Novel Biocompatible Magnetoelectric MnFe2 O4 Core@BCZT Shell Nano-Hetero-Structures with Efficient Catalytic Performance.

Magnetoelectric (ME) small-scale robotic devices attract great interest from the scientific community due to their unique properties for biomedical applications. Here, novel ME nano hetero-structures based on the biocompatible magnetostrictive MnFe2 O4 (MFO) and ferroelectric Ba0.85 Ca0.15 Zr0.1 Ti0.9 O3 (BCZT) are developed solely via the hydrothermal method for the first time. An increase in the temperature and duration of the hydrothermal synthesis results in increasing the size, improving the purity, and inducing morphology changes of MFO nanoparticles (NPs). A successful formation of a thin epitaxial BCZT-shell with a 2-5 nm thickness is confirmed on the MFO NPs (77 ± 14 nm) preliminarily treated with oleic acid (OA) or polyvinylpyrrolidone (PVP), whereas no shell is revealed on the surface of pristine MFO NPs. High magnetization is revealed for the developed ME NPs based on PVP- and OA-functionalized MFO NPs (18.68 ± 0.13 and 20.74 ± 0.22 emu g-1 , respectively). Moreover, ME NPs demonstrate 95% degradation of a model pollutant Rhodamine B within 2.5 h under an external AC magnetic field (150 mT, 100 Hz). Thus, the developed biocompatible core-shell ME NPs of MFO and BCZT can be considered as a promising tool for non-invasive biomedical applications, environmental remediation, and hydrogen generation for renewable energy sources.

Piezo-Responsive Hydrogen-Bonded Frameworks Based on Vanillin-Barbiturate Conjugates.

A concept of piezo-responsive hydrogen-bonded π-π-stacked organic frameworks made from Knoevenagel-condensed vanillin-barbiturate conjugates was proposed. Replacement of the substituent at the ether oxygen atom of the vanillin moiety from methyl (compound 3a) to ethyl (compound 3b) changed the appearance of the products from rigid rods to porous structures according to optical microscopy and scanning electron microscopy (SEM), and led to a decrease in the degree of crystallinity of corresponding powders according to X-ray diffractometry (XRD). Quantum chemical calculations of possible dimer models of vanillin-barbiturate conjugates using density functional theory (DFT) revealed that π-π stacking between aryl rings of the vanillin moiety stabilized the dimer to a greater extent than hydrogen bonding between carbonyl oxygen atoms and amide hydrogen atoms. According to piezoresponse force microscopy (PFM), there was a notable decrease in the vertical piezo-coefficient upon transition from rigid rods of compound 3a to irregular-shaped aggregates of compound 3b (average values of d33 coefficient corresponded to 2.74 ± 0.54 pm/V and 0.57 ± 0.11 pm/V), which is comparable to that of lithium niobate (d33 coefficient was 7 pm/V).

Control of piezoelectricity in amino acids by supramolecular packing.

Piezoelectricity, the linear relationship between stress and induced electrical charge, has attracted recent interest due to its manifestation in biological molecules such as synthetic polypeptides or amino acid crystals, including gamma (γ) glycine. It has also been demonstrated in bone, collagen, elastin and the synthetic bone mineral hydroxyapatite. Piezoelectric coefficients exhibited by these biological materials are generally low, typically in the range of 0.1-10 pm V-1, limiting technological applications. Guided by quantum mechanical calculations we have measured a high shear piezoelectricity (178 pm V-1) in the amino acid crystal beta (ß) glycine, which is of similar magnitude to barium titanate or lead zirconate titanate. Our calculations show that the high piezoelectric coefficients originate from an efficient packing of the molecules along certain crystallographic planes and directions. The highest predicted piezoelectric voltage constant for ß-glycine crystals is 8 V mN-1, which is an order of magnitude larger than the voltage generated by any currently used ceramic or polymer.

Nanoplasmonic response of porous Au-TiO2 thin films prepared by oblique angle deposition.

