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Lesson 11 - Nanomaterials

The document provides an overview of nanomaterials, defining them as materials with dimensions in the range of 1-100 nm, and discusses their unique properties and classifications based on dimensionality, composition, and origin. It highlights various applications of nanomaterials across fields such as electronics, medicine, energy, and environmental management, emphasizing their potential for innovation and efficiency improvements. Additionally, the document outlines the role of nanotechnology in advancing scientific research and technological developments.

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0% found this document useful (0 votes)
40 views17 pages

Lesson 11 - Nanomaterials

The document provides an overview of nanomaterials, defining them as materials with dimensions in the range of 1-100 nm, and discusses their unique properties and classifications based on dimensionality, composition, and origin. It highlights various applications of nanomaterials across fields such as electronics, medicine, energy, and environmental management, emphasizing their potential for innovation and efficiency improvements. Additionally, the document outlines the role of nanotechnology in advancing scientific research and technological developments.

Uploaded by

monyeidavid13
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TOPFAITH UNIVERSITY, MKPATAK

FACULTY OF ENGINNERING
GET 202: ENGINEERING MATERIALS
Lesson 11: Nanomaterials

1.0 Introduction to Nanomaterials


The word nano is a unit prefix that originated from the Greek word that means dwarf or similar.
In fact, one nanometre (nm) is a billionth of a meter (i.e. 1 nm = 10-9m = 10Å). or one millionth
of a millimetre. Human hair, for instance, is about 80,000 to 100,000 nanometres and 1nm is
approximately 100,000 times smaller than the diameter of a human hair. These materials are
invisible to the naked eye. This size range is crucial because it imparts unique physical,
chemical, and biological properties to the materials that are not observed in their bulk
counterparts. Nanomaterials show unique properties like increased strength, toughness,
hardness, ductility, melting point, efficient electrical properties, magnetic properties, catalytic
properties, optical properties, and so on as compared to bulk materials.
At the nanoscale, materials exhibit increased surface area to volume ratios, quantum effects,
and other phenomena that can significantly alter their behaviour and interactions. This range is
called the nanoscale or nanoscopic or nanometric range. Nanomaterials can occur naturally, be
created as the by-products of combustion reactions, or be produced purposefully through
engineering to perform a specialised function.
1.1 Definition of Nanomaterials
Nanomaterials are materials having at least one of their dimensions (length or width or height)
in the range of 1-100 nm. On 18 October 2011, the European Commission adopted the
following definition of a nanomaterial: A natural, incidental or manufactured material
containing particles, in an unbound state or as an aggregate or as an agglomerate and for 50%
or more of the particles in the number size distribution, one or more external dimensions is in
the size range 1 nm – 100 nm. In specific cases and where warranted by concerns for the
environment, health, safety or competitiveness the number size distribution threshold of 50%
may be replaced by a threshold between 1% to 50%.
In ISO/TS 80004, nanomaterial is defined as the "material with any external dimension in the
nanoscale or having internal structure or surface structure in the nanoscale",
with nanoscale defined as the "length range approximately from 1 nm to 100 nm". This
includes both nano-objects, which are discrete pieces of material, and nanostructured

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materials, which have internal or surface structure on the nanoscale; a nanomaterial may be a
member of both these categories.
1.2 Nanotechnology
Nanotechnology is the field of science and engineering dedicated to the design, production,
characterisation and application of materials, structures, devices, and systems by manipulating
atoms and molecules at nanoscales (about 1 - 100 nanometres). Nanomaterials have larger
surface area to volume ratio which impacts reactivity.
2.0 Classification of Nanomaterials
These materials can be categorized based on their dimensions, composition, and origin, which
differentiate them from their bulk counterparts.
2.1 Based on Dimensionality: Nanomaterials can be broadly classified into several
categories based on their dimensions. (figure 1)

Figure 1: Classification of Nanomaterials (a) 0D spheres and clusters; (b) 1D nanofibers,


nanowires, and nanorods; (c) 2D nanofilms, nanoplates, and networks; (d) 3D nanomaterials.

2.1.1 Zero-Dimensional (0D) Nanomaterials: These are materials where all three
dimensions are in the nanoscale. Examples include nanoparticles, nanospheres, and
nanoclusters. They are often used in biomedical applications, including drug delivery and
imaging, due to their small size and high surface area.
2.1.2 One-Dimensional (1D) Nanomaterials: These materials have one dimension outside
the nanoscale. Examples include nanowires, nanotubes, and nanorods. One-dimensional
nanomaterials are used in electronics and photonics for their ability to conduct electricity and
light efficiently along their length.
2.1.3 Two-Dimensional (2D) Nanomaterials: These materials have two dimensions outside
the nanoscale. Examples include graphene, nanofilms, and nanocoatings. Two-dimensional
nanomaterials are known for their excellent mechanical, electrical, and thermal properties and
are used in applications ranging from flexible electronics to barrier coatings.
2.1.4 Three-Dimensional (3D) Nanomaterials: These materials have three dimensions
outside the nanoscale but contain nanoscale features, such as nanocomposites and

