GE8073 Unit 3

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UNIT - III
3 Nanomaterials
Syllabus
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Nanoforms of Carbon - Buckminster fullerene - graphene and carbon nanotube, Single
wall carbon Nanotubes (SWCNT) and Multi wall carbon nanotubes (MWCNT) - methods
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of synthesis(arc - growth, laser ablation, CVD routes, Plasma CVD), structure - property
Relationships applications - Nanometal oxides - ZnO, TiO2, MgO, ZrO2, NiO,
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nanoalumina, CaO, AgTiO2, Ferrites, Nanoclays - functionalization and applications -
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Quantum wires, Quantum dots-preparation, properties and applications.
Contents
3.1 Nanoforms of Carbon
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3.2 Buckminsterfullerene nee
3.3
3.4
Graphene and Carbon Nanotube
Structure of Single-Walled Carbon Nanotubes rin
3.5
3.6
Multi-Walled Carbon Nanotubes
Chemical Vapor Deposition (CVD) g.n
3.7
3.8
Structure - Property Relationships
Nanometal Oxides
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3.9 ZnO, TiO2, MgO, ZrO2, NiO
3.10 Nanosized Aluminium Oxide
3.11 CaO, AgTiO2
3.12 Ferrite
3.13 Nanoclays
3.14 Functionalization and Applications
3.15 Quantum Wire
3.16 Quantum Dots
3.17 Preparation, Properties and Applications
3.18 Part A : Short Answered Questions [2 Marks Each]
3.19 Part B : Long Answered Questions
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(3 - 1)
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Fundamentals of Nanoscience (3 - 2) Nanomaterials
 3.1 Nanoforms of Carbon

 The nanoforms of any material demonstrate altered chemical and physical characteristics
compared to the same material in bulk. The quantum size effects and large surface area to
volume ratio present unique properties to their nano counterparts. Similarly, the toxicity
profiles of bulk and nanoforms also differ. Thus, analyzing the toxicity of nanomaterials
based on their bulk forms is not accurate in predicting possible side effects. Nanotoxicology
is the scientific field dealing with the in vitro, in vivo and clinical investigations of the
toxicity of nanomaterials. The toxicity of nanomaterials is often based on their physical and
chemical properties, for example, their size.
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 Investigations on the toxicity profiles of the same materials at different sizes proved that
smaller nanoparticles possess higher toxicity. However, other investigations have shown
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that smaller sized nanomaterials are less toxic. The size-based analysis found that there is
an optimal size for efficient endocytosis of nanomaterials, independent of the particle
composition.
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 Moreover, this critical size can vary with the cell type and surface properties of the
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nanomaterials. Another factor determining toxicity is the synthesis approach and
methodology used to produce nanomaterials. In this case, the source of toxicity could be the
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harsh production environment, noxious reducing agents, toxic solvents, lethal
intermediates, or harmful by-products. Consequently, to analyze the exact reason for
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toxicity, the nanomaterial production flowchart has to be profoundly analyzed. The broad
toxicity analysis investigations of nanomaterials showed an overproduction of Reactive
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Oxygen Species (ROS) in the affected organisms. The presence of excessive ROS can
induce a range of side effects such as oxidative stress, DNA damage, unregulated cell
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signaling, change in cell motility, cytotoxicity, apoptosis and cancer initiation. The critical
factors influencing the generation of ROS include the size, shape, surface area, particle
surface charges, surface-coatings/containing groups, pH of the medium, metal ion release
from nano metals/nano metal oxides, UV light activation, aggregation, mode of interaction
with cells, etc.
 Nanoparticles can interact with living organisms in two major ways external and internal.
In the external mode, nanoparticles present in air, water, food, or any other material is taken
into the body through inhalation, ingestion, or dermal absorption. In the internal mode,
nanoparticles of bio implants are directly introduced into the body. Both internal and
external modes lead to primary effects such as oxidative stress, DNA damage,
inflammation and toxicity. These health impacts gradually lead to secondary effects such as
tissue and organ deposition, systemic inflammation, altered functions and secondary
toxicity.
TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 The disruptive impact of nanomaterials on human health is associated with factors such as
genetics, existing diseases, degree of exposure and nanoparticle properties as already
explained. Clinical and animal model studies proved the inefficiency of macrophage
clearance mechanisms in removing nanoparticles from the body, which induced damage to
the lung, lymphatic system, nervous system and specific organs. Owing to their small size,
nanomaterials are even capable of overcoming the blood brain barrier, which gives them
easy access to most organs. This can lead to nanomaterial induced inflammation,
overproduction of ROS and gradually cell death. In the past decade, there was a trend of
determining the toxicity profile of nanomaterials based on in vitro cell studies, where the
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actual nanotoxicity responses vary drastically from the living organisms. In vivo animal
studies possess a much more complex system that involves the interaction of nanomaterials
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in a range of biochemical processes inside the organism, regulating interaction with
biomolecules, circulation time, biodistribution, immune response, accumulation,
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metabolism, clearance mechanism, etc. The toxicity analysis of nanomaterials thus requires
an animal model analysis to provide a more reliable record of cytotoxicity responses.
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Recently, biomimicking 3D scaffolds proved more efficient in filling the gap between in
vitro and animal model analyses by providing a closely related in vivo experience.
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 The observed adverse impacts of nanomaterials on the environment and human health have
raised serious questions about safely using advanced biomaterials. Consequently, the
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principles of green chemistry were introduced to the synthesis approaches of nanomaterials
to deliver safer nanomaterials.
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 3.2 Buckminsterfullerene
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 Buckminsterfullerene is a type of fullerene with the formula C60. It has a cage-like fused-
ring structure (Truncated icosahedron) that resembles a soccer ball, made of twenty
hexagons and twelve pentagons. Each carbon atom has three bonds. It is a black solid that
dissolves in hydrocarbon solvents to produce a violet solution. The compound has received
intense study, although few real world applications have been found.
 Buckminsterfullerene is the most common naturally occurring fullerene. Small quantities of
it can be found in soot. The molecule has also been detected in deep space. In April 2019,
scientists, working with the Hubble Space Telescope, reported the confirmed detection of
the large and complex ionized molecules of buckminsterfullerene (C60) in the interstellar
medium spaces between the stars.
 Theoretical predictions of buckyball molecules appeared in the late 1960s and early 1970s,
but these reports went largely unnoticed. Buckminsterfullerene was first generated in 1984

by Eric Rohlfing, Donald Cox and Andrew Kaldor using a laser to vaporize carbon in a
supersonic helium beam. In 1985 their work was repeated by Harold Kroto, James R.
Heath, Sean O'Brien, Robert Curl and Richard Smalley at Rice University, who recognized
the structure of C60 as buckminsterfullerene. Kroto, Curl and Smalley were awarded the
1996 Nobel Prize in Chemistry for their roles in the discovery of buckminsterfullerene and
the related class of molecules, the fullerenes.
 Concurrent but unconnected to the Kroto-Smalley work, astrophysicists were working with
spectroscopists to study infrared emissions from giant red carbon stars. Smalley and team
were able to use a laser vaporization technique to create carbon clusters which could
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potentially emit infrared at the same wavelength as had been emitted by the red carbon star.
Hence, the inspiration came to Smalley and team to use the laser technique on graphite to
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generate fullerenes.
 C60 was discovered in 1985 by Robert Curl, Harold Kroto and Richard Smalley. Using
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laser evaporation of graphite they found Cn clusters (where n > 20 and even) of which the
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most common were C60 and C70. A solid rotating graphite disk was used as the surface
from which carbon was vaporized using a laser beam creating hot plasma that was then
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passed through a stream of high-density helium gas. The carbon species were subsequently
cooled and ionized resulting in the formation of clusters. Clusters ranged in molecular
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masses, but Kroto and Smalley found predominance in a C60 cluster that could be enhanced
further by allowing the plasma to react longer. They also discovered that the C60 molecule
formed a cage-like structure, a regular truncated icosahedron.rin
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 For this discovery Curl, Kroto and Smalley were awarded the 1996 Nobel Prize in
Chemistry.
 The experimental evidence, a strong peak at 720 atomic mass units, indicated that a carbon
molecule with 60 carbon atoms was forming, but provided no structural information. The
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research group concluded after reactivity experiments, that the most likely structure was a
spheroidal molecule. The idea was quickly rationalized as the basis of an icosahedral
symmetry closed cage structure. Kroto mentioned geodesic dome structures of the noted
futurist and inventor Buckminster Fuller as influences in the naming of this particular
substance as buckminsterfullerene.
 In 1989 physicists Wolfgang Krätschmer, Konstantinos Fostiropoulos and Donald R.
Huffman observed unusual optical absorptions in thin films of carbon dust (soot). The soot
had been generated by an arc-process between two graphite electrodes in a helium
atmosphere where the electrode material evaporates and condenses forming soot in the
quenching atmosphere. Among other features, the IR spectra of the soot showed four
discrete bands in close agreement to those proposed for C60.

