1

Introduction

1
 2

Introduction

The word Nano comes from Greek means “dwarf” and the word Nano use in different terms

like Nano-seconds, Nano-meters and Nano-technology. The term Nano-technology used and

described for the first time in 1974 [1]. Nano technology basically explains those matters

having sized scale below 100nm [2]. It is considered that Nano-material is a tool for the

explanation between single molecule and bulk molecule. Nano-material show changes in

chemical as well as in physical properties as comparing with bulky material. It occurs due to

very large surface, large diversity and very small size [3]. Diversity in Nano-materials describes

as

a) A molecule b) A model crystal

c). A crystal owing defects, fissured and porous surface

d). A crystal having defects, homogeneous and intact surface

e). A crystal with defects, porous and inner surface

These three parameters (very small size, large surface area and diversity) are also responsible

to show unique magnetic, electrical, optical and other properties [5], which improve the quality

of the materials. These materials help increasing the computers speed [6] and storage capacity

[7]. These materials also used for diagnosis, cancer treatment and many other diseases [8].

These Nano-materials are used for the reduction of salts [9], production of batteries or devices

having more storage [7] and are also used for the creation of proficient lightening [10], non-

stainable clothes and disposable glasses [11].

2
 3

Classification

Basically, Nano-Materials are divided into three classes

 Classification on the base of material

 Classification on the base of dimension

 Classification on the base of structure

Classification on the base of material

a) Metal base material b) Carbon base material c) Composites d) Dendrimers

Metal Based Materials

Metal based Nano-material has largest surface area than bulk particles due to having chemical

groups[2]. Metal based Nano-material includes Nano-gold, Nano-silver, quantum dots [12] and

metal oxides such as titanium oxides. Basically quantum dots are semi-conductor materials.

These shows optical properties and these properties depend upon Nano-particles size [13].

Quantum dots show electronic properties between bulk semi-conductors and discrete

molecules. They also develop in the form of insulators, metal, magnetic materials or magnetic

oxides.

Material based on carbon

Nano-materials that are based upon carbon include cylindrical carbons which are known as

Nano-tubes, Ellipsoid which are known as fullerenes.

A fullerene is any molecule composed of carbon having hollow sphere, ellipsoid or tube like

shape. Fullerene molecules do not combine so they show major potential applications as

lubricants. Fullerene show electrochemical, photochemical and physical properties [14] and it

also shows pentagonal and hexagonal structures. These structures are similar to graphite, when

3
 4

they form sheets [15] from pentagonal, hexagonal and heptagonal rings. Carbon Nano-tubes

are tubular in shapes show allotropic property with graphite [16]. Carbon Nano-tubes show

many types of applications. It enhances coating and improves films in different electronic

materials. It acts as lighter and stronger material in electronic devices. Diamond, Fullerene,

Carbon Nano-tube, Graphite, Graphene, Graphene oxide and Carbon dot are some common

examples of carbon based materials.

Composites

Composites are the materials that have many phases and show many properties. Nano-

composite is a type of matrix in which Nano-particles are added for improving the property of

material. As an example, Nano-sized clay is used to enhance thermal, mechanical and flame

retardant properties in packing materials. Nano-composites are also helpful in improving

electrical, magnetic, and optical, corrosion resistance, tri-biological and protective properties.

Fiber composites, Particle composites, laminar composites, flake composites and filled

composites are types of composites.

Dendrimers

The word “dendrimer” comes from Greek word “Dendron” means dry trees. So dendrimers are

the Nano-particles having branches which are decorated with different functional groups [14].

Dendrimers are also defined as “Nano-sized polymers built from branch units”. Due to these

branch units, dendrimers are used for catalysis, drug delivery and waste water treatment [2]

and a proficient indicative tool for imaging of cancer [19]. Common examples of dendrintic

molecules are

a) dendrimer b) linear dendritic hybrid c) hyper-branched polymer

d) hyper-fragted polymer e) multi arm star polymer f) dendronized polymer

4
 5

Classification on base of Dimension

Dimensionally Nano-materials are classified into four classes [5]. This classification is done

by measuring the dimensions of Nano-particles

 Zero Dimension

 One dimension

 Two Dimension

 Three Dimension

Zero Dimensional

Zero dimension materials include sphere and clusters. Zero dimensional materials have no

dimensional Nano-particles. Zero dimensional particles are larger than one hundred Nano

meters and show different types of surfaces. For example: crystalline, single and poly-

crystalline and amorphous surfaces. These Nano-particles exists in metallic ceramic and

polymeric forms [21].These Nano-particles show different forms and many shapes.

One Dimensional

One dimensional system includes thin films and manufactures surfaces. One dimensional

Nano-material is needle like in shape. One dimensional Nano-material also includes

a) Nano-tubes b) Nano-rods c) Nano-wires

One dimensional Nano-material also shows amorphous, crystalline and metallic surfaces.

These one dimensional Nano-particles chemically adulterated or un-adulterated [23]. These

Nano-materials shows one dimensional (1D) growth.

5
 6

Two Dimensional

Nano-layers, Nano-films and Nano-coating are studies in two dimensional materials. They are

also plate like in nature. For forming 2-d Nano-materials, different chemical compositions are

used. This composition may be ceramic or metallic [21]. The surfaces of the two dimensional

Nano-materials are crystalline and amorphous. Carbon Nano-tubes are the best example of the

2-d Nano-materials. Carbon Nano-tubes may be single layers (SWNT) and multi-layers

(MWNT). Single layer carbon Nano-tubes has three types on the basis of structures

a) Arm chair b) Zigzag c) Chiral

Three Dimensional

Three dimensional Nano-materials contain branches of the Nano-wires and multi-layers [21].

Three dimensional Nano-materials include

 Fullerenes (C-60) which are also known as Bucky Balls. These molecules do not

combine with each other so give major potential as for the application as Lubricants.

 Quantum dots are also studied in 3-d Nano-materials. Quantum dots are traditionally

chalcogenides of metals such as cadmium and zinc. Quantum dots show specific optical

and electrical properties. Quantum dots are also elaborated or decorated as

semiconductors, magnetic materials and insulators.

 Dendrimers also includes in three dimensional Nano-materials. Dendrimers are

considers as essential elements to synthesis of organic and inorganic Nano-structures

in large amount. Dendrimers are similar to organic structures such as: DNA, it also

interacts with metallic Nano-crystals and Nano-tubes to possess an encapsulation

capacity. Dendrimer is divided into three components

a) Core Units b) Branching Dendron c) Surface Ligand

6
 7

Core unit is the central part of the dendrimer. It may be small molecule, Nano-particle

or polymer while branching unit is robust covalent structure and it connects core to

surface. Surface ligand are surface group are known as target directing groups. These

are cationic, anionic and neutral in nature.

Classification on the base of structure

Nano-materials are also classified on the base of structure. Structural nanomaterial includes

a) Spinal structure materials b) Nano porous materials c) Nano capsules

d) Molecular and electronics e) Nano composites f) Nano fibers

g) SWNT and MWNT h) Nano wires i) Fullerenes

All these nanostructures show extensive properties, like visual Electronic and many other

properties, which are helpful in developing industrial and domestic products. For example,

magnetic Nano-particles with ultrathin layers are used in data storage devices. [25, 26]

Spinal structure material

Spinal structure materials are mostly composed of metal oxides. Many magnetic oxides also

show spinal structures. [27] Spinal structures are formed due to octahedral and tetrahedral

positions. General formula for cubic spinal structure is AB2O4.

According to formula A+2is a divalent cat-ion, while B is a trivalent cat-ion. For maintaining

neutrality, divalent “A” always occupied tetrahedral sides. While trivalent are also occupied

from octahedral sides.

Types of Spinal structure

1. Normal spinal structures

2. Inverse spinal structures

3. Mixed spinal structures

7
 8

Normal spinal structures

In these spinal structures, cat-ions are present at their original positions as expected from

general formula [27]

(A)tet(B)octO4

Inverse spinal structures

In inverse spinal structures, half of the trivalent cat-ions present on the tetrahedral side and half

occupy octahedral side. General formula for inverse spinal is

(B)tet(A,B)octO4

Mixed spinal structures

In mixed spinal structures, divalent and trivalent cat-ion both contains tetrahedral sides. γ is

used as a degree of the inversion [27].

For normal spinal, γ=0.

For complete inverse spinal, γ=1.

For mix spinal, 0 < γ< 1.

Synthesis of Nano-materials

In order to controlling size structure, morphology and chemical composition several methods

are developed [28-29], like hydro-thermal method [30-31], co-precipitation method [32-33],

sol-gel[34]and precursor method e.tc [35]. These methods are very helpful for the creation and

preparation of the specific Nano-materials [36-39]. All these Nano-particles are useful in

different fields. If we only talk about energy applications of these synthesized Nano-materials,

8
 9

it shows many applications like, these are useful as solar cells, fuel cells, dye sensitizer cell,

silicon based solar cells, hydrogen fuel cell, and assembly fuel cell and direct methanol fuel

cell are useful and they are beating deficiency of the energy like these Nano-materials many

other Nano-materials are also synthesized which are used for different functioning. Our homes

are covered with Nano-material things. Today our life totally depends on Nano-materials. All

these Nano-materials are synthesized by using different methods.

Methods of Nano-material Synthesis

There are two basic methods which are used to synthesis of Nano-materials

1) Top down method 2) Bottom up method [40]

Top down method

In this method bulk material are broken down into smaller and smaller dimensions to get Nano-

sized particles. This method includes following fabrication techniques

 Solid phase

 Aerosol based

 Liquid phase

Solid phase techniques

These are dry methods through using these methods, Nano-materials are synthesized [42].

Solid phase techniques include

a) Mechanical Grinding b) Etching c) Sputtering

d) Laser-ablation e) Electro-explosion f) Lithography

9
 1
0

Mechanical Grinding (Ball milling) technique

In 1970, John Benjamin and his Co-workers synthesized Nano-materials by using high energy

ball milling technique [43]. In this technique through structural deformation we prepared Nano-

materials. It is very simple and un-expensive method which gives tonnage quantity of material.

