Table of Contents

Title Page

List of Contributors

Preface and Acknowledgments

Chapter 1: Magnetoelectric Effect of Functional Materials: Theoretical Analysis, Modeling, and Experiment

1.1 Introduction of Magnetoelectric Effect
1.2 Applications of Magnetoelectric Effect
1.3 Magnetoelectric Effect of Piezoelectric Ceramic
1.4 Magnetoelectric Effect in Insulating Polymers
1.5 Conclusion
1.6 Acknowledgments
References

Chapter 2: Materials Selection, Processing, and Characterization Technologies

2.1 Introduction
2.2 Materials Selection and Processing
2.3 Characterization Technologies
2.4 Concluding Remarks
Acknowledgments
References

Chapter 3: Types of Polymer-Based Magnetoelectric Materials

3a: Laminates

3a.1 Introduction
3a.2 Laminated Magnetoelectric Composites
3a.3 Piezoelectric Phase for Magnetoelectric Laminates
3.4a Magnetostrictive Phase for Magnetoelectric Laminates
3.5a Bonding Agent for Magnetoelectric Laminates
3a.6 Structures for Magnetoelectric Laminates
3a.7 Limitations and Remaining Challenges
Acknowledgments
References

3b: Polymer-Based Magnetoelectric Composites: Polymer as a Binder

3b.1 Introduction
3b.2 Polymer-Based Tb_1−xDy_xFe_2−y by Magnetic Warm Compaction
3b.3 Multifaceted Magnetoelectric Composites
3b.4 Bonded Cylindrical Composites
3b.5 Multi-electrode Cylinder Composites
3b.6 Polymer Content and Particle Size Effects
Acknowledgments
References

3c: Poly(vinylidene fluoride)-Based Magnetoelectric Polymer Nanocomposite Films

3c.1 Introduction
3c.2 Ferroelectric Polymers
3c.3 The Selection of Magnetic Nanofillers
3c.4 Experimental Methods
3c.5 Characterization
3c.6 Summary
3c.7 Future Directions
Acknowledgments
References

Chapter 4: Low-Dimensional Polymer-Based Magnetoelectric Structures

4.1 Introduction
4.2 Magnetoelectric Spheres
4.3 Magnetoelectric Fibers
4.4 Magnetoelectric Membranes
4.5 Conclusions and Future Perspectives
Acknowledgments
References

Chapter 5: Design of Magnetostrictive Nanoparticles for Magnetoelectric Composites

5.1 Introduction
5.2 Synthesis Approaches to Produce Magnetostrictive Nanoparticles for Magnetoelectric Composites
5.3 Summary and Future Perspectives
Acknowledgments
References

Chapter 6: Applications of Polymer-Based Magnetoelectric Materials

6a: Sensors, Actuators, Antennas, and Memories

6a.1 Introduction
6a.2 Polymer-Based Magnetoelectric Sensors
6a.3 Polymer-Based Magnetoelectric Actuators
6a.4 Polymer-Based Magnetoelectric Antennas
6a.5 Polymer-Based Magnetoelectric Memories
6a.6 Opportunities, Limitations, and Remaining Challenges
Acknowledgments
References

6b: Magnetoelectric Composites for Bionics Applications

6b.1 Introduction
6b.2 Bionics
6b.3 Cell Interactions and Electrical Stimulation
6b.4 Future Biomaterials for ME Composites
6b.5 Characterization Tools for Nanoscale ME
Acknowledgments
References

6c: Energy Harvesting

6c.1 Introduction
6c.2 Magnetoelectric Composites for Energy Harvesting
6c.3 Energy-Harvesting Devices Based on Magnetoelectric Composites
6c.4 Conclusion
References

6d: High-Temperature Polymers for Magnetoelectric Applications

6d.1 Introduction
6d.2 Types of Piezoelectric Polymers
6d.3 ME Effect Using Piezoelectric Polyimides
6d.4 Summary and Conclusions
References

Chapter 7: Open Questions, Challenges, and Perspectives

References

Index

End User License Agreement

List of Illustrations

Chapter 1: Magnetoelectric Effect of Functional Materials: Theoretical Analysis, Modeling, and Experiment

Figure 1.1 Schematic of proposed laminated composites configuration of magnetostrictive and piezoelectric materials [6].
Figure 1.2 Schematic diagrams of (a) the proposed ME/EM composite VEH and (b) the ME/EM composite transducer [10].
Figure 1.3 Design of microstrip ME attenuator and ME resonator [13].
Figure 1.4 Schematic drawing of the experimental system of ME actuator and its torsion velocity measurement [14].
Figure 1.5 Torsion velocity of PZT beam versus the same dc magnetic field.
Figure 1.6 Torsion velocity of PZT beam versus the same dc magnetic field.
Figure 1.7 Schematic diagram of the rectangular shape piezoelectric beam subjected to ac and dc magnetic fields.
Figure 1.8 Torsion velocity of PZT beam versus ac current in conducting wire.
Figure 1.9 ME voltage of PZT beam versus ac current in conducting wire.
Figure 1.10 ME measurement system [16].
Figure 1.11 Comparison of ME current between discharged and nondischarged porous PP.
Figure 1.12 Schematic of equivalent circuit.
Figure 1.13 Comparison of ME effect between charged and noncharged cellular PP and PVC (@Bac = 0.1 mT, f = 1 kHz).

