Energy Conversion and Management 142 (2017) 215–229

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Stability, rheology and thermal analysis of functionalized

alumina- thermal oil-based nanofluids for advanced cooling systems
Suhaib Umer Ilyas a, Rajashekhar Pendyala a,⇑, Marneni Narahari b, Lim Susin c
a
Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
b
Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
c
Vantage Oilfield Solutions Sdn. Bhd., Suite A-8-06, Block A, Oasis Square, No. 2 Jalan PJU 1A/7A, Ara Damansara, 47301 Petaling Jaya, Selangor, Malaysia

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

Article history: Thermal oils are widely used as cooling media in heat transfer processes. However, their potential has not
Received 6 December 2016 been utilised exquisitely in many applications due to low thermal properties. Thermal oil-based nanoflu-
Received in revised form 26 January 2017 ids are prepared by dispersing functionalized alumina with varying concentrations of 0.5–3 wt.% to
Accepted 31 January 2017
enhance thermal properties of oil for advanced cooling systems. The oleic acid coated alumina is prepared
and then dispersed in the oil to overcome the aggregation of nanoparticles in base fluid. The surface char-
acterizations of functionalized nanoparticles are performed using different analysis such as XRD, EDS,
Keywords:
SEM, TEM and FTIR. Dispersion behaviour and agglomeration studies are conducted at natural and
Alumina
Dispersion
functionalized conditions using different analysis to ensure long-term stability of nanofluids. In addition,
Functionalization rheological behaviour of non-Newtonian nanofluids is studied at high shear rates (100–2000 s
1).
Nanofluids Effective densities and enhancement in thermal conductivities are measured for different nanofluids con-
Rheology centrations. Specific heat capacity is measured using Differential Scanning Calorimetry. The correlations
Stability are developed for thermophysical properties of nanofluids. Thermogravimetric analysis is performed
Thermal oil with respect to temperature and time to exploit the effect of the addition of nanoparticles on the
degradation of nanofluids. Significant improvement in the thermal properties of oil is observed using
highly stable functionalized alumina nano-additives.
Ó 2017 Published by Elsevier Ltd.

1. Introduction thermal characteristics but features associated with the mass

In the modern energy-deficient era, studies are being carried
out to explore renewable, conservative, economical and promising
ways to meet cooling requirements and thermal management dur-
ing heat transfer processes. Commercial heat transfer fluids are not
capable of properly dissipating heat from the system. Thermal oil is
used as a cooling media in many heat transfer applications such as
nuclear cooling, chillers, solar collectors, heat exchangers, dis-
tributer transformers, engine and vehicle thermal management
and other high heat flux cooling appliances [1–4]. Conventional
thermal oils can operate at higher temperatures but possess weak
thermal properties. The introduction of nanoparticles in heat trans-
fer oils to improve thermal properties, an idea pioneered by Choi
[5], is a major step towards utilising the full potential of thermal
oils. Nanofluids are one of the emerging technologies due to
promising and remarkable outcomes in heat transfer applications.
The addition of nanoparticles in base fluid not only enhances
⇑ Corresponding author.
E-mail address: rajashekhar_p@utp.edu.my (R. Pendyala).
transfer, chemical reactivity, antibacterial activity and controlled
drug release are also revolutionised. Remarkable outcomes have
been found in the applications of nanofluids in pharmaceuticals,
refrigeration, mini-channel heat sinks, microelectronics, fuel cells
and hybrid-power engines [6,7].
Nanoparticles of range 1–100 nm with high thermal conductiv-
ities are dispersed in the conventional heat transfer fluids to
improve their heat transfer properties. Nanoparticles possess
remarkable properties due to large surface area and smaller size
[8]. Advanced cooling systems require high thermal properties
especially thermal conductivity which leads to improvement in
heat transfer rate. Improved thermal properties of nanofluids can
imply the reduction in equipment size, the increase in life-cycle
of working fluid and improvement in efficiency of the application.
In a recent study by Li et al. [9], SiC-based nanofluids were
prepared in diathermic oil for high-temperature applications. The
increase in thermal conductivity was observed up to 7.36% using
0.8 vol.% of nanofluids. Amiri et al. [10] investigated the
thermal and rheological characteristics of multi-walled carbon
nanotubes based nanofluids in transformer oil. The nanotubes

http://dx.doi.org/10.1016/j.enconman.2017.01.079
0196-8904/Ó 2017 Published by Elsevier Ltd.
216 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Nomenclature
Cpbf specific heat capacity of base fluid (kJ/kg °C)
Cpnf specific heat capacity of nanofluid (kJ/kg °C)
Cpnp specific heat capacity of nanoparticle (kJ/kg °C)
kbf thermal conductivity of base fluid (W/m °C)
knf thermal conductivity of nanofluid (W/m °C)
knp thermal conductivity of nanoparticle (W/m °C)
mbf mass of base fluid (kg)
mnp mass of nanoparticle (kg)
t time (s)
T temperature (°C)
were functionalized with hexylamine for better stability. Natural
and forced convection of nanofluids were examined and an
increase in heat transfer coefficient was observed up to 23% and
28%, respectively, at 0.005 wt. fraction of nanofluids. In a recent
study by Chen et al. [11], the influence of particle size of nanopar-
ticles on the direct absorption solar collector (DASC) during
photo-thermal conversion was experimentally investigated using
gold-based nanofluids. Nanofluids indicated higher photo-
thermal conversion as compared to water due to localised surface
plasmon resonance effect of gold nanoparticles. In another study
[12], TiO2-water-based nanofluids were used in staggered and
inlined pin fin heat sinks at different Reynolds number. A
significant heat transfer enhancement up to 37.78% was found as
compared to distilled water.
Alumina is an amphoteric oxide of aluminium and exhibits
polar characteristics [13]. It is one of the widely used nanoparticles
in the field of nanofluids [14]. Extensive literature is available on
the numerical investigations of alumina-based nanofluids in
numerous applications such as photovoltaic thermal systems
[15], car radiator [4], sinusoidal-corrugated channels [16], jet
impingement cooling system [17], direct absorption solar collector
[18] and forced convection in nuclear reactor [19]. Ho et al. [20]
investigated the thermal characteristics of alumina-water-based
nanofluids up to 1 wt.% in a mini-channel heat sink during natural
circulation loop. It was found that average heat transfer effective-
ness was improved by 22% and 62% at heating and cooling sections,
respectively. In a recent study [21], alumina-synthetic oil- based
nanofluids were numerically investigated in parabolic trough col-
lector absorber tube at different particle loading (up to 5 vol.%).
Heat transfer coefficient was found to be improved during turbu-
lent mixed convection with non-uniform heat flux. Wang et al.
[22] prepared alumina-based nanofluids in engine oil and pump
oil with different concentrations up to 7.4%. The thermal conduc-
tivity of the fluids was found to be increased up to 30% in engine
oil-based nanofluids and up to 20% in pump oil-based nanofluids.
Xie et al. [23] prepared alumina-based nanofluids in pump oil.
Thermal conductivity enhancement was found up to 39% at 5 vol.
% particle concentration. Experimental investigations on the oil-
based nanofluids are getting attention and application of nanopar-
ticles in oil is found to be very promising. Some of the studies on
oil-based nanofluids are tabulated in Table 1.
Extensive literature was published on the numerical and exper-
imental investigations on the improved heat transfer behaviour in
nanofluids. However, few studies were carried out on the stability
and rheological behaviour of nanofluids. Recent reviews have
strongly highlighted on the necessity of experimental investiga-
tions on the stability of nanofluids [33]. Knowledge of stability
and rheological behaviour of nanofluids are very critical in decid-
ing their suitability for conductive and convective heat transfer
applications [8]. It is believed that viscous transport properties
Greek symbols
uP weight fraction of nanoparticles (–)
uv volume fraction of nanoparticles (–)
qbf density of base fluid (kg/m3)
qnf density of nanofluid (kg/m3)
qnp density of nanoparticle (kg/m3)
s shear stress (Pa)
lbf viscosity of base fluid (Pa s)
lnf viscosity of nanofluid (Pa s)
c shear rate (1/s)
are as significant as thermal transport properties in engineering
systems. The pumping power of a fluid, a critical economic interest,
is greatly influenced by pressure drop which is dependent on the
viscous transport characteristics. From the thermal application
point of view, the working fluid should possess high thermal con-
ductivity and low viscosity. A slight improvement in one of the
thermophysical property of the heat transfer fluid can lead to a
huge impact on the heat flux requirement, the design of the appli-
cation and the initial capital investment. Dispersion behaviour of
nanoparticles inside the liquid and the stability of nanofluids is
an important issue that must be well addressed before any indus-
trial application [34]. The stability of nanofluids is often termed as
the validity of nanofluids. Researchers have used different pro-
cesses to stabilise nanofluids such as mechanical mixing, the addi-
tion of surfactants, pH adjustment and functionalization of
nanoparticles.
Functionalization of nanoparticles has the tendency to attach
functional groups on the surface of the nanoparticle. The method
is widely used to reduce or control the van der Waals forces pre-
sent in abundance on the particle surface due to their smaller size
and large surface area. These attractive forces are the main reason
of agglomeration among nanoparticles which causes sedimenta-
tion [33]. Mechanical mixing, such as ultrasonication, breaks the
large agglomerates into primary particles temporary. This method
of stabilisation of nanofluids is not considered as the long term
solution. After a certain period of time, the particles tend to come
closer and agglomerate again due to the presence of attractive
forces on their surfaces. There are several studies available on
the addition of dispersants or surfactants agents to reduce the sur-
face tension and increase the stability of nanofluids. Generally, a
lot of surfactant is required to completely cover the particles,
which affects the thermophysical properties of the nanofluids.
There are studies available in the literature which reports the fail-
ure of surfactants during operations at high-temperature opera-
tions [35,36].
Yarmand et al. [37] prepared functionalized graphene by
introducing carboxylic group on graphene by acid treatment to
change the polarity of nanoparticles and then dispersed in water.
Nanofluids showed high stability after treating with mechanical
and chemicals dispersing technique. Choi et al. [38] prepared
Al2O3 and AlN-based nanofluids in transformer oil at different par-
ticle loading up to 4 vol.%. Oleic acid was added as the surfactant to
stabilise nanoparticles. It was observed that excess amount of sur-
factant caused the negative impact on the viscous and thermal
transport properties of nanofluids. In a recent study by Colangelo
et al. [39], alumina nanoparticles of 45 nm in diatherm oil (Thermi-
nol 66) was dispersed with different volumetric concentrations of
0.3–1%. Oleic acid was introduced as the surfactant with different
concentrations. Thermal and viscous properties were investigated
at different surfactant conditions. It was found that surfactant
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229 217

