UNIT I

I What are nanomaterials?

Nanoscale materials are defined as a set of substances where at least one dimension is
less than approximately 100 nanometers. A nanometer is one millionth of a millimeter -
approximately 100,000 times smaller than the diameter of a human hair. Nanomaterials
are of interest because at this scale unique optical, magnetic, electrical, and other
properties emerge. These emergent properties have the potential for great impacts in
electronics, medicine, and other fields.
Where are nanomaterials found?

Some nanomaterials occur naturally, but of particular interest are engineered

nanomaterials (EN), which are designed for, and already being used in many commercial
products and processes. They can be found in such things as sunscreens, cosmetics,
sporting goods, stain-resistant clothing, tires, electronics, as well as many other everyday
items, and are used in medicine for purposes of diagnosis, imaging and drug delivery.
Engineered nanomaterials are resources designed at the molecular (nanometre)
level to take advantage of their small size and novel properties which are generally not
seen in their conventional, bulk counterparts. The two main reasons why materials at the
nano scale can have different properties are increased relative surface area and new
quantum effects. Nanomaterials have a much greater surface area to volume ratio than
their conventional forms, which can lead to greater chemical reactivity and affect their
strength. Also at the nano scale, quantum effects can become much more important in
determining the materials properties and characteristics, leading to novel optical,
electrical and magnetic behaviours.
Nanomaterials are already in commercial use, with some having been available
for several years or decades. The range of commercial products available today is very
broad, including stain-resistant and wrinkle-free textiles, cosmetics, sunscreens,
electronics, paints and varnishes. Nanocoatings and nanocomposites are finding uses in
 diverse consumer products, such as windows, sports equipment, bicycles and
automobiles. There are novel UV-blocking coatings on glass bottles which protect
beverages from damage by sunlight, and longer-lasting tennis balls using butyl-
rubber/nano-clay composites. Nanoscale titanium dioxide, for instance, is finding
applications in cosmetics, sun-block creams and self-cleaning windows, and nanoscale
silica is being used as filler in a range of products, including cosmetics and dental
fillings.
Advances in Nanomaterials

The history of nanomaterials began immediately after the big bang when Nanostructures
were formed in the early meteorites. Nature later evolved many other Nanostructures like
seashells, skeletons etc. Nanoscaled smoke particles were formed during the use of fire
by early humans. The scientific story of nanomaterials however began much later. One of
the first scientific report is the colloidal gold particles synthesised by Michael Faraday as
early as 1857. Nanostructured catalysts have also been investigated for over 70 years. By
the early 1940‘s, precipitated and fumed silica nanoparticles were being manufactured
and sold in USA and Germany as substitutes for ultrafine carbon black for rubber
reinforcements.
Nanosized amorphous silica particles have found large-scale applications in many
every-day consumer products, ranging from non-diary coffee creamer to automobile tires,
optical fibers and catalyst supports. In the 1960s 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 was published by
Granqvist and Buhrman. Recently it has been found that the Maya blue paint is a
nanostructured hybrid material. The origin of its color and its resistance to acids and
biocorrosion are still not understood but studies of authentic samples from Jaina Island
show that the material is made of needle-shaped palygorskite (clay) crystals that form a
superlattice with a period of 1.4 nm, with intercalates of amorphous silicate substrate
containing inclusions of metal (Mg) nanoparticles. The beautiful tone of the blue color is
obtained only when both these nanoparticles and the superlattice are present, as has been
shown by the fabrication of synthetic samples.
 Today nanophase engineering expands in a rapidly growing number of structural and
functional materials, both inorganic and organic, allowing to manipulate mechanical,
catalytic, electric, magnetic, optical and electronic functions. The production of
nanophase or cluster-assembled materials is usually based upon the creation of separated
small clusters which then are fused into a bulk-like material or on their embedding into
compact liquid or solid matrix materials. e.g. nanophase silicon, which differs from
normal silicon in physical and electronic properties, could be applied to macroscopic
semiconductor processes to create new devices. For instance, when ordinary glass is
doped with quantized semiconductor ''colloids,'' it becomes a high performance optical
medium with potential applications in optical computing.
Classification of Nanomaterials

