Nanotechnology MSc Course Asst. Prof. Dr. Aseel K.

Shyaa

Lecture Two
Synthesis and Characterization of Nano materials and Nano fluids
2.1 Synthesis of Nano structures and Nano materials
Physical properties of materials and systems can often be
categorized as being either intensive or extensive, according to how the
property changes when the size (or extent) of the system changes.
According to International Union of Pure and Applied Chemistry
(IUPAC), an intensive quantity is one whose magnitude is independent of
the size of the system or the amount of material in the system, whereas an
extensive quantity is one whose magnitude is additive for subsystems,
Examples of intensive properties include temperature, density, and
hardness of an object. By contrast, extensive properties such the mass,
volume, entropy of systems are additive for subsystems.

Figure2.1 Extensive and Intensive property

The terms stable and metastable are used in to get an idea of the
changing nature of a material. The key difference between stable and
metastable is that the term stable refers to the state of a material being truly
unchanging whereas the term metastable refers to the state of a material
where a change cannot be observed. in other words, the term stable
describes the unchanging nature of matter, while the term metastable
describes the apparent unchanging nature of matter. Furthermore, stable
has the lowest possible energy level whereas metastable has a
comparatively high energy level.

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

Free energy is an extensive property of a matter hat depends on the

amount of matter in the sample. Nanoparticles are - metastable systems. If
one plots the free energy of : system for a fixed amount of material,
nanoparticles exist at a higher energy than the bulk materials (see Figure
2.2), Nanoparticles constitute a regime in which the energy is in between
that of bulk materials and molecules/atoms. It is possible to convert one
form to the other by physical or chemical means.

Figure 2.2 Nanoparticles shown as a metastable system; their energies

are between atoms, molecules, and bulk. There can be several different
types of nanoparticles with distinct energy, and each nanoparticle can be
converted to bulk.

In the smaller size regime of less than 1 nm, nanoparticles possess

distinct structures and maybe regarded as nano cluster molecules. Various
structures of a given size may have large differences in properties. In the
larger size regine, numerous structural forms can exist, but it is difficult to
distinguish them. When it comes to large changes in the geometry, as in
the case of a nanoparticle and a nano rod, distinctions can e made on the
on basis of their electronic properties. Synthetic methodologies are
available to make some of these structures in the case of a few metals and
ceramics. As is evident from Figure 2.2, transformation from one form to
another is possible. Although the transformation from atoms, molecules,
and nanoparticles to bulk is spontaneous, stabilizing the nanoparticle
regime requires careful control. The formation of nanoparticles from
constituent atoms is referred to as the bottom -up approach, while the
synthesis of nano structures from bulk is referred to as the top-down
approach.
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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

A nanoparticle is composed of two entities: the core, often ceramic,

metallic, or polymeric ,and . thin shell, which may be ionic, molecular,
polymeric, ceramic, or metallic. In most cases, encounter a ceramic or
metallic core and a molecular shell (Figure 2.3) The properties of
nanoparticle are due principally to the core, and the shell is used to provide
a protective layer. Often, the nature of the shell is extremely significant in
number of applications, such as luminescence of the particles. The
solubility of a nanoparticle is determined on the chemical nature of the
shell. Solubility is not the appropriate term, as the solution or fluid formed
is in fact a dispersion, which may be separated by physical means such as
centrifugation

Figure 2.3 Schematic of a nanoparticle, showing the core and shell. The
molecular shell has three distinct regions, although one or more of these
may be absent in a specific case.

2.2 . Synthesis and Preparation of Nanofluid

The performance of the nano fluid depends on various factors
such as concentration of nano particles in the given base fluid,
size of the nano particle, dispersion quality, stability of
suspension, stable chemical composition and non-corrosive
nature of the nano particle with the base fluid etc., in order to
achieve this, the synthesis technique adopted plays an important
role. Synthesis of nano-fluids is widely accepted by two

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

techniques as shown below in figure 2.1 represent the preparation

of nano fluid by one step and two step methods.:
1. One-step process.
2. Two-step process

2.2.1 One-step method

In this method, the production of nanoparticles and the preparation
of nano fluid are performed simultaneously. The required size of
nanoparticles is prepared and concurrently dispersed with the desired
concentration in the host fluid. Therefore, the output of this method is a
nano fluid that can directly be used. Several single-step methods have been
used for nano fluids preparation that can summarized as:

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

a. Vapor Deposition (VD)

