Physica B 404 (2009) 2760–2762

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Physica B
journal homepage: www.elsevier.com/locate/physb

Electric and magnetic properties of PMMA/manganite composites

a,d,×
C. Artale a,b,1, S. Fermepin a,b,1
, M. Forti a,c,1
, M. Latino a,c,1
, M. Quintero a,d
, L. Granja a,d
, J. Sacanell ,
G. Polla a, P. Levy a,d
a
GAIyANN, GIA, Centro Ato´mico Constituyentes, CNEA, Av. Gral. Paz 1499, (1650) San Mart´ın, Prov. de Buenos Aires, Argentina
b
Departamento de F´ısica, FCEN, UBA, Buenos Aires, Argentina
c
Instituto de Tecnolog´ıa ‘‘J.A. Sa´bato’’, UNSAM-CNEA, San Martin, Prov. de Buenos Aires, Argentina
d
CONICET, Buenos Aires, Argentina

article info abstrac t

We present the synthesis and characterization of the La 2/3Sr1/3MnO3 manganite in the form of tapes
Keywords:
using polymethyl methacrylate (PMMA) as binder. We have studied their electric and magnetic
Metal–insulator composites
properties as a function of temperature and magnetic field. The magnetization results have been shown
Manganites
CMR
to be dominated by the intrinsic magnetic properties of the manganite. Resistivity measurements
Magnetic properties showed an insulating behavior in the whole range of temperatures measured, indicating that the
percolation threshold of manganite grains has not been reached even for the sample with 35% of PMMA
relative content. The obtained magnetoresistance is largest in the sample with 35% of PMMA relative
content.
& 2009 Elsevier B.V. All rights reserved.

1. Introduction
2. Experimental

Increasing attention is paid to develop ceramic–plastic com-

The synthesis process consists of preparing a suspension of
posites, both in basic research and application areas, due to
a ceramic powder in a solvent with the addition of dispersants,
their multi purpose and potential technological promise,
a binder and plasticizers.
combining the flexibility of a polymer with the functionality of a
Fine ceramic powders of LSMO (average size of 200–400 nm)
ceramic. Among several compounds [1], complex oxides are
obtained by citrate/nitrate decomposition (see Ref. [5] for a
being the focus of extensive research due to multifunctional
complete description) were mixed with a polymer and solvent
capabilities. However, overall properties could be degraded
(tetrahydrofuran, Baker) to make an homogeneous viscous, de-
during processing [2].
agglomerated dough, rather like plasticine, which was then
Magnetic manganese based oxides with perovskite structure
pressed, rolled and extruded into a wide variety of shapes.
(manganites) exhibit appealing colossal magnetoresistance
A two component binder was used, comprising a major
(CMR) and several unusual properties such as nonvolatile
fraction of polyethylene glycol (PEG) with molecular weight 400
changes on their physical properties that can be induced by the
supplied by Berna and a secondary component, polymethyl
application of external magnetic [3] or electric [ 4 ] fields.
methacrylate (PMMA), supplied by Alfa Aesar, incorporated as a
Among manganites, La2/3Sr1/3MnO3 (LSMO) is unique as it
solution. Samples of different additive compositions were
exhibits ferromagnetic ordering and CMR even well above
studied in order to avoid some difficulties such as a strong
room temperature, a prerequisite for massive technological
adherence of the mass to the rollers, superficial cracking, etc.
applications.
The best result was obtained using 70% PEG:30% PMMA.
In this work we report the feasibility of obtaining plastic
Samples with ceramic/binder weight ratio LSMO 1—x(PMMA0.3
based manganite ceramics as either rigid or flexible tapes, PEG0.7)x; x ¼ 0.25; 0.35; 0.4; 0.5; 0.8 and 0.9 were obtained. In
using a polymer as the binder. We have performed a study of the following we will identify the samples according to their
their electric and magnetic properties as a function of percentual polymer (PMMA+PEG) content. Samples with x40.35
temperature and magnetic field, mainly interested on displayed adequate adherence between grains in order to
magnetotransport. perform
electrical transport measurements. As a preliminary result we
have tested that samples can be slightly deformed and recover
their original shape. A complete study of the mechanical
×
Corresponding author at: GAIyANN, GIA, Centro Ato´ mico Constituyentes, proper- ties is in progress.
CNEA, Av. Gral. Paz 1499, (1650) San Martı´n, Prov. de Buenos Aires, Argentina.
The mixture was used to produce fine tapes (thickness~1
Tel.: +54116772 7657; fax: +54116772 7121.
E-mail address: sacanell@cnea.gov.ar (J. Sacanell).
mm). After the evaporation of the solvent the dried green
1
These authors contributed equally to this work. tape was

0921-4526/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2009.06.081
 C. Artale et al. / Physica B 404 (2009) 2760–2762 2761

80
60
40
20

M (emu/g)
0
-20 T=7K
-40
-60
-80
-3000 -2000 -1000 0 1000 2000 3000
80
25 %
Fig. 1. X-ray diffraction pattern for the pure LSMO powder and the sample with
60 30 %
35% polymer content. The extra peak in the pure LSMO sample corresponds to
40 40 %
the Al sample holder.
50 %
20

M (emu/g)
stripped from the surface and then cut to the appropriate 0
shape. In order to obtain the rigid samples, some green tapes -20 T = 300 K
were heated up to 1000 1C with 1 h of dwell time. -40
X-ray powder diffraction of the samples showed the pure
-60
perovskite structure corresponding to the ceramic LSMO crystal
structure (see Fig. 1). -80
DC magnetization measurements were performed in a Quan- -3000 -2000 -1000 0 1000 2000 3000
tum Design PPMS system. Electrical resistivity was measured H (Oe)
using the standard four probe method with hand painted Ag
Fig. 2. M vs H for samples with 25–50% of relative polymer fraction at 7 and 300 K.
contacts. All samples display ferromagnetic behavior.

