Ferroelectric behavior and polarization mechanism in odd‐odd polyamide 11,11

Ferroelectric and piezoelectric behavior in odd‐odd polyamide 11,11 are successfully detected for the first time. The maximum coercive field (E_c) of 90 MV/m, and a remnant polarization (P_r) of 40 mC/m² are obtained at room temperature. A piezoelectric strain coefficient (d₃₃) value as high as ?3.9 pC/N has been found in stretched polyamide 11,11 film. The structural change of samples before and after poling is investigated by wide‐angle X‐ray diffraction patterns, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The results indicate that the nature of the ferroelectricity originates from amide group dipoles in the γ‐form crystal regions. Hysteresis behavior appears to result from the crystallites reversal mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1094–1099     

A study of the mechanical anisotropy of high-draw,low-draw,and voided PVDF

The mechanical anisotropy of oriented PVDF sheet is examined using a variety of experimental techniques. The mechanical behavior is similar to that observed previously for low-density polyethylene and nylon and consistent with a parallel lamellar crystalline structure. The s₃₁ compliance is reduced in magnitude by drawing to higher draw ratio, but the reduction in the piezoelectric coefficient d₃₁ is less marked, suggesting that the piezoelectric response cannot be related solely to dimensional changes under stress. Drawing to high draw ratio increases the s₃₃ compliance, and this is further increased by introducing voids. The corresponding d₃₃ piezoelectric coefficient is not changed significantly by drawing to high draw ratio, or by the introduction of voids, again indicating that the piezoelectric behavior relates to factors other than dimensional changes.     

A Semiconducting Organic–Inorganic Hybrid Perovskite‐type Non‐ferroelectric Piezoelectric with Excellent Piezoelectricity

Piezoelectric materials are a class of important functional materials applied in high‐voltage sources, sensors, vibration reducers, actuators, motors, and so on. Herein, [(CH₃)₃S]₃[Bi₂Br₉]( 1 ) is a brilliant semiconducting organic–inorganic hybrid perovskite‐type non‐ferroelectric piezoelectric with excellent piezoelectricity. Strikingly, the value of the piezoelectric coefficient d₃₃ is estimated as ≈18 pC N^?1. Such a large piezoelectric coefficient in non‐ferroelectric piezoelectric has been scarcely reported and is comparable with those of typically one‐composition non‐ferroelectric piezoelectrics such as ZnO (3pC N^?1) and much greater than those of most known typical materials. In addition, 1 exhibits semiconducting behavior with an optical band gap of ≈2.58 eV that is lower than the reported value of 3.37 eV for ZnO. This discovery opens a new avenue to exploit molecular non‐ferroelectric piezoelectric and should stimulate further exploration of non‐ferroelectric piezoelectric due to their high stability and low loss characteristics.     

Piezoelectric property improvement of polyethylene ferroelectrets using postprocessing thermal‐pressure treatment

In this work, biaxially stretched polymer foams with well‐defined cellular structures were prepared from polyethylene via blown‐film extrusion and subjected to corona charging to produce a piezoelectric response. The charging parameters were first optimized in terms of charging voltage and needle distance, as well as the gas type and pressure to investigate their effect on the piezoelectric coefficient (d₃₃). The results show that samples charged under nitrogen (N₂) at 100 kPa had better d₃₃ coefficient than those charged under ambient air or N₂ at 20 kPa. Moreover, 2 different thermal pressure treatments were imposed to obtain an optimized eye‐like cellular structure with different cell aspect ratios (AR). The results showed that when the cells were elongated in both the longitudinal and transverse directions (higher AR), higher d₃₃ coefficients were achieved. From all the samples produced, the best results were obtained for a longitudinal aspect ratio (AR‐L) of 7.1, a transversal aspect ratio (AR‐T) of 4.6, and a relative foam density of 0.52 leading to a d₃₃ coefficient of 935 pC/N. This coefficient was further increased using reverse charging and multilayered films, reaching a maximum of 2550 pC/N. This value is much higher than typical ones reported so far for any polyethylene and polypropylene ferroelectrets. These results could increase the use of polyethylene in piezoelectric applications as these materials are very attractive for the large‐scale production of electret‐based sensors and transducers due to their low cost and easy processing.     

