Subject: CMXXXX - Nanotechnology in Chemical Engineering

Semester – 7th

Basic Knowledge

Dimensions

Small and ultra-small scales:

1 meter= 100 cm

1cm = 10(-2) (10 to the power -2= 1/100) meter,

1 millimeter (mm) =0.1 cm= 10(-3) meter,

1 micrometer = 10(-6) meter = 10(-3) mm=μm (micrometer), nanometer (nm) = 10-9 meter
Nanometer= one of a billionth of a meter= 10(-9) m= one of a millionth of a mm= 10(-6) mm 1
micrometer = 10(-6) m & nanometer= 10(-9) m,

Micrometer= 1000 nanometer,

1 nanometer= 10 angstroms; 1 angstroms= 10(-1) nanometer

Large Scales: 1 Km = 1000 m,

1Gm= 1000 Km = 10(+6) m

Objective of Nanotechnology in Chemical engineering

• Enhancing Chemical Processes (Catalysis, Reaction Engineering, Separations, Drug

delivery)
• Improving Material Properties (Strength and Durability, Thermal and Electrical
Conductivity, Corrosion Resistance)
• Creating Novel Applications (Energy, Environment, Healthcare)
Introduction

Nanotechnology refers to the manipulation of matter on an atomic and molecular scale,

typically 1 to 100 nanometres. This field involves designing, producing, and using structures,
devices, and systems by controlling matter at the nanoscale, where unique properties can
emerge. It's essentially about working with incredibly small structures to create new materials
and technologies with potentially groundbreaking applications
Applications of Nanotechnology or Nanoparticles

Nanotechnology has diverse applications in various fields, including Chemical processes,

electronics, energy, environmental science etc.

The main applications in the chemical engineering field are:

1. Advanced Materials

Nanotechnology allows for the creation of materials with enhanced properties like increased
strength, lighter weight, and improved heat resistance. Examples include nanomaterials for
stronger, lighter vehicles and buildings.

2. Catalysis:

Nanoparticles, due to their high surface area, are excellent catalysts in various processes,
including fuel cells and catalytic converters.

3. Sensors:

Nanomaterials are used to develop highly sensitive and selective sensors for detecting various
substances, including gases and chemicals.

4. Environmental Remediation:

Nanomaterials are being used to remove pollutants from wastewater and air, offering solutions
for environmental sustainability.

5. Drug Delivery:

Targeted drug delivery systems utilizing nanoparticles can improve treatment efficacy and
minimize side effects in medicine.

6. Energy:

Nanotechnology is contributing to advancements in energy storage (batteries, fuel cells) and

energy harvesting.

7. Biotechnology:

Bio-inspired nanomaterials and nanobiocatalysts are driving progress in healthcare,

biomanufacturing, and regenerative medicine.

8. Chemical Processes:
Nanotechnology enhances chemical processes by enabling more efficient reactions, improved
separation techniques, and better control over reaction conditions.

Nanotechnology has diverse applications in various fields, including medicine, electronics,

energy, and environmental science.

• Medicine: Targeted drug delivery, regenerative medicine, and diagnostics.

• Electronics: Developing smaller and faster transistors, creating flexible electronics.

• Energy: Enhancing energy storage and efficiency, developing new solar cells.

• Environment: Reducing pollution, creating self-cleaning materials.

Unit 1: Introduction:
Organic Nanoparticles

Organic nanoparticles are nanoscale materials composed of organic molecules. They are of
significant interest in various fields due to their unique properties and potential applications,
especially in biomedical and industrial applications.

Organic nanoparticles typically range from 1 to 100 nanometers in size, with various shapes
and structures like nanospheres, nanocapsules, micelles, liposomes, and dendrimers.

• They are built from organic molecules, which can be natural (e.g., proteins,
polysaccharides) or synthetic (e.g., polymers, lipids) Polymer nanoparticles: Polymeric
micelles, dendrimers
Inorganic Nanoparticles

Inorganic nanoparticles are nanoscale materials composed of inorganic compounds.

Inorganic nanoparticles can be obtained either by division of large chunks of material (the top-
down approach) or by integration of individual atoms and molecules into
wider nanostructures (the bottom-up approach). Both strategies converge in terms of the size
range of attainable objects. The bottom-up approach largely pertains to chemical methods of
preparation of nanosized particles, whereas the top-down approach is generally based on
mechanical/physical methods. Some of the examples are:

• Metal nanoparticles: Gold, silver, platinum, Iron, etc

• Metal oxide nanoparticles: Titanium dioxide, zinc oxide

• Ceramic nanoparticles: Silica, alumina

Carbon-Based Nanoparticles:

Carbon nanomaterials are a diverse class of carbon-based materials with unique properties due
to their nanoscale dimensions. Key examples include graphene, carbon nanotubes (CNTs),
fullerenes, and carbon quantum dots (CQDs). These materials are widely studied for their
potential applications in various fields like electronics, medicine, and energy.