Chapter 2: Materials Selection, Processing, and Characterization Technologies

Figure 2.1 (a) Schematic of the measurement and the ME cantilever consisting of PVDF deposition on Metglas substrate. (b) Frequency dependence of the ME coefficient for an optimum dc field of 6 Oe and an ac field of 0.001 Oe.
Figure 2.2 Illustration of the operation principle of the shear–shear mode ME sensor. The directions of dc and ac magnetic fields in the magnetostrictive layers and the poling direction of PVDF are indicated.
Figure 2.3 Possible movements of the cantilever due to forces acting on the tip. (a) $c02-math-048$ leading to deflection, $c02-math-049$ leading to buckling, and $c02-math-050$ leading to torsion of the cantilever. (b) Side and top views of the cantilever movement. (c) Possible movements of the laser spot on the segmented photodetector.
Figure 2.4 Domain imaging in 12 monolayers P(VDF-TrFE) film after annealing: (a) topography; (b) PFM amplitude; and (c) PFM phase.
Figure 2.5 (a) Topography, (b) PFM amplitude, and (c) PFM phase images of three different regions (virgin state, poling of $c02-math-060$ , and poling of $c02-math-061$ ) in the P(VDF-TrFE) thin films on Au/Si substrates.
Figure 2.6 Working principles of MFM, an optical fiber is used in close vicinity (distance $c02-math-062$ ) to the magnetic cantilever to detect its deflection caused by the magnetic stray field of the specimen.
Figure 2.7 Schematic diagram of MOKE magnetometer apparatus. Abbreviations used are as follows: ND, neutral density filters and half-wave plate/polarizer for laser beam attenuation; BE, beam expander; Pol, polarizer; BS, beam splitter; L, lens; $c02-math-064$ , quarter-wave plate; Var ND, variable neutral density filter; PD1 and PD2, photodiodes for MOKE and reference signals, respectively.
Figure 2.8 (a) Schematic demonstration of magnetocapacitance (or magnetodielectric effect): the change in the frequency-dependent capacitance (or dielectric constant) under an applied magnetic field, which could be contributed only from the magnetoresistance and interfacial capacitive effect in the magnetic–dielectric composite systems without piezo/ferroelectric components. The waveform of (b) the ME voltage $c02-math-080$ and (c) the Faraday-induced electromotive force $c02-math-081$ in real time. The $c02-math-082$ has the same phase as $c02-math-083$ , while the phase of $c02-math-084$ is behind or ahead of 90°. The thin blue lines correspond to $c02-math-085$ , while the thick red dot curves correspond to $c02-math-086$ or $c02-math-087$ .
Figure 2.9 In-plane magnetization ( $c02-math-113$ at 0.01 T and 330 K) of LSMO film grown on single-crystal PMN–PT (001) measured using VSM with external electric field $c02-math-114$ applied across the PMN–PT substrate. The arrows show the direction of the electric field sequence.
Figure 2.10 $c02-math-115$ hysteresis curve showing the magnetic response of the PZT/LSMO heterostructure at 100 K as a function of the applied electric field, measured by a MOKE magnetometer. Insets represent the magnetic and electric states in the thin LSMO layer (blue) and PZT layer (red).
Figure 2.11 MFM images of the BaTiO₃ (BTO)–CFO heterostructure before (a) and after (b) electric poling with 10 V.
Figure 2.12 Images of Ni/BaTiO₃ heterostructure obtained at room temperature for (a) 0 V, (b) 300 V, and (c) 0 V following an initial electrical cycle. These images were spliced together on either side of a zigzag edge in the film, thus combining a PEEM image of the Ni film obtained with XMCD contrast, and a PEEM image of the exposed substrate obtained with XLD contrast.
Figure 2.13 (a) Schematic of CoFe (2.5 nm)/ $c02-math-126$ (200 nm) multiferroic heterostructure for FMR measurements at varying angles α between the magnetic field and the easy axis and (b) relative FMR field dependence after applied voltage pulses along different orientations of the magnetic field.

3a: Laminates

Figure 3a.1 Configuration of magnetoelectric laminates.
Figure 3a.2 (a) Image of a flexible PVDF/Metglas unimorph laminate; (b) unimorph configuration; and (c) the three-layer laminate.
Figure 3a.3 Synthesis of the cross-linked ferroelectric P(VDF-TrFE)s.
Figure 3a.4 (a) ME voltage coefficient of the composites as a function of dc magnetic field. (b) ME voltage coefficients of the P3-Metglas composite as a function of frequency.
Figure 3a.5 Conversion of α-crystalline conformation into the β-crystalline conformation.
Figure 3a.6 (a) Magnetostriction and piezomagnetic properties of the Metglas; (b) magnetoelectric voltage coefficient and phase of Metglas/PVDF LT mode laminates; and (c) photograph of the Metglas/PVDF laminates.

