The physics of magnetoelectric composites

This paper gives an overview about the basic ideas of magnetoelectric materials. Up to now single-phase materials show the magnetoelectric effect only below room temperature. Mixing a magnetostrictive with a piezoelectric component is a way to overcome this limitation. This delivers a composite which can exhibit a magnetoelectric effect even at room temperature and higher. Possible candidates for these composites (piezoelectric as well as magnetostrictive) are shown, examples from literature and own results are given. The most important coupling mechanism (magnetization, magnetostriction, local stress, charge) between the magnetostrictive and the piezoelectric phase are discussed. Hints for a direct coupling between the electric polarization and the magnetization are also presented. Different measurement methods for determining the magnetoelectric coefficient are discussed. Representative results as obtained on a technical useful composite between 50% Co-Ferrite+50% BaTiO₃ are given. The behavior of a simple “mixed” structure with that of a “core-shell” structure is compared. The later gives a 20-times larger magnetoelectric coefficient.     

磁电复合材料的制备和理论分析

压磁-压电复合材料是一种新型的多功能材料,兼具压电性和压磁性,磁电耦合效应远高于单相材料。本文介绍了磁电复合材料的制备方法和理论问题,涉及了磁电复合材料中的缺陷影响,提出了今后的发展方向。     

Studies on lead-free multiferroic magnetoelectric composites

Lead-free multiferroic magnetoelectric composites consisting of ferrimagnetic Ni_0.93Co_0.02Mn_0.05Fe_1.95O₄ (NMF) and ferroelectric Na_0.5Bi_0.5TiO₃ (NBT) phases were synthesized by the solid-state sintering method. The presence of constituent phases in composites was confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). A systematic study of dc conductivity as a function of temperature (RT −450 °C) revealed that the conduction is due to small polarons. The effect of constituent phase variation on the dielectric constant and piezoelectric strength (d₃₃) was examined. The composites exhibited typical magnetic hysteresis (M–H) loops at room temperature. Furthermore, magnetoelectric (ME) output was evaluated as a function of applied magnetic field, which is a product property of the constituent phases. The compound 50% NMF–50%NBT is a new lead-free magnetoelectric composite with 155 μV/cm ME output, which may have potential applications.     

Numerical simulation of nonlinear magnetic-mechanical-electric coupling effect in laminated magnetoelectric composites

Considering the significant nonlinear magnetoelectric (ME) characteristics in laminated ME composites, we build a numerical model of magnetic-mechanical-electric coupling effect based on the nonlinear magnetostrictive constitutive relation. The change of the ME field coefficients with bias magnetic field predicted by this model shows good agreement with the experimental result, both qualitatively and quantitatively. Furthermore, this paper considers and predicts the magnetoelectric conversion charateristics of laminated ME composites, calculates and analyzes the influence of the thickness ratio of magnetostrictive layer, the geometrical size of laminated composites, the saturation magnetization, and the types of piezoelectric materials on the ME conversion coefficient of ME laminated composites. We believe that this research provides a theoretical basis for the production of magnetoelectric devices with good magnetoelectric conversion characteristics.     

Nonlinear magnetoelectric response of a bulk magnetostrictive-piezoelectric composite

Magnetoelectric effect in a bulk composite of nickel ferrite and lead zirconate titanate has been investigated by applying an ac magnetic field with no bias field. The measurements were carried out in the low-frequency region for harmonic magnetic field modulation with amplitude up to 3 kOe. The electric field induced by out-of-plane magnetic field exceeds that induced by in-plane magnetic field by approximately 4 times. Nonlinearity of ferrite magnetostriction of the sample results in a doubling in the frequency and a strong distortion of the ME signals. The magnetically induced voltage can be found by integrating the ordinary ME voltage coefficient over magnetic field.     

