Study of crystallization behavior of neat poly(vinylidene fluoride) and transcrystallization in carbon fiber/poly(vinylidene fluoride) composite under a temperature gradient

The crystallization behavior of poly(vinylidene fluoride) (PVDF) and transcrystallization in carbon fiber (CF)/PVDF composite were investigated under a temperature gradient. The crystallization temperature (T_c) was controlled in the range of 110–180 °C. For neat PVDF, the results showed that exclusive γ phase formed at T_c above 164 °C, but coexisted with α phase at T_c ranging from 137 to 160 °C. The promotion of γ phase to nucleation of α phase at low T_c was observed for the first time. For CF/PVDF composite, a cylindrical transcrystalline (TC) layer formed on the surface of CF when T_c was between 137 and 172 °C. The TC layer was exclusively composed of γ phase at T_c above 164 °C. The hybrid nucleation was dominated by γ phase though some α phase nuclei emerged on the surface of CF when T_c was in the range of 144–160 °C. As T_c decreased, competition between the hybrid nucleation of α and γ phase became more intense. The γ phase nuclei was soon circumscribed by the rapidly developed α phase when T_c was below 144 °C. Furthermore, some α phase nuclei were induced at the surface of the γ phase TC layer, and developed into α phase TC layer when T_c was in the range of 146–156 °C, which resulted in a doubled TC layer of α and γ phase at the interface of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43605.     

Effect of poly(methyl methacrylate) addition on the dielectric and energy storage properties of poly(vinylidene fluoride)

Poly(methyl methacrylate) (PMMA) was introduced into poly(vinylidene fluoride) (PVDF) via a solution blending process, and a series of PVDF/PMMA blends were obtained in an effort to reduce the energy loss of pure PVDF. The effects of the composition and thermal treatment on the properties of the polymer blends were carefully studied. The results show that the introduction of PMMA led to a lower crystallinity and a smaller crystal size of PVDF for its dilution effect. As a result, the dielectric constant and energy storage density of the polymer blends were slightly reduced. Meanwhile, the phase transition of the PVDF crystals from the α phase to the β phase happened during the quenching of the blend melt to ice–water; this was also observed in the untreated or annealed blends with PMMA contents over 50 wt %. Compared with the α‐PVDF, the PVDF crystals in the β phase possessed a lower melting temperature, a higher dielectric constant, and a lower dielectric loss. The addition of PMMA reduced the energy loss of PVDF significantly, whereas the energy storage density decreased slightly. The optimized blend film with about 40 wt % PMMA and PVDF in the β phase showed a relative high energy storage density and the lowest energy loss. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Doubly oriented β-form films of poly(vinylidene fluoride)

PVDF sheets, rapidly quenched, were (1) two-step transversely stretched at various temperatures and (2) stretched at various temperatures, rolled at room temperature and then annealed. The orientation patterns of the β-form crystal (which contains the polar b-axis) in these films were analysed on the basis of X-ray diffraction photographs taken with flat and cylindrical cameras. In the case of (1), when both of the two-step transversely stretching temperatures were below 100°C, a doubly oriented film with the plar b-axis oriented parallel to the film surface was obtained. In the case of (2), when the stretching temperature was below 100°C, the sheets then rolled without annealing, another doubly oriented film with the polar b-axis preferentially oriented at 30° to the film surface was obtained. On the other hand, when these films were annealed above 100°C, or the stretching temperatures were above 100°C, orientation patterns in which the polar b-axis was partially rotated through 60° were obtained. The orientation mechanisms of these films are discussed using the measurements of the lattice spacings of the β-form crystal.     

