Effect of Nanostructures Addition and Enhancement of Poly (Vinylidene Difluoride) (PVDF) Energy Harvesting

With concerns in energy crisis and global warming, researchers are actively investigating alternative energy renewable solutions. Among the various methods, piezoelectric transduction stands out due to its impressive electromechanical coupling factor and coefficient. As a result, piezoelectric energy harvesting has garnered significant attention from the scientific community. In this study, we explored methods to enhance the piezoelectric properties of polyvinylidene fluoride (PVDF) through two distinct approaches. The first approach involved applying external high voltages at various stages during the mixture reaction. The goal was to determine whether this voltage application could alter or enhance PVDF’s piezoelectric conformation by improving the alignment of polarized dipoles. In the second part of our study, we investigated the effects of incorporating various nanostructures (including Iron Oxide, Magnesium Oxide, and Zinc Oxide) into PVDF. To analyze changes in PVDF’s crystalline structure, we utilized Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Diffraction (XRD) techniques. Additionally, we measured the electric polarization of samples using a Precision LC Meter and examined the morphology of nanofibers through Scanning Electron Microscopy (SEM).

Rotational Isomeric State Model of Poly(vinylidene chloride) Based Upon ab Initio Electronic Structure Calculations

The rotational isomeric state（RIS） model was constructed for poly（vinylidene chloride）（PVDC） based on quantum chemistry calculations. The statistical weighted parameters were obtained from RIS representations and ab initio energies of conformers for model molecules 2,2,4,4-tetrachloropentane（TCP） and 2,2,4,4,6, 6-hexachloroheptane（HCH）. By employing the RIS method, the characteristic ratio C∞ was calculated for PVDC. The calculated characteristic ratio for PVDC is in good agreement with experiment result. Additionally, we studied the influence of the statistical weighted parameters on C∞ by calculating δC∞/δlnw. According to the values of δC∞/δlnw, the effects of second-order Cl-CH2 pentane type interaction and C1--C1 long range interaction on C∞ were found to be important. In contrast, first-order interaction is unimportant.

PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

The emeraldine base form of polyaniline (PANI) can be doped by a photo-induced doping method. In this method a. copolymer of vinylidene chloride and methyl acrylate (VCMAC) was used as photo acid generator which can release proton when it is exposed to ultraviolet light (lambda = 254 nm). The structure of PANI-VCMAC system before and after irradiation was characterized by elemental analysis, IR, XTP, anti SEM images. Results obtained indicate that the photo-induced doping characteristics, such as doping position and type of charge carriers, are similar to that of PANI doped with HCl. The poor room-temperature conductivity (similar to 10-S-5/cm) of PANI-VCMAC system after irradiation may be due to low doping degree (similar to pH=3) and the difference in morphology as compared with PANI-HCl film.

Phase Partition of Acrylonitrile(AN)in Vinylidene Chloride(VDC)/Water System and Its Effect on VDC-AN Copolymer Composition

phase partition of acrylvnitrile in the vlnylidene chloride/water system at different temperature and under pressure was studied, A calculation method for average VDC-AN copolymer compeeition with AN phmm partition considered was proposed. The conversion results are in good agreement with the experimental data nearly the entire conversion rauge. VDC-AN copolymer with narrower composltion distribution can be prepared in the suspension process and interpreted with dynamic equilibrium of AN between the oil and water phases continuously.

BARRIER PROPERTIES OF VINYLIDENE CHLORIDE/METHYL ACRYLATE COPOLYMER

A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) as comonomer (3-12wt%), was prepared by free-radical suspension copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor were measured at 30 degrees C and 100% relative humidity. All the VDC/MA copolymers studied are semicrystalline. As the MA content increases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, and water vapor are progressively increased, caused by decrease in crystalline fraction and increase in free volume of VDC/MA copolymers.

THE EFFECT OF MONOMERS FEEDING METHODS ON EMULSION COPOLYMERIZATION OF VINYLIDENE CHLORIDE AND ACRYLATES

The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant differences were found in the physical and mechanical propertiesof the latexes and films, depending on the methods of monomer feeding. The results both intheory and experiments demonstrated that the copolymer composition and the length of the VDC sequences in the copolymer could be controlled by the modes of monomer feeding process.

