Synthesis and characterization of La1-xSr xMnO3±δ powders obtained by the polymeric precursor route

Abstract

Polycrystalline strontium-doped lanthanum manganite (LSM) powders with 0.15, 0.22, and 0.30 mol % Sr were synthesized by the polymeric precursor route using a molar ratio of 3:1 citric acid and metal cations. The powders were characterized by Fourier transform infrared spectroscopy, thermal analysis, high-temperature X-ray diffraction to determine the crystalline perovskite phase and crystallite sizes, scanning electron microscopy for the morphological analysis, nitrogen adsorption to determine the specific surface area, and laser scattering to evaluate the particle size distribution. The LSM perovskite-type oxides containing intermediate 0.22 mol % Sr were found to exhibit a tendency to decrease in crystallite size and increase in specific surface area and, when calcined at 700-900 ºC exhibited a pure phase of perovskite, had a crystallite size of about 17-20 nm and a specific surface area for 900 ºC of 34.3 m².g-1.

perovskite; polymeric precursor; SOFC

Synthesis and characterization of La_1-xSr_xMnO_{3± δ} powders obtained by the polymeric precursor route

Adriano Alves Rabelo^I,*; Marfran Cardoso de Macedo^II; Dulce Maria de Araújo Melo^II; Carlos Alberto Paskocimas^II; Antonio Eduardo Martinelli^II; Rubens Maribondo do Nascimento^II

^IFaculty of Materials Engineering, Federal University of Pará, Folha 17, Quadra 04, Lote Especial, CEP 68505-080, Marabá, PA, Brazil

^IIFederal University of Rio Grande do Norte, P.O. Box 1662, CEP 59072-970, Natal, RN, Brazil

ABSTRACT

Polycrystalline strontium-doped lanthanum manganite (LSM) powders with 0.15, 0.22, and 0.30 mol % Sr were synthesized by the polymeric precursor route using a molar ratio of 3:1 citric acid and metal cations. The powders were characterized by Fourier transform infrared spectroscopy, thermal analysis, high-temperature X-ray diffraction to determine the crystalline perovskite phase and crystallite sizes, scanning electron microscopy for the morphological analysis, nitrogen adsorption to determine the specific surface area, and laser scattering to evaluate the particle size distribution. The LSM perovskite-type oxides containing intermediate 0.22 mol % Sr were found to exhibit a tendency to decrease in crystallite size and increase in specific surface area and, when calcined at 700–900 ºC exhibited a pure phase of perovskite, had a crystallite size of about 17–20 nm and a specific surface area for 900 ºC of 34.3 m².g^-1.

Keywords: perovskite, polymeric precursor, SOFC

1. Introduction

Strontium-doped lanthanum manganite perovskite oxides (La_1-xSr_xMnO_3±δ, LSM) have been widely studied in recent years due to their interesting applications in solid oxide fuel cells (SOFC), oxi-reduction catalysts (automotive catalysis), sensors and memories^1-6. These latter applications are due to the outstanding magnetotransport properties of these oxides^7-9. In the LSM perovskite structure, Mn³⁺ or Mn⁴⁺ ions are the network formers, occupying the octahedral B sites and are associated to the oxygen reduction, whilst the ion La³⁺, partially replaced in the twelve-fold oxygen coordinated sites A, are related to the property of electronic conduction. The intrinsic properties of these materials can be affected by small network distortions (stoichiometry), by the crystallite size, specific surface area and working temperature^10,11. The LSM oxides as the cathode have proved to be very poor oxide ion conductors, but their electronic conductivity is high enough to make them attractive SOFC cathode material, which is particularly interesting when the strontium content is 0.1 to 0.3. The La_0.8Sr_0.2Mn0₃ gives a good combination of electronic conductivity and expansion coefficient matching, and is now available commercially for SOFC applications. Higher conductivity can be obtained at higher dopant levels, but the expansion coefficient then becomes too high^12-20.

There are several routes to synthesize perovskite structured materials. These routes include the polymeric precursor route or the Pechini method^21-23, which stands out for its enhanced stoichiometric control, allowing for doping in a ppm order of magnitude, with good composition homogeneity, depending on the system's composition. This method also allows one to obtain relatively high specific surface area powders when compared with other traditional solid state reaction methods^24-26.

