1 THE EFFECT OF MECHANOCHEMICAL ACTIVATION IN THE MgOAl2O3SiO2 SYSTEM REACTIVITY

C. A. dAzevedo 1,2, F. M. S. Garrido 2, M. E. Medeiros 2 *

1

Instituto de Pesquisas da Marinha - Rua Ipir no. 2, Ilha do Governador, 21931-090, Rio de Janeiro, Brazil Departamento de Qumica Inorgnica, Instituto de Qumica, Universidade Federal do Rio de Janeiro,

Ilha do Fundo, 21945-970, Rio de Janeiro, Brazil

ABSTRACT Samples on the MgOAl2O3SiO2 ternary system, constituted by 28.5mol % of MgO, 28.5mol % of Al2O3 and 43mol % of SiO2, were activated in a roll mill and calcined at different temperatures. The influence of grinding time, the ratio between powder mass and the grinding element mass, the SiO2 precursor and the activation medium, in the system reactivity were studied. The analysis of the infrared spectra and of the X-ray powder diffraction patterns indicates the formation, in some samples, of Mg(OH)2 at room temperature, of forsterite (MgSi2O5) and enstatite (MgSiO3) at 1223K and of spinel (MgAl2O4) between 1223K and 1523K. The presence of cordierite (Mg2Al2Si5O18) was observed at 1523K, a reaction pathway for its formation was proposed.

KEYWORDS: mechanochemistry, enstatite, spinel, cordierite.

__________________________________
*

Corresponding author: E-mail address: martam@iq.ufrj.

INTRODUCTION The energy transfer during the impact in a grinding process and its effect over the reactivity has been the subject of several studies, usually using high-energy mills with speeds higher than 500 rpm. Besides the increase in the homogeneity and the variation of the particle size, the intensity of the locally applied force over a determined powder volume, imprisoned at the contact point during the impact, determines the powder mechanochemical activation. In this process is common the formation of amorphous phases, creation of point defects or deformations in the crystalline network. In some special situations, mechanochemical reactions between the mixture components can occur during the grinding process [1-7].

2 Cordierite based ceramics on the ternary system MgOAl2O3SiO2 present great economic importance. Cordierite composition can vary between the limits expressed by the formulas 2MgO.2Al2O3.5SiO2 and MgO.Al2O3.3SiO2. In these ceramics secondary crystalline phases, such as corundum, mullite, spinel, forsterite, enstatite and cristobalite are presents very often [7-11]. As a consequence, the properties of these ceramics are strongly dependent on the composition, the presence of additives and manufacturing techniques. Recently, it was discussed the importance of spinel in the cordierite formation process [7,9-11]. Some authors proposed that cordierite would be formed from the reaction between spinel and a silica precursor phase [7,9]. However, other authors suggest that the utilization of additives would allow the direct synthesis of cordierite, either by the reaction between MgO, Al2O3 and SiO2 [10] or by the reaction between enstatite and alumina [11]. In this work, the mechanochemical activation of the MgO-Al2O3-SiO2 ternary system was studied. The objective was to produce ceramics based on the cordierite where spinel is present as the main secondary phase, trying to elucidate the influence of the spinel phase in the cordierite formation process.