Rare Earth Stearates as Thermal Stabilizers for Rigid Poly(vinyl chloride)

A series of stearates with different rare-earth ion were investigated as thermal stabilizers for rigid PVC at 180 ℃ in air. Their stabilizing efficiency was based on measuring the rate of dehydrochlorination. The resulted revealed the higher stabilizing efficiency of the investigated rare-earth stearates as thermal stabilizers for rigid PVC compared with the thermal stabilizers for industry: calcium stearate, zinc stearate, butyl stannum mercaptide, phosphite esters, β-diketone and epoxidized sunflower oil. This was well illustrated by longer incubation period (T_S) values and lower rate of dehydrochlorination. The stable efficiency was affected by the nature of rare-earth element's individual electronic shell. The mechanism for the stabilizing effect of rare-earth stearates was proposed. The result was experimentally proved based on IR spectrum.

Creep Behaviour of Wood Flour/Poly(vinyl chloride) Composites

The experimental creep data were focused on wood-flour （WF）/poly vinyl chloride （PVC） composites with the variations in additive concentrations of wood flour, silane coupling agent, organomodified montmorillonite （OMMT） and nano-cacium carbonate （nano-CaCO3）. Their effects were analyzed using the Four-element Burger Model incorporating microscopic mechanisms. Total creep strain was low with increasing WF while elastic strain was high and plastic flow strain was low in modeling. Modification of WF with silane was beneficial to creep resistance, so did adding low ratio of OMMT （1.5 wt%） and nano-CaCO3 in composites. Thus, it was effective in reducing creep either by stiffening the PVC matrix using rigid nano-particles or by improving their adhesion with resin. However, superfluous quantity of any additament did not benefit the improvement owing to either earlier destruction of their agglomerates or stress-concentrated cracks in the over-incrassated interface.

Crystallization Behavior and Mechanical Properties of Poly(vinylidene fluoride)/multi-walled Carbon Nanotube Nanocomposites

Poly（vinylidene fluoride）（PVDF）/multi-walled carbon nanotube（MWCNT） nanocomposites were prepared by means of ultrasonic dispersion method. X-ray diffraction（XRD） results indicate that incorporating MWCNTs into PVDF caused the formation of β phase. A thermal annealing at 130 ℃ confirmed that the β phase was stable in the nanocomposites. Differential scanning calorimetry（DSC） results indicate that the melting temperature slightly increased while the heat of fusion markedly decreased with increasing MWCNT content. The tensile strength and modulus of PVDF were improved by loading the MWCNTs. The scanning electron microscopy（SEM） observations showed that MWCNTs were uniformly dispersed in the PVDF matrix and an interfacial adhesion between MWCNT and PVDF was achieved, which was responsible for the enhancement in the tensile strength and modulus of PVDE.

Poly(vinylidene fluoride)/Clay Nanocomposites by Melt Compounding

The crystalline structures, morphologies, and mechanical properties of poly（vinylidene fluoride）/clay nanocomposites were studied using X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Fourier transform infrared spectroscopy（FTIR）, polarized optical microscopy（POM）, and tensile tests. The results of XRD and TEM show that organoclays are dispersed in the poly（vinylidene fluoride）（PVDF） matrix. A clay-induced crystal transformation from α-phase to β-phase of PVFD was confirmed by XRD and FTIR. Clay layers restricted the growth of spherulite. The tensile tests indicate that the tensile modulus and yield strength as well as the elongation at break decrease when clay is loaded.

Antiplasticizing Effect of MOCA on Poly(vinyl chloride)

An obvious antiplasticizing effect has been observed in PVC with small amount of MOCA, 3,3’-dichloro-4,4’-diamino-diphenylmethane. PVC-MOCA interaction and crystallization behavior of PVC/MOCA blends were investigated in detail to explain the mechanism of antiplasticization on the basis of a series of techniques including DMA, FTIR, and DSC. The results of mechanical properties tests show that the tensile strength of PVC with 5 phr of MOCA reaches a maximum value, 69.5 Mpa, which is about 23 % higher than that of pure PVC. The rise in tensile strength was attributed to an antiplasticizing effect of MOCA on PVC as confirmed by DMA measurements. The evidences from FTIR reveal that a strong hydrogen-bonding interaction takes place between the nitrogen atom of –NH2 groups in MOCA and the methine proton of PVC repeat units. The results of DSC analysis indicate that crystallization behavior of MOCA is suppressed completely and the crystallinity of PVC decreases with the increase of MOCA amount.

