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Dependence of magnetoelectric properties on the magnetostrictive content in 0–3 composites
Mohsin Rafiquea,n, Syed Qamar ul Hassana, M.S. Awanb, Sadia Manzoora,b

Magnetism Laboratory, Physics Department, COMSATS Institute of Information Technology, Park Road, 44000 Islamabad, Pakistan b Center for Micro and Nano Devices (CMND), COMSATS Institute of Information Technology, 44000 Islamabad, Pakistan

Abstract The magnetoelectric response in composites of barium titanate (BTO) and cobalt ferrite (CFO) has been determined by measuring the magnetoelectric susceptibility coefficient. This was done by two different methods: magnetocapacitance measurements and magnetoelectric voltage measurement using a lock-in technique. These composites were prepared by the sol–gel method. Four different compositions with different molar ratios of the magnetostrictive phase (CFO) embedded in a piezoelectric matrix of BTO were studied to investigate the effect of the magnetostrictive content and the number density of interfaces on the magnetoelectric response. It was found from both techniques that the magnetoelectric coupling effect increases with the increase of applied field and it had a non-linear dependence on the percentage of magnetostrictive content in the composites. & 2012 Elsevier Ltd and Techna Group S.r.l All rights reserved.
Keywords: A. Sol–gel processes; B. Composites; C. Piezoelectric properties

1. Introduction Multiferroics are materials which simultaneously exhibit more than one ferroic order [1–4]. The most interesting ferroic orders for technological applications are ferromagnetism and ferroelectricity. Materials in which these orders occur simultaneously and are coupled to each other are called magnetoelectric (ME) multiferroics. These are the most promising materials in achieving an efficient mutual control of magnetism and electricity, i.e. modifying magnetization by using an electric field or controlling electric polarization by a magnetic field [5–9]. ME multiferroics have applications in novel multifunctional devices and a new generation of spinbased low-power-consumption electronics [9–12]. ME coupling is an intrinsic property of some single phase compounds e.g. TbMnO3, BiFeO3 etc. However in these intrinsic multiferroics, the coupling is very weak at device operating temperatures, which hinders their practical applications [13,14]. However, in composites made of piezoelectric and magnetostrictive materials, the two phases

Corresponding author. E-mail address: mmohsin8389@gmail.com (M. Rafique).

mechanically couple to produce a strain mediated ME effect at room temperature, several times higher than that of single phase multiferroics [10–14]. When a composite ME multiferroic is placed in a magnetic field, the magnetostrictive phase gets strained. This strain is transferred to the piezoelectric phase inducing polarization in it. (The converse happens in an electric field.) This polarization can be detected in terms of the electric field induced across the sample (dynamic method) or the change in the dielectric response of the sample (magnetocapacitance (MC) method). Both the above methods can be used to find the magnetoelectric coupling coefficient a which quantifies the strength of the ME coupling. This is the ratio of the electric polarization P induced in a sample when exposed to a magnetic field H (direct ME effect) or the ratio of the magnetization M induced by an electric field E (converse ME effect). Many candidates for ME composites are in fact poor insulators that cannot sustain the electric fields required to switch the polarization making it difficult to measure the ME coefficient directly. In this paper we report a comparison of the results obtained from the dynamic method and the MC method. Both methods give somewhat different values of a but there is a similarity in these results. Both of these methods

0272-8842/$ - see front matter & 2012 Elsevier Ltd and Techna Group S.r.l All rights reserved. http://dx.doi.org/10.1016/j.ceramint.2012.10.064 Please cite this article as: M. Rafique, et al., Dependence of magnetoelectric properties on the magnetostrictive content in 0–3 composites, Ceramics International (2012), http://dx.doi.org/10.1016/j.ceramint.2012.10.064

