International Communications in Heat and Mass Transfer 73 (2016) 62–74

Contents lists available at ScienceDirect

International Communications in Heat and Mass Transfer

journalhomepage:www.elsevier.com/locate/ichmt

Nanodiamond-Fe3O4 nanofluids: Preparation and measurement of

viscosity, electrical and thermal conductivities☆
a b b a a
L. Syam Sundar , E. Venkata Ramana , M.P.F. Graça , Manoj K. Singh , Antonio C.M. Sousa
a Centre for Mechanical Technology and Automation (TEMA), Department of Mechanical Engineering, University of Aveiro, Aveiro, Portugal
b I3N, Department of Physics, University of Aveiro, Aveiro, Portugal

article info abstract

Available online 2 March 2016 Nanodiamond (ND) attached with magnetite (Fe3O4) nanoparticles have been synthesized successfully by in-situ and
3+ 2+
chemical reduction of Fe and Fe cations on the acid treated-ND surface by using sodium hydroxide as a reducing agent.
Keywords:
The synthesized magnetic ND-Fe3O4 nanocomposite was characterized by XRD and TEM. The re-sults indicate that Fe 3O4
In-situ method
nanoparticles were homogeneously dispersed on the outer surface of the ND particles. The stability of ND-soot, acid treated-
Nanocomposite material
Nanofluids ND and ND-Fe3O4 dispersed in distilled water were investigated by zeta po-tential and optical images. The electrical
Electrical property conductivity was measured by using four probe technique by consider-ing dry ND-Fe 3O4 powder make it into 1 cm circular
Thermal property pellet. The stable magnetic nanofluids were prepared by dispersing ND-Fe 3O4 nanocomposite in water and ethylene
Enhancement glycol/water mixtures and then measured both ther-mal conductivity and viscosity with effects of particle loadings and
temperatures experimentally. Results indicate that thermal conductivity enhancements are 17.8%, 13.4%, 13.6%, 14.6% and
viscosity enhancements are 1.72-times, 2.19-times, 1.50-times, 1.79-times for water, 20:80%, 40:60% and 60:40% EG/W-
based nanofluids at 0.2% volume concentration at a temperature of 60 °C, respectively. Correlations for the thermal
conductivity and vis-cosity of nanocomposite nanofluids have been proposed based on the experimental data.

© 2016 Elsevier Ltd. All rights reserved.

1. Introduction ND particles dispersed in 55:45% of water and ethylene glycol. Yeganeh et

Nanofluids are a new class of working fluids with the capability of im-
proved suspension stability and enhanced thermal conductivity under
different industrial settings. The pioneering work of Choi [1], who suc-
cessfully dispersed nanometer sized particles in fluids, commonly known as
nanofluids observed higher thermal conductivity enhance-ment, led to a wide
range of opportunity in heat transfer design. The base fluids may be, for
instance, water, ethylene glycol, propylene glycol, engine oil, and
refrigerants. The nanoparticle may be Al2O3, CuO, Fe3O4, Fe2O3, SiO2, TiO2,
Ag, Cu, ZnO, SiC, nano-diamond (ND), graphite, carbon nanotubes etc.
Compared to the above mentioned nanoparticles, ND nanoparticles have great
applications in various engineering fields. Nanodiamond particles (ND) with a
size of 4–5 nm show a great poten-tial application in fluorescence markers,
biosensors, cosmetic products, polymers and for drug delivery [2]. The
nanodiamond particles are usu-ally aggregates with carbon impurities (size of
100–200 nm), which are not possible in particular applications. De-
aggregation of ND from micron-level to nano-level is very important. Ma et
al. [3] prepared stable nanodiamond-water nanofluids, and observed thermal
conductivity en-hancement of 73% at 0.01% volume concentration. Xie et al.
[4] obtained thermal conductivity enhancement of 18% at 2% volume
concentration of
☆ Communicated by W.J. Minkowycz.
E-mail addresses: sslingala@gmail.com (L.S. Sundar), mksingh@ua.pt (M.K. Singh).
al. [5] have obtained thermal conductivity enhancements of 7.2% and 9.8% at
3.0% volume concentration of ND/water nanofluid at temperature of 30 °C
and 50 °C, respectively. Tyler et al. [6] have obtained viscosity en-hancement
of 80% at 3.0% volume concentration of ND/transformer oil nanofluid.
Branson et al. [7] found 12% thermal conductivity enhance-ment with 0.88%
vol. of ND/EG nanofluid and 11% enhancement with 1.9 vol.%. of
ND/mineral oil nanofluid. Torii and Yang [8] reported pipe convective heat
transfer enhancement of ND/water nanofluids. Ghazvini et al. [9] found 25%
thermal conductivity enhancement with 1 wt.%. of ND dispersed in 20 wt.%.
of water and 50 wt.%. of engine oil. Yu et al.
[10] measured thermal conductivity of ND/EG nanofluid and obtained
17.23% enhancement with ND 1 vol.%. Taha-Tijerina et al. [11] prepared
ND/mineral oil nanofluids and observed thermal conductivity enhance-ment
up to 70% at 0.1% weight fraction.
Magnetic nanofluids are the dispersion of magnetic nanoparticles in the
base fluids. Generally used magnetic nanoparticles are Fe 2O3, Fe3O4, Ni and
Cobalt. Among all the magnetic nanoparticles magnetite (Fe 3O4) having high
saturation magnetization value at room temperatures and also potential
applications in cell separation, drug delivery, and MRI tech-
niques [12]. Therefore magnetic nanoparticle based nanofluids and their
thermal properties are very useful in engineering aspects. Some litera-
ture related to thermal conductivity of magnetic nanofluids is given below:
Philip et al. [13] obtained thermal conductivity enhancement of 300% at 6.3%
volume concentration of Fe3O4/kerosene nanofluid

