Journal of Alloys and Compounds 462 (2008) 142146

Chemical synthesis of nanocrystalline magnesium aluminate spinel via nitratecitrate combustion route
Ali Saberi a, , Farhad Golestani-Fard a , Hosein Sarpoolaky a , Monika Willert-Porada b , Thorsten Gerdes b , Reinhard Simon c
Ceramic Division, Iran University of Science & Technology, Tehran, Iran Chair of Materials Processing, University of Bayreuth, Bayreuth, Germany c Chair of Ceramic Materials Engineering, University of Bayreuth, Bayreuth, Germany
b a

Received 21 May 2007; received in revised form 25 July 2007; accepted 25 July 2007 Available online 2 August 2007

Abstract Nanocrystalline magnesium aluminate spinel (MgAl2 O4 ) was synthesized using metal nitrates, citric acid and ammonium solutions. The precursor and the calcined powders at different temperatures were characterized by X-ray diffraction (XRD), simultaneous thermal analysis (STA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The combustion mechanism was also studied by a quadrupole mass spectrometer (QMS) which coupled to STA. The generated heat through the combustion of the mixture of ammonium nitrate and citrate based complexes decreased the synthesis temperature of MgAl2 O4 spinel. The synthesized MgAl2 O4 spinel at 900 C has faced shape with crystallite size in the range of 1824 nm. 2007 Elsevier B.V. All rights reserved.
Keywords: Oxides; Chemical synthesis; Thermal analysis; X-ray diffraction

1. Introduction Magnesium aluminate spinel, MgAl2 O4 , is a well-known material which due to excellent refractoriness, good chemical inertness, and high mechanical strength, has been widely used in various attractive applications [13]. The properties of obtained powder such as purity, particle size, and chemical homogeneity strongly depend on preparation method. Apart from the solid-state reaction, a variety of techniques have been suggested to synthesis MgAl2 O4 spinel such as hydrothermal technique, plasma spray decomposition of oxides, solgel method, combustion synthesis, freeze drying, controlled hydrolysis of metal alkoxides, and decomposition of organometallic compounds in supercritical uids [49]. Recently, MgAl2 O4 spinel has been synthesized via citratenitrate route (solgel citrate) [10,11]. Simplicity of experimental set-up, cheapness, and good chemical homogeneity of the synthesized powder are the main advantages of this

method [12]. A redox reaction between nitrate ions as an oxidant agent and citrate ions as a fuel agent liberates the required energy to synthesis oxide powder at lower temperatures [10]. The extensive investigations on the inuence of the reactants mixture on both phase composition and microstructure of the obtained MgAl2 O4 spinel have been done; however, the mechanism of the combustion synthesis is still not well understood. In this study MgAl2 O4 spinel powder was synthesized using citratenitrate route and the combustion mechanism and gaseous products of combustion reactions were studied by quadrupole mass spectrometry measurements.
2. Experimental procedure
Magnesium nitrate (Mg(NO3 )2 6H2 O), aluminum nitrate (Al(NO3 )3 9H2 O), citric acid (C6 H8 O7 H2 O), and ammonia solution (NH4 OH, 30%) were used as the starting materials to synthesis MgAl2 O4 spinel. All chemical materials were supplied from Merck Co. Germany. To prepare a transparent sol, 0.021 mol of magnesium nitrate and 0.042 mol of aluminum nitrate were dissolved in 100 ml of distilled water. Then citric acid as chelating-fuel agent was added to the solution. The molar ratio of citrate to metallic ions in the solution was maintained at 0.5:1. Citric acid has two different roles. (1) Citric acid as a chelating agent binds metallic ions (Al3+ & Mg2+ ) and prohibits precipitation of solution during changing pH. (2) Citric acid as a fuel

Corresponding author. Tel.: +49 921 55 7206; fax: +49 921 55 7205. E-mail address: ASaberi@IUST.ac.ir (A. Saberi).