Structural deformation occurs through mechanical milling. Mechanical milling is achieved

using energy shaker, plenty balls and tumbler mills [21, 23, 36]. Mechanical ball milling is also

used to blend different metals or elements to change their chemical properties and combustion

behavior [44-48]. This method is suitable for producing amorphous or Nano-crystal alloy

particles, elements and compound powder [28, 29, 40, 49-52-53]. Disadvantage of this method

is that contamination occurs during milling and it cannot use for the production of Nano-oxide

materials. Principal mechanical milling is required two things

a) Refractory or steel balls b) Preferably inert atmosphere

Etching techniques

Etching is another technique through which Nano-particles or Nano-materials are formed.

Traditionally, corrosive liquids are used on the un-protecting parts of the metals to create design

on the metal surface [54]. Generally, etching technique includes two methods

a) Wet Etching b) Dry Etching

Wet Etching

In this method etchants are used to remove materials from wafers. These etchants are present

in containers, where etchants dissolve the materials. Drawback of this technique is that

sometime material is less dissolved and least etches. Secondly, some crystals show an isotropic

etching in certain chemicals like silicon [54]. Marwa and Hussien prepared silicon Nano-

particles by wet etching technique [55].

10
 1
1

Dry Etching

In this method, ions like chlorine, oxygen, fluoro-carbons, sometimes with addition of nitrogen,

helium and argon are bombarded that dislodge the material potion which is exposed to the ions.

In this technique etching is the basic action through which Nano-materials are formed. If occurs

in the presence of vapor than that known as “vapor phase” etching. If it occurs in the presence

of reactive ions than it is called “Reactive Ion” etching. While physical etching, require high

energy beam that etch of the substrate atoms [56].A common “reactive ion” etching system

consists of

a) Pump b) Gas lit c) Diffuser nozzle

d) Lower electrode holder e) Upper electrode f) Wafers

g) RF signal insulator

Sputtering

The process in which energetically active particles are bombarded to get Nano-particles which

are obtained through ejection, this process is known as sputtering process and method is known

as sputtering method [57]. These constituents are allowed agglomerate to produce Nano-

particles. For creating energetic particles direct current or radio frequency is used. This method

is used for making alloy, carbides and nitrides. Thomson in1996 [58] and Sporn et al in 1997

[59] form Nano-particles of gold and silicon through using sputtering technique. For chemical

sputtering, bonds of the molecules will weakened by the bombardment of the ions at high

temperature [56]. In hydrogen induced sputtering, hydrogen ions are used for breaking bonds.

For example hydrogen sputtering of the organic molecules or materials C-C bond will be break

by entering hydrogen ions.

11
 1
2

Laser ablation

In this method material is removed from the surface by using laser ablation [60]. Laser beam

acts as key exciting which help for preparing specific Nano-materials. Laser ablation device

consists of pulsed laser and ablation chamber [60]. Laser flash is used for the production of

thick films having pour size 2 to 50 nm [61]. So it is good for producing ceramic materials and

coating films. Carbon, silicon and lithium magnate particles are also synthesized by this

method. Pulsed laser synthesis is a powerful, flexible and versatile technique that interacts with

other techniques [62]. Laser ablation that occurs in the form of pulse is used to synthesize of

Nano-ribbons, Nano-tubes, Nano-wires, Nano-flakes and quantum dots [63-64]. It is the

method that is used to synthesize of the organic, inorganic and aluminum Nano-Structure [65-

66]. Patil et al for the first time in 1987 formed Nano-particles of iron oxide having meta-stable

phases through using PLA technique [67]. A laser ablation consists of

a) Gas inlet b) Vacuum pump c) Vacuum chamber

d) Target e) Ablated vapor f) Substrate

g) Telephonic focusing optics h) X-Y scanning mirrors

i) Pico-second pulses with MHz repetition rate j) Mode locked laser

Disadvantage of top down techniques

Particles formed through this method have different shape and geometry. They have

imperfection in the surface structure. Nano-particles form through this method have significant

amount of impurities [49-50].

12
 1
3

Bottom up methods

In this method, atoms or molecules combine in correct way and produce Nano-particles. This

method is more precise for the production of Nano-particles instead of top-down method. This

method includes following techniques;

 Vapor phase techniques

 Solution phase techniques

 Self-assembly techniques

Vapor phase techniques

CVC and CVD are to methods of vapor phase techniques.

Chemical Vapor Condensation (CVC)

In 1994, chemical vapor condensation technique was developed in Germany [68]. Production

of the metallic nuclei through evaporation and gas condensation method is known as chemical

vapor condensation. CVC method includes two steps. First of all, metallic material is vaporized

then control condensation is done. In the reaction chamber, chemical reactions among gas

molecules occur due to input energy. The best reactants used for the formation of the oxide

Nano-particles are chlorides, because chlorides have low vaporization temperature and cost.

An example of this type reaction is given below [60]

SnCl4 (g) + 2H2O (g) → SnO2 (s) + 4HCl (g)

13
 1
4

Brehm and his partners prepared doped Nano-structures of zinc oxide through using chemical

vapor condensation method [69]. In a typical CVC reactor process of formation of Nano-

particles proceeds as

a) Carrier gas b) Resistive heating c) Precursor

d) Reactants e) Cluster formation f) Condensation

g) Scrapper h) Cold finger i) Particle

collection

Chemical vapor deposition (CVD)

In chemical vapor deposition substrate is exposed to single or many vapor phase material which

decomposes and react the substrate to get desired product. Through a chemical reaction, a solid

thin film is formed on the surface. CVD includes Laser CVD, Photo laser CVD, Plasma CVD,

Thermal CVD and metal organic CVD methods [68]. In thermal CVD reaction is activated

more than 9000C.While the reaction which occurs in between three hundred to seven hundred

degree temperature through using plasma is known as plasma CVD reaction [68]. Laser CVD

technique occurs when substrate is heated by laser while UV radiations are used for photo laser

CVD. Because UV radiations break the bond easily, CVD involves surface and gas phase

reactions. CVD shows two types of Nano-material formation

a) Nano-particles formation b) Nano-particle film formation

Solution phase techniques

These techniques include those techniques which relate to solution which are given below

a) Micro-emulsion b) Hydro thermal c) Sol-gel

d) Precipitation e) Chemical reduction

14
 1
5

Micro-emulsion

It is multi fluid method, fluid may be oil, water, surfactant or co-surfactant [70]. Danielson and

Lind man defined micro-emulsion as “A thermodynamically stable and optically isotropic

liquid solution system which consists of oil, water and amphiphile is known as micro-emulsion

” [71]. It is also described as “A multiphase system forming transparent solution described as

micro-emulsion” [72]. Textural organization is done due to these fluids [73]. Schulman and

Hoar first reported spontaneous emulsion by adding strong surface active agent in 1943 [74].

After this report the term micro-emulsion was used [75]. Micro-emulsion is also known as

“micellar emulsion” [76] or “swollen micelles” [77].

Micro-emulsion kinds

“Normal micelle” and “reverse micelle” are two kinds of micro emulsion. In normal micelle

“oil is act as disperse phase while water acts as continuous phase” [79]. In reverse micelle

“water acts as disperse phase, while oil act as continuous phase” [73]. The draw-back of micro-

emulsion technique is that large amount surfactant or co-surfactant is used for stabilizing Nano-

droplets [73].

Hydro thermal

In this method, reactions take place at high temperature and pressure. Water acts both as liquid

and vapor to dissolve and recrystallize the material. We use hydro thermal method for those

materials which are insoluble in water under normal condition [80]. UV radiations are used for

the production of high temperature and pressure [81]. These reactions take place in closed

container at constant volume, pressure and temperature [82]. 3740C considered as critical

temperature for water, above this temperature water exists in both liquid and vapor phases [27].

This method is very important for the synthesis and growth of those materials which are

15
 1
6

unstable at higher temperature [27]. Through this method we can also form doped and other

forms of Nano-materials like, ZnAl2O4 spinal doped with TiO2 [83] and Eu3+ [84]. But there

are few drawbacks of this method as it is time consuming process at any temperature. UV or

microwave hydrothermal is used for increasing rate of reaction [85].

Sol-gel

A fluid have network in a system known as sol-gel system. Through using this method, bulk

Nano-materials of metal oxide are formed [86]. And for solidifying or precipitation chelating

agents are used. These chelating agents may be steric acid or citric acid, which solidify the

smaller molecule [87] and avoid these molecules from the aggregation. By controlling different

chemical parameters micro-structures of the final product is controlled [88]. Nano-materials

synthesize through using sol-gel method are obtained in the form of colloidal powders films.

These powders or films size is affected by temperature, pH, and composition. These are

parameters, which are used to synthesize control Nano-structures. For production of very fine

powder temperature kept low [89]. It is very good process for the production of Nano materials

but the drawback of sol gel method is that is very time consuming process. Sol-gel reaction

consists of two steps one is hydrolysis, in which breakdown of MOR group is done and as a

result MOH and ROH groups are formed. That means alcoholic compounds are formed. Second

step is condensation, in this step MOH and ROH group combines to form MOM compound. In

the same way MOH and HOM condensed to form MOM and water, which is represented below

in reaction. Both these steps are responsible for forming different kind of materials.

M-OH + HO-M → M-O-M + H2O

[90-91]

16
 1
7

Through using sol-gel process we obtained three forms of Nano-particles

a) Thin film b) Powder c) Dense ceramic

Precipitation

Precipitation is defined as “It is a type of condensation process, in which ionic reactions take

place as a result sparingly soluble substances are formed which are named as precipitates ”

purity of precipitates depend upon particle size and particle size is determined by nucleation

and crystalline growth [92]. Some impurities effects on the rate of precipitation, this has been

studied by Von Weimarn. According to Von Weimarn [93]

𝑄−𝑆
Rate of precipitation = K =
𝑆

Types of precipitation

There are two types of precipitation

a) Post-precipitation b) Co-precipitation

Post Precipitation

The process by which an impurity is deposited after precipitation to get a desired product is

known as post precipitation. For example, when calcium oxalate is precipitated in the presence

of magnesium ion, magnesium oxalate does not immediately precipitate, because it tends to

form supersaturated solution, and another example of post precipitation is that when copper

sulfide will precipitate in acidic solution in the presence of zinc ion but eventually zinc ion

sulfide will precipitate.

