A project report

Effect of pH on the stability of Al2O3-Water

Nanofluid
Submitted in partial fulfilment of the requirements for the award of the degree
Bachelor of Technology in
Mechanical Engineering
Submitted by

B.TANAY RAO U20ME061

THALLURI TEJA U20ME072
ANAPARTHI KARTHIK U20ME171
DEVERAKONDA GOPI U20ME009

Guided by
Dr. Rajesh Choudhury
Assistant Professor

Year 2023-2024
Department of Mechanical Engineering
Sardar Vallabhbhai National Institute of Technology Surat
– 395007, Gujarat, India

i
 DECLARATION OF ACADEMIC INTEGRITY

We, the undersigned, registered for the Bachelors’ Degree at Department of Mechanical
Engineering, Sardar Vallabhbhai National Institute of Technology, hereby declare that B. Tech.
Final Year Project entitled “Effect of concentration and pH on the stability of Al2O3-water
Nanofluid ” submitted by Bontala Tanay Rao(U20ME061), Thalluri Teja(U20ME072),
Anaparthi Karhik(U20ME171), and Deverakonda Gopi(U20ME009) is based on our own
work and has been carried out under the guidance and supervision of Dr. Rajesh Choudhury,
Asst. prof, Department of Mechanical Engineering, Sardar Vallabhbhai National Institute of
Technology, Surat. The data and information which we have used from various sources have
been duly acknowledged. We declare that this written submission represents our ideas
presented in our own words and where others’ ideas or words have been included, we have
adequately cited and referenced the original sources. We also declare that We have adhered to
all principles of academic honesty and integrity and have not misrepresented or fabricated or
falsified any idea/data/fact/source in our submission. We understand that any violation of the
above will be a cause for disciplinary action by the Institute and can also evoke penal action
from the source which have thus not been properly cited or from whom proper permission has
not been taken when needed. We further declare that this work has not been previously
submitted by us to any other university/institute for the award of any degree or diploma or for
any other purpose.

Date: 08/12/2023
Place: SVNIT, Surat

Signatures

Bontala Tanay U20ME061 _______________________

T. Teja U20ME072 _______________________
A. Karthik U20ME171 _______________________
D. Gopi U20ME009 _______________________

ii
 ACKNOWLEDGEMENT

First and foremost, we would like to express our deepest gratitude to our project supervisor,
Dr. Rajesh Choudhury(Assistant Professor-DoME) for their invaluable guidance, support,
and encouragement throughout the course of this project. Their expertise, patience, and
dedication have been instrumental in helping us to complete this project successfully.

We would also like to thank the Head of the Department Dr A.A.Shaik(Head DoME) for their
assistance and support during the course of this project. Their contributions have been
invaluable and greatly enriched our project's overall quality.

Finally, we would like to acknowledge the countless hours of hard work and dedication that
have gone into the completion of this project. Despite the challenges and setbacks, we are
grateful for the opportunity to have learned and grown through this experience.

Date: 08/12/2023
Place: SVNIT, Surat

Signatures

Bontala Tanay U20ME061 _______________________

T. Teja U20ME072 _______________________
A. Karthik U20ME171 _______________________
D. Gopi U20ME009 _______________________

iii
 CERTIFICATE FROM THE GUIDE

This is to certify that the Project report entitled “Effect of concentration and pH on the
stability of Al2O3-water Nanofluid” submitted by Bontala Tanay Rao(U20ME061),
Thalluri Teja(U20ME072), Anaparthi Karhik(U20ME171), and Deverakonda
Gopi(U20ME009) in partial fulfilment for the award of the degree in Bachelor of Technology
in Mechanical Engineering during the academic year 2023-24, of the Sardar Vallabhbhai
National Institute of Technology, Surat is a record of their own work carried out under my
supervision and guidance. The matter embodied in the report has not been submitted to any
other university or institute for award of any degree or diploma.

Date: 08/12/2023
Place: SVNIT, Surat

Guide Head , DoME

Dr. Rajesh Choudhury Dr. A.A.Shaik
Assistant Professor Professor

Department of Mechanical Engineering

Sardar Vallabhbhai National Institute of Technology Surat
– 395007, Gujarat, India

iv
 EXAMINERS’ APPROVAL CERTIFICATE

This is to certify that the Project report entitled “Effect of concentration and pH on the
stability of Al2O3-water Nanofluid” submitted by Bontala Tanay Rao(U20ME061),
Thalluri Teja(U20ME072), Anaparthi Karhik(U20ME171), and Deverakonda
Gopi(U20ME009) in partial fulfilment for the award of the degree in Bachelor of Technology
in Mechanical Engineering during the academic year 2023-24, of the Sardar Vallabhbhai
National Institute of Technology, Surat is hereby approved.

Date: 20/12/2022
Place: SVNIT, Surat

Examiners: Signatures

1. ___________________________

2. ___________________________

3. ___________________________

Department of Mechanical Engineering

Sardar Vallabhbhai National Institute of Technology
Surat – 395007, Gujarat, India

v
 ABSTRACT
With excellent thermophysical properties and heat transfer performance, nanofluids offer an
ideal solution as heat transfer fluids for enhanced performance in terms of heat and energy
transfer across various devices. Idealized as solid nano-sized particles measuring less than
100nm, they are dispersed in regular heat transfer fluids such as water, ethylene glycols, and
oils. This report compiles and reviews a detailed literature on the applications, challenges,
and stability of nanofluids. The effect of nanoparticle concentration and pH of the nanofluid
on the stability is examined in this study.

