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Won-Seok Ko
Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH),
Pohang 790-784, Republic of Korea
Jae-Hyeok Shim
Materials/Devices Division, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
Byeong-Joo Leea)
Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH),
Pohang 790-784, Republic of Korea; and Division of Advanced Nuclear Engineering, Pohang University of Science
and Technology (POSTECH), Pohang 790-784, Republic of Korea
(Received 6 December 2010; accepted 17 March 2011)
Second nearest-neighbor modied embedded-atom method (MEAM) interatomic potentials for the
AlH and NiH binary systems have been developed on the basis of previously developed MEAM
potentials of pure Al, Ni, and H. The potentials can describe various fundamental physical properties
of the relevant binary alloys (structural, thermodynamic, defect, and dynamic properties of
metastable hydrides or hydrogen in face-centered cubic solid solutions) in good agreement with
experiments or rst-principles calculations. The applicability of the present potentials to atomic level
investigations of dynamic behavior of hydrogen atoms in metal membranes is also discussed.
I. INTRODUCTION
Hydrogen has been known to form micropores in aluminum alloys and cause the formation of microcracks,
which signicantly reduces mechanical properties of
alloys.16 An atomic scale analysis of the local diffusion
of hydrogen in the liquid and solid aluminum is necessary
for a prediction and control of the pore formation behavior.
Many metallic alloys including the nickel alloys suffer from
hydrogen embrittlement in the usage as structural materials, 710 but the exact mechanism of hydrogen embrittlement
in nickel alloys has not yet been discovered. It is expected
that atomistic simulations can be a good approach to clarify
the mechanism of hydrogen embrittlement.11,12
Use of hydrogen as an energy source is the most efcient
way, and improving methods of hydrogen manufacturing,
separation and purication of pure hydrogen has grown in
recent years.13 Although H2 gases are manufactured by
various processes, membrane separation method has received a great attention owing to its ultimate cost effectiveness and ease of operation.14 Among many possible choices
of materials, metallic membranes are of interest for its high
hydrogen selectivity and cost effectiveness.15,16 Even
though palladium and its alloys are most appropriate for
membrane use, the extremely high cost is dragging down its
practical applications, and recent researches have been
focused on the development of non-palladiumbased membranes using economically feasible metals.17 As a possible
a)
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and
a5
9BX
Ec
1=2
:
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34
Al
Ni34
H35
Ec
re
b(0)
b(1)
b(2)
b(3)
t(1)
t(2)
t(3)
Cmin
Cmax
3.36
4.45
2.37
2.860
2.490
0.741
0.794
1.876
2.960a
1.16
0.94
2.50
3.20
2.56
2.96
2.60
1.50
3.00
6.00
6.00
3.00
2.60
1.50
2.50
3.05
3.10
0.20
0.51
1.80
0.10
7.75
4.36
0.00
0.49
0.81
2.00
2.80
2.80
2.80
0.05
0.05
0.00
The units of the cohesive energy Ec, equilibrium nearest-neighbor distance re, and bulk modulus B are eV, , and 1012dyne/cm2, respectively. The reference
structures of Al, Ni, and H are fcc, fcc, and dimer respectively.
a
This is an a value as dened in Eq. (5). Bulk modulus B is not dened for a gaseous element.
2NN MEAM, second nearest-neighbor modied embedded-atom method; fcc, face-centered cubic.
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TABLE II. 2NN MEAM potential parameter sets for the binary MH
(M 5 Al, Ni) systems.
AlH
NiH
Reference state
FCC_B1
FCC_B1
Ec
0.5 EcAl + 0.5 EcH + 0.680 0.5 EcNi + 0.5 EcH + 0.040
re
1.875
1.865
B
1.122
1.730
d
0.5 dAl + 0.5 dH
0.5 dNi + 0.5 dH
H
qM
1:18
1:18
0 : q0
Cmin (M-H-M)
0.64
0.04
Cmin (H-M-H)
0.09
0.49
0.49
1.80
Cmin (M-M-H)
Cmin (H-H-M)
0.49
[0.5 (CminNi)1/2 + 0.5 (CminH)1/2]2
Cmax (M-H-M)
2.80
2.00
2.80
2.80
Cmax (H-M-H)
Cmax (M-M-H)
2.80
2.80
Cmax (H-H-M)
1.44
2.80
The units of the cohesive energy Ec, equilibrium nearest-neighbor distance
re, and bulk modulus B are eV, , and 1012dyne/cm2, respectively. The
reference structure is NaCl type metastable hydride for both systems.
