ISRN Materials Science

VolumeΒ 2012, Article IDΒ 213905, 6 pages

http://dx.doi.org/10.5402/2012/213905

## The Structural and Magnetic Properties of the Double Rearth Elements Nanoparticles

^{1}Physics Department, Hue University College of Education, Hue City, Vietnam^{2}Faculty of Physics, Hanoi University of Science, VNU, Hanoi City, Vietnam

Received 29 April 2012; Accepted 19 June 2012

Academic Editors: D.Β Adroja and P. K.Β Kahol

Copyright Β© 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.

#### Abstract

The double rearth elements () nanosized powders with orthorhombic structure were prepared by sol-gel method. The particle size of the powder is about 20βnm. The doping of the second rearth element in the A position of the compound ABO_{3} influenced the crystalline structure and magnetic property of the samples. The () dependence shows that the nanosized samples exhibit ferromagnetic behavior in the room temperature and the () 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 ABO_{3}, where A is a rare-earth element, B is 3*d* transition metal that remains prominent [1]. The perovskite AFeO_{3} (A = La, Y, Nd, β¦) and AFeO_{3} doped by transition metal elements, rare-earth elements, or alkaline earth elements show much interesting electric, magnetic phenomena. The ideal AFeO_{3} is isolator and antiferromagnetic. However, the real AFeO_{3} and doped AFeO_{3} are electrical conduction like semiconductor and ferromagnetic, and these materials have important applications in modern telecommunication and fabricating electrical accessories. Especially, nanosized AFeO_{3} and doped AFeO_{3} compounds can be used in fabricating ethanol sensors, methane sensors in mining galleries, and so forth. The orthoferrite LaFeO_{3} 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 LaFeO_{3} can be used as a strong catalyst in synthesizing H_{2} or in removing acid salicylic and axit sulfonic salicylic in sewage water, or in producing electrodes at high temperature (SOFC), and so forth [2β9].

The perovskite materials LaFeO_{3} 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,ββββ() 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}Β·6H_{2}O, Fe(NO_{3})_{3}Β·9H_{2}O, Nd(NO_{3})_{3}Β·6H_{2}O, and citric acid (CA) C_{6}H_{8}O_{7}Β·H_{2}O were used as starting materials. The same mole equivalent amounts of metal nitrates were weighed according to the nominal compositionββββ() and then dissolved in distilled water. The citric acid with the ratios (CA)/Ξ£(Metal ions) = (1.2β1.5) was then proportionally added to the metal nitrates solution. In the above ratio, (CA) and Ξ£ (metal ions) are concentration of (CA) and sum of concentration of metallic ions, respectively. The solution was concentrated by evaporation at 60β700Β°C with continuous stirring and pH controlled by NH_{3} solution. After six hours, we obtained organic gel in dark green. This gel mixture was dried at 150Β°C in 10 hours to obtain xerogel. The organic substances and nitrate were heated at 300Β°C for 4 hours to be decomposited. The nanocrystals of perovskiteββββ() were obtained by decomposition of the dried gel complex at 500Β°C for 10 hours in air.

The determination of structural characterization was performed by means of X-ray diffraction using D5005 diffractometer with Cu Kββradiation and varied in the range of 10β70Β° at a step size of 0.02Β°. 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 samplesββββ( to ) 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 LaFeO_{3} and belong to the Pnma space group. Figure 2 shows the dependence of the lattice parameter on the Nd-doping content, and the value of was decreased with increasing in Nd content. In addition, the diffraction peaks at angle 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 ofββββsamples (; 0.1; 0.15; 0.20; 0.30; 0.50). The lattice distortion may be caused by the difference of radius of Nd^{3+} (0.127βΓ
) and La^{3+} (0.136βΓ
). It leads to the decreasing of the lattice parameters with increasing of the Nd concentration.

Table 1 shows the crystalline sizesββββ(nm) of the samples calculated by Scherrer formula: whereββββis the average size of crystalline particle, assuming that particles are spherical, ,ββββis the wavelength of X-ray radiation,ββββis full width at half maximum of the diffracted peak, andββββis angle of diffraction.

