applied

sciences
Article
Anomalous Increase in Specific Heat of Binary
Molten Salt-Based Graphite Nanofluids for Thermal
Energy Storage
Hyun Jung Kim and Byeongnam Jo * ID

Department of Mechanical Engineering, Ajou University, Suwon 16499, Korea; hyunkim@ajou.ac.kr

* Correspondence: jo798@ajou.ac.kr; Tel.: +82-31-219-2684




Received: 30 June 2018; Accepted: 3 August 2018; Published: 5 August 2018


Abstract: An anomalous increase of the specific heat was experimentally observed in molten salt
nanofluids using a differential scanning calorimeter. Binary carbonate molten salt mixtures were
used as a base fluid, and the base salts were doped with graphite nanoparticles. Specific heat
measurements of the nanofluids were performed to examine the effects of the composition of two
salts consisting of the base fluid. In addition, the effect of the nanoparticle concentration was
investigated as the concentration of the graphite nanoparticles was varied from 0.025 to 1.0 wt %.
Moreover, the dispersion homogeneity of the nanoparticles was explored by increasing amount of
surfactant in the synthesis process of the molten salt nanofluids. The results showed that the specific
heat of the nanofluid was enhanced by more than 30% in the liquid phase and by more than 36% in
the solid phase at a nanoparticle concentration of 1 wt %. It was also observed that the concentration
and the dispersion homogeneity of nanoparticles favorably affected the specific heat enhancement of
the molten salt nanofluids. The dispersion status of graphite nanoparticles into the salt mixtures was
visualized via scanning electron microscopy. The experimental results were explained according to
the nanoparticle-induced compressed liquid layer structure of the molten salts.

Keywords: nanofluids; molten salt; specific heat; compressed liquid layer; nanoparticle dispersion;
thermal energy storage

1. Introduction
Nanofluids have attracted considerable attention in heat-transfer fields because of their enhanced
thermal properties, such as their thermal conductivity and boiling characteristics. In 1993, Masuda et
al. measured the thermal conductivity of suspensions in which Al2 O3 , SiO2 , and TiO2 were dispersed
in water. Authors reported that the thermal conductivity linearly increased with the particle volume
concentration [1]. In 1995, Choi and Eastman proposed nanofluids as innovative heat-transfer fluids,
owing to their enhanced thermal conductivity [2]. In the early 2000s, the dramatic increase of the
critical heat flux in pool boiling of nanofluids gave rise to the consideration of nanofluids as an
alternative to conventional heat-transfer fluids [3,4]. After those publications, related studies into the
thermal property and boiling characteristic have been actively performed under various experimental
conditions. As reviewed by Wang and Mujumdar, various measurement techniques for the thermal
conductivity of nanofluids, such as the hot-wire method, the steady-state parallel-plate technique, and
the temperature oscillation method, have been employed [5]. Various kinds of nanoparticles have been
dispersed into base fluids—generally water, oil, and ethylene glycol—to examine the enhancements in
the thermal conductivity (summarized in [5,6]). The significantly enhanced critical heat flux in pool
boiling of nanofluids was also evaluated to be outstanding. This has been attributed to the change
of the surface wettability due to nanoparticle deposition on heater surfaces. After the observation

Appl. Sci. 2018, 8, 1305; doi:10.3390/app8081305 www.mdpi.com/journal/applsci

Appl. Sci. 2018, 8, 1305 2 of 13

in these pool-boiling experiments, initially modified heater surfaces were employed to confirm the
critical heat flux performance [7,8]. Significant enhancements in the critical heat flux were acquired
from previous studies with the heater surface modified by nanomaterials [9–12].
While numerous studies on the thermal conductivity of nanofluids have been published,
few studies on the specific heat of nanofluids have been performed, and they report that the specific heat
of nanofluids decreases with the addition of nanoparticles [13–16]. Since Nelson et al. reported that the
specific heat of a polyalphaolefin (PAO) nanofluid was significantly increased by adding a small amount
of graphite nanoparticle fibers [17], several research groups reported that the specific heat is increased
by adding nanoparticles. In particular, Dr. Banerjee’s research groups reported that the specific heat of
binary molten salt mixtures (or eutectic), which are considered as thermal energy storage media in
concentrating solar power plants, can be enhanced via doping with nanoparticles. They used various
molten salts (carbonate salts, nitrate salts, and chloride salts) as base fluids, along with both organic and
inorganic nanoparticles. A wide range of parametric studies (effects of the nanoparticle concentration,
particle shape, size, dispersion quality, etc.) have been performed to identify the mechanism underlying
the specific heat increase in the molten salt nanofluids [18–22]. Chieruzzi et al. enhanced the specific
heat of a binary nitrate (NaNO3 –KNO3 ) by dispersing various nanoparticles (Al2 O3 , SiO2 , TiO2 , and
SiO2 –Al2 O3 ) [23,24]. The enhanced specific heat of the molten salt nanofluids was explained in various
ways, e.g., electron microscope images and molecular dynamics simulation [25–30]. Furthermore,
a fundamental experimental study into thermal property variations of carbonate salt mixtures was
performed using a differential scanning calorimeter (DSC) [31]. Additionally, the viscosity of the
molten salt nanofluids was measured at a high temperature of 550 ◦ C [32]. Most recently, Grosu et al.
reported the effect of nanoparticles on the corrosivity of nitrate molten salt [33].
The publications of the diverse aforementioned studies led to extensive research for enhancing
the specific heat of molten salts. Qiao et al. reported numerical and experimental results for enhancing
the specific heat of a binary nitrate salt mixture [34]. In 2017, Luo et al. reported that the mixture
of sodium nitrate and potassium nitrate was enhanced by CuO nanoparticles that are produced in
situ via the high-temperature decomposition of copper oxalate with the nitrate salt mixture [35].
Most recently, in situ synthesized MgO nanoparticles enhanced the specific heat of a nitrate salt by up
to 118% in the solid phase and 168% in the liquid phase [36]. Mondragon et al. explained the specific
heat enhancement of molten salts according to the ionic exchange capacity of nanoparticles using
Fourier-transform infrared spectroscopy tests [37].
Numerous studies have been performed to elucidate the specific heat increase of molten
salt nanofluids and identify the mechanisms underlying the specific heat enhancement. However,
the reason for the increase in the specific heat of molten salt nanofluids has not been clearly investigated.
According to previous studies [20,28], the increase of the specific heat of nanofluids is not solely a
result of the nanoparticles, but is closely associated with interactions between the nanoparticles and
the base fluids. For effectively harnessing thermal energy storage media, such as molten salt mixtures,
it is important to understand their specific heat-enhancing mechanism.
In this study, the specific heat of binary carbonate salt mixture-based graphite nanofluids was
experimentally measured using a DSC. Several parameters—the chemical composition of the base fluid,
the nanoparticle concentration, and the dispersion homogeneity of nanoparticles—were investigated,
which are considered as influential parameters for the specific heat enhancement of nanofluids.
Five different compositions of the base fluid (mole fraction of two salt components) were prepared,
and the thermal property was measured for fixed nanoparticle concentrations. Conversely, the specific
heat of the nanofluids was examined as the concentration of the nanoparticles varies for the uniform
chemical composition of the base fluid. Moreover, concerning the dispersion of the nanoparticles,
concentrations of a surfactant, used in order for the nanoparticles to be well dispersed, were also
increased to appraise the effect of the particle dispersion. The experimental results obtained in this
study helps us in understanding quantitative effects of each parameter on enhancing specific heat of
the molten salt mixture by doping with the nanoparticles.
Appl. Sci. 2018, 8, 1305 3 of 13
Appl. Sci. 2018, 8, x FOR PEER REVIEW 3 of 13