In this work, a versatile method is proposed to increase the sensitivity of optical sensors based on the localized surface plasmon resonance (LSPR) phenomenon. It combines a physical deposition method with the oblique angle deposition technique, allowing the preparation of plasmonic thin films with tailored porosity. Thin films of Au-TiO2 were deposited by reactive magnetron sputtering in a 3D nanostructure (zigzag growth), at different incidence angles (0° ≤ α ≤ 80°), followed by in-air thermal annealing at 400 °C to induce the growth of the Au nanoparticles. The roughness and surface porosity suffered a gradual increment by increasing the incidence angle. The resulting porous zigzag nanostructures that were obtained also decreased the principal refractive indexes (RIs) of the matrix and favoured the diffusion of Au through grain boundaries, originating broader nanoparticle size distributions. The transmittance minimum of the LSPR band appeared at around 600 nm, leading to a red-shift to about 626 nm for the highest incidence angle α = 80°, due to the presence of larger (scattering) nanoparticles. It is demonstrated that zigzag nanostructures can enhance adsorption sites for LSPR sensing by tailoring the porosity of the thin films. Atmosphere controlled transmittance-LSPR measurements showed that the RI sensitivity of the films is improved for higher incidence angles.

Thermal and aqueous stability improvement of graphene oxide enhanced diphenylalanine nanocomposites.

Nanocomposites of diphenylalanine (FF) and carbon based materials provide an opportunity to overcome drawbacks associated with using FF micro- and nanostructures in nanobiotechnology applications, in particular their poor structural stability in liquid solutions. In this study, FF/graphene oxide (GO) composites were found to self-assemble into layered micro- and nanostructures, which exhibited improved thermal and aqueous stability. Dependent on the FF/GO ratio, the solubility of these structures was reduced to 35.65% after 30 min as compared to 92.4% for pure FF samples. Such functional nanocomposites may extend the use of FF structures to e.g. biosensing, electrochemical, electromechanical or electronic applications.

Giant Electric-Field-Induced Strain in PVDF-Based Battery Separator Membranes Probed by Electrochemical Strain Microscopy.

Efficiency of lithium-ion batteries largely relies on the performance of battery separator membrane as it controls the mobility and concentration of Li-ions between the anode and cathode electrodes. Recent advances in electrochemical strain microscopy (ESM) prompted the study of Li diffusion and transport at the nanoscale via electromechanical strain developed under an application of inhomogeneous electric field applied via the sharp ESM tip. In this work, we observed unexpectedly high electromechanical strain developed in polymer membranes based on porous poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) and, using it, could study a dynamics of electroosmotic flow of electrolyte inside the pores. We show that, independently of the separator membrane, electric field-induced deformation observed by ESM on wetted membrane surfaces can reach up to 10 nm under a moderate bias of 1 V (i.e., more than an order of magnitude higher than that in best piezoceramics). Such a high strain is explained by the electroosmotic flow in a porous media composed of PVDF. It is shown that the strain-based ESM method can be used to extract valuable information such as average pore size, porosity, elasticity of membrane in electrolyte solvent, and membrane-electrolyte affinity expressed in terms of zeta potential. Besides, such systems can, in principle, serve as actuators even in the absence of apparent piezoelectricity in amorphous PVDF.

Defect chemistry and relaxation processes: effect of an amphoteric substituent in lead-free BCZT ceramics.

The effect of praseodymium (Pr), an amphoteric substituent, on phase transition, dielectric relaxation and electrical conductivity has been studied and analysed in 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BCZT) ceramics synthesized by a solid state reaction method. Structural investigations showed co-existence of two phases - tetragonal (P4mm) and rhombohedral (R3m) - for compositions with x ≤ 0.05 wt% Pr. Temperature dependent dielectric studies revealed two phase transitions - rhombohedral (R) → tetragonal (T) and T → cubic (C) - that gradually evolved into one T → C transition for x > 0.05 wt% Pr in BCZT. A dielectric relaxation behaviour was observed in the temperature range of 275-500 °C that was attributed to the localized relaxation process (short-range hopping motion of oxygen vacancies) in the bulk of the material. Grain and grain boundary conductivity evaluated from the impedance data revealed that Pr acts as a donor dopant for x ≤ 0.05 wt% while it is an acceptor for higher concentration, in accordance with XRD observations. Defect chemistry analysis for better interpretation of the acquired data is presented. Frequency and temperature dependent ac conductivity studies were also performed and the obtained activation energy values were associated with possible conduction mechanisms.