MATERIALS AND METHODS Merck silicic acid (H4SiO4) (dehydrated by treatment with Merck concentrated perchloric acid) [12] and calcined at 1173K for 4h was used as precursor of silica (SiO2) for the cases of type samples. Another silica precursor was the Merck silica gel HF254 (Type 60) used as it was removed from the bottle, for type samples. The magnesium oxide precursor (MgO, P.A. Merck) was submitted to a thermal treatment at 823K for 4h, forming periclase [13]. The aluminum oxide precursor (Al2O3, Ridel-of-Han) was calcined at 1473K (4h) and used in the -corundum form (-Al2O3) [12, 14]. On the grinding process, 10g to 4,5g of the oxide mixture, with equal composition 28.5mol % of MgO, 28.5mol% of Al2O3 and 43mol% of SiO2, were placed in a Nalgene bottle of 250ml, together with the grinding elements. This composition, with an excess of MgO and Al2O3, was used to evaluate the influence of the spinel phase in the cordierite formation process. The grinding was performed in a US STONEWARE mill of roll at a 100rpm speed. Zirconia cylinders (NETSCH) with 1cm of diameter and 1cm of length were used as the grinding elements in the place of zirconia spheres, to increase the shock area [7]. Absolute ethyl alcohol P.A. (Grupo Qumica) and distilled and deionized water (MILLI-Q Water System equipment - Millipore) were used as activation medium. Table 1 presents the conditions used for grinding each one of the samples. The samples were heated for 2 hours at temperatures of 393K, 1223K, 1423K, 1523K or 1623K. The heating process was performed in two stages: 1) Starting from ambient temperature in steps of 6K/min until to reach 423K, remaining there for 1h; 2) Starting from 423K in steps of 10K/min until

3 to reach the temperature of calcination and remaining there for 2h. A Thermolyne F46240CM electric oven was used for all the thermal treatments. The infrared spectra were obtained with a resolution of 4cm-1 in a FTIR Nicollet Magna 760 Spectrophotometer, using the KBr disc technique. The crystalline phases were determined by X-ray diffraction (XRD) using a Rigaku Miniflex Diffractometer with Ni-filtered Cu K radiation, with a scanning speed of 20/min.

Table 1. Grinding Conditions SiO2 Precursor

Dehydrated Silicic Acid

Activation Medium
Absolute Ethyl Alcohol

Grinding Time (h)

2 18 48 2 48 2 48 2 48

M/C* Ratio
1/20 1/20, 1/40 1/20, 1/40, 1/80 1/20 1/40, 1/80 1/20 1/40, 1/80 1/20 1/40, 1/80

Sample
D0 D1, D2 D3, D4, D5 aD0 aD4, aD5 bD0 bD4, bD5 cD0 cD4, cD5

Absolute Ethyl Alcohol Silica Gel Mixture of Absolute Ethyl Alcohol and Water Water M/C* = powder mass / zirconia cylinders mass

RESULTS AND DISCUSSION Dehydrated and calcined silicic acid as SiO2 precursor Table 2 shows the results of DRX and FTIR for the samples D0 to D5 heated to different temperatures. The XRD results for the samples heated at 394 K and for the samples calcinated at 1223 K (Table 2 and Figure 1) show a progressive decrease in the relative intensity of the peak at 2 = 42.900. This can be associated with a progressive amorphization of the periclase (MgO) [13], that takes place as a consequence of the increase on the grinding time and of the reduction in the M/C ratio. For the samples heated at 1223K (Table 2 and Figure 1), the predominant crystalline phase observed was -Al2O3 [14]. In addition, different amounts of periclase (MgO) were also observed. For the sample D0 the amount of periclase was greater. For all the samples there is also the formation of a small amount of Mg and Al spinel (MgAl2O4), as indicated by the presence of DRX peaks in 2 = 36.800 and 44.800 [15]. However, with exception for the sample D0, bands were observed in IR spectra (at 952cm-1 and 894cm-1, region of Si-O stretching [16, 17]) as well peaks in the DRX (in 2

4 = 22.900, 32.300, 35.700 and 39.800 [18]) that indicate the formation of a small amount of forsterite (Mg2SiO4). In addition, for samples D3, D4 and D5, enstatite (MgSiO3) appears as a minor crystalline phase, this fact being confirmed by IR bands at 1013cm-1 and 860cm-1, and by DRX peaks in 2 = 28.130 and 31.400 [19, 20]. The enstatite occurs in a higher amount in the sample D5, this fact points out the importance of the degree of mechanochemical activation on the enstatite formation.

