1.

INTRODUCTION

A wide variety of industrial processes involve the transfer of heat energy. Throughout any
industrial facility, heat must be added, removed, or moved from one process stream to another and
it has become a major task for industrial necessity. These processes provide a source for energy
recovery and process fluid heating/cooling.

The enhancement of heating or cooling in an industrial process may create a saving in

energy, reduce process time, raise thermal rating and lengthen the working life of equipment. Some
processes are even affected qualitatively by the action of enhanced heat transfer. The development
of high performance thermal systems for heat transfer enhancement has become popular
nowadays. A number of work has been performed to gain an understanding of the heat transfer
performance for their practical application to heat transfer enhancement. Thus the advent of high
heat flow processes has created significant demand for new technologies to enhance heat transfer.

There are several methods to improve the heat transfer efficiency. Some methods are
utilization of extended surfaces, application of vibration to the heat transfer surfaces, and usage of
micro channels. Heat transfer efficiency can also be improved by increasing the thermal
conductivity of the working fluid. Commonly used heat transfer fluids such as water, ethylene
glycol, and engine oil have relatively low thermal conductivities, when compared to the thermal
conductivity of solids. High thermal conductivity of solids can be used to increase the thermal
conductivity of a fluid by adding small solid particles to that fluid.

The feasibility of the usage of such suspensions of solid particles with sizes on the order of
2 millimeters or micrometers was previously investigated by several researchers and the following
significant drawbacks were observed.

1.The particles settle rapidly, forming a layer on the surface and reducing the heat transfer capacity
of the fluid.

2.If the circulation rate of the fluid is increased, sedimentation is reduced, but the erosion of the
heat transfer devices, pipelines etc.,increases rapidly.

3.The large size of the particles tends to clog the flow channels, particularly if the cooling channels
are narrow.

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4. The pressure drop in the fluid increases considerably.

5.Finally, conductivity enhancement based on particle concentration is achieved (i.e., the greater
the particle volume fraction is, the greater the enhancement—and greater the problems, as
indicated above).

Thus, the route of suspending particles in liquid was a well-known but rejected option for
heat transfer applications.

1.1 Emergence of Nanofluids

In recent years, nanofluids have attracted more and more attention. The main driving force
for nanofluids research lies in a wide range of applications. Nanofluids, the fluid suspensions of
nanomaterials, have shown many interesting properties, and the distinctive features offer
unprecedented potential for many applications. Nanofluids are a new class of fluids engineered by
dispersing nanometer-sized materials (nanoparticles, nanofibers, nanotubes, nanowires, nanorods,
nanosheet, or droplets) in base fluids. In other words, nanofluids are nanoscale colloidal
suspensions containing condensed nanomaterials. They are two-phase systems with one phase
(solid phase) in another (liquid phase).

Nanofluids contains nanoparticles (1–100 nm) which are uniformly and stably distributed in
a base fluid. These distributed nanoparticles, generally a metal or metal oxide greatly enhance the
thermal conductivity of the nanofluid, increases conduction and convection coefficients, allowing
for more heat transfer. These distributed nanoparticles have been found to enhance thermo physical
properties such as thermal conductivity, thermal diffusivity, viscosity, and convective heat
transfer coefficients of base fluids like oil or water.

Compared to conventional solid–liquid suspensions for heat transfer intensifications,

nanofluids having properly dispersed nanoparticles possess the following advantages:

❖ High specific surface area and therefore more heat transfer surface between particles and
fluids. High dispersion sstability with predominant Brownian motion of particles.

❖ Reduced pumping power as compared to pure liquid to achieve equivalent heat transfer
intensification.

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 ❖ Reduced particle clogging as compared to conventional slurries, thus promoting system
miniaturization.

❖ Adjustable properties, including thermal conductivity and surface wettability, by varying

particle cconcentrations to suit different applications.

