Materials Letters 58 (2004) 569 572 www.elsevier.

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Synthesis and characterization of spinel pigment CaFe2O4 obtained by the polymeric precursor method
R.A. Candeia a,*, M.I.B. Bernardi b, E. Longo c, I.M.G. Santos a, A.G. Souza a
LTM, Department of Chemistry, CCEN, UFPB, Campus I, Cidade Universitaria, 58059-900, Joao Pessoa, Paraba, Brazil b Crystal Growth and Ceramic Materials Group, USP, 13560-970, Sao Carlos, SP, Brazil c CMDMC, Department of Chemistry, CCT, UFSCar, Rod. Washington Luis, Km 235, Sao Carlos, SP, CP 676, 13565-905, Brazil Received 2 June 2003; accepted 30 June 2003
a

Abstract The CaFe2O4 composition was studied, in order to analyze its physical and chemical behavior, verifying its stability under industrial conditions, when applied as pigments. The characterization was accomplished using thermal analysis, X-ray diffraction (XRD), nitrogen adsorption, scanning electronic microscopy (SEM) and diffuse reflectance. It observed successions exothermics reactions, adequate in events of thermal decomposition of the organic material, reach your stability in 700 jC. The material became completely crystalline at 800 jC. Between 700 and 1100 jC, the color was stabilized, showing an absorption band in the region of 650 to 750 nm, characteristic of the red color. D 2003 Elsevier B.V. All rights reserved.
Keywords: Ceramic pigments; Pechini method; CaFe2O4; Spinel; Ceramics; Characterization methods

1. Introduction Ceramic materials with spinel structure have been studied for decades, due to its wide applicability as ceramic pigments, magnetic devices, semiconductors, refractories and others. In order to obtain powder-ceramics with high quality, there are important factorssynthesis method determines not only stoichiometric and morphologic control but also physical and chemical properties. Color is an optical property that takes to countless applications. For ceramic tiles, pigments give a stable coloration to a glaze, through a simple mechanical dispersion in the middle to be colored. The final color of each pigment is due to the addition of a chromophore ion (usually transition metals) into an inert matrix, or this ion may be part of the own matrix, as in the case of ferrites [1]. In this work, a ferrite pigment was synthesized with applicability as pigments, besides magnetic devices, semiconductors, among others. After synthesis, the Fe2O3/CaO material (consists of calcium ferrite) exhibits a red brick coloration having the

spinel structure [2], which usually leads to a high thermal stability. The spinel structure RO.R2O3, is formed by association of a trivalent oxide (acid character) with a bivalent oxide (alkaline character). Such a ceramic pigment is able to develop stable color in relation to temperature and chemical agents, resisting to the aggressive attacks, specially by glaze material during its melting, in other words, the pigment should be insoluble in glazes (substrate) [3]. The chemical synthesis was based on polymeric precursors method, which was developed by Pechini. This method consists of formation of a polymeric net starting from a polyhydroxy alcohol and an alpha-hydroxycarboxylic acid, with metallic cations homogeneously distributed throughout the matrix [4,5]. After synthesis, CaFe2O4 physical and chemical behavior was studied, verifying its stability as pigment under industrial conditions.

2. Experimental procedure 2.1. Resin preparation using the polymeric precursors method (PECHINI) The polymeric precursor solution was prepared using the Pechini method, which has been used to synthesize poly-

* Corresponding author. E-mail address: gouveia@quimica.ufpb.br (R.A. Candeia). 0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0167-577X(03)00563-9

