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11, 2013
DOI: 10.1007/s11837-013-0741-x
2013 TMS
INTRODUCTION
The MAX phases, as one group of inherent nanolaminated compounds, have the general formula
Mn+1AXn, where n = 1, 2, or 3; M is an early transition metal; A is an A-group element; and X is either C
or N. The A-type atoms (e.g., Al or Si) reside on their
own plane within the MAX crystal structure,
whereas the M and C atoms are clustered on separate
layers (see Fig. 1). In recent years, MAX phases attracted a great deal of attention from researchers, in
both the experimental and simulation fields.14 In
the experimental aspect, various properties of MAX
phases have been investigated.2,3 In the simulation
aspect, the studies are mainly concerned with the
atomic and electronic structures, phase stability,510
and elastic and mechanical properties of bulk MAX
phases.1119 However, the atomistic mechanisms of
the oxidation process for the MAX phases are not
fully understood despite the extensive oxidation and
corrosion studies at the macroscopic level and the fact
that there is a wide range of oxidation resistance
levels exhibited by the MAX phases.2022
For this study, we focused on Cr2AlC as one
example of oxidation-resistant MAX phases that is
also a promising candidate for high-temperature
structural applications. We performed density functional theory (DFT) calculations on a 3 9 3 supercell
structure so as to simulate the adsorption process of
an oxygen atom onto the MAX Al-terminated surface
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potential. We used a cutoff energy of 400 eV, a relatively high accuracy for the ground state electronic
convergence criterion (105 eV), and force conver ). The stress level of the final
gence limit (102 eV/A
equilibrium structure is less than 0.1 GPa. The
relaxation of the present model imposes no restrictions on the volume and lattice vectors of a periodic
supercell. The AIMD simulations on both a single
oxygen and an oxygen molecule as implemented in
VASP29 were performed by means of an NVT (constant volume and temperature) ensemble with each
ionic MD step of 2 fs for duration up to 3 ps.
RESULTS AND DISCUSSION
The O atom is initially placed on four different
sites: top (T), bridge (B), fcc-hollow (H1), and hcphollow (H2) sites of the relaxed Al-terminated
Cr2AlC (0001) surface. The surface model is composed of 13 layers of 3 9 3 9 1 supercell separated
. The first Cr layer is positioned
by a vacuum of 15 A
underneath the Al layer, and the C layer is sandwiched between the two consecutive Cr layers
forming layered Cr-C clusters. The pattern is then
repeated back to the Al layer (see Fig. 1). Our use of
hcp-hollow as well as of fcc-hollow terms here is
only meant for convenience so that we can compare
the results with those from the hcp-hollow and fcchollow sites on the Al(111) surface. Thus, the layer
sequence of the fcc-like ABC for the MAX phase
implies the A layer is the aluminum layer, B
layer is the chromium layer, and C is the carbon
layer (see Fig. 2). The adsorbed structures are also
relaxed, and the absorbed O atom comes to its
(1)
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Fig. 2. Illustration of adsorption of an oxygen atom on (3 9 3)/Al-terminated-Cr2AlC (0001) surface: (a) top (T) site, (b) bridge (B) site, (c) fcchollow (H1) site, and (d) hcp-hollow (H2) site.
Fig. 3. Adsorption energy of one O atom adsorption on (3 9 3)/Alterminated Cr2AlC (0001) surface for different sites: top (T) site,
bridge (B) site, fcc-hollow (H1) site, and hcp-hollow (H2) site.
Top
Bridge
hcphollow
fcchollow
3.179
3.292
5.233
5.696
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Fig. 4. Plan view of the AIMD (NVT) simulation results on (a) single
O atom and (b) and (c) O2 molecule adsorption on Al-terminated
Cr2AlC (0001) surface: Temperature is at (a) 700 K, (b) 700 K, and
(c) 1273 K, with the duration is 3 ps with an ionic step of 2 fs.
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30. C.R. Ashman and G. Pennington, Phys. Rev. B 80, 085318 (2009).
31. C. Lanthony, J.M. Ducere, M.D. Rouhani, A. Hemeryck, A.
Este`ve, and C. Rossi, J. Chem. Phys. 137, 094707 (2012).