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❖ METHODS OF SYNTHESIS OF NANOMATERIALS:

Nanostructure materials have attracted a great deal of attention because their physical,
chemical, electronic and magnetic properties show dramatic change from higher
dimensional counterparts and depends on their shape and size.

• Many techniques have been developed to synthesize and fabricate nanostructure

materials with controlled shape, size, dimensionality and structure.

• The performance of materials depends on their properties. The properties in tern

depend on the atomic structure, composition, microstructure, defects and interfaces
which are controlled by thermodynamics and kinetics of the synthesis.

Classification of Techniques for synthesis of Nanomaterials There are two general

approaches for the synthesis of nanomaterials as shown in Figure:

a) Top- down approach b) Bottom–up approach.

a) Top-down approach

• Top-down approach involves the breaking down of the bulk material into nanosized
structures or particles.
• Top-down synthesis techniques are extension of those that have been used for
producing micron sized particles.
• Top-down approaches are inherently simpler and depend either on removal or division
of bulk material or on miniaturization of bulk fabrication processes to produce the
desired structure with appropriate properties.
• The biggest problem with the top-down approach is the imperfection of surface
structure.
• For example, nanowires made by lithography are not smooth and may contain a lot of
impurities and structural defects on its surface. Examples of such techniques are high-
energy wet ball milling, electron beam lithography, atomic force manipulation, gas-
phase condensation, aerosol spray, etc.

b) Bottom up approach

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• The alternative approach, which has the potential of creating less waste and hence the
more economical, is the ‘bottom- up’.
• Bottom-up approach refers to the build up of a material from the bottom: atom-by-atom,
molecule-by-molecule, or cluster-by cluster.
• Many of these techniques are still under development or are just beginning to be used
for commercial production of nanopowders.
• Oraganometallic chemical route, revere-micelle route, sol-gel synthesis, colloidal
precipitation, hydrothermal synthesis, template assisted sol-gel, electrodeposition etc,
are some of the well- known bottom–up techniques reported for the preparation of
luminescent nanoparticles.

Schematic representation of ‘top-down’ and 'bottom-up’ approaches for synthesis of

nanoscale materials.
❖ COLLOIDAL METHODS
• Colloidal chemical methods are some of the most useful, easiest, and cheapest ways to
create nanoparticles. Colloidal methods may utilize both organic and inorganic
reactants. Typically, a metal salt is reduced leaving nanoparticles evenly dispersed in a
liquid. Aggregation is prevented by electrostatic repulsion or the introduction of a

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stabilizing reagent that coats the particle surfaces. Particle sizes range from 1 to 200 nm
and are precise by the initial concentrations of the reactants and the action of the
stabilizing reagent.
• Figure shows the method of formation of gold nanoparticles as follows: Heat the
solution of chloroauric acid (HAuCl4) up to boiling point. HAuCl4 is a water-solvable
gold salt. Add trisodium citrate, which is a reducing agent. Remain stirring and heating
for around 10 min. Throughout time, Na3C6H5O7 (sodium citrate) reduces the gold
salt (Au3+) to metal gold (Au0 ). The neutral Au atoms cumulate into seed crystals.
The seed crystals continue to grow and ultimately produce Au nanoparticles (Adam D.
McFarland et al.):
• Examples: Gold • A common method for preparing colloidal gold nanoparticles
involves combining hydrogen tetrachloroaurate (HAuCl4) and sodium citrate
(Na3C6H5O7) in a dilute solution.
• Upon dissociation, the citrate ions (C6H5O7 3-) reduce Au3+ to yield 30–40 nm gold
particles.

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❖ Micelles Method
The revert aggregation method is one among the current assuring ways to
nanocrystalline materials. Numerous current research have revealed that this impending
is a potential technique for the synthesis of nanocrystalline ceramic powder with specific
and measured properties. Surfactants are dissolved in organic solvent-type
conglomerations known as reverse micelles. Within the existence of water, the polar
head clusters of the surface-active agent molecules organize themselves around little
water polls, resulting in spread of the liquid phase in the uninterrupted oil phase.
Converse aggregates are utilized to formulate nanoparticles through commissioning
water solution of responsive predecessors and may be modified over to indissoluble
nanomaterials. Nanoparticle synthesis within the micelles may be modified over to
indissoluble nanoparticles. Nanoparticle synthesis within the micelles may be achieved
by various approaches, letting in hydrolysis of responsive precursors, like alkoxides and
metal salt precipitation. Removal of persisted solvent along with calcination process can
able to form the ultimate product. Spreading of the surfactants could be utilized during
accomplishment of these procedures, like decaoxyethylene nonyl phenyl ether (TNT-
10), pentadecaoxyethylene nonyl phenyl ether (TNP-35), poly(oxyethylene) nonyl
phenol ether (NP5), and many other solvents that are commercially accessible. Various
parameters, especially quantity of the reactive precursor within particle, the mass
proportion of the liquid phase in macroemulsion, particle size, distribution of particle
size, and agglomerate size and phases of the eventual ceramic powder. Through
exploration of this method, there will be an associated advantage. Very small particles
can be prepared that have got the potential to regulate the particle size. Difficulties
include low production capacity and being bound to utilize immense quantity of liquid.

