Structural, thermal, dielectric studies on solgel derived MgO from non-alkoxide route

A. Chowdhury* and J. Kumar

Mg oxide powder has been synthesised by solgel process via a novel non-alkoxide route. The precursor Mg oxalate gel was characterised by morphology, pore size distribution and differential thermal analysis, Fourier transformation infrared, TEM, SEM and X-ray diffraction analysis. The TEM studies on this system are reported for the first time depicting a unique morphology. A comparison in the morphology and the dielectric constant values of the solgel derived MgO powder was carried out with MgO powder obtained by Mg ribbon oxidation process. The solgel derived MgO powder was characterised by dielectric constant measurement in the compacted form and it was observed to exhibit a dielectric constant value, quite matching with the polycrystalline MgO in thin film form.
Keywords: MgO, Solgel preparation, Thermal properties, Microstructure, Dielectric properties

Introduction
MgO (Periclase) is an important material extensively used in the eld of ceramics, catalysis, medicine, etc. Generally, MgO prepared by conventional methods often yields a relative small surface area and other inferior properties like higher sintering temperature, lower degree of crystallinity, etc. which is undesirable for most of the advanced application areas. Therefore, new methods to prepare MgO, becomes necessary. Previously, synthesis of MgO powders has been tried from molten inorganic salts.1 MgO nanowires have been prepared from the vapor phase using Mg diboride as a precursor material.2 It is well known that the solgel technique for materials synthesis shows much better surface or bulk properties than those obtained by the conventional methods. MgO powders have been prepared by the sol gel technique taking Mg ethoxide as raw material3 using different hydrolysis catalysts that control the size of the particle. Kim et al.4 has studied the effect of acetic acid addition to Mg methoxide on the stability of the precursor and the crystallisation behaviour of solgel derived MgO nanopowders and thin lm. There have been a few more works in search of high quality solgel MgO,57 but all of them starts with Mg alkoxides followed by modications in different processing parameters. Previously, zinc oxide has been synthesised using ethanolic solution of zinc acetate and ethanolic solution of oxalic acid showing some promising properties for ZnO for varister application.8,9 In the present paper, the idea is to synthesise Mg oxide through an acetate route

and to describe the changes that it brings in terms of surface morphology, thermal and dielectrics properties (acetate being a weaker base than ethoxide). The acetate is much cheaper as well in comparison with the ethoxides of Mg. This investigation of a nonconventional and cost effective solgel MgO has been compared with MgO powder obtained by Mg ribbon oxidation process with respect to their surface morphology and dielectrics properties. The other techniques that have been used to characterise the solgel MgO powder are differential thermal analysis (DTA), Fourier transformation infrared (FTIR), SEM and X-ray diffraction (XRD). Dielectric measurements reveal some important information and suggest that the dielectric constant for polycrystalline MgO should reside in the regime 67 (at 0.36106).

Experimental procedure
Mg acetate tetrahydrate ((CH3COO)2Mg.4H2O) from E. Merck (India) Ltd, ethyl alcohol (C2H5OH) from Hayman Ltd, essex and oxalic acid ((COOH)2.2H2O) from Ranbaxy Laboratories were used as the starting materials for synthesis of solgel MgO. The ow chart is given below in Fig. 1. For the ribbon oxidation process, the Mg ribbon is burnt in liqueed petroleum gas (LPG) oxygen ame to produce white fumes of MgO. These fumes are deposited on a glass dish held just above at a distance, scratched with blade and collected as white powder. The Mg oxide powder obtained with each of the two processes is subjected to grinding and then passed through 240 mesh sieve. Subsequently it is annealed in alumina crucible at 1000uC for 14 h for removal of strains generated during grinding and yielding better crystallinity. However, the solgel derived powder is dried 550uC for 1 h.

Materials Science Programme, Indian Institute of Technology Kanpur, UP 208016, India *Corresponding author, email anirbanchowdhury2001@yahoo.co.in

2006 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 19 February 2006; accepted 14 April 2006 DOI 10.1179/174328406X129896

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1 Flow chart for synthesis of MgO via solgel route

Characterisations
The XRD patterns of Mg oxide powders have been recorded using a RichSeifert X-ray diffractometer (model ISO Debye ex 2002) with Cu Ka radiation. For observing the microscopic nature of the powder, dried Mg oxalate gel, an SEM model FEI. Quanta 200 has been used in the secondary electron mode. The Brunauer2Emmett2Teller (BET) surface area was measured using the Coulter SA 3100 analyser and nitrogen as the gas for adsorption. Mg oxalate gel produced by sol gel process and dried at 90uC for 24 h has been studied in a Perkin Elmer, Pyris diamond (Model SII) thermogravimetric analysis (TGA)/DTA instrument. Temperature is varied from 50 to 1000uC at a heating rate of 10uC min21. A pellet is made of powder derived from Mg oxalate gel treated at 90uC for 24 h with addition of KBr for recording FTIR spectrum and a Bruker (Vertex-70) IR spectrophotometer has been employed in the wave length range of 4000400 cm21. Dielectric constant measurement setup is suited for making measurements in the temperature range of 85480 K and consists of a liquid N2 cryostat, cryo system controller, rotary vacuum pump, sample holder assembly and an impedance analyser (HP 4192A LF) interfaced with a computer for data acquisition and analysis. A pellet is made with a hydraulic press at a pressure of four tons and coated with conductive carbon paint at both ends and placed between the contact electrodes in the sample holder.