http://dx.doi.org/10.1016/j.icheatmasstransfer.2016.02.013
0735-1933/© 2016 Elsevier Ltd. All rights reserved.
 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74
under the influence of magnetic field. Yu et al. [14] also prepared Fe3O4/
kerosene nanofluid with Oleic acid as a surfactant and obtained thermal
conductivity enhancement of 34% at 1.0% volume concentration in the
temperature range between 10 °C to 60 °C. Sundar et al. [15] prepared
magnetic Fe3O4 nanofluids by dispersing them into different base fluids like
20:80%, 40:60% and 60:40% by weight of the ethylene glycol and water
mixture and observed thermal conductivity enhancement of 46% at 2.0 vol.%
of nanoparticles dispersed in 20:80% ethylene glycol and water mixture
compared to other base fluids. Parekh and Lee [16] also prepared
Fe3O4/kerosene nanofluids and observed 30% thermal conduc-tivity
enhancement with a particle loading of 4.7% and in the tempera-tures range
from 25 °C to 65 °C. Gavali et al. [17] observed thermal conductivity
enhancement of 200% with 5.0% volume concentration of water based
ferrofluids. Fertman et al. [18] investigated temperature de-pendent thermal
conductivity of hydrocarbon-based magnetic fluids containing colloidal Fe3O4
particles coated with oleic acid at 0.01% to 0.2% and the temperature range of
20 °C–80 °C.
Nanocomposite synthesis — preparation of nanofluids and its ther-mal
properties are recent interesting topic. Nanocomposite consists of
nanoparticles are two phases of materials in nanometer range, i.e. less than
100 nm are significant part of nanotechnology and the fastest growing area in
materials science and engineering. Strong coupling between different
constituent components results in novel physical phenomena and enhanced
properties, which makes these systems superior to their single components
counterparts for application in bio-medicine, nanoelectronics, optoelectronics
and spintronics applications [19]. Nanostructured diamond composites with
different materials were synthesized by various techniques for different
applications. Shi et al. [20] synthesized ND-Cu nanocomposites for catalytic
applications. Livramento et al. [21] also synthesized ND-Cu with mechanical
alloying method. Nunes et al. [22] investigated Ni-ND and Ni-graphite
compos-ites produced by mechanical synthesis and heat treatment techniques.
Sundar et al. [23] synthesized ND-Ni nanocomposite by in-situ and chemical
co-precipitation method and prepared nanofluids for thermal applications.
Voronin et al. [24] developed a novel method of reactive sintering of ND-SiC
based on thorough mixing of diamond and silicon nanosized powders.
The preparation of nanocomposite-based nanofluids and its thermal
properties are very important for engineering applications. Recent re-search
related to preparation of nanocomposite-based nanofluids and its thermal
conductivity and viscosity are given below: Suresh et al.
[25] have prepared Al2O3–Cu nanocomposite based nanofluids and achieved
heat transfer enhancement of 13.56% at a Reynolds number of 1730. Baby
and Ramaprabhu [26] synthesized Fe3O4-MWNTs and Fe3O4@SiO2-
MWNTs nanocomposites by simple chemical reduction technique and
prepared nanofluids by dispersing them in water and observed thermal
conductivity enhancements for Fe3O4/MWNTs nanofluid is about 20% and
Fe3O4@SiO2/MWNTs nanofluid is about 24.5%, at 0.03% volume
concentration in the presence of magnetic field. Sundar et al. [27] prepared
MWCNT-Fe3O4 based hybrid nanofluids and obtained heat transfer and
friction factor enhancements. It is important to prepare various kinds of
nanocomposite materials and
its nanofluids for thermal properties.
In this regard, a new kind of ND-Fe 3O4 nanocomposite material has been
synthesized by considering simple in-situ and wet-chemical reac-tion method.
Nanocomposite is selected by considering high thermal conductivity and
superior magnetic property. Among all the materials,
nano-diamond (ND) attracts with high thermal conductivity i.e. 2000 W/m K
and magnetite (Fe3O4) attracts with superior-magnetic property. Sodium
hydroxide (NaOH) has been as reducing agent to pre-pare ND-Fe 3O4
nanoparticles. The electrical conductivity has been stud-ied on dry powder of
ND-Fe3O4 by using four probe techniques. The stability of ND-soot, acid
treated-ND and ND-Fe3O4 while dispersed in distilled water has been based
on the zeta potential. The stable nanofluids have been prepared by dispersing
ND-Fe3O4 in various base fluids such as water, 20:80%, 40:60% and 60:40%
EG/W mixture
for the estimation of thermal conductivity and viscosity. New correla-tions
have been proposed for thermal conductivity and viscosity based on the
experimental data.
2. Experimental procedure
2.1. Materials
The detonated ND-soot was purchased from International Technolo-gy
Centre, USA [28]. Their specifications stated purity N98%, primary av-erage
particle size 4–5 nm; cubic shape; gray color; specific surface area of 300–
2
400 m /g and the ND-soot was produced by explosion detonation technique.
The chemicals such as sulfuric acid (99%), nitric acid (98%), FeCl 3·6H2O
(99%), FeCl2·4H2O (99%), sodium hydroxide (99%) and eth-ylene glycol
(99%) were purchased from Sigma-Aldrich chemicals, USA
[29] and used without purification.
2.2. Acid treatment of ND particles
The purchased ND-soot contains large quantities of amorphous car-bon
impurities and it is very important to remove those impurities. 1.5 g of
purchased ND-soot was suspended in 100 ml of 3:1 mixture of con-centrated
H2SO4 (18.4 M)/HNO3 (16 M) and magnetically stirred for 72 h [30]. After
that, the material was washed several times with dis-tilled water and dried at
80 °C up to 12 h. The advantage of this method is the removal of impurities
and the formation of carboxyl groups on the surface of ND particles and
finally attachment of Fe3O4 nanoparticles.
2.3. Synthesis of magnetic ND-Fe3O4 nanoparticles
The magnetic ND-Fe3O4 nanoparticles were synthesized by in-situ growth
and chemical coprecipitation method. 1.5 g of acid treated-ND was dispersed
in 50 ml distilled water and magnetically stirred for 2 h. Then FeCl 3·6H2O
(5.40 g) and FeCl2·4H2O (1.98 g) salts in the molar ratio of 2:1 was added
slowly to ND suspension. A solution of 1 mol of NaOH was added to the ND-
3+ 2+
Fe /Fe till the pH reaches 12 and contin-ued the magnetic stirring for 2 h.
After completion of reaction, the residue ND-Fe 3O4 was washed several times
+ + −
with distilled water to remove ex-cess Fe , Na and Cl 2 ions and dried at 80
°C up to 12 h. The above pro-cedure was repeated for obtaining bulk ND-
Fe3O4 nanocomposite material. Pure Fe 3O4 nanoparticles were synthesized
with the same pro-cedure without adding acid treated ND particles for
comparison purpose.
2.4. Characterization techniques
X-ray diffraction (XRD) patterns were obtained by Siemens D500 at
45 kV and 40 mA system using k ∝ (λ= 1.5404 Å). High resolution–
transmission electron microscope (HR–TEM) was performed by JEOL 2200F
TEM/STEM; 200 kV. Scanning electron microscope (SEM) was
performed by Hitachi SU–70. The SEM samples were prepared by drying a
droplet of the ND-Fe3O4 suspension on a 300 mesh size copper grid coated
with carbon film. Fourier transform infrared (FTIR) spectra were recorded on
Bruker Equinox V70 FT-IR spectrometer in dry KBr pellet in the 400–4000
−1
cm wave number range. Raman spectra was recorded with Jobin–Yvon
LabRam; 514 nm argon ion laser. The satura-tion magnetization was analyzed
by vibrating sample magnetometer (Cryogenic, UK). The zeta potential and
particle size measurements were conducted on a Zetasizer 2000 system
(Malvern, UK) with irradi-ation by a 658 nm HeeNe laser.
2.5. Measurement of electrical conductivity
The ND is a good insulating material and Fe3O4 is a conducting ma-terial
and the electrical conductivity of final synthesized ND-Fe 3O4 nanoparticles
was verified by using four point probes technique [31]. The ND-soot, acid
treated-ND, ND-Fe3O4 and Fe3O4 nanoparticles were
64 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

used for electrical conductivity measurement and each sample was pre-pared
with a quantity of 80 mg powder and made into 1 cm circular pel-let. A
Keithley–238 high current source measure unit was used as high voltage
source and nano-amperometer. It can supply up to ± 110 V and measure up to
±1 A (at ±15 V) and down to 10 mA.
2.6. Preparation of magnetic ND-Fe3O4 nanofluids
The stable nanofluids were prepared by dispersing the synthesized ND-
Fe3O4 in different base fluids. The base fluids of water, 20:80%, 40:60%,
60:40% of ethylene glycol/water (weight ratio) mixtures were used and the
particle concentrations of 0.05%, 0.1%, 0.2% were prepared. The ethylene
glycol/water mixture fluids were commonly used as engine coolant fluids for
most of the cold countries in the world [32]. The quan-tity of ND-Fe 3O4
nanoparticles required for known percentage of volume concentrations of
0.05%, 0.1% and 0.2% were estimated from Eq. (1).
" #
ρND−Fe33O44
W
ND−Fe O
Volume concentration; ϕ ¼
W W
" # "
2.7. Measurement of thermal conductivity
The KD 2 pro instrument (Decagon Devices, USA) was used to mea-sure
the thermal conductivity of magnetic ND-Fe 3O4 nanofluids. The sensor needle
of KS–1 length of 60 mm and diameter of 1.3 mm was se-lected for
measurements. The sensor needle measures the thermal con-ductivity with an
accuracy of ±3% in the range of 0.2–2 W/m K. Before using the instrument
for nanofluids, it was calibrated with a standard fluid i.e. glycerol. The thermal
conductivity of 0.05%, 0.1% and 0.2% vol-ume concentrations of water and
ethylene glycol/water mixture nanofluids were measured in the temperatures
range from 20 °C to 60 °C. Each sample was measured five times and the
average value was considered as a final value.
2.8. Measurement of viscosity
The A&D vibro-viscometer, Japan was used to measure the viscosity of
magnetic ND-Fe3O4 nanofluids. It consists of fluid filling cup, two gold coated
plates and PT–100 sensor (±0.1 °C). The temperature of the fluid filling cup is
controlled by Julabo temperature controller bath, Germany. Each nanofluid
sample of 40 ml was filled in the fluid filling cup; the cup was placed on the
100 ð1Þ
table; the height is adjusted until the vibrating plates immersed in the
#

ND−Fe3 O4 þ bf
nanofluid up to the given mark. The viscometer mea-sures the viscosity in the
ρ ρ range of 0.3–10,000 mPa·s with an accuracy of ± 0.01 mPa·s. Each nanofluid
ND−Fe3 O4 bf
samples were loaded one by one in the fluid filling cup and the measurements
where, ϕ is the percentage of volume concentration; ρND −Fe3O4 is the density were performed.
of ND-Fe3O4; ρbf is the density of base fluid; WND −Fe3O4is the weight of ND-
3. Results and discussion
Fe3O4 and Wbf is the weight of base fluid. In Eq. (1), the density of ND-Fe3O4
was used and it is calculated based on the law of mixtures i.e. Eq. (2).
3.1. Characterization

