NANOMATERIALS

• Nanomaterials materials with at least one external dimension that measures 100
nanometers (nm) or less or with internal structures measuring 100 nm or less.
• Nano size: 1 nm = 10-6 millimeter (mm) = 10-9 meter (m)
• Materials reduced to the nanoscale can suddenly show very different properAes
compared to what they show on a macroscale. For instance, opaque substances
become transparent (copper); inert materials become catalysts (plaAnum); stable
materials turn combusAble (aluminum); solids turn into liquids at room temperature
(gold); insulators become conductors (silicon).

Nanostructured Materials: Nanomaterials can be zero, one, two or three dimensional.

Nanotechnology refers to the branch of science and engineering devoted to designing,

producing, and using structures, devices, and systems by manipulaAng atoms and molecules
at nanoscale, i.e., having one or more dimensions of the order of 100 nanometers or less.

Effects of Nano size:

• ProperAes depends on size, composiAon and structure
• Nano size increases the surface area
• Change in surface energy (higher)
• Change in the electronic properAes
• Change in opAcal band gap
• Change in electrical conducAvity
• Higher and specific catalyAc acAvity
• Change thermal and mechanical stabiliAes
• Different melAng and phase transiAon temperatures
• Change in catalyAc and chemical reacAviAes

SYNTHESIS OF NANOMATERIALS
Two main approaches are used for the synthesis of nanomaterials are top-down approach
and boOom-up approach.
Top-down approach: In top-down approaches, bulk materials are divided to produce
nanostructured materials. Top-down methods include:
mechanical milling, laser abla/on, etching, spu4ering, and electro-explosion.
 BoDom-up approach: This approach refers to the building up of a material from the
boOom: atom-by-atom, molecule-by-molecule, or cluster-by cluster. BoOom up methods
include:
sol-gel method, physical vapor deposi/on, chemical vapor deposi/on, molecular beam
epitaxy, spray conversion processing, wet chemical synthesis, self-assembly.

The difference between top down and boOom up approach are discussed below:

CHARACTERISTICS OF NANOMATERIALS
1. Small parIcle size <100 nm:
As the parAcle size is reduced, the number of atoms on the surface increases as compared to
interior and so the number of ordered electronic spins increases.
So, nanoparAcles or nano crystallites or nano materials exhibit magneAsm or other
properAes derived
from ordered spin.

2. Increased relaIve surface area and surface energy:

In nanomaterials, a large proporAon of molecules, ions are located at surface or grain
boundary. As a result, the surface area as well as surface energy increases.

3. Quantum size effects:

The energy gap in a semiconductor is proporAonal to the inverse of square of size. This effect
is a result of quantum confinement (it increases the spacing between energy levels at the
nano crystallite size decreases). Accordingly, instead of conAnuous energy bands, discrete
energy states exist, the difference of which give rise to absorpAon of wavelengths
characterisAc of the composiAon and nanoparAcle.
4. Specific surface feature:
In crystalline materials, the place where two faces meet or come together is called ‘edge’
and the place where three or more faces come together is known as point (Edges and points
are mostly the locaAon for pronounced catalyAc acAvity).
Crystalline nanoparAcles contain large number of edges and points. So, their catalyAc
acAvity can be minimized or maximized through the selecAon of composiAon and
independently with size.

5. Size distribuIon:
To make full use of unique size dependent properAes of nanomaterial and to derive benefit
from them, the nanomaterials must be composed of monodisperse (parAcles with
same size, shape and mass) or nearly monodisperse nanoparAcles.

APPLICATIONS OF NANOMATERIALS
1. Electronics:
• New devices based on nanotechnology are faster, compact and relaAvely cheaper.
• Flat panel television and computers are products of nanotechnology.
• Nanomaterials are used to make efficient solar cells to produce solar energy.
• E-paper, displays on sunglasses and map on car windshields are products of
nanotechnology.

