Received 17 December 2017; received in revised form 25 February 2017; accepted 28 February 2017.
To cite this article: Sulaiman et al. (2017). Influence of calcination temperatures on structure and magnetic properties of calcium ferrite nanoparticles synthesized via sol-gel method. Jurnal Tribologi 12, pp.38-47.
Influence of calcination temperatures on structure and magnetic properties of
calcium ferrite nanoparticles synthesized via sol-gel method
N.H. Sulaimana, M.J. Ghazalia,*, B.Y. Majlisb, J. Yunasb, M. Razalia,c
a Department of Mechanical and Materials Engineering, Faculty of Engineering and
Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia.
b Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia,
43600 Bangi, Malaysia.
c Department of Management Office, Faculty of Dentistry, Universiti Kebangsaan
Malaysia, 43600 Bangi, Malaysia.
*Corresponding author: [email protected].
HIGHLIGHTS
CaFe2O4 nanoparticles were prepared by sol-gel method.
Highest magnetic properties of samples were calcined at 550°C.
An increase in temperature increases crystal size.
ABSTRACT
Calcium ferrite (CaFe2O4) nanoparticles using calcium nitrate and ferric nitrate as starting materials, and
supplemented with citric acid as chelating agent was carried out. This mixture was synthesized through a sol-gel method and then calcined at 550 °C, 650 °C, and 750 °C. The effects of calcination temperatures on the crystalline structure, the surface morphology and the magnetic properties of CaFe2O4 NPs were
observed. The orthorhombic structure of calcium ferrite NPS was analysed through an X-ray diffraction. The size of calcined samples at 550 °C, 650 °C, 750 °C were (13.59 nm), (18.9 nm), and (46.12 nm), respectively. Magnetic analysis was measured by using a vibrating sample magnetometer (VSM). The magnetic saturation (Ms) of samples calcined at 550 °C was found to possess the highest value of magnetic property; 80.33 emu/g.
Keywords:
| Magnetic nanoparticles | Ferrite | Sol-gel method |
1.0 INTRODUCTION
Nanoparticles (NPs) materials, multilayers, nanowires, and composite materials have been extensively investigated due to their interesting optical, electrical, chemical and magnetic properties (Dariel et al., 1987; Williams, 1986; Whitney, 1993; Piraux, 1994). With these properties and their excellent chemical and physical stability, these materials are different from their bulk counterparts, and thus are of great scientific and technological importance (Brumlik, 1992; Cai, 1989; Chakarvarti, 1991; Chakarvarti, 1993; Chakarvarti 1998). Magnetic nanomaterials have also been widely explored due to their numerous applications. (Robert, 2000). For instance, nanomagnetism (Nicola, 2003) is applied in mapping the scaling limits of magnetic information storage technology, other application includes antenna rod; drug targeting carriers. These applications become possible due to the size of magnetic nanoparticle that are comparable to those of target biological entities of interest such as viruses and proteins.
The outermost surfaces of the magnetic nanoparticles can also be easily modified or appropriately functionalized. Furthermore, magnetic nanoparticles can respond to external magnetic fields and exhibit superparamagnetism; by displaying differences between thermal and magnetic energies, which affect macroscopic magnetic behaviors (Pankhurst, 2003). Magnetic nanoparticles such as ferrites exhibit significant properties including magnetic saturation, coercivity, magnetisation and loss (Teoh et al., 2007). These particles change drastically as particle sizes decrease to the nanometric range (Billas, 1994; Kumar, 2008; George, 2006).
Iron oxide materials are widely utilised in biomedical techniques because of their biocompatibility. Magnetite (Fe3O4) and maghemite (γ-Fe2O3) are iron oxides that exist
in nature (Nguyen et al., 2012; Goldman, 1990). These substancesare mainly considered for biomedical applications, because two compounds satisfy the requirement of (1) chemical stability under physiological conditions, (2) low toxicity, and (3) sufficiently high magnetic moments of ferrite (Shubayev, 2009). Ferrite is generally expressed as MFe2O4 where, M is a divalent metal ion, such as Ni, Co, Cu, Mn, Mg, Zn, and Cd
(Haefeli et al., 1997). Among various ferrites, calcium ferrite has been extensively investigated as magnetic nanomaterials because it is commonly used in various applications, such as oxidation catalysts, high- temperature sensors, and gas absorbers (Ikenaga et al., 2005).
CaFe2O4 also exhibit relevant physical and characteristics, high thermal stability.
is commonly used in conventional synthesis and it is an efficient approach to prepare ultra-fine particles dispersed in different matrices. With this method, sample morphology, texture, structure, and chemical composition can be well controlled by careful monitoring and preparing parameters. This method was successfully used in this study to synthesize nanomaterials; especially magnetic nanoparticles between 10 to 100 nm (Dariel et al., 1987; Williams, 1986; Whitney, 1993; Piraux, 1994). This study is aimed to investigate the effects of calcination temperatures on the morphological, structural, and magnetic properties of calcium ferrite nanoparticles produced via sol-gel route.
2.0 MATERIALS AND METHODS
Calcium nitrate, ferric nitrate, citric acid, ethelenglycol, and ethanol were purchased from Accot. Lab. Supplies Sdn. Bhd. These chemicals were used in the sample synthesis. The reagents were of analytical grade with 90% purity.
