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64 records · Page 4

Giant piezoelectricity in fluoropolymer fiber mats achieved by corona poling in water

Polymer piezoelectrics hold great potential for energy harvesting and wearable electronics. Efforts have been dedicated to enhancing piezoelectric coefficients and thermostability for several decades, but most of these have not been successful. In this report, we demonstrate a straightforward way to achieve high piezoelectric coefficients and output voltages while maintaining high thermostability at temperatures over 110 °C. Poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] 80/20 mol.% nanofiber mats (made by electrospinning) with extremely high crystallinity and Curie temperatures were obtained via a two-step annealing process, from which large ferroelectric domains were formed in extended-chain crystals. After corona poling using water, which is a high dielectric constant medium, giant piezoelectricity (apparent d 33 = 1045 ± 20 pC/N) and high output voltages (29.9 ± 0.5 V) were achieved. It is found that the dimensional effect induced significant polarization changes, which is the key requirement for piezoelectricity. Our finding in this work paves a way to further improve high-performance polymer piezoelectrics.

36 MATERIALS SCIENCE↗

Mechanisms of direct and converse piezoelectricity in ferroelectric polymers

Within the linear regime of mechanical and electrical responses, it is commonly accepted that direct and converse piezoelectric coefficients should be the same. However, we observed a consistently higher converse d 31 (∼54 pm/V) than the direct d 31 (∼42 pC/N) for a quenched, stretched, annealed, and electrically poled poly(vinylidene fluoride-co-trifluorethylene) [P(VDF-TrFE)] 52/48 mol.% sample (abbreviated as coP-52/48QSAP). On the contrary, the direct and converse d 31 values were the same for coP-65/35QSAP and coP-55/45QSAP. Small-angle X-ray scattering results showed that coP-52/48QSAP had a higher amount of relaxor-like secondary crystals (SCs) in the oriented amorphous fraction (OAF) (SC OAF ) than coP-55/45QSAP and coP-65/35QSAP. To explain the experimental observation, we performed molecular dynamics (MD) simulation of the pure PVDF (without TrFE) to estimate direct and converse piezoelectricity for the PVDF OAF. Based on the MD simulation, the direct d 31 had a plateau value around 350 pC/N for the transverse (i.e., along the chain direction) strain up to 1 %, whereas the simulated converse d 31 could be lower (for electric field E < 0.8 MV/m), equal (for E = 0.8 MV/m), or higher (for E > 0.8 MV/m) than the direct d 31 , depending on the poling electric field. From the MD simulation, both mechano-electrostriction and electrostatic interaction were identified in the OAF as the driving force for enhanced piezoelectricity in ferroelectric PVDF. In conclusion, when ferroelectric domains were formed in the OAF by electric poling, the simulated converse d 31 became higher than the direct d 31 . Combining both experimental and MD simulation results, the higher converse d 31 than direct d 31 for coP-52/48QSAP was understood qualitatively.

36 MATERIALS SCIENCE↗

Fabrication of Piezoelectric Polymer and Metal–Organic Framework Composite Thin Films Using Solution Shearing

Polymer-metal–organic framework (polymer-MOF) composites have garnered significant interest as polymers can enhance the processability and industrial applicability of MOFs. Thin films of these composites are particularly attractive for applications in sensing, separations, and flexible electronics. Solution shearing, a meniscus-guided coating technique, has emerged as a scalable process for fabricating thin films of MOFs, and can produce large-area films within minutes. In this study, we utilized solution shearing to fabricate composite thin films of a MOF UiO-66 and a piezoelectric polymer poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), investigating how polymer concentration during MOF synthesis and composite formation influences thin film properties, including crystallinity, surface coverage, and piezoelectric performance. Additionally, solid-state NMR spectroscopy was utilized to probe the interactions between P(VDF-TrFE) and UiO-66 in the composite. Evidence from solid-state NMR indicated polymer-MOF interactions, suggesting that the polymer strands are in close proximity to the UiO-66 pores, supporting a mixed surface coating and pore infiltration model. Furthermore, incorporating P(VDF-TrFE) enhanced the film’s areal coverage from 70% to 100%. While the thermal conductivity remained essentially unchanged, the composite film showed an improved piezoelectric effect. The composite with 91 wt % P(VDF-TrFE) exhibited the highest output voltage of 9.1 V and a sensitivity of 0.26 V/N under applied pressure. This work demonstrates the potential of solution shearing as a scalable technique for fabricating polymer-MOF composite thin films.

P(VDF-TrFE)↗

Distinct Mechanism of Anti-Corrosion and Swelling-Adhesion Modeling of Low-Dimensional Nylon-Fluoropolymer Composite Coatings

Compared to other polymers, composite coatings with fluoropolymers as the matrix have attracted considerable interest due to their mechanical performance, chemical stability, and low surface energy. Herein, we present an anticorrosion mechanism of fluoropolymer composite coatings achieved by dispersing varying amounts of polyamide 12 (PA-12) particles over a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The choice of PVDF-HFP as a coating matrix was driven by its superior processability and mechanical properties over Teflon, while PA-12 afforded swelling capacity, preventing electrolyte permeation, and inhibiting matrix stress crack propagation. The corrosion resistance of the coatings was assessed mainly by potentiodynamic polarization and impedance measurements while being immersed in a NaCl solution. Our electrochemical measurement findings showed that 0.75% w/w PA-12 in the PVDF-HFP matrix significantly enhanced corrosion protection even after 21 days of immersion. Microscopy, dielectric spectroscopy, surface analysis, and mechanical testing (American Society for Testing and Materials standards) corroborated the results. PVDF-HFP coatings containing a minimum percolation threshold of 0.75 wt % PA-12 with 1 mil thickness on mild steel exhibited a remarkable increase in resistance and film adhesion, and a notable corrosion rate decrease. Finite element analysis simulation with a bilinear traction-separation law confirmed the swelling mechanism and adhesion behavior. Finally, this study highlights the potential of nylon particle dispersion in PVDF-HFP matrices as a practical approach to developing advanced anticorrosion coatings with promising practical applications in various industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchal structures tuned electrocaloric and electromechanical performance in PVDF-based tetrapolymers