3b: Polymer-Based Magnetoelectric Composites: Polymer as a Binder

Figure 3b.1 Illustration of the preparation process and ME measurement of the bonded Terfenol-D/PZT bilayered ME composites: (a) warm compaction process; (b) Terfenol-D polymer compacted sample; (c) PZT plate; and (d) ME composite.
Figure 3b.2 Frequency dependence of α_E,31 with H_dc = 1100 Oe.
Figure 3b.3 The ME voltage coefficient dependence on the applied magnetic field H_dc ranging from 0 to 5 kOe.
Figure 3b.4 Magnetostrictive coefficient dependence on the applied magnetic field H_dc of the bonded Terfenol-D composites.
Figure 3b.5 XRD patterns of the bonded Terfenol-D composites.
Figure 3b.6 Schematics of bonded Terfenol-D/Pb(Zr, Ti)O₃ ME composites.
Figure 3b.7 Frequency dependence of α_E,31 in parallel mode with H_dc = 700 Oe: (a) one PZT plate; (b) two PZT plates; (c) three PZT plates; and (d) four PZT plates.
Figure 3b.8 Frequency dependence of α_E,31 in serial mode with H_dc = 700 Oe: (a) one PZT plate; (b) two PZT plates; (c) three PZT plates; and (d) four PZT plates.
Figure 3b.9 The sketch map of (a) parallel mode and (b) serial mode.
Figure 3b.10 (a) Schematic illustration of the TDE/PZT cylindrical composites. Vectors identify the direction of the applied magnetic field, and the corresponding ME voltage coefficients and (b) picture of the actual sample. The scale is in centimeters.
Figure 3b.11 (a) α_E,A dependence on the ac magnetic field frequency (f) at the optimal magnetic field (H_m), corresponding to the maximum ME coupling and (b) α_E,A dependence on H_dc at the resonant frequency.
Figure 3b.12 Schematic illustration of the TDE/PZT planar laminated composites for the differential coefficient calculation.
Figure 3b.13 (a) α_E,32 dependence on the ac magnetic field frequency (f) at the optimal magnetic field (H_m), corresponding to the maximum ME coupling and (b) α_E,32 dependence on H_dc of at the resonant frequency.
Figure 3b.14 Schematics illustrating the geometrical arrangement of Terfenol-D/PZT cylindrical ME composites: (a) P-T-P; (b) T-P; and (c) T-P-T-P.
Figure 3b.15 (a) Schematic of the composite mode (the directions of applied magnetic field and polarization) (showing P-T-P as an example); (b) the α_E,V dependence on the ac magnetic field frequency (f) at the optimal magnetic field (H_m) of the three samples, corresponding to the maximum ME coupling; and (c) the H_dc dependence of a_E,A at the resonance frequency.
Figure 3b.16 Schematics illustrating the contact surfaces and the free surfaces of the composites (without PZT): (a) P-T-P; (b) T-P; and (c) T-P-T-P.
Figure 3b.17 (a) XRD pattern of the crushed Terfenol-D particles and (b) Terfenol-D particles with the 150–180 µm size, observed by SEM.
Figure 3b.18 The ME voltage coefficient, α_E,A, dependence on the volume ratio of epoxy content. The results are for the sample with the particle size of 150–180 µm.
Figure 3b.19 The ME voltage coefficient, α_E,A, dependence on the Terfenol-D particle size. The results are for the samples fabricated with the epoxy content of 0.14 wt%.

3c: Poly(vinylidene fluoride)-Based Magnetoelectric Polymer Nanocomposite Films

Figure 3c.1 Number of publications based on the keyword “Magnetoelectric polymer nanocomposites” as per record available in the website.
Figure 3c.2 Schematic representation of MPNCs from ferroelectric polymer matrix and nanofillers and mutual control of polarization (P) and magnetization (M) by electric (E) and magnetic fields (H).
Figure 3c.3 Molecular structure of (a) α phase and (b) β phase of PVDF.
Figure 3c.4 Orientations of dipoles with and without poling.
Figure 3c.5 XRD patterns of CoFe₂O₄, NiFe₂O₄, and ZnFe₂O₄ nanoparticles.
Figure 3c.6 Photographs of flexible PVDF/ferrite films.
Figure 3c.7 IR spectra of (a) PVDF/CFO, (b) PVDF/NFO. Prabhakaran and Hemalatha 2016 [34]. Reproduced with permission of Royal Society of Chemistry, (c) PVDF/ZFO MPNC films Prabhakaran and Hemalatha 2014 [35]. Reproduced with permission of American Scientific Publishers, and (d) F(β) versus filler concentration.
Figure 3c.8 SEM images of PVDF/CFO, PVDF/NFO, and PVDF/ZFO MPNC films.
Figure 3c.9 M–H loops of (a) CFO, (c) NFO, (e) ZFO particles and (b) PVDF/CFO, (d) PVDF/NFO, (f) PVDF/ZFO films.
Figure 3c.10 Variation of β fraction and ferroelectric parameters of PVDF with respect to (a) NiFe₂O₄, (b) CoFe₂O₄ concentration, and (c) ZnFe₂O₄.
Figure 3c.11 ME response of (a) PVDF/CFO, (b) PVDF/NFO, and (c) PVDF/ZFO films.

