February 1987 Communications of the American Ceramic Society c-35

J . Am. Cernm. SOC., 70 [ 2 ] C-35-C-36 (1987) final products. These results were deduced
from the X-ray diffraction analysis of cal-
Effects of pH and Temperature on Sol-Gel cined powders.
The final products of the calcined gels
Processing within the PbO-Ti02 System prepared at 30°C and pH 1.0 to 4.6 are
titanium dioxide with the anatase structure;
MOON-HOLEE,* YOUNG-HO
PARK,AND CHEUL-KEE
YANG however, those prepared at 40°C and
pH 1.0 to 2.0 are a mixture of anatase and
Department of Metallurgy, Yeung Nam University, Dae-dong, Kyungsan-eup, Kyungsan 632, Korea traces of rutile. It is known that the allo-
tropic transformation temperatures are
600°C (anatase I-anatase 11), 716" to 933°C
Effects of sol formation temperature and pH value on sol-gel processing within the (anatase 11-rutile), and 1316°C (rutile-
PbO-Ti02system were investigated. PbO-Ti02gels were prepared from the mixed brookite).6 Therefore, the mixtures of
solution of lead nitrate and titanium tetrachloride at 30" to 70°C under various pH anatase and rutile at 40°C seem to be
values of I .O to 10.8, and dehydrated at 60" to 80°C for 72 h under vacuum. The caused by the allotropic transformation
dried gels are amorphous. The crystalline phases of the products after calcination during calcination. When prepared at 70°C
at 720°Cfor I h in air are dependent upon the sol formation conditions asfollows: and pH 8.0 to 10.8, the calcined powders
are PbTi03 with the tetragonal structure.
(I) Ti02:30"C,pH 1.Oto4.6;and4O0C,pH l.Oto2.0. ( 2 )PbTi,O,:SO"to 70"C, The thermal analysis and powder charac-
pH 1.0 to 4.6. (3) PbTi03: 70"C, pH 8.0 to 10.8. ( 4 ) PbTi03 and traces of teristics for PbTiO, gels were previously
PbTijU7:30" to 60"C, pH 7.1 to 10.8 e ~ a m i n e d The
. ~ characteristic transforma-
tion from amorphous to crystalline PbTiO,
occurs at 477" to 506"C, and this tem-
methods for the prepara- 60" to 80°C for 72 h under vacuum.
Wtion
. of raw materials
ET-CHEMICAL
are of increas- The transformation temperatures were
perature increases with increasing pH value
used in sol formation.
ing interest. Such methods, especially the monitored by DTA' and thermal runs were PbTi307 is obtained from the gels
sol-gel process, involve low processing carried out for the dried gels at a constant which were prepared at 50" to 70°C and
temperatures and result in better material heating rate of 5"C/min. The crystalline pH 1.O to 4.6. A compound PbTi307 does
homogeneity and stoichiometry. Several phases appearing during thermal treatment not appear on the phase diagram published
investigators have synthesized materials (720°C for Ih in air) were analyzed by by Jaffe,7 but more recent work has shown
i n the PbO-TiOz system by sol-gel means of X-ray diffraction (XRD). the existence of this compound.* Eisa
methods. showed that the compound PbTi,07 is
In our previous study, morphological RESULTSAND DISCUSSION
formed through the reaction between Pb30,
changes of lead titanate prepared by a sol- The sequence of crystallization during and Ti02. This compound has the approxi-
gel method were e ~ a m i n e dIn
. ~ this study, calcination is shown by the results of mate limits of stability 400" to 540°C and
the products of the PbO-Ti02 system Fig. 1. The endothermic peak between then decomposes to PbTiO, and TiOz
prepared by a sol-gel process were ana- 100" and 200°C is due to the evaporation of
(rutile) at higher temperatures. DTA results
lyzed as a function of solution temperature water. The exothermic peaks at 450", 520", for PbTi3O7 gels are shown in Fig. l(b).
and pH value. and 620°C result from the crystallization The exothermic peak at 430°C is due to the
of TiOz, PbTi03, and PbTi307, respec- crystallization of Ti02, which is lower than
EXPERIMENTAL
PROCEDURE tively. Similar results have been observed that of pure TiOz shown in Fig. l(a).The
The raw materials used were lead previously. 3.4 exothermic peak at 620°C shows the crys-
nitrate (purity 99.5%) and titanium tet- In order to obtain crystalline phases in tallization of PbTi307;the crystallization of
rachloride (purity 99.7%). A weighed the PbO-Ti02 system, it was found that the lead oxides is not observed in DTA and
quantity of lead nitrate was dissolved reaction must take place under a desirable XRD results. In XRD results for the final
in distilled water and the titanyl solution combination of the following conditions:
calcined products, TiOz as a form of anatase
was prepared by slowly adding TiCI4 to (a) reaction temperature, (b) pH value of andlor rutile is not traced. Accordingly, a
chilled water. the suspensions, and (c) calcination condi- PbTi307 compound is not formed through
Aqueous solutions of Pb(N03)2 and tions (temperature, atmosphere, time, etc.) the reaction between individual oxides.
TiCI, were mixed in proportions to give the of dried gels. Among these conditions, (a) When gels are prepared at 30" to 60°C
atomic ratio Pbz+/Ti4+=1.O. This was and (b) have been found to be the most and pH 7 . 1 to 10.8, the final products
done in the presence of ammonium nitrate influential. Figure 2 shows the effects
so that insoluble PbC12 was not formed.s of reaction temperature and pH value of
PbO-Ti02 sols were prepared from the the mixed solution on the formation of
mixed solution at 30" to 70°C under various
pH conditions of 1.0 to 10.8, controlled by
the addition of NH,OH. The complex
hydroxide was then dispersed in water and v
filtered thoroughly until free from chlorides 0 ~60-•n n D ,I o 0 0 0

