Morphologies and crystalline forms of polyvinylidene fluoride membranes prepared in different diluents by thermally induced phase separation

We have studied the morphologies and crystalline forms of polyvinylidene fluoride (PVDF) membranes separately prepared in four different diluents bearing >C?O groups, namely 1,2‐propylene glycol carbonate (PGC), dimethyl phthalate (DMP), diphenyl ketone (DPK), and dibutyl phthalate (DBP), by the thermally induced phase separation (TIPS) method. The permittivities of the diluents and PVDF were measured to compare the different PVDF–diluent systems. The results showed the permittivity of PGC to be much greater than that of PVDF, and those of DMP and DBP to be lower than that of PVDF. The permittivity difference between DPK and PVDF was not apparent above 120 °C. On cooling mixtures with a PVDF concentration of 10 wt %, PVDF crystallization was observed in the PVDF–DMP, PVDF–DBP, and PVDF–PGC systems, while liquid–liquid phase separation occurred in the PVDF–DPK system. A cross‐section of the PVDF–PGC membrane presented smooth PVDF particles in the β‐phase crystalline form. Those of the PVDF–DMP and PVDF–DBP membranes presented PVDF particles consisting of a fibrillar network in the α‐phase. The PVDF–DPK membrane preferentially adopted an α‐phase bicontinuous channel structure. When the concentration of PVDF was 60 wt %, the cross‐sections of the above four membranes revealed PVDF polyhedra, among which the PVDF–DMP, PVDF–DBP, and PVDF–DPK membranes retained the α‐phase crystalline form, and the diffraction peak of the α‐phase became visible in the X‐ray diffraction (XRD) spectrum of the PVDF–PGC membrane. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Mechanical and dielectric behavior of poly(vinylidene)–poly(arylene ether nitrile) composites as film capacitors for energy storage applications

Novel polymer composites PEN/PVDF were prepared from poly(arylene ether nitrile) (PEN) and poly(vinylidene fluoride) (PVDF) via solution mixing. Due to the toughening effect of PVDF, PEN/PVDF blends with 5 wt % PVDF exhibit higher tensile strength (106 MPa) and breaking elongation (8.09%) than pure PEN does. Because of introduction of PVDF and interfacial polarization, the dielectric constant of PEN/PVDF blends at 1 kHz and room temperature increases from 3.3 to 4.5 with increasing content of PVDF. The dissipation factor (tanδ) of PEN/PVDF blends is relatively low (<0.04) in a very wide frequency range from 250 Hz to 100 kHz. The PEN/PVDF blends show certain piezoelectric behavior (d ₃₃ from 0.9 to 1 pC/N) due to the contribution of PVDF. After polarization, the piezoelectric coefficient d ₃₃ somewhat increases. The results suggest that PEN/PVDF blends will have potential application in electronic information fields, especially in film capacitors.     

Matrix‐polymer‐functionalized multiwalled carbon nanotubes as a highly efficient toughening agent for matrix polymers

Matrix‐polymer‐functionalized multiwalled carbon nanotubes (MWCNTs) are demonstrated as a highly efficient toughening agent for matrix polymers. With poly(vinylidene fluoride) (PVDF) as the matrix polymer, the PVDF/MWCNT‐PVDF nanocomposite films show high toughness. With a small load amount of MWCNT‐PVDF (0.07 wt %), the nanocomposite film shows a yield point and a constant‐stress extension region in stress–strain tests, compared with the typical low‐extensibility feature of neat PVDF film. The PVDF/MWCNT‐PVDF‐0.7 film exhibits a 180‐fold increase of toughness and about 38‐fold increase in strain at break compared with neat PVDF film. This toughening effect is attributed to (a) homogeneous dispersion of MWCNT‐PVDF in PVDF, (b) the high efficiency of load‐transfer across MWCNT/PVDF interface, and (c) the long length of the MWCNTs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Comparison of PVDF/MWNT,PMMA/MWNT,and PVDF/PMMA/MWNT nanocomposites: MWNT dispersibility and thermal and rheological properties

