Applied Thermal Engineering 110 (2017) 19

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Research Paper

Enhanced thermophysical properties of NEILs as heat transfer fluids for

solar thermal applications
Titan C. Paul a, A.K.M.M. Morshed b, Elise B. Fox c, Jamil A. Khan a,
a
Department of Mechanical Engineering, University of South Carolina, Columbia, SC, USA
b
Department of Mechanical Engineering, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh
c
Savannah River National Laboratory, Aiken, SC, USA

h i g h l i g h t s

Experimental measurements of thermophysical properties of NEILs.

NEILs shows shear thinning behavior and higher effective viscosity compared to base ILs.

Effective thermal conductivity increases by 11% for 2.5 wt% of Al2O3 NEILs.

Heat capacity increases by 62%. for 2.5 wt% of Al2O3 NEILs.

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

Article history: Thermophysical properties of base ionic liquids (ILs) and nanoparticle enhanced ionic liquids (NEILs)
Received 7 March 2016 were measured experimentally. NEILs are formed by dispersing different wt% (0.5, 1.0, and 2.5) of
Revised 26 July 2016 Al2O3 nanoparticles in four base ILs. NEILs show enhanced thermal conductivity, viscosity, and heat
Accepted 1 August 2016
capacity compared to the base ILs. NEILs show shear thinning behavior at all the measured temperatures
Available online 1 August 2016
and the enhancement of viscosity was predicted by the aggregation model with high aggregation factor.
Maximum thermal conductivity enhancement was observed by 11% for 2.5 wt% NEILs. The experimen-
Keywords:
tal effective thermal conductivity could not predicted by the aggregation model with the same aggrega-
Ionic liquids
Nanoparticle enhanced ionic liquids (NEILs)
tion factor. However, the theoretical model considering interfacial layer of the particle/liquid interface
Rheological behavior (with interfacial layer thickness 2 nm and interfacial layer thermal conductivity, klr 3kBL ) could predict
Thermal conductivity the effective thermal conductivity of NEILs. Heat capacity of NEILs shows much higher value compared to
Heat capacity the base ILs and the theoretical model could not predict that enhancement. The strong interaction
Heat transfer fluid between the nanoparticles surface to ions of the ionic liquids was considered as the potential factor
for those enhancements of thermophysical properties.
2016 Elsevier Ltd. All rights reserved.

1. Introduction thermal collector [3]. Solar cells face the problem of lower effi-
ciency and higher cost effective ratio, whereas solar thermal collec-
The environmental community and energy researchers are con- tors possess superior performance over the solar cell [4].
cerned about global warming and the emission of CO2 from the Concentrated solar power (CSP) is one of the forms of solar thermal
burning of fossil fuels in energy production [1]. People are looking collector, which is the growing technology for electricity genera-
for environmental friendly and energy efficient alternate sources of tion. On commercial level application 14 MW Solar Energy Gener-
energy. From the many options of renewable energy, solar energy ating System or SEGS plant was built first in California, US in 1980
is one of the most abundant alternate energy sources in the world and in 2012 it is become 2553 MW worldwide. Also, 2000 MW
[2]. Solar energy can be harvested by means of direct conversion of plants are under construction all over the world [5]. Ashouri
sunlight into energy with photovoltaic effect which is called solar et al. [6] have studied parabolic Trough solar collector driven by
cell and by absorbing heat from the sunlight which is called solar Kalina cycle and compared with the conventional fuel driven
Kalina cycle. They reported that solar collector has the higher leve-
lized cost than the fuel driven cycle but solar collector save huge
Corresponding author at: Department of Mechanical Engineering, University of
amount of fuel burning that produces enormous CO2 emission.
South Carolina, Columbia 29208, SC, USA.
Organic Rankine cycle (ORC) was integrated with CSP system with
E-mail address: [email protected] (J.A. Khan).

http://dx.doi.org/10.1016/j.applthermaleng.2016.08.004
1359-4311/ 2016 Elsevier Ltd. All rights reserved.
2 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19