2. Nanofluid
2. Nanofluid Synthesis
Synthesis and
and Specific
Specific Heat
Heat Measurements
Measurements

2.1. Materials
2.1. Materials
Binary carbonate
Binary carbonate saltsalt mixtures
mixtures were were employed
employed as as aa base
base fluid
fluid ofof the
the nanofluids
nanofluidsin inthis
thisstudy.
study.
The base fluids were composed of lithium carbonate (Li 2 CO 3 , Sigma-Aldrich,
The base fluids were composed of lithium carbonate (Li 2CO3, Sigma-Aldrich, St. Louis, MO, USA) St. Louis, MO, USA)
and potassium carbonate (K CO , Sigma-Aldrich, St. Louis, MO, USA)
and potassium carbonate (K22CO33, Sigma-Aldrich, St. Louis, MO, USA) in various mole fractions. in various mole fractions.
According
According to to aa previous
previous study
study [38],
[38], lithium
lithium carbonate
carbonate and and potassium carbonate have
potassium carbonate have aa eutectic
eutectic
composition (62 mol %
composition (62 mol % of Li2CO of Li CO
2 3 and
3 and 38 mol % of K CO ) in which the carbonate
38 mol % of K2CO23) in3which the carbonate salt eutectic salt eutectic
has a
has a high melting temperature of 488 ◦ C. Recently, Jo and Banerjee reported that the specific heat
high melting temperature of 488 °C. Recently, Jo and Banerjee reported that the specific heat of
of carbonate salt mixtures in the liquid phase changes drastically with the
carbonate salt mixtures in the liquid phase changes drastically with the molar fraction of the two salts molar fraction of the
two salts
[31]. [31]. As mentioned
As mentioned previously,previously,
the base fluid the (chemical
base fluidcomposition
(chemical composition
of two saltsofintwo salts in
a binary salta
binary salt
mixture) mixture)
affects affects the enhancement
the enhancement of the specificofheat theofspecific
the saltheat of theassalt
mixtures wellmixtures
[28]. Foras well
this [28].
reason,
For this reason, five different salt compositions were chosen for the base
five different salt compositions were chosen for the base fluid of the nanofluid tested in this study. fluid of the nanofluid
tested in this
Graphite study. Graphite
nanoparticles nanoparticles
(Sigma-Aldrich, St. (Sigma-Aldrich,
Louis, MO, USA) St. Louis,
less thanMO,50USA)nm less than 50 nm
in diameter werein
diameter were
dispersed into dispersed into the base
the base carbonate salt carbonate
mixtures. salt mixtures.
Figure 1 shows Figure 1 shows a transmission
a transmission electron
electron microscope
microscope (TEM, JEOL JSM-2010) image of the graphite particle. Gum arabic
(TEM, JEOL JSM-2010) image of the graphite particle. Gum arabic (GA, Sigma-Aldrich, St. Louis, MO, (GA, Sigma-Aldrich,
St. Louis,dispersing
USA)—a MO, USA)—a agentdispersing
for carbonagent for carbonparticularly
nanoparticles, nanoparticles, particularly
carbon nanotubes carbon nanotubes
in water [39,40]— in
water [39,40]—was added for the homogeneous dispersion of the graphite
was added for the homogeneous dispersion of the graphite nanoparticles. GA was observed to be nanoparticles. GA was
observed to be
appropriate for appropriate for molten
molten salt-based salt-based
carbon carbonnanofluids,
nanoparticle nanoparticle nanofluids,
compared withcompared with
conventional
conventionalsuch
surfactants surfactants
as sodiumsuchdodecyl
as sodium dodecyl
sulfate andsulfate
sodium and sodiumbenzene
dodecyl dodecyl sulfonate
benzene sulfonate
[21]. All [21].
the
All the chemical agents were used
chemical agents were used as received. as received.

Figure 1. TEM image of a graphite nanoparticle.

Figure 1. TEM image of a graphite nanoparticle.

2.2. Synthesis of Nanofluids

2.2. Synthesis of Nanofluids
Figure 2 shows the procedures for synthesizing the molten salt-based graphite nanofluids [20,28].
Figure 2 shows the procedures for synthesizing the molten salt-based graphite nanofluids [20,28].
First, graphite nanoparticles were dispersed into distilled water with the GA (1 wt %). Then, the
First, graphite nanoparticles were dispersed into distilled water with the GA (1 wt %). Then,
aqueous graphite suspension (aqueous nanofluid) was sonicated in an ultrasonic bath (Branson 2510)
the aqueous graphite suspension (aqueous nanofluid) was sonicated in an ultrasonic bath (Branson
for 2 h. After the sonication process, the water–salt solution was added to the graphite nanofluid. The
2510) for 2 h. After the sonication process, the water–salt solution was added to the graphite nanofluid.
mixture (graphite suspension and water–salt solution) was subjected to the sonication process again
The mixture (graphite suspension and water–salt solution) was subjected to the sonication process
for 3 h. Finally, the water was removed via evaporation on a hot plate at 100 °C using a large petri
again for 3 h. Finally, the water was removed via evaporation on a hot plate at 100 ◦ C using a large
dish 10 cm in diameter. After the water was completely evaporated, the dry power of the molten salt
petri dish 10 cm in diameter. After the water was completely evaporated, the dry power of the molten
nanofluids was scraped from the entire whole petri dish, and lastly, a grinding and mixing process
salt nanofluids was scraped from the entire whole petri dish, and lastly, a grinding and mixing process
was performed to obtain a uniform chemical composition of the base fluid. Pure salt mixtures were
was performed to obtain a uniform chemical composition of the base fluid. Pure salt mixtures were
prepared though the same procedures but were subjected to sonication only once, for 2 h.
prepared though the same procedures but were subjected to sonication only once, for 2 h.
Appl. Sci. 2018, 8, 1305 4 of 13
Appl. Sci. 2018, 8, x FOR PEER REVIEW 4 of 13

Figure 2. Synthesis procedures for molten salt nanofluids.

