Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Thermal conductivity enhancement in MoO3–H2O nano-sheets based

nano-fluids
N. Kana a,b,⇑, A. Galmed a,b,c, T. Khamliche a,b, K. Kaviyarasu a,b, M. Maaza a,b
a
Nano-sciences African Network (NANO-AFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West, Western Cape 7129, PO Box 722, South Africa
b
UNESCO-UNISA Africa Chair in Nano-sciences-Nano-technology, College of Graduate Studies, Muckleneuk Ridge, PO Box 392, Pretoria, South Africa
c
National Institute of Laser Enhanced Sciences (NILES), Cairo University, 1 Gamaa Street, Giza, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: This contribution reports on the thermal conductivity enhancement of MoO3–H2O nano-sheets based
Received 14 September 2019 nano-fluid. The MoO3–H2O based nano-fluid consists of a set of 2D type nano-sheets with a basal size,
Received in revised form 18 April 2020 approximately ranging from 108  200 nm2 to 415  631 nm2. A Higher Resolution Transmission
Accepted 21 April 2020
Electron Microscopy (HRTEM) observation indicated that the nano-sheets consist of a collection of
Available online xxxx
nano-crystallites (Ø7 nm) with various crystallographic orientations with 15 nm in average diameter.
The Molybdenum is mainly in 6+ electronic valence. Their thermal conductivity measured via standard
Keywords:
Pt wire exhibited an enhancement of about 36%.
Nano-fluid
Thermal conductivity enhancement
Ó 2020 Elsevier Ltd. All rights reserved.
Nano-sheets Selection and peer-review under responsibility of the scientific committee of the NANOSMATAFRICA-
MoO3 2018.
Electron microscopy

1. Introduction
Pioneered by Choi as early as 1995 [1], nano-fluids are a novel
hybrid class of heat transfer fluids which have recently been a very
attractive area of research due to their specific enhanced thermo-
physical properties and the corresponding potential benefits and
technological applications in various strategic fields related to heat
transfer & energy efficiency [1–5]. By their nature, nano-fluids con-
sist of a dispersion of nano-particles in standard heat transfer
water or oil based fluid. Generally, the thermal conductivity of
standard oils and water is relatively low compared to that of met-
als & their corresponding oxides [6]. Therefore utilizing them as
base fluids in a suspension within a standard viscous heat transfer
medium would allow the enhancement of the effective thermal
conductivity of the hybrid nano-fluids, as per the additive thermo-
dynamic nature of the thermal conductivity. The thermal conduc-
tivity of metals and their oxides is at least 2 orders of magnitude
relative to organic materials, as well as standard heat transfer flu-
ids including water, Tetradecane, Ethylene Glycol & mineral oils.
The advantage of the oxides is the stability within the host fluid
in view of the chemical interaction within any polar host fluid.
As reported in the literature so far, the stability of the nano-
particles in suspension is significantly governed by the interface
⇑ Corresponding author.
E-mail address: noluthando.ntshangase@gmail.com (N. Kana).
of nano-particles with host liquid as well as their shape [7]. 1-D
& 2-D nano-particles have the advantage in terms of percolation
threshold and ease of heat transfer. Indeed, neighboring 1-D & 2-
D nano-suspensions would reach the percolation threshold (neigh-
boring nano-particles will likely touch each other) for a lower vol-
ume concentrations relatively to the standard spherical nano-
particles. In addition, they exhibit a large total surface in contact
with the host liquid inducing a likely better stability within the
host fluid.
Within the 2-D oxides family resides the Molybdenum oxides
series [10–13]. Due to its lamellar structure (Fig. 1) and weak
van der Waals’ bond between layers, MoO3 has emerged as an aus-
picious candidate for its high-temperature lubricating potential.
Being nano-meter thick, MoO3 nano-sheets were found to maintain
a constant-sliding contact surface area under different loads, and
thus produced load-independent friction [14–16]. In the 2-D oxi-
des family found is the Molybdenum oxides series. These oxides
can form series of crystallographically oxygen-deficient materials
known as Magneli phases [11,12], within which the oxygen vacan-
cies defects induce extended shear structures. Likewise, in their
nano-scale form and the above mentioned pronounced crystallo-
graphic anisotropy in addition to their electronic multi-valence
[13]. Due to this latter rich coordination specificity and besides
to the Magneli phases, molybdenum has four thermodynamically
stable oxides, namely MoO2, Mo2O3, MoO3 and Mo2O5 as well as
the hydrated Pentoxide Mo2O5–H2O in addition to the volatile

https://doi.org/10.1016/j.matpr.2020.04.562
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the NANOSMATAFRICA-2018.

