Cm-1 Oe-1 Research Articles

Greener Solvent-Based Processing of Magnetoelectric Nanocomposites.

Polymer-based magnetoelectric (ME) nanocomposites are an enabling material technology for a wide range of applications in the area of digitalization strategies. Due to its highest piezoelectric response among polymers, poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) is the piezoelectric matrix most used in polymer-based ME materials with over 80% of the total reports, with the resulting composites typically processed from solutions with N,N-dimethylformamide (DMF), a toxic solvent. Nevertheless, environmentally friendlier approaches and sustainable technologies are increasingly being required. This work demonstrates that P(VDF-TrFE)/Co2Fe2O4 nanocomposites can be successfully prepared from solution using three different environmentally friendlier solvents: dimethyl sulfoxide (DMSO), N,N'-dimethylpropyleneurea (DMPU), and triethyl phosphate (TEP) with different dipole moments. It is shown that the prepared composite films, with a maximum ME voltage coefficient of 35 mV cm-1 Oe-1 and a maximum sensitivity of 2.2 mV T-1, are suitable for applications, highlighting the path for a new generation of more sustainable ME sensors.

Design of Ionic-Liquid-Based Hybrid Polymer Materials with a Magnetoactive and Electroactive Multifunctional Response.

Multifunctional materials with sensor and actuator capabilities play an increasing role in modern technology. In this scope, hybrid materials with magnetic sensing and an electromechanical actuator response based on magnetic ionic liquids (MILs) and the polymer poly(vinylidene fluoride) (PVDF) have been developed. MILs comprising different cation alkyl chain lengths [Cnmim]+ and sharing the same anion [FeCl4]- were incorporated at 20 wt % into the PVDF matrix and the morphological, physical, chemical, and functional properties of the materials were evaluated. An increasing IL alkyl chain length leads to the formation of a porous structure, together with an increase in the electroactive PVDF β-phase content of the polymer and a decrease in the crystallinity degree and thermal stability. The magnetic susceptibility of the [Cnmim][FeCl4]/PVDF films reveals a paramagnetic behavior. The multifunctional response is characterized by a magnetoionic response that decreases with increasing IL alkyl chain length, the highest magnetoionic coefficient (1.06 ± 0.015 V cm-1 Oe-1) being observed for [C2mim][FeCl4]/PVDF. The electromechanical actuator response is characterized by a highest displacement of 1.1 mm for the [C4mim][FeCl4]/PVDF film by applying a voltage of 4 V at a frequency of 100 mHz. Further, their solution processing makes these multiresponsive materials compatible with additive manufacturing technologies.

Colossal Magnetoelectric Effect in Core-Shell Magnetoelectric Nanoparticles.

Magnetoelectric coefficient values of above 5 and 2 V cm-1 Oe-1 in 20 nm CoFe2O4-BaTiO3 and NiFe2O4-BaTiO3 core-shell magnetoelectric nanoparticles were demonstrated. These colossal values, compared to 0.1 V cm-1 Oe-1 commonly reported for the 0-3 system, are attributed to (i) the heterostructural lattice-matched interface between the magnetostrictive core and the piezoelectric shell, confirmed through transmission electron microscopy, and (ii) in situ scanning tunneling microscopy nanoprobe-based ME characterization. The nanoprobe technique allows measurements of the ME effect at a single-nanoparticle level which avoids the charge leakage problem of traditional powder form measurements. The difference in the frequency dependence of the ME value between the two material systems is owed to the Ni-ferrite cores becoming superparamagnetic in the near-dc frequency range. The availability of novel nanostructures with colossal ME values promises to unlock many new applications ranging from energy-efficient information processing to nanomedicine and brain-machine interfaces.

Magnetoelectric coupling in nanoscale 0-1 connectivity.