W þ W Fig. 1a shows the schematic procedure of synthesis of ND-Fe 3O4 nano-

ρND ND ρFe3 O4 Fe3 O4
ρ ¼ W þW
ð ND−Fe3 O4Þp ND Fe3 O4 ð2Þ
where, ρND is the density of nanodiamond (3520 kg/m ); ρFe3O4is the den-sity
3 nanoparticles [23]. Fe cations in aqueous solution of Fe and Fe chlo-ride
3
of Fe3O4 (5180 kg/m ); WND and WFe3O4are the weight percentages of ND
and Fe3O4, respectively.
In Eq. (2), the weight percentages of ND and Fe 3O4 were used. These
weight percentages present in the ND-Fe3O4 nanoparticles was ana-lyzed
from its magnetic measurement and observed as 72% weight of ND and 28%
weight of Fe3O4. So, that means each 1 g of ND-Fe 3O4 con-tains 0.72 g of
ND and 0.28 g of Fe3O4. By substituting all the values in Eq. (2) and
3 −1
estimated the density of ND-Fe3O4 nanoparticles is 4715 kg/m . The obtained
3 C_O stretch of carboxylic (COOH); it is proof of a covalent attachment of
value of 4715 kg/m from Eq. (2) is used in Eq. (1) for the estimation of
quantity of ND-Fe3O4 nanoparticles re-quired for the known percentage of
volume concentration. The physical properties of ND, Fe3O4, ND-Fe3O4 and
the base fluids were shown in Table 1. For the preparation of water-based
0.05%, 0.1% and 0.2% volume concentrations nanofluids, an amount of
0.1181, 0.2363 and 0.4731 g of magnetic ND-Fe3O4 nanoparticles were
dispersed in 50 g of distilled water and sonicated in ultrasonic bath for 2 h.
The quantity of magnetic ND-Fe 3O4 nanoparticles required for 0.05%, 0.1%
and 0.2% volume con-centration nanofluids for 20:80%, 40:60% and 60:40%
EG/W-based nanofluids were shown in Table 2. The same procedure was
used for the preparation of different concentrations of water and ethylene gly-
col/water-based nanofluids.
particles. After acid treatment of ND with H2SO4 and HNO3, the carboxyl-
ated groups on ND can be used as a nucleation site for deposition of Fe 3O4
3+ 2+
can interact with carboxyl groups on ND through electrostatic inter-action to
− + +
form –COO Fe and release H ions. Fourier transform infrared (FTIR)
spectra of ND-soot, acid treated-ND and ND-Fe3O4 nano-particles were
plotted in Fig. 2a. It is clear from the IR spectra that acid treatment on ND-
soot particles creates the functional groups on the dia-mond surface. The band
−1
near 1630 cm can be attributed to the O–H bending of physically adsorbed
water and the hydrogen bonding, which arise between neighboring
carboxylated nanoparticles at high concentra-tion [33]. The C_O bond of
carboxylic acid which usually appears around 1755 cm is attributed to the
carboxylic groups on the surface of ND particle. The IR bands at 1750–1760
−1
cm can be assigned as C_O stretching mode for the carboxylic acid. In
addition, O–H stretching from surface –COOH group appears near 3710
−1 −1
cm ; the broad band at 3000–3600 cm can be attributed to the hydrogen-
bonded –OH of physisorbed water on the surface; the broad band near 3000
−1
cm can be caused by the CH stretching on the sample surfaces [34,35].
However, such peaks C_O is not observed in ND-Fe 3O4 nanocomposite
material during the in-situ growth, which means that the carboxylic groups
get re-duced during the formation of Fe3O4 nanoparticles on the surface ND.
The Raman spectra of acid treated-ND and magnetic ND-Fe 3O4
nanoparticles were shown in Fig. 2b. The diamond cores in detonation

