CHAPTER I

INTRODUCTION
1.1. Background
Heat transfer describes the exchange of thermal energy, between physical systems
depending on the temperature and pressure, by dissipating heat. The fundamental modes of heat
transfer are conduction or diffusion, convection and radiation. Heat transfer always occurs from
a region of high temperature to another region of lower temperature. Heat transfer changes the
internal energy of both systems involved according to the First Law of Thermodynamics. The
Second Law of Thermodynamics defines the concept of thermodynamic entropy, by measurable
heat transfer. Thermal equilibrium is reached when all involved bodies and the surroundings
reach the same temperature.

Conduction or diffusion is the transfer of energy between objects that are in physical
contact. Thermal conductivity is the property of a material to conduct heat and evaluated
primarily in terms of Fourier's Law for heat conduction. Heat is transferred by conduction when
adjacent atoms vibrate against one another, or as electrons move from one atom to another.
Conduction is the most significant means of heat transfer within a solid or between solid objects
in thermal contact. Steady state conduction is a form of conduction that happens when the
temperature difference driving the conduction is constant, so that after an equilibration time, the
spatial distribution of temperatures in the conducting object does not change any further.
Transient conduction occurs when the temperature within an object changes as a function of
time. Analysis of transient systems is more complex and often calls for the application of
approximation theories or numerical analysis.

Convection is the transfer of energy between an object and its environment, due to fluid
motion. The flow of fluid may be forced by external processes, or sometimes by buoyancy forces
caused when thermal energy expands the fluid, thus influencing its own transfer. The latter
process is often called natural convection. All convective processes also move heat partly by
diffusion, as well. Another form of convection is forced convection. In this case the fluid is
forced to flow by use of a pump, fan or other mechanical means.

1
 Radiation is energy emitted by matter as electromagnetic waves, due to the pool of
thermal energy in all matter with a temperature above absolute zero. Thermal radiation
propagates without the presence of matter through the vacuum of space. Thermal radiation is a
direct result of the random movements of atoms and molecules in matter. Since these atoms and
molecules are composed of charged particles (protons and electrons), their movement results in
the emission of electromagnetic radiation, which carries energy away from the surface.

1.2. Conventional heat transfer fluids

Fluids are often used as heat carriers in heat transfer equipment. Examples of important
uses of heat transfer fluids include vehicular and avionics cooling systems in the transportation
industry, heating and cooling systems in buildings, and industrial process heating and cooling
systems in petrochemical, textile, pulp and paper, chemical, food, and other processing plants.
Conventional fluids such as water, oil and ethylene glycol are widely used as cooling fluids,
which are of major importance to many industrial sectors. The fluids play a significant role in
transferring the heat. However, conventional fluids are poor heat transfer fluids. Despite
considerable previous research and development focusing on industrial heat transfer
requirements, major improvements in heat transfer capabilities have been lacking because of the
low thermal conductivity of conventional heat transfer fluids. As a result there is a strong need to
develop advanced heat transfer fluids with significantly higher thermal conductivities and
improved heat transfer characteristics than presently available.

1.3. New heat transfer fluids

It is well known that metal in solid form have higher thermal conductivities than those of
fluids. For example, the thermal conductivity of copper at room temperature is 700 times greater
than that of water and 3000 times greater than that of engine oil. Therefore, fluids containing
suspended solid particles are expected to display significantly enhanced thermal conductivities
relative to those of conventional heat transfer fluids. An innovative way of improving the
thermal conductivities of fluids is to suspend small solid particles in the fluids. Various types of
powders such as metallic, non-metallic and polymeric particles can be added into fluids to form
slurries.

2
 The thermal conductivity of metallic liquids is much greater than that of non-metallic
liquids. Therefore, the thermal conductivities of fluids that contain suspended solid metallic
particles are expected to be significantly enhanced when compared with conventional heat
transfer fluids. In fact, numerous theoretical and experimental studies of the effective thermal
conductivity of dispersions that contain solid particles have been conducted since Maxwell's
theoretical work was published more than 100 years ago. However, all of the studies on thermal
conductivity of suspensions have been confined to millimeter or micrometer-sized particles.
Maxwell's model shows that the effective thermal conductivity of suspensions that contain
spherical particles increases with the volume fraction of the solid particles. It is also known that
the thermal conductivity of suspensions increases with the ratio of the surface area to volume of
the particle.

It is proposed that nanometer sized metallic particles can be suspended in industrial heat
transfer fluids such as water, ethylene glycol, or engine oil to produce a new class of engineered
fluids with high thermal conductivity. The new class of engineered fluids are called nanofluids,
which contain metallic particles with average particle sizes of about 10-100 nanometers.
Nanofluids are expected to exhibit superior properties when compared with conventional heat
transfer fluids and fluids that contain micrometer-sized metallic particles. Because heat transfer
takes place at the surface of the particle, it is desirable to use a particle with a large surface area.
Nanoparticles have extremely large surface areas and therefore have a great potential for
application in heat transfer. The much larger relative surface areas of Nano-powders, when
compared with conventional micrometer-sized powders, should markedly improve the heat
transfer capabilities and stability of the suspensions.

Nanotechnology is defined as fabrication of devices with atomic or molecular scale

precision. Devices with minimum feature sizes less than 100 nanometers (nm) are considered to
be products of nanotechnology. A nanometer is one billionth of a meter and is the unit of length
that is generally most appropriate for describing the size of single molecules. The nanoscale
marks the nebulous boundary between the classical and quantum mechanical worlds; thus,
realization of nanotechnology promises to bring revolutionary capabilities. Fabrication of
nanomachines, nanoelectronics and other nanodevices will undoubtedly solve an enormous
amount of the problems faced by mankind today. Nanotechnology gives a big devotion in this

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area. Modern nanotechnology provides great opportunities to process and produce materials with
average crystallite sized below 50nm. By applying nanotechnology to this area, “nanofluids”
were developed as a new concept of heat transfer fluids. Nanofluids are expected to exhibit
superior properties relative to those of conventional heat transfer fluids and fluids containing
micrometer sized particles. Because heat transfer takes place at the surface of the particle, it is
desirable to use particles with a large total surface area. The ratio of surface area to volume is
1000 times larger for particles with a 10nm diameter than for particles with a 10μm diameter.
The much larger surface areas of nanoparticles relative to those of conventional particles should
not only improve heat transfer capabilities, but also increase the stability of the suspensions. It is
known that the thermal conductivity of nanofluids is strongly dependent on the volume fraction
dimensions and properties of nanoparticles.

1.4. Objectives
The objectives of the present work are given below.
 Synthesis of Fe2O3 and Zno nanoparticles using one step sol-gel chemical method.
 Characterization of the nanoparticles prepared.
 Preparation of nanofluid: The nanoparticles are mixed with the base fluid (water) and
nanofluid is prepared.
 Calibration of experimental setup
 Performing the experiment using nanofluid in a double pipe heat exchanger
 Comparing the results with the base fluid

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 CHAPTER II
LITERATURE SURVEY

2.1. Introduction
Particles of size range 1-100 nm are considered nanoscale. These nanoparticles, and
structures and devices comprised of them, display unique mechanical, optical, electrical, and
magnetic properties that differ radically from the corresponding bulk material. Applications of
nanostructured materials include catalysts, electrolyte membranes, films, and fibers. Current
intense research in nanoparticles has created a great demand for their efficient production.
Nanoparticles can be produced through either chemical or physical means. They can be made
physically by ball milling, a process in which coarse particles are ground to nanoscale particles.
Disadvantages of ball-milling include the high mechanical energy needed (resulting in strain in
the particles) and contamination by the material of which the ball mill is made. In chemical
methods, by-products form during reactions but they can generally be removed. Chemical
techniques provide the power to mix at the molecular level, allowing for the production of highly
homogeneous materials. Nanoparticles can be synthesized chemically through sol-gel
processing, electrochemical methods, hydrothermal techniques, and chemical vapor deposition.
In the present work Zno and Fe2O3 nanoparticles are prepared by sol-gel method.

2.2. Heat Transfer Enhancement with Nanofluids

Many researchers have investigated the heat transfer performance and flow
characteristics of various nanofluids with different nanoparticles and base fluid materials. Pak
and Cho [1] investigated experimentally the heat transfer performance of Al 2O3 and TiO2
nanoparticles dispersed in water flowing in a horizontal circular tube with a constant heat flux
under turbulent flow conditions. The results showed that the Nusselt number of nanofluids
increased with increasing Reynolds number and the volume concentration. However, they still
found that the convective heat transfer coefficient of the nanofluids with 3 volume concentration
nanoparticles was 12% lower than that of pure water at a given condition. Finally, a new heat
transfer correlation for predicting the convective heat transfer coefficient of nanofluids in a

5
turbulent flow regime was proposed. Lee et al. [2] observed the enhancement of thermal
conductivity of nanofluids while using CuO and Al2O3 nanoparticles with water and ethylene
glycol compared to base fluids only. The thermal conductivities of nanofluids with CuO and
Al2O3 nanoparticles have been determined experimentally using steady-state parallel-plate
technique by Wang et al. [3], for different base fluids such as water, ethylene glycol and engine
oil. The thermal conductivity of these nanofluids increased with increasing volume fraction of
the nanoparticles. Xuan and Li [4] experimentally investigated flow and convective heat transfer
characteristics for Cu-water based nanofluids through a straight tube with a constant heat flux at
the wall. Results showed that the nanofluids give substantial enhancement of the heat transfer
rate compared to pure water. They also claimed that the friction factor for the nanofluids at low
volume fraction did not produce an extra penalty in the pumping power.