1. These were labeled as the 20–80.5625 ♦ 1400 1200 CFO-BTO powder (50-50) 0 annealed at 1000 C ∗ CFO ♦ ΒΤΟ 2. Preparation of composites The sol–gel method was used to prepare the cobalt ferrite–barium titanate nanocomposites. Fig. Silver paste was used to paint electrodes onto the faces of the pellets. and 50–50 CFO–BTO composites respectively.1625 35. Ceramics International (2012). 3.7375 200 0 20 ∗ ∗ 30 40 50 60 70 70. 30–70. The transverse (voltage measured perpendicular to applied magnetic field) and longitudinal (voltage measured parallel to applied magnetic field) ME effect was studied as a function of the AC magnetic field frequency. Magnetic properties of the nanocomposites were measured by a vibrating sample magnetometer (Riken-Denshi). SR 830) in differential mode.102 50–50 3.2125 50. The ME votlage was detected by using a lock-in amplifier (Standford Research System. 30–70.org/10. which were calcined at 850 1C for 2 h in air.5375 43. The gels were dried at 120 1C to obtain the composite powders.9125 62. The amplitude of the AC field is measured using a guassmeter (Lakeshore 475 DSP) in RMS mode. 2 shows the magnetically ordered structure of CFO–BTO composites. Dependence of magnetoelectric properties on the magnetostrictive content in 0–3 composites.1875 600 22. Characterization of composites Crystalline phase and structure of the CFO-BTO composites were studied by using an X-ray diffractometer (Xper Pro. 3. The magneto-capacitance of the composites was measured using a permanent magnet and a Wayne Kerr Precision Component Analyzer (6440B). 1 shows the XRD result for the 50–50 sample.2. Rafique. The experimental set-up to measure the ME effect using the lock-in technique consists of a Helmholtz coil driven by an AC current generated by an Escort EGC-2230 function generator at frequencies up to 20 kHz. The powders were subsequently pressed into pellets using cold isostatic pressing and then sintered at 1000 1C for 12 h. et al. 31.1. The gels of both constituents were prepared with equal molarities and mixed in four different molar ratios: 20–80. Another similarity is the linear dependence of a on the applied magnetic field strength.doi. Panalytical company) with Cu Ka radiation.2. Magnetization hysteresis loops of CFO–BTO composites. We find that the two methods complement each other in different frequency ranges. 2.404 30–70 3.2012. 40–60 and 50–50. 2. The normalized intensities of the major peaks were also found to be in proportion to the content of the CFO or BTO phase.10.024 -30 -10000 -5000 0 5000 10000 H (Oe) Fig. The saturation and remnant magnetizations increase with the increase of CFO content. Please cite this article as: M. / Ceramics International ] (]]]]) ]]] –]]] show a non-linear dependence of the coupling coefficient on the ratio magnetostrictive content in the composites.1016/j. Crystallography The X-ray diffraction confirmed the presence of the spinel and perovskite phases representing the CFO and BTO respectively in all samples. Magnetic and ferroelectric properties The M-H loops in Fig. The densities of the samples are given in Table 1.2 M.8875 ∗ ♦ ♦ ♦ ♦ ♦ ♦ ∗ ♦ ♦ ∗ ∗ ∗ 80 2Θ Fig.8375 ∗♦ 65. No peaks corresponding to impurity phases were found in the diffraction pattern of any sample. Intensity (counts ) 1000 800 44.4375 74.8625 400 ♦ 38. Experiment 2.064 .6375 56. Sample name Density (g cm À 3) 20–80 3. http://dx. Results and discussion 3. 30 20 CFO-BTO 20-80 30-70 50-50 M (emu/g) 10 0 -10 -20 Table 1 Densities of the prepared samples. Rafique et al. X-ray diffraction pattern of the 50–50 CoFe2O4–BaTiO3 composite.284 40–60 3.ceramint. 1.. 40–60.

doi. (a) H for different compositions of the CFO–BTO composite. Rafique. This is due to the compound effect of an increase in the magnetostrictive phase as well as an increase in the number density of CFO–BTO interfaces. / Ceramics International ] (]]]]) ]]] –]]] 8 7 6 H = 1315 Oe CFO-BTO 20-80 30-70 40-60 50-50 3 a 8 6 ΔC/C % 20-80 30-70 40-60 50-50 5 4 3 2 1 0. The MC is quite small and increases linearly at low fields for all samples.1016/j.org/10.18]. These data were used to calculate the magnetoelectric voltage coefficient according to the following relation: aV ¼ Vout tHAC ð2Þ where Vout is the output voltage t is the thickness of the pellet and HAC is amplitude of the AC magnetic field. 3. 3. 3.5 1. 4 shows the variation of MC with CFO concentration for a fixed field H ¼ 1315 Oe and different frequencies. In order to confirm 25 30 35 40 45 50 CFO content Fig.3. Rafique et al.16] and CFO–BTO core-shell nanocomposites.064 . there is a sharp increase in the MC for all samples and this was verified several times in experiment. 4.10. Magnetocapacitance Magnetocapacitance is defined as the change in capacitance in the presence of a magnetic field normalized by the zero-field capacitance.0 ΔC/C % 1. 4(a). b 8 7 6 f = 0.1 MHz f = 0. Fig. Dependence of magnetoelectric properties on the magnetostrictive content in 0–3 composites. All samples show a linear dependence of the transverse voltage on AC field amplitude.0 4 2 f (MHz) Fig. We find a strong nonlinear dependence of MC on the CFO content. There is an ongoing controversy in the literature that the MC effect in composite multiferroics may not be a measure of the magnetoelectric coupling [19]. http://dx. It has been argued that magnetoresistive samples with Maxwell–Wagner behavior could show magnetocapacitance. This effect is the largest for the 50–50 composite. 0 0 300 600 900 1200 1500 H (Oe) 3. and (b) CFO content in CFO–BTO composites at a fixed field of H ¼ 1315 Oe. Ceramics International (2012).5 MHz.ceramint. but this will be done in the future.. Percentage magnetocapacitance vs. After about 1100 Oe. This is related to the ME coupling coefficient by a ¼ e o e r aE .e. Frequency dependence of magnetocapacitance for different samples. The Please cite this article as: M. the existence of ME coupling we have measured the magnetoelectric voltage coefficient aE in the following section.0 0.8% in the 50–50 composite. The results are shown in Fig. Magnetoelectric voltage coefficient The dependence of the output voltage on the amplitude of the applied AC magnetic field measured for different samples is shown in Fig. The above data were used to extract the magnetic field dependence of the magnetocapacitance at a fixed frequency of 0.4. 5. MC increases from about 1% in the 20–80 composite to 7. Higher DC fields could not be used due to experimental limitations. et al.5 MHz f = 1 MHz ΔC/C % C ðH Þ2 C ðH ¼ 0Þ DC MC ¼ ¼ C ð H ¼ 0Þ C 5 4 3 2 1 20 ð 1Þ The magnetocapacitance as a function of the frequency of the AC voltage (1 V) applied to the sample capacitor is shown in Fig. This voltage was measured transverse to the applied AC field using a lock-in amplifier at a frequency of 1 kHz. this cannot be taken as evidence of magnetoelectric coupling. All samples display a positive magnetocapacitance.2012.5 2.M. i. The reason for this sharp increase is not entirely clear but we believe that this is due to the sudden sharp increase in the magnetostriction of CFO at about the same values of the DC field [17. This is in agreement with similar results obtained on CFO–PZT composite films [15.

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