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6th International Conference on Engineering Technology, Science and Management Innovation (ICETSMI-2017)

at Institution of Electronics and Telecommunication Engineers (IETE) , Lodhi Road, Delhi, India

on 11th June 2017 ISBN: 978-81-934083-2-2

485 A.M. Tamboli, Dr. S.M. Rathod, Dr. Gulam Rabbani

Comparison of Magnetic properties of Ni 2+, Co2+ and

Cu2+substituted in CuCo, NiCu and CoNi Nanocrystalline

Spinel Ferrite respectively Prepared by Sol Gel Auto

Combustion Method.

A.M. Tamboli1*,Dr. S.M. Rathod3, Dr. Gulam Rabbani2 1Department of Electronic Science, Poona College, Camp, Pune-411 001, INDIA.

2Department of Physics and Electronics, Maulana Azad College, Aurangabad-431 001 INDIA 3Department Of Physics, Abasaheb Garware College, Pune- 411 004, INDIA

ABSTRACT:

Herein, the magnetic properties such as Saturation magnetization [Ms(emu/gm)], Magnetic moment [Mr(emu/gm)],

Coercivity [Hc(Oe)], are reported for the series[NixCu(constant) Co0.8-x Fe2O4][CoxNi(constant) Cu0.8-x Fe2O4]and

[CuxCo(constant)Ni0.8-x Fe2O4]where constant=0.2 with x=0.2, 0.4 and 0.6 of nanocrystalline spinel ferrites, synthesized

by using metal nitrates with the help of Sol-Gel auto-combustion technique. The variation in the Saturation

magnetization [Ms(emu/gm)], Magnetic moment [Mr(emu/gm)], Coercivity [Hc(Oe)] are studied at room temperature

due to the effect of substitution of Ni2+, Co2+ and Cu2+ density ‘x’ in [NixCu(constant) Co0.8-x Fe2O4],[CoxNi(constant)

Cu0.8-x Fe2O4]and [CuxCo(constant)Ni0.8-x Fe2O4] respectively. The nanocrystallinespinalStructural of ferrite material is

confirm by Fourier Transform Infrared Spectroscope (FT-IR). The magnetic properties are studied by using Vibrating

Sample Magnetometer (VSM). The effect of substitution of Ni2+, Co2+ and Cu2+ on magnetic properties of the prepared

ferrite material is discussed.

Keywords -Sol-gel auto-combustion,VSM meter, FT-IR.

I. INTRODUCTION

The magnetic properties of nanocrystalline ferrite materials make them suitable for magnetic storage devices

and high frequency applications in the field of information technology andsignal processing. The ferrite

material of specific magnetic properties is alsoused to reduce electromagnetic noise, electromagnetic wave

absorber, in fabricating multilayer chip indicators (MLCIs), in design of light weight transformer and in

various frequency filters. Frequency ferrites are widely used in microwave devices such as insulators,

circulators, and phase splitter and shifters because of their high resistivity, low eddy current loss and excellent

magnetic properties. The general formula of ferrite is MFe2O4 and magnetic propertiesof ferrites are

dependent on the distribution of metal cation at tetrahedral A-site and at octahedral B-site. Where M=Ni2+,

M=Cu2+, M=Co2+, M=Mg2+, M=Zn2+ etc. [1-4].

II. MATERIALS AND METHODS

2.1 Synthesis

In Sol Gel method auto combustion process takes place which is a self-sustaining combustion synthesis

technique and it produces fine homogeneous powder of metal-oxide. The auto combustion process takes place

in two steps namely (i) formation of a gel or precursor and (ii) auto-ignition. Aqueous precursor solution

contains various metal nitrates and fuel such as ascorbic acid, urea, glycine, and citric acid, this solution were

heated until the excess water gets evaporated. In present research work citric acid is used as fuel. At the end of

reaction the viscous liquid foam gets ignited and undergoes self-sustained combustion and produces ashes

containing the oxide product. Very large amount of heat is generated during combustion process in the form of



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either fire or a flame and therefore, the process is called as auto-ignition process or auto combustion process.