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nanostructured bulk materials. Three-dimensional nanomaterials combine the properties of
their nanoscale components with those of bulk materials, making them suitable for structural
applications and advanced material design.
2.2 Based on Composition:
2.2.1 Carbon-based nanomaterials: Carbon-based nanomaterials are composed of carbon
include five main materials, namely, carbon nanotubes, Graphene, fullerenes, Carbon Nano
fibre and Carbon black as shown in Figure 3. Spherical and ellipsoidal nature configured of
carbon nanomaterials are referred as fullerenes are called Bucky balls. Fullerenes are the
spherical structure with diameters up to 8.2 nm for a single layer and from 4 to 36 nm for multi-
layered fullerenes, which form from 28 to 1500 carbon atoms.
2.2.2 Metal-based nanomaterials: Silver, gold, zinc oxide, titanium dioxide nanoparticles.
Metal-Based Nanomaterials: Nanoparticles based on Metals such as gold, silver, and platinum
at the nanoscale. These particles are used in catalysts, sensors, and medical imaging. Quantum
Dots, in which Semiconductor particles that possess quantum mechanical properties. They are
used in applications like solar cells, medical imaging, and quantum computing.
2.2.3 Ceramic-based nanomaterials: Ceramic nanomaterials are inorganic solids made up
of carbides, carbonates, oxides, carbides, carbonates, and phosphates synthesized via heat and
successive cooling. The ceramic nanoparticles can be formulated in drug delivery systems,
especially in targeting tumours, glaucoma, and some bacterial infections and nanomaterials are
also getting great attention from researchers due to their use in applications such as catalysis,
photo catalysis, photo degradation of dyes, and imaging applications
2.2.4 Polymeric nanomaterials: Polymer-based nanomaterials are solid colloidal particles
with a particle size of 10–500 nm. They are used for controlled release of drugs. These materials
are biocompatible, cost-effective, biodegradable, and efficient nanocarriers for drug delivery
to specific target cells. They include dendrimers, nanogels, nanocapsules.
2.2.5 Composite nanomaterials: Composites Nanomaterials are made up of nanoparticles
combined with other nanoparticles, nanoparticles combined with larger-scale materials, and
nanomaterials combined with bulk-type materials. Nanomaterials are already being used to
improve mechanical, thermal, and flame-retardant properties in products ranging from auto
parts to packaging materials.
2.2.6 Metal oxide nanoparticles:
Metal oxide nanoparticles, also known as metal oxide nanomaterials, are composed of positive
metallic ions and negative oxygen ions. Examples of metal oxide nanoparticles that are
frequently synthesized include silicon dioxide (SiO2), titanium oxide (TiO2), zinc oxide
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(ZnO), and aluminium oxide (Al2O3). These nanoparticles exhibit remarkable properties
compared to their metal analogs.
2.2.7 Semiconductor nano materials
Semiconductor nanomaterials exhibit the same properties as metals and insulators. They are
classified into three groups.
1. Concentrated magnetic semiconductor nanomaterials. It exhibits spontaneous magnetic
order and can be a binary compound such as EuTe (anti-ferromagnetic).
2. Non-magnetic semiconductor nanomaterials. Nonmagnetic semiconductors that contain no
magnetic ions and are used for information processing and communications have had great
success using the charge of electrons in semiconductors but are not used for mass storage of
information in dispensable information technology.
3. Diluted magnetic semiconductor nanomaterials. The semiconducting materials are made
magnetic by adding a few magnetic impurities to the host matrix, in which some of the
diamagnetic host cations are randomly replaced by magnetic (TM) cations. These materials not
only retain semiconducting properties, but also possess magnetic properties that are a mixture
of ordinary and magnetic semiconductors.
2.3 Based on Origin
Natural, engineered and incidental nanoparticles are the three groups into which nanomaterials
are divided based on origin.
2.3.1 Natural nanomaterials: Natural nanomaterials can be found in a variety of forms in
nature, including viruses, protein molecules, minerals like clay, natural colloids like milk and
blood (liquid colloids), fog (aerosol type), gelatin (gel type), mineralized natural materials like
shells, corals, and bones, insect wings and opals, spider silk, lotus leaves, gecko feet, volcanic
ash, and ocean spray.
2.3.2 Engineered nanomaterials: Engineered nanomaterials have been deliberately
engineered and manufactured by humans to have certain required properties. Carbon nanotubes
and semiconductor nanoparticles like quantum dots (QDs) are examples of artificial
nanomaterials that are made consciously using precise mechanical and manufacturing
procedures. Nanomaterials are categorized as metal-based materials, dendrimers, or
composites depending on their structural makeup
2.3.3 Incidental nanomaterials: Nanomaterials may be unintentionally produced as a
byproduct of mechanical or industrial processes through combustion and vaporization. Sources
of incidental nanoparticles include vehicle engine exhausts, smelting, welding fumes,
combustion processes from domestic solid fuel heating and cooking. For instance, the class of
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nanomaterials called fullerenes are generated by burning gas, biomass, and candle. It can also
