Ionic liquids as co-solvents for zwitterionic copolymers and the preparation of poly(vinylidene fluoride) blend membranes with dominated β-phase crystals

A new series of green solvents that constituted with ionic liquids (ILs) and dimethyl acetamide (DMAc) were developed as good solvents for zwitterionic copolymers, and the dissolutions of amphiphilic copolymers carrying carboxylbetaine and sulfonatebetaine in these new solvents were studied. It was determined that the commonly found ILs such as 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF₄), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF₆) and many others were all effective co-solvents for zwitterionic copolymer with carboxylbetaine groups. However, the 1-methylimidazolium trifluoromethanesulfonic ([MIM]CF₃SO₃) instead of the [BMIM]BF₄ was proved as an effective co-solvent for the copolymer carrying sulfonatebetaine units. These newly designed mix-solvents were also good solvents for poly(vinylidene fluoride) (PVDF) and their influences on the crystallization as well as the formation of PVDF membranes were investigated. Our results had demonstrated that blend membranes with zwitterionic additives could be facilely prepared with many new solvent candidates.     

The effect of fibre concentration on the α to β-phase transformation, degree of crystallinity and electrical properties of vapour grown carbon nanofibre/poly(vinylidene fluoride) composites

Vapour growth carbon nanofibres/poly(vinilidene fluoride) - VGCNF/PVDF - composites prepared by solution casting were studied. The spherulitic crystallisation morphology of the pure polymer is maintained for the composites. Mechanical stretching of the composite films induces the α to β-phase transformation within the polymer matrix. This phase transition is accompanied by the destruction of the spherulitic microstructure in favour of a microfibrillar one. The incorporation of the VGCNF in the PVDF matrix increases the degree of crystallinity of the polymer composites for concentrations lower than ∼1%, remaining stable for higher VGCNF concentrations. With respect to the electrical properties, the stretching associated to the phase transformation induces a change in the conduction mechanism: the α-phase composite demonstrates a percolative behaviour on the measured conductivity whereas the β-phase demonstrates typical ionic conduction behaviour. Dielectric measurements in conjunction with the the two exponent percolation phenomenological equation demonstrates that in the β-phase an effective reduction in the ratio VGCNF length/domain length could induce the observed percolation behaviour.     

Modulation of electromagnetic wave absorption by carbon shell thickness in carbon encapsulated magnetite nanospindles–poly(vinylidene fluoride) composites

A series of Fe₃O₄/C core–shell nanospindles with different shell thickness have been synthesized by a wet chemical method and subsequent high-temperature carbonization. The thickness of carbon shell can be well adjusted from 9 to 32 nm by changing the addition amounts of resorcinol and formaldehyde precursors during the coating process. Structure and morphology characterizations reveal that the carbon shell is amorphous structure and uniformly encapsulates on porous Fe₃O₄ nanospindles. For the first time, a flexible Fe₃O₄/C/poly(vinylidene fluoride) (PVDF) composite absorber was prepared by embedding the core–shell Fe₃O₄/C nanospindles in PVDF matrix. The electromagnetic properties of the composite show strong dependence on the carbon-shell thickness. The impedance matching for electromagnetic absorption is improved by the synergy effect between Fe₃O₄ nanospindles and encapsulated carbon shell. The Fe₃O₄/C/PVDF composite with thick carbon shell exhibits strong electromagnetic wave absorbing ability with thin absorber thickness. The minimum reflection loss for the absorber with thickness of 2.1 mm can reach −38.8 dB.     

Fabrication of dual-layer poly(styrene-b-4-vinyl pyridine)–poly(vinylidene fluoride) membranes with tailored pore sizes under 10 nm via surface quaternization

Block copolymer membranes can be applied to precise size-based separation because of their highly ordered surface morphology and adjustable pore sizes. However, there is a lower limit of the scale of block copolymer self-assembly; this makes it a challenge to tailor the pore size down to below 10 nm. In this study, poly(styrene-b-4-vinyl pyridine) membranes were modified to quaternized selective layers with pores smaller than 10 nm and were supported by poly(vinylidene fluoride) hollow fibers as the substrate to provide a high mechanical strength. Two reactants, methyl iodide and 2-chloroacetamide, were used in the quaternization. With this one-step chemical modification, the molecular weight cutoff was reduced from 190 to 8 kDa, and the surface pore sizes were narrowed down from 20–30 to 3 nm; this bridged the gap of tailored pore sizes down to below 10 nm. Such membranes are promising candidates for low-molecular-weight separation with high resolution. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47137.     

