Home Search Collections Journals About Contact us My IOPscience

Preparation of YBa2Cu3O7-δ by citrate synthesis and pyrolysis

This article has been downloaded from IOPscience. Please scroll down to see the full text article.

1988 J. Phys. D: Appl. Phys. 21 226

(http://iopscience.iop.org/0022-3727/21/1/036)

View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 111.68.103.25
The article was downloaded on 19/08/2013 at 19:01

Please note that terms and conditions apply.

J. Phys. D: Appl. Phys. 21 (1988) Printed in the UK
226-227.

D H A Blank?, H KruidhofS and J Flokstrat

t Department of Applied Physics, University of Twente, PO Box 21 7, 7500 AE
*
Enschede, The Netherlands
Laboratory of Inorganic Chemistry, Materials Science and Catalysis, Universityof
Twente, PO Box 217, 7500 AE Enschede, The Netherlands

Received 10 November 1987

Abstract. A recent preparation method by citrate synthesis in combination with

pyrolysis has been applied to the new high-T, superconductors. A step-by-step
procedure is given to obtain the ultra-fine and homogeneous powder. X-ray
diffraction analyses were performed to characterise the powder and to study the
influence of the calcination temperature. Resistance measurements exhibit
complete superconductivityat 91.2 K.

In generalY B ~ & U ~ is O prepared,

~-~ startingfrom the solutions areputtogetherand citric acid(126g)is
oxides, by a number of solid state reactions with grind- added. Besides themetal-organic complexes, apre-
ing in between [l].Although good results are obtained, cipitate of barium, Ba3(C6H507)2, forms. During the
this method takesmuch time to get good quality single- neutralisation with ammonia (NH,OH, 25% solution),
phase powder, without impurities such as CuO, all reactants disappear andthe liquid becomes dark
BaCu02 and 'Y2BaCu0,. Extensive grinding increases blue at a pH of 6.5-7.0. The pH value isof utmost
the homogeneity of thematerial, but the minimum importance, for hydroxides and base salts will appear
obtainable particle size of the starting oxides (-1 pm) if it becomes larger than seven.
severely hampers the solid state reaction. A method The solution (pH = 6.8) is heated in equal pro-
that solves this problem is citrate synthesis. The powder portions of 100 m1 on a hot plate in an oversized Pyrex
obtained by such a preparation technique is ultra-fine two-litre breaker. During the heating a viscous mass
and already hasthe correct stoichiometric values. forms, followed by a large swelling due to the citric
Therefore this type of preparation is fast and also acid, and, finally, spontaneous combustion is initiated
simple. After the pyrolysis
only one calcination by the ammonium nitrate (NH,N03). The risen
(including the solid state reaction) is needed. powder fills the glass completely and theresultant foam
In this paper we reportonthepreparation con- consists of homogeneous flakes with particles sizes of
ditions of this citrate synthesis in combination with 50 to 100 nm. It is important that during the dry-up, no
pryolysis. X-ray diffraction analyses were performed precipitates form and none of the citrate components
on the powder, in order to get information about the ignites separately. The liquid has to stay clear until the
purity of the powder and the role of the calcination glow front arises.
temperature, and
on sintered pellets. Resistance After the pyrolysis it is necessary to calcinate the
measurementsonthese pellets show an onset tem- powder.This can bedone in combination with the
perature of 93.5 K and complete superconductivity at solid state reaction. Good results were obtained with a
91.2 K. calcination temperature of 920 "C over 10 h and then
We prepared the YBa2Cu307- with the citrate syn- cooling at a rate of 50 "C h-', both procedures taking
thesis technique in combination with pyrolysisto attain place in an oxygenflow. Afterwards pellets were
a homogeneous and ultra-fine powder without impurit- pressed and sintered in an oxygen flow at 920 "C for
ies [2]. The following recipe holds for 0.1 mol 10 h and cooled down with 50 "Ch-'. The density of
YBa2C~307-6. The BaC03 (5 moll-', 39.47 g) is dis- the sintered pellets was 86% of the theoretical value.
solved in 60 m1 nitric acid (65%) with 80 m1 Q2-water Using micro-element analysis we found in general
(it is necessary to heat the Ba(N03)2 solution). The less than 0.2% C in calcinated powder made by this
Y203(4 mol l-l, 11.29 g) and CuO (5 mol l-l, 23.86 g) citrate synthesis technique.
are solved in 40 m1 nitric acid (65%) each. The three In order to characterise thepowder made by citrate