0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2007.07.101

A. Saberi et al. / Journal of Alloys and Compounds 462 (2008) 142146 helps to progress the synthesis at relatively low temperatures [13]. The solution was agitated using a magnetic stirrer at room temperature for 1 h. To increase the efciency of chelating agent, citric acid, pH of the solution was adjusted to six by adding ammonia drop-wisely [14,15]. This solution was gelled by in situ formation of polyacrylamide network while heating the primary sol at 120 C. By further heating, the citric acid melts at around 173 C and converts to aconitic acid (reaction (R.1)). The aconitic acid then converts to itaconic acid according to reaction (R.2). The itaconic acid (melting point 166 C), upon continued heating, undergoes polymerization and swells with the decarboxylation (releasing CO2 ) [14]. Thus, the gel was heated at 180 C in an electric oven to get a pale yellowish mass. Then the obtained mass, hereinafter referred to as precursor, was ground into powder by a pestle and mortar and subsequently heat-treated in an atmosphere control furnace at various temperatures for 1 h with a heating rate of 10 C/min and 50 ml/min dry air ow rate. C6 H8 O7 C6 H6 O6 + H2 O C6 H6 O6 C5 H6 O4 + CO2 (R.1) (R.2)

143

Differential scanning calorimetry (DSC) and thermogravimetric (TG) analyses of precursor were carried out with a Netzsch STA-449C with a heating rate of 10 C/min in a continuous air ow (50 ml/min). Concurrently, the gases exiting the STA cell were analyzed by a quadrupole mass spectrometer (QMS). In order to avoid throwing out any amount of solid product when the gases leave the specimen under analysis, a lid with a little hole was put on the crucible. Phase evaluation of the calcined precursor at different temperatures was studied using a Philips (PW-3040) diffractometer with Cu K radiation. JCPDS cards 21-1152 and 47-0867 were used for identication of MgAl2 O4 spinel and NH4 NO3 (ammonium nitrate), respectively. The crystallite size of the MgAl2 O4 spinel powder was determined using Scherrer equation (Eq. (1)): L= k (2) cos 0 (1)

Fig. 1. XRD patterns of the dried and calcined precursor at different temperatures, precursor (a), 300 C (b), 400 C (c), 500 C (d), 600 C (e), 700 C (f), 900 C (g), 1000 C (h), and 1100 C (i).

reaction (R.3). The peaks related to ammonium nitrate disappear in the calcined powder at 300 C. The XRD pattern shows MgAl2 O4 spinel formation at around 400 C. As calcination temperature increases, gradual increase in peak intensities accompanied by sharpening of the peaks is observed, which indicates the crystallite size of spinel is arising. Al(NO3 )3 + Mg(NO3 )2 + 5NH4 OH Al(OH)3 + Mg(OH)2 + 5NH4 NO3 (R.3)

where is the wavelength (=0.15406 nm), 0 the Bragg angle, k the constant (=0.94), and L is the crystallite size. The half-width of the diffraction line (2) (in radians) was taken as the experimental half-width (exp ) and was corrected for experimental broading (instr ) according to Eq. (2) [16]:
2 2 (2) = (exp instr ) 1/2

(2)

instr was measured experimentally by a silicon powder. FTIR spectra were obtained by a Shimadzu FTIR-8400S spectrophotometer. Further, eld emission scanning electron microscope (LEO 1530, FE-SEM) and transmission electron microscope (LIBRA 200, TEM) were used for microstructural observation. The surface area of synthesized powders was measured with an ASAP-2010, Gimini according to BET technique.

3. Results and discussion The X-ray diffraction patterns of the precursor and the calcined powders at different temperatures are shown in Fig. 1. According to XRD results, the precursor is a mixture of amorphous matrix and crystalline ammonium nitrate (NH4 NO3 ) (Fig. 2a). Ammonium nitrate forms from the reaction of ammonium cations (NH4 + ) with nitrates (NO3 ) corresponding to

Table 1 presents the approximate crystallite size and characteristics of the spinel powders calcined at different temperatures. Three diffraction peaks (3 1 1), (4 0 0), and (4 4 0) were chosen for measuring the crystallite size. The average crystallite size of calcined spinel at 900 C is in the range of 1820 nm. The lattice constant of the synthesized MgAl2 O4 spinel above 900 C is about 8.08 A, which is in agreement with JCPDS cart No. 21-1152. The simultaneous thermal analysis (DSC-TG) of the precursor has been shown in Fig. 2a. The small endothermic peak about 170 C in DSC accounted for 20 wt.% of the initial weight loss in TG, is assigned to the dehydration of the precursor. QMS results also prove the evaporation of H2 O at this temperature range (Fig. 2b). The outstanding and sharp exothermic peak at around 280 C with a 70 wt.% corresponding weight loss is due to combustion of ammonium nitrate and citrates. These exothermic reactions