Crystallization kinetics of γ phase poly(vinylidene fluoride)(PVDF) induecd by tetrabutylammonium bisulfate

The phase transition behavior of poly(2-ethyl-2-oxazoline) (PEtOx) under complexation with star-shaped poly(acrylic acid) (PAA) having various arm numbers (two, three, four, and six) has been studied by turbidity and laser light scattering measurements. The change in cloud point temperature (T _cp) of PEtOx was monitored as a function of pH, ionic strength, and arm number of the star polyelectrolyte. The shift in T _cp to a lower value than that of pure PEtOx was more pronounced at pH 4.2 (pH?a), when the carboxylic acid groups are protonated as compared to pH 7.0 (pH?>?pK_a ), when the acid moieties are partially ionized. Dynamic light scattering showed that these complexes may have micellar core-shell type structure with a mean hydrodynamic radius (R _h) ranging from 12 nm to ～200 nm depending upon the temperature. Significant shift in T _cp was observed for six-arm star poly(acrylic acid) complexes at both pH values. This change in the T _cp is accredited to the differences in the driving forces of phase transition, including hydrogen bonding between carboxylic acid groups of PAA and the carbonyl moiety of PEtOx as well as the hydrophobic interactions.     

Improved dielectric properties of poly(vinylidene fluoride)–BaTiO3 composites by solvent-free processing

Composites of poly(vinylidene fluoride) (PVDF) and BaTiO₃ nanoparticles (average diameter ca. 125 nm) are fabricated by a solvent-free and industrially scalable technique, that is, melt blending, followed by compression molding. The effect of processing parameters on the spectroscopic, microstructural, thermal, mechanical and dielectric properties are evaluated as a function of composition (loading up to 30 vol%). The presence of nanoparticle inclusions as well as specific compression molding parameters demonstrate both to affect the molecular relaxations of the PVDF matrix, studied by correlating the results of different techniques, and to induce the PVDF crystallization as β phase. Processing parameters also play a key role for optimizing the dielectric properties. An improved dielectric behavior of the composites is obtained in terms of both permittivity, whose value increases up to four times that of neat PVDF, and dielectric losses, lower than 5% between 10 and 3·10⁴ Hz. The obtained performances resulted enhanced compared to analogous composites prepared with the use of solvents.     

Influence of Spray Drying Parameters on the Formation of β-Phase Poly(vinylidene fluoride)

A simple one-step spraying method to produce poly(vinylidene fluoride) (PVDF) in the desired conformation is presented. The content of the piezoelectric β-phase is measured at different spray drying conditions and during electrospray. The influence of a strong electrical field and charges on the droplet are investigated separately from the electrospray setup with a pneumatic atomizer. For this purpose, the electric field is integrated into a pneumatic atomization process by a plate capacitor and the charge of the droplets by corona discharge. To investigate the drying properties, the drying temperature and the flow rate of dry air are examined. The presented process offers the possibility to deposit PVDF films or to produce PVDF powders, in their piezoelectric β- and γ-phases or in the nonpolar α-phase.     

Degradation of the dielectric and piezoelectric response of β-poly(vinylidene fluoride) after temperature annealing

The effect of annealing temperature and time on the dielectric and piezoelectric response of poly(vinylidene fluoride), PVDF, was studied. The observed decrease in the value of the dielectric, ε′, and piezoelectric, d ₃₃, constants is related to depoling of the material and not to variations of the degree of crystallinity or the electroactive β-phase content. In a general way, the dielectric and piezoelectric responses decrease strongly in the first 4 h at a given temperature, in particular for temperatures higher that 80 °C, reaching stable values for longer annealing times. For most applications, the temperature of 100 °C will set the limit of suitable performance. Nevertheless, the material still retains a stable piezoelectric response of ca. 4 pC/N after reaching temperatures of 140 °C. The mechanisms behind the observed behavior are discussed.     

Non-isothermal crystallization behavior of poly(vinylidene fluoride)/ethylene–vinyl acetate copolymer blends

