Time and thermal stability improvement of polyethylene ferroelectrets

Ferroelectrets with good piezoelectric coefficients have been produced based on cellular polyethylene (PE) via extrusion film blowing. The quasi-static piezoelectric coefficient (d₃₃) value obtained (935 pC/N) was well above typical values for cellular polypropylene (PP) considered as the workhorse of piezoelectric polymers. Here, a focus was made on increasing the time and thermal stability of cellular PE piezoelectric activity. To do so, specific thermal treatments were applied on the films to improve their microstructure. First, films crystallinity was increased via thermal annealing at 80 °C for 5 min leading to a 32% increase of the initial d₃₃ value as well as its time stability. However, thermal treatment did not give a significant thermal stability improvement because the treated films almost completely lost their piezoelectric activity (96%) at 80 °C. Therefore, the films were treated with orthophosphoric acid resulting in substantial charge stability improvements, especially at higher temperature. Overall, it was possible to increase the continuous service temperature (CST) of PE ferroelectrets from 40 to 80 °C, which is similar to the typical CST of PP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47646.     

Energy absorption capacity of ferroelectrets based on porous polypropylene

Ferroelectret materials are special group of piezoelectric materials obtained from the cellular structure of nonpolar polymers. They are under investigation for a variety of applications such as actuators, vibration control, speakers, microphones, sensors, as well as healthcare monitoring systems. In this work, the effect of morphological and mechanical properties of ferroelectret films on their capacitance and stored energy capacity was studied. Different eye‐like cellular structure of porous polypropylene films with different cell aspect ratio (AR) and mechanical properties were used. The optimized sample was obtained with AR = 6.6 using nitrogen (N₂) as the ionizing gas to give a quasi‐static piezoelectric coefficient (d₃₃) of about 800 pC/N, an electrode charge density of about 2.10 mC/m², a maximum capacitance of about 465 pF, as well as a maximum stored energy capacity of about 1,824 pJ. It was observed that replacing air with N₂ as the ionizing gas led to an increase in charge/voltage output. Moreover, by replacing air with N₂ as the ionizing gas, the capacitance and stored energy of the samples were improved by about 20% and 80%, respectively. Hence, it can be concluded that the capacitance was mostly related to the cellular morphology of the samples while the stored energy was also function of the ionizing gas used. POLYM. ENG. SCI., 58:300–309, 2018. © 2017 Society of Plastics Engineers     

Small Reduction of the Piezoelectric d33 Response in Potassium Sodium Niobate Thick Films

We have investigated the electromechanical response of potassium sodium niobate (K_0.5Na_0.5NbO₃ or KNN) thick films. The high‐field strain hysteresis loops and weak‐field converse piezoelectric d₃₃ coefficient of the films were measured and compared with those of KNN bulk ceramics under the same electric field conditions. The converse d₃₃ values of the thick films and bulk ceramics were equal to 82.5 and 138 pm/V, respectively, at 0.4 kV/mm. The fundamental difference between the piezoelectric response of the KNN films and the ceramics was studied in terms of the effective (“clamped”) piezoelectric d₃₃ coefficient. The reduction in the piezoelectric d₃₃ coefficient of the KNN films, resulting from the clamping by the substrate, was compared to lead‐based ferroelectric thick films, including Pb(Zr,Ti)O₃ (PZT) and (1 ? x)Pb(Mg_1/3Nb_2/3)O₃?xPbTiO₃ (PMN‐PT). We propose a possible explanation, based on the particular elastic properties of KNN, for the small relative difference observed between the “clamped” and “unclamped” (“bulk”) d₃₃ of KNN, in comparison with lead‐based systems.     