Nomenclature

T temperature [K] l dynamic viscosity [centipoise]

k thermal conductivity [W/mK] / nanoparticle volume fraction []
A, B, C constant [] /m maximum particle packing fraction []
cp heat capacity [J/gK] /a effective volume fraction of aggregates []
D fractal index []
h interfacial layer thickness [nm] Subscripts
a average radius [nm] NEIL nanoparticle enhanced ionic liquid
BL base liquid
Greek symbols n nanoparticle
c, c1 constant [] a aggregate
q density [kg/m3] lr interfacial layer

different working fluids [7], and reported that the cycle running tetra-fluoroborate ([HMIM]BF4) IL based IoNanofluids with gra-
with benzene has the higher thermal efficiency. pheme (GE) and MWCNTs. They reported thermal conductivity of
In CSP system, electricity is generated by concentrating sunlight IoNanofluids increases, but heat capacity decreases with nanopar-
from a large area using mirrors or lenses and stored in heat transfer ticles concentration. Menbari et al. [23] have studied CuO/Water
fluid (HTF). Later on the energy of those HTF is used to produce nanofluids effect on direct absorption concentrating solar collector
steam for power generation by using conventional Rankine cycle and found higher thermal efficiency of the collector. Although sev-
[8]. The energy efficiency of the CSP system is mostly dependent eral research groups work on thermophysical properties of NEILs,
on the operating temperature and thermal stability of the HTF. the mechanisms of thermophysical properties enhancement of
Currently, the commercially available and used HTFs are Therminol NEILs are under investigation.
VP-1 (eutectic mixture of biphenyl and diphenyl oxide), molten This paper presents the rheological behavior, thermal conduc-
salts, and mineral oil. Therminol VP-1 has a high vapor pressure tivity, and heat capacity of NEILs containing Al2O3 nanoparticles
at higher operating temperature which is harmful to the storage at different concentration (0.5%, 1.0%, and 2.5% by wt) with
tank [9]. Molten salts have a higher operating temperature over [C4mim][NTf2], [C4mmim][NTf2], [C4mpyrr][NTf2], and [N4111]
500 C but have higher melting temperatures which help to freeze [NTf2] ILs. The rheological behavior, thermal conductivity, and heat
up the liquid during the winter season [10], and mineral oil has capacity were studied within the temperature ranges 2090 C,
lower decomposition temperature [11]. The above mentioned 1070 C, and 25345 C respectively. The experimental data were
properties of currently used HTFs are affecting the energy storage compared with the existing theoretical models and plausible rea-
capacity and reducing the overall system efficiency, resulting in sons of enhancement of thermophysical properties are discussed.
increased operating cost. Therefore, there is an acute need for the
new energy-efficient HTF.
2. Experimental measurements
Ionic liquids (ILs) are the organic salts having a low melting
point (below 100 C), which are already considered as a potential
2.1. Materials and synthesis of Nanoparticle Enhanced Ionic Liquids
candidate for HTF in the solar thermal collector [12] and potential
(NEILs)
replacement of several organic solvents in chemical industry for
reaction and separation systems [13]. The great interests of ILs
The experimental investigated base ionic liquids (ILs) are
are due to their excellent physical and chemical properties includ-
1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide
ing negligible vapor pressure, high thermal stability, high ionic
([C4mim][NTf2]); Chemical Abstracts Service (CAS) registry num-
conductivities, high solvating capability [14], and exposure to air
ber: 174899-83-3; molecular formula: C10H15F6N3O4S2; molecular
and moisture stable [15]. However, thermophysical properties of
weight: 419.36 g/mol, N-butyl-N-methylpyrrolidinium bis{trifluo-
ILs can be enhanced further by dispersing small percentage of
romethyl)sulfonyl} imide ([C4mpyrr][NTf2]); CAS: 223437-11-4;
nanoparticles, which is called Nanoparticle Enhanced Ionic Liquids
molecular formula: C11H20F6N2O4S2; molecular weight:
(NEILs). Bridges et al. [16] have reported higher heat capacity of
422.41 g/mol, N-butyl-N,N,N-trimetylammonium bis(trifluorme
Al2O3 nanoparticles enhanced ILs without detrimental effect on
thylsulfonyl)imide ([N4111][NTf2]); CAS: 258273-75-5; molecular
the thermal stability. Fox et al. [17] have studied different
formula: C9H18F6N2O4S2; molecular weight: 396.37 g/mol, and 1-
nanoparticles effect on thermophysical properties of NEILs and
butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide,
reported that whisker-shaped Al2O3 nanoparticles show highest
([C4mmim][NTf2]) CAS 350493-08-2 molecular formula:
thermal conductivity enhancement. Paul et al. [18,19] have
C11H17F6N3O4S2: molecular weight: 433.39 g/mol. 99% pure ILs
reported the higher forced convection heat transfer coefficients
were purchased from io-li-tec Company (Germany) [24] . The
[18] and deterioration of the natural convection [19] heat transfer
chemical structure of cation and anion of all ILs are shown in Fig. 1.
of NEILs compared to base ILs. Nieto de Castro et al. [20] have stud-
Al2O3 nanoparticles were purchased from Sigma-Aldrich, USA
ied several imidazolium and pyrrolidinium ILs and multi wall car-
[25]. Nanoparticles are c-phase with particle size < 50 nm (TEM),
bon nanotubes (MWCNTs) based IoNanofluids (ionic liquid based
and surface area >40 m2/g (BET). Al2O3 were dispersed in the base
nanofluids) and reported enhanced thermal conductivity and heat
ILs using a vortex mixture (Mini Vortexture from Fisher Scientific)
capacity. Shear thinning behavior and favorable friction reduction
to produce NEILs which was further agitated for 90 min to break
properties of ILs based nanofluids was observed by Wang et al.
any possible agglomeration of nanoparticles. The weight percent-
[21]. They have performed their studies on IoNanofluids containing
age of nanoparticles were 0.5, 1.0, and 2.5. The thermophysical
1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF6])
properties measurements were done just after synthesis of NEILs.
IL and gold nanoparticle. Wang et al. [22] have studied the
SEM image of the Al2O3 nanoparticles and a flow diagram of NEILs
thermophysical properties of 1-hexyl-3-methylimidazolium
preparation is presented in Fig. 2.
 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19 3