Direct evaporation and condensation of the nano particulate
materials in the base liquid are done
to produce stable nano fluids. The two main categories of vapor
deposition (VD) are physical vapor deposition (PVD) and chemical
vapor deposition (CVD).
In the physical vapor deposition (PVD) method, the bulk metal is
evaporated in an inert-gas atmosphere, which is then followed by vapor
condensation. The size of nanoparticles depends on degree of heat applied
for evaporation, as with increase in superheat, the particle size reduces. The
particle size decreases with increase in pressure of the inert gas. During
vapor condensation,nanoparticle sizes and the particle size distribution are
controlled by regulating the condensation conditions.
While in the chemical vapor deposition (CVD) method, nano
fluids can be produced by the condensation of the nanoparticles from the
vapor phase into a flowing low vapor pressure fluid, such as oil. In this
method, drying, storage, transportation, and dispersion of nanoparticles are
avoided, so the agglomeration of nanoparticles is minimized and the
stability of the nanofluids is increased.

.A water-based Cu nano fluid was prepared by Liu, Lin, Tsai, and

Wang (2006) using the one-step chemical reduction method for the first
time. Without using any surfactant, Cu-water nano fluids were prepared
with volume concertation less than 0.2%. Using a one-step method,
Eastman, Choi,Li, Yu, and Thompson (2001) had synthesized ethylene
glycol (EG)-based Cu nano fluids. In the preparation method, the contact
between a metallic vapor (Cu) and a flowing low vapor pressure liquid
(EG) resulted in a direct condensation of Cu nanoparticles. The diameter
of the prepared Cu nanoparticles was less than 10 nm, and the volume
concentration was about 0.3%.
b. Electrical Explosion of Wire
A promising one-step method is the electrical explosion of wire
(EEW) in the desired base fluid. EEW technique uses high electric voltage
and current to cause explosion of a thin metal wire a in a container of base
fluid to produce the nano fluid.

The one-step method is desirable to prepare nanofluids containing

metal nanoparticles to prevent oxidation. Higher dispersion stability of
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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

nanofluids can be obtained by this method due to reduced agglomeration

of nanoparticles. However, there are some limitations for this method such
as it is only applicable to fluids with low vapor pressure, can only be used
for synthesizing nano fluids in small scale, and relatively expensive.

2.2.2 Two-step method

In this method, preparation of and nanofluid requires two steps. In the first
step, the nanoparticles are produced as dry powders. Then, the second step
is the dispersion of these nanoparticles in any suitable host fluid. The
stability of the nanofluids prepared by this method represents : challenge
because suspending solid nanoparticles in a base fluid will not result in a
simple mixture. Owing to the high specific surface area (SSA) of
nanoparticles, they will have acapability to agglomerate over time due to
high surface tension between them. Agglomeration of the nanoparticles
will cause them to settle down and block the flow channels. This is a
drawback for this method, but its main feature is the ability for synthesizing
nanofluids in large scale for industrial applications. There are several
methods available to prevent or reduce the effect of agglomeration, such as
the addition of surfactants or using ultrasonication.

2.3 Characterization of Nanomaterials and Nanofluids

The most commonly used methods for the characterization of the various
nano materials and nanofluids will be presented in the following sections.

2.3.1 Scanning Electron Microscope (SEM)

There are many types of microscopes, and they may be grouped in different
ways. One way is to describe the method an instrument uses to a interact
with a sample and produce images, either by sending a beam of light or
electrons through a sample a in its optical path, by detecting photon
emissions from sample, or by scanning across and a short distance
from the surface of a sample using a probe. The most common
microscope (and the first to be invented) is the optical (light) microscope
(see Figure 2.4), which uses visible light (400-700 nanometers) to
illuminate the sample and lenses to refract the light that passed through a
thinly sectioned sample to produce an observable image. Other major types
of microscopes are the fluorescence microscope (which is an optical
microscope that uses fluorescence, much higher intensity light source, to
generate an image),electron microscope (both the transmission electron
microscope and the scanning electron microscope), and various types of
scanning probe microscopes.

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

An electron microscope is a microscope that uses a beam of

accelerated electrons as a source of illumination. As the wavelength of an
electron can be up to 100,000 times shorter than that of visible light
photons, electron microscopes have higher resolving power than light
microscopes and can reveal the structure of smaller objects

Figure 2.4 Types of microscopes illustrated by the principles of

their beam paths.