Figure 2. Synthesis procedures for molten salt nanofluids.

Two sample groups were prepared in this study: Group 1 and Group 2. With the nanofluids in
Group Two sample
1, the effectgroups werefluid
of the base prepared in this
(chemical study: Group
composition 1 and
of the twoGroup
carbon2.salts)
Withon thethe
nanofluids
increase of in
Group 1, the effect of the base fluid (chemical composition of the two
the specific heat was investigated. That is, in the Group 1 samples, the chemical composition of thecarbon salts) on the increase of the
specific
base fluid heat
waswas investigated.
varied, and the That is, in theconcentration
nanoparticle Group 1 samples, was the chemical
fixed. composition
In contrast, of the base
the nanofluids of
fluid was varied, and the nanoparticle concentration was fixed.
Group 2 were used to explore the effect of the nanoparticle concentration on the specific In contrast, the nanofluids of Group
heat.
2 were used
Therefore, thetochemical
explore composition
the effect of the nanoparticle
of the base fluid concentration
(mole fraction on of the specific
the two heat.
salts) wasTherefore,
fixed (75
mol % of Li2CO3 and 25 mol % of K2CO3), and the concentration of the graphite nanoparticles %
the chemical composition of the base fluid (mole fraction of the two salts) was fixed (75 mol was of
Li
varied
2 CO and 25 mol % of K CO ), and the concentration of the graphite nanoparticles
3from 0.025 to 1.0 wt2 %. 3As reported in a previous study [31], because the specific heat of the was varied from
0.025 tocarbonate
binary 1.0 wt %. salt
As reported
mixturesin is astrongly
previousinfluenced
study [31],by because the specific
the chemical heat of the
composition binary
of the basecarbonate
salt, the
salt mixtures is strongly influenced by the chemical composition
mole fraction of the two salt components (lithium carbon and potassium carbonate) of the base salt, the mole fraction
was
of the two salt components (lithium carbon and potassium carbonate)
experimentally measured using inductively coupled plasma-mass spectrometry (ICP-MS) for the was experimentally measured
using inductively
sample after DSC tests.coupled plasma-mass spectrometry (ICP-MS) for the sample after DSC tests.
The mole fractions
The mole fractions of of the
the base
base fluid
fluid for
for the
the nanofluids
nanofluids in in Group
Group 1, 1, which
which were were measured
measured via via
ICP-MS, are
ICP-MS, are presented
presented in in Table
Table 1. 1. The
The mole
mole fraction
fractionof of lithium
lithiumcarbonate
carbonatevariedvariedfrom from40% 40%to to90%,
90%,
and the mole fraction of potassium carbonate varied from 10%
and the mole fraction of potassium carbonate varied from 10% to 60%. The initial concentrations ofto 60%. The initial concentrations
of graphite
graphite nanoparticles
nanoparticles werewere 0.1 and
0.1 and 1.0 wt1.0%,wtand
%, and
GA of GA of 1%wt
1 wt was% included
was included in eachin each nanofluid.
nanofluid. The
The mole
mole fractionfraction of lithium
of lithium carbonatecarbonate and potassium
and potassium carbonate carbonate for the2Group
for the Group nanofluids2 nanofluids
was 75:25was in
75:25 in molar ratio, where the maximum specific heat was measured
molar ratio, where the maximum specific heat was measured for the binary carbonate salt mixtures for the binary carbonate salt
mixtures
in a previous in a study
previous [31].study [31]. The
The mole mole of
fractions fractions
the baseoffluid
the base fluid via
obtained obtained
ICP-MS viafor
ICP-MS
the Groupfor the 2
Group 2 nanofluids were not exactly the same for all of the samples.
nanofluids were not exactly the same for all of the samples. However, the deviations in the mole However, the deviations in the
mole fraction
fraction of theoftwo the salts
two salts
werewere between
between 0.8 0.8
andand1.9 1.9
mol mol %,%,which
whichisisacceptable
acceptablefor for analyzing
analyzing
measurements of
measurements of the
the specific
specific heat.
heat. Finally,
Finally, the
the amount
amount of of GA
GA waswas increased
increased to to 55 wt
wt % % to
toimprove
improve the the
dispersion homogeneity of the nanoparticles. The specific heat of the
dispersion homogeneity of the nanoparticles. The specific heat of the nanofluids produced with GA nanofluids produced with GA of
5 wt % was compared with that of other nanofluids with GA of 1
of 5 wt % was compared with that of other nanofluids with GA of 1 wt % for the same base fluid and wt % for the same base fluid and
nanoparticle concentration.
nanoparticle concentration.

Table1.
Table Chemicalcompositions
1. Chemical compositionsand
andspecific
specific heat
heat of
of carbonate
carbonate salt
salt mixtures
mixtures for
for Group
Group 11 samples.
samples.

MoleMole Fraction of Each

Fraction Salt
of Each Salt
Specific Heat Heat
Specific in Liquid Phase
in Liquid [J/g·
Phase K]·K]
[J/g
Sample Name
Sample Name Li2Li
CO 3 [mol %]
2 CO3 [mol %]
K 2CO3 [mol %]
K2 CO3 [mol %]
Sample 1
Sample 1
9090 10 10 2.5822.582
Sample22
Sample 8080 20 20 2.5032.503
Sample33
Sample 6262 38 38 1.6461.646
Sample
Sample44 5050 50 50 1.5431.543
Sample 5 40 60 1.325
Sample 5 40 60 1.325

