Synthesis fabrication and

characterization of nanostructured
materials:
Contents
Introduction:...............................................................................................................................................3
Synthesis of nanomaterials..........................................................................................................................3
Physical route of synthesis of nanomaterials:.............................................................................................5
Top-down syntheses:...................................................................................................................................6
Bottom-Up Method:....................................................................................................................................6
Pattern of XRD:............................................................................................................................................7
Other Methods:...........................................................................................................................................9
Synthesis of nanomaterials by the use of microorganisms:.........................................................................9
Use of bacteria:...........................................................................................................................................9
Use of fungi:..............................................................................................................................................10
Algae use:..................................................................................................................................................10
Using biological templates to synthesize nanomaterials:..........................................................................10
Using plant components to make nanomaterials:.....................................................................................11
Laser evaporation method:.......................................................................................................................11
RF plasma method:....................................................................................................................................12
Thermal breakdown or thermolysis:.........................................................................................................12
Oxide nanoparticles via thermal breakdown technique:...........................................................................12
Chemical route of production of nanomaterials:.......................................................................................13
Co-precipitation method:..........................................................................................................................13
The reduction reaction is:..........................................................................................................................15
Hydrothermal:...........................................................................................................................................16
Sonochemical:...........................................................................................................................................18
Microwave-aided synthase:.......................................................................................................................18
Fabrication of Nanomaterials:...................................................................................................................18
What Basically nano particle is?................................................................................................................19
Characterization of nanoparticles:.............................................................................................................20
X-ray methods:..........................................................................................................................................20
Magnetic nanostructures characterization:...............................................................................................21
Focus on NP size — multiple strategies for characterization:....................................................................22
Conclusion:................................................................................................................................................23
Introduction:
Dr Baig's group is working on the development of various nanomaterials for a range of
applications. They are particularly interested in developing Nano composite membranes for
enhanced performance for desalination. Various top-down and bottom-up approaches are
discussed by Dr Baig, Dr Irshad, and Dr Wail.

Nanomaterials have emerged as an exciting class of materials that are in high demand for a
range of practical applications. The history of nano-material utilization is ancient, and human
beings used nano-materials a long time ago for various applications. The term nanometer was
first used in 1914 by Richard Adolf Zsigmondy.5 The American physicist and Nobel Prize
laureate Richard Feynman introduced the specific concept of nano- technology in 1959 in his
speech during the American Physical Society’s annual meeting.

Synthesis of nanomaterials
Various methods can be employed for the synthesis of NPs, but these methods are broadly
divided into two main classes i.e. (1) Bottom-up approach and (2) Top-down approach

(Wang and Xia, 2004) as shown in Scheme 1 (Iravani, 2011).

This Figure represents a Scheme Representation of nanoparticles

and their applications.

These approaches further divide into various subclasses based on the operation, reaction
condition and adopted protocols.

Physical route of synthesis of nanomaterials:

Physical methods are classified as top-down and bottom-up. Using mechanical milling, bigger
materials are pulverized into smaller particles. That it is difficult to obtain the desired particle
size and shape. The magnetic properties of milled samples differ from those of ordinary
particles of the same size due to faults in the lattice parameters caused by the milling process.
This process condenses liquid or gaseous nanoparticles, forming bigger materials by combining
smaller ions.

This Figure represents methods for NPs for the top down approach And Bottom up approach.
Top-down syntheses:
In this method, destructive approach is employed. NPs are formed by starting from larger
molecule, which decomposed into smaller units. The raw CS powders were finely milled for
different lengths of time using a well-known planetary mill.

Spherical magnetite NPs can be synthesized by a simple top-down destructive approach with a
particle size ranging from 20 to 50 nm in the presence of organic oleic acid. The synthesis
technique was based on the continuous chemical adsorption of polyoxometalates on the
carbon interfacial surface.

It also revealed from the micrographs, that the size of the carbon particles become smaller with
sonication time. A series of transition-metal dichalcogenide Nano dots (TMD-NDs) were
synthesized by combination of grinding and sonication top-down techniques from their bulk
crystals.

