Caspian Journal of Applied Sciences Research, 1(12), pp. 1-7, 2012 Available online at http://www.cjasr.

com ISSN: 2251-9114, 2012 CJASR

Full Length Research Paper Synthesis and Characterization of Al2O3:Fe Nanoparticles Prepared via Aqueous Combustion
Saeid Kakooei1*, Jalal Rouhi2, Arash Dehzangi3, Ehsan Mohammadpour1, Mahmoud Alimanesh2
Department of Mechanic Engineering, UniversitiTeknologi PETRONAS, Tronoh 31750, Bandar Seri Iskandar, Malaysia. 2 Nano-Optoelectronic Research (NOR) Lab, School of Physics, Universiti Sains Malaysia, Malaysia. 3 Institute of Microengineering and Nanoelectronics(IMEN) Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia. *Corresponding Author: skakooei59@hotmail.com
Received 3 September 2012; Accepted 6 October 2012
1

Iron-doped Al2O3 nanoparticles were prepared via an aqueous combustion synthesis technique using stoichiometric amounts of aluminum nitrate [(Al9NO3)3.9H2O], ferric nitrate [Fe(NO3)3.9H2O], and sucrose (C12H22O11). The heat treatment of the nanoparticles at two temperatures (900 C and 1100 C) formed porous agglomerated iron-doped alumina nanoparticles. The heat-treated powders were characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Characterization results showed existence of -Al2O3 calcined at 1100 C. In this study, iron-doped alumina particles with average crystallite size (38.94 nm) were successfully synthesized by using sucrose as dispersion agent and carbon source. Al2O3:Fe nanoparticles can be used in different fields as catalyst support and biocompatible material and for electrical applications. Key words: Nanomaterials; Iron Doped Alumina; Heat Treatment; Combustion Synthesis

1. INTRODUCTION The combustion synthesis of Fe and Al2O3 composite method was reported by Holt and Kelly for the first time in 1993 (Holt et al., 1993). This method is a particularly safe, simple, and rapid fabrication process, and its main advantages are its time and energy efficiency (Mukasyan et al., 2007; Deraz et al., 2009). The aqueous combustion technique was recently used to synthesize alumina nanopowders (Cordier et al., 2006; ZHAI et al., 2006; Edrissi et al., 2007). However, the combustion reaction mechanism is quite complex. The main parameters influencing the reaction include the main fuel type, ratio of fuels, fuel-tooxidizer ratio, pH level of the solution, amount of excess oxidizer, and calcination rate. In general, fuels should not react violently nor produce toxic gases and must act as a complexing agent for metal cations (Pathak et al., 2002; de Andrade et al., 2006; Lima et al., 2006; Edrissi et al., 2008). Alumina or -Al2O3 (corundum) has been widely investigated because of its important applications in advanced engineering as, for example, catalyst support (Breen et al., 2002), biocompatible material, and nanocomposite for

structural and electrical applications (Pathak et al., 2002; Toniolo et al., 2005; Meng et al., 2010). The phase transition temperature can be decreased by doping -Fe2O3 (hematite) with alumina. In addition, smaller -Al2O3 particles can be synthesized (Bye et al., 1974; Cordier et al., 2006). Fe atoms in substitute solid solutions have been known to change the diffusion properties of alumina (Bataille et al., 2005). These effects are related to the enhancement of the cation lattice diffusion (via vacancies and interstitials) with rapid oxygen diffusion in grain boundaries. The diffusion changes are attributed to the presence of Fe2+ cations which have relatively low solubility in alumina. On the contrary, Fe3+ cations slightly influence species diffusion properties and present higher solubility in alumina (Bataille et al., 2005; Cordier et al., 2006; Lucio-Ortiz et al., 2011). Kobayashi et al. (2012) reported adding a small quantity of Fe2O3 to the Al2O3 base catalyst considerably enhanced catalyst stability and catalytic activity (Kobayashi et al., 2012). The doping agent modified catalytic behavior with an influence on the morphology and textural porosity in the alumina catalyst (Nomura et al., 2012).

Kakooei et al. Synthesis and Characterization of Al2O3:Fe Nanoparticles Prepared via Aqueous Combustion

The -Al2O3 is the primary intermediate phase created from -Al2O3 containing Fe3+ in solid solution, although crystallinity significantly decreased with addition of Fe. The conversion rate of intermediate phase to -Al2O3 was increased by the additions of Fe (Bye et al., 1974). In this research, sucrose (C12H22O11) was used as fuel and dispersion agent. Then, the effects of different heat treatment temperatures on the crystallite size of the combustion-synthesized alumina powders were investigated. The powders obtained via combustion synthesis were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential

thermal analysis (DTA), and energy-dispersive Xray spectroscopy (EDX). 2. MATERIALS and METHODS The iron-doped alumina nanoparticles were prepared by using the solution combustion method. Al(NO3)3.9H2O was used as an Al source, whereas sucrose (C12H22O11) was used as a water-soluble organic carbon source. As shown in Figure 1, 14.7 g aluminum nitrate and 12.86 g sugar were mixed with deionized water respectively. Then, the mixtures were combined to obtain a stable suspension. Subsequently, 0.1 g of Fe(NO3)39H2O was dissolved into the mixture.