Large Area Thick Films of PVDF‐TrFE and Relaxor‐Ceramics for Piezo‐ and Pyroelectric Applications

Wearable electronics, sensors, and energy harvesting devices are gaining an ever increasing importance in consumer products. Their success is, however, contingent on the availability of flexible and cost‐effective functional materials. The present paper presents an up‐scaled processing route for 0–3 thick film composites of the ferroelectric polymer polyvinylidenefluoride‐trifluoroethylene and a relaxor ceramic. Different compositions are investigated for pyro‐ and piezoelectric applications. Various samples are produced via tape casting and spin‐coating as freestanding and supported films of up to 600 × 200 mm² and on 150 mm silicon wafers, respectively. The samples are characterized in terms of thickness and roughness reproducibility, mechanical properties, and impedance. It is shown that good reproducibility and quality of the films can be realized. Depending on the application targeted (pyroelectric or piezoelectric), specific compositions together with the suitable poling process are presented. For instance, a composite with 24 vol% ceramic shows highest pyroelectric properties together with lowest piezoelectric thickness coefficient (d₃₃) when poled for pyroelectric applications. On the other hand, a composite with 50 vol% ceramic exhibits a d₃₃ of 100 pm V^?1 that is unsurpassed for this type of composites. These properties are advantageous in a large variety of applications, including wearable devices.     

Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO₂) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO₂ was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44094.     

Effects of butyl acrylate modified polypropylene on structural and thermal properties of foamed polypropylene

In this work, the melt strength of PP matrix was reinforced by crosslinking‐modified PP (CM‐PP) which was yielded by peroxide‐initiated crosslinking of linear PP with butyl acrylate (BA). The nano‐silica aerogel (nano‐SiO₂) worked as a nucleating agent for foaming. The effects of CM‐PP with the various contents of BA on the foaming behavior and thermal property of PP were studied by measurements of density, thermal conductivity, Vicat softening temperature and SEM. The results showed that the foamed PP got the best properties when the crosslinking PP modified with the weight ratio of butyl acrylate was 10 wt %. The density of the obtained foamed PP with uniform closed cells was as low as 0.23 g/cm³, the thermal conductivity was 0.044 W/(m K), and the Vicat softening temperature was 120 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44340.     

Fabrication of super‐ductile PP/LDPE blended parts with a chemical blowing agent

The mechanical blending of polypropylene (PP) and low density polyethylene (LDPE) is an economical and simple method for producing new polymeric materials for specific applications. However, the reduction in strain‐at‐break of the blend is one of its main shortcomings. In this study, PP/LDPE foamed parts were fabricated by conventional injection molding (CIM) with azodicarbonamide as a chemical blowing agent (CBA) and tested for tensile properties at two test speeds. Also, the fracture surfaces of the parts were investigated by scanning electron microscopy (SEM). In addition, to investigate the underlying mechanism of the super‐ductility, the tested samples were carefully analyzed and compared, and further characterized by differential scanning calorimetry and SEM. The results suggest that fabricating PP/LDPE super‐ductile parts using CIM with a CBA is feasible. The results also indicate that there is a close relationship between the mechanical properties and morphological structures, which are deeply influenced by the dosage of CBA, the PP/LDPE ratio, and the packing parameters. Furthermore, compared to conventional injection molded solid parts, the ductility of the foamed parts can be dramatically improved by the formation of microfibrils in the PP phase, which come into being under certain processing conditions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44101.     

Investigation of MnO2‐doped (Ba,Ca)TiO3 lead‐free ceramics for high power piezoelectric applications

x% mol MnO₂‐doped Ba_0.925Ca_0.075TiO₃ ceramics (abbreviated as BCT‐Mnx, x=0‐1.5) were synthesized by conventional solid‐state reaction method. The effects of MnO₂ addition and (Ba+Ca)/Ti mole ratio (A/B ratio) on the microstructure and electrical properties of the ceramics were investigated. The internal bias filed E_i was determined from the asymmetrical polarization hysteresis loops and found to increase with the doping concentration of MnO₂. High mechanical quality factors (Q_m>1200) and low dielectric loss (tanδ<0.5%) were found in the BCT‐Mn0.75 and BCT‐Mn1.0 ceramics with E_i>3 kV/cm, meanwhile, the piezoelectric and electromechanical properties were found to decrease compared with the pure BCT, exhibiting a typical characteristic of “hard” behavior. Of particular interest is that the microstructure of BCT‐Mn0.75 ceramics could be controlled by changing the A/B ratio, where enhanced piezoelectric coefficient d₃₃ on the order of 190 pC/N was obtained in the BCT‐Mn0.75 ceramics with A/B=1.01 due to its fine‐grained microstructure, with yet high Q_m, being on the order of 1000. The high d₃₃ and Q_m in MnO₂‐doped BCT ceramics make it a promising candidate for high power piezoelectric applications.     

