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JOM, Vol. 65, No.

11, 2013

DOI: 10.1007/s11837-013-0741-x
2013 TMS

Oxidation of Cr2AlC (0001): Insights from Ab Initio Calculations


NENG LI,1,2,3 RIDWAN SAKIDJA,1 and WAI-YIM CHING2
1.Department of Physics and Astronomy, University of Missouri-Kansas City, Kansas City,
MO 64110, USA. 2.Center for Photovoltaics and Solar Energy, Shenzhen Institutes of Advanced
Technology, Chinese Academy of Sciences, Shenzhen 518055, P. R. China. 3.e-mail: lineng@
umkc.edu

We performed an investigation of the initial stage of oxidation onto a relevant


Cr2AlC (0001) surface by ab initio calculations. For the most energetically
stable Al-terminated Cr2AlC (0001) surface, a detailed model describing the
oxygen-surface interaction is developed by exploring the adsorption energetics. Based on the evaluation of the energetics and the structural properties of
the atomistic models generated, the results point to an initial stage of the
Cr2AlC (0001) surface oxidation with some similarities with those observed in
the Al (111) layer. Our findings on the bonding mechanism of single O
adsorption atoms of the surface may lead to further alloying strategies to
enhance oxidation resistance in a wide range of refractory-metal-based MAX
phases.

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

(Published online September 5, 2013)

both at the ground state (T = 0 K) as well as at room


temperature (T = 298 K) via ab initio molecular
dynamics (AIMD) as implemented in the VASP
Vienna ab initio simulation package (VASP).2325
The main objective of this work is to gain insights
into the atomistic mechanisms and in particular
into the site preference on the (0001) Al layer surface of Cr2AlC as the first step toward the formation
of the Al-oxide monolayer. We chose the Al-terminated Cr2AlC (0001) surface based on the previous
theoretical studies26,27 with a 1 9 1 9 1 and
2 9 2 9 1 supercells showing that it has the lowest
surface energy. The DFT study comprises the
adsorption of single O atoms, through the sampling
of several adsorption sites. Based on the evaluation
of the energetics and the structural properties of the
atomistic models generated, the results here reported delineate a consistent picture of the initial
stage of the surface oxidation.
METHODOLOGY
To perform efficient surface structure and O
adsorption simulations on Cr2AlC (0001), we employed a DFT-based, plane-wave, projector-augmented wave method as implemented in VASP. The
structural relaxation is carried out by using VASP.
For structural relaxation, the PAW-PBE potential28
with generalized gradient approximation as supplied
in the VASP is used for the exchange-correlation

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Li, Sakidja, and Ching

favorable position. The oxygen-surface interactions


on the (3 9 3)/Al-terminated Cr2AlC (0001) surface
are performed by exploring thoroughly the adsorption energetics (Eads), which is a key quantity in
predicting the adhesive property of an adsorption
system. The Eads, which is defined as the reversible
energy required to separate an adsorption system
into a bare surface and an adsorbed atom, can be
expressed by subtracting the sum of the total energy
of the half-optimized O molecule (1/2EO2 ) and the
bare surface (Esurf) from the total energy of the
adsorption system (Eads)30
DEads Eads  Esurf  1=2EO2

Fig. 1. Relaxed structure of (3 9 3)/Al-terminated-Cr2AlC (0001)


surface: (a) side view and (b) top view.

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)

