ABSTRACT

Nanotechnology is described as "research and technology development at the atomic,

molecular, or macromolecular levels in the length scale of about 1 to 100nm range to give a

basic knowledge of processes and materials at the nanoscale, as well as the creation and usage

of structures, devices, and systems with unique features and functionalities due to their tiny or

intermediate sizes" [1]. Nanocomposite materials are the materials of the twenty-first century.

These unique materials are thought to have the potential to meet the rising need for

breakthrough technologies [2]. Because of the rapid development of nanotechnology, heat

transfer fluids (HTF) significantly boost the efficiency of thermal systems. As a result, several

investigations are being undertaken in this sector to improve the thermo-physical

characteristics of HTFs. Therminol (TH) is one of the HTFs that has lately been used in

medium-temperature solar thermal collectors and other industries [3]. TH has a comparatively

low freezing point but with a high boiling point [4].

This work intends to present a comprehensive study on the synthesis and

characterization of Copper Oxide-Barium Oxide (CuO-BaO) based TH nanofluid along with

the study of their rheological characteristics for advanced heat transfer applications. The

nanocomposite was synthesized using the chemical co-precipitation method. Therminol (base

fluid) was used to prepare the nanofluids with nanocomposite whose weight percentage is taken

as 0.25. The thermophysical properties of nanocomposites are important for a wide range of

real-world heat transfer applications and were tested at various temperatures of the nanofluid.

1
CHAPTER-1

INTRODUCTION

Science and technology are so integrated into today’s life that they have generated

new knowledge that greatly contributed to the development and progress of human

beings. There are tremendous changes that have been taking place in all the areas of

scientific knowledge. These new changes create new opportunities as they cross over to

practical applications. A new field of science is just emerging that unifies both physical

science and life science which can revolutionize our concept of science and technology

in the present century. This new field is called ‘nanoscience and nanotechnology’ which

is based on our ability to measure, manipulate, and organize matter in the nanoscale

which is a billionth of a meter (10-9 m). The original version of nanotechnology is

sometimes termed ‘molecular manufacturing’. It involves research and technological

development at the 1nm to 100nm range. It creates and uses structures that have novel

properties because of their small size. It builds upon the ability to control or manipulate

at the atomic scale.

Nanotechnology will eventually enable us to create custom-made materials and

products with improved properties, as well as new nanoelectronics components, smart

medicines, and sensors. Nanoparticles are larger than atoms and molecules but smaller

than bulk solids. Many popular materials have unusual properties at the nanoscale such

as significantly lower resistance to electricity, lower melting points, or faster chemical

reactions. As a result, they don't follow either absolute quantum chemistry or classical

physics rules, and their properties are vastly different from those expected [13]. These

property differences are caused by two major factors:

2
(1) Spatial quantization of charge carriers

This is particularly noticeable in semiconductors. It is known as size quantization,

and it occurs when the size of a nanoparticle is comparable to the de Broglie

wavelength of its charge carriers (electrons and holes). Because of the spatial

confinement of the charge carriers, the edge of the valence and conduction bands split

into discrete, quantized electronic levels. As a result, the bandgap of semiconductor

nanoparticles increases [23].

(2) Large surface-to-volume ratio of nanomaterials

A large number of atoms are associated with interfaces in nanostructured materials,

such as grain boundaries, surfaces, or interface boundaries. These characteristics

should be considered. Numerous physical and chemical techniques are being used to

advance the preparation of nanoparticles. The most difficult task at the moment is

property characterization and device fabrication.

Today, nanotechnology has become an applied science, a rapidly growing industry

generating a diverse array of nanoscale materials and processes. Manipulation of

materials and processes on a nanometer scale is opening a world of creative

possibilities. The benefits afforded by nanoscale technologies are expected to have

substantial impacts on almost all industries and all areas of society. Nanoparticle

research is currently an area of intense scientific research, due to a wide variety of

potential applications in biomedical, optical, and electronic fields.

[1.1] THE ORIGIN OF NANOTECHNOLOGY

The origin of nanotechnology traces the development of the concepts and experimental

work falling under the broad category of nanotechnology. One of the first scientific

3
reports is the colloidal gold particles synthesized by Michael Faraday as early as 1857.

In the 1960’s and 1970’s metallic nanopowders for magnetic recording tapes were

developed. In 1976, for the first time, nanocrystals produced by the now-popular inert-

gas evaporation technique were published by Granqvist and Buhrman. The emergence

of nanotechnology in the 1980’s was caused by the convergence of experimental

advances such as the invention of the scanning tunneling microscope in 1981 and the

discovery of fullerenes in 1985. The early 2000s also saw the beginnings of

commercial applications of nanotechnology, although these were limited to bulk

applications of nanomaterials rather than the transformative applications envisioned by

the field.

[1.2] CLASSIFICATION OF NANOSTRUCTURES

Nanomaterials include clusters, colloids, nanoparticles, nanocrystals, nanostructured or

nanoscale materials, nanophase materials, and quantum dots [1, 2].

1.2.1 NANOCLUSTERS: They are made up of a small number of atoms, usually in the

tens. These nanoclusters can be made up of single or multiple elements and are typically

smaller than 2nm in size. When compared to their larger counterparts, such nanoclusters

have appealing electronics, optical, and chemical properties.

Figure 1: Nanoclusters

4
1.2.2 COLLOIDS: Colloids are liquid-solid mixtures. The size of the particle determines

the properties of the colloid. Colloids include gels, sols, and emulsions.

Figure 2: colloids

1.2.3 NANOPARTICLE: A solid particle which is in the 1 to 100 nm range that could

be non-crystalline an aggregate of crystallites

1.2.4 NANOCRYSTAL: A nanocrystal is a crystalline particle with at least one

dimension smaller than 100 nanometers (nm). Nanocrystals can be used in a wide range

of applications, both current and future. They have been used to make filters for

converting crude oil into diesel fuel. Solar panels can also be made by layering

nanocrystals and applying them to flexible substrates.

1.2.5 NANOPHASE MATERIALS: Any solid material which is in nanometer

dimension;three dimensionsparticles; two dimensions thin films; one dimension
thin wire.

Figure 3:Nanophase materials

5
1.2.6 QUANTUM DOTS: Semiconductor nanoparticles (quantum dots) were theorized

in the 1970s and first created in the early 1980s. Recent advances in chemistry have

resulted in the production of high-quality, monodispersed, crystalline quantum dots.

Quantum dots have the potential to be used in single-electron transistors, solar cells,

LEDs, lasers, single-photon sources, second-harmonic generation, quantum computing,

and medical imaging.

Figure 4: quantum dots

1.2.7 NANOTUBES: Nanotubesare members of the fullerene structural family. Their

name comes from their long, hollow structure, which has walls made of one-atom-thick

sheets of carbon called graphene. Nanoparticles and nanopores are particles with

diameters ranging from 1 to 100 nanometers. The constituent atoms or molecules of

nanoparticles may be randomly arranged. Nanowires, nanorods, monofilaments, and

nanotubes are all examples of nanoparticles.

1.2.8 NANOPORES: A nanopore is a very small hole. It may, for example, be created

by a pore-forming protein or as a hole in synthetic materials such as silicon or graphene.

6
 Figure 5: Nanopores

1.2.9 FULLERENE: A fullerene is a carbon molecule that can take the shape of a hollow

sphere, an ellipsoid, a tube, or a variety of other shapes. Spherical fullerenes, also known

as Buckminster fullerenes, are a type of fullerene that is shaped like a sphere. Carbon

60(C60) was discovered in the mid-1980s as a new class of carbon material. TheC60

species was named 'Buckminsterfullerene' after the architect Buckminster Fuller.

Fullerenes are being considered for a variety of applications, including miniature 'ball

bearings' to lubricate surfaces.