Pristine multi-walled carbon nanotubes (MWNTs) were incorporated into poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA), and PVDF/PMMA blends to achieve binary and ternary nanocomposites. MWNTs were more compatible with the PVDF matrix than with the PMMA-containing matrices. MWNT addition did not alter the development of α-form PVDF crystals in the binary/ternary composites. Nucleation and overall isothermal crystallization of PVDF were enhanced by the presence of MWNTs, and enhancements were optimal in the PVDF/MWNT binary composites. Avrami analysis revealed that addition of MWNTs led to more extensive athermal-type nucleation of PVDF, and that PMMA slightly decreased the crystal growth dimension of PVDF. The equilibrium melting temperature (T_m°) of PVDF increased in the binary composites but remained nearly constant in the ternary system. Thermal stability was enhanced in the binary/ternary composites, and enhancements were more evident in the air environment than in nitrogen. Rheological property measurements revealed that the intensely entangled chains of high-molecular weight PVDF dominated the rheological response of PVDF-included samples in the melt state. A (pseudo)network structure was developed in each of the PVDF-included samples as well as in the 1 phr MWNT-added PMMA/MWNT composite. The storage moduli of the PVDF, PMMA, and PVDF/PMMA:1/1 blend increased to 37%, 22% and 34%, respectively, at 40 °C after addition of 1 phr MWNT.     

聚偏氟乙烯-稀释剂间介电常数差异对热致相分离法制膜微观结构的影响

采用1,4-丁内酯、邻苯二甲酸二甲酯、水杨酸甲酯、邻苯二甲酸二丁酯、三醋酸甘油酯和卡必醇醋酸酯作为稀释剂, 研究了在以热致相分离(TIPS)法制备聚偏氟乙烯(PVDF)微孔膜过程中, 聚偏氟乙烯-稀释剂间介电差异对PVDF膜微观结构的影响. 实验发现, PVDF-稀释剂间介电常数的差异与PVDF膜微观结构有一定关联. 当PVDF介电常数大于稀释剂的介电常数时, PVDF的分子间作用以引力为主导, PVDF分子易于聚集结晶, 形成松散球粒结构. 当PVDF介电常数与稀释剂的介电常数相近时, PVDF的分子间引力作用与斥力作用相均衡, 在淬冷条件下可形成近似双连续结构. 当PVDF介电常数小于稀释剂的介电常数时, PVDF分子间有一定的斥力效应, PVDF分子结晶困难.     

聚偏氟乙烯/聚醚型热塑性聚氨酯弹性体共混物的相互作用及增容机理

采用流延成膜法制备了4种增容改性的聚偏氟乙烯（PVDF）与聚醚型热塑性聚氨酯弹性体（TPU）固体共混物（PVDF/TPU）.结合分子动力学模拟研究了PVDF/TPU的相互作用,并探讨了其增容机理.研究结果表明,与PVDF/TPU-1,PVDF/TPU-2及PVDF/TPU-3相比,加入γ-缩水甘油醚氧丙基三甲氧基硅烷-端氨基丁腈橡胶（GPTMS-ATBN）后,PVDF/TPU-4的2个玻璃化转变温度（T_g）相互靠近,两相界面存在分布梯度,构成了双相连续的微观结构,表明GPTMS-ATBN增容PVDF/TPU共混物具有显著效果.同时,PVDF/TPU-4的共混结合能大幅减小,二面角扭转能、键角弯转能等明显增大,表明PVDF及TPU与GPTMS-ATBN之间发生相互作用.傅里叶红外光谱（FTIR）及X射线光电子能谱（XPS）证实了GPTMS-ATBN增容PVDF/TPU的机理为GPTMS-ATBN中ATBN链段与PVDF彼此缠绕,相互混溶,而水解后两端GPTMS中大量羟基与TPU分子链中氨基甲酸酯键及醚键相互吸附,从而生成了氢键.     

Surface characteristics and hemocompatibility of PAN/PVDF blend membranes

Polyacrylonitrile (PAN) was blended with polyvinylidine fluoride (PVDF) at various ratios and made into membranes. The hemocompatibility of the resulting membranes was evaluated based on human plasma proteins adsorption, platelet adhesion, thrombus formation, and blood coagulation time. The PAN/PVDF blends exhibited partial miscibility according to the inward shifting of their two glass transition temperatures. The microstructures of blend membranes examined using atomic force microscopy (AFM) indicated that the roughness increased with the PVDF content, and the phase separation was too severe to form a membrane when the PVDF content was more than 30%. The water contact angle of PAN/PVDF blend membranes increased with the PVDF content. By blending with 20 wt% apolar PVDF the adsorption of blood proteins could be reduced, and hence the platelet adhesion and thrombus formation was also reduced. However, when the PVDF content was 30 wt%, severe thrombogenicity was observed due probably to the more porous structure of blend membrane. These results demonstrated that the hemocompatibility would be improved for PAN/PVDF blend membranes with appropriate hydrophilicity and roughness. Copyright © 2005 John Wiley & Sons, Ltd.     