[C4mpyrr]+
+
[C4mim]

H3C
+ N N
N
H3C CH3

[C4mmim]+
+
[N4111]

[NTf2]-
Anion
Fig. 1. Chemical structure of cation and anion of all ionic liquids.

Base ionic liquid SEM image of Al2O3 nanoparticles

Vortex mixture Nanoparticle Enhanched Ionic Liquids (NEILs)

Fig. 2. Sysnthesis of NEILs, IL sample, SEM image, vortex mixture, and NEILs sample.

2.2. Rheological behavior, thermal conductivity, and heat capacity ature within accuracy of 0.1 C. A thermal bath (Thermo NESLAB)
measurements was used to maintain constant temperature of the measuring sam-
ple. Temperature accuracy of the bath is within 0.01 C. The vis-
Rheological behavior of base ILs and NEILs was measured using cometer was calibrated by using standard oil.
cone and plate type rotary viscometer (LVDV-II + ProCP, from Thermal conductivity of base ILs and NEILs were measured
Brookfield Engineering Co.) [26]. The sample size required for the using KD2 Pro thermal property analyzer (Decagon Device, USA)
cone and plate arrangement is 1 mL. The cone and plate arrange- [27]. The measurement principle is based on the transient hot wire
ment have a thermal jacket to maintain a constant sample temper- method. The meter has a probe of 60 mm length and 1.3 mm
4 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19

diameter with a heating element and a thermoresistor that is independent runs were performed using reported experimental
inserted vertically into the test sample. The probe is connected to procedures [29].
a microcontroller for controlling and conducting the measure- Dispersion of nanoparticles into ILs was observed by an Olym-
ments. Before using it for ILs and NEILs measurements, the meter pus ix70 inverted microscope. Also, the nanoparticles size distribu-
was calibrated with distilled water and standard glycerin. The tion into NEILs was observed by using the time resolved dynamic
same thermal bath was used to maintain the constant sample light scattering (TRDLS) technique.
temperature.
Heat capacity of ILs and NEILs were measured using Differential 3. Results and discussion
Scanning Calorimetry (DSC Q2000 from TA instruments Inc.) [28].
The sample having an average mass of 12.89 mg was placed in a 3.1. Rheological behavior of NEILs
standard aluminum hermetic pan which is covered with a lid.
Nitrogen was used as the cooling system at a flow rate of 40 ml/ The rheological behavior of base ILs and 0.5, 1.0, and 2.5 wt%
min and DSC was operated at a heating rate of 10 C/min. Three Al2O3 NEILs was measured for different temperature ranging from