 Another paper on the characterization and verification of the molecular structure followed
on in the same year (1990) from their thin film experiments and detailed also the extraction
of an evaporable as well as benzene soluble material from the arc-generated soot. This
extract had TEM and X-ray crystal analysis consistent with arrays of spherical C60
molecules, approximately 1.0 nm in van der Waals diameter as well as the expected
molecular mass of 720 u for C60 (and 840 u for C70) in their mass spectra. The method was
simple and efficient to prepare the material in gram amounts per day (1990) which has
boosted the fullerene research and is even today applied for the commercial production of
fullerenes.
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 The discovery of practical routes to C60 led to the exploration of a new field of chemistry
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involving the study of fullerenes.
3.3 Graphene and Carbon Nanotube
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 Graphene and CNTs are both made of carbon atoms. A carbon nanotube can be thought of
as a sheet of graphene (A hexagonal lattice of carbon) rolled into a cylinder. Accordingly,
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CNTs can be used as a starting point for making graphene, by “unzipping” them.
 Both graphene and CNTs have exceptional mechanical and electronic properties, which can
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often be similar. Hence, they are often regarded as rivals for a host of similar applications.
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It should be noted that there is also an area of research focused on combining graphene and
CNTs and using them together for various applications like electronics, batteries, sensors
and more.
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 Despite these similarities between the materials, there are still differences between
them.While graphene is considered 2D, CNTs are often used but regarded as 1D. Also,
graphene (When ideally structured with atom purity and perfect honeycomb lattice) is
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a zero-band-gapsemiconductor, whereas single-walled CNTs show either metallic or
semiconducting properties, with a bandgap that varies from zero to about 2 eV.
 Working with CNTs is often considered challenging due to the intrinsic difficulty in
positioning them accurately and connecting them. Graphene, which came into the scene
later than veteran CNTs, can be easier to interconnect and dope, but carries its own set of
challenges, like extraction, manipulation and stability burdens.
 Carbon - A building block for many materials
 Carbon is a non-metallic chemical element often regarded as a common element of all
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known life. It is the 15 most abundant element in the Earth's crust and the fourth most
abundant element in the universe by mass. www.EasyEngineering.net

 Carbon can be found in many forms, each of which has its own physical characteristics.
These forms include well-known materials like diamond and graphite, that only differ in
physical properties due to variations in the arrangement of atoms in their structures. Other,
less well-known forms are fullerenes - Spherical, closed-cage fullerenes are called
buckerminsterfullerenes, or “buckyballs,” and cylindrical fullerenes are called
nanotubes. Another form, composed only of carbon atoms in a flat, 2D lattice structure is
called graphene. Other forms of carbon atoms arrangements exist, like amorphous carbon,
Q-carbon and more.
 What is grapheme ?
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 A single, 2 dimensional layer of graphite is called graphene. So, graphene is basically a
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sheet of carbon atoms arranged in a hexagonal layout. Graphene is considered the first 2D
material ever discovered and is also called a ”wonder material” thanks to an enormous
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group of properties it holds. For example, graphene is one of the strongest materials in
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universe, has superior thermal and optical properties, excellent tensile strength, relative
transparency, amazing electrical conductivity and impermeability to most gases and liquids
and more.
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 Graphene’s many attributes make it an attractive material for researchers and developers,
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which are working hard all over the world to find endless uses for the material. Graphene’s
tial is vast and the applications include : Touchscreens (for LCD or OLED displays),
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computer chips, batteries. energy generation, supercapacitors, medical equipment, water
filters, solar cells and more.
 What are carbon nanotubes ? g.n
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 Carbon nanotubes (often abbreviated to CNTs) are cylindrically-shaped molecules made of
carbon atoms. A sheet of graphene can be rolled-up to make a carbon nanotube. CNTs can
be single-walled (SWCNT) if made from one layer of carbon atoms, or multi-walled
(MWCNT) when consisting of several layers of graphene sheets. In fact, carbon nanotubes
come in various diameters, lengths and functional group content which can tailor their use
for specific applications. Single wall carbon nanotubes.
 (SWCNT) and multi wall carbon nanotubes (MWCNT)
 Single-wall carbon nanotubes (SWNTs) are a special class of carbon materials known as
one-dimensional materials. They consist of sheets of graphene, rolled up to form hollow
tubes with walls one atom thick. Due to its chemical structure and dimensional constraints,
this material exhibits exceptional mechanical, electrical, thermal and optical properties. As
such, carbon nanotubes have become of great interest for both stand-alone studies and for
use in composite materials. www.EasyEngineering.net

 At Ossila, we sell a range of SWNTs with different purities, lengths and wall types.
Additionally, we sell carbolic acid (-COOH) and hydroxyl (-OH) functionalised nanotubes.
 Single-walled carbon nanotubes (SWCNT), as its name suggests are formed by a single
layer of graphite which is arranged in a cylindrical shape. SWCNTs are very important
because they have certain properties that other nanotubes do not have. These properties
have allowed the creation of interesting applications in different sectors. This SWCNT and
MWCNT will discuss the structure, properties and remarkable properties of
SWCNTs.
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3.4 Structure of Single-walled Carbon Nanotubes
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 The central part of the tube is formed by sp hybridization of carbon atoms, while the ends
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are formed by a particular distribution of pentagonal and hexagonal rings, which gives the
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right curvature and allow the closure of the graphite cylinder.
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 Single-walled carbon nanotubes have diameters between 0.7 and 10 nm (generally less than
2 nm) and a length ranging from a few nm to some m. Consequently, SWCNTs have a
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high length/diameter ratio and for this reason, they can be considered as "almost" one-
dimensional structures. This gives these species peculiar properties.
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 SWCNTs may differ from each other due to the arrangement of the aromatic rings
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(Graphene lattice) with respect to their central axis. In other words, they differ in the way in
which the plane of the graphite is rolled up.
 Properties of Single-walled Carbon Nanotubes
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 The conductivity properties of SWCNTs are studied, in particular, because under certain
conditions, they behave as ballistic conductors, in this state, there is no scattering of the
electrons passing through the nanotube and therefore the conduction takes place.
 The mechanical resistance of single-walled carbon nanotubes depends on many features,
the most significant of which is the strength of the atom-atom bonds of the essential
material and the absence of structural defects in the lattice. The existence of defects plays
an important role in the procedures of breaking by traction since to break an entirely defect-
free sample, it is essential to overwhelm the cohesion forces of the entire surface
perpendicular to the direction of traction. In reality, the existence of defects greatly reduces
the force required to break the sample.