Xuan and Roetzel [5] concluded from their findings that the heat transfer enhancement is
due to increase in thermal conductivity or due to thermal dispersion caused by random motion of
the particles coupled with enhanced thermal conductivity. Choi et al. [6] studied the
enhancement of thermal conductivity of carbon nanotube–oil mixture nanofluid at room
temperature. Xie et al. [7] dispersed carbon nanotube in distilled water and ethylene glycol and
concluded that a small amount of carbon nanotubes have significantly increased the thermal
conductivities compared to base fluid. Chien et al. [8] investigated gold (17 nm)/water
nanofluids flowing in a disk-shaped miniature heat pipe with diameter of 9 mm and height of 2
mm. Their data showed that the thermal resistance of the heat pipe fell appreciably with
increased nanoparticle concentration. Das et al. [9] investigated the variation of thermal
conductivity of nanofluids (Al2O3-water and CuO-water) with temperature using temperature
oscillation technique. They observed an increase in thermal conductivity with temperature.

Xue [10] developed a novel approach in the modeling of nanofluid by considering the
particles to be ellipsoids interacting with spherical fluid particles. The model utilize as field
factor approach with depolarization factor and effective dielectric constant. Yu and choi [11]
introduced the classical Maxwell model in which the liquid layer around the particle behaves like
as a solid. Wen and Ding [12] reported experimental results for the convective heat transfer of γ -
Al2O3 (27-56 nm)/water based nanofluids flowing through a copper tube (D = 4.5 mm, L = 970
mm) in laminar regime. They found that the inclusion of Al2O3 particles can significantly

6
enhance the convective heat transfer coefficient, which increases with increasing Reynolds
number and particle concentrations. Furthermore, the improvement of the heat transfer
coefficient was particularly large in the entrance region, and decreased with the axial distance.
Apart from the improved effective thermal conductivity, they also attributed the improvement of
heat transfer to particle migration, which caused a non-uniform distribution of thermal
conductivity and viscosity field along the cross-section in the tube. Tsai et al. [13] also employed
aqueous solutions of various sized (2-35 nm and 15-75 nm) gold nanoparticles, which were
prepared by the reduction of HAuCl4 with tri sodium citrate and tannic acid. They found a large
decrease of thermal resistance of the heat pipe with nanofluids as compared with de-ionized
water. The thermal resistance of the circular heat pipe ranged from 0.17 to 0.215 K/W with
different nanoparticle solutions. The reason is that the included nanoparticles can bombard the
vapor during the bubble formation. Hence, the reduction of thermal resistance was obtained due
to the smaller resulting bubble size.

Hwang et al. [14] through experimental investigation of flow and convective heat transfer
characteristics of Al2O3/water nanofluid, with convective heat transfer characteristics of
Al2O3/water nanofluid with particles varying in the range of 0.01–0.3% in a circular tube of
1.812 mm inner diameter with the constant heat flux in fully developed laminar regime reported
improvement in convective heat transfer coefficient in the thermally fully developed regime.
Yang et al. [15] measured experimentally the convective heat transfer coefficients of several
nanoparticle-in-liquid dispersions under laminar flow in a horizontal tube heat exchanger.
Assael et al. [16] studied experimentally the thermal conductivity of nanofluids using the
transient hot-wire method. They observed a significant increase in thermal conductivity of
nanofluid.

Koo and Kleinstreuer [17] have shown that the Brownian motion has more impact on the
thermal properties of nanofluid than thermo-phoresis. However Boungiorno [18] showed
analytically that thermal dispersion has a negligible effect on increase in convective heat transfer
rather Brownian diffusion and thermo-phoresis are the main mechanisms that contribute to the
heat transfer enhancement. Heris et al. [19] investigated laminar flow of CuO/water and
Al2O3/water nanofluids through a 1 m annular copper tube with 6 mm inner diameter and with
0.5 mm thickness and 32 mm diameter outer stainless steel tube, where saturated steam was

7
circulated to create a constant wall temperature boundary condition rather than the constant heat
flux condition employed by other researchers. Comparison of experimental results showed that
the heat transfer coefficient enhanced with increasing volume fraction of nanoparticles, as well
as Peclet number, while Al2O3/water showed more enhancement. Heris et al. [19] claimed that
the heat transfer enhancement of nanofluids is not only caused by the thermal conductivity
increase, but also attributed to other factors such as dispersion and chaotic movement of
nanoparticles, Brownian motion and particle migration, and so on.
Zhang et al. [20] measured the thermal conductivity and thermal diffusivity of Au-
toluene, Al2O3-water, TiO2-water, CuO-water and carbon nanotubes-water nanofluids using the
transient short-hot-wire technique. They observed no enhancement in the thermal conductivity as
well as thermal diffusivity of nanofluids, above that of predictions of the Hamilton-Crosser
model [21]. Mirmasoumi and Behzadmehr [22] have studied the effects of nanoparticle mean
diameter on the heat transfer and flow behavior into a horizontal tube under laminar mixed
convection condition. Their calculated results demonstrate that the convection heat transfer
coefficient significantly increases with decreasing the nanoparticles means diameter.
Zamzamian et al. [23] investigated the effects of forced convective heat transfer
coefficient with Al2O3/EG and CuO/EG nanofluid in double pipe and plate heat exchangers.
Their results indicate that increasing the nanoparticle concentration and temperature could
enhance the convective heat transfer coefficient of nanofluid, leading to a 2–50% enhancement
in convective heat transfer coefficient of the nanofluid. This thesis is aimed at studying the heat
transfer enhancement and flow characteristics of Al2O3–water nanofluids at a low concentration
flowing in a horizontal shell and tube heat exchanger under a turbulent flow condition

2.3. Scope of the present work

The objective of this report is to provide improvements through Nano fluids in place of
pure working fluid in heat exchangers. In this study, Fe2O3 and ZnO nanoparticles are prepared
by sol-gel method and the nanoparticle with concentration up to 0.5% by volume has been
selected as a coolant in a typical horizontal double-tube heat exchanger because of their
reasonably good thermal properties and easy availability. Water has been chosen as heat transfer
base fluid. The experiments are conducted in the heat exchanger for different concentrations of
nanoparticles and Reynolds numbers.

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 CHAPTER III
SYNTHESIS AND CHARACTERIZATION
OF NANOPARTICLES

Nanoparticles can be produced using many different techniques, typically classified as

bottom-up or chemical methods and top-down or physical methods. In the bottom-up approach,
the structure of nanoparticles is constructed by atoms, molecules or clusters. In top-down
approaches, a bulk piece of a required material is reduced to nano-sized dimensions using
cutting, grinding and etching techniques, i.e., nano-materials are prepared from larger entities
without atomic-level control. Chemical reduction, micro-emulsion (colloidal) techniques,
electrochemical, microwave-assisted, and hydrothermal syntheses are the main techniques for the
synthesis of nanoparticles through the chemical approach. Biological or biosynthesis techniques
are also considered as bottom-up or chemical processes. Physical methods for nanoparticles
synthesis are laser (pulse) ablation, vacuum vapour deposition, pulsed wire discharge and
mechanical milling. A wide range of nanoparticles can be produced using physical methods with
little modification for different metals, but the main disadvantages of these methods are the
quality of the product, which is less as compared to nanoparticles produced by chemical
methods. Usually these methods require costly vacuum systems or equipment to prepare
nanoparticles (plasmas).

The fundamental of nanotechnology lies in the fact that properties of materials change
dramatically when their size is reduced to the nanometer range. But measuring this nano
dimension is not a very easy task. Although research is going on to synthesize
nanostructured and Nano phasic materials, characterizing these nano sized materials is also an
emerging field posing lot of challenges to scientists and technologists. Thus, nanotechnology
has motivated the upsurge in research activities on the discovery and invention of sophisticated
nano characterization techniques to allow a better control of morphology, size and dimensions of
materials in nano range.

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3.1. Synthesis Techniques
3.1.1. Mechanical Milling
Mechanical milling as a solid state synthesis usually performed using ball milling
equipment that generally divided to “low energy” and “high energy” category based on the value
of induced the mechanical energy to the powder mixture. The objective of milling is to reduce
the particle size and blending of particles in new phases. The different type of ball milling can be
used for synthesis of nano-materials in which balls impact upon the powder charge.

High-energy ball milling is a convenient way to produce nano-sized powders. It is the

most common method reported in the literature for the synthesis of intermetallic nanoparticles.
Before a mechanical milling is started, powder(s) is loaded together with several heavy balls
(steel or tungsten carbide) in a container. By vigorously shaking or high-speed rotation, a high
mechanical energy is applied on the powders because of collision with heavy balls. A type of
ball mill is shown in Figure.

