ABSTRACT
Material thermal conductivity is a key factor in various applications, from thermal management to energy harvesting. With microstructure engineering being a widely used method for customizing material properties, including thermal properties, understanding and controlling the role of extended phonon-scattering defects, like grain boundaries, is crucial for efficient material design. However, systematic studies are still lacking primarily due to limited tools. In this study, we demonstrate an approach for measuring grain boundary thermal resistance by probing the propagation of thermal waves across grain boundaries with a temperature-sensitive scanning probe. The method, implemented with a spatial resolution of about 100 nm on finely grained Nb-substituted SrTiO3 ceramics, achieves a detectability of about 2 × 10-8 K m2 W-1, suitable for chalcogenide-based thermoelectrics. The measurements indicated that the thermal resistance of the majority of grain boundaries in the STiO3 ceramics is below this value. While there are challenges in improving sensitivity, considering spatial resolution and the amount of material involved in the detection, the sensitivity of the scanning probe method is comparable to that of optical thermoreflectance techniques, and the method opens up an avenue to characterize thermal resistance at the level of single grain boundaries and domain walls in a spectrum of microstructured materials.
ABSTRACT
Triboelectric and piezoelectric energy harvesters can hardly power most microelectronic systems. Rotational electromagnetic harvesters are very promising alternatives, but their performance is highly dependent on the varying mechanical sources. This study presents an innovative approach to significantly increase the performance of rotational harvesters, based on dynamic coil switching strategies for optimization of the coil connection architecture during energy generation. Both analytical and experimental validations of the concept of self-adaptive rotational harvester were carried out. The adaptive harvester was able to provide an average power increase of 63.3% and 79.5% when compared to a non-adaptive 16-coil harvester for harmonic translation and harmonic swaying excitations, respectively, and 83.5% and 87.2% when compared to a non-adaptive 8-coil harvester. The estimated energy conversion efficiency was also enhanced from ~80% to 90%. This study unravels an emerging technological approach to power a wide range of applications that cannot be powered by other vibrationally driven harvesters.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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).
Subject(s)
Barbiturates , Oxygen , Barbiturates/chemistry , Benzaldehydes , Hydrogen , Hydrogen Bonding , Models, MolecularABSTRACT
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.
ABSTRACT
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.
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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.
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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.
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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.
ABSTRACT
Ferroelectric materials based on lead zirconate titanate (PZT) are widely used as sensors and actuators because of their strong piezoelectric activity. However, their application is limited because of the high processing temperature, brittleness, lack of conformal deposition, and a limited possibility to be integrated with the microelectromechanical systems (MEMS). Recent studies on the piezoelectricity in the 2-D materials have demonstrated their potential in these applications, essentially due to their flexibility and integrability with the MEMS. In this work, we deposited a few layer graphene (FLG) on the amorphous oxidized Si3N4 membranes and studied their piezoelectric response by sensitive laser interferometry and rigorous finite-element modeling (FEM) analysis. Modal analysis by FEM and comparison with the experimental results show that the driving force for the piezoelectric-like response can be a polar interface layer formed between the residual oxygen in Si3N4 and the FLG. The response was about 14 nm/V at resonance and could be further enhanced by adjusting the geometry of the device. These phenomena are fully consistent with the earlier piezoresponse force microscopy (PFM) observations of the piezoelectricity of the graphene on SiO2 and open up an avenue for using graphene-coated structures in the MEMS.
ABSTRACT
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.
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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.
Subject(s)
Nanotubes, Peptide/chemistry , Peptides/chemistry , Phenylalanine/chemistryABSTRACT
Evolution of the crystal structure of ceramics BiFeO3-BaTiO3 across the morphotropic phase boundary was analyzed using the results of macroscopic measuring techniques such as X-ray diffraction, differential scanning calorimetry, and differential thermal analysis, as well as the data obtained by local scale methods of scanning probe microscopy. The obtained results allowed to specify the concentration and temperature regions of the single phase and phase coexistent regions as well as to clarify a modification of the structural parameters across the rhombohedral-cubic phase boundary. The structural data show unexpected strengthening of structural distortion specific for the rhombohedral phase, which occurs upon dopant concentration and temperature-driven phase transitions to the cubic phase. The obtained results point to the non-monotonous character of the phase evolution, which is specific for metastable phases. The compounds with metastable structural state are characterized by enhanced sensitivity to external stimuli, which significantly expands the perspectives of their particular use.
