko, V. A. Dekhtyarenko, and T. V. Pryadko, Metalloznavstvo ta
Obrobka Metaliv, 1: 4 (2010) (in Ukrainian).
14. R. Pucci and G. Piccito, Molecular Systems under High Pressure (Amsterdam:
Elsevier: 1991), p. 139.
15. R. I. Wasilewski and G. L. Kehl, Меtаllurgiya, 50, No. 301: 225 (1954).
16. M. M. Antonova, Ukrayins’kyy Khimichnyy Zhurnal, 32, No. 6: 661 (1996) (in
Russian).
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/ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
>>
/Namespace [
(Adobe)
(Common)
(1.0)
]
/OtherNamespaces [
<<
/AsReaderSpreads false
/CropImagesToFrames true
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(InDesign)
(4.0)
]
/OmitPlacedBitmaps false
/OmitPlacedEPS false
/OmitPlacedPDF false
/SimulateOverprint /Legacy
>>
<<
/AddBleedMarks false
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/ConvertColors /ConvertToCMYK
/DestinationProfileName ()
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/FlattenerPreset <<
/PresetSelector /MediumResolution
>>
/FormElements false
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/PreserveEditing true
/UntaggedCMYKHandling /LeaveUntagged
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/UseDocumentBleed false
>>
]
>> setdistillerparams
<<
/HWResolution [2400 2400]
/PageSize [612.000 792.000]
>> setpagedevice
|