The key point of this route is to obtain a polymeric precursor resin, a branched chain polymer, in which the cations are distributed randomly. The method involves the complexation reactions of citric acid with the metal ions and polyesterification with ethylene glycol. The progressive heating in air up to around 95 ºC promotes the condensation reaction with the formation of water molecules. At this temperature the polyesterification reaction takes place and excess water is eliminated, resulting in a polymeric resin from which the powder is obtained. In the present work, the polymeric precursor method was used to prepare strontium-doped lanthanum manganite, La_1-xSr_xMnO₃, where x = 0.15, 0.22 and 0.30, with the purpose of obtaining powders with high specific surface areas.

2. Experimental

2.1. Chemical synthesis

The La_1-xSr_xMnO₃ samples were synthesized by the polymeric precursor route, based in Pechini method, which has been used to synthesize polycation oxides. The starting materials were lanthanum nitrate (>99.0%, Vetec), strontium nitrate (>99.0%, Vetec), manganese nitrate (>97.0%, Vetec), citric acid (>99.0%, Chromato), ethylene glycol (>99.5%, Vetec) and distilled water. The concentrations of nitrate solutions were previously determined by gravimetry.

Manganese citrate solution was prepared from Mn(NO₃)₂.4H₂O and citric acid, using the citric acid/metal cation molar ratio of 3:1, under stirring at 70 ºC for 2 hours. The network modifier and the dopant were later added. The resulting solution was subjected to mechanical stirring and heating at 90 ºC. Afterwards ethylene glycol was added at a 60:40 citric acid/ethylene glycol mass ratio.

This solution was kept at mechanical agitation and heating at 95 ºC for 2 hours to form the polymeric resin, which was later heat-treated at 300 ºC for 2 hours, yielding a fragile and porous solid. Such material was initially disaggregated in a mortar and later ground for 2 hours in a planetary mill (Pulverisette 2000, Fritsch). Subsequently, the powders were calcined at 450, 700 and 950 ºC for 4 hours at a heating rate of 5 ºC/min. The heat-treated powders were again dried and disaggregated in the planetary mill down to a mesh size of less than 200 in a Tyler sieve.

2.2. Characterization methods

The heat-treated powders were subjected to Fourier transform infrared spectroscopy analyses (FTIR, Perkin-Elmer/16PC), in a range of 500 to 4000 cm^-1. The TG/DTG (Shimadzu/TGA-50H) curves for the samples synthesized and pre-calcined powders at 300 ºC for 2 hours were obtained in air, at a heating rate of 10 ºC/min, up to 1000 ºC. The average crystallite sizes and the constituent phases were determined by high-temperature X-ray diffraction, using the Cu-K_α radiation at a step of 0.02º/s with 2θ = 10 to 60º (Shimadzu/XRD-6000 diffractometer). Scherrer's equation was used to calculate the average crystallite size (t), adopting an average of the five most intense XRD peaks, as follows:

where κ is a constant equal to 0.9; λ is the X-ray wavelength, and β is the full width at half-maximum of the X-ray reflection.

The average particle sizes (d₅₀) of powders were obtained by laser scattering (CILAS/1064) in distilled water with an ultrasonic treatment for 120 seconds. The wide of distribution particle sizes was analyzed using the values of the relation d₉₀/d₅₀.

The specific surface area (S_BET) values were determined by the BET method (Nova 2000, Quanta-Chrome) in five points of linear region in the adsorption isotherm. The average pore size (D_p) was calculated by the BJH method²⁷. The equivalent spherical diameter, d_BET, was calculated by Equation 2, in which d_BET is the equivalent spherical diameter, S_BET is the specific surface area (m².g^-1) and ρ is the theoretical phase density. The adopted density values were 6.6 g.cm^-3 for La_0.85Sr_0.15MnO₃, 6.5 g.cm^-3 for La₀₇₈Sr_0.22MnO₃ and 6.4 g.cm^-3 for La_0.70Sr_0.30MnO₃.

The morphology of the powders was analyzed by scanning electron microscopy (SEM, Philips/XL-30 FEG).

Apparent density (% of theoretical density) measurements were taken by the Archimedes method, using samples pressed at 37 MPa and sintered at 1350 ºC for 4 hours in air (Jung/2314 furnace).