Enhanced β phase of polyvinylidene fluoride with addition of polyamide 6: role of interfacial interactions

In this study, the polymer blends composed of polyvinylidene fluoride (PVDF) and polyamide 6 (PA6) were prepared via precipitation method, and then, the effects of PA6 on the crystallization behavior of PVDF, including the polymorphism and crystallization kinetice, were systematically investigated. For this aim, time-resolved Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimeter were utilized to study the influence of PA6 on crystallization behavior of PVDF. Furthermore, the morphologic images from scanning electron microscopy also supply the corresponding evidences. The results obtained shows that PA6 is immiscible with PVDF, while the PA6 component could form polar environment around the PVDF segment which is conducive to the formation of β phase of PVDF. In addition, calorimetric studies via DSC on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics demonstrated conclusively that PA6 segments could effectively hinder the subsequent PVDF crystallization process because of the interfacial hydrogen bonds and incompatibility between PVDF and PA6.     

Crystallization and morphology of poly(vinylidene fluoride)/poly(3‐hydroxybutyrate) blends. III. Crystallization and phase diagram by differential scanning calorimetry

The crystallization of poly(vinylidene fluoride) (PVDF)/poly(3‐hydroxybutyrate) (PHB) blends was studied with differential scanning calorimetry, from which the phase diagram was derived. Strong miscibility was underlined by the large negative Flory–Huggins interaction parameter (?0.25). The crystallization of the blend components differed remarkably. Whereas PVDF always crystallized in the surroundings of a homogeneous melt, PHB crystallized in a volume that was confined by the already existing PVDF spherulites, partly in their surroundings and partly inside. Under isothermal conditions, PVDF usually crystallized regularly in three dimensions with predominant quench‐induced athermal nucleation. The Avrami exponent for PVDF dendritic spherulitic growth was, however, distinctly smaller than that for compact growth, and this revealed the two‐dimensional lamellar growth inside. This deviation from ideal Avrami behavior was caused by the development of compositional inhomogeneities as PVDF crystallization proceeded, and this decelerated the kinetics. PHB crystallized three‐dimensionally with mixed thermal and athermal nucleation outside the PVDF spherulites. Inside the PVDF spherulites, PHB crystallization proceeded in a fibrillar fashion with thermal nucleation; the growth front followed the amorphous paths inside the dendritic PVDF spherulites. The crystallization was faster than that in the melt of uncrystallized PVDF. Solid PVDF acts possibly heterogeneously nucleating, accelerating PHB crystallization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 287–295, 2005     

Crystallization and morphology of poly(vinylidene fluoride)/poly(3‐hydroxybutyrate) blends. I. Spherulitic morphology and growth by polarized microscopy

The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003     

聚偏氟乙烯-磺化聚醚砜相容性及其成膜性能

研究了聚偏氟乙烯(PVDF)-磺化聚醚砜(SPES)的相容性及其成膜性能.首先通过溶解度参数、粘度法和目测法研究共混溶液的相容性,接着采用浊度法测定了共混溶液的热力学性质,最后采用浸没沉淀法制备了共混膜并探讨了成膜性能.结果显示,PVDF和SPES为部分相容体系,随着SPES含量的增加,共混溶液相容性逐渐减小,当SPES含量增加到50wt%时,体系发生分相.共混溶液的成膜性能良好,SPES含量增加有利于体系发生液液分相,生成高孔隙率膜,并且极大的提高了PVDF膜的亲水性和水通量.     