17
 1
8

Co-precipitation

In this process, impurity is deposited during precipitation reaction is known as co-precipitation

[94]. To produce co-precipitate, we mostly used hydroxides, carbonates, oxalates, formats or

citrates [95-97]. Subsequently these precipitates are calcined at specific temperature to give

final product [98]. Calcination of the precipitates is necessary to get small size Nano-particles

[99]. For production of specific precipitates, we use special conditions of pH, temperature, and

stirring speed [100-101]. Co-precipitation is divided into four classes.

a) Surface Adsorption

b) Mixed Crystal Formation

c) Occlusion

d) Mechanical Entrapment.

In Co-precipitation method, occlusion and mechanical entrapment occur due to kinetics of

crystal growth, while others are equilibrium process. Co-precipitation method is very

beneficial method than others [80].In this, method is reduced due to homogeneous mixing

and it is very simple and low cost method. It is best method for preparation of metal oxides.

Literature Survey

CBD technique is very good technique. Basically, it is a deposition process through using this process

C.Wu. et al (2014) [102] synthesized 3D NiO/UDG/NF scaffold. This 3D-Nano material is also prepared

through using Nano-casting technique from amorphous carbon. 3D NiO/UDG/NF scaffold shows high

conductivity, because of high graphitization and efficiency to transport e- to NiO. NiO/UDG/ NF, hybrid

electrodes shows good and improved pseudo capacitive function as compared to NiO/NF electrode. These

3D materials show many important admirable Applications in electronics and in sensors.

18
 1
9

M.yarestani et al (2014) [103] synthesized Nano-particles of Cobalt oxide (Co3O4) by using

mixture of Cobalt (II) Chlorine, Triton X-100 as surfactant and kolt as precipitating agent and

by using hydro-thermal process where heating of material is necessary. If we used auto-clave

than temperature is kept 180 0C and time taken is 6- hours. FTIR, XRD and SEM, TEM results

are used for characterization. For confirmation of purity of a product for vibrating sample, we

use magneto-meter (VSM).

M.Y.Nasar.et al (2014) [104] formed spinel Nano-particles of magnesium aluminates

(MgAl2O4) through using the process of sol-gel auto combustion. This process is so good and

in this process oxalic acid, citric acid, and urea are used. The product is divided into many parts

and energy parts heated at different temperature. For characterizing the sample FT-IR, SEM,

UV-visible spectroscopy, TEM and XRD techniques are used. About 90.0 to 95.5 percent dye

degraded under the action of U.V or sunlight radiation.

S.Shiri. (2014) [ 105] examined that the hardness of cement is due to reinforce of Nano-

particles of SiO2. During the examination, he introduced Nano-Calcium aluminates cement

through using High Energy ball milling and annealing process. He came to know that physical

and mechanical properties of cement became better and hydration process also improved, when

we add one percent Nano-SiO2 particles, instead of plain cement.

K.F.WadeKor.. (2017) et al [106] prepared or synthesized Nano-particles of Cobalt Oxide

(Co3O4) through using co-precipitation process .By using (XRD) X-Ray diffraction, structural

purity of Nano-particles was investigated. For estimation of optical bond gap UV-Visible

spectroscopy was used. The direct bond gap of Co3O4 was found 4.07eV.

D.Fejes and K.Hernadi. (2010) [107] explains CVD (chemical vapor deposition) route to

synthesize carbon Nano tubes. According to Now a day’s research, it is considered that, for

the production of carbon Nano-Coils CVD is the only process which is used. It is hoped that

19
 2
0

Nano-Coils have extra-ordinary stiffness in all straight Nano-tubes. Regular coiled Nano-tubes

having helix morphology and charming properties showing electrical, magnetic and

mechanical properties. Atomic force micro-scope is used for measuring mechanical properties

of Coiled Nano-tubes.

S.Saleem . (2014) [108] using combustion technique formed spinal cobalt Aluminates which

are non-crystalline in nature. Pigments, morphology and particles size were determined using

TEM technique. Where colorant behavior was studied using X-ray and Raman spectroscopy.

After annealing, blue and green powders were obtained and powders shows normal and inverse

spinal.

CoAl2O4is a Nano-pigment material which is formed through using many techniques but J.H.

Kim et al (2012) [109] synthesize this pigment material by using ultrasonic hydrothermal

technique which acts as coloring agent in cover tile composition. They characterized and

difference between optical and physiochemical properties of CoAl2O4 pigments by using

TELAB, XRD (x-ray diffraction), DRS, TG-DTA, HRTEM colorimetric technique.

Sh.Salem. et al (2011) [110] used combustion method for synthesizing Nano-sized powder

of carbon Aluminates Through using hot stage microscopy. Thermal behavior of Nano-sized

particles of ceramic glaze is also studied. BET, DTA, SEM, TEM and TG are used as

characterization techniques.

L.Rakirtal (2010) [111] worked on concrete materials, for improving properties of concretes

material. They modified structure of cement hydrates, control delivering of a mixture and add

Nano-particles and Nano-tubes.

J.Chandradass et al (2010) [112] by means of micro-reactors synthesized spinal structure

magnesium Aluminates. They realized that water to surfactant ratio directly relate with the size

20
 2
1

of particle. They observed that for controlling size of spinal Nano-particles, we should be

control water to surfactant ratio. FTIR and X-ray diffraction are used by them. FTIR Explained

lower frequently Bands where X-ray diffraction explained single-phase spinal structure.

N.Bayal et al (2012) [113] through using sol-gel method prepared metal Aluminates and also

investigated their reactivity. They explained that calcination temperature is important for

synthesis and size of metal Nano-particles. They obtained three types of Aluminates at different

temperatures and characterized them through using (TGA) Thermo gravimetric analysis, UV-

visible defuse reflectance and scanning electron microscopy. Through using paraoxon catalytic

reduction and destructive adsorption of 4-Nitro Phenol investigated the reactivity of

synthesized particles.

C.Ragupathi et al (2014) [114] by using microwave combustion process, they prepared Nano-

particles of nickel Aluminates. For this purpose they used extract of sesame plant. Through

using X-ray, FTIR, HR-SEM, HR-TEM, Photoluminescence, VSM, Brunauer-Emmett-Teller

and diffuse reflectance spectroscopy techniques are used for investigation of morphology and

texture. Regular Morphology of Nano-particles of nickel Aluminates were obtained by using

microwave combustion process. For determination of magnetic properties, we used VSM and

for confirmation of synthesis of nickel aluminates Nano-particles, we used FTIR, HR-TEM

and HR-SEM techniques.

C.Bhavya et al (2015) [115] prepared calcium Aluminates Nano-particles using Acetamide

which is an energy source through using combustion process. To characterize the calcium

Aluminate Nano-particles, UV-Absorption microscopy XRD and SEM techniques are used.

Through using calcium Aluminate Nano-particles, photo-catalytic degradation of Coralline

violet 3R and coralline blue 3G is studied in aqueous solution. They come to know that, by

varying pH, catalyst and dye concentration; photo-catalytic degradation will vary. For studying

21
 2
2

photo-catalytic degradation, each experiment is done in the sight of natural light. Observations

showed that pH best for maximum degradation is about 86.25%.

B.Ismail et al (2013) [116] by using co-precipitation process prepared Nano-particles of

Magnesium Aluminates having spinal structure. They also studied these Nano-particles

adsorption on methyl blue. Nano-Particles of spinal Magnesium Aluminates were confirmed

through XRD technique. Crystalline size, which is about 20nm for Nano-spinal Magnesium

Aluminates, was calculated by Scherrer formula. For determination of pore surface area, they

used N2 vapor adsorption technique and pore surface area for Nano-spinal Magnesium

Aluminates was 343m2/g. SEM and TEM were used to determine about aggregation and Nano-

size of particles. Experiments also showed that pH and shaking time affected on the rate of

adsorption. To study of mechanism of adsorption, the calculated data of binding force, binding

energy, separation factor heterogeneous factor degree of adsorption and heat of adsorption was

fitted in Freund-lich Langmuir, and Tem-kin adsorption model. At room temperature, they

calculated Gibbs free energy from given adsorption data.

R.G.-Chaudhary et al (2015) [117] successfully synthesized nickel Nano-particles which has

crystalline size round about 30nm, via chemical reduction process. At 800C by using ethylene

di-amine as protective agent, Nickel Nano-particles were obtained from hydrazine hydrate salt.

These synthesized particles were characterized through using TG/DTG, EDS, TEM and SEM.

For studying Morphology and size SEM, TEM and XRD are used. Nickel Nano-particles as

catalyst show recyclability and reusability about 4-times without any additional treatment.

Nano-particles of nickel formed through using Aromatic compounds are useful as Anti-

bacterial for human pathogens like staphylococcus, aureus, pseudomonas, Escherichia Coli,

Klebsiella sp. and Enterococcus. Nickel Nano-particles shows highest capacity to kill or

destroy aureus and sptaphylococus. (21mm) Pseudomonas, aeruginosa and Klebsiella sp.

(20mm).
22
 2
3

S.-Salem et al (2015) [118] through using auto-ignition technique prepared Nano-particles of

Cobalt Aluminates. In this, he controlled pH 2.5-10.5. He also explained that gelation time is

affected through varying the pH and gelation time is also effect on the synthesis and size of the

Nano particles. For forming gelation, solution is temperate about 1100C and time viscosity is

also recorded.

By using chemical co-precipitation process, A.F.-Osorio et al (2015) [119] prepared Zinc

Aluminates Nano-crystalline and doped terbium (111) Zinc Aluminates. Characterization

technique, which is used for confirmation of Nano crystal size and doping of terbium (111) on

zinc aluminates is XRD. It is also used for the study of concentration effect of terbium

(111).They also explained that these Nano-crystalline show very stable illuminant and pigment

properties.