Influence of extrusion,stretching and poling on the structural and piezoelectric properties of poly (vinylidene fluoride‐hexafluoropropylene) copolymer films

Three types of poly (vinylidene fluoride‐hexafluoropropylene) (PVDF–HFP) copolymer films were prepared by extrusion, stretching as well as simultaneously stretching and static electric field poling (SSSEP), respectively, and measured by the differential scanning calorimetric, wide angle X‐ray diffraction, fourier transformation infrared‐attenuated total reflection, and Dynamic mechanical analysis. The experimental results showed that the films prepared by stretching and SSSEP have higher crystallinity and β phase than by extrusion. SSSEP improved the chain orientation enormously both in crystalline and amorphous regions, resulting in the highest storage modulus. Because of the lower β phase content, the extruded films exhibited the lowest piezoelectric coefficient d₃₃. For the stretched and SSSEP films, although the β phase content was similar, the d₃₃ was distinct because of the different potential energy for the rotation of the dipoles. In addition, the SSSEP films gave the maximum d₃₃ (24 pC/N), higher than the other PVDF–HFP copolymer films that have been reported. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 858–862, 2007     

Morphology and mechanical properties of polypropylene/high‐impact polystyrene blends from postconsumer plastic waste

The compatibilizing effect of the triblock copolymer poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) on the morphological and mechanical properties of virgin and recycled polypropylene (PP)/high‐impact polystyrene (HIPS) blends was studied, with the properties optimized for rigid composite films. The components of the blend were obtained from municipal plastic waste, PP being acquired from mineral water bottles (PP_b) and HIPS from disposable cups. These materials were preground, washed only with water, dried with hot air, and ground again (PP_b) or agglutinated (HIPS). Blends with three different weight ratios of PP_b and HIPS (6:1, 6:2, and 6:3) were prepared, and three different concentrations of SEBS (5, 6, and 7 wt %) were used for investigations of its compatibilizing effect. Scanning electron microscopy showed that SEBS reduced the diameter of dispersed HIPS particles in the globular and fibril shapes and improved the adhesion between the disperse phase and the matrix. However, SEBS interactions with PP_b and HIPS influenced the mechanical properties of the compatibilized PP_b/HIPS/SEBS blends. An adequate composition of PP/HIPS, for both virgin and recycled blends, for applications in composite films with characteristics similar to those of synthetic paper was obtained with a minimal amount of SEBS and a maximal HIPS/PP ratio in the range of concentrations studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2861–2867, 2003     

Facile preparation of ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) thick films by solution casting

We investigated the effects of annealing temperature and vacuum treatment on the crystallinity and ferroelectric properties of solution‐casted poly(vinylidenefluoride‐co‐trifluoroethylene), P(VDF‐TrFE), thick films. We varied the annealing temperature from 70°C to 150°C and achieved high‐quality ferroelectric thick films annealed at 130°C. Ferroelectric domains and their properties were confirmed using X‐ray diffraction, Fourier transform infrared spectroscopy with attenuated total reflection mode and ferroelectric/piezoelectric measurement systems. Drying and/or annealing in the vacuum allowed for the improvement of crystallinity and ferroelectric/piezoelectric properties. Importantly, the piezoelectric coefficient, d₃₃, of our optimal P(VDF‐TrFE) films after sufficient poling treatment was 36 pC/N and our P(VDF‐TrFE) power generator produced an output voltage of ～6 V under periodic bending and unbending motions. POLYM. ENG. SCI., 54:466–471, 2014. © 2013 Society of Plastics Engineers     