Amino acids functionalized graphene oxide for enhanced hydrophilicity and antifouling property of poly(vinylidene fluoride) membranes

Herein, functionalized graphene oxide (GO) was prepared by the covalent functionalization with amino acids (lysine, glycine, glutamic acid and tyrosine) in this study. Zeta potential results demonstrated that covalent functionalization of GO with amino acids was favourable for their homogeneous dispersion in water and organic solvents. Based on the higher absolute value of zeta potential and the better dipersion stability of GO-lysine, the PVDF/GO-lysine hybrid membranes were then prepared via the phase inversion induced by immersion precipitation technique. SEM images showed a better pore diameter and porosity distribution on the PVDF/GO-lysine membrane surface. The zeta potential absolute value of the PVDF/GO-lysine membrane surface was higher than that of the virgin PVDF membrane. Furthermore, the PVDF/GO-lysine membranes surface exhibited good hydrophilicity. The water flux of PVDF/GO-lysine membranes can reach to two times of that of the virgin PVDF membrane. And the BSA adsorbed amount on PVDF/GO-lysine surface was decreased to 0.82 mg/cm² for PVDF/GO-lysine-8% membrane. Filtration experiment results indicated that the fouling resistance was significantly improved for the PVDF/GO-lysine membranes. As a result, lysine functionalized GO will provide a promising method to fabricate graphene oxide based hybrid membranes with effective antifouling property and hydrophilicity.     

Confined crystallization of PVDF and a PVDF‐TFE copolymer in nanolayered films

Layer‐multiplying coextrusion was used in conjunction with isothermal recrystallization to study the confined crystallization of polyvinylidene fluoride (PVDF) and polyvinylidene fluoride‐tetrafluoroethylene (PVDF‐TFE) using polycarbonate (PC) and polysulfone (PSF) as confining materials. Three layered systems were produced (PC/PVDF, PSF/PVDF, and PC/PVDF‐TFE) with layer thicknesses ranging from 525 to 28 nm. The crystal morphology was affected by both layer thickness and recrystallization temperature. Specifically, increased recrystallization temperature and decreased layer thickness facilitated the formation of high aspect ratio in‐plane crystals in both PVDF based polymers. On the other side of the spectrum, thicker layers and lower recrystallization temperatures produced on‐edge PVDF crystals and isotropic PVDF‐TFE crystals. The morphology was correlated with oxygen permeability, which decreased by almost two orders of magnitude compared with the bulk. A variety of crystal structures were obtained and explained with nucleation and diffusion theory. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Effects of partial replacement of silicone rubber with flurorubber on properties of dynamically cured poly(vinylidene fluoride)/silicone rubber/flurorubber ternary blends

Blends of poly(vinylidene fluoride) (PVDF), silicone rubber (SR) and flurorubber (FKM) were prepared via peroxide dynamic vulcanization. The effect of FKM loading on the morphology, mechanical properties, crystallization behavior, rheology and dynamic mechanical properties of the PVDF/SR/FKM ternary blends was investigated. A “network” was observed in the PVDF/SR binary blends, which disappeared in the ternary blends, but a core-shell-like structure was formed. The mechanical properties were significantly improved. The Izod impact strength of PVDF/SR/FKM blend with 19 wt% FKM was 18.3 kJ/m², which was 3–4 times higher than the PVDF/SR binary blend. The complex viscosity and storage modulus of the PVDF/SR/FKM blends decreased with increasing FKM content, hence the processability was improved. The increase of FKM content seemed to show a favorable effect on the crystallization of the PVDF component. It promoted the nucleation process of PVDF, leading to increased polymer crystallization rate and higher crystallization temperature. The glass-rubber transition temperature of the PVDF phase moved to a lower temperature.     

Enhanced Pervaporation Performance of Multi-layer PDMS/PVDF Composite Membrane for Ethanol Recovery from Aqueous Solution

Multi-layer PDMS/PVDF composite membrane with an alternative PDMS/PVDF/non-woven-fiber/PVDF/PDMS configuration was prepared in this paper. The porous PVDF substrate was obtained by casting PVDF solution on both sides of non-woven fiber with immersion precipitation phase inversion method. Polydimethylsiloxane (PDMS) was then cured by phenyltrimethoxylsilane (PTMOS) and coated onto the surface of porous PVDF substrate one layer by the other to obtain multi-layer PDMS/PVDF composite membrane. The multi-layer composite membrane was used for ethanol recovery from aqueous solution by pervaporation, and exhibited enhanced separation performance compared with one side PDMS/PVDF composite membranes, especially in the low ethanol concentration range. The maximum separation factor of multi-layer PDMS/PVDF composite membrane was obtained at 60 °C, and the total flux increased exponentially along with the increase of temperature. The composite membrane gave the best pervaporation performance with a separation factor of 15, permeation rate of 450 g/m²h with a 5 wt.% ethanol concentration at 60 °C.     

