International Scholarly Research Notices

International Scholarly Research Notices / 2012 / Article

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Volume 2012 |Article ID 213905 | https://doi.org/10.5402/2012/213905

Nguyen Thi Thuy, Bach Thanh Cong, Dang Le Minh, "The Structural and Magnetic Properties of the Double Rearth Elements La1−𝑥Nd𝑥FeO3 Nanoparticles", International Scholarly Research Notices, vol. 2012, Article ID 213905, 6 pages, 2012. https://doi.org/10.5402/2012/213905

The Structural and Magnetic Properties of the Double Rearth Elements La1−𝑥Nd𝑥FeO3 Nanoparticles

Academic Editor: D. Adroja
Received29 Apr 2012
Accepted19 Jun 2012
Published27 Aug 2012

Abstract

The double rearth elements La1−𝑥Nd𝑥FeO3 (0≤𝑥≤0.5) nanosized powders with orthorhombic structure were prepared by sol-gel method. The particle size of the La1−𝑥Nd𝑥FeO3 powder is about 20 nm. The doping of the second rearth element in the A position of the compound ABO3 influenced the crystalline structure and magnetic property of the samples. The 𝑀(𝐻) dependence shows that the nanosized La1−𝑥Nd𝑥FeO3 samples exhibit ferromagnetic behavior in the room temperature and the 𝑀(𝐻) curves are well fitted by Langevin functions.

1. Introduction

The vast majority of catalysts used in modern chemical industry are based on mixed metal oxides including perovskite oxides ABO3, where A is a rare-earth element, B is 3d transition metal that remains prominent [1]. The perovskite AFeO3 (A = La, Y, Nd, …) and AFeO3 doped by transition metal elements, rare-earth elements, or alkaline earth elements show much interesting electric, magnetic phenomena. The ideal AFeO3 is isolator and antiferromagnetic. However, the real AFeO3 and doped AFeO3 are electrical conduction like semiconductor and ferromagnetic, and these materials have important applications in modern telecommunication and fabricating electrical accessories. Especially, nanosized AFeO3 and doped AFeO3 compounds can be used in fabricating ethanol sensors, methane sensors in mining galleries, and so forth. The orthoferrite LaFeO3 has been researched in many laboratories in the world as a catalyst in synthesizing fuel gas using in aerospace industry, pure fuel and nanosized powder LaFeO3 can be used as a strong catalyst in synthesizing H2 or in removing acid salicylic and axit sulfonic salicylic in sewage water, or in producing electrodes at high temperature (SOFC), and so forth [2–9].

The perovskite materials LaFeO3 used in synthesizing gas sensors can be prepared by different chemical methods: coprecipitation method, sol-gel method, hydrothermal, sonochemical synthesis [10], and so forth. The sol-gel method is used broadly due to its advantage in which precursors can be admixed at atomic scale. The products prepared by sol-gel method are pure, homogeneous, small grain size, great surface area, and compatible with synthesizing gas sensors [11].

In this paper,  La1−𝑥Nd𝑥FeO3  (0≤𝑥≤0.5) in which the A position was occupied by double rearth elements was prepared by citrate-gel method. In addition to investigating the crystalline structure of the material, we also investigated the influence of the grain size on the magnetic property.

2. Experimental

In the sol-gel method, the analytical grade La(NO)3·6H2O, Fe(NO3)3·9H2O, Nd(NO3)3·6H2O, and citric acid (CA) C6H8O7·H2O were used as starting materials. The same mole equivalent amounts of metal nitrates were weighed according to the nominal composition  La1−𝑥Nd𝑥FeO3  (0≤𝑥≤0.5) and then dissolved in distilled water. The citric acid with the ratios (CA)/Σ(Metal ions) = (1.2–1.5) was then proportionally added to the metal nitrates solution. In the above ratio, (CA) and Σ (metal ions) are concentration of (CA) and sum of concentration of metallic ions, respectively. The solution was concentrated by evaporation at 60–700°C with continuous stirring and pH controlled by NH3 solution. After six hours, we obtained organic gel in dark green. This gel mixture was dried at 150°C in 10 hours to obtain xerogel. The organic substances and nitrate were heated at 300°C for 4 hours to be decomposited. The nanocrystals of perovskite  La1−𝑥Nd𝑥FeO3  (0≤𝑥≤0.5) were obtained by decomposition of the dried gel complex at 500°C for 10 hours in air.