Nanomaterials have extremely small size which having at least one dimension 100 nm or
less. Nanomaterials can be nanoscale in one dimension (eg. surface films), two
dimensions (eg. strands or fibres), or three dimensions (eg. particles). They can exist in
single, fused, aggregated or agglomerated forms with spherical, tubular, and irregular
shapes. Common types of nanomaterials include nanotubes, dendrimers, quantum dots
and fullerenes. Nanomaterials have applications in the field of nano technology, and
displays different physical chemical characteristics from normal chemicals (i.e., silver
nano, carbon nanotube, fullerene, photocatalyst, carbon nano, silica).
According to Siegel, Nanostructured materials are classified as Zero dimensional,
one dimensional, two dimensional, three dimensional nanostructures.

Fig. 3. Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D nanofibers,

wires, and rods, (c) 2D films, plates, and networks, (d) 3D nanomaterials.
 Nanomaterials are materials which are characterized by an ultra fine grain size (< 50 nm) or
by a dimensionality limited to 50 nm. Nanomaterials can be created with various modulation
dimensionalities as defined by Richard W. Siegel: zero (atomic clusters, filaments and
cluster assemblies), one (multilayers), two (ultrafine-grained overlayers or buried layers),
and three (nanophase materials consisting of equiaxed nanometer sized grains) as shown in
the above figure 3.
1. Zero-Dimensional Nanomaterials
These materials have diameters <100 nm, and are denoted by nanoparticles, nanoclusters, or
nanocrystals. The term nanoparticle is generally used to encompass all 0 D nanosized building
blocks (regardless of size and morphology), or those that are amorphous and possess a relatively
irregular shape.
For the fabrication of nanoparticles, a small size is not the only requirement. For any practical
application, the processing conditions need to be controlled in such a way that resulting
nanoparticles have the following characteristics:
alled monosized or with uniform size distribution)

monodispersed, i.e. no agglomeration. If agglomeration does occur, nanoparticles should be

readily redispersible

Materials wherein all the dimensions are measured within the nanoscale
• The most common representation of zero dimensional nanomaterilas are nano dots

2. One-Dimensional Nanostructures

Nanotube, Nanofiber, Nanowire, and Nanorod

The common thread among all of these structures is that their diameters must be within the 1–
100 nm range; typically, their lengths are within the micron (or larger) regime.
One dimension is outside the nanoscale and other two dimensions
are in the nanoscale. This leads to needle like-shaped nanomaterials
• 1-D materials include nanotubes, nanorods and nanowires.
• 1-D nanomaterials can be a morphous or crystalline
• Single crystalline or poly crystalline
• Chemically pure or impure
• Metallic, ceramic or polymeric.
3. Two-Dimensional Nano Structured Materials

One dimension lies in the nanometer range and other two dimensions are not confined to the
nanoscale
• 2D nanomaterials exhibit plate like shapes
• Two dimensional nanomaterials include nanofilms, nanolayers and nanocoating
4. Three-Dimensional materials
Three dimensional materials are not confined in the nanoscale in any dimension. These materials
are thus characterized by having three arbitrarily dimensions above 100nm
• Materials possess a nanocrystalline structure or involve the presence of features at the
nanoscale
• Example: nanoballs (dendritic structures), nanocoils, nanocones, nanopillers and nanoflowers
5. The first Nanostructures

In 1985, Harold W. Kroto, Robert F. Curl Jr. and Richard E. Smalley discovered the first
important nanostructure the C-60 fullerene consisting of 60 Carbon atoms. They shared the 1996
Nobel Prize in Chemistry for this discovery The C-60 particle was named ‗fullerene‘ or
‗Buckyball‘ after the name of R. Buckminister Fuller who invented geodesic domes. The
structure of C-60 resembles the structure of these domes.
II Nano Composites and their properties :

Polymer nanocomposites (PNCs) are a new class of reinforced hybrid materials that are formed
by the dispersion of nanoscale clay particles throughout a polymer matrix. PNCs is an
appropriate synonym for nanoparticles in the form of rods, spheres, or sheets dispersed within
the polymer matrix, has aroused tremendous interest, both in academia and industry.
Nanocomposites consist of an organic polymer matrix embedded with inorganic particles, which
have at least one of the dimensions in the nano range. The particles may be spherical (metallic or
ceramic), fibrillar (CNT) or lamellar. The polymer nanocomposites combine the concept of
both composites and nanomaterials. Though nanocomposite can include porous media, colloids,
gels and copolymers, mainly it is considered to mean the solid combination of nano-dimensional
phases differing in properties due to dissimilarities in structure and chemistry. There is the
presence of nanocomposite in nature, such as the structure of abalone shell, tooth, nacre and
bone.