External heat is given till the formation of gel and till the starting of auto combustion. When ignition takes

place at that time dried gel burnt in a self-propagating combustion manner until all gels were completely burnt

out to form a fluffy loose structure and converted in to ash.

Instead of using a high temperature furnace to supply the energy needed to react the component

oxides, in auto combustion reaction the energy is supplied itself due to fuel citric acid. During the auto

combustion process, exothermic redox reactions associated with nitrate decomposition and fuel oxidation take

place. Gases such as CO2, H2O and N2 gets evolve, and formation of fine particle ashes takes place after only

a few minutes. The auto combustion method uses the energy produced by the exothermic decomposition of a

redox mixture of an organic compound with metal nitrates. In the combustion organic compounds, nitrates and

mixture behave like conventional oxidants and fuels. Very huge amount of heat of combustion (or flame

temperature) helps in crystallization and formation of the required phase. The properties of the final product in

the form of ash such as surface area, particle size and porosity depend on the method of combustion. The

departure of gases helps the desegregation of the products due to which porosity increases and heat dissipation

also takes place due to departure of gases. Exothermicity of combustion is controlled by the ratio of oxidizer

to fuel and nature of the fuel used in chemical reaction[5-9].

Due to ignition the dried gel starts burning in a self-propagating combustion manner until all gels gets

completely burnt out. The reaction is self-continue to propagate and is able to sustain this from 1 to 5 seconds

only, to produce the desired product in the form of ash. The Sol Gel auto combustion synthesis process is used

to synthesis pure NiCuCo Fe2 O4 ferrite material. Auto combustion synthesis is also called as self-propagating

synthesis; it was initially developed in Russia by Merzhanov and had been successfully used to speed up the

synthesis of complex oxide material such as high temperature superconductors and ferrite materials.

Auto combustion synthesis offers a unique way of synthesis via a highly exothermic redox reaction between

an organic fuel and metal nitrates produce multi-elements oxides. In auto combustion high temperature

furnace is not required to supply the energy needed to react the component oxides because the auto

combustion reaction itself supplies the energy. Organic fuel and Metal nitrates are mixed in water to form an

aqueous solution and this method also maximizes molecular mixing of the components. The solution is then

heated such that it gets transform into gel.

Without the use of costly and expensive high temperature furnaces this technique produces a homogeneous

product in a very short amount of time. Auto combustion synthesis reaction can be influenced by many

parameters such as the fuel-to-oxidizer ratio, the type of fuel, the ignition temperature and the hardness of

water of the precursor mixture. The fuel to oxidizer ratio also plays a very important role in influencing the

reaction and reducing the time. A way to control the flame temperature of the reaction is by varying the ratio

of fuel to oxidizer.

The elemental stoichiometric coefficient, φe, is used to control the ratio of fuel to oxidizer in the reaction. φe

represents the ratio between the oxidizing and reducing components of the metal nitrate fuel mixture. When φe

is less than one (φe<1) it is fuel rich and when φe is greater than one (φe>1), the mixture does not have enough

fuel for the completion of reaction [6-9].Fig. 1 shows the auto combustion synthesis flow chart that was used for

the synthesis of the ferrite powders.

Ferrite powder is prepared by using sol-gel auto combustion method. Analytical grade Nickel Nitrate

[Ni(NO3)2.6H2O], Copper Nitrate [Cu(NO3)2.3H2O], Cobalt Nitrate[Co(No3)2 6H2O], Iron Nitrate

[Fe(NO3)3.9H2O], Citric Acid [C6H8O7.H2O], Distilled water is prepared in the laboratory using all quick fit

glass assembly and liquid ammonia were used as raw materials in sol gel auto combustion method.

The series [NixCu(constant)Co0.8-xFe2 O4], [CoxNi(constant)Cu0.8-x Fe2 O4] and [CuxCo(constant)Ni0.8-x

Fe2 O4 ] where, constant=0.2 with x= 0.2, 0.4 and 0.6 of ferrites have been prepared in three Sets namely

SET-I ,SET-II and SET-III using Sol-Gel Auto-combustion method. All the chemicals were from E-mark,

India (AR grade with 98% purity to 99.9% purity). Table 1 indicates Label and composition of ferrite

materials for all Sets.