1.2.10 DENDRIMERS: Dendrimers are spherical polymeric molecules formed by a

nanoscale, hierarchical self-assembly process. Dendrimers come in a variety of sizes, the

smallest being a few nanometers. Dendrimers are used in traditional applications such as

coatings and inks, but they also have several interesting properties that could lead to

useful applications.

Figure 6: Fullerenes Figure 7: Dendrimers

7
[1.3] NANOCOMPOSITE AND NANOFLUID

Nanocomposite is a multiphase solid material where one or more phases have

nano-sized dimensions (zero-dimension, one dimension, and two dimensions) which is

less than 100 nanometers (nm) or structures having nanoscale repeat distances between

the different phases that make up the material. They are found in nature such as in the

structure of the abalone shell and bone. The use of nanoparticle-rich materials long

predates the understanding of the physical and chemical nature of these materials. It

investigated the origin of the depth of color and the resistance to acids and bio-corrosion

of Maya blue paint, attributing it to a nanoparticle mechanism. From the mid-1950s

nanoscale organo-clays have been used to control the flow of polymer solutions (e.g. as

paint viscosities) or the constitution of gels (e.g. as a thickening substance in cosmetics,

keeping the preparations in homogeneous form). By the 1970s polymer/clay composites

were the topic of textbooks, although the term "nanocomposites" was not in common

use.

Nanofluid is a fluid containing nanometer-sized particles, called nanoparticles.

These fluids are engineered colloidal suspensions of nanoparticles in a base fluid. The

nanoparticles used in nanofluids are typically made of metals, oxides, carbides, or carbon

nanotubes. Common base fluids include water, ethylene glycol, and oils. They have

novel properties that make them useful in many applications including

microelectronics, fuel cells, pharmaceutical processes, hybrid-powered engines, engine

cooling/vehicle thermal management, domestic refrigerators, chiller, heat exchanger, in

grinding, machining and boiler flue gas temperature reduction. They exhibit

enhanced thermal conductivity and the convective heat transfer coefficient compared to

the base fluid. Knowledge of the rheological behavior of nanofluids is found to be critical

8
in deciding their suitability for convective heat transfer applications. They also have

special acoustical properties and in ultrasonic fields display additional shear-wave

reconversion of an incident compressional wave; the effect becomes more pronounced

as concentration increases [26].

Figure 8: nanocomposite Figure 9: nanofluid

[1.4] PROPERTIES OF NANOSTRUCTURE MATERIALS

Nanoscience and nanotechnology are thought to be the most important

developments of this century. Because of their large surface area, nanoparticles dominate

the contributions produced by the small bulk. As the size of a material is reduced to the

nanometer scale, its properties change drastically. Reduced elastic modulus, enhanced

diffusivity, reduced density, improved strength/hardness, higher electrical resistivity,

increased specific heat, higher thermal expansion coefficient, lower thermal

conductivity, and super soft magnetic properties are some of the properties of

nanostructured materials [15, 23].

1.4.1 PHYSICAL PROPERTIES

Nanoparticles are distinct in that they have a large surface area, which outweighs

the contributions of the material's small bulk. The ability of nanoparticles to form

suspensions is a crucial physical characteristic. The particle surfaces interaction with the

solvent is high enough to resolve density differences, making this possible. An important

9
physical property of nanoparticles is their ability to form suspension. This is possible

since the interaction of the particle surface with the solvent is strong enough to overcome

density differences. In bulk materials, these interactions usually result in a material either

sinking or floating in a liquid. Other examples of the physical properties of nanoparticles:

• Gold nanoparticles melt at far lower temperatures than gold slabs (1064°C), (300°C

for 2.5 nm size).

• Solar radiation absorption in photovoltaic cells is much higher in nanoparticles than

in thin films of continuous sheets of bulk material because the particles are smaller

and absorb more light.

1.4.2 MECHANICAL STRENGTH

All the nanomaterials possess high mechanical strength as compared to their

conventional counterparts. The mechanical strength of nanomaterials may be one or two

times higher in magnitude than that of single crystals in the bulk form. Defects in the

form of atomic vacancies can lower the tensile strength of the materials by up to 85%.

Conversion of materials into nanoscale increases crystal perfection or reduction of

defects, which would result in enhancement in mechanical strength.

1.4.3 ELECTRONIC AND OPTICAL PROPERTIES

Nanoparticles have a greater degree of interdependence between their optical and

electronic properties. Noble metal nanoparticles, for example, have size-dependent

optical properties and have a large UV-visible extinction band that is absent from the

bulk metal's spectrum. This excitation band is missing from the bulk metal's spectrum.

This excitation band is known as the Localized Surface Plasmon Resonance (LSPR) and

occurs when the incident photon frequency is constant with the collective excitation of

10
the conduction electrons. The optical bandgap increases with the decrease in particle size,

especially for the semiconductor nanomaterials. Thus the colloidal gold or silver

nanoparticles produce different colors for different sizes, especially in the range of 1–

10nm. SPR effect changes due to the change in particle size which in turn changes the

color of metallic nanoparticles. The coherent excitation of entire free electrons in the

conduction bands may produce an in phase oscillation, called Surface Plasmon

Resonance (SPR).

1.4.4 MAGNETIZATION AND OTHER PROPERTIES

Magnetic nanoparticles have stimulated the interest of researchers in a wide

variety of fields, including heterogeneous and homogeneous catalysis, biomedicine,

magnetic fluids, data storage, magnetic resonance imaging, and environmental

remediation, such as water decontamination. Nanoparticles have properties like quantum

confinement in semiconductors, surface plasmon resonance in some metal particles, and

super-paramagnetism in magnetic materials.

1.4.5 DIFFUSION PROPERTIES

Nanoparticles, in particular, can diffuse at high temperatures. Sintering of smaller

particles may occur at lower temperatures and over shorter timescales than sintering of

larger particles. Although this does not affect the final product's density, there is a risk of

agglomeration.

[1.5] APPLICATIONS OF NANOTECHNOLOGY

While most nanotechnology applications are restricted to the bulk usage of passive

nanomaterial, the 2000s saw the beginnings of nanotechnology applications in consumer

goods. Titanium dioxide and Zinc oxide nanoparticles are used in sunscreen, cosmetics,

11
and some food products; silver nanoparticles are used in food processing, clothes,

disinfectants, and household applications like silver naphthalene [12].

The physical properties of materials and products can change as a result of shrinking

scale with nanotechnology. The increased surface-area-to-volume ratio of nanoparticles

is advantageous; for example, fluorescence changes as the diameter of the nanoparticle

changes. Nanoparticles affect the mechanical properties of bulk materials, such as

stiffness and elasticity, when they are combined with them. Modern polymers, for

example, can be reinforced with nanoparticles, resulting in new lightweight materials

that could be used instead of metals. Weight reduction increased stability, and improved

performance would all be possible with nanotechnology-enhanced materials.

There are several fields in which nanotechnology applications have become well-known

in recent years and these applications are increasing day by day. Nanotechnology's

applications in different fields of research are discussed [23].

1.5.1 NANOMEDICINE

Nanomedicine is the use of nanotechnology in medicine. Nanomedicine encompasses

anything from medical nanomaterials and biological devices to nanoelectronics

biosensors and even potential molecular nanotechnology applications such as biological

machines. Nanomedicine's current challenges include determining the toxicity and

environmental effects of nanoscale materials. Recent research showed that ZnO

nanoparticles exhibited impressive antibacterial properties against an important

foodborne pathogen, E. coli O157: H7, and the inhibitory effects increased as the

concentrations of ZnO nanoparticles increased [30].

12
1.5.2 TAGGING OF DNA AND DNA CHIPS

The boundaries of molecular diagnostics are pushed to the nanoscale by nanotechnology.

