PVDF Research Articles

Flexible pressure sensor based on thermoplastic polyurethane/polyvinylidene fluoride nanofiber membranes

The mechanical flexibility of flexible sensors primarily originates from sensitive flexible materials. Therefore, the key to developing new flexible mechanical sensors lies in constructing high-performance sensitive flexible materials. In this study, we employ a coaxial electrostatic spinning technique to prepare thermoplastic polyurethane (TPU)/polyvinylidene fluoride (PVDF) nanofiber membranes (NFM) with a core–shell structure for the construction of flexible piezoelectric mechanosensors. The utilization of TPU/PVDF NFM in flexible mechanosensors for human health monitoring and environmental sensing is investigated. As a result, the excellent performance of this composite membrane was demonstrated by its high mechanical strength and flexibility, resulting in high sensitivity (GF: 0.42 V/kPa), low response time (100 ms), and wide sensing range (0.2∼5.0 kPa). Additionally, The TPU/PVDF NFM not only demonstrates excellent pressure sensing performance but also exhibits exceptional capabilities for human body sensing applications. Therefore, these results highlight that the TPU/PVDF NFM exhibits excellent pressure-sensing properties and holds significant potential for applications in the fields of flexible robotics and wearable devices such as human-computer interfaces, intelligent healthcare systems, and artificial intelligence skin technologies.

Scaffold-Based Poly(Vinylidene Fluoride) and Its Copolymers: Materials, Fabrication Methods, Applications, and Perspectives.

Tissue engineering involves implanting grafts into damaged tissue sites to guide and stimulate the formation of new tissue, which is an important strategy in the field of tissue defect treatment. Scaffolds prepared in vitro meet this requirement and are able to provide a biochemical microenvironment for cell growth, adhesion, and tissue formation. Scaffolds made of piezoelectric materials can apply electrical stimulation to the tissue without an external power source, speeding up the tissue repair process. Among piezoelectric polymers, poly(vinylidene fluoride) (PVDF) and its copolymers have the largest piezoelectric coefficients and are widely used in biomedical fields, including implanted sensors, drug delivery, and tissue repair. This paper provides a comprehensive overview of PVDF and its copolymers and fillers for manufacturing scaffolds as well as the roles in improving piezoelectric output, bioactivity, and mechanical properties. Then, common fabrication methods are outlined such as 3D printing, electrospinning, solvent casting, and phase separation. In addition, the applications and mechanisms of scaffold-based PVDF in tissue engineering are introduced, such as bone, nerve, muscle, skin, and blood vessel. Finally, challenges, perspectives, and strategies of scaffold-based PVDF and its copolymers in the future are discussed.

Kirigami-inspired, three-dimensional piezoelectric pressure sensors assembled by compressive buckling

Piezoelectric sensors whose sensing performances can be flexibly regulated hold significant promise for efficient signal-acquisition applications in the healthcare field. The existing methods for regulating the properties of polyvinylidene fluoride (PVDF) films mainly include material modification and structural design. Compared to material modification, which has a long test period and an unstable preparation process, structural design is a more efficient method. The irigami structure combined with compressive buckling can endow the flexible film with rich macrostructural features. Here, a method is fabricated to modulate the sensing performance by employing distinct 3D structures and encapsulation materials with varying Young’s moduli. The relationship among the aspect ratio (α), pattern factor (η), elastic modulus of encapsulation materials, and equivalent stiffness is obtained by finite element simulation, which provides theoretical guidance for the design of the 2D precursor and the selection of encapsulation materials. In the demonstration applications, the sensor accurately captures pulse waveforms in multiple parts of the human body and is employed for the pressure monitoring of different parts of the sole under various posture states. This method of structure design is efficient, and the preparation process is convenient, providing a strategy for the performance control of piezoelectric pressure sensors.