1200
200
Base IL
1000 20C 30C 40C 50C
0.5 wt%
150 60C 70C 80C 90C
800 1.0 wt%
Viscosity, cP

Viscosity, cP
2.5 wt%
600 100

400
50
200

0 0
0 2 4 6 8 10 0 5 10 15 20
Shear rate, 1/s Shear rate, 1/s
(a) (c)
100
400
80 350
Base IL
300
0.5 wt%
60
Viscosity, cP

Viscosity, cP

250
1.0 wt%
200 2.5 wt%
40
0.5 wt% [C4mim][NTf2] 150
0.5 wt% [C4mmim][NTf2] 100
20 0.5 wt% [C4mpyrr][NTf2]
50
0.5 wt% [N4111][NTf2]
0 0
0 5 10 15 20 25 290 310 330 350 370
Shear rate, 1/s Temperature, K
(b) (d)
1000

100
Viscosity, cP

10
0.5 wt%, exp. 1.0 wt%, exp.
2.5 wt%, exp. Power (0.5 wt%, equ.)
Power (1.0 wt%, equ.) Power (2.5 wt%, equ.)
1
2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5
T/1000, K-1
(e)
Fig. 3. Rheological behavior of (a) base [C4mmim][NTf2] IL and NEILs at 30 C (b) 0.5 wt% Al2O3 loading of four ILs (c) 1 wt% [C4mmim][NTf2] NEILs at different temperature
(d) viscosity of [C4mmim][NTf2] NEILs as a function of temperature, (e) viscosity of [C4mmim][NTf2] NEILs compared with equation.
 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19 5

20 to 90 C. Fig. 3(a) shows the rheological behavior of [C4mmim] results of viscosity enhancement with nanoparticles concentration
[NTf2] IL and NEILs at 30 C. The base IL shows that the shear vis- were compared with numerous theoretical models.
cosity is independent of shear rate which shows the Newtonian Firstly, the Einsteins model [31] for calculating viscosity of fluid
behavior of the IL. It is clear from Fig. 3(a) that NEILs shows non containing low volume fraction (<0.02) of spherical particles was
Newtonian shear thinning behavior, which means the shear viscos- considered:
ity is higher in low shear rate and shear viscosity decreases with lNEIL
the shear rate increases. Fig. 3(b) represents the rheological behav- 1 2:5/ 2
lBL
ior of 0.5 wt% of four NEILs at 30 C and it is clear that all of the
NEILs show shear thinning behavior. The rheological behavior of Brinkman [32] modified the Einsteins model for fluid contain-
1.0 wt% [C4mmim][NTf2] NEILs at different temperatures is pre- ing high concentration nanoparticles:
sented in Fig. 3(c) and shear thinning behavior observed at all mea-
lNEIL 1
sured temperatures. The same shear thinning behaviors of ILs 3
based nanofluids were observed by Wang et al. [21]. It is also
lBL 1  /2:5
observed that the shear viscosity shows the strong temperature After that, Batchelor [33] modified the Einsteins model with
dependency that is clearer in Fig. 3(d), where the viscosity of base considering the Brownian motion of particles in nanofluids:
[C4mmim][NTf2] IL and NEILs is presented as a function of temper-
lNEIL
ature. The temperature dependent viscosity data of NEILs were 1 2:5/ 6:2/2 4
found to be fit very well with Eq. (1) [30] and is presented in
lBL
Fig. 3(e): where lNEIL and lBL are the viscosity of NEIL and base liquid, and /
1000  B is the nanoparticle volume fraction. Fig. 5 shows that the above
ln l A 1 mentioned model failed to predict the experimental results and
T C
predicted effective viscosity shows lower value compared to the
where l is the shear viscosity, T is the temperature in Kelvin (K) experimental measurements. The models (Eqs. (2)(4)) only consid-
unit, and A, B, and C are the constants. ered the nanoparticles volume fraction and did not take into
Fig. 4 shows the viscosity of four ILs and NEILs at 30 C and it is account other effects like the agglomeration of nanoparticles, liquid
clear that 2.5 wt% NEILs shows much higher viscosity compared to layering on nanoparticles which are common for the NEILs.
the base ILs and [C4mim][NTf2] shows lowest viscosity of all four The present experimental results, then tried to explain consid-
ILs and NEILs. The effective viscosity of [C4mmim][NTf2] NEILs at ering the agglomeration of nanoparticles in NEILs. Nielson [34]
30 C as a function of the nanoparticles volume fraction is pre- proposed the power law model considering the agglomeration
sented in Fig. 5 and it is clear that viscosity enhancement with packing fraction for high concentration of the nanoparticles:
nanoparticle volume fraction is nonlinear. The experimental lNEIL /
1 1:5/e1/m 5
lBL
300 where /m is the maximum particle packing fraction which is typi-
Base IL cally considered 0.605. This model also underpredict the experi-
250 0.5 wt% mental results which can be observed in Fig. 5.
1 wt% Finally the Krieger-Dougherty (K-D) model [35] was considered
200
2.5 wt% to predict the experimental results take into consideration the
Viscosity, cP