Microfluidic/lab-on-a-chip technology has expanded to include nanotechnology on a

chip. The identification of genetic sequence in a sample can be done with gold

nanoparticles marked with short DNA segments. Binding (hybridization) happens when

these are exposed to full DNA. This allows the colloidal gold particles to accumulate,

resulting in a color shift. Microarrays of up to 1, 00, 000 different known DNA sequences

have been created to detect and help classify DNA samples. For homogeneous assays,

DNA nanomachines can be used as biomolecular detectors.

1.5.3 CHEMICAL SENSORS

Bio/chemical sensor technology has enormous potential for use in a variety of fields,

including biomedicine, food production, defense, and environmental protection. Ultra-

sensitive sensor systems that are both clinically and economically feasible are in high

demand. Sensors based on nanotechnology can detect very small amounts of chemical

vapors. In nanotechnology-based sensors, various types of detecting elements, such as

carbon nanotubes, zinc oxide nanowires, or palladium nanoparticles, can be used. The

electrical properties of the sensing elements can be changed with only a few nanowires

or nanoparticles. This enables the detection of chemical vapors at extremely low

concentrations.

1.5.4 ELECTRONICS

In graphene, researchers have devised an intriguing method for forming PN junctions, a

crucial component of transistors. The p and n regions of the substrate were patterned.

Depending on the doping of the substrate, electrons were either added to or taken from

13
the graphene film as it was applied to it. A Nanoparticle Organic Memory Field-Effect

Transistor (NOMFET) transistor is made by combining gold nanoparticles with organic

molecules.

Due to the higher density of chips, the design of electronic components with more

compact makes heat dissipation more difficult. Nanofluids with higher thermal

conductivities are predicated convective heat transfer coefficients compared to those of

base fluids. Recent research illustrated that nanofluids could increase the heat transfer

coefficient by increasing the thermal conductivity of a coolant. It reduces both the

thermal resistance and the temperature difference between the heated microchannel wall

and the coolant.

1.5.5 SOLAR CELLS

Solar energy is the most plentiful of the numerous renewable energy sources.

Photovoltaic devices, which turn solar energy directly into electricity, have a bright

future ahead of them. If the amount of solar light harvested can be increased, solar cells

can be very useful. Some solar cells are more efficient when using plasmonic

nanostructures. Semiconductor nanoparticles with size-tunable bandgaps hold the

promise of more efficient photovoltaic (electricity production) and water-splitting

(hydrogen production) solar cells.

The conventional direct absorption solar collector is a well-established technology. The

efficiency of these collectors is limited by the absorption properties of the working fluid,

which is very poor for typical fluids used in solar collectors. Recently, this technology

has been combined with the emerging technologies of nanofluids and liquid-nanoparticle

suspensions to create a new class of nanofluid-based solar collectors. The efficiency

improvement was up to 5% in solar thermal collectors by utilizing nanofluids as the

14
absorption media. Theoretical investigation showed that the presence of nanoparticles

increased the absorption of incident radiation by more than nine times over that of pure

water.

1.5.6 NANOBATTERY

Using nanotechnology in the manufacture of batteries offers the following benefits:

 Reducing the possibility of batteries catching fire by providing less-flammable

electrode material.

 Increasing the available power from a battery and decreasing the time required to

recharge a battery. These benefits are achieved by coating the surface of an

electrode with nanoparticles. This increases the surface area of the electrode

thereby allowing more current to flow between the electrode and the chemicals

inside the battery. This technique could increase the efficiency of hybrid vehicles

by significantly reducing the weight of the batteries needed to provide adequate

power.

 Increasing the shelf life of a battery by using nanomaterials to separate liquids in

the battery from the solid electrodes when there is no draw on the battery. This

separation prevents the low-level discharge that occurs in a conventional battery,

which increases the shelf life of the battery dramatically.

1.5.7 SPACE AND DEFENCE

Nanotechnology may be the secret to making space travel more available.

Lightweight solar sails and a cable for the space elevator are now feasible thanks to

advances in nanomaterials. These advancements could lower the cost of reaching orbit

and traveling in space by drastically reducing the amount of rocket fuel needed.

15
Furthermore, new materials combined with nano-sensors and nano-robots can improve

the performance of spaceships, spacesuits, and equipment used to explore planets and

moons, making nanotechnology an essential part of the "final frontier."

Due to the restriction of space, energy, and weight in space stations and aircraft, there is

a strong demand for highly efficient cooling systems with smaller sizes. Nanofluids with

high critical heat fluxes have the potential to provide the required cooling in such

applications as well as in other military systems, including military vehicles, submarines,

and high-power laser diodes. Therefore, nanofluids have wide applications in space and

defense fields, where power density is very high, and the components should be smaller

and weightless.

1.5.8 INFORMATION STORAGE

In terms of color, coverage, and colorfastness, ultra-fine dye particles also result

in higher quality inks. Nano-opens (atomic force microscopes) can also write letters with

features as small as 5 nanometers. Nanoparticles have already made their way into

modern audio and videotapes and discs, which depend on fine particles' magnetic and

optical properties.

1.5.9 AEROSPACE AND VEHICLE MANUFACTURERS

Aircraft manufacturers will benefit greatly from lighter and stronger materials,

which will result in improved performance. Spacecraft will gain as well, as weight is a

big consideration. As a result, nanotechnology could be able to help lower the size of the

equipment and the amount of fuel needed to get it airborne. With the use of nanotech

materials, hang gliders can be able to reduce their weight while increasing their strength

and endurance. Nanotechnology is reducing the mass of supercapacitors, which will be

16
gradually used to power assistive electrical motors used to launch hang gliders from

flatland to thermal-chasing altitudes [16].

1.5.10 TRANSPORTATION

Nanofluids have great potential to improve automotive and heavy-duty engine

cooling rates by increasing efficiency, lowering the weight, and reducing the complexity

of thermal management systems. The improved cooling rates for automotive and truck

engines can be used to remove more heat from higher horsepower engines with the same

size cooling system. Alternatively, it is beneficial to design a more compact cooling

system with smaller and lighter radiators. Ethylene glycol-based nanofluids have

attracted much attention in the application as engine coolant due to the lowpressure

operation compared with a 50/50 mixture of ethylene glycol and water, which is the

nearly universally used automotive coolant.

17
[1.6] LITERATURE REVIEW

Nanofluids are attracting a great deal of interest with their enormous potential to

provide performance properties, particularly concerning heat transfer. They are

important aspects of energy management systems, functioning as mediums for efficient

thermal energy absorption or heat transfer. Nanofluid, which has much greater thermal

conductivity, homogeneity, stability, and other properties compared to traditional fluids

and is beneficial in refrigeration and engineering applications [1, 2].

A review on "Nanosynthesis" by Yeh et al. described the various synthesis

methods for nanomaterials and problems associated with chemical synthesis are

ecotoxicity, health hazards to humans and animals etc. In recent past, scientists have

developed several biological methods for the rapid and cost-effective synthesis of

nanoparticles. A review on "Characterization techniques for nanoparticles" by Pallares

et al. provides a detailed view on XRD characteristics of nanoparticles. In their study,

they reveal that "In fact, quite often a wider characterization of NPs is necessary,

requiring a comprehensive approach, by combining techniques in a complementary

way". Higher thermal conductivity and decreased viscosity among ethylene glycol-based

nanofluids integrating metal oxide nanoparticles were explored by Huaqing Xie et al.

CHAPTER-2

EXPERIMENTAL METHODS

[2.1] SYNTHESIS METHODS

The ability to fabricate and process nanomaterials, as well as nanostructures, is

the first cornerstone of nanotechnology for exploring novel physical properties and

18
phenomena and realizing future applications of nanostructures and nanomaterials. There

are several ways to make nanomaterials, which can be divided into two categories: top-

down and bottom-up approaches. The top-down approach includes solid-state routes

such as ball milling, while bottom-up approaches include wet chemical routes such as

sol-gel, co-precipitation, combustion, and others.