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TABLE III. Physical properties of metal hydrides calculated using the present 2NN MEAM potentials, in comparison with experimental data or other
calculations.
Compound
a-AlH3 (R-3c)
Property
MEAM
Experimental
Lattice parameter ()
a
c
Bulk modulus (1012 dyne/cm2)
Heat of formation (eV/atom)
Lattice parameter ()
Bulk modulus (1012 dyne/cm2)
Heat of formation (eV/atom)
4.40
11.25
0.537
0.017
3.73
1.73
0.040
4.4537, 4.4638
11.8037, 11.8338
0.47939
0.03040
3.7245, 3.7346
0.046a,47, 0.026b,48
First-principles
4.4241, 4.4942
11.8041,11.8242
0.40043
0.03941, 0.03044
1.9850
0.07841
EAM
3.6027
0.06227
X(H/Ni) 5 0.5.
X(H/Ni) 5 0.7.
MEAM, modied; EAM, embedded-atom method.
a
FIG. 1. Molar volume change of AlH3 for pressures 035 GPa, calculated
using the present second nearest-neighbor modied embedded-atom
method (2NN MEAM) potential, in comparison with experimental
data.39,43
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TABLE IV. Physical properties of hydrogen in fcc AlH and NiH alloys calculated using the present 2NN MEAM potential, in comparison with
experimental data or other calculations.
Property
AlH
NiH
MEAM
Experimental
First-principles
0.64
0.73
0.35
0.39c
0.6941
0.8241
0.3341
0.18d,41
0.79
0.18
0.61
0.56c
0.120.246773
0.4374, 0.4475
0.4076, 0.4277
EAM
0.58b,27
0.1625, 0.1827
0.47d,78
0.35d,27, 0.45d,25
around the defect. However, the calculated values converge to certain values as the sample size (number of
atoms) increases. In this study, a sample containing 1372
R2 t
6t
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TABLE V. Adsorption energies (eV) of a hydrogen atom for several possible adsorption sites on the (100), (110), and (111) surfaces of nickel,
calculated using the present 2NN MEAM potential, in comparison with experimental data or other calculations.
Surface
(100)
(110)
(111)
Site
MEAM
Hollow
Bridge
Top
Hollow
Pseudo-threefold
Long bridge
Short bridge
Top
Hollow (fcc)
Hollow (hcp)
Bridge
Top
Experimental
89
0.50
0.08
0.91
0.41
0.29
0.47
0.11
0.90
0.28
0.26
Unstable
0.89
0.50
0.4789
0.4791
First-principles
90
0.58
0.3990
0.1790
0.1990
0.4490
0.4190
0.4290
0.2190
0.5790
0.5590
0.3590
0.2090
EAM
0.2625, 0.5128
0.1425, 0.4028
0.1425, 0.3528
0.1325
0.3125, 0.4628
0.2825, 0.3228
0.2325, 0.4928
0.0625, 0.4328
0.1625, 0.4528
0.1625
Unstable25, unstable28
0.1925, 0.3428
Em
RT
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and heat of formation of metastable hydrides. The potentials also reproduce the diffusivity of hydrogen in fcc Al or
Ni solid solution phases in good agreement with experiments, which indicates the suitability of the potentials for
atomistic investigations of dynamic behavior of hydrogen
atoms and effect of point defects on it in relevant materials.
Being combined with already developed 2NN MEAM
potentials for other alloy systems (e.g., the VH binary
system), the present potentials can be easily extended to
higher order multicomponent alloys systems, e.g., the
V(Al,Ni)H ternary systems.
ACKNOWLEDGMENT
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