PVDF膜改性的方法研究

本文介绍了目前国内外聚偏氟乙烯(PVDF)超滤膜改性中常用的膜表面改性方法和膜材料改性方法。PVDF膜表面改性主要通过膜表面的物理改性、磺化改性、表面接枝改性、光化学改性、低温等离子体改性等方法来实现;而PVDF膜材料的改性主要是通过PVDF与亲水性高分子材料或小分子无机粒子的共混以及膜材料本体的化学改性来实现。改性PVDF膜的亲水性增强,使水通量增加,提高了机械性能,改善了抗污染性,增加了膜的使用寿命。     

聚偏氟乙烯MBR膜制备及改性研究进展

膜生物反应器技术作为一种新型、高效的水处理技术,已成功应用于废水处理系统。在膜分离工程领域,聚偏氟乙烯(PVDF)作为一种优异的膜材料,成为人们热衷的研究对象。本文综述了目前应用于MBR的PVDF膜制备方法,重点介绍了Fe(OH)3、TiO2t、ween-20+戊二醛、PEBAX、PVDF-g-POEM、PVDF-g-PEGMA、TPU、Al2O3、SiO2微粒等对PVDF膜的改性研究,并对PVDF制备MBR膜的发展前景进行了展望。经过改性后的膜在一定程度上能够有效增强亲水性和抗污染能力,延长膜的寿命,降低运行成本,而且出水水质更好,若增强其机械强度,将会有更广泛的用途。     

Crystallization behavior and hydrophilicity of poly (vinylidene fluoride) (PVDF)/poly (styrene-<Emphasis Type="Italic">co</Emphasis>-acrylonitrile) (SAN) blends

Poly (styrene-co-acrylonitrile) (SAN) is a hydrophilic non-crystalline copolymer, which is initially used in this paper to improve the hydrophilicity of poly (vinylidene fluoride) (PVDF). Investigation of the crystallization behavior of PVDF/SAN blends showed that the samples presented only α phase regardless of SAN content as cooling from the melt. A double-melting phenomenon was related to the perfection or crystal size of PVDF crystals. As the SAN content is increasing, crystallization of PVDF was limited, leading to a decreased crystallinity and lamellar growth. Besides, the hydrophilicity of PVDF was improved by blending with SAN. The sample containing 70 wt.% SAN performed a similar surface property of the neat SAN owing to the besieging of the PVDF phase by SAN. Observed from the cross section of the blends, PVDF/SAN blends were partially miscible with less than 50 wt.% SAN addition. As the SAN content was more than 50 wt.%, the crystalline PVDF particles clearly dispersed in the amorphous matrix.     

Preparation and dielectric properties of composites based on PVDF and PVDF-grafted graphene obtained from electrospinning-hot pressing method

In this work, graphene was modified by the grafting of poly(vinylidene fluoride) (PVDF) using Friedel-Crafts reaction to form PVDF-grafted graphene (PGG) filler, which was confirmed by transmission electron microscope, Fourier transform infrared, Raman spectroscopy, wide angle X-ray diffraction, and thermogravimetric analysis. The solution containing as-prepared PVDF-grafted graphene and PVDF was electrospun to form fibrous membranes, which was subjected to hot pressing in the laminating mode to prepare solid PGG/PVDF composite films. The structures of electrospun fibrous membrane and solid PGG/PVDF composite film were investigated by scanning electron microscope. Furthermore, it could be found that the dielectric constants of PGG/PVDF composites exhibiting relatively low dielectric loss factors were significantly higher than that of pure PVDF.     

EFFECT OF GAS FLOW RATE ON CRYSTAL STRUCTURES OF ELECTROSPUN AND GAS-JET/ELECTROSPUN POLY(VINYLIDENE FLUORIDE) FIBERS

The effect of gas flow rate on crystal structures of electrospun and gas-jet/electrospun poly(vinylidene fluoride) (PVDF) fibers was investigated.PVDF fibers were prepared by electrospinning and gas-jet/electrospinning of its N,N-dimethylformamide (DMF) solutions.The morphology of the PVDF fibers was investigated by scanning electron microscopy (SEM).With an increase of the gas flow rate,the average diameters of PVDF fibers were decreased.The crystal structures and thermal properties of the PVDF fibers w...