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Accurately weighted quantity of Metal nitrates and citric acid is added in to distilled water of 100ml and a

solution is prepared. The solution in a glass beaker was homogenized by continuous stirring with the help of

magnetic needle by using the instrument so called magnetic stirrer. The magnetic stirrer is having the facility

of controlling the revolution per minit (RPM) of magnetic needle as well as temperature of base plate. The

acidic or alkaline level (pH) of the solution was adjusted to 7 using liquid ammonia and the solution is

continuously heated at 100ºC on a hot plate with magnetic stirrer with the help of hard glass beaker. With

continuous heating it initially transformed into sol then gel and it requires five to six hours shown in above

Fig.1. When liquid gets converted in to gel the magnetic needle is removed and gel stick with magnetic needle

is used for IR characterization.

The dried gel burnt in a self-propagating manner due to auto combustion and it continues to burn until all gel

is completely burnt out to form a fluffy loose structure in the form of ash as explain in above Fig. 1. When gel

starts burning at that time heater of magnetic stirrer is turn off. The fluffy material of burnt ash was crush and

ground in crucible to get ferrite powder.

The ferrite powder material was sintered in an electrical furnace with super kanthal (MoSi2) heating elements

and alumina insulation boards as chamber walls. The size of the chamber is 250x150x150 mm. The thermal

regime of the furnace was controlled through a “Eurotherm” programmer-cum-controller by using

microcontrollers with an accuracy of ± 2°C. The already crushed and grounded samples are heated from room

temperature to 400oC at a rate 1oC/min followed by a soaking at 400oC for 4 hours.

The ferrite powder was sintered at 400°C for 4 hours in air medium to get better crystallization and

homogeneous cation distribution in the spinel and finally ground to get [(Ni.0.2 Cu.0.2Co0.6 )Fe2O4], [(Ni.0.4

Cu.0.2Co0.4 )Fe2O4], [(Ni.0.6 Cu.0.2Co0.2 )Fe2O4], [(Ni.0.2 Cu.0.6Co0.2 )Fe2O4], [(Ni.0.2 Cu.0.4Co0.4)Fe2O4]and [(Ni.0.4

Cu.0.4Co0.2)Fe2O4]ferrite powders.

2.2 Characterization of Saturation magnetization [Ms (emu/gm)],Coercivity

[Hc(Oe)] and Magnetic moment[Mr(emu/gm)].

Vibrating Sample Magnetometer (VSM) is used for collecting the data. Properly weighted powder of

ferrite samples is place in hard glass tube and hard glass tube is placed under the strong magnetic field. The

samples are set in to vibration by using the crystal oscillator of very high frequency. The computerized

controlled data acquisition system is used for the measurement of Saturation magnetization [Ms

(emu/gm)],Magnetic moment [Mr(emu/gm)] and Coercivity [Hc(Oe)].

III. RESULTS AND DISCUSSIONS

3.1 Analysis of Saturation magnetization [Ms (emu/gm)], Coercivity [Hc(Oe)] and

Magneticmoment[Mr(emu/gm)].

With increasing Ni2+ density ‘x’ in [(Nix Cu(constant)Co0.8-x)Fe2O4] for constant=0.2 with x=0.2,0.4 and

0.6 , Saturation magnetization [Ms (emu/gm)] of ferrite material increases and Coercivity [Hc(Oe)] decreases

for three materials namely A, B and C. The total magnetization of the Spinel ferrites comes from the

difference in the magnetization of B-sites and A-sites and it is also known that the octahedral (B) site has

larger magnetic moment than the tetrahedral (A) site [10-15]. Table 2 shows the Values of Saturation

magnetization [Ms (emu/gm)], Coercivity [Hc(Oe)] and Magnetic moment [Mr(emu/gm)].