Recent literature has demonstrated the profitability and efficiency of replacing conventional
coolants with nanofluids. These heat transfer fluids find applications in diverse fields,
including semiconductor chips in mobiles, electronic cooling applications like air
conditioners, medical applications such as cancer detection, drug delivery, and coolants in
space and defense. This paper identifies challenges faced by nanofluids, with a particular
focus on their stability period. High thermal conductivity is a known characteristic of
nanofluids, greatly dependent on temperature at very low nanoparticle concentrations in the
fluid, providing advantages and excellent performance over normal conventional fluids.
Despite these benefits, barriers and challenges persist, hindering the widespread use of
nanofluids. A comprehensive study on applications and stability challenges is presented to
understand the potential use and key role of nanofluids in the near future.

Guide Team Members

Dr. Rajesh Choudhury B. Tanay Rao (U20ME061)

Assistant Professor A. Y. Karthik (U20ME171)

T. Teja (U20ME072)

D. Gopi (U20ME009)

vi
 Table of Contents

DECLARATION OF ACADEMIC INTEGRITY..................................................................Ⅱ

ACKNOWLEDGEMENT.....................................................................................................Ⅲ
CERTIFICATE FROM THE GUIDE....................................................................................Ⅳ
EXAMINERS’ APPROVAL CERTIFICATE........................................................................Ⅴ
ABSTRACT..........................................................................................................................Ⅵ
List of Figures.......................................................................................................................Ⅸ
List of Tables.........................................................................................................................Ⅹ
Chapter 1 ..............................................................................................................................1
1.1 Advantages and Challenges of Nanofluid................................................................1
1.2 Stability of Nanofluids.............................................................................................2
1.3 Methods to Measure Stability...................................................................................3
1.3.1 Sedimentation photography Method .............................................................3
1.3.2 Centrifugation Method ..................................................................................4

1.3.3 Zeta Potential .................................................................................................5

1.3.4 Spectral absorbance and transmittance measurement.....................................6

1.3.5 3ω Method ......................................................................................................7

1.3.6 Transmission electron microscopy .................................................................8

1.3.7 Dynamic light scattering ................................................................................9

1.4 Factors affecting Sedimentation............................................................................10

Chapter 2.............................................................................................................................11

Literature Review................................................................................................................11

2.1 DLVO Theory of aggregation..................................................................................11

2.2 Stability enhancement techniques............................................................................12

2.2.1 Chemical Stabilization..................................................................................12

2.2.2 Mechanical Stabilization.............................................................................17

2.3 Summary of Review................................................................................................20

vii
Chapter 3............................................................................................................................24

Experimental procedure.....................................................................................................24

3.1 Nanofluid used........................................................................................................24

3.2 Preparation Techniques..........................................................................................24

3.3 Stability measurement techniques...........................................................................26

Chapter 4............................................................................................................................27

Results................................................................................................................................27

Chapter 5............................................................................................................................32

Conclusions........................................................................................................................32

References..........................................................................................................................33

viii
 List Of Figures

Figure no Description pg. No

Figure 1.1 Samples of Al2O3 nanofluids stability change with time ..........................3
Figure 1.2 Centrifugation Method...............................................................................4
Figure 1.3 Charge distribution close to a negatively charged particle........................5
Figure 1.4 Transmission Electron Microscopy Components......................................8
Figure 1.5 Dynamic Light Scattering Apparatus.......................................................9
Figure 2.1 Illustration of DLVO-Curve.....................................................................11
Figure 2.2 Mechanism of Electrostatic stabilization.................................................13

Figure 2.3 Mechanism of Steric Stabilization...........................................................14

Figure 2.4 Effect of pH value on size distribution....................................................16

Figure 2.5 Mechanism of electrostatic stabilization............................................17

Figure 2.6 Acoustic Cavitation by ultrasonication.............................................18

Figure 2.7 Planetary Ball milling......................................................................19

Figure 2.8 Pie-chart showing the use of nanoparticles in the literature....................23

Figure 3.1 Ultrasonic Sonicator................................................................................25

Figure 3.2 Zeta potential apparatus..........................................................................26

Figure 4.1 Result for zeta potential for A1 sample (24 hours) ................................30

Figure 4.2 Result for zeta potential for A1 sample(initial).......................................30

Figure 4.3 Result for zeta potential for B1 sample (24 hours) ................................30

Figure 4.4 Result for zeta potential for B1 sample (initial)......................................30

Figure 4.5 pH vs zeta Potential.................................................................................31

ix
 List Of Tables

Table no Description pg. No

Table 1.1 Stability measurement results of Cu-Al LDH using transmittance........7

Table 2.1 Literature review for different nanofluid stabilization technique..........20
Table 2.2 Literature review for thermal conductivity of nanofluids.....................22
Table 4.1 Initial vs Final zeta potential ................................................................31

x
 CHAPTER – 1

INTRODUCTION

Nanofluids represent a recent development in fluid dynamics, characterized by a colloidal

suspension of nanosized particles ranging from 1 nm to 100 nm in a base fluid. These
nanoparticles, typically composed of metals, metal oxides, carbides, and carbon nanotubes,
are combined with base fluids such as water, kerosene, glycerine, and engine oils. Notably,
nanofluids demonstrate enhanced thermal conductivity and a heightened convection heat
transfer coefficient compared to their base fluids. Ex: copper/ethylene glycol nanofluid,
where copper nanoparticles are dispersed within an ethylene glycol base fluid.

1.1. Advantages and Challenges of Nanofluid

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

nanofluids possess the following advantages.