be a byproduct of wear and corrosion products.
3.0 Applications of Nanomaterials
The scope of nanomaterials extends across various scientific disciplines and industries,
reflecting their versatility and significant potential for innovation.
3.1 Scientific Research and Development: The study of nanomaterials is a rapidly evolving
field within scientific research. It involves the synthesis, characterization, and manipulation of
materials at the atomic and molecular levels. Researchers investigate the fundamental
principles governing the behaviour of nanomaterials to understand how their unique properties
arise and how they can be harnessed for practical applications. This research spans physics,
chemistry, biology, materials science, and engineering.
3.2 Electronics and Computing: Nanomaterials play a pivotal role in the advancement of
electronics and computing technologies. Their small size and exceptional electrical properties
make them ideal for creating faster, smaller, and more efficient electronic devices. For
example, carbon nanotubes and graphene are being explored for use in transistors, sensors, and
flexible electronics. Quantum dots are utilized in displays and solar cells, enhancing their
performance and efficiency.
3.3 Medicine and Healthcare: In the medical field, nanomaterials offer revolutionary
possibilities for diagnosis, treatment, and drug delivery. Nanoparticles can be engineered to
target specific cells or tissues, allowing for precise drug delivery with minimal side effects.
They are also used in imaging techniques to provide high-resolution images of biological
structures, aiding in early disease detection. Additionally, nanomaterials are being developed
for applications such as tissue engineering, regenerative medicine, and biosensors.
3.4 Energy: The energy sector benefits significantly from nanomaterials through improved
energy storage and conversion technologies. Nanomaterials enhance the performance of
batteries and supercapacitors, leading to longer-lasting and faster-charging energy storage
solutions. For instance, silicon nanowires and carbon nanotubes are used to create high-
capacity lithium-ion batteries. In solar energy, nanomaterials like perovskite nanoparticles
improve the efficiency of photovoltaic cells, making solar power more viable and cost-
effective. Nanomaterials also play a role in developing fuel cells and hydrogen storage systems,
contributing to cleaner and more sustainable energy solutions.
3.5 Oil and gas: The application of nanotechnology in enhanced oil recovery (EOR) involves
the injection of fluids with some nano ultra-fine particles which interacts with the rock-oil
system to create a favourable environment for oil recovery.
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3.6 Environment: Nanomaterials are crucial in addressing environmental challenges through
pollution control and resource management. They are used in water purification systems to
remove contaminants, including heavy metals and organic pollutants, with high efficiency.
Nanomaterials like titanium dioxide nanoparticles can degrade harmful substances through
photocatalysis, breaking down pollutants into less harmful compounds. In air purification,
nanomaterials help capture and neutralize pollutants, contributing to cleaner air. Additionally,
nanotechnology enables the development of sustainable agricultural practices, such as
controlled-release fertilizers and pesticides, reducing environmental impact and improving
crop yields.
3.7 Materials and Manufacturing: The incorporation of nanomaterials into traditional
materials can enhance their properties and performance. For instance, adding carbon nanotubes
to polymers can improve their strength, conductivity, and thermal stability. Nanocomposites
are used in a wide range of applications, from aerospace and automotive components to sports
equipment and consumer products. Nanostructured coatings provide improved durability,
corrosion resistance, and self-cleaning properties.
3.8 Cosmetics and Personal Care: Nanomaterials are increasingly used in the cosmetics and
personal care industry. They are incorporated into products such as sunscreens, anti-aging
creams, and hair care products to improve their effectiveness and delivery. For example, zinc
oxide and titanium dioxide nanoparticles are used in sunscreens for their superior UV-blocking
properties, providing better protection against harmful radiation.
3.9 Agriculture and Food: In agriculture, nanomaterials are being explored for applications
such as precision farming, where they can deliver nutrients or pesticides directly to plants,
reducing waste and environmental impact. In the food industry, nanomaterials are used for
packaging to improve shelf life and safety. They can also be employed in sensors for
monitoring food quality and detecting contaminants.
3.10 Defence and Security: Nanomaterials have applications in defence and security,
including the development of advanced materials for protective gear, sensors for detecting
chemical and biological threats, and components for stealth technology. Their unique
properties enable innovations in lightweight armour, explosives detection, and secure
communication systems.
3.11 Aerospace and Automotive: Nanocomposites reduce the weight of vehicles and
aircraft, leading to improved fuel efficiency and performance. Nanomaterials improve the
efficiency and lifespan of lubricants and fuels by reducing friction and wear.

