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Nano Progress
Research Article
Structural, Thermal and Morphology Studies of Cu-CoZnFe2O4 Nano Ferrites by Combustion Method
1. Introduction
Nanotechnology, shortened to "nanotech", is the study of controlling matter on an atomic and molecular scale. Generally, nanotechnology deals with structures of the size 100 nanometers or smaller in at least one dimension, and involves developing materials or devices within that size. Nanotechnology is very diverse, ranging from extensions of conventional device physics to completely new approaches based upon molecular self-assembly, from developing new materials with dimensions on the nanoscale to investigating whether we can directly control matter on the atomic scale.
Nanotechnology has the potential to create many new materials and devices with a vast range of applications, such as in medicine, electronics and energy production. On the other hand, nanotechnology raises many of the same issues as with any introduction of new technology, including concerns about the toxicity and environmental impact of nanomaterials and their potential effects on global economics.[1,2]
Materials reduced to the nanoscale can show different properties compared to what they exhibit on a macroscale, enabling unique applications. The nanotechnology can offer the following: opaque substances become transparent (Cu); stable materials turn combustible (Al); insoluble materials become soluble (Au). A material such as gold, which is chemically inert at normal scales, can serve as a potent chemical catalyst at nanoscales. Much of the fascination with nanotechnology stems from these quantum and surface phenomena that matter exhibits at the nanoscale. The application of cobalt ferrite is a kind of drug delivery system, cobalt modified for recording materials, magnetic materials, and light spin filter.[3] These properties and suitability have made the cobalt ferrite one of the most highly studied magnetic materials. The general nature of the spinel ferrite nanoparticles is that their properties can be changed to meet the requirements by varying the synthesis process, precursor pH, catalyst ion substitution, annealing conditions, agglomeration, and the like.[4] In spinel ferrite, nickel-copper-cobalt ferrite has mixed spinel structure and belongs to the cubic system. It is a magnetic recording material with good performance. In the field of material science, magnetic materials have become a subject of considerable interest in the field of power storage devices. Especially in magnetic data storage, magnetic fluid technology, magnetic targeting drug delivery, magnetic resonance imaging has important applications.[5] Nickel-Copper-cobalt ferrite also has high magnetic anisotropy, high coercivity, high resistivity and good magnetic spectrum properties. Meanwhile, this ferrite is not easy to wear and corrosion and it has good performance in high frequency and ultra-high frequency applications. More and more researchers are improving the magnetic properties of spinel ferrite by doping and substitution.[6,7]
2. Experimental Section
2.1. Materials
All chemicals and reagents used for synthesis were of analytical grade. Cobalt nitrate {Co(No3)2.6H2O}, Zinc nitrate {Zn(No3)2.6H2O}, Ferric nitrate {Fe(No3)3.9H2O}, Urea NH2CONH2, HCl (37%) were purchased from Thomas Baker chem. Pvt. Ltd. India and used directly without further purification.
2.1.1. Synthesis of Cu-CoZnFe2O4 Nanocomposites
The Cu-CoZnFe2O4 nanocomposites have been prepared by solution combustion method (Fig. 1). The stoichiometric amounts of cobalt nitrate, zinc nitrate and ferric nitrate as oxidizers and urea as a fuel were dissolved in distilled water to prepare homogeneous aqueous solution. The above solution containing redox mixture is heated in a muffle furnace maintained at around 600℃ and 500℃ till complete combustion. The mixture finally yields porous and voluminous powder containing Cu-CoZnFe2O4 nanocomposites.
The X-ray diffraction patterns of the synthesized samples were recorded using Panalytical X-Pert Pro MPD instrument.
The morphological analysis of the synthesized samples was performed using the FESEM CARL ZEISS instrument.
The thermal properties of prepared nanocomposite samples were studied using a TA-STD Q600 instrument under dry nitrogen.
Atmosphere at the flow rate of 100mL/min. The samples were heated from room temperature to 700°C at predetermined rate of 20°C/ min.