possible reaction may be written as, Mg(CH3 COO)2 :4H2 Oz(COOH)2 :2H2 O? MgC2 O4 :nH2 Oz2 CH3 COOHz(6 n) H2 O drying MgC2 O4 :nH2 O
0

heating MgC2 O4 ? 550 C,2h (powder)

0

? 90 C,24h

MgO

(gel)

(dried gel)

Figure 4 shows transmission electron micrographs (studied for the rst time) of Mg oxalate gel depicting clearly the existence of a network of a tubular/cellular structure (y100 nm) and pores. The pH during the reaction has been 8.8. The agglomeration in the gel network and the interlinking of tubular spices at both ends can be seen, suggesting the presence of some nuclei

Results and discussion

X-ray diffraction pattern of solgel MgO powder annealed at 1000uC for 14 h is shown in Fig. 2. The analysis of the diffraction pattern suggests existence of a single phase of MgO with cubic (NaCl type) structure and lattice parameter is found to be 4.2130.001A. In the solgel process, ethanol has been used as a solvent for both the Mg acetate tetra hydrate and the oxalic acid. Upon mixing of the solutions, gel is formed and allowed to grow into a network for y24 h. The

2 X-ray diffraction patterns of MgO powder obtained by solgel process: XRD peaks of aluminium are also marked and used as standard

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3 Scanning electron micrographs (in SE mode) of MgO powder obtained by a and b burning Mg ribbon and c and d heating Mg oxalate gel at 550uC for 2 h

regions from where the tubular growth is occurring (Fig. 4a and b). However, each individual tube/cell depicts a uniform distribution of varied size (17 25 nm) nanopores. Both spherical and oval shaped pores have been observed. Figure 5a shows scanning electron micrographs of Mg oxalate gel dried at 90uC for 24 h. The prominent effects being isolation of the interlinked network after dehydration owing to disappearance of pores from neck connecting regions, formation of long tube structure with varying length/ thickness ratio and faceting in some of the tubes. Figure 5b shows the morphology of gel network after aging of 30 days. The dried MgO powder shows spherical particle morphology with a uniform size distribution in the range of 250300 nm (Fig. 3c and d). The MgO powder obtained by heating the Mg oxalate gel at 550uC for 1 h shows an extremely high surface area value of 103.5 m2 g21 (Table 1). The lower value of surface area for Mg oxalate gel dried at 90uC for 24 h is attributed to their unique tube like morphology with interlinked ends exhibiting a brous nature (Fig. 5a). The surface area value of the solgel derived powder is

found to decrease substantially after heat treatment at 1000uC for 14 h, which may be due to agglomeration and grain growth of individual particles. Plot of DTA contains three major peaks at 199, 495 and at 856uC (Fig. 6). The rst peak at 199uC is an endothermic peak arising owing to the removal of chemically adsorbed water, e.g. Mg acetate itself has four molecules of water which remains attached to the gel network after reaction and acetic acid, a reaction byproduct; boiling point y120uC. The weight loss (y22%) is also noted in the range 175200uC from the TGA plot. Such a change leads to contraction of gel volume. The second peak at 495uC is a broad endothermic peak and corresponds to the removal of residual organics, e.g. oxalate precursor and conversion of Mg(OH)2 to MgO .350uC, if present. This is contained with substantial weight loss y50% observed in the temperature range 450500uC in TGA plot and is also responsible for the formation of micropores in the gel network. The third peak at 856uC is a small but sharp exothermic peak representing the onset of crystallisation process. The system passes through

Table 1 Surface area (BET) values of MgO powders and Mg oxalate gel Sample MgO powder Mg oxalate gel MgO powder Processing and treatment Sieving through 240 mesh, annealing at 1000uC, 14 h Drying at 90uC, 24 h Heating at 550uC for 1 h Surface area, m2 g21 23.7 21.0 103.5 Average particle size*,nm 69 2 16

*Calculated using the formula d56/sr; where d5average particle size, s5surface area and r5density of MgO (taken as 3.65 g cm23).

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4 Transmission electron micrographs of Mg oxalate gel showing network of a tubular and b cellular structure and pores

a
5 Scanning electron micrographs of Mg oxalate gel after a drying at 90uC for 24 h and b aging for 30 days