Please cite this article as: N. Kana, A. Galmed, T. Khamliche et al., Thermal conductivity enhancement in MoO3–H2O nano-sheets based nano-fluids, Mate-
rials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.04.562
2 N. Kana et al. / Materials Today: Proceedings xxx (xxxx) xxx

Fig. 1. (a) MoO6 octahedral as found in the thermodynamically stable a-MoO3 composed of molybdenum and oxygen atoms. (b) Thermodynamically stable orthorhombic a-
MoO3 with layered structure held together by van der Waals’ forces. (c) Metastable monoclinic b-MoO3 (d) e-MoO3, also known as MoO3-II. (e) Metastable h-MoO3. (f) Tunnel
structure along the c-axis of h-MoO3 unit cell [9].

Fig. 2. (a) Scanning Electron Microscopy, (b) High Resolution Transmission Electron Microscopy & (c) Selected Area Electron Diffraction of the centrifuged MoO3 powder from
the yellow solution.

MoO3(OH)2 [10]. It was shown that MoO3-d nano-suspension can This contribution reports on the thermal conductivity enhance-
be stable for a relatively long period (1 year) as in the case of those ment of MoO3 nano-sheets–H2O based nano-fluid. Such a nano-
synthesized by Laser Liquid Solid Interaction [8]. fluid was engineered by dissolution in H2O2 of pure Mo target.

