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J. MATER. CHEM., 1992,2(6), 591-594

59 1

Sol-Gel Synthesis of Barium Titanate Powders of Various Cornposit ions
Gerhard Pfafft Department of Chemistry of the friedrich Schiiler University, August-Bebel-StraBe 2, D(0) 6900 Jena, FRG

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The barium titanates BaTiO,, Ba,TiO,, BaTi,O, and BaTi,O, can be synthesized by a sol-gel method at low temperatures. The reaction between barium acetate solutions and titanium(1v) isopropoxide leads to the formation of barium titanate gels. The gels can be converted to the barium titanates by drying and calcination. The resulting ultrafine, phase-pure barium titanate powders have a small impurity content. They are very sinter active above 1200°C. The rate of densification (which considers the green densities, the densities at a given time and the theoretical densities of the titanates for the calculations) during the sintering of compacts increases as BaTi,O, < Ba,TiO,< BaTiO,< BaTi,O,. The barium titanate gels and the titanate powders were characterized by DTA, TG, XRD and chemical analysis. Keywords: Sol-gel processing ; Barium titanate ; Sintering

Barium titanates are interesting compounds, in particular with regard to their electrical properties. The phase equilibria in the BaO-TiO, system have been studied extensively and the existence of seven stable phases, Ba2Ti04, BaTiO,, BaTi,OS, Ba6Ti17040, Ba4Ti13030,BaTi409 and Ba2Ti9020, has been reported in the literature.',, BaTiO,, the most important of these compositions, is a well known dielectric material of technological importance and is normally synthesized at relatively high temperatures of ca. 1350°C by solidstate reaction between BaC03 and TiO,. Such conditions lead normally to powders of relatively large and varied grain sizes and varying impurity content. There are often problems obtaining phase-pure material because of the intermediate formation of other phases, such as Ba,TiO,, during the BaTi03 ~ y n t h e s i s .A ~ ,few ~ per cent of barium orthotitanate influences unfavourably the electrical properties of ceramics based on BaTi03.3-5 On the other hand, in the manufacture of multilayer capacitors, the high formation temperatures necessitate the use of noble metals during co-sintering.6 Relatively inexpensive metals (Cu, Ni etc.) can replace noble-metal electrodes if the multilayer capacitors are processed at temperatures below 1000 "C. Low-temperature synthesis and processing of electroceramic materials such as barium titanate therefore provide an interesting alternative to the hightemperature processes. Possible ways of reducing the reaction temperatures are the use of low firing dielectric compositions of sintering aids (e.g. LiF), and low-temperature synthesis of high-purity and ultrafine electroceramic powders. Suitable methods consist of the direct separation of BaTiO, from solution or the preparation of precursors, from which the barium titanate is formed as a very fine powder with high sinterability as a result of thermal decomposition at relatively low temperature. BaTi0, is formed by thermal degradation of precipitated barium titanyl oxalate7 or of the peroxoprecursor BaTiO2(O2)3H20.8The direct synthesis of fine crystalline BaTiO, from aqueous solution succeeds by hydrolysis of Ti(OC4H9), in the presence of Ba(OH)2.9The sol-gel method is known likewise for the preparation of BaTi0,.6i'0-13 Similar procedures are described for the low-temperature preparation of Ba2Ti04, BaTi, 05 , 16and BaTi,0,.'9-21
~ ~ ~ ~ ~~~~

The primary objective of the present research was the synthesis of the four barium titanates BaTiO,, Ba2Ti04, BaTi,OS, and BaTi40, uia a sol-gel method. Barium acetate and titanium(1v) isopropoxide were used as the starting compounds to obtain high-purity, homogeneous, stoichiometric and ultrafine titanate powders. The preparation of the gel precursors, their thermal decomposition to the titanates and the characterization of both intermediate products and the final titanate powders as well as the results from sintering experiments are described here.