Large Piezoelectricity and Ferroelectricity in Mn‐Doped (Bi0.5Na0.5)TiO3‐BaTiO3 Thin Film Prepared by Pulsed Laser Deposition

Mn‐doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (MnBNBT) thin films were prepared on SrRuO₃ (SRO)‐coated (001) SrTiO₃ (STO) single crystal substrates by pulsed laser deposition under different processing conditions. Structural characterization (i.e., XRD and TEM) confirms the epitaxial growth of STO/SRO/MnBNBT heterostructures. Through the judicious control of deposition temperature, the defect level within the films can be finely tuned. The MnBNBT thin film deposited at the optimized temperature exhibits superior ferroelectric and piezoelectric responses with remanent polarization P_r of 33.0 μC/cm² and piezoelectric coefficient d₃₃ of 120.0 ± 20 pm/V.     

Effect of processing parameters of the continuous wet spinning system on the crystal phase of PVDF fibers

Poly(vinylidene difluoride) (PVDF) has been widely used in piezoelectric applications as films and nanofiber mats, but there are limited publications on piezoelectric wet‐spun fibers. In this work, PVDF fibers were prepared using the wet spinning method, and the processing parameters, including the drawing ratio and heat setting temperature, were controlled in the continuous wet spinning system to increase the β‐phase crystallinity of the fibers. In addition, the wet‐spun PVDF fibers were compressed by a rolling press to eliminate voids in the fibers. Then, the compressed PVDF fibers were poled to align the molecular dipoles. The crystal structures of the PVDF fibers were investigated using X‐ray diffraction and Fourier‐transform infrared spectroscopy. Single filament tensile tests were performed to measure the tensile strength of the fibers. The morphologies of the PVDF fibers with respect to the processing parameters were observed by scanning electron microscope (SEM) and polarization optical microscopy. The piezoelectric constant of the prepared PVDF fibers was then measured using a d₃₃ meter. The wet‐spun PVDF fibers showed the highest β‐phase and piezoelectric constants when the drawing ratio and heat setting temperature were 6 and 150 °C, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45712.     

Influence of LNO Top Electrodes on Electrical Properties of KNN/LNO Thin Films Prepared by RF Magnetron Sputtering

Highly (001) oriented (K,Na)NbO₃ (KNN) lead‐free piezoelectric thin films were grown on LaNiO₃ (LNO)‐coated silicon by RF magnetron sputtering. The effects of the top electrodes on the electrical properties of KNN thin films were investigated. The dielectric and piezoelectric properties were remarkably improved in LNO/KNN/LNO (ε_r = 899 at 1 kHz, d₃₃ = 58 pm/V), compared with that in Pt/KNN/LNO (ε_r = 584 at 1 kHz, d₃₃ = 26 pm/V). An enhanced ferroelectricity was also obtained in LNO/KNN/LNO, with a remnant polarization of 12 μC/cm² and a maximum polarization of 23 μC/cm² at the applied field of 200 kV/cm. Besides, the temperature dependence of piezoelectricity of the films was characterized in this study.     

New piezoelectric damping composites of poly(vinylidene fluoride) blended with clay and multi‐walled carbon nanotubes

Damping materials are used to control mechanical vibrations, and piezoelectric damping composite is a very promising material due to its unique mechanism. In this study, a potential piezoelectric damping composite was developed by simply melt mixing poly(vinylidene fluoride) (PVDF) with small amounts of organic modified montmorillonite (OMMT) and multi‐walled carbon nanotubes (MWCNTs). The piezoelectric, mechanical and electrical properties were investigated using a dynamic mechanical analyser, direct current electrical resistivity measurements, X‐ray diffraction, Fourier transform infrared spectroscopy and the direct quasi‐static d₃₃ piezoelectric coefficient method. It was found that the damping property of PVDF can be greatly improved by adding both MWCNTs and OMMT, and the composite containing 1.9 wt% of MWCNTs and 3 wt% of OMMT showed the best damping property. A model and an approximate calculation were applied to explain the improved damping property. Moreover, similar mechanical properties of PVDF composites were observed in the tensile testing and dynamic mechanical analyser measurements. Copyright © 2012 Society of Chemical Industry     