Ferroelectrics with multifunctionalities are gaining increased interest in self-actuated electrocaloric effect (ECE) refrigerators. However, achieving high ECE and electromechanical (EM) coupling concomitantly for maximum heat transfer remains challenging. Here we present the structure-property relationship for poly(vinylidene fluoride-co-trifluoroethylene-co-chlorofluoroethylene-co-double bond), P(VDF-TrFE-CFE-DB), tetrapolymer, which exhibited a high ECE entropy change of 66.5 J Kg −1 K −1 and EM strain of −6.1%. We show that thermal treatment can be a key factor influencing multifunctional properties. High-temperature annealing incorporates DB and CFE units into crystalline grains to form extended-chain crystals, enabling CFE units to induce relaxor behavior and DB units to induce large structural changes at low electric fields. This synergy leads to an enhancement in both ECE and EM performances. Furthermore, at an optimized temperature of 50 °C, the annealed films exhibit giant cross-energy coupling, achieving ECE and EM performances of 100.8 J Kg −1 K −1 and −7.6%. This study provides insights into developing new ferroelectric polymers with electroactive multifunctionalities.

36 MATERIALS SCIENCE↗

Toroidal polar topology in strained ferroelectric polymer

Polar topological texture has become an emerging research field for exotic phenomena and potential applications in reconfigurable electronic devices. Here, we report toroidal topological texture self-organized in a ferroelectric polymer, poly(vinylidene fluoride-ran-trifluoroethylene) [P(VDF-TrFE)], that exhibits concentric topology with anticoupled chiral domains. The interplay among the elastic, electric, and gradient energies results in continuous rotation and toroidal assembly of the polarization perpendicular to polymer chains, whereas relaxor behavior is induced along polymer chains. Such toroidal polar topology gives rise to periodic absorption of polarized far-infrared (FIR) waves, enabling the manipulation of the terahertz wave on a mesoscopic scale. Our observations should inform design principles for flexible ferroic materials toward complex topologies and provide opportunities for multistimuli conversions in flexible electronics.

36 MATERIALS SCIENCE↗

Relaxor ferroelectric polymer exhibits ultrahigh electromechanical coupling at low electric field

Electromechanical (EM) coupling—the conversion of energy between electric and mechanical forms—in ferroelectrics has been used for a broad range of applications. Ferroelectric polymers have weak EM coupling that severely limits their usefulness for applications. Here, we introduced a small amount of fluorinated alkyne (FA) monomers (<2 mol %) in relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) terpolymer that markedly enhances the polarization change with strong EM coupling while suppressing other polarization changes that do not contribute to it. Under a low–dc bias field of 40 megavolts per meter, the relaxor tetrapolymer has an EM coupling factor (k 33 ) of 88% and a piezoelectric coefficient (d 33 ) >1000 picometers per volt. These values make this solution-processed polymer competitive with ceramic oxide piezoelectrics, with the potential for use in distinct applications.

36 MATERIALS SCIENCE↗

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗

Theoretical Evaluation of Electroactive Polymer Based Micropump Diaphragm for Air Flow Control

An electroactive polymer (EAP), high energy electron irradiated poly(vinylidene fluoride-trifluoroethylene) [P(VDFTrFE)] copolymer, based actuation micropump diaphragm (PAMPD) have been developed for air flow control. The displacement strokes and profiles as a function of amplifier and frequency of electric field have been characterized. The volume stroke rates (volume rate) as function of electric field, driving frequency have been theoretically evaluated, too. The PAMPD exhibits high volume rate. It is easily tuned with varying of either amplitude or frequency of the applied electric field. In addition, the performance of the diaphragms were modeled and the agreement between the modeling results and experimental data confirms that the response of the diaphragms follow the design parameters. The results demonstrated that the diaphragm can fit some future aerospace applications to replace the traditional complex mechanical systems, increase the control capability and reduce the weight of the future air dynamic control systems. KEYWORDS: Electroactive polymer (EAP), micropump, diaphragm, actuation, displacement, volume rate, pumping speed, clamping ratio.

Xu, Tian-Bing↗

Optimizing the Fabrication of Electrospun Nanofibrous Membrane Using Fractional Factorial Design

Electrospinning, a simple and easily tunable technique that utilizes the force balance between the electrostatic force and the solution surface tension to fabricate membranes out of 1D nanostructured fibers, has garnered much interest especially from the nanotechnology community. Depending on the morphology of the fibers, electrospun membrane has found its way in a wide range of applications, such as oil-water separation, desalination, tissue engineering, and batteries. During an electrospinning process, many factors can affect the morphology of the products, such as viscosity of the solution, voltage supply, discharge distance, feed rate of the solution, and electrospinning time. In this work, we investigated the impacts of the most important parameters on the morphology of electrospun fibrous membrane based on the fractional factorial design. We evaluated the electrospun fibrous membrane morphology using scanning electron microscopy (SEM) and capillary flow porometry. Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was chosen for the current study due to its interesting and versatile functionalities including superior hydrophobicity, high free volume, and piezoelectricity. This work provides valuable insight for the fabrication of electrospun membranes, especially for tailoring membrane properties in accordance with any targeted applications.

Zhao, Yajing↗