Experimental
BaO (E. Merck, Darmstadt) (0.3 mol) was dissolved in 30 cm3 conc. acetic acid, and methanol (50cm3) was added to this solution. The resultant mixtures were added slowly to 1 : 1 solutions of titanium(1v) isopropoxide (E. Merck, Darmstadt) and dried n-butanol at 25°C while stirring (Ba:Ti in the desired ratios). The necessary amount of water was then added to the reaction solutions. The liquids were allowed to evaporate, forming gels. The gels were dried at 110 "C to form white gel powders. These were calcined in air at temperatures up to 1200 "C. The oven-dried and heat-treated powders were investigated by thermogravimetric analysis (TG), differential thermal analysis (DTA),X-ray diffraction (XRD),and chemical analysis (Ti as TiO, after precipitation with cupferron and annealing, Ba as BaSO,). The impurity content of certain elements was measured using atomic absorption spectrometry (AAS) or atomic emission spectrometry (AES). Surface characterization of the titanate powders was carried out by B.E.T.-measurements and by scanning electron microscopy (SEM). For the sintering experiments, the four barium titanate powders calcined at 900°C for 1 h were mixed with a binder solution (65% H 2 0 , 25% glycerol, 10% PVA) in a mortar, deagglomerated for 20 min in a ball mill, dried and sieved out 80 mesh. The powders were pressed in the form of discs under a pressure of 125 MPa and sintered at 1200 "C. The densities of the specimens were determined by weighing and by measuring dimensions using a micrometer before and after each heating step.

Results and Discussion

t Present address: E. Merck, Research & Development, Pigment Division, Frankfurter Strasse 250, D-6100 Darmstadt 1, FRG

The results of the analysis of the powders obtained after calcination of the gel precursors at 900°C (at 1200°C in the

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case of BazTi04) are presented in Table 1. The barium and titanium contents of the four barium titanate powders are very close to the expected values. The Ba :Ti ratio, an important determinant of the variation of the dielectric constant with temperature, usually ranges from 0.977 to 1.03 for BaTi03.6*22 The results in Table 1 show that the Ba : Ti ratio for the titanates synthesized using the described sol-gel technique almost reach the theoretical values. Table 2 contains surface data and further analytical values for the barium titanate powders. The titanates possess relatively large specific surface areas resulting from very small particles. The high surface energies effect a strong agglomeration which is evident in the electron micrographs. The impurity analysis shows that there are only small amounts of other components in the barium titanate powders. Carbonate was not detected in any case. A comparison of the impurity results with those of commercial electronic-grade BaTiO, powders for multilayer capacitors? shows that the sol-gelderived titanates with their distinctly smaller impurity values would be acceptable for multilayer capacitor manufacture.

The TG, DTG and DTA curves of the thermal degradation of the four oven-dried gel powders are shown in Fig. 1. In all cases there are three stages of weight loss: (1) initial weight loss resulting from the evaporation of alcohol and desorption of the adsorbed moisture; (2) pyrolysis of the organic compounds (acetic acid, alcohols, species formed during the hydrolysis reaction and the gelation process, isopropyl acetate); (3) pyrolysis of the residual organics. The total weight loss amounts to 25-30% for the four gel precursors. Endothermic effects are registered for the three steps. An exotherm above 700°C observed in all cases is attributed to the crystallization of the gel. The powders obtained after thermal treatment above 700 "C are essentially white, indicating the departure of the organics. Simultaneously, with the continuation of the thermal degradation, the specific surface area of the powders is increasing. Table 3 shows the results of B.E.T. measurements including the calculated mean particle sizes for the powders formed during thermal decomposition of the gel precursor for BaTiO,. X-Ray diffractograms for the decomposition products of
Table 3 Specific surface area and mean particle diameter dependence on the calcination conditions for the powders obtained during BaTiO, formation
conditions (h/"C)
8/200 8/400 81500 8/600 8/700 8/800 8/900