M.J.Iqbal et al (2007) [120] synthesized and characterized Magnesium Aluminates (MgAl2O4)

substituted with divalent (Ca2+,Br2+,Sr2+) and trivalent (Cr3+Mn3+Fe3+) cat-ions. Sol-gel process

is used of MgAl2O4 synthesis, XRD and dc-electrical resistivity is used for characterization.

XRD showed that the size of crystalline is 6-35nm. Doped metal cat-ion radii, affects on X-

ray density as well as on lattice constant. They also explained that density and X-ray density

of bulk material land doped material enhanced, but porosity decreases by increasing

substitution concentration. To determine dc-electrical resistivity in 400-6000C temperature two

point probe method is used. It showed by increasing temperature, electrical resistivity will be

reduced and increases by doping alkaline earth metal.

M.S.Niasari et al (2009) [89] prepared Nano-Crystalline copper Aluminates. For this purpose,

they adopted sol-gel method and used copper Nitrate, Aluminum Nitrate, citric acid and di-

ethylene glycol mono-ethyl ether as precursor materials. Precursor materials are heated for

2hour at 6000C. After that, for investigate of the crystalline nano-copper aluminates. They used

23
 2
4

UV-visible for concentration and density, SEM and TEM for structural properties, TGA for

mass and composition, FTIR for surface composition or arrangement.

D.mohapatra et al (2007) [121] using solid state method formed magnesium oxide which has

rich in Mg Al2 O4 from α-alumina and sintered salt water magnesium. A calculated value of the

magnesium oxide are mixed to get spinel crystal of magnesium aluminates which is obtained

through calcination and calcination is done 1000 0C for 2 hours and sintered at 1600 0C for 4

hours . During calcination 70% volume spinellisation was monitored. Calcination effects on

the micro-structure and crystallization behavior.

S.Farhadi et al (2010) [122] characterized and synthesized Nano-particles of zinc aluminates

by using co-precipitation method. Ammonia solution is used as precipitation agent.

Characterization of these Nano-particles is done by using X-ray diffraction, SEM and FTIR.

Zinc aluminate Nano-particles are used for acetylation of several amines, alcohols and phenols.

They came to know that for the production of organic Nano-particles, co-precipitation method

is safe, cleaned and low cost technique. They also observe that catalyst is re-useable and

productions of the Nano-particles are greater through using this technique as compare to the

bulk Zn Al2 O4.

M.M.Byranvand et al (2013) [123] synthesized TiO2 which shows unique electronic and optical

properties due to formation of different kind of morphology, Nano crystalline structures. Many

types of methods are used for synthesis of TiO2 .Through using these methods new and

modified Nano-structures are obtained. By using these methods, TiO2 shows improved and

modified applications and properties. By using different methods, we obtained many types of

Nano-rods, Nano-tubes, Nano-wires and miso-porous structures. For preparation TiO2 at

industrial level, large scale preparation method should be developed.

24
 2
5

Nano-film shows important and interesting application at industrial level (2006) [124]. It also

increase the performance of the functional layers like catalytic layers, fuel cell membranes,

electronic component batteries and bio-compatible surfaces by incorporating physical and

chemical properties and through using Nano-particles as building blocks. Gas phase method is

used for the production of Nano-structure films, through manipulation and deposition. In

clusters beam deposition technique, through using flames and hot wall reactors Nano-films are

synthesized. For controlling Nano-particle size beam formation is controlled by controlling

aerodynamic lenses or electric changing, and expansion nozzles. For production of highly

porous films and highly precise films having 1D, 2D and 3D fabricate in micro-sensors and

catalytic micro-reactors. Draw-back of the cluster beam technique is that the production rate of

Nano-particle is low and combination of the aero-cells and vacuum causes integration of Nano-

fabrication.

M.E.Povarnitsyn et al (2010) [125] synthesized colloidal Nano-particles which shows several

applications in many fields. For the production of colloidal Nano-particles laser ablation

method is commonly used. Many types of Nano-particles, which show different fluencies,

wavelengths, shapes and pulse duration are synthesized from laser ablation method. Gold

Nano-particles are also produces through using this method. Laser pulse method is used to

synthesize Nano-structures of gold. They also studied the interaction between fold target and

femto-second which is a type of laser and that is done in the existence of water which is used

as liquid. In this process, from metastable layer, primary Nano-particles are originated during

several seconds through ablation process while only small portion of Nano-particles formation

is obtained using condensation process. For the more growth collision is taken for longer time,

in the liquid colloid.

F.Davar et al (2011) [126] synthesized zinc aluminates Nano-particles. For this purpose they

used di-ethylene glycol mono-ethylene ether and citric acid as solvent and chelating agent,
25
 2
6

because they prepared zinc aluminates through sol-gel method. For preparation of zinc

aluminate Nano-particles, they used Zn (en)2 complex and aluminum nitrate chemicals. Solid

homogenous intermediates were formed from precursor complex. This complex was temperate

at 350 0C in the presence of air. After two hours zinc-oxide and zinc-aluminate Nano-crystals

were obtained. For characterization of these Nano-crystals, SEM is used to study morphology,

FTIR, for adsorption, surface composition, density and arrangement, while XRD for

determination size, shape and crystal structures. Through using these methods, they came to

know that those particles size, shape and texture depend on calcination temperature,

synthesizing method and also precursor.

A.V.Kabashin and M.Meunier (2003) [127] synthesized colloidal Nano-particles through

femto-second laser radiation and ablate a gold target to produce or synthesized colloidal Nano-

particles of gold in the presence water. Two femto-second lasers radiation oblation method are

used for the production of these gold Nano-particles. One is thermal free femto-second method.

Through using this method we obtained small sized Nano-colloidal particles about 3-10

nanometers due to low laser fluencies. which is less than 400 j/cm2. Second method is plasma

induced heating method obtaining particles from this method has very large size and broad

distribution. In that method high fluencies also takes place.

W.lv et al (2010) [128] through using precursor method formed cobalt aluminates Nano-

particles. For this purpose ultrasound and different irradiations are used. For the preparation of

different size and structure Nano-particles, different parameters are used. They also came to

know that different parameters like temperature, calcination temperature, precipitating agent,

synthesis time and synthetic methods can effects on the particle size and structure. Precursor

and Nano-particles were analyzed by using characterization techniques. They observed and

explained the mechanism of the formation of cobalt aluminates by using (FTIR)

26
 2
7

S.Sathish et al (2014) [160] prepared the Nano-particles of indium aluminates (InAlO3) at

various temperatures through using wet chemical technique. For chemical examination FTIR

and EDX techniques were used. XRD designed pattern show that the synthesized samples have

hexagonal phase with cubic bits. SEM revealed about the synthesized material having irregular

anomalous ball like lumps and to study or investigate caloric behavior, differential scanning

calorimeter (DSC) was applied .Dielectric loss, linear temperature coefficient and temperature

coefficient of capacitance were found to be very low. The acquired result revealed that, due to

the artifact of field affect, thin films of transistors. They synthesized InAlO3nano/thin films by

thermal evaporation.

Kadam et al (2013) [161] synthesized dysprosium doped Ni-Co ferrite through using simple

ceramic method having formula Ni0.8Co0.2Fe2-xDyxO4 in the range of 0 to 0.2 in step and 0.025

and they came to know that this ferrite shows electrical, magnetic and structural properties of

spinal ferrites. They revealed magnetic properties by measuring M-H plots and FCC structure

by studying XRD. They also came to know the phase development of ferrites by using TGA

and XRD. During study of the magnetic properties of these ferrites they revealed that increase

of the dysprosium concentration and frequency lose tangent increases while dielectric loss was

decreased. Ferrites have small coercive field property due to which it is used in magnetic

preserving devices.

R. Sharma (2015) [162] used combustion method to synthesize strontium aluminate phosphors

Nano-particles which are activated by DY3+. By using combustion technique at a reaction

temperature of 600 0C, they prepared Nano-phosphor particles and use X-ray diffraction

method to characterized the prepared samples. XRD pattern reveals that the synthesize Nano-

particles have monoclinic phase.The size of the Nano-particles was about 35nm. Scanning

electron microscope show uneven shape of synthesized Nano-phosphor. It seemed that ML and

27
 2
8

PM strength increases by increasing DY concentration and it go maximum when DY3+ is 3%

[162].

Through using co-precipitation method Mazz et al (2012) [163] synthesized Nano-particles of

NixCo1-xFe2O4 where x=0.3, which shows magnetic properties. For examination of these

particles they use XRD for recognizing the polycrystalline contrary spinal Ni-Co and TEM is

used for measuring size. They observed that the size of crystal calculated by TEM was better

than XRD results and they also came to know that particles size could be enlarge, if they

increases the annealing temperature. Saturation magnetization and corecivity could be

increased by increasing Nano-particle size. By controlling the rate of nucleation and growth

we can get suitable size and size division of Nano-particles. Due to these developments in the

Nano-ferrites they are used for recording and data storage purposes.

Kambale et al (2009) [164] studied polycrystalline nickel ferrite having composition Ni(1-

x)CoxFe2O4 substituted with cobalt by using ceramic standard methods, while in these ferrites

x=0.0 to 0.8 having measurement steps of 0.2. XRD technique was used to determine the spinal

structure of cobalt reserved nickel ferrite. To examine the dc electric resistivity two methods

was used and temperature taken from 250C to 6000C. At 250C the resistivity was decreased by

increasing nickel ferrite content in spinal and results showed that the samples have

semiconductor characteristics. By increasing minute replacement in the nickel ferrite,

coercivity and magnetization ratio increases, but it reduced by increasing cobalt concentration.

Mishra et al (2010) [165] used photoluminescence and optical absorption for growing Ni-doped

BiFeO3 (BFO) films which are synthesized by sol-gel method. Absorption of optical and

photoluminescence were occurs due to oxidation state of Bi2+ and Ni3+ . This absorption shows

four peaks at five hundred thirteen Nano meters, four hundred fifty-one Nano meters and six

28
 2
9

hundred eighty-nine Nano meter. Absorption reveals many properties of the materials.

Absorption is also helpful for calculation of the band gap which is about 2.75eV.