Table 1
The physical property of ND, Fe3O4, ND-Fe3O4 nanoparticles and base fluids. Table 2
The amount of ND-Fe3O4 nanoparticles required for known volume concentrations.
3
Nanoparticles/base fluid ρ (kg/m ) k (W/m K)
(ϕ), (%) Quantity of ND-Fe3O4 required for various base fluids (g)
ND 3520 1000
Fe3O4 5180 72
ND-Fe3O4 4715 –
Water 998.5 0.602
20:80% EG/W 1029.72 0.492
40:60% EG/W 1059.68 0.404
60:40% EG/W 1086.27 0.334
Water 20:80% EG/W 40:60% EG/W 60:40% EG/W
0.05 0.1181 0.1145 0.1112 0.1085
0.1 0.2363 0.2291 0.2226 0.2172
0.2 0.4731 0.4588 0.4458 0.4344
 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74
Fig. 1. ND-soot, acid treated-ND and ND-Fe 3O4 nanoparticles (a) schematic diagram of synthesis procedure (b) TEM results (ND-soot; left-side), (acid treated-ND; middle), (ND-Fe 3O4
nanoparticles; right-side).
soot seem to be completely covered by graphitic shells, and this is con-firmed
by the Raman spectrum, which is dominated by the G-band of graphitic
−1
carbon at 1590 cm and has no diamond peak. Acid treated-ND peak can be
−1
seen at 1328 cm in the Raman spectrum. The broad feature at 1500 cm
−1
and 1700 cm in the spectrum of acid treated-ND originates from surface
functional groups and adsorbed molecules, with some contribution from sp
[2] carbon atoms. The Raman spectra of synthesized magnetic ND-Fe 3O4
−1
peak can also be seen at 1328 cm with a shoulder at 1130 cm that
originates from smaller ND particles or smaller coherent scattering domains
separated by defects in larger ND particles [36].
Fig. 3a represents the XRD patterns of synthesized magnetic ND-Fe 3O4
nanoparticles. The ND is confirmed by crystalline planes (111) and (220)
reflection at 2θ values 43.69°, 75.36°, respectively. Reflection peaks at 2θ
values 30.09°, 35.49°, 43.28°, 53.93°, 56.99° and 62.62° which can be
indexed as (220), (311), (400), (422) (511) and (440), re-spectively that
corresponds to Fe3O4 nanoparticles [13]. There are no characteristic peaks of
iron chloride and Fe2O3 from the spectrum. Fig. 3b represents the magnetic
hysteresis loops for synthesized magnet-ic ND-Fe3O4 and Fe3O4
nanoparticles at room temperature (20 °C). Pure Fe 3O4 nanoparticles were
used for comparison purpose. It is observed from the figure that the saturation
magnetization of pure Fe3O4 nanopar-ticles are 47 emu/g and the magnetic
ND-Fe3O4 nanoparticles are 13.2 emu/g. The saturation magnetization of ND-
Fe3O4 nanoparticles were decreased compared to pure Fe3O4 nanoparticles
because of non-magnetic ND particles present in the nanocomposite. But it is
noticed that the synthesized ND-Fe 3O4 nanocomposite particles are showing
good magnetic property. So, this magnetization is sufficient to prepare
magnetic nanofluids. In the presence of magnetic field, the non-magnetic
particles act as voids and break the magnetic circuits resulting in the de-crease
of total magnetization. Similar results were reported in literature for the
assemblies of magnetic and non-magnetic particles [37]. The sum rule is used
to calculate the weight percentages of ND and Fe 3O4 present in ND-Fe3O4
and obtained as 72% of ND and 28% of Fe3O4.
The transmission electron microscopy (TEM) is a powerful technique to
study the surface morphology of ND-soot, acid treated-ND and ND-Fe 3O4.
The TEM sample was prepared by dispersing very low quantity of ND-soot,
−1
acid treated and ND-Fe3O4 in distilled water and then dropped on to copper
grid. From the high resolution-TEM (Fig. 1b) the amorphous carbon
impurities on the surface of ND particles (Fig. 1b; left side), the almost single
nanodiamond crystals from the acid treat-ment (Fig. 1b; middle) and
−1 attachment of ND particles on the surface of the Fe 3O4 (Fig. 1c; right side)
was clearly observed. It is clearly ob-served from the TEM results that the
spherical Fe3O4 nanoparticles are well deposited adjacent of ND and there is
no evidence of isolated Fe 3O4 nanoparticles. The carboxyl groups attribute
more advantage for the attachment of Fe 3O4 nanoparticles on the surface of
ND. During the wet-chemical synthesis, the carboxyl group on the ND
particles get re-duced and finally causes the formation of ND-Fe 3O4
nanoparticles.
The scanning electron microscopy (SEM) results were shown in Fig. 4.
The above TEM sample holder for ND-Fe3O4 is used for SEM analysis. The
general scan (Fig. 4a) and the elemental mapping shows that the synthe-sized
nanocomposite contains diamond (Fig. 4b), iron (Fig. 4c) and oxy-gen (Fig.
4d) elements (Fig. 4e). The energy dipsersive X-ray spectra (Fig. 4f) and the
corresponding quantitative atomic weight analysis re-veals that the sample
contains 77.61% of carbon, 0.19% of iron, 13.90% of oxygen and 8.30% of
copper. The sample was prepared on copper grid, that is the reason copper
peak also appeared in the spectra. The atomic weight percentages obtained for
various elements are at local measure-ments. The magnetic measurements
data for weight percentages of ND and Fe 3O4 was used for further analysis,
because the magnetic measure-ments were done for bulk quantity of ND-
Fe3O4.
3.2. Electrical conductivity of ND-Fe3O4 nanocomposite
The electrical conductivity of ND-soot, acid treated-ND and ND-Fe 3O4
was measured by using four point probe technique. The electrical
conductivity of Fe3O4 nanoparticles was also measured for comparison
66 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74
Fig. 2. (a) FTIR spectra for ND-soot, acid treated-ND and ND-Fe 3O4 nanoparticles (b) Raman
spectra for acid treated-ND and ND-Fe3O4 nanoparticles.
purpose. The samples were prepared with a quantity of 80 mg powder and
made circular (diameter 1 cm; Fig. 5c) pellet for measurements. The current–
voltage (I–V) measurements were performed at room temperature (20 °C). To
create the connections directly onto our sam-ples surface, in an easy, fast and
reproducible way, the silver conductive paste was chosen [38], which does
not require any particular equipment (such as metals sputtering or thermal
evaporators devices) [39,40].
Each sample was measured three times to have a statistical average value
for the resistance and to see if the behavior observed was repro-ducible. For
this purpose electrical connections between the voltage supplier and the board
were removed every time before each measure-ment. For samples with ND-
soot and ND-treated the I-V measurements were performed in the range
between ± 110 V with a voltage step of
1 V, and observed values of conductivity are 2.8 × 10 −4 (W-cm)−1 and 7.4 ×
−3 −1
10 (W-cm) , respectively. This indicates that the ND-soot sample is highly
insulating material (Fig. 5a). With acid treatment of ND-soot, the conductivity
of ND enhanced up to 37.83-times and this is possible due to the formation of
carboxyl groups on ND particle sur-
face and turns insulating materials into semiconducting material. The
conductivity of ND-Fe3O4 and Fe3O4 samples were measured with the same
technique and the results were shown in Fig. 5b. The conductivity of Fe3O4 is
−3 −1 −3
60 × 10 (W-cm) whereas the conductivity of ND-Fe 3O4 is 20 × 10 (W-
−1
cm) . It is known that ND is an insulating material
Fig. 3. (a) XRD patterns of ND-Fe3O4 nanoparticles (b) M–H curve of Fe3O4 and ND-Fe3O4
nanoparticles.
and Fe3O4 possesses a moderate resistivity and the resulting nanocom-posite
value changes according to the weight ratio of Fe3O4.
3.3. Colloidal stability of ND-Fe3O4 nanofluid
The zeta potential is the electric potential difference between charged ND-
Fe3O4 particles and a liquid medium. The zeta potential represents the
repulsion force between ND-Fe 3O4 particles in dispersed medium. The
nanofluids with high zeta potential above ± 30 mV are stable and nanofluids
with low zeta potential are not stable [41]. Table 3 represents the zeta
potential of aqueous dispersion of ND-soot, acid treated-ND and ND-Fe 3O4.
The higher zeta potential of acid treated-ND should be attributed to
carboxylic groups on the surface of ND particles. Zeta potential of ND-Fe 3O4
is less than acid treated-ND, be-cause of consuming carboxylic groups by
Fe3O4 nanoparticles to decora-tion on ND particles. The reduction of zeta
potential in ND-Fe3O4 is a point of positive effect of carboxylic group for ND
with Fe3O4.
The stability behavior of ND-soot, acid treated-ND and ND-Fe 3O4 in
distilled water after sonication of 0.5 h and 72 h was explained with op-tical
image. The ND-soot has less carboxyl groups as described in FTIR and zeta
potential analysis, therefore exhibits poor dispersion in dis-tilled water after
sonication of 0.5 and 72 h (Fig. 6a). The acid treated-ND has more carboxyl
+ −
groups, ionization of these groups form H and COO that repulsion forces
increase and provides good stability after 72 h (Fig. 6b). Few of the carboxyl
groups on acid treated-ND sacrificed after decoration by Fe 3O4 nanoparticles;
therefore ND-Fe3O4 has less
 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74
Fig. 4. SEM results and elemental mapping of the ND-Fe3O4 nanoparticles (a) general scan, (b) diamond, (c) iron, (d) oxygen, (e) all elements and (f) EDX spectra.
COOH groups than acid treated-ND particles. Nevertheless the stability of
aqueous ND-Fe3O4 solution is much better than ND-soot because of residual
carboxyl groups after decoration. The water-based 0.05%, 0.1% and 0.2%
volume concentrations of magnetic ND-Fe3O4 nanofluids were shown in Fig.
6c. The synthesized ND-Fe3O4 nanoparticles show magnetic behavior under
magnetic field (Fig. 6d). The particle size dis-tribution of synthesized ND-
Fe3O4 dispersed in water and measured form DLS method and observed as
~21.24 nm (Fig. 6e).
3.4. Thermal conductivity of ND-Fe3O4 nanofluids
Before using the apparatus for nanofluids, the bench mark studies for
thermal conductivity of base fluids such as water, 20:80%, 40:60% and
60:40% EG/W were conducted. Fig. 7a represents the comparison of
experimental thermal conductivity and the data from ASHRAE [42],
Incropera and Dewitt [43] and observed a maximum deviation of
± 2.8%. The experimental thermal conductivity data of water-based magnetic
ND-Fe3O4 nanofluid was shown in Fig. 8 with effects of parti-cle
concentrations and temperatures. To the best of our knowledge, a new kind of
nanocomposite-based nanofluids and its thermal
properties were reported. It is observed from the results that the ther-mal
conductivity of nanocomposite nanofluid increases linearly with in-crease of
particle concentrations and temperatures as observed earlier [1]. The thermal
conductivity enhancements are 9.15% and 17.8% at 0.2% volume
concentrations and at a temperature of 60 °C, respectively compared to water.
The reason for the thermal conductivity enhance-ment is, when the
nanoparticles suspended in base fluid, the heat trans-fer in solid–liquid
suspension occurs at the particle–fluid interface, an increase in the interfacial
area can lead to more efficient heat transfer properties. Another reason for the
enhancement is nanoparticles Brownian motion in the base fluid, so these
nanoparticles contact with the adjacent water molecules and creates micro-
convection [44,45]. Therefore, adding nanocomposite nanoparticles to the
fluids results higher thermal conductivity enhancements. So, this enhancement
de-pends on the particle concentrations. If the particle concentrations are
more, large number of nanoparticles interacts with the adjacent water
molecules and causes higher thermal conductivities. Especially for higher
particle concentrations, there may be possibility of nanoparticle clusters in the
base fluid. These clusters may break into primary nano-particles with help of
sonication. Sonication time is also important for
68 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74
Fig. 5. Current (I)-voltage (V) curves (a) ND-soot and acid treated-ND (b) Fe 3O4 and ND-
Fe3O4 (c) pressed ND-Fe3O4 nanoparticles into 1 cm pellet for I–V measurements.
the preparation of stable nanofluids. In the present work, nanofluids are
sonicated at 0.5 h and 72 h and observed no clusters at 72 h (Fig. 6b).
Therefore, higher sonication time indicates the lesser nano-clusters in the base
fluid. There are some reports on the formation of clusters and aggregates in
the fluid that enhance the thermal conductivity of the fluid [46]. There were
no ND-Fe3O4 nanoparticle agglomerations in the base fluids observed up to
the prepared volume concentrations.
The size of the nanoparticles is also an important parameter for ther-mal
conductivity enhancement. Few reports explained [47,48] that smaller
particle-size attributes higher thermal conductivities because of larger
Brownian motion. In the present work, nanocomposite nano-particles were
used for the preparation of stable nanofluids. Therefore, there may be a
question about the size of nanocomposite nanoparticles. So, the size of
nanocomposite should be less than 100 nm. Nanocompos-ite material is
combination of two or more nanoparticles. ND and Fe 3O4 were selected for
nanocomposite nanoparticle. The nanocomposite
Table 3
Zeta potential of ND-soot, acid treated-ND and ND-Fe3O4 nanoparticles
dispersed in distilled water.
Sample Zeta Potential (mV)
ND-soot −21.5
Acid treated-ND −35.5
ND-Fe3O4 −34.6
particle size depends on the individual size of ND and Fe 3O4. From the TEM
analysis, the size of ND and Fe3O4 obtained as 5 nm and 13 nm, re-
spectively. The final ND-Fe3O4 nanocomposite particle size was mea-sured
from the DLS measurement, while dispersed in distilled water and obtained as
~21.24 nm (Fig. 6c). In the wet chemical synthesis pro-cess for
nanocomposite materials the addition of reducing agent plays an important
role on the particle size [49,50]. For the thermodynamical-ly balanced
chemical reaction, the solution pH should be maintained as 12 after adding
the reducing agent.
Experimental thermal conductivity data for 20:80% EG/W-based
nanofluids were shown in Fig. 9 at various particle concentrations and
temperatures. The thermal conductivity enhancement of 0.2% volume
concentration of nanofluid is 6.6% at 20 °C and 13.4% at 60 °C compared to
20:80% EG/W without nanoparticles. Experimental thermal conductiv-ity
data for 40:60% EG/W-based nanofluids were shown in Fig. 10 at var-ious
particle concentrations and temperatures. The thermal conductivity
enhancement of 0.2% volume concentration of nanofluid is 5% at 20 °C and
13.6% at 60 °C compared to 40:60% EG/W without nanoparticles. Ex-
perimental thermal conductivity data for 60:40% EG/W-based nanofluids
were shown in Fig. 11 at various particle concentrations and tempera-tures.
The thermal conductivity enhancement of 0.2% volume concentra-tion of
nanofluid is 4.1% at 20 °C and 14.6% at 60 °C compared to 60:40% EG/W
without nanoparticles. The thermal conductivity enhancement of nanofluids
with effects of particle concentrations, temperatures and base fluids were
studied. The nanofluids prepared in all the base fluids of-fering the same trend
of increased thermal conductivity with increase of particle volume
concentrations and temperatures, but the order magni-tude varies from one
base fluid to other base fluid. The thermal conduc-tivity enhancement of
nanofluids with effect of base fluids is clearly observed. At same particle
concentrations of ϕ = 0.2% and temperatures of 60 °C water-based nanofluids
offering more thermal conductivity en-hancement compared to other 20:80%,
40:60% and 60:40% EG/W-based nanofluids. The selection of base fluid is
important for obtaining higher thermal conductivities. Based on the literature
[42,43], the thermal con-ductivity of water is more compared to other
20:80%, 40:60% and 60:40% EG/W mixtures. That is the reason nanofluids
prepared with water as a base fluid is offering more thermal conductivities
compared other base fluids. Karthikeyan et al. [51] used two different base
fluids such as water and ethylene glycol for the preparation of CuO nanofluids
and obtained thermal conductivity enhancements of 31.6% for water and 54%
for ethylene glycol at 1% volume concentrations. It is also ob-served that
thermal conductivity enhancement is not constant for all the base fluids; it
varies from one base fluid to other base fluid. In the present study also thermal
conductivity enhancement for all the nanofluids is not constant. Present study
reveals that the thermal conduc-tivity enhancement of nanofluids not only
depends on the particle con-centrations and temperatures but it also depends
on the base fluids.
The thermal conductivity ratio (knf/kbf) of water-based ND-Fe3O4
nanofluids were shown in Fig. 12a in comparison with the data of Sundar et
al. [52] and Abareshi et al. [53] for water-based Fe3O4 nanofluid, be-cause no
literature on ND-Fe3O4 nanofluids. They observed similar trend of increase in
thermal conductivity for water-based Fe 3O4 nanofluids with increase of
particle concentrations and temperatures. In the estimated particle
concentration of ϕ = 0.2% and temperature of
60 °C, nanofluid prepared with ND-Fe3O4 nanoparticles shows 1.02-times
higher thermal conductivity compared to nanofluid prepared with Fe3O4
nanoparticles. This indicates that the nanocomposite nanofluids are much
better than single-nanoparticle nanofluids. The thermal conductivity ratio
(knf/kbf) of 60:40% EG/W-based ND-Fe 3O4 nanofluids were shown in Fig.
12b in comparison with the data of Sundar et al. [13] for 60:40% EG/W-based
Fe3O4 nanofluids and Vajjha and Das [54] for 60:40% EG/W-based CuO
nanofluid. In the estimated particle concentration of ϕ = 0.2% and temperature
of 60 °C, nanofluid prepared with ND-Fe3O4 nanoparticles shows 1.03-times
higher thermal conduc-tivity compared to nanofluid prepared with Fe3O4
nanoparticles. Nanofluids prepared with nanocomposite material show better
values
 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