7 Ticon Barium Titanate. Product Information, TAM Ceramics Inc.
Table 1 Analytical date of the barium titanate powders obtained after thermal decomposition of the dried gel precursors at 900°C for 1 h (1200 "C for Ba2Ti04)
Ba content (wt.%) exp. BaTiO, Ba2Ti04 BaTi20, BaTi,O,
58.9 71.1 43.8 29.0

specific surface area/m2 g-'
125 105 80 55 37 23 14

mean particle diameter/pm
0.0 1 0.0 1 0.0 1 0.02 0.03 0.04 0.07

Ti content (wt.Yo) exp.
20.5 12.4 30.7 40.6

calc.
58.9 71.0 43.9 29.0

calc.
20.5 12.4 30.6 40.5

Ba:Ti
1.oo 2.00 0.50 0.25

TG

A DTG
I
I
1

I

I

I

I
I

I \

TG DTG

I
I

I

I

I

~~

200

400

600 800

200

400

600 800

T/"C

T/"C

Fig. 1 DTA, TG and DTG curves of the four oven-dried gel precursors for (a) BaTiO,, (b) Ba2Ti0,, (c) BaTi20, and ( d ) BaTi,O,

Table 2 Surface area and analytical data of the barium titanate powders obtained after thermal treatment of the dried gel precursors at 900 "C for 1 h
impurity (atom YO) specific surface area/m2 g BaTiO, Ba2Ti04 BaTi20 BaTi,O,
19 23 21 22

dBET/pm
0.05 0.05 0.06 0.06

dElmi/pm

A120, 0.012 0.0 10 0.013 0.013

CaO
0.009 0.010 0.007 0.005

Na20
0.012
0.015 0.0 10

SO2
0.005 0.003 0.005 0.007

SrO
0.007
0.010

> 10 aggl. > l o aggl. > 10 aggl. > 10 aggl.

0.010

0.006 0.006

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the four gel precursors are shown in Fig. 2 for different calcination temperatures (in each case calcined for 8 h). All dried gels and the powders obtained after heating to 500°C are X-ray amorphous. This is in contrast to the crystalline dried gel powders formed using barium i ~ opr opoxi de~~ or barium hydroxide24 for the BaTiO, synthesis. Very broad peaks indicating the cubic perovskite structure of BaTi0, are obtained in the XRD patterns of the dried barium titanate formed using an alkoxide precursor of barium (prepared using Ba0).16 These results show the dependence of the structure of the barium titanate gel precursor for BaTiO, on the mechanism of the hydrolysis and polycondensation reactions6 At 550"C, small broad reflections appear indicating the formation of titanate phases. Further heating leads to the evidence of BaC0, and BaTi0, as intermediate steps besides Ba2Ti04 in the case of the Ba2Ti04 formation. There is no evidence for intermediate products during the thermal decomposition of the gel precursors for BaTiO,, BaTi,O, and BaTi40, from the X R D patterns. These three titanates are obtained in their pure form upon calcination at 900°C for 1 h. Pure Ba2Ti04 is formed at first at temperatures of ca. 1200 "C. Using an argon atmosphere, Ba2Ti04 is obtained as a single phase already at 850 "C. The percentage of Ba2Ti04 after 8 h calcination at 900°C in air amounts to ca. 80% and increases above 1200 "C. This behaviour has been observed previously for the formation of Ba2Ti04 using the peroxide route.I5 Further calcination of BaTi,O, above 1100 "C leads to a slow decomposition of this compound, and a mixture of BaTi,O, with BaTi0, and Ba6Ti1@40 is indicated in the X-ray diffractograms. Analogous behaviour has been found for BaTi,OS synthesis starting from mixed ethoxide solutions16 or peroxo precursors.18

a

0.L

0.2

I

I

0

60

120

180

240

t/min

Fig. 3 Densification parameter a of BaTiO, (0), Ba2Ti04 (a), BaTi,O, (x) and BaTi,Og ( 0 )compacts as a function of isothermal heating time at 1200°C