to form a stable sol. This sol was gelled by

adding it to isopropyl alcohol (proportion
5 PbTi307 ,:
of sol to alcohol is 1:7), and dehydrated at
40- = :.='
rw+30-.
110 0 0 0 0
CL \;

EDITOR- W. 1. LACKEY
CONTRIBUTING z
Ti02 '\
>, 0 0 0 0

w
Received March 13, 1986; revised copy received 100 300 500 700
April 29, 1986; approved July 11, 1986.
*Present address: Materials Research Laboratory, TEMPERATURE ("C)
The Pennsylvania State University, University Park,
PA 16802. Fig. 2. Effects of sol formation temperature
'990 DSC equipment, E. I. du Pont de Nemours Fig. 1. DTA curves for dried PbO-TiO, gel; and pH value on the products after calcination at
& Co.. Wilmington, DE. (a)TiO,, ( b ) PbTi,O,, and ( c ) PbTiO,. 720°C for 1 h in air.
C-36 Communications of the American Ceramic Society February 1987

are composed of PbTiO, and traces of
PbTi307. It could be due to the following
reaction:’
PbTi307+$Pb304=3PbTi03+@02 (1)
When calcined at 550°C for 1 h under Oz
atmosphere, TiOz and lead oxides are not
traced, but PbTiO, and PbTi307 coexist.
This calcination temperature (550°C)
is lower than the crystallization tempera-
ture (620°C) of pure PbTi307 and higher
than that of pure PbTi03. That is, the
crystallization of PbTi03 decreases the
crystallization temperature of PbTi307.
Therefore, the reaction of Eq. (1) may not
influence the coexistence of PbTiO,
and PbTi307.
REFERENCES
IS. R. Gurkovich and J. B. Blum, “Preparation
of Monolithic Titanates by a Sol-Gel Process,” Am.
Cerum. Soc. Bull., 61 [3] 411 (1982).
’ S . R. Gurkovich and J . B. Blum, “Preparation of
Monolithic Lead Titanate by a Sol-Gel Process”;
pp. 152-60 in Ultrastructure Processing of Ceramics,
Glasses, and Composites. Edited by L. L. Hench and
D. R. Ulrich. Wiley, New York, 1984.
’D. M. lbrahim and H. W. Hennicke, “Preparation
of Lead Zirconate by a Sol-Gel Method: Part I. Sample
Preparation,” Trans. J. Br. Ceram. SOC., 80, 8-12
(1981).
4 M . H . Lee, G . I . K i m , and C . K . Y a n g ,
“Morphology of Lead Titanate Prepared by a Sol-Gel
Process”; unpublished work.
5V.R. Palkar and M. S . Multani, “High-Density
PZT Materia1,”Mafer. Res. Bull., 14, 1353-56 (1979).
6 J . R . Hague, J.F. Lynch, A. Rudnick, F . C .
Holden, and W. H. Duckworth, Refractory Ceramics
for Aerospace. American Ceramic Society, Columbus,
OH, 1964.
’ 8 . Jaffe, W. R. Cook, and H . Jaffe, Piezoelectric
Ceramics. Academic Press, New York, 1971.
*M.A. Eisa, M. F. Abadir, and A . M . Gadalla,
“The System Ti0,-Pb-0 in Air,” Trans. J. Br. Cerum.
Soc., 79, 100-104 (1980). 0