Fig. 6. Stability behavior of nanofluids (002 mg/ml) (a) sonication after 0.5 h (b) sonication after 72 h (ND-soot; left-side), (acid treated-ND; middle), (ND-Fe 3O4; right-side) (c) 0.05%, 0.1% and
0.2% volume concentrations of water-based magnetic ND-Fe 3O4 nanofluids (d) ND-Fe3O4 nanoparticles showing magnetic behavior under magnetic field (e) ND-Fe3O4 nanoparticle size distribution
while dispersed in distilled water measured from dynamic light scattering method (~21.24 nm).

compared to single-nanoparticle. In the measured particle volume con- fluid, nanofluid and particle, respectively. The Maxwell's model is good for
centration of ϕ = 0.2% and temperature of 60 °C, thermal conductivity spherical shaped particles with low particle volume concentrations.
enhancements order is (knf)w N (knf)60:40% N (knf)40:60% N (knf)20:80%. The Hamilton and Crosser [56] model is the extended version of Maxwell
present experimental thermal conductivity values for all the nanofluids were model. They introduced shape factor to account for the effect of the shape of
represented in Table. 4. particles. The effective thermal conductivity of the solid– liquid mixture is
The Maxwell [55] model for effective thermal conductivity of solid– given as
liquid mixtures is given for micro or millimeter sized particles suspended in "
knf ¼ kbf kp n−1 kbf ϕ kbf −kp # ð4Þ
base fluids.
" þ kp þ ðn −1Þkbf −ðn −1Þϕ kbf −kp
knf ¼ kbf kp 2kbf −ϕ kp−kbf # ð3Þ
kp 2kbf þ 2ϕ kp−kbf
þð Þ þ
where n is the empirical shape factor given by 3/ψ, and ψ is the particle
þ sphericity, defined as surface area of a sphere (with the same volume as the
where k is the thermal conductivity, the suffix bf, nf, p stands for base given particle) to the surface area of the particle.
70 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

Fig. 9. Present data of thermal conductivity and viscosity for 20:80% EG/W-based ND-Fe 3O4
nanofluids at different volume concentrations and temperatures.

as Al2O3, CuO, SiO2, TiO2, ND and Fe3O4 etc., but for the case of nanocom-
posites detailed study on the thermal conductivity is required. The above Eqs.
(4) and (5) are valid only to estimate the thermal conductivity of single-
nanoparticles based nanofluids. It is doubtful to study to estimate thermal
conductivity of nanocomposite nanofluids.
The experimental results of thermal conductivity derived from four
different nanofluids combined into a generalized form and developed
correlation by assuming linear increase of nanofluid thermal conductiv-ity
with respect to particle volume concentrations(ϕ). The equation is valid in the
temperature range from 20 °C to 60 °C and concentrations range from 0.05%
to 0.2%.
k
nf

k
bf ¼aþbϕ ð5Þ
o
T ¼ 20 C ⇒ a ¼ 1:0149; b ¼ 0:2403
Fig. 7. Benchmark study of the base fluids such as water, 20:80%, 40:60% and 60:40% EG/W
(a) thermal conductivity (b) viscosity. o
T ¼ 30 C ⇒ a ¼ 1:0188; b ¼ 0:3751
For spherical particle the value of n is 3. In the theoretical Eqs. (4) and
o
(5) the term kpstands for the thermal conductivity of nanoparticles. It is easy T ¼ 40 C ⇒ a ¼ 1:0157; b ¼ 0:4728
to understand the thermal conductivity of single-nanoparticles such
o
T ¼ 50 C ⇒ a ¼ 1:0168; b ¼ 0:5697