Chapter 4: Low-Dimensional Polymer-Based Magnetoelectric Structures

Figure 4.1 (a) The fabrication process flow of the nanocomposites. (b) Optical image of a fabricated ME nanocomposite. (c) Focused ion beam tomography of the 3D distribution of magnetic nanowires aligned inside of the ferroelectric polymer matrix, cross-sectional plane is perpendicular to the plane of the nanocomposite film.
Figure 4.2 Scheme of a basic laboratory colloid-electrospinning setup.
Figure 4.3 SS-PFM mapping and analysis of ME materials.

Chapter 5: Design of Magnetostrictive Nanoparticles for Magnetoelectric Composites

Figure 5.1 (a) Multiferroic material, coupling of a ferroelectric (piezoelectric) and a ferromagnetic (magnetostrictive) to provide additional functionalities (magnetoelectric). (b) Illustration of preparation of a magnetoelectric particle composed of a ferrite core and piezoelectric shell. AB₂O₄ stands for the chemical structure of spinel ferrites with magnetostrictive properties. ABO₃ stands for the chemical structure of perovskite with piezoelectric properties. (c) Coupling mechanism in a magnetoelectric material when a magnetic or electric field is applied to the multiferroic ME nanomaterial.
Figure 5.2 (a) Schematic of the elongation of a ferromagnetic material in the direction of an applied magnetic field: transverse and longitudinal magnetostriction. (b) Schematic showing that the rotation of magnetic domains under applied magnetic field causes internal strain and the stretching of the material in the direction of the applied magnetic field. (c) Magnetostriction measured at room temperature versus the external magnetic field.
Figure 5.3 (a) Classification of ferrites according to their crystal structure, crystal chemistry, and magnetic behavior. (b) The spinel structure of ferrites is shown indicating the tetrahedral and octahedral sites. Reproduced with permission of Issa et al. 2013 [13].
Figure 5.4 (a) Perovskite structure. (b) Transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) images, and X-ray diffraction (XRD) pattern of barium titanate (BaTiO₃) (BTO) NPs. Kim et al. 2014 [18]. Reproduced with permission of American Chemical Society. (c) Some perovskites and their properties as ferroelectric materials.
Figure 5.5 Schematic representation of top-down and bottom-up approaches to produce nanomaterials. Classification of synthesis approaches to produce magnetoelectric nanomaterials.
Figure 5.6 Production of ME nanomaterials by solid-state reaction route. Scanning electron microscopy images of (a, b) pure MZF nanoparticles, (c, d) BTO1–MZF2 nanoparticles, (e, f) BTO2–MZF1 nanorods, and (g, h) pure BTO nanorods. BTO, BaTiO₃; MZT, Mn_0.5 Zn_0.5 Fe₂O₄. Yang et al. 2009 [40]. Reproduced with permission of Wiley.
Figure 5.7 Hydrothermal method. (a–d) TEM image, energy-dispersive X-ray (EDX) spectra, XRD pattern of nanocrystals reacted for 10 and 20 h, and HRTEM of CoFe₂O₄ nanocrystals. Inset: its corresponding fast Fourier transform indicating that the particle is oriented along the zone axis [100]. Liu 2013. http://nanoscalereslett.springeropen.com/articles/10.1186/1556-276X-8-374. Used under CC BY 2.1 license. Sol–gel method. (e) TEM image of ZnFe₂O₄ nanoparticles, (f) TEM images of NiFe₂O₄ nanoparticles, (g) particle size distribution of ZnFe₂O₄ nanoparticles, and (h) particle size distribution of NiFe₂O₄ nanoparticles. Atif and Nadeem 2014 [66]. Reproduced with permission of Springer. (i–k) Solvothermal method. TEM images of the NFO nanoparticles with varying particle size after varying the solvents, amount of surfactants, and heating rates. Bedekar et al. 2009 [25]. Reproduced with permission of Springer.

