Powder Technology 307 (2017) 1024

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Powder Technology
journal homepage: www.elsevier.com/locate/powtec

Experimental investigation on the effect of dispersant addition on

thermal and rheological characteristics of TiO2 nanouid
Samarshi Chakraborty a, Ishita Sarkar a, Dinesh K. Behera a, Surjya K. Pal b, Sudipto Chakraborty a,
a
b

Department of Chemical Engineering, Indian Institute of Technology Kharagpur, India

Department of Mechanical Engineering, Indian Institute of Technology Kharagpur, India

a r t i c l e

i n f o

Article history:
Received 21 February 2016
Received in revised form 9 November 2016
Accepted 14 November 2016
Available online 15 November 2016
Keywords:
Nanouid
TiO2
Dispersants
Thermal conductivity
Surface tension
Rheological model

a b s t r a c t
In the current work, TiO2 nanouid has been synthesized via two-step co-precipitation method. TEM analysis has
been carried out to measure the average particle size and to check the particle distributions which conrm the
formation of a suspension having an average particle size of b 100 nm. Thermogravimetric analysis of TiO2 nanoparticle conrms its suitability for high-temperature cooling application without the concern of thermal degradation (up to 800 C weight loss b1%). However, the prime objective of the present study focuses on the
numerous thermo-physical aspects (i.e. thermal conductivity, surface tension, and viscosity) and rheological
properties of TiO2 nanouid at different uid temperature. Thermal conductivity is considered as the most crucial
thermo-physical properties of any nanouid. In the present study with increasing particle concentration, the
thermal conductivity value increased up to an optimum concentration then reduced. For temperature dependency study, with increasing temperature the thermal conductivity values for all particle concentration increases.
Dispersant (Polyvinylpyrrolidone, Tween 20) addition in nanouid plays a crucial role not only in terms of stability but also regarding thermal and rheological properties which have also been investigated in details in this
work. Different rheological models have been tted with experimentally obtained viscosity value to assess the
ow behaviour of TiO2 nanouids with and without dispersants. Rheological analysis revealed that for all the
temperatures, both TiO2, TiO2-Tween 20 nanouid follows Carreau model whereas TiO2-PVP nanouid follows
Cross model. Effect of dispersants addition on nanouid stability is another key aspect of the present investigation
and the study shows that TiO2-PVP nanouid shows the best stability.
2016 Elsevier B.V. All rights reserved.

1. Introduction
With the advancement in the eld of heat transfer and thermal engineering, high-performance cooling is the crucial need for various industrial applications. Improvement in coolant medium has its direct
benets for power production, air conditioning system, electronics,
transportation, chemical process, aerospace and manufacturing application. Thermal conductivity of uid plays a major part in heat transport
efciency of the same. Traditional coolant for example oils, water, ethylene glycol and different alcohol are commonly used in various industries for heat extraction. The poor thermal conductivity of the
conventional coolant restricts the thermal performance. Improved thermal performance of the coolant can lead to smaller and highly efcient
heat transfer apparatus. Substantial growth in the eld of telecommunication, electronics and nanotechnology have led to the advancement of
miniaturized devices with greater storage capacity and faster processing efciency. This miniaturization gives rise to several problems related
Corresponding author at: Chemical Engineering Department, IIT Kharagpur,
Kharagpur 721302, West Bengal, India.
E-mail address: sc@che.iitkgp.ernet.in (S. Chakraborty).

http://dx.doi.org/10.1016/j.powtec.2016.11.016
0032-5910/ 2016 Elsevier B.V. All rights reserved.

to thermal management of those devices. This problem can be addressed by developing sophisticated heat transfer uid with enhanced
thermal conductivity. Suspension of solid particle with higher thermal
conductivity, in turn, leads to the improved thermal conductivity of
the coolant medium. However, suspending micron size particle in the
base uids gives rise to several other problems such as poor stability,
particle aggregation, increased pressure drop, channel erosion, high
pumping cost, etc. With advancement in nanotechnology in past two
decades, synthesis of the nanosized particle is now possible. Using suspension of nanoparticle in the base uids, scientists can overcome most
of the problems faced by micron-sized particle suspension. Nanoparticle
(particle size b 100 nm) suspension in base uid is termed as nanouid.
In the year 1993 from Argonne National Laboratory (ANL, USA),
Stephan Choi [1] rst introduced the idea of using nanouids for enhancing heat transfer rate. Metals (Cu, Al, Ag, Au, etc.) and metal oxides
(like CuO, Al2O3, ZnO, SiO2, TiO2) particles are normally used as additives in nanouids while water, ethylene glycol, silicon oil, and polymers are used as base uids. Nanoparticle addition in the base uid
leads to several improved features such as incredible improvement in
thermal conductivity, improved stability than micron sized particle suspension. Nanoparticle addition in small concentration has minimal

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

effect on viscosity and pressure drop. Lower particle size also leads to
better thermal conductivity.
Among several benecial features of nanouids as a coolant, thermal
conductivity enhancement is the most signicant one. Thermal conductivity improvement of nanouids depends on several features like:
Brownian/random motion of nanoparticle: Impact of higher temperature particle with lower temperature ones [2].
Particle dispersion: Thermal conductivity rises due to the uniform
dispersion of nanoparticle by adding surface active agents [3,4].
Effect of turbulence: Due to turbulent eddies, effective thermal conductivity is much greater than actual thermal conductivity [5].
The size of nanoparticle: Particle having diameter lesser than 20 nm
has a higher amount of surface atoms which enhances its thermal interactions [6].
The shape of nanoparticle: Thermal conductivity is greater for higher
aspect ratio particle. Therefore, nano-cylinders show higher thermal
conductivity than nano-spheres [7].
Inuence of the liquid-solid interface: Liquid molecules in contact with
the solid nanoparticle forms a liquid layer which is more ordered
than bulk liquid. This layer acts as a thermal link between the solid
nanoparticle and bulk liquids and enhances thermal conductivity
[8].
Xuan and Li [4] rst prepared copper based nanoparticle suspension
in transformer oil and achieved 55% enhancement in thermal conductivity with 5 vol.% loading. Eastman et al. [9] used copper nanoparticle
(10 nm size) in ethylene glycol and achieved 40% increment in thermal
conductivity with a nominal concentration of nanoparticle (0.3%). Silver, gold [10] and iron [11] nanoparticle were also used for preparing
nanouids by several researchers. Numerous work on carbon nanotube
based nanouids is present in the open literature. Choi et al. [12] used
multi-wall carbon nanotube (MWCNT) and obtained 150% enhancement in thermal conductivity with 1 vol.% addition. Assael et al. [13] reported thermal conductivity of MWCNT and double wall carbon
nanotube (DWCNT) in water. For MWCNT, thermal conductivity enhancement was 34% (0.6 vol.%), whereas for DWCNT it was 8%
(1 vol.%). In spite of having high thermal conductivity, metallic and
CNT-based nanouids are not feasible for bulk application due to its
high cost.
In this regard, metal oxide based nanouid gives moderate thermal
conductivity at a much lower cost. A brief summary on some of the selected works about metal-oxide nanouids are reported in Table 1.
In this present study, Titanium dioxide nanoparticle is selected for
nanouid preparation. The main reason behind choosing TiO2 is attributed to its low cost. In addition to this, titanium dioxide has limited
health hazard as it is used in many sunscreen lotions, paints and also
in toothpaste. Application of this nanoparticle as a food coloring agent
indicates its harmless nature. It also has much less impact on the environment as compared to other oxide-based nanoparticles.
In the current study, authors have mainly focussed on the effect of
particle concentration, temperature and dispersant addition on the
thermo-physical properties (thermal conductivity, surface tension,
and viscosity) of nanouid. Thermo-physical properties of nanouids

11

include thermal conductivity, surface tension, viscosity, and stability.