Table 1
Investigations on the oil-based nanofluids using different nanoparticles.

Investigator Nanomaterial Base fluid Loading Dispersion technique Remarks

Choi et al. [24] MWCNT (25 nm, Synthetic Up to 1 vol.% – 160% enhancement in thermal conductivity by
length 50 lm) poly (a- dispersing 1 vol.% of MWCNT
olefin) oil
Amiri et al. [25] MWCNT (<30 nm, Turbine oil 0.001–0.1 vol.% Nanoparticle Stability, rheology and laminar convective heat
length 5–15 lm) functionalization transfer were investigated. Nanofluids showed
(hexylamine) stability over 6 months
Liu et al. [26] MWCNT (20–50 nm) Engine oil 1–2 vol.% Ultrasonication and 30% enhancement in thermal conductivity was
N-hydroxysuccinimide found by dispersing 2 vol.% CNT
(5 vol.%)
Farzin et al. [27] TiO2 Turbine oil 0.1–0.5 vol.% Ultrasonication Heat transfer coefficient increased after dispersing
nanoparticles. The performance index increased up
to 1.15
Razi et al. [28] CuO (50 nm) Base-oil (sN- 0.2–2 wt.% Ultrasonication Nanofluids were found to be stable after 24 h. Heat
500) transfer enhanced in flattened tubes up to 26.4%
and performance index 1.056 for 2 wt.% nanofluid
Heris et al. [29] CuO (30–50 nm), TiO2 Turbine oil 0.1–0.5 vol.% High-speed mixer and Nanofluids were found to be stable for at least two
(10–30 nm), and c- ultrasonication weeks. Higher Nusselt number values were found
Al2O3 (50 nm) as compared to pure turbine oil. CuO-oil-based
nanofluids (0.5 vol.%) exhibits maximum
performance index (1.32)
Fontes et al. [30] Diamond (6 nm), Transformer 0.005–0.05 vol.% High-pressure Effective thermal conductivity and effective
MWCNT (5–15 nm, oil homogenizer viscosity increased up to 27% and 25%, respectively
length 10–50 lm)
Kole and Dey [31] CuO (40 nm) Gear oil 0.5–2.5 vol.% Oleic acid surfactant Increasing vol. fraction of nanoparticles in gear oil
and ultrasonication increased effective viscosity by 3 times
Taha-Tijerina et al. [32] Hexagonal Boron Transformer 0.01–0.1 wt.% Ultrasonication 76% enhancement in thermal conductivity for
Nitride (2D) oil 0.1 wt.% of nanofluid

increased the stability of nanofluids. However, the marginal incre- Table 2

ment in viscosity was observed in nanofluids by the addition of
oleic acid.
In the present work, oil-based nanofluids are prepared and
investigated using alumina nanoparticles. The dispersion beha-
viour and thermal analysis of functionalized alumina nanoparticles
in thermal oil is not found in literature. Alumina is functionalized
using oleic acid and complete nanoparticle characterizations are
performed. To fully understand the potential capabilities of func-
tionalized alumina/oil-based nanofluids, rheology and thermal
analysis are carried out, which are not available in previous stud-
ies. The correlations are developed for thermophysical properties
as a function of temperature and nanoparticle concentration. Ther-
mogravimetric analysis is performed to investigate the effect of
nanoparticles on the degradation and life-cycle of oil. The prepara-
tion of novel nanofluids with high stability is expected to gain
more attraction for advanced industrial cooling applications.
2. Materials and methods
2.1. Materials
Aluminium oxide (alpha phase  90%) nanoparticles with aver-
age particle size of 40 nm and 99.5% purity are acquired from MK
Nano, Canada. The impurities contain very low amount of Ca
(1.6 ppm), Co (0.8 ppm), Fe (0.2 ppm), Na (<300 ppm) and Si
(3.5 ppm). Thermal oil is acquired from a commercial brand which
consists of highly refined mineral oil. The thermal oil consists of
C15 - C50 hydrocarbons in the range of 70–99 wt.%. The character-
istics of commercial thermal oil and alumina nanoparticles are
given in Table 2. Other laboratory reagents required for functional-
ization of alumina such as oleic acid, o-xylene, toluene and ethanol
are acquired from Sigma-Aldrich Co., Selangor, Malaysia.
2.2. Functionalization of alumina
The introduction of functional groups on the surface of
nanoparticles helps to reduce attractive forces among nanoparti-
Properties of thermal oil and nanoparticles.
Properties Thermal oil Alumina
Colour Colourless to mild yellow White powder
Density (kg/m3) at15 °C 8545 3965
Viscosity (m2/s) at 40 °C 4  10
6 –
Thermal conductivity (W/m2 °C) 0.133 36.2
at 35 °C
Specific heat capacity (kJ/kg °C) 1.970 0.815
at 45 °C
cles which origin agglomeration process. Alumina nanoparticles
exhibit polar characteristics while thermal oil exhibits non-polar
behaviour. The polar and non-polar components are hard to dis-
perse in each other. The polarity of the nanoparticles can be chan-
ged using surface modification technique to disperse in non-polar
base fluids. Limited studies are found on dispersion behaviour of
surface modified nanoparticles in non-polar base fluids. Prepara-
tion of oleic acid modification of nanoparticles such as zinc oxide
[40], silver [41], silica [42] and iron oxide [43] for different
applications are found in the literature. The only study found in
the literature on the surface modification of alumina was by Lash-
anizadegan et al. [13]. They dispersed oleic acid modified alumina
(15 nm) in methyl metacrylate, butyl acrylate and styrene and
reported improved stability in non-polar base fluids.
Surface modification of alumina nanoparticles is executed by
the functionalization of the carboxylic group on the surface of
nanoparticles using oleic acid. At first, oleic acid (3 ml) and o-
xylene (100 ml) are stirred with a magnetic stirrer for 30 min at
a constant temperature of 50 °C. The acid treatment process is per-
formed by adding 2 g of alumina nanopowder in oleic acid into the
oleic acid/o-xylene solution to react for 90 min at 50 °C under con-
stant stirring conditions. The mixture is then sonicated for 2–3 min
in an ultrasonic homogenizer (Biologics Inc. 150V/T, 20 kHz) to
ensure maximum coating of carboxylic function on the surface of
nanoparticles. The particles are collected using centrifuge
(LaboGene 1580R) at 4000 rpm for one hour. The collected
218 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229