6a: Sensors, Actuators, Antennas, and Memories

Figure 6a.1 (a) Schematic representation of an ME sensor in a 2-2 geometry that is oscillating due to an external applied magnetic field. (b) Digital image of the ME sensor with two Schottky contacts. (c) Schematic representation of the ME sensor design. (d) Scanning electron microscope (SEM) image of a ZnO microneedle with a length of several millimeters. The SEM image (d) of the ZnO microneedle clearly features the hexagonal base plane of the wurtzite structure. (Gröttrup et al. 2016 [4]. Reproduced with permission of Wiley.)
Figure 6a.2 Representation of the ME magnetic field sensing mechanism. (Martins and Lanceros-Méndez 2013 [5]. Reproduced with permission of Wiley.)
Figure 6a.3 Representation of the ME magnetic field sensing mechanism. (Jahns et al. 2013 [22]. Reproduced with permission of The American Ceramic Society.)
Figure 6a.4 (a) “Cell clinic” for single-cell studies. (b) Functionalizing the lid and cavity floor with electrical, chemical, and optical stimulation. (Smela 2003 [37]. Reproduced with permission of Wiley.)
Figure 6a.5 Geometry of the proposed antenna. (a) x-Axis side view; (b) y-axis side view; (c) structure of elliptical ring; and (d) part of transition balloon at the bottom layer. (Wang et al. 2015 [41]. Reproduced with permission of Wiley.)
Figure 6a.6 Representation of a four-state memory based on ME materials. (Martins and Lanceros-Méndez 2013 [5]. Reproduced with permission of Wiley.)

6b: Magnetoelectric Composites for Bionics Applications

Figure 6b.1 ME composite particles, consisting of ferroelectric and ferromagnetic phases, in the form of dispersible, injectable electrodes for targeting electrical stimulation at the level of single cells and cell surface molecules.
Figure 6b.2 (a–d) LIVE/DEAD staining of MC3T3-E1 preosteoblasts cultured on (a) nonpoled PVDF and (b) nonpoled PVDF with titanium; (c) poled PVDF or (d) poled PVDF with titanium after cell culture for 3 days. The scale bar is 50 mm for all the images. Ribeiro et al. 2012 [28]. Reproduced with permission of Royal Society of Chemistry. (e) MC3T3-E1 osteoblast cell density (cell mm⁻²) on the nonpoled P(VDF-TrFE) (blue, A), nonpoled P(VDF-TrFE)/TD (red, B), or poled P(VDF-TrFE)/TD (green, C) under static and dynamic conditions for 72 h.
Figure 6b.3 Three types of nanostructured ME materials: (a) spherical core–shell nanoparticles with magnetostrictive core encapsulated in piezoelectric shell, (b) core–shell nanofiber with magnetostrictive core and piezoelectric coating, and (c) a composite superparticle with magnetic nanoparticles embedded into piezoelectric polymer [49].
Figure 6b.4 Morphology of (a and b) PVDF polymer and the multiferroic CFO/PVDF microspheres with (c) 5 wt%, (d) 21 wt%, and (e) 27 wt% CFO nanoparticles.
Figure 6b.5 Illustration of a field-controlled targeted drug (PTX) delivery by MENs through a capillary. (a) Applying a local magnetic field, H, enhances the targeted delivery efficacy by localizing MENs into the tumor region. (b) Schematic of controlled release of PTX by the application of magnetic field.
Figure 6b.6 (a) Transmission electron microscopy (TEM) image of core–shell MENs. (b) EEG waveforms from the two EEG channels with MENs in the brain under exposure to an external 100-Oe ac magnetic field at a frequency of 10 Hz. The vertical scale bar for the waveform signal is 5 mV. (c) Schematic illustration of the novel concept to use MENs for “mapping” the brain for noninvasive electric field stimulation of selected regions deep in the brain. (i) MENs are forced into the brain across BBB via application of a dc magnetic field gradient. (ii) When in the brain, MENs are distributed over the entire brain or in selected regions by applying spatially varying dc magnetic field gradients. The presence of MENs effectively creates a “new brain microenvironment,” in which the intrinsic electric signals due to the neural activity are strongly coupled at the subneuronal level to the external magnetic fields generated by remote sources. (iii) Such coupling can be used for noninvasive high-efficacy stimulation of selected regions deep in the brain by applying focused and relatively low (∼100 Oe) near-dc (<1000 Hz) magnetic field.
Figure 6b.7 Illustration of uniaxially oriented dipole moments in piezoelectric biopolymers. (a) Collagen and (b) DNA. The red arrows indicate the dipole direction of each moment.
Figure 6b.8 (a) Schematic view of atomic force microscopy system used to measure the piezorsponse and (b) vertical displacement of CNC. (Csoka et al. 2012 [74]. Reproduced with the permission of American Chemical Society.) (c) Schematic view of atomic force microscopy system to measure the piezoelectricity and vertical displacement of M13 Phage films.
Figure 6b.9 (a) Schematic view of cellulose-based ME laminate. The ordered sections of cellulose (b) provides crystalline structure in which the aligned dipoles of saccharide (c) give rise to piezoelectric properties. (d) Frequency-dependent trace of the ME voltage coefficient of hot-press cellulose/Metglas laminate under H_dc = 10.8 Oe and H_ac = 0.5 Oe.
Figure 6b.10 (a) Schematic diagrams of the experimental setup. (b) Principle of the dual-frequency excitation-based resonant-amplitude tracking.
Figure 6b.11 Amplitude PFM curves of the piezoresponse of the PTO–NFO bilayered structure collected in DART mode under different magnetic fields. The plots have been translated vertically to increase their visibility.
Figure 6b.12 Bio-atomic force microscopy approaches for measuring biomolecular interactions at magnetoelectric composite surfaces. (a) Single-molecule force spectroscopy for measuring binding forces of single proteins.