Present work, in particular, gives added attention to rheological behaviour prior and post dispersant (polymer and non-ionic surfactant) addition in the temperature range of 3050 C.

2. Material and methods

2.1. Materials
Titanium Dioxide powder (AR grade, 99.5% pure, M.W 79) was procured from Loba Chemie, India. Two types of dispersants were used in
this study, one is a water soluble polymer namely Polyvinylpyrrolidone
(PVP, chemical formula: (C6H9NO)n, M.W ~40,000) whereas the other
one is a non-ionic surfactant known as Polyoxyethylene sorbitan
monolaurate (Tween 20, chemical formula: C58H114O26) which were
purchased from Sisco Research Laboratory Private Limited and Merck
India, respectively. Distilled water was used to synthesize the nanouid
solution.

2.2. Synthesis of TiO2 nanouids

Nanoparticles can be synthesized via two different approaches; one
is top down, and another one bottom up. Bottom-up approach can be
classied into few methods such as pyrolysis, inert gas condensation,
solvothermal reaction, sol-gel fabrication, co-precipitation, etc. Recently, Saleh et al. [20] used co-precipitation method for the preparation of
TiO2 nanoparticle. In the current work, also co-precipitation method
has been used to produce TiO2 nanoparticle. Nanouid synthesis, in
general, can be classied into two methods i.e. single-step and twostep method. Present process involves two steps. The rst step is the
production of dry nanopowder (particle size b100 nm). The second
stage is to disperse the nanoparticle in the uid to form nanouid. Initially, 600 ml of 0.17 M titanium dioxide solution is prepared and then
placed in an ultrasonic cleaner (Citizon Ultrasonic Cleaner, model no:
YJ5120-1, 40 kHz frequency, Ultrasonic Power 120 W) under continuous pulse for 2 h. Subsequently, the sonicated solution is put on the
magnetic stirrer, and slowly 0.1 M NaOH is added in TiO2 solution to increase the pH up to 12. The solution is then allowed to age under continuous stirring for 1518 h. It is then centrifuged (REMI R-24) for 30 min
at 8000 RPM to separate the impurities and the liquid phase. The TiO2
particles obtained from the bottom of centrifuge tubes are dried in a
mufe furnace for 2 h at 200 C to get the powder form of TiO2 particles
which are in nano range. The solid nanoparticle is then added to distilled
water in different concentrations. This solution is again stirred for 2 h
and sonicated for 1 h to get a homogeneous nanouid solution. Detailed
schematic diagram of TiO2 nanouid synthesis is displayed in Fig. 1.
Two types of dispersants, one polymeric PVP and second one nonionic Tween 20 were used in the present study along with TiO2
nanouids for studying its effect on thermo-physical, rheological properties and stability. Both the dispersants were added to the nanouid in
trace amount (30 ppm PVP and 56 ppm Tween 20) and initially stirred
for 30 min followed by 30 min of ultrasonication.

Table 1
Summary of selected experimental studies on different oxide based nanouid in terms of thermal conductivity enhancement.
Authors

Base uid

Nanoparticle

Concentration

Thermal conductivity enhancement%

Lee et al. [14]

Water
Ethylene glycol
Water
Water
Deionized water
Water
Water
Deionized water

Al2O3
CuO
CuO
Al2O3
TiO2
ZnO
Fe3O4
SiO2

4 vol.%
4 vol.%
3.5 vol.%
0.1 vol.%
5 vol.%
5 vol.%
2 vol.%
0.5 vol.%

10
20
12
4
33
18
48
14

Ravikumar et al. [15]

Murshed et al. [16]
Jeong et al. [17]
Sundar et al. [18]
Pang et al. [19]

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S. Chakraborty et al. / Powder Technology 307 (2017) 1024

Fig. 1. Detailed schematic diagram of TiO2 nanouid synthesis.

2.3. Measurement methods used for TiO2 nanoparticle and nanouid

characterisation
Morphological features of TiO2 nanoparticles were characterized
using scanning electron microscope (SEM EVO 60, Carl Zeiss). A thin
layer of the powdered nanoparticle was deposited on a carbon grid by
using a tiny amount of the sample; the excess powder was removed
using a blower. The deposited layer of particles on the SEM grid was
dried by keeping the sample beneath a mercury lamp. The powdered
sample is then coated with a conductive layer of gold metal before the
characterisation. All these pre-processing steps are essential for capturing superior SEM images.
Thermogravimetric analysis (TGA, TA Instruments, Model: Q50
V20.13 Build 39) were used to investigate the thermal stability of TiO2
nanoparticles for high-temperature application. Measurements
were carried out with two different heating rates (20 C/min and
30 C/min) in a nitrogen atmosphere to study thermal degradation
nature and weight loss of TiO2 nanoparticle up to 800 C.
Nanouid tends to form cluster due to the high surface activity of
nanoparticles. Van der Waal attraction force in case of the nanoparticle
is high enough to cause signicant clustering. Therefore, Transmission
Electron Microscope (TEM, TECNAI G2 20S Twin) was utilized to study
particle size distribution of TiO2, with and without dispersant.
Nanouid with lower surface tension is benecial for heat transfer
application as it displays better spreadability over a heated surface.
The methodology used for surface tension measurement is Du Noy
ring technique. Surface tension was measured using Surface Tensiometer of Testing Instrument, Test master. A platinum ring is immersed into
the liquid pool. Force required to pull the ring from the liquid surface is
precisely measured. Force needed for ring detachment is related to the
liquid surface tension [21]. All the measurements were taken three
times for error analysis. Necessary precautions were taken to remove
any contamination during each measurement. The platinum ring was
rst burnt using Bunsen burner and then dipped in acetone and distilled
water consecutively to remove the contamination and to obtain accurate results.
The most important feature of a nanouid lies in its enhanced thermal conductivity value which plays a major part in heat transfer enhancement. Thermal conductivity was evaluated using both transient
hot-wire method and transient needle probe method. Thermal conductivity measurement of TiO2 nanouid was carried out using Flucon

Lambda Thermal Device (Manufacturer: F5 Technologie, Germany).