Table 2. Observed phases on samples using dehydrated silicic acid as SiO2 precursor. Temperature
393K

Sample
D0 to D5 D0

Observed Phases
-Al2O3, SiO2, MgO -Al2O3, SiO2, MgO, MgAl2O4 -Al2O3, SiO2, MgO, MgAl2O4, Mg2SiO4 -Al2O3, SiO2, MgO, MgAl2O4, Mg2SiO4, MgSiO3 -Al2O3, -SiO2, MgAl2O4 -Al2O3, -SiO2, MgAl2O4, Mg2Al4Si5O18

1223K

D1, D2 D3, D4, D5 D0, D1, D2

1523K D3, D4,D5

1623K D0 to D5 -Al2O3, -SiO2, MgAl2O4, Mg2Al4Si5O18 SiO2 = amorphous silica (observed by IR), -SiO2 = -cristobalite

1200 1000 800 600 400 200 0 1 2 0100 1000 800 600 400 200 0 1 2 0100 1000 800 600 400 200 0 10

C
20 30 40 50 60

B
20 30 40 50 60

A
20 30 40 50 60

F ig 1 . X -ra y p o w d e r d iffra c tio n p a tte r n s o f s a m p le s A ) D 0 , B ) D 3 a n d C ) D 5 c a lc in e d a t 1 2 2 3 K . c o ru n d u m p e ric la s e fo rs te rite e n s ta tite s p in e l

5 Table 2 and Figures 2 and 3 show that spinel (MgAl2O4) [15,21] and -cristobalite [22-24] are the predominant phases in the samples calcined at 1523K, with exception of the sample D0 where a great amount of -Al2O3 is still observed. However, a small amount of cordierite (Mg2Al4Si5O18) was formed in the samples D3, D4 and D5, as indicated by IR bands at 1179cm-1 (asymmetrical stretching of tetrahedral Si-O), 960cm-1 (stretching of Al-O bonding) and 770cm-1 (symmetrical stretching of Si-O bonding), and by a DRX peak in 2 = 28.490 [17, 25-27]. As can be seen in Figures 2 and 3 the amount of cordierite increases with the increasing in the mecanochemical activation, and therefore it is maximum for the sample D5. This corresponds to the case where the amount of enstatite is the highest for the samples heated at 1223K. This fact suggests a correspondence between the presence of enstatite, on the samples heated at 1223K, and the cordierite formation at 1523K. In all samples calcined at 1623K the formation of cordierite (Mg2Al4Si5O18) ocurred. As the grinding time increased and the M/C rate decrease, the amount of cordierite increased with a simultaneous diminishing of cristobalite (-SiO2). Therefore, the amount of cordierite formed on sample D0 is the lower one according to data obtained from DRX and FTIR. These results indicated that calcined and dehydrated silicic acid is not an adequate SiO2 precursor for the synthesis of cordierite at 1523K, and hence another precursor was studied.

2500 2000 1500 1000 500 0 800 700 600 500 400 300 200 100 0 600 500 400 300 200 100 0

0 .0 5

C
0 .0 0

C
20 30 40 50 60
1 4 0 0 0 .2 5 0 .2 0 0 .1 5 0 .1 0 0 .0 5 0 .0 0 1 5 0 0 0 .1 6 0 .1 4 0 .1 2 0 .1 0 0 .0 8 0 .0 6 0 .0 4 0 .0 2 0 .0 0 1 5 0 0 1 2 0 0 1 0 0 0 8 0 0 6 0 0

10

B
10 20 30 40 50 60

B
1 0 0 0 5 0 0

A
10 20 30 2 40 50 60

A
1 0 0 0 5 0 0
-1

c m

Fig 2. X-ray podwer diffraction patterns of samples A) D0, B) D3 and C) D5 calcined at 1523K. -corundum cristobalite spinel cordierite

Fig 3. IR spectra of samples A) D0, B) D3 and C) D5 calcined at 1523K. -corundum cristobalite spinel cordierite

6 Silica gel as SiO2 precursor On this stage a variation of the activation medium was also introduced, as well a different SiO2 precursor. The options used were: absolute ethyl alcohol (samples aD), a mixture of distilled and deionized water 10% v/v in absolute ethyl alcohol (samples bD), or distilled and deionized pure water (samples cD). The results of DRX and FTIR are resumed on Table 3 for the samples aD0 to cD5, heated at different temperatures.