maximum packing fraction and effect of variable packing fractions:

150
g/m
lNEIL /
1 a 6
100 lBL /m
where the typical value of the intrinsic viscosity g is 2.5 and /a is
50
the effective volume fraction of aggregates which is given by the
ratio of the radii of aggregate and primary nanoparticles:
0
[C4mim][NTf2] [C4mmim][NTf2] [C4mpyrr][NTf2] [N4111][NTf2] a 3D
a
/a / 7
Fig. 4. Viscosity of four base ILs and NEILs at 30 C. a
where aa and a are the average radii of the aggregate and primary
nanoparticles respectively, D is the fractal index, and the typical
12 value of fractal index is 1.8 for nanofluids. Finally, the model can
Einstein model
be rearranged as:
Batchelor model
Relave viscosity, NEIL/BL

10

1:5125
Brinkman model
lNEIL / aa 1:2
Nielson model 1 8
8
K-D model lBL 0:605 a
Experimental data
6 The experimental results were fitted with Eq. (8) at aggregation
 
factor aaa 21:5 and are presented in Fig. 5. In literature, aggrega-
4 tion factor was observed up to 16 for nitrate-silica nanofluids [36].
The aggregation of NEILs was also observed by Fox et al. [16], and
2 they found that the [C4mmim][NTf2] + Al2O3 NEILs average cluster
size was average 100 lm where the primary particle size was
0 <50 nm. For better observation of the experimental results, the
0 0.2 0.4 0.6 0.8 1 1.2
Volume fracon, % optical image of 0.5 wt% NEILs was also presented in Fig. 6. It is
clear that the nanoparticles have agglomerated in ILs. The same
Fig. 5. Effective viscosity as a function of nanoparticle volume fraction. particle agglomeration of NEILs was also observed by the DLS par-
6 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19

