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CHAPTER-3
SYNTHESIS METHODS

3.1: Introduction:

There are several Synthesis methods for creating nanoparticles

like, Physical vapor deposition, Chemical vapor deposition, Sol-gel Method, RF

Plasma Method, Pulsed Laser Method, Thermolysis and Solution Combustion

Method.

a. Physical vapor deposition (PVD):

By using this deposition technique, thin films of different

metals are deposited on different surfaces. This technique involves

condensation from the vapor phase. There are three main steps involved in this

process.

1)By the sublimation of evaporating of a material corresponding vapor phase.

2)Transportation of the material to the substrate from source.

3)Formation of the thin film and particle by nucleation and growth.The source

can beavaporated by using electron beams,thermal energy,sputtering

technique,cathode arc plasma.

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b. Chemical vapor deposition (CVD):

This process is mostly used in semiconductor industry for depositing

thin films of various materials. This is mainly chemical process. In this process

the substrate is exposed one or more volatile precursors. These precursors

decompose on the substrate and produce the desired deposit . In CVD, the

vaporized precursors are introduced into a CVD reactor and adsorb onto a

substance held at an elevated temperature.

In CVD process ,vaporized precursors are made to adsorb onto a

substance held at a high temperature.The adsorbed molecules,react with other

or decompose and produce crystals.There are three main steps in CVD

process.1)reactants are transported on the growth surfaceby a boundary

layer.2)chemical reactions take place on the growth surface.3)by products

formed by the gas-phase reaction have to to be removed from the

surface.Homogeneous nucleation takes place in gas phase.heterogeneous

nucleation takes nucleation takes place insubstrate.

c. Sol-gel Method:

In this chemical procedure, the solution gradually converts into a gel like

diphasic system,which contains both liquid phase and solid phase . the

morphologies of these two phases range from discrete particles to continues

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polymer networks . Initially a significant amount of fluid may have to be

removed from solution to recognize the gel like properties. Sol-gel method is a

low temperature technique and moreover it is cheap . In this method the

chemical composition of the product can be controlled .In this method the

solution can be doped with organic dyes and rare earth metals. The dopants

are uniformly dispersed in the final product. This technique can be used in

ceramics processing and producing thin films of metal oxides. Nano materials

derived by this method have wide applications in electronics, medicine,

separation technology, and optics.

RF Plasma method:

In the synthesis of nanoparticles by RF plasma method , a plasma is

utilized . This plasma is generated by RF heating coils. The starting metal is

contained in a pestle and this pestle is contained in an evacuated chamber.

The metal is heated above its evaporation point by using high voltage RF coils

wrapped around the evacuated chamber. Helium gas is allowed to enter the

system and this gas forms a high temperature plasma in the region of the coils.

The metal vapor nucleates on the helium gas atoms and diffuses up to a cold

collector rod, where nanoparticles are collected . Finally these nanoparticles are

passivated by the introduction of appropriate gas (Oxygen).

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Figure 3.1.1: Synthesis of nanoparticles using RF Plasma method

e. Pulsed Laser Method:

This method is capable of high rate of production of 3gm/min. This method is

mainly used in the synthesis of silver nanoparticles . Silver nitrate solution and

reducing agent are allowed to follow into a blender like device . This device

consists of a solid disc and this disc rotates with solution. Hot spots are

created on the surface of the disc by subjecting it to pulses from a laser beam.

Silver nitrate reacts with reducing agent at this hot spots and as a result, small

silver particles are formed . These particles can be separated by centrifuge. The

size of the particles is controlled by the energy of the laser and angular velocity

of the disc.
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Figure 3.1.2: Synthesis of nanoparticles using a Pulsed Laser method

f. Thermolysis:

The process in which nanoparticles are formed by decomposing the

solids into metal cations and molecular anions or metal organic compounds at

high temperature is called thermolysis . As an example we can look at

production of lithium nanoparticles by decomposing lithium azide (LiN3). LiN3

decomposes nearly at 3700C and N2 gas is released. Pressure is increased due

to release of N2 gas. This can be observed by a vacuum gauge. After a few

minutes the pressure fall back to its original value. This is an indication that

all N2 gas is removed. The remaining Li atoms combine to form small colloidal

metal particles. Passivation can be achieved by the introduction of appropriate

gas. Particles less than 5nm can be produced by this method.