The technology of nanocomposites involves the use of very small amount of Nanofillers. The
addition of nanofillers can strongly impact the macroscopic properties of the polymer
nanocomposite. The properties of nanocomposites are quite superior to conventional composites
as nanoscale organic–inorganic materials are mixed on a nearly molecular level in the former. In
nanocomposites, there is a substantial improvement in the following properties when compared
with the base polymer as well as conventional filler counterparts:

 Improved mechanical properties (e.g. strength, modulus and dimensional stability);

 Reduced permeability to gases, water and hydrocarbons;
 Improved thermal stability and heat distortion temperature (HDT);
 Reduced thermal expansion coefficient;
 Enhanced flame retardancy;
 Reduced smoke emissions;
 Improved chemical resistance;
 Better surface appearance;
 Higher electrical conductivity and
 Improved optical clarity.
Nanocomposites are promising for use in various areas such as automotive, aerospace, defense,
and biomedicine fields. Nanocomposites allow design and characteristic choices that are
impossible with conventional composites. Based on their light weight and multifunctionality,
nanocomposites cater the needs without compromising aesthetics and comfort of textiles. In
smart textiles, nanocomposites take part in sensors, actuators, mediators, biosensors,
thermoregulation, energy storing, and harvesting elements, among others. Nanocomposites are
especially promising for sophisticated niche areas. Nanocomposites have already started to be
used in a number of applications; nevertheless, there are still various potential areas where
nanocomposites can be utilized in the future.

Classification of Nanocomposites:
Composites can be defined as an ensemble of two phases, blended/mixed to obtain the desired
properties, tailor-made for specific applications. Nanocomposites constitute a subgroup of this
bigger domain of multifunctional materials having at least one of the components in the
nanoscale range. The arena of nanocomposites with unusual property combinations and design
possibilities at a very low concentration of fillers has gained a special status in recent years
owing to a high matrix to filler interfacial area (the so-called ―Nano effect‖) and greater aspect
ratio. The best example appears in Mother Nature in the form of bones, shells, and wood.

Nanocomposites can be classified in three groups in terms of their matrices:

1. Ceramic-matrix nanocomposites,
2. Metal-matrix nanocomposites, and
3. Polymer-matrix nanocomposites.

Their flexibility and conformability with textiles render polymer-matrix nanocomposites more
suitable for smart textiles use.

PNCs have reached a phenomenal status in industrial and real-life applications due to their ease
of production, lightweight, ductile nature, high strength, better resistance to corrosion, fire, and
acids, higher fatigue strength, and much more. Polymer matrices can be broadly divided into two
major groups based on their response to heat: (i) thermosetting polymers and (ii) thermoplastic
polymers, and are discussed in the following sections.

The nanocomposites can be divided into three categories according to the strength of interfacial
interactions between the polymer matrix and layered silicate, such as-

1. Intercalated nanocomposites,
2. Flocculated nanocomposites and
3. Exfoliated nanocomposites

Intercalated Nanocomposites
In this class of nanocomposites, the polymer matrix is inserted into the layered silicate structure
in a crystallographically regular fashion so as to swell the spacing between the platelets.
Generally, these nanocomposites are interlayered by a few molecular layers of polymer, and the
properties are very similar to ceramics.
Flocculated Nanocomposites
These nanocomposites are very similar to intercalated nanocomposite. Sometimes, in this class
of composite, the silicate layers are flocculated because of hydroxylated edge–edge interaction of
the silicate layers.

Exfoliated Nanocomposites
In exfoliated nanocomposites, depending upon clay loading, the individual clay layers are
separated in a continuous polymer matrix. The clay content of this class of nanocomposite is
much lower than intercalated nanocomposite.