Fig.3.1. Rock tumbler ball mill

3.1.2. Mechanochemical Synthesis

Mechanochemical synthesis is the coupling of mechanical and chemical phenomena on a
molecular scale and includes mechanical breakage and chemical behavior of mechanically-
stressed solids. Mechanochemical synthesis differs from standard ball milling. A standard ball
milling process under inert atmosphere results in a moderate reduction of powder particle size

10
and eventually the formation of nano-sized grains within micron-sized particles. The
mechanochemical method involves the initiation of a solid-state displacement reaction during the
ball milling process which can result in nano-sized particles (down to 5 nm in size) embedded
within larger by-product phase particles.

In mechanochemical processes that utilize to change the chemical composition of

precursors, the high energy ball milling equipment‟s is generally used. The mechanochemical
synthesis process has been used in the past to synthesize a broad range of metal nanoparticles
(e.g. Ag, Co, Cr, Cu…) as well as other compounds such as oxides and sulphides. Particle size
control can be gained by adjusting factors such as: the volume fraction of the by-product phase
formed during milling, milling time, milling collision energy (ball-to-powder mass ratio and ball
size), milling temperature, and the use of process control agents.

3.1.3. Laser ablation

Pulsed laser ablative deposition (PLD) is an attractive synthetic method owing to its
ability to produce nanoparticles with a narrow size distribution and a low level of impurities.
Aluminium nanoparticles with diameters of tens to 500 nm of various shapes can be prepared by
irradiating an aluminium foil with 50 fs pulses of a 0.8 μm wavelength laser beam. Three main
steps contribute in laser ablation synthesis method and formation of nanoparticles from a target
immersed in liquid. Laser pulse, first, heats up the target surface to the boiling point, and thus,
plasma plume containing vapour atoms of target is generated. Then, plasma expands
adiabatically; and finally, nanoparticles will be generated when condensation occurs. Synthesis
parameters such as laser wavelength, laser energy, pulse width, liquid media type, and ablation
time can notably affect the product characteristics.

Aluminium nanoparticles can be synthesized by pulsed laser ablation of Al targets in

ethanol, acetone, and ethylene glycol. Comparison between ethanol and acetone clarified that
acetone medium leads to finer nanoparticles (mean diameter of 30 nm) with narrower size
distribution (from 10 to 100 nm). Hur et al. [24] report the synthesis of Mg-Al and Zn-Al-layered
double hydroxides using the laser ablation in the liquid technique. Average diameters of these
structures were about 500 nm and the thickness of a single layer was approximately about 6.0
nm.

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 Fig 3.2 Schematic representation of laser ablation

3.1.4. Exploding Wire

Electro-explosion of metal wires has only recently been applied to make aluminium
nanoparticles. In electro-explosion, a brief but powerful current pulse creates an electromagnetic
field around the wire that holds it together while it is superheated to tens of thousands of degrees.
When the current ceases, the electromagnetic field disappears and the wire fragments into nano-
sized particles. The shapes and sizes of the resulting particles depend on many factors, such as
the shape and size of the wire, the voltage, and the nature of the electrical pulse.

Sen et al. [25] described a process for the production of nanoparticles of Cu, Ag, Fe and
Al which involves exploding their respective wires, triggered by large current densities in the
wires. The explosion was carried out in a dense medium, typically water or some heavy alcohol
where the particles remain suspended and is collected in the following manner. An initial
centrifuge of the suspension at 5000 RPM separates the fluid from the solid mass. While the
former is rejected, the solid mass is dispersed in electronic grade acetone.

3.1.5. Decomposition Process

The chemical route based on thermal and/or catalytic decomposition of alane in the
presence of a surface passivation agent for particle protection and stabilization has been
identified as being particularly promising. The passivation agent for Al nanoparticles could be a
metal coating or organic molecules such as per fluorinated carboxylic acids, which could also

12
serve as an oxidant source under energetic conditions. This method has generally yielded Al
particles of 50-200 nm in average sizes, though smaller particles have been obtained recently in
sonochemical environment with oleic acid as the surface passivation agent. Li et al. [26] reported
the use of nano-scale cavities in per fluorinated ionomer membrane as templates for the facile
synthesis of small Al nanoparticles (diameters on the order of 10 nm) via catalytic decomposition
of an alane precursor. Aluminium nanoparticles can be obtained on a larger scale by
decomposing isolated samples of the alane amine adduct H3Al (NMe2Et) in mesitylene at 164
°C. The aluminium nanoparticles aggregates synthesized by this method were with diameters of
44 – 82 nm.

3.1.6. Gas Evaporation

The most common method to synthesize nanoparticles is the evaporation of material from
the molten state into a chamber filled with an inert gas, where the gaseous metal condenses. The
purity of the material, and the type and purity of the inert gas atmosphere strongly influence the
properties of the nanoparticles obtained. A modified inert gas evaporation method called
cryomelting can also be used to make nanoparticles. In the cryomelting process, the evaporated
metal is rapidly condensed in region cooled to about 70 K. This method can produce 20 – 500
nm nanoparticles in which 60% of the particles are smaller 70 nm in size, as observed by TEM.

3.1.7. Sol-gel method

The sol-gel process is a wet-chemical technique (also known as Chemical Solution
Deposition) widely used recently in the fields of materials science and ceramic engineering. Such
methods are used primarily for the fabrication of materials (typically a metal oxide) starting from
a chemical solution (sol, short for solution) which acts as the precursor for an integrated network
(or gel) of either discrete particles or network polymers.

 Colloid: A colloid is a type of mixture in which one substance is dispersed evenly

throughout another. A colloidal system consists of two separate phases: a dispersed phase
(or internal phase) and a continuous phase (or dispersion medium). Generally, the gravity
of the dispersed phase is negligible, and the interaction between particles is always a
short-range interaction.

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  Sol: A sol is a colloidal suspension of solid or macromolecular particles (1 - 1000 nm in
size) in a liquid.
 Gel: A gel a colloidal system of solid properties, in which the dispersed substances form
continuous and cross linked networks within liquid or gas. The content of dispersed phase
in the gel is very low (1% to 3%).

Fig.3.3. Schematic drawing of the magnetic stirring

Advantages of sol-gel synthesis

 Starting materials are in molecular level, and final products prepared are homogeneous.
 Products are relatively higher in purity.
 Have rheological behaviour, which may be used in the preparation of products with
different applications.
 Controllable degree of porosity.
 Easy to prepare various shapes.
 Cheap and convenient to carry out.
 Enable synthesis at a low temperature.
 Allow for fine control of the product‟s chemical composition, especially suitable for
preparing multicomponent materials.

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  Enable small quantities of dopants to be introduced in the sol and end up uniformly
dispersed in the final product.

Disadvantages of sol-gel synthesis

 Relatively higher in the cost of raw materials.
 Micropores may be left after the synthesis.
 Relatively longer in reaction times.
 Organic solvents may be harmful to the human body.

3.2. Preparation of Nano-particles by sol-gel method

3.2.1. Zno nanoparticles
Materials required: zinc nitrate (or chloride), ammonium hydroxide, cetyl trimethyl ammonium
bromide, polyvinylpyrolidene (PVP), burette, 250ml beaker, magnetic needle, magnetic stirrer,
whattmann filter paper, sample bags, crucible,

Process A: (Sample Code: ZnO-200)

Step 1: weigh 16g of zinc nitrate (or chloride) and transfer it into 250 ml beaker and add 30 ml
isopropyl alcohol to it and stir the contents moderately for about 20 min to get a clear solution of
copper sulfate

Step 2: weigh 3.2 g of cetyl trimethyl ammonium bromide and transfer it into a 100 ml beaker
and add 20 ml of isopropyl alcohol and stir the contents thoroughly. In case CTB does not
dissolve add few drops of HCl and stir the contents for 15 min.

Step 3: Weigh 2.2 g of polyvinyl pyrolidene (PVP) and transfer it into a 100 ml beaker and add
20 ml of isopropyl alcohol and stir the contents thoroughly for about 15 min to get a clear
solution.

Step 4: Transfer step 2 solution into a 50 ml burette and add drop-wise the solution of CTAB to
Step 1 contents while stirring moderately for about 30 min.

Step 5: Transfer step 3 solution into a 50 ml burette and add drop-wise the solution of PVP to
Step 1 contents while stirring moderately for about 30 min.

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Step 6: Take 35 ml of ammonium hydroxide in burette and then add drop-wise to step 1 content
while stirring the contents moderately

Step 7: A whitish precipitate will form and leave the contents stirring for about 30 min to get the
homogeneous

Step 8: Filter the precipitate using a whatman filter paper and wash the precipitate with distilled
water at least 5 to 6 times

Step 9: Leave the precipitate by covering the funnel by petri dish over night

Step 10: the dried precipitate can be transferred on to a petri dish and dry the precipitate by
covering with another petri dish cover in oven at 700C for 8 hours

Step 11: Collect carefully the dried precipitate and weigh it and note down the value. Then sinter
it at temperatures 2000C for 3 h in air ambient. Check that the crucible has a cap to avoid the dust
particle.