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cationic powders. The process is based on metallic citrate polymerization using ethylene glycol. A hydrocarboxylic acid, such as citric acid, is used in an aqueous solution in order to chelate cations. The addition of a polyalcohol, such as ethylene glycol, leads to the formation of an organic ester. Polymerization, promoted by heating, results in a homogeneous resin in which metal ions are uniformly distributed throughout the organic matrix. The citric acid (Vetec) was added into water with constant agitation, at 60 70 jC. Then, the polymeric net former was addediron III nitrate (Vetec). After its dissolution, the polymeric net modifier was placedcalcium acetate (Reagen). After the mixture of the salts and their total dissolution, ethylene glycol (Synth) was added into the solution, with a proportion (in mass) of citric acid/ethylene glycol of 60:40 [4,5]. The temperature was increased up to 90 110 jC, in order to promote the sterification. At the end of the reaction, a polymeric gel (resin) was obtained. 2.2. Powder preparation The resin was heat treated at 300 jC for 1 h (primary calcination), leading to the partial decomposition of the polymeric gel forming an expanded resin, constituted of a semi-carbonized material, of black color, with aspect similar to a foam. The resultant material of the primary calcination was removed from the becker, deagglomerated in porcelain mortar, going by 100-mesh sieve. The thermal decomposition of the organic precursor, as well as the crystalline phase formation, was evaluated by differential thermal analysis (Shimadzu, DTA-50) and thermogravimetry (Shimadzu TGA-50), in order to analyze the mass loss and possible energy transitions. After primary calcination, the powders, rich in organic residues, were calcined on aluminum plates at temperatures varying from 500 to 1100 jC for 1 h, with a heating rate of

Fig. 2. X-ray diffraction patterns for the CaFe2O4 powder as a function of calcination temperature.

10 jC min 1 in ambient atmosphere. The pigment powder was gone by 200-mesh sieve. The crystalline phases and cell volume measurements were carried out by X-ray diffraction (XRD), using SiO2 as an external standard. The measurements were obtained with a Siemens D-5000 Diffractometer with CuKa radi ation (k = 1.5406 A and h = 20j to 70j), at room temperature. The surface area measurements of the pigments were accomplished in a Micromeritcs, ASAP 2000 equipment, using N2 as the adsorption/desorption gas. Scanning electronic microscopy (SEM) was used to characterize the fired pigments by employing a ZEISS DSM, 940 A. L*a*b* color parameters and diffuse reflectance of fired pigments were measured by the Gretac Macbeth Color-eye spectrophotometer 2180/2180 UV, from 300 800 nm range, using the D65 illumination. The CIEL*a*b* colorimetric method was used, as recommended by the Commission Internationale de lEclairage (CIE), [6]. In this method, L* is the lightness axis [black

Fig. 1. TG/DTA curves for the CaFe2O4 powder.

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Fig. 3. Crystallite size as a function of temperature. Fig. 5. SEM micrographs of surface topography for CaFe2O4 system at 1000 jC.

(0) ! white (100)], b* is the blue ( ) ! yellow (+) axis, a* is the green ( ) ! red (+) axis, and DE is the hue variation.

3. Results and discussion Fig. 1 shows the thermal analysis of the expanded resin. Several exothermic peaks were observed during thermal decomposition of the organic material, due to different chain sizes. The DTA results indicate two steps: the first one between 108 and 200 jC, due to water and adsorbed gases elimination; and the second one between 200 and 650 jC, due to polymeric chain decomposition, leading to CO2 elimination, besides the decomposition of carboxyls linked to metals, with oxide formation from 650 jC. Fig. 2 presents the X-ray diffraction results, after calcination from 500 to 1100 jC. The samples calcined

at 500 and 600 jC are amorphous. Above this temperature, the first nuclei of the desired phase are formed, becoming totally crystalline at 800 jC. This displays the effectiveness of the synthesis method, leading to the desired phase at low temperatures. The obtained phase has orthorhombic structure, whose space group is Pnam (62), being identified by the index card JCPDS 32-0168. The experimental lattice parameters are: a = 9.23 (7), b = 10.68 (2) and c = 3.01 (4). Crystallite size (Fig. 3) increased about 30% between 700 and 800 jC, probably due to amorphous material crystallization. It almost does not increase ( f 40 nm) up to 1000 jC, reaching the value of 57 nm at 1100 jC. This change in crystallite size evolution indicates a change in growth mechanism.

Fig. 4. Particle diameter as a function of thermal treatment temperature.

Fig. 6. Diffuse reflectance of CaFe2O4 system, between 500 and 1100 jC.