Nanoparticles of metals, metal oxides, and nonmetal oxides are utilized in nanocomposites as
reinforcement components. These nanocomposites show unique mechanical, thermal, and
electrical characteristics. Metal nanoparticles have found use in nanocomposites developed for
catalyst and biomedical applications. Nanoparticles of metal oxides are added to nanocomposites
to obtain mechanical strength, electrical and thermal conductivity, barrier effect, antibacterial
effect, UV protection, and self-cleaning property. Among metal oxide particles, TiO2 and
SiO2 are commonly utilized.

Nanoclay-reinforced nanocomposites have been extensively studied in terms of their special

properties including thermal resistance, flame retardancy, stiffness, and strength. Nanowire-
based nanocomposite have found use in energy storing and harvesting applications.

Characterization of Nanocomposites:
The macroscopic morphology and surface texture of nanocomposites are mainly investigated by
scanning electron microscopy (SEM), transmission electron microscopy (TEM), wide angle X-
ray diffraction (WAXD) and small angle X-ray scattering (SAXS). SEM is very simple and most
widely used for morphological analysis. Though TEM is used by many researchers as an
essential tool for qualitative analysis, structural defect analysis and spatial distribution study, it is
time consuming and does not provide quantitative information. WAXD is also widely used to
study the structure by monitoring the position, shape and intensity of basal reflections. WAXD
does not provide much information regarding the spatial distribution or any structural defects in
nanocomposite.

DSC is used to analyze the thermal behavior of nanocomposites. The molecular structure of
nanocomposite can be characterized by various techniques such as nuclear magnetic resonance,
Fourier transform infrared, SAXS and optical birefringence. X-ray photoelectron spectroscopy
and water contact angle measurement techniques can be used for the analysis of chemical
properties.

Properties of Nanocomposites:
The properties of the nanocomposite depend upon the clay and polymer combination, the
characteristics of the nanofiller and polymer as well as the structure of the composite produced.
The nanocomposite possess noticeable differences in their thermal, mechanical, barrier and
electrical properties when compared with traditional composites.
The optimal structure of a nanocomposite for one physical property may not be the best for
another physical property. This section highlights the properties of nanocomposites.

Mechanical Properties:
The mechanical properties of nanocomposites, such as tensile strength, elongation and modulus,
are affected by the surface morphology and the material used for production. The improvement
of mechanical properties of polymer nanocomposite can be attributed to the good affinity
between the polymer and nanofiller along with the high rigidity and high aspect ratio of
nanofillers.

Electrical Properties:
The electrical properties of nanocomposites depend on several factors, such as aspect
ratio, dispersion and alignment of the conductive nanofillers in the structure. The
nanocomposites containing CNTs have superior electrical properties (high energy densities and
low driving voltages). The nanocomposite of ether/clay (organically modified) exhibit ionic
conductivity that is several orders of magnitude higher than that of the corresponding clay. The
electrical conductivity increased by several orders of magnitude with a very small loading (0.1
wt.% or less) of nanotubes to the nanocomposite, without altering other properties such as optical
clarity, mechanical properties and low melt flow viscosities. The conductive nanocomposite has
found applications in many fields such as electrostatic dissipation, electrostatic painting,
electromagnetic interference shielding, printable circuit wiring and transparent conductive
coating.

Optical properties:

The advances in the technology and utilization of telecommunication devices and electronics
have increased electromagnetic pollution. The resulting electromagnetic interference (EMI)
could disrupt equipment, systems, and the electronic devices used in critical fields, such as
military, aerospace, and medicine. Long-term exposure to electromagnetic waves could cause
adverse effects on human health. Electronic systems and equipment generate waves that exist in
the microwave range of the electromagnetic radiation spectrum. These radiations have to be
shielded. In this context, electromagnetic shielding is defined as the practice of electromagnetic
field reduction in a space using a blocking field with barriers composed of a magnetic or
conductive material. Shielding is achieved within enclosures used for isolating the electrical
devices from the ―outside world‖ and isolating the wires from the environment through which
the cables run [160]. Figure 13 presents the schematic representation of EMI shielding. The
mechanisms that are exploited for shielding could be categorized into three main classes—
reflection, absorption, and multiple reflections. Reflection is the primary mechanism exploited in
EMI shielding. In order to shield radiation through reflection, the shield has to contain the
mobile charge carriers—either electrons or holes—that would interact with the electromagnetic
field in the radiation to be shielded. Absorption is the secondary mechanism of EMI shielding. In
order to shield radiation mainly through absorption, the shield must have magnetic or/and
electric dipoles that would interact with the electromagnetic field in the radiation. The electric
dipoles could be provided by BaTiO or other materials with a high value of the dielectric
constant, while the magnetic dipoles could be provided by FeO or other materials with a high
degree of magnetic permeability. The third mechanism of EMI shielding is multiple reflections,
in which reflections occur at various interfaces or surfaces in the shield. This mechanism of
shielding requires a large interface or surface area in the shield. The loss owing to multiple
reflections is negligible when the distance between the reflecting interfaces or surfaces is large
compared to the skin depth. Shielding effectiveness (dB) of a material is defined as the sum of all
the losses that have occurred due to reflection, absorption and multiple reflections