3. Results and Discussion

Figure 1 shows the infrared spectra of the synthesized La_1-xSr_xMnO₃ precursor powders (x = 0.15, 0.22 and 0.30) heat-treated at 450 ºC for 4 hours. The broad band in the region of 3500 cm^-1 is related to the O-H group, which is associated to citrates and/or water molecules coordinated with the metal ions. The band positioned between 3200 and 2500 cm^-1 was referred to the intramolecular hydrogen with C=O bond. A band observed at 1750 cm^-1 is related to the C=O bond of acid with axial deformation. The bands observed between 1546 and 1362 cm^-1 are ascribed to the stretching vibrations of the carboxilate (COO^-) groups, or C-H bonds. At 1000 cm^-1, the band observed was referred to C-O bond from esters²⁸. It was observed for the strontium doping sample with x = 0.15 a strong band related to metal–oxygen bond at 600 cm^-1, indicating the formation of the respective oxide.

For the synthesized precursor powders heat-treated at 700 ºC for 4 hours (Figure 2), only the strontium-doped sample with x = 0.22 showed the band related to O-H bond, in the region of 3500 cm^-1. This same composition showed a band related to the metal–oxygen bond at 600 cm^-1, indicating the formation of the respective oxide. The remaining absorption bands were similar to the ones described for the samples calcined at 450 ºC.

When the precursor powder was heat-treated at 950 ºC for 4 hours, the spectrum did not show any characteristic band of organic compounds in a range from 4000 to 500 cm^-1, as depicted in Figure 3. Accordingly, the band observed at 600 cm^-1, which was ascribed to the metal–oxygen bond, indicates the formation of the corresponding oxides.

The thermogravimetric and differential thermogravimetric (TG/DTG) analyses of La_0.85Sr_0.15MnO₃ precursor powder are shown in Figure 4. The first stage of thermal decomposition from 30 to 200 ºC was related to the elimination of water, derived from the esterification reaction, and from ethylene glycol excess. The second stage, from 300 to 570 ºC, corresponded to the breakage of the polymeric chain formed by the polyesterification, whereas the third thermal decomposition stage, from 600 to 820 ºC, was ascribed to decomposition of the remaining organic compounds. For higher temperatures, mass losses associated to organic compounds were no longer detected. The overall mass loss was approximately 12%. For temperatures as higher as 830 ºC the material became stable in terms of mass loss, with only the formation of the oxide.

The thermal decomposition process of La_0.78Sr_0.22MnO₃ took place in five steps, according to Figure 5. The overall mass loss was 11%, which occurred between 30 and 750 ºC. The first thermal decomposition stage, from 30 to 200 ºC, was attributed to the exit of water molecules associated to the organic matter. In the second and third steps the polymer decomposition took place, characterized by an abrupt mass loss at approximately 500 ºC, whereas in the subsequent steps from 600 to 760 ºC, the mass loss was attributed to the decomposition of carbonaceous materials. After these events, only formation of the respective oxide occurred at a temperature of about 880 ºC.

The TG/DTG curves of the sample La_0.70Sr_0.30MnO₃ are depicted in Figure 6 and presented a thermal behavior similar to the ones of the samples La_0.85Sr_0.15MnO₃ and La_0.78Sr_0.22MnO₃. The overall mass loss was 14%, most of it associated to decomposition of the organic matter. The first stage from 30 to 200 ºC referred to the exit of water, either from the polyesterification reaction or coordination water. The second stage, from 300 to 570 ºC, corresponded to the breakage of the polymer chain formed by the polyesterification reaction and the third and the fourth stages, from 600 to 820 ºC, referred to decomposition of organic compounds. Sample mass increased at temperatures exceeding approximately 850 ºC owing to oxidation of the material. With regard to the higher mass loss of La_0.70Sr_0.30MnO₃ powder precursor, it is probably attributable to the higher content of strontium, which was added in the form of nitrate.

By the thermal analyses of the three compositions synthesized in this work, it was possible to observe a small mass gain from about 820 ºC, which was associated to oxidation of lanthanum manganite and strontium manganite in the perovskite structure, due to the variation of oxidation state of manganese cation. For the case of 22% strontium doping, in which the mass loss is finished at a temperature lower than the case of the remaining doping levels, this oxidation also took place.