particles are then washed multiple times using toluene to ensure electron microscopy (TEM) to inspect the functional groups, crys-
the removal of free ions and unreacted components present inside tallinity, elemental analysis, aggregation, and ultrastructure,
the functionalized nanoparticle. The collected particles are mixed respectively, of pure and functionalized alumina nanoparticles.
in toluene using ultrasonic mixing followed by centrifugal separa- Stability of nanofluids is investigated in a batch sedimentation
tion. The collected particles after washing are dried in a vacuum apparatus for natural and functionalized nanofluids with various
oven (Memmert, VO400) at 50 °C and 500 mbar for 8 h. Character- concentrations. Rheological properties of nanofluids are studied
izations are performed for the resultant powder to ensure the pres- at high shear rates and different concentrations. Thermal charac-
ence of functional groups on the nanoparticles. teristics of nanofluids such as effective density, effective thermal
conductivity, and specific heat capacity are experimentally investi-
2.3. Preparation of nanofluids gated. Correlations are developed for all thermophysical properties
based on experimental data. Experimental data is compared with
Nanofluids are prepared using two-step method. Alumina theoretical models by converting the weight fractions into the vol-
nanoparticles at natural and modified conditions are dispersed into umetric fraction using Eq. (1). Thermogravimetric analysis is per-
the thermal oil. Nanofluids are prepared in different weight percent- formed at a wide temperature range to examine the effect of
ages in the range of 0.5–3 wt.%. Nanoparticles are dispersed in ther- nanoparticle on the degradation of thermal oil.
mal oil using the ultrasonic bath (Bandelin, Sonorex Digitec) and
ultrasonic homogenizer (Biologics Inc. 150V/T, 20 kHz). Ultrasonic 3. Results and discussion
homogenizer shows better nanoparticles dispersion as compared
to the ultrasonic bath. All nanofluids are kept under ultrasonication 3.1. Characterization of functionalized nanoparticle
for 25 min at 70% power and 30% pulse. The probe-type ultrasonic
homogenizer generates heat during operation because all energy 3.1.1. Infrared spectroscopy
is dispersed into the nanofluid. Therefore, a cooling water circula- Fourier transform infrared (FTIR) analysis (Perkin Elmer) is per-
tion bath (Hahnshin, HS 3005N) is used to dissipate heat from the formed to confirm the adsorption of the oleic acid group on the
nanofluids during ultrasonic homogenization. alumina surface. IR spectrums of pure alumina and functionalized
Few studies are found in the literature on the addition of oleic alumina are compared in Fig. 1. The typical AlAOAAl bending
acid as the surfactant in oil-based nanofluids to stabilise nanopar- vibration is detected at 1128.41 cm
1 and 1154.5 cm
1 for pure
ticles. Generally, an excess amount of surfactant is required to alumina and functionalized alumina, respectively [52]. Two sharp
completely stabilise nanoparticles in the base fluid. The addition bands are clearly seen at 2929.5 cm
1 and 2857.7 cm
1, which
of the third component in nanofluid affects thermophysical proper- are accredited to the asymmetric and symmetric CH2 stretch,
ties especially viscosity of the nanofluid. The grading of thermal oil respectively. These bands indicate the presence of carboxylic group
for different applications depends on the viscosity index of oil. A on the surface of alumina. The CH2 stretch is considered as one of
slight change in viscosity of the oil can make it unsuitable for the the main proof of presentation of acid groups on the metal surface.
desired application. Studies have mentioned negative aspects of Similar results for IR analysis are found in the literature for pure
surfactants especially during high-temperature operations [44]. oleic acid [53] and oleic acid attachment on magnetite nanoparti-
The alternative solution is to attach the desired functional group cles [54]. The OAH in-plane band of carboxylic acid is observed
with the particle using surface modification method.
An extensive literature review has revealed that many studies
have expressed the preparation of nanofluids in volumetric con-
centrations. It should be addressed that nanoparticle density is
one of the main factors towards the stability of nanofluids and is
significantly affected by interactions and agglomeration among
particles [45]. Therefore, nanofluid concentrations expressed in
weight fractions are more suitable and accurate as compared to
volumetric expressions. Available conventional theoretical models
for the estimation of thermophysical properties usually cannot
estimate explicit properties of nanofluids due to the change in
nanoparticle density because of the interactive forces among
nanoparticles. There are several studies, which have concluded
that theoretical models can give qualitative agreements with the
experimental values but not with precision [46–49]. Available
conventional thermophysical models have used volumetric
concentrations. The conversion equation of concentration from
volumetric to weight fractions, used in many investigations
[9,36,50,51], is shown in Eq. (1).