Single- and multi-frequency detection of surface displacements via scanning probe microscopy.

Piezoresponse force microscopy (PFM) provides a novel opportunity to detect picometer-level displacements induced by an electric field applied through a conducting tip of an atomic force microscope (AFM). Recently, it was discovered that superb vertical sensitivity provided by PFM is high enough to monitor electric-field-induced ionic displacements in solids, the technique being referred to as electrochemical strain microscopy (ESM). ESM has been implemented only in multi-frequency detection modes such as dual AC resonance tracking (DART) and band excitation, where the response is recorded within a finite frequency range, typically around the first contact resonance. In this paper, we analyze and compare signal-to-noise ratios of the conventional single-frequency method with multi-frequency regimes of measuring surface displacements. Single-frequency detection ESM is demonstrated using a commercial AFM.

Local bias induced ferroelectricity in manganites with competing charge and orbital order states.

Perovskite-type manganites, such as Pr1-xCaxMnO3, La1-xCaxMnO3 and La1-xSrxMnO3 solid solutions, are set forth as a case study of ferroelectricity formation mechanisms associated with the appearance of site- and bond-centered orbital ordering which breaks structural inversion symmetry. Even though the observation of macroscopic ferroelectricity may be hindered by the finite conductivity of manganites, polarization can still exist in nanoscale volumes. We use Piezoresponse Force Microscopy to probe local bias induced modifications of electrical and electromechanical properties at the manganite surface. Clear bias-induced piezocontrast and local hysteresis loops are observed for La0.89Sr0.11MnO3 and Pr0.60Ca0.40MnO3 compounds providing convincing evidence of the existence of locally induced polar states well above the transition temperature of the CO phase, while the reference samples without CO behavior show no ferroelectric-like response. Such coexistence of ferroelectricity and magnetism in manganites due to the charge ordering (CO) under locally applied electric field opens up a new pathway to expand the phase diagrams of such systems and to achieve spatially localized multiferroic effects with a potential to be used in a new generation of memory cells and data processing circuits.

Revealing an important role of piezoelectric polymers in nervous-tissue regeneration: A review.

Nerve injuries pose a drastic threat to nerve mobility and sensitivity and lead to permanent dysfunction due to low regenerative capacity of mature neurons. The electrical stimuli that can be provided by electroactive materials are some of the most effective tools for the formation of soft tissues, including nerves. Electric output can provide a distinctly favorable bioelectrical microenvironment, which is especially relevant for the nervous system. Piezoelectric biomaterials have attracted attention in the field of neural tissue engineering owing to their biocompatibility and ability to generate piezoelectric surface charges. In this review, an outlook of the most recent achievements in the field of piezoelectric biomaterials is described with an emphasis on piezoelectric polymers for neural tissue engineering. First, general recommendations for the design of an optimal nerve scaffold are discussed. Then, specific mechanisms determining nerve regeneration via piezoelectric stimulation are considered. Activation of piezoelectric responses via natural body movements, ultrasound, and magnetic fillers is also examined. The use of magnetoelectric materials in combination with alternating magnetic fields is thought to be the most promising due to controllable reproducible cyclic deformations and deep tissue permeation by magnetic fields without tissue heating. In vitro and in vivo applications of nerve guidance scaffolds and conduits made of various piezopolymers are reviewed too. Finally, challenges and prospective research directions regarding piezoelectric biomaterials promoting nerve regeneration are discussed. Thus, the most relevant scientific findings and strategies in neural tissue engineering are described here, and this review may serve as a guideline both for researchers and clinicians.

Local nanoelectromechanical properties of multiferroics Gd-doped BiFeO3-BaTiO3 solid solution.