The crystalline phase transformation of poly(vinylidene fluoride)/poly(vinyl fluoride) blend films

Poly(vinylidene fluoride) (PVDF), poly(vinyl fluoride) (PVF), and their blends were prepared by solution casting, followed by quenching in ice water after melting to obtain an α-crystalline phase. The films were drawn by solid state extrusion at two different drawing temperatures, 50°C and 110°C. The crystalline phases were analyzed by DSC and FTIR. In the undrawn films, the content of β-crystalline phase in the blend of PVDF/PVF 88.5/11.5 was higher than in the PVDF homopolymer, but it was lower than in the PVDF film with a draw ratio higher than 4. The α-crystalline phase in PVDF/PVF blends was mostly transformed into the β-crystalline phase beyond a draw ratio of 4, regardless of the draw temperature and PVF content. The α-crystalline phase of PVDF systematically transformed into the β-crystalline phase with increasing draw ratio. The crystallinity of PVDF/PVF blend films drawn at 110°C was higher than those drawn at 50°C. In the drawn blend films, characteristic IR bands of the α form were shifted to those of the β form and completely changed into those of β form at draw ratio of 4, regardless of the draw temperature and PVF content.     

Interfacial polarization and layer thickness effect on electrical insulation in multilayered polysulfone/poly(vinylidene fluoride) films

In this study, we report layer thickness effect on the electrical insulation property of polysulfone (PSF)/poly(vinylidene fluoride) (PVDF) multilayer films having a fixed composition of PSF/PVDF = 30/70 (vol./vol.). Breakdown strength, dielectric lifetime, and electrical conductivity were studied for 32- and 256-layer films having various total film thicknesses. Among these films, those having thinner PVDF and PSF layers exhibited lower breakdown strength, shorter lifetime, and higher electrical conductivity than those having thicker layers. These experimental results were explained by Maxwell–Wagner–Sillars interfacial polarization due to contrasts in dielectric constant and electronic conductivity for PVDF and PSF, respectively. When both PVDF and PSF layers were thick (ca. > 100–200 nm), more space charges were available in PVDF and no electronic conduction was allowed for PSF. These accumulated interfacial charges could serve as effective traps for injected electrons from metal electrodes under high electric fields. As a result, reduced electrical conductivity and enhanced breakdown strength/dielectric lifetime properties were obtained. When both layers were thin (ca. < 100 nm), fewer space charges were available in PVDF and significant electronic conduction through PSF resulted in low interfacial polarization. Consequently, higher electrical conductivity, lower breakdown strength, and shorter lifetime were observed. These results provide us insights into potential physics to enhance electrical insulation property of polymer films using a multilayered structure having large dielectric constant contrast.     

Chemical dehydrofluorination and electrical conductivity of poly(vinylidene fluoride) films

The dehydrofluorination of poly(vinylidene fluoride) (PVDF) powder and films was studied using several kinds of base solution. Especially the reactivity of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) in ethanol, KOH in 2-propanol and aqueous NaOH solution with tetrabutylammonium bromide was investigated by the change in infrared (IR) and ultraviolet-visible (UV-VI) absorptions of PVDF films. The elimination reactions by DBU or KOH were considered to be accompanied by substitution reaction. The electrical conductivity of dehydrofluorinated PVDF films increased markedly by doping with iodine, and the activation energies of conduction were found to be between 0.4 and 0.5 eV. When a drawn PVDF film was dehydrofluorinated and doped with iodine, anisotropy in conductivity was observed.     

Miscibility of poly(vinylidene fluoride) and potassium salt of poly(methyl methacrylate-ran-methacrylic acid)

The crystalline–amorphous polymer pair of poly(vinylidene fluoride) and poly(methyl methacrylate) is known to be miscible over a wide composition range. The effects of ionic moieties on the miscibility were studied by replacing the poly(methyl methacrylate) with a series of random copolymers of methyl methacrylate and potassium salt of methacrylic acid. The interaction parameter (χ) for the miscible blends in their molten state was obtained by thermal analysis using a melting-point depression calculation. The parameter decreased to a minimum at c.2% ion content (χ=minus;0.514) and approached a positive value at above 10% ion concentration.     