mnp =qnp
uv ¼ ð1Þ
mnp =qnp þ mbf =qbf

2.4. Characterizations and analysis

Different characterization techniques are applied to understand

the surface modification of alumina nanoparticles. The characteri-
zation techniques include Fourier transform infrared spectroscopy
(FTIR), X-ray powder diffraction (XRD), Energy Dispersive X-ray Fig. 1. FTIR spectra of alumina nanopowder: (a) natural state (b) functionalized
(EDX), Scanning electron microscopy (SEM), and Transmission with oleic acid.
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
at 1466 cm
1. Generally, peaks of C@O stretch band in pure oleic
acid exhibits in the range of 1700–1730 cm
1, which are found
to be absent in the functionalized nanoparticles. However, two
new bands are exhibited in the spectrum of the functionalized alu-
mina at 1585.5 cm
1 and 1643.6 cm
1, which are attributed to the
asymmetric and symmetric C@O stretch. A similar trend was found
in the literature [54]. It can be explicated that the carboxylic acid
functional groups are attached symmetrically and at an angle on
the surface of alumina nanoparticles. Similar behaviour was
observed in the literature [55] for silver, copper and aluminium
nanoparticles. IR analysis has confirmed that carboxylic acid is suc-
cessfully chemisorbed on alumina surface as the carboxylates.
OAH stretching spectrums are observed in natural and functional-
ized conditions of nanoparticles at 3436.23 cm
1 and
3440.55 cm
1. This is attributed to the presence of humidity in
the air as the IR analysis is performed in open-air. The smaller size
and large surface area of nanoparticles result in quick adsorption of
water on the particle surface from the atmosphere [52].
Interactions among carboxylates and metals are categorised
into four types; chelating bidentate, bridging bidentate, monoden-
tate and ionic interaction [56,57]. The type of interaction between
the carboxylates head and metal atom can be discerned by the
difference (D) between IR bands wave number of (COOA)symmetric
and (COOA)asymmetric [54]. The small difference (D < 110 cm
1),
medium difference (D = 140–190 cm
1) and large difference
(D = 200–320 cm
1) are ascribed to the chelating bidentate,
bridging bidentate, and monodentate interaction. In this study,
the difference is found to be D = 1643.6–1585.5 cm
1 = 58.1 cm
1
which are attributed to the chelating bidentate interaction
between Al atom and COOA group and exhibiting covalent
bonding. A schematic structure of the functional group attached
to alumina nanoparticles is shown in Fig. 2.
3.1.2. Crystallinity of nanoparticle
The introduction of functional groups can alter the crystallinity
index of the particles which can give negative impact on the ther-
mophysical properties of nanofluids. X-ray diffraction (XRD) anal-
ysis can be used to investigate phase distribution, crystalline
structure, lattice strain fields and stored defect content [58,59].
To evident any change in the crystalline structure of nanoparticle,
XRD analysis (Bruker, D8 Advance) is performed. Fig. 3 shows the
XRD patterns of functionalized alumina nanoparticles. The analysis
shows major XRD reflections at 45.43° and 66.76° exhibiting the
crystalline structure of alumina nanoparticles. The high intensity
at these major reflections indicates the presence of alpha-phase
crystalline structure. The reflections of any other alumina
transition phases are not detected and all reflections are accredited
to the pure alpha-phase alumina. This analysis is reported in
previous studies and obtained results are in agreement with the
literature [13,60–62]. All XRD analysis proved that the surface
modification of alumina nanoparticles does not alter crystallinity
of nanoparticles.
3.1.3. Elemental analysis
The energy dispersive X-ray spectroscopy (Phenom Pro X) is
performed to identify the elemental compositions in pure and
functionalized alumina. This technique can be applied to investi-
gate the properties of a broad range of chemicals. However, light
elements (atomic number, Z < 11) cannot be detected such as
hydrogen (Z = 1) or helium (Z = 2). Elemental concentrations of alu-
Fig. 2. Schematic interaction between the COOA group of oleic acid and the aluminium atom.
219
Fig. 3. XRD reflections of functionalized alumina nanoparticles.
minium, oxygen and carbon are investigated using EDX at ten dif-
ferent positions of nanoparticle samples. Average weight
concentrations of both nanoparticles are compared in Fig. 4(a).
The average deviations are shown in y-error bars. EDX spectra of
one of the readings for both samples are compared in Fig. 4(b). A
small average percentage of carbon (0.18%) is found in pure alu-
mina which is attributed to the impurities in the sample. The aver-
age weight concentration of carbon is found to be 15.94% in the
samples of functionalized alumina. The average concentration of
oxygen reduces from 51.9% to 36.48%. A slight change in average
aluminium concentration from 47.92% to 47.58% is observed. The
analysis confirms the high purity of pure alumina nanoparticles
and the presence of carboxylic group on the surface of functional-
ized alumina.
3.1.4. Electron microscopy
Electron microscopy is a useful technique to characterise mate-
rial properties such as morphology and crystalline structure. SEM
(Phenom Pro X) and TEM (Zeiss, 200 kV) analysis are performed
to investigate the morphological structure of alumina. SEM images
of pure and functionalized alumina are shown in Fig. 5(a) and (b),
respectively. It is observed that alumina nanoparticles in pure and
functionalized conditions exhibited big agglomerates at micron
level. TEM images confirm the primary size and crystalline struc-
ture of nanoparticles. Fig. 5(c) and (d) represents the agglomerated
pure alumina and functionalized alumina nanoparticles, respec-
tively. The morphology and crystallinity of nanoparticles are found
to be in agreement with XRD analysis.
3.2. Stability of nanofluids
3.2.1. Dispersion behaviour of nanofluids
The dispersion behaviour of nanoparticles in the base fluid has
significant importance towards nanofluid stability. Settling charac-
teristics of alumina-based nanofluids are investigated in a batch
sedimentation apparatus using conventional visualisation tech-
nique [63–66]. The photographs are taken at different time inter-
vals for alumina nanofluids in natural and functionalized
conditions at room temperature. Both types of nanofluids are ultra-
sonicated using ultrasonic homogenizer for 25 min. The low con-
centrations of natural Al2O3-based nanofluids, 0.5 wt.%, exhibit
220 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 4. (a) Elemental weight concentrations in pure and functionalized alumina and
(b) EDX spectra of pure and functionalized alumina.
dispersed-type and high concentrations, 0.75–3 wt.%, show floccu-
lated settling behaviour and all nanoparticles settle down within
4 days. The functionalized nanoparticles exhibit excellent disper-
sion behaviour. All samples of functionalized nanofluids do not
show any sediment for over a month. A slight sediment for a high
concentration of functionalized alumina at 3 wt.% is observed at
the bottom of the nanofluid sample after four weeks. A compara-
tive settling characteristic of natural alumina and functionalized
alumina-based nanofluids at maximum concentrations of 3 wt.%
is shown in Fig. 6(a) and (b), respectively. All nanofluid samples
are found to be highly stable and are proceeded for estimation of
thermophysical properties. It is found that functionalization of alu-
mina surface by carboxylates changed the polarity of nanoparti-
cles. The high stability of functionalized nanoparticles can be
attributed to the non-polar behaviour of functionalized alumina
dispersion in non-polar thermal oil.
3.2.2. Particle size distribution
To further verify the effect of functionalization on the stability
of alumina-based nanofluids, particle size distribution analysis,
Malvern Zetasizer Nano s90, is performed at low concentrations
(0.5 wt.%) of alumina at natural and functionalized conditions.
The samples are sonicated equally as mentioned earlier and the
analysis is performed after 3–4 h of sample preparation. Particle
size distributions for both of the samples are compared in Fig. 7.
Alumina-based nanofluid at natural condition exhibits agglomera-
tion of micron size. The volumetric particle size distribution for
functionalized alumina-based nanofluid is found to be close to
the primary size of nanoparticles. The quantitative result of
nanoparticle size is found to be in agreement with the settling
characteristics of alumina nanofluids.
3.3. Rheological behaviour of nanofluids
Studies on the rheological behaviour of nanofluids include the
relationship between dynamic viscosity, shear rate and shear
stress at different temperatures and nanoparticle loading. The
dynamic viscosity of nanofluids are estimated experimentally
using rotational rheometer (Anton Paar, MCR 102) at different
shear rates (100–2000 s
1), temperatures (25–90 °C) and nanofluid
concentrations (0–3 wt.%). Dynamic viscosities of pure oil and
functionalized alumina-based nanofluids are shown in Fig. 8. The
dynamic viscosity of the thermal oil and thermal oil-based
nanofluids decreases with the increase in temperature with a
non-linear trend, shown in Fig. 8. It is ascribed to the dissociation
of bonds due to the weakening of intermolecular force of attraction
between molecules of thermal oil.
It is explicable that if the shear rate and shear stress exhibit lin-
ear behaviour, the fluid can be categorised as the Newtonian fluid
and the viscosity of the fluid is not dependent on the shear rate.
The characteristics between shear rate and shear stress are inves-
tigated and a linear incremental relation is found, shown in Fig. 9
(a). An insignificant finite yield stress is found at a shear rate of
zero, which is attributed to the Bingham plastic non-Newtonian
fluid behaviour. Amiri et al. [25] found the similar behaviour for
MWCNT-turbine oil-based nanofluids. There are few studies avail-
able in the literature [51,67], which have reported the Newtonian
behaviour of thermal oil-based nanofluids. A slight insignificant
decline of dynamic viscosity for all nanofluid samples is found with
the increase in shear rate, shown in Fig. 9(b). It is found that the
change in viscosity at different shear rates for the high tempera-
ture of operation is negligible.
It is found that particle concentration has a significant effect on
the viscosity of nanofluid. However, the effect is found to be
insignificant at high shear rates. A slight increase in the dynamic
viscosity of nanofluids is observed with the increase in nanoparti-
cle weight concentrations. The effect of nanoparticle concentration
on the shear stress is investigated. A slight increase in the shear
stress is observed by the addition of nanoparticles at different
temperatures, shown in Fig. 10(a). The shear stress is directly pro-
portional to viscosity which decreases with an increase in temper-
ature. The resistance between different layers of molecules starts
to decrease as the temperature is increased due to abating shear