Environmentally Friendly Photothermal Membranes for Halite Recovery from Reverse Osmosis Brine via Solar-Driven Membrane Crystallization

Modern society and industrial development rely heavily on the availability of freshwater and minerals. Seawater reverse osmosis (SWRO) has been widely adopted for freshwater supply, although many questions have arisen about its environmental sustainability owing to the disposal of hypersaline rejected solutions (brine). This scenario has accelerated significant developments towards the hybridization of SWRO with membrane distillation–crystallization (MD-MCr), which can extract water and minerals from spent brine. Nevertheless, the substantial specific energy consumption associated with MD-MCr remains a significant limitation. In this work, energy harvesting was secured from renewables by hotspots embodied in the membranes, implementing the revolutionary approach of brine mining via photothermal membrane crystallization (PhMCr). This method employs self-heating nanostructured interfaces under solar radiation to enhance water evaporation, creating a carefully controlled supersaturated environment responsible for the extraction of minerals. Photothermal mixed matrix photothermal membranes (MMMs) were developed by incorporating graphene oxide (GO) or carbon black (CB) into polyvinylidene fluoride (PVDF) solubilized in an eco-friendly solvent (i.e., triethyl phosphate (TEP)). MMMs were prepared using non-solvent-induced phase separation (NIPS). The effect of GO or GB on the morphology of MMMs and the photothermal behavior was examined. Light-to-heat conversion was used in PhMCr experiments to facilitate the evaporation of water from the SWRO brine to supersaturation, leading to sodium chloride (NaCl) nucleation and crystallization. Overall, the results indicate exciting perspectives of PhMCr in brine valorization for a sustainable desalination industry.

Controlled Molecular Orientation through Intercalation in PVDF Thin Films: Exhibiting Ultralong Retention and Improved Leakage Current.

Ferroelectric switching and retention performance of poly(vinylidene fluoride) (PVDF) thin films improve by the incorporation of unmodified smectite montmorillonite (MMT) clay nanodielectric. In the present study, an intercalated PVDF (clay/PVDF) thin film with edge-on β-crystallite is fabricated via a heat-controlled spin coating (HCSC) technique. This provides an efficient and simple way to fabricate the edge-on oriented crystallite lamellae with an electroactive β-phase, facilitating nanoscale ferroelectric switching at a lower voltage compared to the face-on orientation. Here, we demonstrate the polarization retention for periods longer than 20 days (∼480 h, i.e., 1.8 × 106 s), with no degradation in switched nanoscale domains. In addition, by maintaining the relatively high dielectric constant, the incorporation of nanoclay effectively lowers the leakage current by 102 factors. The obtained memory window in the edge-on orientation is 7 V, approximately twice the memory window obtained in the face-on orientation. In short, our findings provide a simple and promising route to fabricate edge-on oriented PVDF thin films, with ultralong retention, high dielectric constant, and improved leakage current.

Characterization and calibration of a piezo-energetic composite film as a reactive gauge

The field of multifunctional energetics encompasses a range of materials including propellants, explosives, and pyrotechnics that possess the ability to be manipulated through various characteristics that can be switched between go and no-go, or those that have controllable energy release levels or have additional functions beyond energetic output. The development of multifunctional energetics harnessing electromechanical or piezoelectric properties of polymeric materials or binder systems has garnered increasing interest in recent years. Among polymers, fluoropolymers such as poly(vinylidene fluoride) (PVDF) and copolymers such as poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)], which are used as the binder and oxidizer in the energetic formulations, have demonstrated the highest piezoelectric coefficients. In this study, we fabricated piezo-energetic composite films using aluminum nanopowders (10 wt. % active content) as fuel and P(VDF-TrFE) (70/30) as an oxidizer and investigated the piezoelectric response using a small-scale drop weight setup. Additionally, we employed a shaker setup to investigate the response of the films to vibrations. Our findings demonstrate that these piezo-energetic films can replicate the behavior of a commercial PVDF gauge at relatively low-pressure impacts, indicating their potential use as shock or pressure sensors in various fields, as well as an accelerometer gauge. Additionally, aging studies of up to one year indicated minimal loss in the energetic content of the created films, enabling the use of energetic gauges for an extended period. Our findings support the effectiveness of piezo-energetic composite films as pressure sensors or accelerometers and highlight their potential for energetic applications.