6c: Energy Harvesting

Figure 6c.1 Interactions involved in magnetoelectric energy harvesting. When a magnetoelectric composite device is placed in the vicinity of an ac magnetic field, such as near by electronic devices transmitting electromagnetic signals or current-carrying wires in electricity pylons, the magnetostrictive component of the device will lengthen or shorten. This results in strain, which is coupled to the piezoelectric component, therefore, inducing the direct piezoelectric effect, and thus a voltage is generated across an external electrical load. An electronic device can then be powered directly or the energy can be stored.
Figure 6c.2 In the presence of an externally applied magnetic field, ferromagnetic materials experience magnetostriction. Within the ferromagnetic material, there are many magnetic domains, which are regions of aligned magnetic dipole moments. Within each domain, there can be multiple crystallites. The material deforms due to the realignment of the magnetic domains (a). This is from either domain growth or rotation and hence deformation of the domains (b).
Figure 6c.3 polyvinylidene fluoride in α and β crystalline phases. Only the β phase is piezoelectric because of its all-trans conformation.
Figure 6c.4 Composite structures: (a) (0–3), (b) (1–3), (c) (2–2), (d) (1–1), and (e) (0–1). Green represents the magnetostrictive component and beige represents the piezoelectric component.
Figure 6c.5 (a) A cross-sectional schematic of the magnetoelectric multilayered capacitor used by Israel et al., where E_z is the z-component of the electric field, which is generated by a voltage applied between the terminals in the BaTiO₃ dielectric layers. (b) The easy-axis magnetization M versus applied magnetic field μ₀H for E = 0 (black) and E = 306 kV cm⁻¹ (red). The ME coefficient $c01-math-191$ taken as $c01-math-192$ here (dashed) and the hard-axis magnetization $c01-math-193$ (dotted) are also included. The magnetoelectric responses (M vs E) for (c) a saturating $c01-math-194$ applied and (d) μ₀H = 45 mT, where $c01-math-195$ shows a peak value. Red dotted lines are the corresponding y-component of strain of the device.
Figure 6c.6 (a) ME coupling coefficient, $c01-math-268$ versus dc magnetic field $c01-math-269$ for three ME devices of different lengths. (b) The normalized power densities of the same three devices versus the length of each.

6d: High-Temperature Polymers for Magnetoelectric Applications

Figure 6d.1 Scheme of a ferroelectret with metal electrodes on both sides showing the flow of charges resulting from a thickness variation.
Figure 6d.2 Molecular structures of some ferroelectret polymers. (a) PP, (b) PET, (c) COC, (d) PEN, (e) FEP, and (f) CYTOP.
Figure 6d.3 Molecular structures of some bulk semicrystalline piezoelectric polymers. (a) Nylon-11, (b) polyurea-9, (c) PLLA, (d) polypropylene oxide, (e) poly(β-hydroxybutyrate) (PHB), and (f) Parylene-C.
Figure 6d.4 All-trans conformation of polyamides: (a) odd-numbered nylon and (b) even-numbered nylon. The dipole directions are indicated by arrows.
Figure 6d.5 Scheme of polyaddition reaction for the synthesis of polyureas with some of the diamine and diisocyanate molecules used.
Figure 6d.6 Molecular structures of some bulk amorphous piezoelectric polymers. (a) PDVC, (b) PVAc, (c) PAN, (d) PPEN, (e) poly(1-bicyclobutanecarbonitrile), (f) p-(2,2,3,3-tetracyanocyclopropyl)phenoxyethyl acrylate (g) P(VDCN-VAc), and (h) 2,6(β-CN)APB/ODPA.
Figure 6d.7 Scheme of the two repetitive units of the copolyimides with the polar groups. Maceiras et al. 2014 [171]. Reproduced with permission of Institute of Physics.
Figure 6d.8 Schematic of a three-layer sandwich laminate formed by a poled polyimide among two ribbons of magnetostrictive Vitrovac 4040® (a) and a CoFe₂O₄ nanoparticles/copolyimide 0CN–2CN nanocomposite (b).

List of Tables

3b: Polymer-Based Magnetoelectric Composites: Polymer as a Binder

Table 3b.1 Typical characteristics of some representative ME composites
Table 3b.2 ME voltage coefficients (α_E,V), ME efficiency factor (ME-EF), and effective working surface specific value (A_eff) of the three samples

3c: Poly(vinylidene fluoride)-Based Magnetoelectric Polymer Nanocomposite Films

Table 3c.1 PVDF films poled at different experimental conditions
Table 3c.2 The list of few magnetic nanoparticles with noticeable magnetostriction coefficients
Table 3c.3 Saturation magnetization of PVDF/ferrite films
Table 3c.4 Percentage enhancement in polarization of PVDF/CFO
Table 3c.6 Percentage enhancement in polarization of PVDF/ZFO
Table 3c.5 Percentage enhancement in polarization of PVDF/NFO
Table 3c.7 Comparison of present work with the reported ME coefficient values