PNN‐PZN‐PMN‐PZ‐PT Multilayer Piezoelectric Ceramic with Low Sintering Temperature

Multilayer piezoelectric ceramic material with a composition of 0.1Pb(Ni_1/3Nb_2/3)O₃‐0.35Pb(Zn_1/3Nb_2/3)O₃‐0.15Pb(Mg_1/3Nb_2/3)O₃‐0.1PbZrO₃‐0.3PbTiO₃‐4 mol% excess NiO (0.1PNN‐0.35PZN‐0.15PMN‐0.10PZ‐0.3PT‐0.04NiO) was fabricated by a roll‐to‐roll tape casting process and co‐fired with Ag/Pd electrode at low temperature of 950°C. Their dielectric, piezoelectric, and ferroelectric properties were evaluated. The effective piezoelectric coefficient d₃₃ of the obtained multilayer piezoelectric material was 412 pm/V, while d₃₃ for the ceramic pellet was 503 pm/V. Piezoelectric displacement measurements revealed small displacement hysteresis for the multilayer material. The combined characteristics of the multilayer piezoelectric material using the selected composition showed the potential for high power, high strain, and high force actuation applications. In addition, as the composition had a tetragonal phase, which substantially deviated from morphotropic phase boundary (MPB), the excellent properties may be more tolerant to stoichiometric fluctuation, which can allow larger processing and composition window as desired for scalable production.     

Polypropylene/clay nanocomposites prepared by in situ grafting‐melt intercalation with a novel cointercalating monomer

Polypropylene (PP)/clay nanocomposites were prepared by melt‐compounding PP with organomontmorillonite (OMT), using maleic anhydride grafted polypropylene (PP‐g‐MA) as the primary compatibilizer and N‐imidazol‐O‐(bicyclo pentaerythritol phosphate)‐O‐(ethyl methacrylate) phosphate (PEBI) as the cointercalating monomer. X‐ray diffraction patterns indicated that the larger interlayer spacing of OMT in PP was obtained due to the cointercalation monomer having a large steric volume and the d‐spacing further increased with the addition of PP‐g‐MA, as evidenced by transmission electron microscopy. Thermogravimetric analysis revealed that the PEBI‐containing PP nanocomposites exhibited better thermal stability than PEBI‐free PP composites. Dynamic mechanical analysis demonstrated that the storage modulus was significantly enhanced, and the glass transition temperature (T_g) shifted slightly to low temperature with the incorporation of clay for PP/OMT hybrids. PEBI‐containing PP/OMT composites gave a lower T_g value because of the strong internal plasticization effect of PEBI in the system. Cone calorimetry showed that the flame‐retardancy properties of PP nanocomposites were highly improved with the incorporation of PEBI. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Natural weathering of polypropylene films. II. Ultimate properties and exposure time

Changes in the ultimate properties brought about by outdoor weathering during the rainy season of polypropylene (PP) films were studied. The results obtained showed that the draw ratio λ_d, tensile stress σ_b, breaking ratio λ_b, breaking factor (BF), work draw U_d, and work for rupture U_r all increased with increase in outdoor exposure time, attaining a maximum at about 240-h exposure time, before decreasing with further increases in exposure time. On the other hand, the draw ratio δ_s remained practically constant up to about 100-h exposure time. The changes in the former set of properties were corroborated by the changes in the apparent crystallinity of the PP samples. In addition, it was shown that a 504-h exposure time was not enough to reduce the properties to damaging levels. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2533–2540, 1998