Bi(1-x-y)GdxBayFe(1-y)TiyO3 (x = 0.1 and y = 0.1, 0.2, 0.3) solid solutions have been prepared via solid state reaction method with the aim to obtaining magnetoelectric coupling (i.e., linear relation between magnetization and electric field) at room temperature. Optimum calcination and sintering strategies for obtaining pure perovskite phase, high density ceramics and homogeneous microstructures have been determined. The maximum ferroelectric transition temperature (Tc) of this system was 150-170 degrees C with the dielectric constant peak of 2300 at 100 kHz for y = 0.1. Well saturated piezoelectric loops were observed for all composition indicating room temperature ferroelectricity. Hardness and Young's modulus decrease with depth and with increasing concentration y.

Core-Shell Magnetoactive PHB/Gelatin/Magnetite Composite Electrospun Scaffolds for Biomedical Applications.

Novel hybrid magnetoactive composite scaffolds based on poly(3-hydroxybutyrate) (PHB), gelatin, and magnetite (Fe3O4) were fabricated by electrospinning. The morphology, structure, phase composition, and magnetic properties of composite scaffolds were studied. Fabrication procedures of PHB/gelatin and PHB/gelatin/Fe3O4 scaffolds resulted in the formation of both core-shell and ribbon-shaped structure of the fibers. In case of hybrid PHB/gelatin/Fe3O4 scaffolds submicron-sized Fe3O4 particles were observed in the surface layers of the fibers. The X-ray photoelectron spectroscopy results allowed the presence of gelatin on the fiber surface (N/C ratio-0.11) to be revealed. Incubation of the composite scaffolds in saline for 3 h decreased the amount of gelatin on the surface by more than ~75%. The differential scanning calorimetry results obtained for pure PHB scaffolds revealed a characteristic melting peak at 177.5 °C. The presence of gelatin in PHB/gelatin and PHB/gelatin/Fe3O4 scaffolds resulted in the decrease in melting temperature to 168-169 °C in comparison with pure PHB scaffolds due to the core-shell structure of the fibers. Hybrid scaffolds also demonstrated a decrease in crystallinity from 52.3% (PHB) to 16.9% (PHB/gelatin) and 9.2% (PHB/gelatin/Fe3O4). All the prepared scaffolds were non-toxic and saturation magnetization of the composite scaffolds with magnetite was 3.27 ± 0.22 emu/g, which makes them prospective candidates for usage in biomedical applications.

Hybrid Triboelectric-Electromagnetic Nanogenerators for Mechanical Energy Harvesting: A Review.

Motion-driven electromagnetic-triboelectric energy generators (E-TENGs) hold a great potential to provide higher voltages, higher currents and wider operating bandwidths than both electromagnetic and triboelectric generators standing alone. Therefore, they are promising solutions to autonomously supply a broad range of highly sophisticated devices. This paper provides a thorough review focused on major recent breakthroughs in the area of electromagnetic-triboelectric vibrational energy harvesting. A detailed analysis was conducted on various architectures including rotational, pendulum, linear, sliding, cantilever, flexible blade, multidimensional and magnetoelectric, and the following hybrid technologies. They enable highly efficient ways to harvest electric energy from many forms of vibrational, rotational, biomechanical, wave, wind and thermal sources, among others. Open-circuit voltages up to 75 V, short-circuit currents up to 60 mA and instantaneous power up to 144 mW were already achieved by these nanogenerators. Their transduction mechanisms, including proposed models to make intelligible the involved physical phenomena, are also overviewed here. A comprehensive analysis was performed to compare their respective construction designs, external excitations and electric outputs. The results highlight the potential of hybrid E-TENGs to convert unused mechanical motion into electric energy for both large- and small-scale applications. Finally, this paper proposes future research directions toward optimization of energy conversion efficiency, power management, durability and stability, packaging, energy storage, operation input, research of transduction mechanisms, quantitative standardization, system integration, miniaturization and multi-energy hybrid cells.