A scanning electron microscope (SEM) is a type of electron microscope

that produces images of a sample by scanning the surface with a focused
beam of electrons. The electrons interact with atoms in the sample,
producing various signals that contain information about the surface
topography and composition of the sample. The electron beam is scanned,
and the position of the beam is combined with the intensity of the detected
signal to produce an image. In the most common SEM mode, secondary
electrons emitted by atoms excited by the electron beam are detected using
a secondary electron detector. The number of secondary electrons that can
be detected, and thus the signal intensity, depends, among other things, on
specimen topography.

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

Figuren2.5 SEM images of expanded graphite

2.3.2 Transmission electron Microscopy(TEM)

size and shape of the nano materials can be The scattering (distribution)
characterized using a very beneficial tool that is Transmission Electron
Microscopy (TEM). However, for nanofluids and due to the use of dried
samples in this method of characterization, the actual state of the nano
materials in the nanofluid cannot be obtained. In this microscopy method,
an ultra-thin specimen is used that interacts with a beam of electrons as it
passes it through it. The image formed from the interaction is
enlarged and focused onto an imaging device. For preparing the specimen
for TEM, a drop of dilute
nanofluid is placed onto a special grid and oven-dried
The formation of nanoparticles is best studied by transmission electron
microscopy (TEM),which gives two types of information in routine
examination. The first is the particle size distribution, is
which is normally represented in terms of a mean diameter and a standard
deviation. The second type of information is the crystallinity of a sample,
obtained through electron diffraction or nano-diffraction. More detailed
information on particle shape, phase transitions, two- and three-
dimensional ordering, in-situ nano-measurements, and evaluation of other
properties are possible using TEMThe TEM images for samples of pristine
Graphene Nanoplatelets (GNPs) and Sodium Dodecylbenzene Sulfonate
(SDBS) Surfactant/GNPs aqueous nanofluids are displayed in the figure

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

below. All the TEM images reveal the presence of some multi-layer
structure of GNPs. Images of the pristine GNPs sample (a, b) illustrate
flakes with relatively smooth layer's surface and edge. On the other hand,
images of the SDBS-GNPs sample (c and d) provide layer's surface full of
wrinkles. Although TEM images are not able to show minute SDBS
surfactant, some changes in morphology
and surface deterioration can be considered as an evidence for
functionalization. The wrinkles (waviness) seen in the TEM images are
attributed to the inherent instability of 2D structures, which
is increased during the ultrasonication process, resulting from appropriate
flexibility of GNP flakes after treatment. Undoubtedly, SDBS can increase
the wettability of GNP layer's surface, implying
higher tendency for wrinkling during ultrasonication and/or drying process
in preparing the TEM samples. Consequently, higher dispersion stability

was obtained as a result of higher wettability of

the GNP layer's surface.

Figure 2.6 TEM images of water-based 0.1-wt% GNPs 300

nanofluids. (a, b) Pristine GNPs, and
(c, d) GNPs with surfactants.

2.3.3 Atomic Force Microscope (AFM)

Scanning probe microscopy (SPM) is a branch of microscopy that forms
images of surfaces using physical probe that scans the specimen. SPM was

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

founded in 1981, with the invention of the scanning tunneling

microscope (STM), an instrument for imaging surfaces at the atomic level.
The first successful scanning tunneling microscope (STM) experiment was
done by Gerd Binnig and Heinrich Rohrer in 1981. The key to their success
was using a feedback loop to regulate gap distance between the sample and
the probe. In 1984, the scanning near field optical microscope SNOM by
Pohl et al. was added to the family of SPMs and followed by the atomic
force microscopy (AFM) by Binnig, Gerber, and Quate in 1986 Atomic
force microscopy (AFM) is type of scanning probe microscopy (SPM),
with demonstrated resolution on the order of fractions of a nanometer,
more than 1000 times better than the optical diffraction limit. The
information is gathered by "feeling" or "touching" the surface with a
mechanical probe. Piezoelectric elements that facilitate tiny but accurate
and precise movements on (electronic) command enable precise scanning.

Figure 2.7 Typical configuration of an AFM. (1) Cantilever, (2) Support

for cantilever, (3) Piezoelectric element (to oscillate cantilever), (4) Tip
(acts as the probe), (5) Detector of deflection and motion of the antilever,
(6) Sample to be measured by AFM, (7) xyz drive, (moves sample in x, y,
and z directions with respect to a tip), and (8) Stage.

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

Figur2.8 (c and d) AMF of graphene on mica and (e and f) the height

profiles along the black imaged lines above in panels c and d
respectively .