• High specific surface area and therefore more heat transfer surface between particles
and fluids.
• High dispersion stability with predominant Brownian motion of particles.
• Reduced pumping power as compared to pure liquid to achieve equivalent heat transfer
intensification.
• Adjustable properties, including thermal conductivity and surface wettability, by
varying particle concentrations to suit different applications.

Along with the advantages, nanofluid also faces a few challenges, as given below:

• Dispersion of nanoparticles is stable only for short-term. The creation of homogenous

suspension is still technically difficult because the extremely strong Vander Waals
interaction causes the nanoparticles to constantly form aggregates.
• The elevated viscosity and density contribute to an increased pressure drop,
consequently necessitating higher pumping power to uphold a consistent flow rate.

1
 • The viscosity of nanoparticle-water suspensions escalates proportionally with the
concentration of suspended particles. Consequently, the continuous elevation of particle
mass fraction becomes unfeasible. This leads to the inference that substituting
conventional fluids with nanofluids in industrial heat exchangers, where substantial
nanofluid volumes are required and turbulent flow is typically established, appears
unfavourable.
• According to existing literature, nanofluids manifest a lower specific heat compared to
base fluids. Reports indicate that base fluids exhibit higher specific heat values than
CuO/ethylene glycol nanofluids, SiO2/ethylene glycol nanofluids, and Al2O3/ethylene
glycol nanofluids. To effectively dissipate more heat from the environment, a coolant
should possess a higher specific heat value.
• A potential impediment to the industrial use of nanofluids lies in their elevated
production costs. Both one-step and two-step processes for creating nanofluids
necessitate sophisticated and expensive equipment.

1.2. Stability of Nanofluids

Nanoparticle stability refers to the preservation of their thermophysical properties

over time, a significant challenge in nanofluids and colloidal suspensions. This issue often
manifests as the formation of large clusters due to van der Waals forces among nanoparticles,
impacting thermal system efficiency by reducing nanofluid performance. Changes in particle
shape, size, and quantity due to agglomeration can compromise stability. Higher nanoparticle
volume fractions in nanofluids increase the risk of destabilization [30].

The main reasons for the particle agglomeration are following mechanisms:

• Transverse or lift forces: A fluid flowing around a particle exerts a force on it. Lift is the
component of this force perpendicular to flow direction.
• Electric Interactions: Attraction between the opposite charges and like charges formed
on the electrical double layer. Attraction and repulsion forces decide the extent of
agglomeration.
• Hydrodynamic Interactions: Particles immersed in fluid exited long ranged flows as they
move in response to fluid motion. By generating and reacting to a fluids local velocity,

2
 colloidal particles experience hydrodynamic interactions with each other and with the
walls of the container.
• Brownian Motion: It is the random or zig-zag motion of the particles in the fluid. This
movement occurs even there is no externally applied forces. They will not completely stay
still. These will arise because of constant collision with adjacent particles.
• Chemical potential forces: Chemical potential is described as the increment in energy of
system when some other element is added to it. Surface energy is commonly defined for
this purpose. And nanoparticles have high surface energy due to high surface area to
volume ratio.

1.3. Methods to Measure Stability

1.3.1 Sedimentation photography Method
It is the most basic and easiest method to quantify the stability of nanofluids. Any
colloidal particles after sometime undergoes sedimentation process (i.e., settling at the base
under the action of gravitational or any other external forces). Now the sediment volume or
weight is observed as the time passes and it directly relates to the measure of the instability.

A nanofluid is said to be stable if the particle concentration and the size of the particle remains
same with relative to time and space. There are special cameras which can be used to
photograph the sediment at the base of fluid. Sediments on sedimentation tray were weighed
and particle volume fraction of solution was measured for a particular time. Thus, different
time periods are taken and measure the change in the weight and volume fraction and can
quantify the stability of the nanofluids, as depicted in the figure 1.1. However, if measure for
a long period of time, there may be the possibility of occurrence of the error. So, this has led
to introducing the centrifugation method for sedimentation.[34]

Figure 1.1: Samples of Al2O3 nanofluids stability change with time [31]

3
1.3.2 Centrifugation Method

It is based on the same principle as of the sedimentation method. It is time saving

method compared to sedimentation photograph method. Here we rotate the test tube in which
sample of nanoparticles are taken and acted under the centrifugal force w.r.t a vertical axis.
Sedimentation in this case takes place quickly as centrifugal force is much stronger than the
gravitational force. Singh et al centrifuged the silver nanoparticles at 3000 rpm for 10 hours
with no sedimentation at the end, this shows the particles were stable in solution.

Figure 1.2: Centrifugation Method

Now to compare stability of Nanofluids and also to quantify the stability of each nanofluid
the term sedimentation coefficient is introduced. Sedimentation Coefficient describes its
sedimentation during centrifugation. It is defined as “the ratio of a particle’s sedimentation
velocity to applied acceleration causing the sedimentation.” Sedimentation velocity is the
constant settling velocity acquired by the nanoparticles after sometime due to the balance of
applied external force by the fluid friction drag force. Practically sedimentation coefficient
measures how long it takes a particle moving at a given acceleration to achieve its terminal
velocity.

Considering a simpler case by assuming the nanoparticles as the perfect spheres and applying
stokes.

4
 𝑣𝑡 𝑚
𝑆= = (1.1)
𝑟𝜔2 6𝛱𝜂𝑟0

1.3.3 Zeta Potential

The Nanoparticle surfaces in the colloidal solutions are electrically charged. Because of this
the fluid around the particle will be ionized and the ion distribution will be changed around
interfacial region (shown in Figure 1.3).