Synthesis methods for nanoparticles first involve the division of a massive solid

into smaller and smaller portions, successively reaching nanometer size. This approach

may involve milling or attrition. The second, “bottom-up”, method involves pyrolysis.

Pyrolysis is the process of forcing a vaporous precursor (liquid or gas) through an orifice

at high pressure and burning it. To recover oxide particles from by-product gases, the

resulting solid (a form of soot) is air graded. Rather than singleton primary particles,

pyrolysis also produces aggregates and agglomerates.

Other synthesis methods are divided into two categories depending on the phase

of the starting material: gas phase and condensed phase synthesis methods. Gas-phase

synthesis necessitates the use of highly advanced and costly equipment. Chemical or

physical vapor deposition, chemical precipitation, and other similar techniques are

examples. Processed bulk precursors can also be used to make nanoparticles. Examples

include mechanical attrition, crystallization from amorphous states, phase separation, and

so on. Nanoparticles may also be made from biological systems found in nature.

Nanomaterial fabrication with tight control over scale, shape, and crystalline structure

has become critical for nano technological applications.

19
2.1.1 PHYSICAL METHODS

Monomer gas aggregation: This approach entails establishing a monomer population,

cooling the monomers, and increasing the cluster by adding monomers one at a time.

Vacuum sputtering: Clusters are sputtered out of a solid target using high-energy ions

or laser ablation in this experiment.

Ion Beam Method: This is a physical method based on thin film deposition in which

clusters are generated using a source such as an oven or a laser. The clusters are then

ionized by an electron beam and accelerated onto a substrate, where they are deposited

as thin films that are stable and do not coalesce to form a bulk.

Consolidation: Small clusters were collected and consolidated in the first attempt to

make and analyze bulk nanocrystalline materials. Resistive heating evaporates the

material, which condenses into small crystallites and is transported to the liquid nitrogen-

filled cold finger through convection. After that, the powder is scraped from the cold

finger, collected with a funnel, and consolidated in the low-pressure and then high-

pressure compaction units.

Ball Milling: By mechanical deformation, the grain size in powder samples can be

reduced to the nanometer scale in a high-energy ball-milling process. It can be used with

pure bcc metals (Cr, Nb), immiscible structures (Fe-Al), and so on. Ball milling has the

advantage of being a quantity operation, allowing kilograms of materials to be processed

in up to 100 hours (about 4 days).

20
2.1.2 CHEMICAL METHODS

Combustion route: Combustion synthesis leads to highly crystalline particles with large

surface areas [16]. The process involves rapid heating of a solution containing redox

groups. During combustion, the temperature reaches approximately 650°C for one or two

minutes making the material crystalline.

Chemical Capping: Chemical methods fall into the category of having more control

over synthesis parameters such as reactant concentration, pH, solvent, and so on. These

are easier and less costly, with higher yields in a shorter period. To make nanoparticles,

chemical salts are reacted in the presence of an organic or inorganic capping agent. To

prevent cluster oxidation, the synthesis is carried out primarily in an inert atmosphere.

Deoxy Ribose Nucleic Acid (DNA) can also be used as a capping agent to make

nanoparticles [21].

Hydrothermal Method: Hydrothermal synthesis is normally performed in a pressurized

vessel known as an autoclave, with the reaction taking place in an aqueous solution. The

autoclave's temperature can be increased above the boiling point of water, resulting in

vapor saturation pressure. By adjusting the solution composition, reaction temperature,

strain, solvent properties, additives, and aging time, the hydrothermal method can be used

to monitor grain size, particle morphology, crystalline phase, and surface chemistry. It is

commonly used for the preparation of metal oxide nanoparticles, [7] which can be easily

obtained by hydrothermal treatment of peptized metal precursor precipitates with water.

Gas-phase method: For the development of thin films, gas-phase methods are suitable.

Chemical or physical methods may be used to create a gas-phase synthesis. Chemical

vapor deposition (CVD) is a commonly used industrial technique for coating vast areas

21
quickly [21]. Physical vapor deposition (PVD) is a thin film deposition method in which

metal oxide is produced by a chemical reaction. The method is similar to chemical vapor

deposition (CVD), except that the raw materials/precursors, i.e., the material to be

deposited, begin in solid form, while in CVD, the material begins in liquid form. The

mechanism is atomistic in nature and does not require many chemical reactions. Various

methods for removing growth species from the source or target have been established.

The deposit thickness can range from a few angstroms to several millimeters.

Microwave synthesis: Microwave synthesis is a relatively recent and interesting

technique for the synthesis of oxide materials. Under microwave irradiation, various

nanomaterials have been synthesized in a relatively short period [19]. Microwave

techniques remove the need for long periods of high-temperature calcinations and allow

for the rapid and repeatable synthesis of crystalline metal oxide nanomaterials. Because

of the shorter synthesis time and highly concentrated local heating, using microwave

energy for thermal treatment usually results in a very fine particle in the nanocrystalline

regime.

Microemulsions: Metallic semiconductor, silica, barium sulphate, magnetic, and

semiconductor nanoparticles have all been synthesized using these methods. These

microemulsions are generated spontaneously without the need for substantial mechanical

agitation by regulating the very low interfacial tension with the addition of a co-surfactant

(e.g., alcohol of intermediate chain length). The method can be used to make

nanoparticles on a wide scale using a relatively simple and inexpensive process.

Sol-gel Method: The sol-gel method is a capable wet chemical process for creating

ceramic and glass products. The conversion of a system from a colloidal liquid, known

as sol, to a semi-solid gel phase is the aim of this synthesis technique. Sol-gel technology

22
can be used to make ultra-fine or spherical shaped powders, thin-film coatings, ceramic

fibers, microporous inorganic membranes, monolithic, or highly porous aerogels out of

ceramic or glass materials. The low processing temperature, the ability to monitor the

composition on a molecular scale, and the porosity to produce large surface area

materials are all advantages of this technique. The sol-gel method can produce high-

quality films with a micron thickness that is difficult to achieve with physical deposition

techniques. Furthermore, diverse composition materials can be synthesized, as well as

coatings for complex geometries. The starting materials for the preparation of the sol are

normally inorganic metal salts or metal-organic compounds, which are transformed into

the sol by hydrolysis and poly condensation reactions [5].

The sol-gel method is a wet chemical synthesis technique that uses gelation

precipitations and hydrothermal treatment to produce nanoparticles. During the gelation

process, a network is formed, and the pore size is in the nanometer range, limiting the

particle size. The sol-gel process has been used to make a variety of fine ceramics using

various metal ion precursors. Depending on the experimental conditions, the particle size

in this phase ranges from 50 to 300nm.

Co-precipitation Method: Co-precipitation is a simple, economical and industrially

viable technique that can be used for the synthesis of oxide materials. In many cases, co-

precipitation is the only way to separate an element. Since the trace element is too diluted

to precipitate by traditional means (sometimes less than a part per trillion), it is usually

co-precipitated with a material that has a similar crystalline structure and can incorporate

the desired element. The formation of solid precipitation is followed by the separation of

the solid with a filtration step in the co-precipitation phase. This process is perhaps the

most used to produce ceramic powders. Co-precipitation is the precipitation of a multi-

23
component system. A solution of inorganic or organic salt may be used as a co-

precipitating agent. Because of their strong stoichiometry, purity, homogeneity, and

regulated morphology, organic salt-based co-precipitating agents have favored choices

for large-scale development of fine powders. Inclusion, occlusion, and adsorption are the

three primary processes of co-precipitation. Magnetic nanoparticle synthesis can also be

done using co-precipitation.

[2.2] PREPARATION METHODS OF NANOFLUIDS

Nanofluid is prepared by suspending a small quantity of nanoparticles in base

fluids such as water, ethylene glycol, therminol etc. with or without stabilization

techniques. Generally, nanofluids are prepared by two methods; one-step method and

two-step method [29].