• Carbon-based nanoparticles: Fullerenes, carbon nanotubes, graphene, Carbon fibers

etc.

Nanoparticles are also classified based on their chemical composition (like metal, ceramic,
carbon-based, or polymer) and physical properties such as size, shape, and surface morphology,
which significantly influence their behaviour and potential applications.

Based on Chemical composition:

• Metal nanoparticles: Gold, silver, platinum, Iron, etc

• Metal oxide nanoparticles: Titanium dioxide, zinc oxide

• Carbon-based nanoparticles: Fullerenes, carbon nanotubes, graphene

• Ceramic nanoparticles: Silica, alumina

• Polymer nanoparticles: Polymeric micelles, dendrimers

Physical properties:
 • Size: Measured in nanometers, often categorized as "ultra-fine" or "nano-sized"

• Shape: Spherical, rod-like, plate-like

• Surface area: High surface area due to small size, impacting reactivity

• Surface charge: Can be positive, negative, or neutral, affecting interactions with other
molecules

Based on their size

with the most recognized categorization being based on the dimension of the particle,
including 0D (zero-dimensional, like spherical nanoparticles), 1D (one-dimensional, like
nanorods), 2D (two-dimensional, like graphene sheets), and 3D (three-dimensional, like
nanocubes)

Based on their shape (morphology)

meaning their shape and structure, which is a key factor in determining their properties and
potential applications in various fields like medicine, electronics, and materials science.

According to their morphologies Nanoparticles can be categorized as spherical, rod-like, plate-

like, tubular, or even more complex shapes depending on their synthesis method and material
composition.

Some of the examples are:

• Spherical nanoparticles: Often used in drug delivery due to their high surface area
and stability.

• Rod-shaped nanoparticles: Can exhibit anisotropic properties, useful in applications

like solar cells.

• Carbon nanotubes: Cylindrical structures with unique electrical and mechanical

properties.

Properties of nanostructures and nanomaterials

Nanostructures and nanomaterials exhibit unique properties compared to their bulk

counterparts due to their extremely small size, with at least one dimension falling within the
nanoscale (1-100 nanometers), leading to significantly increased surface area-to-volume ratio,
quantum confinement effects, and altered interactions at the atomic level, resulting in distinct
electrical, optical, magnetic, mechanical, and chemical properties that can be tuned by
controlling size, shape, and composition; these properties include enhanced reactivity,
improved conductivity, altered melting point, and unique optical phenomena like surface
plasmon resonance depending on the material and its nanostructure.

Key properties of nanostructures and nanomaterials:

• High Surface Area:

Due to their small size, nanomaterials have a significantly larger surface area relative to their
volume, leading to increased reactivity and adsorption capabilities, making them ideal for
catalysis and drug delivery applications.

• Quantum Confinement:

When the size of a nanomaterial becomes comparable to the wavelength of electrons, their
energy levels become quantized, leading to changes in optical properties like emission
wavelength and band gap.

• Tailored Mechanical Properties:

Depending on the nanostructure, materials can exhibit enhanced strength, hardness, and
elasticity compared to their bulk counterparts.

• Optical Properties:

Nanomaterials can exhibit unique optical phenomena like surface plasmon resonance (SPR),
where light interacts with the collective oscillation of electrons on the surface, leading to color
changes depending on the size and shape of the nanoparticles.

• Electrical Properties:

Nanomaterials can have significantly altered electrical conductivity depending on their size
and structure, with potential for applications in electronics and sensors.

• Magnetic Properties:

At the nanoscale, magnetic properties can be significantly altered, allowing for the
development of superparamagnetic materials with high magnetic moment and low coercivity.

• Thermal Properties:
Nanomaterials can exhibit different thermal properties compared to bulk materials, including
enhanced thermal conductivity or altered melting points.

