Argon-neon binary diagram and ArNe2

Laves phase
Cite as: J. Chem. Phys. 151, 124708 (2019); https://doi.org/10.1063/1.5119419
Submitted: 11 July 2019 . Accepted: 09 September 2019 . Published Online: 27 September 2019

Agnès Dewaele , Angelika D. Rosa , and Nicolas Guignot

J. Chem. Phys. 151, 124708 (2019); https://doi.org/10.1063/1.5119419 151, 124708

© 2019 Author(s).
 The Journal
ARTICLE scitation.org/journal/jcp
of Chemical Physics

Argon-neon binary diagram and ArNe2

Laves phase
Cite as: J. Chem. Phys. 151, 124708 (2019); doi: 10.1063/1.5119419
Submitted: 11 July 2019 • Accepted: 9 September 2019 •
Published Online: 27 September 2019

Agnès Dewaele,1,a) Angelika D. Rosa,2 and Nicolas Guignot3

AFFILIATIONS
1
CEA, DAM, DIF, F-91297 Arpajon, France
2
ESRF, BP220, F-38043 Grenoble, France
3
Synchrotron Soleil, F-91192 Saint Aubin, France

a)
agnes.dewaele@cea.fr

ABSTRACT
Mixtures of argon and neon have been experimentally studied under high pressure. One stoichiometric compound, with ArNe2 composition,
is observed in this system. It is a Laves phase with a hexagonal MgZn2 structure, stable up to at least 65 GPa, the highest pressure reached
in the experiments. Its equation of state follows closely the one of an ideal Ar+2Ne mixture. The binary phase diagram of the Ar–Ne system
resembles the diagram predicted for hard sphere mixtures with a similar atomic radius ratio, suggesting that no electronic interactions appear
in this system in this pressure range. ArNe2 can be a convenient quasihydrostatic pressure transmitting medium under moderate pressure.
Published under license by AIP Publishing. https://doi.org/10.1063/1.5119419., s

I. INTRODUCTION depending on the hard spheres radius ratio, in particular, Laves

The physical and chemical properties of dense rare gases are a
subject of interest for natural system modeling (helium is a major
constituent of large planets), high pressure technologies (helium,
neon, and argon being often used as pressure transmitting media in
high pressure apparatus), and fundamental chemistry or synthesis (a
rich chemistry in heavy rare gases—xenon to argon—has been dis-
closed recently in the Mbar range1–3 ). In fact, high pressure enhances
the possibility for these atoms to establish bonding, a behavior which
goes beyond the simple octet rule taught at university. The standard
approach to describe this enhanced reactivity under high compres-
sion is the density functional theory, which the standard output is
the electronic enthalpy in the fundamental (athermal) state. How-
ever, rare-gas crystals are challenging systems to describe with this
framework because long-range correlations of van der Waals type
play a decisive role in their cohesion. For instance, it has been noted
that density functional theory is not able to correctly describe the
equations of state of dense argon and neon,4,5 while a many-body
expansion of the enthalpy does a better job.
When no (or weak) chemical interaction exists between two
chemical species, the pressure effect on their mixtures can be
described in a large part in terms of space-filling arguments.6 This
modeling predicts the existence of different binary compounds
phases.6 Such phases have been observed for several gases mixtures
under pressure,7–11 some of them being eventually destroyed by
heating under high compression, which produces strongly bonded
solids.2 Theoretical descriptions adapted to systems such as colloids
or granular media are reviewed in Ref. 12. They remain scarce in the
field of high pressure science and are based on density functional
theory.13 Here, we present the binary phase diagram of argon and
neon, measured as a function of pressure at ambient temperature, by
visual observations and X-ray diffraction (XRD) measurements up
to 65 GPa. One Laves phase is found to be stable in a wide pressure
range. This study can be used to benchmark the theoretical descrip-
tion of rare gases. We also suggest a practical use of this Laves phase.
II. METHODS
A total of 13 samples have been loaded in diamond-anvil cells
with culet diamond sizes of 500 μm–300 μm. Ar–Ne mixtures with
concentrations varying from 6.8 mol. % Ar to 92 mol. % Ar (here-
after, % corresponds to mol. %) were prepared and subsequently
loaded, using a 1200 b compressor for the smallest diamond culet
size or directly at the bottle pressure for the large diamond sizes. The
concentrations were calculated from the partial pressure of the gases,