Figure 1.3: Charge distribution close to a negatively charged particle[32]

The liquid layer which surrounds the particles is segregated into two parts. The inner region
called the Stern layer and the outer region called the diffuse layer. This is also called as
electrical double layer. If the nanoparticle is negatively charged then the charges in the stern
layer will be positive, which are strongly bound to the particle, whereas at the end of the
diffuse layers a greater amount of negative charges are found along with some positive ions
which are less organized and allowed to move freely.[34]

The ions and particles within a specific defined boundary of the diffuse layer constitute a
stable entity. Therefore, the ions present at this boundary are travelling with the particle. Zeta
potential is the name given to the electric potential at this border. As we considered that most
of the ions at the end of the electrical double layer or diffuse layer as negative and the ions in
the vicinity of nanoparticles as positive. We can simulate the zeta potential as the electrical
potential at the centre of sphere because of two concentric spheres with opposite charges, q
and -q, at the two radii α and α + D from the centre of the sphere.

5
Thus, the expression for zeta potential is given by:

(1.2)
Now, the zeta potential may be positive or negative based on the surface charge of
nanoparticles. Zeta potential is also a measure for the measure of the stability. Lets take
an example to observe the stability of aqueous CNT suspensions, the rate of settling at
different values of zeta potential from the book “nano fluidics by Efstathios [29].

1. At ζ = 0 mV: the suspension showed no stability and the particles formed quickly aggregates
and settled out of the suspension.

2. At ζ =15 mV: moderate aggregation and settling were observed.

3. At ζ = 30 mV: the suspension appeared stable, but some settling was observed.

4. At ζ = 45 mV: the suspension appeared stable with only a slight indication of aggregate
settling.

5. At ζ = 60 mV: the suspension was stable and no settling was visibly observed.

Based on above observations we can conclude that higher the zeta potential value higher will
be the repulsions between the particles and the lesser aggregation which leads to the greater
stability.

1.3.4 Spectral absorbance and transmittance measurement

This method can give us the quantitive measure of nanofluid stability. This method of stability
evaluation is mostly used when the nanoparticle suspended in the base fluid can absorb the
radiation of wavelength between 190 and 1100 nm as the wavelength of UV rays and visible
spectrum falls under this category. The nanoparticles have the ability to absorb and transmit
the light in the visible and ultraviolet frequency range. Now we have to check absorbance
using UV-VIS spectrophotometer and how it varies with time. The amount of absorbance is
directly related to the particle concentration in the suspension.[32]

6
Now decrease in absorbance with time indicates agglomeration of particles and decrease in
concentration and thus instability of nanofluid suspension. Relation between absorbance and
concentration is given by:

𝐼
𝐴𝜆 = 𝑙𝑜𝑔 ( 𝐼0 ) = 𝛼 × 𝐿 × 𝐶 (1.3)

where I, I0, α, l and c, represent intensity of laser light beam after passing through the colloidal
suspension, intensity of incident laser light, absorptivity, optical length of light path and
concentration of particle respectively.

Not only absorbance but also transmittance can also be considered for measuring stability of
nanoparticles.

λ = I/Io
%Transmittance
Sample Concentration
Day – 1 Day – 2 Day – 3
Water 0 100 100 100
1 77.21 81.70 85.22
Cu-Al LDH
2 72.78 77.78 81.72
nanofluid
4 30.03 36.34 42.34

Table 1.1: Stability measurement results of Cu-Al LDH nanofluid using transmittance
criterion [32]

1.3.5. 3ω Method

The 3 technique of stability analysis uses the change in thermal conductivity of the nanofluid
as an indicator of instability owing to particle agglomeration and sedimentation. In this
method the thermal conductivity of the nanofluid increases for some time as a result of
particle agglomeration . But after a particular instant further agglomeration of particles will
lead to decrease in thermal conductivity due to agglomeration and subsequent sedimentation
of nanofluids . Reduced thermal conductivity is accounted for particle clustering which
reduces surface area to volume ratio and effective thermal heat transfer area .[32]

7
1.3.6.Transmission electron microscopy

Transmission electron microscopy(TEM) is used to observe the size and shapes of the
nanoparticles and enables us to find the degree of agglomeration and particle size distribution
can be considered as a measurement factor for nanofluid stability. In TEM high energy
electron beams are allowed to pass through the sample . Thicker region of the sample blocks
more electron, so fewer electrons transmit reach onto the detector making this region darker
. The region where there are no particles will transmit more electrons and look brighter. Thus,
we can differentiate the particle size distributions at different regions of sample.[32]

Figure 1.4. Transmission Electron Microscopy Components

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1.3.7. Dynamic light scattering:

In this technique we first measure the Brownian motion of the particles which is directly
related to the diffusion coefficient of particles. From the stokes-Einstein equation we can get
the size of the particles by using this diffusion coefficient.[32]

Figure 1.5. Dynamic Light Scattering Apparatus

Brownian motion or diffusion of particles happens from the collisions with fluid particles.
But each particle will have different diffusion rates based on the shape and size. The smaller
particles will diffuse quickly and the larger particles diffuses slowly .When the laser is
illuminated on the sample the nanoparticles scatter it and the intensity of the scattered light
is measured by a detector. If particles are still the scatter intensity will be the same. But in
dispersion medium because of the Brownian motion there will be the fluctuation of scattered
light intensity. Now this fluctuation will be based on the diffusion rate of the particles which
is correlated to the size of the particle. The measured diffusion coefficient is used to calculate
the particle size using Stokes-Einstein equation as.

