ELSEVIER Physica C 341-348 (2000) 2459-2460
www.elsevier.nl/Iocate/physc
Synthesis of (Hg,Re-1223) by Sol-Gel technique
A.Sin a, P.Odier a, F.Weissb, M.Nfifiez-Regueiroc
aLaboratoire de Cristallographie-CNRS, 25 Av. Des Martyrs, Bp166, F38042 Grenoble CEDEX09, France
bLaboratoire des Mat6riaux et du G6nie Physique - ENSPG-INPG-CNRS UMR5628, F-38402 St Martin
d'H6res Cedex, France
CCentre de Recherche sur les Tr6s Basses Temp6ratures-CNRS, 25 Av. des Martyrs, Bp166, F38042 Grenoble
Cedex09, France
In this work we prepare (Hg,Re)-1223 superconducting samples using the acrylamide gelification for
obtaining nanoparticles of precursor phase of mercury-cuprates such as "Reo.25BazCa2Cu30×". This chemical
method is fast, cheap, reproducible and easy to scale up. Also, we demonstrate that sol-gel processing is a
more efficient than solid state reaction for obtaining the superconductor phase. Finally, diagram of Pressure of
synthesis versus. 1/T are shown and discussed.
1.-INTRODUCTION
The mercury-cuprates are generally
synthesised by the sealed quartz tube technique in
a two step process: the formation of a precursor
first and then its mercuration. Starting with a high
degree of homogenisation of all precursor oxides
is essential to obtain superconducting ceramics of
high quality. Wet chemistry, and particularly sol-
gel processing is one of the most promising way
to get an excellent homogenisation at an atomic
scale of the elements and a high reactivity of the
precursors.
We have studied a sol-gel method for
processing the precursors "RexBa2Ca2Cu3Ox". We
use the gelification of a solution by an in-situ
polymerisation of acrylamide monomers. This
method is much more rapid and safe than the so-
called nitrate-citric route that involves nitrates,
citrates and also ethylene glycol. In-situ pressure
measurements (TBA) [1,2]] were carried out to
monitor the mercuration synthesis of the
precursors in closed tubes.
2.-EXPERIMENTAL
The synthesis of fine powders of complex
oxides are carried out by dissolving separately
each cations in their stoichiometric ratio (CaCO3
(DIOPMA 99.95%),), BaCO3 (DIOPMA 99.9%),
CuO (99.99% DIOPMA) and Re (99.9% Aldrich)
in nitric acid. The Cu 2+ and Re 6+ cations are
complexed with addition of acid-EDTA:
(H4Y)=[CHzN(CH2COOH)2]2 (Prolabo 98%) in
the ratio 1:1 and the pH is adjusted to be in a
range of pH where the solution is perfectly clear
(pH=3). Finally they are mixed all together.. To
this solution (150ml) are added (10g/lg)
Acrylamide monomers (Aldrich 99 %) and N,N'-
Methylenebisacrylamide (Aldrich 99%). A few
mg of a chemical initiator c~ ct'-Azo-
isobutyronitrile=AIBN (Fluka 98 %) is added to
initiate the polymerization. With AIBN the
polymerization is fast at 80°C. The gel is then
dried a few minutes in a microwave oven. It
results from this treatment an extremely porous
foam material. The xerogels obtained are then
homogenized in a ceramic mortar and one
subsequent thermal treatment, optimized to each
particular composition is sufficient to get the pure
phase. Its temperature is a higher than 700 °C, a
temperature necessary to remove most of the
organic phase (>90 %). In our case it we used
850°C for 10h in a rich N2 flux flow. This
precursor is then mixed with HgO (99%, Aldrich)
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