Haj et al (2010) [166] use x-ray diffraction for characterization and ceramic method technique

to synthesize multi-ferric compounds Bi0.9Gd0.05Ca0.05FeO3,Bi0.9 Sm0.05Ca0.05FeO3 and

Bi0.9Sm0.1FeO3.The structure of the compound is like rhombohedral. By using enhanced

remnant magnetization method magnetic hysteresis loop. It was a attained for those compounds

having Gd. By partial suppression, Spiral spin structure shows better behavior and stronger

interaction for those compounds having ‘Gd’ and the temperature remains in the range of 300
0
C to 310 0C for these compounds. But interaction between magnetic transistors and ions

becomes stronger.

AIM and OBJECT

AIM
Nano materials show several applications. They are very helpful in every field of life. we

prepared to characterized(Co0.5Ni0.5Al2-xBaxO4) Nano-particles. In order to use in storing to

make and improve etc.

OBJECT

The synthesized material would be characterized among; FTIR, XRD, SEM etc

29
 3
0

Experimental

30
 3
1

Experimental Work

According to Plank “An experiment is a question which possess in nature”. These questions

are solved or try to solve by using some experimental work. This experimental work is consists

of few techniques. These techniques are known as experimental techniques. These

experimental techniques are very helpful for finding or understanding these hidden questions.

Experimental techniques are divided into two classes

a) Synthesizing technique b) Characterization technique

Synthesizing Technique

The word synthesizes means to take something and make them into new thing, so we can define

it as “Those techniques which helps in forming new things from old things”. These new things

or materials are also known as man-made materials. These materials include Nano-materials,

composites and polymers. All these materials are very useful in daily life. In this experiment,

we prepared Nano-particles by using co-precipitation technique. A correct procedure of

forming Nano-materials includes chemical used, contamination control, solution preparation,

instrumentation and sample preparation to product formation.

Chemical used

For getting good result, it is necessary that chemical used for experiment must be pure. All the

chemicals were obtained from sealed bottles, specification of the chemical is given in the table

2(E)

31
 3
2

Table 2(E) chemical used in the work.

Compound Formula Molecularmass Supplied by Purity

(g/mol) declared %

Sulphuric Acid H2SO4 98.07 MERCK 99

Nickel Acetate Ni(CH3COO)2.4H2O 248.84 SIGMA.ALDRICH 99

Cobalt Nitrate Co(NO3)2.6H2O 291.03 Daejing 97

Aluminum AlCl3 133.34 MERCK 98

Chloride

Ammonia NH4OH 35.00 SIGMA.ALDRICH 33

Solution

Barium Chloride BaCl2.2H2O 244.28 MERCK 98.9

Potassium K2Cr2O7 293.9 MERCK 98.9

Dichromate

Contamination Control

The procedure which is used to remove impurities temporary or permanently is known as

contamination control. To prepare chromic acid, potassium dichromate and Sulphuric acid

were used. 2mL chromic acid was poured into each glass ware and left that for 24 hours, than

washed with de-ionized water. De-ionized water is obtained from local fertilizer factory lab

and the pH of the de-ionized water is 6.85+,- 0.15.

32
 3
3

Instrumentation

Specification of the instrumentation, used in this work are given;

Weighing Balance

Used “SHIMADZ BX 300” weighing balance at room temperature. Its range is 0.01 to 300g.

Stirrer

“EISCO” scientific stirrer was used for stirring purpose at room temperature.

pH meter

WTW series 720 pH meter is used for measuring pH at room temperature.

Oven

“SANFA” oven was used at 50 to 600C for drying purposes of the Nano-precipitate.

Furnace

Ney-Vulcan D-550 furnace is used which temperature range is about 00C to 15000C.

Solution preparation

Solution is a homogenous mixture of two or more substances with correct ratio in relative

amount that can be varied solution to solution.

33
 3
4

Stock Solution

In this experiment we prepare following stocks solution. The detail of the Preparing of stock

solution is given in table 2(F)

Table 2(F) gives detail of stock solutions, prepared and used in this experiment.

Compound Formula Molarity Mass of Metal Salt

in 250mL

Co(NO3)2 0.1 7.27g

Ni(CH3COO)2.2H2O 0.1 6.22g

AlCl3 0.2 6.66g

Solution Calculations

Stoichiometric calculations for different solutions are

a) Co0.5Ni0.5Al1.9Ba0.1O4 f) Co0.5Ni0.5Al1.4Ba0.6O4

b) Co0.5Ni0.5Al1.8Ba0.2O4 g) Co0.5Ni0.5Al1.3Ba0.7O4

c) Co0.5Ni0.5Al1.7Ba0.3O4 h) Co0.5Ni0.5Al1.2Ba0.8O4

d) Co0.5Ni0.5Al1.6Ba0.4O4 i) Co0.5Ni0.5Al1.1Ba0.9O4

e) Co0.5Ni0.5Al1.5Ba0.5O4 g) Co0.5Ni0.5Al1.0Ba1.0O4

34
 3
5

Calculation for the barium chloride

Q : R :: S : T

R.S = Q.T

𝑄.𝑇
S=
𝑅

S= required amount of molarity

“Q” is the molarity of the AlCl3, while the “R” is relative amount of Al, “S” is demanded

molarity of BaCl2 and “T” is demanded ratio of the BaCl2.

Concentration of BaCl2 in 250ml flask.

1000ml water contain amount of BaCl2.2H2O = 244.28

244.28
1ml water contain amount of BaCl2.2H2O =
1000

244.28
250ml water contain amount of BaCl2.2H2O = × 250 = 61.07g
1000

“S” contains BaCl2.2H2O = 61.07g×S = “X”grams

By using these calculations we can find the required molarity and required amount of barium

chloride for these solutions, which are given below in table 2(G). And molarity of the aluminum

chloride in all these solutions remains constant which is almost “0.1”.

35
 3
6

Table 2(G) shows required amount and molarity of barium chloride for each sample.

Samples Required Molarity (M) Required Amount (g)

Co0.5Ni0.5Al1.9Ba0.1O4 0.005 0.305

Co0.5Ni0.5Al1.8Ba0.2O4 0.01 0.6107

Co0.5Ni0.5Al1.7Ba0.3O4 0.015 0.916

Co0.5Ni0.5Al1.6Ba0.4O4 0.02 1.22

Co0.5Ni0.5Al1.5Ba0.5O4 0.025 1.52

Co0.5Ni0.5Al1.4Ba0.6O4 0.03 1.8321

Co0.5Ni0.5Al1.3Ba0.7O4 0.035 2.13

Co0.5Ni0.5Al1.2Ba0.8O4 0.04 2.44

Co0.5Ni0.5Al1.1Ba0.9O4 0.045 2.74

Co0.5Ni0.5Al1.0Ba1.0O4 0.05 3.0

36
 3
7

Calculation for aluminum chloride

Q : R :: S : T

R.S = Q.T

𝑄.𝑇
S=
𝑅

S = required amount of molarity

“Q” is the molarity of the AlCl3, while the “R” is relative amount of Al, “S” is demanded

molarity of BaCl2 and “T” is demanded ratio of the BaCl2.

Stock solution Required Solution

M1V1 = M2V2

0.2×V1 = S×250

𝑆×250
V1 =
0.2

V1 = “Y”ml

Through using above calculations we can calculate the required molarity and required amount

for aluminum chloride which are given below in table 2(H). And molarity of the aluminum

chloride in all these solutions remains same which is almost “0.1”.

37
 3
8

Table 2(H) shows required molarity and amount 0f aluminum chloride for each sample.

Samples Required Molarity (M) Required Amount (ml)

Co0.5Ni0.5Al1.9Ba0.1O4 0.0095 118.75

Co0.5Ni0.5Al1.8Ba0.2O4 0.09 112.5

Co0.5Ni0.5Al1.7Ba0.3O4 0.085 106.25

Co0.5Ni0.5Al1.6Ba0.4O4 0.08 100

Co0.5Ni0.5Al1.5Ba0.5O4 0.075 93.75

Co0.5Ni0.5Al1.4Ba0.6O4 0.07 87.5

Co0.5Ni0.5Al1.3Ba0.7O4 0.065 81.25

Co0.5Ni0.5Al1.2Ba0.8O4 0.06 75

Co0.5Ni0.5Al1.1Ba0.9O4 0.055 68.75

Co0.5Ni0.5Al1.0Ba1.0O4 0.05 62.5

38
 3
9

Sample Preparation

For preparation of sample, used co-precipitation method. For this purpose, first of all mixed

the solutions of different compositions for preparing samples in 2000mL beakers. After mixing

these solutions, With a magnetic stirrer “EISCO scientific stirrer” at room temperature for 10

minutes. After homogenize the solutions, added NaOH as precipitating agent and maintain pH

at “12”. Due to this, Precipitate were formed. The solution for a night was left to settle down

the precipitate. After that, washed those precipitate with de-ionized water and then precipitates

are dried. For this purpose, Used an oven “SANFA oven” and precipitates are left at 500C to

600C temperature in this oven overnight. The dried precipitates were grinded with the help of

pestol and motor. The precipitates were present in the form of hydroxide, for converting those

hydroxide precipitates into oxide precipitates, used annealing process. Annealed these

precipitates at 8500C temperature in a furnace “Ney-Vulcan D-550”. For annealing those grind

precipitates, I used ceramic crucibles. After annealing, samples changed the color due to

conversion of precipitates from hydroxides to oxides.

Characterization Techniques

Nano-materials show different properties instead of their bulk materials like mechanical,

chemical and electronic [129]. For describing different properties of these materials, used

different techniques [130].

Classification of characterization technique

Characterization technique is divided into three main classes

 X-ray based techniques

 Further techniques

39
 4
0

 Microscopy techniques

X-ray Based Techniques

These techniques include XAS (EXAFS, XANES), SAXS, XPS. All these techniques are very

helpful for investigate samples and these techniques provide us information about structure,

orientation, order, disorder, phase and size of crystal of Nano-particles [132].

Principle of XRD

Monochromatic x-ray beam falls on the crystal planes and cause diffraction which is calculated

by Bragg’s condition [132-133]

nλ= 2dsinθ

Where Scherer formula is used to determine the size of the crystal [134-135].These diffraction

calculations give different peaks. These peak intensities and positions explain all the

characterizations of the sample [133].