 It has been intended that the theoretical Young module of single-walled carbon
nanotubes can reach up to 4 TPa and its tensile strength must be around 220 GPa (100
times larger than that of steel and 6 times lesser in weight).
 A mechanical deformation can significantly change the electrical behavior of the SWCNTs.
 The thermal conductivity of SWCNTs is determined by phonons, which propagate easily
along the tube; this is why single-walled carbon nanotubes are good thermal conductors
and good insulators.
 3.5 Multi-Walled Carbon Nanotubes

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Fig. 3.5.1 : Multi Wall Carbon Nanotubes (MWCNT)
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 Multi-walled carbon nanotubes (MWNTs) consist of multiple rolled layers of graphene.
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MWNTs have not been well-defined due to their structural complexity and variety when
compared to SWNTs. Nonetheless, MWNTs exhibit advantages over SWNTs, such as ease
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of mass production, low product cost per unit and enhanced thermal and chemical stability.
In general, the electrical and mechanical properties of SWNTs can change when
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functionalized, due to the structural defects occurred by C = C bond breakages during
chemical processes. However, intrinsic properties of carbon nanotubes can be preserved by
the surface modification of MWNTs, where the outer wall of MWNTs is exposed to
chemical modifiers.
 Surface modification of CNTs is performed to introduce new properties to carbon
nanotubes for highly specific applications which often require organic solvent or water-
solubilization, enhancement of functionality, dispersion and compatibility or lowering the
toxicity of CNTs. Fig. 3.5.1 illustrates many of the routes to chemically modify the surface
of CNTs. Common functionalized CNTs, such as MWNT-COOH are obtained via
oxidation using various acids, ozone or plasma, which creates other oxygen functional
groups (e.g., – OH, – C = O). The presence of oxygen-containing groups promotes the
exfoliation of CNT bundles and enhances the solubility in polar media and the chemical
affinity with ester containing compounds, such as polyesters. www.EasyEngineering.net
COOH groups on nanotube
surfaces are useful sites for further modification. Various molecules, such as synthetic and
natural polymers can be grafted through the creation of amide and ester bonds.
Material Thermal conductivity Electrical conductivity
[W/(m·K)] [S/m]
6 7
Carbon Nanotubes > 3,000 10 – 10
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Copper 400 6  10
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Carbon Fiber - Pitch 1,000 2 – 8.5  10
6
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Table 3.5.1 : Transport properties of carbon nanotubes and other conductive materials
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 Double-walled Carbon Nanotubes
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 Double-walled carbon nanotubes (DWNTs) are a synthetic blend of both single-walled and
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multi-walled nanotubes, showing properties intermediate between the two types. DWNTs
are comprised of exactly two concentric nanotubes separated by 0.35 - 0.40 nm, with
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sufficient band gaps for use in field-effect transistors. The inner and outer walls of DWNTs
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have optical and Raman scattering characteristics of each wall. Theoretically, if each wall
behaves like a SWNT, DWNTs can consist of four combinations based on the electronic
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type (metallic or semiconducting) according to (n, m) values of their inner and outer walls,
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e.g., metallic-metallic (inner-outer), metallic-semiconducting, semiconducting-metallic and
semiconducting-semiconducting. Some experimental studies found that even though both
walls are semiconducting, DWNTs may behave as a metal. This complication of their
overall electrical behavior has limited the utility of DWNTs to applications such as thin
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film electronics. However, DWNTs also exhibit several beneficial properties observed from
MWNTs, such as improved lifetimes and current densities for field emission and high
stability under aggressive chemical, mechanical and thermal treatments along with the
flexibility observed with SWNTs. Selective functionalization of the outer wall has led to
the use of DWNTs as core-shell systems made of a pristine carbon nanotube core and
chemically-functionalized nanotube shells, which are applicable as imaging and therapeutic
agents in biological systems. DWNTs can be utilized in gas sensors as sensitive materials
for the detection of gases such as H2, NH3, NO2 or O2, dielectrics and technically
demanding applications, such as field-emission displays and photovoltaics.

 We offer high quality SWNTs, MWNTs and DWNTs, some of which are the most
electrically conductive additives available today, for your innovative and advanced
materials research needs. When indicated, these nanotubes are produced via the Catalytic
Chemical Vapor Deposition (CCVD) technique, a proven industrial process well-known for
its reliability and scalability and are purified or functionalized to increase the performance
for research applications where special chemical properties like high surface area,
transparency, or high field emission characteristics are required.
 Carbon nanotubes can be used for a wide range of new and existing applications :
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o Conductive plastics
o Structural composite materials
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o Flat-panel displays
o Gas storage
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o Antifouling paint
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o Micro- and nano-electronics
o Radar-absorbing coating ngi
o High functional textiles nee
o Ultra-capacitors
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o Atomic Force Microscope (AFM) tips
o Batteries with improved lifetime g.n
o Biosensors for harmful gases
o Extra strong and conductive fibers
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o Targeting drug delivery
o Bioengineering applications such as energy storage and conversion devices, radiation
sources and hydrogen storage media methods of synthesis (Arc-growth, laser ablation,
CVD routes, Plasma CVD).
 Techniques have been developed to produce carbon nanotubes in sizable quantities,
including arc discharge, laser ablation, high-pressure carbon monoxide disproportionation
and Chemical Vapor Deposition (CVD). Most of these processes take place in a vacuum or
with process gases. CVD growth of CNTs can occur in vacuum or at atmospheric pressure.
Large quantities of nanotubes can be synthesized by these methods; advances in catalysis
and continuous growth are making CNTs more commercially www.EasyEngineering.net
viable.

 Types
1. Arc discharge
 Nanotubes were observed in 1991 in the carbon soot of graphite electrodes during an arc
discharge, by using a current of 100 amps, that was intended to produce fullerenes.
However the first macroscopic production of carbon nanotubes was made in 1992 by
two researchers at NEC's Fundamental Research Laboratory. The method used was the
same as in 1991. During this process, the carbon contained in the negative electrode
sublimates because of the high-discharge temperatures.
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 The yield for this method is up to 30 % by weight and it produces both single- and
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multi-walled nanotubes with lengths of up to 50 micrometers with few structural
defects.
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Arc-discharge technique uses higher temperatures (above 1,700 °C) for CNT synthesis
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which typically causes the expansion of CNTs with fewer structural defects in
comparison with other methods.
2. Laser ablation ngi
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 In laser ablation, a pulsed laser vaporizes a graphite target in a high-temperature reactor
while an inert gas is led into the chamber. Nanotubes develop on the cooler surfaces of
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the reactor as the vaporized carbon condenses. A water-cooled surface may be included
in the system to collect the nanotubes.
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 This process was developed by Dr. Richard Smalley and co-workers at Rice University,
who at the time of the discovery of carbon nanotubes, were blasting metals with a laser
to produce various metal molecules. When they heard of the existence of nanotubes they
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replaced the metals with graphite to create multi-walled carbon nanotubes. Later that
year the team used a composite of graphite and metal catalyst particles (the best yield
was from a cobalt and nickel mixture) to synthesize single-walled carbon nanotubes.
 The laser ablation method yields around 70 % and produces primarily single-walled
carbon nanotubes with a controllable diameter determined by the reaction temperature.
However, it is more expensive than either arc discharge or chemical vapor deposition.
 The effective equation for few cycle optical pulse dynamics was obtained by virtue of
the Boltzmann collision-less equation solution for conduction band electrons of
semiconductor carbon nanotubes in the case when medium with carbon nanotubes has
spatially-modulated refractive index. www.EasyEngineering.net

3. Plasma torch
 Single-walled carbon nanotubes can also be synthesized by a thermal plasma method,
first invented in 2000 at INRS (Institut national de la recherche scientifique) in
Varennes, Canada, by Olivier Smiljanic. In this method, the aim is to reproduce the
conditions prevailing in the arc discharge and laser ablation approaches, but a carbon-
containing gas is used instead of graphite vapors to supply the necessary carbon.
 Doing so, the growth of SWNT is more efficient (decomposing the gas can be 10 times
less energy-consuming than graphite vaporization). The process is also continuous and
low cost. A gaseous mixture of argon, ethylene and ferrocene is introduced into a
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microwave plasma torch, where it is atomized by the atmospheric pressure plasma,
which has the form of an intense 'flame'.
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 The fumes created by the flame contain SWNT, metallic and carbon nanoparticles and
amorphous carbon.
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 Another way to produce single-walled carbon nanotubes with a plasma torch is to use
the induction thermal plasma method, implemented in 2005 by groups from the
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University of Sherbrooke and the National Research Council of Canada.
 The method is similar to arc discharge in that both use ionized gas to reach the high
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temperature necessary to vaporize carbon-containing substances and the metal catalysts
necessary for the ensuing nanotube growth. The thermal plasma is induced by high-
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frequency oscillating currents in a coil and is maintained in flowing inert gas.
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 Typically, a feedstock of carbon black and metal catalyst particles is fed into the plasma
and then cooled down to form single-walled carbon nanotubes. Different single-wall
carbon nanotube diameter distributions can be synthesized.
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 The induction thermal plasma method can produce up to 2 grams of nanotube material
per minute, which is higher than the arc discharge or the laser ablation methods.
 3.6 Chemical Vapor Deposition (CVD)