Step 12: After cooling down transfer and the material and weigh it and note down the value in
lab note book. Check the weight loss before and after.

Step 13: Make the each sintered material into 2 parts one for the characterization (1g) and
remaining for the testing for heat exchange experiments.

Fig 3.4 (a) Zno nanoparticles before sintering (b) Zno nanoparticles after sintering

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3.2.2. Fe2O3 Nano-particles
Materials required: ferric chloride, ammonium hydroxide, cetyl trimethyl ammonium bromide,
polyvinylpyrolidene (PVP), burette, 250ml beaker, magnetic needle, magnetic stirrer, Wattmann
filter paper, sample bags, crucible,

Process B: (Sample code: FeO-200)

Step 1: weigh 12g of ferric chloride and transfer it into 250 ml beaker and add 30 ml isopropyl
alcohol to it and stir the contents moderately for about 20 min to get a clear solution of copper
sulfate

Step 2: weigh 3.8 g of cetyl trimethyl ammonium bromide and transfer it into a 100 ml beaker
and add 20 ml of isopropyl alcohol and stir the contents thoroughly. In case CTB does not
dissolve add few drops of HCl and stir the contents for 15 min.

Step 3: Weigh 1.8 g of polyvinyl pyrrolidene (PVP) and transfer it into a 100 ml beaker and add
20 ml of isopropyl alcohol and stir the contents thoroughly for about 15 min to get a clear
solution.

Step 4: Transfer step 2 solution into a 50 ml burette and add drop-wise the solution of CTAB to
Step 1 contents while stirring moderately for about 30 min.

Step 5: Transfer step 3 solution into a 50 ml burette and add drop-wise the solution of PVP to
Step 1 contents while stirring moderately for about 30 min.

Step 6: Take 35 ml of ammonium hydroxide in burette and then add drop-wise to step 1 content
while stirring the contents moderately

Step 7: A brownish red precipitate will form and leave the contents stirring for about 30 min to
get the homogeneous

Step 8: Filter the precipitate using a Whatman filter paper and wash the precipitate with distilled
water at least 5 to 6 times

Step 9: Leave the precipitate by covering the funnel by petri dish over night

17
Step 10: the dried precipitate can be transferred on to a petri dish and dry the precipitate by
covering with another petri dish cover in oven at 700C for 8 hours

Step 11: Collect carefully the dried precipitate and weigh it and note down the value. Then sinter
it at 2000C temperature for 3 hours in air ambient. Check that the crucible has a cap to avoid the
dust particle.

Step 12: After cooling down transfer and the material and weigh it and note down the value in
lab note book. Check the weight loss before and after.

Step 13: Make the sintered material into 2 parts one for the characterization (1g) and remaining
for the testing for heat exchange experiments.

Fig.3.5. (a) Fe2o3 nanoparticles before sintering (b) Fe2o3 nanoparticles after sintering

3.3. Sintering
Sintering is the process of compacting and forming a solid mass of material by heat
and/or pressure without melting it to the point of liquefaction. Trough process particles join
together via solid state diffusion and/or reaction to form compound (sometimes with the help of
small amount of liquid phase). Shrinkage of product takes place and the weight of the final
product will be less compared to the initial product.

Many different furnaces are available for this process and muffle furnace has been used
in this project. The ZnO and Fe2O3 nanoparticles with initial weights of 30gms and 64gms were
18
taken for sintering process. The temperature was set to 200°C and samples are placed in
crucibles and covered with a lid so that the foreign particle does not fall into nanoparticles and
placed in furnace for duration of 3hr. The final product i.e. after sintering, the weights of the
particles were 15gms and 32gms.

3.4. Applications of Nanoparticles

Silicate nanoparticles can be used to provide a barrier to gasses (for example oxygen), or
moisture in a plastic film used for packaging. This could slow down the process of spoiling or
drying out in food. Zinc oxide nanoparticles can be dispersed in industrial coatings to protect
wood, plastic and textiles from exposure to UV rays. Silicon dioxide crystalline nanoparticles
can be used to fill gaps between carbon fibers, thereby strengthening tennis racquets. Silver
nanoparticles in fabric are used to kill bacteria, making clothing odor-resistant. Iron
nanoparticles are being used to clean up carbon tetrachloride pollution in ground water. Iron
oxide nanoparticles are being used to clean arsenic from water wells. A lead free solders reliable
enough for space missions and other high stress environments using copper nanoparticles.
Silicon nanoparticles coating anodes of lithium-ion batteries can increase battery power and
reduce recharge time. Semiconductor nanoparticles are being applied in a low temperature
printing process that enables the manufacture of low cost solar cells.
3.4.1. Iron Oxide (Fe2O3) Nanoparticles
The key applications of iron oxide nanoparticles are as follows:
 In magnetic resonance imaging to provide enhanced contrast at very low
concentrations in the nano molar range for studying tumors
 As a targeted delivery vehicle and as a drug delivery coating for nano scale anti-
cancer drugs
 For magnetic data storage
 In coatings, plastics, nanowires, nanofibers, and textiles and in specific alloy and
catalyst applications
3.4.2. Zinc Oxide (ZnO) Nanoparticles
Some of the applications of zinc oxide nanoparticles are given below.
 Zinc oxide is used in the manufacture of rubber and cigarettes (used as a filter).

19
  Popularly known calamine lotion is made out of zinc oxide powder. It is also used in
a host of other creams and ointments that are used to treat skin diseases.
 As an additive in the manufacture of concrete.
 Ceramic industry has a number of uses for zinc oxide powder.
 It is also used as an additive in food products such as breakfast cereals.
 Various paints use zinc oxide as a coating agent.

3.5. Characterization of Nanoparticles

3.5.1 Nanomaterial Characterization by Microscopy
Optical microscopes are generally used for observing micron level materials with
reasonable resolution. Further magnification cannot be achieved through optical microscopes due
to aberrations and limit in wavelength of light. Hence, the imaging techniques such as scanning
electron microscopy (SEM), transmission electron microscopy (TEM/HRTEM), scanning
tunneling microscopy (STM), atomic force microscopy (AFM), etc. have been developed to
observe the sub-micron size materials. Though the principles of all the techniques are different
but one common thing is that they produce a highly magnified image of the surface or the
bulk of the sample. Nano materials can only be observed through these imaging techniques as
human eye as well as optical microscope cannot be used to see dimensions at nano level. Basic
principles and applications of all these imaging techniques used in nanotechnology research are
described below.

3.5.1.1 Scanning Electron Microscopy (SEM)

The scanning electron microscope is an electron microscope that images the sample
surface by scanning it with a high energy beam of electrons. Conventional light microscopes use
a series of glass lenses to bend light waves and create a magnified image while the scanning
electron microscope creates the magnified images by using electrons instead of light waves.
When the beam of electrons strikes the surface of the specimen and interacts with the atoms of
the sample, signals in the form of secondary electrons, back scattered electrons and
characteristic X-rays are generated that contain information about the sample's surface
topography, composition, etc. The SEM can produce very high-resolution images of a
sample surface, revealing details about 1-5 nm in size in its primary detection mode i.e.

20
secondary electron imaging. Characteristic X-rays are the second most common imaging mode
for an SEM. These characteristic X-rays are used to identify the elemental composition of the
sample by a technique known as energy dispersive X- ray (EDX). Back-scattered electrons
(BSE) that come from the sample may also be used to form an image. BSE images are often used
in analytical SEM along with the spectra made from the characteristic X-rays as clues to the
elemental composition of the sample. In a typical SEM, the beam passes through pairs of
scanning coils or pairs of deflector plates in the electron column to the final lens, which
deflect the beam horizontally and vertically so that it scans in a raster fashion over a rectangular
area of the sample surface. Electronic devices are used to detect and amplify the signals
and display them as an image on a cathode ray tube in which the raster scanning is
synchronized with that of the microscope. The image displayed is therefore a distribution
map of the intensity of the signal being emitted from the scanned area of the specimen. SEM
requires that the specimens should be conductive for the electron beam to scan the surface and
that the electrons have a path to ground for conventional imaging. Non-conductive solid
specimens are generally coated with a layer of conductive material by low vacuum sputter
coating or high vacuum evaporation. This is done to prevent the accumulation of static electric
charge on the specimen during electron irradiation. Non-conducting specimens may also be
imaged uncoated using specialized SEM instrumentation such as the "Environmental
SEM" (ESEM) or in field emission gun (FEG) SEM operated at low voltage, high vacuum
or at low vacuum, high voltage.

