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Magnetic properties and characterization of spinel XFe2O4

2+
2+
2+
2+
2+
(X=Mn , Co , Ni , Cu y Zn ) obtained by molten salt synthesis
G.A. Covarrubias-Cortés 1, J.A. Herrera-Pedroza 1, A. Sánchez Martínez 3, C. Ostos-Ortíz 4, A. Durán-Hernández 5, M.L García-Guaderrema 2
1
Centro universitario de Tonalá (CUTONALA), Av. Nuevo Periférico No. 555, ejido San José Tatepozco, 48525 Tonalá, Jal, México.
2
Departamento de Ingeniería de Proyectos, Centro universitario de Ciencias Exactas e Ingeniería (CUCEI), Universidad de Guadalajara, Zapopan, Jalisco. CP. 45100.
3
Catedrática CONACYT-Centro universitario de Ciencias Exactas e Ingenierías (CUCEI), Universidad de Guadalajara, Zapopan, Jalisco. CP. 45100.
4
Instituto de Química, Universidad de Antioquia, AA 12-26, Medellín, Colombia.
5
Universidad Nacional Autónoma de México, Centro de Nanociecias y Nanotecnología, Ensenada, B.C., México
Key words: Spinel, Molten Salt-Synthesis, Magnetism

e-mail: covarrubias.cga@outlook.com; anthonyhpdz@hotmail.com

Abstract:
Spinel ferrites with XFe2O4 structure where X represents a X2+ cation of Mn, Co, Ni, Cu or Zn, these were synthesized by molt en salt in relation 4:1 of salt
a n d o x i d e s a n d c a l c i n e d a t t e m p e r a t u r e s o f 8 5 0 , 9 0 0 a n d 9 5 0 ° C , a f t e r w a r d s w e r e c h a r a c t e r i z e d w i t h X - r a y d i ff r a c t o m e t e r, t h e n i n a Vi b r a n t S a m p l e M a g n e t o m eter (VSM) in a physical properties measure system, magnetic hysteresis (M vs H), magnetic properties respect to type of meta l ion with temperature variations
and finally scanning electron microscopy (SEM).

Methodology:
Molten Salt Synthesis

Mixture of precursor oxides
with KCl / NaCl salts

Melting salts process: to 850°C— 900°C—950°C
Grinding to homogeneity

XO + Fe2O3

4(KCl 1M/NaCl 1M) + (XO + Fe2O3)

XFe2O4

Dry at 150°C

Desalting Washes

Analysis

Heating Ramps
1.- Δ 10°C/min
100°C before final temp.
2.- Δ 5°C/min
to final temp
3.- 8hrs. in final temp
4.- Cooling
10°C/min to 24°C

Results Y Discussions
X-Ray Diffraction

Scanning Electron Microscopy (SEM)
The morphology of the materials has many similarities
between them, indicating that the synthesis method used will
result in the growth of "crystals “, on the other hand, the EDS
spectrum indicates that the materials are in the appropriate
atomic distribution for spinel structure.

The result of the X-ray Diffraction shows the presence of the crystalline phase in the spinel’s cations of nickel (trevorite), Copper
(copper ferrite) and Zinc (franklinite), presenting sizes of crystallite up to 29nm for copper, 104nm for cobalt, 85nm for nickel and
103nm for zinc according to the Scherrer Equation (formula 1), affirming that the phases presented the optimum magnetic
properties at the highest temperature of reaction (image 11 and 12), as it is presented in the case of manganese (Image 4) the
Iwakiite (MnFe2O4) phase is only present at 950°C of heating reaction, however this phase is not pure and shows hematite
(Fe2O3) and manganese-iron oxide ((Mn0.983Fe0.017)2O3) like impurities.

Formula 1: Scherrer Equation

Element

Unn (wt.%) Norm (wt.%)

Atom (at.%) Comp.C (wt.%)

3 Sigma (wt. %)

Oxygen

17.82

21.99

50.00

0.00

6.64

Iron

42.12

51.98

33.86

66.87

3.47

Nickel

21.1

26.06

16.14

33.13

1.83

Magnetic Properties
(Hysteresis)

Image 1: X ray parameters for the material X= Ni

Image 6: S.E.M. photography of
NiFe2O4 spinel.
Image 11: Magnetization versus field at a temperature of
300K for different samples synthetized at 950°C and those
obtained pure phase.

