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Pressure, mm.Hg.
60
c d
e f
Fig. 2. Formation of growth patterns characteristic of the given system with gradual melting of the sample
After the equilibrium process is established, with a At a distance of less than 1 mm from the heated upper
constant beam power that corresponds to the melting surface of the sample, the crystals completely “absorb”
point of the eutectic and a constant heat removal rate, the surrounding eutectic and grow to the maximum size
i.e., we have a constant temperature gradient, the melt limited by neighboring formations. Considering the
and crystallization centers create optimal conditions for duration of the annealing process (about 3 h), significant
polycrystalline grain growth. As can be seen from formations up to 500 m in size are formed (Fig. 3).
Fig. 2,e,f the growth patterns characteristic of this Since the gradual melting of the sample occurs, all
system are formed. As these formations grow, the of the above processes occur in layers as the sample is
amount of surrounding eutectic decreases accordingly. melted, i.e. simultaneously: in a layer located 3 mm
a b
c d
Fig. 3. Spherical formations consisting of square pyramids and octahedrons (a, b); reflow of previously formed
spherical formations consisting of square pyramids and octahedrons (c, d)
Thus, the obtained sample contains various accordingly, the active diffusion of released hydrogen in
structural elements that are formed during the long-term a sample heated to a pre-melting temperature.
exposure of the initial sample (TiH2)30Zr45Ni25 electron
beam. The stages characteristic for each stage can be PHASE ANALYSIS OF SAMPLES Ti30Zr45Ni25
distinguished: fusion of the initial components Ti, Zr, X-ray diffraction patterns of the samples are shown
Ni → formation of growth structures surrounded by in Fig. 4. The results of studies of the phase
eutectics → conglomerates of square pyramids → composition of the samples showed that 4 phases were
fusion of previously formed square pyramids and identified in the melted upper part of the sample (see
octahedrons. An additional factor for the formation of Fig. 4,a): (Ti,Zr)2Ni, Laves phase L-TiZrNi, Ti-α, and
structural features in this sample is the dissociation of Zr-α. The lattice parameter of the (Ti,Zr)2Ni phase is
titanium hydride into hydrogen and titanium. And a = 11.761 Å. The lattice parameters of the Laves phase
are a = 5.222 Å; c = 8.558 Å. The lattice parameters of
titanium are a = 2.964 Å; c = 4.618 Å. The lattice
b
Fig. 4. Diffraction pattern of the sample
(TiH2)30Zr45Ni25: upper melted part (a);
lower not melted part (b)
Since there was no zirconium hydride in the initial
sample, therefore, the presence of ZrH2(δ) in the lower
non-melted part of the sample confirms that the
hydrogen formed during the decomposition of titanium
hydride is absorbed by zirconium. And only then, with a
further increase in temperature, does the sample leave.
The presence in the sample of unusual structural b
formations shown in Figs. 2, 3 gave a prerequisite for Fig. 5. Dependences of the temperature of sample (a)
research on the interaction of this material with and the pressure in the reaction chamber (b) on time,
hydrogen. when the Ti30Zr45Ni25 sample is saturated with hydrogen
at room temperature
THE STUDY OF SORPTION-DESORPTION
For conducting research, a sample of the upper After saturation with hydrogen at room temperature,
molten portion weighing 2.8 g was previously ground the sample was subjected to thermal desorption by
by grinding in an alundum mortar. Grinding was carried heating to 900 °C and cooling to room temperature with
b a
Fig. 6. The dependence of the pressure in the reaction
chamber on the temperature of the sample when the
sample is heated at a constant rate of evacuation of the
reaction chamber to vacuum after the first
saturation (a), after re-saturation (b)
After degassing, the sample was re-saturated with
hydrogen at room temperature Fig. 7. The initial
hydrogen pressure in the reaction chamber was 260 kPa.