❖ POLYMERS
• Polymers are high molecular weight organic compounds in which a large number of
simple units repeat themselves in a regular fashion. The simple units are called as
monomers. For any compound to be recognized as a true monomer, it should possess
at least two functionalities (Not two functional groups necessarily---- as in some
compounds, one functional group gives rise to only one functionality while in some
compounds, one functional group gives rise to two functionalities), e.g.,
✓ CH3OH has one functional group and one functionality (Not a true monomer)

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✓ CH2=CH2 has one functional group and two functionalities (A true monomer)
✓ HO-CH2-CH2-OH has two functional groups and two functionalities (A true
monomer)
• Therefore, it is clear that what is actually required for polymerization, is presence
of at least two functionalities and not two functional groups, in the monomer.

Classification of Polymers
• Polymers have been classified on different basis as follows:

(A). Classification on the basis of Origin/Source On this basis, polymers have been
broadly classified into two types:

1. Natural Polymers They occur naturally and are found in plants and animals.
Examples: Proteins, Nucleic acids, Starch, Cellulose and Natural rubber.

2. Synthetic Polymers These are man-made polymers. Plastic is the most common and
widely used synthetic polymer. e.g., Nylons, Polythene, PVC, Synthetic rubbers, etc.

(B). Classification on the basis of Structure On this basis, polymers have been
broadly classified into three types:

a. Linear Polymers: Polymers comprising of long and straight chains are called as linear
or straight chain polymers. e.g., High density polyethene (HDPE)

b. Branched-chain Polymers Polymers comprising of linear chains with branches are

called as branched chain polymers. e.g., Low-density polyethene (LDPE)

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3. Cross-linked Polymers Polymers in which various individual chains are connected
together by covalent bonds (cross links) are called as cross linked polymers. These
polymers are formed from bi-functional and tri-functional monomers and the additional
functionality produces the cross links. e.g., Bakelite and Melamine

(C). Classification on the basis of nature of Monomers

On this basis, polymers have been broadly classified into two types:

1. Homo-polymers
Polymers which are comprising of only one type of monomers are called as homo-
polymers. e.g., Polyethene, PVC, Nylon-6, etc. This can be represented as: -A-A-A-
A-A-A-A-A-A-A-A-A-A-A-, or -(A-)n

2. Co-polymers
Polymers which are comprising of more than one (generally two) types of monomers are
called as homo-polymers. e.g., Nylon-6'6, Terylene, SBR, etc. Co-polymers have
further been classified into four types on the basis of relative arrangement of the
monomer units with respect to each other.
These are:
i). Alternate Co-polymers: Polymers comprising of alternating A and B units. The order
is regularly followed throughout the chain. This can be represented as
-A-B-A-B-A-B-A-B-A-B-A-B-A-B-, or -(A-B)n.

ii). Block Co-polymers: Polymers comprising of regular alternating blocks of A and B

units. The order is regularly followed throughout the chain. This can be represented
as:

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-A-A-A-A-A-B-B-B-B-B-A-A-A-A-A-B-B-B-B-B.

iii). Graft Co-polymers: Polymers in which the main chain is comprising of one type of
monomers and the other monomer forms the branches. Therefore, for being a graft co-
polymer, the polymer must be branched. This can be represented as:
B-B-B -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-B-B-B

iv). Random Co-polymers: Polymers in which no regular order of arrangement is

followed by the monomer units. This can be represented as:
-A-A-A-A-A-B-B-A-B-B-B-B-B-B-B-A-A-A
The most common type of co-polymers are alternate co-polymers

(D). Classification on the basis of Inter-molecular Forces

On this basis, polymers have been broadly classified into four types:
1. Elastomers
Polymers in which intermolecular (inter-chain) forces are very weak (van der Waals
forces) are called as elastomers. These are rubber-like solids weak interaction forces
are present. e.g., Rubber.
2. Fibres
Polymers in which intermolecular (inter-chain) forces are very strong (Hydrogen bond or
dipole-dipole interaction) are called as Fibres. These are strong, tough, with high
tensile strength. e.g., Nylons, Terrylene, etc.
3. Thermo-plastics
Polymers in which intermolecular (inter-chain) forces are intermediate are called as
thermoplastics. These polymers on heating become soft and on cooling again become
hard and retain their original shape. In this case, the intermolecular forces, on heating,
get weaken and the polymer becomes soft and vise-versa. It is purely a physical change
and physical changes are generally reversible. Therefore, these polymers are
recyclable, i.e., they can be moulded and re-moulded again and again. e.g., Polyethene,
Polyvinyl chloride, Polystyrene, etc.