understand the exact mechanism of thermal conductivity enhance-

ment, the experimental results were compared with the conven-
tional models for thermal conductivity prediction. The Maxwell
model [40] for spherical nanoparticles with homogeneous suspen-
sion was considered:
kNEIL kn 2kBL  2/kBL  kn
9
kBL kn 2kBL /kBL  kn
where kNEIL , kBL , kn 36 W=mK are the thermal conductivity of NEIL,
base IL, and Al2O3 nanoparticles respectively. U is the nanoparticle
volume fraction. This model underpredicts the experimental results
because it only considers the nanoparticles volume fraction and
thermal conductivity of base liquid and nanoparticles.
50m The Bruggeman model [41] predicted little bit more enhance-
ment than the Maxwell model because it considers the clustering
of nanoparticles. The model for calculating the thermal conductiv-
Fig. 6. Optical image of 0.5 wt% NEILs. ity of nanofluids is:
1 kBL p
kNEIL 3/  1kn 2  3/kBL  D 10
4 4
"
2
#
kn kn
D 3/  12 2  3/2 22 9/  9/2
kBL kBL
11
The aggregation of nanoparticles was considered to predict the
effective thermal conductivity [42] and the aggregation factor
a 
a
a
21:5 was considered the same as the shear viscosity pre-
dicted. Maxwell model can be rearranged with the aggregation
45 sec factor:
141 sec kNEIL ka 2kBL  2/a kBL  ka
201.9 sec 12
kBL ka 2kBL /a kBL  ka
where ka is the aggregates thermal conductivity
0 50 100 150 200 The aggregates thermal conductivity was calculated from the
correlation:
Average Particle Size, nm (
ka 1 kn
Fig. 7. Nanoparticle size with respect to time. 3/in  1 31  /in  1
kBL 4 kBL
"
2 #1=2 9
kn kn =
ticle size measurement in Fig.7. It was observed that the average 3/in  1 31  /in  1 8
hydrodynamic radii of nanoparticles increase with time. It is clear kBL kBL ;
that the particles have a huge tendency in agglomerate and this    
D3
might be one reason for the enormous enhancement of viscosity. where /in aaa is the aggregates solid volume fraction.
However, including this phenomenon, there may be other vari- Although considering clustering and aggregation give higher
ables like the interaction of ILs and nanoparticles surface needed effective thermal conductivity compared to the Maxwell model,
to take into consideration for further discussion. it is clear from Fig. 8(c) that still could not predict the experimental
effective thermal conductivity. However, the predicted and exper-
3.2. Effective thermal conductivity of NEILs imental results are consistent with previously studied thermal
conductivity measurements [20].
The thermal conductivity of all base ILs and NEILs was mea- The interfacial layer of nanoparticles in NEILs was considered to
sured within 1070 C temperature ranges. Fig. 8(a) shows the predict the effective thermal conductivity of NEILs by Murshed
thermal conductivity of four ILs and NEILs at 30 C and it is clear et al.s model [43]:
that 2.5 wt% NEILs shows the highest enhancement of thermal
conductivity. The enhanced percentage is clearer in Fig. 8(b) kn  klr /klr 2c21  c2 1 kn 2klr c21 /c2 klr  kBL kBL 
kNEIL
where, the effective thermal conductivity of [C4mmim][NTf2] NEILs c21 kn 2klr  kn  klr /c21 c2  1
is presented as a function of temperature. It is clear from Fig. 8(b) 14
that the thermal conductivity increases with the wt% of nanoparti-
cles over the measured temperature range and there is a weak where klr is the thermal conductivity of interfacial layer which
temperature dependency observed. From all of the NEILs the max- would be kBL < klr < kn ; here klr 3kBL considered.
imum enhancement was observed 11% for 2.5 wt% loading of h
nanoparticles. The possible mechanisms of thermal conductivity c1 15a
a
enhancement of traditional nanofluids are Brownian motion of
nanoparticles, the nature of heat transport to the nanoparticles h
[37], liquid layering in liquid/nanoparticle surface interface [38],
c1 1 15b
2a
and the effect of nanoparticle cluster and structure [39]. To
 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19 7

0.14 simulations of nanofluids containing ruthenium nanoparticle in

Base IL ILs were performed by Pensado et al. [44] and they reported that
Thermal conducvity, W/m.K

0.5 wt% nanoparticles are in contact with the anion and cation of ILs. Com-
0.135
1.0 wt% plex interaction of IL and Al-O surface was observed by the theoret-
2.5 wt% ical model [45].
0.13
3.3. Heat capacity
0.125
The heat capacity of all four ILs and 0.5, 1.0, and 2.5 wt% NEILs
was measured within the temperature ranges 25345 C. Fig. 9(a)
0.12 shows the heat capacity of four ILs and NEILs at 30 C and it is clear
that 2.5 wt% NEILs shows much higher heat capacity compared to
0.115 base ILs. The heat capacity of [C4mmim][NTf2] base IL and NEILs
[C4mim][NTf2] [C4mmim][NTf2] [C4mpyrr][NTf2] [N4111][NTf2] over 25345 C with an interval of 10 C is presented in Fig. 9(b).
It is clear from Fig. 9(b) that the heat capacity of NEILs is much
(a)
higher than the base IL over the measured temperature range
1.1 and the heat capacity increases almost linearly with temperature.
Eecve thermal conducvity rao