2. Medical field:
• Provide new opAons for targeted drug delivery and drug therapies.
• Nanobots can clear the blockage in arteries.
• Gold nanoparAcles can be used to detect early-stage Alzheimer’s disease.
• We can prevent blindness by treaAng glaucoma using nano parAcle eye drops.

3. MagneIc random-access memory (MRAM): MRAM can quickly and effecAvely save
even encrypted data during a system shutdown or crash, enable resume play features, and
gather vehicle accident data.

4. TexIle:
• Making water and stain repellent clothing.
• Manufacturing bullet proof jackets.
• Making spill & dirt resistant, anAmicrobial, anAbacterial fabrics.

5. Household applicaIon of nanotechnology:

• Self-cleaning or “easy-to-clean" surfaces on ceramics or glasses.
• Nano ceramic parAcles have improved the smoothness and heat resistance of common
household equipment such as the flat iron.

[Link] in space and defence:

• Nano porous materials are used to make some special light weight jackets etc.
• NanoparAcles can be injected into the material on soldiers’ uniforms to make the
material more durable, and to protect soldiers from many different dangers such as high
temperatures, impacts and chemicals.
7. Automobiles:
• Nano composites have beOer mechanical strength than steel.
• NanoparAcle spray painAng can provide smooth, thin aOracAve coaAng.

8. Environment:
• Nanomaterials help in reducing the polluAon and environment related problems.
• Nanomaterials based sensors are useful in water purificaAon systems, detecAon of toxic
ions, metal ions, pesAcides, etc.

9. CosmeIcs:
• Zinc oxide and Atanium oxide nanoparAcles are able to absorb ultraviolet light and
protect the skin.
• NanoparAcle based creams are used in small amount and gives a smooth appearance.
• Nano based dye and colors are quite harmless to skin and can be used in hair creams or
gels.

10. Chemical Industry:

• The main area of applicaAon of nanotech in chemical industry is the catalysis process.
• Used in fuel cells, catalyAc converters, photolyAc converters and photo catalyAc devices.

11. Displays:
• Displays for TVs, laptop computers, cell phones, digital cameras etc, nowadays uses
organic light-emifng diodes, or OLEDs.
• OLED screens offer brighter images in a flat format, as well as wider viewing angles,
lighter weight, beOer picture density, lower power consumpAon, and longer lifeAmes.

12. Nano transistors:

• Nanoscale transistors those are faster, more powerful, and increasingly energy-efficient.

13. Nanotechnology in energy:

• New solar panel films incorporate nanoparAcles to create light weight, flexible solar cells.

14. Hydrogen storage:

Nano tubes are used for storing hydrogen fuel.

CARBON NANO TUBES (CNT)

Discovered by Sumio Lizima in 1991.

When we roll up 2D graphite (Graphene) sheet into a cylindrical tube, we get CNT. The
diameter of CNT is about 1-3 nm and can have length up to few micrometres. CNT exhibit
extraordinary mechanical proper/es.
Carbon nanotubes are large molecules of pure carbon those are long and thin and
shaped like tubes, about 1-3 nm in diameter, and hundreds to thousands of nm long.
• They exhibit extraordinary strength and unique electrical properAes, and are efficient
conductors of heat.
• They are configuraAonally equivalent to two-dimensional graphene sheet rolled into a
cylindrical shape.
• The cylindrical nanotubes have at least one end capped with hemisphere of Bucky ball
structure.

SALIENT FEATURES OF CNTs

• Under high pressure the nanotubes can merge together.