Control of microstructure and functional properties of PZT thin films via UV assisted pyrolysis

The influence of ultraviolet (UV) light during pyrolysis of sol-gel fabricated Pb(Zr_0.52Ti_0.48)O₃ thin films on (111)Pt/Ti/SiO₂/Si substrates has been investigated. The UV treated films show a homogeneous fine grain structure with (100) preferential orientation, whereas a bimodal grain structure and (111) preferential orientation were found for the untreated film. This is explained in terms of specific template layers formed during pyrolysis. The ferroelectric, dielectric and piezoelectric properties are also reported for both films. It is shown that while the ferroelectric properties are higher for the (111) films, the (100) films show better dielectric and piezoelectric properties with an effective piezoelectric coefficient, d _33eff, of 183 pm/V vs. 101.8 pm/V for the (111) films.     

Vibrational energy-harvesting performance of bio-sourced flexible polyamide 11/layered silicate nanocomposite films

The energy-harvesting efficiency of melt processed polyamide 11 (PA11) films and its nanocomposites have been investigated as a function of filler type and content. In the present work, nanoclays have been used as structural modifiers in a PA11 matrix. The nanocomposites were prepared using layered clays, Cloisite 20A, 10A, and Na⁺, by extrusion process through varying the filler content, 1, 2, 4, and 5?wt.%. The crystalline structure of these nanocomposites has been studied by X-ray diffractometer. It has been demonstrated that layered silicates are not significant for the structural quality of the obtained nanocomposites. Regarding the interlayer peak of different clays, it has also been revealed that Cloisite 20A is partially exfoliated, whereas 10A and Na⁺ are totally exfoliated in the PA11 matrix. From mechanical and dynamic mechanical analyses, it was found that the addition of layered silicates results in an increase in mechanical properties. The piezoelectric strain coefficient d₃₃ and dielectric constant ε_R have been measured on polarized films at ambient temperature. Among all the prepared nanocomposites only Cloisite Na⁺-loaded PA11 nanocomposites showed the best piezoelectric constant. This observation showed that piezoelectric constant not only depends on the crystalline phases but also on the nature of the filler. Cloisite Na⁺ is more polar than other modified clays and high polarity leads to a better polarization response. A specific method for the quantification of energy vibration recovery has been developed for these nanocomposites. The capabilities of vibrational energy recovery were studied on PA11 loaded with Cloisite Na⁺.     

Ferroelectric and piezoelectric properties of nylon 11/poly(vinylidene fluoride) bilaminate films

The ferroelectric and piezoelectric properties of a new class of polymer ferroelectric and piezoelectric materials, nylon 11/polyvinylidene fluoride (PVF₂) bilaminate films, prepared by a co-melt-pressing method, is presented. The bilaminate films exhibit typical ferroelectric D-E hysteresis behavior with a remanent polarization, P_r, of about 75 mC/m², which is higher than the value of 52 mC/m² observed for PVF₂ or nylon 11 films measured under the same conditions. The coercive field, E_c, of the bilaminate films is ～ 78 MV/m, which is higher than that of either PVF₂ or nylon 11 films. Measurements of the temperature dependence of the piezoelectric strain coefficient, d₃₁, and the piezoelectric stress coefficient, e₃₁, were also carried out. The bilaminate films exhibit a piezoelectric strain coefficient, d₃₁, of 41 pC/N at room temperature, which is significantly higher than the PVF₂ films (25 pC/N) and the nylon 11 films (3.1 pC/N). When the temperature is increased to 110°C, d₃₁ of the bilaminate films reaches a maximum value of 63 pC/N, more than five times that of PVF₂ (11 pC/N) and more than four times that of nylon 11 (14 pC/N) at the same temperature. The piezoelectric stress coefficient, e₃₁, of the bilaminate films shows a value of 109 mC/m² at room temperature, almost twice that of the PVF₂ films (59 mC/m²) and about 18 times that of the nylon 11 films (6.2 mC/m²). Measurement of the temperature dependence of the hydrostatic piezoelectric coefficient, d_h, of the bilaminate films also shows an enhancement with respect to the individual components, PVF₂ and nylon 11. ©1995 John Wiley & Sons, Inc.     

