Available online at www.sciencedirect.

com

ScienceDirect
Materials Today: Proceedings 2 (2015) 3750 – 3757

4th International Conference on Materials Processing and Characterization

Synthesis and Characterization of Nickel Ferrite (NiFe2O4)

Nanoparticles Prepared by Sol- Gel Method
Ravindra Sena, Pranat Jainb, Ravi Patidara,Sanjay Srivastavab, R. S. Ranac, Nitish Guptaa *
a Department of Applied Chemistry, Shri G.S. Institute of Technology & Science, 23 Park Raod, Indore (452003) India
b Department of Metarial Sci. and Metallurgical Eng., Maulana Azad National Inst. of Tech., Bhopal (462003) India
c Department of Mechanical Eng., Maulana Azad National Inst. of Tech., Bhopal (462003) India

Abstract

Nickel ferrite nanoparticles were syntheiszed by sol-gel method using urea as a fuel. The nanoparticles were characterized by XRD,
SEM,TGA, FTIR and UV–visible techniques. TGA showed that the gel decomposed around 230◦C followed by crystallization.
XRD revealed the formation of spinel structure with space group of Fd3m. Scherrer and Williamson-Hall method is applied to
determine crystal size and strain present in sample. FTIR showed fundamental absorption bands related to octahedral and
tetrahedral sites, in the range 400–600cm-1. SEM showed agglomerated flakes having void and pores on the surface. UV–vis
indicated the bandgap of sample is 5.5 eV.
© 2014 The Authors. Elsevier Ltd. All rights reserved.
© 2015 Elsevier Ltd. All rights reserved.
Selection andpeer-review
Selection and peer-review under
under responsibility
responsibility of theofconference
the conference committee
committee membersmembers
of the 4th of the 4th International
International conference onconference
Materials on
Materials
ProcessingProcessing and Characterization.
and Characterization.

Keywords: NiFe2O4; ferrite; sol-gel; combustion; X-ray diffraction

Corresponding author: Tel.: +91 731 2582182; fax: +91 731 2432540
E-mail address: nitish.nidhi75@gmail.com

2214-7853 © 2015 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the conference committee members of the 4th International conference on Materials Processing
and Characterization.
doi:10.1016/j.matpr.2015.07.165
 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757 3751

1. Introduction

Recently nanocrystalline magnetic ferrite has receiving great attention due to their wide range of
technological applications in various fields; such as magnetic fluids for storage of informations, ferrofluids, magnetic
guided drug delivery, sensors, catalyst and magnetic resonance imaging (MRI) enhancement[1-3]. Among these,
spinel ferrite, inverse ferrites is particularly interesting due to its high magnetocrystalline anisotropy, high saturation
magnetization from typical crystal and magnetic structure [4]. Nickel ferrite is an inverse spinel ferrite in which the
tetrahedral (A) sites are occupied by ferric ions and the octahedral (B) sites by ferric ions and nickel ions. Thus NiFe 2O4
can be represented as (Fe3+)A [Ni2+Fe3+]B O42− [4]. There are various chemical as well as physical techniques have been
developed to synthesize nanocrystalline nickel ferrite, such as sol-gel [5], hydrothermal [6], RF –plasma torch method
[7], chemical route [8], and auto combustion method [9]. In the present study the sol- gel method was carried out to
prepare NiFe2O4 particles using aqueous solution of ferric nitrate, nickel nitrate and urea. This method has the
advantage of simple preparation, economic and gentle chemistry route resulting nanocrystalline powder.

2. Experimental

NiFe2O4 were synthesized by the sol-gel route, using stiochiometeric amount of the corresponding metal
nitrates; Fe(NO3)3. 9H2O (Merck, India), Ni (NO3)2. 6H2O (Merck, India) and Urea (Fischer scientific) as a fuel. All
the reagents were used without further purification. According to propellant chemistry, the oxidizing and reducing
valences of different elements are as follows: Ni = +2; Fe = +3; C = +4; H = +1; O = -2. In a uera to nitrate reaction,
total reducing valences of urea is + 6 and total oxidizing valencies of nitrates (Ni(NO3)2 : Fe(NO3)3; 1:2) is - 40.
Therefore, fuel (NH2CONH2) – nitrate composition become -40+6n = 0; n = 6.67 mol in the reaction. Hence fuel –
nitrate composition indicates urea/NO-3 = 2.22 stochiometric ratio. Under equilibrium condition, chemical reaction can
be expressed as follows:

Ni(NO3)2.6H2O + 2Fe(NO3)3.9H2O + 6.67Ф NH2CO NH2 + (9.99 Ф - 10) O2 NiFe2O4 + 6.67Ф CO2(g) +
(24+13.34Ф) H2O(g) + (4+6.66 Ф)N2(g) (28+ 26.64 Ф) moles of gas

The stoichiometeric amounts of precursors were dissolved in 10 ml distilled water at room temperature. Then
urea was added into the solution of iron and nickel nitrate in the ratio 2.22. The resulting solution was stirred with
heating at 80 0C on magnetic stirrer untill H2O is evoporated and converted into brownish viscous gel. The viscous gel
is transferred to a Porcelain dish. The temperature of the dish is maintained at about 400 0C for 10 min in the open air.
After combustion a puffy solid remains. Prior to characterization, the puffy solid was crushed into powder.
Subsequently, powder were equally divided and calcined for 3 Hrs at 500ͼC and 600ͼC in muffle furnace, to obtain
desired phase. The final samples were then characterized by different techniques, such as XRD, SEM, EDAX, FTIR
and UV-visible.

3. Results and Discussion

3.1. TGA analysis

In order to access the degree of thermal decomposition of gel precursor, TGA have been carried out (fig. 1).
The TGA curve shows that thermal decomposition of gel precursor possesses two regions. They are 50-110 0C and
175- 210 0C. The first region starts around 50 0C and ends at 110 0C, and is accompained by a weight loss of 11% due
to the evoporation of residual water in the gel. The second region begins ~ 175 0C and ends at 210 0C with a weight
loss of 69% which might be due to the initial breakdown of complexes and spontanious combustion of reactants. The
thermal decomposition of gel precursor at low temperature is due to the in situ oxidizing environment created by the
interaction of uera (fuel) and metal nitrates (oxidizer) [10]. Almost no weight loss over ~417 0C indicates the
completion of thermal decomposition and formation of spinel ferrite.
3752 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757

Fig.1. Thermogravimeteric analysis (TGA) curve of gel precursor.

3.2. XRD analysis

XRD pattern of annealed NiFe2O4 samples are shown in fig. 2. The sample was a single phase of NiFe2O4 and
corresponds to JCPDS file (No.44-1485). The sample represents a cubic structure with the space group Fd-3m (No.
227). There is no secondary phase was observed in XRD data, this provides the clearest indication of the formation of
desired product at 500 ͼC.

3.2.1. Crystalline Size and Strain

The crystalline size and lattice strain of the nickel ferrite sample calcined at 500 0C was estimated by using
the Debey–Scherrer’s relation (fig. 3) and Williamson-Hall method (fig. 4), respectively. The FWHM corresponding
to 2θ is the combination both sample as well as instrumental effect. The total broadening (ߚ௧ ), was evaluated for each
XRD peak from the relation [11]:

ଶ ଶ
ߚ௧ ൌ ඥߚெ௘௔௦௨௥௘ௗ െ ߚூ௡௦௧௥௨௠௘௡௧௔௟ (1)

Here, the instrumental broadening of Si has taken. Now, the Debey–Scherrer’s relation was applied to
calculate the average nanocrystalline size (D) of the NiFe2O4.

௄ఒ
‫ ܦ‬ൌ (2)
ఉ೟ ୡ୭ୱ ఏ

In this relation K = 0.94 and λ is the wavelength of Cu source.The obtained average noncrystalline size
through this relation is 113.30 nm. The line broadening arising due to induced strain in the material. The cause behind
the strain is due to high temperature treatment that leads the crystal imperfections and distortion in the materials. For
the determination of strain the Williamson and Hall have proposed the method [12]. According to that, the total burden
ߚ௧ is a sum of broadening βsize due to crystallinesize and lattice strain βstrain present in the material. Both contribution
effects give the total broadening:

ߚ௧ ൌ ߚ௦௜௭௘ ൅ ߚ௦௧௥௔௜௡ (3)

 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757 3753

Where, ߚ‫ ݁ݖ݅ݏ‬ൌ ݇ߣȀ‫( ߠݏ݋ܿܦ‬from Sherrer’s formula) andߚ‫ ݊݅ܽݎݐݏ‬ൌ Ͷߝ‫ߠ݊ܽݐ‬, where, ε = strain. Therefore the
equation become

௞ఒ
ߚ௧ ൌ ൅ Ͷߝ‫ߠ݊ܽݐ‬ (4)
஽௖௢௦ఏ

After the rearrangement, the equation (2) was plotted between ߚ௧ ܿ‫ ߠݏ݋‬and 4sinθ. The crystalline size was
estimated by intercept with y and the strain from the slope of the linear fit line.The obtained particle size and lattice
strain was estimated to be 113.30 nm and 0.383 x 10-3, respectively.