• They are sAff as diamond.
• They are light weight.
• Their density is 1/4th of that of steel and thermal opacity is 20 Ames more than steel.
• In CNT each carbon atom is bounded to 3 other carbon atoms through covalent
bonds and forms a lafce in the shape of hexagons
• Outer diameter : 2-20 nm ; Inner diameter: 1-3 nm; Length: 1-6 μm
• MWCNT are different from carbon nanofiber (CNF). CNF have diameter of 200 nm
and they are not hollow from inside.
• CNF have been in use for several decades to strengthen compound but their lafce is
different from CNT.
• CNT (carbon nano tube) is improved version of CNF (carbon nano fiber)
• CNT are elasAc, tensile strength of CNT is about 200 Giga Pascal and therefore CNT
can be stretched 20% of their rest length and can be bent and even Aed a knot with
no resulAng effect.
• CNT are good conductor of heat- they have very high thermal capacity. So thermal
expansion produced in CNT is very small
• CNT have good electrical conducAvity – CNTs have very few defect so they can carry
billion ampere of current /cm
• CNT are very strong- CNTs are 10 Ames stronger than steel.
• Chemically stable- They are resistant to corrosion.
DIFFERENT TYPES OF CARBON NANOTUBES
a. Single Walled Nanotubes (SW-CNTs):
• Formed by rolling a single layer of graphite, called graphene layer into a cylinder.
• Diameter 0.5-2.5 nm (nano meter), length 2 μm (micro meter)
• Aspect raAo is typically greater and oqen goes up to 10,000
• It possess 1-D structure and is called Nanowire.
• SWCNT (single walled carbon nano tube) is used in electronics
• Their bandgap is from 0 to 2 eV (electron volt) and they can exhibit both metallic and
semiconducAng behavior.

b. Double walled carbon nanotubes (DW-CNTs):

• Formed of double layers
• Have funcAonalizaAon (to add new properAes to carbon nanotubes)
• only outer wall is modified

c. MulI walled nanotubes (MW-CNTs):

• Consists of mulAple concentric nanotube cylinders.
• The interlayer distance between concentric cylinders is equal to distance between
graphene layers in graphite (approximately 3.3 Å)
• It consist of several nested coaxial single walled CNTs.
• Aspect raAo is typically between 50 and 4,000
 PREPARATION OF CARBON NANOTUBES (CNTs)

Method 1: Synthesis of CNTs by Electric Arc discharge method

• In this method, a potenAal of 20–25 V is applied across the pure graphite electrodes
separated by 1 mm distance and maintained at 500 torr pressure of flowing helium
gas filled inside the quartz chamber

CondiIons for synthesizing CNT by arc method:

• Larger amount of Helium (He) gas (0.65 atm or 500 torr pressure)
• Distance between the graphite electrode -1mm.
• Arc evaporaAon of graphite with He or Ar (Argon) or CH4 (methane) or H2 (effecAve)
• Maintaining Plasma condiAon.
• Carbon fiber like deposit on the negaAve graphite electrode.

(Note: 1 atm = 760 torr, 101,325 Pa = 1.01325 bars;

1 torr = 133.322 Pascal therefore 500 torr = 66661.2 Pa = 0.657895 atm)

Method 2:
In this method Carbon Nano Tubes (CNTs) are prepared by the catalyAc
decomposiAon of Methane (CH4) at 680 degree Celsius for 120 minute, by using Nickel Oxide
(NiO/NiO2)- Silica binary aerogels as the catalyst.

APPLICATIONS OF CNTS

• Composite material containing CNT are being used in sports accessories, like bicycle
frames, tennis rackets, hockey sAcks etc.
• CNTs are used to make Bullet Proof Jackets
• CNTs can reduced the weight of aircraq and spacecraq up to 30%.
• CNTs can be used to build high performance transistors to replace silicon based
transistors because of semi-conducAng properAes of SWCNT.
• CNTs can be used to manufacture biosensors and electrochemical sensors which are
used to sense greenhouse gases (CO2, CH4) in environment.
• CNTs can be used to make electrodes.

LIQUID CRYSTALS

• A unique state of maOer which has properAes between those of convenAonal liquids
and solid crystals are known as Liquid Crystals.
• These compounds display properAes of both solid state and liquid state.
• They may flow like liquids and exhibit long-range order in one or two dimensions like
solids. (For example, a liquid crystal may flow like a liquid, but its molecules may be
oriented in a crystal-like way).
• They possess some posiAonal order but with a lower degree of organizaAon when
compared with a crystalline solid.
• The liquid-crystalline state is also known as mesomorphic state (mezos meaning
"intermediate").