forces. An increase in the viscosity of thermal oil can give negative
impact on the efficiency of heat transfer application. Therefore, a
significant increase in the viscosity index is not preferred at indus-
trial operations for specific applications. The enhancement in rela-
tive viscosity of nanofluid is calculated using Eq. (2). Fig. 10(b)
shows the relative viscosity enhancement at different shear rates
and nanofluid concentrations at 25 °C. It is found that high concen-
trations of nanofluids exhibited large increment in dynamic rela-
tive viscosity (up to 18%). It is also observed that relative
viscosity enhancement at high shear rates was less than the low
shear rates.
" #
l
lnf ;enhancement ¼ nf
1  100% ð2Þ
lbf
It is observed that the dynamic viscosities of nanofluids are not
affected at high shear rates. Li et al. [68] explained the phenomenon
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 5. SEM images of (a) pure and (b) functionalized alumina nanoparticles. TEM images of (c) pure and (d) functionalized alumina nanoparticles.
of de-agglomeration of nanoparticles during operation at high shear
rates. Typically, viscosities decrease for low shear rates up to 40 s
1
and then remain constant for high shear rates. Low concentrations
of nanofluids can exhibit high stability but high concentrations of
nanofluids may experience shear thinning behaviour at low shear
rates which cause agglomeration. At low shear rates (0.1–10 s
1),
collisions among the particles are relatively low as compared to
high shear rates. The agglomerations among the nanoparticles are
broken at high shear rates which result in the reduction of viscosity.
This explanation is in agreement with the experimental studies
available in the literature [8,31,39,68].
The experimental data is compared with the conventional the-
oretical viscosity model of Einstein [69], given in Eq. (3). The theo-
retical models for the estimation of dynamic viscosity have used
particle loading in volume fractions. First, the experimental data
is converted into volume fractions using Eq. (1) where the bulk
density of nanoparticles is used (Table 1). Then, the experimental
data is compared with Einstein model of viscosity at different tem-
peratures, shown in Fig. 11. As mentioned earlier that the experi-
mental results of thermophysical properties have a strong
dependency on many factors such as particle size, particle shape,
individual particle density and degree of aggregation
[46,47,70,71]. Available theoretical models are unable to consoli-
date these factors.
lnf ¼ ð1 þ 2:5uv Þlbf
It is found that the classical theoretical model is unable to pre-
dict the experimental dynamic viscosities. The estimated experi-
mental values are found to be much bigger than the predictions
221
from the theoretical model. It is attributed mainly towards the
change in particle density due to agglomeration, which adduces
that the model is not suitable for these nanofluids. It is found
that the difference between the theoretical values and experi-
mental values became much significant at higher concentrations
of nanofluids. The significant difference can also be attributed to
the surface adsorption (due to intermolecular forces) of nanopar-
ticles from neighbouring particles in the fluid to form aggregates.
Similar trends were found and explained in the literature [72–
75].
The correlation for the experimental values of dynamic viscos-
ity of pure oil (uP ¼ 0) and nanofluids are developed as a function
of temperature (T), shear rate (c) and weight fraction (uP ) of
nanofluids. It is found that the shear rate has a negligible effect
on the dynamic viscosity. The viscosity model proposed by Khana-
fer and Vafai [76] is followed with new equation parameters. The
proposed correlation for dynamic viscosities of alumina-based
nanofluids is given in Eq. (4). The performance of the equation is
shown in Fig. 12. The average absolute deviation (AAD), sum of
squared errors (SSE) and the R2 of the regression are estimated to
be 3.64%, 0.001 and 98.14%, respectively. The parity plot shows
that 99% of predicted values from the correlation of the effective
viscosity are within a mean absolute error of ±15%.
lnf ¼
1:6752
0:7856
T
þ 0:9125ð1
uP Þ þ 3:4862ð1
uP Þ2
ð3Þ
þ134:8479 ð1
Tu2 P Þ
2:7263ð1
uP Þ3
2347:62 ð1
T u
2
PÞ
3
25 6 Tð CÞ 6 80 0:97 6 1
uP ðwt: frÞ 6 1 100 6 cðs
1 Þ 6 2000
ð4Þ
222 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 6. Settling characteristics of Al2O3-thermal oil-based nanofluids at (a) natural
and (b) functionalized conditions.
Fig. 7. Particle size distribution of natural and functionalized alumina in thermal
oil-based nanofluid (0.5 wt.%).
3.4. Effective density
Effective densities of nanofluids are measured using density
meter, Mettler Toledo DM 40. The highly stable functionalized-
alumina based nanofluids are tested at different concentrations
from 0 to 3 wt.% and temperature range of 20–60 °C. Nanofluids
show both typical characteristics, (i) Effective densities increase
with the increase in nanoparticle concentration and (ii) effective
densities decrease with the increase in temperature. The decrease
in density with the rise in temperature is because of the increase in
liquid volume. Fig. 13 shows the experimental effective densities of
nanofluids at varying nanoparticle concentrations and tempera-
tures. It must be noted that introduction of nanoparticles in
thermal oil can lead to enhancement in effective thermal conduc-
tivity of nanofluids for heat transfer applications. However, this
advantage may be nullified due to increase in fluid density. The
buoyancy driven free convection is highly dependent on the den-
sity and viscosity of nanofluids. The increase in density and viscos-
ity can reduce the overall heat transfer coefficient.
The experimental effective densities of functionalized alumina-
based nanofluids are compared with the theoretical model pro-
posed by Pak and Cho [36], given in Eq. (5). This model is based
on volumetric concentration and is widely used for the estimation
of the effective density of nanofluids. The volumetric concentra-
tions based experimental values are calculated using Eq. (1), which
is based on the bulk density of nanoparticles (Table 1). Fig. 14
shows the comparative relation between the theoretical model
and experimental results at different temperatures. It is found that
the predictions from the model are close to experimental results
for low concentrations only. It is observed that the density differ-
ence between the model predictions and experimental results
become significant at high concentrations of nanofluids. It can be
attributed to the surface-modification of nanoparticle and degree
of agglomeration.
qnf ¼ uv qnp þ ð1
uv Þqbf ð5Þ
The correlation for the measured experimental values of effective
densities of pure oil (uP ¼ 0) and nanofluids are developed as a
function of temperature (T) and weight fraction (uP ) of nanofluids,
shown in Eq. (6). The developed correlation exhibits 99.7% coeffi-
cient of determination (R2). The performance of the correlation is
shown in Fig. 15. The average absolute deviation (AAD) of the cor-
relation is calculated to be 0.045% and sum of squared errors
(SSE) was estimated to be 8.85  10
6. Parity plot revealed that
all points are perfectly matched with a mean absolute error of
±0.5%.
762:91
qnf ¼
1012:83
þ 1578:311ð1
uP Þ0:4211
T 0:7125
671:4463 ð6Þ
þ
ð1
uP Þ3:2992 T 0:1938
20 6 Tð CÞ 6 60 0:97 6 1
uP ðwt: frÞ 6 1
3.5. Thermal conductivity
The enhancement in effective thermal conductivity of thermal
oil is the main motivation towards their usage in heat transfer pro-
cesses. Thermal conductivity is mainly a function of the motion of
free electrons and molecular vibrations. Energy transfer takes place
by the increase in the temperature difference. The molecules
become excited and colloids with each other due to increase in
kinetic energy. The rate of collision between particles is enhanced
with the increase in temperature due to Brownian motion. There
are several theoretical models available in the literature to predict
the thermal conductivity enhancement in nanofluids. However,
these models do not predict precise values as they are developed
for specific base fluid, nanoparticle, nanoparticle size, and concen-
tration of nanofluids. There are many factors which are not consid-
ered in the conventional theoretical models such as degree of
aggregation, shape and size of nanoparticles.
KD2 Pro KS-1 was used to measure the thermal conductivity of
pure oil and nanofluids. The device works on the principle of tran-
sient hot wire method with a maximum deviation of 5.0% and
accuracy of ±0.01 W/m °C. This technique to measure the thermal
conductivity of nanofluids is reported in many investigations
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 8. Dynamic viscosities of pure oil (THO) and nanofluids at different shear rates (a) 100 s
1 (b) 500 s
1 (c) 1000 s
1 and (d) 2000 s
1.
[9,25,51,77]. Thermal conductivity is measured from the tempera-
ture difference acquired by the temperature sensors equipped
inside the probe. The device corrects the temperature drift and
analyses the data for precise thermal conductivity measurement.
The probe is inserted into the nanofluids samples, which are placed
at different constant temperatures inside thermostatic bath. The
measurements are performed several times and the error bars
are shown in Fig. 16. It is observed that the error in the measure-
ments increased at high-temperature testing.
Typical behaviour of thermal conductivity reduction with tem-
perature is observed for pure oil. Nanofluids show an increase in
thermal conductivity with temperature. Similar trends are found
in the literature [9] for SiC-diathermic oil-based nanofluids. The
thermal conductivity of nanofluids is found to be enhanced with
the increase in particle concentration due to the higher thermal
conductivity of alumina nanoparticles as compared to thermal
oil. The maximum enhancement is observed at the higher concen-
tration of nanoparticle at 3 wt.%. The increase in thermal conduc-
tivity by the addition of nanoparticles is attributed to the
increase in Brownian motion of nanoparticles. This motion of the
particle is intensified with the rise in temperature. This increase
in thermal conductivity depends on the average particle size and
concentration. Agglomeration among particles can reverse the
phenomenon of improved thermal properties of nanofluids.
Colangelo et al. [39,78] investigated the effective thermal con-
ductivity of alumina-thermal oil-based nanofluids using Therminol
223
66 and diathermic oil. The enhancement in relative thermal
conductivity of nanofluids is calculated using Eq. (7) and are com-
pared with the experimental investigations of Coleangelo et al.
[39,78], shown in Fig. 17(a). The comparison illustrated that
functionalize-alumina based thermal oil shows high thermal con-
ductivity enhancement as compared to experimental results from
Coleangelo et al. [39,78]. The reason may be attributed to the intro-
duction of the carboxylic functional group on the alumina
nanoparticles and less agglomeration of nanofluids.
 