Thermal conductivity meter consists of 100 m thick platinum wire
which acts both as a heat source as well as a transducer. A constant current is passed through the hot wire to increase the temperature of the
surrounding medium. On the other hand, the hot wire resistance also
gets inuenced by the viscosity of the surrounding medium. Alteration
in resistance changes the voltage in hot wire. This voltage change can directly be linked with the change in temperature of surrounding medium. Then, this change in temperature divided by time gives the
thermal conductivity value. A constant temperature jacket was used to
maintain the uid temperature at the time of measurement. The other
thermal conductivity technique is transient needle probe method
using Decagon Devices KD2 Thermal Conductivity Meter. According to
manufacturer information, thermal conductivity meter contains a single
probe (length is 60 mm and diameter is 1.28 mm). Thermal conductivity probe consists of a thermistor which measures the temperature
change and the time data is recorded by a microprocessor. Change in
temperature divided by time gives the thermal conductivity value. For
both the techniques, all the measurements were made within the
temperature variation of 1 C from the desired measurement
temperature.
Analyses of ow characteristics of nanouid with and without dispersants are crucial for its applicability in industry. Rheological and
ow behaviour properties of TiO2 nanouid, before and after stabilizer
addition, were investigated by Anton Paar MCR 301 using cone and
plate geometry for both constant (100 s1) and variable shear rate
(0.1100 s1).
Stability remains the major concern regarding its applicability in
bulk scale for different industries. Clustering, agglomeration, and precipitation tendency are considered as the key drawback of nanouid,
as with time nanouid tends to lose its stability. In this work, stability
analyses for nanouid in pre and post dispersants addition were carried
out by sedimentation photography (Nikon D7100 DSLR Camera).
3. Results and discussion
3.1. Surface morphology study
The SEM analysis was used to determine the shape and morphology
of the TiO2 particle as received and after synthesis was formed. SEM
image depicted in Fig. 2 indicates that the raw TiO2 powder without

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

13

Fig. 2. (a) SEM image of raw TiO2 powder. (b). SEM image of TiO2 powder after treatment.

treatment is present in an agglomerated form whereas the synthesized

TiO2 nanoparticle is signicantly smaller in size as the clusters have
been broken due to prolonged ultrasonication at 40 kHz frequency.
TiO2 nanoparticles are spherical in shape.

3.2. Thermal degradation study

TGA was conducted to evaluate the thermal degradation characteristics of TiO2 nanoparticle and to check its applicability for high-temperature application. From Fig. 3, it quite evident that up to an initial
temperature of 200 C thermal degradation of TiO2 nanoparticle for
both heating rate (20 C/s and 30 C/s) followed the almost similar
path and showed nominal thermal degradation. It is owed to the fact
that prior to TGA analysis TiO2 nanoparticle is preheated to 200 C for
2 h in a vacuum oven, therefore, the initial weight loss due to solvent
loss is absent in this present case. Muneer et al. [22] also carried out
thermal degradation study of TiO2 particle up to a temperature of
800 C which is similar to the present case. In their work, weight loss occurs in three stages. In the rst stage, the weight loss is attributed to solvent loss. The second stage of weight loss is owed to organic compound
decomposition, whereas, in the present study since no organic solvents
were used, the aforementioned cause does not arise. The third stage of
degradation is credited to the transformation of TiO2 from anatase
phase to rutile phase [23]. In our case also the third stage can clearly
be observed from Fig. 3. Fig. 3 shows a distinct change in thermal degradation curve in case of both heating rate beyond 550 C which is owed
TiO2 phase transformation. Therefore it can be concluded that weight

loss is mainly attributed to two reasons such as loss of solvent molecules

attached with the nanoparticle and TiO2 phase transformation.
All the heating rates displayed similar thermal degradation pattern
with a nominal weight loss of 0.6% (for 30 C/min) and 0.7% (for
20 C/min) on initial weight (see Fig. 3). Thermal degradation results
are in sync with the manufacturer data which show 0.5% weight loss
at 800 C. Thermal degradation analysis in this case clearly suggests
TiO2 nanoparticle is suitable for high-temperature operation.
3.3. Particle size analysis
To precisely determine particle size and shape, TEM analysis was
carried out. From different TEM images of raw and treated TiO2 particles, it was observed that mostly the particles were sphere shaped
whereas in some cases shapes vary from hexagonal, square to rectangular forms. Fig. 4(a) and (b) indicate the TEM image and its histogram
plot representing the diameter data of raw TiO2 particle dispersed in
water. The obvious conclusion from the TEM analysis is that the particle
sizes are above 100 nm (average particle diameter is 135 nm) and,
therefore, these cannot be termed as nanoparticles. In order to bring
down the particle size to b 100 nm, raw TiO2 is needed so that nano
ranged particles can be made from the procured powder. After the treatment, the suspended solid can be termed as a nanoparticle as majority
of the particles are having a dimension b100 nm. Average particle diameter obtained from TEM image (Fig. 4(c)) and its histogram plot (Fig.
4(d)) is 95 nm.
Energy dispersive X-ray analysis (EDAX) was utilized to quantify
and detect different elements present in the sample. Cu and C present
in the graph correspond to the carbon coated copper grid on which particle was deposited. Ti and O represent the element present in the sample (see Fig. 5).
3.4. Surface tension study

Fig. 3. Thermogravimetric analysis of TiO2 nanoparticle.

Reduction in the surface tension leads to better wettability between

the coolant and a heated surface which in turn leads to superior heat
transfer. In this section, authors have discussed the surface tension variation of TiO2-water nanouid with increasing particle concentration
and varying measuring temperature (Fig.6). In the present study, for a
particular measuring temperature, surface tension value of TiO2
nanouid initially decreases with increasing concentration with respect
to the base uid; then it starts to rise beyond a certain particle concentration. This trend has been maintained in case of all the measuring temperature starting from 30 C to 50 C. All the measurement has been
repeated thrice to ensure the repeatability of measured data and all
the data has been plotted along with its standard deviation value in
Fig. 6. Several scientists working in the eld of nanouid have observed
many contradictory trends regarding surface tension variation.

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S. Chakraborty et al. / Powder Technology 307 (2017) 1024

Fig. 4. (a) TEM image of raw TiO2 nanoparticle. (b) Histogram plot of TEM image of raw TiO2 nanoparticle. (c) TEM image of TiO2 nanoparticle after treatment. (d) Histogram plot of TEM
image of TiO2 nanoparticle after treatment.

Murshed et al. [24] concluded that reduction in surface tension values

for TiO2-DI water nanouid was credited to Brownian motion and adsorption of nanoparticles in the liquid-gas interfaces. Opposite trend
was also observed in the study of Kumar et al. [25], where surface tension values increased for carbon nanotube based nanouids as compared to the base uid. However, the research ndings achieved in the
present work are in accordance with the work of Vafaei et al. [26].
They studied the surface tension of Bi2Te3-water nanouid and

Fig. 5. EDAX image of TiO2 nanoparticle.

observed both decreasing and increasing trends with increasing particle

loading separated by an optimum concentration level. According to the
nding of Tanvir and Qiao [27], high particle concentration, in general,
leads to increasing surface tension value whereas at lower particle concentration trends varies with different particle and base uids. At higher
particle concentration when interparticle gap reduces, Van der Waal attractive force dominates over electrostatic repulsive force hence both

Fig. 6. Surface tension vs. concentration curve of TiO2-water nanouid at various

measuring temperatures.

