Abstract
(magnesiowustite) nanopowder samples synthesized by solution-combustion method and fuel to oxidizer ratio () are used as a control parameter to investigate how particle size and morphology vary with . The method is inexpensive and efficient for synthesis of oxide nanoparticles. The average crystallite size of nanoparticles was estimated from the full-width-half maximum of the X-ray diffraction peaks of powders using Debye-Scherrer’s formula; the average crystallite size varies from 16 nm to 51 nm. From X-ray diffraction analysis, it was observed that nanoparticles have cubic structure. The particle size measured by particle size analyzer ranges from 37.7 nm to 73 nm which is in the order of XRD results. Thermal analysis was done by thermal gravimetric-differential thermal analyzer. The particle size and morphology of the synthesized powder were examined by transmission electron microscope and scanning electron microscope. The crystal size and particle size were compared with some of the most recently published research works by XRD and TEM. FTIR conforms formation of the .
1. Introduction
Magnetic Nanoparticles (NPs) have many unique magnetic properties such as super paramagnetic, high coactivity, low Curie temperature, high magnetic susceptibility, and so forth. Magnetic NPs are of great interest for researchers from a broad range of disciplines [1–5], microwaves devices, magnetic recording media, fabrication of radio frequency coils, transformer cores, chock coils, noise filters, and recording, heading, and rod antennas [6–8] and also are very important in heterogeneous catalysis, adsorption, and sensors [9, 10]. Especially, magnetic Ferro fluids and data storage are the applied researches that have led to the integration of magnetic NPs in a myriad of commercial applications.
In recent years, various physical and chemical techniques such as sol-gel [11], coprecipitation method [12, 13], microwave hydrothermal method [14], micro emulsion method [15], electrospinning [16], and ball milling [17] have been successfully employed for the synthesis of nanoparticles.
In the present work, Solution Combustion Synthesis technique (SCS) has been used and is known as one of the effective and economic method [18]. Solution Combustion synthesis (CS) [19] has emerged as an important technique for the synthesis and processing of advanced ceramics (structural and functional), catalysts, composites, alloys, and intermetallic and nanomaterial. The method exploits self-sustaining solid flame combustion reaction for the internal development of very short period [20]. Fuel to oxidizer ratio [21] is very crucial and effective amount in this method [22], it can change the properties of the Nanomaterial as the reaction temperature depends on fuel to oxidizer ratio. It is well recognized that the fuel is an important component for the preparation of oxides by SCS. However, there are not many studies that have been found in the literature correlating the microstructure and effect of grain size with the magnetic properties of powders.
2. Experimental
The powders were prepared by using combustion synthesis in solution under different molar compositions of fuel (glycine, NH2CH2COOH) and fuel to oxidizer ratio and . The iron nitrate () and magnesium nitrate () were dissolved in a beaker with sufficient deionized water with glycine in appropriate amount and the solution was placed under thermal stirring with the temperature of 60°C; at this temperature, different molar amounts of the fuel were added. The precursor solutions were maintained under thermal stirring for few minutes to ensure homogeneity, subsequently these solutions were placed in a hot plate. As the temperature reached 100°C, water started to boil and evaporate from the solution which increased solution viscosity substantially. The obtained precursor is annealed for 2 h at 300°C. The decomposition reactions of starting compositions are
The overall combustion reaction in air may be written as
The crystal phase of the synthesized powders were determined by X-ray diffraction (XRD, Bruker D8 Advance, Germany) using Cu Kα as radiation source (40 kV, step size 0.02, scan rate 0.5 min−1). The particle sizes were measured by nanoparticle size analyzer (SZ-100 Nanoparticle, Horiba, Japan). The thermal decomposition behaviors of the precursors were investigated by thermogravimetric analysis (TGA/DTA, SII EXSTAR 6300R, Japan). Fourier transform infrared spectroscopy was used as well (FTIR, PERKIN ELMER, India). The particles size and morphology of the synthesized powder were examined by scanning electron microscope (SEM, S-3400N-hitachi-Japan), transmission electron microscope (TEM, JEM-2100, Jeol).
3. Result and Discussion
3.1. Crystal Analysis
The crystalline phases present in the different samples were identified by X-ray diffraction (XRD) on a Bruker axis D8 diffractometer using Cu-Kα ( Å) radiation and secondary monochromator in the range 2θ from 20°C to 80°C. The crystallite size of magnesiwuestite present was investigated based on X-ray diffraction line broadening and calculated by using full-width at half-maximum (FWHM) of the XRD all peaks by making use of the Debye-Scherrer formula [32], then the average was extracted where is the crystallite size, λ is the wavelength of Cu-Kα radiation, θ is a diffraction angle, and β is full-width at half-maximum (FWHM) of the XRD all peaks. Figure 1 shows the XRD pattern of the synthesized nanopowder; the graphs show different values. It is clear cut that a spinel structure of magnesiwuestite which is described in (JCPDS 89–4924) is detected in all samples. Seven peaks centered at 2θ = 30.28°C, 35.66°C, 43.33°C, 53.77°C, 57.31°C, 62.93°C, and 74.44°C, which correspond to diffraction planes of (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0), and (5 3 3), respectively, are detected.