Magnetic,ferroelectric and magnetoelectric properties of Ba-doped BiFeO3

Bi_1–xBa_xFeO₃ (0.0≤x≤0.25) ceramics are prepared by chemical synthesis route. At room temperature, antiferromagnetic BiFeO₃ is converted to ferromagnetic on doping Ba. A large change in the magnetization is observed around 370 °C which is close to the Neel temperature (T_N) of parent compound. Another magnetic transition is also observed near 600 °C. Spin canting or impurity phase could be a probable reason for the origin of ferromagnetism in both cases. Ferroelectric and magnetic transitions of the compounds shift towards higher temperature with Ba-doping concentration. Anomaly in the dielectric constant is also observed near the T_N of BiFeO₃. The composition x=0.15 shows the maximum magnetic moment at room temperature while better fatigue resistance and maximum magnetoelectric coupling are observed for x=0.20 composition.     

Optimal magnetoelectric coupling performance of Terfenol-D/PZT composites in resonance state under bias magnetic field

Laminated magnetoelectric (ME) composites with various thickness ratios were optimized, fabricated and experimentally investigated in this work. The Terfenal-D/PZT specimens with optimal thickness ratio between the magnetostrictive phase and piezoelectric phase, and two other values were tested for their ME coupling performance. The coupling voltage output increases linearly with the increase of DC bias magnetic field. The ME voltage coefficient increases more than 100 times in the resonance state for the optimal laminate. The DC bias magnetic field affects the ME voltage coefficient significantly, and also has little effect on the resonant frequency. The strength of AC magnetic field also slightly affects the ME voltage coefficient in resonance state, but does not affect the resonant state under which the same DC magnetic field is required. The experimental results can help understand the coupling performance of ME composite under bias magnetic field and prompt the application of ME devices.     

Direct and inverse magnetoelectric effect in layered composites in electromechanical resonance range: A review

A model is presented for the increase in magnetoelectric (ME) coupling in magnetostrictive-piezoelectric bilayers in the electromechanical resonance region. The ME voltage coefficients α_E have been estimated for transverse field orientations corresponding to minimum demagnetizing fields and maximum α_E. We solved the equation of medium motion taking into account the magnetostatic and elastostatic equations, constitutive equations, Hooke's law, and boundary conditions. The resonance enhancement of ME voltage coefficient for the bilayer is obtained at antiresonance frequency. To obtain the inverse ME effect, a pick up coil wound around the sample is used to measure the ME voltage due to the change in the magnetic induction in magnetostrictive phase. The measured static magnetic field dependence of ME voltage has been attributed to the variation in the piezomagnetic coefficient for magnetic layer. The frequency dependence of the ME voltage shows a resonance character due to the longitudinal acoustic modes in piezoelectric layer. The model is applied to specific cases of cobalt ferrite–lead zirconate titanate and nickel–lead zirconate titanate bilayers. Theoretical ME voltage coefficients versus frequency profiles are in agreement with data.     

Frequency response of magnetoelectric effect in piezoelectric-magnetostrictive disk-ring composite structures

A theoretical model is presented for frequency dependence of magnetoelectric (ME) effect in piezoelectric-magnetostrictive disk-ring composite structures. Expressions for ME voltage coefficients in piezoelectric-magnetostrictive (PE-MS) disk-ring and MS-PE disk-ring are obtained by solving elastodynamic equations. The calculated resonance frequency and frequency dependence of ME voltage coefficients are in good agreement with the experimental results. This model indicates better mechanical coupling in disk-ring structure than that in traditional layered structure, and this may be responsible for the enhancing ME effect. The analysis suggests the disk-ring composites structures are promising for magnetoelectric applications.     

A novel frequency multiplier based on magnetoelectric laminate

We report a novel frequency multiplier based on the magnetoelectric (ME) effect in a simple multiferroic laminate, made up of an amorphous FeBSiC magnetic layer bonded onto a Pb(Zr,Ti)O₃ plate wrapped with a coil. By applying an input signal with a frequency f to the coil, an output signal with 2f can be generated from the PZT plate due to the ME coupling. This ME laminate-based device can be operated in a broad frequency range and switched by a low bias magnetic field, offering potential opportunities for frequency multipliers in electrical applications.     