Fig. 3.6. Schematic diagram of SEM

21
3.5.1.2 Transmission Electron Microscopy (TEM)
Transmission electron microscopy is a microscopy technique whereby a beam of
electrons is transmitted through an ultra-thin specimen and interacts as passes through the
sample. An image is formed from the electrons transmitted through the specimen, magnified and
focused by an objective lens and appears on an imaging screen. The contrast in a TEM image is
not like the contrast in a light microscope image. In TEM, the crystalline sample interacts with
the electron beam mostly by diffraction rather than by absorption. The intensity of the diffraction
depends on the orientation of the planes of atoms in a crystal relative to the electron beam; at
certain angles the electron beam is diffracted strongly from the axis of the incoming beam,
while at other angles the beam is largely transmitted. Modern TEMs are equipped with
specimen holders that allow to tilt the specimen to a range of angles in order to obtain specific
diffraction conditions. Therefore, a high contrast image can be formed by blocking electrons
deflected away from the optical axis of the microscope by placing the aperture to allow only un-
scattered electrons through. This produces a variation in the electron intensity that reveals
information on the crystal structure. This technique, particularly sensitive to extended crystal
lattice defects, is known as „bright field‟ or „light field‟. It is also possible to produce an image
from electrons deflected by a particular crystal plane which is known as dark field image. The
specimens must be prepared as a thin foil so that the electron beam can penetrate. Materials that
have dimensions small enough to be electron transparent, such as powders or nanotubes, can
be quickly produced by the deposition of a dilute sample containing the specimen onto support
grids.

Fig.3.7. Schematic diagram of a TEM

22
3.5.1.3 Atomic Force Microscopy (AFM)

Atomic Force Microscopy is a form of Scanning Probe Microscopy. It uses a mechanical

probe to feel the surface of a sample. A cantilever with a nanoscale probe is moved over the
surface of a sample and the forces between the probe tip and the sample measured from the
deflection of the cantilever. The deflection moves a laser spot that reflects into an arrangement of
photodiodes. This can offer a 3D visualization. Air samples or liquid dispersions can be looked
at and AFM is less costly and time consuming that TEM or SEM. However the sample must
adhere to a substrate and be rigid and dispersed on it. The roughness of the substrate must be less
than the size of the nanoparticles being measured. Atomic force microscopy can be used to
explore the nanostructure, properties of surface and interfaces of fiber and fabric. For example
structural characteristics of nanofiber materials, nano level surface modification of textile
surfaces can be addressed by this sophisticated technique.

Fig.3.8. Schematic diagram of a AFM

23
3.5.2 Characterization of Nano materials by X-ray
3.5.2.1 Wide Angle X-Ray Diffraction (XRD)
X-rays are electromagnetic radiation similar to light, but with a much shorter
wavelength. They are produced when electrically charged particles of sufficient energy are
decelerated. In an X-ray tube, the high voltage maintained across the electrodes draws electrons
toward a metal target (the anode). X-rays are produced at the point of impact, and radiate in all
directions. If an incident X-ray beam encounters a crystal lattice, general scattering occurs.
Although most scattering interferes with itself and is eliminated (destructive interference),
diffraction occurs when scattering in a certain direction is in phase with scattered rays
from other atomic planes. Under this condition the reflections combine to form new enhanced
wave fronts that mutually reinforce each other (constructive interference). The relation by which
diffraction occurs is known as the Bragg‟s law. As each crystalline material including the semi
crystalline polymers as well as metal and metal oxide nanoparticles and layered silicate
nano clays have a characteristic atomic structure, it will diffract X-rays in a unique characteristic
diffraction order or pattern.

Fig.3.9. Schematic illustration of basic 2D WAXD setup

24
3.5.2.2 X-Ray Photoelectron Spectroscopy (XPS)
It is a quantitative spectroscopic surface chemical analysis technique used to estimate the
empirical formula or elemental composition, chemical state and electronic state of the elements
on the surface (up to 10 nm) of a material. XPS is also known as ESCA, an abbreviation of
electron spectroscopy of chemical analysis. X-ray irradiation of a material under ultra-high
vacuum (UHV) leads to the emission of electrons from the core orbitals of the top 10 nm of the
surface elements of the material being analyzed. Measurement of the kinetic energy (KE)
and the number of electrons escaping from the surface of the purified montmorillonite and
organo-clay-material gives the XPS spectra. From the kinetic energy, the binding energy of the
electrons to the surface atoms can be calculated. The binding energy of the electrons reflects the
oxidation state of the specific surface elements. The number of electrons reflects the proportion
of the specific elements on the surface.

Fig.3.10. Schematic illustration of XPS

25
 CHAPTER IV
NANO FLUID PREPARATION

4.1. Introduction
Nanofluids are colloidal suspension of ultra-fine metallic or non-metallic particles in a
given fluids. Despite all other properties, it is well known for its high thermal conductivity and
better response as heat transfer medium. Nanofluids can be of two kinds such as metallic
nanofluids and non-metallic nanofluids. Metallic nanofluids are prepared by dispersing
nanoparticle made from metals such as aluminium, copper, nickel etc. and non-metallic
nanofluids are made by dispersing nanoparticles of non-metals i.e. metal oxides, various
allotropes of carbon (Graphene, CNT) etc. Synthesis and stability of nanofluids are the two very
primary requirements to study nanofluids. The proper utilization of the potential of nanofluids
depends on the preparation and stability of nanofluids.

4.2. Nanofluid Preparation Methods

Several studies, including the earliest investigations of nanofluids, used a two-step
method in which nanoparticles or nanotubes are first produced as a dry powder and then
dispersed into a fluid in a second processing step. In contrast, the one-step method entails the
synthesis of nanoparticles directly in the heat transfer fluid.

4.2.1. Single-step preparation process

The single-step preparation process indicates the synthesis of nanofluids in one-step.
Few methods exist for the preparation of nanofluids through a one step process. These methods
include the thermal decomposition of an organometallic precursor in the presence of a stabilizer,
chemical reduction and polyol synthesis. The polyol method is one of the most well-known
pathways to noble metal nanoparticles. In the polyol process, a metal precursor is dissolved in a
liquid polyol (usually ethylene glycol), after which the experimental conditions are adjusted to
achieve the reduction of the metallic precursor by the polyol, followed by atomic metal
nucleation and metal particle growth. The direct-evaporation technique was developed by Choi
et al [6]. It consists of a cylinder containing a fluid which is rotated. In the middle of the

26
cylinder, a source material is vaporized. The vapor condenses once it comes into contact with the
cooled liquid. The drawbacks of this technique however, are that the use of low vapor pressure
liquids are essential and only limited quantities can be produced. A submerged arc nanoparticle
synthesis system (SANSS) was developed to prepare CuO nanoparticles dispersed uniformly in a
dielectric liquid (deionized water). The method successfully produced a stable nanofluid (Lo et al
[27]). In principle, a pure copper rod is submerged in a dielectric liquid in a vacuum chamber. A
suitable electric power source is used to produce an arc between 6000 - 12000 °C which melts
and vaporizes the metal rod in the region where the arc is generated. At the same time, the
deionized water is also vaporized by the arc. The vaporized metal undergoes nucleation, growth
and condensation resulting in nanoparticles dispersed in deionized water.

4.2.2. Two-step preparation process

Two-step preparation process is extensively used in the synthesis of nanofluids by mixing
base fluids with commercially available nano powders obtained from different mechanical,
physical and chemical routes such as milling, grinding, and sol-gel and vapor phase methods. An
ultrasonic vibrator or higher shear mixing device is generally used to stir nano powders with host
fluids. Frequent use of ultra-sonication or stirring is required to reduce particle agglomeration.
Two-step method can also be used for synthesis of carbon nanotube based nanofluids. Single -
walled and multi-walled carbon nanotubes are first produced by pyrolysis method and then
suspended in base fluids with or without the use of surfactants. Two-step process is very suitable
to prepare nanofluids containing oxide nanoparticles than those containing metallic
nanoparticles. Since nano powders can be obtained commercially in large quantities, some
economic advantage exists in using two-step synthesis methods that rely on the use of such
powders. Stability is a big issue that inherently related to this operation as the powders easily
aggregate due to strong van der Walls force among nanoparticles. In spite of such disadvantages
this process is still popular as the most economic process for nanofluids production. The most
common two-step method is shown in Figure 4.1.

27
 Fig.4.1. Two-step preparation process of nanofluids

4.3. Stability of nanofluids

Nanofluids which can lose their potential to transfer heat due to their proneness to
coagulation. Therefore, investigation on stability is an unavoidable issue that can alter the
thermo-physical properties of nanofluids for application and also important to analyze the
influential factors to the stability of such suspensions. The stability of nanofluids can be
enhanced by following procedures.

4.3.1. Addition of surfactants

Surfactants can be defined as chemical compounds added to nanoparticles in order to
lower surface tension of liquids and increase immersion of particles. Several literatures talk
about adding surfactant to nanoparticles to avoid fast sedimentation; however, enough surfactant
should be added to particle at any particular case. In researches, several types of surfactant had
been utilized for different kinds of nanofluids. Some important surfactants are: Sodium dodecyl
sulphate (SDS), Salt and oleic acid, Dodecyl trimethyl ammonium bromide (DTAB), Hexa
decyltrimethyl ammonium bromide (HCTAB), Polyvinylpyrrolidone (PVP), Gum Arabic. It
should be noted that this technique cannot be applicable for nanofluids working in high
temperature on account of probable damage of bonding between surfactant and nanoparticle.
Additionally surfactants may hamper heat transfer produce foam when heating. Furthermore

28
surfactants may increase the thermal resistant between the nanoparticle and the base fluids which
may lead diminish the enhancement in the thermal conductivity.