𝑘𝐵 𝑇
𝑅𝐻 = .
6𝛱𝑢𝐷

Measurement of particle size acquired at different time intervals over a long period of time
indicates the nanoparticle agglomeration tendency and the instability.

9
1.4. Factors affecting Sedimentation
a. Shape and Size of particle
The smaller particles takes longer time to sediment . The larger particles formed by
coagulation and flocculation will sediment easily . Shape of particles also play an important
role in sedimentation time. If the particles are rounded and smooth the viscosity on the
particles will be lower and settle out quicker.

b. Density of particles
Density also have a indirect relation with the sedimentation time .If the density difference
between particles and basefluid is more then the particles sediment easily. And conversely if
density of the particle is less then time taken to sediment is more.

c. Temperature of Fluid
It is directly proportional to the settling rate. Lower temperatures will cause the settling rate
to decrease. At higher temperatures then settling velocity and the sedimentation coefficient
will be more. Thus we need to change the chemical dosage or particle concentrations at the
particular temperature to change the settling velocity.

10
 CHAPTER – 2

LITERATURE REVIEW

In the present chapter, a rigorous review of literature related to the stability of

nanofluid has been conducted, and summarized.

2.1 DLVO Theory of Aggregation

In this technique, all attractive and repulsive forces of particles are taken into
consideration and represented as a single dimensionless potential energy function. Normal
DLVO-curve looks something like the figure 2.1 [27,28].

Figure 2.1: Illustration of DLVO-Curve

Let’s consider two particles which are separated at larger distance. Because of Brownian
motion or some other random forces particles start to approach each other. Because of the
Vander walls forces and high surface energy the particles tend to share bond with other
particles. Now the particles will achieve a weaker stable state which falls under secondary
minimum potential energy. This process is called as flocculation and the formed clusters are
known as flocs. However, the secondary minimum of potential energy is quite shallow, which
means that flocs are relatively unstable clusters. i.e., if there is slight increase attractive force
like Vander walls force then particles further approach each other and in the same way if there
is slight repulsive force due to the double layer then flocculated particles will be separated

11
from each other. Thus, if there is an attraction force then the particles will approach each other
and then form a stable cluster, which corresponds to the primary minimum potential of
potential energy and will be held more stable. This process is called coagulation and the
formed clusters are known as coagulants. Now to sperate these stable clusters and form a
stable nanofluid there is a need of strong chemical, electrical or mechanical force .

Now the exact form of the DLVO-Curve is drawn based on the magnitude of the barrier
between flocculation and coagulation. If this barrier is less, then it is more likely to form
stable agglomerates and thus leads to instability of nanofluids. In the same way if this barrier
is huge then there will be hindrance in forming these stable coagulants and thus promoting
the stability of the nanofluids.

2.2 Stability Enhancement Techniques

2.2.1 Chemical Stabilization

When the Base fluid and the nanoparticle are having same nature (i.e., Both are
polar or Both are non-polar) then nanoparticles dissolve easily and form stable colloidal
dispersion. But if they have different natures then nanoparticles try to react with other
nanoparticles rather than the fluid. Thus, in these cases we have to add some dispersants or
surfactants in order to increase the repulsions between the nanoparticles so that they don’t
aggregate and form clusters which leads to instability.

a. Electrostatic Stabilization

It mainly depends on the concept of electrical double layer (EDL) which we discussed in the
case of zeta potential and the DLVO theory. The phenomenon lying in this technique is
counterbalancing the Vander walls force of attraction by the repulsive forces of similar
charges present in the EDL. As nanoparticles surface is charged because of adsorption of ions
from the base fluid, the charged nanoparticles now attract the counter ions which felicitates
the formation of double layer. So, when two nanoparticles try to come into contact these
double layers which have high positive charge density overlap with each other and high
repulsion forces opposes the Vander walls attraction forces due to opposite charges. So high
the charge density on the nanoparticle high will be the stability of nanofluid.

The highest potential will be present at the surface of nanoparticle. As we gradually

move outwards towards the electrical double layer it becomes zero at the end. And the

12
electrical potential present at the slipping plane is called as the zeta potential. Now the main
of this stabilization process is to increase this zeta potential value so that two particles can’t
come closer. Now to make it possible different type of ionic surfactants are added.

There are mainly four types of surfactants.

• Cationic
• Anionic
• Non-ionic
• Amphoteric or zwitterionic

Figure 2.2: Mechanism of Electrostatic stabilization.

The advantage of using amphoteric surfactants is it can change into cation or anion based on
the Ph value of the base fluid.

Limitations of Electrostatic Stabilizations:

• It can be only used when the nanoparticle suspension is dilute.
• The multivalent ions cannot be used because it is observed that in some way it converts
the repulsion forces into attractive Vander walls forces and subsequently results in stable
aggregates. It is also not suitable for saline environments (high salt concentration).
• It is only applicable for aqueous suspension which is contributed to its high Dielectric
constant and ease of formation of ions around the nanoparticles.
• Redispersion of the already formed aggregates is not possible.

13
b. Steric Stabilization:

In this technique, the polymers used to be adsorbed on the surface of the nanoparticles and
thus creating steric hinderance between the particles approaching each other. As this process
includes addition of polymers it is also called as polymeric stabilization technique. In this
technique we use non-ionic surfactants or dispersants unlike in the case of electrostatic
stabilization.

