Muhammad Anshory 18/433751/PPA/05566

Structural and Magnetic Studies of Mg Substituted cobalt

composite oxide Catalyst Co 1−x MgxFe2O4
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 ABSTRACT
Tujuan : Mensintesis Co1-xMgxFe2O4 Metode :
Sol-Gel auto-combustion

Hasil :
Lattice Parameter (+), X-Ray Density (-), Average Crystal size (-) → Mg (+)
Average crystallite (+) → Tcalcinating (+)
All sample ferrimagnetic behaviour at Room Temperature
H (magnetic hyperfine) (-) → Mg (+)
Tcalcinating mempengaruhi H & distribusi Fe3+ pada A-Site dan B-Site
Mg (+) → Saturation (-) , Coercivity (-) Soft Magnetic
Mg(+) → particle size (+), distance (+), magnetic moment B-site (-)

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INTRODUCTION

Ferrite is an important magnetic material. CoFe2O4 is a kind of hard

magnetic ferrite materials

Some of typical physical parameters of CoFe2O4 are listed: a moderate saturation

magnetization of about 80 emu/g, a high coercivity of 5000 Oe

CoFe2O4 has been widely used in the field of recording materials

Joshi et al. synthesized Co1−xMgxFe2O4 ferrites by co-precipitation, and observed

that the Mössbauer spectrum. Ferrites were in an ordered magnetic structure
after calcination at a high temperature

Ahmed et al. further concluded that the crystal size and the magnetic properties of
the Mg2+ substituted cobalt magnesium ferrites were enhanced.
Magnetic susceptibility with Mg content is the decrease, which was also
interpreted on the basis of redistribution of iron ions between the two sublattices.

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INTRODUCTION

Ferrites prepared by Nlebedim et al, using hydrolysis method, wet chemical method
and standard ceramic preparation techniques have been used to prepare
Co1−xMgxFe2O4. Mg concetration influences the magnetism of the sample.

In This Paper :
Due to the sol-gel auto-combustion method not only has excellent sinterability with a
single phase, but also requires relatively simple equipment at a lower cost.

Using Mössbauer spectroscopy to investigate the magnetic properties of

Co1−xMgxFe2O4 ferrite.

5
INTRODUCTION

Tujuan penelitian :

Mensitesis Co1−xMgxFe2O4
dalam bentuk single phase
spinnel

Memastikan sampel
terdistribusi homogen dan
dalam ukuran nanometer

Mengetahui sifat magnet akibat

perlakuan konsentrasi doping Mg
dan akibat Suhu calcinating

Mengetahui pengaruh perlakuan

pemberian Mg terhadap magnetic
saturasi dan koersivitas

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SAMPLE PREPARATION

Magnesium doping → Cobalt Ferrite

Co1-xMgxFe2O4

x= 0 ; 0.1 ; 0.3 ; 0.5 ; 0.7 ; 0.9

Sol-gel Auto-Combustion Method

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SAMPLE PREPARATION

Co(NO3)2·6H2O Mg(NO3)2·6H2O Fe(NO3)3·9H2O Citric acid

dropped

Deionized water Solution of PH~7 amonia

Metal nitrates

stirring Heating
gel Thermostat water bath at
80 °C

Dried-oven 120 oC 2h Add small Alcohol

burning in an
Sample → fluffy auto - combustion way
Grounded
Powder
1) 400 oC
annealed 2) 800 oC
in a muffle furnace
3h
Sampel Siap Karakterisasi

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CHARACTERIZATION

XRD
Untuk karakterisasi struktur
dan crystallite size
Spesifikasi XRD :
D/max-2500 V/PC, Japan
2θ range 20–70 °
Cu-K α radiations
(λ = 0.15405 nm)
Crystallite size dihitung
menggunakan persamaan
Scherrer
Mössbauer spectroscopy
The Mössbauer spectrum
Fast Com Tec PC-mossII,
The γ-rays were provided by
a 57 Co source in rhodium
matrix.
Often used to investigate the
Magnetic properties of
magnetic nanoparticles

SEM MPMS series XL-7

Untuk melihat tampilan 2D Untuk menganalisis
SEM yang digunakan Saturation magnetization
(Hitachi S-4800)

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The X-ray diffraction analysis

The XRD patterns show a

single phase spinel structure
for all samples and all
diffraction peaks can be
indexed to the cubic spinel
structure

JCPDS Card No. 22-1086

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The X-ray diffraction analysis

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The X-ray diffraction analysis

Berdasarkan hasil XRD :

Lattice parameter bertambah besar , seiring dengan
meningkatnya konsentrasi ion Mg2+
X-Ray Density semakin menurun, seiring dengan meningkatnya
konsentrasi ion Mg2+

M is the relative molecular mass, N is the Avogadro’s constant

and a is the lattice parameter
Crystallite size dihitung pada (3 1 1) menggunakan Debye Scherrer :

Crystallite Size menurun, seiring dengan meningkatnya

konsentrasi ion Mg2+

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The X-ray diffraction analysis

Co0.9Mg0.1Fe2O4
a single-phase cubic
spinel structure

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The X-ray diffraction analysis

Co0.9Mg0.1Fe2O4

Semakin meningkat suhu saat annealed, Average Crystallite Size

meningkat

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Structures and Grain Sizes – SEM
CoFe2O4

Co0.9Mg0.1Fe2O4

Both samples have a

uniform-sized
distribution of grains
and they are well
crystallized

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Structures and Grain Sizes – SEM

average average
grain size crystallite
size

CoFe2O4
96.3 nm 56 nm

Co0.9Mg0.1Fe2O4
116.9 nm 46 nm
The activation energy for grain
boundary diffusion < Energy for The
lattice diffusion.