Magnetic properties:

Nanocomposites that can respond to an external stimulus are of increased interest due to
the fact that, because of the large amount of interaction between the phase interfaces, the
stimulus response can have a larger effect on the composite as a whole. The external stimulus
can take many forms, such as a magnetic, electrical, or mechanical field. Specifically, magnetic
nanocomposites are useful for use in these applications due to the nature of magnetic material's
ability to respond both to electrical and magnetic stimuli. The penetration depth of a magnetic
field is also high, leading to an increased area that the nanocomposite is affected by and therefore
an increased response. In order to respond to a magnetic field, a matrix can be easily loaded with
nanoparticles or nanorods The different morphologies for magnetic nanocomposite materials are
vast, including matrix dispersed nanoparticles, core-shell nanoparticles, colloidal crystals,
macroscale spheres.Magnetic nanocomposites can be utilized in a vast number of applications,
including catalytic, medical, and technical. For example, palladium is a common transition metal
used in catalysis reactions. Magnetic nanoparticle-supported palladium complexes can be used in
catalysis to increase the efficiency of the palladium in the reaction.Magnetic nanocomposites can
also be utilized in the medical field, with magnetic nanorods embedded in a polymer matrix can
aid in more precise drug delivery and release. Finally, magnetic nanocomposites can be used in
high frequency/high-temperature applications. For example, multi-layer structures can be
fabricated for use in electronic applications. An electrodeposited Fe/Fe oxide multi-layered
sample can be an example of this application of magnetic nanocomposites.

Application of Nanocomposites:
Polymer nanocomposites with their unprecedented property combinations and exceptional design
possibilities are establishing themselves as high-performance materials of the twenty-first
century and are used in multifarious cutting-edge technology

Aerospace:
Projecting heavy lift systems to the earth‘s lower atmosphere incurs a huge cost in terms of fuel
prices. The fuel cost amounts to about 30% of the operational cost even in general aviation. So
the implementation of polymer/CNT nanocomposite in a space shuttle and commercial aircraft
such as Boeing 787 and Airbus A380 as shown in Figure 2.
 Figure 2: Polymer nanocomposites used in different parts of the Airbus A380.

Automotive:
With increasing global concerns for low fuel economy and low emissions in the case of land
transportation systems, research is trending toward the low cost, high performance, and
lightweight polymer nanocomposite. This class of novel materials is expected to increase the
speed of production, environmental and thermal stability, and recyclability, while reducing the
weight.

Infrastructures/Civil Structures:
Polymer composites with nanofillers have always acted as game-changers about their use in
structural components (buildings, bridges, and other engineered structures) which can be
attributed to the high strength-to-weight ratio of the class of materials. They are also highly
durable in terms of thermal, mechanical, and barrier properties. One of the important components
of civil structures is concrete. But a lot of improvements are expected in it concerning its
increased durability, tensile strength, and reduced brittleness. Composites with organo-clays are
commonly used as barrier coatings to protect the civil structures against environmental aging and
corrosion. A coating based on epoxy polymer with nano-ceramic fillers could shield the concrete
structures from UV radiations, contamination, and deterioration.