Fig. 2 indicates variation in [Ms (emu/gm)] with substitution x of Ni2+ , Fig. 3indicates variation in [Hc(Oe)]

with substitution x of Ni2+ and Fig. 4 shows the Hysteresis loop of ferrite samples of A, B and C.

With increasing Ni2+ density ‘x’ in [(Nix Cu(constant)Co0.8-x)Fe2O4] Saturation magnetization [Ms

(emu/gm)] of ferrite material increases, Coercivity [Hc(Oe)] decreases and Mr(emu/gm) also tend to decrease

for all three materials namely A, B and C.

With increasing Co2+ density ‘x’ in [Cox (Ni(constant)Cu0.8-x)Fe2O4] for constant=0.2 with x=0.2, 0.4

and 0.6, Saturation Magnetization [Ms (emu/gm)], Magnetic moment [Mr(emu/gm)] and Coercivity [Hc(Oe)]

of ferrite material increases for three materials namely D, E and A. Table 3shows the Values of Saturation

magnetization [Ms (emu/gm)], Coercivity [Hc(Oe)] and Magnetic moment [Mr(emu/gm)]. Fig. 4 indicates



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variation in [Ms (emu/gm)] with substitution x of Co2+ , Fig. 6indicates variation in [Hc(Oe)] with

substitution x of Co2+ and Fig. 7 shows the Hysteresis loop of all three ferrite samples of D, E and A.

With increasing Cu2+ density ‘x’ in [(Ni0.8-xCux Co(constant))Fe2O4] where constant=0.2 with x=0.2,

0.4 and 0.6, Saturation magnetization [Ms (emu/gm)], Magnetic moment [Mr(emu/gm)] and Coercivity

[Hc(Oe)] is maximum only for [(Ni.0.4 Cu.0.4Co0.2 )Fe2O4]due to equal quantity of Nickel and Copper.Table

4shows the Values of Saturation magnetization [Ms (emu/gm)], Coercivity [Hc(Oe)] and Magnetic moment

[Mr(emu/gm)].

The total magnetization of the spinel ferrites comes from the difference in the magnetization of B-

sites and A-sites and it is also known that the octahedral (B) site has larger magnetic moment than the

tetrahedral (A) site. When the Cu2+ ions replace the Fe3+ ions at A-site, the Fe3+ ions migrate to B-site and this

increases the saturation magnetization, it is happening because the Fe3+ ions have larger magnetic moment

than the Cu2+ ions. With further increase in the concentration of Cu2+ ions, the magnetic moment on the B-

sites increases and it increases the B–B exchange interaction. This increased B–B exchange interaction

induces anti-parallel spin coupling, which decreases the magnetization [16-20]. From Table 4 it is observed

that saturation magnetization [Ms (emu/gm)] increases and then decreases. Fig. 8indicates variation in [Ms

(emu/gm)] and Mr(emu/gm)with substitution of Cu2+ density x.Fig. 9indicates variation in [Hc(Oe)] with

substitution x ofCu2+ ions and Fig. 10 shows the Hysteresis loop of all three ferrite samples of D, F and C.

The FTIR spectroscopy confirms the single phase nature of the prepared sample. The peak 536.114 cm -1

gives the confirmation of Fe2O4. Fig. 11 shows the IR absorption peak at 536.114 cm -1[21-23].

Fig. 1: Flow chart of Sol Gel Auto Combustion Process.

Calcination at 4000c for four hours

Nickel

Nitrate

Copper

Nitrate

Cobalt

Nitrate

Ferric

Nitrate

Citric Acid

Mixing in 100 ml Distilled Water

Heating at 1000c by Magnetic

Stirrer

Nitrate Citrate Gel gets converted in to Sol Gel

Due to continuous heating at 1000c after 5 to 6 hours Auto Combustion takes

place

Gel gets converted in to Burnt Ash.

Ni Cu Co Fe2 O4 Ferrite Powder

Characterization FT-IR, VSM

pH is maintained by liquid Ammonia at 7

Mixing in 100 ml Distilled Water



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Fig. 2. Ms (emu/gm) Verses Ni2+ substitution x=0.2, 0.4 and 0.6.