Development of hierarchical surface roughness on porous poly (vinylidene fluoride) membrane for membrane distillation process

The surface hydrophobicity of a poly (vinylidene fluoride) membrane was increased through the phase separation of polycarbonate (PC) solution on the membrane surface. A variety of characterization techniques including surface contact angle measurement, scanning electron microscopy, liquid entry pressure measurement, atomic force microscopy, porosity measurement, pore size measurement, and attenuated total reflectance-Fourier transform infrared spectroscopy were performed to investigate the membrane surface modification. According to the results, the formation of PC deposits on the membrane surface provided hierarchical structures consisting of micro and nanoscale roughness which enhanced the surface hydrophobicity. Direct contact membrane distillation (DCMD) experiments, in which an aqueous solution of sodium chloride (3.5 wt%) resembling the seawater was used as feed, were carried out to assess the performance of membranes. This surface modification technique led to the improved pore wetting resistance of the coated membrane in DCMD application. This novel method is believed to have a great potential to apply on a wide variety of membranes for MD application.     

Sulfonation of styrene‐grafted poly(vinylidene fluoride) films

Electron‐beam irradiated and styrene‐grafted poly(vinylidene fluoride) films are sulfonated with chlorosulfonic acid in dichloroethane under various conditions. The impact of the reaction time, the concentration of the sulfonating agent, and the reaction temperature on the properties of the sulfonated film is examined. Sulfonation proceeds via a reaction front mechanism. Sulfonation of surface‐grafted films is incomplete at room temperature. The number of side reactions taking place appears to be linearly dependent on the concentration of the sulfonation solution. Dimensional changes suggest that sulfone crosslinking is significant at higher concentrations. This reduces the ion‐exchange capacity and proton conductivity of the films but increases the resistance to oxidation in a H₂O₂ solution. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1572–1580, 2001     

Properties of poly(vinylidene fluoride)

The properties of fluorocarbon plastics have made them desirable for numerous new applications. Poly(vinylidene fluoride) (PVF₂) can be easily extruded into films or fibers or injection molded into a variety of shapes. It was found that crystallinity, molecular weight distribution and polymer structure are important in establishing resin properties. Highly crystalline PVF₂ with a narrow Gaussian molecular weight distribution gives specimens with optimum physical and chemical properties.     

Study of thermally poled and corona charged poly(vinylidene fluoride) films

The effect of thermal poling and corona charging on the structure and characteristics of poly(vinylidene fluoride) films (PVDF) was investigated. The structure and chemical change of PVDF films with different polarizing treatments was examined using Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy, respectively. The characteristics including piezoelectric coefficients, ferroelectric hysteresis, and leakage current were measured. It was found that both polarized methods contribute to dramatic improvement on the piezoelectricity and ferroelectricity of PVDF films, while thermal poling leads to structure change with the generation of new carbon composition. The reason to cause leakage current was also analyzed. POLYM. ENG. SCI., 47:1344–1350, 2007. © 2007 Society of Plastics Engineers     

Effect of X-rays on poly(vinylidene fluoride) in X-ray photoelectron spectroscopy

The polymer poly(vinylidene fluoride) (PVDF) was irradiated with X-rays produced by a nonmonochromatic (MgKα) source and the structural and electronic PVDF surface modifications were studied by X-ray photoelectron spectroscopy (XPS). Changes in the shape and intensity of the C_1s and F_1s lines show that a PVDF degradation consisting of the polymer defluorination takes place. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2125–2129, 1998     

Preparing polymer brushes on poly(vinylidene fluoride) films by free radical polymerization

Grafting of polymer brushes on the poly(vinylidene fluoride) (PVDF) films was carried out by the surface‐initiated free radical polymerization. Surface‐initiators were immobilized on the PVDF films by surface hydroxylation and esterification of the surface‐tethered hydroxyl groups with 4,4′‐azobis(4‐cyanopentanoic acid) (ACP). Homopolymer brushes of methyl methacrylate (MMA) were prepared by free radical polymerization from the azofunctionalized PVDF surface. The chemical composition and topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FTIR spectroscopy, and atomic force microscopy (AFM). Kinetics study revealed an exponential increase in the graft concentration of polymer brushes with the reaction time, indicating that the chain growth from the surface was consistence with a chain polymerization. Water contact angles on PVDF films were reduced by surface grafting of MMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 857–862, 2006     