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3. Results and Discussions
3.1. X-Ray Diffraction Studies on prepared Cu-CoZnFe2O4 Nano Ferrites
Structural analysis of the CuZnFe2O4 and CoZnFe2O4 Nano Ferrites samples has been performed using the powder XRD patterns and is presented in Figs. 2 & 3. The XRD peaks (111), (022), (113), (222), (004), (224), (333), and (044) indicate that the prepared sample has a Single-phase spinel cubic structure. The other prepared samples have partial formation of secondary hematite phase with spinel-phase cubic structure. In the reported literature, it has been found that the Co-Zn ferrite nanoparticles prepared using a sol gel method and annealed below 600⁰C have single-phase Figs. 2 and 3 shows the XRD spectra of CuZnFe2O4 and CoZnFe2O4 nano ferrites spinel structure.[8-10] The diffraction peaks have good agreement with standard (JCPDS card nos. 52-0277 and 89-0599) corresponding to the spinel Co-Zn ferrite and secondary hematite phase, respectively. The peak intensity of secondary hematite phase and it also found that secondary phase diminished at high concentration of cobalt doping. The average crystallite size of all prepared samples was calculated from full width at half maximum (FWHM) of most prominent peak (113) of XRD patterns using Scherer’s.[11,12] D = 0.9λ/β cos θ where D is the average crystallite size, β is the FWHM of the peak intensity measured in radians, λ = 1.54 °A is the wavelength of X-ray, and θ is Bragg’s angle. It is found that crystallite size (D) increases with cobalt doping from 25 to 31 nm. The crystallite size (D) obtained at x = 0.5% (28 nm) and x = 0.5% (30 nm) is nearly the same. Also, other calculated structural parameters at x = 0.03 and 0.09 possess approximately the same values by virtue of this small dopant variation. Hence, the calculated crystallite size (D). The effect of Co doping on structural parameters includes d spacing (d) and lattice constant (a) that have been calculated using the following relations: 2d sin θ = nλ.[13,14]
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3.1.1. FE-SEM Studies on Cu-CoZnFe2O4 Nano Ferrites
Fig. 4 shows the SEM images of CuZnFe2O4 and CoZnFe2O4 Nano Ferrites synthesized powder dried at 900⁰C in vacuum (Fig. 4a) and calcined at 5000⁰C for 45 min (Fig. 4b), respectively. In Fig. 4a, it is seen that agglomeration of crystals takes place. Usually, agglomeration is formed by smaller size of crystals. There are very large number of spherical crystals with much smaller size i.e., nanometer dimensions below 100 nm. This agrees well with XRD pattern where peak broadening appeared for these powder specimens. The fine particles and their agglomerates are clearly seen in the SEM image.[15,16]
However, after the heat treatment at 500⁰C, the crystal size increases and the grain size was measured from SEM micrograph (Fig. 4b). This value is in agreement with the results obtained from XRD data where sharp peaks are the indication of well define crystallization of CuZnFe2O4 and CoZnFe2O4 Nano Ferrites. The XRD peaks are very narrow indicating the higher grain size falls beyond the nano-scale region. SEM microstructures of CuZnFe2O4 and CoZnFe2O4 Nano Ferrites specimens sintered at 500⁰C are shown in Fig. 4c–d, respectively. The effect of heat treatment (500⁰C) on specimens morphology are very obvious from the low resolution micrographs, the specimens have small grains (Fig. 4c). The effect of these partial melting causes dramatic changes in impedance results.[17-19]
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3.1.2. DSC/TGA Studies on Cu-CoZnFe2O4 Nano Ferrites
Fig. 5 shows the DSC/TGA curve of CuCoZnFe2O4 Nano Ferrites. The DSC/DTG curve shows that there were about initial 10% weight loss at lower temperature (less than 100⁰C) due to the vaporization of water in the CuZnFe2O4 and CoZnFe2O4 Nano Ferrites. The weight change was not significant and the sample was thermally stable.
In the second step there is a weight loss of about 50% in the temperature range 100 to 450⁰C, which is ascribed to the degradation of the polymer chains and larger weight loss (about 68%) at the temperature between 500-800⁰C. The decomposition temperature of the CuCoZnFe2O4 Nano Ferrites was found to depend on the amount of CuCoZnFe2O4 Nano Ferrites present in the composite.[20,22]
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4. Conclusions
The present study demonstrated the structural, chemical and thermal properties of CuZnFe2O4 and CoZnFe2O4 Nano Ferrites synthesized using a solution combustion method. Significant results obtained are summarized below:
As-prepared samples were examined by using XRD, FT-IR, FE-SEM and DSC analysis techniques. XRD study revealed that samples have single phase spinel cubic structure. There is partial formation of secondary hematite phase (α-Fe2O3) with spinel phase cubic structure of CuZnFe2O4 and CoZnFe2O4 Nano Ferrites. The crystallite size (D) increases with Co and Cu because of larger ionic radii of Co2+ ions as compared to Cu2+ ions. The crystallinity of prepared samples increases and has been investigated by FESEM. Thermal stability of the samples was analyzed using TGA.
Acknowledgements
The Authors wish to acknowledge University of Mysore, Vignana Bhavana, Mysore for FESEM analysis facility.
Conflicts of Interest
The authors declare no conflict of interest.
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