The polymeric chains will get adsorbed onto the nanoparticle surface and restraints the
free movement of them in the base fluid and also from aggregation of the particles. And the
extent of Stability is depended on the adsorption ability of nanoparticle surface and the chain
length of the polymer. Long chain length and good absorptivity(chemisorption) are the
favourable conditions. The polymer will be made of two parts. One is anchor and the another
one is tail part. The anchor of the polymer will get attached to the nanoparticle surface and
the tail part is more interactive with base fluid which makes it less reactive towards other
nanoparticles by the help of osmotic pressure(Base fluid pressure).

Two factors that facilitate towards the stability are strong enthalpic interaction between
molecule of the dispersing media and solvated polymeric tail, and length and density of the
polymeric tail attached to the nanoparticle surface for minimizing Vander walls attraction
between two approaching nanoparticles.

Figure 2.3: Mechanism of Steric Stabilization.

14
The nanoparticles stability can also be given in terms of Gibbs Free energy of system which
represents the total interaction potential between the solvent-Nanoparticle or Nanoparticle-
Nanoparticle. Thus, we are dealing the stability with thermodynamic aspects

Total Gibbs free energy is given by the following equation:

→ GT=GA+GST=GA+GOS+GVR

GA, GST, GOS and GVR represent Gibbs free energy of attraction, steric repulsion, osmotic
repulsion, and volume restraint interaction respectively. Now the equation will drive towards
the stability if the GT will be positive.

Now the polymers used can be of two types, Polymers made of same
monomers are called homopolymers and which are made of two different monomers are
called co-polymers. The point to be considered here in case of co-polymers is one of the
monomer is more attracted to nanoparticle surface(particle loving monomer) and other
one has more affinity towards the solvent(Solvent loving monomer).

Advantages of Steric stabilization over electrolytic stabilization

• At it is a thermodynamic method hence agglomerated particles can re-dispersible

unlike the electrostatic process.
• Very high concentrated solution can be used whereas we can only use dilute solution
in electrostatic process.
• It is not electrolyte sensitive in steric stabilization case. It is dependent on the
electrolyte in electrostatic stabilization.
c. pH adjustment:

Iso electric point(IEP) is the value of pH of system at which there will be no net charge
on the nanoparticle surface(i.e., zeta potential will be zero). Thus, we have to maintain
the pH level higher or lower compared to IEP. So, at an optimum level of pH,
nanoparticles will have high surface charge density which increases and help in
increasing repulsions of the nanoparticles and promote stability of the nanofluid.

15
 Figure 2.4: Effect of pH value on size distribution

Several researchers have concluded that the synthesized particles have more tendency to
agglomerate at normal pH 7 and have less changes to agglomerate at pH greater or lesser. But
having very less pH also prone to corrosion of heat transfer surface area. Thus maintain an
optimum level of pH value is important.

Another example is uniform dispersion of CNT in water . we have to do acid treatment in

order to introduce hydroxyl group and make it soluble in water. Thus, it becomes hydrophilic
from hydrophobic CNT.

d. Electrosteric Stabilization:

This technique is the combination of both steric and electrostatic stabilization. We will
add ionic polymers which gets adsorbed on the nanoparticle surface which will be helpful
in creating steric hindrance as well as electrical potential barrier between two
approaching particle. Because of presence of two stability mechanisms the stability of
the system will be improved significantly.

16
 Figure 2.5. Mechanism of electrostatic stabilization

These stabilizing polymers will be made of two parts (1) Anchor part (2) Stabilizing
polymer ionic chain . The long chain gives it steric stabilization and the ionic polymer
makes it to have electrostatic stabilization. The polymer used for this purpose is known as
polyelectrolyte which is made of repeating polymer units having an ionisable group
(carboxylic, sulfonic acid group etc.). These ionizable groups will dissociate and form
electrically charged polymers. And preferably we need to take the polyelectrolyte having
opposite charge to nanoparticle surface so that the adsorption will be maximum. We can also
use ionic liquids to increase surface charge density and also the electrostatic repulsions.

2.2.2 Mechanical Stabilization

Unlike the chemical energy used in previous literature for the stabilization, here the
means of energy used is mechanical energy. We will discuss about the Ultrasonication and
Ball Milling process in the successive stabilization techniques.

17
a. Ultrasonic vibration (or) Sonication

In this technique we use sound of frequency more than 20Khz to dissociate the
aggregated particles and also to increase homogeneity in dispersion. The nanoparticles
which needed to be dissociated or break down to smaller size are kept in a liquid. In this
process the phenomenon called the ultrasonic cavitation takes place.

b. Ultrasonic cavitation

This is the reason for dispersion and deagglomeration by ultrasonication. When the liquid
is exposed to the ultrasound waves that transfers in the liquid creates an alternating high
pressure and low-pressure intensity points. Which in wave terms are called compression
and rare fraction. At time of low intensity bubbles are created which will grow up to
some time and when it reaches to the size where it can hold the maximum energy it will
burst when a high-pressure intensity strikes it. This phenomenon is known as cavitation.
This implosion will create high temperature and pressures at that point and time. This
will cause the liquid in its surroundings to accelerate up to a velocity of 250 -300m/s.
Because of these mechanical stresses will be produced which will help in
deagglomeration of particles and thus making it more stable.

Figure 2.6: Acoustic Cavitation by ultrasonication

18
c. Ball Milling Method:

As the name milling suggests in this process the nanoparticle sizes goes on reducing .
So, it is called as top-down approach. All the structural and chemical changes that
happens in this method is due to the applied mechanical energy. It contains balls and a
cylindrical drum(or)wheel chamber. These balls are made of hardened steel or silicon
carbide. This drum can be rotated and as the drum rotates the balls will rotate along with
that. The powder of the material for which nanomaterial should be formed is kept inside
this steel cylindrical drum. As these hardened steel balls rotate it acts abrasives and
crushes the nano powder into very smaller particles. To get uniform fine powder we will
operate this process approximately 100-150 hours.