ARRANGEMENT OF MOLECULES IN DIFFERENT STATES OF MATTER

 Following character describe the crystalline structure:

• PosiIonal Order: the extent to which an average molecule or group of molecules

shows translaAonal symmetry (as crystalline material shows).
• OrientaIonal Order: represents a measure of the tendency of the molecules to align
along the director on a long-range basis.

ESSENTIAL CHARACTERISTICS OF LIQUID CRYSTALS

• Bond OrientaIonal Order: describes a line joining the centres of nearest neighbour
molecules without requiring a regular spacing along that line.
 • PosiAonal order + OrientaAonal order = Crystal Phase
• Varying PosiAonal order + OrientaAonal order = Liquid Crystalline Phase
• No posiAonal order + No OrientaAonal order = Isotropic (Liquid) Phase

ESSENTIAL REQUIREMENTS FOR A MOLECULE TO BE A LIQUID CRYSTAL

• Shape of the molecule must be rod like or disc like.

• Molecule must be anisotropic in nature.
• Molecule must have some rigidity in its central region and the ends must be flexible
• Molecules have strong dipole moment.
•
ProperIes of Liquid Crystals
• The molecules are rod shaped or disc shaped.
• All liquid crystals are mesogens but all mesogens are not liquid crystals.
• Molecules are anisotropic in nature.
• These molecules possess very strong dipole moment.
• Assuming that the direcAon of preferred orientaAon in a liquid crystal (LC) is ↑, this
direcAon can be represented by an arrow, called the director of the LC and each
molecule is orientated at some angle to the director.
• The liquid crystal molecules prefer to align parallel to each other because of the
strong intermolecular aOracAon (n-n interacAon)
• A typical Liquid Crystal molecule is represented by a central rigid part, known as
mesogen (generally aromaAc) and the flexible ends (generally aliphaAc groups).
• It consists of two or more ring systems connected by a central linkage group.
 • Although Liquid Crystals combine the properAes of a crystalline solid and an isotropic
liquid, they exhibit very specific electro-opAcal phenomena, which have no
equivalent analogues in solids or in liquids.

CLASSIFICATION OF LIQUID CRYSTALS

LIQUID CRYSTALS

THERMOTROPIC LC LYOTROPIC LC
(Temperature
Dependent) (Solvent Dependent)

CALAMiTIC LC DISCOTIC LC Lamellar Hexagonal Cubic

(Rod shaped) (Disc Shaped)

SMECTIC LC NEMATIC LC CHOLESTERIC LC DISCOTIC NEMATIC LC DISCOTIC COLUMNAR LC

*Smectic A *Ordinary Nematic (Rod Shaped having
*Smectic C *Nematic Cholesteric chiral centre)

1. THERMOTROPIC LIQUID CRYSTALS

They are formed by change of temperature. They occur as liquid crystals over a certain
temperature range between the solid and liquid phase.
Example – LCD TV’s, alarm clocks.
Thermotropic liquid crystals are further classified into:

a) CalamiIc Liquid Crystals (Rod like or elongated molecules)

• CalamiAc liquid crystals are elongated, rod shaped molecules. They are further
classified as NemaIc, SmecIc and Cholesteric liquid crystals.

b) DiscoIc Liquid Crystals (Disc shape molecules)

NEMATIC LIQUID CRYSTALS

• Word NemaAc derived from Greek word Nema which

means "thread".
• No posiIonal order, but possess orientaIonal order.
• Molecule have elongated rod like shape and are thread like.
• Do not have layered structure.
• Flow like normal liquids.
• They have low viscosity.
• Formed at relaAvely higher temperature.
• Can be aligned by the applicaAon of electric on magneAc
field.
• Molecules are free to move in all the direcAons.
• Flow in all direcAons & not in layers.
 O
N
N
O O

(Z)-1,2-bis(4-methoxyphenyl)diazene 1-oxide
• E.g.- p-azoxy anisole (first syntheAc liquid crystal to be produced).

