PVDF Research Articles

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.

Uniaxially drawn poly (L-lactic acid)/ poly (vinylidene fluoride) polymer blend as a promising piezoelectric material: Hysteresis and resonance spectroscopy study

This study explores the potential for piezoelectricity in a blend of polyvinylidene fluoride (PVDF) and poly-L-lactic acid (PLLA) prepared using the solution casting method. Dielectric frequency measurements across a range of 102 to 106 Hz revealed piezoelectric resonance within a broader dielectric relaxation regime. Analysis of the resonance spectra for length and width vibrational modes enabled the determination of the piezoelectric tensor components of the PVDF/PLLA blend. The blend exhibited enhanced ferroelectric polarization reversal, remnant polarization, and coercive field compared to pristine PVDF samples. The piezoelectric constants d31 and d14 (d36 of the blend) were determined. Mechanical drawing and poling techniques were employed to generate multiple piezoelectric constants, allowing for efficient energy harvesting from various directions. This flexible blend offers promising prospects for versatile energy conversion applications.

Application of Pure and Modified Polyvinylidene Fluoride Materials for Wastewater Treatment Using UASB Reactor Technologies: A Review

Wastewater treatment is now required because of the problems caused by water constraints. Wastewater is anaerobically digested to produce biogas, which can be used as a source of energy for things like lighting and heating. The upflow anaerobic sludge blanket (UASB) reactor has been recognized as an important wastewater treatment technology among anaerobic treatment methods. Although their treated effluent typically does not meet most discharge criteria, UASB reactors are generally stated to have a chemical oxygen demand (COD) reduction ranging from 60 to 90% for most types of wastewater. In comparison to traditional anaerobic procedures, anaerobic municipal wastewater treatment using membranes can produce higher effluent quality in terms of COD, suspended solids (SSs) and pathogen counts, as well as a steady treatment performance to fulfill strict discharge regulations. The objective of this review was to perform a literature review on parameters to consider when selecting a membrane to include in a UASB reactor. Membranes that are available in the market were compared in terms of both physical and chemical properties. Polyvinylidene fluoride (PVDF) membranes were found be superior to the others, and their modification also reduced the fouling propensity. When comparing modified PVDF (PVDF/PVDF-g-PEGMA) to pristine PVDF (116 L·m−2 h−1), a higher pure water flux (5170 L·m−2 h−1) was noted. The main drawback of such modifications could significantly increase the final membrane production costs. Research is still lacking when it comes to research on comparing the membranes and PVDF and UASB reactor technology interaction, including effects of its modification as discussed (stability, longevity of improved flux, etc.

Antibacterial PVDF Coral-Like Hierarchical Structure Composite Film Fabrication for Self-Cleaning and Radiative Cooling Effect.

Passive radiative cooling (PRC) is a zero-energy-consumption technology that reflects sunlight and radiates heat to cold outer space. In this work, a porous poly(vinylidene fluoride)-poly(methyl methacrylate) (PVDF-PMMA) composite film is fabricated by decorating zinc-imidazolate metal-organic framework (MOF) (ZIF-8) particles obtained by phase inversion. Due to the competent scattering via the coral-like hierarchical structures and the vibration excitations of specific functional groups, the prepared film exhibits good solar reflectance (92.6%) and intermediate infrared emittance (99.1%), with an average sub-ambient cooling of 10.4 °C under a solar radiation intensity of 0.6 AM1.5. Additionally, poly(vinylidene fluoride) has a low surface energy, while the ZIF-8 particles and coral-like hierarchical structures enhance the surface roughness, endowing the surface with significant superhydrophobicity characterized by a water contact angle (WCA) of 157.5° and a sliding angle (SA) of 2°. These films exhibit excellent antibacterial properties. When the content of ZIF-8 particles in the film is 300 mg·L-1, the antibacterial rate reaches 100% after 1 h of treatment. Thus, the ZIF-8 porous poly(vinylidene fluoride)-poly(methyl methacrylate) composite (ZPPP) film has potential application prospects in areas with high health and environmental requirements, such as cold chain transportation and public spaces.

Enhanced magnetoelectric and energy storage performance of strain-modified PVDF-Ba0.7Ca0.3TiO3-Co0.6Zn0.4Fe2O4 nanocomposites

The experimental development of thin films that exhibit higher room-temperature low-field magnetoelectric (ME) sensing without compromising reliable electrical energy storage capabilities is rare. Here, an improved ferroelectric polarization, ME coupling and energy storage performance of polymer-based nanocomposites, which find applications in portable high-power dielectric capacitors, are studied. Multiferroic nanofiller-based three-phase flexible nanocomposites, polyvinylidene fluoride (PVDF)-(Ba0.7Ca0.3)TiO3-(Co0.6Zn0.4)Fe2O4, were fabricated using compression molding to enhance polarization which is pivotal for applications. PVDF with a high β-phase content (92.4 %), switchable ferroelectric behavior and higher breakdown strength (510 kV/mm) was obtained under optimized process conditions (500 MPa at 165 °C). The fabrication assisted alteration of intermolecular chain distance results in a tensile strain (1.42 %) of β-crystallites corresponding to an internal stress of ~21 MPa. The progressive increase of nanofiller content has led to enhanced polarization (11 μC/cm2), soft ferromagnetic properties, and enhanced ME coupling of 59 mV/cm-Oe due to switchable magnetostriction (λ11 = −18 ppm and dλ11/d = −22 × 10−9 Oe−1) at lower saturation field of 1.2 kOe. The ME sensitivity was found to be more than two-folds enhanced compared to solution-cast films making them prospective self-biased flexible devices for wearable electronics. Simultaneously, enhanced change of magnetization (19.6 %) under electric field was obtained. Detailed energy storage characteristics confirm that the nanofiller inclusion up to 7.12 vol% effectively improved the recoverable energy storage density (21.2 J/cm3) with an efficiency of 67 %. The experimental and simulation results corroborate a significantly improved breakdown strength of 617 kV/mm with reliable performance. Thus, careful processing provides viable polymer dielectrics with beneficial storage characteristics.