2.3. Specific
2.3. Specific Heat
Heat Measurements
Measurements
The specific
The specific heat
heat was
was measured
measured using
using aa DSC
DSC (TA
(TA Instruments,
Instruments, New New Castle,
Castle, DE,
DE, USA,
USA, Q20)
Q20) up
up
to 560 ◦
560 °CC with
with aa ramping
ramping rate
rate of
of 20 ◦
20 °C/min.
C/min.According
Accordingto tothe
themeasured
measuredheat-flow
heat-flowdata,
data, the
the specific
specific
to
heat of the nanofluids was determined via the standard test method ASTM
heat of the nanofluids was determined via the standard test method ASTM E1269 [41]. For everyE1269 [41]. For every
measurement, DSC runs of an empty pan (denoted as “baseline run”) and
measurement, DSC runs of an empty pan (denoted as “baseline run”) and sapphire (denoted as sapphire (denoted as
“sapphire run”)
“sapphire run”) were
were conducted
conducted prior
prior to
to DSC
DSC runs
runs of
of the
the nanofluid
nanofluid (denoted
(denoted asas “sample
“sample run”)
run”) and
and
were employed to calculate the specific heat of each nanofluid. The specific heat capacity
were employed to calculate the specific heat of each nanofluid. The specific heat capacity in the liquidin the liquid
phase was ◦ C. Avoiding inaccurate measurements
phase wasaveraged
averaged within the temperature
within range of
the temperature 525 toof555525
range to 555 °C. Avoiding inaccurate
measurements of the heat flow supplied to the aluminum pans due to the warming of the heaters in
the calorimeter, we executed a heating cycle with the same ramping rate in the DSC and maintained
Appl. Sci. 2018, 8, 1305 5 of 13

of the heat flow supplied to the aluminum pans due to the warming of the heaters in the calorimeter,
we executed a heating cycle with the same ramping rate in the DSC and maintained an isothermal
state of 560 ◦ C for more than 5 min prior to recording the heat flows. Hermetically sealed aluminum
pans were employed for the sample runs to prevent mass loss during the thermal cycles. The same
thermal cycle from 150 to 560 ◦ C was repeated five times for the sample runs to check for variations
and deteriorations in the specific heat of the nanofluids. Finally, the enhancements were calculated
as follows.
c p,Nano f luid − c p,pure
Enhancement[%] = × 100 (1)
c p,pure
The specific heat of pure carbonate salt eutectic was measured in this study to check the sample
preparation and measurement protocol by comparing the measurement to a reference value. On the
other hand, the specific heat values of the pure salt mixtures were obtained from a previous study [31]
in which the specific heat was measured via the same protocol employed in this study. Using the
specific heat values of the pure salt mixtures, the specific heat enhancement was determined for each
nanofluid. According to our experimental measurements, it was observed in this study that the GA
cannot increase the specific heat of the carbonate salt mixtures. Moreover, it is well known that the
GA is thermally decomposed between 250 and 350 ◦ C [42]. Therefore, the GA is decomposed during
the first DSC ramping process. For these reasons, the effect of the GA on the specific heat increase of
the molten salt nanofluids is negligible or even unfavorable. Hence, the increase of the specific heat is
solely attributed to the nanoparticles dispersed into the salt mixture. Scanning electron microscopy
(SEM, JSM-7500F, JEOL, Japan) was used to capture images of the nanoparticles in the salt mixtures
and examine the dispersion homogeneity of the nanoparticles.

2.4. Uncertainty Analysis

As mentioned previously, the specific heat capacity was determined via the ASTM method,
as follows.
∆qs · mst
cs = cst (2)
∆qst · ms
Here, c is the specific heat, ∆q is the heat-flow difference between the specimen and the pan, m is
the mass, the subscript s indicates the specimen, and the subscript st indicates the standard materials
(sapphire in this study). The experimental uncertainty is represented as follows [43].
s
U (∆qs ) U (∆qst )
        
Ucs U (cst ) U (ms ) U (mst )
= + + + + (3)
cs cst δ(qs ) δ(qst ) ms mst

The uncertainty resulted from the curve-fitting specific heat of sapphire, the heat flow of the
specimen and the sapphire, and the mass of the specimen and the sapphire. The uncertainties of the
curve-fitted specific heat of the sapphire and heat flow are ±0.3% and ±2%, respectively. The maximum
uncertainty in the determination of the specific heat capacity is estimated as ±2.8%.

3. Results and Discussion

The specific heat of the pure carbonate salt eutectic (62 mol % of Li2 CO3 and 38 mol % of K2 CO3 )
was measured prior to the specific heat measurements of the nanofluids. The specific heat of the pure
eutectic was 1.646 [J/g·K], which exhibits good accordance with the value of 1.6 [J/g·K] reported by
Araki et al. [44]. As shown in Figure 3, the heat-flow curve of the pure eutectic exhibits typical features,
such as a linearly increasing specific heat in the solid phase and an almost uniform specific heat in the
liquid phase. The specific heat values of the pure salt eutectic measured in this study and the pure
salt mixtures obtained from the previous study are presented in Table 1. Additionally, the specific
heat of the carbonate salt eutectic–1 wt % GA mixture was measured to examine whether the GA
increased the specific heat of the molten salt mixtures. The specific heat of the eutectic–GA mixture was
Appl. Sci. 2018, 8, 1305 6 of 13

measured to be 1.592 [J/g·K], which is approximately 3.3% lower than that of the pure eutectic. Thus,
Appl. Sci. 2018, 8, x FOR PEER REVIEW 6 of 13
the GA is not attributed to the specific heat increase of the molten salt nanofluids. For the nanofluids,
thenanofluids,
enhancement of the specific
the enhancement of heat was calculated
the specific using the using
heat was calculated specific
theheat values
specific heatof the pure
values of thesalt
mixtures shown in Table 1.
pure salt mixtures shown in Table 1.

Figure 3. Heat-flow curves of the pure salt eutectic and the nanofluids, obtained via DSC
Figure 3. Heat-flow curves of the pure salt eutectic and the nanofluids, obtained via DSC measurements.
measurements.