1.2 Hybrid Nanofluids

Recently, a new class of nanofluid, “hybrid nanofluid” is being used to further enhance the
heat transfer rate. Hybrid nanofluids are very new kind of nanofluids, which can be prepared by
suspending (i) different types (two or more than two) of nanoparticles in base fluid, and (ii) hybrid
(composite) nanoparticles in base fluid. A hybrid material is a substance which combines physical
and chemical properties of different materials simultaneously and provides these in a
homogeneous phase. Synthetic hybrid nanomaterials exhibit remarkable physicochemical
properties that do not exist in the individual components. A significant amount of research has
been done regarding the properties of these composites and hybrid materials consisting of carbon
nanotubes (CNTs) have been used in electrochemical-sensors, bio-sensors, nanocatalysts, etc. but
the use of these hybrid nanomaterials in nanofluids has not developed as such. Work on hybrid
nanofluids is very limited and a lot of experimental study is still being done.

The main objective of synthesizing hybrid nanofluids is to obtain the properties of its
constituent materials. A single material does not possess all the favorable characteristics required
for a particular purpose; it may either have good thermal properties or rheological properties. But
in many practical applications, it is required to trade-off between several properties and that is
where the use of hybrid nanofluid comes. Furthermore, the hybrid nanofluid is expected to yield
better thermal conductivity compared to individual nanofluids due to synergistic effect. Carbon
nanotubes have a multitude of unique properties like its physical strength, chemical stability,
mechanical resistance, very high electrical and thermal conductivity, etc. These characteristics
have attracted the researchers towards carbon nanotubes as well as in development of a new
category of hybrid nanomaterials consisting of a composite of carbon nanotubes with metallic,
semi-conductive or non-conductive nanoparticles.

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1.3 Nanoparticle material

The nanoparticle materials include chemically stable metals(e.g. gold, copper), metal oxides
(e.g. alumina, silica, zirconia, titania), oxide ceramics (e.g. Al2O3, CuO), metal carbides (e.g. SiC),
metal nitrides (e.g. AIN, SiN), carbon in various forms (e.g. diamond, graphite, carbon nanotubes,
fullerene) and functionalized nanoparticles . Most of the research works were focused mainly on
water and ethylene glycol based nanofluids, very few reports of the synthesis of oil- based
nanofluids have been found. Xuan and Li have found that oil based nanofluids exhibited better
enhancement of heat transfer characteristics compared to water based nanofluids, and that the
viscosity of the oil could be crucial for the dispersion and stability of nanofluids . Hwang et al.have
also showed similar conclusion that a higher thermal conductivity enhancement can be obtained if
a base fluid of lower thermal conductivity is used. Therefore, oil-based nanofluids containing
carbon nanotubes, TiO2, CuO, Al2O3, AlN and SiO2, for industrial and engineering applications,
have attracted some more attention in recent. Hence the project aims on preparation of hybrid
nanoparticle of TiO2 & CuO in which CuO adds the property of high thermal conductivity and
TiO2 adds stability of nanofluid.

1.4. Thermophysical properties of Nanofluids:

Thermo physical properties of the nanofluids are quite essential to predict their heat transfer
behavior. It is extremely important in the control for the industrial and energy saving perspectives.
There is great industrial interest in nanofluids. Nanoparticles have great potential to improve the
thermal transport properties compared to conventional particles fluids suspension, millimetre and
micrometer sized particles. In the last decade, nanofluids have gained significant attention due
to its enhanced thermal properties.

Experimental studies show that thermal conductivity of nanofluids depends on many factors
such as particle volume fraction, particle material, particle size, particle shape, base fluid material,
and temperature. Amount and types of additives and the acidity of the nanofluid were also shown
to be effective in the thermal conductivity enhancement. Hence the project also pays attention to
study all these factors.