Figure 3 shows the SEM images of the samples with ; 0.2; 0.3; 0.5 calcined at 500Β°C for 10βh in air. It can be estimated from Figure 3 that the average particle size is about 20βnm. Figure 4 shows that the () curves of the prepared nanosizedββββwere measured in the maximum magnetic field up to 1.5βT at 300βK. We can see that the samples were not magnetized to the saturated state. The () curves of samplesββββ() showed that the samples are ferromagnetic at room temperature.

Magnetic properties of nanosized samples are much influenced by grain size. With increasing grain sizeββ, the coercivity was increased following the law of () [12, 13]. The ferromagnetic materials are in nano-size of about single domain, and they have the superparamagnetic state with , , and [14]. Nevertheless, the ferromagnetic materials are of multidomains size, and the value of , , andββββwill be different from zero. Clearly, based on the value of , , andββ, 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 theββββsamples is similar with superparamagnetic state and the values of both the remanent magnetizations () and ββare approaching zero.

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: where is the contribution from the superparamagnetic () nanoparticles (single domains), and is the contribution of ferromagnetic () nanoparticles (multiple domains). where is saturation magnetization of ferromagnetic phase (), and ββisββrectangular coefficient of ferromagnetic hysteresis loop.

The noninteraction magnetization process of the superparamagnetic monodisperse nanoparticles is commonly defined by the expression where is particle magnetic moment andββββis the Langevin function, [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: where is magnetic moment of the particle, and is weighted terms of the Langevin functions [16].

It is suggested that the particles have spherical shape, then the distribution function of particle sizeββββis given by expression [17] whereββββis standard deviation and is the average particle size.

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

#### 4. Conclusion

We have investigated the effect of Nd dopant on the structural and magnetic properties ofββ. The compounds with orthorhombic single phase can be formed until . 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 nanosizedββββsystem has superparamagnetic behavior and can be fitted by the Langevin functions with size-dependent distribution funtion.