Fig. 2. X- ray diffraction patttern of nickel ferrite calcined at 500 0C (a) 5000C (b) 6000C.

Fig. 3. Sherrer curve of nickel ferrite calcined at 600 0C Fit to the data, the crystalline size D is extracted from the slope of the fit.
3754 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757

Fig. 4. The W-H analysis of nickel ferrite calcined at 600 0C. Fit to the data, the strain is extracted from the slope and the crystalline size is
extracted from the y-intercept of the fit.

3.3. FTIR analysis

The FTIR spectra of annealed nickel feritte samples were recorded in the range from 400 cm-1 to 1000 cm-1
(fig. 5). No absorption bands were obsorved above 1000 cm-1 as a common feature of all the ferrites. All the spectra
show two main absorption bands around 600 and 400 cm-1. Accroding to group theoritcal calculations the spinel ferrites
are known to exhibit four fundamentals IR active modes in the vibration spectra, which are high frequency and low
frequency bands [13]. The FTIR spectra show strong absorption bands at 591 cm-1, 561 cm-1 and at 481 cm-1 , 468 cm-
1
for the nickel ferrite sample annealed at 5000C. Similarly nickel ferrite sample annealed at 600 0C show absorption
bands at 584 cm-1, 559 cm-1 and at 474 cm-1, 464 cm-1. The band around 600 cm-1, corresponds to intrinsic stretching
vibration of metal at the tetrahedral site i.e Mtd ↔O, where as the band at 400 cm-1 is assigned to octahedral-metal
stretching i.e. M 0h↔O [14,15]. The IR absorption bands of solids below 1000 cm-1 are usualy assigned to vibration of
ions in the crystal lattice [16].

3.3. SEM analysis

The microstructure of the calcined nickel ferrite (500 0C and 600 0C) samples and their chemical composition
is analyzed using SEM-EDAX data. The SEM micrographs in Fig. 6 show nanoparticles have uniform, almost
spherical structural morphology with narrow size distribution but with agglomeration to some extent. This
agglomeration is due to the high energy generated during the combustion process. The surface of particles possesses
void and pores, which are attributed to the release of large amount of gases librated during the combustion. The
presence of a porous network is one of the characteristics of combustion-synthesized powders [17]. The EDAX
(Energy Dispersive X-Ray Analysis) data of the NiFe2O4 sample annealed at 600 0C showed that nanoparticles formed
without any impurity and the metal ions of the respective concentration of ferrites are present in the required
stoichiometric ratio (fig. 7).
 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757 3755

Fig. 5. FTIR curve of nickel ferrite calcined at 500 0C and 600 0C.

a b

Fig. 6. SEM images of NiFe2O4 calcined at (a) 5000C (b) 6000C.

3.4. UV-visible spectral analysis

The Uv-Visible spectra of nickel ferrite sample calcined at 600 0C are shown in fig. 8. The absorbance of sample
was measured in the wavelength range 200–400 nm. The absorption spectrum reveals that the nickel ferrite has low
absorbance in visible region and close to infrared region; however, absorbance in UV region is high. The band gap
energies were obtained by extrapolating the linear portion of a plot of (α x hυ) 2 versus the photo energy (hυ) to the
energy axis for zero absorption. The estimated band gap for nickel ferrite sample is 5.2 eV. Our result of the optical
behavior is analogues to those reported by srivastava et.al for nickel ferrite thin film synthesized via microwave
assisted non-aqueous sol–gel process [18 ].
3756 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757

Fig. 7. UV-visible absoption spectra of NiFe2O4 calcined at 6000C.

4. Conclusions

Sol–gel method has been used to prepare NiFe2O4 nanoparticles. TGA reveals that the sol–gel auto-
combustion process could take place at a relatively low temperature to form spinel ferrite. The XRD analysis reveals
that, the formation of single phase nickel ferrite with Fd-3m space group. The obtained particles are in nanometer
range as confirmed by Scherrer and Williamson-Hall method. FTIR analysis show characteristic IR absorption bands
of the spinel nickel ferrite phase. SEM analysis shows that the sample have almost spherical structural morphology,
however, some agglomeration of the nanoparticles were observed. EDAX analysis shows the presence of metal ions
in the required stoichiometric ratio. The UV–visible spectra indicate the band gap of sample is calculated to be 5.5 eV.