The evolution of the crystalline phase with increasing temperature at the three levels of doping, which was observed by high-temperature XRD, is illustrated in Figures 7, 8 and 9. The XRD patterns indicated that the formation of the perovskite structure of La_1-xSr_xMnO₃ was completed at a temperature of 600 ºC. The occurrence of secondary phases was attributed to oxidation of Mn cations on the surface. A decomposition of manganite phases above 900 ºC is a possible immiscibility gap of the perovskite, lanthanum manganite and strontium manganite phases at high temperatures, which was more evident with larger amounts of strontium.

Analyzing the average crystallite sizes obtained at different temperatures (Table 1), it can be noticed that the LSM perovskite-type oxides containing the intermediate 22% strontium showed a tendency to decrease the crystalline size and increase the specific surface area (Table 2). This result was not in agreement with that verified for La_xSr_1-xFeO₃^[29] and La_1-xSr_xCoO₃ perovskites³⁰ in which a size increase, associated to the increase of doping level took place. This can be attributed to the change of orthorhombic phase, for 10% of strontium, to rhombohedral phase for 22% or more of strontium. Substitution of La with lower valence cations (such as Sr²⁺ and Ca²⁺) or A-site deficiency increases the concentration of Mn⁴⁺ in the LaMn0₃ lattice. This eventually decreases the orthorhombic to rhombohedral (> 600 ºC) transformation temperature.

Table 2

The XRD patterns of the specimens calcined demonstrated the existence of a structure of which was identified as perovskite-type in all the compositions. The lattice parameter of each sample was obtained considering JCPDS information card (Nº 35-1353) existing of undoped lanthanum manganites material, which it allowed to find the lattice parameters at 800 ºC. The identification was of visual and comparative character. The lattice parameter decreases with increasing Sr²⁺ concentration from 5.5318 to 5.4960 Å when the doping level changes from 0.15 to 0.22 mol %, and then increases again with addition of 0.30 mol % to 5.5391 Å. Since the ionic radii of Sr²⁺ and La³⁺ are 1.44 and 1.36 Å respectively³¹, there is a substitutional solid solution as the La³⁺ was replaced by the larger Sr²⁺ cation, which presents the largest ray, limiting the substitution of the La³⁺ by the Sr²⁺ in the LaMnO₃ perovskite-type structure. When two moles of SrO dissolves into LaMnO₃, there form a negative charged divalent substituted strontium site and a positive charged divalent oxygen vacancy. And it is implied by the lattice parameter that the perovskite-type changes from orthorhombic distortion to rhombohedral when the doping level was greater than 0.22 mol %. The nonlinear variation of the lattice parameter is attributed to this phase change.

The average crystallite size was in the range of 20 nm. The average particle size (d₅₀) for the powders heat-treated at 450, 700 and 950 ºC for 4 hours revealed the presence of agglomerates, since approximately 100-fold higher values were obtained, as well as the width of the distribution (D₉₀/D₅₀), which was very wide for all the powders. The wide particle size distribution, allied to the presence of agglomerates, contributed to the formation of density gradients, thus generating internal stresses in the pressed bodies.

The average pore diameter indicated that the powders were in the inferior region of porosity, classified as mesoporous (200-500 nm). The apparent density after sintering at 1350 ºC for 4 hours was in the range form approximately 70 to 80% of the theoretical density in these conditions. These physical characteristics indicate possible applications such as in solid oxide fuel cells or in catalysis.

It has been reported a value of 20.2 m².g^-1 for the specific surface area of La_1-xMn_xMnO₃^[8], synthesized by the polymeric precursor method, when heat-treated at 700 ºC for 6 hours. When the synthesis was carried out by the co-precipitation method, the specific surface area value obtained was only 8.3 m².g^-1. Accordingly²⁶, it was reported a comparison between the different specific surface area values for strontium-doped lanthanum manganite obtained from different sources, carbonates, oxalates and citrates, in which the highest specific surface area value, 30 m².g^-1, was obtained for the synthesis starting from citrates. Some disparity in values is due to a fluctuation in the texture of the particles, showing morphologies with different degrees of agglomeration, as can be observed for the sample with 30% strontium treated at 700 ºC.