where Eads and Esurf are the total energies of the


final adsorbate system and the bare (3 9 3)/
Cr2AlC(0001) surface, respectively, and EO2 is the
total energy of a free O2 molecule in its ground
. With this sign
state, computed in a box of side 20 A
convention, a positive value of the adsorption energy corresponds to the energetic gain of an exothermic reaction. In general, a negative Eads
indicates that the oxygen adsorption is exothermic,
and thus, the adsorption system is energetically
stable. The relative comparison quantitatively between calculated Eads for different atomic geometries of the same adsorption system is the focus of
our study.
The adsorption energy of the corresponding geometrical structures is presented in Fig. 3 and listed
in Table I. One can clearly see that from Fig. 3, the
fcc-hollow (H1) site, is the most stable binding site
for O with an adsorption energy of 5.696 eV and
for Al-O. The
an average bond length of 2.09 A
second most favorable adsorption energy, 5.233 eV
of O is for the hcp-hollow (H2) site. The top (T site)
and bridge sites (B site) exhibit much less favorable
adsorption energy of 3.179 eV and 3.292 eV,
respectively. These sites may be considered transition states for the O to diffuse on the Cr2AlC (0001)
surface between the two more preferred H1 and H2
sites. Similar to that observed in the MAX phase,
these two sites are the more favorable sites on the
Al layer despite the fact that the atom types constructing the B and C layer structure are not
made of Al. In the case of fcc Al, the fcc-hollow site is
actually the one with the lowest binding energy
followed by the hcp-site with the slightly lower
biding energy. In addition, the magnitude of the
binding energy is 1 eV  2 eV higher (e.g., fcc site = 7.65 eV31) than our results for the MAX
phase. To some extent this can be explained by the
nature of the bonding mechanism that is within the
MAX phase. The interlayer directional bonding between the A layer and the (M + X) layer is typically
weaker than the strong MX bonds that exist
within the M + X clustered layer.1 As a result, the A
layers response to the oxidation, at least at the
initial stage, may be quite similar to that observed
on Al(111), meaning that the oxidation response is

Oxidation of Cr2AlC (0001): Insights from Ab Initio Calculations

1489

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.

Table I. Adsorption energy of an oxygen atom onto


different sites at (3 3 3)/Al-terminated Cr2AlC
(0001) surface
Adsorption
site
Eads (eV)

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.

mostly governed by the top Al layer. Nevertheless,


there is indeed a difference in terms of the nature of
the interlayer bonding between the fcc and the
layered MAX phases as there is still directional
bonding between the two types of layers (i.e., M-Al
and M-C) that is expected to be much stronger than
that of the Al-Al interlayer metallic bonding present
within the fcc metal. It is reasonable to assume that
as a consequence the Al-O binding energy on the
MAX surface should be less in magnitude than that
of the Al-O on Al-fcc. Nevertheless, this suggests
there is a linkage between the oxidation responses
of the two types of phases for the first time. In

Top

Bridge

hcphollow

fcchollow

3.179

3.292

5.233

5.696

addition, the possible existence of partly ionic


bonding between Cr and O may not be neglected
and may quite possibly skew the site preference
toward the hcp-hollow (H2) site.
As a further verification on the adsorption process, we carried out AIMD for both a single oxygen
atom and a single O2 molecular adsorption using a
(3 9 3) unit cell with 117 atoms at 700 K. The single-oxygen atom as well as O2 molecule was placed
on top of the Al atom at the initial configuration on
each case, and the initial velocities were randomly
assigned according to a MaxwellBoltzmann distribution at room temperature. The final configurations after the 3-ps simulation both types of shows
the oxygen species favorably reside on the same
hcp-hollow site (see Fig. 4) which is different with
predicted by the DFT calculation at the ground
state, because the final configurations depends on
the temperature in AIMD simulation. Certainly,
further work is required to fully assess the effect of
higher temperature exposure on the dynamics site
preferences and at a longer time, but the current
finding suggests that some similarities between the
initial stage of oxygen absorption of Al(0001) in

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Li, Sakidja, and Ching

surfaced in a Cr-based Cr2AlC MAX phase. The O


strongly bonds to the surface Al and formed Al-O
bond whose mechanisms appear to be quite similar
to that observed at the initial stage of oxidation on
the Al (111) surface of fcc Al. The oxidation of the
Cr2AlC (0001) surface is a complex reaction involving many atomistic processes, and thus, this study
is an initial step to elucidate some aspects of the
oxidation reaction for the refractory-metal-based
MAX in general.
ACKNOWLEDGEMENTS
This work is supported by U.S. DOE-NETL, the
award FE0005865. This research used the resources
of the National Energy Research Scientific Computing Center supported by DOE under Contract
No. DE-AC03-76SF00098.
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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.

MAX phase and Al(111) fcc can indeed be drawn.


This can potentially improve the alloying strategy
needed to address the lack of oxidation resistance in
other Al-containing MAX phases (e.g., Nb-based
MAX).
SUMMARY AND CONCLUSIONS
In this article, we have evaluated the adsorption
process of a single O atom onto the Al layered

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