Fig. 3.Hc(Oe) Verses Ni2+ substitution x=0.2, 0.4 and 0.6.

Fig. 4. Hysteresis Loop of three ferrite materials in SET-I (A,B,C).



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Fig. 5. Ms (emu/gm) Verses Co2+ substitution x=0.2, 0.4 and 0.6.

Fig. 6.Hc(Oe) Verses Co2+ substitution x=0.2, 0.4 and 0.6.

Fig. 7: Hysteresis Loop of three ferrite materials in SET-II (D, E, A).



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Fig.8. Ms (emu/gm) and Mr(emu/gm)Verses Cu2+ substitution x=0.2, 0.4 and 0.6.

Fig. 9.Hc(Oe) Verses Cu2+ substitution x=0.2, 0.4 and 0.6.

Fig. 10. Hysteresis Loop of three ferrite materials in SET-III (C. F, D).



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Fig. 11. Hysteresis loop of Ni.0.6 Cu.0.2Co0.2 Fe2O4

Fig. 12. Hysteresis loop of Ni.0.4 Cu.0.4Co0.2 Fe2O4

Fig. 13. FTIR graph for SET-I (C) [(Ni.0.6 Cu.0.2Co0.2)Fe2O4]



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Table 1: Label and Composition of Ferrite Material

SET Number Label Composition of Ferrite Material

SET-I A [(Ni.0.2 Cu.0.2Co0.6 )Fe2O4]

B [(Ni.0.4 Cu.0.2Co0.4 )Fe2O4]

C [(Ni.0.6 Cu.0.2Co0.2)Fe2O4]

SET-II D [(Ni.0.2 Cu.0.6Co0.2 )Fe2O4]

E [(Ni.0.2 Cu.0.4Co0.4 )Fe2O4]

A [(Ni.0.2 Cu.0.2Co0.6 )Fe2O4]

SET-III C [(Ni.0.6 Cu.0.2Co0.2)Fe2O4]

F [(Ni.0.4 Cu.0.4Co0.2 )Fe2O4]

D [(Ni.0.2 Cu.0.6Co0.2 )Fe2O4]

Table 2. Comparison of VSM data for SET-I, A, B and C

SAMPLE Hc(Oe) Mr(emu/gm) Ms (emu/gm)

(A) Ni.0.2 Cu.0.2Co0.6 Fe2O4 1796.6049 025.3758 035.1130

(B) Ni.0.4 Cu.0.2Co0.4 Fe2O4 1022.1605 022.9072 036.3335

(C) Ni.0.6 Cu.0.2Co0.2 Fe2O4 560.8642 022.9151 043.7550

Table 3. Comparison of VSM Data for SET – II, D, E and A


(D) Ni.0.2 Cu.0.6Co0.2 Fe2O4 1004.9383 019.2974 026.5841

(E) Ni.0.2 Cu.0.4Co0.4 Fe2O4 1317.9630 022.9967 031.6586

(A) Ni.0.2 Cu.0.2Co0.6 Fe2O4 1796.6049 025.3758 035.1130

Table 4. Comparison of VSM data for SET-III, C, F and D


(C) Ni.0.6 Cu.0.2Co0.2 Fe2O4 560.8642 022.9151 43.7550

(F) Ni.0.4 Cu.0.4Co0.2 Fe2O4 71817.90 026.2112 44.0776

(D) Ni.0.2 Cu.0.6Co0.2 Fe2O4 1004.9383 019.2974 26.5841

IV. CONCLUSION

We have successfully fabricated the Six different types of Nanocrystalline Ferrite materials namely and

materials C and F with material composition [(Ni.0.6 Cu.0.2Co0.2)Fe2O4] and [(Ni.0.4 Cu.0.4Co0.2 )Fe2O4]

respectively exhibit good magnetic properties and it can be used as core in transformer as well as fabricating

antenna and in magnetic storage devices.



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