The morphology of La_0.85Sr_0.15MnO₃ and La_0.70Sr_0.30MnO₃ powders heat-treated at 450 and 950 ºC is illustrated in the SEM micrographs of Figures 10 to ¹³. These micrographs confirmed the powder agglomeration. Such agglomerates formation can be reduced, adopting lower heat treatment temperatures and also by means of more efficient milling and de-agglomeration processes after the heat treatment, which should improve the size homogeneity of the sintered samples.

4. Conclusions

The synthesis by the polymeric precursor method proved to be adequate for the production of La_1-xSr_xMnO₃ powder oxides, with a formed perovskite structure starting from 600 ºC. These powders show a low crystallite sizes and also relatively high specific surface areas. The nanocrystallite sizes of the powders ranged between 17 to 35 nm. It can be noted that the average crystallite sizes obtained for LSM perovskite-type oxides containing the intermediate 0.22% Sr showed a tendency for decreasing crystallite size and increasing specific surface area.

Acknowledgements

The authors gratefully acknowledge the financial support of the Brazilian Research Funding Institutions ANP (2001.6956-0), FAPERN (300266/2004-9) and FAPESPA (025/2008).

Received: November 26, 2010

Revised: February 25, 2011

• 1. Capon F, Horwat D, Pierson JF, Chapusot V and Billard A. Strontium-doped lanthanum manganite coatings crystallised after air annealing of amorphous co-sputtered films. Materials Chemistry and Physics 2009; 116:219-222.
• 2. Smith JR, Chen A, Gostovic D, Hickey D, Kundinger D, Duncan KL et al. Evaluation of the relationship between cathode microstructure and electrochemical behavior for SOFCs. Solid State Ionics 2009; 180:90-98.
• 3. Chen X, Zhen Y, Li J and Jiang SP. Chromium deposition and poisoning in dry and humidified air at (La_0.8Sr_0.2)_0.9MnO_3+δ cathodes of solid oxide fuel cells. International Journal of Hydrogen Energy 2010; 35:2477-2485.
• 4. Yang J, Muroyama H, Matsui T and Eguchi K. A comparative study on polarization behavior of (La,Sr)MnO₃ and (La,Sr)CoO₃ cathodes for solid oxide fuel cells. International Journal of Hydrogen Energy 2010; 35:10505-10512.
• 5. Genchu T., Yun Y., Wei C. and Yunzhen C. The electrical resistivity and thermal infrared properties of La_1xSr_xMnO₃ compounds. Journal of Alloys and Compounds 2008; 461:486-489.
• 6. Tang G, Yu Y, Chen W and Cao Y. The electrical resistivity and thermal infrared properties of La_1xSr_xMnO₃ compounds. Journal of Alloys and Compounds 2008; 461:486-489.
• 7. Budak S, Özdemir M and Aktas B. Temperature dependence of magnetic properties of La_0.67Sr_0.33MnO₃ compound by ferromagnetic resonance technique. Physica B. 2003; 339:45-50.
• 8. Yang W-D, Huang S-H and Chang Y-H. Microstructure, magnetoresistance and electrical properties of La_0.67Sr_0.33MnO₃ films synthesized from citric acid and ethylene glycol. Thin Solid Films 2005; 478:42-48.
• 9. Sakthipandi K, Rajendran V, Jayakumar T, Raj B and Kulandivelu P. Synthesis and on-line ultrasonic characterisation of bulk and nanocrystalline La_0.68Sr_0.32MnO₃ perovskite manganite. Journal of Alloys and Compounds 2011; 509:3457-3467.
• 10. Fleig J. Solid oxide fuel cell cathodes: polarization mechanisms and modeling of the electrochemical performance. Annual Review of Materials Research 2003; 33:361-382.
• 11. Matsuzaki Y and Yasuda I. Electrochemical properties of reduced-temperature SOFCs with mixed ionicelectronic conductors in electrodes and/or interlayers. Solid State Ionics 2002; 152-153:463468.
• 12. Berenov AV, MacManus-Driscoll JL and Kilner JA. Oxygen tracer diffusion in undoped lanthanum manganite. Solid State Ionics 1999; 122:41-49.