J. Chem. Phys. 151, 124708 (2019); doi: 10.1063/1.5119419 151, 124708-1

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using equations of state including a virial correction. The pressure

was measured using ruby luminescence gauge14 or a small sphere
of gold as an X-ray pressure calibrant.15 For all samples, the liquidus
and solidus pressures at room temperature (295 K–298 K) have been
measured by visual observation. The solidus (liquidus) pressure cor-
responds to the observed disappearance of the fluid (solid) phase on
a pressure increase (decrease), in order to prevent errors due to the
metastability of the liquid phase.
Five samples were also characterized with X-ray diffraction
(XRD) at the Psiche beamline, synchrotron Soleil, France. The tem-
perature in the experiment room was controlled to 296 K. The
angular-dispersive XRD technique has been used, with an X-ray
wavelength of 0.3738 Å and a Pilatus-CdTe bidimensional detector.
The X-ray spot size on the sample was 10 × 15 μm FWHM, and the
sample to detector distance was calibrated using a CeO2 reference
sample. The diamond anvil cell was rotated by ±10○ during XRD
exposures.

III. OBSERVATIONS
Argon and neon are miscible in the fluid phase. In the mix-
ture with the highest argon content, 92%, a solid-solid demixtion
indicated that less than 8% of neon could be incorporated into the FIG. 2. Ar–Ne binary phase diagram. It has been established on the basis of visual
argon-rich solid. Similarly, the miscibility of argon in neon is lower observations of 13 samples. The diagram presents one eutectic and one peritectic
points. Melting points for pure argon and neon are from the literature.16,17 Blue
than 6.8%. The solidus exhibits a discontinuity around 33% Ar, with
symbols indicate the conditions where X-ray diffraction measurements have been
an increase from 4.6 GPa on the Ar-rich side to 5.15 GPa on the Ne- performed. “Ar” indicates an argon-rich solid with less than 8% neon and “Ne” a
rich side. When xAr ≥ 0.22, the first solid forms below 4.6 GPa and neon-rich solid (see text).
adopts a dendritic shape which transforms into smooth and round

FIG. 1. Pictures of three Ar–Ne samples. They have been taken on a pressure
increase at 59% Ar and 13.4% Ar and decrease at 25% Ar. The dark spheres
are ruby gauges. 59% Ar: a solid which crystallizes around 2.7 GPa adopts a
round surface and grows up to 4.7 GPa. The remaining liquid freezes at 4.7 GPa
(solidus). 25% Ar: the solid which crystallizes between 4.6 GPa and 5.1 GPa mas-
sively transforms into another solid with a dendritic shape when the pressure is
decreased below 4.6 GPa. 13.4% Ar: a single crystal with a hexagonal shape
grows between 4.75 and 5.2 GPa; remaining liquid freezes at 5.2 GPa (solidus).
surfaces in a few minutes (see Fig. 1, 59% Ar). When 0.068 ≤ xAr
≤ 0.13, the first solid crystallizes above 4.6 GPa and has a hexagonal
shape (see Fig. 1, 13.4% Ar). This suggests that two different com-
pounds crystallize below and above 4.6 GPa. In the 22%–33% Ar
range, when the pressure is increased, a first (second) solid appears
below (above) 4.6 GPa and three phases (two solids and one liq-
uid) are seen to coexist in the sample chamber up to the solidus at
5.15 GPa, which apparently contradicts the phase rule. However, the
solid formed at low pressure disappears if the diamond anvil cell is
left to stand above 4.6 GPa for one day: it is only metastable. The
solidus, liquidus, and phase stability domains measured by visual
observations of the sample are plotted in Fig. 2. The continuity of
liquidus at 33% Ar proves that this metastable solid is an Ar-rich
solid, similar to the solid formed above 33% Ar. In the 22%–33%
Ar mixtures, when the high pressure solid is decompressed below
4.6 GPa, it completely transforms into another solid with a dendritic
shape: such a solid-solid transformation indicates a peritectic behav-
ior (see Fig. 1, 25% Ar). From the position of the solidus discontinu-
ity around 33% Ar, we hinted that the solid which crystallizes above
4.6 GPa is a stoichiometric compound and has an ArNe2 composi-
tion, a hypothesis which has been confirmed by XRD measurements
(see Sec. IV). A maximum in the liquidus is observed at 5.0 GPa for a
6.8% Ar mixture; this suggests that an eutectic point is present in its
vicinity.
IV. STUDY OF THE ArNe2 COMPOUND
We measured the structure and the equation of state of ArNe2
up to 65 GPa with XRD. For ArNe2 single crystals (see Fig. 1,