2.2. ONE- STEP METHOD

In this method, the processes of drying, storage, transportation, and dispersion of

nanoparticles are avoided, so the agglomeration of nanoparticles is minimized, and the

stability of fluids is increased. A stable nanofluid is prepared by the Physical Vapor

Deposition (PVD) technique in which direct evaporation and condensation of

nanoparticles are carried in the base fluid. Pure and uniform nanoparticles are produced

by this method. Hence accumulation of nanoparticles is reduced. The main drawbacks of

the one-step method are that the residual reactants are left in the nanofluids and the cost

is high.

2.2.2 TWO-STEP METHOD

This is the most economical method for large-scale preparation of nanofluid. In

a two-step method, the nanoparticles, nanofibers, nanotubes, or other nanomaterials used

are first produced as dry powders by chemical or physical methods. Then, the nano-sized

24
powder will be dispersed into a base fluid in the second processing step with the help of

intensive magnetic force agitation, ultrasonic agitation, high shear mixing,

homogenizing, and ball milling for the desired nanofluid. This production process is

inexpensive and massive. The main drawback of the two-step method is the aggregation

of nanoparticles due to the high surface area and surface activity. The important

technique to enhance the stability of nanoparticles in fluids is the use of surfactants. This

is the commercial method used for the preparation of nanofluids.

Figure 10: Preparation methods for nanofluids

[2.3] GENERAL CHARACTERIZATION TECHNIQUES

During the first decade of the twentieth century, the first observations and

measurements of nanoparticles were made. They are most often identified with the name

Zsigmondy, who studied gold sols and other nanomaterials with sizes as small as 10nm.

He used an ultra-microscope, which uses a technique for seeing particles smaller than the

wavelength of light.

Characterization of the nanomaterials can be done using conventional techniques

developed in Interface and Colloid Science during the twentieth century. Several

25
strategies for characterizing particle size distribution are included in these approaches.

Many materials that are supposed to be nanoscale are aggregated in solutions,

necessitating this characterization. Light scattering is used in some of the processes.

Other ultrasound applications include ultrasound attenuation spectroscopy, which is used

to measure concentrated nano dispersions and microemulsions

X-ray diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Ultraviolet

Visible (UV-Vis) spectroscopy, Infrared (IR) spectroscopy, Scanning Electron

Microscopy (SEM), Tunneling correlation spectroscopy, Wide Angle X-ray Scattering

(WAXS), Small Angle X-ray Neutron Scattering (SAXS/SANS), Energy Dispersive X-

Ray Analysis (EDAX) are the general methods used for the characterization of nano

samples.

2.3.1 X-RAY DIFFRACTION

The dual wave/particle existence of X-rays is used in X-ray diffraction (XRD) to

gain knowledge about the structure of crystalline materials. The technique is primarily

used to identify and characterize compounds based on their diffraction patterns. X-ray

diffraction uses X-rays to determine the geometry or form of a molecule. The elastic

scattering of X-rays from structures with long-range order is the basis for X-ray

diffraction techniques. The dynamical theory of diffraction provides the most detailed

explanation of scattering from crystals. X-ray diffraction is a useful method for

identifying phases and quantifying changes in cell parameters, orientation, crystallite

size, and other structural parameters by comparing data from known structures. It's also

used to figure out the (crystallographic) structure of a novel or unknown crystalline

material (cell parameters, space group, and atomic coordinates). One of the most widely

used methods for determining the crystal structure of materials is X-ray Diffraction

(XRD). Using an automated X-ray diffractometer and special evaluation programs, this

26
technique has become a common procedure. X-ray powder diffraction has been used for

fingerprint characterization and structure determination of crystalline materials. Each

crystalline solid has its own distinct X-ray powder pattern, which can be used to identify

it as a "fingerprint." The crystal structure can also be determined using X-ray

crystallography. The Scherrer equation, the broadening of X-ray diffraction peak can be

used for the calculation of the size of the crystalline nano sample [18].

Instrumentation: X-ray diffractometers consist of three basic elements: an X-ray tube, a

sample holder, and an X-ray detector. X-rays are generated in a cathode ray tube by heating

a filament to produce electrons, accelerating the electrons toward a target by applying a

voltage, and bombarding the target material with electrons. When electrons have sufficient

energy to dislodge inner shell electrons of the target material, characteristic X-ray spectra are

produced. These spectra consist of several components, the most common being Kα and Kβ.

Kα consists, in part, of Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the

intensity as Kα2. The specific wavelengths are the characteristics of a target material (Cu, Fe,

Mo, Cr). Filtering is required to produce monochromatic rays needed for diffraction. Kα1and

Kα2 are sufficiently close in wavelength such that a weighted average of the two is used.

Copper is the most common target material for single-crystal diffraction, with Cu Kα

radiation = 1.5418Å. These X-rays are collimated and directed onto the sample. As the

sample and detector are rotated, the intensity of the reflected X-rays is recorded.

27
 Figure 11: XRD Machine

When the geometry of the incident X-rays impinging the sample satisfies the Bragg

Equation, constructive interference occurs and a peak in intensity occurs. A detector records

and processes this X-ray signal and converts the signal to a count rate which is then output

to a device such as a printer or a computer monitor.

The geometry of an X-ray diffractometer is such that the sample rotates in the

path of the collimated X-ray beam at an angle θ while the X-ray detector is mounted on

an arm to collect the diffracted X-rays and rotates at an angle of 2θ. The instrument used

to maintain the angle and rotate the sample is termed a goniometer. Peak positions occur

where the X-ray beam has been diffracted by the crystal lattice. The unique set of d-spacing

derived from this pattern can be used to ‘fingerprint’ the material.

THEORY

X-ray diffraction is based on constructive interference of monochromatic X-rays and

a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce

monochromatic radiation, collimated to concentrate, and directed toward the sample. The

28
interaction of the incident rays with the sample produces constructive interference (and a

diffracted ray) when conditions satisfy Bragg's Law (nλ=2d sin θ). This law relates the

wavelength of electromagnetic radiation to the diffraction angle and the lattice spacing in a

crystalline sample. These diffracted X-rays are then detected, processed, and counted. By

scanning the sample through a range of 2θangles, all possible diffraction directions of the

lattice should be attained due to the random orientation of the powdered material. Conversion

of the diffraction peaks to d-spacing allows identification of the mineral because each

mineral has a set of unique d-spacings. Typically, this is achieved by comparison of d-

spacing with standard reference patterns.

Scherrer Equation:

Bragg’s law is given by, 2d Sin  = n  ----------------------------------- (1)

For first-order diffraction n=1, then; 2d Sin  =  ------------------------------------- (2)

Multiplying both sides by an integer m such that md = t, the thickness of the crystal

2 md Sin  = m  or, 2t Sin  = m  ------------------------------------(3)

(2) can also be interpreted as the mth order reflection of a set of planes with interplanar

distance ’t’.

Differentiating both sides of (3), remembering m is a constant

2t Cos  ∆ + 2 Sin  ∆t = 0 -------------------------------- (4)

∆ can be positive or negative. Considering magnitude only (4) leads to

29
Since the smallest increment in t is d, using ∆t = d, and substituting /2 for dSin from

(2), we get t= /2θcosθ--------------------------------- (5)

Let 1 =  + ∆, be the highest possible angle that can be got before completing

destructive interference, and let 2 =  - ∆, be the lowest angle that can be got before

completing destructive interference. Now we can interpret 2∆ as the angular width of

the X-ray diffraction line.