Variations in the Ferroelectricity and Piezoelectricity of Poly(vinylidene fluoride) Accompanying the Phase Transformation

Variations in the Ferroelectricity and Piezoelectricity of Poly(vinylidene fluoride) Accompanying the Phase Transformation

Multiscale Polyvinylidene Fluoride/Magnesium–Aluminum Layered Double Hydroxide Gel Electrolytes for Lithium Batteries

A multiscale of porous polyvinylidene fluoride–hexafluoropropylene copolymer/magnesium–aluminum layered double hydroxides (MgAl‐LDHs) composite gel polymer electrolyte is prepared by phase separation method. It is discovered that the ionic conductivity of the electrolyte reaches a maximum value of 1.36 × 10−3 S cm−1, the lithium ions’ mobility is 0.66, and the chemical performance is steady within the 4.85 V window along with the concentration of MgAl‐LDHs up to 0.4 wt% at room temperature. The density functional theory calculations show that the adsorption energy of Li+ with MgAl‐LDH is −3.59 eV and the diffusion potential barrier is 0.37 eV, which is favorable for the dissociation and transport of Li+. Moreover, the anode's initial discharge capacity at 0.1 C achieves 144 mAh g−1, keeping 84.7% of the theoretical capacity of 170 mAh g−1, and the capacity retention and the columbic efficiency maintain 92.4% and 95.7% after 100 cycles at 0.2 C, respectively, through assembling into a Li/PVP–MgAl/LiFePO4 battery.

Study of the high-energy alpha particles influence on the styrene accumulation kinetics and functional groups during the synthesis of proton-exchange membranes based on PVDF.

The study investigates the effect of alpha irradiation on the graft copolymerization of styrene with polyvinylidene fluoride (PVDF). Using methods of radiation-chemical modification, a proton exchange membrane (PEM) with a uniform distribution of functional sulfate groups throughout the entire volume was developed. Grafting of styrene was carried out at different temperatures and solution concentrations. Functional sulfo-groups were added to the graft polymer by sulfonation, with the addition of solvents. The degree of grafting (DG), water absorption (W) and exchange capacity (IEC) correlate well with the absorbed dose and alpha particle fluence. Research into this method will allow us to develop an affordable industrial technology for widespread implementation.

PVDF‐Based Electrospun Nanofibers for Oil/Water Separation: A Review

AbstractThe rising widespread oil‐impacted wastewater warrants an urgent call for innovative approaches to the handling of oily wastewater. A variety of techniques has been investigated to treat oil‐impacted water, and they are found to be inefficient. Electrospun nanofibers emerge as the viable technique to treat oily wastewater precisely owing to their high specific surface areas and interconnected nanoscale pore structures. In this review, a brief background on the study is provided followed by the environmental pollution by the oily wastewater. Subsequent to that, the polyvinylidene fluoride (PVDF) modification methods are also presented followed by the physicochemical properties of both the electrospun PVDF blends and the PVDF‐based composites. Furthermore, the performances of the PVDF‐based composites in oil/water separation are described. It is concluded with the future prospects for using PVDF‐based composites for oil/water separation.

Enhancing piezoelectric properties of PVDF-HFP composite nanofibers with cellulose nanocrystals

With the increasing interest in flexible self-powering energy devices, piezoelectric polymers such as poly(vinylidene fluoride) (PVDF), PVDF-trifluoroethylene (PVDF-TrFE and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) have garnered substantial research attention. Among these, PVDF-HFP has demonstrated immense research potential in harvesting mechanical energy and converting it to electric energy. It is also particularly attractive due to its low cost compared to some other PVDF co-polymers. In this study, PVDF-HFP nanofibers were produced by electrospinning with cellulose nanocrystal (CNC) employed as a filler to improve their piezoelectric performance. Smooth and bead-free fibers were obtained with up to 1 wt% of CNC in the solution. The inclusion of CNC increased the uniformity of fiber diameter and improved thermal stability. Higher CNC concentration (2–3 wt%) engendered agglomeration and adversely impacted the conversion of non-polar phase to electroactive phase for PVDF-HFP molecules. At the optimal CNC concentration of 1 wt%, the voltage and current sensitivities for 1 cm2 samples were obtained as 0.146±0.048 mV/mN and 0.009±0.003 nA/mN, respectively. The open-circuit voltage output of 2.69±1.11 V was achieved under an average impact force of 40 N, and this increased with increased magnitude and frequency of the applied force. The mechanical properties of composite nanofibers maximized at 0.5 wt% CNC with tensile strength of 37.85±4.35 MPa, elastic modulus of 124.96±42.17 MPa, and strain at failure of 82.32±14.84 %. The improved piezoelectric and mechanical properties of the CNC-aided electrospun PVDF-HFP fibers will open new pathways for flexible energy harvesting systems.