J. Chem. Phys. 151, 124708 (2019); doi: 10.1063/1.5119419 151, 124708-2

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13.4% Ar), only a limited number of XRD peaks could be collected
in the angular aperture/rotation angle of the diamond anvil cell. We
therefore used Ar-rich mixtures, where ArNe2 crystallizes as a coarse
powder between Ar crystals (see Fig. 1, 59% Ar), to determine its
structure. Several crystals in this sample could be simultaneously
probed by the X-ray beam, as seen in the bidimensional spectrum
presented in Fig. 3; however, due to their extended size, their number
was too low to form a statistically suitable powder. The integrated
XRD spectrum can be indexed with a hexagonal cell, P63 /mmc space
group, with a = 5.0942 Å and c = 8.2985 Å at 8.5 GPa. The difference
between the predicted and measured intensities can be explained by
the low number of crystals in diffraction conditions. The volume of
the cell, 186.5 Å3 , is 0.7% lower than the volume of 8 × VNe + 4
× VAr at the same pressure, 8.5 GPa.18,19 The small number of crys-
tals in the powder does not allow refining (with the Rietveld method)
the atomic positions in the crystallographic cell. In runs where a sin-
gle crystal of ArNe2 was grown in neon-rich liquid, the crystals have
a c axis perpendicular to the diamond anvil surface, as indicated by
FIG. 3. X-ray diffraction (XRD) spectrum collected in a 59% Ar Ar–Ne mixture at
8.5 GPa. Top image: part of the raw 2D diffraction pattern. Black surfaces cor-
respond to space between detector sections. The low number of spots indicates
the low number of crystals in the sample analyzed with XRD. Bottom image: inte-
grated pattern. Ticks indicate the positions and intensities of XRD peaks for perfect
powders of Ar (Fm3m, a = 4.5188 Å), Au (Fm3m, a = 4.0192 Å), and ArNe2 Laves
phase with the MgZn2 structure (P63 /mmc, a = 5.0942 Å and c = 8.2985 Å). Internal
parameters x and z corresponding to the positions of Ne (6h) and Ar (4f ) positions
have been fixed to their ideal values of z = 1/16 and x = 5/6. The inset is a picture
of the sample used to collect this spectrum (sample diameter 110 μm). The large
crystals are Ar, and ArNe2 fills the remaining space between these crystals. The
cross indicates the position of the XRD beam.
J. Chem. Phys. 151, 124708 (2019); doi: 10.1063/1.5119419
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their hexagonal shape, precluding the measurement of XRD peaks
with Miller indexes such as (002) or (101). The remaining peaks are
compatible with those measured in Ar-rich mixtures, confirming the
existence of only one compound (apart from Ar-rich and Ne-rich
solids) in the Ar–Ne binary system.
A P63 /mmc hexagonal cell with Z = 4 can be a Laves phase
with the MgZn2 structure. Laves phases are adopted by a large num-
ber of binary intermetallic AB2 compounds,20,21 as well as several
van der Waals-bonded solids formed under high pressure [NeHe2 ,7
Ar(H2 )2 ,8 CH4 (H2 )2 ,9 Xe(O2 )2 ,10 etc.]. They are topologically close
packed structures, representing the best space filling√ for 1:2 mixtures
of A and B spheres with a radius ratio rA /rB ≃ (3/2 ) = 1.225;20
this value corresponds to the highest packing for these structures. In