Table 3. Observed Phases on samples using silica-gel as SiO2 precursor. Temperature Sample
aD0, aD4 aD5 bD0, cD0, bD4, bD5 393K cD4 SiO2, -Al2O3, Mg(OH)2 SiO2, -Al2O3, Mg(OH)2 * SiO2, -Al2O3, MgO, Mg2SiO4 a D0,bD0, cD0 -SiO2, -Al2O3, MgAl2O4, Mg2Al4Si5O18

Observed Phases
SiO2, -Al2O3, MgO SiO2, -Al2O3, MgO, Mg(OH)2

Temperature

Sample
aD4, bD4, cD4, aD5, bD5, cD5

Observed Phases

1423K

-SiO2, -Al2O3, MgSiO3, MgAl2O4

cD5

aD0, bD0

cD0 1223K aD4,aD5 bD4, cD4, bD5, cD5

SiO2, -Al2O3, MgO, Mg2SiO4, MgSiO3 SiO2, -Al2O3, Mg2SiO4, MgSiO3 SiO2, -Al2O3, MgSiO3

1523K

aD4, bD4, cD4, aD5

-SiO2, -Al2O3, MgSiO3, MgAl2O4, Mg2Al4Si5O18

-SiO2, MgAl2O4, Mg2Al4Si5O18 cD5 MgAl2O4, Mg2Al4Si5O18 SiO2 = amorphous silica, * = amorphous Mg(OH)2 (observed by IR), -SiO2 = -cristobalite

bD5

For all samples that suffered activation in the presence of water (bD and cD), the presence of an IR band at 3700cm-1 was observed and attributed to the O-H stretching of Mg(OH)2 [28]; meanwhile, a DRX peak in 2 = 18,590 [29] was observed for some samples (Figure 4 and Figure 5). These data indicated the formation of the magnesium hydroxide - Mg(OH)2 - during the grinding process (Table 3). On samples cD4 and cD5, as it is showed on Figure 4, all MgO reacted since the DRX peak at 2 = 42,900 was not observed [13]. For the sample cD5 (Figure 4F) the DRX peak at 2 = 18,590 [29] was not observed, what indicated that in this sample the Mg(OH)2 produced is amorphous or reacted with the SiO2 , forming an amourphous magnesium silicate as observed by MacKenzie for the MgO-SiO2 system [29]. 6

7
700 600 500 400 300 200 100 0 20 30 40 50 60010 500 400 300 200 100 0 70010 600 500 400 300 200 100 0 6 0 10

100 0 80 0 60 0 40 0 20 0 0 90 0 10 80 0 70 0 60 0 50 0 40 0 30 0 20 0 10 0 0 10 140 0 120 0 100 0 80 0 60 0 40 0 20 0 0 10

F
20 30 40 50 60

0 ,1 5 0 ,1 4 0 ,1 3 0 ,1 2 0 ,1 1 0 ,1 0 0 ,0 9 0 ,0 8 0 ,0 7 0 ,0 6 0 ,0 5 0 ,0 4 0 ,0 3 0 ,0 2 0 ,0 1 0 ,0 0 -0 ,0 1 -0 ,0 2 3 8 0 0 0 ,0 5

0 .1 0 0 .0 5

C
0 .0 0
3 7 0 0 3 6 0 0 3 5 0 0 3 4 0 0 3 3 0 0

F
3 6 0 0 3 4 0 0 3 2 0 0

3 2 0 0 3 8 0 0

B
20 30 40 50

E
0 ,0 0
20 30 40 50 60

B
0 .0
3 8 0 0 0 ,0 8 0 ,0 6 0 ,0 4 0 ,0 2 0 ,0 0 -0 ,0 2 3 8 0 0 3 7 0 0 3 6 0 0 3 5 0 0 3 4 0 0 3 3 0 0 3 2 0 00 3 8 0 0 .0 5 0 .0 4 0 .0 3 0 .0 2 0 .0 1 0 .0 0 -0 .0 1 -0 .0 2 -0 .0 3 3 2 0 0 3 8 0 0