Table 1 The approximate crystallite size and characteristics of the MgAl2 O4 powder calcined at different temperatures for 1 h T ( C) 700 900 1000 1100 d3 1 1 (A) 2.449 2.438 2.437 2.437 D (nm) 9 19 28 37 d4 0 0 (A) 2.063 2.028 2.023 2.022 D (nm) 10 21 27 38 d4 4 0 (A) 1.464 1.432 1.429 1.427 D (nm) 10 18 29 41 Ave. lattice constant (A) 8.218 8.102 8.087 8.084

144

A. Saberi et al. / Journal of Alloys and Compounds 462 (2008) 142146

Fig. 2. (a) STA curves of MgAl2 O4 spinel precursor, QMS curves of (b) H2 O, (c) CO + N2 , (d) CO2 + N2 O, (e) NO2 , (f) NO, and (g) O2 .

tack place very quickly, involving the rapid formation of rather large quantity of gaseous products like NO, N2 O, NO2 , N2 , O2 , CO, CO2 , and H2 O (Fig. 2bg). In spite of NO, N2 O, NO, and NO2 gases exiting in a short range of temperature (280300 C),

the QMS results related to N2 + CO (a.m.u. = 28) show a broad peak at the range of 280340 C (Fig. 2c). Therefore, it can be concluded that at the rst ammonium nitrate decomposes at around 280 C and consequently the resulted heat helps com-

A. Saberi et al. / Journal of Alloys and Compounds 462 (2008) 142146

145

bustion of citrates. The combustion of citrates is accompanied by evolution CO (g) and CO2 (g) (Fig. 2c and d). According to the literature, ammonium nitrate can decompose between 260 and 300 C at 760 mmHg pressure. Its thermal decomposition can occur in a complex way. Some of the possible reactions of ammonium nitrate decomposition are listed below ((R.4)(R.7)) [12,17]: NH4 NO3 (3/4)N2 + (1/2)NO2 + 2H2 O NH4 NO3 (1/2)N2 + NO + 2H2 O NH4 NO3 N2 O + 2H2 O NH4 NO3 N2 + 2H2 O + (1/2)O2 (R.4) (R.5) (R.6) (R.7)

However, it seems that all of the above reactions ((R.4)(R.7)) take place during the combustion, the lower amount of N2 O and O2 gases in exiting gases in comparison with NO, NO2 , and N2 gases states that ammonium nitrate decomposition happened mostly via (R.4) and (R.5). Further heating produces a small and broad exothermic peak at around 390 C, which corresponds to the crystallization of MgAl2 O4 spinel. The crystallization temperature of MgAl2 O4 is lower than the reported results by the others used similar synthesis technique [10,11]. The third exothermic peak (550 C) is due to the oxidation of residue carbon admitted by the results of QMS showing the presence of CO (g) at this temperature range (530560 C) (Fig. 2c). However, the most amount of carbon has been oxidized while the rst exothermic reaction at 280 C. Fig. 3 displays the recorded IR spectra for the precursor and the calcined powders at 500, and 900 C. Common bands are

Fig. 4. FE-SEM micrograph of MgAl2 O4 spinel powder calcined at 900 C.

seen in precursor spectrum (Fig. 3a) such as the broad OH band centered around 3400 cm1 and the 1630 cm1 H2 O vibration band. The peaks at around 28002900 cm1 related to stretching CH vibrations are coming from the organic compounds (citrates) used along the synthesis. The peaks appearing at 1384 cm1 and 829 cm1 correspond to vibration modes of NO3 groups. In the calcined sample at 500 C (Fig. 3b) CH groups are still present but in the calcined powders at higher temperatures (Fig. 3c), all organic bands are disappeared and inorganic band at 600 cm1 corresponding to the metaloxygenmetal bond (MOM), become sharper and stronger [18,19]. FE-SEM micrograph (Fig. 4) depicts agglomerated particles morphology of the calcined powder at 900 C. The synthesized powder has faced shape and in spite of partial agglomeration of the calcined powder, the size of agglomerates is in the range of 100300 nm. Fig. 5 illustrates the specic surface area of synthesized MgAl2 O4 spinel at different temperatures. By increasing the calcination temperature, due to neck formation between particles, the value of specic surface area of samples shows a dramatic decrease. The released heat during the combustion

Fig. 3. FTIR spectra of precursor (a), the calcined powders at 500 C (b), and 900 C (c).