 Nanotubes being grown by plasma enhanced chemical vapor deposition.
 The catalytic vapor phase deposition of carbon was reported in 1952 and 1959, but it was
not until 1993 that carbon nanotubes were formed by this process. In 2007, researchers at
the University of Cincinnati (UC) developed a process to grow aligned carbon nanotube
arrays of length 18 mm on a FirstNano ET3000 carbon nanotube growth system.
 During CVD, a substrate is prepared with a layer of metal catalyst particles, most
commonly nickel, cobalt, iron, or a combination. The metal nanoparticles can also be
produced by other ways, including reduction of oxides orwww.EasyEngineering.net
oxides solid solutions. The

diameters of the nanotubes that are to be grown are related to the size of the metal particles.
This can be controlled by patterned (or masked) deposition of the metal, annealing, or by
plasma etching of a metal layer. The substrate is heated to approximately 700 C. To
initiate the growth of nanotubes, two gases are bled into the reactor : A process gas (such as
ammonia, nitrogen or hydrogen) and a carbon-containing gas (such as acetylene, ethylene,
ethanol or methane). Nanotubes grow at the sites of the metal catalyst; the carbon-
containing gas is broken apart at the surface of the catalyst particle and the carbon is
transported to the edges of the particle, where it forms the nanotubes. This mechanism is
still being studied. The catalyst particles can stay at the tips of the growing nanotube during
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growth, or remain at the nanotube base, depending on the adhesion between the catalyst
particle and the substrate. Thermal catalytic decomposition of hydrocarbon has become an
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active area of research and can be a promising route for the bulk production of CNTs.
Fluidised bed reactor is the most widely used reactor for CNT preparation. Scale-up of the
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reactor is the major challenge.
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 CVD is the most widely used method for the production of carbon nanotubes. For this
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purpose, the metal nanoparticles are mixed with a catalyst support such as MgO or Al2O3 to
increase the surface area for higher yield of the catalytic reaction of the carbon feedstock
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with the metal particles. One issue in this synthesis route is the removal of the catalyst
support via an acid treatment, which sometimes could destroy the original structure of the
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carbon nanotubes. However, alternative catalyst supports that are soluble in water have
proven effective for nanotube growth.
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 If a plasma is generated by the application of a strong electric field during growth (plasma-
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enhanced chemical vapor deposition), then the nanotube growth will follow the direction of
the electric field. By adjusting the geometry of the reactor it is possible to synthesize
vertically aligned carbon nanotubes (i.e., perpendicular to the substrate), a morphology that
has been of interest to researchers interested in electron emission from nanotubes. Without
the plasma, the resulting nanotubes are often randomly oriented. Under certain reaction
conditions, even in the absence of a plasma, closely spaced nanotubes will maintain a
vertical growth direction resulting in a dense array of tubes resembling a carpet or forest.
 Of the various means for nanotube synthesis, CVD shows the most promise for industrial-
scale deposition, because of its price/unit ratio and because CVD is capable of growing
nanotubes directly on a desired substrate, whereas the nanotubes must be collected in the
other growth techniques. The growth sites are controllable by careful deposition of the
catalyst. In 2007, a team from Meijo University demonstrated a high-efficiency CVD
technique for growing carbon nanotubes from camphor. Researchers at Rice University,

until recently led by the late Richard Smalley, have concentrated upon finding methods to
produce large, pure amounts of particular types of nanotubes. Their approach grows long
fibers from many small seeds cut from a single nanotube; all of the resulting fibers were
found to be of the same diameter as the original nanotube and are expected to be of the
same type as the original nanotube.
 Super-growth CVD
 Super-growth CVD (water-assisted chemical vapor deposition) was developed by Kenji
Hata, Sumio Iijima and co-workers at AIST, Japan. In this process, the activity and lifetime
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of the catalyst are enhanced by addition of water into the CVD reactor. Dense millimeter-
tall Vertically Aligned Nanotube Arrays (VANTAs) or "forests", aligned normal to the
{\displaystyle
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substrate, were produced. The forests height could be expressed, as
H(t)={\beta }{\tau }_{o}({1-e^{-t/{\tau }_{o}}}).}H(t)={\beta }
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{\tau }_{o}({1-e^{-t/{\tau }_{o}}}).
 In this equation,  is the initial growth rate and {\displaystyle {\tau }_{o}}{\tau }_{o} is
the characteristic catalyst lifetime.
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2
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 Their specific surface exceeds 1,000 m /g (capped) or 2,200 m /g (uncapped),surpassing
2
the value of 400–1,000 m /g for HiPco samples. The synthesis efficiency is about 100 times
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higher than for the laser ablation method. The time required to make SWNT forests of the
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height of 2.5 mm by this method was 10 minutes in 2004. Those SWNT forests can be
easily separated from the catalyst, yielding clean SWNT material (purity > 99.98 %)
without further purification. For comparison, the as-grown HiPco CNTs contain about
5 - 35 % of metal impurities; it is therefore purified through dispersion and centrifugation
et
that damages the nanotubes. Super-growth avoids this problem. Patterned highly organized
single-walled nanotube structures were successfully fabricated using the super-growth
technique.
3
 The mass density of super-growth CNTs is about 0.037 g/cm . It is much lower than that of
3
conventional CNT powders (~1.34 g/cm ), probably because the latter contain metals and
amorphous carbon.
 The super-growth method is basically a variation of CVD. Therefore, it is possible to grow
material containing SWNT, DWNTs and MWNTs and to alter their ratios by tuning the
growth conditions. Their ratios change by the thinness of the catalyst. Many MWNTs are
included so that the diameter of the tube is wide. www.EasyEngineering.net

 The vertically aligned nanotube forests originate from a "zipping effect" when they are
immersed in a solvent and dried. The zipping effect is caused by the surface tension of the
solvent and the van der Waals forces between the carbon nanotubes. It aligns the nanotubes
into a dense material, which can be formed in various shapes, such as sheets and bars, by
applying weak compression during the process. Densification increases the Vickers
3
hardness by about 70 times and density is 0.55 g/cm . The packed carbon nanotubes are
more than 1 mm long and have a carbon purity of 99.9 % or higher; they also retain the
desirable alignment properties of the nanotubes forest.
 Liquid electrolysis method
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 In 2015, researchers in the George Washington University discovered a new pathway to
synthesize MWCNTs by electrolysis of molten carbonates. The mechanism is similar to
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CVD. Some metal ions were reduced to a metal form and attached on the cathode as the
nucleation point for the growing of CNTs. The reaction on the cathode is,
+ CNTs + O2}}} a
{\displaystyle {\ce {Li2CO3 -> Li2O + CNTs + iO2}}}{\displaystyle {\ce {Li2CO3 -> Li2O
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 The formed lithium oxide can in-situ absorb carbon dioxide (if present) and form lithium
carbonate, as shown in the equation.
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{\displaystyle {\ce {Li2O + CO2 -> Li2CO3}}}{\displaystyle {\ce {Li2O + CO2 ->
Li2CO3}}}
 Thus the net reaction is, rin
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{\displaystyle {\ce {CO2 -> CNTs + O2}}}{\displaystyle {\ce {CO2 -> CNTs + O2}}}
et
 In other words, the reactant is only greenhouse gas of carbon dioxide, while the product is
high valued CNTs. This discovery was highlighted by Science, BBC news, MIT technology
news, etc., as a possible technology for carbon dioxide capture and conversions.
 Natural, incidental and controlled flame environments
 Fullerenes and carbon nanotubes are not necessarily products of high-tech laboratories; they
are commonly formed in such mundane places as ordinary flames, produced by burning
methane, ethylene and benzene and they have been found in soot from both indoor and
outdoor air. However, these naturally occurring varieties can be highly irregular in size and
quality because the environment in which they are produced is often highly uncontrolled.
Thus, although they can be used in some applications, they can lack in the high degree of
uniformity necessary to satisfy the many needs of both research and industry. Recent efforts
have focused on producing more uniform carbon nanotubes in controlled flame
environments. Such methods have promise for large-scale, low-cost nanotube synthesis
based on theoretical models, though they must compete with rapidly developing large scale
CVD production. www.EasyEngineering.net