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

surface free energy and surface tension increase [28]. Particle agglomeration is another reason behind increased surface tension value. However, for lower particle concentration electrostatic repulsive force
dominates over Van der Waal attractive force which could result in reduced surface tension values. Effect of temperature also plays a crucial
part in the surface tension of TiO2water nanouid as with increasing
uid temperature surface tension values reduces for all TiO2 concentration. Current research nding is in accordance with the work of
Murshed et al. [24]. They have observed that with increasing temperature surface tension values of both TiO2-water and TiO2-oil nanouid
decreases. Similar trends were also observed by Godson et al. [29]
when working with silver-water nanouids. Ahammed et al. [30]
worked with grapheme-water nanouid where they also observed
that with an increase in temperature (1090 C) surface tension value
reduces. According to their work, lower surface tension value is owed
to the weakening of intermolecular attractive forces. Khaleduzzaman
et al. [31] in their review article have concluded that with an increase
in temperature leads surface tension reduction by comparing the
work of various scientists. Effects of surfactant and polymer addition
on surface tension have been discussed in the later portion.
3.5. Viscosity study
Viscosity is a vital parameter for considering heat transfer application. The rheological behaviour of nanouid is dependent on several factors such as the method of synthesis, particle size, and shape, particle
concentration, the viscosity of base uid and temperature [3234]. Effect of increasing particle concentration on viscosity increment is
owed to numerous factors such as Van Dar Waal attractive force, particle aggregation, internal friction between the nanoparticle and liquid
molecule, etc. Increased viscosity of nanouid could lead to higher residence time on the heated surface thereby leading to better heat transfer
[35]. A signicant increase in viscosity could lead to higher pumping
cost for the cooling application. In the present study, viscosity has
been measured with constant shear rate (100/s) as well as with variable
shear rate (0.1100 s1) at three different uid temperatures. Fig.7
shows the variation of viscosity by varying measuring temperature
and particle concentration of TiO2 nanouid at a constant shear rate.
All the viscosity values shown in Fig. 7 is the average value of 10 data
points at 100 s1 shear rate along with its standard deviation value.
The viscosity increases with increasing particle loading which is in accordance with the literature [3538]. There are several contradictory results reported on particle size related to viscosity increment for various
nanouids. According to some researchers increase in particle size leads
to increase in viscosity [24,36], whereas others have found opposite

Fig. 7. Viscosity vs. concentration curve of TiO2-water nanouid at various measuring

temperatures.

15

trend [3941]. In terms of the temperature effect on viscosity, with an

increase in temperature viscosity in general shows decreasing trend.
With the increase in temperature, the intermolecular attractive force
acting between the nanoparticle and the molecule of base uid reduces
which in turn reduces viscosity values. According to Andrade equation
[42],
ln A

B
T

Viscosity is inversely proportional to temperature therefore with an

increase in temperature would lead to viscosity reduction. Ferrouillat et
al. [43] worked with SiO2-water and ZnO-water nanouid in a wide
temperature range (2080 C) and found viscosity reduces with increasing temperature. A similar nding was also observed for Fe3O4water nanouid [44] with increasing temperature (2060 C).
Rheological behaviour of TiO2water nanouid was investigated by
varying the shear rate. The shear rate was varied between (0.1
100 s1). Fig. 8 showed the effect of variation of shear rate on viscosity
for 40 ppm TiO2 nanouids in water for three different temperatures.
There are several contradictory opinions regarding ow behaviour of
TiO2 nanouids. Some suggest that the solution shows Newtonian behaviour [34,45].Other suggests it displays non-Newtonian behaviour especially pseudoplastic/shear thinning ow characteristics with
changing shear rate [46,47]. However, in the present study, TiO2
nanouid follows Carreau law model at all three temperatures (30 C,
40 C and 50 C) where the values of shear thinning parameter (m)
1.13, 1.16 and 1.09, respectively. The value of m is close to 1 in the all
cases which indicate the shear thinning ow nature of TiO2 nanouid.
Detailed study of different dispersant addition on rheological properties
has been discussed in the later section.
3.6. Thermal conductivity study
The most important factor for consideration of any nanouid for
thermal application is largely dependent on its thermal conductivity.
Higher thermal conductivity implies better heat transfer characteristics.
Fig. 9(a and b) shows the effect of nanoparticle concentration on the
thermal conductivity of TiO2 nanouid and its improvement as compared to base uid (water) for three different uid temperatures. The
thermal conductivity value of nanouid is directly dependent on its
temperature. Therefore, temperature dependency study is crucial for
understanding thermal properties of any nanouid. Thermal conductivity was measured using two different measurement techniques known

Fig. 8. Effect of varying shear rate on viscosity of TiO2-water nanouid at various

measuring temperatures.

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S. Chakraborty et al. / Powder Technology 307 (2017) 1024

Fig. 9. (a) Thermal conductivity vs. concentration curve of TiO2-water nanouid at various measuring temperatures using transient hot-wire technique. (b) Thermal conductivity vs.
concentration curve of TiO2-water nanouid at various measuring temperatures using transient needle probe technique.

as transient hot wire and transient needle probe method. All the measurements were taken at least three times at three different temperatures, and the average value along its standard error value has been
plotted in Fig. 9(a and b). Initially, the thermal conductivity increases
with increasing particle loading. However, there exists an optimum particle concentration beyond which thermal conductivity declines again
(see Fig. 9(a and b)). Such nature could be a possible contribution of
particle aggregation or clustering tendency of nanoparticle with increasing concentration. The enhancement factor is calculated by formulae given in literature [19]
Ek = (Knf Kbf)/Kbf
where, Ek is taken as thermal conductivity enhancement factor, Knf and
Kbf represents the thermal conductivities of nanouid and base uid, respectively. At 30 C, the maximum thermal conductivity enhancement of
1.1% was achieved with 40 ppm TiO2 nanoparticle loading using transient
hot wire method. The thermal conductivity measurements were taken in
a conned space where there is no effect of convection on thermal conductivity value. However, for any practical application, the effect of convection
is needed to be taken into account. The same measurements were taken
using KD2 thermal analyzer where the effect of convection is considered
while measuring the thermal conductivity. The maximum thermal conductivity increment is 8.3% at a particle loading of 40 ppm (30 C). The thermal
conductivity of nanouid can get inuenced by the effect of container wall
[48]. Authors of the aforementioned work have found that when the needle
is immersed near the wall, thermal conductivity value of nanouid was
found to increase. On the other hand, when the needle is placed at the center of the container, the thermal conductivity values were observed to be
lower as compared to what measured near the wall. In order to ensure minimum wall effect on measurement data, measurements made using KD2
thermal analyzer were measured in a 100 ml (beaker diameter 50 mm)
beaker where the needle (needle diameter 1.28 mm) was immersed into
the nanouid sample at the center of the beaker during the measurement.
The fundamental factors inuencing thermal conductivity increment by nanoparticle addition are owed to distribution of suspended
particle in nanouid [3,4], random motion of nanoparticle [2], particle
size [6], particle shape [49], the effect of solid-liquid interface [8], convection [50,51] etc. Particle aggregation also plays a crucial role in thermal conductivity increment as shown by several scientists [52,53].
According to their studies, an optimum level of aggregation is needed
for achieving maximum thermal conductivity. However, such claims
are contradictory to the claim made by Pak and Cho [3]. According to
particle aggregation theory, clustered nanoparticle provides an easier
and faster path for heat conduction. Present experimental results are
in line with this theory. The sudden decline in thermal conductivity