NemaIc liquid crystals further classified as:

a) Ordinary nemaIc phases: These molecules possess ordinary nemaAc phase
characterisAcs as discussed earlier.
b) Cholesteric nemaIc phases: This phase is also known as chiral nemaAc phase. The
molecules are essenAally chiral and resembles nemaAc molecules in nature.

SMECTIC LIQUID CRYSTALS

• They are soap like and are clayey or greasy.

• Molecules are cigar shaped.
• Have short range orientaAonal as well as posiAonal
order.
• These are arranged in layers i.e., have layered
structure.
• They do not flow like normal liquids and have
limited mobility.
• Molecules flow in layers, they can move within the
layers but not from one layer to another.
• Flow is in layers and different layers can slide over
one another.
• They have high viscosity.
• Formed at comparaAvely lower temperature. Fig. SmecAc A and SmecAc C
• Not affected by external electric or magneAc field.
• SmecAc LCs are of two types : SmecAc A and SmecAc C.

O
N
N
O O
(Z)-1,2-bis(4-ethoxyphenyl)diazene 1-oxide
• Example: p-azoxyphenetole.

CHOLESTERIC LIQUID CRYSTALS (or CHIRAL NEMATIC LCs)

• Cholesteric liquid phase is composed of nemaAc mesogenic molecule containing a

chiral center which produces intermolecular forces that favor alignment between
molecules at a slight angle to one another.
• This phase is usually observed from cholesterol derivaAves.
• The molecules are essenAally chiral.
• These are formed by adding chiral twisAng agent to the nemaAc liquid crystals.
• The molecules are arranged in layers like SmecAc liquid crystals.
• Each layer in Cholesteric liquid crystal is Alted with respect to the other one, and
hence the molecules take a one complete turn of 360 degrees to make a helix.

• The distance covered by the director in making a one complete turn is known as
pitch
• Pitch is inversely proporAonal to the temperature. It is affected by temperature,
pressure as well as electric & magneAc fields.

• Cholesteric Liquid Crystal reflects light approximately equal to pitch.

• Pitch is affected by temperature, pressure as well as by electric and magneAc fields.
 H
H
O
H H
O

cholesten-3-yl benzoate
• Example: Cholesteryl benzoate (it was the first liquid crystal to be idenAfied)

b. DISCOTIC LIQUID CRYSTALS

• Molecules are essenAally disc shaped.

• DiscoAc mesogens are typically composed of an aromaAc core surrounded by flexible
alkyl chains. The aromaAc cores allow charge transfer in the stacking direcAon
through the π-conjugate systems. The charge transfer allows the discoAc liquid
crystals to be electrically semi conducAve along the stacking direcAon.

They are of two types: DISCOTIC NEMATIC PHASE and COLUMNAR PHASE.

• Disc-shaped molecules have a tendency to lie on top of one another forming either
discoAc nemaAc phases (with discs oriented similar to that of nemaAc phase i.e. not
having posiAon order but having orientaAon order) or columnar phases (have
column-like structure).

2. LYOTROPIC LIQUID CRYSTALS

• Lyotropic liquid crystals are two component systems, where an amphiphile is

dissolved in a solvent.
• Thus, lyotropic mesophases are solvent and concentraIon dependent.
 • The amphiphilic compounds are characterized by two different moieAes, a
hydrophilic polar head and a hydrophobic (or lipophilic fat loving/water haAng) tail.
• LLC are made by adding solvent to the solid unAl criIcal micelle concentraIon (CMC)
is reached. On further addiAon of solvent LLC changes into liquid phase.