Factors affecting nanomaterial properties / Explain the effect of nanosize on the

properties and performance of materials. / Describe the effect of nanostructure on the
performance of nanomaterials

• The performance of nanomaterials is significantly influenced by their

nanostructure. Properties like mechanical strength, thermal conductivity, electrical
conductivity, and magnetic behavior are all affected by the size, shape, and arrangement
of nanomaterials at the nanoscale. For instance, nanomaterials often exhibit enhanced
mechanical properties due to a higher proportion of surface atoms and interfaces.
• When materials are reduced to the nanoscale (typically <100 nm), their properties
significantly change due to increased surface area and quantum effects. Here's how
nanosize affects materials:

1. Increased Surface Area to Volume Ratio

At nanoscale, a large proportion of atoms are on the surface, enhancing reactivity, strength, and
interaction with other substances.

Example: Nanocatalysts have high activity due to more active sites.

2. Mechanical Properties Enhancement

Nanomaterials often exhibit greater hardness, strength, and wear resistance due to fewer defects
and grain boundaries.

Example: Nanocrystalline metals are harder than their bulk counterparts.

3. Optical Properties Change

Quantum confinement alters how nanomaterials absorb and emit light.
Example: Gold nanoparticles appear red or purple (not yellow like bulk gold).

4. Electrical & Magnetic Properties Shift

Electrical conductivity and magnetic behaviour can change dramatically.
Example: Carbon nanotubes can be metallic or semiconducting; magnetic nanoparticles exhibit
superparamagnetism.
5. Thermal Properties Modification
Thermal conductivity can increase or decrease depending on the structure.
Example: Nanofluids show better heat transfer than regular fluids.

Various structures and mechanisms of nanomaterials

• A nanostructure is a structure of intermediate size between microscopic and molecular
structures. Nanostructural detail is microstructure at the nanoscale.
• In describing nanostructures, it is necessary to differentiate between the number of
dimensions in the volume of an object which are on the nanoscale.
• Nanomaterials, materials with at least one dimension between 1 and 100 nanometers,
exhibit diverse structures and mechanisms. These materials can be categorized based
on dimensionality (0D, 1D, 2D, 3D) and composition (organic, inorganic, composite)

1. Zero-dimensional (0D):
Zero-dimensional (0D) nanomaterials, like nanoparticles and quantum dots, exhibit unique
properties due to quantum confinement effects, where all three spatial dimensions are confined
to the nanoscale (typically less than 100 nm). i.e, Nanoparticles, quantum dots,
nanoclusters. These are essentially particles with all three dimensions in the nanoscale. This
confinement leads to discrete electronic energy levels and altered optical, electrical, and
chemical properties compared to their bulk counterparts.

2. One-dimensional (1D):
Nanotextured surfaces have one dimension on the nanoscale, i.e., only the thickness of the
surface of an object is between 0.1 and 100 nm. Nanowires, nanotubes, nanorods,
nanofibers. These structures have one dimension in the nanoscale while the other two are larger.
One-dimensional (1D) nanomaterials, like nanowires and nanotubes, have unique properties
due to their high aspect ratio and large surface area, making them useful in various applications
like electronics, sensors, and catalysis. Their synthesis often relies on methods that control the
growth along one dimension, such as vapor deposition, hydrothermal methods, or template-
based techniques

3. Two-dimensional (2D):
Two-dimensional (2D) nanomaterials are atomically thin materials with a high surface-to-
volume ratio, leading to unique properties and diverse applications. Their mechanisms
are often tied to their reduced dimensionality, leading to quantum confinement effects, and their
large surface area, which enhances interactions with other molecules or materials.
Nanotubes have two dimensions on the nanoscale, i.e., the diameter of the tube is between 0.1
and 100 nm; its length can be far more.
Nanofilms, nanosheets, nanolayers. These have two dimensions in the nanoscale and one larger
dimension.

4. Three-dimensional (3D):
Finally, spherical nanoparticles have three dimensions on the nanoscale, i.e., the particle is
between 0.1 and 100 nm in each spatial dimension.
Three-dimensional (3D) nanomaterials are materials with at least one dimension in the
nanoscale (1-100 nm) and exhibit unique properties due to their complex structures. Their
mechanisms involve self-assembly, directed assembly, and template-based growth, often
utilizing interconnected pores and high surface areas for diverse applications.
Nanocomposites, nanoporous materials, nanostructured solids. These structures can have
nanoscale features throughout their volume.
.
• Examples:

• Spherical nanoparticles: Often used in drug delivery due to their high surface
area and stability.

• Rod-shaped nanoparticles: Can exhibit anisotropic properties, useful in

applications like solar cells.

• Carbon nanotubes: Cylindrical structures with unique electrical and

mechanical properties.