The narrow size distribution of nearly all TMD-NDs smaller than 10 nm was shown to produce
excellent dispersion (Zhang et al., 2015). In recent times, a highly photoactive active Top-down
laser fragmentation was used to create Co3O4 NPs.

Bottom-Up Method:
From the bottom up, As NPs are made up of relatively simple chemicals, this strategy is likewise
used in reverse built-up method. As an illustration, consider the following situations: sedi-
thoughts and ways for cutting them down. Sol gel, as well as a variety of other colors, are
included, syntheses, spindle spinning, and biological syntheses 2011). NPs were created by
Mogilevsky et al. using TiO2 anatase NPs.

By using this method, graphene domains can be created 2014), Pre-treatment methods that
included the addition of alizarin and titanium isopropoxidephotocatalytic composite must be
synthesized methylene blue's breakdown. As a result, Alizarin was chosen. Axial hydroxyl
terminals of TiO2 have considerable binding capacity. Tests on anatase proved it to be the case.

Pattern of XRD:
Scheme 2 shows SEM pictures of various samples with reaction schemes.

Scheme 2: This figure shows the synthesis of TiO2 via Bottom up approach.
SEM images showing the TiO2 Naps (Mogilevsky et al…, 2014).

SEM shows that NP size rises with warming Mogilevsky et al. Uniform spherical Au
nanosphereslaser irradiation produced monocrystalline top-down method (Liu et al., 2015a,
2015b). Liu et al. turn octahedral into round shape by adjusting laser treatment time and other
factors parameters. The SEM and TEM of the 75 mm diameter gold Nano spheres 2.6 nm Au
Nano spheres, 3.1 octahedral edge length per particle.

(A) A molecular precursor is dissolved into simpler metal atoms, which then develop into
colloids. (B) Top-down approach: large metal drops split down into tiny drops (Wang
and Xia, 2004).
The reduction reaction is:
Mn ne! Metal M0 Mn Simultaneously, an oxidation reaction happens, Xm ne! Xmn Xm is a
reducer. The reaction takes place in liquid, yet the ultimate product is solid. This is known as
reactive crystallization.

The reduction reaction is:

Mn ne! Metal M0 Mn Simultaneously, an oxidation reaction happens, Xm ne! Xmn Xm is a

reducer. The reaction takes place in liquid, yet the ultimate product is solid. This is known as
reactive crystallization.

SOL-GEL TECH

Initially, the sol–gel process was created for low-temperature glass and ceramic preparation.
The metal alkoxide solution is first hydrolyzed with water or alcohols in the presence of acid or
base, then polycondensed. Polycondensation transformed the liquid phase into the gel phase
by removing water molecules from the solution and increasing viscosity. After all water
molecules have been condensed, the gel phase turns to powder. To acquire the fine crystalline
form of the powder, it needs to be heated.

This process produced oxides, composites, and organic-inorganic hybrids. The sol–gel process is
based on inorganic polymerization. This method's key benefit is its simplicity. However, this
method's purity is reduced due to composite production. Purification of the sample requires
post-treatment.

Hydrothermal:
The solutions are heated and pressed in this process. This process produces high-quality crystals
with controlled composition. Divalent and trivalent transition metal salts are combined 1:2 mol
ratio. Stir with the organic solvent to obtain a homogenous solution.
Then the solutions are put into a sealed vessel (autoclave) (bomb). Heating causes an
autogenous increase in pressure, directly raising the solvents' boiling points. The temperature
and time required for nanoparticle synthesis vary. This is a good way for making small
nanoparticles that can be used in biology. Copper ferrites, a common magnetic nanoparticle,
were produced hydrothermally and tested for cytotoxicity using MTT. The MCF-7 breast cancer
cells responded to them. Nanoparticles can be synthesized by selecting suitable solvents and
adjusting parameters such as temperature, pressure, pH, ageing time, reaction concentration
and reaction time. Using this method produces highly homogenous nanoparticles. This
approach allows for the creation of the smallest nanoparticles in the required crystalline phase
at lower temperatures without post-annealing. This drew more researchers than the old
approaches. This process produces single crystals, zeolites, oxides, numerous doped metals,
selenides, and sulphides.