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4.0 Scientific Application of Nanomaterials
4.1 Technological Advancements: Nanomaterials play a critical role in driving technological
advancements across various fields. In electronics, for example, the miniaturization of
components is made possible by nanomaterials. This has led to the development of smaller,
faster, and more efficient electronic devices. Semiconductors at the nanoscale, such as quantum
dots and nanowires, are fundamental to the production of advanced transistors and memory
devices. These materials enable higher performance and lower power consumption, which are
essential for modern computing and communication technologies. In the realm of energy,
nanomaterials contribute significantly to the development of more efficient energy storage and
conversion systems. Nanostructured materials are used in batteries, supercapacitors, and fuel
cells to enhance their performance. For instance, lithium-ion batteries with nanostructured
anodes and cathodes have higher energy densities and longer life cycles. Additionally,
nanomaterials are employed in solar cells to improve light absorption and conversion
efficiency, paving the way for more cost-effective and sustainable solar energy solutions.
4.2 Medical Applications: The medical field has seen revolutionary changes due to the
integration of nanomaterials. Nanomedicine, which involves the use of nanomaterials for
diagnosis, treatment, and monitoring of diseases, has opened new frontiers in healthcare.
Nanoparticles are used for targeted drug delivery, ensuring that medications are delivered
directly to diseased cells, minimizing side effects and improving therapeutic efficacy. For
example, liposomes and dendrimers can carry drugs and release them at specific sites within
the body. Furthermore, Gold nanoparticles are used in cancer therapy for targeted drug delivery
and hyperthermia treatment, where they heat up and kill cancer cells upon exposure to certain
types of light. Additionally, quantum dots and other nanomaterials are employed in imaging
techniques to provide high-resolution images, aiding in early disease detection and accurate
diagnostics.
4.3 Environmental Impact: Nanomaterials also offer solutions for environmental challenges.
They are used in water treatment processes to remove contaminants more efficiently than
conventional methods. Nanomaterials such as titanium dioxide and silver nanoparticles have
antimicrobial properties and can be employed in filtration systems to purify water. In addition,
nanomaterials play a role in pollution control and environmental remediation. Nanocatalysts
can break down pollutants in the air and water, reducing environmental damage. For instance,
nanoparticles of iron are used to degrade organic contaminants in groundwater.
4.4 Material Science and Engineering: The field of material science and engineering has
been transformed by the advent of nanomaterials. These materials exhibit superior mechanical,
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electrical, thermal, and optical properties compared to their bulk counterparts. For example,
carbon nanotubes and graphene have exceptional strength and conductivity, making them ideal
for developing lightweight and high-performance composite materials. Nanomaterials also
enable the creation of new types of materials with tailored properties. By manipulating the size,
shape, and composition of nanoparticles, scientists can design materials with specific
characteristics for various applications. This ability to engineer materials at the nanoscale has
led to innovations in fields such as aerospace, automotive, and construction.
4.5 Industrial Applications: In various industrial applications, nanomaterials enhance product
performance and durability. They are incorporated into coatings and paints to provide
properties such as scratch resistance, UV protection, and antimicrobial effects. For example,
silver nanoparticles are used in textiles and surfaces to prevent bacterial growth. In
construction, nanomaterials like carbon nanotubes and nanoclays are added to materials to
improve strength and reduce weight, leading to more durable and efficient structures. The
automotive and aerospace industries also benefit from nanomaterials, with applications ranging
from lightweight composite materials to advanced lubricants and fuel additives
4.6 Scientific Research: The study of nanomaterials has deepened our understanding of
fundamental scientific principles. Research in this field has provided insights into quantum
mechanics, surface chemistry, and material behaviour at the atomic and molecular levels.
Techniques developed for studying nanomaterials, such as electron microscopy and
spectroscopy, have advanced our ability to observe and manipulate matter at unprecedented
scales.
5.0 Types of Nanomaterials
There are various Types of Nanomaterials:
5.1 Dendrimers: Branched, tree-like structures that are synthesized from monomer units.
Dendrimers have a high degree of surface functionality and versatility, useful in drug delivery
and material science.
5.2 Nanoclays: Naturally occurring or synthetically produced clay materials at the nanoscale.
They improve mechanical and thermal properties of polymers and are used in packaging,
automotive parts, and coatings.
5.3 Biological Nanomaterials: Materials derived from biological sources, such as proteins,
DNA, and viruses. These are used in biotechnology and medical applications, including drug
delivery systems and biosensors.