Upon repeated saturation, the absorption of hydrogen by
the sample began with approximately the same delay as
at the first saturation. The heat generation impulsivity
was also observed. The intensity of the heat during the
second saturation was significantly lower, but it took a
longer time. The amount of heat was proportional to the b
magnitude of the change in pressure in the reaction Fig. 7. Dependences of the temperature of the sample
chamber. Upon re-saturation, the sample absorbed and heater (a), the pressure in the reaction chamber (b)
0.34 wt.% hydrogen for 4 h. Thus, it was found that this on time upon re-saturation of the Ti30Zr45Ni25 sample
material is capable of absorbing hydrogen at room with hydrogen at room temperature
temperature after a dehydrogenation cycle. Subsequent To confirm the obtained data, duplicate experiments
dehydrogenation showed identical kinetics of thermal on hydrogen sorption-desorption were carried out with a
desorption (see Fig. 6,b).
80
discussing the results.
Pressure, mm.Hg.
70
60
REFERENCES
50 1. H.G. Hakobyan, A.G. Aleksanyan, S.K. Dolu-
40
khanyan, N.L. Mnatsakanyan. Zirconium inter-
30
metallides and their hydrides as obtained by the hydride
20
10
cycle route // International Journal of Self-Propagating
0
High-Temperature Synthesis. 2010, v. 19(1), p. 49-51.
0 100 200 300 400
Temperature, °С
500 600 700 800
2. S.K. Dolukhanyan, A.G. Aleksanyan, O.P. Ter-
Galstyan, V.Sh. Shekhtman, M.К. Sakharov,
b G.E. Abrosimova. The peculiarities of the formation of
Fig. 8. Dependence of the pressure in the reaction alloys structure in the Ti-Zr-H system // Chemical
chamber on the temperature of the Ti30Zr45Ni25 sample Physics. 2007, v. 26 (11), p. 36-43.
(7 days in the air) for: sorption (a) and thermal 3. S.K. Dolukhanyan, A.G. Aleksanyan, O.P. Ter-
desorption (b) of hydrogen Galstyan, V.Sh. Shekhtman, M.К. Sakharov,
G.E. Abrosimova. Specifics of the formation of alloys
Thus, it can be argued that the presence of the
and their hydrides in the Ti-Zr-H system // Russian
ground Ti30Zr45Ni25 sample in air leads to a gradual
Journal of Physical Chemistry B. 2007, v. 2(6) p. 563-
increase in the incubation period before the absorption
569.
of hydrogen at room temperature and subsequently
4. S.K. Dolukhanyan, M.D. Nersesyan, A.B. Nal-
completely eliminates this process. Nevertheless, the
bandyan, I.P. Borovinskaya, A.G. Merzhanov.
detected temperature ranges of sorption-desorption and
Combustion of transition metals in hydrogen // Doc.
the corresponding sorption capacity are unique for the
USSR Academy of Sciences. 1976, v. 231(3), p. 675-678.
Ti-Zr-Ni system and most other known metal hydride
5. S.K. Dolukhanyan, H.G. Hakobyan, and
systems. This material can be an extremely promising
A.G. Aleksanyan. Combustion of metals in hydrogen
hydrogen accumulator, research is ongoing.
and hydride production by self propagating high
CONCLUSION temperature synthesis // Int. J. of SHS. 1992, v. 1(4),
The Ti30Zr45Ni25 intermetallic material was p. 530-535.
synthesized using the hydride cycle technology with 6. A.G. Aleksanyan, D.G. Mayilyan, S.K. Doluk-
dehydrogenation of a portion of the (TiH2)30Zr45Ni25 hanyan, V.Sh. Shekhtman, O.P. Ter-Galstyan. Synthesis
sample by an electron beam in vacuum. The of hydrides and production of alloys in the Ti-Hf-H
establishment of a stationary process of gradient heating system // International journal Alternative Energy and
of a sample by an electron beam made it possible to Ecology. 2008, v. 9(65), p. 22-26.
form a layered structure in the sample and fix all stages 7. A.G. Aleksanyan, S.K. Dolukhanyan, A.A. Man-
tashanyan, D.G. Mayilyan, O.P. Ter-Galstyan, V.Sh.