Food Packaging:
Polymer nanocomposites, owing to their superior functionality, antibacterial properties,
lightweight, and cheap and simple processing techniques, have proved to be better replacements
for the conventional packaging materials such as metals, ceramics, and paper. The inherent
barrier properties (mechanical and thermal), biodegradability, self-healing, and self-cleaning of
those composites increase the shelf life of the packaged food items. Polymer/clay has
considerable performance in the packaging of processed foods like cheese, meats, confectionary,
cereals, boil-in-bag foods, and even for fruit juices and carbonated drinks.
Energy:
Materials with high dielectric constant, optimum piezoelectric properties are often searched for
their importance in energy storage and harvesting application. Low dielectric constant polymers,
when blended with dielectric / piezoelectric ceramics nanofillers, form a good combination with
requisite properties. Flexible polymer-based nanocomposite suitable for energy harvesting serve
as the new generation functional materials.

Bio-Medical:
Polymer nanocomposites form the basic building blocks of life systems starting right from bone
(a combination of ceramic phosphate crystallites and collagen fibers forming strong and dense
cortical bone or spongy shear resistant cancellous bone), teeth (enamel, cementum, and dentin
containing different volume fractions of hydroxyapatite crystals along with collagenous or non-
collagenous proteins), or wood (consisting of cellulose and lignin). Hence, polymers blended
with other nanoparticles open up great avenues for a multitude of applications in a biomedical
field such as tissue engineering, bone replacement/repair, dental applications, controlled drug
delivery, and many more. Some of the applications of polymer nanocomposites are shown in a
representative Figure 4. Several magnetic polymer nanocomposite have been used in biomedical
and environmental applications.

Conclusion:
The polymer nanocomposites are very important in the field of material science for the past two
decades. Even though the development of this promising technique is just in its infancy, it has an
emerging future in various applications. Polymer nanocomposite have a great potential marking
it as a vibrant area of work in the recent years. The improvement and application of
nanocomposites will depend upon how effectively we can handle the challenges.

Reference

https://textilelearner.net/nanocomposites-classification-properties/

III Nano materials versus Bulk materials :

Metals nanoparticle has been received attention by the enhanced properties due to minimizing
the scale to the nanoscale. These better properties have been used in many applications in

 medicine,
 electric and
 electronic,
 catalytic, and so on.

An example,

i) gold nanoparticles smaller than 10 nm has relevant optical and electronic properties that can be
used as photocatalytic. Even more, the rhodium nanoparticle between 2 to 2.5 nm has the B5
sites that are very important active sites to catalysis.

ii) The silver nanoparticle in the range of 1 to 10 nm has the bactericidal effect.

iii) The scientists have been exploring the potential for nickel nanoparticles in the form of
nanorings as memory cells, alloys of copper and nickel at the nanometer scale are being
investigated for use in controlled magnetic hyperthermia applications, due to the unique
bioactivity and challenges to human health, electrode materials, in batteries and solar cells.These
properties are only possible in consequence of nanoscale level, promoting the interest in
experimentation and use in industry.

iv) The wide applications and properties of nanomaterials just can be appreciated due to the
nanoscale. Decrease the particle size change the relation of surface atoms and internal atoms, it
represents the surface energy and internal energy.

In consequence, the decrease in the internal energy to compensate for the increase of surface
energy, thus providing the enhanced effects, shown in Figure 1.
Fig 1: (A) Reduction scale from bulk to nano, (B) surface of bulk material, and (C) surface of
nanomaterial.

The bulk material is a macroscopic material with micrometers or more. These materials are very
stable in consequence of the number of internal atoms to compensate for the surface energy.

 In Figure 1B illustrates this phenomenon in a bulk material surface, the dotted line
represents the inexistent atoms that the surface atoms had made linked promoting the
increase in the energy level in these atoms. It possible to note, that the bulk atoms are
more distant from each other, as internal atoms get closer to surface atoms, the atoms
getting closer and closer to each other, compensating for surface energy.
 In Figure 1C showed the surface of nanomaterial. The number of inexistent atoms in
nanomaterial is higher than bulk materials, in consequence, the surface energy is much
higher. In contrast to bulk material, the nanomaterials have few amounts of extension
atoms, resulting in closer atoms in the nanoparticle, thereby, does not having enough
atoms to compensate the surface energy and increasing the total energy in nanoparticle to
promote the enhanced effects and properties. Also, according to the electron-sea model,
in bulk, the electron has the sea as the mean free path, in comparison to the nanoparticles,
the electron has a lake as a mean free path, increasing the surface energy. It can be seen
in gold nanoparticles with 2 and 3 nm to become reactive.

