The Effects of Radiationon Crystal Transformationsof Poly（vinylidenefluoride）

his paper covers the effects of γ-radiation on crystal transformations of Poly-(vinylidene fluoride)before and after drawing as well as during annealing process.The results show that the drawing results in a drastic increase in both crystallinityalong the meridian direction and β-form crystal content for the irradiated samples.When the drawn samples were irradiated under appropriate dose and then annealedat 140℃ , transformation from β-form to a-form was subjected to an inhibition.The transformation mechanisms between the two types of crystals are discussed onthe basis of results of WAXD and DSC.

Electrospun poly（vinylidene fluoride-trifluoroethylene）/ zinc oxide nanocomposite tissue engineering scaffolds with enhanced cell adhesion and blood vessel formation

Piezoelectric materials that generate electrical signals in response to mechanical strain can be used in tissue engineering to stimulate cell proliferation. Poly （vinylidene fluoride-trifluoroethylene） （P（VDF-TrFE））, a piezoelectric polymer, is widely used in biomaterial applications. We hypothesized that incorporation of zinc oxide （ZnO） nanoparticles into the P（VDF-TrFE） matrix could promote adhesion, migration, and proliferation of cells, as well as blood vessel formation （angiogenesis）. In this study, we fabricated and comprehensively characterized a novel electrospun P（VDF-TrFE）/ZnO nanocomposite tissue engineering scaffold. We analyzed the morphological features of the polymeric matrix by scanning electron microscopy, and utilized Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry to examine changes in the crystalline phases of the copolymer due to addition of the nanoparticles. We detected no or minimal adverse effects of the biomaterials with regard to blood compatibility in vitro, biocompatibility, and cytotoxicity, indicating that P（VDF-TrFE）/ZnO nanocomposite scaffolds are suitable for tissue engineering applications. Interestingly, human mesenchymal stem cells （hMSCs） and human umbilical vein endothelial cells cultured on the nanocomposite scaffolds exhibited higher cell viability, adhesion, and proliferation compared to cells cultured on tissue culture plates or neat P（VDF-TrFE） scaffolds. Nanocomposite scaffolds implanted into rats with or without hMSCs did not elicit immunological responses, as assessed by macroscopic analysis and histology. Importantly, nanocomposite scaffolds promoted angiogenesis, which was increased in scaffolds pre-seeded with hMSCs. Overall, our results highlight the potential of these novel P（VDF-TrFE）/ZnO nanocomposites for use in tissue engineering, due to their biocompatibility and ability to promote cell adhesion and angiogenesis.

Modification on crystallization of poly（vinylidene fluoride） （PVDF） by solvent extraction of poly（methyl methacrylate） （PMMA） in PVDF/PMMA blends

The crystallization modification of poly（vinylidene fluoride） （PVDF） was investigated for the blend films of PVDF and poiy（methyl methacrylate） （PMMA）. The mass crystallinity （Xc） and further, the β-phase content （F（β）） of PVDF, were studied for the asprepared blend films with different mass ratios. In addition, the variations of Xc and F（β） were systematically probed once the PMMA component was removed from the related blend systems. DSC, FTIR and XRD measurements all indicated that 1）Xc, F（β） and even the content of a-phase （F（a）） decreased with the addition of PMMA; 2） with the extraction of PMMA, both Xc and F（β） increased while F（a） decreased. It is worth noting that the increase of Xc and F（β） depended on the relative amount of extracted PMMA （EpMMA）, i.e., the more PMMA was removed, the more Xc and F（β） increased. These results reveal the hindrance effect from the PMMA constituent to the crystallization of PVDF, and consequently, this restriction would be released when the PMMA was extracted.

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.

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...

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...

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.

A simple and controllable nanostructure comprising non-conductive poly（vinylidene fluoride） and graphene nanosheets for supercapacitor

An effective method was used to Ioidal suspensions of highly reduced graphene produce stable and homogeneous coloxide （RGO） in N,N-dimethylformamide （DMF） without the assistance of dispersing agents. According to the results of general characterization, relatively pure graphene sheets with the morphology of single layer or few-layer structure were obtained. Then nanocomposite powders of RGO and poly （vinylidene fluoride） （PVDF） were prepared by vacuum filtration of the mixed dispersions of both components. The nanocomposites exhibit a high-frequency capacitative response with small equivalent series resistance （ESR） at 0.4Q, a nearly rectangular cyclic voltammogram and possess a rapid current response as electrodes for supercapacitor in 5mol/L KOH electrolyte. Furthermore, after 600 galvanostatic charge/ discharge cycles, the supercapacitor still performs a very high stability and efficiency of capacitance.

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.