5.4 Nanoparticles: Nanoparticles are one of the most common forms of nanomaterials. They
can be made from metals, metal oxides, polymers, and other materials. Gold nanoparticles, for
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instance, are used in medical diagnostics and treatments due to their biocompatibility and
unique optical properties. Silver nanoparticles have antimicrobial properties and are used in
coatings and textiles to prevent bacterial growth.
5.5 Nanotubes and Nanowires: Carbon nanotubes (CNTs) and various nanowires (such as
silicon nanowires) are prominent examples of one-dimensional nanomaterials. CNTs are
renowned for their exceptional strength, electrical conductivity, and thermal conductivity,
making them valuable in composite materials, electronics, and energy storage. Nanowires, with
their high aspect ratio and electrical properties, are crucial in developing nanoscale electronic
devices and sensors.
5.6 Nanofilms and Nanocoatings: These are thin layers of material applied at the nanoscale.
Graphene, a single layer of carbon atoms arranged in a hexagonal lattice, is a notable example
of a 2D nanomaterial. Its extraordinary mechanical strength, electrical conductivity, and
transparency have led to its use in flexible displays, batteries, and composite materials.
Nanocoatings are used to enhance the surface properties of materials, providing benefits such
as increased durability, corrosion resistance, and antimicrobial properties.
5.7 Nanocomposites: Nanocomposites combine nanoscale materials with other materials to
enhance their properties. Polymer-based nanocomposites, for instance, incorporate
nanoparticles into polymer matrices to improve mechanical strength, thermal stability, and
barrier properties. Ceramic-based nanocomposites are used in high-temperature applications
and as structural materials due to their enhanced mechanical properties and thermal resistance.
6.0 Properties of Nanomaterials
Nanomaterials exhibit several unique properties that make them highly desirable for various
applications:
6.1 Surface Area to Volume Ratio: Nanomaterials have a high surface area to volume ratio,
which significantly affects their reactivity and strength. A large proportion of atoms are located
on the surface of nanomaterials, enhancing their interaction with other materials and making
them excellent catalysts. This high surface area also contributes to increased mechanical
strength and durability.
6.2 Quantum Effects: At the nanoscale, materials exhibit quantum effects that influence their
optical, electrical, and magnetic properties. Quantum confinement, for instance, occurs when
the dimensions of a material are reduced to a scale comparable to the wavelength of electrons,
leading to discrete energy levels. This can result in phenomena such as size-dependent color in
quantum dots. These effects can be harnessed in applications such as quantum computing,
imaging, and photovoltaics.
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6.3 Mechanical Strength: Many nanomaterials exhibit superior mechanical properties. For
example, carbon nanotubes and graphene have tensile strengths much higher than that of steel,
making them ideal for use in lightweight, high-strength materials.
6.4 Optical Properties: Nanomaterials can interact with light in unique ways. For example,
gold nanoparticles exhibit different colours based on their size and shape, which can be utilized
in sensors and imaging applications.
6.5 Electrical Conductivity: Nanomaterials such as graphene and carbon nanotubes have
excellent electrical conductivity, making them suitable for use in electronic devices, conductive
films, and energy storage systems.
6.6 Self-Assembly and Nanofabrication: The ability of nanomaterials to self-assemble into
ordered structures is a key concept. Self-assembly involves the spontaneous organization of
molecules into stable, well-defined structures through non-covalent interactions.
Nanofabrication techniques, including bottom-up and top-down approaches, are employed to
create and manipulate nanomaterials with precision.
6.7 Intermolecular Forces: At the nanoscale, intermolecular forces such as van der Waals
forces, hydrogen bonding, and electrostatic interactions play a significant role. These forces
influence the stability, assembly, and properties of nanomaterials. Understanding these forces
is crucial for designing nanomaterials with desired characteristics.
6.8 Size-Dependent Properties: The properties of nanomaterials are highly dependent on their
size. As the size decreases, the surface-to-volume ratio increases, leading to enhanced surface
properties. For example, gold nanoparticles exhibit different optical properties compared to
bulk gold due to the influence of size on surface plasmon resonance.
6.9 Surface Effects: At the nanoscale, surface atoms constitute a larger fraction of the total
number of atoms in the material. This leads to surface effects becoming dominant, influencing
the chemical reactivity, mechanical strength, and thermal stability of nanomaterials. The large
surface area also enhances the potential for surface functionalization and interaction with other
substances.
6.10 Scalability and Fabrication: The fabrication of nanomaterials involves techniques
that can precisely control size and shape at the nanoscale. Top-down approaches, such as
lithography and milling, involve the removal of material to create nanostructures. Bottom-up
approaches, including chemical vapor deposition (CVD) and self-assembly, build up structures
from atomic or molecular precursors.