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2. LITERATURE SURVEY
2.1 Synthesis of Alumina-Copper/water hybrid nanofluids using two step method and its
thermo physical properties [1]

S.Suresh, K.P.Venkitaraj, P.Selvakumar, M.Chandrasekar

OBJECTIVE

To synthesis Al2O3-Cu hybrid nanoparticle by hydrogen reduction technique and to study

thermal as well as physical properties of different nanofluid with water as base fluid at different
concentration of hybrid nanoparticle.

PROCEDURE

Al2O3-Cu hybrid nanoparticles were synthesized by hydrogen reduction technique from the
powder mixture of Al2O3 and CuO in 90:10 weight proportions obtained from a chemical route
synthesis. The steps consisted of following stages: spray-drying, oxidation of precursor powder,
reduction by hydrogen and homogenisation. The SEM and XRD were then done on the obtained
hybrid nanopowder. Then Al2O3/water hybrid nanofluids with volume fractions from 0.1 to 2%
were prepared using two step method by dispersing it in deionized water. Thermal conductivity
was then measured with the help of a thermal property analyser. The viscosity of the nanofluid
was measured using Brookfield cone and plate viscometer. The stability of the nanofluids were
measured by using pH and Zeta potential measurements.

RESULT AND DISCUSSION

It was found that the nanofluids were least stable at the isoelectric point. At isoelectric point,
the repulsive forces between particles are too weak, allowing the particles to approach each other
and eventually agglomerate affecting the stability of the suspensions. It was observed that pH
values of the hybrid nanofluid increased with increase in concentration indicating stability of the
nanofluids are dependent on the volume concentration of nanoparticles. From the values obtained
from the thermal property analyzer it was found that thermal conductivity decreased with time
ultimately reaching a constant value. Also thermal conductivity increased with increase in
nanoparticle concentration in nanofluid. The viscosity measurements of the nanofluids showed
that viscosity was independent of shear rate. The viscosity of the hybrid nanofluid increased with
volume concentrations.

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CONCLUSION

The experimental results show that there was a significant enhancement in effective thermal
conductivity of the prepared hybrid nanofluids compared with deionised water. It was also
observed that the thermal conductivity of nanofluids increased remarkably with increase in volume
fraction of nanoparticles. Viscosity measurements indicate that Al2O3/water nanofluids behave as
Newtonian fluids. The viscosity values for hybrid fluids are higher when compared to the viscosity
of alumina/water nanofluids.

2.2 Experimental study on heat transfer and rheological characteristics of hybrid nanofluids
for cooling applications [2]

D. Madhesh &S. Kalaiselvam

OBJECTIVE

Effects of Nusselt number, Peclet number, Reynolds number, heat transfer coefficient and
pressure drop were investigated for various volume concentrations of copper-titania hybrid
nanocomposite (HyNC).

PROCEDURE

The HyNF was prepared by the following procedure: Initially 5 g of Titania was dispersed
in aqueous solution. Subsequently 0.5 g of Copper Acetate was mixed in aqueous solution by
intense stirring. Ascorbic acid and Sodium borohydride which act as reducing agents were then
added to the blend of Titania and Copper Acetate solution. The prepared solution was allowed to
stand for 2 hours at 45 °C temperature and ambient pressure to obtain HyNC colloids. The HyNC
colloids were then washed and filtered, followed by vacuum drying. To prepare the HyNF, the as-
prepared HyNC powder was re-dispersed in the base fluid, in volume concentrations ranging from
0.1% to 1.0% using the ultrasonic vibrator.Various characterization techniques such as XRD and
EDAX were performed in order to confirm the material homogeneity and particle size are within
limits.

RESULTS AND DISCUSSION

The fine dispersion of nanoparticles in the base fluid showed rise in thermal conductivity.
Thermal conductivity depended not only on particle size and temperature but also on chemical

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parameters such as Hamaker constant, Zeta potential, PH value and ion concentration. Formation
of fine crystalline and heat conductive nature of the Copper nanoparticles on the surface of Titania
particles was different and an important reason to dissipate the thermal transport to the surrounding
fluids.