Polarization study of poly(vinylidene fluoride) films under cyclic electric fields

Poly(vinylidene) fluoride (PVDF) is a prototypical piezoelectric polymer, which exhibits a strong piezoelectricity after a poling treatment. In this work, we investigate the polarization behaviors of PVDF film under cyclic electric fields by measuring polarized currents. A compensation method is used to distinguish the polarized current from the capacitive and resistive currents. The PVDF samples with a thickness of 20 or 30 μm and an electrode area of 3 × 3 or 4 × 4 mm² are employed, respectively. From the observations, we find that the electrode area does not affect the current density, but a thicker film has a higher residual polarization due to its larger fraction of effective switchable dipoles. The amplitude of the applied field primarily determines the residual polarization. Impressively, an α- to β-phase transformation occurs above 225 MV · m⁻¹ and the polarized current reaches the maximum and becomes converges at 350 MV · m⁻¹. Moreover, a high degree and reproducible residual polarization is obtained through gradually increasing applied field from 50 to 350 MV · m⁻¹, and the relative standard deviation is 3.74% for 20 available samples. Furthermore, a dipole switching model is used to describe the polarization behaviors of PVDF with a form of f(E) = Ae^{−B|E + C|} and the fitting parameters give a further illustration of polarization behaviors in PVDF. POLYM. ENG. SCI., 60:645–656, 2020. © 2020 Society of Plastics Engineers     

Tensile yield in poly(chlorotrifluoroethylene) and poly(vinylidene fluoride)

Uniaxial tension tests to the yield point were performed on poly(chlorotrifluoroethylene) (PCTFE) and poly(vinylidene fluoride) (PVF2) from room temperature to near the melting point at a strain rate of 2 min^?1. At room temperature and at least two elevated temperatures, measurements were also made at strain rates from 0.02 to 8 min^?1. The properties of these polymers were found to be similar to those of other semicrystalline polymers. In the absence of other transitions, yield energy was found to be a linear function of temperature extrapolating to zero near the melting temperature. The ratio of thermal to mechanical energy to produce yielding is smaller than for glassy polymers. Yield stress is a linear function of log strain rate. The ratio of yield stress to (initial) Young's modulus is about 0.03 at room temperature for both polymers. Yield stress is a linear function of unstrained volume. Yield strain, elastic, and plastic strain all initially increase with temperature, but PCTFE shows a decrease with temperature starting at about 100°C, thus behaving like a glassy amorphous polymer in this region.     

Effect of evaporation temperature on the crystalline properties of solution-cast films of poly(vinylidene fluoride)s

The crystalline properties of poly(vinylidene fluoride) (PVdF) and its copolymer films, prepared from the solvent (N-methyl-2-pyrrolidone) evaporation at different temperatures and subsequent slow cooling to ambient temperature, were investigated by using polarized optical microscopy, differential scanning calorimetry, wide-angle X-ray diffractometry, and Fourier-transform infrared spectroscopy. The results can provide helpful data for determining the optimal processing conditions of PVdFs as the polymer binder materials in making the electrodes of rechargeable lithium batteries. The morphology analysis gives useful information that the residual solvent remaining after the evaporation shows distinguishable amounts with respect to the temperature regions dividing by the crystallization (T_c) and melting (T_m) points of original PVdF samples. It is also proved that smallest spherulitic state coexisting with dominant α- and minor γ-phase crystals, simultaneously showing the lowest heat of fusion (e.g., the lowest crystallinity), can be obtained when the solvent is evaporated at a temperature between T_c andT _m. Letting the minor γ-phase crystals exist by controlling the evaporation temperature like this can be one of the best drying (evaporation) conditions of PVdF-containing slurry in lithium rechargeable battery system.     