Influence of non-woven antistatic substrate materials on polyvinylidene fluoride electrospun nanofibers: fabrication, characterization, and performance evaluation

Influence of non-woven antistatic substrate materials on polyvinylidene fluoride electrospun nanofibers: fabrication, characterization, and performance evaluation

Charging Properties of Electrospun Poly(l‐lactic acid) Submicrofiber Mat and Its Electrical Applications

Wearable pressure sensors have attracted significant attention owing to their potential applications in health monitoring and connectivity to internet‐based apps. Polymers such as poly(vinylidene fluoride) have been used in sensors. However, being petroleum‐derived materials, they do not decompose and remain in the soil when disposed. Poly(l‐lactic acid) (PLLA) is a promising material because of its biodegradable nature and its derivation from plant‐based materials. In addition, the electrospun PLLA fiber mat contains real charges and exhibits electromechanical properties. However, the detailed charging properties of the PLLA fiber mats remain unclear. Herein, the charge distribution of these fiber mat is presented, and a charging model of the fiber mat and a numerical model of the output charges from the fiber mats with electrodes are proposed. Additionally, the retention properties of the stored charges are determined using surface potential measurements at different temperatures. In addition, a self‐power‐generating touch sensor and mask‐type sensor are developed using biodegradable materials produced from biomass. These studies contribute to the improvement in the charge properties of PLLA fiber mats and the resulting wearable biodegradable sensors.

Poling induced changes in polarization domain structure of polymer ferroelectrics for application in organic thin film transistors

While electrical poling of organic ferroelectrics has been shown to improve device properties, there are challenges in visualizing accompanying structural changes. We observe poling induced changes in ferroelectric domains by applying differential phase contrast (DPC) imaging in the scanning transmission electron microscope, a method that has been used to observe spatial distributions of electromagnetic fields at the atomic scale. In this work, we obtain DPC images from unpoled and electrically poled polyvinylidene fluoride trifluorethylene films and compare their performance in polymer thin film transistors. The vertically poled films show uniform domains throughout the bulk compared to the unpoled film with a significantly higher magnitude of the overall polarization. Thin film transistors comprising a donor–acceptor copolymer as the active semiconductor layer show improved performance with the vertically poled ferroelectric dielectric film compared with the unpoled ferroelectric dielectric film. A poling field of 80–100 MV/m for the dielectric layer yields the best performing transistors; higher than 100 MV/m is seen to degrade the transistor performance. The results are consistent with a reduction in deleterious charge carrier scattering from ferroelectric domain boundaries or interfacial dipoles arising from electrical poling.

Efficient Dye Extraction from Wastewater Using Indium-MOF-Immobilized Polyvinylidene Fluoride Membranes with Selective Filtration for Enhanced Remediation.

Industrial activities have led to releasing harmful substances into the environment, necessitating the elimination of these toxic compounds from wastewater. Organic dyes, commonly found in industrial effluents, pose a threat to ecosystems and human health. Conventional treatment methods often suffer from limitations such as high cost and poor efficiency. Metal-organic frameworks (MOFs) have emerged as promising materials for selective separation, including membrane filtration (MF). Mixed-matrix membranes (MMMs) combining MOFs with polymers offer improved filtration properties. In this study, MMMs were fabricated by incorporating synthesized In-MOF with a polyvinylidene fluoride (PVDF) polymer (In-MOF@PVDF MMMs) using the nonsolvent-induced phase separation process. The MMMs were evaluated for the MF of various organic dyes, achieving notable removal efficiencies. The membrane containing 20% In-MOF (M4) demonstrated exceptional performance, removing 99% of the methylene blue (MB) dye. Additionally, membrane M4 effectively filtered Azure A (AZA), Azure B (AZB), and toluidine blue O (TOLO) with a removal efficiency of 99%. However, for Rhodamine B (RHB) and methyl orange (MO), the removal efficiencies were slightly lower at 74 and 39%, respectively. Further, these membranes are utilized in selective dye filtration in the MB+/RHB+ and MB+/MO- systems, where the selectivity was found for MB. The isothermal and DFT studies revealed the membrane's behavior with dye mixtures, while water stability and regeneration studies confirmed its durability. Thus, these findings highlight the potential of In-MOF@PVDF MMMs for effective and selective dye removal in wastewater treatment applications.