E
3 6 0 0 3 4 0 0 3 2 0 0

A
20 30 40 50

D
20 30 40 50 60

A
3 6 0 0 3 4 0 0

3 6 0 0

3 4 0 0

3 2 0 0

C M

-1

C M

-1

Fig 4. X-ray podwer diffraction patterns of samples A) aD4, B) bD4, C) cD4, D) aD5, E) bD5, F) cD5 dried at 393K . -corundum periclase magnesium hidroxide

Fig 5. IR spectra of samples A) aD4, B) bD4, C) cD4, D) aD5, E) bD5, F) cD5 dried at 393K . magnesium hidroxide

From Figure 6 and Table 3 we can conclude that there was no spinel formation for the samples calcined at 1223K, as it was observed for the D samples calcined at same temperature. However, when compared with D5 sample (Figure 1) these D samples contain a higher amount of enstatite. The analysis of X-ray diffraction patterns and IR spectra also indicated that the amount of enstatite formed in the sample aD5 was greater than that formed in the sample aD4, and that the amount of forsterite was greater in aD4 than in aD5. In addition, the absence of DRX peaks at 2 = 22.900, 32.300, 35.700 and 39.800 demonstrated that there was no formation of forsterite [19] in those samples that suffered activation in presence of water (bD4, bD5, cD4 and cD5). Therefore, it can be affirmed that a decrease in the M/C ratio and an increase in the amount of water in the activation medium result in an increase in the amount of enstatite formed, as well a inhibition of the forsterite formation.
800 700 600 500 400 300 200 100 0 10 900 800 700 600 500 400 300 200 100 0 10 1200 1000 800 600 400 200 0 10 20 30 40 50 60 20 30 40 50 60 1000 800 600 20 30 40 50 60 800 700 600 500 400 300 200 100 0 10 20 30 40 50 60 900 800 700 600 500 400 300 200 100 0 10 20 30 40 50 60

C C

F F

B B

E E

A A

400 200 0 10

D D
20 30 40 50 60

Fig6. X-ray podwer diffraction patterns of samples A) aD4, B) bD4, C) cD4, D) aD5, E) bD5, F) cD5 calcined at 1223K. -corundum enstatite forsterite

8 The above results suggest that the utilization of water as activation medium allowed a higher degree of mechanochemical activation of silica gel and MgO, resulting in increasing of reaction between the silica gel and the magnesium precursor at 1223K. The final result is the formation of enstatite and the inhibition of spinel formation, since all the magnesium precursor probably reacted with silica gel. As can be seen in the Figures 7 and 8 (X-ray diffraction patterns and IR spectra), when these samples are calcined at 1523K some DRX peaks appear at 2 = 10.500 and 28.490 and IR bands are observed at 1179cm-1, 960cm-1 and 770cm-1, confirming the formation of the cordierite [17,25-27]. In addition to an increasing in the intensity of these peaks and bands, a gradual reduction of intensity of cristobalite IR band at 1090cm-1 [22, 23] is observed which indicates that the silica consumption is associated with the formation of cordierite. As the degree of mechanochemical activation and the amount of water in the activation medium are increased we can also observe a gradual disappearance of the DRX peaks related to enstatite and -Al2O3. Therefore, the formation of the cordierite is also associated with the consumption of these phases. There is also the formation of a MgAl2O4 phase in all the samples, since DRX peaks in 2 = 36.800, 44.800, 59.400 [15] and an IR band at 690cm-1 [21] were found. This phase is in a larger amount in the sample aD5.