 3.7 Structure - Property Relationships

 Structure - Property relationships why is a particular drug effective ? Why is a certain
chemical toxic ? Why does a particular pesticide not break down in the environment ? Why
does a bullet-proof vest work the way it does ? The answer to all of these questions is that
the structure of the molecules comprising these materials determines the properties that the
materials have. “Structure determines properties” is a powerful concept in chemistry and in
all fields in which chemistry is important including, but not limited to, environmental
science, biology, biochemistry, polymer science, medicine, engineering and nutrition. What
is meant by structure ? How does one describe the structure of a molecule ? This can be
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done at various levels of sophistication. - The molecular formula, e.g., C12H17ClNO3, tells
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us which elements are present and in what ratio. - The relative overall size and
3-dimensional shape, known as the steric properties, give additional detail. - Functional
a
groups in the molecule indicate electrostatic properties (Polarity, Hydrogen Bonding).
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A description of chirality is necessary to account for the spatial relationship of the atoms.
A further piece of information at a still higher level of sophistication would be the heat of
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formation. - To be precise, a description of the exact structure would require defining the
exact positions of all atoms in the molecule. Simple molecular model kits and molecular
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modeling software are very helpful in visualizing the structure of a molecule. High-level
calculations can accurately describe structures. Experimental methods of studying structure
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include spectroscopy such as NMR spectroscopy and X-ray crystallography, which can
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define the exact positions of the atoms in a molecule. What is meant by properties ? These
fall into three general categories. - Chemical (e.g., reaction rates, position of equilibria).
et
Why does an SN2 reaction occur well on a primary center but not at all on a tertiary center?
Answer : Steric effects. Why is trichloroacetic acid 10,000 times more acidic than acetic
acid ? Answer : Electrostatic or polar effects. - Physical (e.g., Melting points, boiling
points, solubility, spectra) Compare dimethyl ether, CH3-O-CH3 (BP – 24°) and its isomer,
ethanol, CH3CH2-O-H (BP 78°). Structure determines the boiling points. The molecules of
alcohol, having the ability to H-bond, attract one another with stronger forces (H-bonds)
than do the molecules of ether, which only have normal dipole-dipole forces holding them
together. - Biological (e.g., Odor, color, taste, drug action, toxicity) Why does vanilla taste
so different than chocolate ? Why do we perceive the color of a banana as yellow and an
orange as orange ? Different molecules, because of their structures fit differently into the
biological receptors present in living systems, consequently causing different neural
responses. (Note that biological properties are actually a subset of chemical properties, in
which at least one of the interacting chemicals is a biological www.EasyEngineering.net
chemical such as an enzyme.)

Why is chirality such an important structural characteristic ? As an example, compare the

enantiomers of thalidomide. Thalidomide was used as a sedative for pregnant women in the
1950’s in Europe. The drug was a mixture of the two enantiomers. Severe birth defects
resulted. It turns out that one enantiomer is an effective antidepressant while the other is
teratogenic (causes birth defects). Why might this be ? The biologically active sites in
living systems are chiral themselves. Thus enantiomers fit differently into those sites and
consequently have different biological effects.
 3.8 Nanometal Oxides
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 In its most basic form, a material synthesized on the nanoscale infers a smaller, more
reactive particle. In order to exercise control over the design and presentation of a particle
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in this size regime, several research groups have developed alternative approaches to
synthesizing nanostructured materials under ambient conditions.
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 The well - defined, structural organization witnessed in biologically derived minerals such
as these has inspired low - temperature syntheses that are favorable because they minimize
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the onset of particle degradation, which is often a factor in high - temperature reaction
processes.
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 Generally, a biomineral can be induced, controlled or mediated by its reaction environment.
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 Induced syntheses are most common in single - celled organisms, such as fungi or bacteria
and typically occur within a charged, open environment. The mineralized product remains
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dynamic and typically does not have a specific function within the system.
 Biologically controlled, or constrained, reactions yield minerals with a minimal size
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distribution that are localized to a confined area, defined by a cell wall, lipid bilayer or
vesicle. This mineralized product has functional properties that are dependent on its origin
of synthesis (extra -, inter - or intracellularly).
 On the other hand, biologically mediated mineralization is often genetically controlled by
the organism within unconstrained, open environments, while incorporating peptides,
proteins, nucleic acids or polymers as templates during synthesis. For instance, the proteins
in diatoms, radiolarian and sponges produce SiO2 that serves as their exoskeleton in the
ocean, while biopolymers associated with echinoderms and nacreous layers mediate the
production of single calcite crystals that serve as their protective coating.
 The valuable properties associated with constrained or unconstrained metal oxide synthesis
in specific biological systems has inspired the development of functionalized
nanomaterials. www.EasyEngineering.net

 3.9 ZnO, TiO2, MgO, ZrO2, NiO

 Metal oxide systems have attracted a great deal of attention in recent years on account of
their special electronic and chemical properties. Among the metal oxide semiconductors,
compounds such as TiO2, ZrO2 and ZnO have been investigated extensively due to their
chemical stability and good photocatalytic properties.
 Titanium dioxide is the most widely used metal oxide for environmental applications,
paints, electronic devices, gas sensors and solar cells. It is a well-known semiconductor
with excellent photocatalytic properties, which has been widely used in environmental
pollutant elimination, antibacterial dopes, self-cleaning surface, etc.
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 Its unique antibacterial properties make it a candidate for applications in medical devices
and sanitary ware surfaces. Moreover, titania incorporated into polyester fabric and related
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materials can be used as an absorber of harmful UV irradiation. Zinc oxide, due to its
antibacterial and photocatalytic activity, as well as its wide bandgap, has found applications
a
in various areas based on its optical, piezoelectric and gas sensing properties and in addition
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zinc compounds have generally been regarded as safe.
 Zirconia is one of the most intensively studied materials owing to its technologically
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important applications in gas sensors, fuel cell electrolytes, catalysts and catalytic supports,
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metal oxide-semiconductor devices and in view of its superior thermal and chemical
stability and other properties. Among synthetic hybrid oxide systems, particular attention is
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given to TiO2-ZrO2 materials, which thanks to the addition of zirconium dioxide have
much greater surface area and mechanical strength than pure TiO2.
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 Conjugation of zirconia together with titania leads to obtain products which are
characterized with higher specific surface in comparison to pristine TiO2. Moreover, the
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addition of ZrO2 to TiO2 inhibits phase transformation of anatase-to-rutile and creates more
active site groups on titania surfaces. There are many publications concerning the
application of TiO2-ZrO2 hybrids in photocatalysis]. The use of TiO2-ZrO2 hybrid
materials in the photo-oxidation of organic compounds or degradation of dyes originating
from various industrial plants is well known. They also have applications in the photo-
reduction of atmospherically harmful oxides, like CO2 and NOx, resulting for example
from the combustion of fossil fuels.
 The advantages of the TiO2-ZrO2 hybrid are its mechanical strength, non-toxicity and
corrosion resistance and the ability to conduct photocatalytic processes using sunlight.
These may be causes of increasing demand for this material in the near future.
 Combining Titania with zinc oxide can also lead to a hybrid oxide system with good
photocatalytic properties. The resulting material can be used, for instance, in the
degradation of organic impurities such as detergents, dyes and pesticides present in various
types of wastewater. A TiO2-ZnO hybrid material can be synthesized by both physical and

chemical processes, which enables enhancement of its properties, for example by widening
its spectrum of light absorption.
 Additionally, the photocatalytic activity of oxides may help reduce the tendency of
pollutants to form aggregate structures. The combination of TiO2 with a semiconductor,
such as molybdenum disulfide, allows the creation of a hybrid system that not only exhibits
activity under the influence of visible radiation, but also allows the separation of
photogenerated electron-hole pairs, which increases the catalytic capacity of the material.
The presented review focuses on recent stage on knowledge about sol-gel, hydrothermal
and electrospinning synthesis of advanced, multifunctional materials based on titanium
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dioxide with strictly defined physico-chemical and structural properties, which significantly
determine their multidirectional application.
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 It is known that different properties of hybrid systems, such as TiO2 - ZnO, TiO2 - ZrO2
and TiO2 - MoS2, depend on their morphology, crystallites size and crystalline structure,
a
which can be modified by selecting the appropriate method for their synthesis, as well as
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selecting the right components which together with TiO2 will create advanced hybrid
materials with unique properties.
 3.10 Nanosized Aluminium Oxide ngi

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 Nanosized aluminium oxide (Nanosized alumina) occurs in the form of spherical or nearly
spherical nanoparticles and in the form of oriented or undirected fibers.
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 Properties, of the final material, defined as the set of properties of the solid aluminium
oxide and specific properties of nanostructures.
 Properties of nanoscale colloidal alumina particles :
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 Small diameter of the particles/fibers (2-10 nm)
 High specific surface area (> 100 m /g)
2
et
 High defectiveness of the material surface and specific structure of the nanoparticles (The
volume and size of pores, degree of crystallinity, phase composition, structure and
composition of the surface - Modification possibility)
 Properties of the nanoscale fibers of aluminium oxide :
 The ratio of length-diameter about 20,000,000 : 1
 A high degree of orientation of the fibers
 The weak interaction of the fibers among themselves
 Absence of surface pores
 High surface concentration of hydroxyl groups.