Figure
Figure 4 shows
4 showsthe thevariation
variationof of the
the specific heat of
specific heat ofthe
thenanofluids
nanofluidswith withGA GA ofof
1 wt1 wt%% (Group
(Group 1) 1)
with thethe
with changing
changingmole molefraction
fractionof ofthe
thetwotwo carbonate
carbonate salts saltsin
inthe
thebase
basefluid.
fluid.AsAs observed
observed in in Figure
Figure 4, 4,
thethe specificheat
specific heatofofthe
thepure
pure salt mixture
mixtureininthe theliquid
liquidphasephasedrastically
drastically increases withwith
increases the increase of
the increase
of the
the lithium
lithiumcarbonate
carbonate around
around thethe
eutectic composition
eutectic composition with with
the increase of lithium
the increase carbonate
of lithium salt.
carbonate
Regarding
salt. Regarding the the
specific heat heat
specific of the
of molten salt nanofluids,
the molten the increment
salt nanofluids, the incrementin the inspecific heat was
the specific heat
wasmeasured
measured to betohigher in thein
be higher nanofluids whose composition
the nanofluids whose composition was far fromwasthe fareutectic
from the point (62 molpoint
eutectic %
(62ofmol
Li2CO
% of 3). For instance, the increment of the specific heat for sample 5 (90 mol % of Li 2CO3) was
Li2 CO3 ). For instance, the increment of the specific heat for sample 5 (90 mol % of Li2 CO3 )
higher than
was higher than thatthat
for for
sample
sample4 (804 mol % of%Liof
(80 mol 2CO3) in both the 0.1 and 1.0 wt % conditions. The
Li2 CO3 ) in both the 0.1 and 1.0 wt % conditions.
enhancement of the specific heat exhibited a similar increment. This feature is clearly indicated by
The enhancement of the specific heat exhibited a similar increment. This feature is clearly indicated by
the enhancement graph of Figure 5. The enhancements of the specific heat for the nanofluids with the
the enhancement graph of Figure 5. The enhancements of the specific heat for the nanofluids with the
chemical composition of sample 1 (90:10) were 20.0% and 25.4% for the nanoparticle concentrations
chemical composition of sample 1 (90:10) were 20.0% and 25.4% for the nanoparticle concentrations of
of 0.1 and 1.0 wt %, respectively. For the nanofluids with the chemical composition of sample 5 (40:60),
0.1 and 1.0 wt %, respectively. For the nanofluids with the chemical composition of sample 5 (40:60),
the specific heat enhancements were 21.6% and 30.1% for nanoparticle concentrations of 0.1 and 1.0
the specific heat enhancements were 21.6% and 30.1% for nanoparticle concentrations of 0.1 and
wt %, respectively. However, the specific heat enhancements for the nanofluids with the chemical
1.0compositions
wt %, respectively.
of samplesHowever,
2 and 4the
were specific
between heat enhancements
12.2% and 24.8%. Thefor the nanofluids for
enhancements with saltthe chemical
mixtures
compositions
2 and 4 were of smaller
samplesthan2 and 4 were
those for between
samples 112.2% and 5. and 24.8%.
This The enhancements
distinctive for saltby
feature is indicated mixtures
a V-
2 and 4 were smaller than those for samples 1 and 5. This distinctive feature
shaped bar graph with the eutectic composition as the center in Figure 5. According to these results is indicated by a V-shaped
barfor
graph with the
the specific heateutectic composition
of the molten as the center
salt nanofluids, in Figure
two possible 5. According
issues are important to these results for the
for understanding
specific heat of the
the increase of themolten salt nanofluids,
specific heat of the two binarypossible issuessalt
carbonate are mixtures:
importantthe for understanding
concentration ofthe
increase of the specific
nanoparticles and the heat of the homogeneity
dispersion binary carbonate salt mixtures: the concentration of nanoparticles
of nanoparticles.
and theMoreover,
dispersionstability
homogeneityof theof enhanced
nanoparticles. thermal characteristics of the nanofluids has been
considered
Moreover, tostability
be a significant issue. Forthermal
of the enhanced engineering applications,
characteristics the nanofluids
of the stability should be examined.
has been considered
to In
bethis study, theissue.
a significant DSC thermal cycles (specific
For engineering heat measurements)
applications, the stabilitywere
should repeated 5 times for
be examined. Inthe same
this study,
samples to check whether or not the degradation of the specific heat
the DSC thermal cycles (specific heat measurements) were repeated 5 times for the same samples enhanced was arisen. Figure 6 to
shows
check the specific
whether or notheat
theratio to the first
degradation ofcycle measurement.
the specific In other words,
heat enhanced FigureFigure
was arisen. 6 represents
6 shows thethe
relative change of the specific heat of the molten salt nanofluids to the specific
specific heat ratio to the first cycle measurement. In other words, Figure 6 represents the relative change heat measured at the
of first thermalheat
the specific cycleofinthe
DSC. As shown
molten in Figure 6,
salt nanofluids to no
theremarkable
specific heatdecrease
measured wasatnotthefound except one
first thermal cycle
case (nanoparticle concentration of 0.1 wt % for the base fluid containing
in DSC. As shown in Figure 6, no remarkable decrease was not found except one case (nanoparticle 62 mol % Li 2CO3). Although

a little decrease was observed as repeating thermal cycles (liquefaction and solidification), the
concentration of 0.1 wt % for the base fluid containing 62 mol % Li2 CO3 ). Although a little decrease
degradations for most nanofluids were less than 10%. Thus, the nanofluid synthesis protocol
was observed as repeating thermal cycles (liquefaction and solidification), the degradations for most
employed in this study is appropriate for molten salt-based nanofluids. However, relatively large
nanofluids were less than 10%. Thus, the nanofluid synthesis protocol employed in this study is
decreases were also observed in a case. Hence, the stability of the nanofluids is a significant issue for
appropriate for molten salt-based nanofluids. However, relatively large decreases were also observed
engineering applications like thermal energy storage.
Appl. Sci. 2018, 8, 1305 7 of 13

in a case. Hence, the stability of the nanofluids is a significant issue for engineering applications like
thermal
Appl. Sci.energy
2018, 8, xstorage.
FOR PEER REVIEW 7 of 13
Appl. Sci. 2018, 8, x FOR PEER REVIEW 7 of 13

Appl. Sci. 2018, 8, x FOR PEER REVIEW 7 of 13

Figure 4. Specific heat of pure carbonate salt mixtures and nanofluids in the liquid phase.
Figure4.4.Specific
Figure Specificheat
heatof
ofpure
pure carbonate salt mixtures
carbonate salt mixturesand
andnanofluids
nanofluidsininthe
theliquid
liquid phase.
phase.

Figure 4. Specific heat of pure carbonate salt mixtures and nanofluids in the liquid phase.

Figure 5. Enhancements of the specific heat for five different chemical compositions of base fluid.
Figure 5. Enhancements of the specific heat for five different chemical compositions of base fluid.
Figure 5. Enhancements of the specific heat for five different chemical compositions of base fluid.
Figure 5. Enhancements of the specific heat for five different chemical compositions of base fluid.