Fig. 1: Schematic diagram of stages of Fe-doped Al2O3 nanoparticles synthesis by aqueous combustion method; (1) Aqueous combustion reaction of mixtures leading to sponge-shape

The excess water from the mixtures was evaporated on a hot plate until a gelatinous mixture was formed. The chemical reaction of the mentioned process is as follows: 2Al(NO3)3 + C12H22O11 + Fe(NO3)3 Al2O3 + 11H2O + 9NO2 + 6CO + 6C+Fe3++3e- (1) The as-prepared powders were then submitted to two thermal treatments in flowing air to obtain the corundum () phase. The first heat treatment was at 900 C for 5 h, whereas the second heat treatment was at 1100 C for 5 h. Both heat treatments utilized natural furnaces to cool the heated powders to room temperature. The same heating rate of 5 C/min was applied to both samples. The iron-doped alumina powders were

ground by using an agate pestle and mortar to break the agglomerates. The schematic diagram of these stages is shown in Figure 1. All powders (as-prepared, calcined at 900 C, and calcined at 1100 C) were examined via XRD using Cu K radiation (Bruker D4 Endeavor). The XRD data were analyzed to study the phase formation and to identify unit cell parameters, which were calculated using the Eva software. In flowing air, differential thermal analyses (DTA, Netzsch 404S) were performed on the powders calcined at 900 C and 1100 C (from 25 C to 1100 C) at heating rates of 10 C/min. Both calcined powders were observed by using SEM.

Caspian Journal of Applied Sciences Research, 1(12), pp. 1-7, 2012

3. RESULTS and DISCUSION The XRD patterns of the powders calcined at 900 C and 1100 C for 5 h are shown in Figure 2. The -Al2O3 and -Al2O3 phases are evident in the sample calcined at 900 C. Pure phase diffraction peaks of -Al2O3 were predominant in the XRD patterns of the sample calcined at 1100 C. This

finding is significantly consistent with earlier results (Pathak et al., 2002; Peng et al., 2006; Jamil et al., 2011). The peak broadening method was used to calculate the average crystallite size. The full width at half maximum (FWHM) of the peak was measured and the average crystallite sizes were estimated using the Scherrer equation:

0.9

cos

(2)
2 2

B b

Where D is the average crystallite size, the wavelength of the radiation, Braggs angle and B and b are the FWHMs observed for the sample and standard, respectively. Terms B and 2 were obtained from XRD pattern. The average crystallite size for each sample was calculated using the above formula. The results demonstrated that the average particle size of Al2O3:Fe nanoparticles was about 38.94 nm. The iron-doped alumina nanoparticles were also subjected to DTA analyses to investigate the phase transformations. Figure 3 shows that the DTA curve has two significant steps. The curve for the powder calcined at 900 C first progressed upward until 500 C and then peaked at 1000 C. However, no peaks were observed at this temperature for the powders calcined at 1100 C because of the phase transition during calcination. Edrissi et al.(2007) have also observed this phase transition at 1100 C (Edrissi et al., 2007). The DTA results confirmed the possibility of phase transformation into a thermodynamically stable crystallographic alpha alumina at about 1100 C. This finding is consistent with previous XRD data. The SEM micrographs of the powders calcined at 900 C and 1100 C for 5 h are shown in Figures 4 and 5. The synthesized powders are generally foamy in nature and agglomerated. As shown in Figure 5, the void formations on the powder structures are created by the evolution of large amounts of gases during combustion and heat treatment. The sizes of the voids on the Al2O3:Fe nanopowders significantly increased as the heat treatment temperature increased. This development can be a result of increasing gas moles, that is, the agglomerates tend to break up and become more

porous. Toniolo et al. (Toniolo et al., 2005) and Kishan et al. (Kishan et al., 2010) have also observed the growth of void sizes due to increasing gas moles. The mixture compounds can be estimated via EDX. Figure 6 shows the even distribution of Al, O, and Fe elements. In addition, the figure clearly shows that carbon already emerged. Table 1 summarizes the results of the energy-dispersive analysis of the alumina samples sintered at 900 C. The values are given in weight and atomic percent. 4. CONCLUSION Iron-doped alumina particles with average crystallite sizes (38.94 nm) were successfully synthesized by using sucrose (C12H22O11) as fuel and dispersion agent. The results show that combustion synthesis has more outstanding potential in producing nanocrystalline iron-doped alumina powders compared with other conventional methods. As a water-soluble organic carbon source, sucrose had a significant influence on the synthesis of Al2O3:Fe nanopowders via the carbothermal reduction during the combustion synthesis. The characteristics of the produced nanopowders significantly depend on the total effects of releasing gas and heat. More specifically, higher calcination temperatures resulted in crystallite growth and agglomeration. Fe doped alumina nanoparticles are widly used in different fields such as catalyst support, biocompatible material, and electrical applications.

Kakooei et al. Synthesis and Characterization of Al2O3:Fe Nanoparticles Prepared via Aqueous Combustion

Fig. 2: The XRD patterns of Al2O3:Fe powders calcined at a) 900 C and b) 1100 C for 5h

Caspian Journal of Applied Sciences Research, 1(12), pp. 1-7, 2012

Fig. 3: The DTA curve of Al2O3:Fe powders calcined at 900 C and 1100 C

Fig. 4: SEM images of the Al2O3:Fe powders heated at 900 C

Kakooei et al. Synthesis and Characterization of Al2O3:Fe Nanoparticles Prepared via Aqueous Combustion

Fig. 5: SEM images of the Al2O3:Fe powders heated at 1100 C

Fig. 6: EDX spectra of iron doped alumina nanoparticles calcined at 900 C

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