Figure 2.7. Planetary Ball milling

Advantages Disadvantages

1.Nanopowders of 2 to 20 nm in size can be 1.As the process is not much sophisticated

Produced. Size is depended on the speed of the particle shape can be irregular.

Rotation of drum.

2.It is inexpensive and easy process. 2.There may be contaminants inserted

from ball and milling additives.

19
 2.3 Summary of Review

In the following Table 2.1, a review on the stability for different types of nanofluids is
summarized.

Table 2.1: Literature review for implementation and performance of different nanofluid
stabilization technique.

Stability
Reference Nanoparticle Base Fluid Surfactants Stabilization
Duration and
No. Technique
Zeta Potential
Carbon based nanofluids

[1] CNT Water None 20.5 mV None

Sebacic Acid,
Carboxylated
[2] CNT 2 Ethylexanoic 38.2 mV Electrostatic
Water
Acid
[3] SWCNT Water GA 3 months Steric
[4] SWCNT Water Humic Acid 10 days Electrostatic
[5] SWCNT Water SDBS 3 months Electrostatic
[5] MWCNT Water PVP 2 months Steric
[6] MWCNT Water Triton X-100 2 months Steric
[7] MWCNT Water SDS 3 months Electrostatic
[7] MWCNT Water SDBS 1 day Electrostatic
[8] MWCNT Water CTAB 1 day Electrostatic
[8] MWCNT Water SDS 1 month Electrostatic
[9] MWCNT Water SDBS 1 month Electrostatic

Single Wall 35 mV
None None
[9] Cabon Water 15 days, −40
SDS Electrostatic
Nanohorn mV

[10] Carbon Black Water SDS −26.9 mV Electrostatic

Metal based nanofluid
7 days, 28.1
[11] Cu Water CTAB Electrostatic
mV
7 days, −43.8
[11] Cu Water SDBS Electrostatic
mV

20
 7 days, −8.3
[11] Cu Water Triton X-100 Steric
mV
[12] Cu Water SDBS −43.8 mV Electrostatic
[12] Ag Silicon Oil Oleic Acid 2 months Steric
Oleic Acid &
[13] Ag n-heptane 1 month Steric
N-Butylamine
Metal Oxide based nanofluid
[14] CuO Water SDS 2 days, 40 mV Electrostatic
7 days 32.3
[15] CuO Water PVP Steric
mV
Water-EG
[15] CuO SDS 4 days, 47 mV Electrostatic
(50:50)
Water-EG 28 days, 57
[15] Al2O3 None None
(50:50) mV,
[16] Al2O3 Water None 14 mV None
16 days −30
[16] Al2O3 Water SDS Electrostatic
mV
[17] Al2O3 Water SDBS −40.1 mV Electrostatic
[18] TiO2 Water SDS 12 days Electrostatic
2 days, −33.3
[19] TiO2 Water None None
mV
7 days & −55
[19] TiO2 Water SDS Electrostatic
mV
Hybrid nanofluids
10 days, −70
[22] Stainless steel Water SDBS Electrostatic
mV
10 days, 60.1
[22] Stainless steel Water CTAB Electrostatic
mV
Cu-Zn-Al
[23] Water None 18 h, 38.6 mV None
LDH
Cu-Zn-Al > 1 day, −50.6
[24] Water SDS Electrostatic
LDH mV
Cu-Zn-Al
[24] Water Tween 20 12 h, 24.3 mV, Steric
LDH

21
In the following Table 2.2, a review on the thermal conductivity enhancement for different
types of nanofluids and volume fraction is summarized.

Table 2.2: Literature review for thermal conductivity of nanofluids

Thermal
Particle Base fluid Volume fraction conductivity
enhancement
Cu (10 nm) Ethylene glycol 0.3% 40%
Cu (100nm) Water 7.5% 78%
Fe (10 nm) Ethylene glycol 0.55% 18%
Au (10-20nm) Water 0.026% 21%
Ag (60-80nm) Water 0.001% 17%
Al2O3 (13nm) Water 4.3% 30%
Al2O3 (33nm) Water 4.3% 15%
Al2O3 (68nm) Water 5% 21%
CuO (36nm) Water 3.4% 12%
CuO (50nm) Water 0.4% 17%
SiC (26nm) Water 4.2% 16%
TiO2 (15nm) Water 5% 30%
MWCNT (25nm) Synthetic Oil 1% 150%
MWCNT (15nm) Ethylene Glycol 1% 13%
MWCNT (100nm) Water 0.6% 18%

22
Findings from literature:

From the above table we can find the relation between thermal conductivity enhancement and
the volume fraction of added nanoparticles. Also, it shows the relation between the particle size
and thermal conductivity.

As the volume fraction increases the thermal conductivity increases as there will be more
surface area to carry the heat. But if it increases above certain point thermal conductivity starts
to decrease as agglomeration tendency increases and the viscosity increases. Also as the particle
size decreases thermal conductivity increases because of increase in surface area to volume
ratio.

23
 CHAPTER 3

Experimental Procedure

3.1. Nanofluid used

In this project, the nanofluid used is the composition of aluminium oxide (Al2O3)
nanoparticles and distilled water solution. It has been proven in previous literatures that the
stability period of Al2O3 nanofluids are much higher than the rest and used for better study
purposes. The specifications of the constituents are as follows.