knf
knf ;Enhancement ¼
1  100% ð7Þ
kbf
In most cases, theoretical models do not predict accurate thermal
conductivity of nanofluids due to special properties of nanoparti-
cles. These factors include aggregation, particle size, particle size
distribution, Brownian motion and ballistic phonon transport
[48,49]. The experimental results are compared with the Maxwell
model [79]. The equation for Maxwell model is given in Eq. (8).
The Maxwell model is suitable for relatively large particles [76].
The experimental results are converted to volume fractions using
Eq. (1) and compared with the Maxwell model of thermal conduc-
tivity, shown in Fig. 17(b). The theoretical model does not match
the experimental thermal conductivity. The difference between
experimental values and model predictions is found to be signifi-
224 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229

Fig. 9. (a) Shear stress and shear rate relationship for alumina-based nanofluids at
different temperatures and (b) change in dynamic viscosity of alumina-based
nanofluid (1 wt.%) with the shear rate at different temperatures.

cant. Such deviations are reported in the literature for different

nanofluids [9,80–83]. Fig. 10. (a) Effect of particle loading on shear stress at different temperatures and
 
knp þ 2kbf þ 2uv ðknp
kbf Þ
(b) relative viscosity enhancement of nanofluids at different shear rates and
knf ¼ kbf ð8Þ nanoparticle concentrations.
knp þ 2kbf
uv ðknp
kbf Þ
Limited studies have proposed correlations based on experimental
investigations of thermal conductivity for different nanofluids. A
correlation is proposed for the experimental data obtained for ther-
mal conductivity of functionalized alumina-based nanofluids as a
function of temperature (T) and weight fraction (uP ) of nanofluids,
shown in Eq. (9). Parity plot for the proposed correlation is shown in
Fig. 18. The experimental and predicted values are observed to be in
good agreement with a mean absolute error of ±2%. The average
absolute deviation (AAD) and the sum of squared errors (SSE) of
the proposed correlation are determined to be 0.62% and
3.19  10
5, respectively. The R2 of regression is estimated to be
96%.