Friction‐induced electroactive β polymorph of poly(vinylidene fluoride)

Poly(vinylidene fluoride) (PVDF) has been widely used in electric devices due to electroactive β polymorph. In this article, we probe the formation of β phase under friction by spectroscopy and thermal analysis. During continuous friction, entire sliding of PVDF is identified with two regimes, i.e., running‐in and steady‐state. At initial running‐in period, friction surfaces are dominated by plastic strain, which leads to striking formation of β phase from α polymorph (α→β). Subsequently, melting‐flow domains almost cover friction surfaces at steady‐state. Thus, formation of β crystal is correspondingly induced by shear crystallization. Nevertheless, β‐crystal content at steady‐state is lower than that at running‐in. With sliding proceeding, moreover, β‐crystal content exhibits a gradually decreasing tendency, attributed to rising surface temperature. Besides, the friction‐induced β phase is further confirmed by evaluation of wear debris. Overall, friction plays a crucial role as to the formation of β phase. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46395.     

Crystallization kinetics of poly(vinylidene fluoride)

Specimens of poly(vinylidene fluoride) were crystallized isothermally at a series of temperatures in the vicinity of the melting point. The -form was the only crystalline polymorph present in the crystallized samples. Crystallization rates have been measured by differential scanning calorimetry. The results were analysed in terms of the Avrami equation. The rates of crystallization depend upon the undercooling and the data agree with a process of growth of spherulites controlled by a secondary surface coherent nucleation mechanism. The equilibrium melting temperature, the Avrami exponent, the free energy of formation of a nucleus of critical dimensions and the surfaces free energy of the lamellar crystallites were determined.     

Crystal phase transition dependence of the energy storage performance of poly(vinylidene fluoride) and poly(vinylidene fluoride‐hexafluoropropene) copolymers

Large‐scale mechanical stretching has been performed to modify the crystal phase structures of the pristine poly(vinylidene fluoride) (PVDF) and its copolymer poly(vinylidene fluoride‐hexafluoropropylene) [P(VDF‐HFP)] with various molar contents HFP in an attempt to improve their energy storage performances. It is found that the physical stretched PVDF and P(VDF‐HFP) 95.5/4.5 mol % films have a phase transition from the nopolar α‐phase to highly polar β‐phase, which is different from the P(VDF‐HFP) films with relative high HFP molar contents (α to γ phases). The following results show that the phase transition in these PVDF‐based polymers has a significant effect on their dielectric and energy storage performances. On account of the reformation of the crystalline property and elimination of the impurity defects, an ultra‐high breakdown electric field of ∼900 MV/m has been obtained in all the stretched samples. Consequently, the higher discharged energy densities of 27.1 and 27.7 J/cm³ are calculated from the D–E loops of the β‐PVDF and β‐P(VDF‐HFP) 95.5/4.5 mol % films, respectively. Regarding their excellent discharging energy density of ∼10 J/cm³ under 600 MV/m for thousands of times, the stretched PVDF and its copolymer P(VDF‐HFP)s are promising candidates for high power capacitors applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46306.     

Synthesis of carbon quantum dots to fabricate ultraviolet-shielding poly(vinylidene fluoride) films

The paper presents a simple and effective approach to fabricating a poly(vinylidene fluoride) (PVDF) film with excellent ultraviolet (UV) shielding performance. Carbon quantum dots (CQDs) with a highly UV absorbing property were made via a hydrothermal reaction and were then added to a poly(vinyl alcohol) (PVA) solution. The PVDF membrane pretreated with an alkaline solution was immersed in the prepared CQD/PVA solution to coat a UV-shielding layer on the film surface. Fourier transform infrared spectroscopy, X-ray photoelectron spectrometry, X-ray diffraction, transmission electron microscopy, and UV–visible spectrophotometry were applied to study the structure, morphology, and optical performance of the CQD particles. The stability and UV-shielding performance of the obtained PVDF-OH@CQDs/PVA composite film were further investigated. The results showed that the CQD particles with diameter of 18 nm could be well dispersed in solution. Additionally, the CQDs had fairly high UV absorbance, and the PVDF-OH@CQDs/PVA composite film could shield the UV light completely. The method described in this paper is a promising one for fabricating UV-shielding composite films. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47555.