beyond an optimum nanoparticle loading could be owed excess clustering of the nanoparticle. Due to the smaller size, nanoparticle possesses
higher attractive force which in turn lead to undesired shape modication and sedimentation [54]. Higher aspect ratio is required for achieving higher thermal conductivity as it gives larger surface area and heat
transport via particle-particle collision [55]. From the TEM images (Fig.
4(c)), it is quite clear that TiO2 nanoparticle shows clustering tendency
which could lead to undesired shape modication. When the temperature is increased the thermal conductivity values also increases which
owed to increase in convection effect and Brownian motion of the nanoparticle [50,56]. However, the enhancement in thermal conductivity
with increasing temperature is not signicant when measurements
were made by the Flucon Lambda Device. Since the instrument prevents
the effect of convective heat ow on the measured parameter. Such
measurements are only possible in a conned and controlled environment and the thermal conductivity value is measured without any effect
of the temperature gradient. However, in the case of any practical application, the effect of temperature gradient would certainly enhance the
rate of convection and Brownian motion which in turn would affect
the effective thermal conductivity of nanouid [50,51]. Due to the effect
of thermophoresis, the effective thermal conductivity of nanouid increases [57]. The results obtained by the KD2 thermal analyzer include
the effect of convection in thermal conductivity results. Das et al. [58]
achieved signicant increment in thermal conductivity water-Al2O3
and water-CuO nanouids with increasing temperature. They have observed 24 times enhancement in the temperature range 2151 C.
However, in the present study, the maximum thermal conductivity increase in the temperature range of 3050 C is approximately 1.4 times.
In the next section, authors have investigated the effect of polymer
and surfactant addition on the overall properties of TiO2-water
nanouid.
3.7. Effect of dispersant addition on thermo-physical properties of TiO2
nanouid
The impact of different types (cationic and anionic surfactants) of
surfactant addition in TiO2 nanouid has been studied by few scientists
for its potential in enhancing thermal properties. Effect of cationic
(cetyltrimethylammonium bromide, CTAB, Chemical Formula
(C16H33)N(CH3)3Br) surfactant addition on thermal properties has
been studied by Murshed et al. [16]. Authors reported 29.7% (particle
size 15 nm) enhancement in thermal conductivity as compared to the
thermal conductivity of base uid for the TiO2 volume fraction of 5%
with CTAB volume percentage of 0.02%. Saleh et al. [20] investigated
the impact of anionic (Sodium Dodecyl Sulphate, SDS, Chemical Formula NaC12H25SO4), cationic (Cetyltrimethylammonium Bromide, CTAB,

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

Chemical Formula (C16H33)N(CH3)3Br) and non-ionic (Span-80, Chemical Formula C24H44O6) surfactant on thermal properties of TiO2
nanouids. They achieved 10.5, 11 and 12.5% enhancement in thermal
conductivity for non-ionic, cationic and anionic surfactant with particle
volume percentage of 1%, whereas without dispersant enhancement
was 7.5%. On the other hand, the effect of dispersant addition on properties such as surface tension and viscosity are missing in the open literature. In this present study, authors have chosen polymer (PVP) and
non-ionic surfactant (Tween 20) as a dispersant and investigated its impact on thermal conductivity, surface tension and viscosity as these
properties are crucial for heat transfer application.
The addition of dispersant has both benecial and detrimental effects on the thermo-physical properties of TiO2 nanouid. Alteration
in thermo-physical properties of TiO2 nanouid prior and post dispersant addition has been reported in Tables 2 and 3. In this study, Polyvinylpyrrolidone (PVP) and Tween 20 (non-ionic surfactant) have been
used as dispersants. It was noted earlier that the maximum thermal
conductivity enhancement of the nanouid was achieved at 40 ppm
concentration of TiO2 nanoparticle. Therefore, this concentration was
taken as the base concentration and both the dispersants were added
in this concentration to observe their effects on thermal properties.
Dispersant addition into TiO2 nanouids alters the dispersion nature
of the nanouid. TEM images of pure TiO2 nanouid (40 ppm), TiO2
(40 ppm)-PVP (30 ppm) nanouid and TiO2 (40 ppm)-Tween 20
(56 ppm) nanouid give a clear picture on nanoparticle dispersion
(see Fig. 10(ac)). The addition of PVP dispersion improves slightly
whereas Tween 20 addition has no positive contribution in this regard.
In terms of thermal conductivity (K), the addition of dispersant has no
benecial effect (see Table 2).
Surface tension () is one of the key factors to be considered for heat
transfer properties of nanouids. Nanouid with lower surface tension
value has greater contact, spreadability and wettability over the heated
surface which is considered to be benecial for heat transfer application.
Effect of surface tension reduction in heat transfer enhancement has
been reported by several researchers [5963]. The addition of both
PVP and Tween 20 in water (base uid) leads to a reduction in surface
tension value as reported in existing literature [60,64]. In this present
study, surface tension value of water-TiO2 nanouid also reduces with
PVP and Tween 20 addition, which is in line with earlier work (see
Table 3).
A change is also observed for viscosity () value with the addition of
both dispersants. The addition of PVP enhances the viscosity of
nanouid by trace amount as PVP is a polymer and has a higher viscosity
in general due to polymeric chain interaction. These results are synchronous with the ndings of other researchers [64,65]. On the other hand,

17

the addition of Tween 20 reduces the viscosity value slightly. Reduction

in viscosity by the addition of Tween 20 is in accordance with the nding by Ravikumar et al. [60]. The possible cause behind obtaining such
results is owed to the monomeric state of surfactant at low concentration which is responsible for reduced viscosity [66] (see Table 3).
Table 2 illustrates the difference in thermal conductivity value TiO2
nanouid measured by both the techniques (transient needle probe
and transient hot wire method) with and without dispersant addition
for three different temperatures. Table 3 shows the variation in surface
tension and viscosity values of TiO2-water nanouid prior and post dispersants addition for same three temperatures. Both the tables also consist of standard deviation percentage to check the measurement
uncertainty of data and percentage of alteration in each property with
increasing temperature.
Standard deviation (x), deviation percentage (%) and standard
error were calculated using following equation:
s
1
x
x hxi2
z1 i


%


x
 100
hxi

x
Standard error p
z

where, z is the number of data points, b xN is the mean value of all data
point and xi is the ith measured value of the parameter.
Detailed rheological aspects of dispersant addition have been
discussed in the next section.
3.8. Rheological properties of TiO2 nanouid with and without dispersants
In this current study, authors have given specic attention to the
rheological behaviour of TiO2 nanouid prior and post dispersant addition. There exist several contradictory opinions on the ow behaviour of
TiO2 nanouids as discussed in earlier section. Knowledge regarding the
ow behaviour of nanouid and the dependency of its viscosity with
shear rate is essential for industrial and engineering application of
nanouid. Rheological features are key to understanding the structure
and assembly of nanoparticle in a nanouid. To obtain a denite idea
of the ow behaviour of the TiO2 nanouids, authors have used four different rheological models.

