Proceedings of International Conference on X-ray Microscopy and Smart Materials (ICXSM 2011), June 13, 2011, Solo,Indonesia

Rietveld X-Ray Diffraction Data Analyses for Magnesium Titanate Powders Produced by Mg and Ti Mixing in HCl
Istianah*, Rina Lestari, Malik A Baqiya, Suminar Pratapa
Department of Physics, Faculty of Mathematics and Sciences Institute of Technology Sepuluh November (ITS). Jl. Arif Rahman Hakim, Surabaya 60111 Email: istianah09@mhs.physics.its.ac.id

ABSTRACT
Syntheses of MgTiO3 powders produced by Mg and Ti powders mixing in HCl have been conducted. The raw materials were Mg and Ti powders with Mg-to-Ti mass ratios of 1,16: 2 and 1,18: 2 weighed in gram. MgCl2 + TiCl4 solutions were made by independently dissolving the metal powder with HCl followed by mixing with time variation for 2 and 4 hrs. The mixtures were dried in air at 80C and then calcined at 800C for 1 hr. Formation of MgTiO3 is evident from qualitative x-ray diffraction (XRD) data analysis. The calcined 2h-mixing sample contained the desired titanate phase but with the presence of rutile and periclase. Mixing up to 4 hours followed by calcination eliminates the periclase with a slight rutile leftover. Employment of Rietveld method for relative-weight-fraction phase composition showed that the latter sample exhibits MgTiO3 purity up to 99,6%. Keywords

: MgTiO3, Rietveld method, X-ray Diffraction, dissolution mixing.

Rietveld X-Ray Diffraction Data Analyses for Magnesium Titanate Powders Produced by Mg and Ti Mixing in HCl Istianah

1. INTRODUCTIONS
Magnesium titanate (MgTiO3, abbreviated as MT) is a ceramic material with ilmenite structure, rhombohedral with space group R -3 H, and cell parameters a = b = 5.086 , c = 14.093 , which can be used as multilayer

capasitors (MLCC) with r ~17 [1]. The closest oxygen ions form hexagonal closed-packed (HCP) structure 2+ with the 2/3 of the cation position occupied by Mg dan 4+ Ti while the rest 1/3 octahedral sites is vacant [2].

where wi is relative weight fraction of phase i (%), is Rietveld phase scale, Z is number of formula in unit cell, M is formula weight and V is volume of unit cell.

3. RESULTS AND DICUSSION

3.1 X-ray Diffraction Measurements.

MT has many interesting applications such as chip capasitors, high frequency capasitors and temperature compensating capasitors [3], resonators, filters, antennas for communication, radar and direct broadcasting satellite [4]. Thermodinamically, group of MT includes several phases, such as stable phase (corundum-type structure), MgTi2O5 MgTiO3 (pseudobrookite structure) and Mg2TiO4 (spinel structure) [5]. There were synthesis methods which have been employed by others including optimized mixing [6], solid-state reaction [7-10], sol-gel [4, 8, 11, 12], mechanochemical activation [13, 14], stearic acid gel (SAG) method [4, 15], and co-precipitation [16]. However, these methods have some disanvantages such as high sintering temperature, durable processing, contamination by impurities, nonuniform particle size distribution and irregular morphologies. This reported study used a wet mixing method, with acid-dissolved metals, which will be proved more efficient, low sintering temperature and high purity level.

Figure 1. X-ray diffraction pattern (cuK = 1.5418 ) at MT62, MT82, MT64 and MT84 calcined at 800C for 1h as described above. Note: = MgTiO3, = rutile dan = periclase. Figure 1 shows the x-ray diffraction (XRD) patterns for the MT62, MT82, MT64 and MT84. The diffraction patterns for the samples show no significant difference. MgTiO3 (PDF No. 06-0494) is dominant with peaks found at 2 around 19.1; 21.2; 24.0; 32.8; 35.5; 40.6; 43.2; dan 49.1. The presence of rutile (PDF ) No. 34-0180 with peaks around 2 of 27.4; and 36.0 and periclase (PDF No. 43-1022 of 42.9), however, is evident, particularly in MT62 and MT82 samples. The appearance of rutile and periclase phase on mixing for 2h because they have not reacted perfectly to form MgTiO3. Mixing up to 4h followed by calcination eliminates the periclase with a slight rutile leftover. These results show that such wet mixing procedure can be used to produce MgTiO3 and prolonged mixing time of the metal solutions may increase the homogeneity of the ionic distribution in order to complete the formation of MgTiO3. To support the arguments, following passage presents the quantitative analysis results of the XRD data. 3.2 Refinement with Rietveld Method Rietveld refinement for each data was performed using Rietica [17]. Figure-of-merits (FoMs) of the refinement are presented in Table 1. A typical refinement plot is shown in Figure 2. Table 1 describes the acceptability of the refinements since Rwp is less than 20% and goodness-of-fit (GoF) is less than 4%, which have been determined as the criteria of successful refinement [18], as addition to insignificant fluctuations of difference plot indicated in Figure 2. The success on the refinement leads to the acquiescence of further analysis including phase composition calculation.
2