Strengthened Poly(vinylidene fluoride)/Epoxidized Natural Rubber Blend by a Reactive Compatibilizer Based on an Amino Acid-Modified Fluorocarbon Elastomer

Strengthened Poly(vinylidene fluoride)/Epoxidized Natural Rubber Blend by a Reactive Compatibilizer Based on an Amino Acid-Modified Fluorocarbon Elastomer

Quenching induced modified nanoarchitectonics in the dielectric and energy storage behavior of poly (vinylidene fluoride)/Ba0.7Sr0.3TiO3 composites thick films

Quenching induced modified nanoarchitectonics in the dielectric and energy storage behavior of poly (vinylidene fluoride)/Ba0.7Sr0.3TiO3 composites thick films

Gamma-irradiated janus electrospun nanofiber membranes for desalination and nuclear wastewater treatment

This study presents the fabrication of double-layer electrospun nanofibrous membranes (DL-ENMs) using polyvinylidene fluoride (PVDF) and polyether sulfone (PES) based polymers with different degrees of hydrophilicity (PES, sulfonated PES, and PES with hydroxyl terminals). A comparative analysis was carried out with single-layer electrospun nanofiber membranes (SL-ENM) with a total thickness of about 375 μm. Using feed solutions, including sodium chloride, sodium nitrate, and simulated nuclear wastewater (SNWW), the performance of DL-ENMs was evaluated for desalination and radionuclide decontamination by direct contact membrane distillation (DCMD) and air gap membrane distillation (AGMD) techniques. The results showed that DL-ENMs, especially those incorporating a sulfonated PES-based hydrophilic layer, exhibited superior permeate fluxes, reaching values of 72.72 kg/m2.h and 73.27 kg/m2.h in the DCMD using aqueous feed solutions of NaCl and NaNO3, respectively, and 70.80 kg/m2.h and 41.96 kg/m2.h using aqueous feed solutions of SNWW in DCMD and AGMD, respectively. Both SL-ENMs and DL-ENMs exhibited high rejection efficiencies and decontamination factors for the feed solutions (>99.9%). In addition, the prepared ENMs were exposed to gamma radiation to evaluate their applicability in real-life applications. The result of irradiation revealed the negative impact of gamma radiation on the fluorine content of PVDF which could be a critical point in using PVDF as a hydrophobic material for decontaminating nuclear wastewater by membrane distillation.

Biopolymer Binders for Low‐Temperature Operation of TiNb2O7 Anode in Li‐Ion Batteries

The widespread use of lithium‐ion batteries underlines the criticality of a more sustainable cell fabrication. Here, three biopolymers gelatin, pectin, and deoxyribonucleic acid (DNA) are investigated as binders for the TiNb2O7 anode material in Li cells in a temperature range between 0 and 60 ºC and compared to conventional binder polyvinylidene fluoride (PVDF). The use of biopolymers is motivated by their own environmental friendliness and the possibility to implement an aqueous electrode processing. A specific charge capacity of at least 200 mAh g−1 is found for all binders at 0 °C when testing the cycling performance of TiNb2O7 at 77.5 mA g−1 (1C rate). However, low‐rate cycling at 60 °C shows decreasing capacity for all biopolymers due to the swelling effect and continuous contact loss to the current collector, what also reflects in lowering the overall Li‐diffusion coefficient. This effect becomes less pronounced at 0 °C and high current densities, making biopolymers competitive with commercial PVDF. The electrodes with DNA binder demonstrate overall the most stable performance, arising from the biopolymer intactness and a thin solid–electrolyte interface layer. At 0 °C, the electrode with DNA provides 150 mAh g−1 at 775 mA g−1 for at least 500 discharge–charge cycles.

Heart rate monitoring system based on piezoelectric poly(vinylidene fluoride-co-trifluoroethylene) composites with barium strontium titanate ceramic particles

A heart rate sensor device has been designed and developed based on a composite material based on poly(vinylidene fluoride – co – trifluoroethylene), P(VDF-TrFE) as polymer matrix and barium strontium titanate (BST) particles as ceramic fillers. The composite films were prepared by solvent casting varying the ceramic particles content between up to 40 wt%, allowing to tailor the dielectric and piezoelectric response. The morphology, polymer phase and thermal properties are independent of the ceramic filler content, whereas the dielectric constant increases significantly with increasing filler content, the largest dielectric constant, ε’ = 38 at 1 kHz, being obtained for the composite with 40 wt% of ceramic particles. Further, the highest piezoelectric response, also dependent on ceramic filler content, is |d33|= 29 pC/N, being obtained for the 10 wt% ceramic particle content film. It is also shown by piezoresponse force microscopy that higher ceramic particles are characterized by more stable ferroelectric domains. The composite has been successfully proved for its potential in heart rate monitoring applications, exhibiting high levels of precision as well as reliability. This work on heart rate sensing presents a material suitable for its incorporation into wearable gadgets, medical devices, and sports equipment, compatible with integration by printing technologies, enabling consumers to access immediate data relevant to their cardiovascular health.