4. Thermo-settings

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Polymers in which there is extensive cross linking, are called as thermo-settings. These
polymers on heating become soft and on cooling again become hard but do not retain
their original shape. In this case, the cross links get broken and rearranged on heating.
It is purely a chemical change and chemical changes are generally irreversible.
Therefore, these polymers are not recyclable, i.e., once moulded, they cannot be
moulded again. These polymers greatly improve the material’s mechanical properties.
e.g., Bakelite, Epoxy resins, etc.

(E). Classification Based on Synthesis

On this basis, polymers have been broadly classified into two types:

1. Addition Polymers Polymers which are formed by addition reaction are called as
addition polymers. e.g., Poly ethane, Teflon, Polyvinyl chloride, etc. For addition
polymerization to take place, the monomer must be unsaturated. Taking the example of
polyethene, the addition polymerization reaction can be shown as:

Addition polymerization is a chain reaction, which once initiated, propagates itself till the
chain is not terminated. It involves three steps: Chain initiation, Chain propagation and
Chain termination. Addition polymerization can take place via three different types of
mechanisms: I). Cationic Mechanism II). Anionic Mechanism III). Free Radical
Mechanism

I). Cationic Mechanism: In this mechanism, the reaction is initiated by an electrophile

resulting in the formation of a carbocation as intermediate, thus known as cationic
mechanism. The reaction can be terminated by a nucleophile. We can summarize that in
this reaction, Initiator is Electrophile, Intermediate is Carbocation, Inhibitor
(Terminator) is Nucleophile. The mechanism can be shown as:

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II). Anionic Mechanism: In this mechanism, the reaction is initiated by a nucleophile

resulting in the formation of a carbanion as intermediate, thus known as anionic
mechanism. The reaction can be terminated by an electrophile. We can summarize
that in this reaction, Initiator is Nucleophile, Intermediate is Carbanion, Inhibitor
(Terminator) is Electrophile. The mechanism can be shown

• In case of free radical mechanism, in addition to the normal chain termination by introducing
a free radical, there are also other ways wherein the chains can terminate themselves.
• These are:
i). By Coupling: There is possibility that two propagating chains can collide with each other
and couple. In this way, both the chains are terminated and the polymer chain obtained has
molecular weight more than expected.

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ii). By Dis-proportionation: There is possibility that a hydrogen radical from one propagating
chain can be abstracted by another, thereby terminating both the chains, however, unsaturation
is created in the chain from which H-radical is being abstracted

❖ Some Commercially Important Addition Polymers

Polyethene
Polyethene is a homo-polymer and its monomer unit is ethene (ethylene). It is the most
common and with simplest structure among all plastics. The reaction for preparation of
polyethene can be shown as:
Polyethene is broadly of two types:
i). Low DensityPolyethene (LDPE)
ii). High Density Polyethene (HDPE)

i). Low Density Polyethene (LDPE): As the name itself indicates, it is a polymer of
very low density. It is prepared via free radical mechanism at a temperature of 80 to
350 o C under high pressure (1000 to 3000 atm) in presence of a oxygen or a peroxide
(Benzoyl peroxide) as initiator, wherein extensive branch formation takes place and the
density of the resultant polymer is very low in the range of 0.910–0.940 g/cm3.
Properties: ·
1. It is a waxy translucent material, exhibits high impact strength, low brittleness
temperature, film transparency and outstanding electrical insulating properties.

2. It is chemically inert and has good resistance to acids and alkalis. However, it
swells in and is permeable to oils.

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3. It melts in temperature range of 107-120o C. Its Tg (Glass Transition) value is
-120o C. ·

4. It is flexible over a wide temperature range.

• Applications: It is used in making packaging materials for food, garments, etc.

It is used in production of squeeze bottles, coatings, wrappings, etc. It is also
used in cable and wire insulations.