The strain-mediated magnetoelectric (ME) coupling between piezoelectric (PE) and magnetostrictive (MS) components are established in various connectivities. Discovering new ME connectivity and elucidating the key factors governing the performance of ME composite are of critical importance to find advanced materials for modern electronics. Reported here is a novel ME coupling in 0-1 connectivity. The unique self-assembling ability of 1-dimension crystalline nanocellulose (CNC) nanowhiskers enables the establishment of ME coupling with 0-dimension cobalt ferrite (CFO) nanoparticles without the use of binder. The developed CFO/CNC 0-1 ME composites display a significant ME voltage coefficient (αME) as high as 0.135 mV cm-1 Oe-1. The CFO nanoparticles are also modified with a cationic surfactant, cetyltrimethylammonium bromide (CTAB), to reduce their dispersion ability. A ME response related to the rearrangement of aggregated MS nanoparticles is observed in the CTAB-CFO/CNC composites, which differs from the typical magnetostriction induced ME effect in nanoparticulate ME composites.

Abstract 2199: Magnetoelectric nanoparticles for high-specificity treatment of cancer

Abstract Introduction: Delivering a drug specifically into the tumor cell past its membrane and then releasing the drug into the tumor cells without affecting the normal cells remains a formidable challenge. Unlike any other nanoparticles, magnetoelectric nanoparticles (MENs) display a non-zero magnetoelectric (ME) effect and thus present a unique capability to use external magnetic fields to control intrinsic electric fields associated with cell membranes and the interaction between MENs and therapeutic loads. Because cancer and normal cells of the same type have different electric properties, MENs is used for high-specificity targeted delivery. An a.c. magnetic field is used to trigger drug release off the nanoparticles. Brief Methods: 30-nm CoFe2O4-BaTiO3 core shell MENs, with a magnetization of 1 emu/g, a coercivity of 300 Oe, and a ME coefficient of 10-100 mV cm-1 Oe-1 were prepared with a coprecipitation process. MENs were coated with fluorescein isothiocyanate to monitor their intra-cellular transport through a high-contrast confocal microscopy. Three cancer cell lines including Skov-3 (Ovarian adenocarcinoma), U87-MG (Glioblastoma), and MCF-7A (Breast adenocarcinoma), and two normal cell lines including brain endothelial cells (Brain EC) and ovarian cells HOMEC were cultured at 37°C. The transport of MENs loaded with drugs, peptides, and RNAs through the cell membranes and the consequent release of the load under different d.c. and a.c. magnetic fields were studied through confocal microscopy and photoabsorption spectroscopy, respectively. Trypan-blue viability count was used to assess cell growth inhibition under different study conditions. Atomic force microscopy of the cell membranes was conducted to understand the interaction between the nanoparticles and the cells. Summary of new data: Comparison of MENs with purely magnetic iron oxide nanoparticles showed that the penetration through the cancer cell membrane could be achieved only with MENs. It took d.c. fields of 100 Oe and over 1000 Oe to nanoelectroporate the membranes of SKOV-3 and HOMEC cell lines, respectively. An a.c. magnetic field with a strength of 50 Oe and a near-d.c. frequency of 100 Hz was sufficient to enable release of a therapeutic load off MENs. All the cancer cell lines under study showed membrane penetration threshold d.c. fields at least a factor of ten smaller compared to their normal counterparts. Conclusion: MENs displayed unique capabilities for externally controlled high-specificity targeted anticancer drug delivery and release on demand via application of d.c. and a.c. magnetic fields, respectively. Because MENs rely on a physical mechanism rather than antibody-mediated delivery, they can be used for high specificity delivery and high-efficacy controlled release of a broad range of therapeutic loads including drugs, peptides, and RNAs to treat many different cancers. Citation Format: Emmanuel Stimphil, Abhi Nagesetti, Tiffanie S. Stewart, Alexa Rodzinski, Rakesh Guduru, Ping Liang, Carolyn Runowicz, Sakhrat Khizroev. Magnetoelectric nanoparticles for high-specificity treatment of cancer [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2017; 2017 Apr 1-5; Washington, DC. Philadelphia (PA): AACR; Cancer Res 2017;77(13 Suppl):Abstract nr 2199. doi:10.1158/1538-7445.AM2017-2199

Correlation of Interface Impurities and Chemical Gradients with High Magnetoelectric Coupling Strength in Multiferroic BiFeO3-BaTiO3 Superlattices.

