Formation Kinetics Of Barium Zirconate Obtained By Oxalate Method

L. Ciontea, T. Ristoiu, R.-C. Suciu, T.Petrisor -Jr., T. Petrisor

Technical University of Cluj Napoca, Cluj Napoca, Romania, Lelia.Ciontea@chem.utcluj.ro
Abstract. Barium zirconate is the most attractive material used to induce artificial pinning centers both in melt textured and YBa2Cu3Ox (YBCO) thin films, in order to increase the critical current density. In the present work a systematic investigation of the crystallization kinetics of nanocrystalline BaZrO3 (BZO) obtained by the thermal decomposition of an oxalate precursor has been made. The crystallization process was analyzed by thermal analyses, infrared spectroscopy and X ray diffraction and have shown that between 700 - 900C the barium zirconate phase is partially formed, while between 1000 - 1200C a pure barium zirconate phase appears. The as-obtained nanocrystalline BZO powders have been successfully used in YBCO-BZO composite targets manufacturing for pulsed laser deposition of superconducting YBCO thin films. Keywords: Barium zirconate, crystallization kinetics, pinning centers PACS: 61.46 Df

(200) BZO

Intensitate (u.a.)

(211) BZO

The barium zirconyl oxalate hydrate BaZrO(C2O4)24.5H2O precursor has been prepared by the quantitative precipitation of barium acetate and zirconium oxychloride with ammonium oxalate [1]. The X - ray and FT - IR analyses (Figure 1 and 2) evidence that the crystallization process of BZO is complex and can be considered a two step process. First, it starts at about 600oC when it takes place the decomposition of the dehydrated barium zirconyl oxalate to BaCO3, ZrO2, CO2, CO and initiates the crystallization of BaZrO3 due to the initial atomic scale mixing of the precursor. Carbon has been also traced at the disproportionate reaction of carbon monoxide and is eliminated by combustion. Secondly, simultaneously with the on-going of the decomposition process takes
C=O 1200 C 700 C 650 C
O O O

FIGURE 1. FT-IR spectra of BZO at different temperatures for 2 hours

place the second crystallization step at about 800oC by the decomposition of the barium carbonate and the formation BZO, equivalent to a solid state reaction. Since at 1000oC a pure BZO phase is evidenced, we conclude that the sintering can be lowed down to this temperature. This mechanism is in good agreement with the TG-DTA analysis. The results obtained from the analyses of the X-ray peak profile have indicated a mean powder size of about 100 nm, adequate for the composite target preparation [2].
(110) BZO o BaCO * ZrO2
3

(220) BZO

(310) BZO

(100) BZO

(111) BZO

O-H

Intensity (a.u.)

CO

2-

Zr-O

(222) BZO

1200 C 1100 C 1000 C O 900 C O 800 C O 700 C

O O

Absorbance (a.u.)

CO3

2-

* * *o

650 C 600 C
O O

600 C 500 C
O

500 C

O-H H-bonding C-O

20 30 40 50 2 ( 60
O

100 C

70

80

(312) BZO 90

100OC 4000 3500 3000 2500 2000

-1

C-O 1500 1000 500

FIGURE 2. BZO crystallization vs. temperature by X-ray diffraction REFERENCES 1. N. M. Kirby et al. J. of Mat. Science, 40, 97, (2005)

Wavenumber (cm )

2. C. Cancellieri, L. Ciontea, T. Petrisor, IEEE Trans. On. Appl. Superconductivity, 15 (2 Part III), 3038, (2005)