Mg has low activation energy

compared to other elements.

The lower activation energy for

diffusion of Mg may account for the
increased grain size,

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Mössbauer spectroscopy

Seluruh sampel
menunjukkan two split
- sextet pattern

Mengindikasikan
penyebaran ion Fe3+
pada tetrahedral (A-
site) dan octahedral (B-
site)

All sample
Ferrimagnetic

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Mössbauer spectroscopy
I.S (B) > I.S (A)

Interaksi ion Fe3+ dengan

O punya Larger Band
Separation

Isomer Shift
Fe2+ = 0.6–1.7 mm/s
Fe3+ = 0.1–0.5 mm/s
magnetic hyperfine field
(H) (-) → Mg (+)
Karena A-B
superexchange
interaction (-)
Quadrupole shift (Q.S)
close to zero, ferrites have
a symmetric charge
distribution in a cubic
system

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Mössbauer spectroscopy

two sextet subpatterns

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Mössbauer spectroscopy

magnetic hyperfine field (B site) HB (+) → Tanneling (+)

XRD show Co0.9Mg0.1Fe2O4 , excellent crystallinity for all temperature

The average crystallite size (+) → Tcalcinating (+)

Absorption area A0 Sextet A-site (-) → Sextet B-site (+)

Tcalcinating → distribution of Fe3+ ions at A and B sites

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 MPMS series XL-7
Magnetic property of particles

Konsentrasi Mg Naik,
Nilai Saturasi Turun

75.6 emu/g to 25.4 emu/g

σs = saturation magnetization
nB = the magnetic moment
M= The relative molecular
mass Co1-xMgxFe2O4
X (naik) → M (turun)

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 MPMS series XL-7
The change of the magnetic moment nB can be explained with the Néel’s theory

magnetic AB2O4 Spinnel Structure

moment A= Divalent
B= Trivalent
Mg2+ 0 μB
CoFe2O4
Co1-xMgxFe2O4
Fe3+ 5 μB

Co2+ 3 μB
Cation distribution

(Fe) [Co1−xMgxFe] O4
Co2+ prefers to occupy the octahedral site [ ] in the inverse spinel structure of CoFe2O4
material.

Mg2+ distributes in both sites, but has a strong preference for the octahedral site [ ]

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 MPMS series XL-7
The theoretical magnetic moment nB is expressed as :
MB = [3(1 − x) + 0 + 5] μB
nB = MB − MA = 3(1 − x ) = 3 − 3 x
MA = 5 μB

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MPMS series XL-7

CoFe2O4

Co0.1Mg0.9Fe2O4

Mg content x meningkat, saturation magnetization (Ms) menurun

Mg content x meningkat, Koersivitas (Hc) Co1-xMgxFe2O4 menurun
The decrease in the coercivity with the increasing magnesium concentration in the
substituted cobalt ferrite may be explained with Mg2+ has no unpaired electrons,
which lead to zero total electron spin.

The increased particle size with Mg substitution causes an increase in the distance
between the cations, which reduces A-B exchange interactions. Thus, it led to the
decrease in magnetization (Ms).

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CONCLUSION

The XRD analysis reveals Co1−xMgxFe2O4 ferrite has a single phase cubic spinel
structure.

The XRD patterns of Co0.9Mg0.1Fe2O4 annealed at different temperatures indicate all samples
prepared by the sol-gel auto-combustion process have excellent crystallinity.

The SEM results indicate that the grains are homogeneously distributed and well
crystallized.
The average grain size of CoFe2O4 ferrite powers is in the nanometer scale from SEM
analysis.

The Mössbauer absorption spectra of Co1−xMgxFe2O4 have two normal Zeeman-split

sextets, which display the ferrimagnetic behavior for all samples.

The Mössbauer spectra of Co0.9Mg0.1Fe2O4 annealed at different temperatures show that

the calcining temperature influences the magnetic property.

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CONCLUSION

Magnesium substituted cobalt ferrite has been shown to have strong effects on both
saturation magnetization and coercivity.
The decrease in the saturation magnetization is correlated with the decrease in the magnetic moment. The decrease
in the coercivity is attributed to the reduction in the magneto crystalline anisotropy.

For the Co0.1Mg0.9Fe2O4 ferrite, it’s coercivity is 150 Oe, which suggests that the sample
towards soft magnetic material transformation with increase in Mg concentration.

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