2.3.4 Fourier Transform Infrared Spectroscopy (FTIR)

The goal of absorption spectroscopy techniques (FTIR, ultraviolet-
visible ("UV-Vis") spectroscopy, etc.) is to measure how much light a
sample absorbs at each wavelength. Fourier transform infrared
spectroscopy (FTIR) is a method in which an infrared spectrum of
absorption or emission can be obtained for a liquid, solid, or gas. In FTIR,
when the infrared radiation passes through a sample, some is transmitted
and the other is absorbed by the sample. The spectrum obtained from this
test represents the absorption and transmission of molecules, and thus
generating a unique fingerprint for the molecules in the in sample.

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

Figure 2.9 characterization of the pristine and triethanolamine-treated

graphene nanoplatelets (TEA-GNPs) using FTIR spectral measurements

Table 2.1 Ranges of FTIR vibration peaks and their corresponding

chemical bonds for TEA-GNPs with a specific surface area (SSA) of 750
m 2/g

2.3.5 Raman Spectroscopy

Raman spectroscopy is a method used to detect the rotational,
vibrational, and other low-frequency modes in a system through which an
identification pattern for the molecules can be obtained. It depends on the
scattering, of monochromatic light such as laser in the visible, near
infrared, or near ultraviolet range. The energy of the laser photons is shifted

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

up or down when it interacts with molecules in the system. The

identification pattern is detected from the information about the vibrational
modes in the system given by this shift in energy.
The D band is related to the amorphous/disordered carbon (sp') and
the G band to the graphitic
carbon (sp?). The increase in the Raman intensity ratio (Ip/Ic) means that
some of the hybridized carbons have changed from sp? to sp' because of
the covalent functionalization. While pristine GNP 750 shows a ratio of
0.508 for the Ip/la, the TEA-GNPs 750 depicts a ratio of 0.999. Larger
(ID/Ic) ratio indicates the presence of higher number of sp3 carbons and
the happening of an electrophilic
addition reaction.

Figure 2.10 Characterization of the pristine and TEA-GNPs using Raman

spectral measurement.

2.3.6 Energy Dispersive X-Ray Spectroscopy (EDS)

Energy dispersive X-ray spectroscopy (EDS, EDX, EDXS, or
XEDS) is a chemical microanalysis technique used in conjugation with
scanning electron microscope (SEM) and the measurement procedure is
based on the interaction of a sample with some source of X-ray excitation
and used for the elemental analysis or chemical characterization. The
characterization using this technique is based on the essential theory that
the unique atomic structure of any element has its
unique set of peaks in the X-ray emission spectrum.
For example, to confirm the electrophilic addition reaction,
elemental analysis was performed by EDS spectroscopy for the three SSAs
used in a study (i.e., 300, 500, and 750 m⅔) and presented in the below
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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

figure. The EDS spectra of the TEA-GNPs illustrate traces amount of

nitrogen, oxygen, and carbon in their chemical structures. Furthermore,
EDS results are presented in the below table to accurately ascertain the
exact amount of each element. EDS analysis illustrates the same degree of
functionalization for the different SSAs of GNPs. Note that the presence of
O and N elements in the TEA-GNPs is a good evidence of successful
functionalization.

Figure 2.11 Characterization of the pristine and TEA-GNPs using EDS

traces for different SSAs of the TEA-GNPs: (c) 300, (d) 500, and (e) 750
m°/.

Table 2.2 EDS results for TEA-GNPs with different SSAs.

2.3.7 Dynamic Light Scattering (DLS)

Dynamic light scattering (DLS) is an analytical method in physics that can
be used to generate a profile for the size distribution of nanomaterials in

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Nanotechnology MSc Course Asst. Prof. Dr. Aseel K. Shyaa

colloidal dispersion. In a DLS system, a laser beam is concentrated on a

dilute dispersion of a sample contained in special quartz cuvette, and as it
transmits through the colloidal dispersion, the laser light is scattered at
different intensities in all directions by the Brownian motion of the
dispersed particles. From the analysis of the scattered lightand using the
Stokes-Einstein relationship, the particle size distribution can be
calculated.
The Stokes-Einstein equation is the equation first derived by
Einstein in his Ph.D thesis for the diffusion coefficient of a "Stokes"
particle undergoing "Brownian Motion" in a quiescent fluid at uniform
temperature. The result was formerly published in Einstein's (1905) classic
paper on the theory of Brownian motion.

Figure 2.12 Average particle size for the 0.1-wt% water-based GNPs 300
nano fluid with different surfactants

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