The determination of structural characterization was performed by means of X-ray diffraction using D5005 diffractometer with Cu K𝛼  radiation and 2𝜃 varied in the range of 10–70° at a step size of 0.02°. The particle size and morphology of the calcined powders were examined by SEM (S-4800) (Hitachi, Japan). The magnetic parameters were determined by VSM-LakeShore 7404 (LakeShore, USA).

3. Result and Discussion

X-ray diffraction patterns of the samples  La1−𝑥Nd𝑥FeO3  (𝑥=0 to 𝑥=0.5) are shown in Figure 1. Based on the diffraction peaks, we can see that all samples are the single phase with standard orthorhombic structure of LaFeO3 and belong to the Pnma space group. Figure 2 shows the dependence of the lattice parameter ğ‘Ž on the Nd-doping content, and the value of ğ‘Ž was decreased with increasing in Nd content. In addition, the diffraction peaks at angle 2𝜃=32∘ tend to shift toward the larger angle. This shift demonstrates that the lattice parameters decrease with increasing of Nd-doping content. The top right side of Figure 2 shows the diffraction peaks at angle 2𝜃=32∘ of  La1−𝑥Nd𝑥FeO3  samples (𝑥=0.0; 0.1; 0.15; 0.20; 0.30; 0.50). The lattice distortion may be caused by the difference of radius of Nd3+ (0.127 Å) and La3+ (0.136 Å). It leads to the decreasing of the lattice parameters with increasing of the Nd concentration.

Table 1 shows the crystalline sizes  𝐷  (nm) of the samples calculated by Scherrer formula: 𝐷=𝑘𝜆,𝐵cos𝜃(1) where  𝐷  is the average size of crystalline particle, assuming that particles are spherical, 𝑘=0.94,  𝜆  is the wavelength of X-ray radiation,  𝐵  is full width at half maximum of the diffracted peak, and  𝜃  is angle of diffraction.


Samples 𝑥 = 0 . 0 0 𝑥 = 0 . 1 0 𝑥 = 0 . 1 5 𝑥 = 0 . 2 𝑥 = 0 . 3 𝑥 = 0 . 5

D (nm)20.316.919.616.421.319.3

Figure 3 shows the SEM images of the samples with 𝑥=0.1; 0.2; 0.3; 0.5 calcined at 500°C for 10 h in air. It can be estimated from Figure 3 that the average particle size is about 20 nm. Figure 4 shows that the (𝑀-𝐻) curves of the prepared nanosized  La1−𝑥Nd𝑥FeO3  were measured in the maximum magnetic field up to 1.5 T at 300 K. We can see that the samples were not magnetized to the saturated state. The (𝑀-𝐻) curves of samples  La1−𝑥Nd𝑥FeO3  (0≤𝑥≤0.5) showed that the samples are ferromagnetic at room temperature.

Magnetic properties of nanosized samples are much influenced by grain size. With increasing grain size  𝐷, the coercivity 𝐻𝐶 was increased following the law of (𝐻𝑐∼𝐷6) [12, 13]. The ferromagnetic materials are in nano-size of about single domain, and they have the superparamagnetic state with 𝐻𝑐=0, 𝑀𝑟=0, and 𝑆=(𝑀𝑟/𝑀𝑠)=0 [14]. Nevertheless, the ferromagnetic materials are of multidomains size, and the value of 𝐻𝑐, 𝑀𝑟, and  𝑆  will be different from zero. Clearly, based on the value of 𝐻𝑐, 𝑀𝑟, and  𝑆, we can discuss the limited size of single domain, the homogeneity of the nanosized particles and magnetic property existing in the ferromagnetic nanosized samples. From Table 2, we can see that the magnetic property of the  La1−𝑥Nd𝑥FeO3  samples is similar with superparamagnetic state and the values of both the remanent magnetizations (𝑀𝑟) and 𝑆(𝑀𝑟/𝑀𝑠)  are approaching zero.