Figure 6. Change of specific heat ratio comparing to the first cycle measurement: (A) 0.1 wt %
Figure 6. Change
nanoparticle of specific
concentration; (B)heat ratio
1.0 wt comparing to
% nanoparticle the first cycle measurement: (A) 0.1 wt %
concentration.
nanoparticle concentration; (B) 1.0 wt % nanoparticle concentration.
Figure 6. Change of specific heat ratio comparing to the first cycle measurement: (A) 0.1 wt %
Figure 6. Change
To examine of specific
the effects of theheat ratio comparing
nanoparticle to the and
concentration first the
cycle measurement:
dispersion, (A) 0.1
additional wt %
nanofluid
nanoparticle
To examine concentration;
the effects of (B) nanoparticle
the 1.0 wt % nanoparticle concentration.
concentration and the dispersion, additional nanofluid
nanoparticle
samples concentration;
were prepared (B) 1.0
as Group wt %the
2, and nanoparticle concentration.
specific heat was measured using the DSC. As mentioned
samples
in were prepared asthe
theToprevious Group 2, andcompositions
the specific heat
of was measured using
were the DSC. As formentioned
in the examine section,
previous the effects
section, ofchemical
the the nanoparticle
chemical compositions of
the base
concentration
the and
base
fluid
the dispersion,
fluid were
identical
additional
identical
all of the
for nanofluid
allnanofluid
of
samples
To
samples in Group
examine
were the 2,
prepared and
effects
asthe
of concentrations
the
Group nanoparticle
2, and the of the nanoparticles
concentration
specific heat was and were
the
measured 0.025, 0.05,
dispersion,
using the 0.1, and
additional
DSC. As 1.0 wt the
mentioned %.
samples
Figure 7 in Group
shows the 2, and the
specific concentrations
heat of the of theinnanoparticles
nanofluids both the solid were
phase0.025, 0.05, 0.1,
(averaged and 1.0
between 390wtand%.
samples
in the were prepared
previous as Group
section, theheat 2, and the
chemical specific heat
compositions ofwas
the measured
base fluidusing
were the DSC. As
identical formentioned
all390 the in
of and
Figure
410 7 shows
°C) and the
the liquidspecific
phase. of the nanofluids
The results forofthe in both the solid phase (averaged between
samples
410 in Group
°C) and 2, and
the liquid the concentrations
phase. The results thesolid
for the solid
phase are were
nanoparticles
phase are
not readily
0.025, convincing,
notsmall
readily 0.05, 0.1, andbecause
convincing, 1.0 wt %.
because
of
of
the large
Figure increase
7 shows even
theeven in
specificthe case
heat of
of the doping the
nanofluids salt mixture
in both with
the solid amounts of nanoparticles.
the large increase in the case of doping the salt mixture withphase
small(averaged
amounts of between 390 and
nanoparticles.
410 °C) and the liquid phase. The results for the solid phase are not readily convincing, because of
the large increase even in the case of doping the salt mixture with small amounts of nanoparticles.
Appl. Sci. 2018, 8, 1305 8 of 13

the previous section, the chemical compositions of the base fluid were identical for all of the samples in
Group 2, and the concentrations of the nanoparticles were 0.025, 0.05, 0.1, and 1.0 wt %. Figure 7 shows
the specific heat of the nanofluids in both the solid phase (averaged between 390 and 410 ◦ C) and the
Appl. Sci. 2018, 8, x FOR PEER REVIEW 8 of 13
liquid phase. The results for the solid phase are not readily convincing, because of the large increase
even in thein
However, case of dopingstudy,
a previous the saltamixture
similarwith small
result wasamounts
reported of nanoparticles.
for carbonate However, in a previous
salt mixture–graphite
study, a similar
nanofluids [28]. result was reported
A nanoparticle for carbonate
concentration of salt
onlymixture–graphite
0.1 wt % led to ananofluids
specific heat[28]. A nanoparticle
enhancement of
more than 30% for a carbonate salt mixture with almost the same chemical compositionaofcarbonate
concentration of only 0.1 wt % led to a specific heat enhancement of more than 30% for the two
salt mixture
salts with almost
[20]. In addition, the same chemical
it appeared composition
that the increase of theofspecific
the twoheatsaltswas
[20].limited
In addition, it appeared
even though the
nanoparticle concentration increased. The specific heat increase was not significant for eitherincreased.
that the increase of the specific heat was limited even though the nanoparticle concentration the solid
Theliquid
or specific heat increase
phases. wasdispersing
Therefore, not significant for either the
an abundant solid or
amount of liquid phases. Therefore,
the nanoparticles dispersing
is meaningless,
an abundant
because surplusamount of the nanoparticles
nanoparticles result in theisagglomeration
meaningless, because surplus nanoparticles
of the nanoparticles; thus, the result
addition in the
of
agglomeration of the nanoparticles; thus, the addition of nanosized-particles
nanosized-particles is no longer effective. In the liquid phase, the effect of the nanoparticle is no longer effective.
In the liquid phase,
concentration on thethe effect ofofthe
increase thenanoparticle
specific heatconcentration
was observed, on as
theshown
increase
in of the specific
Figure 7. Theheat was
specific
observed,
heat of the as shown in was
nanofluids Figure 7. The specific
measured heat
to exceed 3.1of[J/g·
the K]nanofluids was measured
at a nanoparticle to exceedof3.1
concentration wt ·%,
1.0[J/g K]
at a nanoparticle concentration of 1.0 wt %, which
which is almost double that of the pure carbonate eutectic. is almost double that of the pure carbonate eutectic.

Figure 7. Specific heat of nanofluids in the solid and liquid phases with respect to the nanoparticle
Figure 7. Specific heat of nanofluids in the solid and liquid phases with respect to the
concentration.
nanoparticle concentration.