6 DTA and TGA plots of Mg oxalate gel after drying at 90uC for 24 h, the rate of heating being maintained at 10uC min21

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7 FTIR spectrum of Mg oxalate gel dried at 90uC for 24 h

various stages of network consolidation and pore texture evolution .495uC. The crystallisation of the produced begins at y856uC, which indicates that the resulting product can be sintered at 850900uC in contrast to normally pure magnesia requiring a very high temperature (y1400uC). The total weight loss throughout this process is quite high (y73%) as expected from any solgel reaction. The FTIR spectrum of Mg oxalate gel after drying at 90uC for 24 h is shown in Fig. 7. The broad peak at 3374 cm21 is due to the OH bond conrming the presence of chemically bound water, retained alcohol (C2H5OH) as it escapes from the surface only during evaporation process and the acetic acid (CH3COOH). The next peak at 2965 cm21 suggests the presence of saturated CH bonds in Mg oxalate and acetic acid. The most important peak at 1670 cm21 conrms the existence of a carbonyl group. This is due to the chelating interaction of Mg with carbonyl group, resulting in an inorganic ester formation (Mg oxalate). The sharp peaks at 1372 and 1322 cm21 (CO stretching) can be attributed to the carbonate ions emerging at the surface, via adsorption of atmospheric carbon dioxide. The short band at 1140 cm21 (CO stretching) is appearing owing to the acetic acid. Therefore, the spectroscopic analysis conrms the formation of Mg oxalate with acetic acid as a byproduct. Figure 8 shows the room temperature frequency spectra of the dielectric constant er of different MgO powders. For this another MgO powder sample has been used for comparison. Synthesis of Mg oxide has been carried out by oxidation of Mg ribbon. The burning of Mg ribbon in LPG oxygen ame is undertaken to produce white fumes of MgO. These fumes are deposited on a glass dish held just above at a distance, scratched with blade and collected as white powder. MgO powder thus obtained shows the presence of very sharply dened cubes with average size of 180 nm.

However a few large cubes of size y1 mm are also noted in scanning electron micrographs (Fig. 3a and b). MgO powder obtained by burning Mg ribbon sintered at 600uC for 2 h and by solgel method (sintered at 1000uC for 14 h) has been used for measurements. It can be seen that the frequency dependence of dielectric constant of the samples tends to follow a general pattern which is similar to that for any bulk dielectric materials. The difference in the dielectric constant values may be attributed to the porosity content in the system. The pellet of MgO powder obtained by burning Mg ribbon has been sintered at 600uC for 2 h leading to non uniform grain growth, poor compaction and emergence of many pores. The pellet formed with MgO powder synthesised by solgel process is sintered at 1000uC. It shows an improved value of dielectric constant owing to

8 Dielectric constant as function of frequency of MgO pellets made with combustion of Mg ribbon and sol gel process: marked line indicates value of dielectric constant at frequency of 36105 Hz

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better compaction and less porosity mainly because of smaller particle size and higher temperature. The above data are totally inconsistent with that for MgO sintered samples10 but matches reasonably well with the ndings of Ho et al.11 polycrystalline MgO thin lms, the values of the dielectric constant being 3.2 (at frequency of 36105 Hz) and 6.2 (at frequency of 105 Hz). In contrast, single crystal of MgO is known to display the dielectric constant value of 9.8.11

Acknowledgements
The authors are grateful to Mr Umashankar, Mr Thapa and Mr Karthikeyan for their help throughout the experimental work.

References
1. Y. Du and D. Inman: J. Mater. Sc., 1997, 32, 23732379. 2. Y. Yin, G. Zhang and Y. Xia: Adv. Funct. Mater., 2002, 12, 293 298. 3. Bokhimi, A. Morales, T. Lopez and R. Gomez: J. Sol. State Chem., 1995, 115, 411415. 4. J. Y. Kim, H. S. Jung and K. S. Hong: J. Am. Ceram. Soc., 2005, 88, 784787. 5. J. A. Wang, O. Novaro, X. Bokhimi, T. Lopez, R. Gomez, J. Navarrete, M. E. Llanos and E. Lopez-Salinas: Mater. Lett., 1998, 35, 317323. 6. J. A. Wang, X. Bokhimi, O. Novaro, T. Lopez and R. Gomez: J. Mol. Catal. A, 1999, 145A, 291300. 7. T. Lopez, R. Gomez, J. Navarrete and E. Lopez-Salinas: J. Sol-Gel Sci. Technol., 1998, 13, 10431047. 8. S. C. Pillai, J. M. Kelly, D. E. McCormack and R. Ramesh: J. Mater. Chem., 2004, 14, 15721578. 9. S. C. Pillai, J. M. Kelly, D. E. McCormack, P. OBrien and R. Ramesh: J. Mater. Chem., 2003, 13, 25862590. 10. G. V. Samsonov: The oxide handbook, 105; 1973, New York, IFI/ Data Plenum Corporation. 11. C. Ho, Y. Xu and J. D. Mackenzie: J. Sol-Gel Sci. Technol., 1997, 9, 295301.

Conclusions
The solgel derived MgO through acetate oxalate route shows a very high degree of crystallinity and surface area, interesting morphology along with some promising thermal and dielectric properties. The MgO powders at 550uC shows some agglomeration (size range about 250 300 nm), although from BET surface values, existence of particle of 16 nm is also found. Studies of oxalate gel using TEM indicates this route to be a favourable one for obtaining tube/rod like morphology, however, more studies is to be conducted one other oxide systems also for a nal statement in this direction. The dielectric constant value of 67 at 0.3 MHz seems quite reasonable for polycrystalline MgO sintered samples and it matches well with the polycrystalline MgO thin lm samples studied earlier.

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