4天香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响

目的:探讨短期香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响。方法:BALB/c小鼠随机分为4组:对照组、熏烟组、poly(I:C)组和熏烟联合poly(I:C)组。检测支气管肺泡灌洗液(BALF)中总细胞数及细胞分类计数;普通光镜下观察各组细胞形态;荧光定量PCR检测肺组织细胞因子、趋化因子和干扰素及干扰素刺激基因表达。结果:与对照组相比,熏烟联合poly(I:C)组总细胞数计数、巨噬细胞与中性粒细胞计数明显升高(P<0.05),且熏烟联合poly(I:C)组巨噬细胞计数高于poly(I:C)组;与poly(I:C)组比较,熏烟联合poly(I:C)组小鼠气道灌洗液巨噬细胞体积较大,呈圆形或不规则形,细胞质较多空泡;与对照组相比,熏烟联合poly(I:C)组小鼠肺组织中性粒细胞趋化因子CXCL1(P<0.05)、CXCL2(P<0.01)和淋巴细胞趋化因子CCL2(P<0.01)mRNA表达升高,肺组织IL-1β、IL-6、TNF-αmRNA表达明显升高(P<0.01),肺组织IFN-β(P<0.01)、IFN-γ(P<0.05)、MX2(P<0.01)和IP-10(P<0.01)表达显著升高,且与poly(I:C)组小鼠相比,熏烟联合poly(I:C)组小鼠肺组织CXCL2(P<0.05)、TNF-α(P<0.01)和IFN-β(P<0.05)mRNA表达明显升高。结论:熏烟联合poly(I:C)诱导了小鼠肺部炎症反应和干扰素及干扰素刺激基因表达。同时,香烟暴露加剧了poly(I:C)诱导的小鼠肺部急性炎症反应和Ⅰ型干扰素表达。

Fabrication of Poly(vinylidene fluoride) /Polysulfone Flat Blend Membranes via Thermally Induced Phase Separation Process for Water Treatment

Poly(vinylidene fluoride) /polysulfone(PVDF/PSF) flat blend membrane was prepared via thermally induced phase separation(TIPS) technique.The membrane formation mechanism and membrane structure were investigated and the effects of PSF/PVDF weight ratio on morphology,crystallinity,porosity,and mechanical properties of the membrane were discussed.The relationship between membrane structure and performances,such as pure water flux and the rejection of carbonic black,was also discussed.It was found that solid-liquid(S-L) phase separation occurred for the PVDF/PSF/diluent system.The addition of PSF influences structure and crystallinity of the membrane,which in turn influences mechanical properties and performances of the membrane.The results reveal that it is possible to obtain network structure via S-L phase separation by blending the polymer,which has a partial compatibility with PVDF.

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.

Insight into fouling behavior of poly(vinylidene fluoride)(PVDF)hollow fiber membranes caused by dextran with different pore size distributions

Membrane fouling is the key problem that occurs in membrane process for water treatment. However, how membrane microstructure influences the fouling behavior is still not clear. In this study, fouling behavior caused by dextran was deeply and systematically investigated by employing four poly(vinylidene fluoride)(PVDF)membranes with different pore sizes, ranging from 24 to 94 nm. The extent of fouling by dextran was accurately characterized by pore reduction, flux decline, and the change of critical flux. The result shows that membrane with the smallest pore size of 24 nm experienced the smallest fouling rate and the lowest fouling extent. As the membrane pore size increased, the critical flux ranges were 105-114, 63-73, 38-44 and 34-43 L·m^(-2)·h^(-1),respectively. The critical flux and fouling resistances indicated that the fouling propensity increases with the increase of membrane pore size. Two pilot membrane modules with mean pore size of 25 nm and 60 nm were applied in membrane filtration of surface water treatment. The results showed that serious irreversible membrane fouling occurred on the membrane with pore size of 60 nm at the permeate flux of40.5 L·m^(-2)·h^(-1).On the other hand, membrane with pore size of 25 nm exhibited much better anti-fouling performance when permeate flux was set to 40.5,48 and 60 L·m^(-2)·h^(-1).

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.

Determining the degree of grafting for poly(vinylidene fluoride) graft-copolymers using fluorine elemental analysis

Acrylic acid (AAc) and styrene (St) were grafted onto poly(vinylidene fluoride) (PVDF) powder or membrane samples by pre-irradiation graft copolymerization.The grafted chains were proved by FT-IR spectroscopy analysis.The degree of grafting (DG) of the grafted PVDF was determined by fluorine elemental analysis (FEA) method,and was compared with the DGs determined by weighing method,acid-base back titration method and quantitative FT-IR method.The results show that the FEA method is accurate,convenient and universal,especially for the grafted polymer powders.

Effects of Stretching Ratio and Temperature on Phase Transition of Melt-spun Poly(Vinylidene Fluoride) Fibers

The effects of stretching ratio and stretching temperature on pbase transition of melt-spun poly （ vinylidene fluoride ） fibers were investigated and analyzed by using scanning electron microscopy, wide angle X- ray diffraction, differential scanning calorimetry and Fourier transfer infrared spectroscopy. The β phase exists in the as-spun fiber. The β phase content increases as the stretching ratio increases. When the stretching temperature is lower than 100 ℃ , enhancing temperature is good for the transition of phase a to ft. By contrast, when the stretching temperature is higher than 100 ℃ , enhancing temperature is unfavourable for the transition of phase a to β. Increasing the draw temperature increases the α-phase content.

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.

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.