Chapter 5: Design of Magnetostrictive Nanoparticles for Magnetoelectric Composites

Table 5.1 Room-temperature saturation magnetostrictive coefficient of some materials

6c: Energy Harvesting

Table 6c.1 Magnetic material properties of some magnetostrictive materials
Table 6c.2 Piezoelectric material properties for ceramic, single-crystal, and polymer materials
Table 6c.3 Magnetoelectric coupling coefficient, α comparison for various magnetoelectric composite devices, both polymer-based and others
Table 6c.4 Power outputs of the same devices from Table 6c.3 where energy is harvested from the magnetic field, vibrations, and both

6d: High-Temperature Polymers for Magnetoelectric Applications

Table 6c.1 Summary of the most promising piezoelectric polymers for applications at temperatures higher than 100 °C

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List of Contributors

Chess Boughey

University of Cambridge

Department of Materials Science & Metallurgy

27 Charles Babbage Road

Cambridge CB3 0FS

Xiao Chen

Northeast Electric Power University

School of Electrical Engineering

169 Changchun Road

Jilin 132013

China

Renato Gonçalves

Universidade do Minho

Departamento de Física

4710-057 Braga

Portugal

Hong-Yan Guo

Northeast Electric Power University

School of Electrical Engineering

169 Changchun Road

Jilin 132013

China

Jawaharlal Hemalatha

National Institute of Technology

Advanced Materials Lab

Department of Physics

Tiruchirappalli

Tamilnadu 620015

India

Michael J. Higgins

University of Wollongong

ARC Centre of Excellence for Electromaterials Science

Intelligent Polymer Research Institute/AIIM Faculty

Innovation Campus

Squires Way

NSW 2522

Australia

Sohini Kar-Narayan

University of Cambridge

Department of Materials Science & Metallurgy

27 Charles Babbage Road

Cambridge CB3 0FS

Senentxu Lanceros-Mendez

Universidade do Minho

Centro de Física

Campus de Gualtar

Braga 4710-057

Portugal

and

BCMaterials, Basque Center for Materials

Applications and Nanostructures

Parque Científico y Tecnológico de Bizkaia

Bld 500, 48160 Derio

Spain

and

IKERBASQUE

Basque Foundation for Science

Maria Diaz de Haro 3

48013 Bilbao

Spain

Luis Manuel León

University of the Basque Country (UPV/EHU)

Macromolecular Chemistry Research Group (LABQUIMAC)

Department of Physical Chemistry

Faculty of Science and Technology

Spain

and

BCMaterials, Basque Center for Materials, Applications and Nanostructures

Parque Científico y Tecnológico de Bizkaia

Bld 500, 48160 Derio

Spain

Chen Liu

Tsinghua University

School of Materials Science and Engineering, and State Key Lab of New Ceramics and Fine Processing

Beijing 100084

China

Jing Ma

Tsinghua University

School of Materials Science and Engineering, and State Key Lab of New Ceramics and Fine Processing

Beijing 100084

China

Alberto Maceiras

University of the Basque Country (UPV/EHU)

Macromolecular Chemistry Research Group (LABQUIMAC)

Department of Physical Chemistry

Faculty of Science and Technology

Spain

Pedro Martins

Universidade do Minho

Centro de Física

Campus de Gualtar

Braga 4710-057

Portugal

De'an Pan

Beijing University of Technology

Institute of Circular Economy

100 Ping Le Yuan

Beijing 100124

China

Thandapani Prabhakaran

National Institute of Technology

Advanced Materials Lab

Department of Physics

Tiruchirappalli

Tamilnadu 620015

India

Sílvia Reis

Universidade do Minho

Departamento de Física

Braga 4710-057

Portugal

Victor Sebastian

University of Zaragoza

Institute of Nanoscience of Aragon

R+D Building

C/Mariano Esquillor, s/n

Zaragoza 50018

Spain

and

Networking Research Center on Bioengineering, Biomaterials and Nanomedicine

CIBER-BBN

Madrid 28029

Spain

and

University of Zaragoza

Department of Chemical Engineering and Environmental Technology

Zaragoza

Spain

Marco Silva

Universidade do Minho

Centro de Física

Campus de Gualtar

Braga 4710-057

Portugal

Lu Song

Tsinghua University

School of Materials Science and Engineering, and State Key Lab of New Ceramics and Fine Processing

Beijing 100084

China

Yang Song

University of Science and Technology Beijing

Department of Mechanical Engineering

Institute for Advanced Materials and Technology

30 Xueyuan Road

Beijing 100083

China

and

University of South Florida

College of Engineering

Department of Mechanical Engineering

4202 E Fowler Ave

Tampa, FL 33620

USA

José Luis Vilas

University of the Basque Country (UPV/EHU)

Macromolecular Chemistry Research Group (LABQUIMAC)