In X-ray diffractometer what is recorded is the variation in the intensity of the

diffraction lines with 2. So, in the X-ray diffractogram, we can see diffracted X-rays

overall scattering angles between 21 and 22. If we assume a triangular shape for the

peak, the full width at half minimum (FWHM) will be

β = (21 - 22)/2 = 1 - 2

= ( + ∆) – ( - ∆)

= 2∆------------------------------------------------------------ (6)

30
 Figure 12: Graphical variation of intensity and 2angle

Diffraction from a finite thickness of crystallite

Substituting β for 2∆ in (5) we get; t = / β Cos  --------------------- (7)

This is essentially the Scherrer equation. A more rigorous treatment (using a Gaussian

function rather than a triangular function) gives, t = 0.9/ β Cos  ------------------- (8)

For spherical crystals of diameter/thickness ‘t’ knowing the wavelength () of the X-ray

and analyzing the spectrum, the thickness ‘t’ of the crystalline sample can be determined.

2.3.2 ELECTRON MICROSCOPE

An electron microscope is a type of microscope that illuminates a specimen with

a particle beam of electrons and magnifies the image. The resolving power of an electron

microscope is much greater than that of a light microscope that uses electromagnetic

radiation, and it can achieve magnifications of up to 2 million times. Since the

wavelength of an electron, its de Broglie wavelength, is far smaller than that of a photon

of visible light, the electron microscope can achieve higher resolution and magnification.

31
TYPES

1) Transmission Electron Microscope (TEM)

2) Scanning Electron Microscope (SEM)

3) Reflection Electron Microscope (REM)

4) Scanning Transmission Electron Microscope (STEM)

5) Scanning Tunneling Microscope (STM)

(1) TRANSMISSION ELECTRON MICROSCOPE

For material science, the transmission electron microscope is an extremely useful

instrument. A high-energy electron beam is shone through a very thin sample, and the

interactions between the electrons and the atoms are used to detect characteristics like

the crystal structure and structural features like dislocations and grain boundaries. In

semiconductors, TEM can be used to investigate layer growth, composition, and defects.

Quantum wells, wires, and dots can be analyzed using high resolution to determine their

consistency, form, scale, and density. The transmission electron microscope (TEM) is

the first type of electron microscope, and it creates images using a high-voltage electron

beam. An electron gun, which is usually equipped with a tungsten filament cathode as

the electron source, emits the electrons. The electron beam is accelerated by an anode

that is usually +100 KeV in relation to the cathode, focused by electrostatic and

electromagnetic lenses, and transmitted via a specimen that is partially transparent to

electrons but scatters them out of the beam. The electron beam holds information about

the composition of the specimen as it emerges from the specimen, which is magnified by

the microscope's objective lens system [8]. By projecting the magnified electron image

onto a fluorescent viewing screen coated with a phosphor or scintillator material such as

zinc sulphide, the spatial variance in this information can be seen. The picture can be

32
photographed by directly exposing a photographic film or plate to the electron beam, or

a high-resolution phosphor can be coupled to the sensor of a Charge Coupled Device

(CCD) camera through a lens optical system or a fiber optic light guide. The picture

captured by the CCD can be viewed on a screen or monitor.

Spherical aberration limits TEM resolution, however, a new generation of

aberration correctors have been able to partially resolve spherical aberration and increase

resolution. For high resolution, software correction of spherical aberration is used. At

magnifications of 50 million times, TEM has enabled the creation of images with

sufficient resolution to display carbon atoms in diamond separated by only 0.89 angstrom

and atoms in silicon separated by 0.78 angstrom. The HRTEM has become a valuable

tool for nanotechnology research and development because of its ability to determine the

location of atoms within materials.

Because of the short de Broglie wavelength of electrons, TEMs can image at a

far higher resolution than light microscopes. This allows the instrument to analyze fine

detail, down to a single column of atoms, which is tens of thousands of times smaller

than the smallest resolvable material in a light microscope. In a variety of scientific fields,

including physical and biological sciences, TEM is a popular method of study. TEMs are

used in cancer research, virology, material science, pollution research, and

semiconductor research.

Additional stages and detectors, which are often incorporated on the same

microscope, may enhance the TEM's capabilities. A cryoTEM is an electron microscope

with a specimen holder that can keep the specimen at liquid nitrogen or liquid helium

temperatures.

This enables imaging of specimens prepared in vitreous ice, which is the preferred

method for imaging single or macromolecular assemblies. Max Knoll and Ernst Ruska

33
designed the first TEM in 1931, followed by the first TEM with resolution greater than

that of light in 1933 and the first commercial TEM in 1939.

Figure 13: Transmission Electron Microscope (TEM)

(2) SCANNING ELECTRON MICROSCOPE

The scanning electron microscope (SEM) is a type of electron microscope that

produces a variety of signals at the surface of a solid specimen using a directed beam of

high-energy electrons. The electrons communicate with the atoms in the sample to

produce signals that include details about the sample's surface topography, composition,

and other properties including electrical conductivity. Max Knoll produced the first SEM

image in 1935 when he captured an image of silicon steel with electron channeling

contrast. Manfred Von Andenne, who developed a British patent but never made a

practical instrument, did further pioneering work on the physical principles of the SEM

34
and beam specimen interactions in 1937. Professor Sir Sharles Oatley and his

postgraduate student Gary Stewart further invented the SEM, which was first sold in

1965 by the Cambridge Instrument Company as the "stereo scan." Dupont was the first

to receive the instrument.

The shape, size, and arrangement of the object's particles that are lying on the

sample's surface or have been revealed by grinding or chemical etching; detectable

features limited to a few manometers. Only useful on single-crystal particles >20

micrometers is the arrangement of atoms in the specimen and their degree of order.

Figure 14: Scanning electron microscope

(3) REFLECTION ELECTRON MICROSCOPE

An electron beam is incident on a surface in the reflection electron microscope,

just as it is in the TEM, but instead of transmitting secondary electrons, the reflection

beam of elastically dispersed electrons is observed. This method is often used in

conjunction with RHEED (Reflection High Energy Electron Diffraction) and RHELS

(Reflection High Energy Loss Spectrum).

(4) SCANNING TRANSMISSION ELECTRON MICROSCOPE

35
 The STEM raster an oriented incident probe through a thinned specimen to detect

electrons dispersed across the specimen. STEM may thus benefit from the TEM's high

resolution. In the STEM, the focusing happens before the electrons reach the specimen,

but in the TEM, it happens afterward. The STEM's use of SEM-like beam rastering

makes annular dark-field imaging and other analytical techniques easier, but it also

ensures image data acquired in serial rather than parallel.

(5) SCANNING TUNNELING MICROSCOPE

A scanning tunneling microscope is an effective tool for examining surfaces at

the atomic level. Its inventors, Gerd Binnig and Heinrish Rohrer, were awarded the Nobel

Prize in Physics in 1986 for their work in 1981. The tunneling current is used in STM to

probe a material's density of states. In STM, a good resolution is described as a lateral

resolution of 0.1nm and a depth resolution of 0. 01nm.The STM can be used in a variety

of environments, including air, liquids, and gases, and at temperatures varying from near

zero Kelvin to a few hundred degrees Celsius. The STM is focused on the quantum

tunneling principle.

2.3.3 BROOKFIELD DV-II+PRO VISCOMETER

The Brookfield DV-II+Pro Viscometer measures fluid viscosity at given shear

rates. Viscosity is a measure of a fluid’s resistance to flow. The principle of operation of

the DV-II+Pro is to drive a spindle (which is immersed in the test fluid) through a

calibrated spring. The viscous drag of the fluid against the spindle is measured by the

spring deflection. Spring deflection is measured with a rotary transducer. The

measurement range of a DV-II+Pro (in centipoise or millipascal seconds) is determined

36
by the rotational speed of the spindle, the size and shape of the spindle, the container the

spindle is rotating in, and the full-scale torque of the calibration spring.