knf ¼ 1:4408
0:829ðln TÞ þ 0:1588ðln TÞ
0:0702ð1
uP Þ

2

0:2151ðln TÞð1
uP Þ þ 0:5965T

ð1
uP Þ

0:39T
ð1
uP Þ2

24:47 6 Tð CÞ 6 54:65 0:97 6 1
uP ðwt: frÞ 6 1



ð9Þ

Fig. 11. Comparison of theoretical model with experimental data of dynamic

3.6. Effective specific heat capacity viscosities at varying nanoparticle concentrations.

Specific heat capacities of functionalized alumina-based calorimeter (DSC), TA Instrument Q2000. The equipment measures
nanofluids are experimentally measured at varying concentrations temperature dependent heat flux of the nanofluid samples. The
and a wide range of temperatures using differential scanning equipment is set to be in isothermal conditions. A constant heating
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 12. Performance of the proposed correlation for the dynamic viscosity of
functionalized alumina-thermal oil-based nanofluids.
Fig. 13. Effective densities of nanofluids at varying nanoparticle concentrations.
Fig. 14. Comparison of model predictions and experimental results for the effective
densities of nanofluids.
225
Fig. 15. Parity plot of correlation for effective densities of nanofluids.
Fig. 16. Thermal conductivity of functionalized alumina-based nanofluids.
rate of 10 °C/min is applied to all nanofluid samples. Heat flows
and specific heat capacities are estimated and plotted in Fig. 19
(a) and Fig. 19(b), respectively. It is found that all samples of
nanofluids show an onset at about 160 °C which indicated the
beginning of evaporation. The onset temperature of the thermal
oil is reduced by an average of 8 °C after addition of nanoparticles.
Similar results are obtained by others in the literature [84] for var-
ious nanofluids. The endothermic peaks obtained at 180 °C can be
attributed to the evaporation of nanofluid. Similar peaks are
obtained for all nanofluid samples which accredited to non-
reaction nature of the nanoparticle and thermal oil. It is found that
specific heat capacities of nanofluids decrease with the increase in
nanoparticle concentration. It is attributed to the low specific heat
capacity of nanoparticles as compared to thermal oil. The typical
decreasing trend of specific heat capacities of nanofluid samples
with temperature is observed.
There are two classical models available in the literature for the
estimation of specific heat capacity of nanofluids. The first model,
given in Eq. (10), is based on the straight average of specific heat
capacities of the nanoparticle, base fluid and their volume fractions
[85]. The second model, given in Eq. (11), is based on the thermal
equilibrium between the fluid and nanoparticles [50,85,86]. The
226 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 17. Comparison of thermal conductivity enhancement with literature (a)
Coleangelo et al. [39,78] and (b) Maxwell model [79].
Fig. 18. Parity plot of thermal conductivity measurements for functionalized
alumina-based nanofluids.
density, volumetric fraction and specific heat capacity of solid par-
ticles and base-fluid are considered in this model. The effective
specific heat capacity from the model and experimental values
are compared in Fig. 20. Bulk properties are used to estimate the
volumetric fraction and specific heat capacity of nanofluids. The
results clearly suggest that the theoretical models are unable to
Fig. 19. (a) Heat flows and (b) specific heat capacities at different concentrations of
nanofluids with varying temperatures.
predict the experimental specific heat capacities. The reason may
be attributed to the actual density of nanoparticles, degree of
aggregation, size effects and presence of functional group on the
nanoparticle surface [87,88].
Cpnf ¼ uv Cpnp þ ð1
uv ÞCpbf ð10Þ
uv Cpnp qnp þ ð1
uv ÞCpbf qbf
Cpnf ¼ ð11Þ
uv qnp þ ð1
uv Þqbf
A correlation is developed based on the experimental values of
specific heat capacities for the nanofluids. Limited studies are found
on the correlations for specific heat capacities as a function of par-
ticle concentration and temperature. The proposed equation is
shown in Eq. (12). To evaluate the performance of correlation, parity
plot is plotted for the equation, shown in Fig. 21. The regression R2
for the proposed equation is estimated to be 99%. The average abso-
lute deviation (AAD) and the sum of squared errors (SSE) of the pro-
posed correlation are determined to be 0.88% and 0.0634,
respectively. The experimental and predicted values are observed
to be in good agreement with a mean absolute error of ±5%. The
developed correlation shows large exponent value with nanoparti-
cle concentration. The reason may be attributed to the significance
of particle concentration on the effective specific heat capacity of
nanofluids.
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 20. Comparison of model predictions and experimental specific heat capacities
of nanofluids.
Fig. 21. Performance of proposed correlation for specific heat capacities of
nanofluids.
2 between the decomposition rates of thermal oil and nanofluids
Cpnf ¼ 1:2674 þ ½
0:0026
0:4167ð1
uP Þ150
0:0414T 0:602 
44 6 Tð CÞ 6 100 0:97 6 1
uP ðwt: frÞ 6 1
ð12Þ
3.7. Thermogravimetric analysis
Thermogravimetric analysis, Perkin Elmer Pyris 1 TGA, is per-
formed to investigate the effect of the addition of nanoparticles
on the degradation of thermal oil. This analysis can be useful to
assess the potential possibility of increasing the life of the thermal
oil. All samples are tested from room temperature to 700 °C at a
constant heating rate of 20 °C/min. The weight loss in temperature
is estimated with respect to time and temperature, shown in
Fig. 22. It is found that thermal oil and nanofluids started to
degrade slowly from 180 °C to 250 °C. A sudden degradation curve
of the material is found after 250 °C until 400 °C, which is attribu-
ted to the complete decomposition of the thermal oil. The decom-
position rate difference between the thermal oil and nanofluid
227
Fig. 22. Thermogravimetric analysis of nanofluids at varying concentrations with
respect to (a) temperature and (b) time.
samples is observed to be insignificant. However, the difference
becomes significant with respect to time.
Derivative of Thermogravimetric analysis (DTGA) is determined
for all nanofluid samples to completely understand the degrada-
tion phenomenon and significance of nanoparticle concentrations
on the life of thermal oil. The peak positions are analysed, shown
in Fig. 23(a). It is found that maximum change in weight loss for
pure thermal oil exhibited at 376.93 °C but alumina-based nano-
fluid (3 wt.%) shows at 394.89 °C. The results clearly suggest the
change in degradation temperature by the addition of nanoparti-
cles. The change in weight loss is observed with respect to time,
shown in Fig. 23(b). A slight shift in time is observed with an
increase in nanoparticle concentration. It can be attributed
towards the improved thermal properties of nanofluids. The max-
imum weight loss is observed for pure oil at 1078.98 s, however,
nanofluid with 3 wt.% exhibits the peak at 1119 s. The results
clearly indicate the potential of nanofluids of bearing more heat
and an increase in life. It is believed that this analysis can be fur-
ther used in future to investigate the potential of different nanoflu-
ids with improved life.
228 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
Fig. 23. Derivative thermogravimetric analysis (DTGA) of nanofluids at varying
concentrations with respect to (a) temperature and (b) time.
4. Conclusion
Thermal oil-based nanofluids are prepared using functionalized
alumina nanoparticles for advanced cooling applications. Nanopar-
ticles are functionalized with oleic acid to change the polarity and
to increase the stability of nanofluids. Different characterizations
and analysis are performed. Infrared spectroscopy and elemental
analysis have confirmed the presence of carboxylates functional
group on the particle surface. The surface modification does not
disturb the crystallinity of nanoparticle. Stability of nanofluids is
observed to be increased from few hours to at least one-month
using functionalization process. Particle size distribution curves
illustrate that the agglomerates are broken to the primary size of
the nanoparticle by surface modification. Rheological properties
are investigated and it is found that viscosity increased with the
increase in particle concentrations. Effective thermal conductivity
of nanofluids is improved as compared to pure oil. A slight increase
in effective density of nanofluids is observed. Correlations are
developed for thermophysical properties. Thermogravimetric anal-
ysis has proved the possibility of improved life and degradation
temperature of nanofluids.
Acknowledgment
This work is supported by Chemical Engineering Department.
The financial assistance is provided by the grant number: YUTP
0153AA-E28.
References
[1] Verma SK, Tiwari AK. Progress of nanofluid application in solar collectors: a
review. Energy Convers Manage 2015;100:324–46.
[2] Kumar V, Tiwari AK, Ghosh SK. Application of nanofluids in plate heat
exchanger: a review. Energy Convers Manage 2015;105:1017–36.
[3] Pendyala R, Ilyas SU, Lim LR, Marneni N. CFD analysis of heat transfer
performance of nanofluids in distributor transformer. Proc Eng
2016;148:1162–9.
[4] Pendyala R, Chong JL, Ilyas SU. CFD analysis of heat transfer performance in a
car radiator with nanofluids as coolants. Chem Eng Trans 2015;45:1261–6.
[5] Choi SUS. Enhancing thermal conductivity of fluids with nanoparticles. ASME-
Publi-Fed 1995;231:99–106.
[6] Khoshvaght-Aliabadi M, Sahamiyan M. Performance of nanofluid flow in
corrugated minichannels heat sink (CMCHS). Energy Convers Manage
2016;108:297–308.
[7] Saidur R, Leong KY, Mohammad HA. A review on applications and challenges of
nanofluids. Renew Sust Energy Rev 2011;15:1646–68.
[8] Kole M, Dey TK. Viscosity of alumina nanoparticles dispersed in car engine
coolant. Exp Therm Fluid Sci 2010;34:677–83.
[9] Li X, Zou C, Zhou L, Qi A. Experimental study on the thermo-physical properties
of diathermic oil based SiC nanofluids for high temperature applications. Int J
Heat Mass Transfer 2016;97:631–7.
[10] Amiri A, Kazi SN, Shanbedi M, Mohd Zubir MN, Yarmand H, Chew BT.
Transformer oil based multi-walled carbon nanotube-hexylamine coolant
with optimized electrical, thermal and rheological enhancements. RSC Adv
2015;5:107222–36.
[11] Chen M, He Y, Zhu J, Kim DR. Enhancement of photo-thermal conversion using
gold nanofluids with different particle sizes. Energy Convers Manage
2016;112:21–30.
[12] Ali HM, Arshad W. Thermal performance investigation of staggered and inline
pin fin heat sinks using water based rutile and anatase TiO2 nanofluids. Energy
Convers Manage 2015;106:793–803.
[13] Lashanizadegan M, Farzi G, Nia GE. Synthesis and surface modification of
aluminum oxide nanoparticles. J Ceram Process Res 2014;15:316–9.
[14] Sridhara V, Satapathy LN. Al2O3-based nanofluids: a review. Nanosc Res Lett
2011;6:1–16.
[15] Khanjari Y, Pourfayaz F, Kasaeian AB. Numerical investigation on using of
nanofluid in a water-cooled photovoltaic thermal system. Energy Convers
Manage 2016;122:263–78.
[16] Khoshvaght-Aliabadi M. Influence of different design parameters and Al2O3-
water nanofluid flow on heat transfer and flow characteristics of sinusoidal-
corrugated channels. Energy Convers Manage 2014;88:96–105.
[17] Lam PAK, Prakash KA. Thermodynamic investigation and multi-objective
optimization for jet impingement cooling system with Al2O3/water nanofluid.
Energy Convers Manage 2016;111:38–56.
[18] Turkyilmazoglu M. Performance of direct absorption solar collector with
nanofluid mixture. Energy Convers Manage 2016;114:1–10.
[19] Hadad K, Rahimian A, Nematollahi MR. Numerical study of single and two-
phase models of water/Al2O3 nanofluid turbulent forced convection flow in
VVER-1000 nuclear reactor. Ann Nucl Energy 2013;60:287–94.