The dispersion of nanoparticles has been a fundamental issue since the early stages of nanofluid
The dispersion
research. The two-step of nanoparticles
synthesis methodhas beenforathefundamental
molten salt issue since the employed
nanofluids early stagesinofthisnanofluid
study
research.the
utilizes The two-step
high watersynthesis
solubilitymethod
of the for
saltthe molten salt nanofluids
components, employed in
but the evaporation this study
process mayutilizes
cause
the high water solubility of the salt components, but the evaporation process
unfavorable agglomeration of nanoparticles. In particular, this is a critical problem for carbon may cause unfavorable
agglomerationsuch
nanoparticles of nanoparticles. In particular,
as graphite and this is a critical
carbon nanotubes, whichproblem
need a for carbon nanoparticles
surfactant to be dispersed such
intoas
graphite
water. Toand carbon the
determine nanotubes,
effect of which need a surfactant
the nanoparticle to beondispersed
dispersion intoheat
the specific water. To determine
enhancement the
of the
effect of the nanoparticle dispersion on the specific heat enhancement of
carbonate salt mixture, the amount of the surfactant—GA—was increased from 1 to 5 wt %, and the the carbonate salt mixture,
the amount
specific heatofwas
thecompared
surfactant—GA—was
with that of increased
the nanofluid from at
1 to
the5 wt
same %, and the specific
nanoparticle heat was compared
concentration with 1
wt % GA. As shown in Figure 7, the specific heat values of the nanofluids with 5 wt % GA were 1.917,
with that of the nanofluid at the same nanoparticle concentration with 1 wt % GA. As shown in Figure
the K]
[J/g·specific
in theheat
solidvalues of the
phase andnanofluids
3.36 [J/g·K]with 5 wtliquid
in the % GAphase.were 1.91 [J/g8·K]
Figure in theSEM
shows solidimages
phase and
for
3.36 [J/g·K]
nanofluids in the liquid
produced with phase.
5 wt % GA:Figure 8 showselectron
secondary SEM imagesimages forand
nanofluids
backscatterproduced
images.withThese5 SEM
wt %
GA: secondary
images electron images
differ significantly and backscatter
from those images.
in other studies. These
Small SEM images
particles differ
exhibiting significantly
a spherical from
shape in
those in other studies. Small particles exhibiting a spherical shape in the
the secondary electron images (Figures 8-A and 8-B) were homogeneously dispersed into the salt secondary electron images
(Figures(base
mixture 8-A and
fluid)8-B) were homogeneously
without any agglomeration. dispersed into the salt
The backscatter mixture
images (base8-C
(Figures fluid)
andwithout any
8-D) show
agglomeration. The backscatter images (Figures 8-C and 8-D) show the
the dispersion homogeneity of the nanoparticles, which were black-colored. The diameters of thedispersion homogeneity of
the nanoparticles,
particles in Figure which were
8 appear black-colored.
larger than thoseThe diameters
of the graphiteofnanoparticles
the particles in Figurein8Figure
shown appear1.larger
It is
than those of the graphite nanoparticles shown in Figure 1. It is thus hypothesized
thus hypothesized that the particles in Figure 8 are single structures of the nanoparticle-induced that the particles
compressed liquid layer. Unfortunately, because energy-dispersive X-ray spectroscopy analysis was
not performed for the images in Figure 8, our hypothesis is not verified. However, it was visually
conformed that the homogeneously dispersed particles existed in the nanofluids. Even though the
images in Figure 8 were obtained in solid phase, the dispersion homogeneity of the graphite
nanoparticles in liquid phase was well maintained under repeating thermal cycles in DSC. According
Appl. Sci. 2018, 8, 1305 9 of 13

in Figure 8 are single structures of the nanoparticle-induced compressed liquid layer. Unfortunately,
because energy-dispersive X-ray spectroscopy analysis was not performed for the images in Figure 8,
our hypothesis is not verified. However, it was visually conformed that the homogeneously dispersed
particles existed in the nanofluids. Even though the images in Figure 8 were obtained in solid phase,
the dispersion
Appl. Sci. 2018, 8, homogeneity of the graphite nanoparticles in liquid phase was well maintained under
x FOR PEER REVIEW 9 of 13
repeating thermal cycles in DSC. According to the DSC measurements and the SEM images, it may be
concluded
to the DSC thatmeasurements
the homogeneousanddispersion
the SEM ofimages,
the nanoparticles
it may befavorably influences
concluded thehomogeneous
that the specific heat
enhancement
dispersion of of thethe nanofluids. favorably influences the specific heat enhancement of the nanofluids.
nanoparticles

Figure8.8.SEM
Figure SEMimages
imagesof
ofthe
thenanofluid
nanofluid(1
(1wt
wt%%nanoparticles
nanoparticlesandand55wt wt%%GA):
GA):secondary
secondaryelectron
electron
images (A,B) and backscatter images (C,D). The red circles indicate the single compressed liquid layer.
images (A,B) and backscatter images (C,D). The red circles indicate the single compressed liquid layer.

Regarding the enhanced specific heat of molten salt nanofluids, the higher heat capacity of the
Regarding the enhanced specific heat of molten salt nanofluids, the higher heat capacity of the
nanoparticles, the interfacial thermal resistance at the solid–liquid interface, and the formation of the
nanoparticles, the interfacial thermal resistance at the solid–liquid interface, and the formation of the
compressed liquid layer near the nanoparticles were proposed as mechanisms contributing to the
compressed liquid layer near the nanoparticles were proposed as mechanisms contributing to the
increase of the specific heat [19,23,45].
increase of the specific heat [19,23,45].
Many researchers have presented SEM images of unique structures in nanofluids. Needle-
Many researchers have presented SEM images of unique structures in nanofluids. Needle-shaped
shaped structures and network-like structures are often shown in research papers concerning the
structures and network-like structures are often shown in research papers concerning the specific heat
specific heat of molten salt nanofluids [23,45]. It is reasonable to consider that the special structures
of molten salt nanofluids [23,45]. It is reasonable to consider that the special structures are relevant to
are relevant to the specific heat increase. Oh et al. experimentally observed ordered liquid aluminum
the specific heat increase. Oh et al. experimentally observed ordered liquid aluminum atoms adjacent
atoms adjacent to the crystalline interface with sapphire [46]. Additionally, molecular dynamics
to the crystalline interface with sapphire [46]. Additionally, molecular dynamics simulations showed
simulations showed the formation of a dense (compressed) layer with a certain thickness at the
the formation of a dense (compressed) layer with a certain thickness at the interface between a solid
interface between a solid nanoparticle and liquid molecules [30]. This compressed liquid layer in
nanoparticle and liquid molecules [30]. This compressed liquid layer in which the solvent molecules
which the solvent molecules (molten salt molecules) acquire an ordered structure can be regarded as
(molten salt molecules) acquire an ordered structure can be regarded as a quasi-crystalline structure.
a quasi-crystalline structure. The compressed liquid layer of binary carbonate salt mixtures has
The compressed liquid layer of binary carbonate salt mixtures has different chemical compositions of
different chemical compositions of the two salts from the overall (bulk) compositions of the base fluid
the two salts from the overall (bulk) compositions of the base fluid [20,28]. The compressed liquid layer
[20,28]. The compressed liquid layer has a higher concentration of potassium carbonate than the bulk
has a higher concentration of potassium carbonate than the bulk salt mixture (base fluid). Because
salt mixture (base fluid). Because of the different chemical composition of the compressed liquid layer,
of the different chemical composition of the compressed liquid layer, this region has significantly
this region has significantly different thermophysical properties than the bulk salt mixture (base fluid)
different thermophysical properties than the bulk salt mixture (base fluid) [31]. Thus, the compressed
[31]. Thus, the compressed liquid layers adjacent to the nanoparticles create special structures by
liquid layers adjacent to the nanoparticles create special structures by joining each layer, and these
joining each layer, and these structures enhance the specific heat of the nanofluids. Ultimately, the
structures enhance the specific heat of the nanofluids. Ultimately, the compressed liquid layers amplify
compressed liquid layers amplify the capacity of the nanofluids for thermal energy storage.
the capacity of the nanofluids for thermal energy storage.
Figure 9 shows the nanoparticle-induced compressed liquid layer structures of the molten salt
mixtures in solid phase. The network like structures in Figure 9 are presumed as the compressed
liquid layer structures in solid phase. The dispersion effect can be explained by these special
structures of the solvent material. If the nanoparticles are homogeneously dispersed in the base fluid,
a significantly larger volume of the compressed liquid layers can be formed, and the compressed
liquid layer structures should be increased. Thus, the individually dispersed nanoparticles shown in
Figure 8 allow a large volume of the compressed liquid layer structures to be created in the nanofluids.
Appl. Sci. 2018, 8, 1305 10 of 13