The detailed understanding of magnetoelectric (ME) coupling in multiferroic oxide heterostructures is still a challenge. In particular, very little is known to date concerning the impact of the chemical interface structure and unwanted impurities that may be buried within short-period multiferroic BiFeO3-BaTiO3 superlattices during growth. Here, we demonstrate how trace impurities and elemental concentration gradients contribute to high ME voltage coefficients in thin-film superlattices, which are built from 15 double layers of BiFeO3-BaTiO3. Surprisingly, the highest ME voltage coefficient of 55 V cm-1 Oe-1 at 300 K was measured for a superlattice with a few atomic percent of Ba and Ti that diffused into the nominally 5 nm thin BiFeO3 layers, according to analytical transmission electron microscopy. In addition, highly sensitive enhancements of the cation signals were observed in depth profiles by secondary ion mass spectrometry at the interfaces of BaTiO3 and BiFeO3. As these interface features correlate with the ME performance of the samples, they point to the importance of charge effects at the interfaces, that is, to a possible charge mediation of ME coupling in oxide superlattices. The challenge is to provide cleaner materials and processes, as well as a well-defined control of the chemical interface structure, to push forward the application of oxide superlattices in multiferroic ME devices.

Enhanced Resonance Magnetoelectric Coupling in (1-1) Connectivity Composites.

Bulk-magnetoelectric (ME) composites consisting of various piezoelectric and piezomagnetic materials with (3-0), (3-1), (2-2), and (2-1) connectivity are proposed in a bid to realize strong ME coupling for next-generation electronic-device applications. Here, 1D (1-1) connectivity ME composites consisting of a [011]-oriented Pb(Mg,Nb)O3 -PbTiO3 (PMN-PT) single-crystal fiber laminated with laser-treated amorphous FeBSi alloy (Metglas) and operating in L-T mode (longitudinally magnetized and transversely poled) are reported, which exhibit an enhanced resonant ME coupling coefficient of ≈7000 V cm-1 Oe-1 , which is nearly seven times higher than the best result published previously, and also a superhigh magnetic sensitivity of 1.35 × 10-13 T (directly detected) at resonance at room temperature, representing a significant advance in bulk magnetoelectric materials. The theoretical analyses based on magnetic-circuit and equivalent-circuit methods show that the enhancement in ME coupling can be attributed to the reduction in resonance loss of laser-treated Metglas alloy due to nanocrystallization and the strong magnetic-flux-concentration effect in (1-1) configuration composites.

Switchable 3-0 magnetoelectric nanocomposite thin film with high coupling.

A mixed precursor solution method was used to deposit 3-0 nanocomposite thin films of PbZr0.52Ti0.48O3 (PZT) and CoFe2O4 (CFO). The piezoelectric behavior of PZT and magnetostrictive behavior of CFO allow for magnetoelectric (ME) coupling through strain transfer between the respective phases. High ME coupling is desired for many applications including memory devices, magnetic field sensors, and energy harvesters. The spontaneous phase separation in the 3-0 nanocomposite film was observed, with 25 nm CFO particle or nanophases distributed in discrete layers through the thickness of the PZT matrix. Magnetic-force microscopy images of the nanocomposite thin film under opposite magnetic poling conditions revealed in-plane pancake-like regions of higher concentration of the CFO nanoparticles. The constraints on the size and distribution of the CFO nanoparticles created a unique distribution in a PZT matrix and achieved values of ME coupling of 3.07 V cm-1 Oe-1 at a DC bias of 250 Oe and 1 kHz, increasing up to 25.0 V cm-1 Oe-1 at 90 kHz. Piezo-force microscopy was used to investigate the ferroelectric domain structure before and after opposite magnetic poling directions. It was found that in this nanocomposite, the polarization of the ferroelectric domains switched direction as a result of switching the direction of the magnetization by magnetic fields.

ELECTROLESS DEPOSITION OF NICKEL ON LEAD ZIRCONIUM TITANATE CERAMICS: PREPARATION, MAGNETIC AND MAGNETOELECTRIC PROPERTIES

The Ni layers with good soft magnetic properties have been successfully electroless deposited on PZT layers. To study the thermodynamics and kinetics of electroless Ni -deposition, the effect of bath parameters such as pH and temperature has been discussed. The structural, magnetic and magnetostrictive properties of Ni layers deposited at various pH and temperature are characterized by X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and standard strain-gauge technique. The grain size, deposition rate, magnetic properties and magnetostrictive properties of Ni layers and magnetoelectric effect of Ni /PZT/ Ni trilayers depend strongly on the thermodynamics and kinetics of electroless deposition processes. A maximum ME voltage coefficient of αE,31 = 5.8 V cm-1 Oe-1 is obtained at a frequency of about 101 kHz. These trilayers exhibit a promising potential in actuators, transducers and sensors.