Wake-up Free Ferroelectric Rhombohedral Phase in Epitaxially Strained ZrO2 Thin Films.

Zirconia- and hafnia-based thin films have attracted tremendous attention in the past decade because of their unexpected ferroelectric behavior at the nanoscale, which enables the downscaling of ferroelectric devices. The present work reports an unprecedented ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown directly on (111)-Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal (111)-oriented ZrO2 films under epitaxial compressive strain exhibiting switchable ferroelectric polarization of about 20.2 µC/cm2 with a coercive field of 1.5 MV/cm. Moreover, the time-dependent polarization reversal characteristics of Nb:SrTiO3/ZrO2/Au film capacitors exhibit typical bell-shaped curve features associated with the ferroelectric domain reversal and agree well with the nucleation limited switching (NLS) model. The polarization-electric field hysteresis loops point to an activation field comparable to the coercive field. Interestingly, the studied films show ferroelectric behavior per se, without the need to apply the wake-up cycle found in the orthorhombic phase of ZrO2. Overall, the rhombohedral ferroelectric ZrO2 films present technological advantages over the previously studied zirconia- and hafnia-based thin films and may be attractive for nanoscale ferroelectric devices.

Nanoscale Piezoelectric Properties and Phase Separation in Pure and La-Doped BiFeO3 Films Prepared by Sol-Gel Method.

Pure BiFeO3 (BFO) and doped Bi0.9La0.1FeO3 (BLFO) thin films were prepared on Pt/TiO2/SiO2/Si substrates by a modified sol-gel technique using a separate hydrolysis procedure. The effects of final crystallization temperature and La doping on the phase structure, film morphology, and nanoscale piezoelectric properties were investigated. La doping and higher crystallization temperature lead to an increase in the grain size and preferred (102) texture of the films. Simultaneously, a decrease in the average effective piezoelectric coefficient (about 2 times in La-doped films) and an increase in the area of surface non-polar phase (up to 60%) are observed. Phase separation on the films' surface is attributed to either a second phase or to a non-polar perovskite phase at the surface. As compared with undoped BFO, La-doping leads to an increase in the average grain size and self-polarization that is important for future piezoelectric applications. It is shown that piezoelectric activity is directly related to the films' microstructructure, thus emphasizing the role of annealing conditions and La-doping that is frequently used to decrease the leakage current in BFO-based materials.

Local Polarization Reversal by Ion Beam Irradiation in SBN Single Crystals Covered by Dielectric Layer.

Formation of the domain structure by ion beam irradiation was studied in thermally depolarized Ce-doped strontium barium niobate single crystals covered by a dielectric layer. Three types of irradiation regimes were used: dot exposure, stripe exposure, and line exposure. The dependences of the domain size and depth on the irradiated dose were measured. The circular shape of the isolated domains with partially switched broad domain boundary was obtained. Isotropic domain growth was attributed to the step generation at the wall by merging with the residual nanodomains that appeared after thermal depolarization. The obtained linear dose dependence of the switched area was attributed to the screening of the depolarization field by the injected charge. The shape distortion of the domains growing in the neighborhood with already created ones was attributed to the electrostatic interaction of the approaching charged domain walls. The obtained results can be applied for the creation of precise domain patterns with arbitrary orientation and shape to produce nonlinear optical devices with improved characteristics, including electrically tunable diffractive optical elements.

Natural and Eco-Friendly Materials for Triboelectric Energy Harvesting.

Triboelectric nanogenerators (TENGs) are promising electric energy harvesting devices as they can produce renewable clean energy using mechanical excitations from the environment. Several designs of triboelectric energy harvesters relying on biocompatible and eco-friendly natural materials have been introduced in recent years. Their ability to provide customizable self-powering for a wide range of applications, including biomedical devices, pressure and chemical sensors, and battery charging appliances, has been demonstrated. This review summarizes major advances already achieved in the field of triboelectric energy harvesting using biocompatible and eco-friendly natural materials. A rigorous, comparative, and critical analysis of preparation and testing methods is also presented. Electric power up to 14 mW was already achieved for the dry leaf/polyvinylidene fluoride-based TENG devices. These findings highlight the potential of eco-friendly self-powering systems and demonstrate the unique properties of the plants to generate electric energy for multiple applications.