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7.0 Processing of Nanomaterials
Two main approaches are used for the synthesis of nanomaterials: top-down approaches and
bottom-up approaches. Figure 2.

Figure: The synthesis of nanomaterials via top-down and bottom-up approaches.


7.1 Bottom-up approach: In this approach, nanomaterials are assembled from the smaller
starting materials such as atoms, molecules, or clusters. Examples of bottom-up techniques
include chemical vapor deposition (CVD), sol-gel, spinning, pyrolysis, and biological synthesis
7.1.1 Wet Chemical Synthesis of Nanomaterials In principle we can classify the wet
chemical synthesis of nanomaterials into two broad groups.
1. The top-down method: where single crystals are etched in an aqueous solution for producing
nanomaterials, For example, the synthesis of porous silicon by electrochemical etching.
2. The bottom-up method: consisting of sol-gel method, precipitation etc. where materials
containing the desired precursors are mixed in a controlled fashion to form a colloidal solution.
7.1.2 Chemical Vapor Deposition (CVD): CVD is the deposition of a thin film of gaseous
reactants onto a substrate. When a heated substrate comes into contact with a combined gas, a
chemical reaction occurs.[8] This reaction forms a thin film of product on the substrate surface,

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which is recovered and reused. The disadvantages of CVD are the requirement of special
equipment and the fact that the gaseous by-products are highly toxic.
7.1.3 Physical Vapor Deposition (PVD): Physical Vapor Deposition (PVD) is a versatile
and widely used bottom-up synthesis method for fabricating nanomaterials. It involves the
physical transfer of material from a source to a substrate, forming thin films or nanostructures.
7.1.4 Sol-Gel Process: The Sol-Gel process is a widely used bottom-up synthesis method for
creating nanomaterials. This process involves the transition of a system from a liquid "sol"
(mostly colloidal) into a solid "gel" phase. It allows for precise control over the material's
chemical composition and microstructure, making it suitable for producing a variety of
nanostructured materials such as oxides, ceramics, and glasses.
7.1.5 Hydrothermal and Solvothermal Synthesis: Hydrothermal and solvothermal
synthesis are bottom-up methods used to create nanomaterials with controlled size, shape, and
composition. These methods involve chemical reactions in a solvent at high temperature and
pressure, which can promote the formation of nanomaterials.
7.1.5.1 Hydrothermal Synthesis: Hydrothermal synthesis involves crystallizing substances
from high-temperature aqueous solutions at high vapor pressures. This method is typically
conducted in a sealed vessel known as an autoclave.
7.1.5.2 Solvothermal Synthesis: Solvothermal synthesis is similar to hydrothermal synthesis
but uses organic solvents instead of water. This method allows reactions to occur at
temperatures higher than the boiling point of water, enabling the synthesis of a wider range of
materials.
7.1.6 Self-Assembly: Self assemble is a bottom up process which allows molecules or
nanoparticles to spontaneously organize into structured, functional assemblies without human
intervention.
7.1.7 Biological Methods: Utilizing biological systems such as bacteria, fungi, or plants to
synthesize nanomaterials, often in an environmentally friendly manner.
7.1.8 Spinning method: The synthesis of nanoparticles by spinning is carried out by a
spinning disc reactor (SDR). It consists of a rotating disc contained within a chamber or reactor
where physical parameters such as temperature can be controlled. It is determined by several
factors, including disc surface, liquid/precursor ratio, disc rotation speed, liquid flow rate, and
feed location. Magnetic nanoparticles were created using spinning disc processing.
7.1.9 Pyrolysis method: Pyrolysis is the most commonly used process in industries for the
large-scale production of nanoparticles. The advantages of pyrolysis are that it is simple,
efficient, cost-effective and a continuous process with high yield.
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7.1.10 Soft and hard templating methods:
Soft and hard template methods are extensively used to produce nanoporous materials. The soft
template method is a simple conventional method for the generation of nanostructured
materials. In this method, nano porous materials are produced using plenty of soft templates,
such as block copolymers, flexible organic molecules, and anionic, cationic, and non-ionic
surfactants.
7.1.11 Reverse micelle method
The reverse micelle method is also useful for producing nanomaterials with the desired shapes
and sizes. In nature, reverse micelles are formed in the case of a water-in-oil emulsion, with
the hydrophilic heads pointing towards a water-containing core.
7.1.12 Biosynthesis/biological method
Biosynthesis is an environmentally friendly and green approach to the synthesis of non-toxic
and biological nanoparticles. Green synthesis nanoparticles have distinct and enhanced
properties that make them suitable for biomedical applications. Microorganisms (bacteria,
algae, and fungi), biological templates, and various plant parts are used in biosynthesis.
1. Biosynthesis method using microorganisms
Bacteria, fungi, and algae can be used to prepare various nanomaterials from metal salt aqueous
solutions. For example, at the bottom of the sea, magnetotactic bacteria prepare magnetic
particles under anaerobic conditions; photosynthetic bacteria such as Rhodopseudomonas
capsulate prepare 10–20 nm-sized gold nanoparticles extracellularly; the Fusarium oxysporum
fungus is used to prepare extracellular silver nanoparticles; and extracellular gold nanoparticles
are prepared using Sargassum wightii algae. The disadvantage of this process is that some
bacteria, fungi, and algae are pathogenic, so care must be taken.
2. Biosynthesis method using biological templates
Biological templates such as DNA and proteins create unique and sophisticated nanostructures.
These nanoparticles can be used to create biosensors, bioNEMS, and bioelectronic systems.
Proteins are the primary constituents of nanocomposite materials. Ferritin, for example, is the
intracellular iron storage protein in prokaryotes and eukaryotes. It stores it as iron oxide and
releases it in a controlled manner. It acts as a buffer in humans, regulating iron deficiency and
overload.