Tuning magnetic properties of magnetoelectric BiFeO3-NiFe2O4 nanostructures

Multifunctional thin film nanostructures containing soft magnetic materials such as nickel ferrite are interesting for potential applications in microwave signal processing because of the possibility to shrink the size of device architecture and limit device power consumption. An essential prerequisite to future applications of such a system is a firm understanding of its magnetic properties. We show that nanostructures composed of ferrimagnetic NiFe₂O₄ pillars in a multiferroic BiFeO₃ matrix can be tuned magnetically by altering the aspect ratio of the pillars by depositing films of varying thickness. Magnetic anisotropy is studied using ferromagnetic resonance, which shows that the uniaxial magnetic anisotropy in the growth direction changes sign upon increasing the film thickness. The magnitude of this anisotropy contribution can be explained via a combination of shape and magnetostatic effects, using the object-oriented micromagnetic framework (OOMMF). The key factors determining the magnetic properties of the films are shown to be the aspect ratio of individual pillars and magnetostatic interactions between neighboring pillars.     

Dispersion characteristics for low-frequency magnetoelectric coefficients in bulk ferrite-piezoelectric composites

Ferrite-piezoelectric composites are magnetoelectric (ME) due to the interaction between magnetic and electrical subsystems through mechanical forces. A theory for the low-frequency Maxwell-Wagner relaxation in ME coefficients is discussed for bulk composites of nickel or cobalt ferrite and lead zirconate titanate (PZT). ME coefficients versus frequency spectra show two types of relaxation, over 0.1-100 μHz and 1-1000 Hz. The relaxation frequencies and the magnitude of the ME coefficients are dependent on the electrical and composite parameters and volume fraction for the two phases. The ME coefficient α_E is in the range 10⁻¹-10⁴ mV/cm Oe, higher in cobalt ferrite-PZT than for nickel ferrite-PZT, and is strongly dependent on PZT volume fraction v. Estimates of α_E and relaxation frequencies versus v provided here are useful for engineering composites with maximum ME effects for specific frequency bands.     

Low-frequency and resonance magnetoelectric effects in nickel ferrite-PZT bulk composites

The direct and inverse magnetoelectric effects in nickel ferrite spinel-PZT bulk composites are experimentally studied at low frequencies and in the range of electromechanical resonance. The frequency and field dependences of the magnetoelectric effect are analyzed. It is shown that the direct effect resonantly grows at the antiresonance frequency and the inverse effect grows at the resonance frequency. The dependences of the resonance and antiresonance frequencies on the composition of the composite material are determined.     

Phase switching phenomenon in magnetoelectric laminate polymer composites: Experiments and modeling

This article reports on the magnetoelectric (ME) effect observed in bi- and trilayered polymers consisting of polyvinylidene fluoride (PVDF) and polyurethane (PU) filled with magnetically hard magnetite Fe₃O₄ or Terfenol-D(TeD) magnetostrictive material. The samples had the following compositions: (PU+2 wt% Fe₃O₄/PVDF), (PU+2 wt% Fe₃O₄/PVDF/PU+2 wt% Fe₃O₄), (PU+50 wt% TeD/PVDF) and (PU+50 wt% TeD/PVDF/PU+50 wt% TeD). A model, based on a driven damped oscillation system, has been developed to evaluate and study the influence of the first and second-order ME coefficients on the dc magnetic field-induced phase switching phenomenon between dynamic ME current and the applied ac magnetic field. A good agreement between the simulated results and experimental data was obtained and it was found that phase switching characteristics are mainly influenced by the ME losses induced by magnetostriction losses.     

Bath temperature effect on magnetoelectric performance of Ni-lead zirconate titanate-Ni laminated composites synthesized by electroless deposition

Magnetoelectric (ME) Ni-lead zirconate titanate-Ni laminated composites have been prepared by electroless deposition at various bath temperatures. The structure of the Ni layers deposited at various bath temperatures was characterized by X-ray diffraction, and microstructures were investigated by transmission electron microscopy. The magnetostrictive coefficients were measured by means of a resistance strain gauge. The transverse ME voltage coefficient α_E,31 was measured with the magnetic field applied parallel to the sample plane. The deposition rate of Ni increases with bath temperature. Ni layer with smaller grain size is obtained at higher bath temperature and shows higher piezomagnetic coefficient, promoting the ME effect of corresponding laminated composites. It is advantageous to increase the bath temperature, while trying to avoid the breaking of bath constituents.     