 3.11 CaO, AgTiO2

 The design of TiO2 - based photoactive materials has been a major research topic during the
last two decades. TiO2, as a semiconductor, is activated under UV irradiation promoting
charges that lead to the formation of reactive oxygen species when they interact with H2O
and O2 from the reaction media. Nowadays, recombination of the photogenerated charges
and visible (vis) light response are two drawbacks still to surpass in order to achieve
efficient photocatalysts to be used under solar light or interior-lighting irradiations.
 Water disinfection using TiO2 had attracted research interest since the oxidative attack of
photoproduced ROS may cause total inactivation of bacteria without generating harmful
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byproducts. In order to increase its photooxidative effect, towards bacteria inactivation,
TiO2 has been modified with Ag, which increases vis light absorption and has been
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proposed to decrease recombination, on TiO2 thin films and powdered materials. New
insights have proposed electronic transitions arising from vis-excited Ag aggregates to the
a
TiO2 conduction band promoting its photobactericidal effect, as it has been observed on
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plasmonic photocatalysis. Furthermore, Ag-containing antimicrobial devices are designed
due to the well-known Ag bacteriostatic activity.
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 Ag-modified TiO2 photocatalysts have been synthesized using the hydrothermal method
since this is a relatively simple route to load TiO2 nanoparticles with Ag, with a wide range
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of optimum silver content from 0.1 to 6.5 % wt correspondent to the major increase in
photoactivity. Ag has been proposed to be as aggregates located in crystals borders of TiO2
+ 4+  rin
particles. Since Ag and Ti ionic radii are 1.16 and 0.64 A respectively, it is not expected
that Ag may be embedded into the TiO2 structure.
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et
 The aim of this work is to present the performance of Ag-TiO2 photocatalyst, obtained
using the hydrothermal synthesis route, under different light irradiations setups such as
solar-simulated and interior-lighting lamps with different irradiation powers, towards the
photocatalytic inactivation of E-coliin water. Moreover, materials were characterized using
TEM, XPS, DRS and N2 adsorption-desorption isotherms in order to elucidate properties
affecting the photoactivity. Results show an effective modification of TiO2 with enhanced
visible light absorption capacity as well as photoactivity.
 3.12 Ferrite
 A ferrite is a ceramic material made by mixing and firing large proportions of iron(III)
oxide (Fe2O3, rust) blended with small proportions of one or more additional metallic
elements, such as barium, manganese, nickel and zinc. They are ferrimagnetic, meaning
they can be magnetized or attracted to a magnet. Unlike other ferromagnetic materials, most
ferrites are not electrically conductive, making them useful in applications like magnetic
cores for transformers to suppress eddy currents. Ferrites can be divided into two families
based on their resistance to being demagnetized (Magnetic coercivity).
 Hard ferrites have high coercivity, so are difficult to demagnetize. They are used to make
permanent magnets for applications such as refrigerator magnets, loudspeakers and small
electric motors.
 Soft ferrites have low coercivity, so they easily change their magnetization and act as
conductors of magnetic fields. They are used in the electronics industry to make efficient
magnetic cores called ferrite cores for high-frequency inductors, transformers and antennas
and in various microwave components.

Ferrite compounds are extremely low cost, being made of mostly iron oxide and have
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excellent corrosion resistance. Yogoro Kato and Takeshi Takei of the Tokyo Institute of
Technology synthesized the first ferrite compounds in 1930.
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 Ferrites are usually ferrimagnetic ceramic compounds derived from iron oxides. Magnetite
a
(Fe3O4) is a famous example. Like most of the other ceramics, ferrites are hard, brittle and
poor conductors of electricity.
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 Many ferrites adopt the spinel structure with the formula AB2O4, where A and B represent
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various metal cations, usually including iron (Fe). Spinel ferrites usually adopt a crystal
nee 2–
pattern consisting of cubic close-packed (fcc) oxides (O ) with A cations occupying one
eighth of the tetrahedral holes and B cations occupying half of the octahedral holes,
2+
i.e., A
3+
B2 O4.
2–
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 Ferrite crystals do not adopt the ordinary spinel structure, but rather the inverse spinel
structure : One eighth of the tetrahedral holes are occupied by B cations, one fourth of the
octahedral sites are occupied by A cations. and the other one fourth by B cation. It is also
2+
et3+
possible to have mixed structure spinel ferrites with formula [ M1 –  Fe  ]
2+ 3+
[ M  Fe2 –  ] O4 where  is the degree of inversion.
3+
 The magnetic material known as "ZnFe" has the formula ZnFe2O4, with Fe occupying the
2+
octahedral sites and Zn occupy the tetrahedral sites, it is an example of normal structure
spinel ferrite.
 Some ferrites adopt hexagonal crystal structure, like barium and strontium ferrites
BaFe12O19 (BaO:6Fe2O3) and SrFe12O19 (SrO:6Fe2O3).
 In terms of their magnetic properties, the different ferrites are often classified as "soft",
"semi-hard" or "hard", which refers to their low or high magnetic coercivity as follows.

 3.13 Nanoclays
 Nanoclays are nanoparticles of layered mineral silicates. Depending on chemical
composition and nanoparticle morphology, nanoclays are organized into several classes
such as montmorillonite, bentonite, kaolinite, hectorite and halloysite. Organically-
modified nanoclays (organoclays) are an attractive class of hybrid organic-inorganic
nanomaterials with potential uses in polymer nanocomposites, as rheological modifiers, gas
absorbents and drug delivery carriers.
 Montmorillonite Nanoclays
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 Plate-like montmorillonite is the most common nanoclay used in materials applications.
Montmorillonite consists of ~ 1 nm thick aluminosilicate layers surface-substituted with
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metal cations and stacked in ~ 10 μm-sized multilayer stacks. Depending on surface
modification of the clay layers, montmorillonite can be dispersed in a polymer matrix to
form polymer-clay nanocomposite. Within the nanocomposite individual nm-thick clay
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layers become fully separated to form plate-like nanoparticles with very high (nm  m)
aspect ratio. Sigma-Aldrich, in collaboration with the Nanocor Corporation, offers a range
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of montmorillonite nanoclay products with different organic modifications optimized to be
compatible with various polymer systems.
 3.14 Functionalization and Applications nee

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 In order to understand the electronic absorption spectra of CNTs, it is necessary to return to
the description of their electronic energy levels : The electronic DOS shows the existence
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of singular peaks, called "van Hove singularities". The possible transitions between the
peaks corresponding to the valence and conduction bands account for the possible
absorptions of the CNTs. However, the position of these peaks depends on the chiral
indices (n, m) of the tubes.
et
 We thus see that electron absorption spectroscopy is a technique of great interest because it
makes it possible to analyze the types of CNTs present in a sample, each absorption peak
characterizing a given chirality. Sii denotes the transitions vi  ci of the semiconducting
CNTs and Mii the corresponding transitions for the metallic CNTs.
 Note that it is the quantum selection rules that indicate (via the Fermi golden rule) that only
the transitions i  i are possible in absorption, the transitions i  j (with j  i) being
forbidden. These transitions are revealed by narrow peaks in the UV-visible-near-IR
absorption spectra of a CNT sample (see Fig. 3.14.1). The difference in energy between
these singularities depends on the diameter of each CNT present in the sample analyzed. It
is thus possible to present the energy of these transitions as a function of 20 the diameter of
the nanotubes. The difficulty of such an experiment lies inwww.EasyEngineering.net
the suspension of the CNT