𝑋 𝑀 𝑟 ⋅ 1 0 − 3 (emu/g)( 𝑀 𝑟 / 𝑀 𝑠 ) 𝐻 𝑐   (T)

𝑥 = 0 . 0 0.1010.0460.005
𝑥 = 0 . 1 0.1030.0530.001
𝑥 = 0 . 1 5 0.5090.0100.012
𝑥 = 0 . 2 0.2140.0740.001
𝑥 = 0 . 3 0.2270.0750.010
𝑥 = 0 . 5 0.2350.0800.011

In order to explain the magnetic property of the samples, it can be assumed that it can be contributed partly by superparamagnetic grains. It is suggested that samples were annealed for a long time that caused the inhomogeneity in the grain sizes and the total magnetization of the samples is considered as the sum of two components: 𝑀(𝐻)=𝑀sp(𝐻)+𝑀𝑓(𝐻),(2) where 𝑀sp(𝐻) is the contribution from the superparamagnetic (sp) nanoparticles (single domains), and 𝑀𝑓(𝐻) is the contribution of ferromagnetic (𝑓) nanoparticles (multiple domains). 𝑀𝑓(𝐻)=2𝑀𝑓𝑠𝜋tan−1𝐻±𝐻𝑐𝐻𝑐tan𝜋𝑆2,(3) where 𝑀𝑓𝑠 is saturation magnetization of ferromagnetic phase (𝑀𝑓𝑠=𝑀𝑟/0.866), and 𝑆  is  rectangular coefficient of ferromagnetic hysteresis loop.

The noninteraction magnetization process of the superparamagnetic monodisperse nanoparticles is commonly defined by the expression 𝑀(𝐻)=𝑀(∞)𝐿𝑚𝐻𝑘𝐵𝑇,(4) where 𝑚 is particle magnetic moment and  𝐿(𝑥)=coth(𝑥)−1/𝑥  is the Langevin function, 𝑥=𝑚𝐻/𝑘𝐵𝑇 [14, 15]. To take into account the size dispersion effects that are always presented in any real system, the magnetization of superparamagnetic particles, in this case, is better described by following expression: 𝑀sp(𝐻)=𝑀sp(∞)𝑗𝑓𝑚𝑗𝐿𝑚𝑗𝐻𝑘𝐵𝑇,(5) where 𝑚𝑗 is magnetic moment of the particle, and 𝑓(𝑚𝑗) is weighted terms of the Langevin functions [16].

It is suggested that the particles have spherical shape, then the distribution function of particle size  𝑓(𝐷)  is given by expression [17] 1𝑓(𝐷)=√⎛⎜⎜⎜⎝−2ğœ‹ğœŽğ·expln𝐷/𝐷22ğœŽ2⎞⎟⎟⎟⎠,(6) whereâ€‰â€‰ğœŽâ€‰â€‰is standard deviation and 𝐷 is the average particle size.

Because the magnetic moment of a nanoparticle depends on its shape and size, it is proposed that 𝑓(𝑚𝑗) has the same form like 𝑓(𝐷). Then, 𝑓(𝑚𝑗) can be derived from (6) knowing the average particle size  𝐷. Figure 5 shows the Langevin function fitting result for the magnetization curves of the nanosized  La1−𝑥Nd𝑥FeO3.

4. Conclusion

We have investigated the effect of Nd dopant on the structural and magnetic properties of  La1−𝑥Nd𝑥FeO3. The compounds with orthorhombic single phase can be formed until 𝑥=0.5. With the Nd doping, the crystalline particle size decreases and the lattice structure is strongly distorted. It leads to the variation of the magnetic property of the samples. The nanosized  La1−𝑥Nd𝑥FeO3  system has superparamagnetic behavior and can be fitted by the Langevin functions with size-dependent distribution funtion.

Acknowledgment

This work was supported by Vietnam’s National Foundation for Science and Technology Development (NAFOSTED) with the Project Code 103.03.69.09.