Non-isothermal crystallization behavior of poly(vinylidene fluoride) (PVDF) and ethylene–vinyl acetate (EVA) copolymer and their binary blends with different blending ratios were investigated by the use of differential scanning calorimetry (DSC). With the increasing cooling rates, PVDF, EVA and their binary blends showed wide crystallization temperature range and high crystalline enthalpy. Jeziorny and Mo’s models were applied to calculate non-isothermal crystallization kinetics parameters of neat PVDF, EVA and their binary blends. By Jeziorny method, the crystallization process of neat PVDF, EVA and PVDF/EVA = 7/3 blend can be divided into two parts: primary and secondary crystallization processes. The Avrami exponent n ₁ indicated that the primary crystallization process was a mixture model of three-dimensional and two-dimensional space extensions. In comparison, PVDF/EVA = 5/5 and PVDF/EVA = 3/7 blends showed a single crystallization process. Through Mo’s analysis, faster cooling rate was demanded to reach higher relative crystallinity. Crystallization rate coefficient (CRC) was used to describe the effect of crystallization rates on the interaction between PVDF and EVA. CRC reached a maximum value when the mass ratio of PVDF and EVA was 7/3. The maximum CRC values of PVDF system and EVA system were 98.1 and 179.9 h^?1, respectively. The activation energy was closely related to the extent of conversion and the neat samples had a maximum value of crystallization activation energy. This was consistent with the observation for the parameters from Jeziorny analysis and could be correlated to the heterogeneous nucleation.     

Remarkable change in the broadband electrical behavior of poly(vinylidene fluoride)–multiwalled carbon nanotube nanocomposites with the use of different processing routes

Poly(vinylidene fluoride) (PVDF) nanocomposites have plenty of applications in the electronic realm. In this study, we produced nanocomposites based on PVDF and multiwalled carbon nanotubes (MWCNTs), with various MWCNT loadings, using three different processing routes: solution mixing, melt mixing, and electrospinning. The broadband electrical behavior of these nanocomposites was studied and compared via impedance spectroscopy. The morphologies of the nanocomposites were characterized by transmission electron microscopy and scanning electron microscopy. The results reveal that the electrical behaviors of the samples were completely different according to the processing route used. Solution mixing was the most suitable method for producing nanocomposites with the highest conductivities, at low MWCNT loadings, whereas electrospinning was the most suitable method for producing nanocomposites with the lowest dielectric permittivity. These differences were attributed to the different arrangements of the MWCNTs caused by the different processes. Although the solution-mixed samples exhibited long and twisted MWCNTs, the melt-mixed samples had shorter MWCNTs, and the electrospun samples had MWCNTs embedded and aligned inside the insulating polymer nanofibers. Thus, these results project a vast horizon for tailoring the structure and thereby the broadband electrical behavior of PVDF–MWCNT nanocomposites for different types of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47409.     

Effect of polarization switching on piezoelectric and dielectric performance of electrospun nanofabrics of poly(vinylidene fluoride)/Ca–Al LDH nanocomposite

At present, highly flexible, durable, and lightweight piezoelectric nanogenerators with high-power density and energy conversion efficiency are of great interest. The present study reports a new synthetic route for Ca–Al layered double hydroxide (LDH) nanosheets and incorporation of these two-dimensional nanosheets as filler material into poly(vinylidene fluoride) (PVDF) to produce composite nanofabrics by electrospinning. The polymorphism, crystallinity, and the interaction between PVDF and LDH were studied by Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry techniques. The synergetic effect of PVDF–LDH interaction and in situ stretching due to electrospinning facilitates the nucleation of electroactive β phase up to 82.79%, which makes it a suitable material for piezoelectric-based nanogenerators. The piezoelectric performance of PVDF/Ca–Al LDH composite nanofabrics was demonstrated by hand slapping and frequency-dependent mechanical vibration mode, which delivered a maximum open circuit output voltage of 4.1 and 5.72 V, respectively. Moreover, the composite nanofabrics exhibited a high dielectric constant and low dielectric loss due to superior interfacial polarization at low-frequency region with LDH loading, promising its potential applications in electronic devices. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48697.     

Excellent oil/water separation performance of poly(styrene-alt-maleic anhydride)/fluorocarbon surfactant membrane filter with functionalized multiwalled carbon nanotubes

Polymer/fluorocarbon surfactant membranes have been reported to display excellent oleophobic/hydrophilic behavior and outstanding oil/water separation properties. In this work, multiwalled carbon nanotubes (MWNTs) enhanced poly(styrene-alt-maleic anhydride)/fluorocarbon surfactant (PSMA/MWNTs/FS) membrane filters were prepared by dip-coating PSMA/MWNTs/FS on stainless steel meshes for efficient oil/water separation. The microstructure, thermal properties, wettability, oil/water separation ability, and recyclability were investigated. The results revealed that the MWNTs are suitably dispersed in the membrane, further increasing the thermal stability, oil/water separation efficiency, and recyclability. The oil/water separation efficiency of the complex membrane filter containing MWNTs was 99% initially and 97% after 20 cycles. This work provides a simple, low-cost, and environmentally friendly approach for efficient oil/water separation.     