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Table 1 Chromatic coordinates, tonality variation and the color number in the Pantone system, related to the CaFe2O4 pigments, obtained by Pechini method, as a function of temperature Heating rate Standard/jC 500 600 700 800 900 1000 1100 L* 96.253 34.855 33.259 33.077 47.450 41.284 38.277 34.125 a* 0.059 13.618 12.794 12.151 20.645 19.396 19.854 12.437 b* 1.140 14.272 12.605 10.753 23.647 17.656 15.304 7.524 DE 96.260 40.050 37.798 36.842 56.894 48.911 45.755 37.092 Color White CV 4985 CV 478 CV 499 CV 471 CV 1807 CV 1807 CV 697 CV

technological potential. However, application tests must be done in order to evaluate pigment stability during glazing.

4. Conclusion The Pechini method leads to a material with high degree of homogeneity at molecular level, as well as finer powders presenting thus higher surface areas. The color of the pigment depends on the oxidation state of the chromophore ion. Monophasic powders are obtained at temperatures as low as 800 jC and a completely defined color is observed at 900 jC. Between 800 and 1100 jC, the color is stabilized, showing an absorption band in the region of 650 to 750 nm, characteristic of the red color. Therefore, the samples obtained from heat treatments at 900 and 1000 jC can, at first, be considered as the ones of highest technological potential.

The surface area results, calculated by BET method [7], are presented in Fig. 4. The average diameter, dBET, was calculated by Eq. (1). dBET 6 ; As q 1

where As is the specific surface area (m2/g) and q is the theoretical density of the phase (qCaFe2O4 = 4.805 g/cm3) [8]. The specific surface area of the CaFe2O4, calcined at 1000 jC, is 2.24 m2/g, while the equivalent spherical diameter is 556 nm. An increase of the particle diameter was verified as a function of temperature, according to Fig. 4. This increase is probably due to the presence of nanometric particles and therefore more reactivates, favoring coalescence at smaller temperatures, as presented in Fig. 5. Fig. 6 shows the curves of diffuse reflectance, which are in agreement to XRD results. After calcination at 500 and 700 jC, samples present low crystallinity, without the desired color. Above 800 jC, the material is crystalline and presents a characteristic band around 650 nm, with a dark red color. Table 1 presents the colorimetric coordinates (L*, a*, b*), the tonality variation (DE) and the color number in the Pantone system. The decrease in the L* parameter with the temperature increase can be associated with the abrupt increase of the particle diameter from 200 to 1100 nm, which leads to the decrease of the overall reflecting surface of the power. Therefore, the samples obtained after calcination at 900 and 1000 jC can be considered as the ones of highest

Acknowledgements The authors gratefully acknowledge the financial support of the Brazilian research funding institution CNPq, FAPESP/CEPID.

References
[1] F. Bondioli, T. Manfredini, A.P.N. Oliveira, Ceram. Ind. 3 (4 6) (1998) 13. [2] A. Burgyan, R.A. Eppler, Ceram. Bull. (1982) 1001. [3] P.E. Lopez, J.P. Castello, E.C. Cordoncillo, Esmaltes y Pigmentos Ceramicos, Faeza Edictre Iberica, Castellon, 2001, pp. 189 246. [4] M. Kakihana, J. Sol-Gel Sci. Technol. 6 (1996) 7. [5] M.P. Pechini, Method of Preparing Lead and Alkaline-Earth Titanates and Niobates and Coating Method Using the Same to Form a Capacitor-US PAT., 3.330.697, 1967. [6] CIE, Recommendations of Uniform Color Spaces, Color Difference Equations, Phychometrics Color Terms. Supplement No. 2 of CIE Publ. no. 15 (E1-1.31) 1971, Bureau Central de la CIE, Paris, 1978. [7] L.S. Ettre, Pigment surfaces, in: P.A. Lewis (Ed.), Pigment Handbook, Wiley-Interscience Publication, Ohio, 1987, pp. 139 153. [8] Handbook 128. Handbook of Chemistry and Physics, 47th ed., The Chemical Ruber, pp. 1966 1967.