Sample Characterization

For characterizing sample, x-rays are bombarded on the sample holder, containing sample in

powder form. X-ray imitation patterns were recorded between ten to eighty degree at different

scanning rates and these scanning rates are compared with JCPDS data or with ICDD data for

understanding composition. But ICDD data is not suitable for comparing amorphous materials.

Further Techniques

Further techniques are also used to study structure, composition and many other important

properties. These techniques give complete quantitative and qualitative information [137].

These techniques give information due to the absorption, emission and inter-relation of I.R

40
 4
1

radiations with sample [138-139] so, these techniques are known as FTIR. It is a good

technique for quantitative analysis [140]. In these technique, intensities of band is directly

proportional to the sample concentration. FTIR techniques include thermal analysis techniques

(TG/DTA, DSC), SIMS, all types of NMR, LEIS, UV-visible, PL spectroscopy, DLS, NTA,

ICRMS, SQUID-Nano-SQUID, VSM, Mossbauer, FMR, XMCD etc.

Principal of FTIR

When specific radiation passes through sample they create specific vibrations in the molecule

on adsorption which provides us information about the sample. FTIR also inform about the

concentration of the sample [141].

Sample Preparation

Taking FTIR for solids, solid sample is mixed to form a fine powder and then compress to thin

transparent layer. In case of any polymer, sample dissolved in methylene chloride, and solution

is places on NaCl single crystal, which form single layer on evaporation. In case of liquid, one

drop is put onto the single crystal of NaCl which forms thin film on the plate.

Characterization

For taking FTIR, it is necessary that prepared sample must be calcined. By using any spectro-

photometer having specific frequency, FTIR of samples are taken at room temperature.

Thermal Analysis

TG/DTA and DSC are known as thermal analysis techniques. These techniques are used to

study the materials by changing surrounding temperature..

41
 4
2

TG/DTA

Sample holder, Furnace and temperature programmer are the major components of TG/DTA.

These three components are responsible for giving information about the materials.

Sample Holder

Two types of holder are present in TG/DTA. One is reference holder and other is sample

holder. Both are formed of high density sintered alumina crucible. For measuring sample

temperature and getting better results thermo couples are used. If the sample temperature

is below 8500C than chromel-alumel thermo couples are used. If temperature is above

8500C than platinum-rhodium or platinum thermo couple is used.

Furnace

In TG/DTA uniform temperature is provided to both sample and sample holder.

Temperature programmer and Recorder

This system provides the information about the changing of temperature in the furnace

which helps in understanding the characteristics of the material.

TGA

In this technique, we can measure the mass of a sample correctly. For this purpose sample is

heated or cooled at fix temperature and then again weighted and this weighting range is

sensitive about micro-gram.

42
 4
3

DTA

In DTA difference is measured between sample temperature and reference temperature. This

difference gives information about heat emission or absorption. This shows in the form of data

curve. In data curve, emission shows upward deflection and absorption downward deflection.

[143-144]

DSC

It is the technique in which we measure the required energy that maintains the zero degree

temperature difference by comparing sample and reference material [146-147]. Heat flux and

power compensation are two types of DSC.

In former technique , only one furnace is present. Sample change enthalpy causes the difference

between sample and reference. While in lateral technique sample and reference materials are

controlled by independently furnace [143-144].

Characterization

Commonly 3mg of sample is used for characterization TG/DTA. It is carried out at room

temperature to 8000C and employed heating rate is 100C/minute. While DSC of sample is

carried out from 300C to 5000C and heating rate is same as like in TG/DTA.

Microscopy Techniques

Microscopy techniques include TEM, HRTEM, Liquid TEM, ELS, SEM, EBSD, AFM, MIM

etc. These techniques are used to provide facts and details of size, morphology and crystal

structure.

43
 4
4

TEM

TEM is used for characterization of the electronic and chemical structure at Nano-scale. TEM

is an admirable tool to characterize Nano-materials. It is very important tool for biologically

and medically related research [149]. In TEM, a beam of electron is passed through the sample.

This beam of electron excited the molecules and cause vibrations and show interactions with

sample molecules. And produces light and x-rays. These formed the image and which provides

all the information of the materials.

SEM

It mostly used for the investigation of the polymeric intermediates as well as final synthesized

product [151].

Principal

A beam of electron strike the sample which is generated by electron gun and after striking it is

collected by Back Scatter detector. That is spread on the grid of the CRT and x-ray image is

obtained [151-152].

SEM Analysis of Polymeric Intermediates

For taking SEM, we take small piece of polymeric intermediate and coated it on gold or carbon

as sputter coater in order to get better image.

SEM Analysis for Final Product

Little concentration of sample is spread in Acetone than radiated it for some minutes. After that

a droplet is dispersed on carbon tape that has ability of conduction. After that a very narrow

44
 4
5

film of gold was applied to get better conduction. If sample powder is metal oxide then recoded

it at different magnifications.

45
 4
6

Results

&

Discussion

46
 4
7

Historical Background

In early days, mankind discovered variety of materials like, fired clay, stones, various metals

and biological materials for different purposes. As an example, synthesis of copper beads and

ceramics date back to millennium B.C. And in 3rd millennium B.C. Metal alloys were made.

The smelting of minerals was done in 5000 B.C. In 1200 B.C in Iran steel was made

while in 500 B.C. china produced cast iron for the first time. These materials are developed

century by century. And show different types of uses. But no one wants to investigate these

materials. In 17th century investigation of these materials started.

Rene Fer worked on iron. For this purpose, he done different laboratory experiments in

1772.while micro-structures studied in the last of the 19thcentury. In 1864 henry Clifton

discovered the micro-structure of steel. Lawrence and his companions used XRD for studying

the structure of solids. For understanding the imperfection in the material, first chemical than

electrical and mechanical error are studied. Many metals or substances show many defects

which are not studied by using it. In 19th century, organic chemistry was discovered. It came

to know that several those compounds having a like composition, show change properties. With

this in chemistry, especially in organic chemistry molecular structure formation is started that

is joined in x-ray crystallography and help in understanding the complicated structures.

Material Characterization

In 1930 basic material characterization starts, while in 1964 many new alloys and non-metallic

materials are formed. New analytical techniques also came into being in these days. In early

1960 materials, characterization show different applications in engineering. These

characterization techniques are also good, but they show many limitations. To remove these

limitations and improve characterization of materials, the national material advisory board

47
 4
8

NMAB requested in 1967 to established a committee for material characterization.

Characterization is very helpful for building a stronger and effective material. Characterization

is also helpful understanding or knowing unknown materials.

Characterization of any material is determined by phases and their distributions, composition,

defects, structure and residual stress. To characterize or understanding any material. It is

necessary to understand phases and their distributions. There are three types of phases (solid,

liquid and gas). And characterization for each phase is different.

Characterization of solid phase material

In the form of solid Nano-materials exist in powder or encapsulated form. Powder form exists

in the form of loose powder, wet or dry powder and powder cakes, according to their convenient

for handling. Size of the particle is measured by using electron microscopy, layer diffraction

and x-ray diffraction. Nitrogen adsorption method is based on the BET isotherm, is used for

measuring surface area while electron micrograph is used to determine the morphology of any

particle.

Liquid phases

In liquid phase Nano-materials are suspended in liquid. In this phase for characterization of

structure, we used light scattering and centrifugation techniques. Where NMR and simple

titration methods are used for calculating surface area while zeta potential is measured by using

electrophoretic methods, for measuring morphology mass spectroscopy is used.

Gas phase

In the form of aerosols sizes of the Nano-particles are measured, using optical and aerodynamic

methods, and for morphology electron microscopy is used.

48
 4
9

Characterization

Characterized the Co0.5Ni0.5Al2-xBaxO4 Nano-particles by using following techniques

 XRD

 SEM

 FTIR

XRD

Structure of any material is judged and explained by using XRD [154-155]. Diffraction occurs

when radiation interacts with molecular structure and distance remain same. X-ray wavelength

follows the angstrom when interact with the crystalline solids and show repeated patterns,

which is helpful for characterization, crystalline materials and yielding information on crystal

structure [156].

When two x-ray beams strike the surface of crystalline material under examination making an

angle θ with the outer surface and inner surface respectively of the reflected waves are in phase.

Their means that the path difference between would be integral multiple of their wavelength

(nλ), according to the Bragg’s law [157-158]

nλ = 2dsinθ

From this equation, inter-planer spacing (d) can be determined as beam wavelength and

incident angle can be known. In this way, their diffraction data can be utilized to study unit of

crystalline lattice completely [159], by comparing this data with TCDD data. XRD is also used

for the determination of the crystalline size by using formula

𝐾
T= 𝛌
𝐵×Cosθ

49
 5
0

It is also used for the confirmation of doped composites for my samples. The XRD results

confirm the formation aluminate composites with Ba doping. The hkl values 220, 311, 400,

and 511 well matched with PDF card 00-003-08996 and 01-07-0965 of cobalt aluminates and

nickel aluminates with respect. The doping of barium confirmed by optimizing results with

barium and we find that 002, 110, 112, and 103 peaks in XRD reveal doping of barium in the

form of BaO with respect to card.

XRD patterns of Co0.5Ni0.5Al1.7Ba0.3O4

311

1100

1000
Intensity( a.u.)

222

440
220

511

900
110

400
112

422

800
002

700

600

20 40 60 80
2 (Theta)

This graph shows that the crystalline size of (Co0.5Ni0.5Al1.7Ba0.3O4) crystal is 0.2364 nm.

50
 5
1

XRD patterns of Co0.5Ni0.5Al1.2Ba0.8O4

1000

311
900
220
Intensity (a.u)

440
511
400
800

112
110

103
700
002

600

500

20 40 60 80
2(Theta)

This graph shows that the crystalline size of (Co0.5Ni0.5Al1.2Ba0.8O4) crystal is 0.6049 nm.