Examples: molecules of soaps, phospholipids (present in cell membranes), toothpaste, many

proteins and cell membranes, tobacco mosaic virus.
Three types of lyotropic liquid crystals are well known: lamellar, hexagonal and cubic phases.

i) The simplest liquid crystalline phase that is formed by spherical micelles is the
‘micellar cubic’, denoted by the symbol I1. This is a highly viscous, opAcally isotropic
phase in which the micelles are arranged on a cubic lafce.
ii) At higher amphiphile concentraAons the micelles fuse to form cylindrical aggregates
of indefinite length, and these cylinders are arranged on a long-ranged hexagonal
lafce. This lyotropic liquid crystalline phase is known as the ‘hexagonal phase’, and
is generally denoted by the symbol HI.
iii) At higher concentraAons of amphiphile the ‘Lamellar Phase' is formed. This phase is
denoted by the symbol Lα. This phase consists of amphiphilic molecules are arranged
in bilayer sheets separated by layers of water.

APPLICATIONS OF LIQUID CRYSTALS

• Liquid crystals are used for decoraAve purpose in cosmeAcs.

• LLC’s based delivery system such as cream, ointment, transdermal patches etc have
been used in pharmaceuAcal.
• Thermotropic Cholesteric liquid crystals are used in body care cosmeAcs.
• Due to their colour effect Cholesteric liquid crystals are used in nail paints, eye
shadows etc.
• DiscoAc liquid crystals are used in photovoltaic devices, organic light emifng diodes
(OLED), and molecular wires.
• Liquid crystals are used for displays in LCD's, Calculator, wrist watches etc.
• Have Medical applicaAons, like localized drug delivery.
• To detect radiaAons & pollutants in atmosphere.
• Used in non-destrucAve tesAng.
• Cholesteric liquid crystals are used in coloured thermometers.
• Used to locate tumours, veins, arteries, infecAons, foetal placenta etc.
 INDUSTRIALLY IMPORTANT LIQUID CRYSTAL
Liquid Crystal have been intensively studied as funcAonal materials. Industrially important
materials based on liquid crystals are nonmaterial, polymer blends, reinforced materials,
elastomers, flexible glass are follows.
1. Liquid Crystal polymer (LCP’s)
2. Liquid Crystal Elastomers (LCE’s)
3. Liquid Crystal Glass
4. Nonmaterial enhanced liquid crystalline Material
5. Liquid Crystal as reinforced material

1. Liquid Crystal polymer (LCP’s)

• Liquid crystal polymers are polymers with the property of liquid crystal, usually
containing aromaAc rings as mesogens. They have excellent mechanical and electrical
properAes and outstanding chemical resistance.
• Example:Ultra-high strength and light weight fibers and cables, bulletproof vest,
tennis strings and hockey s/cks. These includes Kevlar and vectra polymer.

2. Liquid Crystal Elastomers (LCE’s)

• LCE films can be used as opAcal retarders due to their anisotropic structure because
they can control the polarizaAon state of transmiOed light . They are commonly used
in 3D-glass, paOerned retarders for transflecAve displays and flat panel LC display.
(Note: Transflec/ve:- transmissive + reflec/ve)
• LCEs are used to make actuators and arAficial muscles for roboAcs.
• Azobenzene containing liquid crystal elastomers (AzBz-LCE) can be chosen as one of
the opAmal electronic liquid crystal elastomer for structuring organic electronic
systems used for applicaAon in drugs and foods because they have properAes of both
liquid crystal and elastomers.

3. Liquid Crystal Glass

• Liquid Crystal glasses are most widely used in digital devices industry. These glasses
provide the flexibility and reduced thickness in the displays.
• E.g. Amorphous silicon acAve matrix LCD (AM LCD)

4. Nonmaterial enhanced liquid crystalline Material

• Nonmaterial enhanced liquid crystalline properAes, such as threshold voltage,
response Ame, viscosity, dielectric anisotropy, refracAve index which are important in
the area of LC displays (LCD’s).

5. Liquid Crystal as reinforced material

• By the copolymerizaAon of p-hydroxy benzoic acid and phthalic acid with ethylene
glycol resulted in the reinforced material which provide the strength and sAffness to
thermotropic polymer. These are also used as a reinforcing fillers in thermoplasAcs.