Table 2
Effect of dispersant addition on thermal conductivity alteration of TiO2 nanouid using transient hot wire and transient needle probe method.
Transient hot wire (without considering the effect of
convection)
Coolant
Temperature 30 C
Water
TiO2 nanouid (40 ppm)

Temperature 40 C
Water
TiO2 nanouid (40 ppm)

Temperature 50 C
Water
TiO2 nanouid (40 ppm)

Transient needle probe (considering the effect of

convection)

Additive

Thermal conductivity (W/mK)

Change%

Thermal conductivity (W/mK)

Change%

PVP: 30 ppm
Tween 20: 56 ppm

0.594
0.601
0.599
0.597

0.08
0.27
0.16
0.22

+1.11
+0.77
+0.58

0.603
0.653
0.647
0.633

2.53
2.34
4.72
3.29

+8.29
+7.18
+4.97

PVP: 30 ppm
Tween 20: 56 ppm

0.603
0.608
0.608
0.607

0.75
0.10
0.04
0.42

+0.89
+0.89
+0.64

0.635
0.698
0.686
0.665

5.04
4.36
5.60
5.78

+9.89
+8.06
+4.76

PVP: 30 ppm
Tween 20: 56 ppm

0.616
0.620
0.618
0.617

0.07
0.13
0.05
0.05

+0.71
+0.38
+0.22

0.65
0.725
0.698
0.705

2.85
3.03
4.92
2.74

+11.55
+7.32
+8.45

18

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

Table 3
Effect of dispersant addition on surface tension and viscosity alteration of TiO2 nanouid at various measuring temperature.
Coolant
Temperature 30 C
Water
TiO2 nanouid (40 ppm)

Temperature 40 C
Water
TiO2 Nanouid (40 ppm)

Temperature 50 C
Water
TiO2 nanouid (40 ppm)

Additive

Surface tension (mN/m)

Change %

Viscosity (Pa-s)

Change%

PVP: 30 ppm
Tween 20: 56 ppm

71.10
70.85
64.47
38.53

0.56
0.17
0.24
0.73

0.35
9.32
45.81

0.0010
0.00150
0.00155
0.00136

2.30
2.79
0.75
4.98

+50.32
+55.12
+35.11

PVP: 30 ppm
Tween 20: 56 ppm

69.80
68.89
62.17
37.49

0.15
0.09
0.25
0.58

1.30
10.93
46.29

0.00079
0.00121
0.00135
0.00113

0.93
3.51
1.96
5.04

+52.96
+70.01
+42.69

PVP: 30 ppm
Tween 20: 56 ppm

68.00
64.93
61.37
36.13

0.23
0.16
0.09
1.16

4.51
12.40
46.87

0.00065
0.00108
0.00115
0.00096

3.96
2.92
4.09
3.13

+65.38
+76.92
+48.03

Power law model [67] is the most commonly used model for ow
behaviour analysis. The model is expressed by following expression,
k:

k: n1

4
5

where, , , , k, and n, represents shear stress, shear rate, apparent viscosity, consistency index and ow behaviour index, respectively. Different types of uids can be classied in terms of the values of n. When n is
1, then the uid nature is Newtonian. If n b 1, then the uid is shear thinning in nature whereas n N 1, indicates towards shear thickening
behaviour.
The second model used in this study is Sisko model [68] which has
been used for analyzing ow characteristics in upper Newtonian and
Power law regions.
Sisko model is expressed via following equation:
k: n1

where, , k, and n, represent parameters similar to the power law model.

is termed as viscosity at the innite shear rate. For the present study,
is taken as viscosity at a nal shear rate (at 100 s1).
The third and fourth model used for ow behaviour analysis are
Carreau [69] and Cross [70] model. These two models are mainly used
for analyzing ow characteristics of activated sludge, polymeric suspension and blood ow, etc. In this current study, PVP is used as an additive
which is a water soluble polymer. Therefore, TiO2-PVP nanouids could
potentially follow Carreau or Cross model.

Carreau model is represented by below expression [67]:



0

N
1  2

Cross model is expressed by below expression [67]:



0


1  m

where, , 0 are the viscosity of nanouid at innite or nal shear rate

and at initial or zero shear rate, respectively. is the relaxation time, N
(N = m/2) is the extent of shear thinning behaviour and m is dimensionless index. If the value of m is close to 1 then it is shear thinning
in nature whereas when m is close to zero then it is Newtonian in
nature.
Power law model is applicable for medium shear rate ranges whereas for wide shear rate range the model is unable to compute the accurate
viscosity value. For low shear rate value viscosity attains constant value
and at the high shear rate it displays Newtonian behaviour. Sisko model
incorporates correction in power law model to obtain steady state value
of apparent viscosity at high shear rate. This model combines both Newtonian and power law expression with various viscosity functions. Cross
model is used to explain rheological properties for numerous suspensions and it covers a wide range of shear rate. With several simplifying
assumptions, this model can be reduced to both Sisko and Power law
model. When b b 0, ( )N N 1 and is very small, Cross model
can be reduced to Sisko and Power law model [71]. Carreau model follows Cross model in low and high shear rate whereas diverges when

Fig. 10. (a) TEM image of TiO2 nanoparticle (40 ppm). (b) TEM image of TiO2 nanoparticle (40 ppm) with water soluble polymer, PVP (30 ppm). (c) TEM image of TiO2 nanoparticle
(40 ppm) with a non-ionic surfactant, Tween 20 (56 ppm).

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

( ) ~ 1 [71]. Therefore, the basic difference between all of these

models lies in its assumptions. In the case of power law model, viscosity
at an innite shear rate (), viscosity value at zero shear rate (0) and
yield stress are neglected making it only applicable to medium
shear rate region. Sisko model computes viscosity at medium and
high shear rate region as it only neglects viscosity value at zero
shear rate ( 0 ). Cross and Carreau model considers both , 0 in
their expressions which enables those models applicability for a
wide range of shear as it also considers yield stress value making it
suitable for polymeric and many other suspensions. Viscosity at
zero shear rate is key to understand the microstructure of any polymeric suspension.
Experimentally obtained rheological data of all three samples were
tted with the aforementioned models to assess the ow characteristics. The majority of the nanouids show shear thinning behaviour
[72]. Carreau model was best suited for TiO2 and TiO2-Tween 20
nanouids for all three temperatures (3050 C). Both the samples
showed highest regression coefcient value (R2, close to 1) in the case
of Carreau model as compared all other models. These results indicate
that Carreau model tted data ts best with the experimentally measured data (see Supplementary Information Table 1). For both TiO2
and TiO2-Tween 20 nanouids (at all temperatures, 3050 C), the
value of m is N1 which indicates towards its shear thinning behaviour.
For example, at 30 C for TiO2, and TiO2-Tween 20 nanouid, the values
of m are 1.13 and 1.41, respectively. In terms of the regression coefcient value, both TiO2 and TiO2-Tween 20 nanouids also display very
high R2 value for Power law, Sisko, and Cross model. Rheological analysis of both the aforementioned nanouid revealed that the ow behaviour index (n) value (Power law and Sisko Model) is b 1 conrming their
shear thinning ow behaviour. Similarly, in the case of Cross model, the
value of m is N1 which further conrms shear thinning nature of TiO2
and TiO2-Tween 20 nanouids. On the other hand, TiO2-PVP nanouid
does not follow both Power law and Sisko model (poor R2 value). In
the case of TiO2-PVP nanouid, the best R2 value was achieved for
Cross model. However, both the Carreau and Cross model display significantly high R2 value for all three samples and temperatures. Therefore,
further investigation is required to identify the best model in each case.
The summary of all the non-linear regression parameter along with its
regression coefcient values are reported as supplementary information (see Supplementary Information Table 1).
Calculated viscosity data (model predicted) were plotted against
measured viscosity data for all samples and temperatures to determine
the best-tted model in each case. The 45 line in the Fig. 11(ai) is
known as the line of equivalence. If a data point lies on this line, then
it is considered to be a perfectly tted data. For TiO2 nanouid (Fig.
11(ac)), Carreau model tted data lies closest to the 45 line for all
three temperatures. For, TiO2-PVP and TiO2-Tween 20 nanouid,
Cross, and Carreau model tted data lies closest to the 45 line whereas
other two models deviates from 45 line (Fig. 11(df)). Therefore further analysis is required before selecting the accurate model in each
case.
In order to further establish this claim, standard error was calculated
using following equation,
X
SE