4.3.2. Surface modification techniques

Use of functionalized nanoparticles is a promising approach to achieve long-term
stability of nanofluid. It represents the surfactant-free technique. Yang and Liu [28] presented a
work on the synthesis of functionalized silica (SiO2) nanoparticles by grafting silanes directly to
the surface of silica nanoparticles in original nanoparticle solutions. One of the unique
characteristics of the nanofluids was that no deposition layer formed on the heated surface after a
pool boiling process. Hwang et al. [14] introduced hydrophilic functional groups on the surface
of the nanotubes by mechanochemical reaction. The prepared nanofluids, with no contamination
to medium, good fluidity, low viscosity, high stability, and high thermal conductivity, would
have potential applications as coolants in advanced thermal systems. A wet mechanochemical
reaction was applied to prepare surfactant-free nanofluids containing double- and single-walled
CNTs. Results from the infrared spectrum and zeta potential measurements showed that the
hydroxyl groups had been introduced onto the treated CNT surfaces (Chen and Xie [29]). The
chemical modification to functionalize the surface of carbon nanotubes is a common method to
enhance the stability of carbon nanotubes in solvents. Here, we present a review about the
surface modification of carbon nanotubes (Wepasnick et al. [30]. Plasma treatment was used to
modify the surface characteristics of diamond nanoparticles (Yu et al. [11]). Through plasma
treatment using gas mixtures of methane and oxygen, various polar groups were imparted on the
surface of the diamond nanoparticles, improving their dispersion property in water. A stable
dispersion of titania nanoparticles in an organic solvent of diethylene glycol dimethylether
(diglyme) was successfully prepared using a ball milling process. In order to enhance dispersion
stability of the solution, surface modification of dispersed titania particles was carried out during
the centrifugal bead mill process. Surface modification was utilized with silane coupling agents,
(3-acryl-oxypropyl) trimethoxysilane and trimethoxypropylsilane. Zinc oxide nanoparticles
could be modified by polymethacrylic acid (PMAA) in aqueous system. The hydroxyl groups of
nano-ZnO particle surface could interact with carboxyl groups of PMAA and form poly (zinc
methacrylate) complex on the surface of nano-ZnO. PMAA enhanced the dispersibility of nano-

29
ZnO particles in water. The modification did not alter the crystalline structure of the ZnO
nanoparticles.

4.4. Preparation of Fe2O3-Water and ZnO-Water Nanofluids

Choi et.al [6] pioneered the work in the nanofluids by dispersing nanometer sized
particles into liquids. They suggested that compared with the suspension of larger particles,
nanoparticles can be kept in dispersions for much longer time. Because nanoparticles are so
small, they may act like macromolecules in solution, dramatically reducing erosion and clogging
and their larger surface areas improve heat transfer. After that, numerous experimental results
have been reported and this concept has been proved.
4.4.1. Step by Step Procedure
 Calculate the required concentration of nanoparticles and take the mixer proportions
(nanoparticles and base fluid) into a small beaker.
 Add 10% of surfactant (CTAB- Cetyl trimethyl ammonium bromide) to stabilize the
nanofluid.
 Now fix the beaker under the probe.
 Maintain some gap between the probe and the glass beaker to produce vibrations and also
to avoid breakage of the glass beaker.
 The timer is set to 30seconds on time and 5seconds off time.
 Now switch on the probe sonicator and set it to 15times which is one cycle.
 Vibration of probe mixes the nanoparticles with the base fluid.
 As the mixing continues the beaker is heated up because of the vibration.
 So Place the beaker in an ice bath so that it gets cooled or it transfers the heat produced in
the beaker.
 Repeat the above process at least for four cycles to get a completely dispersed nano fluid.
 Use the nanofluid before the nanoparticles settle down.

30
4.4.2. Equipment used for preparation of nanofluid
A Sonicator system is comprised of 3 major components: Generator, Converter and Horn
(also known as a probe). The ultrasonic electronic Generator transforms AC line power to high
frequency electrical energy. The generator features a keypad or buttons which allow the user to
control the sonication parameters. The
generator provides high voltage pulses of
energy at a frequency of 20 kHz that
drives a piezoelectric Converter. The
converter is a cylindrical device which is
connected to the generator by a high
voltage cable. The converter transforms
electrical energy to mechanical vibration
due to the characteristics of the internal
piezoelectric crystals. The vibration is
amplified and transmitted down the length of the Probe/Horn. Probes have threaded ends and
attach to the converter. During operation, the probe‟s tip longitudinally expands and contracts.
Amplitude is the distance the tip travels and is dependent on the amplitude setting selected by the
user. Sonication generates heat so the system can be pulsed on/off to reduce this effect. If
heating of the sample is not an issue, the continuous sonication option can be selected. To ensure
a positive outcome, it is important to select the appropriate generator and probe to match the
volume, viscosity and other parameters of each particular application.

Direct Sonication (inserting a probe directly into a sample vessel) is the most common
way to process a sample. Energy is transmitted from the probe directly into
the sample with high intensity and the sample is processed quickly. The
diameter of the probe‟s tip dictates the liquid volume that can be effectively
processed. Smaller tip diameters (Micro tip probes) deliver high intensity
sonication and the energy is focused within a small, concentrated area.
Larger tip diameters can process larger volumes, but offer lower intensity.
Boosters and High Gain horns can be used to increase the output of large
diameter probes.

31
 Indirect Sonication eliminates the need for a probe to come in contact with your sample.
This technique is often described as a high intensity ultrasonic bath. The ultrasonic energy is
transmitted from the horn, up through the water and into a vessel or
multiple sample tubes. Indirect sonication is most effective for very
small samples because foaming and sample loss are eliminated. Horns
(also known as probes) are made from titanium and machined to
specific sizes and shapes. Probes are offered with replaceable or solid
tips. Probe tips will pit or erode over time and require replacement.
Replaceable tip probes are used with aqueous samples only. In
addition to aqueous samples, Solid probes can be used with organic solvents, alcohols and low
surface tension liquids.

Sonicators are extremely loud devices and will cause discomfort to

the user and anyone nearby. The Sound Enclosure reduces noise by
approximately 20 dBa and is made to work with all accessories. In addition
to reducing noise, the Sound Enclosure has an internal support rod and
converter mounting system. Two ports are located on either side of the
enclosure for coolant tubing or a temperature monitoring probe. The interior
walls are lined with acoustical foam and the door has a window so
experiments can be visually monitored.

32
 CHAPTER V
EXPERIMENTAL SETUP
5.1. Description of experimental facility
The system consists of a double pipe heat exchanger. The inner tube is made of
copper and the outer tube is made of stainless steel. It consists of a heating unit to heat the water,
and temperature measurement system. The temperature measurement system consists of 4
thermocouples, placed at the inlet and outlet of the inner and outer tube respectively. The hot
water flows through the inner tube and the nano fluid/other fluid flows through the annulus. Each
flow loop includes a pump with a flow meter, a reservoir and a bypass valve to maintain the
required flow rate.

To design a project that could be used to transfer heat from hot water in a heat
exchanger to nano-fluid stored in a separate tank and make temperature calibrations for the same
by employing two thermocouples. Also, flow meters will be installed in the pipes carrying
nanofluid to check its flowing rate. The complete system will be very dynamic and easy to use.
Mechanical structured design is shown in Fig. 5.1.

5.2. Specifications of heat exchanger

Length Of Heat Exchanger 1100mm

Inner tube material Copper

Inner Diameter ( ) 21mm

Outer Diameter( ) 25mm

Outer tube material Stainless steel

Inner Diameter( ) 30mm

Outer Diameter( ) 35mm

Table5.1. Specifications of heat exchanger

33
 Fig.5.1 Double pipe heat exchanger

As with any process the analysis of a heat exchanger begins with an energy and material
balance. Before doing a complete energy balance a few assumptions can be made. The first
assumption is that the energy lost to the surroundings from the cooling water is negligible. We
also assume negligible potential or kinetic energy changes and constant physical properties such
as specific heats and density.

5.3. Experimental Procedure

The main switch is switched on and the console and heater is also turned on. The cold
water from the reservoir is pumped to the heat exchanger by maintaining a constant flow rate.
The hot water flow rate valve is kept open. After attaining steady state conditions, the inlet and
outlet temperature readings of both the pipes are noted down from the temperature scanner which
can be run manually or kept in auto mode. The flow rate of cold water is known with the help of
a water flow sensor. The hot water flow rate can be adjusted according to the requirements with
the help of a hot water flow meter. The readings of both hot and cold water flow rates are noted
down. This completes the first set of readings. Depending upon the requirement of the cold
water flow rate, next set of readings can be noted down.