High‐Temperature Elastic Moduli of Flux‐Grown α‐GeO2 Single Crystal

From high‐precision Brillouin spectroscopy measurements, six elastic constants (C₁₁, C₃₃, C₄₄, C₆₆, C₁₂, and C₁₄) of a flux‐grown GeO₂ single crystal with the α‐quartz‐like structure are obtained in the 298–1273 K temperature range. High‐temperature powder X‐ray diffraction data is collected to determine the temperature dependence of the lattice parameters and the volume thermal expansion coefficients. The temperature dependence of the mass density, ρ, is evaluated and used to estimate the thermal dependence of its refractive indices (ordinary and extraordinary), according to the Lorentz–Lorenz equation. The extraction of the ambient piezoelectric stress contribution, e₁₁, from the C′₁₁–C₁₁ difference gives, for the piezoelectric strain coefficient d₁₁, a value of 5.7(2) pC N^?1, which is more than twice that of α‐quartz. As the quartz structure of α‐GeO₂ remains stable until melting, piezoelectric activity is observed until 1273 K.     

Evaluation of piezoelectric poly(vinylidene fluoride) polymers for use in space environments. I. Temperature limitations

Smart materials, such as thin‐film piezoelectric polymers, are interesting for potential applications on Gossamer spacecraft. This investigation aims to predict the performance and long‐term stability of the piezoelectric properties of poly(vinylidene fluoride) (PVDF) and its copolymers under conditions simulating the low‐Earth‐orbit environment. To examine the effects of temperature on the piezoelectric properties of PVDF, poly(vinylidenefluoride‐co‐trifluoroethylene), and poly(vinylidenefluoride‐co‐hexafluoropropylene), the d₃₃ piezoelectric coefficients were measured up to 160 °C, and the electric displacement/electric field (D–E) hysteresis loops were measured from ?80 to +110 °C. The room‐temperature d₃₃ coefficient of PVDF homopolymer films, annealed at 50, 80, and 125 °C, dropped rapidly within a few days of thermal exposure and then remained unchanged. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with d₃₃ remaining almost unchanged up to 125 °C. The HFP copolymer exhibited poor retention of d₃₃ at temperatures above 80 °C. In situ D–E loop measurements from ?80 to +110 °C showed that the remanent polarization of the TrFE copolymer was more stable than that of the PVDF homopolymer. D–E hysteresis loop and d₃₃ results were also compared with the deflection of the PVDF homopolymer and TrFE copolymer bimorphs tested over a wide temperature range. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1310‐1320, 2005     

Dielectric and piezoelectric properties of dense and porous PZT films prepared by sol-gel method

PZT films with different microstructure and Zr:Ti ratios were fabricated on ITO/glass and platinized silicon wafer substrates by dip-coating. A dense film of 2% porosity and a porous film of 19% porosity were obtained by repetition of thin and thick coatings, respectively. Development of pores during heating the film was examined and heating process factors were investigated. In the film fabricated on ITO/glass substrates, an existence of non-perovskite and low permittivity layer was confirmed by measurement of film thickness dependence of the dielectric constant. Among the films studied, the film with molar composition of Ti:Zr = 5:5 exhibited the largest dielectric constant and apparent piezoelectric coefficient, d ₃₃, though the values were small. Apparent piezoelectric coefficients of d ₃₃ and g ₃₃ of the porous films were larger than those of the dense films.     

Dependence of dielectric,ferroelectric, and piezoelectric properties on crystalline properties of p(VDF‐co‐TrFE) copolymers

Thermal processing at various temperatures has been used to fabricate poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐co‐TrFE)] films with varied crystalline properties in an attempt to improve their piezoelectric properties. Although the dielectric constant of the films annealed at higher temperature is smaller than that of cooled and quenched ones, it has been shown that the annealed films possess larger crystallinity and stacked lamellar crystal grain size. The ferroelectric domains deriving from crystal region in all the samples are effectively improved by hot polarization. As a result, the remnant polarizations (P_r) and coercive electric field (E_c) of the corresponding films are improved at a low frequency due to the response of dipoles in crystal phase, and the largest piezoelectric constant in the longitudinal thickness mode (d₃₃=?25 pC/N) is obtained in an annealed copolymer film. The results illustrate improving the crystal structure of P(VDF‐co‐TrFE) is an effective way to realize high electromechanical properties, which provides broadly applied scenery for this kind of copolymer in piezoelectric components. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

A very promising piezoelectric property of Ta2O5 thin films. II: Birefringence and piezoelectricity