Microstructure, Growth Mechanism, Magnetoelectricity, and Raman Scattering of Featherlike CoFe2O4–BaTiO3 Nanostructures

Featherlike (CoFe2O4)0.3–(BaTiO3)0.7 (CFO–BTO) nanostructures were synthesized by a hydrothermal reaction and polymer-assisted deposition. With CFO nanopillars embedded in the BTO matrix, the nanostructures show an average diameter of 250 nm and lengths of up to 5 µm. The microstructure and growth mechanism of the nanostructures were investigated. A large magnetoelectric (ME) coefficient of 51.8 mV cm-1 Oe-1 at room temperature and a strong phonon abnormality between 110 and 140 °C are discussed.

Magnetoelectric Coupling in Tb0.3Dy0.7Fe1.92/PbZr0.3Ti0.7O3Bilayer Thin Films

The magnetoelectric (ME) properties of Tb0.3Dy0.7Fe1.92 (Terfenol-D)/PbZr0.3Ti0.7O3 (PZT) thin films grown on a Pt(111)/Ti/SiO2/Si(100) substrate were investigated. The ferroelectric behavior of a Terfenol-D/PZT bilayer film stack was examined by polarization–electric field hysteresis measurement. The remnant polarization (Pr) and coercive field (Ec) values were found as 31 µC/cm2 and 124 kV/cm, respectively. The magnetic behavior was observed using a vibration sample magnetometer (VSM) at 300 K with saturation magnetization (Ms) and coercivity (Hc) values of 6.7 emu/cm3 and 70 Oe, respectively. The application of magnetic field caused a piezomagnetic strain in the Terfenol-D layer hence, the piezoelectric voltage or charge in the PZT thin film was induced. The maximum magnetoelectric voltage coefficient (dE/dH) value of approximately 40 mV cm-1 Oe-1 was obtained at the magnetic field of 5 kOe.

Magnetoelectric Coupling in Tb0.3Dy0.7Fe1.92/PbZr0.3Ti0.7O3 Bilayer Thin Films

The magnetoelectric (ME) properties of Tb0.3Dy0.7Fe1.92 (Terfenol-D)/PbZr0.3Ti0.7O3 (PZT) thin films grown on a Pt(111)/Ti/SiO2/Si(100) substrate were investigated. The ferroelectric behavior of a Terfenol-D/PZT bilayer film stack was examined by polarization–electric field hysteresis measurement. The remnant polarization (Pr) and coercive field (Ec) values were found as 31 µC/cm2 and 124 kV/cm, respectively. The magnetic behavior was observed using a vibration sample magnetometer (VSM) at 300 K with saturation magnetization (Ms) and coercivity (Hc) values of 6.7 emu/cm3 and 70 Oe, respectively. The application of magnetic field caused a piezomagnetic strain in the Terfenol-D layer hence, the piezoelectric voltage or charge in the PZT thin film was induced. The maximum magnetoelectric voltage coefficient (dE/dH) value of approximately 40 mV cm-1 Oe-1 was obtained at the magnetic field of 5 kOe.

Giant Magnetoelectric Coefficient in 3–2 Nanocomposite Thick Films

In this study, we report the success in synthesis and characterization of magneto-electric (ME) 3–2 nanocomposite thick films using aerosol-deposition (AD). Piezoelectric and magnetostrictive materials were simultaneously deposited on a platinized silicon substrate using AD method and a 13-µm-thick nanocomposite film was realized with repeatable nozzle scanning. Upon annealing, magnetostrictive phase was found to form a layered structure inside the piezoelectric matrix. Detailed microstructural analysis revealed the connectivity of individual phases. This nanocomposite thick film was found to exhibit the ME coefficient of the order of 150 mV cm-1 Oe-1 which is significantly higher in comparison to other results reported in literature on ME thin/thick films.