34
5.3. Overall Heat Transfer Coefficient
The determination of the overall heat-transfer coefficient is necessary in order to
determine the heat transferred from the inner pipe to the outer pipe. This coefficient takes into
account all of the conductive and convective resistances (k and h, respectively) between fluids
separated by the inner pipe, and also takes into account thermal resistances caused by fouling
(rust, scaling, i.e.) on both sides of the inner pipe. As the heat exchanger is relatively new the
fouling resistances are neglected in the present work. For a double-pipe heat exchanger the
overall heat transfer coefficient based on outer radius, U0, can be expressed as

(5.1)

Where h0 is heat transfer coefficient of fluid flowing through annulus

hi is heat transfer coefficient of fluid flowing through pipe

k is the thermal conductivity of inner pipe material

ro is outer radius of pipe

ri is inner radius of pipe

5.3.1. Experimental Overall Heat Transfer Coefficient

The procedure to calculate the experimental overall heat transfer coefficient (U0, E) is
given below.

In a heat exchanger the log-mean temperature difference is the appropriate average

temperature difference to use in heat transfer calculations. The equation for the log-mean
temperature difference is

(5.2)

Where and
Tci is the cold water inlet temperature
Tco is the cold water outlet temperature
Thi is the hot water inlet temperature
Tho is the hot water outlet temperature

35
The heat transfer rate (Q) can be calculated by
̇ ̇ (5.3)

where mh mass flow rate of hot fluid

Cp,h Specific heat of hot fluid

The experimental overall heat transfer coefficient (U0, E) can be determined by

̇ (5.4)
where Ao is the outer surface area of the pipe.

5.4.2. Theoretical Overall Heat Transfer Coefficient

The procedure to calculate the theoretical overall heat transfer coefficient (U0, T) is given
below.
The properties density (ρ), kinematic viscosity (γ), Prandtl number (Pr) and thermal

conductivity (k) of cold fluid can be calculated at average temperature of Tf = from the

data book [31]

The velocity of the cold fluid is calculated by
Q = AV (5.5)
Where Q=flow rate
A= area of cross section of annulus =

V= velocity of fluid
The Reynolds number can be calculated by

Re = (5.6)

Where Di inner diameter of outer pipe

The Nusselt number is calculated by Dittus-Boelter equation
Nu = 0.023 × Re0.8 × Prn (n=0.4 for heating) (5.7)
The heat transfer coefficient for cold water ( is determined by

(5.8)

The average temperature for hot fluid is calculated by

Tf = (5.9)

36
The velocity of the hot fluid is calculated by
Q = AV
The Reynolds number for hot fluid can be calculated by

Re = (5.10)

The Nusselt number for hot fluid is given by

Nu = 0.023 × Re0.8 × Prn (n=0.3 for cooling) (5.11)
The heat transfer coefficient for hot fluid is calculated by

(5.12)

The theoretical overall heat transfer (U0,T) can be determined by

(5.13)

5.5. Calibration of Experimental set up

The experimental data taken for various flow rates of hot and cold water are tabulated
below.
Flow rate (Lts/min) Tci (0C) Tco(0C) Thi(0C) Tho(0C)
3 30.9 33.3 43.8 42.3
2.5 30.2 32.8 44.2 42.2
2 31.3 35 51.5 48.8
1.5 30.9 36 52.8 48.8
1 31.3 40.6 66.8 58.2
Table5.2. Observation table for calibration of experimental setup

The reliability and accuracy of the experimental system are estimated by using water as
working fluid. The experimental and theoretical overall heat transfer coefficients are found by
the procedure given in sections 5.4.1 and 5.4.2. As shown in Fig. 5.2, the good coincidence
between the experimental results and the calculated values for water reveals that the precision of
the experimental setup is good

37
Fig.5.2. Calibration curve of experimental setup

38
 CHAPTER VI
RESULTS AND DISCUSSION
Fe2O3 nano particles are prepared by using of sol-gel process in which ferric chloride is
used as precursor, the raw material from which Fe2O3 is extracted at the end of the process.
Isopropyl alcohol (IPA) acts as a solvent and is used to dissolve the raw material in it
homogenously, polyvinylpyrolidene (PVP) is used so that the formation of a metal oxide
involves connecting the metal centers with oxo (M-O-M) bridges, therefore generating metal-oxo
polymers in solution. Thus, the sol evolves towards the formation of a gel-like biphasic system
containing both a liquid phase and a solid phase. Cetyl trimethyl ammonium bromide (C-TAB) is
used as surfactant which decreases the surface tension of the solution and helps in maintaining
the stability of nanoparticles. Colloidal particles slowly aggregate after the aging of sols to form
gels with three dimensional network structures. Ammonium hydroxide helps in precipitating the
nanoparticles present in the solution, thus it is used as a catalyst. The precipitate is passed
through various processes such as drying and sintering, where nanoparticles are obtained. ZnO
nanoparticles are also prepared by using sol-gel technique undergoing same procedure, but zinc
chloride is used as a raw material from which ZnO nanoparticles are extracted. Nanofluids are
prepared at different volumetric concentrations (0.1 to 0.5%) by using probe sonicator. For the
stability of nanoparticles 10% surfactant is added to the nanofluid. The experiment is conducted
before the particles are settled down for different flow rates of nanofluids and different volume
fractions of nanoparticles.

The experimental overall heat transfer coefficients are calculated using the procedure
given in the section 5.4.1. Fig.6.1 and fig.6.2 shows the effect of Reynolds number of nano fluid
flowing through the annulus on experimental overall heat transfer coefficient for different
nanoparticle concentrations in base fluid stored in the vessel. It can be observed from curves of
Fig.6.1, that the overall heat transfer coefficient is increased by 14% with the volume fraction 0.5
percent of Fe2O3 nanoparticles and from fig.6.2 it is increased by 11% with volume fraction of
0.5 percent of ZnO nanoparticles compared with water. The increase in heat transfer coefficient
is due to increase in thermal conductivity of water with the addition of nanoparticles, and also
due to increase in heat transfer to the cold fluid due to random motion of nanoparticles

39
suspended in water and availability of larger surface area with nano sized particles . The
experimental results also indicate that the experimental heat transfer coefficient of a Fe2O3-water
nanofluid and ZnO-water nanofluid increases with the increase in volume fraction of
nanoparticles in base fluid. The curves of the same figure show the same trend i.e., the heat
transfer to the cold fluid increases with the increase in volume fraction of nanoparticles in the
base fluid. As expected, it can be observed from Fig.6.1 and fig.6.2 that the heat transfer
coefficient of the nanofluid increases with the flow rate.

Fig.6.1. Variation of experimental overall heat transfer of Fe2O3 nanofluids at different flow rates
and volume fractions of nanoparticles

40
Fig.6.2. Variation of experimental overall heat transfer of ZnO nanofluids at different flow rates
and volume fractions of nanoparticles

The properties of the nanofluid are calculated using the correlations available in
literature. The thermal conductivity of nanofluid depends on thermal conductivity of both base
fluid and nanoparticles material, volume fraction of nanoparticles, surface area of nanoparticles
and shape of nanoparticles in the liquid. Hamilton and Crosser [21] developed a model for the
effective thermal conductivity of two-component mixture. The model is the function of the
thermal conductivity of both particle and base fluid, volume fraction of nanoparticles, and the
shape of the particles. Xuan and Li [4] used the Hamilton and Crosser model to find the thermal
conductivity of nanofluid for different volume fractions of nanoparticles. They concluded that
the agreement between the thermal conductivity obtained from Eq. 4.1 and experimental data is
good. Hence to evaluate the thermal conductivity of Al203-water nanofluid Hamilton and Crosser
[21] correlation is used.

K nf [K p  (n  1)K f  (n  1)(K f  K p ]
 (6. 1)
Kf K p  (n  1)K f  (K f  K p )

41
 3
Where „n‟ is the shape factor defined as n = , in which  is sphericity, defined as the

ratio of the surface area of the sphere to that of the particle for the same volume for spherical
particles (  =1). Al2o3 nano-particles are spherical particles according to Transmission Electron
Microscopy.
The effective viscosity of nanofluid greatly affects the heat transfer. The dynamic
viscosity of nanofluid up to 3% of solid volume fraction is estimated from the correlation given
by Brinkman [32], which is expressed as,
f
 nf  (6.2)
(1  )2.5
The evaluation of effective density and effective specific heat of nanofluid can be
estimated based on rule of mixtures. For this purpose nanofluid can be defined as a mixture
consisting of two components namely the base fluid and particles. The subscript „f‟ represents
the base fluid component and the subscript „p‟ represents particles in base fluid.

m m  mp f Vf  p Vp
nf     f   (1  )f  p (6.3)
 V nf Vf  Vp Vf  Vp

Assuming that the nanoparticles and the base fluid are in thermal equilibrium, the
nanofluid specific heat, Cp,nf, can be calculated as follows:
 Q  Qf  Q p (mCp )f T  (mCp ) p T
nf Cp,nf  nf    nf  nf
 mT nf (mf  mp ) (mf  m p )T

(Cp )f Vf  (Cp ) p Vp
 nf  (1  )(Cp )  (Cp ) p
f Vf  p Vp

(1  )(Cp )f  (Cp ) p
 Cpnf  (6.4)
(1  )f  p

The theoretical overall heat transfer coefficients are calculated using the procedure given
in the section 5.4.2. Fig.6.3 and Fig.6.4 shows the effect of Reynolds number of nano fluid
flowing through the annulus on theoretical overall heat transfer coefficient for different
nanoparticle concentrations in base fluid.