CONCLUSION

Without surfactant, the surface functionalized and highly crystalline nature of HyNC has
contributed to creating effective thermal interfaces with the fluid medium, thereby achieving
improved thermal conductivity and heat transfer potential of nanofluids.For the volume
concentration up to 0.7%, convective heat transfer coefficient of HyNF was enhanced by 59.3%.

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3. SCOPE AND OBJECTIVES

3.1 PROJECT VISION

The preliminary study suggests that nano fluids have begun to replace normal coolants used
in heat transfer equipments used in process industry. Even though most of the nano fluids possess
several inherent advantages such as , high thermal conductivity and improved heat transfer
characteristics resulting in a higher economy in industries , proper choice of nano fluids with
optimal characteristics is still a barrier due to their low thermal and oxidative stability and poor
temperature characteristics. With the addition of certain synthetic and natural additives, the
drawbacks of such Nano fluids can be overcome. In such scenario we are trying to incorporate
higher heat transfer character of copper which has a decreased stability and TiO2 which has a
higher stability but poor thermal conductivity in a single base fluid. This study aims at achieving
the following objectives:

 Preparation of hybrid nanoparticles of copper and TiO2

 Characterisation of prepared samples using

1. X-ray diffraction

2. FTIR

3. SEM

4. EDAX

To ensure the size of prepared samples are within limits

 Preparation of Nano fluids by dispersing the prepared sample in base fluids( water and ethylene
glycol)

 Vary the concentrations of fluids from 0.01% to 0.1% (wt %)

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 Visual observation of stability or determination of settling time of samples

 Application of prioritised samples in miniature heat exchanger to find the enhancement ratio.

 Find the optimal fluid in terms of stability ,cost and heat transfer characteristics

 Find the optimal temperature range of nanofluids

4. MATERIALS AND METHOD

Table 4.1: Materials Used

Name Type

Copper acetate

Ascorbic acid
Titanium dioxide

Deionized water

Ethylene glycol

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 Table 4.2: Apparatus used

Apparatus Lab
Hot air oven ct lab
Sonicator mechanical nano technology research
lab
Centrifuge dryer mechanical nano technology research
lab
FTIR Chemical department ftir lab
XRD chemistry xrd
idax mechanical nano technology research
lab
Weighing balance

Beakers

Vials

Cultural tubes

Table 4.3: Sample Details

Sample Composition Composition

(base fluid water) (base fluid ethylene
glycol)
Wt %
Wt %
1 0.01 0.01
2 0.03 0.03
3 0.05 0.05
4 0.07 0.07
5 0.09 0.09
6 0.1 0.1

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4.1 METHODS USED
In order to study the properties and characteristics of various samples, different tests were
performed on the samples prepared .They are listed below.

1. FTIR

2. XRD

3. EDAX

4.4.1 FTIR

Fourier transform infrared spectroscopy (FTIR) is a technique which is used to obtain an infrared
spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer simultaneously
collects high spectral resolution data over a wide spectral range. This confers a significant advantage
over a dispersive spectrometer which measures intensity over a narrow range of wavelengths at a time.

4.4.2 XRD

X-ray diffraction (XRD) is a powerful nondestructive technique for characterizing

crystalline materials. It provides information on crystal structure, phase, preferred crystal
orientation (texture), and other structural parameters, such as average grain size, crystallinity,
strain, and crystal defects. X-ray diffraction peaks are produced by constructive interference of a
monochromatic beam of X-rays diffracted at specific angles from each set of lattice planes in a
sample. The peak intensities are determined by the distribution of atoms within the lattice.
Consequently, the X-ray diffraction pattern is the fingerprint of the periodic atomic arrangements
in a given material. A search of the ICDD (International Centre for Diffraction Data) database of
X-ray diffraction patterns enables the phase identification of a large variety of crystalline samples.