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Figure 3.1.3: Synthesis of nanoparticles using a Thermolysis method

h . C ombustion Method:

We have synthesized Fe3O4 nano particles and MgxFe(1-x)O by using

Combustion Method, detailed explanation about this method in 3.2

3 . 2 : C ombustion Synthesis:

Combustion synthesis (CS) or self-propagating high-temperature

synthesis (SHS).This is an effective, ecofriendly and low-cost method for

production of various industrially useful nanomaterials. Today CS has become

a very popular approach for preparation of nanomaterials and is practiced in

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65 countries.Number of breakthroughs in this field have been made due to the

extensive research carried in last 5 years. Notable breakthroughs are,

development of new catalysts and nano carriers with properties better than

those of similar traditional materials. The extensive research carried out in last

five years emphasized the SHS capabilities for materials improvement, energy

saving and environmental protection. The importance of industrialization of the

SHS process is also realized during this research. All these aspects were

adequately highlighted and discussed in the international conference devoted

to the 40th anniversary of SHS, which was held at ISMAN (Chernogolovka,

Russia) in October 2007[10].

Several books and reviews have been published on this subject in recent

years. The book on chemistry of nano crystalline oxide materials gives the

recipes for the preparation of different nano size oxide materials. An attempt

has been made to critically evaluate the recent rogress and novel trends in the

Chemical Synthesis of nano materials and their applications. Thus the results

on CS of nano materials are discussed using the processes Classification that

is based on the physical nature of the initial reaction medium:

• Conventional SHS of nanoscale materials, i.e. initial reactants are

in solid state (condensed phase combustion).

• Solution-combustion synthesis (SCS) of nanosized powders, i.e.

Initial reaction medium is aqueous solution.

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• Synthesis of nanoparticles in flame, i.e. gas-phase combustion.

3 . 3 : E x p e r i m e n ta l P r o c e d u r e f o r t h e s y n t h e s i s o f F e 3 O 4

Magnetite nano paticles were synthesized by the combustion of aqueous

solutions, which contain the corresponding metal nitrate, ferric nitrate and

urea. The composition of the mixture can be calculated by basing on the

oxidizing valancies of oxidizer and reducing valancies of the fuel by changing

the F/O ratio from 0.25 to 2. The aqueous solution containing the redox

mixture in a Pyrex container is introduced in a muffle furnace. The muffle

furnace is preheated to 400 °C, boils foams and undergoes smoldering

(flameless) combustion to produce the corresponding oxides. The product left

behind is voluminous and erupts like a volcano.

The combustion can also be carried out by using a kitchen microwave

oven (IFB, 750 W, 2.45 GHz, 1.2 ft3). The combustion reaction in a microwave

oven takes place in a short interval of time compared to that in a muffle

furnace.The products obtained by this method are also voluminous and fluffy.

Equation for the formation of Ferric nitrate with urea can be written as follows.

6Fe (NOз) з (s) + 10CH4N2O (s ) →2 FeзO4 (s) +20CO₂ (g) + 40H₂O (g) +14N₂ (g)

(3-3.1)
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Similar equations can be written for the formation of other oxide

materials.

Apparatus Used:

1. Ferric nitrate Fe (NO₃)₃

2. Urea, CH4N2O

3. Sensitive Balance

4. Magnetic Stirrer

5. Hotplate

6. Muffle Furnace
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Flow Chart for Experimental Procedure:

Figure 3.2.1. Flow chart for preparation of Iron oxide using Solution

combustion method

The required amount of Fe (NO3)3 was dissolved in distilled water along

with fuel Urea(CH4N2O). Stoichiometric compositions of the metal nitrates and

fuel are calculated based on the total oxidizing and reducing valencies of the

fuel and oxidizer. The heat of combustion is maximum for the fuel to oxidizer

ratio (F/O) equals to 1. The fuel to oxidizer ratios (Ψ) are calculated using the

equation(3-3.2). Based on the concepts used in the propellant chemistry, the

elements Fe considered as reducing elements with valences 3+, 2+ (or valency

of metal ion in that compound), respectively. Oxygen with a valency of 2-

,plays the role of oxidizer. The valency of nitrogen is taken as zero because
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,during the combustion,Nitrogen is converted into moleculer nitrogen. The fuel

to oxidizer ratios are calculated using the equation(3-3.2)

(3-3.2)

Where n is no.of moles of fuel and a is the no. of moles of nitrate.

