Comparative Study On Phase Development of Lead Titanate Powders
Comparative Study On Phase Development of Lead Titanate Powders
Comparative Study On Phase Development of Lead Titanate Powders
Abstract
Ultrafine lead titanate ŽPbTiO 3 . powders in tetragonal form have been successfully prepared via two processing routes,
namely, conventional coprecipitation ŽCPC. and microemulsion-refined coprecipitation ŽMCP.. The formation process of
lead titanate from the resulting precursors was monitored using techniques such as thermal analyses, FTIR spectroscopy,
Raman scattering spectroscopy and X-ray diffraction for the phase identification. It was found that the microemulsion-re-
fined processing route led to a lower formation temperature for lead titanate than that observed in the conventional
coprecipitation route, and there is no detectable pyrochlore phase during the formation of PbTiO 3 in the former case. The
two PbTiO 3 powders have also been comparatively studied in particle morphology and specific surface areas. It indicates
that the microemulsion-refined coprecipitation is the technique that results in the formation of the finer powder of lead
titanate than the conventional coprecipitation does in the present work. q 2002 Elsevier Science B.V. All rights reserved.
Keywords: Lead titanate; Microemulsions; Ultrafine powder; Coprecipitation; FTIR and Raman spectra
00167-577Xr02r$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X Ž 0 1 . 0 0 4 1 1 - 6
J. Fang et al.r Materials Letters 52 (2002) 304–312 305
YBa 2 Cu 3 O 7yx superconductor w33,34x, ceramic hy- tion Ž12 wt.%. was then added into the solution,
droxyapatite w35x, g-Fe 2 O 3 w36x and complex per- resulting in the formation of titanium hydroxide hy-
ovskite compounds w37x. During the inverse mi- drate. The gelatinous precipitates were filtered and
croemulsion processing, precursor particles are washed repeatedly using deionized water until the
formed in the nanometer-sized aqueous domains sur- pH of filtrate was close to 7.0, in order to remove
rounded by oil phase, and their sizes are therefore chloride ions. Titanium oxynitrate in aqueous solu-
limited in the range of nanometers w32,35,37x. This tion was prepared by dissolving the white precipi-
isotropic dispersion of nanometer-sized aqueous tates in an appropriate amount of 3.0 M HNO 3 ,
droplets in microemulsions may well restrict the immediately followed by the concentration determi-
particle growth of PbTiO 3 precursors when the pre- nation of Ti 4q using inductively coupled plasma
cipitationrcoprecipitation is effected in such syn- ŽICP, Thermo Jarrell Ash, IRISrAP.. The concentra-
thetic medium, and makes the formation temperature tion of TiOŽNO 3 . 2 was then adjusted to 0.30 M by
for PbTiO 3 significantly lowered due to the homo- adding an appropriate amount of deionized water. To
geneity of the resulting PbTiO 3 precursors. Although prepare the aqueous solution containing 0.30 M
PbTiO 3 powders have been synthesized via various wPbŽNO 3 . 2 –TiOŽNO 3 . 2 x at equimolar ratio of
chemical processes, there have been little reports of Pb 2qrTi 4q, an appropriate amount of lead nitrate
applying an inverse microemulsion technique to this was dissolved into the aqueous solution of titanium
synthetic task. The objective of the present work is oxynitrate.
to investigate the phase development of PbTiO 3 from
microemulsion-derived precursor, in close compari- 2.3. Preparation of PbTiO3 powders
son with that from conventional coprecipitated pre-
cursor. PbTiO 3 powders were prepared via two process-
ing routes, namely conventional coprecipitation
Žhereafter CPC. and microemulsion-refined copre-
2. Experimental procedures cipitation Žhereafter MCP.. In the CPC route, an
aqueous solution containing 0.30 M wPbŽNO 3 . 2 –
2.1. Starting materials TiOŽNO 3 . 2 x was titrated into a 12 wt.% ammonia
solution in a beaker while being vigorously agitated
The starting materials used in the present investi- using a mechanical stirrer. The precipitates were
gation included leadŽII. nitrate Ž) 99.7% in purity, recovered by centrifugation and washed repeatedly
J.T. Baker, USA., titanium ŽIV. chloride Ž) 99.0% using deionized water, followed by drying at 140 8C
in purity, Hayashi Pure Chemical Industries, Japan., in an oven. In the MCP route, two microemulsion
ammonia solution Žconcentration: 28.0–30.0 wt.%, systems consisting of two common components, i.e.