Molecular weight (g/mol)

Saturation magnetization σs

ɳB

40

1.6786

CoFe2O4 234.6208

63.2

2.6549

CuFe2O4 239.2336

25

1.0708

NiFe2O4

234.3810

Table 1: Experimental Calculated magnetization of TMFe2O4
(TM = Co,Ni & Cu) Samples at 300K.

Image 2: X ray parameters for the material X= Cu

Image 7: S.E.M. photography of
CuFe2O4 spinel.

The results show that all samples have magtetic response at
300K with ferromagnetic order,
except nickel spinel. This last
exhibits antiferromagnetic property (Image 11). At 10K the
magnetic order is maintained,
no significant changes were observed preserving their magnitudes at this temperature. The
thermal effects not take precedence
on
magnetoelastic
energy. About zinc spinels increases are observed in the
magnetization assicuated with
possible paramagnetic property
(Image 12).

Table 3: EDS quantitative analysis for ZnFe2O4 spinel.
Acquisition: 787

Image 14: EDS spectrum NiFe2O4 spinel
Element

Unn (wt.%) Norm (wt.%)

Atom (at.%) Comp.C (wt.%)

3 Sigma (wt. %)

Oxygen

21.38

21.32

50.00

0.00

8.39

Iron

46.67

49.53

33.27

63.71

4.07

Zinc

29.24

29.15

16.73

36.29

2.55

Table 4: EDS quantitative analysis for ZnFe2O4 spinel.
Acquisition: 789

Image 15: EDS spectrum ZnFe2O4 spinel
Element

Unn (wt.%) Norm (wt.%)

Atom (at.%) Comp.C (wt.%)

3 Sigma (wt. %)

Oxygen

18.60

16.30

41.43

0.00

7.72

Iron

64.93

56.91

41.43

73.21

5.28

Copper

30.57

26.79

17.14

26.79

2.62

Table 5: EDS quantitative analysis for CuFe2O4 spinel.
Acquisition: 791

Magnetic Properties
(Type metal ion)

Image 3: X ray parameters for the material X= Co

Image 8: S.E.M. photography of
CoFe2O4 spinel.

Image 12: Magnetization versus field at a temperature of
10K for different samples synthetized at 950°C and those
obtained pure phase.

Molecular weight (g/mol)

Saturation magnetization σs

ɳB

43

1.8171

CoFe2O4 234.6208

72.8

3.0582

CuFe2O4 239.2336

28

1.1993

NiFe2O4

234.3810

Table 2: Experimental Calculated magnetization of TMFe2O4
(TM = Co,Ni & Cu) Samples at 10K.

Image 4: X ray parameters for the material X= Mn

Image 5: X ray parameters for the material X= Zn

Image 9: S.E.M. photography of
MnFe2O4 spinel.

Image 10: S.E.M. photography of
ZnFe2O4 spinel.

Image 13 shows the tendency
of saturation magnetization
(Ms) with respect to type metal
ion. At room temperature and at
low temperatures the Ms remains the same, Ms starts above of 0.5T. This property it can
attributed of type spinel formed
according to site A. considering
the spinel formula (AB2O4) where A is= metalic ion located in
tetrahedral sites and B = ion located in Octahedral site. About
this can determine that the
Magnetization may decrease
depending on the location of
metal ion of different subnets
( A and B)

Image 13: Ms, Hc vs metal ion of samples synthetized at
950°C and those obtained pure phase and magnetic properties.
a) Temperature at 300K

b) Temperature at 10K

Image 16: EDS spectrum CuFe2O4 spinel
Element

Unn (wt.%) Norm (wt.%)

Atom (at.%) Comp.C (wt.%)

3 Sigma (wt. %)

Oxygen

15.73

15.47

39.43

0.00

6.19

Iron

54.91

53.99

39.43

69.45

4.49

Cobalt

31.07

30.55

21.14

30.55

2.61

Table 6: EDS quantitative analysis for CoFe2O4 spinel.
Acquisition: 794

Image 17: EDS spectrum CoFe2O4 spinel

Conclusion:
The X-Ray Diffraction show how the highest temperatures
presents the purest phases of material, with a morphology of
polydisperse crystals by the synthesis method used. In the
EDS analysis we can see how the atomic distribution is according to the AB2O4 spinel formula in all cases. The magnetic measurements by vibrant sample magnetometer (VSM)
denote a high magnetic response to the samples with Co, Ni
and Cu (3.05, 1.81 and 1.19 Bohr Magnetons respectively),
all the samples has been measured under the same conditions.

Acknowledgements