3. Results and discussion

300
a
Hco (Oe)

Magnetization of all samples as a function of the external 200 LSMO

magnetic field display the characteristic ferromagnetic behavior, 100
resembling that of bulk LSMO, with increasing magnetic
moment while reducing T (see Ref. [6]) (Fig. 2). Magnetization 0
Msat (emu/g) Mrem (emu/g)

was normalized using the LSMO weight. 18

b
A noticeable difference between our composite samples and 12
the bulk LSMO is the appearance of a significant coarsening of
6
the hysteresis loops at low temperatures.
The temperature dependence of the saturation magnetization 0
(Msat, at 3 T), the coercive field (Hco) and the remnant 60 c
magnetization (Mrem) are shown in Fig. 3. We see an increase 25 %
40 30 %
of both Hco and Mrem while reducing T. The dependence of 40 %
Msat vs T indicates a ferromagnetic behavior with TC above 350 20 50 %
K. 0
In Fig. 4(a) we show the dramatic increase of the room
0 50 100 150 200 250 300 350
temperature resistivity that results from the addition of
polymer. This result suggests that LSMO grains are T (K)
disconnected. On the other hand, all samples display MR at
Fig. 3. (a) Coercive field (Hco), (b) remnant magnetization and (c) saturation
room temperature, which is undoubtedly related with transport
magnetization as a function of temperature, extracted from M vs H
within LSMO, as it is shown for samples with 35% and 50% of measurements. Results are presented for all samples, including pure LSMO.
polymer content (Figs. 4(b) and (c), respectively).
We see the two field regimes characteristic of CMR
manganites [6]. This feature is attributed to intra-grain MR for in resistivity is around 2% in 1 h). This behavior is
Ho300 Oe, and grain boundary MR for larger magnetic fields. characterized by a reduction of the resistivity which is more
Several previous works have shown a strong dependence of significant for high polymer to LSMO ratios. This instability
the magnetotransport properties on manganite–insulator disappears after the removal of organic compounds used to
composites [7–10], particularly near the percolation threshold of obtain rigid samples, which undoubtedly relates its origin to the
the manga- nite. In our case (Fig. 5), we observed a slight presence of the polymer.
dependence of the MR for samples with polymer content in the Previous works have shown that MR in manganite–insulator
range from 40% to 80%, and a noticeable increase for 35%. composites is enhanced near the percolation threshold of the
We obtained rather small MR values in comparison with the manganite. In this case we see that decreasing the insulating
typical corresponding to bulk LSMO at this temperature and component to 35%, results in a larger MR. However, we have to
magnetic field (around 10% [6]). note that it is not likely that we have reached the percolation
We have to remark that an instability of the resistivity was threshold because a 35% polymer weight corresponds to near
observed when samples are measured for a long time (the 20%
change
2762
 0
 (ohm cm) 10 C. Artale et al. / Physica B 404 (2009) 2760–2762

-2
4 10
10 sample with the higher LSMO relative content displays
2 a 300 K insulator- type behavior, confirming that no percolation of
10
LSMO occurs on our samples.
0 10 20 30 40 50 4. Conclusions
Polymer content %
In summary, we have synthesized LSMO/polymer composite
12.00 samples that display room temperature MR, the reason being
b 50% that the electrical and magnetic properties of LSMO are
11.98
unaltered by the presence of the polymer.
11.96 The increase of both Hco and Mrem shows that the gradual
R(KOhm)

hardening of ferromagnetism that occurs while reducing T, is

-1500 -1000 -500 0 500 1000 1500
more significant in the composite samples than in the pure
17.3 ceramic.
17.2 c 35% The magnetotransport study indicates that samples with low
17.1 a polymer content are best candidates for magnetoresistive
17.0 devices, as they show the largest MR ratios.
-8000 -6000 -4000 -2000 0 2000 4000 6000 8000 According to previous works [7–10], it is desirable to obtain
samples in which manganite grains organize percolative paths,
H(Oe)
in order to increase MR. We found that more than 35% of
Fig. 4. (a) Electrical resistivity as a function of polymer content at room polymer is needed to obtain good adherence between grains. On
temperature. (b) and (c) Electric resistance at 300 K as a function of magnetic the other hand, the electrical properties of samples with more
field for samples with 35% and 50% relative polymer fraction, respectively. than 80% were highly unstable. Some instability has also been
observed for less polymer content; further work is needed to
0.0150 solve this feature. A possible solution for this kind of behavior
is to slightly increase the pressure used to conform the
2000
% pol = 35% samples.
R (kΩ)

0.0125 1000 A major goal will be to develop a procedure to obtain

samples with manganite as near to the percolation threshold as
0 possible, and having stable and enhanced mechanical
-Δ/

0.0100 100 200 300 properties.

T(K)

0.0075
H=5000 Oe
0.0050
20 40 60
% PMMA
Fig. 5. Magnetoresistance at room temperature (300 K) for samples with 35–80%
polymer fraction (H ¼ 5000 Oe). Inset: resistance as a function of temperature for
the sample with 35% polymer content, showing an insulator-type behavior.
of LSMO volume ratio. The percolation threshold for a 3D
system can range from approximately 15% to 20% [11]. Taking
into account that our samples have not been pressed nor
sintered, and that they are highly porous, it seems possible that
this threshold has not been reached. The inset of Fig. 5 shows
that even the
Acknowledgments
This work was partially supported by ANPCyT (PICT03-13517
80 and PICT06-01549).
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