Enhancing thermal conductivity and electromagnetic shielding performance of Ni-CNT/Al2O3/PVDF composite film with a multi-layered structure

To develop thermal interface materials with both high thermal conductivity and electromagnetic interference shielding, the polyvinylidene fluoride (PVDF) composite film was prepared by electrospinning and hot-pressing, using strategies of multi-layered structure and two fillers synergy of nickel modified carbon nanotube (Ni-CNT) and Al2O3 microspheres. The composite film consisted of a Ni-CNT filled PVDF electrospun fiber film as the top and bottom surface layers, and a PVDF electrospun fiber film electrostatically adsorbing Al2O3 microspheres and surface-sprayed with Ni-CNT as the middle layer. At a 20 wt% Ni-CNT in the surface layers and a 16.7 wt% Al2O3 and 5 wt% Ni-CNT in the middle layer, the composite film with a thickness of 0.1 mm exhibited optimal performances with electromagnetic wave shielding efficiency of 65 dB in the frequency range of 8.2–12.4 GHz, with 86% of the electromagnetic waves being absorbed. At the same time, the composite film had a high in-plane thermal conductivity of 4.02 W m−1 K−1, while maintaining a tensile strength of 25 MPa and flexibility.

Sea and brackish water desalination through a novel PVDF-PTFE composite hydrophobic membrane by vacuum membrane distillation

The present study aims to evaluate the performance of porous hydrophobic Polyvinylidene fluoride − Polytetrafluoroethylene (PVDF-PTFE) composite membranes for desalination by vacuum membrane distillation (VMD) technique. The effect of operating parameters such as feed NaCl concentration (10,000 to 40,000 mg/L), feed temperature (50 °C to 80 °C), and downstream pressure (80 to 120 mmHg) on water permeation rate was studied. The increase in feed temperature enhanced the water permeation rate due to a rise in driving force across the membrane. For a constant downstream pressure of 80 mmHg, feed temperature of 80 °C and feed flow rate of 80 L/h, the membrane exhibited a maximum water flux of 3 kg/m2h with 99.86% salt rejection when aqueous NaCl concentration of 10,000 mg/L was charged as feed. Membrane characterization was performed using various analytical tools to determine physico-chemical properties such as pore size, structural elucidation, thermal stability, crystallinity, and hydrophobicity of the membrane material. Further, a temperature and concentration polarization coefficient-based analysis was performed by solving the mass and heat transport model equations using MATLAB software. The proposed research study promotes the application of VMD for recovering potable water from highly saline sea/brackish water and alleviates brine disposal issues.

Investigation of the effect of permeation and antifouling characteristics of hybrid poly(vinylidene fluoride) membranes tailored with ZIF‐67 metal–organic frameworks

AbstractHerein the ZIF‐67, a hydrophilic cobalt‐based zeolitic imidazolate framework is synthesized and incorporated with a poly(vinylidene fluoride) (PVDF) to fabricate hybrid ultrafiltration membranes by phase inversion method. The characteristics of PVDF/ZIF‐67 membranes are examined using different analytical techniques such as Fourier‐transform infrared spectroscopy, X‐ray diffractometer, scanning electron microscope, atomic force microscope, and contact angle analysis. The membrane performance is probed using pure water flux (PWF), bovine serum albumin (BSA), and humic acid (HA) rejection. The maximum water flux of 162.5 Lm2 h−1 with BSA and HA rejection of 97% and 98.2%, respectively, exhibited by 1.5 wt% ZIF‐67. The contact angle value is reduced from 83.5 to 58.6° indicating the increase in hydrophilic nature of PVDF membranes by the addition of ZIF‐67. The presence of ZIF‐67 in the PVDF membrane matrix showed outstanding anti‐bacterial properties against Escherichia coli and Staphylococcus aureus. Overall, the PVDF/ZIF‐67 ultrafiltration membranes demonstrate the potential for water treatment applications.