[20] Ho CJ, Chung YN, Lai C-M. Thermal performance of Al2O3/water nanofluid in a
natural circulation loop with a mini-channel heat sink and heat source. Energy
Convers Manage 2014;87:848–58.
[21] Sokhansefat T, Kasaeian AB, Kowsary F. Heat transfer enhancement in
parabolic trough collector tube using Al2O3/synthetic oil nanofluid. Renew
Sust Energy Rev 2014;33:636–44.
[22] Wang X, Xu X, Choi SUS. Thermal conductivity of nanoparticle - fluid mixture. J
Thermophys Heat Transfer 1999;13:474–80.
[23] Xie H, Wang J, Xi T, Liu Y, Ai F, Wu Q. Thermal conductivity enhancement of
suspensions containing nanosized alumina particles. J App Phys
2002;91:4568–72.
[24] Choi SUS, Zhang ZG, Yu W, Lockwood FE, Grulke EA. Anomalous thermal
conductivity enhancement in nanotube suspensions. App Phys Lett
2001;79:2252–4.
[25] Amiri A, Shanbedi M, Yarmand H, Arzani HK, Gharehkhani S, Montazer E, et al.
Laminar convective heat transfer of hexylamine-treated MWCNTs-based
turbine oil nanofluid. Energy Convers Manage 2015;105:355–67.
[26] Liu M-S, Ching-Cheng Lin M, Huang IT, Wang C-C. Enhancement of thermal
conductivity with carbon nanotube for nanofluids. Int Commun Heat Mass
2005;32:1202–10.
[27] Farzin F, Heris SZ, Rahimi S. Laminar convective heat transfer and pressure
drop of TiO2/turbine oil nanofluid. J Thermophys Heat Transfer
2013;27:127–33.
[28] Razi P, Akhavan-Behabadi MA, Saeedinia M. Pressure drop and thermal
characteristics of CuO–base oil nanofluid laminar flow in flattened tubes under
constant heat flux. Int Commun Heat Mass 2011;38:964–71.
 S.U. Ilyas et al. / Energy Conversion and Management 142 (2017) 215–229
[29] Heris SZ, Farzin F, Sardarabadi H. Experimental comparison among thermal
characteristics of three metal oxide nanoparticles/turbine oil-based nanofluids
under laminar flow regime. Int J Thermophys 2015;36:760–82.
[30] Fontes DH, Ribatski G, Bandarra Filho EP. Experimental evaluation of thermal
conductivity, viscosity and breakdown voltage AC of nanofluids of carbon
nanotubes and diamond in transformer oil. Diamond Relat Mater
2015;58:115–21.
[31] Kole M, Dey TK. Effect of aggregation on the viscosity of copper oxide–gear oil
nanofluids. Int J Therm Sci 2011;50:1741–7.
[32] Taha-Tijerina J, Narayanan TN, Gao G, Rohde M, Tsentalovich DA, Pasquali M,
et al. Electrically insulating thermal nano-oils using 2D fillers. ACS Nano
2012;6:1214–20.
[33] Ilyas SU, Pendyala R, Marneni N. Preparation, sedimentation, and
agglomeration of nanofluids. Chem Eng Technol 2014;37:2011–21.
[34] Farzaneh H, Behzadmehr A, Yaghoubi M, Samimi A, Sarvari SMH. Stability of
nanofluids: molecular dynamic approach and experimental study. Energy
Convers Manage 2016;111:1–14.
[35] Wen D, Ding Y. Experimental investigation into the pool boiling heat transfer
of aqueous based c-alumina nanofluids. J Nanopart Res 2005;7:265–74.
[36] Pak BC, Cho YI. Hydrodynamic and heat transfer study of dispersed fluids with
submicron metallic oxide particles. Exp Heat Transfer 1998;11:151–70.
[37] Yarmand H, Gharehkhani S, Shirazi SFS, Amiri A, Alehashem MS, Dahari M,
et al. Experimental investigation of thermo-physical properties, convective
heat transfer and pressure drop of functionalized graphene nanoplatelets
aqueous nanofluid in a square heated pipe. Energy Convers Manage
2016;114:38–49.
[38] Choi C, Yoo HS, Oh JM. Preparation and heat transfer properties of
nanoparticle-in-transformer oil dispersions as advanced energy-efficient
coolants. Curr Appl Phys 2008;8:710–2.
[39] Colangelo G, Favale E, Miglietta P, Milanese M, de Risi A. Thermal conductivity,
viscosity and stability of Al2O3-diathermic oil nanofluids for solar energy
systems. Energy 2016;95:124–36.
[40] Hong R, Pan T, Qian J, Li H. Synthesis and surface modification of ZnO
nanoparticles. Chem Eng J 2006;119:71–81.
[41] Li D, Hong B, Fang W, Guo Y, Lin R. Preparation of well-dispersed silver
nanoparticles for oil-based nanofluids. Ind Eng Chem Res 2010;49:1697–702.
[42] Cheng B, Wang X, Wang L, Wu Y. Surface modification of sub-micron spherical
SiO2 particles with butanedioic acid for electrophoresis in tetrachloroethylene.
Mater Lett 2007;61:1350–3.
[43] Shete PB, Patil RM, Tiwale BM, Pawar SH. Water dispersible oleic acid-coated
Fe3O4 nanoparticles for biomedical applications. J Magn Magn Mater
2015;377:406–10.
[44] Yu W, Xie H. A review on nanofluids: preparation, stability mechanisms, and
applications. J Nanomater 2012;2012:17.
[45] Ilyas SU, Pendyala R, Marneni N. Stability of nanofluids. In: Korada VS,
Hamid NHB, editors. Engineering applications of nano-
technology. Switzerland: Springer Inter Publishing; 2017. p. 1–31.
[46] Mahbubul IM, Chong TH, Khaleduzzaman SS, Shahrul IM, Saidur R, Long BD,
et al. Effect of ultrasonication duration on colloidal structure and viscosity of
alumina-water nanofluid. Ind Eng Chem Res 2014;53:6677–84.
[47] Mahbubul IM, Saidur R, Amalina MA. Latest developments on the viscosity of
nanofluids. Int J Heat Mass Transfer 2012;55:874–85.
[48] Keblinski P, Phillpot SR, Choi SUS, Eastman JA. Mechanisms of heat flow in
suspensions of nano-sized particles (nanofluids). Int J Heat Mass Transfer
2002;45:855–63.
[49] Joshi AA, Majumdar A. Transient ballistic and diffusive phonon heat transport
in thin films. J App Phys 1993;74:31–9.
[50] O’Hanley H, Buongiorno J, McKrell T, Hu L-W. Measurement and model
validation of nanofluid specific heat capacity with differential scanning
calorimetry. Adv Mech Eng 2012;4:1–6.
[51] Aberoumand S, Jafarimoghaddam A, Moravej M, Aberoumand H, Javaherdeh K.
Experimental study on the rheological behavior of silver-heat transfer oil
nanofluid and suggesting two empirical based correlations for thermal
conductivity and viscosity of oil based nanofluids. App Therm Eng
2016;101:362–72.
[52] Damayanti NP. Preparation of superhydrophobic PET fabric from Al2O3–SiO2
hybrid: geometrical approach to create high contact angle surface from low
contact angle materials. J Sol-Gel Sci Technol 2010;56:47–52.
[53] Conceição BMd, Costa MAS, Santa Maria LCd, Silva MR, Wang SH. A study of
the initiator concentration s effect on styrene-divinylbenzene polymerization
with iron particles. Polímeros 2011;21:409–15.
[54] Zhang L, He R, Gu H-C. Oleic acid coating on the monodisperse magnetite
nanoparticles. Appl Surf Sci 2006;253:2611–7.
[55] Tao YT. Structural comparison of self-assembled monolayers of n-alkanoic
acids on the surfaces of silver, copper, and aluminum. J Am Chem Soc
1993;115:4350–8.
[56] Nakamoto K. Infrared and Raman spectra of inorganic and coordination
compounds. Handbook of vibrational spectroscopy. John Wiley & Sons, Ltd;
2006.
[57] Ren Y, Iimura K-I, Kato T. Structure of barium stearate films at the air/water
interface investigated by polarization modulation infrared spectroscopy and
p
A isotherms. Langmuir 2001;17:2688–93.
229
[58] Pradeep A, Priyadharsini P, Chandrasekaran G. Sol–gel route of synthesis of
nanoparticles of MgFe2O4 and XRD, FTIR and VSM study. J Magn Magn Mater
2008;320:2774–9.
[59] Zhang F, Chan S-W, Spanier JE, Apak E, Jin Q, Robinson RD, et al. Cerium oxide
nanoparticles: Size-selective formation and structure analysis. App Phys Lett
2002;80:127–9.
[60] Teng T-P, Hung Y-H, Teng T-C, Chen J-H. Performance evaluation on an air-
cooled heat exchanger for alumina nanofluid under laminar flow. Nanosc Res
Lett 2011;6:1–11.
[61] Wu YQ, Zhang YF, Huang XX, Guo JK. Preparation of platelike nano alpha
alumina particles. Ceram Int 2001;27:265–8.
[62] Huang CL, Wang JJ, Huang CY. Sintering behavior and microwave dielectric
properties of nano alpha-alumina. Mater Lett 2005;59:3746–9.
[63] Ilyas SU, Pendyala R, Marneni N. Stability and agglomeration of alumina
nanoparticles in ethanol-water mixtures. Proc Eng 2016;148:290–7.
[64] Ilyas SU, Pendyala R, Marneni N. Dispersion behaviour and agglomeration
effects of zinc oxide nanoparticles in ethanol–water mixtures. Mater Res Innov
2014;18:S6-179-S6-83.
[65] Rehman H, Batmunkh M, Jeong H, Chung H. Sedimentation study and
dispersion behavior of Al2O3/H2O nanofluids with dependence of time. Adv
Sci Lett 2012;6:96–100.
[66] Ilyas SU, Pendyala R, Marneni N. Settling characteristics of alumina
nanoparticles in ethanol-water mixtures. App Mech Mater 2013;372:143–8.
[67] Asadi M, Asadi A. Dynamic viscosity of MWCNT/ZnO–engine oil hybrid
nanofluid: an experimental investigation and new correlation in different
temperatures and solid concentrations. Int Commun Heat Mass 2016;76:41–5.
[68] Li X, Zou C, Wang T, Lei X. Rheological behavior of ethylene glycol-based SiC
nanofluids. Int J Heat Mass Transfer 2015;84:925–30.
[69] Einstein A. Eine neue bestimmung der molekuldimensionen. Ann Phys
1906;19:289–306 [Leipzig].
[70] Demir H, Dalkilic AS, Kürekci NA, Duangthongsuk W, Wongwises S. Numerical
investigation on the single phase forced convection heat transfer
characteristics of TiO2 nanofluids in a double-tube counter flow heat
exchanger. Int Commun Heat Mass 2011;38:218–28.
[71] Zyła G, Cholewa M, Witek A. Rheological properties of diethylene glycol-based
MgAl2O4 nanofluids. RSC Adv 2013;3:6429–34.
[72] Penkavova V, Tihon J, Wein O. Stability and rheology of dilute TiO2-water
nanofluids. Nanosc Res Lett 2011;6:1–7.
[73] Li Y, Zhou J, Tung S, Schneider E, Xi S. A review on development of nanofluid
preparation and characterization. Powder Technol 2009;196:89–101.
[74] Sekhar YR, Sharma KV. Study of viscosity and specific heat capacity
characteristics of water-based Al2O3 nanofluids at low particle
concentrations. J Exp Nanosci 2015;10:86–102.
[75] Chandrasekar M, Suresh S, Chandra Bose A. Experimental investigations and
theoretical determination of thermal conductivity and viscosity of Al2O3/water
nanofluid. Exp Therm Fluid Sci 2010;34:210–6.
[76] Khanafer K, Vafai K. A critical synthesis of thermophysical characteristics of
nanofluids. Int J Heat Mass Transfer 2011;54:4410–28.
[77] Michael JJ, Iniyan S. Performance of copper oxide/water nanofluid in a flat
plate solar water heater under natural and forced circulations. Energy Convers
Manage 2015;95:160–9.
[78] Colangelo G, Favale E, de Risi A, Laforgia D. Results of experimental
investigations on the heat conductivity of nanofluids based on diathermic oil
for high temperature applications. Appl Energy 2012;97:828–33.
[79] Maxwell-Garnett JC. Colours in metal glasses and in metallic films. R Soc Lond
Philos Trans A 1904;203:385–420.
[80] Lin CY, Wang JC, Chen TC. Analysis of suspension and heat transfer
characteristics of Al2O3 nanofluids prepared through ultrasonic vibration.
Appl Energy 2011;88:4527–33.
[81] Nikkam N, Saleemi M, Haghighi EB, Ghanbarpour M, Khodabandeh R,
Muhammed M, et al. Fabrication, characterization and thermophysical
property evaluation of SiC nanofluids for heat transfer applications. Nano-
Micro Lett 2014;6:178–89.
[82] Akhavan-Behabadi MA, Pakdaman MF, Ghazvini M. Experimental
investigation on the convective heat transfer of nanofluid flow inside
vertical helically coiled tubes under uniform wall temperature condition. Int
Commun Heat Mass Transfer 2012;39:556–64.
[83] Pakdaman MF, Akhavan-Behabadi MA, Razi P. An experimental investigation
on thermo-physical properties and overall performance of MWCNT/heat
transfer oil nanofluid flow inside vertical helically coiled tubes. Exp Therm
Fluid Sci 2012;40:103–11.
[84] Chieruzzi M, Cerritelli GF, Miliozzi A, Kenny JM. Effect of nanoparticles on heat
capacity of nanofluids based on molten salts as PCM for thermal energy
storage. Nanosc Res Lett 2013;8:1–9.
[85] Zhou S-Q, Ni R. Measurement of the specific heat capacity of water-based
Al2O3 nanofluid. Appl Phys Lett 2008;92:093123.
[86] Buongiorno J. Convective transport in nanofluids. J Heat Transfer
2006;128:240–50.
[87] Wang BX, Zhou LP, Peng XF. Surface and size effects on the specific heat
capacity of nanoparticles. Int J Thermophys 2006;27:139–51.
[88] Zhou LP, Wang BX, Peng XF, Du XZ, Yang YP. On the specific heat capacity of
CuO nanofluid. Adv Mech Eng 2010;2:1–4.