Birefringent and piezoelectric properties of Ta₂O₅ ceramic thin films of monoclinic and trigonal structures were analyzed. The birefringence, observed by reflected polarized light microscopy, yields information on thin film microstructures, crystal shapes and sizes and on crystallographic orientations of grains of trigonal structure. Such an information was considered for investigating piezoelectric properties by laser Doppler vibrometry and by piezoresponse force microscopy. The vibration velocity was measured by applying an oscillating electric field between electrodes on both sides of a Ta₂O₅ film deposited on a Si substrate which was pasted on an isolating mica sheet. In this case, it is shown that the vibration velocity results were not only from a converse piezoelectric effect, proportional to the voltage, but also from the Coulomb force, proportional to the square of the voltage. A huge piezoelectric strain effect, up to 7.6%, is found in the case of Ta₂O₅ of trigonal structure. From an estimation of the electrical field through the Ta₂O₅ thin film, this strain likely corresponds to a very high longitudinal coefficient d₃₃ of several thousand picometers. Results obtained by piezoresponse force microscopy show that trigonal grains exhibit a polarization at zero field, which is probably due to stress caused expansion in the transition monoclinic-trigonal, presented in a previous article (part I).     

Polymer ferroelectret based on polypropylene foam: piezoelectric properties prediction using dynamic mechanical analysis

Thin polypropylene (PP) foam films were produced by continuous extrusion using supercritical nitrogen (N₂) and then charged via corona discharge. The samples were characterized by dynamic mechanical analysis as a simple method to predict the piezoelectric properties of the cellular PP obtained. The results were then related to morphological analysis based on scanning electron microscopy and mechanical properties in tension. The results showed that the presence of a nucleating agent (CaCO₃) substantially improved the morphology (in terms of cell size and cell density) of the produced foam. Also, an optimization of the extrusion (screw design, temperature profile, blowing agent, and nucleating agent content) and post‐extrusion (calendering temperature and speed) conditions led to the development of a stretched eye‐like cellular structure with uniform cell size distribution. This morphology produced higher storage and loss moduli in the machine (longitudinal) direction than for the transverse direction, as well as higher piezoelectric properties. The morphological and mechanical results showed that higher cell aspect ratio led to lower Young's modulus, which is suitable to achieve higher piezoelectric properties. Finally, the best quasi‐static piezoelectric d₃₃ coefficient was 550 pC/N for a cellular PP ferroelectret having a uniform eye‐like cellular structure using N₂ as the ionizing gas inside the cells, while the highest value was only 250 pC/N when air was used. Hence, the value of d₃₃ can be improved by more than 100% just by replacing air with N₂ as the ionizing gas. Copyright © 2016 John Wiley & Sons, Ltd.     

Orientation dependence of the dielectric and piezoelectric properties for the Ba0.98Ca0.02Ti0.96Sn0.04O3 thin films

Lead free Ba_0.98Ca_0.02Ti_0.96Sn_0.04O₃ (BCST) thin films with (110), (111) and (001) orientations were processed via chemical solution deposition, and effects of orientation on the dielectric and piezoelectric properties were investigated in some aspects. The (110) orientated BCST thin films exhibit highest Curie temperature (T _c of 85 °C) and lowest dielectric loss (tan δ of 0.02). While, the (111) orientated BCST thin films exhibit highest dielectric tunability (74 %) and largest piezoelectric coefficient (d ₃₃ of 78 pm/V), which indicate that it is a promising lead-free replacement for lead-based applications. The anisotropic dielectric and piezoelectric properties in the three kinds of oriented BCST films has been attributed to the difference of structure, in-plane stress and polarization rotation in orientation engineered BCST films. This work clearly reveals the dielectric and piezoelectric properties of BCST films exhibit a strong sensitivity to orientation.     