References

  1. M. A. Peña and J. L. G. Fierro, “Chemical structures and performance of perovskite oxides,” Chemical Reviews, vol. 101, no. 7, pp. 1981–2018, 2001. View at: Publisher Site | Google Scholar
  2. S. J. Blundell and M. Katherine Blundell, Concepts in Thermal Physics, 2006.
  3. S. Nakayama, “LaFeO3 perovskite-type oxide prepared by oxide-mixing, co-precipitation and complex synthesis methods,” Journal of Materials Science, vol. 36, no. 23, pp. 5643–5648, 2001. View at: Publisher Site | Google Scholar
  4. O. M. Hemeda, M. M. Barakat, and D. M. Hemeda, “Structural, electrical and spectral studies on double rare-earth orthoferrites La1xNdxFeO3,” Turkish Journal of Physics, vol. 27, no. 6, pp. 537–549, 2003. View at: Google Scholar
  5. K. Kobayashi, S. Yamaguchi, T. Tsunoda, and Y. Imai, “Thermoelectric properties and defect structure of La0.45Nd0.45Sr0.1FeO3δ,” Solid State Ionics, vol. 144, no. 1-2, pp. 123–132, 2001. View at: Publisher Site | Google Scholar
  6. M. W. Son, J. B. Choi, H. J. Kim, K. S. Yoo, and S. D. Kim, “Fabrication and characterization of La1xSrxFeO3 formaldehyde gas sensors for monitoring air pollutions,” Journal of the Korean Physical Society, vol. 54, no. 3, pp. 1072–1076, 2009. View at: Publisher Site | Google Scholar
  7. G. Chern, W. K. Hsieh, M. F. Tai, and K. S. Hsung, “High dielectric permittivity and hole-doping effect in La1xSrxFeO3,” Physical Review B, vol. 58, no. 3, pp. 1252–1260, 1998. View at: Google Scholar
  8. J. Yang, T. Aizawa, A. Yamamoto, and T. Ohta, “Effect of processing parameters on thermoelectric properties of p-type (Bi2Te3)0.25(Sb2Te3)0.75 prepared via BMA-HP method,” Materials Chemistry and Physics, vol. 70, no. 1, pp. 90–94, 2001. View at: Publisher Site | Google Scholar
  9. K. Świerczek, J. Marzec, and J. Molenda, “La1xSrxCO1yzFeyNizO3 perovskites—possible new cathode materials for intermediate-temperature solid-oxide fuel cells,” Materials Science-Poland, vol. 24, no. 1, 2006. View at: Google Scholar
  10. M. Sivakumar, A. Gedanken, W. Zhong et al., “Sonochemical synthesis of nanocrystalline LaFeO3,” Journal of Materials Chemistry, vol. 14, no. 4, pp. 764–769, 2004. View at: Google Scholar
  11. M. W. Son, J. B. Choi, H. J. Kim, K. S. Yoo, and S. D. Kim, “Fabrication and characterization of La1xSrxFeO3 formaldehyde gas sensors for monitoring air pollutions,” Journal of the Korean Physical Society, vol. 54, no. 3, pp. 1072–1076, 2009. View at: Publisher Site | Google Scholar
  12. G. Herzer, “Grain size dependence of coercivity and permeability in nanocrystalline ferromagnets,” IEEE Transactions on Magnetics, vol. 26, no. 5, pp. 1397–1402, 1990. View at: Publisher Site | Google Scholar
  13. D. Xue, G. Chai, X. Li, and X. Fan, “Effects of grain size distribution on coercivity and permeability of ferromagnets,” Journal of Magnetism and Magnetic Materials, vol. 320, no. 8, pp. 1541–1543, 2008. View at: Publisher Site | Google Scholar
  14. J. P. Vejpravova D Niznnasky, J. Plocek, A. Hutlova, and J. -Lrehspringer, “Superparamagnetism of co-ferrite nanoparticles,” in Proceeding of Contributed Paper, Part III (WDS '05), pp. 518–523, 2005. View at: Google Scholar
  15. G. F. Goya, T. S. Berquó, F. C. Fonseca, and M. P. Morales, “Static and dynamic magnetic properties of spherical magnetite nanoparticles,” Journal of Applied Physics, vol. 94, no. 5, pp. 3520–3528, 2003. View at: Publisher Site | Google Scholar
  16. F. C. Fonseca, A. S. Ferlauto, F. Alvarez, G. F. Goya, and R. F. Jardim, “Morphological and magnetic properties of carbon-nickel nanocomposite thin films,” Journal of Applied Physics, vol. 97, no. 4, Article ID 044313, 7 pages, 2005. View at: Publisher Site | Google Scholar
  17. S.-J. Lee, J.-R. Jeong, S.-C. Shin, J.-C. Kim, and J.-D. Kim, “Synthesis and characterization of superparamagnetic maghemite nanoparticles prepared by coprecipitation technique,” Journal of Magnetism and Magnetic Materials, vol. 282, no. 1–3, pp. 147–150, 2004. View at: Publisher Site | Google Scholar

Copyright © 2012 Nguyen Thi Thuy et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


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