+ 02
0022-3727/88/010226 @ 1988 IOP Publishing Ltd
$02.50
 Letter to the Editor

IT- -1- 850 'C I

TI To

Flgure 2. Relative specific resistivity versus temperatureof

YBa2Cu307-6with a currentdensity of; A, 2 A B,
10 A cm-2; C, 40 A cm-2. Parameters are p. =
z e (degl 8.7x Q m andTo = 93.5 K.
Figure 1. Powder x-ray diffraction patterns for powders
produced at three calcination temperatures T = 850 "C,
900 "C and 920 "C.
strips on which we soldered the contact wires. We
varied the measuring current from 2 to 40 A cm-'. In
figure 2the influence of thecurrent density on the
synthesis, x-ray diffraction measurements were per-
resistivity is presented. The onset temperature is T,, =
formed. We used a Debye-Scherrer diffractometer
93.5 K and is independent of the applied current. The
with Cu Ka source. These investigations give insight
specific resistivity (po)is 8.7 X S2 m at T = 93.5 K,
into the occurrence of the correct orthorhombiccrystal
which is low compared to data from the literature. We
structureandthepresence of impurities like CuO,
relate this low value to the very good sample homo-
BaCuOz and YzBaCu05. The spectra of the powders
geneity obtained by our citrateand pyrolysis technique.
obtained at three different calcination temperatures are
The influence of the current density on the resistance
given in figure 1.
gives information about the sintering process and is not
The pattern of the powder, calcinated at 850 "C,
a qualification of our powder preparation technology.
already shows the main reflections of YBa2C~307-6.
We succeeded in preparing an ultra-fine, homo-
Apart from this, reflections are recognisable from CuO
geneous powder of the new high-T, superconducting
(28 = 35.55 and 48.76 deg).The difference of cal-
material. This powder appears to be useful for a num-
cination at 900"Cis thatthepure YBa2C~307-6
ber of applications. Besides its properties as a bulk
powder gave x-ray reflections corresponding to a more
material, it can be used with good results in a painting
tetragonal phase. The (hkl) reflections-(100), (013),
technique for the preparation of thick films. Also, tar-
(200) and (213)"are shifted with respect to the ortho-
gets for sputter deposition can be easily made.
rhombic phase, indicating that the values of the lattice
parameters a and b are levelling up. Clear reflections
We would like to acknowledge the members of the
of impurities are not observed. Calcination at 920 "C
Laboratory of Inorganic Chemistry, Materials Science
gives the expected x-ray pattern. The observed values
and Catalysis fortheir helpfulness in preparing the
of 28 correspond with the orthorhombic lattice par-
samples and Guus Velders for carrying out the resist-
ameters a = 3.828,, b = 3.89 8, and c = 11.67 8, [3].
ance measurements.
It is worth mentioning that the (0, 0, l ) reflection
intensities are larger in the sintered pellets than the
corresponding values of the powder samples, indicating References
a preferential orientation of the c axis perpendicular to
the surface. Again no impurities have been observed. [l]Wu M K, Ashburn J R, Torng C J , Hor P H, Meng R
We performed resistivity measurements on sintered L, Gao L, Huang Z J , Wang Y Q and Chu C W
pellets by a four terminal AC technique as a function 1987 Phys. Rev. Lett. 58 908
of temperature. The sample was placed in acopper [ 2 ] van de Graaf M A C G , van Dijk T, de Jong M A and
Burggraaf A J 1977 Sci. Cerum. 9 75
housing together with a platinum resistance ther- [3] Blank D H A, Flokstra J , Gerritsma G J , van de
mometer and cooled by a helium gas flow. Good elec- Klundert L J M and Velders G J M 1987 Physicu B
trical contacts were obtained by evaporating copper 145 222

227