Base Fluid:

Fluid: Distilled Water

Quantity: 550ml

Nanoparticles:

Material: Al2O3 Particles

grams:2.09 gm (0.1% vol by weight)

3.2. Preparation Technique

1. Materials and Equipment:

- Aluminum oxide (Al2O3) nanoparticles

- Distilled water

- Sonicator

- Container for mixing

2. Measure Ingredients:

- Measure the desired amount of distilled water based on the concentration of the nanofluid
you want to achieve.

- Weigh the appropriate amount of Al2O3 nanoparticles based on the desired nanoparticle
concentration.

24
3. Add Al2O3 Nanoparticles:

- Gradually add the pre-weighed Al2O3 nanoparticles to the stirring water. Ensure a slow
and steady addition to prevent clumping.

4. Sonication:

- Transfer the mixture to a sonication container suitable for the sonicator.

- Place the container in the sonicator bath.

- Turn on the sonicator and set the parameters (frequency, power) based on the
manufacturer's recommendations.

Fig 3.1. Ultrasonic Sonicator

- Sonicate the mixture for a specific duration, ranging from 1 to 3 hours. The sonication
helps break down agglomerates and disperse the nanoparticles uniformly in the solution.

5. Cooling:

- The sonication process can generate heat. If the solution temperature rises significantly,
allow it to cool to room temperature or the desired operating temperature.

6. Final Stirring:

- After sonication, continue stirring the nanofluid for a brief period to ensure a well-mixed
and stable solution.

25
3.3. Stability Measurement Technique
(a) Photograph sedimentation method:

➢ Fix the Imhoff cone with nanofluid to specific level, making sure its well-mixed.
➢ Take an initial photograph of the nanofluid in the Imhoff cone, capturing any details
that may be relevant to analysis.
➢ Allow the nanofluid to stand undisturbed for a predetermined period.

➢ Start the timer once you’ve setup the sedimentation.

➢ Take photographs at regular intervals during the sedimentation process. The frequency
of photographs depends on the expected settling time.
➢ After sedimentation process is complete, analyze series of photographs.

(b) Zeta potential method:

➢ Take the mixed and homogeneous mixture of nanofluid into the violas from the Imhoff
cone
And add up to 10ml level.
➢ During extraction of sample from cone keep utmost care as sample should be left
undisturbed or the value will be changed.
➢ Before pouring into violas use a filter paper to remove any solid particles as filtrate as
the tubes used in zeta potential tube are very sensitive and may break.

Fig 3.2 Zeta potential apparatus

26
 CHAPTER 4

RESULTS
(a) With Sedimentation photography Method:
Solution details:Al2O3-Distilled water nanofluid

Particle concentration:0.1 vol %(2.09 gm)

Particle size:40nm.

Sample 1:
Sonication time: 1 hour

After 16 hours After 24 hours After 42 hours

Sample 2:
Sonication time: 2 hours

After 16 hours After 24 hours After 42 hours

27
 Sample 3:

Sonication time: 3 hours

After 6 hours After 24 hours After 42 hours

Solution details:Al2O3-Distilled water nanofluid with HCL and NaOH

Particle concentration:0.1 vol %(2.09 gm)

Particle size: 40nm.

pH of solutions: Normal- 7.24

Base 1- 9.71

Base 2- 10.12

Acid 1- 6.01

Acid 2- 2.99

Initial After 24 hours

Acid 1 (a) Acid 1(b)

28
 Acid 2 (a) Acid 2(b)

Base 1(a) Base 1(b)

Base 2 (a) Base 2(b)

Neutral(a) Neutral(b)

29
 (b) With Zeta Potential test:

Figure 4.1 result for zeta potential for A1 sample (24 hours)

Figure 4.2 result for zeta potential for A1 sample (Initial)

30
 Figure 4.3 result for zeta potential for B1 sample (24 hours)

Figure 4.4 result for zeta potential for B1 sample (Initial)

31
 pH Initial Final(24 hr)

47.8
2.99 52.6

6.01 -9.4 -29.1

7.24 -34.2 -29.9

9.71 -34.3 -30.7

10.12 -15.2 -33.4

Table 4.1 Initial vs Final zeta potential

pH vs Zeta potential
60 52.6
47.8
50
40
30
Zeta Potential

20
10 Initial

0 After 24 hours
2.99 6.01 7.24 9.71 10.12
-10
-9.4
-20 -15.2
-30
-29.1 -29.9 -30.7
-40 -34.2 -34.3 -33.4
pH Value

Figure. 4.5 pH vs zeta potential

32
 CHAPTER 5

CONCLUSIONS

In conclusion, the investigation into the stability of nanofluids has provided

valuable insights and findings that contribute significantly to our understanding of the
behavior of these innovative fluid systems. Through experimentation, analysis, and
interpretation of results, we have successfully addressed the key objectives outlined in this
report.

The comprehensive review of literature laid the groundwork for our research,
establishing a foundation of existing knowledge and highlighting gaps that our study aimed
to fill. The experimental methodologies employed were carefully designed to ensure accuracy
and reliability in our measurements, allowing us to capture essential data on the stability of
nanofluids under various conditions.

The results obtained have shedded light on factors such as nanoparticle concentration and
fluid composition. Our findings not only confirm existing theories but also introduce novel
perspectives that could influence future research in this rapidly expanding field. The
correlation between stability and specific parameters is now better understood, providing a
basis for optimizing nanofluid formulations for various applications.

33
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