 In this way, the properties are strongly dependents of the size, shape, and
structure.However, to these properties, be reproducible all particles have to be similar to
each other, and it is possible through controlled synthesis. To produce monodisperse
nanoparticles with these characteristics the nucleation and growth processes are hardly
important. To it, these both moments must separate and divided to produce homogenous
 nucleus and growth with similar size and ratio. It can be explained by the LaMer plot in
Figure 2.

 LaMer plot is divided into three stages,

 in Stage I, which occur the generation of atoms. Here, the metal ions are reduced to
produce the metallic atoms, in this stage, the atoms do not have enough energy to form
seed and nucleus. When the concentration of atoms reaches the minimum concentration
to achieve the energy barrier to the homogeneous nucleation (Equation 1)[13] the nucleus
are formed. This moment is the critical radius (red dot) in LaMer plot, that the seeds have
the surface free energy per unit area (γ), minimum radius (r), and free energy change
(DGv) to be stable in solution.

 In sequence, Stage II occurs the nucleation, in this part, the seeds come together to form
the nucleus. It is interesting in the controlled synthesis that this part happens in the
shortest time possible to the nucleus has the same size. On the other hand, if this part
happens in a long time, the nucleus will have different sizes and a large particle size
distribution, in consequence of the nucleus aggregate.

 Then, Stage III occurs the growth, that the nucleus comes together to form nanoparticles
and nanocrystal. In this part can be used the same strategy in the nucleation, the growth
happens in the shortest time possible to have a narrow particle size distribution.
 Figure 2. LaMer Plot describing three stages of metal nanoparticle formation in the
solution system. Stage I: Generation of atoms, stage II: Nucleation, and stage III: Growth.

 The capping agents could be additives (organic molecules, polymers, or surfactants) or

anions such as counterions of precursors to fixed in a specific crystalline surface making
a steric stabilization and protect to growth, but the exposed plane continuous grow at the
point that surface is normalized.[17,18] Figure 3 illustrates this phenomenon, that started
in nucleation and growth theory by LaMer curve[15], every crystal was once an ion and
through in nucleation process to produce atom, at the moment the concentration of the
atoms is sufficient to atoms start to aggregate to form small nuclei via self-
nucleation.[14] Thereby, the concentration of the atoms decreases while the cluster
concentration increases, over time the nuclei size increases at the point to form small
crystals. At this moment, the capping agent is important to control the shape and/or size,
because the crystalline surface is well-defined, and the capping agent can perform more
efficiently. In Figure 3a represent the crystal grow without capping agent, so the nuclei
incorporate into all surface crystal, and the crystal has uniform growth. In Figure 3b, it
was used a moderate amount of capping agent to control the synthesis to form a cube due
to the CeO2 truncated octahedral, in this example, has {111} and {100} plane, and the
capping agent preferentially interacts in {100} plane, inhibiting this plane grow, in other
hands, the exposed {111} plane has been grown at the point of the surface is level. In
Figure 3C was used an excessive amount of capping agent, consequent, it fixed and
protecting all surface, inhibiting the crystal growth remaining in small size. [19–21]

 In this way, considering that nanoparticles exhibit a narrow size, morphology, and
structure by the well-defined nucleation and growth process, it is possible discussed
which parameters influence these aspects, for example, the solvent, the surfactant and its
amount, the reduction agent and its amount, temperature reaction, time reaction, and so
on. The solvent can influence the ion diffusion velocity, in consequence, modify the size
and shape. In some cases, it can have multiple functions, as a capping agent and reduction
agent, like ethylene glycol. The surfactant and capping agent influence morphology, size,
and structure through the amount, as shown in Figure 3. During the nucleation and
growth, the protective agent fixes in a determinate crystal face to blocking this growth
face and prioritize other crystal faces. The reduction agent can control the speed
nucleation and growth depending on the reduction potential, it can influence how well
defined is the nanoparticles. The temperature reaction influence solvent viscosity, in
consequence, in the diffusion of ions, nuclei, and particles. The metal salt and amount are
important parameters.

Reference:
 https://www.linkedin.com/pulse/difference-between-bulk-nano-what-synthesis-influence-felipe-
anchieta