4.4.3 DLS

Dynamic Light Scattering (DLS) measures the translational diffusion coefficients Dt of

nanoparticles and colloids in solution by quantifying dynamic fluctuations in scattered light. Sizes
and size distributions, in turn, are calculated from the diffusion coefficients in terms of
hydrodynamic radius rh or hydrodynamic diameter dh.DLS is suitable for ensemble measurements

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ranging from rh values of 0.2 nm up to 5,000 nm. Wyatt offers high-throughput, automated DLS
as well as conventional, cuvette-based formats.

5. PROCEDURE
5.1 PREPARATION OF HYBRID NANO PARTICLE

 About 0.5g of copper acetate , 5g of ascorbic acid and titanium dioxide was mixed in
aqueous medium
 The mixture was well agitated and set in a hot air oven at 45 degree Celsius for two hours
 The resulting solution was washed several times and dried using centrifugal drying
technique
 Following centrifugal drying the obtained dry powder was finely ground using mortar.
 The sample was preserved in vacuum desiccator.
5.2 PREPARATION OF NANO FLUIDS

 For the preparation of nanofluids base fluids selected were water and ethylene glycol
 Two sets of samples were prepared each set with different base fluid
 Each of the set consisted of 6 samples of with concentration varying from 0.01% to
0.1%(mass percentage) of hybrid nanoparticles .(concentration range was arbitrarily
chosen preferring lower concentrations.)
 For fine dispersing the powder in base fluid all samples are kept in sonication bath for a
minimum time period of 12 hours
5.3 PREPARATION OF SAMPLE FOR DLS

To 15 ml of DI water about 5 mg of a hybrid nanopowder is added. The mixture is then kept

in sonication bath for 10 to 15 minutes. After sonication a uniform dispersed solution was formed
which was taken for DLS analysis.

5.4 XRD AND FTIR

For XRD and FTIR dry powder form of hybrid is used. In FTIR the powder is initially
pelletized before performing analysis.

5.5 STABILITY ANALYSIS

For stability analysis visual observation of the synthesised nanofluids is preferred. The
prepared samples of different concentrations are kept under surveillance till they settle. The time
from synthesising to settling is considered as the stable period for storage of the nanofluids.

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RESULTS AND DISCUSSION

6.1 FTIR Analysis

Figure 6.1: FT-IR Spectrogram

6.1.1 Discussions

Strong band absorptions were observed in the region of 3500– 3200 𝑐𝑚−1and 1636.3 𝑐𝑚−1
caused by corresponding to O–H stretching vibrations. The stretching vibrations of Cu-O can be
seen at frequencies of 670.9 𝑐𝑚−1. The stretching vibrations of Ti-O bond can be seen at 500-600
𝑐𝑚−1 indicating the presence of TiO2.

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6.2 XRD Analysis

Figure 6.2: XRD analysis

Fig 6.2 represents the XRD of the material Rigaku Miniflex 600 Cu - K alpha radiation
source (𝜆= 1.504𝛬) 10 to 90 degree with an increment of 0.12 angle was used to determine the
diffraction of the material. The synthesized hybrid nano powder was taken for XRD. The peaks
found were satisfactory confirming the following results on comparison with a standard range of
theta values of TiO2 and Cu:
● The major peak in the range of 20 - 30 degrees of theta are indicative of the presence of
𝑇𝑖𝑂2 and a minor peak is also found in the neighbourhood of 55 degree for TiO2.
● The presence of CuO is confirmed from the peaks appearing near to 40 degrees and at 62
degree of theta.

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6.3 DLS Analysis

Fig 6.3: DLS Analysis

On conducting DLS the following results were obtained.

● The observed major peak was found to be at the size of 389.1nm.
● The size of the sample can be averaged as 341.9 nm which is quite satisfactory to confirm
the particle size in the nano region.
● The PDI (particle distribution index) is an indication of uniformity of the mixture. A higher
PDI indicates less uniformity in the sample.
● The PDI observed is 0.216 which implies that the sample is uniform in size and has a lower
settling tendency.