The average enhancements of heat capacity are 9%, 28%, and

62% of 0.5, 1, and 2.5 wt% NEILs respectively. Measured heat
capacities of NEILs were compared with the existing classical the-
1.05 oretical model of heat capacity for a mixture where base IL and
nanoparticles are assumed at thermal equilibrium [46]:
/n qn C p;n /BL qBL C p;BL
cp;NEIL 16
/n qn /BL qBL
0.5 wt%
1
1.0 wt%
where cp;NEIL , cp;n 0:791 J=g  K, and cp;BL are the heat capacity of
2.5 wt%
NEILs, nanoparticles, and base IL respectively, / is the nanoparticles
volume fraction. qn and qBL are the density of nanoparticles and
0.95 base IL respectively. Most of the previous studies for water based
280 290 300 310 320 330 340 350
nanofluids show lower heat capacity and are predicted well by
Temperatrure, K
(b)
3
1.1
Base IL 0.5 wt% 1.0 wt% 2.5 wt%
2.5
Thermal conducvity rao

Heat capacity, J/g.K

1.05 2

1.5

1 Experimental data 1
Maxwell's model
Bruggeman's model 0.5
Aggregaon model
Murshed et al's model
0.95 0
0 0.2 0.4 0.6 0.8 1 1.2 [C4mim][NTf2] [C4mmim][NTf2] [C4mpyrr][NTf2] [N4111][NTf2]
Volume fracon, %
(a)
(c)
3.5
Fig. 8. (a) Thermal conductivity of all four ILs and NEILs, (b) thermal conductivity of
[C4mmim][NTf2] NEILs as a function of temperature and (c) thermal conductivity as 3
function of nanoparticles volume fraction.
Heat capacity, J/g.K

2.5

where h is the interfacial layer thickness, taken into consideration 2

h 2 nm and a 20 nm. As of Fig. 8(c) the enhancement of thermal
1.5
conductivity of NEILs is predicted well with the interfactial layer
model. Nieto de Castro et al. [20] also used the Mursheds model 1
to predict the thermal conductivity of [C4mim][NTf2] and multi wall Base IL 0.5 wt%
carbon nanotubes (MWCNT) considering h 1 nm and klr 1:2kBL 0.5 1.0 wt% 2.5 wt%
and they found reasonably good agreement with the experimental
results. Although the interfacial layer model predicted well the 0
0 40 80 120 160 200 240 280 320 360
experimental thermal conductivity with arbitrary interfacial layer Temperature, C
thickness and thermal conductivity, there may be other parameter
like complex interactions of nanoparticles surface with ILs which
(b)
should be considered. In literature, there is evidence of strong Fig. 9. (a) Heat capacity of all ILs and NEILs at 30 C, (b) heat capacity of [C4mmim]
interactions of nanoparticles and ILs [44,45]. Molecular dynamic [NTf2] NEILs as a function of temperature.
8 T.C. Paul et al. / Applied Thermal Engineering 110 (2017) 19

the theoretical model [47]. But based on the equation, the predicted accomplished under Contract No. DEAC09-08SR22470 with the U.
heat capacity of NEILs shows slightly lower value than the base IL S. Department of Energy. The author would like to thank Dr. Niru-
whereas the experimental measured heat capacity of NEILs shows pam Aich of Dr. Navid Saleh group for helping in DLS measure-
much higher value compared to the base ILs. That means the model ments and Dr. Fang Yang from Dr. Guiren Wang group for
failed to predict the significant enhancement of heat capacity of helping in optical image.
NEILs and more sophisticated investigations will be required to
explain these enhancements. Meanwhile, the significant enhance-
ment in heat capacity of NEILs was observed by Bridges et al. [17] References
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