We prepared FeзO4 for different fuel to oxidizer ratios Ψ = 0.25, 0.5, 0.75, 1,

1.25, 1.5, 1.75 and 2 by doing stoichiometric calculations using the Eq3-

2.1.Based on the equation what we obtained, we will consider the molecular

weights of the Ferric Nitrate and Urea. By using the molecular weights we will

make the calculations for the quantities of the Ferric Nitrate and Urea what we

have to take in the experiment based on the fuel to oxidizer ratio varying from

0.25 to 2.
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S.No F/O Ratio(Ψ) Fe(NO₃)₃ in gm CH4N2O in gm

1 0.25 5 0.387118

2 0.5 5 0.774237

3 0.75 5 1.161355

4 1 5 1.548474

5 1.25 5 1.95592

6 1.5 5 2.32271

7 1.75 5 2.709829

8 2 5 3.096947

3.2.1. Table for magnetite and Urea composition varying F/O

ratio from 0.25 to 2

Experimental procedure for the synthesis of solid solution MgxFe(1-x)O

(O<x<1):
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The required amounts of magnesium nitrate and ferric nitrate were

dissolved in distilled water along with urea.The elements C,H,Mg,N,Fe are

considered as reducing elements and their valancies are +4,+1,+2,0,+3

respectively.oxygen plays the role of oxidizerwith valency -2.Nitrogen is

interconvertible to moleculer nitrogen during combustion. Hence it’s valency is

taken to be zero.

Ψ= n{1*4C+4*1H+2*ON+1*-2O}

{a[1*2Mg+2(1*ON+3*-2O)]+ b[1*3Fe+3(1*ON+3*-2O)]}

Where n is mole of fuel and a, b are the mole fractions of Mg and Fe

nitrates respectively. The aqueous solution is stirred thoroughly with a

magnetic stirrer until the solid reagents form a clear solution .The solution

thus obtained is placed on a hot plate. When the temperature of hot plate

reaches to zero, water boils from the solution as a result of which, the viscosity

of the solution increases. Meanwhile the compound catches fire and a black,

light weight powder will be obtained. The obtained sample was taken through

the annealing process for two hours at a temperature of 2500C . The chemical

combustion is a self-propogating reaction. we need not supply any heat from

any external source. Chemical combustion automatically goes to completion

after ignition. The reaction equations assuming complete combustion, of the

redox mixture used for the synthesis of MgFeO solid solution may be given as
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Mg(NO3)2+Fe(NO3)3 + CH4N2O --------- MgFeO(s)+H2O(g)+CO2(g)+N2(g)

S.No MgxFe(1- F/O Mg(NO₃)₃ in Fe(NO₃)₃ in CH4N2O in

x)O Ratio(Ψ) Gms Gms gm

1 Mg0.1Fe0.9O 1.25 0.32937 4.6703 2.3304

2 Mg0.2Fe0.8O 1.25 0.68469 4.3151 2.2636

3 Mg0.3Fe0.7O 1.25 1.06919 3.93081 1.83295

4 Mg0.4Fe0.6O 1.25 1.4866 3.5134 2.3575

5 Mg0.5Fe0.5O 1.25 1.94128 3.05872 2.3682

6 Mg0.6Fe0.4O 1.25 2.43853 2.56147 2.3797

7 Mg0.7Fe0.3O 1.25 2.98465 2.01535 2.3925

8 Mg0.8Fe0.2O 1.25 3.5871 1.4129 2.4066

9 Mg0.9Fe0.1O 1.25 4.25507 0.74490 2.42019

3.2.2. Table for magnesium ferrite and urea composition

From the above calculations we have taken the compounds by measuring them

using sensitive balance. The measured compounds are taken in a beaker and

required quantity of distilled water is added. The contents in the beaker are

stirred well until the compounds are dissolved. We have taken care that no
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dust particles are present in the solution and also no compounds left un-

dissolved. After all the compounds are dissolved, the entire setup is placed on a

hot plate and the heating process started. We observed different in the heating

process, Boiling takes place in th first stage.Frothing takes place in the second

stage.In the third stage, firing takes place. Heating process was continued until

all the water is evaporated. Finally, we got a powdered black and brownish

sample as shown in the figure 3.1.1.we have annealed the obtained product for

two to three hours at 573K. The sample is taken out and stored in a air tight

veil by crushing it.

Figure 3.2.2.a: Formation of Volcano Magnetite nano particles.