51
 5
2

Scanning electron microscopy (SEM)

SEM analysis shows that these particles are cubic in nature. SEM results of some samples are
given below. SEM results of Co0.5Ni0.5Al1.7Ba0.3O4

52
 5
3

53
 5
4

54
 5
5

SEM results of Co0.5Ni0.5Al1.2Ba0.8O4

55
 5
6

56
 5
7

57
 5
8

58
 5
9

59
 6
0

FTIR

FTIR Peaks, which are present in finger print region confirm the formation of

aluminate composites in all the samples. While the peaks, which are present out

of the finger print region in many graphs confirm the formation of nickel

aluminates, barium aluminates and nickel oxide. In these graphs the peeks

comes from 525 to 570 shows presence of cobalt nickel aluminates while the

peeks 722,827 and 3450 represents the nickel aluminates. 815,857 and 1300 are

the peaks, which represent the presence of barium aluminates.

60
 6
1

FTIR Spectra of annealed“Co0.5Ni0.5Al2.0Ba0.0O4”.

In this graph in finger print region cobalt nickel aluminates are confirmed because cobalt

nickel peek seems in many compounds at 436 and nickel oxide peek seems at 480. And

the peek at near about 547 confirms nickel oxide while the peek at 722 confirms nickel

aluminates.

61
 6
2

FTIR Spectra of annealed“Co0.5Ni0.5Al1.9Ba0.1O

In this graph in finger print region peeks become smaller changes their positions due to

interaction with barium as barium peek seems at 430. And 722 peek shows presence of

nickel aluminates.

62
 6
3

FTIR Spectra of annealed“Co0.5Ni0.5Al1.8Ba0.2O4”.

As increase in the barium amount finger print peeks slightly increases. And very small peeks seem in

the other region.

63
 6
4

FTIR Spectra of annealed“Co0.5Ni0.5Al1.7Ba0.3O4”.

In this graph two peeks seems above the finger print region, one at 1440 which reveals barium

aluminates while other seems at 722.

64
 6
5

FTIR Spectra of annealed“Co0.5Ni0.5Al1.6Ba0.4O4”.

In this graph bending show at 525-570 which reveals presence of cobalt nickel aluminates.

65
 6
6

FTIR Spectra of annealed“Co0.5Ni0.5Al1.5Ba0.5O4”.

66
 6
7

FTIR Spectra of annealed“Co0.5Ni0.5Al1.4Ba0.6O4”.

67
 6
8

FTIR Spectra of annealed“Co0.5Ni0.5Al1.2Ba0.8O4”.

68
 6
9

FTIR Spectra of annealed“Co0.5Ni0.5Al1.1Ba0.9O4”.

69
 7
0

FTIR Spectra of annealed“Co0.5Ni0.5Al1.0Ba1.0O4”.

70
 7
1

FTIR Spectra of Un-Annealed“Co0.5Ni0.5Al10Ba0.0O4”.

71
 7
2

FTIR Spectra of Un-Annealed“Co0.5Ni0.5Al1.7Ba0.3O4”.

72
 7
3

FTIR Spectra of Un-Annealed“Co0.5Ni0.5Al1.6Ba0.4O4”.

73
 7
4

FTIR Spectra of Un-Annealed“Co0.5Ni0.5Al1.5Ba0.5O4”.

74
 7
5

FTIR Spectra of Un-Annealed“Co0.5Ni0.5Al1.3Ba0.7O4”.

75
 7
6

FTIR Spectra of Un-Annealed“Co0.5Ni0.5Al1.1Ba0.9O4”.

76
 7
7

Conclusion

 Co-Precipitation method is very good and more precise method for the synthesis of

doped and un-doped nano particles.

 This method has been adopted for preparing of barium doped aluminates.

 SEM characterization shows cubic structure for these barium doped aluminates.

 XRD shows 0.24nm crystalline size of sample “Co0.5 Ni0.5 Al1.7 Ba0.3 O4” Composition

and it is 0.61 for sample “Co0.5 Ni0.5 Al1.2 Ba0.8 O4” Composition.

 XRD peaks of 002, 110, 112 and 103 of these samples compositions confirms the

doping of the barium on cobalt aluminates.

 FTIR peaks, which are present in finger print region confirm the formation of

aluminates composites in all the samples.

77
 7
8

References

1. G. Xiong, D. Wie, X. Yang, L. Lu and X. Wang, Journal of Material Science,35 931 (2000)

2. D.K. Tiwari, J. Behari and P. Sen, World Applied Sciences Journal, 3 (3), 418(2008)

3. K.M.M. Abou El-Nour, A. Eftaiha, A.Al-Warthan and R.A.A. Ammar, Arabian Journal of

Chemistry, 3, 135(2010)

5. P. Sharma and M. Bhargava, International Journal of Civil, Structural, Environmental and

Infrastructure Engineering Research and Development, 3, 63 (2013).

6. J.Corbah, P. A.Mckewn, G.N. Peggs and R. Whatmore, CIRP Annals-Manufacturing

Technology, 49, 523(2000)

7. S. Panero, B. Scrosati, M. Wachtler and F.Croce, Journal of Power Sources, 129, 90(2004)

8. E.S. Kawasaki and A. Player Nanomedicine: Nanotechnology, Biology and Medicine, 1,

101(2005)

9. F. Macedonio and E. Drioli, Comprehensive Membrane Science and Engineering, 4,

241(2010).

10. A. Wadeasa, G. Tzamalis, P. Sehati, O. Nur, M. Fahlman, M. Willander, M. Berggren and

X. Cripin, Letter of Chemistry and Physics, 90,200(2010).

11. B. Bhushan, Y.C. Jung, Progress Material Science, 56, 1(2011).

12. X. Qu, P.J.J. Alvarez and Q. Li, Water Research, 47, 3931(2013).

14. S. Nazir T.Hussain,A.Ayub, U.Rashid and A.J.MacRobert, Nanomedicine:

Nanotechnology, Biology and Medicine, 10, 19(2014).

15. B. T. Zhang, X. Zheng, H. F. Li and J. M. Lin, AnalyticaChimicaActa, 784, 1(2013).

78
 7
9

16. R. Hirlekar, M. Yamagar, H. Garse, M. Vij, V. Kadam, Asian Journal of Pharmaceutical

and Clinical Research, 2, 17(2009).

19. R. Misra, S. Acharaya and S. K. Sahoo, Drug Discovery Today, 15, (2010).

26. A. G. Vogtlander and Markopoulos, A.Mamalis Nanotechnology and Nanostructured

Materials: Tendin Carbon Nanotubes. (2004)

27. A. R. West, Solid State Chemistry and Its Application, John Wiley and Sons, New York,

(1984).

30. M. Rozman and M.Drofenik , J. Am. Ceram. Soc 78, 2449(1995).

31. S. Komarneni, E. Fregeau, E. Breval and R. Roy, J. Am .Ceram. Soc., 71

(1988).

32. A. Goldman and A. M. Laing., J. Phys. Coll. 4 ,297(1977).

33. A. Attaie, M. R. Piramoon, I. R. Harris, C. B. Ponton, J. Mater.

Sci.30, 5600(1995).

34. M. Seki, T. Sato and S. Usui, J. Appl. Phys. 63(1988) 1424.

35. A. Thakur and M. Singh, Ceram. Int.29(2003) 505.

36. K. K Rao, T. Banu, M. Vithal, G. Y. S. K. Swamy and K. R. Kumar, Material Letter, 54,

205 (2002).

37. D.Chen and R. Xu, Material Research Bulletin, 33, 409(1998).

38. Y.Matsumura, M.Yoshinaka, K. Hirota and O. Yamaguchi, Solid State Communication,

104, 341 (1997).

79
 8
0

40. N. Kumar and S. Kumbhat, “Essential in Nanoscience and Nanotechnology” Published by

john Wily and Sons (2016).

42. E. Auzans, D. Zins, E. Bulms and R. Massart, Journal of Material Science, 34, 1253(1999).

43. O. Masala and R. Seshadri, “Synthesis Routes for Large Volumes of Nanoparticles “(2004).

45. H. R. Ghorbani “A Review of Methods for Synthesis of Al Nanoparticles“(2014).

51. L. S. Wang and R. Y. Hong “Synthesis, Surface Modification and Characterization of

Nanoparticles”, Advances in Nanocomposites –Synthesis, Characterization and Industrial

Application (2011).

52. E. Gaffet, M. Tachikart, O. El Kedim, R. Rahouadj, “Nanostructural Materials Formation

by Mechanical Alloying: morphologic analysis based on transmission and scanning electron

microscope observation’’ (1996).

54. T.A.Schoolcraft and B.J.Garrison, Journal of the American Chemical Society, 22, :

8221(1991).

55. Marwah, Nabil and Hussien, A. Motawah, Applied Mechanics and Materials, 749, 155-

158(2015).

56. M. Nie, K. Sun, and D. D.Meng, Journal of Applied Physics, 106, 05431(2009).

57. R. Behrisch , Springer ISBN 978-3-540-10521-3(1981).

58. M. W. Thomsan Philos. Mag. 18(152):377(1962).

59. M.Sporn, Libiseller, G.Neidhart, T. Schmid, M. Anumayar, F. Winter, HP. Varga, P.

Grether, M.Nieman, D. Stolterfoht, N. et al. Physical Review Letters, 79:945(1997).

67. P. Patil, D. Phase,S. Kulkarni ,S. Ghaisas,S. Kanetkar, O. Bhide,V Physics Review

Letters;58 ,238-241(1987).

80
 8
1

68. N. Rajput, A Review of International Journal of Advances in Engineering & Technology,

Vol. 7, Issue 4, pp. 1806-1811(2015).

69. J. U. Brehm, M. Winterer and H. Hahn, J.Appl.Phys.100, 064311(2006).

70. A. E. Giannakas, A. k. Ladavos and P. J. Pomonis, Applied Catalysis B: Environmental,

49, 147(2004).

71. Danielsson, I; Lindman, B. Colloids Surface 3, 391,1981.

72. K. Shinoda, S. Friberg. Advanced Colloidal Interface Science 4,281 (1975).

73. O. P. Agrawal and S. Agrawal, Asian Journal of Pharmaceutical Science and Technology,

2, 5(2012).