#### Acknowledgment

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

#### References

- M. A. Peña and J. L. G. Fierro, βChemical structures and performance of perovskite oxides,β
*Chemical Reviews*, vol. 101, no. 7, pp. 1981β2018, 2001. View at Publisher Β· View at Google Scholar Β· View at Scopus - S. J. Blundell and M. Katherine Blundell,
*Concepts in Thermal Physics*, 2006. - S. Nakayama, βLaFeO
_{3}perovskite-type oxide prepared by oxide-mixing, co-precipitation and complex synthesis methods,β*Journal of Materials Science*, vol. 36, no. 23, pp. 5643β5648, 2001. View at Publisher Β· View at Google Scholar Β· View at Scopus - O. M. Hemeda, M. M. Barakat, and D. M. Hemeda, βStructural, electrical and spectral studies on double rare-earth orthoferrites ${\text{La}}_{1-x}{\text{Nd}}_{\text{x}}{\text{FeO}}_{3}$,β
*Turkish Journal of Physics*, vol. 27, no. 6, pp. 537β549, 2003. View at Google Scholar Β· View at Scopus - K. Kobayashi, S. Yamaguchi, T. Tsunoda, and Y. Imai, βThermoelectric properties and defect structure of ${\text{La}}_{0.45}{\text{Nd}}_{\text{0}\text{.45}}{\text{Sr}}_{\text{0}\text{.1}}{\text{FeO}}_{3-\delta}$,β
*Solid State Ionics*, vol. 144, no. 1-2, pp. 123β132, 2001. View at Publisher Β· View at Google Scholar Β· View at Scopus - M. W. Son, J. B. Choi, H. J. Kim, K. S. Yoo, and S. D. Kim, βFabrication and characterization of ${\text{La}}_{1-x}{\text{Sr}}_{\text{x}}{\text{FeO}}_{3}$ formaldehyde gas sensors for monitoring air pollutions,β
*Journal of the Korean Physical Society*, vol. 54, no. 3, pp. 1072β1076, 2009. View at Publisher Β· View at Google Scholar Β· View at Scopus - G. Chern, W. K. Hsieh, M. F. Tai, and K. S. Hsung, βHigh dielectric permittivity and hole-doping effect in ${\text{La}}_{1-x}{\text{Sr}}_{\text{x}}{\text{FeO}}_{3}$,β
*Physical Review B*, vol. 58, no. 3, pp. 1252β1260, 1998. View at Google Scholar Β· View at Scopus - J. Yang, T. Aizawa, A. Yamamoto, and T. Ohta, βEffect of processing parameters on thermoelectric properties of p-type (Bi
_{2}Te_{3})_{0.25}(Sb_{2}Te_{3})_{0.75}prepared via BMA-HP method,β*Materials Chemistry and Physics*, vol. 70, no. 1, pp. 90β94, 2001. View at Publisher Β· View at Google Scholar Β· View at Scopus - K. Świerczek, J. Marzec, and J. Molenda, β${\text{La}}_{1-x}{\text{Sr}}_{x}{\text{CO}}_{1-y-z}{\text{Fe}}_{y}{\text{Ni}}_{z}{\text{O}}_{3}$ perovskites—possible new cathode materials for intermediate-temperature solid-oxide fuel cells,β
*Materials Science-Poland*, vol. 24, no. 1, 2006. View at Google Scholar - M. Sivakumar, A. Gedanken, W. Zhong et al., βSonochemical synthesis of nanocrystalline LaFeO
_{3},β*Journal of Materials Chemistry*, vol. 14, no. 4, pp. 764β769, 2004. View at Google Scholar Β· View at Scopus - M. W. Son, J. B. Choi, H. J. Kim, K. S. Yoo, and S. D. Kim, βFabrication and characterization of ${\text{La}}_{1-x}{\text{Sr}}_{x}{\text{FeO}}_{3}$ formaldehyde gas sensors for monitoring air pollutions,β
*Journal of the Korean Physical Society*, vol. 54, no. 3, pp. 1072β1076, 2009. View at Publisher Β· View at Google Scholar Β· View at Scopus - G. Herzer, βGrain size dependence of coercivity and permeability in nanocrystalline ferromagnets,β
*IEEE Transactions on Magnetics*, vol. 26, no. 5, pp. 1397β1402, 1990. View at Publisher Β· View at Google Scholar Β· View at Scopus - D. Xue, G. Chai, X. Li, and X. Fan, βEffects of grain size distribution on coercivity and permeability of ferromagnets,β
*Journal of Magnetism and Magnetic Materials*, vol. 320, no. 8, pp. 1541β1543, 2008. View at Publisher Β· View at Google Scholar Β· View at Scopus - J. P. Vejpravova D Niznnasky, J. Plocek, A. Hutlova, and J. -Lrehspringer, βSuperparamagnetism of co-ferrite nanoparticles,β in
*Proceeding of Contributed Paper, Part III (WDS '05)*, pp. 518β523, 2005. - G. F. Goya, T. S. Berquó, F. C. Fonseca, and M. P. Morales, βStatic and dynamic magnetic properties of spherical magnetite nanoparticles,β
*Journal of Applied Physics*, vol. 94, no. 5, pp. 3520β3528, 2003. View at Publisher Β· View at Google Scholar Β· View at Scopus - F. C. Fonseca, A. S. Ferlauto, F. Alvarez, G. F. Goya, and R. F. Jardim, βMorphological and magnetic properties of carbon-nickel nanocomposite thin films,β
*Journal of Applied Physics*, vol. 97, no. 4, Article ID 044313, 7 pages, 2005. View at Publisher Β· View at Google Scholar Β· View at Scopus - S.-J. Lee, J.-R. Jeong, S.-C. Shin, J.-C. Kim, and J.-D. Kim, βSynthesis and characterization of superparamagnetic maghemite nanoparticles prepared by coprecipitation technique,β
*Journal of Magnetism and Magnetic Materials*, vol. 282, no. 1–3, pp. 147β150, 2004. View at Publisher Β· View at Google Scholar Β· View at Scopus