3. Biosynthesis method using different plant parts


Plants and plant extracts have also been used in the synthesis of nanoparticles. The
phytochemicals found in plants reduce the metal nanoparticles. Flavones, organic acids, and

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quinones are naturally good reducing agents for nanoparticle preparation. Gold nanoparticles
of various shapes are synthesized from the biomass of the Medicago sativa (alfalfa) and
Pelargonium graveolens (geranium) plants. The leaves of Azadirachta indica (neem) are used
to make bimetallic Au, Ag, and bimetallic Au core-Ag shell nanoparticles. Aloe vera leaf
extract is used to create gold nano triangles. Silver, nickel, cobalt, zinc, and copper
nanoparticles are also synthesized using plants such as Brassica juncea, Helianthus annuus, and
sunflower.

7.2 Top-down Approach: In top-down approaches, bulk materials are divided to produce
nanostructured materials. Top-down methods include lithography, mechanical grinding or ball
milling, laser ablation, sputtering, electron explosion arc discharge, and thermal
decomposition.
7.2.1 Mechanical Grinding: Mechanical grinding, a top-down synthesis method, is a widely
used technique in the fabrication of nanomaterials. It involves the mechanical breakdown of
large materials into nanoscale particles using high-energy ball milling. This method is simple,
cost-effective, and can be used to produce a wide variety of nanomaterials with different
compositions and morphologies.
7.2.1.1 High-Energy Ball Milling: In high-energy ball milling, powder particles are subjected
to repeated deformation, fracturing, and cold welding by high-energy collisions with the balls.
The milling media, typically stainless steel or tungsten carbide balls are placed in a rotating
mill. Milling Time: Longer milling times generally lead to finer particles but can also increase
the risk of contamination. Milling speed: Higher speeds increase the impact energy, resulting
in smaller particle sizes. Ball-to-Powder Ratio (BPR): Higher ratios can lead to finer particles
but also increase the chances of particle agglomeration. Atmosphere: Milling can be conducted
under various atmospheres (air, inert gases) to prevent oxidation or other undesirable reactions.
Mechanisms: Impact: Balls impact the powder particles, causing fracturing and size
reduction. Shear: Shear forces contribute to further size reduction and mechanical mixing.
Cold Welding: Particle surfaces may cold weld during milling, causing agglomeration, which
is often counteracted by the addition of process control agents (PCAs).
Advantages: Scalability: Mechanical milling can be scaled up for industrial production.
Versatility: Capable of producing various nanomaterials, including metals, alloys, ceramics,
and composites. Cost-Effectiveness: Relatively low-cost equipment and process. Limitations:
Contamination: The milling media and environment can introduce impurities.