74. J. Lindber, R Friberg, Sjoblom, ,S.E. Advanced Colloidal Interface (1996).

75. J. H. Stoeckenius, W. Prince, Schulman M. J. Phys. Chem. 63,1667(1959).

76. A. W. Adanson Colloidal Interface Science, 29,261,3(1969)

79. A. D. Gadhave and J. T. Waghmare, International Journal of Research in Engineering and

Tehnology, 3, 147(2014).

80. A. B. Corradi, F. Bondioli and B. Focher, Journal of American Ceramic Society, 88,

2639(2005).

81. K. Byrappa and T. Adschiri, Progress in Crystal Growth and Characterization of

Materials, 53, 117(2007).

82. Bell, A. T: The Impact of Nanoscience on Heterogeneous Catalysis (2003).

83. M. N. Ashiq, M. Athar, M. A. Farid M. A. Ashgar and M. F. Eshan, Materials Research

Bulletin, 59, 405(2014).

81
 8
2

84. I. Miron, C. Enache and I. Grozesu, Digest Journal of Nanomaterials and Biostructures, 7,

967(2012).

85. S. Komarneni, V. C. Meon, Q. H. Li, R. Roy and F. Ainger, Journal of the American

Society, 79 , 1409(1996).

86. Lu, C. H. and Jagannathan, J, Applied Physics Letters, Vol. 80 ,pp 3608-3610(2002).

87. C. Burda, X. Chen, R. Narayana and M. A. EI-Sayed, Chemical Review, 105, 1025(2005).

88. Morita, M. Rau, D. Kajiyama, S. Sakurai, T. Baba, M. and Iwammura, M, Material

Science-Poland, Vol. 22, pp 5-15(2004).

89. M. S. Niasari, F. Davar and M. Farhdi, Journal of Sol-Gel Sciences and Technology, 51,

48(2009).

90. J. N. Hasnidawani, H. N. Azlina, H. Norital, N. N. Bonnia, S. Ratina and E. S Ali, Procedia

Chemistry; 19, 211-216(2016).

91. U. Ashraf and B. Khan, International Journal of Sciences and Research: 45, pp, 2405-

2408(2013).

92. Nielsen, A. E. Acta ChemicaScandinavica, Vol. 14, p.1654,(1960).

93. Von Weirman, P. P. Chemical Reviews, Vol. 2, p. 217,(1925).

94. Fifield, F. W. and Kealey, D. Principles and Practice of Analytical Chemistry. Japan: Black

Well Science Ltd. (2000).

95. Y. Zhang, H. Cao, J. Zhang, B. Xia, Solid State Ionics, 177, 3303-3307(2006).

96. T. H. Cho, Y. Shiosaki, H. Noguchi, J. Power Sources, 159,1322-1327(2006).

98. A. R. West, Solid State Chemistry and its applications, John Wiely Sons, India

82
 8
3

(2005).

99. A. B. Gaikwad, S. C. Navale, V. Samuel, A. V. Murugan, V. Ravi, Mater. Res. Bull.,

41,347-353(2006).

101. G. Xu, X. Zhang, W. He, H. Liu, H. Li, R. I. Boughton, Materials Letters 60,962-965 (2006).

102. S.Deng ,H.Wang, Y.Sun, J.Liu, C.Wu and H.Yan. Applied Materials and Interfaces .6, 1106

-1112 (2014).

103. M. Yarestani, A. D .Khalayi, A. Rohaxi and D. Das Journal of Sciences ,Islamic Republic of

Iran 25,339-343 (2014).

104. M.Y.Nassar, I.S.Ahmed and I.Samir spectro-chimicaActa part A.Molecular and

B.Molecular spectroscopy, 131,329 (2014).

105. S.Shiri, M.H.Abbasi, A.Monshi, and F.Karimzadeh; Composite Part B, 56, 30 (2014).

106. K.F.WadeKar, K.R.Nemade and S.A.waghuley Research Journal of Chemical sciences Vol.

7(1), 53-55, January (2017).

107. D.Fejes and K.Hernadi, Materials, 3, 2618-2642 (2010).

108. S.Saleem Journal of Industrial and Engineering Chemistry,20,818 (2014).

109.J.H.Kim, B.R.Son, D.H.Yoon, K.T.Hwang,H.G.Noh,W.S.Cho and V.S.Kim, Ceramic

International,38,5707 (2012).

110. Sh.Salem, S.H.Jazayeri, F.Bondioli, A.Allahverdi, M.Shrvani, thermochemical Acta, 521,

191 (2011).

111. L.Raki,J.Beaudoin, R.AliZadeh, J.Makar and T.Sato, Materials, 3, 918-942 [2010].

83
 8
4

112. J,Chandradass, M,Bala Subramanian, D.S.Base, J.Kim and K.H.Kim, Journal of Alloys and

Compounds, 491, L25 (2010).

113. N.Bayal and P.Jeevanandam, Journal of Alloys and Compounds, 517, 27 (2012).

114. C.Ragupathi, J.JVijaya and L.J.Kennedy,Material Sciences and Engineering B, 184,

18(2014).

115. C.Bhavya, K.Yogendra, K.M.Mahadevan, International Journal of Research in Chemistry

and Environment, 5, 28 (2015).

116. B.Ismail, S.T.Hussain and S.Akram, Chemical Engineering Journal ,219, 395(2013).

117. R.G.-Chaudhary, J.A.-Tanna, N.V-.Gandhare, A.R.-Rai, and H.D.Juneja Adv. Material Lett.

, 6, 990-998, (2015).

118. S.-Salem, Material letters 139, 498, (2015).

119. A.F. - Osorio, C.E.-Rivera, A.V.-Olmos and J.-Chavez, Dyes and Pigments, 119, 22 (2015).

120. M.J.Iqbal and S.Farooq, Material sciences and Engineering B, 136, 140 (2007).

121. D.mohapatra and D.sarka Journal of Materials Processing, Technology,189 , 279 (2007).

122. S.Farhadi and Panahandehjoo , Applied Catalysis A. General , 382 , 293(2010).

123. M.M.Byranvand, A.N.Kaharat, L.Fatholahi, Z.M.Beiranvand, JNS 3, 1-9 (2013)

124. K.Wegner, E.Barborini, P.Piseri and P.Milani, KONA No. 24 , 54-64(2006).

125. M.E.Povarnitsyn,T.F.Itina,P.R.Levashor and K.V.Knishchenko. Journal of Royal Society of

Chemistry 1-8 ,(2010).

126. F.Davar and M.S.Niasari, Journal of Alloys and Compounds, 509, 2487 (2011).

84
 8
5

127. A.V.Kabashin and M.Meunier, J.Appl.Phys, 94, 12-15 December (2003).

128. W.Lv,Q.Qiu, F.Wang, S. wei, B. Liu and Z. Luo, UltrasonicsSonochemistry, 17, 793(2010).

129. N. T. K. Thanh, N. Maclean and S. Mahiddine, Chem. Rev., 114, 7610, (2013).

130. Y. Wang, D. Wan, S. Xie, X. Xia, C. Z. Huang and Y. Xia, ACS Nano,7, 4586,(2013).

134. H. G. Jlang, M. Ruhle, E. J. Lavernia, J. Mater. Res., 14,. 2.549- 559,(1999).

135. M. T. Weller, Inorganic Materials Chemistry Oxford Chemistry Primers, UK, (2001).

137. G. E. A. Swann and S. V. Patwardhan, Chim past, 7, 65(2011).

138. N. Vlachos, Y. Skopeltis, M. Psaroudaki, V. Kontantinidou, A. Chatzilazarou and E.

Tegou, Analytica Chemica Acta, 459, 573(2006).

139. G. Socrates, Infrared and Rarnan Characteristic Group Frequencies, John Wiley and Sons,

New York, 2001.

141. R. M. S~lverstein, G. C. Bassler, T. C. Momll, SpectrometncIdent~fication of Organic

Compounds, 4th ed., Wiley, (1981).

143. R. A. Mayers, Encyclopedia of Analytical Chemistry, J. Wiely, New York, 15, 2000.

144. R. W. Cahn, Concise Encyclopedia of Materials Characterization, Second Edition,

Elsevier, Amsterdan, 1992

146. Brown, Michael E. Introduction to Thermal Analysis: Techniques and Applications. New

York, NY: Chapman and Hall. P. 5-13(1998).

147. Hohne, Gunther, Hemminger, Wolfgang F., Flammersheim, H.J., Differential Scanning

Calorimetry 2 ed. New York, NY: Springer. P. 5-13(1988).

149. D. B. Williams, C. B. Carter, Transmission Electron Microscopy: A textbook for materials

science, Springer, USA, 2004.

151. R. W. Cahn, P. H. Haasen, E. J. Kramer, Volume 2A, VCH, Germany, (1992).

85
 8
6

152. C. Richard Brundle, C. A. Evans, Encyclopedia of Materials Characterization,

ButtenWorth-Heinemann, Boston, 1992

154. C. Kittle, “Introduction to Solid State Physics”, New York, Plenum (1966)

155. B.D. Cullity, “X-ray Diffraction”, Addison-Wesley, New York (1972)

160. S. Sathish, B. C. Shekar and D. Nataraj, Advanced Power Technology, 25, 1007 (2014).

161. Kadam, A.A., et al, Structural, morphological, electrical and magnetic properties of

Dydoped Ni-Co subsititutional spinel ferrite. Journal of Magnetism and Magnetic Materials,

329(0): p. 59-64 (2013)..

162. R. Sharama, D. P. Bisen and B.P. Chandra, Journal of Luminescence, 168,49(2015).

163. Maaz, K, S. Karim, and G.-H. Kim, Effect of particle size on the magnetic properties of

NixCol-xFe204 nanoparticles. Chemical Physics Letters,.549(0):p.67-71(2012).

164. Kambale, R.C. et al, Effect of cobalt substitution on structural, magnetic and electric

properties of nickel ferrite. Journal of Alloys and Compounds,478(1-2): p.599-603 (2009).

165. K. Dillip, X. Mishra, Qi, J. Alloy. Comp. 504 27-31 (2010).

166. M. Al-Haj, Cryst. Solid State Communication, 150 1088-1091 (2010).

86