samples (Weisman, 2008). We chose to work in deuterated water, which offers a spectral
window through which to analyze our samples easily up to 1900 nm wavelength.
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a syE Fig. 3.14.1
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 The procedure generally consists of dissolving about 0.1 to 1 mg / mL of nanotubes by
adding 2 % by weight of a surfactant, then subjecting the suspension to sonication with a
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sonotrode at 300 W for ten two thirty minutes and then centrifuging at 4000 rpm to recover
only the supernatant. We tested different surfactants and finally we chose Sodium Dodecyl
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Sulfate (SDS). The problem with this technique is that the CNTs that remain agglomerated
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in bundles are removed from the analysis because they are located in the pellet
centrifugation. The CNT suspensions thus prepared can also be used to make luminescence
experiments (electron emission). In this case, only the semiconducting tubes give rise to
this luminescence phenomenon, which is inhibited for metallic CNTs. et
 3.15 Quantum Wire
 In mesoscopic physics, a quantum wire is an electrically conducting wire in which
quantum effects influence the transport properties. Usually such effects appear in the
dimension of nanometers, so they are also referred to as nanowires. Instead, an exact
calculation of the transverse energies of the confined electrons has to be performed to
calculate a wire's resistance. Following from the quantization of electron energy, the
electrical conductance (the inverse of the resistance) is found to be quantized in multiples
of {\displaystyle 2e^{2}/h}2e^{2}/h, where {\displaystyle e}e is the electron charge and
{\displaystyle h}h is the Planck constant. The factor of two arises from spin degeneracy. A
single ballistic quantum channel (i.e. with no internal scattering) has a conductance equal to
this quantum of conductance.

 The conductance is lower than this value in the presence of internal scattering. The
importance of the quantization is inversely proportional to the diameter of the nanowire for
a given material. From material to material, it is dependent on the electronic properties,
especially on the effective mass of the electrons.
 Physically, this means that it will depend on how conduction electrons interact with the
atoms within a given material. In practice, semiconductors can show clear conductance
quantization for large wire transverse dimensions (~100 nm) because the electronic modes
due to confinement are spatially extended.
 As a result, their Fermi wavelengths are large and thus they have low energy separations.
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This means that they can only be resolved at cryogenic temperatures (within a few degrees
of absolute zero) where the thermal energy is lower than the inter-mode energy separation.
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 For metals, quantization corresponding to the lowest energy states is only observed for
atomic wires. Their corresponding wavelength being thus extremely small they have a very

temperature. a
large energy separation which makes resistance quantization observable even at room
3.16 Quantum Dots

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 Quantum Dots (QDs) are man-made nanoscale crystals that, that can transport electrons.
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When UV light hits these semiconducting nanoparticles, they can emit light of various
colors. These artificial semiconductor nanoparticles that have found applications in
composites, solar cells and fluorescent biological labels.
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 Nanoparticles of semiconductors - quantum dots - were theorized in the 1970s and initially
created in the early 1980s. If semiconductor particles are made small enough, quantum
effects come into play, which limit the energies at which electrons and holes (The absence
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of an electron) can exist in the particles. As energy is related to wavelength (or color), this
means that the optical properties of the particle can be finely tuned depending on its size.
Thus, particles can be made to emit or absorb specific wavelengths (colors) of light, merely
by controlling their size.
 Self-Assembly Method
 Self-assembly method means that the basic structure of Graphene Oxide (GO) is
spontaneously translated into a stable 3D graphene structure under the interaction of non-
covalent π-π bond. It is considered an effective approach for fabricating GBH. Various self-
assembly methods such as hydrothermal process, chemical reduction and metal ion induced
process have been developed for 3D GBH. They can obtain some unique structures and
characteristics, such as porous network structure, ultra-low density, excellent thermal
properties and thermal stability.

 Self-assembled GBH was first prepared by one-step hydrothermal method from GO

solution in 2010. The moisture content of the GBH reached up to 97.4 wt % and it
demonstrated high levels of strength. Furthermore, the electrical conductivity of the GBH
–3
was 5  10 S/cm and the storage modulus (450-490 kPa) was greater several orders than
the traditional hydrogels. The 3D multifunctional GBH, which was self-assembled by
combining DNA and GO sheets, possessed good mechanical property, big dye-adsorption
capacity and excellent self-cure capability. In order to further improve the reduction degree
of graphene for better GBH, some chemical reducing agent, such as hydrazine hydrate,
oxalic acid, ascorbic acid et al., were added to GO solution.
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 Compared with traditional hydrogel, an increase in strength and excellent energy storage
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performance has been found from self-assembled GBH. However, the applications of pure
self-assembled GBH are restricted by their relatively low mechanical properties. Therefore,
graphene used as high quality nano-fillers for polymer composite hydrogels is the focus of
a
nowadays researches.
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Fig. 3.16.1 : Quantum dots are nanoscale man-made crystals that have the ability to
convert a spectrum of light into different colors. Each dot emits a different color
depending on its size
 Quantum dots are artificial nanostructures that can possess many varied properties,
et
depending on their material and shape. For instance, due to their particular electronic
properties they can be used as active materials in single-electron transistors.
 The properties of a quantum dot are not only determined by its size but also by its shape,
composition and structure, for instance if it's solid or hollow. A reliable manufacturing
technology that makes use of quantum dots' properties - For a wide-ranging number of
applications in such areas as catalysis, electronics, photonics, information storage, imaging,
medicine, or sensing - Needs to be capable of churning out large quantities of nanocrystals
where each batch is produced according to the exactly same parameters.

 Because certain biological molecules are capable of molecular recognition and self-
assembly, nanocrystals could also become an important building block for self-assembled
functional nanodevices.
 The atom-like energy states of QDs furthermore contribute to special optical properties,
such as a particle-size dependent wavelength of fluorescence; an effect which is used in
fabricating optical probes for biological and medical imaging.
 So far, the use in bioanalytics and biolabeling has found the widest range of applications for
colloidal QDs. Though the first generation of quantum dots already pointed out their
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potential, it took a lot of effort to improve basic properties, in particular colloidal stability
in salt-containing solution. Initially, quantum dots have been used in very artificial
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environments and these particles would have simply precipitated in 'real' samples, such as
blood. These problems have been solved and QDs have found numerous use in real
applications. a syE
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nee
rin
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et
Fig. 3.16.2 : Vials of quantum dots producing vivid colors. For instance, a cadmium-
based quantum dot showing pure, highly specific green color response
 Quantum dots have found applications in composites, solar cells (Grätzel cells) and
fluorescent biological labels (for example to trace a biological molecule) which use both the
small particle size and tuneable energy levels.
 Advances in chemistry have resulted in the preparation of monolayer-protected, high-
quality, monodispersed, crystalline quantum dots as small as 2 nm in diameter, which can
be conveniently treated and processed as a typical chemical reagent.
 Quantum dots in medicine

 Quantum dots enable researchers to study cell processes at the level of a single molecule
and may significantly improve the diagnosis and treatment of diseases such as cancers. QDs
are either used as active sensor elements in high-resolution cellular imaging, where the
fluorescence properties of the quantum dots are changed upon reaction with the analyte, or
in passive label probes where selective receptor molecules such as antibodies have been
conjugated to the surface of the dots.
 Quantum dots could revolutionize medicine. Unfortunately, most of them are toxic.
Ironically, the existence of heavy metals in QDs such as cadmium, a well-established
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human toxicant and carcinogen, poses potential dangers especially for future medical
application, where q dots are deliberately injected into the body.
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 As the use of nanomaterials for biomedical applications is increasing, environmental
pollution and toxicity have to be addressed and the development of a non-toxic and
a
biocompatible nanomaterial is becoming an important issue.
 Quantum dots in photovoltaics syE
ngi
 The attractiveness of using quantum dots for making solar cells lies in several advantages
over other approaches : They can be manufactured in an energy-saving room-temperature
nee
process; they can be made from abundant, inexpensive materials that do not require
rin
extensive purification, as silicon does; and they can be applied to a variety of inexpensive
and even flexible substrate materials, such as light weight plastics.
g.n
 Although using quantum dots as the basis for solar cells is not a new idea, attempts to make
photovoltaic devices have not yet achieved sufficiently high efficiency in converting
sunlight to power. et
 A promising route for quantum dot solar cells is a semiconductor ink with the goal of
enabling the coating of large areas of solar cell substrates in a single deposition step and
thereby eliminating tens of deposition steps necessary with the previous layer-by-layer
method.
 Graphene quantum dots
 Graphene, which basically is an unrolled, planar form of a carbon nanotube therefore has
become an extremely interesting candidate material for nanoscale electronics. Researchers
have shown that it is possible to carve out nanoscale transistors from a single graphene
crystal (i.e. graphene quantum dots). Unlike all other known materials, graphene remains
highly stable and conductive even when it is cut into devices one nanometer wide.