There are four basic spring torque series offered by Brookfield: Model and corresponding

Spring Torque (dyne/cm) is given by,

a. LVDV-II+Pro - 673.7

b. RVDV-II+Pro - 7,187.0

c. HADV-II+Pro - 14,374.0

d. HBDV-II+Pro - 57,496.0

Figure 15: Viscometer DV-II+ PRO

CHAPTER-3

IMPORTANCE OF SELECTED MATERIALS AND

PREPARATIONS

[3.1] IMPORTANCE OF SELECTED MATERIALS

CuO, categorized into the transition metal oxide group, is a p-type, narrow

bandgap (1.2 eV) semiconductor. It has a melting point of 1201°C and a boiling point of

37
2000°C. The density of CuO nanoparticles is 6.31g/cm3 and its molar mass is

79.55g/mol. It has a monoclinic structure and many interesting characteristics like

superthermal conductivity, photovoltaic properties, high stability, and antimicrobial

activity. Due to such exclusive properties, CuO can be used in many technological fields,

for example, active catalysts, gas sensors, high-efficiency thermal conducting material,

magnetic recording media, with very good selectivity, or solar cell applications. In

addition to some shared properties of metal oxide nanostructures, such as TiO2, ZnO,

WO3, and SnO2, CuO nanostructures have other unique magnetic and superhydrophobic

properties. Furthermore, these nanostructures show very promising applications in

heterogeneous catalysis in the complete conversion of hydrocarbons into carbon dioxide,

enhancement of thermal conductivity of nanofluid, nano energetic materials, and super-

hydrophobic surfaces or anode materials for lithium-ion batteries (LIBs). However, this

material has not got the attention of scientists at right level until recent years. Compared

with other oxides of transition metal such as Fe2O3, TiO2, and ZnO only few reports have

described the synthesis strategies adopted for CuO nanostructures along with the

introduction of their related applications.

Barium Oxide (BaO) is a highly insoluble thermally stable Barium source

suitable for glass, optic and ceramic applications. It is a white hygroscopic solid often

formed through the decomposition of barium salts, it forms barium hydroxide when

reacted with water. It has a melting point of 3493°F (1923°C) and a boiling point of about

3632°F (~2000°C). The nanoparticles have a molecular weight of 153.3 grams and a

density of 5720 Kg/m3. It has good fluxing properties and good colour response.

Barium oxide is used as a coating for hot cathodes, for example, those in

cathode ray tubes. It replaced lead (II) oxide in the production of certain kinds of glass

38
such as optical crown glass. While lead oxide raised the refractive index, it also raised

the dispersive power, which barium oxide does not alter. Barium oxide also has use as

an ethoxylation catalyst in the reaction of ethylene oxide and alcohols, which takes place

between 150 and 200°C. It is also a source of pure oxygen through heat fluctuation. It

readily oxidizes to BaO2 by the formation of a peroxide ion. The complete peroxidation

of BaO to BaO2 occurs at moderate temperatures but the increased entropy of the O2

molecule at high temperatures means that BaO2 decomposes to O2 and BaO at 1175K.

The reaction was used as a large-scale method to produce oxygen before air separation

became the dominant method in the beginning of the 20th century. The method was

named the Brin process, after its inventors.

Therminol is a thermally stable heat transfer fluid with a high boiling point and

low vapor pressure. Boosting the heat conductivity of therminol is a potential way to

increase the efficacy of therminol-based systems. It will improve performance while

compensating for the drawback of poor thermal system performance. It is believed to be

more efficient than traditional fluids. It is one of the heat transfer fluids that have lately

been used in medium-temperature solar thermal collectors and other industries.

Therminol has a comparatively low freezing point but with high boiling point. The

limited heat conductivity of therminol oil is one of its most severe drawbacks. It was used

as the base fluid for the fabrication of CuO-BaO-based nanofluid. It exhibits a

considerable shift in heat conductivity and viscosity. To assess the potential changes in

the thermal conductivity of the base fluid, thorough tests were carried out at various

temperatures of CuO-BaO nanocomposites.

[3.2] PREPARATIONS

3.2.1 SYNTHESIS OF COPPER OXIDE-BARIUM OXIDE NANOCOMPOSITE

39
 Copper Oxide-Barium Oxide (CuO-BaO) nanocomposite was prepared through

the chemical co-precipitation method using Copper Nitrate and Barium Nitrate as the

major reagents. 50ml solutions of 0.1 molar Copper Nitrate and 0.1 molar Barium Nitrate

were prepared and mixed well in a conical flask. 0.5 molar solution of NaOH was allowed

to fall drop by drop into a conical flask containing the prepared solution and 0.02 molar

citric acid, which acts as the capping agent. The whole reagents in the conical flask are

mixed well using a magnetic stirrer. After a few hours, the solution is precipitated. Then

the mixture is allowed to settle down and nanoparticles are filtered using filter paper and

it is washed several times by using distilled water to remove the impurities. The

precipitate is dried under sunlight. Then it is powdered using an agate motor to obtain

the metal precursor in the form of fine powder. On heating the sample at a temperature

of 8000C, the hydroxide precursor decomposes to form their corresponding metal oxides,

and thereafter the sample is subjected to XRD characterizations.

3.2.2 PREPARATION OF COPPER OXIDE-BARIUM OXIDE NANOFLUID

In the next step, the synthesized CuO-BaO nanocomposite was made to suspend

in the therminol fluid and stirred for an hour. The suspension is then agitated at 4000Hz

using an ultrasonication agitator which results in the formation of a nanofluid. Later, the

viscosity and thermal conductivity of the nanofluid is investigated.

40
CHAPTER-4

RESULTS AND DISCUSSIONS

[4.1] ANALYSIS OF XRD PATTERN

X-Ray Diffraction (XRD) pattern reveals that the particles are nanosized and

crystalline in nature. The sharp peaks obtained from the XRD patterns indicate the

crystalline nature of the sample. The XRD patterns are drawn by using angle (2Ɵ) along

the X-axis and intensity (counts) along the Y-axis. The XRD patterns of Copper Oxide-

Barium Oxide nanocomposite annealed at 8000C are shown below in Figure 17. The

particle sizes are calculated using the Scherrer equation, d = 0.9/Cos[9], which 

represents the full width at half maximum (FWHM) of XRD lines,  = 1.54060 [Å].

Using the β-values obtained from the XRD analysis, the average particle size of the

nanocomposites is found. The particle size was found to be 39nm for the Copper Oxide-

Barium Oxide nanocomposite. The broadening of the peaks in the XRD pattern may be

due to the microstraining of the crystal structures arising from defects like dislocations

and twinning. These are believed to be associated with chemically synthesized

nanocrystals. As the crystals grow spontaneously during a chemical reaction, the ligands

take negligible time to diffuse to an energetically favorable site resulting in large crystal

defects [7].

41
Figure 16: XRD Pattern of Copper Oxide-Barium Oxide nanocomposite annealed at

8000C

[4.2] VISCOSITY STUDIES

Figure 17 represent the viscosity of nanofluid measured at different temperatures ranging

from 30°C to 50°C, at a step size of 5°C. As the temperature increases, the viscosity of

Copper Oxide-Barium Oxide nanofluid decreases. It was observed that at temperature

30°C, the viscosity equals 42.50cP and at temperature 40°C, the viscosity equals 27.50

cP. From this data it is clear that as the temperature of nanofluid increases from 30°C to

40°C, a decrease of 15cP has been observed for the viscosity. Moreover, when the

temperature increases from 300C to 50oC the viscosity shows a decrease of 25 cP. Higher

temperatures can enhance the fluidity of the base fluid, making it easier for nanoparticles

to move within the fluid. Improved fluidity can promote better dispersion of

nanoparticles, preventing them from agglomerating. When nanoparticles are well-

dispersed, they experience less resistance to flow, leading to lower viscosity . At higher

temperatures, the interparticle forces between nanoparticles, such as van der Waals

42
forces, may weaken. Weaker forces between particles result in reduced resistance to flow,

leading to a lower viscosity.