❖ i). High Density Polyethene (HDPE):

It is a linear polymer with little or no branching. It is prepared via ionic mechanisms at
a low temperature of 60 to 70 o C and very low pressure (6 to 7 atm), wherein little or
no branch formation takes place and the density of the resultant polymer is high in the
range of 0.945–0.965 g/cm3. However, HDPE is also prepared by coordination
polymerization using Ziegler-Natta catalyst (Triethyl aluminium and Titanium
tetrachloride)
• Properties: · It is opaque and has less impact strength, but, better barrier
properties than LDPE. · It has better chemical resistance than LDPE. · It melts
in temperature range of 130-138o C. Its Tg (Glass Transition) value is -20o C.
It is exhibits better stiffness, toughness, good tensile strength and heat
resistance. Applications: It is used in manufacture of dust bins, cans, buckets,
fuel tanks, etc. It is used for making corrugated pipes. It is also used in cable
and wire insulations.

❖ Mechanical Alloying or High Energy Milling:

• Mechanical alloying was originally invented as a method to manufacture oxide
dispersion strengthened nickel alloys It is a high energy ball milling process,
where alloying is the result of the repeated fracture and cold welding of the
component particles. Highly metastable materials such as amorphous alloys and
nanostructured materials can be prepared by the process. Scaling up to industrial
quantities seems straight forward. In addition to attrition and agglomeration,
high energy milling can induce chemical reactions, which can be used to
influence the milling process and the properties of the product. This fact was

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utilized to prepare magnetic oxide-metal nanocomposites via mechanically
induced displacement reactions between a metal oxide and a more reactive
metal. High energy ball milling can also induce chemical changes in non-
metallurgical binary systems, including silicates, minerals, ferrites, ceramics,
and organic compounds. The research area of mechanochemistry was developed
to study and utilize these processes. As many mechanical alloying processes
involve chemical changes, the distinction between mechanical alloying and
mechanochemistry is often arbitrary.
• PROCESS VARIABLES
Mechanical alloying is a complex process and hence involves optimization of a
number of variables to achieve the desired product phase and/or microstructure.
Some of the important parameters that have an effect on the final constitution
of the powder are:
Type of mill
• Milling container
• Milling speed
• Milling time
• Type, size, and size distribution of the grinding medium
• Ball-to-powder weight ratio
• Extent of filling the vial
• Milling atmosphere
• Process control agent
• Temperature of milling.

All these process variables are not completely independent. For example, the
optimum milling time depends on the type of mill, size of the grinding medium,
temperature of milling, ball-to-powder ratio, etc
• TYPE OF MILLING EQUIPMENTS USED FOR MECHANICAL
ALLOYING
Different types of high-energy milling equipment are used to produce mechanically
alloyed powders. They differ in their capacity, efficiency of milling and additional
arrangements for cooling, heating, etc.
SPEX shaker mills

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Attritor mills
Commercial mills
Planetary ball mills

• SPEX shaker mills

Shaker mills such as SPEX mills, which mill about 10±20 g of the powder at a time, are most
commonly used for laboratory investigations and for alloy screening purposes.

• Attritor mills
A conventional ball mill consists of a rotating horizontal drum half-filled with
small steel balls. As the drum rotates the balls drop on the metal powder that is
being ground.

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• Planetary ball mills: Another popular mill for conducting MA experiments is the
planetary ball mill (referred to as Pulverisette) in which a few hundred grams of the
powder can be milled at a time. The planetary ball mill owes its name to the planet-like
movement of its vials. These are arranged on a rotating support disk and a special drive
mechanism causes them to rotate around their own axes. The centrifugal force produced
by the vials 12 rotating around their own axes and that produced by the rotating support
disk both act on the vial contents, consisting of material to be ground and the grinding
balls. Since the vials and the supporting disk rotate in opposite directions, the
centrifugal forces alternately act in like and opposite directions. This causes the
grinding balls to run down the inside wall of the vial the friction effect, followed by the
material being ground and grinding balls lifting of and traveling freely through the inner
chamber of the vial and colliding against the opposing inside wall the impact effect

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Even though the disk and the vial rotation speeds could not be independently controlled
in the earlier versions, it is possible to do so in the modern versions. Grinding vials and
balls are available in eight different materials agate, silicon nitride, sintered corundum,
zirconia, chrome steel, Cr+Ni steel, tungsten carbide, and plastic polyamide. Even
though the linear velocity of the balls in this type of mill is higher than that in the SPEX
mills, the frequency of impacts is much more in the SPEX mills.

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• MECHANISM OF MECHANICAL ALLOYING

In the planetary ball mill its vials are arranged on a rotating support disk.
A special drive mechanism causes them to rotate around their own axes.
The force of the impact plastically deforms the powder particles.
The particles get work hardened and fracture.
The new surfaces created enable the particles to weld together.
Particle contains substantially all of the starting ingredients, in the proportion
they were mixed together

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