Recent development and status of magnetoelectric materials and devices

The magnetoelectric (ME) materials and related devices have been attracting increasing research attention over the last few years. They exhibit strong ME coupling effect at room temperature, and electric field control of magnetization or magnetic field control of ferroelectric polarization can be achieved. The ME coupling effect brings novel functionalities to develop ultra-fast, low-power, and miniaturized electronics. Recent progress shows the performance of ME materials is further improved and the materials are used to develop many new types of electronics such as high-speed memory, radio frequency resonator, compact ME antenna, and weak magnetic field sensor. In this review, we present the overview in those fields with emphasis on both the opportunities and challenges for the application of ME materials and devices in the cutting-edge technologies.     

In-situ X-ray microdiffraction analysis of local strain-field across the interface in a Pb(Zr0.52Ti0.48)O3/Ni0.8Zn0.2Fe2O4/Pb(Zr0.52Ti0.48)O3 tri-layered structure

We have performed a synchrotron X-ray microdiffraction to investigate the variation of the local strain-field across the interface in Pb(Zr_0.52Ti_0.48)O₃/Ni_0.8Zn_0.2Fe₂O₄/Pb(Zr_0.52Ti_0.48)O₃ (PZT–NZFO–PZT) tri-layered structure. In this study, we show that the in-plane lattice parameters of the NZFO lattice depend strongly on the piezoelectric strain of the PZT layer. This result explains that an electric-field-induced piezoelectric strain from the PZT layer is effectively transferred to the NZFO layer. Furthermore, the local strain persists within 20 μm away from the interface, inducing changes of magnetic responses via the inverse magnetostrictive effect.     

Magnetoelectric properties of particulate and bi-layer PMN-PT/CoFe2O4 composites

Our studies comprise electrical dielectric and magnetoelectric properties of CoFe₂O₄ (CFO) and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ [PMN-PT] magnetoelectric composites. The individual phases were prepared by conventional ceramic method. The particulate composites of ferrite and ferroelectric phases were prepared in ferroelectric rich region. Presence of both the phases in the composites was confirmed using X-ray diffraction techniques. The scanning electron microscopic images recorded in backscattered mode were used to study the microstructure of composites. Lattice constant, dielectric constant, electrical resistivity, ferroelectric, and magnetic properties of individual as well as particulate composites were studied. Further the bi-layer composites were made using the discs obtained from the powders of individual phases where hot press technique was employed to obtain disc of individual phases. CFO phase used in bi-layer composites was obtained using chemical co-precipitation technique. Magnetoelectric (ME) measurements were carried out on both, particulate and layered magnetoelectric composites. Comparison of ME signal obtained from particulate and layered composites revealed that the layered composites gives superior magnetoelectric signal. ME data obtained for layered composites show good agreement with the theoretical model.     

Magnetoelectric properties of Gd and Nd-doped nickel ferrite

Ferromagnetic and ferroelectric characteristics of Gd and Nd-substituted nickel ferrite were investigated. The materials formed in the cubic inverse spinel phase with small amounts of GdFeO₃ and NdFeO₃ as the additional phases in the respective materials. Substitution of Gd and Nd for Fe caused decrease in the saturation magnetization and Curie temperature of the nickel ferrite. However, the saturation magnetostriction is seen not to change significantly by the substitution of Gd and Nd. The existence of the ferroelectricity was confirmed from the ferroelectric loops and magnetocapacitance of −2% and −3% were observed. The large frequency dependence of the (high) dielectric constant reveals a wide dispersion of relaxation times. The ferroelectric transition temperature values of NiO.Fe_1.95Gd_0.05O₃ and NiO.Fe_1.95Nd_0.05O₃ were found to be 498 and 544 K, respectively.