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Thermodynamic analysis of Al clusters formation over aluminum melt

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Physica Scripta
Authors:
Alexey Zhokh at L.V. Pisarzhevskii Institute of Physical Chemistry
Alexey Zhokh
Peter Strizhak
Peter Strizhak
Peter Strizhak
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Maksym Goryuk
Maksym Goryuk
Maksym Goryuk
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Anatolii Narivskiy
Anatolii Narivskiy
Anatolii Narivskiy
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Abstract and Figures

The formation of the aluminum nanoparticles with the size of up to 60 atoms in a gas phase is theoretically studied. Thermodynamic modeling has been applied to investigate the effect of the synthesis conditions on the distribution of the nanoparticles. The magic numbers of the particles have been estimated and found to be consistent with the available data. Furthermore, the simulations showed that higher amounts of larger nanoparticles are obtained during condensation from the supercooled aluminum vapor. In contrast, lower amounts of smaller clusters may be formed in a gas phase over the aluminum melt. Varying the temperature and concentration of supercooled aluminum vapor in a broad range results in no significant change in cluster size distribution. This effect is governed by the equilibrium shift.
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Phys. Scr. 96 (2021)125725 https://doi.org/10.1088/1402-4896/ac3b31
PAPER
Thermodynamic analysis of Al clusters formation over
aluminum melt
Alexey Zhokh
1
, Peter Strizhak
1
, Maksym Goryuk
2
and Anatolii Narivskiy
2
1
L V Pisarzhevskii Institute of Physical Chemistry of National Academy of Sciences of Ukraine, Prospekt Nauki, 31, Kiev, 03028, Ukraine
2
Physico-Technological Institute of Metal and Alloys of National Academy of Sciences of Ukraine, Acad. Vernadskogo Boul., 34/1, Kiev,
03142, Ukraine
E-mail: al.zhokh@gmail.com
Keywords: aluminum, nanoparticle, cluster
Abstract
The formation of the aluminum nanoparticles with the size of up to 60 atoms in a gas phase is
theoretically studied. Thermodynamic modeling has been applied to investigate the effect of the
synthesis conditions on the distribution of the nanoparticles. The magic numbers of the particles have
been estimated and found to be consistent with the available data. Furthermore, the simulations
showed that higher amounts of larger nanoparticles are obtained during condensation from the
supercooled aluminum vapor. In contrast, lower amounts of smaller clusters may be formed in a gas
phase over the aluminum melt. Varying the temperature and concentration of supercooled aluminum
vapor in a broad range results in no significant change in cluster size distribution. This effect is
governed by the equilibrium shift.
1. Introduction
Small metal particles with a size of 1–100 nm typically differ in their properties from bulk metal [1]. Due to their
unique characteristics, metal nanoparticles are widely used in the field of biomedicine, pharmacy, optics, new
materials manufacturing, sensing devices, microelectronics, energy storage, and heterogeneous catalysis [2–7].
Various techniques of small metal particle synthesis have been developed, e.g. mechanical milling, laser ablation,
sputtering, chemical vapor deposition, biosynthesis, polyol method, etc [8–11]. Controlling the size of small
metal particles is a key feature for the quantitative synthesis of nano-sized material. An effect of the process
conditions on the yield of the particles with a certain size may be deduced using the relevant thermodynamic
parameters of the particle formation.
The aluminum nanoparticles exhibit essential properties allowing their application in various fields, e.g.
powder metallurgy, preparation of highly-resistant paints, plastics, and composites, termite welding [12,13].
Nano-sized aluminum is also a promising component of hydrogen storage materials characterized by
exceptionally high capacity [14]. Al nanoparticles may be used in heterogeneous catalysis due to their essential
catalytic performance in a process of catalytic conversion of various chemicals [15]. In the military, small Al
particles are typical parts of explosives, particularly, TNT-Al nanoparticles composites exhibit a significant
increase in explosive performance compared to pristine TNT [16].
Both, physical and chemical properties of the aluminum nanoparticles strongly depend on the size of the
corresponding particle. For instance, the plasmon resonance depends on the size of the tetrahedral aluminum
nanoparticle because of smaller energy level gaps for larger nanoparticles [17]. Increasing the size of the
aluminum nanoparticle from 2 nm to 8 nm governs an increase in the melting temperature of the corresponding
nanoparticle from 473 Kto 937 K [18]. The reactivity of small-size Al nanoparticles with either oxygen or MoO
3
is considerably higher compared to large-size nanoparticles [19]. The oxidation rate is higher for smaller Al
nanoparticles and vice versa for the reaction temperature [20]. Due to a significant difference in the properties of
the Al particles with unequal size, controlling the size of the aluminum nanoparticles is an important task. An
attempt to obtain Al nanoparticles with an average size of 196 nm using micro-electrical discharge in
RECEIVED
6 October 2021
REVISED
14 November 2021
ACCEPTED FOR PUBLICATION
18 November 2021
PUBLISHED
29 November 2021
© 2021 IOP Publishing Ltd
... 27 Similarly, in the case of sodium nanoparticles, Joshi et al. observed that Na 40 and Na 55 show sharper heat capacity peaks than Na 50 , further emphasizing the link between magic-number configurations and thermodynamic behavior in finite-size systems. For aluminum, Zhokh et al. predicted that Al 51 exhibits maximum thermal stability near 2000 K. 28 In our previous study, however, Al 55 demonstrated an even sharper peak in the heat capacity compared to Al 51 , reinforcing its magic-number character and thermodynamic robustness. 18 We have chosen Al 55 as a representative system because its magic-number character leads to pronounced thermodynamic signatures, such as enhanced thermal stability and distinct melting behavior, making it an ideal candidate for studying size-dependent thermodynamic properties. ...
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