Please cite this article as: N. Kana, A. Galmed, T. Khamliche et al., Thermal conductivity enhancement in MoO3–H2O nano-sheets based nano-fluids, Mate-
rials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.04.562
 N. Kana et al. / Materials Today: Proceedings xxx (xxxx) xxx
Fig. 3. XPS spectrum of Mo3d & O1s of the centrifuged yellow nano-sheets.
Fig. 4. Typical optical Absorbance of the MoO3–H2O nano-fluid.
Not only, have they exhibited a good stability, likely favored by the
polar interaction with the surrounding H2O molecules’ dipoles.
Please cite this article as: N. Kana, A. Galmed, T. Khamliche et al., Thermal conductivity enhancement in MoO3–H2O nano-sheets based nano-fluids, Mate-
rials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.04.562
3
Fig. 5. Thermal conductivity of MoO3 nano-particles hybrid nano-fluid at different
volume concentration and temperature.
2. Experiments, results & discussion
A piece of Mo was cut into two strips of equal dimensions
(5 cm  1 cm). The two pieces were then cleaned and sonicated
for 10 min in ethyl alcohol to remove any impurities on the metal.
Each Mo metal piece was put in a small test tube (25 ml) then sub-
merged in 35% H2O2. During the dissolution, and as expected, an
excess of Oxygen bubbles was observed. The final solution was yel-
low in color pointing to the formation of likely hydrated Molybde-
num oxide MoO3–H2O. In view of the lamelar structure of the
various Molybdenum oxides, it is expected that the Molybdenum
oxidation would be likely followed by the exfoliation phenomenon
and hence the formation of the nano-sheets as summarized in
Fig. 1 because the low Wan der Waals interaction between the
lamelae. The then yellow nano-fluid was investigated by UV–VIS
spectroscopy at room temperature. Transmission Electron Micro-
scopy (TEM), Electron Dispersion Spectroscopy (EDS) as well as
X-rays Photoelectron Spectroscopy (XPS) were conducted on the
so formed nano-fluid.
2.1. Morphological & structural properties
Fig. 2(a) reports the Scanning Electron Microscopy of the MoO3
nano-particles. They deviate from the classically quasi-spherical
nano-particles obtained by various physical & chemical standards
methods. More precisely, in this case, they consist rather of a set
of 2D type sheets with a basal size, approximately ranging from
108  200 nm2 to 415  631 nm2. A Higher Resolution Transmis-
sion Electron Microscopy (HRTEM) observation Fig. 2(b) indicate
that the nano-sheets consist of a collection of nano-crystallites
(Ø7 nm in diameter) with various crystallographic orientations.
This latter is in line with the polycrystalline pattern as shown in
the Selected Area Electron Diffraction of Fig. 2(c).
2.2. Elemental & electronic valence
Fig. 3 reports the XPS spectra of the Mo3d & O1s of the cen-
trifuged yellow powder. One can distinguish crystal clearly the
major peak located at 233.03 eV corresponding to the Mo3d5/2
pointing to the 6+ state. There are no peaks within the range of
229.5–233 eV hence, no Mo4+ [20]. In a pre-conclusion, the Mo is
mainly in 6+ oxidation state & hence, likely, in the form of MoO3.
Ideally, the Mo3d5/2 peak should have been deconvoluted to extract
4 N. Kana et al. / Materials Today: Proceedings xxx (xxxx) xxx
any Mo5+ component if any which could be attributed to surface
reduction [21].
2.3. Optical properties
The absorption for MoO3 nanoparticles arises at approximately
300 nm (Fig. 4). The maximum absorption peak is observed at
321 nm in UV region. The strong absorption below 400 nm is
intrinsic and rises from inter band (valence band to conduction
band) and exciton transitions. The result indicated that the absorp-
tion of MoO3 nano-particles will enlarged to the visible spectrum
due to the existence of MoO3 that improved the optical absorption
edge. If the concentration of the parameters increases, then the
absorption intensities of MoO3 nano-particles will increase. The
optical absorption near the band edge can be calculated by using
the relation (ahm)n = A (hm Eg), where, a is the absorption co-
efficient, h is the plank’s constant, m is the frequency, A is a con-
stant, Eg is the energy and n is the number that characterize the
transition process (for direct allowed n = 2 and for in-direct
allowed transition n = 1/2). As well known, MoO3 is an n-type
semiconductor. Its bandgap is calculated from the plot of (ahm)2
versus hm. The direct band gap value obtained from the plot of
(ahm)2 versus hm for MoO3 nanoparticles giving a straight-line plot.
The intercept of the tangent to the x-axis l gives a good calculation
of the bandgap, so the expected band gap of MoO3 nanoparticles is
2.75 eV. The similar value can be obtained according to the band
edge of the band–band transition in SPS spectrum of as prepared
MoO3 nanoparticles. The obtained results are in full agreement
with several results published in the literature so far [17–19].
2.4. Thermal conductivity properties
Fig. 5 reports the thermal conductivity versus temperature of
the yellow nano-fluid within the range of 25–45 °C measured using
the standard Platinum wire technique. More precisely, it reports
the thermal conductivity of the MoO3–H2O nano-fluids at various
concentrations; High concentration (67%), low concentration
(8.6%) and a mid-concentration (37.8%) in addition that of the
deionized H2O, reported as a reference. There is a net enhancement
of the thermal conductivity in the MoO3–H2O based nano-fluids
whatever the concentration. A general trend, the thermal conduc-
tivity of the nano-fluid seems to increase in a quasi-linear with the
temperature. At 25 °C, the thermal conductivity enhancement is
about 9%, 17% & 30% for 8.6%, 37.8% and 67% concentrated
MoO3–H2O nano-fluids respectively. At 45 °C, the thermal conduc-
tivity enhancement is relatively significant; it reaches up to30%,
21% & 44% for 8.6%, 37.8% and 67% concentrated MoO3–H2O
nano-fluids respectively.
3. Conclusions
In this contribution, it was demonstrated the possibility of engi-
neering molybdenum oxide based nano-sheets by a direct dissolu-
tion of Metallic Mo in H2O2. At 25 °C, the thermal conductivity
enhancement is about 9%, 17% & 30% for 8.6%, 37.8% and 67% con-
centrated MoO3–H2O nano-fluids respectively. At 45 °C, the ther-
Please cite this article as: N. Kana, A. Galmed, T. Khamliche et al., Thermal conductivity enhancement in MoO3–H2O nano-sheets based nano-fluids, Mate-
rials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.04.562
mal conductivity enhancement is relatively significant; it reaches
up 44% for 67% concentrated MoO3–H2O nano-fluids respectively.
It is intended to validate with other meals such as tungsten.
CRediT authorship contribution statement
N. Kana: Validation, Visualization, Writing - original draft,
Writing - review & editing. A. Galmed: Writing - original draft,
Writing - review & editing. T. Khamliche: Visualization. K. Kavi-
yarasu: Visualization. M. Maaza: Funding acquisition, Investiga-
tion, Methodology, Supervision, Data curation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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