Figure 9 shows the nanoparticle-induced compressed liquid layer structures of the molten salt
mixtures in solid phase. The network like structures in Figure 9 are presumed as the compressed liquid
layer structures in solid phase. The dispersion effect can be explained by these special structures of the
solvent material. If the nanoparticles are homogeneously dispersed in the base fluid, a significantly
larger volume of the compressed liquid layers can be formed, and the compressed liquid layer
structures should be increased. Thus, the individually dispersed nanoparticles shown in Figure 8 allow
a large volume of the compressed liquid layer structures to be created in the nanofluids. Regarding
the concentration effect of the nanoparticles, the specific heat of the nanofluids can be modified
Appl. Sci. 2018, 8, x FOR PEER REVIEW 10 of 13
significantly via doping with a minute concentration of the nanoparticles in the salt mixtures, and the
enhancement analysis,
experimental increases such
with as
theenergy
nanoparticle concentration.
dispersive However,
spectroscopy, experimental
is necessary analysis,
to reveal such as
the identity of
energy dispersive spectroscopy,
the structures in Figure 9. is necessary to reveal the identity of the structures in Figure 9.

Figure 9. SEM images of the nanofluid (1 wt % nanoparticle and 5 wt % GA): nanoparticle-induced

Figure 9. SEM images of the nanofluid (1 wt % nanoparticle and 5 wt % GA): nanoparticle-induced
compressed liquid layer structures in solid phase.
compressed liquid layer structures in solid phase.

Conventional theoretical models are unable to explain and predict the specific heat
Conventional
enhancements theoretical
achieved in thismodels
study. are unable
While to explain
the thermal and predict
equilibrium the specific
model heatby
suggested enhancements
Buongiorno
achieved in this study. While the thermal equilibrium model suggested by
[47] is known to predict well the specific heat of aqueous nanofluids, it is only applicableBuongiorno [47]for
is
known to predict well the specific heat of aqueous nanofluids, it is only applicable for
conventional nanofluids—not molten salt nanofluids—because it fails to predict the increase of the conventional
nanofluids—not
specific molten
heat. Thus, salt nanofluids—because
in addition to experimental works, it fails to predict
intensive the increase
theoretical studies of
on the
the specific
specific
heat of nanofluids—particularly high-temperature nanofluids—are needed to determine heat
heat. Thus, in addition to experimental works, intensive theoretical studies on the specific the
of nanofluids—particularly
parameters and elucidate thehigh-temperature
physics resultingnanofluids—are
in the enhanced needed
specific to determine the parameters
heat.
and elucidate the physics resulting in the enhanced specific heat.
4. Conclusions
4. Conclusions
The specific heat of the carbonate salt mixture-based graphite nanofluids was measured within
The specific heat of the carbonate salt mixture-based graphite nanofluids was measured within
a wide temperature range of 150–560 °C. The effects of the chemical compositions of the base fluid,
a wide temperature range of 150–560 ◦ C. The effects of the chemical compositions of the base fluid,
the nanoparticle concentration, and the dispersion homogeneity on the specific heat were
the nanoparticle concentration, and the dispersion homogeneity on the specific heat were investigated.
investigated. The knowledge gained in this study is summarized as follows.
The knowledge gained in this study is summarized as follows.
(a) The specific heat was anomalously enhanced by up to >30% in the liquid phase and 36% in the
(a) solid
The specific
phase heat
via thewasdispersion
anomalouslyof enhanced by up to >30%The
graphite nanoparticles. in the liquid phase and
enhancements were36% in the
strongly
solid phaseon
dependent viathethechemical
dispersion of graphiteofnanoparticles.
composition the base fluid:The theenhancements
increments, as werewellstrongly
as the
dependent on inthe
enhancements thechemical composition
specific heat, increasedofwhen
the base fluid: thecomposition
the chemical increments,ofas thewell
baseasfluid
the
enhancements
was far from theineutectic
the specific heat, increased when the chemical composition of the base fluid
composition.
was far from the eutectic composition.
(b) The specific heat increased with the concentration of the nanoparticles. A noticeable increase
(b) was
The observed
specific heat increased
at the with the
nanoparticle concentration
concentration of of the wt
0.025 nanoparticles. A noticeable
% for the base increase
fluid including was%
75 mol
observed
lithium at the nanoparticle
carbonate and 25 molconcentration of 0.025 wtA%critical
% potassium carbonate. for theconcentration
base fluid including 75 mol %
of nanoparticles
was observed. For nanoparticle concentrations exceeding 0.1 wt %, the increment was negligible.
(c) The specific heat enhancements increased as the amount of the surfactant (GA) increased from
1 to 5 wt %. Larger enhancements were measured for the nanofluids with 5 wt % GA, and the
actual specific heat value was almost double that of the eutectic.
(d) The homogeneous dispersion of the graphite nanoparticles was visually confirmed via SEM
(secondary electron images and backscatter images) for the nanofluid after a DSC test. In the
Appl. Sci. 2018, 8, 1305 11 of 13

lithium carbonate and 25 mol % potassium carbonate. A critical concentration of nanoparticles

was observed. For nanoparticle concentrations exceeding 0.1 wt %, the increment was negligible.
(c) The specific heat enhancements increased as the amount of the surfactant (GA) increased from
1 to 5 wt %. Larger enhancements were measured for the nanofluids with 5 wt % GA, and the
actual specific heat value was almost double that of the eutectic.
(d) The homogeneous dispersion of the graphite nanoparticles was visually confirmed via SEM
(secondary electron images and backscatter images) for the nanofluid after a DSC test. In the SEM
images, the graphite nanoparticles were spherical, having smooth curvature (not disks), so it was
presumed that special structures, nanoparticle-induced compressed liquid layer, were formed in
the nanofluids. The SEM images conclusively proved that the dispersion homogeneity (quality)
of the nanoparticles is due to the specific heat enhancements of the nanofluids.

Author Contributions: Hyun Jung Kim analyzed the data; Byeongnam Jo performed the experiments, analyzed
the data and wrote the paper. All authors have read and approved the final version of the paper.
Acknowledgments: This work was supported partly by the New Faculty Research Fund of Ajou University and
partly by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education (NRF-2018RIA2B2001082).
Conflicts of Interest: The authors declare no conflict of interest.

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