Fig. 5. BET surface area of the synthesized MgAl2 O4 spinel powder at different temperatures for 1 h.

146

A. Saberi et al. / Journal of Alloys and Compounds 462 (2008) 142146

4. Conclusion Nanocrystalline magnesium aluminate spinel (MgAl2 O4 ) was synthesized by an auto-ignition process using citric acid, metal nitrates, and ammonia at relatively low temperatures. The initial crystallization temperature of MgAl2 O4 spinel was at 400 C, whereas that of the fully crystallized magnesium aluminate spinel appeared at temperatures above 900 C. The mechanism of combustion synthesis of magnesium aluminate spinel was studied. The results showed that by increasing the calcination temperature beyond 280 C, ammonium nitrate suddenly decomposes due to a redox reaction between excess nitrate ions and citrate ions. Then the released heat helps combustion of citrates. The generated heat of the combustion of ammonium nitrate as well as citrates helps to synthesis magnesium aluminate spinel at relatively lower temperatures. References
[1] J. Parmentier, M. Plouet, S. Vilminot, Mater. Res. Bull. 33 (1998) 1717. [2] R. Smith, D. Bacorisen, B.P. Uberuaga, K.E. Sickafus, J.A. Ball, R.W. Grimes, J. Phys. Condense. Matter 17 (2005) 875. [3] G. Baudin, R. Martinez, P. Pena, J. Am. Ceram. Soc. 78 (1995) 1857. [4] C.R. Bickmore, K.F. Waldner, D.R. Treadwell, R.M. Laine, J. Am. Ceram. Soc. 79 (1996) 1419. [5] R.J. Bratton, Am. Ceram. Soc. Bull. 48 (1969) 759. [6] M. Barj, J.F. Bocquet, K. Chhor, C. Pommier, J. Mater. Sci. 27 (1992) 2187. [7] C. Pommier, J.K. Chhor, F. Bocquet, M. Barj, Mater. Res. Bull. 25 (1990) 213. [8] N. Yang, L. Chang, Mater. Lett. 15 (1992) 84. [9] O. Varnier, N. Hovnanian, A. Larbot, P. Bergez, L. Cot, J. Charpin, Mater. Res. Bull. 29 (1994) 479. [10] H. Zhang, X. Jia, Z. Liu, Z. Li, Mater. Lett. 58 (2004) 1625. [11] S.K. Behera, P. Barpanda, S.K. Pratihar, S. Bhattacharyya, Mater. Lett. 58 (2004) 1451. [12] S. Biamino, C. Badini, J. Eur. Ceram. Soc. 24 (2004) 3021. [13] S.P. Lin, K.Z. Fung, Y.M. Hon, M.H. Hon, J. Cryst. Growth 226 (2001) 148. [14] J. Tsay, T. Fang, J. Am. Ceram. Soc. 82 (1999) 1409. [15] R.D. Purohit, A.K. Tyagi, J. Mater. Chem. 12 (2002) 312. [16] P. Klug, L.E. Alexander, X-Ray Diffraction Procedure for Polycrystalline and Amorphous Materials, Wiley, New York, 1974, p. 634. [17] C. Oommen, S.R. Jain, J. Hazard. Mater. A 67 (1999) 253. [18] E.G. Brame, J. Grasselli, Infrared and Raman Spectroscopy, Part A, Marcel Dekker, New York, 1976. [19] K. Vivekanandan, S. Selvasekarapandian, P. Kolandaivel, Mater. Chem. Phys. 39 (1995) 284.

Fig. 6. Bright eld TEM micrograph and SAEDP of MgAl2 O4 spinel powder calcined at 900 C.

brings down the crystallization temperature of the magnesium aluminate spinel. Actually the main benet of nitratecitrate synthesis technique is short period of synthesis. The fast and low temperature synthesis prohibit the powder from sintering, thus the obtained powder has higher surface area as well as good sinterability in comparison with other common synthesis techniques [12]. Magnesium aluminate spinel powder resulting from the combustion reactions, were characterized by TEM (Fig. 6). The bright eld TEM image and selected area electron diffraction pattern (SAEDP) of synthesized powder at 900 C show that the synthesized MgAl2 O4 spinel is polycrystalline with crystallite size in the range of 2025 nm. The observed results are in good corresponding to the calculated crystallite size by Scherrer equation.