• 13. Gupta RK, Kim EY, Kim YH and Whang CM. Effect of strontium ion doping on structural, thermal, morphological and electrical properties of a co-doped lanthanum manganite system. Journal of Alloys and Compounds. 2010; 490:56-61.
• 14. Souza S, Visco SJ, De Jonghe LC. Thin-film solid oxide fuel cell with high performance at low temperature. Solid State Ionics 1997; 98:57-61.
• 15. Sahu AK, Ghosh A, Suri AK. Characterization of porous lanthanum strontium manganite (LSM) and development of yttria stabilized zirconia (YSZ) coating. Ceramics International 2009; 35:2493-2497.
• 16. Hamedani HA, Dahmen K-H, Li D, Peydaye-Saheli H, Garmestani H and Khaleel M. Fabrication of gradient porous LSM cathode by optimizing deposition parameters in ultrasonic spray pyrolysis. Materials Science and Engineering B 2008; 153:1-9.
• 17. Chen K, Lü Z, Chen X, Ai N, Huang X, Du X et al. Development of LSM-based cathodes for solid oxide fuel cells based on YSZ films. Journal of Power Sources 2007; 172:742-748.
• 18. Silva WJ, Melo DMA, Soares SFCX, Pimentel PM, Nascimento RM, Martinelli AE. et al. Síntese de manganita de lantânio com substituição parcial do La por Sr pelo método citrato. Revista Matéria 2007; 12(1):65-71.
• 19. Bidrawn F, Kim G, Aramrueang N, Vohs JM, Gorte RJ. Dopants to enhance SOFC cathodes based on Sr-doped LaFeO₃ and LaMnO₃ Journal of Power Sources 2010; 195:720-728.
• 20. Giraud S and Canel J. Young's modulus of some SOFCs materials as a function of temperature. Journal of the European Ceramic Society 2008; 28:77-83.
• 21. Pechini M. Method of preparing lead and alkaline earth titanates and niobates and coating methods using the same to form a capacitor. 1967. U. S. Pat. Number 3.330.697.
• 22. Yang W-D, Chang Y-H and Huang S-H. Influence of molar ratio of citric acid to metal ions on preparation of La_0.67Sr_0.33MnO₃ materials via polymerizable complex process. Journal of the European Ceramic Society 2005; 25:3611-3618.
• 23. Conceição L, Silva CRB, Ribeiro NFP and Souza MMVM. Influence of the synthesis method on the porosity, microstructure and electrical properties of La_0.7Sr_0.3MnO₃ cathode materials. Materials Characterization 2009; 60:1417-1423.
• 24. Kakihana M, Arima M, Yoshimura M, Ikeda N and Sugitani Y. Synthesis of high surface area LaMnO_3+δ by a polymerizable complex method. Journal of Alloys and Compounds. 1999; 283(1-2):102-105.
• 25. Berger D, Fruth V, Jitaru I and Schoonman J. Synthesis and characterisation of La_1xSr_xCoO₃ with large surface area. Materials Letters 2004; 58(19):2418-2422.
• 26. Fritsch SG, Alphonse P, Calmet C, Coradin H, Pailhades P and Rousset A. Du choix du précurseur pour la synthèse de poudres d'oxydes La_1xSr_xMnO₃ Comptes Rendus Chimie 2005; 8(2);219-227.
• 27. Barret EP, Joyner LG and Halenda PH. The determination of pore volume and area distribution in porous solids. I: computation from nitrogen isotherms. Journal of the American Chemical Society 1951; 73:373-380.
• 28. Nakamoto K. Infrared and raman spectra of inorganic and coordination compounds 3^rd ed. New York: John Wiley & Sons, 1978.
• 29. Liou Y-C. Effect of strontium content on microstructure in (La_xSr_1x)FeO₃ ceramics. Ceramics International 2004; 30(5):667-669.
• 30. Berger D, Fruth V, Jitaru I and Schoonman J. Synthesis and characterisation of La_1xSr_xCoO₃ with large surface area. Materials Letters 2004; 58(19):2418-2422.
• 31. Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chaleogenides. Acta Crystallographica 1976; A32:751-767.

Publication Dates

• Publication in this collection
  01 Apr 2011
• Date of issue
  Mar 2011

History

• Accepted
  25 Feb 2011
• Received
  26 Nov 2010