Fig. 8. Present data of thermal conductivity and viscosity for water-based ND-Fe 3O4 Fig. 10. Present data of thermal conductivity and viscosity for 40:60% EG/W-based ND-
nanofluids at different volume concentrations and temperatures. Fe3O4 nanofluids at different volume concentrations and temperatures.
 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

Fig. 11. Present data of thermal conductivity and viscosity for 60:40% EG/W-based ND-Fe 3O4
nanofluids at different volume concentrations and temperatures.

o
T ¼ 60 C ⇒ a ¼ 1:0150; b ¼ 0:6818

3.5. Viscosity of ND-Fe3O4 nanofluids

The experimental viscosity data for water, 20:80%, 40:60% and 60:40%
EG/W fluids were compared with the AHSRAE and Incropera and Dewitt and
we noted a maximum deviation of ±2% (Fig. 7b). Exper-imental viscosity
data for water-based ND-Fe 3O4 nanofluids were shown in Fig. 8 at various
particle concentrations and temperatures. It observed that viscosity of
nanofluids increases with particle concentra-tions, but decreases with increase
of temperatures. The viscosity en-hancement for 0.2% volume concentration
nanofluid is 1.59-times at 20 °C and 1.72-times at 60 °C compared to water
without nanoparticles. We also observed that the viscosity enhancement of
nanofluids shows non-linear behavior with increase of particle concentrations.
The reason for viscosity enhancement for nanofluids is due to higher
resistance be-tween the two fluid layers. This resistance is low for lower Fig. 12. Comparison of present thermal conductivity ratio of ND-Fe 3O4 nanofluids with the
volume con-centrations and high for higher volume concentrations. published literature (a) water (b) 60:40% EG/W-based nanofluids.
Experimental viscosity data for 20:80% EG/W-based ND-Fe3O4 nanofluids
were shown in Fig. 9 at various particle concentrations and temperatures. The because no literature on ND-Fe 3O4 nanofluids. They observed similar trend of
viscosity enhancement for 0.2% volume concentration nanofluid is 2.03-times increase in viscosity for Fe3O4/water and Al2O3/propylene glycol nanofluids
at 20 °C and 2.19-times at 60 °C compared to 20:80% EG/W without with increase of particle concentrations. In the measured par-ticle
nanoparticles. Experimental viscosity data for 40:60% EG/W-based ND- concentration of ϕ = 0.2% and temperature of 60 °C, ND-Fe 3O4/ water
Fe3O4 nanofluids were shown in Fig. 10 at various particle concentrations and nanofluid showing 1.57-times higher viscosity compared to Fe 3O4/water [52]
temperatures. The viscosity enhancement for 0.2% volume concentration nanoparticles and 1.27-times higher viscosity com-pared to Al 2O3/propylene
nanofluid is 2.08-times at 20 °C and 1.50-times at 60 °C compared to 40:60% glycol [50] at 3.0% volume concentration. This higher viscosity for the case
EG/W without nanoparticles. Experimental viscosity data for 60:40% EG/W- of nanocomposite nanoparticles compared
based ND-Fe3O4 nanofluids were shown in Fig. 11 at various particle
concentrations and temperatures. The vis-cosity enhancement for 0.2% Table 4
Experimental thermal conductivity of different concentrations of ND-Fe 3O4 nanofluids.
volume concentration nanofluid is 1.71-times at 20 °C and 1.79-times at 60 °C
compared to 40:60% EG/W with-out nanoparticles. The viscosity
enhancement for all the nanofluids prepared with various base fluids is not
constant; it varies from fluid to fluid. Each fluid is having its own viscosity
properties. Hence, the vis-cosity enhancement depends on particle
concentrations, temperatures and base fluids. Among all the nanofluids,
20:80% EG/W-base nanofluids are offering more viscosity enhancements
compared to other base fluids.

The viscosity ratio (μnf/μbf) of water-based ND-Fe 3O4 nanofluids was

shown in Fig. 13a in comparison with the data of Sundar et al. [52] for
Fe3O4/water and Prasher et al. [50] for Al2O3/propylene glycol nanofluids,
Base fluid Temp., (°C) ϕ = 0.0% ϕ = 0.05% ϕ = 0.10% ϕ = 0.20%
Water 20 0.602 0.6158 0.6345 0.6571
40 0.631 0.6489 0.6706 0.7036
60 0.653 0.6842 0.7177 0.769
20:80% EG/W 20 0.492 0.5075 0.5123 0.5244
40 0.515 0.5345 0.5564 0.5765
60 0.53 0.5561 0.58823 0.6012
40:60% EG/W 20 0.404 0.4169 0.4198 0.4243
40 0.419 0.4356 0.4494 0.4579
60 0.43 0.4479 0.4657 0.4887
60:40% EG/W 20 0.334 0.3392 0.3444 0.3478
40 0.343 0.3542 0.3653 0.3787
60 0.35 0.3628 0.3757 0.4013
72 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

Table 5
Experimental viscosity of different concentrations of ND-Fe 3O4 nanofluids.

Base fluid Temp., (°C) ϕ = 0.0% ϕ = 0.05

Water 20 0.79 1.2
40 0.48 0.58
60 0.24 0.37
20:80% EG/W 20 1.55 2.02
40 0.91 1.21
60 0.63 0.69
40:60% EG/W 20 2.94 4.52
40 1.8 2.08
60 1.18 1.39
60:40% EG/W 20 5.75 8.5
40 2.61 3.93
60 1.62 2.56

experimental viscosity data for all the nanofluids were shown in Table. 5.

Einstein model [59] is a well-known theoretical model to predict the

effective viscosity of the solid–fluid mixture. However, the applicability of
this model is limited to low volume concentrations (φb 0.02%); the
formulation of this model is given as:
μ
nf

μ
¼ 1 þ 2:5ϕ:
bf ð6Þ
The extended Einstein's formula for use with moderate particle con-
centrations proposed by Brinkman [60] is formulated as follows:

μnf 1

Fig. 13. Comparison of present viscosity ratio of ND-Fe 3O4 nanofluids with the published
literature (a) water (b) 60:40% EG/W-based nanofluids.
to single-nanoparticles attributes more resistance between the fluid layers.
μ 2:5
¼ ð1−ϕÞ
bf : ð7Þ
The Einstein model for nanofluids is based on the assumption of a
Newtonian fluid containing suspensions of spherical nanoparticles; it does not
take into consideration temperature dependence and, in gen-eral, viscosity of
liquids is strongly dependent on the temperature. In the above Eqs. (6) and
(7), the viscosity ratio μnf/μbf is purely depends on the particle concentration
only. But there may be a doubt to predict those equations for nanocomposite
nanofluids. The present data is ver-ified manually by substituting the values
and both the equations predicting same values at volume concentration and
temperatures. The experimental viscosity data for four nanofluids is fit into a
general-ized correlation by considering viscosity nanofluids increases
exponen-tially with increase of particle volume concentration (ϕ). The
o o
equation valid in the temperature range of 20 C b T b 60 C and
concentrations range of 0.05 % b ϕb 0.2%.