ABSTRACT
With the recent thriving of low-power electronic microdevices and sensors, the development of components capable of scavenging environmental energy has become imperative. In this article, we studied bidomain congruent LiNbO3 (LN) single crystals combined with magnetic materials for dual, mechanical, and magnetic energy harvesting applications. A simple magneto-mechano-electric composite cantilever, with a trilayered long-bar bidomain LN/spring-steel/metglas structure and a large tip proof permanent magnet, was fabricated. Its vibration and magnetic energy harvesting capabilities were tested while trying to optimize its resonant characteristics, load impedance, and tip proof mass. The vibration measurements yielded a peak open-circuit voltage of 2.42 kV/g, a short-circuit current of [Formula: see text]/g, and an average power of up to 35.6 mW/g2, corresponding to a power density of 6.9 mW/(cm [Formula: see text]), at a low resonance frequency of 29.22 Hz and with an optimal load of 40 [Formula: see text]. The magnetic response revealed a resonant peak open-circuit voltage of 90.9 V/Oe and an average power of up to [Formula: see text]/Oe2, corresponding to a relatively large magnetoelectric coefficient of 1.82 kV/(cm · Oe) and a power density of [Formula: see text]/(cm [Formula: see text]). We thus developed a system that is, in principle, able to scavenge electrical power simultaneously from low-level ambient mechanical and magnetic sources to feed low-power electronic devices.
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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.
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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.
ABSTRACT
The formation of the domain structure by electron beam irradiation in thermally depolarized Ce-doped strontium barium niobate single crystals with free surface and surface covered by a dielectric layer has been studied. The dependences of the domain sizes and domain depth on the irradiated dose have been measured. The circular shape of the isolated domains was obtained. The isotropic domain growth was attributed to step generation at the wall as a result of merging with the residual nanodomains which existed after thermal depolarization. The linear dose dependence of the switched area was attributed to the screening of the depolarization field by the injected charge. The electrostatic interaction of the approaching charged domain walls was revealed. The better quality of the domain patterns was achieved in the samples with electron localization in the dielectric layer. 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.
ABSTRACT
Piezoelectric materials based on lead zirconate titanate are widely used in sensors and actuators. However, their application is limited because of high processing temperature, brittleness, lack of conformal deposition and, more importantly, intrinsic incompatibility with biological environments. Recent studies on bioorganic piezoelectrics have demonstrated their potential in these applications, essentially due to using the same building blocks as those used by nature. In this work, we used piezoresponse force microscopy (PFM) to study the domain structures and polarization reversal in the smallest amino acid glycine, which recently attracted a lot of attention due to its strong shear piezoelectric activity. In this uniaxial ferroelectric, a diverse domain structure that includes both 180° and charged domain walls was observed, as well as domain wall kinks related to peculiar growth and crystallographic structure of this material. Local polarization switching was studied by applying a bias voltage to the PFM tip, and the possibility to control the resulting domain structure was demonstrated. This study has shown that the as-grown domain structure and changes in the electric field in glycine are qualitatively similar to those found in the uniaxial inorganic ferroelectrics.
ABSTRACT
Low-frequency vibration energy harvesting is becoming increasingly important for environmentally friendly and biomedical applications in order to power various wearable and implanted devices. In this paper, we propose the use of piezoelectric congruent LiNbO3 (LN) single crystals, with an engineered bidomain structure, as an alternative to the widely employed lead-based PZT. We thus compared experimentally the pure vibration energy scavenging performance of square-shaped bidomain and single-domain Y+128°-cut LN crystals and a conventional bimorph soft PZT ceramic bonded to long spring-steel cantilevers as a function of the frequency, load resistance, and tip proof mass. At a low bending resonance frequency of ca. 32.2 Hz, the bidomain LN yielded an open-circuit voltage of 1.54 kV/g, almost one order of magnitude larger than that observed in PZT. The maximum extractable average power was found to be of 9.2 mW/g2 in the bidomain LN, 6.2 mW/g2 in the single-domain LN, and 1.8 mW/g2 in the PZT piezo-elastic cantilevers. With five times higher output power density of up to 11.0 mW/(cm [Formula: see text]) under resonance conditions, bidomain LN was thus shown to be a reliable lead-free and high-temperature alternative to PZT, thanks to its considerably larger quality factor and electromechanical conversion efficiency.