A

550 O C
1

oven dried
2 3 x
Y

20

40

60 20

40

60

The results of sintering experiments at 1200°C are shown in Fig. 3. The different green densities, po, of the compacts (2.89 g cm-,for BaTiO,, 3.06 g cm-, for Ba2Ti04,2.76 g cm-, for BaTi205,2.60 g cm-, for BaTi409)are included by using the densification parameter a= (p, -pO)/@th -po) (Pt =density at a given time, Pth =theoretical density). Isothermal sintering at 1200°C leads to good densification in all cases, increasing in the order BaTi409< BazTi04< BaTiO, < BaTi,05. The highest densities after 4 h at 1200°C are 4.86 g cm-, for BaTiO, (80% of pth), 4.35 gem-, for Ba2Ti04 (82%), 4.56 g cm-, for BaTiz05 (89%) and 3.68 g cm-, for BaTi409 (8 1 %). BaTi,OS has a significantly higher sinterability than the other three titanates at this temperature. Sintering at 1300°C leads after 4 h to densities of 5.00 g cm-, (98% of pth) for BaTi,05, 5.95 g cm-, (98%) for BaTiO,, 5.02 g cm-, (95%)for Ba2Ti04and 4.41 g cm-, (97%)for BaTi,O,. Note, however, that in the case of metastable BaTi20s at these high temperatures an intimate mixture of this compound with BaTiO, and Ba6Ti1,Om is present. The values for BaTi,O, are therefore not directly comparable with the other densities. The comparison of the sintering results of the here described sol-gel-derived powders with those of barium titanates obtained by the solid-state reaction at temperatures of ca. 1350 "C shows a significantly better sinterability for BaTiO,, BazTi04, BaTiz05 and BaTi409 formed by the sol-gel process. This means, that the described sol-gel method could be used for the preparation of barium titanates and functional electroceramic elements at distinctly lower temperatures than in the case of the conventional solid-state reaction.

References
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700° C

I
20
40

55OOC oven d r i e i oven dried 40

60 20
2t)ldegrees

60

Fig. 2 X-Ray diffractograms of the oven-dried gel precursors and of the decomposition products obtained during formation of (a) BaTiO,, (b) Ba2Ti04, (c) BaTi20S and ( d ) BaTi,O,. 0, BaTiO,; 0, BaCO,, x , Ba,Ti,,O,

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594 13 A. Larbot, F. Garcia and C. Guizard, Eur. J. Solid State Inorg. Chem., 1989,26, 327. 14 0.Marks, J. R. Gunter and F. Hofer, React. Solids, 1988,6,217. 15 G. Pfaff, J. Muter. Sci. Lett., 1991, 10, 1059. 16 J. J. Ritter, R. S. Roth and J. E. Blendell, J. Am. Ceram. SOC., 1986, 69, 155. 17 J. Javadpour and N. G. Eror, J. Am. Ceram. SOC., 1988,71,206. 18 G. Pfaff, J. Muter. Sci. Lett., 1990, 9, 1145. 19 S. G. Mhaisalkar, W. E. Lee and D. W. Readey, J. Am. Ceram. SOC.,1989, 72, 2154.

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21 G. Pfaff, J. Muter. Sci. Lett., 1991, 10, 129. 22 Advanced Ceramic Materials: Technological and Economic Assessment, Noyes, Park Ridge, NJ, 1985. 23 K. S. Mazdiyasni, R. T. Dolloff and J. S. Smith 11, J. Am. Ceram. SOC.,1969, 52, 523. 24 J. C. Bernier, S. Vilminot, J. L. Rehspringer, S. El Hadiqui and

P. Poix, in High Tech Ceramics, ed. P. Vincenzini, Elsevier, Amsterdam, 1987, p. 1443.
Paper 21009035; Received 20th February, 1992

20 P. P. Phule and S. H. Risbud, Mater. Res. SOC. Symp. Proc.,
1988,121, 275. Published on 01 January 1992. Downloaded by FAC DE QUIMICA on 22/04/2014 17:16:07.