The viscosity ratio (μnf/μbf) of 60:40% EG/W-based ND-Fe3O4 nanofluids μnf

was shown in Fig. 13b in comparison with the data of Sundar et al. [57] for ¼ a eb ϕ 8
60:40% EG/W-based Fe3O4 nanofluids and Namburu et al. [58] for 60:40% μ
bf ðÞ
EG/W-based CuO nanofluid. In the estimated particle concentration of ϕ =
o
0.2% and temperature of 60 °C, nanofluid prepared with ND-Fe3O4 T ¼ 20 C ⇒ a ¼ 1:444; b ¼ 1:402
nanoparticles showing 1.398-times higher viscosity compared to nanofluid
o
prepared with Fe3O4 nanoparticles [58] and 1.556-times higher compared to T ¼ 30 C ⇒ a ¼ 1:368; b ¼ 1:472
CuO nano-particles [53]. Nanofluids prepared with nanocomposite material
o
show better values compared to single-nanoparticle. We observed that, even T ¼ 40 C ⇒ a ¼ 1:277; b ¼ 1:625
for low particle concentrations, the relative viscosity of the ND-Fe 3O4
o
nanofluid is higher than that of the data of Sundar et al. [57] and Namburu et T ¼ 50 C ⇒ a ¼ 1:288; b ¼ 1:771
al. [58]. For 60:40% EG-water based ND-Fe 3O4 nanofluids, the viscosity
o
remains unchanged with increasing temperature; however, Namburu et al. T ¼ 60 C ⇒ a ¼ 1:338; b ¼ 1:655
[58] observed a decrease in relative viscosity with increasing temperature and
Sundar et al.
4. Conclusions
[57] obtained an increase in relative viscosity with increasing tem-
perature. In the measured particle concentration of ϕ = 0.2% and temperature In summary, we have successfully synthesized a new kind of magnet-ic
of 60 °C, viscosity enhancement follow the below ND-Fe3O4 nanoparticles by simple in-situ and chemical coprecipitation
order (μ20:80%)nf N (μ 60:40%)nf N (μ w)nf N (μ40:60%)nf. The present method. The TEM and XRD analysis confirms that Fe3O4 nanoparticles were
attached on the surface of ND particles homogeneously. The results
 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

of zeta potential indicate that, magnetic ND-Fe 3O4 nanoparticles were good [14] W. Yu, H. Xie, L. Chen, Y. Li, Enhancement of thermal conductivity of kerosene-
dispersion in distilled water. The magnetic result reveals that ND-Fe 3O4 based Fe3O4 nanofluids prepared via phase-transfer method, Colloids Surf. A Physicochem.
Eng. Asp. 355 (2010) 109–113.
nanoparticles contain 72% of ND and 28% of Fe 3O4 present in the ND-
[15] L.S. Sundar, M.K. Singh, A.C.M. Sousa, Thermal conductivity of ethylene glycol
Fe3O4. The electrical conductivity of powder ND-Fe 3O4 nano-particles shown and water mixture based Fe3O4 nanofluid, Int. Commun. Heat Mass Transfer 49 (2013) 17–24.
26-times higher compared to ND-soot. The thermal con-ductivity of 0.2%
volume concentration of water, 20:80%, 40:60% and 60:40% EG/W nanofluid
[16] K. Parekh, H.S. Lee, Magnetic field induced enhancement in thermal conductivity
of magnetite nanofluid, J. Appl. Phys. 107 (2010) 09A310.
is 17.8%, 13.43%, 13.6% and 14.6% at a tempera-ture of 60 °C, respectively
compared to its base fluids. The thermal con-ductivity enhancement of
nanofluids does not only depend on the particle concentrations and
temperatures but it also depends on the base fluid thermal conductivity. The
classical theories of Maxwell and Hamilton–Crosser is not suitable to predict
the thermal conductivity of nanocomposite nanofluids.

The viscosity of 0.2% volume concentration of water, 20:80%, 40:60%

and 60:40% EG/W nanofluids is 1.72-times, 2.19-times, 1.50-times and 1.79-
times at a temperature of 60 °C, respectively compared to its base fluids. The
classical viscosity models of Einstein and Brinkman is doubtful to predict the
viscosity of nanocomposite nanofluids. At same particle concentrations and
temperatures, viscosity enhancements are more compared to thermal
conductivity enhancements. Development of new theoretical models are
necessary for composite nanofluids. Finally, the thermal conductivity and
viscosity of fluids prepared with composite nanoparticles are better than
conventional single-phase nanoparticles.

Acknowledgment

The authors acknowledge the financial support received from Foun-dation

for the Science and Technology (FCT, Portugal) and, in particular, the
funding through the post-doctoral grant SFRH/BPD/100003/2014 (LSS) and
the 2013 FCT Investigator program (MKS).

References

[1] S.U.S. Choi, Enhancing thermal conductivity of fluids with nanoparticles, Proceed-ings of
the ASME International Mechanical Engineering Congress and Exposition San Francisco, USA,
1995.
[2] V.Y. Dolmatov, Detonation synthesis ultra dispersed diamonds: properties and ap-
plications, Russ. Chem. Rev. 70 (2001) 607–626.
[3] H.B. Ma, C. Wilson, B. Borgmeyer, K. Park, Q. Yu, S.U.S. Choi, T. Murli, Effect of
nanofluid on the heat transport capability in an oscillating heat pipe, Appl. Phys. Lett. 88 (2006)
143116 (3 Pages).
[4] H. Xie, W. Yu, Y. Li, Thermal performance enhancement in nanofluids containing di-
amond nanoparticles, J. Phys. D. Appl. Phys. 42 (2009) 095413 (5 Pages).
[5] M. Yeganeh, N. Shahtahmasebi, A. Kompany, E.K. Goharshadi, A. Yousse fi, L. Šiller,
Volume fraction and temperature variations of the effective thermal conductivity of
nanodiamond fluids in deionized water, Int. J. Heat Mass Transf. 53 (2010) 3186–3192.

[6] T. Tyler, O. Shenderova, G. Cunningham, J. Walsh, J. Drobnik, G. McGuire, Thermal

transport properties of diamond-based nanofluids and nanocomposites, Diam. Relat. Mater. 15
(2006) 2078–2081.
[7] B.T. Branson, P.S. Beauchamp, J.C. Beam, C.M. Lukehart, J.L. Davidson, Nanodiamond
nanofluids for enhanced thermal conductivity, ACS Nano 7 (2013) 3183–3189.
[8] S. Torii, W.J. Yang, Heat transfer augmentation of aqueous suspensions of nanodiamonds
in turbulent pipe flow, J. Heat Transf. 131 (2009) 043203 (5 Pages).
[9] M. Ghazvini, M.A. Akhavan-Behabadi, E. Rasouli, M. Raisee, Heat transfer properties of
nanodiamond–engine oil nanofluid in laminar flow, Heat Transfer Eng. 33 (2011) 525–532.
[10] W. Yu, H. Xie, Y. Li, L. Chen, Q. Wang, Experimental investigation on the
thermal transport properties of ethylene glycol based nanofluids containing low volume
concentration diamond nanoparticles, Colloids Surf. A Physicochem. Eng. Asp. 380 (2011) 1–
5.
[11] J.J. Taha-Tijerina, T.N. Narayanan, C.S. Tiwary, K. Lozano, M. Chipara, P.M.
Ajayan, Nanodiamond-based thermal fluids, Appl. Mater. Interfaces 6 (2014) 4778–4785.
[12] Z.L. Liu, Z.H. Ding, K.L. Yao, J. Tao, Preparation and characterization of
polymercoated core-shell structured magnetic microbeads, J. Magn. Magn. Mater. 265 (2003)
98–105.

[13] J. Philip, P.D. Shima, B. Raj, Enhancement of thermal conductivity in magnetite