This Figure shows the Schematic representation of Sol-Gel Method.

Sonochemical:
Sonochemical is the safest and quickest. This approach uses ultrasonic irradiation to create the
cavities (bubbles). With a temperature of over 5000 K and a pressure of 20 MPa inside the
bubble, this ultrasonic energy autogenously collapses the bubbles, causing chemical excitation
of matter inside and outside. These include metals like CoS2, alloys like CoS2, oxides and
selenides like CdSe and ZnSe.

Microwave-aided synthase:
Microwave assisted approach started in 1950s but got general acceptance in last two decades.
Using EMR, microwave radiations are directly transmitted to materials. The electromagnetic
energy is now thermal. Temperatures of 100–200C are generated by employing 1–2.5 GHz
frequencies. It demands faster reaction times so that slower reactions can be done quickly.
This approach can produce narrowly distributed tiny particles. This process creates colloidal
metals, ferrites, oxides, and selenides. The microwave polyol method was invented by Fievet et
al. Microwaves are used on metal pre-cursors containing polyalcohols. Then they make colloid
metals.

Fabrication of Nanomaterials:
The unique optical, magnetic, electrical, mechanical, and chemical capabilities of nanomaterials
have increased interest in their synthesis. Achieving potential uses in science and technology
requires understanding the manufacturing and processing of nanomaterials. Making
nanomaterials has been investigated in several ways.

The following are the main concerns or challenges in fabricating nanostructured materials:

 Control the particle size.

 Can you shape nanoparticles?

• Can you manage crystalline or amorphous structure?

• Particle sizing (monodespersive: all particles are of same size).

What Basically nano particle is?
This depends on the material and the property of interest. In detail, some metal particle
properties change for sizes below 5 nm, while oxide properties change for sizes tens of
nanometers. Many literature papers on nanostructured materials production contain no
information regarding the qualities or range of attributes that are influenced by size. As stated
previously, size matters, but knowledge on how size matters is often lacking or impossible to
determine. In this case, the particle behavior changes due to three factors: the impact of size
when material properties remain constant (classical behavior); changes in behavior when
material properties remain unchanged but a characteristic length is approximately equal to
particle size (quantum confinement); and fundamentally new material properties due to small
object size (quantum confinement).

Characterization of nanoparticles:
Nanostructures are a fast-expanding class of materials with various applications. Nanoparticles'
size, crystal structure, elemental content, and other physical features have been studied
extensively. In some circumstances, multiple techniques can evaluate the same physical
property. The pros and limits of each methodology make choosing the best method difficult.
Furthermore, given the growing importance of nanoparticles in basic research and applications,
it is imperative that researchers from many domains work together to tackle the obstacles of
reproducible and reliable nanomaterial characterization. This review's main goal is to synthesize
current knowledge on the use, advancements, advantages, and disadvantages of several
experimental approaches for characterization of nanoparticles. Characterization techniques are
classed by the information they can supply or the materials they are intended for. We outline
the approaches' essential features and principles of operation, and provide instances of their
application, comparing them to the attribute being researched in each case.
X-ray methods:
X-ray diffraction is a widely used technique for characterizing NPs. XRD typically offers
information on crystalline structure, phase, lattice parameters, and grain size. The latter
parameter is determined using the Scherrer equation and the broadening of the sample's
highest intense peak. The advantage of XRD techniques is that they produce statistically
representative, volume-averaged values. The particle composition can be established by
comparing the peak positions and intensities to the reference patterns in the International
Centre for Diffraction Data (ICDD) database. However, the XRD peaks are too broad for particles
smaller than 3 nm.

Using X-ray line broadening, Upadhyay et al. determined the typical crystallite size of magnetite
NPs to be 9–53 nm. Other than instrumental broadening, particle/crystallite size and lattice
stresses influenced XRD peak broadening. 7 The XRD-derived size is frequently larger than the
magnetic size because even though the particle is single domain, there are smaller domains
where all moments are aligned in the same direction. For samples with very large particles, the
TEM-derived size was higher than the XRD-derived size; in reality, particles larger than 50 nm
have more than one crystal border on their surface. Because XRD cannot discriminate between
the two limits, the true (TEM) size of some samples may be larger than the Scherrer formula's
50–55 nm. Dai and coworkers generated ultra-small Au NPs that were predicted to be more
developed along the direction (rather than the 220 one) based on their XRD measurements. 8
Similarly, Li and coworkers discovered that the relative intensities between XRD peaks varied
depending on the particle shape.