Resource Recovery of Spent Lithium-Ion Battery Cathode Materials by a Supercritical Carbon Dioxide System.

The increasing global market size of high-energy storage devices due to the boom in electric vehicles and portable electronics has caused the battery industry to produce a lot of waste lithium-ion batteries. The liberation and de-agglomeration of cathode material are the necessary procedures to improve the recycling derived from spent lithium-ion batteries, as well as enabling the direct recycling pathway. In this study, the supercritical (SC) CO2 was innovatively adapted to enable the recycling of spent lithium-ion batteries (LIBs) based on facilitating the interaction with a binder and dimethyl sulfoxide (DMSO) co-solvent. The results show that the optimum experimental conditions to liberate the cathode particles are processing at a temperature of 70 °C and 80 bar pressure for a duration of 20 min. During the treatment, polyvinylidene fluoride (PVDF) was dissolved in the SC fluid system and collected in the dimethyl sulfoxide (DMSO), as detected by the Fourier Transform Infrared Spectrometer (FTIR). The liberation yield of the cathode from the current collector reaches 96.7% under optimal conditions and thus, the cathode particles are dispersed into smaller fragments. Afterwards, PVDF can be precipitated and reused. In addition, there is no hydrogen fluoride (HF) gas emission due to binder decomposition in the suggested process. The proposed SC-CO2 and co-solvent system effectively separate the PVDF from Li-ion battery electrodes. Thus, this approach is promising as an alternative pre-treatment method due to its efficiency, relatively low energy consumption, and environmental benign features.

Enhanced Photocatalytic and Filtration Performance of TiO2-Ag Composite-Coated Membrane Used for the Separation of Oil Emulsions

Polyvinylidene fluoride (PVDF) membranes were coated with TiO2 and TiO2-Ag to enhance their efficiency for oil-in-water emulsion separation. The photocatalytic activities of the two modified membranes and their filtration performances were compared in detail. The significantly enhanced photocatalytic activity of the TiO2-Ag composite was proved using a methyl orange (MO) solution (c = 10−5 M) and a crude oil emulsion (c = 50 mg·L−1). The TiO2-Ag-coated membrane reduced the MO concentration by 87%, whereas the TiO2-modified membrane reached only a 46% decomposition. The photocatalytic reduction in the chemical oxygen demand of the emulsion was also ~50% higher using the TiO2-Ag-coated membrane compared to that of the TiO2-coated membrane. The photoluminescence measurements demonstrated a reduced electron/hole recombination, achieved by the Ag nanoparticle addition (TiO2-Ag), which also explained the enhanced photocatalytic activity. A significant improvement in the oil separation performance with the TiO2-Ag-coated membrane was also demonstrated: a substantial increase in the flux and flux recovery ratio (up to 92.4%) was achieved, together with a notable reduction in the flux decay ratio and the irreversible filtration resistance. Furthermore, the purification efficiency was also enhanced (achieving 98.5% and 99.9% COD and turbidity reductions, respectively). Contact angle, zeta potential, scanning electron microscopy (SEM), and atomic force microscopy (AFM) measurements were carried out to explain the results. SEM and AFM images revealed that on the TiO2-Ag-coated membrane, a less aggregated, more continuous, homogeneous, and smoother nanolayer was formed due to the ~50% more negative zeta potential of the TiO2-Ag nanocomposite compared to that of the TiO2. In summary, via Ag addition, a sufficiently hydrophilic, beneficially negatively charged, and homogeneous TiO2-Ag-coated PVDF membrane surface was achieved, which resulted in the presented advantageous filtration properties beyond the photocatalytic activity enhancement.