based nanofluid due to chainlike structures, Appl. Phys. Lett. 91 (2007) 203108–203111.
[17] A. Gavili, F. Zabihi, T.D. Isfahani, J. Sabbaghzadeh, The thermal conductivity of [46] J.J. Vadasz, S. Govender, P. Vadasz, Heat transfer enhancement in nano- fluids
water base ferrofluids under magnetic field, Exp. Thermal Fluid Sci. 41 (2012) 94–98. sus-pensions: possible mechanisms and explanations, Int. J. Heat Mass Transf. 48 (2005) 2673–
2683.
[18] V.E. Fertman, L.E. Golovicher, N.P. Matusevich, Thermal conductivity of
magnetite magnetic fluids, J. Magn. Magn. Mater. 65 (1987) 211–214. [47] P. Keblinski, S.R. Phillpot, S.U.S. Choi, J.A. Eastman, Mechanisms of heat flow
in sus-pensions of nano-sized particles (nanofluids), Int. J. Heat Mass Transf. 45 (2002) 855–
[19] H. Zeng, J. Li, J.P. Liu, Z.L. Wang, S. Sun, Exchange-coupled nanocomposite 863.
magnets by nanoparticle self-assembly, Nat. Lett. 420 (2002) 395–398.
[48] S.P. Jang, S.U.S. Choi, The role of brownian motion in the enhanced thermal
[20] X.Q. Shi, X.H. Jiang, L.D. Lu, X.J. Yang, X. Wang, Structure and catalytic conduc-tivity of nanofluids, Appl. Phys. Lett. 84 (2004) 4316–4318.
activity of nanodiamond/Cu nanocomposites, Mater. Lett. 62 (2008) 1238–1241.
[49] K.S. Hong, T.K. Hong, H.S. Yang, Thermal conductivity of Fe nanofluids
[21] V. Livramento, J.B. Correia, N. Shohoji, E. Ōsawa, Nanodiamond as an effective depending on the cluster size of nanoparticles, Appl. Phys. Lett. 88 (2006) 031901.
rein-forcing component for nano-copper, Diam. Relat. Mater. 16 (2007) 202–204.
[50] R. Prasher, E. William, P. Meakin, F. Jacob, P. Patrick, P. Keblinski, Effect of
[22] D. Nunes, M. Vilarigues, J.B. Correia, P.A. Carvalho, Nickel–carbon aggrega-tion on thermal conduction in colloidal nanofluids, Appl. Phys. Lett. 89 (2006) 143119.
nanocomposites: synthesis, structural changes and strengthening mechanisms, Acta Mater. 60
(2012) 737–747.
[51] N.R. Karthikeyan, J. Philip, B. Raj, Effect of clustering on the thermal
[23] L.S. Sundar, M.K. Singh, E.V. Ramana, B.K. Singh, J.J.A. Gracio, A.C.M. Sousa, conductivity of nanofluids, Mater. Chem. Phys. 109 (2008) 50–55.
Enhanced thermal conductivity and viscosity of nanodiamond-nickel nanocomposite nanofluids,
Sci. Rep. 4 (2014) 4039.
[52] L.S. Sundar, M.K. Singh, A.C.M. Sousa, Investigation of thermal conductivity
and vis-cosity of Fe3O4 nanofluid for heat transfer applications, Int. Commun. Heat Mass
[24] G.A. Voronin, T.W. Zerda, J. Qian, Y. Zhao, D. He, S.N. Dub, Diamond –Sic Transfer 44 (2013) 7–14.
nanocom-posites sintered from a mixture of diamond and silicon nanopowders, Diam. Relat.
Mater. 12 (2003) 1477–1481.
[25] S. Suresh, K.P. Venkitaraj, P. Selvakumar, M. Chandrasekar, Effect of Al 2O3–
Cu/water hybrid nanofluid in heat transfer, Exp. Thermal Fluid Sci. 38 (2010) 54–60.
[26] T.T. Baby, S. Ramaprabhu, Surfactant free magnetic nanofluids based on core-
shell type nanoparticle decorated multiwalled carbon nanotubes, J. Appl. Phys. 110 (2011)
064325–064331.
[27] L.S. Sundar, M.K. Singh, A.C.M. Sousa, Enhanced heat transfer and friction
factor of MWCNT–Fe3O4/water hybrid nanofluid, Int. Commun. Heat Mass Transfer 52 (2014)
73–83.
[28] www.itc-inc.org/nanodiamond.html

[29] www.sigma-aldrich.com

[30] M.K. Singh, T. Shokuhfar, J.J.A. Gracio, A.C.M. Sousa, J.M.F. Fereira, H.
Garmestani, S. Ahzi, Hydroxyapatite modified with carbon-nanotube-reinforced poly (methyl
methacrylate): a nanocomposite material for biomedical applications, Adv. Funct. Mater. 18
(2008) 694–700.
[31] F.M. Smits, Measurements of sheet resistivities with the four-point probe, Bell
Syst. Tech. J. (1958) 711–718.
[32] F.C. McQuiston, J.D. Parker, J.D. Spitler, Heating, Ventilating, and Air
Conditioning: Analysis and Design, sixth ed. John Wiley & Sons, New York, 2000.
[33] L.C.L. Huang, H.C. Chang, Adsorption and immobilization of cytochrome C on
nanodiamonds, Langmuir 20 (2004) 5879–5884.
[34] T. Ando, S. Inoue, M. Ishii, M. Kamo, Y. Sato, O. Yamada, T. Nakano, Fourier-
transform infrared photoacoustic studies of hydrogenated diamond surfaces, J. Chem. Soc. Far-
aday Trans. 89 (1993) 749–751.
[35] P.H. Chung, E. Perevedentseva, J.S. Tu, C.C. Chang, C.L. Cheng, Spectroscopic
study of bio-functionalized nanodiamonds, Diam. Relat. Mater. 15 (2006) 622–625.
[36] A.C. Ferrari, J. Robertson, Raman spectroscopy of amorphous, nanostructured,
diamond-like carbon, and nanodiamond, Phil. Trans. A. 362 (2004) 2477–2512.
[37] M.A.C. Duarte, M. Grzelczak, V.S. Maceira, M. Giersig, L.M.L. Marzan, M.
Farle, K. Sierazdki, R. Diaz, Alignment of carbon nanotubes under low magnetic fields through
attachment of magnetic nanoparticles, J. Phys. Chem. B. 109 (2005) 19060.
[38] A. Chiolerio, P. Allia, A. Chiodoni, F. Pirri, F. Celegato, M. Coisson, Thermally
evaporat-ed Cu–Co top spin valve with random exchange bias, J. Appl. Phys. 101 (2007)
123911.

[39] N. Hu, Y. Karube, C. Yan, Z. Masuda, H. Fukunaga, Tunneling effect in a

polymer/carbon nanotube nanocomposite strain sensor, Acta Mater. 56 (2008) 2929–2936.

[40] J.N. Coleman, S. Curran, A.B. Dalton, A.P. Davey, B. McCarthy, W. Blau, R.C.
Barklie, Percolation-dominated conductivity in a conjugated-polymer-carbon-nanotube
composite, Phys. Rev. B 58 (1998) 7492–7495.
[41] J. Kim, D.F. Lawler, Characteristics of zeta potential distribution in silica
particles, Bull. Kor. Chem. Soc. 26 (2005) 1083–1089.
[42] ASHRAE handbook—refrigeration, American Society of Heating, Refrigerating
and Air-Conditioning Engineers, John Wiley & Sons, USA, 2006.
[43] F.P. Incropera, D.P. Dewitt, Introduction to Heat Transfer, sixth ed. Wiley
Publishers, 2006.
[44] C.H. Li, G.P. Peterson, Experimental investigation of temperature and volume
frac-tion variations on the effective thermal conductivity nanoparticle suspensions (nanofluids),
J. Appl. Phys. 99 (2006) 084314.
[45] S.K. Das, N. Putra, P. Thiesen, W. Roetzel, Temperature dependence of thermal
con-ductivity enhancement for nanofluids, J. Heat Transf. 125 (2003) 567–574.
74 L.S. Sundar et al. / International Communications in Heat and Mass Transfer 73 (2016) 62–74

[53] M. Abareshi, E. Goharshadi, S. Zebarjad, H.K. Fadafan, A. Youssefi, Fabrication [57] L.S. Sundar, E.V. Ramana, M.K. Singh, A.C.M. Sousa, Viscosity of low volume
charac-terization and measurement of thermal conductivity of Fe 3O4 nanofluids, J. Magn. Magn. concen-trations of magnetic Fe3O4 nanoparticles dispersed in ethylene glycol and water
Mater. 322 (2010) 3895–3901. mixture, Chem. Phys. Lett. 554 (2012) 236–242.
[54] R.S. Vajjha, D.K. Das, Experimental determination of thermal conductivity of [58] P.K. Namburu, D.P. Kulkarni, D. Misra, D.K. Das, Viscosity of copper oxide
three nanofluids and development of new correlations, Int. J. Heat Mass Transf. 52 (2009) nanoparti-cles dispersed in ethylene glycol and water mixture, Exp. Thermal Fluid Sci. 32
4675–4682. (2007) 397–402.
[55] J.C. Maxwell, A Treatise on Electricity and Magnetism, second ed. Oxford [59] A. Einstein, A new determination of molecular dimensions, Ann. Phys. 19 (1906)
University Press, Cambridge, 1904 (UK). 289–306.
[56] R. Hamilton, O. Crosser, Thermal Conductivity of Heterogeneous Two [60] H.C. Brinkman, The viscosity of concentrated suspensions and solution, J. Chem.
Component Systems, I and EC Fundamentals, 1251962 187–191. Phys. 20 (1952) 571–581.