800 700 600 500 400 300 200 100 0 900 800 700 600 500 400 300 200 100 0 800 700 600 500 400 300 200 100 0 800 700 600 500 400 300 200 100 0

D
10 20 30 40 50

C
10 20 30 40 50

B
10 20 30 40 50

A
10 20 30 40 50 60

0, D 0, 0, 0, 1 1 1 8 C 0 0 0 0 1 1 1 8 0 B 0 0 0 0 0 1 1 1 8 0 A 0 0 0 0 0 0 0 1400 1200 1000 800 cm

-1

6 6 6
600

Fig 7. X-ray podwer diffraction patterns of samples A) aD0, B) aD5, C) bD5 and D) cD5 calcined at 1523K . -corundum cristobalite enstatite spinel cordierite

Fig 8. IR spectra of samples A) aD0, B) aD5, C) bD5 and D) cD5 calcined at 1523K . -corundum cristobalite enstatite spinel cordierite

9 Figures 9 and 10 present X-ray diffraction patterns and IR spectra that illustrate the evolution of the formation of phases with the temperature on sample cD5. For the sample, ground and dried at 393K, the X-ray diffraction pattern (Figure 9A) indicates that -Al2O3 [14] is the only crystalline phase presents. IR spectrum (Figure 10A) indicates the presence of -Al2O3 by bands at 640cm-1 and 590cm-1, and of amorphous SiO2, due to the presence of a characteristic band around 1110cm-1. The amorphous magnesium hydroxide - Mg(OH)2, is indicated by the presence of IR band around 3700cm-1 (Figure 5F). There are also a series of shoulders that in principle can be associated to other amorphous phase, as for example the amorphous magnesium silicate observed by MacKenzie for the MgO-SiO2 system [29]. When heated at 1223K, an expressive amount of enstatite is formed (Figure 9B). An IR band related to the amorphous SiO2 is observed around 1110cm-1, in addition to the Al2O3 referring bands (Figure 10B). For the sample calcined at 1423K, the DRX peaks and IR bands found are an indication of the presence of -cristobalite [22-24], -Al2O3 [14,16], enstatite [19,20] and a small amount of MgAl2O4 [15,21]. For the sample heated at 1523K, the almost disappearance of the IR band at 1090cm-1 is observed [22, 23], what indicates a pronounced consumption of SiO2 (Figure 10D). The main peaks observed in the X-ray diffraction pattern of this sample, are those referring to cordierite [27], the main phase, and to the MgAl2O4 [21], the secondary phase. For the sample calcined at 1623K, there are no significant alterations in the X-ray diffraction patterns and in the IR spectrum with respect to the sample heated at 1523K. Therefore, this sample is composed basically by the cordierite, the main phase, and by the secondary phase MgAl2O4.

800 600 400 E 200 0 800 700 600 500 400 D 300 200 100 0 400 300 C 200 100 0 800 700 600 500 B 400 300 200 100 0 500 400 300 A 200 100 0 10 20 30 40 50 60

0.165 0.160 0.155 0.150 0.145 0.140 0.135

14 00

12 00

10 00

800

6 00

10

20

30

40

50

60

D
0 .0 0 14 00 0 .1 6 12 00 10 00 800 6 00

10

20

30

40

50

60

0 .1 4

C
14 00 12 00 10 00 800 6 00

10

20

30

40

50

60

0 .3 2 0 .3 0 0 .2 8 0 .2 6 0 .2 4

B
14 00 12 00 10 00 800 6 00

0 .6

10

20

30

40

50

60

0 .4

A
14 00 12 00 10 00 800 6 00

c m

-1

Fig9. X-ray powder diffraction patterns of sample cD5 A) grounded and dried at 393K, B) 1223K, C) 1423K, D) 1523K and E) 1623K. -corundum SiO2 spinel enstatite cordierite

Fig10. IR spectra of sample cD5 A) grounded and dried at 393K, B) 1223K, C) 1423K, D) 1523K and E) 1623K. -corundum SiO2 spinel enstatite cordierite

10 From these results it is evident that the formation of enstatite at 1223K has a major influence on the temperature and reaction pathway of cordierite formation. It is also clear that the degree of mechanochemical activation and the amount of water in the activation medium are the most important factors to the formation of enstatite. Similar results were reported in the literature when the synthesis of cordierite was made in the presence of additives such as fluorite [11] or when the mecanochemical activation was made in an attrition mill at 4500rpm and clay minerals were used as starting materials [30]. However, in these papers [11,30] it was not clear the importance of enstatite in the cordierite formation process. With respect to the influence of spinel phase on the cordierite formation process, some authors proposed that cordierite would be formed from the reaction between spinel and a silica precursor at around 1600K [9]. Our results show that for the samples with high degree of mechanochemical activation the spinel phase do not participate on the cordierite formation process.