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 ● The shifted peaks towards the right indicate the presence of large sized particles in the
sample with a lower intensity. The large sized particles are responsible for settling tendency
of nanofluids.
● From the results of DLS analysis the resultant quality of the sample is obtained as good. It
resembles the prepared sample is having a uniform size distribution.
6.5 Stability Analysis
The stability of the prepared sample were primarily analyzed by visual observation and the
time period for each sample to settle down was noted. The results are tabulated below:

Table 6.1

SL NO BASE FLUID CONCENTRATION SETTLING PERIOD

( Wt%) (days)

1 Water 0.01 -

2 Water 0.03 -

3 Water 0.05 3

4 Water 0.07 2

5 Water 0.09 4

6 Water 0.1 1

7 Ethylene Glycol 0.01 7

8 Ethylene Glycol 0.03 3

9 Ethylene Glycol 0.05 2

10 Ethylene Glycol 0.07 1

11 Ethylene Glycol 0.09 1

12 Ethylene Glycol 0.1 1

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 (a) (b)

(c) (d)

Fig: 6.5.a to 6.5.d - represents nanofluids with base fluid water for a given time period.

(a) Day 1 (b) Day 2 (c) Day 3 (d) Day 4

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 (e) (f)

(g) (h)

Fig: 6.5.e to 6.5.h - represents nanofluids with base fluid ethylene glycol for a given time period.

(a) Day 1 (b) Day 2 (c) Day 3 (d) Day 7

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6. CONCLUSION
In any chemical industries heating and cooling utilities have a high significance,since
throughout any industrial facility, heat must be added, removed, or moved from one process stream
to another and it has become a major task for industrial necessity. They are a major factor of cost
expenditure. The incorporation of these nanofluids as a coolant produces a large reduction in the
cost expenditure by reducing the utilities requirement since nanofluids are having a high heat
transfer enhancement than the common process fluids or base fluids.

By means of combing through relevant papers we have shortlisted that a hybrid nanofluids
have better thermal conductivity than the common fluids like water and other synthesised
nanofluids.

We realised that two step method is the most appropriate and stable method than the one step
method for the hybrid nanofluids through investigation of different journals.

The hybrid nanoparticle Cu-TiO2 is selected on the basis of following reasons:

● High conductivity of Cu
● High stability of TiO2
Since the high thermal conductivity of Cu particle enhances the thermal of conductivity of
the nanofluid while it destabilizes also. In Order to encounter the stability problem TiO2 is used
for high stabilization in the nanofluid. Nanofluids have different effects and variation with the
physical parameters:
● Temperature
● Type of base fluids
● Concentration
● Acidity
● Particle material
● Viscosity of base fluid
The following experimental conclusions were obtained from the synthesis and
characterization of hybrid Cu-TiO2 nanofluid:
1. We observed from the stability test that the lower concentration nanoparticle in any base
fluid is having the highest stability.
2. The base fluid water is showing more stability for Cu-TiO2 nanoparticle than ethylene
glycol as settlement of the particle is high in ethylene glycol.
 3. The characterisation is an important factor to check the stability of nanoparticle and from
the DLS results, we obtained a size range of 300 nm which resembles the good stability of
nanofluid and also obtained a good PID value.
It was observed that more the brownian motion in the nanofluid, the better will be the
stability and we are able to observe that agglomeration is very small in the low concentration
samples which showed the desired results in the stability test. The nanofluid will become
successful only when it meets the stability requirements and it's important to check it after the
synthesis which will eventually produce better results in the heat enhancement process. Therefore
characterisation and stability test are the most relevant step to the production of a better nanofluid.

Nanofluids ability to enhance the heat transfer and optimisation of utility make it a better
source of utility to any chemical industry and most of the refineries are developing nanofluids in
order to replace the conventional fluids nowadays. It can expected that in the coming years the
nanofluid technology will be implemented in most of the industries and make it more reliable.

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