The compressive electrical field electrostrictive coefficient M33 of electroactive polymer composites and its saturation versus electrical field,polymer thickness,frequency, and fillers

Electroactive polymers are widely studied because of their large electrical‐field‐induced strain. Their flexibility and their ability to be deposited on large surfaces make them promising candidates as electroactive materials for actuators or energy‐harvesting devices. For actuation purposes, the material efficiency is directly related to the electrical‐field‐related electrostrictive coefficient M₃₃ through S₃₃ = M₃₃E², where S₃₃ is the electrical‐field‐induced strain and E is the applied electrical field. Numerous studies concern the increase of M₃₃, but very few have been devoted to its saturations versus electrical field. To this end, the present paper describes the variation of M₃₃ versus thickness, composition, frequency, and electrical field for polyurethane‐based composites. Based on the saturation of the electrical‐field‐induced polarization within the studied polymer composites, a model of the M₃₃ behavior was also proposed, and it was found to show a good agreement with the experimental data. In addition, this model predicts the dielectric constant and the saturation electrical field to be the key parameters ruling the M₃₃ saturation. Copyright © 2011 John Wiley & Sons, Ltd.     

Harnessing Plasticity in an Amine-Borane as a Piezoelectric and Pyroelectric Flexible Film

We demonstrate that trimethylamine borane can exhibit desirable piezoelectric and pyroelectric properties. The material was shown to be able operate as a flexible film for both thermal sensing, thermal energy conversion and mechanical sensing with high open circuit voltages (>10 V). A piezoelectric coefficient of d₃₃≈10–16 pC N⁻¹, and pyroelectric coefficient of p≈25.8 μC m⁻² K⁻¹ were achieved after poling, with high pyroelectric figure of merits for sensing and harvesting, along with a relative permittivity of 6.3.     

Harnessing Plasticity in an Amine‐Borane as a Piezoelectric and Pyroelectric Flexible Film

We demonstrate that trimethylamine borane can exhibit desirable piezoelectric and pyroelectric properties. The material was shown to be able operate as a flexible film for both thermal sensing, thermal energy conversion and mechanical sensing with high open circuit voltages (>10 V). A piezoelectric coefficient of d₃₃≈10–16 pC N^?1, and pyroelectric coefficient of p≈25.8 μC m^?2 K^?1 were achieved after poling, with high pyroelectric figure of merits for sensing and harvesting, along with a relative permittivity of 6.3.     

Flexible and environment-friendly regenerated cellulose/MoS2 nanosheet nanogenerators with high piezoelectricity and output performance

Flexible piezoelectric nanogenerators for energy harvesting are getting more and more attention nowadays by converting the mechanical energy to electric energy. Here, an environment-friendly piezoelectric nanogenerator based on the regenerated cellulose (RC)/MoS₂ nanosheet nanocomposite successfully exhibited a relative high output voltage of 2 V and current of 150 nA under slight press which were 5 and 7.5 times higher than those of the neat RC film, i.e. 0.4 V and 20 nA, respectively. In particular, the MoS₂ nanosheets were obtained through a simple, facile and low-cost pathway by mechanical exfoliation in triethanolamine. The nanocomposite film with MoS₂ nanosheets content of 4% exhibited a high piezoelectric constant (d₃₃) of 19 pC/N, which was 6.3 times higher than that of the neat RC film (i.e. 3 pC/N). Thus, the RC/MoS₂ piezoelectric nanogenerator has great potential applications in the fields of energy harvester, sensors and is of great significance to environment protection.

     

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)₃P]₃[Bi₂Br₉] ( MTPBB ) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 μC cm⁻². Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d₃₃) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 μW cm⁻² at an optimal load of 4 MΩ. Moreover, the potential of MTPBB -based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.     

Piezoelectric PVDF-TrFE nanocomposite mats filled with BaTiO3 nanofibers: The effect of poling conditions

BaTiO₃ nanofibers (BT NFs), prepared by electrospinning, were used as a filler for electrospun poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) nanocomposite mats. The phase structure and the effect of poling conditions on the piezoelectric properties of PVDF-TrFE/BT nanocomposites were investigated. The results showed an improved degree of crystallinity (78.6%) and a high β-crystal phase (up to 98.3%) in all electrospun samples, independent of the nanofiber content. The two-step poling method, applying electric fields of opposite polarity, led to significantly improved piezoelectric constants d₃₃ (−31.7 pC N⁻¹), strongly dependent on the added BaTiO₃ nanofibers. The inclusion of piezoelectric ceramic nanofibers into a polymer matrix, easily carried out by means of electrospinning, followed by an ad hoc optimized poling treatment, allowed to develop flexible materials with enhanced piezoelectric properties, potentially exploitable in innovative conversion systems used in wearable and sensing devices.