metallic systems, Laves phases are observed for a range of rA /rB span-
ning from 1.05 to 1.7.21 Three structures of Laves phases: MgCu2
(Fd3m, Z = 8), MgZn2 (P63 /mmc, Z = 4), and MgNi2 (P63 /mmc,
Z = 8) are described in the literature.13,20,21 For all those related
phases, the large A atoms’ sublattice forms a cubic/hexagonal dia-
mond net and the small B atoms’ sublattice forms an arrangement
of B4 tetrahedra. Here, the ratio rAr /rNe , estimated from argon and
neon equations of state,18,19,22,23 varies between 1.228 and 1.243 and
between 6 GPa and 100 GPa, and is thus close to the value ideal for
the formation of Laves phases. In √ addition, the measured c/a ratio of
≃1.63 is close to the ideal value of (8/3 ). This suggested our inter-
pretation of Fig. 3 XRD pattern. We stress the similarity between the
binary phase diagram measured for the Ne-Ar system and the phase
diagram predicted for hard spheres of 1:2 A-B mixtures with similar
rA /rB ratio,6 with one AB2 Laves phase, one eutectic point, and one
peritectic point.
Stein et al. did not find any clear correlation between rA /rB
and the structure adopted by the Laves phase in metallic binary sys-
tems, although the MgCu2 structure seems to be preferred for very
high ratios (1.3–1.7).21 In the case of high-pressure molecular sys-
tems, Cazorla et al. predicted that for NeHe2 , the MgZn2 structure
is stabilized by entropy over the MgCu2 structure under high tem-
peratures,13 while MgCu2 is favored by high compression. Experi-
mentally, the MgCu2 structure has been observed for Xe(O2 )2 (rA /rB
≃ 1.17) and Xe(N2 )2 (rA /rB ≃ 1.14), while NeHe2 (rA /rB ≃ 1.19),
Ar(H2 )2 (rA /rB ≃ 1.24), and CH4 (H2 )2 crystallize under the MgZn2
structure. The number of molecular Laves phases reported to date
does not allow us to establish any statistics of the phases adopted; we
can note that the MgNi2 phase has never been observed (it is also
the rarest among metallic Laves phases) and that for rare gases bina-
ries, both ArNe2 and NeHe2 adopt a MgZn2 phase. This suggests
that electronic effects, expected in compressed argon1 but not neon
or helium, do not affect the structure of ArNe2 .
For hard sphere systems, Laves phases are expected to be sta-
ble in a limited range and to decompose into pure end-members
on a pressure increase.6 Displacive transformations have also
been reported in molecular solids under pressure, for instance, in
Xe(N2 )2 11 or in pure rare gases (from face-centered cubic to hexag-
onal close packed) with a stacking fault disorder mechanism.25–27
Here, we compressed ArNe2 up to 65 GPa without observing any
sign of destabilization (such as XRD peak intensity decrease or vari-
ations in c/a ratio). The ArNe2 equation of state is plotted in Fig. 4;
points collected in run 2 are more precise than points collected in
run 1 where only a few peaks constrained the ArNe2 lattice parame-
ter c due to the orientation of the sample. The P − V points collected
151, 124708-3
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of Chemical Physics

ACKNOWLEDGMENTS
We acknowledge synchrotron Soleil for the provision of beam-
time under Proposal No. 20180418. We thank Florent Occelli and
Gaston Garbarino for their help with sample loading.

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