2.1 Sample Synthesis
Calcium ferrite NPs were synthesized using a sol-gel method. Calcium nitrate Ca(NO3)2 and Fe(NO3)3, as starting materials, were mixed initially at a molar ratio of 1:1
M. The mixture was then dissolved in 100 mL of distilled water containing 2M of citric acid as the chelating agent. Next, 6mL of ethelenglycol was added to the mixture. The solution was continuously stirred for 3 h and heated on a magnetic stirrer at 80-90 °C. The colour of viscous gel changed from orange to brown color. The gel was subsequently dried in an oven at 100 °C over-night. The resulting particles were collected and subjected to different calcination temperatures at 550 °C, 650 °C, and 750 °C in a furnace for 2 h as shown in Table (1). The final product, namely; calcium ferrite nanoparticles were then ground to be in powder form.
Table 1: Synthesized of CaFe2O4 NPs and sample conditions
No. Sample name Synthesis method
Calcination temperature [0C]
Calcination Time
1 Sample 1 Sol-gel 550 2h
2 Sample 2 Sol-gel 650 2h
2.2 Characterization of CaFe2O4 NPs
The crystallite structure and size of the synthesized CaFe2O4 samples were
determined by an X-ray powder diffractometer ((XRD; model D8 Advance bruker axs) with Cu Kα radiation (1.5406 A) in a 2θ scan range of 20–80. The magnetic properties of the powders were examined by using a vibrating sample magnetometer ((VSM) Lakeshore 7404 Series model).
3.0 RESULTS AND DISCUSSION
3.1 XRD Analysis
XRD patterns of calcined CaFe2O4 NPs at 550 °C, 650 °C, and 750 °C, are shown
in Figure 1. The diffraction peaks were attributed to the orthorhombic structure of CaFe2O4 nanoparticles for Sample a, Sample b, and Sample c with crystal sizes of 13.59,
18.09 and 46.12nm shown in Figure 1. (a), (b), (c), respectively. In sample (b) can observed the sharper peak and the crystallinity appeared more than the sample (a), and (c) (Rajabi et. al, 2015; Najara et al., 2016; Mukhopadhyay et al., 2016). During heat treatment, the crystal sizes of the samples increases as the calcination temperature increases, which confirm the results reported by (Gharagozlou, 2011). This crystallite size evolution indicates a change in growth mechanism (Candeia et al., 2014).
The average crystallite size was calculated using Scherer’s equation expressed as follows (1):
D = Kλ/βcosθ (1)
Where K is Scherer’s constant (K=0.89), λ is the X-ray wavelength, β is the peak width at
Figure 1: XRD Pattern for CaFe2O4 nanoparticles calcined at (a) 550°C, (b) 650°C, (c),
750°C
A
Operations: Background 1.000,1.000 | Import
A - File: N.raw - Type: Locked Coupled - Start: 5.000 ° - End: 80.011 ° - Step: 0.025 ° - Step time: 19.2 s - Temp.: 25 °C (Room) - Time Started: 0 s - 2-Theta: 5.000 ° - Theta:
Lin (C oun ts) 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250
2-Theta - Scale
5 10 20 30 40 50 60 70 80
2Theta (degree) In tensity 2Theta (degree) In te ns ity A
Operations: Background 1.000,1.000 | Import
A - File: J.raw - Type: Locked Coupled - Start: 5.000 ° - End: 80.011 ° - Step: 0.025 ° - Step time: 19.2 s - Temp.: 25 °C (Room) - Time Started: 0 s - 2-Theta: 5.000 ° - Theta:
Lin (C ou nts ) 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
2-Theta - Scale
5 10 20 30 40 50 60 70 80
3.2 Magnetic Property Analysis
The influence of calcination temperatures from 550 °C, 650 °C, and 750 °C on magnetic properties of nanoparticle samples, were analysed using a VSM, as illustrated in Figures 2(a) - (c). Magnetic saturation (Ms) of sample 1 was found to be 80.33 emu/g and the magnetization constantly increased and became saturated at higher magnetic fields. In case of sample 2 and 3 the Ms values were 5.58, and 16.32 emu/g, respectively. The Ms
of sample 3 increased with increasing temperature. The changes in the magnetic properties of the samples can be attributed to crystallite sizes that are dependent on the calcination temperature (Gharagozlou, 2011). The energy of a magnetic particle in the external field is proportional to its particle sizes via the number of molecules in a single magnetic domain. Therefore, Ms values decrease as particle sizes decreased due to the
surface effects that resulted from the finite-size scaling of the nanocrystallites (Mohallem, 2003).
CONCLUSION
The crystallinity and structure of CaFe2O4 naoparticles were determined based on
their XRD patterns. The obtained CaFe2O4 NPs were found to be magnetic. The magnetic
saturation of calcined samples at 550 °C was 80.33 emu/g, which was the highest compared to other samples. These magnetic properties indicate that CaFe2O4 NPs can be
used in biomedical applications such as drug delivery.
ACKNOWLEDGMENT
The authors acknowledge the financial support from Universiti Kebangsaan
Malaysia for supporting this project under FRGS Grant No.
Figure 2: M-H curve (VSM) of the calcium ferrite nanoparticles calcined at (a) 550°C, (b) 650°C, (c) 750°C
-100 -80 -60 -40 -20 0 20 40 60 80 100
-15000 -10000 -5000 0 5000 10000 15000
M agn tiz ation (e m u /g) Field (G) -8 -6 -4 -2 0 2 4 6 8
-15000Magn -10000 -5000 0 5000 10000 15000
et ization (e m u /g ) Field (G) -20 -15 -10 -5 0 5 10 15 20
-15000 -10000 -5000 0 5000 10000 15000
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