2. RESEARCH METHOD
The raw materials were Mg and Ti metal powders, whereas the solution was HCl 37%. Mg-to-Ti mass ratios of 1,16: 2 and 1,18: 2 (weighed in gram) were used. The Mg powder was dissolved in HCl by stirring at room temperature for 10 mins and resulted in yellowish clear solution, while the Ti powder was dissolved in a similar way but at 65C for 2h and resulted in blackish purple solution. The solutions were mixed by stirring at room temperature with mixing time of 2 and 4h. Numenclature for the samples are given as follows MT62 = MgTiO3 from 1,16:2 Mg-to-Ti ratio after mixing for 2h, MT82 = MgTiO3 from 1,18:2 Mg-toTi ratio after mixing for 2h, MT64 = MgTiO3 from 1,16:2 Mg-to-Ti ratio after mixing for 4h and MT84 = MgTiO3 from 1,18:2 Mg-to-Ti ratio after mixing for 4h. The mixtures were dried in air at 80C. The dry MT agglomerates were continuously crushed with mortar for 30 mins which was then calcined at 800C for 1h at 10C/min heating and cooling rates. Phase formation was determined using x-ray diffractometry with conditions of 2 range of 15-50, 0.04 step size and 1s/step collecting time. Rietveld compositional phase analyses were performed using Rietica [17]. Assuming that the sample contains totally crytalline, the relationship between Rietveld phase scale and relative phase weight fraction is in the form of [19]

Rietveld X-Ray Diffraction Data Analyses for Magnesium Titanate Powders Produced by Mg and Ti Mixing in HCl Istianah

MgTiO3 Sample MT62 MT82 MT64 MT84 MgTiO3 Sample MT62 MT82 MT64 MT84

Figures-of-Merit Rp 13,3 11,3 11,4 12,7 Rwp 19,9 19,3 18,5 19,9 Rexp 17,0 16,9 17,2 17,1
-3

Fraksi % berat Sampel GoF 1,4 1,3 1,2 1.3 MT82 MT64 MT84 96,2(37) 98,5(36) 99,6(29) 1,8(4) 1,4(2) 0,4(1) 2,0(2) 0,1(3) MT62 MgTiO3 94,8(37) Rutile 1,8(4) Periclase 3,5(3)

Phase Scale (10 ) MgTiO3 0,1286 (3) 0,1369 (3) 0,1387 (4) 0,1280 (3) Rutile Periclase

0,0528 (10) 0,0864 (6) 0,0579 (12) 0.0529 (5) 0,0562 (5) 0,0572 (5) 0,0807 (8)

Table 2. Rietveld weight fraction phase produced by Mg and Ti powder mixing in HCl with time variation for 2 and 4 hs. For comparison, syntheses of MgTiO3 have been undertaken by Sreedhar et al (2001) through solid state powder with reaction of MgO and TiO2 stoichiometrically excessive MgO [20]. In this study to producing high purity MgTiO3 can only be achieved with calcination at temperature above 800C and with the formation of MgTi2O5 where in the present study is absent. Another study was conducted by Pfaff (1993) using peroxide route method [3]. In this study metastable phases Mg2TiO4 and MgTi2O5 were found when the precursor was calcined at 500-700C for 8h and high purity MgTiO3 was produced after calcination at 1000C for 8h.

Table 1. Rietveld refinement output of the whole-pattern diffraction data for MgTiO3

MT 1,16:2_2 h

4. CONCLUSION
We have shown that high purity MgTiO3 powder can be synthesized by dissolving Mg and Ti powders in HCl and mixing the solutions for 4h followed by calcination at 800C for 1h. The purity reaches 99.6% and the calcination temperature is relatively lower than that with other methods. Longer mixing time resulted in more homogenous mixture which then favour the completion of the reaction between the constituents.

5. ACKNOWLEDGEMENT
Figure 2. Rietveld refinement plot for MT62 calcined at 800C for 1h. Red peak is calculated diffraction pattern, black peak (+++) is measured diffraction pattern, blue vertical lines indicate peak positions of each phase (top= MgTiO3, middle=rutile,bottom= periclase) and the lines below the plot is the difference profile. I is grateful to the Ministry of Religious Affairs who provides financial support through Teacher Scholarship Program for the period 2009/2011. 6. REFERENCES 1. Huang, C.-L., C.-L. Pan, and J.-F. Hsu, Dielectric properties of (1-x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency. Materials Research Bulletin, 2002. 37(15): p. 2483-2490. Anichini, A., et al., The incorporation and the 2+ reducibility of Ni in MgTiO3. Journal of Solid State Chemistry, 1983. 49(3): p. 309-317. Pfaff, G., Peroxide route for synthesis of magnesium titanate powders of various compositions. Ceramics International, 1994. 20(2): p. 111-116. Kang, H., et al., Synthesis of tetragonal flake-like magnesium titanate nanocrystallites. Journal of Alloys and Compounds, 2008. 460(1-2): p. 160163. Cheng, H., Xu, B., dan Ma, J., Preparation of MgTiO3 by an improved chemical co-precipitation
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3.3 Relative Weight Fraction Phase

Table 2. shows the relative weight fraction for the samples. Most interesting result is shown by MT84 sample which exhibits MgTiO3 purity up to 99,6%. It contains only 0,4% rutile. As qualitatively discussed previously, MgTiO3 dominates the samples. This quantitative analysis confirmed the argument where in all cases, at least 94,8% of MgTiO3 is found. The amount of periclase and rutile was only in the range of 3,5% and 1,8%, respectively. Further inspection shows that prolonged mixing reduces the amount of periclase by MT84

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Rietveld X-Ray Diffraction Data Analyses for Magnesium Titanate Powders Produced by Mg and Ti Mixing in HCl Istianah

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