Preparation of quaternized poly(vinylidene fluoride) membranes by γ-ray irradiation induced graft polymerization and their antibacterial property

PVDF microfiltration membranes were modified by γ-ray irradiation induced grafting polymerization of 4-vinyl pyridine (4-VP) and then quaternization by n-butyl chloride. The effects of grafting method (simultaneous irradiation, pre-irradiation/UV), grafting conditions (absorbed dose, UV irradiation time, and 4-VP concentration) and quaternization conditions (temperature, time, and concentration of n-butyl chloride) were investigated. It was found that, the grafting degree initially increases with the absorbed dose and then reaches a plateau. The optimal concentration of 4-VP is around 15 wt.%. The ion exchange capacity increases with quaternization temperature, time, and concentration of n-butyl chloride. After modification, the pores size, permeation flux, as well as elongation at break, of quaternized membrane decreases, while the retention coefficient, tensile strength and Young’s modulus increase apparently. Upon contacting with the membranes, the Escherichia coli concentration decreases gradually. It is the adsorption mechanism for the pristine membranes whereas contact-killing mechanism for the quaternized membranes. Simultaneous irradiation is more effective than pre-irradiation/UV in the improvement of antibacterial property of membranes.     

Molecular dynamics simulations of α- to β-poly(vinylidene fluoride) phase change by stretching and poling

The mechanism of inducing a phase change from α-poly(vinylidene fluoride) (α-PVDF) to β-PVDF is addressed using molecular dynamics simulations based on a molecular mechanics force field. The effect of applying a strain to the α-PVDF crystal along the axis of the molecules is investigated, as well as poling the crystal before or after stretching. Rather large (at least 10¹⁰ V/m) electric fields that are perpendicular to the axis of the PVDF molecules are required to induce α- to β-PVDF phase change when no strain is applied to the α-PVDF crystal. However, at a strain of 1.0475 (i.e., when the crystal is stretched by 4.75%) α-PVDF changes to a β-PVDF like structure, where the β-PVDF molecules orientate anti-parallel relative to each other. Transformation of the anti-parallel β-PVDF to β-PVDF can be induced by poling (even at the lowest electric field of 10⁵ V/m studied here) or by thermal annealing.     

Reduced graphene oxide (RGO)-induced compatibilization and reinforcement of poly(vinylidene fluoride) (PVDF)–thermoplastic polyurethane (TPU) binary polymer blend

Compatible blends of nonreactive thermoplastic fluoropolymer, poly(vinylidene fluoride) (PVDF) and thermoplastic polyurethane (TPU) at 70/30 weight ratio, were prepared by utilizing the unique structural feature of reduced graphene oxide (RGO). Here, RGO acts as a compatibilizer as well as a reinforcing filler. RGO interacts with both polymers and reduces the interfacial tension between them, leading to compatibilization. RGO content in the blends was varied from 0 to 0.5 wt %, and the best result was found at 0.3 wt % loading. Excellent compatibilization between PVDF and TPU was established by mechanical, morphological, and thermal property studies. Chemical interaction between the RGO/TPU and RGO/PVDF was proved by FTIR–ATR study. With the incorporation of 0.3 wt % RGO, tensile strength, Izod impact strength, and elongation at break of the blend were increased by 42%, 83%, and 43%, respectively. FESEM and AFM images of blends without loading of filler after etching out of TPU phase show nonuniformly distributed hole morphology. RGO-containing blend has shown much finer and uniformly distributed holes that confirm improved compatibility between the two incompatible polymers. RGO also improves the thermal stability of the compatible blends considerably. At 0.3 wt % loading, the onset of thermal degradation increased by about 10 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47010.     

Modification of poly(vinylidene fluoride) membranes with aluminum oxide nanowires and graphene oxide nanosheets for oil–water separation

To improve the hydrophilic and oleophobic properties of membrane, we adopted aluminum oxide (Al₂O₃) nanowires and graphene oxide (GO) nanosheets to modify poly(vinylidene fluoride) (PVDF) membranes. The experimental results show that the intercalation of Al₂O₃ nanowires between GO nanosheets effectively improved the roughness of the GO–Al₂O₃–PVDF membrane, and the permeability of the membrane with an optimal mass ratio of Al₂O₃ to GO of 7.5 was 31 times that of the GO–PVDF membrane. Furthermore, the addition of Al₂O₃ nanowires significantly enhanced both the hydrophilic and oleophobic properties of the GO–Al₂O₃–PVDF membrane. On the basis of the extended Derjaguin–Landau–Verwey–Overbeek theory, the energy barriers between the oil droplets and GO–PVDF and GO–Al₂O₃–PVDF membranes were 0.63 and 0.9 KT, respectively; this indicated improvements in the anti-oil-fouling ability of the GO–Al₂O₃–PVDF membranes. We also found that both the GO–PVDF and GO–Al₂O₃–PVDF membranes had great oil–water separation rates (97.9 and 99.4%, respectively) with an initial oil concentration of 200 mg/L. The findings of this study show that the GO–Al₂O₃–PVDF membrane is a promising oil–water separation membrane, and further investigation of the cleaning procedure is needed to promote its practical application in oil–water separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47493.     