Thermal Properties
• Heat transfer in NPs primarily depends on energy conduction due to electrons as well
as photons (lattice vibration) and the scattering effects that accompany both.
• The major components of thermal properties of a material are thermal conductivity,
thermoelectric power, heat capacity, and thermal stability.
• NP size has a direct impact on electrical and thermal conductivity of NPs. As the NP
size decreases, the ratio of particle surface area respective to its volume increases
hyperbolically. Since the conduction of electrons is one of the two main ways in which
heat is transferred, the higher surface-to-volume ratio in NPs provides higher number
of electrons for heat transfer compared to bulk materials.
• Moreover, thermal conductivity in NPs is also promoted by microconvection, which
results from the Brownian motion of NPs.
• Nevertheless, this phenomenon only happens when solid NPs are dispersed in a liquid
(generating a Nanofluid).
• As an example, the addition of Cu NPs to ethylene glycol enhances the thermal
conductivity of the fluid up to 40%
• Nanostructures significantly influence the thermal properties of materials, leading
to enhanced or suppressed thermal conductivity, altered melting points, and changes in
specific heat capacity.
• The size and arrangement of these nanostructures, along with factors like grain
boundaries and interfaces, play a crucial role in dictating the material's thermal
behaviour.

Mechanical Properties
• Mechanical properties refer to the mechanical characteristics of a material under
different conditions, environments, and various external forces.
• As for traditional materials, the mechanical properties of nanomaterials generally
consist of ten parts: strength, brittleness, hardness, toughness, fatigue strength,
plasticity, elasticity, ductility, rigidity, and yield stress.
• Most inorganic, non-metallic materials are brittle materials and do not have significant
toughness, plasticity, elasticity, or ductility properties. Organic materials on the other
hand, are flexible materials and do not necessarily have brittleness and rigidity
properties.
• Due to surface and quantum effects, NPs display different mechanical properties
compared to bulk materials. For example, conventional FeAl powder which is
composed of microparticles (larger than 4 μm), is brittle, while ultrafine FeAl alloy
powder displays a good combination of strength and ductility as well as enhanced
plasticity.
 • These new properties are believed to arise due to the diverse interaction forces between
NPs or between them and a surface. The most important interaction forces involved are
van der Waals forces. Other relevant interaction forces are electrostatic and electrical
double layer forces, normal and lateral capillary forces, solvation, structural, and
hydration forces.
• Nanostructures significantly enhance the mechanical properties of materials by altering
their microstructure at the nanoscale. This leads to increased strength, hardness, and
wear resistance, often by hindering dislocation movement or refining grain
boundaries. However, the specific effects can vary depending on the material, the type
of nanostructure, and the processing methods used.

Methods of Synthesis of Nanoparticles

Various methods are used to synthesize nanoparticles, but these methods are divided into two
approaches, i.e. (1) Top-down approach and (2) Bottom-up approach.

1) Top-down approach

This method is based on bulk material to small size. In this method, by means of physical
methods such as milling, crushing, ablation, lithography etc., the bulk or large material is
converted into micro-sized particles [34]. This method is easy to perform. Generally, this
method is not used because of its several significant drawbacks. This is not a suitable method
for preparing uniform size and tiny size particles. Due to physical force application, highly
energized equipment is required. Since this imperfection of method can cause a significant
impact on the surface chemistry and physical properties of particles.
Physical method:

1. Ball-milling
2. Evaporation-Condensation
3. Arc-discharge
4. Laser ablation
5. Spray pyrolysis
6. Ultrasonication
7. Lithography
8. Photoirradiation
9. Sputtering

• Mechanical ball Milling:

This involves grinding or milling bulk materials to reduce their size into nanoparticles. It's a
widely used method for producing various nanoparticles, including oxide- and carbide-
strengthened aluminum alloys and nano composite materials.
• Lithography:
Primarily used in semiconductor fabrication, lithography involves patterning materials on a
surface to create nanoscale structures.
• Laser Ablation:
A high-energy laser is used to vaporize a target material, and the resulting vapor condenses into
nanoparticles.
• Sputtering:
Bombarding a target material with high-energy ions causes atoms to be ejected and deposited
as nanoparticles on a substrate.

1) Bottom -up approach

The bottom-up approach to nanomaterial synthesis involves building nanostructures from the
atomic or molecular level, essentially assembling materials from the ground up. This contrasts
with the top-down approach, which involves breaking down larger materials into nanoscale
structures. Key methods in bottom-up synthesis include chemical reactions, self-assembly, and
vapor deposition techniques.