ym yc 2
z1

!1=2
9

analysis of various rheological models for estimating viscosity of

TiO2 nanouids are reported in additional information section (see,
Supplementary Information Table 2).
3.9. Stability analysis
Stability is one of the crucial characteristics of nanouid. Due to high
Van der Waal attraction force nanoparticle tends to form cluster and agglomerates which precipitate with time. Nanouid preparation
methods play a critical role in this phenomenon. Prolonged stirring
and ultrasonication are required to break this cluster which is an energy
inefcient process. Therefore, different dispersants are added with the
nanouids to ensure stability. In this work, sedimentation photography
has been selected as the method of stability analysis. Photographs were
captured by Nikon D7100 digital single-lens reex camera with 18
105 mm zoom lens. Images were taken at 4 magnication in autofocus mode.
Several researchers have used this technique for assessing the stability of their nanouids [73,74]. Fig. 12 shows images taken at different
time intervals to check the stability of 40 ppm TiO2 nanouids with
and without dispersants. Higher particle size leads to poor stability
and faster sedimentation of nanouid, therefore the stability analysis
reported in this work is directly linked with average particle size
which is 95 nm. For initial 2 h, images show no signicant change in stability for all solutions. Within this period, all the samples display stable
nature and can be used for cooling experiments. However, with further
time nanouids start to get destabilized and after 4 h both TiO2 and
TiO2-Tween 20 nanouids start to shows signs of phase separation.
Phase separation is clear in the case of TiO2-Tween 20 nanouid after
4 h whereas pure TiO2 nanouid takes 8 h to show a clear sign of
phase separation and precipitation. TiO2-PVP nanouids showed the
best stability among all the samples after 8 h. Photograph taken after
24 h showed that TiO2 and TiO2-Tween 20 nanouids completely precipitated whereas TiO2-PVP nanouid had started to show phase separation. In this work, a trace amount of dispersants (30 ppm PVP and
56 ppm Tween 20) were added with 40 ppm TiO2 nanoparticles as excess dispersant addition would lead to poor thermal conductivity. Excessive polymer addition can also lead to increase in clustering
tendency.
3.10. Estimation of heat transfer potential of TiO2 nanouid using gure of
merit analysis:
The overall thermal performance of any coolant is not only dependent on its thermal conductivity (k) but also dependent on specic
heat (cp), density (), and viscosity () of the coolant. The concept of
Mouromtseff number (Mo) was rst introduced by Simons [75] to
study the thermal effectiveness of any heat transfer uid for electronics cooling. The ratio between Mo of nanouid and Mo of base
uid gives an idea about the thermal capability of any coolant. According to Ellsworth [76], higher the Mo better would be its heat
transfer characteristics. Mouromtseff number is considered as the
Figure of merit (FOM) for comparing the thermal capability of any
coolant. The mathematical expression of Mouromtseff number for
fully developed internal ow is,
b

Mo
Measured values and calculated values at every data location are
denoted ym and yc, respectively. z is dened as the number of data
points.
From the standard error analysis, it is quite clear that TiO2-PVP
nanouid follows Cross model for all three temperatures whereas
both TiO 2 and TiO2 -Tween 20 nanouids follows Carreau model.
Summary of the rheological analysis for three nanouid samples at
three temperatures are reported in Table 4. Detailed standard error

19

a cdp k
e

where, a, b, d, and e values are dependent on the mode of heat transfer under consideration. For fully developed internal laminar ow,
the formula of FOM is [75]:
FOMla minar

Monf knf

Mobf
kbf

20

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

For fully developed internal turbulent cooling at constant ow velocity, the FOM is [77]:

FOM turbulent

Monf

Mobf

 0:6
knf

kbf

nf
bf

!0:8



cpnf 0:4


cpbf

nf
bf

!0:4

For the measurement of Mo, the density of nanouid has been measured using standard density bottle. Specic heat of TiO2 nanoparticle is
measured using Differential Scanning Calorimetry (TA Instrument, DSC
Q20 V24.11 Build 124). From the nanoparticle specic heat, the specic
heat of nanouid was calculated using the mixing theory [3]. In the case
of any ow condition, the effective thermal conductivity includes the effect of convection. Therefore, thermal conductivity data measured by
the KD2 thermal analyzer is taken for FOM calculation. FOM for both
fully internal laminar as well as turbulent ow for all nanouid concentration are given below (see Table 5).
From Table 5, it is quite clear that for internal laminar ow, 40 ppm
TiO2 nanouid shows the best heat transfer capability as compared to
other coolants. However, in the case of internal turbulent ow, water
shows the best heat transfer capability as compared to any other coolant. In terms of internal turbulent ow, TiO2 nanouid cannot be considered as an efcient coolant as compared to pure water. It is also to be
noted that, this analysis does not take into account the effect of surface
tension which is considered to be one of the crucial factors for heat
transfer enhancement as suggested by several researchers [59,60]. For
an application such as spray and jet cooling of hot steel plate, this analysis may not hold true, as several other factors inuence the heat transfer results which are not considered for this analysis.

below the bottom plate. All the nanouid solution prior to measurement was kept on the top of the heated plate for at least 5 min before
any measurements were carried out. During thermophysical property measurement of nanouid, the temperature can vary between
1 C. Surface tension measurements were carried out using DuNuoy ring surface tensiometer. Maximum uncertainty during surface
tension measurement is 0.42 mN/m (Maximum precision index:
0.27). The thermal conductivity is measured using transient hotwire (Flucon Lambda Device, F 5 Technologie, Germany) and transient needle probe (KD2 thermal analyzer, Decagon Devices, USA).
According to manufacturer information, the device rst device
works with an accuracy of 1%, whereas the second device has an
accuracy of 5%. However, maximum uncertainty for thermal conductivity measurement using transient hot wire method is
0.004 W/m K (Maximum precision index: 0.001) whereas maximum measurement uncertainty using transient needle probe method is 0.06 W/m K (Maximum precision index: 0.04). Viscosities were
measured by using a cone & plate rheometer with an uncertainty of
5.70 10 5 Pa-s (Maximum precision index of 1.47 10 5).
4. Conclusion
In the current study, a two-step method was implemented to synthesize water based TiO2 nanouids. A key focus of this study is to determine different thermophysical properties of TiO2 nanouid like thermal
conductivity, surface tension, viscosity and particle size and investigate
the effect of dispersant (PVP, Tween 20) addition on thermal and rheological properties of TiO2 nanouids. The present study also includes the
effect of temperature variation on thermophysical and rheological properties of nanouid. Major ndings of the present work are given below:

3.11. Measurement uncertainties

In the present work, measurement uncertainties may arise from
several factors such nanoparticle concentration, measurement temperature, instrumentation error etc. During particle and additive
concentration measurement, an error may arise due to inaccuracy
in weighing machine. The uncertainty analysis has been carried out
following ASME test code: ANSI/ASME PTC 19.1-1983 [78]. The uncertainty of experimental measurement is signied by the range of
values between which the actual value is expected to lie with some
condence level. Measurement uncertainty is dened based on the
standard deviation value. The precision error is determined by taking
n number of repeated measurement from the parameter population.
Precision error of the experimental data determines gap or closeness
between the values of two or more measurement of the same parameter. It can also be termed as repeatability or reproducibility. Precision index of a measured parameter is dened by the following
expression:
Precision Index

Standard Deviation
p
N

where N is the number of sample size. All the thermo-physical properties of TiO2 nanouids with and without dispersants are measured
at three different temperatures. For viscosity measurement at elevated temperature, Anton Paar 301 cone & plate rheometer is
equipped computer controlled internal heating system placed

1) Particle size analysis using TEM revealed that average particle

size is below 100 nm (95 nm.) which implies to the successful formation of the nanouid suspension. TEM analysis (see Fig. 10)
also reveals that only PVP improves the dispersion of nanoparticle whereas Tween 20 addition has limited effect on dispersion
quality.
2) TGA analysis proved that TiO 2 nanoparticle is suitable for the
high-temperature application. It showed a nominal weight loss
of 0.7% (heating rate, 20 C/min) with respect to initial weight
at 800 C.
3) Thermal conductivity measurements made by transient hot wire
method eliminates the effect of convection during measurement.
The maximum thermal conductivity improvement of 1.1% was
achieved as compared to the base uids with a nanoparticle loading
of 40 ppm at 30 C.
4) On the other hand, thermal conductivity measurement using
transient needle probe method considers convection effect during measurement. The enhancement in thermal conductivity
using this technique was found to be 8.3% (with 40 ppm particle
loading at 30 C). Increase in temperature (3050 C), leads to
minor enhancement in thermal conductivity value due to increased Brownian motion. However, increase in particle loading
beyond 40 ppm leads to decrease in thermal conductivity (k nf)
value.
5) Surface tension showed no signicant change with TiO2 nanoparticle
(70.85 mN/m) addition as compared to the surface tension of base

Fig. 11. (a) Comparison between viscosities calculated by different rheological models with experimentally obtained viscosity data for pure TiO2-water nanouid at 30 C. (b) Comparison
between viscosities calculated by different rheological models with experimentally obtained viscosity data for pure TiO2-water nanouid at 40 C. (c) Comparison between viscosities
calculated by different rheological models with experimentally obtained viscosity data for pure TiO2-water nanouid at 50 C. (d) Comparison between viscosities calculated by
different rheological models with experimentally obtained viscosity data for TiO2-water nanouid with Tween 20 surfactant at 30 C. (e) Comparison between viscosities calculated by
different rheological models with experimentally obtained viscosity data for TiO2-water nanouid with Tween 20 surfactant at 40 C. (f) Comparison between viscosities calculated by
different rheological models with experimentally obtained viscosity data for TiO2-water nanouid with Tween 20 surfactant at 50 C. (g) Comparison between viscosities calculated by
different rheological models with experimentally obtained viscosity data for TiO2-water nanouid with PVP at 30 C. (h) Comparison between viscosities calculated by different
rheological models with experimentally obtained viscosity data for TiO2-water nanouid with PVP at 40 C. (i) Comparison between viscosities calculated by different rheological
models with experimentally obtained viscosity data for TiO2-water nanouid with PVP at 50 C.

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

21

22

S. Chakraborty et al. / Powder Technology 307 (2017) 1024

Table 4
Selection of different rheological model suitable for TiO2 nanouid with and without
dispersants.
Temperature (C)
Nanouid

30 C

40 C

50 C

TiO2 (40 ppm)

TiO2 (40 ppm) + PVP (30 ppm)
TiO2 (40 ppm) + Tween 20
(56 ppm)

Carreau
Cross
Carreau

Carreau
Cross
Carreau

Carreau
Cross
Carreau

6)

7)

8)
9)

uid which is 71 mN/m. With the addition of PVP or Tween 20, surface tension starts to decline which improves the heat transfer by
higher spreadability and wettability (see Table 3). The increase in
uid temperature leads to decrease in surface tension value for
nanouid with and without dispersants. Such reduction in surface
tension is owed to the weakening of intermolecular attractive forces.
Viscosity increases with increasing particle loading whereas it reduces with increasing uid temperature both the outcomes are in
sync with many researchers work. TiO2-Tween 20 nanouid showed
lower viscosity than pure TiO2 nanouids whereas TiO2-PVP
nanouids showed slightly higher viscosity value (see Table 3).
Rheological or ow behaviour analysis revealed that in the temperature range of (3050 C) pure TiO2 and TiO2-Tween 20 nanouids
followed Carreau law model whereas TiO2-PVP nanouid followed
Cross model.
Stability analysis showed all the samples remained stable up to initial 2 h. The best stability was obtained by TiO2-PVP nanouid.
To study the heat transfer potential, Mouromtseff number and respective FOM was calculated. A higher value of FOM indicates better
cooling efciency. For fully developed internal laminar ow, 40 ppm
TiO2 nanouid shows the highest FOM as compared to all other coolants. However, for fully developed internal turbulent ow, highest
FOM is attained by water.

Table 5
Figure of merit analysis for both internal laminar and turbulent ow at 30 C using different concentration of TiO2 nanouid.
Concentration

FOMLaminar

FOMTurbulent

0
10
40
70
100

1
1.033149
1.082873
1.044199
1.027624

1
0.978853
0.89457
0.860145
0.836219

Nomenclature
Thermal conductivity enhancement factor
Ek
k
Consistency index
Thermal conductivities of nanouid
Knf
Thermal conductivities of base-uid
Kbf
m
Dimensionless index
n
Flow behaviour index
N
Extent of shear thinning behaviour
Measured value
ym
Measured value
ym
Calculated value
yc
z
Number of data points
Vol.%
Volume percentage
Greek letter

x
%

Standard deviation
Deviation percentage
Shear stress
Shear rate
Dynamic viscosity
Apparent viscosity
Viscosity at nal/innite shear rate
Viscosity at initial/zero shear rate
Relaxation time

Abbreviation

CNT
Carbon nanotube
DWCNT Double wall carbon nanotube
EDAX
Energy dispersive X-ray analysis
FOM
Figure of merit
Mo
Mouromtseff number
MWCNT Multi-wall carbon nanotube
PVP
Polyvinylpyrrolidone
RPM
Rotation per minute
SE
Standard error
SEM
Scanning electron microscope
TGA
Thermogravimetric analysis
TEM
Transmission electron microscope
Tween 20 Polysorbate 20
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.powtec.2016.11.016.
References

Fig. 12. Sedimentation photography of TiO2 nanouids with and without dispersants.

[1] S.U.S. Choi, J.A. Eastman, Enhancing Thermal Conductivity of Fluids with Nanoparticles, 1995.
[2] P. Keblinski, S.R. Phillpot, S.U.S. Choi, J.A. Eastman, Mechanisms of heat ow in suspensions of nano-sized particles (nanouids), Int. J. Heat Mass Transf. 45 (2002)
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