CONCLUSION From the results obtained by DRX and IR spectroscopy, we concluded that: i. Conditions of grinding with t = 18h or M/C higher than 1/40 do not present good results respecting to the formation of cordierite (Mg2Al4Si5O18); ii. For the objective of cordierite synthesis, silica gel as SiO2 precursor works better than dehydrated and calcined silicic acid. iii. The formation of Mg(OH)2 during the mechanochemical activation in the samples where water was used as the activation medium provides the formation of enstatite (MgSiO3); iv. In the samples with high degree of mechanochemical activation, the formation of the cordierite at 1523K can be describe by the following reaction: 2MgSiO3 + 2Al2O3 + 3SiO2 Mg2Al4Si5O18 v. The mechanochemical activation, using water as activation medium, allows a great amount of cordierite to be formed at 1523K.

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11 4 5 6 7 8 M. Senna, Mater. Science and Eng. A, 304-306 (2001) 39. V. V. Boldyrev, Powder Technol. 122 (2002) 247. J. Alkebro, S. Bgin-Clin, A. Mocellinb, R. Warren, J. Solid State Chem., 164 (2002) 88. S. Tamborenea, A. D. Mazzoni, E. F. Aglietti, Thermochim. Acta 411 (2004) 219. D. U. Tulyaganov, M. E. Tukhtaev, J. J. Escalante, M. J. Ribeiro, J. A. Labrincha, J. Eur. Ceram. Soc., 22 (2002) 1775. 9 10 11 12 M. K. Naskar, M. Chatterjee, J. Eur. Ceram. Soc., 24 (2004) 3499. Z. M. Shi, K. M. Liang, S. R. Gu, Mater. Lett., 51 (2001) 68. S. Taruta, T. Hayashi, K. Kitajima, J. Eur. Ceram. Soc., 24 (2004) 3149. I. M. Kolthoff, E. B. Sandell, Textbook of Quantitative Inorganic Analysis, 3th edition, MacMillan Company,1963. 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Powder Diffraction File, JCPDS, Index card 4-0829 (1972). Powder Diffraction File, JCPDS, Index card 10-173 (1972). Powder Diffraction File, JCPDS, Index card 5-0672 (1972). M. T. Tsai, Mater. Res. Bull., 37 (2002) 2213. Fiveash Data Management, (1997). Powder Diffraction File, JCPDS, Index cards 4-0768 and 4-0769 (1972). B. D. Saksena, Trans. Faraday Soc., 57 (1961) 242. Powder Diffraction File, JCPDS, Index card 7-216 (1972). N. W. Grimes, Spectrochim. Acta, 28A (1972) 2217. M. Haccuria, Bull. Soc. Chim. Belge, 62 (1953) 428. F. Matossi, J. Chem. Phys., 17(1949) 679. Powder Diffraction File, JCPDS, Index card 4-0379 (1972). B. Gttler, E. Salje, A. Putnis, Phys. Chem. Miner., 16 (1989) 365. Gouby, P. Thomas, D. Mercurio, T. Merle-Mjean, B. Frit, Mater. Res. Bull., 30 (1995) 593. Powder Diffraction File, JCPDS, Index card 12-303 (1972). Powder Diffraction File, JCPDS, Index card 7-239 (1972). J. Temuuijin, K. Okada, K. J. D. MacKenzie, J. Solid State Chem., 138 (1998) 169. F. A. Costa Oliveira, J. Cruz Fernandes, Ceram. Int., 28 (2002) 79.

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