J.T. Baker., a high-purity nitric acid ŽHetalab Chem- 56.0 wt.% cyclohexane and 24.0 wt.% NP5 q NP9
ical, USA., a high-purity cyclohexane ŽAjax Chemi- and differing only in aqueous phase, were prepared.
cals, Australia. and mixed polyŽoxyethylene.5 nonyl The aqueous phase for one of the systems was 20.0
phenol ether ŽNP5. and polyŽoxyethylene. 9 nonyl wt.% of 0.30 M wPbŽNO 3 . 2 –TiOŽNO 3 . 2 x, while 20.0
phenol ether ŽNP9. Žin weight ratio: 2:1, Albright wt.% of 2.85 M ammonia solution for the other.
and Wilson Asia, Singapore.. They were then mixed together by vigorous stirring
for more than 20 min. The resulting precursor was
2.2. Preparation of aqueous solution containing 0.30 retrieved by washing away the oil and surfactant
M [TiO(NO3 )2 –Pb(NO3 )2 ] using distilled ethanol, followed by centrifugal re-
covery and drying at 140 8C for 12 h.
Aqueous solution of titanium oxynitrate was pre-
pared by following the procedures of Yamamura et. 2.4. Powder characterization
al. w38,39x. Weighed titanium tetrachloride ŽTiCl 4 .
was dissolved in an appropriate amount of deionized The as-dried precursors were characterized using
water at ice-bath temperature. Cold ammonia solu- thermogravimetric analysis ŽTGA. and differential
306 J. Fang et al.r Materials Letters 52 (2002) 304–312
Fig. 6. Ža. IR spectra of PbTiO 3 powders prepared via the direct coprecipitation route and calcined for 1 h at various temperatures; Žb. IR
spectra of the PbTiO 3 powders coprecipitated in microemulsions and calcined for 1 h at various temperatures.
310 J. Fang et al.r Materials Letters 52 (2002) 304–312
calcined at various temperatures. For comparison, single-phase PbTiO 3 was obtained when the precur-
the IR spectra of PbO were recorded as standard sor was calcined at 500 8C. This is in close agree-
references using commercial PbO powders with high ment with what has been revealed by phase analysis
purity, exhibiting a strong characteristic absorption using XRD technique.
band at ; 1394 cmy1 , together with other absorp-
tion bands at 678 and 460 cmy1 . The IR spectrum 3.4. Morphology of PbTiO3 powders
for CPC-derived powder calcined at 400 8C in Fig.
6Ža. clearly indicates the presence of anatase TiO 2 The PbTiO 3 powders prepared via both process-
characterized by the absorption bands at 554, 676, ing routes are different in particleragglomerate size
2855, 2929 and 3446 cmy1 . These bands coincide and morphology. Figs. 7Ža,b. are two SEM micro-
well with the characteristic wave numbers of anatase graphs showing the microstructure of both powders.
TiO 2 w48x. The strong absorption at 1394 cmy1 Both of them were calcined at 600 8C for 1 h. The
indicates the presence of PbO as a major phase. It CPC-derived PbTiO 3 powder consists of primary
was reported that absorption bands over the range of particles of micrometers in size. In contrast, discrete
900–1700 cmy1 are mainly related to the organic particles of ; 100 nm are observed in the powder
groups w11x. Therefore, absorption bands at 1052, via MCP route, together with a more or less rounded
1563 and 1651 cmy1 are attributed to the organic particle morphology. Fig. 8 is a TEM micrograph
residuals in the powder. Increasing the calcination
temperature to 550 8C results in decrease in intensity
of the organic and PbO absorption bands and the
further enhancement of anatase TiO 2 phase. The
organic residuals were completely eliminated when
the CPC-derived precursor was calcined at 600 8C,
where the corresponding IR spectrum exhibits appar-
ent bands from anatase TiO 2 and a further decreased
band of PbO. PbTiO 3 started to form and the inter-
mediate phase such as PbO and TiO 2 became minor
phases when the calcination temperature was further
raised, as shown by the spectra of the powders
calcined at 650 and 700 8C. Eventually, an IR spec-
trum corresponding to the single-phase PbTiO 3 w49x
was obtained when the precursor was calcined at 800
8C. Fig. 6Žb. shows the IR spectra of MCP-derived
precursors calcined at various temperatures. Based
on these spectra, the powder calcined at 350 8C
consisted of a mixture containing anatase TiO 2 , PbO,
and organic residuals as indicated by the band group
of 554, 680, 2855, 2929, 3446 cmy1 , band at 1394
cmy1 and band at 1039 cmy1 w11,48x. Heating up to
400 8C led to an enhancement in the intensity for
anatase TiO 2 and a rapid decrease in intensity of the
absorption band for PbO, together with a decrease in
intensity for organic residuals. The spectrum for the
powder calcined at 450 8C indicates the vanishing of
anatase TiO 2 bands and a further reduction in the
Fig. 7. SEM micrographs showing the microstructure of PbTiO 3
intensity related to the organic residuals. It also powders prepared via Ža. direct coprecipitation and Žb. coprecipi-
demonstrates an apparent formation of PbTiO 3 phase. tation in microemulsions. All the three powders were calcined at
An IR spectrum corresponding to well developed 600 8C for 1 h, followed by treatment in 5 wt.% acetic acid.
J. Fang et al.r Materials Letters 52 (2002) 304–312 311
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