Chemical Method:

1. Sol-gel method
2. Reverse micelle
3. Chemical vapor deposition
4. Wet-chemical Synthesis
• Chemical Vapor Deposition (CVD): Gaseous precursors react on a substrate to form a
thin film or nanostructure.
• Sol-Gel Process: A solution (sol) transitions into a gel, leading to the formation of
nanomaterials.
• Wet Chemical Precipitation: Nanoparticles are formed through chemical reactions in a
solution.
Biological Method:

Biological Methods: Utilizing biological systems like bacteria, fungi, or plants to synthesize
nanomaterials.

1. Plant extract mediated synthesis

2. Fungi-mediated Synthesis
3. Virus/VLP-mediated Synthesis
4. Algae-mediated Synthesis
5. Bacteriogenic Synthesis

Plant-mediated Synthesis: Plant extracts, rich in biomolecules like alkaloids, phenolic

compounds, and terpenoids, act as reducing agents to convert metal ions into nanoparticles.

Fungi-mediated Synthesis: Fungi are particularly attractive for this process due to their ability
to produce a wide range of biomolecules, including enzymes and proteins, that facilitate
nanoparticle synthesis

Ceramic Nanoparticles

• These types of nanoparticles are inorganic solids composed of oxides, carbides,

carbonates and phosphates. Ceramic nanoparticles have high heat resistance and
chemical inertness and have applications in photocatalysis, photodegradation of dyes,
and biological imaging.
• One of the most important applications of ceramic nanoparticles is in drug delivery. By
controlling their specific characteristics like size, surface area, porosity, and surface
area-to-volume ratio, these nanomaterials perform as good drug delivery agents. They
 have been used effectively as a drug delivery system for several diseases like bacterial
infections, glaucoma, and cancer. More recently, scientists have developed these
nanoparticles for use in bone repair.

Metal Nanoparticles

• Metal nanoparticles are types of nanoparticles prepared from metal precursors and can
be synthesized by chemical, electrochemical, or photochemical methods.
• In chemical methods, the metal nanoparticles are obtained by reducing the metal-ion
precursors in solution with chemical reducing agents. The resultant nanomaterials can
adsorb small molecules and have high surface energy.
• The most common types of metal nanoparticles include silver, gold, palladium,
titanium, zinc, and copper nanoparticles.
• Metal nanoparticles are utilized across several research fields, including the detection
and imaging of biomolecules and in environmental and bioanalytical applications. For
example, gold nanoparticles are used to coat the sample before scanning electron
microscope (SEM) analysis to enhance SEM and produce high-quality electron
microscopy images.
• Metal nanoparticles also have important applications in drug delivery when they are
extensively used for a variety of therapeutic agencies, including antibodies, nucleic
acids, peptides, and more.

Semiconductor Nanoparticles

• Semiconductor nanoparticles are a type of nanoparticle with properties like those of

metals and non-metals, and are found in the periodic table in groups II-VI, III-V or IV-
VI. These nanoparticles have wide bandgaps, which upon tuning show different
properties. Some examples of semiconductor nanoparticles are GaN, GaP, InP, InAs
from group III-V, ZnO, ZnS, CdS, CdSe, CdTe are II-VI semiconductors and silicon
and germanium are from group IV.
• Semiconductor nanoparticles are applied to photocatalysis, electronics
devices, nanophotonics and water-splitting applications. Modern devices such as
computers, cell phones, television remote controls, satellite dishes, and fiber networks
often contain semiconductor nanoparticles.

Polymeric Nanoparticles
• Polymeric nanoparticles are organic-based nanoparticles. Depending upon the
preparation method, these types of nanoparticles have structures shaped like
nanocapsules or nanospheres.
• A nanosphere nanoparticle has a matrix-like structure, whereas nanocapsules have core-
shell morphology. In nanosphere polymeric nanoparticles, the active compounds and
the polymer are uniformly dispersed, while in nanocapsule nanoparticles, the active
compounds are confined and surrounded by a polymer shell.
• Some advantages of polymeric nanoparticles include controlled release, protection of
drug molecules as they travel within the internal and external environment, the ability
to combine therapy and imaging, and specific targeting.
• Polymeric nanoparticles have applications in drug delivery and diagnostics. Drug
delivery systems with polymeric nanoparticles have the benefit of being highly
biodegradable and biocompatible.

Lipid Nanoparticles

• Lipid nanoparticles are generally spherical, with a diameter ranging from 10 to 100nm.
Their structure consists of a solid core made of lipids and a matrix containing soluble
lipophilic molecules, and surfactants and emulsifiers stabilize the external core.

• This type of nanoparticle has applications in the biomedical field as drug carriers and
RNA release in cancer therapy. In particular, they have been successful in transporting
drugs and oligonucleotides that are poorly water-soluble in gene therapy applications