According to JCPDS 89–4924, the obtained phase has a cubic structure. The existence of a peak around the diffraction angle (2θ) equal to 35.66°C corresponding to (3 1 1) plane confirms the formation of spinel ferrites. A careful analysis of XRD patterns helps to determine their respective planes and face-centered cubic structure of these ferrites. Another method used to calculate particle size is Williamson-Hall equation [33]: where β is full-width at half-maximum (FWHM) of the XRD all peaks, λ is the wavelength of radiation (constant), is Scherrer constant, is the crystallite size, is the micro strain, and θ is the Bragg angle. Using a linear line to this plot, the slope gives the strain and the intercept gives the particle size ().
Based on the diffraction peak positioned at different degrees, the crystallite size is estimated by plotting crystallite size versus peak positions and extrapolation of the straight line by linearly fitting the points (Figure 2).
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Table 1 Shows crystallite size () (nm) with Williamson-Hall equation, XRD, and particle size analyzer (SZ-100). Particle size of is done by particle size analyzer (SZ-100). Small amount of sample is dissolved in ethanol then sonicated to form clear solution. The particle sizes which were estimated by particle size analyzer (SZ-100) are greater than the particle sizes which were estimated by XRD with Dybe-Scherrer’s formula.
3.2. Thermal Analysis
Figure 3 illustrates the thermogravimetric curve of the powder precursor after calcination at 300°C. Thermal analysis of samples was carried out in air atmosphere. It is well known that materials with a cubic crystal structure are prone to grow into a spherical shape [34–36] to minimize the surface tension. Thermogravimetric method measures the mass of a sample as the temperature increasing. This method is useful for determining sample purity of water, carbonate, and organic content and for studying decomposition reaction. TG curve shows consistent weight loss as it is illustrated in Figure 3. Among the samples which are placed in TG-DTA after calcination, less weight loss and impurity were observed. The net weight loss is illustrated in Table 2.
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3.3. Fourier Transform Infrared Spectroscopy Analysis
The FTIR spectra measurement of fresh Nanoparticles in the range of 4000–450 cm−1 are shown in Figure 4. A broad absorption spectrum is seen around 3430 cm−1 which is a characteristic stretching vibration of hydroxylate group (O–H). Peaks localized at 1560 cm−1 and 1411 cm−1 are assigned to asymmetrical and symmetrical stretching vibration of carboxylate (O–C–O), respectively.
IR spectrum of magnesiwuestite is found to exhibit two major bands in the range of 450–700 cm−1. The bands in the region 450 to 700 cm−1 are attributed to the fundamental vibrations of the ions of the crystal lattice. For the analysis of such spectra, it is necessary to consider the vibrational spectrum of periodic structures. The 1400 cm−1 (broad) characterizes the formation of surface sulfate species with S=O bond. The high frequency band is around 1561 cm−1. This band is a common feature to all the ferrites [37]. Absorption bands due to the iron-oxygen (Fe–O) are observed in the range 450–550 cm−1. The other peaks are due to the presence of magnesiwuestite. Same peaks are observed for all samples.
3.4. Morphology
Figures 5–7 show the detailed morphology and crystalline structure of the nanopowder which is calcined at 300°C for 2 h, then further investigated by SEM, TEM, and selected-area electron diffraction (SAED). TEM can be used to measure the particle size of individual particles, which is one of the most basic parameters in nanoparticle research. Transmission electron microscopy (TEM) shows the particle’s morphology, distribution, and size. The particle size estimated from TEM is smaller than the crystallite size estimated from XRD using Dybe-Scherer’s formula. The same is perceived from EDS graph for six samples and EDS also shows the percentage of element in the powders. It can be seen in Figure 6 that the particles are quite well dispersed and not much agglomerations are present. The percentage of element is shown in the EDS table. Comparison table for crystallite and particle size from XRD and TEM characterizations of present and previous papers are given in Table 3.
was observed to have high porous structure which was shown in Figure 5.
4. Conclusion
The nanostructured powder samples were synthesized by simple eco-friendly solution-combustion with economically and environmentally beneficial method. The average crystallite size of nanoparticles was estimated from the full-width-half maximum of the X-ray diffraction peaks and particle size analyzer and the results are in the same order. It was observed from XRD pattern that nanoparticles have cubic structure. Thermal analysis was done by Thermogravimetric-Differential thermal analyzer which shows weight loss percentage. FTIR conforms formation of the . The results reported in this study could be applied for establishing a simple method for the preparation of nanopowders. The synthesis process is economically and environmentally beneficial, inexpensive, and efficient method when compared to other solid state reactions. It was observed that has porous structure as it is shown in Figure 5 and has finer dispersion with spherical morphology of particles as illustrated in Figure 6.
Acknowledgments
The authors would like to thank the School of Engineering Sciences and Technology, Hyderabad University for providing XRD, EDS, SEM, Regional Sophisticated Instrumentation Centre for TEM, Mr. Masoud Ahmadipour, Department of Electrical and Computer Science, Semnan University, and Iran for cooperation and special thanks to K. V. Rao, Head of Center of Nano Science and Technology, Jawaharlal Nehru Technological University Hyderabad.