42
Fig.6.3. Variation of theoretical overall heat transfer of Fe2O3 nanofluids at different flow rates
and volume fractions of nanoparticles

Fig.6.4. Variation of theoretical overall heat transfer of ZnO nanofluids at different flow rates
and volume fractions of nanoparticles

43
 CHAPTER VII
CONCLUSIONS
Fe2O3 and ZnO nano particles are prepared by using a chemical method named as sol-gel
technique. The raw material is passed through different stages such as dissolving, preparation of
solution, formation of gel, filtration and drying to get the nano sized particles. To remove the
liquid traces completely from nanoparticles they are sintered at 200oC for 3 hours. The
nanofluids are prepared by using method given by choi at.el [6] in probe sonicator at different
volumetric concentration (0.1 to 0.5%). For the stability of nanoparticles 10% of surfactant is
added to the nanofluids.

The experiment is conducted in a double pipe heat exchanger. Before conducting the
experiment the heat exchanger is calibrated and then ZnO and Fe2O3 nanofluids are sent through
annulus and readings are noted down. The nanofluid readings are compared with base fluid
readings (water). The overall heat transfer coefficient for Fe2O3-water nanofluid is increased by
14% with the volume fraction of 0.5% of nanoparticles and the overall heat transfer coefficient
for ZnO-water nanofluid is increased by 11% with volume fraction 0.5% compared with water.
The increase in heat transfer coefficient is due to increase in thermal conductivity of water with
the addition of nanoparticles, and also due to increase in heat transfer to the cold fluid due to
random motion of nanoparticles suspended in water and availability of larger surface area with
nano sized particles.

44
References
[1] Pak B., Cho Y., Hydrodynamic and heat transfer study of dispersed fluids with sub-
micron metallic oxide particles, Experimental Heat Transfer, 11 (1998) 151-170.
[2] Lee S, Choi S.U.S, Li S, Eastman J.A., Measuring thermal conductivity of fluids
containing oxide nanoparticles. ASME J Heat Transfer, 121 (1999) 280–289.
[3] Wang X, Xu X, Choi S.U.S., Thermal conductivity of nanoparticle–fluid mixture, J
Therm Phys Heat Transfer, 13 (1999) 474–80.
[4] Xuan Y, Li Q, Heat transfer enhancement of nanofluids, Int J Heat Fluid Flow 21 (2000)
58–64.
[5] Xuan Y, Roetzel W, Conceptions for heat transfer correlation of nanofluids, Int. J. Heat
and Mass Transfer, 43 (2000) 3701-3707.
[6] Choi S.U.S, Zhang Z.G, Yu W, Lockwood F.E, Grulke E.A., Anomalous thermal
conductivity enhancement in nanotube suspension, Appl Phys Lett 79 (2001) 2252–2254.
[7] Xie H, Wang J, Xi T, Liu Y, Ai F, Wu Q., Thermal conductivity enhancement of
suspensions containing nanosized alumina particles, J Appl Phys 91(2002) 4568–4572.
[8] Chien, H.T., Tsai, C.-I., Chen, P.-H., and Chen, P.-Y. Improvement on thermal
performance of a diskshaped miniature heat pipe with nanofluid. ICEPT Packaging
Technology. Proceedings. (IEEE Cat. No.03EX750), 389. IEEE, Shanghai, China (2003).
[9] Das S.K, Putra N, Thiesen P, Roetzel W., Temperature dependence of thermal
conductivity enhancement for nanofluids, ASME J Heat Transfer 125 (2003) 567–574.
[10] Xue Q.Z., Model for effective thermal conductivity of nanofluids, Phys. Lett. A., 307
(2003) 313-317.
[11] Yu W, Choi S.U.S., The role of interfacial layer in the enhanced thermal conductivity
of nanofluids- A renovated Maxwell model, Journal of Nanoparticles Research, 5 (2003)
167-171.
[12] Wen, D. and Ding, Y. Effective thermal conductivity of aqueous suspensions of carbon
nanotubes (carbon nanotube nanofluids). Journal of Thermophysics and Heat Transfer,
18, no. 4, 481–485 (2004a).
[13] Tsai, C. Y., Chien, H. T., Ding, P. P., Chan, B., Luh, T. Y., and Chen, P. H. Effect of
structural character of gold nanoparticles in nanofluid on heat pipe thermal performance.
Material Letters, 58, 1461–1465 (2004).

45
[14] Hwang, Y. J., Ahn, Y. C., Shin, H. S., Lee, C. G., Kim, G. T., Park, H. S., and Lee, J. K.
Investigation on characteristics of thermal conductivity enhancement of nanofluids.
Current Applied Physics, 6, no. 6, 1068–1071 (2005).
[15] Yang Y, Zhang Z.G., Grukle A.K., Anderson W.B., Wu G., Heat transfer properties of
nanoparticle-in-fluid dispersions (nanofluids) in laminar flow, Int. J. Heat and Mass
Transfer, 48 (2005) 1107-1116
[16] Assael M., Metaxa I., Arvanitidis J., Christofilos D., Lioutas C., Thermal conductivity
enhancement in aqueous suspensions of carbon multi-walled and double-walled
nanotubes in the presence of two different dispersants, Int J Thermophysics, 26 (2005)
647-664.
[17] Koo J, Kleinstreuer C., Impact analysis of nanoparticle motion mechanisms on the
thermal conductivity of nanofluids, Int. Comm. Heat Mass Transfer, 32 (2005) 1111–
1118.
[18] Buongiorno J., Convective transport in nanofluids, ASME J Heat Transfer, 128 (2006)
240-250.
[19] Heris, S., Esfahany, M., and Etemad, S. G. Experimental investigation of convective
heat transfer of Al2O3/water nanofluid in circular tube. International Journal of Heat and
Fluid Flow, 28, no. 2, 203–210 (2007).
[20] Zhang X, Gu H, Fujii M, Effective thermal conductivity and thermal diffusivity of
nanofluids containing spherical and cylindrical nanoparticles, Expt. Thermal Fluid
Sciences, 31 (2007) 593-599.
[21] Hamilton R.L., Crosser O.K., Thermal conductivity of heterogeneous two-component
systems, I&EC Fundam., 1 (1962) 182–191.
[22] Mirmasoumi A, Behzadmehr A: Numerical study of laminar mixed convection of a
nanofluid in a horizontal tube using two-phase mixture model.Appl Therm
Eng 2008, 77:717-727.
[23] Zamzamiana A, Nasseri Oskouieb Sh, Doosthoseinic A, Joneidic A, Pazoukia M.
Experimental investigation of forced convective heat transfer coefficient in nanofluids of
Al2O3/EG and CuO/EG in a double pipe and plate heat exchangers under turbulent flow.
Exp Therm Fluid Sci 2011; 35: 495e502.

46
[24] Hur S.H, Kocabas C, Gaur A, Shim M, Park OO, Rogers JA, Voltage carbon nanotube
thin film transistors and complementary logic gates, J. Am. Chem. Soc., 13808(2005)
[25] P Sen, Joyee Ghosh, Alqudami Abdullah, Prashant Kumar , Vanada, Proc. Indian Acad.
Sci. (Chem. Sci.) 2003, 115, 499–508
[26] Heting Li, Mohammed J. Meziani, Fushen Lu, Christopher E. Bunker, Elena A.
Guliants, and Ya-Ping Sun, J. Phys. Chem. C 2009, 113, 20539–20542
[27] C.H. Lo, T-T. Tsung, L.C. Chen, C.-H. Su and H.-M.Lin, ―Fabrication of Copper
Oxide Nanofluid Using Submerged Arc Nanoparticle Synthesis System
(SANSS)‖.Journal of Nanoparticle Research 7: 313–320, 2005.
[28] X. Yang and Z. H. Liu, A kind of nanofluid consisting of surface-functionalized
nanoparticles, Nanoscale Research Letters, vol. 5, no. 8, pp. 1324–1328, 2010.
[29] W. Yu, H. Xie, L. Chen, and Y. Li, “Investigation of thermal conductivity and viscosity
of ethylene glycol based ZnO nanofluid,” Thermochimica Acta, vol. 491, no. 1-2, pp. 92–
96, 2009.
[30] Smith, B., Wepasnick, K., schrote, K.E.et al. 2009. Influence of surface oxiddes on the
colloidal stability of multi-walled carbon nanotubes: A structure-property relationship,
Langmuir 25;9767-9776
[31] Heat and Mass transfer data book by C. P. Kothandarman and S. Subramanyan, 8th
edition, New Age International Publishers, 2014.
[32] Brinkman HC. The viscosity of concentrated suspensions and solutions, J Chem Phys
1952; 20:571–581

47