Department of Physical Chemistry

Faculty of Science and Technology

Spain

and

BCMaterials, Basque Center for Materials, Applications and Nanostructures

Parque Científico y Tecnológico de Bizkaia

Bld 500, 48160 Derio

Spain

Alex Alexei Volinsky

University of South Florid

College of Engineering

Department of Mechanical Engineering

Tampa, FL 33620

USA

Gordon G. Wallace

University of Wollongong

ARC Centre of Excellence for Electromaterials Science

Intelligent Polymer Research Institute/AIIM Faculty

Innovation Campus, Squires Way

NSW 2522

Australia

Chengzhou Xin

Tsinghua University

School of Materials Science and Engineering, and State Key Lab of New Ceramics and Fine Processing

Beijing 100084

China

Zhilian Yue

University of Wollongong

ARC Centre of Excellence for Electromaterials Science

Intelligent Polymer Research Institute/AIIM Faculty

Innovation Campus, Squires Way

NSW 2522

Australia

Jia-Wei Zhang

Northeast Electric Power University

School of Electrical Engineering

169 Changchun Road

Jilin 132013

China

and

Harbin University of Science and Technology Key Laboratory of Engineering Dielectric and its Application of Ministry of Education

Harbin

China

Tian Zheng

University of Wollongong

ARC Centre of Excellence for Electromaterials Science

Intelligent Polymer Research Institute/AIIM Faculty

Innovation Campus, Squires Way

NSW 2522

Australia

Yan Zong

University of Wollongong

ARC Centre of Excellence for Electromaterials Science

Intelligent Polymer Research Institute/AIIM Faculty

Innovation Campus, Squires Way

NSW 2522

Australia

Zhijun Zuo

Functional Materials Research Institute

Central Iron and Steel Research Institute

No. 76 Xueyuan South Road

Beijing 100081

China

Preface and Acknowledgments

In every branch of knowledge the progress is proportional to the amount of facts on which to build, and therefore to the facility of obtaining data.

James Clerk Maxwell (1831–1879)

This book was motivated by the desire for providing a suitable and complete account of the evolution, state of the art, and main challenges of the interesting and growing field of polymer-based magnetoelectric (ME) materials. In this scope, an overview of the frontline research of this fascinating research field has been presented by selected authors with innovative and preponderant work.

The book provides an introduction to polymer-based ME materials and their physicochemical insights, design for technological applications, and implementation into devices.

Chapter 1 deals with the theoretical analysis and modeling of the ME effect of functional materials. The ME effect and its application in single crystal, multilayered composites, and piezoelectrics under the Lorentz force induced by eddy currents have been discussed.

Chapter 2 deals with materials selection, processing, and characterization technologies. Almost two decades of research, innovation, and development on different systems with various compositions and structures are summarized.

Chapter 3 comprises three contributions toward the different types of polymer-based ME materials that we can find in the literature: laminates, polymer “as a binder,” and nanocomposites. Many exciting results are presented, new concepts are addressed, and future studies are suggested to be carried out for further research on these scientifically interesting and industrially relevant materials.

In the same line, Chapter 4 focuses on the new opportunities and challenges that low dimensionality offers to the nanocomposite structure.

The subject of Chapter 5 is the design of magnetostrictive nanoparticles for ME composites. This chapter focuses on those nanomaterials that, after being coupled to a piezoelectric polymer matrix, can provide unique ME responses.

Chapter 6 presents three contributions concerning the applications of polymer-based ME materials: sensors and actuators, biomedical materials, energy harvesters, and high-temperature devices are presented and discussed. With this application-oriented chapter, it is intended to provide an overview of the ME effect-based devices, the figures of merit, and the problems concerning materials selection, applicability, and design considerations.

Finally, Chapter 7 indicates some of the open questions, challenges, and perspectives of this research field.

This book would have not been possible without the dedicated and insightful work of the authors of the different chapters. The editors truly thank the kindness, dedication, and excellence in providing the different high-quality chapters that show the strength, direction, dimension, and potential of the world of ME polymer-based materials. Truly thanks for sharing with us this important landmark in the area!

This book could have not also been possible without the continuous support, dedication, and understanding from our colleagues from the Electroactive Smart Materials Group of the Center of Physics, University of Minho, Portugal, and from the research group at the BCMaterials, Basque Center for Materials, Applications, and Nanostructures, Leioa, Spain. Thank you all for working together, sharing knowledge together, growing together, and living together as a Group!

Last but not least, we truly thank the team from Wiley for their excellent support: from the first contacts with Jolke Perelaer to the last with Samanaa Srinivas and Sujisha Kunchi Parambathu, passing through the different colleagues who supported this work; their kindness, patience, technical expertise, ideas, perspectives, and insights were essential to make this book come true. We are deeply grateful to them for their generous assistance.

Let us hope this book fulfills its purpose of bringing together the best and most relevant issues on polymer-based ME materials, allowing for a deeper understanding, and pointing out the main challenges and directions for the near future so that we together contribute to a bright future of innovation and implementation in this relevant field!

Braga, Portugal

Pedro Martins and Senentxu Lanceros-Mendez

Magnetoelectric Polymer-Based Composites

Fundamentals and Applications

List of Contributors

Preface and Acknowledgments