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Fig. 3.16.3 : Quantum dot carved from a graphene sheet
 Graphene Quantum Dots (GQDs) also show great potential in the fields of photoelectronics,
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photovoltaics, biosensing and bioimaging owing to their unique photoluminescence (PL)
properties, including excellent biocompatibility, low toxicity and high stability against
photobleaching and photoblinking.
ngi
 Scientists still are working on finding efficient and universal methods for the synthesis of
nee
GQDs with high stability, controllable surface properties and tunable PL emission
wavelength.
 Perovskite quantum dots rin
g.n
 Luminescent quantum dots (LQDs), which possess high photoluminescence quantum
yields, flexible emission color controlling and solution process ability are promising for
applications in lighting systems (warm white light without UV and infrared irradiation) and
et
high quality displays.
 However, the commercialization of LQDs has been held back by the prohibitively high cost
of their production. Currently, LQDs are prepared by the HI method, requiring at high
temperature and tedious surface treating in order to improve both optical properties and
stability.
 Although developed only recently, inorganic halide perovskite quantum dot systems have
exhibited comparable and even better performances than traditional QDs in many fields.
 By preparing highly emissive Inorganic Perovskite Quantum Dots (IPQDs) at room
temperature, IPQDs' superior optical merits could lead to promising applications in lighting
and displays. www.EasyEngineering.net

 Quantum dot TVs and displays

 The most commonly known use of quantum dots nowadays may be TV screens. Samsung
and LG launched their QLED TVs in 2015 and a few other companies followed not long
after.
 Quantum dots, because they are both photo-active (photoluminescent) and electro-active
(electroluminescent) and have unique physical properties, will be at the core of next-
generation displays. Compared to organic luminescent materials used in Organic Light
Emitting Diodes (OLEDs), QD-based materials have purer colors, longer lifetime, lower
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manufacturing cost and lower power consumption. Another key advantage is that, because
QDs can be deposited on virtually any substrate, you can expect printable and flexible -
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even rollable - quantum dot displays of all sizes.

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3.17 Preparation, Properties and Applications
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Materials can be compared and classified by their large-scale physical properties.
 Mechanical properties
ngi
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Mechanical properties determine how a material responds to applied forces.
 Examples include
 Stiffness rin
 Strength
g.n
 Toughness
 Hardness
et
 Thermal properties
 Materials may degrade or undergo changes of properties at different temperatures.
Thermal properties also include the material's thermal conductivity and heat capacity,
relating to the transfer and storage of thermal energy by the material.
 Other properties
 Materials can be compared and categorized by any quantitative measure of their
behavior under various conditions. Notable additional properties include the optical,
electrical and magnetic behavior of materials.

 Materials can be broadly categorized in terms of their use, for example :

o Building materials are used for construction
o Building insulation materials are used to retain heat within buildings
o Refractory materials are used for high-temperature applications
o Nuclear materials are used for nuclear power and weapons
o Aerospace materials are used in aircraft and other aerospace applications
o Biomaterials are used for applications interacting with living systems
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o Material selection is a process to determine which material should be used for a
given application.
 w.E
3.18 Part A : Short Answered Questions [2 Marks Each]
Q.1
 Ans. : a
Define nanoforms of carbon.
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The nanoforms of any material demonstrate altered chemical and physical
characteristics compared to the same material in bulk.
Q.2 Define buckminsterfullerene. ngi
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 Ans. : Buckminsterfullerene is a type of fullerene with the formula C60. It has a cage-
like fused-ring structure (truncated icosahedron) that resembles a soccer ball, made of
twenty hexagons and twelve pentagons.
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Q.3 Define graphene and carbon nanotube.
g.n
 Ans. : Graphene and CNTs are both made of carbon atoms. A carbon nanotube can be
et
thought of as a sheet of graphene (a hexagonal lattice of carbon) rolled into a cylinder.
Q.4 What are carbon nanotubes ?
 Ans. : Carbon nanotubes (often abbreviated to CNTs) are cylindrically-shaped
molecules made of carbon atoms. A sheet of graphene can be rolled-up to make a carbon
nanotube. CNTs can be Single-Walled (SWCNT) if made from one layer of carbon atoms,
or Multi-Walled (MWCNT) when consisting of several layers of graphene sheets.
Q.5 Define Multi-walled carbon nanotubes.
 Ans. : Multi-Walled Carbon Nanotubes (MWNTs) consist of multiple rolled layers
of graphene. MWNTs have not been well-defined due to their structural complexity and
variety when compared to SWNTs. Nonetheless, MWNTs exhibit advantages over
SWNTs, such as ease of mass production, low product cost per unit,and enhanced
thermal and chemical stability. www.EasyEngineering.net

Q.6 Define Double-walled carbon nanotubes.

 Ans. : Double-Walled Carbon Nanotubes (DWNTs) are a synthetic blend of both
single-walled and multi-walled nanotubes, showing properties intermediate between the
two types.
Q.7 Define nanometal oxides.
 Ans. : In its most basic form, a material synthesized on the nanoscale infers a smaller,
more reactive particle. In order to exercise control over the design and presentation of a
particle in this size regime, several research groups have developed alternative approaches to
Q.8
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synthesizing nanostructured materials under ambient conditions.
Define nano-sized aluminium oxide.
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 Ans. : Nano-sized aluminium oxide (nano-sized alumina) occurs in the form of spherical
or nearly spherical nanoparticles and in the form of oriented or undirected fibers.
Q.9
 Ans. :
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Define properties of nanoscale colloidal alumina particles.
ngi
 Small diameter of the particles/fibers (2-10 nm)
 High specific surface area (> 100 m /g)
2
nee
rin
 High defectiveness of the material surface and specific structure of the nanoparticles
(the volume and size of pores, degree of crystallinity, phase composition, structure and
composition of the surface - modification possibility).
g.n
Q.10 Define properties of the nanoscale fibers of aluminium oxide.
 Ans. :
et
 The ratio of length-diameter about 20,000,000 : 1
 A high degree of orientation of the fibers
 The weak interaction of the fibers among themselves
 Absence of surface pores
 High surface concentration of hydroxyl groups.

 3.19 Part B : Long Answered Questions

Q.1 Explain Nanoforms of carbon. (Refer section 3.1)
Q.2 Describe Grapheme and carbon nanotube. (Refer section 3.3)
Q.3 Explain Single Wall Carbon Nanotubes (SWCNT) and Multi Wall Carbon
Nanotubes(MWCNT). (Refer section 3.4)
Q.4 Describe Structure-property relationships applications. (Refer section 3.6)
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
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 3.1 Nanoforms of Carbon

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

3.3 Graphene and Carbon Nanotube

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.5 Multi-Walled Carbon Nanotubes

ww Carbon Fiber - PAN 8 - 105 6.5 – 14  10

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.6 Chemical Vapor Deposition (CVD)

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TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.7 Structure - Property Relationships

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

Why is chirality such an important structural characteristic ? As an example, compare the

 3.8 Nanometal Oxides

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.9 ZnO, TiO2, MgO, ZrO2, NiO

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.10 Nanosized Aluminium Oxide ngi

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.11 CaO, AgTiO2

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.14 Functionalization and Applications nee

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

3.16 Quantum Dots

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 Self-assembled GBH was first prepared by one-step hydrothermal method from GO

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 Quantum dots in medicine

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 Quantum dot TVs and displays

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 Materials can be broadly categorized in terms of their use, for example :

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

Q.6 Define Double-walled carbon nanotubes.

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

 3.19 Part B : Long Answered Questions

Q.2 Describe Grapheme and carbon nanotube. (Refer section 3.3)

Q.4 Describe Structure-property relationships applications. (Refer section 3.6)

TECHNICAL PUBLICATIONS® - An up thrust for knowledge

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