Piezoelectric Properties of Pb1-xLax(Zr0.52Ti0.48)1-x/4O3 Thin Films Studied by In Situ X-ray Diffraction.

The piezoelectric properties of lanthanum-modified lead zirconate titanate Pb1-xLax(Zr0.52Ti0.48)1-x/4O3 thin films, with x = 0, 3 and 12 mol% La, were studied by in situ synchrotron X-ray diffraction under direct (DC) and alternating (AC) electric fields, with AC frequencies covering more than four orders of magnitude. The Bragg reflections for thin films with low lanthanum concentration exhibit a double-peak structure, indicating two contributions, whereas thin films with 12% La possess a well-defined Bragg peak with a single component. In addition, built-in electric fields are revealed for low La concentrations, while they are absent for thin films with 12% of La. For static and low frequency AC electric fields, all lanthanum-modified lead zirconate titanate thin films exhibit butterfly loops, whereas linear piezoelectric behavior is found for AC frequencies larger than 1 Hz.

Efficient Water Self-Diffusion in Diphenylalanine Peptide Nanotubes.

Nanotubes of self-assembled dipeptides exemplified by diphenylalanine (FF) demonstrate a wide range of useful functional properties, such as high Young's moduli, strong photoluminescence, remarkable piezoelectricity and pyroelectricity, optical waveguiding, etc., and became the object of intensive research due to their ability to combine electronic and biological functions in the same material. Two types of nanoconfined water molecules (bound water directly interacting with the peptide backbone and free water located inside nanochannels) are known to play a key role in the self-assembly of FF. Bound water provides its structural integrity, whereas movable free water influences its functional response. However, the intrinsic mechanism of water motion in FF nanotubes remained elusive. In this work, we study the sorption properties of FF nanotubes directly considering them as a microporous material and analyze the free water self-diffusion at different temperatures. We found a change in the regime of free water diffusion, which is attributed to water cluster size in the nanochannels. Small clusters of less than five molecules per unit cell exhibit ballistic diffusion, whereas, for larger clusters, Fickian diffusion occurs. External conditions of around 40% relative humidity at 30 °C enable the formation of such large clusters, for which the diffusion coefficient reaches 1.3 × 10-10 m2 s-1 with an activation energy of 20 kJ mol-1, which increases to attain 3 × 10-10 m2 s-1 at 65 °C. The observed peculiarities of water self-diffusion along the narrow FF nanochannels endow this class of materials with a new functionality. Possible applications of FF nanotubes in nanofluidic devices are discussed.

To switch or not to switch - a machine learning approach for ferroelectricity.

With the advent of increasingly elaborate experimental techniques in physics, chemistry and materials sciences, measured data are becoming bigger and more complex. The observables are typically a function of several stimuli resulting in multidimensional data sets spanning a range of experimental parameters. As an example, a common approach to study ferroelectric switching is to observe effects of applied electric field, but switching can also be enacted by pressure and is influenced by strain fields, material composition, temperature, time, etc. Moreover, the parameters are usually interdependent, so that their decoupling toward univariate measurements or analysis may not be straightforward. On the other hand, both explicit and hidden parameters provide an opportunity to gain deeper insight into the measured properties, provided there exists a well-defined path to capture and analyze such data. Here, we introduce a new, two-dimensional approach to represent hysteretic response of a material system to applied electric field. Utilizing ferroelectric polarization as a model hysteretic property, we demonstrate how explicit consideration of electromechanical response to two rather than one control voltages enables significantly more transparent and robust interpretation of observed hysteresis, such as differentiating between charge trapping and ferroelectricity. Furthermore, we demonstrate how the new data representation readily fits into a variety of machine-learning methodologies, from unsupervised classification of the origins of hysteretic response via linear clustering algorithms to neural-network-based inference of the sample temperature based on the specific morphology of hysteresis.