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Agglomeration: Fine particles tend to agglomerate, which may require additional processing
steps. Limited Control: Precise control over particle size and distribution can be challenging.
Applications: Metal and Alloy Nanoparticles: Used in catalysts, magnetic materials, and
structural applications. Oxide Nanoparticles: Applications in sensors, batteries, and coatings.
Composite Nanomaterials: Enhanced properties for structural materials and functional
applications.
7.3 Gas Phase synthesis of nanomaterials: In gas-phase synthesis, nanoparticles are made by
“building” them from individual atoms or molecules up to the desired size: cluster embryos are
formed either by physical means such as condensation of a supersaturated vapor or by chemical
reaction of gaseous precursors. Gas phase synthesis generally involves the following steps:
1. Precursor vaporization: Solid or liquid precursors are converted into gaseous form.
2. Reaction in the gas phase: Gaseous precursors undergo chemical reactions such as
decomposition, oxidation, or reduction to form desired products (e.g., nanoparticles, clusters).
3. Particle nucleation and growth: Products nucleate and grow into particles as they travel
through a reactor.
4. Collection: The synthesized materials are collected on a substrate (for thin films) or in a
filter system (for powders or nanoparticles).
7.3.1 Common Types
1. Chemical Vapor Deposition (CVD)
o Used for coatings and thin films.
o Precursors react or decompose on a heated substrate.
o Example: SiH₄ → Si (solid) + 2H₂ (gas)
2. Flame Spray Pyrolysis (FSP)
o Combustion-based synthesis of nanoparticles.
o High temperature leads to rapid formation of fine particles.
o Used for oxides like TiO₂, ZnO.
3. Laser Ablation in Gas Phase
o Laser vaporizes a target in a controlled gas atmosphere.
o Nucleation occurs in the gas plume.
o Useful for producing metal and semiconductor nanoparticles.
4. Plasma Synthesis
o Plasma is used to enhance reaction kinetics.
o Allows synthesis of materials like carbon nanotubes, nanodiamonds.
5. Gas-Phase Condensation (GPC)
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o Physical process: vaporized material condenses into nanoparticles.
o Carried out under low pressure and temperature gradients.
7.3.2 Advantages
• High purity and uniform composition.
• Fine control over particle size and morphology.
• Scalable for industrial production (e.g., aerosol reactors).
• Suitable for a wide range of materials (metals, oxides, carbides, etc.).
7.3.3 Limitations
• Requires precise control of temperature and pressure.
• Handling and collection of nanoparticles can be challenging.
• Some methods (e.g., FSP) can be energy-intensive.
7.3.4 Applications
• Catalysts: High surface area nanoparticles (e.g., Pt, Pd).
• Electronics: Thin films for semiconductors.
• Energy: Electrodes for batteries and fuel cells.
• Medical: Drug delivery and imaging agents.
7.4 Lithography: Lithography is a useful tool for developing nanoarchitectures using a
focused beam of light or electrons. Lithography can be divided into two main types: masked
lithography and maskless lithography. In masked nanolithography, nano patterns are
transferred over a large surface area using a specific mask or template. Masked lithography
includes photolithography, nanoimprint lithography, and soft lithography. Maskless
lithography includes scanning probe lithography, focused ion beam lithography, and electron
beam lithography. In maskless lithography, arbitrary nanopattern writing is carried out without
the involvement of a mask. 3D freeform micro-nanofabrication can be achieved via ion
implantation with a focused ion beam in combination with wet chemical etching. There are
several types of lithography techniques, each with unique advantages and applications. Here
are the details of various lithography techniques used in top-down synthesis:
7.5 Photolithography: Photolithography is the most widely used technique in semiconductor
manufacturing. It uses light to transfer a geometric pattern from a photomask to a light-sensitive
photoresist on the substrate.
7.6 Electron Beam Lithography (EBL): EBL uses a focused beam of electrons to create
patterns on a substrate coated with an electron sensitive resist.
7.7 Focused Ion Beam Lithography (FIB): FIB uses a focused beam of ions (typically
gallium ions) to pattern the substrate directly by sputtering material away.
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7.8 Nanoimprint Lithography (NIL): NIL involves pressing a mold with nanoscale patterns
into a soft resist to create the pattern.
7.9 Extreme Ultraviolet Lithography (EUVL): EUVL uses extreme ultraviolet (EUV) light
with a wavelength of 13.5 nm to achieve very high resolution.
7.10 Laser ablation is a versatile and efficient technique used for the synthesis of
nanomaterials. It involves the removal of material from a solid target through the interaction
with a high-energy laser pulse. This process can produce a wide range of nanostructures,
including nanoparticles, nanowires, and thin films. The following sections provide a detailed
description of the laser ablation technique and its application in nanomaterial synthesis.
7.11 Etching: Top-down synthesis methods for nanomaterials often involve etching
techniques to achieve the desired nanoscale features. These techniques remove material from
a larger bulk structure to create nanoscale patterns or structures. Here, we'll detail some
common etching techniques used in top-down nanomaterial synthesis:
7.12 Reactive Ion Etching (RIE): Uses chemically reactive plasma to etch away materials.
The substrate is placed in a reactor where gases are introduced and ionized.
7.13 Wet Chemical Etching: Uses liquid chemicals to selectively remove material from a
substrate.
7.14 Plasma Etching: Similar to RIE but typically uses a less energetic plasma, focusing
more on chemical etching.
7.15 Sputtering: Sputtering is a process used to produce nanomaterials via bombarding
solid surfaces with high-energy particles such as plasma or gas. Sputtering is considered to be
an effective method for producing thin films of nano materials. In the sputtering deposition
process, energetic gaseous ions bombard the target surface, causing the physical ejection of
small atom clusters depending upon the incident gaseous-ion energy. The sputtering process
can be performed in different ways, such as utilizing magnetron, radio-frequency diode, and
DC diode sputtering. In general, sputtering is performed in an evacuated chamber, to which the
sputtering gas is introduced. A high voltage is applied to the cathode target and free electrons
collide with the gas to produce gas ions. The positively charged ions strongly accelerate in the
electric field towards the cathode target, which these ions continuously hit, resulting in the
ejection of atoms from the surface of the target. Magnetron sputtering is used to produce WSe2-
layered nanofilms on SiO2 and carbon paper substrates. The sputtering technique is interesting
because the sputtered nanomaterial composition remains the same as the target material with
fewer impurities, and it is cost-effective compared with electron-beam lithography

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