Acknowledgement

The authors RS and NG are highly grateful to IUC-UGC-DAE Consortium, Indore for extending the instrumentation
facility for XRD, SEM and EDAX characterization.

References

[1] Yin H, Too HP, Chow GM. The effects of particle size and surface coating on the cytotoxicity of nickel ferrite. Biomaterials; 2005;
26(29):5818–5826.
[2] Hasmonay E, Depeyrot J, Sousa MH, Tourinho FA, Bacri JC, Perzynski R. Optical properties of nickel ferrite ferrofluids. J. Magnetism &
Magnetic Mater; 1999; 201(1–3): 195–199.
[3] Kale A, Gubbala S, Misra RDK. Magnetic behavior of nanocrystalline nickel ferrite synthesized by the reverse micelle technique. J. Magnetism
& Magnetic Mater; 2004; 277(3): 350–358.
[4] Niasari MS, Davar F, Mahmoudi T. A simple route to synthesize nanocrystalline nickel ferrite (NiFe 2 O4) in the presence of octanoic acid as a
surfactant. J. Poyhedron; 2009; 28: 1455-1458.
[5] Chen DH, He XR. Synthesis of nickel ferrite nanoparticles by sol –gel method. J. Mater. Res. Bulletin; 2001; 36: 1369-1377.
[6] Huo J, Wei M. Characterization and magnetic properties of nanocrystalline nickel ferrite synthesized by hydrothermal method. J. Mater. Let.;
2009; 63: 1183-1184.
 Ravindra Sen et al. / Materials Today: Proceedings 2 (2015) 3750 – 3757 3757

[7] Son S, Taheri M, Carpenter E, Harris VG, McHenry ME. Synthesis of ferrite and nickel ferrite nanoparticles using radio-frequency thermal
plasma torch. J. Appl. Phys; 2002; 91: 7589–7591.
[8] Jiang J, Yang YM. Facile synthesis of nanocrystalline spinel NiFe2O4 via a novel soft chemistry route. J. Mater. Letters; 2007;61; 4276-4279.
[9] Ebrahimi SAS, Azadmanjiri J. Evaluation of NiFe2O4 ferrite nanocrystalline powder synthesised by sol gel auto combustion method. J. Non
crystalline solids; 2007; 353; 802-804.
[10] Chen DH, He XR. Synthesis of nickel ferrite nanoparticles by sol-gel method. J. Mater. Res. Bull; 2001; 36; 1369-1377.
[11] Prabhu YT, Venkateswara Rao K, Kumar VSS, Kumari BS. X-ray analysis of Fe doped ZnO nanoparticles by Williamson-Hall and size-
strain plot. Inter. J. Eng. and Ad. Technol; 2013; 2(4); 268-274.
[12] Mote VD, Purushotham Y, Dole BN. Williamson-Hall analysis in estimation of lattice strain in nanometer-sized ZnO particles. J. Theoretical
and Applied phys; 2012; 6:6.
[13] Balaji S, Selvan RK, Berchmans LJ, Angappan S, Subramanian K, Augustin CO. Combustion synthesis and characterization of Sn 4+ substituted
nanocrystalline NiFe2O4. J. Mater. Sc. Eng. B; 2005; 119: 119–124.
[14] Nakamoto K, Huang D, Wang R, Infrared and Raman spectra of inorganic and coordination compounds. The Press of Chemical Industry,
Beijing; 1986; 231–244.
[15] R.D. Waldron, Infrared spectra of ferrites. Phys. Rev.1955; 99; 1727.
[16] Brabers VAM, Infrared spectra of cubic and tetragonal manganese ferrites. Phys. Stat. Sol. 1969; 33: 563–572.
[17] Fu YP, Lin CH, Liu CW. Preparation and magnetic properties of Ni 0.25Cu0.25Zn0.5 ferrite from microwave-induced combustion. J. Magn. Magn.
Mater.2004; 283; 59–64.
[18] Srivastava M, Ojha AK, Chaubey S, Materny A, Synthesis and optical characterization of nanocrystalline NiFe 2O4 structures. J. of Alloys and
Comp. 2009; 481; 515-519.