RHEOLOGICAL PROPERTIES OF POLY(VINYLIDENE FLUORIDE) IN MOLTEN STATE

The theological behavior of poly(vinylidene fluoride)(PVDF)samples of different molecular weights was investigated by means of high pressure capillary rheometer and rotational rheometer.Information on the rheological properties of such materials above melt temperatures is of interest as this can lead to an improved understanding of polymer behavior in processing and fabrication technologies.Shift factors derived from time-temperature superposition showed good fit to the Arrhenius equation with a flow activa...

Influence of Annealing and Additives on the Crystallization Behavior and Properties of Poly(vinyl chloride)

Acetanilide （AC）, adipic acid （AA） and potassium hydrogen phthalate （PHP） were chosen as additives to accelerate PVC crystallization and improve its mechanical properties. The influences of the additives and annealing on the crystallization behavior, micromorphology and the tensile properties were investigated by the thermal analysis, scanning electron microscopy （SEM） and the tensile test. Based on the analysis results, it was concluded that the melting peaks ranging from 110 to 200 ℃ and 200 to 240 ℃ were caused by the fusion of the fringed micelle crystals and chain-folded crystals respectively. AC advanced the fringed micelle crystal to develop, while AA and PHP promoted obviously the chain-folded crystal to grow. The addition of the foreign additives did not change the growth pattern ofPVC crystallites, the growth of the micelle crystal was favorable at 110 ℃, and the chain-folded crystal was developed at higher temperature. For PVC/ AA and PVC/PHP, when annealed at 110 ℃, a regular nest like network was formed, the crystallinity and the crystallite size were increased as well, and as a result, the tensile strength, Young＇s modulus and the elongation at break point were improved simultaneously and greatly.

Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL),1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6)as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF)membranes via thermally induced phase separation(TIPS).Phase diagram of PVDF/[BMIM]PF6 was measured.The effects of polymer concentration and quenching temperature on the morphologies,properties,and performances of the PVDF membranes were investigated.When the polymer concentration was 15 wt%,the pure water flux of the fabricated membrane was up to nearly 2000 L·m-2·h-1,along with adequate mechanical strength.With the increasing of PVDF concentration and quenching temperature,mean pore size and water permeability of the membrane decreased.SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6)presented spherulite structure.And the PVDF membranes were represented asβphase by XRD and FTIR characterization.It provides a new way to prepare PVDF membranes with piezoelectric properties.

Structures of LDHs Intercalated with Ammonia and the Thermal Stability for Poly(vinyl chloride)

MgAl-NH3 LDHs (layered double hydroxides), ZnAl-LDHs and ZnAl-NH3 LDHs with different molar ratio of Al/ammonia were synthesized by co-precipitation method. The synthetic LDHs samples were characterized by XRD, FT-IR, TGA-DTG and SEM techniques and tested by Congo red method. In addition, after PVC (Poly vinyl chloride) and DOP (Dioctylphthalate) were added to LDHs, the thermal stability for PVC was characterized by TGA-DTG. The results indicated that LDHs intercalated with ammonia improved thermal stability for PVC significantly, MgAl-NH3 LDHs (Mg2+:Al3+: NH3·H2O = 3:1:0.5) and ZnAl-NH3 LDHs (Zn2+:Al3+:NH3·H2O=2:1:1.5) showed the best thermal stability for PVC, interlayered space of LDHs became larger by intercalating ammonia.