Interfacial characteristics of poly(ε-caprolactone)-grafted-halloysites nanotubes bionanocomposites

Dielectric and thermal characterization of nanohybrid films based on poly(ε-caprolactone) biopolymer were investigated. Nano-composites samples with distinct loadings of halloysite nanotubes (HNT) were prepared by in situ Ring Opening Polymerisation of ε-caprolactone. The effect of the incorporated HNT on the molecular relaxation process and interfacial polarization of PCL was studied via broadband dielectric spectroscopy (BDS) on a frequency domain starting from 1E-1 to 1E6 Hz and at temperatures ranging from −70°C to 50°C. The BDS measurements revealed four significant dielectric processes α-primary relaxation attributed to glass transition, β-secondary relaxation and two interfacial polarizations due to the semi-crystalline character of PCL and the added HNT fillers. According to our results, the weight ratio of HNT ranging between 3% and 5% is recommended for achieving the highest performing nanocomposite that can be used in several applications.     

β-Polymorph enhancement in poly(vinylidene fluoride) by blending with polyamide 6 and barium titanate nanoparticles

Polyamide 6 (PA6) as a cost-effective polar polymer and barium titanate (BT) as piezoelectric ceramic nanofiller were melt compounded with poly(vinylidene fluoride) (PVDF) matrix to enhance the β electroactive phase. A series of samples with two blending ratios of PVDF/PA6 (90/10 and 70/30 [wt%/wt%]) each containing 1, 3, and 5 wt% of BT were prepared. The SEM results revealed that the addition of BT to the neat blends refined the biphasic morphology which is mainly due to selective localization of BTs in PA6 dispersed phase as confirmed by TEM observation and wetting parameter predictions. The EDX analysis demonstrated a uniform distribution of BT nanoparticles in the filled systems. FTIR and XRD results showed that β content increased as a result of blending while the α phase was suppressed. The BT nanoparticles inclusion to the blends showed a synergistic effect on the β-polymorph content. These results in combination with the data derived from DSC (indicating reduction of the total crystallinity) complement the idea of β enhancement by the addition of BT nanoparticles and PA6 into PVDF.     

On the deformation mechanisms of β-polypropylene: 1. Effect of necking on β-phase PP crystals

PP samples containing β-phase crystals were prepared by doping with a β-nucleating agent. The β-PP specimens were tensile stretched at room temperature under various crosshead rates and the yielding behaviour was analyzed on the basis of Eyring's theory. After tensile testing, the β-phase was examined with WAXS and D.S.C. over the necking region and the deformation mechanisms were discussed. The β-phase was found to be mechanically stable at room temperature up to yielding point. However, once the samples were stretched to necking, the β-phase began to transform to the -phase; this phase transformation continued over the necking region. The phase transformation implied that local melting and crystallization occurred during cold drawing and gave powerful support to Flory's model of the deformation mechanism of crystalline plastics.     

Effect of immobilization of poly(γ-glutamic acid) on the biocompatibility of electrospun poly (L-lactide) mats

In this study, poly(L-lactide) (PLLA) non-woven mats were prepared by electrospinning technique, followed by treating with oxygen plasma and grafting with 3-aminopropyl triethoxysilane (APTES), then immersed in poly(γ-glutamic acid) (γ-PGA) solution to form a layer of γ-PGA on the surface. In so doing, hydrophobic PLLA would become highly hydrophilic. Through characterization of hydrophilicity and biocompatibility, the feasibility of these modified mats for wound dressing was evaluated. The results show that after the grafting of γ-PGA, the swelling ratio increased greatly from 7% for pristine PLLA mat to 321% for γ-PGA-grafted PLLA mat, and the contact angle decreased from 112° to 25°. In vitro cytocompatibility tests against L929 fibroblast show that γ-PGA-grafted PLLA was non-cytotoxic. In addition, the proliferation of fibroblasts was higher on γ-PGA-grafted PLLA than on pristine PLLA.