Magnetic nanostructures characterization:

Magnetic NPs are used in several fields, including MRI contrast media and cancer therapy.
Akbarzadeh et al. reviewed the synthesis, characteristics, and applications of magnetic
nanoparticles, with a focus on biomedical applications. This section focuses on the
characterization procedures used to assess these NPs' magnetic characteristics. SQUID
magnetometry measures the magnetic characteristics of nanoscale materials. Due to their small
size and sensitivity to local circumstances, nanomaterials have different characteristics than
bulk materials. As a material's size reduces, it goes from multi-domain to single domain to super
paramagnetic. SQUID measurements typically provide features like magnetization saturation,
permanence, and blocking temperature (TB). 88 SQUID can measure the magnetic response of
individual molecules as well as NPs. A scanning magnetic microscope with a Nano SQUID on the
tip of a sharp quartz was recently constructed. Nano SQUID is a potential nanoscale magnetic
imaging and spectroscopic probe. A Nano SQUID sensor requires two Dayem Nano bridges
(nano-constriction of a superconducting film) with length and width similar to the coherence
length.

A SQUID designed to detect magnetic NPs must have a very small SQUID area. The loop size
should be comparable to the NPs directly linked to it to achieve the optimal coupling factor. 256
In magnetic resonance force microscopy or magneto-optic spin detection, Nano Squids allow
for direct magnetization measurement in small spin systems. A Nano Squid’s Dayem
nanobridges are resistant to the magnetic field applied in the plane of the SQUID loop.
This figure shows the Optical system for dynamic light measurements of a nanoparticle
suspension in a conventional experimental setting. The setup can be used from a variety of
angles. Reproduced with the author's permission (Copyright 2013 Springer. Ref. 166).

Focus on NP size — multiple strategies for characterization:

This section provides examples of how different approaches are used to quantify sample size, as
this is one of the most basic properties of NPs and needs special attention. Akbari et al. studied
alumina NPs using TEM, PCS, BET, and XRD. The NP size was discovered to be 5–95 nm. These
particles' XRD and TEM sizes matched. The authors of the study advocate comparing PCS to
other approaches for systems where agglomeration occurs. The BET size value agreed with TEM
and XRD, as expected for spherical particles, however the PCS value was greater. They
compared multiple methods for measuring the size of silica NPs dispersed in water and cell
culture media. DLS, CLS (centrifugal liquid sedimentation), SAXS, and PTA were used (particle
tracking analysis). PTA is similar to NTA, except it covers a wider range of particle sizes. The
presence of agglomerates in the cell culture media reduced the DLS accuracy. PTA increased
significantly due to particle aggregation caused by the cell growth media, although NP size
remained steady for SAXS and CLS studies. SAXS provided accurate numbers, but CLS provided
detailed size distributions that provided additional agglomeration state information.

But DCS and TRPS readings were very close. The DCS agglomeration was larger than the TRPS
agglomeration. Unlike DLS and DCS, TRPS measures particles individually, producing a statistical
distribution of data rather than average values.
Conclusion:
Nanomaterials of appropriate size, shape, and orientation can be synthesized using several
methods. These technical approaches are classified as Top-down or Bottom-up. Both
technologies have their advantages and disadvantages in the device and nano industries. The
main flaw in top-down (physical) techniques is surface structural imperfection. These flaws
would alter the physical and chemical properties of nanostructures and nanomaterials. The
bottom-up technique is preferred over top-down synthesis for nanoparticle production due to
fewer flaws, more homogeneous chemical composition, and better ordering. From the bottom-
up, the primary methodologies include Gibbs free energy, thermodynamic equilibrium, and
kinetic approaches.