A FACILE APPROACH FOR THE SURFACE MODIFICATION OF POLY(VINYLIDENE FLUORIDE) MEMBRANE VIA SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

A novel approach for the surface modification of poly(vinylidene fluoride)(PVDF)membrane was successfully realized through alkaline treatment,UV-induced bromine addition,and followed by surface-initiated atom transfer radical polymerization(ATRP)of methyl methacrylate(MMA).Chemical changes on the PVDF membrane before and after modification were analyzed with attenuated total reflectance Fourier transform infrared spectroscopy(ATR/FT-IR)and X-ray photoelectron spectroscopy(XPS).Primary kinetic study revealed...

Acetylcholinesterase Biosensor Based on Poly(diallyldimethylammonium chloride)-multi-walled Carbon Nanotubes-graphene Hybrid Film

In this paper, an amperometric acetylcholinesterase(ACh E) biosensor for quantitative determination of carbaryl was developed. Firstly, the poly(diallyldimethy-lammonium chloride)-multi-walled carbon nanotubes-graphene hybrid film was modified onto the glassy carbon electrode(GCE) surface, then ACh E was immobilized onto the modified GCE to fabricate the ACh E biosensor. The morphologies and electrochemistry properties of the prepared ACh E biosensor were investigated by using scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. All variables involved in the preparation process and analytical performance of the biosensor were optimized. Based on the inhibition of pesticides on the ACh E activity, using carbaryl as model compounds, the biosensor exhibited low detection limit, good reproducibility and high stability in a wide range. Moreover, the biosensor can also be used for direct analysis of practical samples, which would provide a new promising tool for pesticide residues analysis.

Synthesis of Bio-Plasticizer from Soybean Oil and Its Application in Poly(Vinyl Chloride) Films

Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.

Molecular Modulation of Structure and Ferroelectric Performance of Poly(vinylidene fluoride)Free Standing Films from Aspects of Molecular Weight and Crystallization Temperature

Ferroelectric polymer poly(vinylidene fluoride)(PVDF)has received great research interest because of its special electroactive properties which are strongly dependent on the crystalline structures and in turn processing conditions.The effect of molecular weight and crystallization temperature on the micro-structure and macro-properties of PVDF films casted from dimethyl sulfoxide(DMSO)solvent is investigated.The results demonstrated that a low molecular weight(180 kg/mol)and a low evaporation temperature(50℃)favored the formation of polarγ-phase,while a high molecular weight(1000 kg/mol)and a high evaporation temperature(125℃)made PVDF crystallize intoα-phase.Compared with films casted at 50℃,films casted at 125℃exhibited higher dielectric loss at a low electric field and less loss conductivity at a high electric field,which was due to their low degrees of crystallinity and fine evaporation of the solvent,respectively.PVDF with a molecular weight of 180 kg/mol casted at 125℃exhibited the highest remnant polarization(0.062 C/m^(2))among all of the solution-processed films,being a result of high chain mobility resulted from the low molecular weight.

Highly efficient and stable perovskite solar cells with strong hydrophobic barrier via introducing poly(vinylidene fluoride)additive

Perovskite solar cells(PSCs)have become the promising next-generation photovoltaic devices due to their excellent photoelectric performances,and the power conversion efficiencies(PCEs)have experienced unprecedented rapid increase in recent years.However,to realize the practical application of PSCs,high performance and long-term stability are required and the preparation of high-quality perovskite film is the key.Herein,we adopt a simple and effective method to prepare high-quality perovskite films by introducing the poly(vinylidene fluoride)(PVDF)polymer additive with abundant hydrophobic F.As the growth template,the PVDF promotes the growth of perovskite crystal,improves the crystallinity and film morphology,thus reducing defect density and inhibiting carrier recombination.The results show that the photovoltaic performances of the perovskite device with PVDF are meaningfully improved,and a high PCE of 21.42%is achieved with an improvement of 10.87%,More importantly,the PVDF-based perovskites display greatly enhanced humidity and heat stability due to the protection of strong hydrophobic barrier from F and PVDF long chain.Aging at 45%±5%relative humidity(RH)for 2400 h and 850 C for300 h,respectively,the unsealed PVDF devices can maintain over 90%of the initial PCE.It indicates that suitable polymer additives can improve the film quality to acquire high-performance and stable PSCs and lay a foundation to design new perovskite light absorption layer with different polymers for the further development of PSCs.