Figure 17: Viscosity variation of Copper Oxide-Barium Oxide nanofluid with

temperature

[4.3] THERMAL CONDUCTIVITY STUDIES

Figure 18 shows the variation of thermal conductivity of the prepared nanofluid

at various temperatures. The thermal conductivity of CuO-BaO nanofluid increased

43
with an increase in temperature of the nanofluid. Several researchers investigated the

effect of nanoparticle concentration in nanofluid. Some of them discovered the thermal

conductivity relation to be linear while some others found it non-linear. From the graph,

it is clear that when the temperature of the nanofluid is at 30°C, the thermal

conductivity is 0.139W/mK and when the temperature of the nanofluid is further

increased to 40°C, the thermal conductivity also shows an increase to 0.145W/mK.

Therefore, we can conclude that as the temperature increases from 30°C to 40°C, the

thermal conductivity also increased by 0.006W/mK. Furthermore, when the

temperature increases from 30oC TO 50OC, the thermal conductivity increases by

0.008W/mK. The inclusion of nano-sized particles as heat carriers improves the

thermal conductivity of TH-66 oil. The enhancement in thermal conductivity is

attributed to several factors including temperature, concentration gradients, and forces

acting on the nanoparticles. These forces cause different types of motions like

thermophoretic motion, osmophoretic motion, and Brownian motion. Thermophoretic

motion refers to the movement of particles in response to temperature gradients.

Osmophoretic motion, on the other hand, involves the movement of particles due to the

concentration gradients. Both of these motions can contribute to increasing the thermal

conductivity of nanofluids. Brownian motion is the random movement of small

particles suspended in a fluid due to collisions with other particles. In the case of

nanofluids, the collision of nanoparticles with each other is responsible for the elevated

heat transfer property of the nanofluids .

44
Figure 18: Variation in thermal conductivity of Copper oxide–Barium oxide
nanofluid with temperature

45
CONCLUSION

The nanocomposite of Copper Oxide-Barium Oxide (CuO-BaO) was

synthesized through the chemical co-precipitation method. XRD patterns of the

samples reveal that they were nanocrystalline in nature. The broad and sharp peaks

were the characteristics of the nanocrystalline nature of the samples. The average

particle size of the nanocomposite was calculated using the Scherrer equation. The

particle size of CuO-BaO nanocomposite was found to be 39nm. Further, the nanofluid

was prepared by a two-step method by dispersing CuO-BaO nanocomposite into a

base-fluid, therminol. It was observed that the viscosity decreases with the rise in

temperature of the mixture. When the temperature of the nanocomposite increased

from 30oC to 40oC, a decrease of 15cP has been observed in viscosity of CuO-BaO

nanofluid. The study also concludes that, as the temperature increased from 30°C to

40°C, the thermal conductivity increased correspondingly by 0.006W/mK.

46
FUTURE SCOPE

The nanocomposite of CuO-BaO was synthesized through the chemical co-

precipitation method. Other methods of synthesis with different particle sizes and surface

morphologies can also employed for the same. This nanocomposite may exhibit unique

catalytic, chemical, mechanical, electrical, and ion exchange properties compared with

their counterparts such as the nanoparticles of copper oxide and barium oxide to use them

for future technological applications. The nanofluid prepared using the nanocomposite

may exhibit immense applications by improving heat transfer properties and energy

efficiency in several areas such as automobiles, micro-electronics, nuclear, space, power

generation, etc. We know that the National Education Policy 2020 has proposed the

introduction of a four-year undergraduate degree, with multiple exit options and

opportunities for skill development. Our work has been done from a multidisciplinary

perspective, thereby providing opportunities for wider areas of exploration.

47
REFERENCE

1. Z Wang, Y Liu, Z Zhang, Handbook of nanophase and nanostructure material,

2002.

2. J Cami, J Bernard-Salas, E Peeters, S E Malek, Detection of C60 and C70 in a

Young Planetary Nebula,2010.

3. J Clark, T Frost, and M. A. Russell, UV spectroscopy: techniques,

instrumentation, data handling, Chapman & Hall, 1993.

4. C J Brinker, BC Bunker, D R Tallant, K J Ward, R J Kirkpatrick, Structure of

Sol-Gel Derived Inorganic Polymers: Silicates and Borates, 1988, Vol. 360.

5. C J Brinker, S W Scherer, Sol-Gel Science: the physics and chemistry of sol-gel

processing, 1990.

6. C K Mann, T J Vickers, and W WGulick, Instrumental analysis, Harper & Row,

1974.

7. D Mohanta, S SNath, N C Mishra and A Choudhury, Bull. Mater. Sci, 2003.

8. David B Williams and C Barry Carter, Transmission electron microscopy, 1996.

9. H C Warad, S CGhosh and Hemtanon, Sci. Technol. Adv. Mater. 6, 2005.

10. N.Ramjeyanthi, M. Alagar, D.Muthuraman, Synthesis, Structural and Optical

Characterization of Uncalcined Lanthanum Oxide Nanoparticles by Co-

Precipitation Method. International Journal of Interdisciplinary Research and

Innovations.Vol. 6, Issue 3, pp: (389-395), Month: July - September 2018.

11. A Alimuddin and MRafeeq,Synthesis and Characterization of Copper Oxide

Nano Particle by Sol-Gel Method. Orient J Chem2021.

12. H HPerkampus, UV-VIS spectroscopy and its applications, Springer-Verlag,

Berlin, Germany, 1992.

48
13. J H Park, J Y Kim, B D Chin, Y C Kim, J K Kim, and O O Park, Nanotechnology

15, 2004.

14. A Guinier, X-ray diffraction in Crystals, Imperfect Crystals, and Amorphous

Bodies. San Francisco: W.H. Freeman & Co., 1963.

15. Touloukian, Thermal Expansion of Nonmetallic

Solids,ThermophysicalProperties of Matter,1977,Vol 13.

16. K Nagaveni, M S Hedge, N Ravishankar, G N Subbanna, G Madras, Langmuir

20, 2004.

17. Kenneth J Klabunde, Nanoscale Materials in Chemistry Wiley InterScience,

2001.

18. L V Azaroff, Elements of X-ray Crystallography, 1968.

19. M H Bhat, B P Chakravarthy, P. A Ramakrishnan, A Levasseur, K J Rao, Bull.

Mater. Sci. 23, 2000.

20. A D Yoffe, Advances in Physics 50, 2001.

21. O Carp, C L Huisman, AReller, Progress in Solid State Chem, 2004.

22. P W Atkins and J de Paula, Atkins Physical Chemistry, 2002, 7th edition.

23. P W Atkins and R S Friedman, Molecular Quantum Mechanics, 1997, 3rd edition.

24. Peter Hrisch, Electron microscopy of crystals, 1965.

25. R W Jones, Fundamental Principles of Sol-Gel Technology, 1989.

26. Y.Naresh,A.Dhivya,K.S.Suganthi,andK.S.Rajan,“High-temperaturethermo-

physicalpropertiesofnovel CuO-therminol®55 nanofluids

27. Vajjha, R. S., and Das, D. K.,Specific Heat Measurement of Three Nanofluids

and Development of New Correlations, 2009

28. A. Bianco, K. Kostarelos, and M. Prato, ―Applications of carbon nanotubes in

drug delivery,2008

49
29. X. Zhang, and J. Huang, ―Preparation and melting/freezing characteristics of

Cu/paraffin nanofluid as phase-change material (PCM),‖( Energy and Fuels

vol.24),2009

30. C R Indulal, S Cuuthy, Leo Binoy, R Ravikumar, and Waseem Gani,

―Lanthanum Oxide-Barium Oxide Nanofluid With Enhanced Thermal

Engineering Application, 2023

50