由结晶动力学评价含结晶聚合物共混物相容性的研究进展

介绍了用结晶动力学分析的方法评价含结晶聚合物共混物的混合状态的基本理论和解析原理,综述了最新研究进展.     

香草醛系列化合物分子印迹聚合物膜的渗透特性

以香草醛(Van)或邻香草醛(o-Van)为模板分子, 用紫外光引发原位聚合, 分别制备了以尼龙和聚偏氟乙烯微孔滤膜为支撑材料的分子印迹复合膜, 并用紫外分光光度法研究了模板分子与功能单体之间的相互作用. 模板分子及竞争物的混合溶液渗透实验结果表明, 支撑材料对膜选择性传输趋势基本没有影响, 但选用合适的支撑材料会得到更理想的分离效果; 当竞争物尺寸小于模板分子时, 尺寸效应起主要作用, 竞争物优先传输; 当模板分子与竞争物尺寸相近时, 尺寸效应不起作用, 模板分子的选择性识别位点及与其相匹配的孔穴起主要作用, 模板分子优先传输; 当竞争物尺寸大于模板分子时, 则尺寸效应和模板分子的选择性识别位点及与其相匹配的孔穴同时起作用, 故模板分子优先传输.     

Study on polyvinylidene fluoride as alignment layer in twist-nematic liquid crystal display

The material with high dielectric constant can significantly affect the distribution of the electric field, so this kind of material has great potential in liquid crystal display. In this paper, polyvinylidene fluoride (PVDF) as alignment layer in liquid crystal display was analysed. The optical property, mechanical property, thermal stability and electrical property of PVDF were measured. Experiments show that the absorbance of PVDF material is 0.2 (or less) in visible light, which is better than the conventional alignment material polyimide (PI). The alignment effect can be generated by mechanical friction and the liquid crystal molecules are ordered or aligned, and PVDF can maintain good thermal stability as temperature is lower than 400°C. Since the dielectric constant of PVDF is usually between 6.0 and 8.0, it has significant effect on the distribution of the electric field in the liquid crystal display, and its dielectric loss is also less than PI. The lower operating voltage and the faster response time are obtained from the experiment. It can be confirmed by the experiments that PVDF could be used in liquid crystal display (LCD) as the alignment layer to improve LCD’s characteristics.     

非晶态与晶态的压电热电铁电高聚物

本文综述了晶态与非晶态两类高聚物的压电性,热释电性和铁电性。这些现象近年来研究得愈来愈广泛。文中以聚氯乙烯作为非晶态高聚物的例子;以PVDF及其共聚物,还有尼龙11作为晶态高聚物的例子。按照偶极子模型,高聚物一般假定需具备四个条件,就可显示出较大的压电性,热释电性和铁电性。本文探讨了上述高聚物的结构与性能,这些对识别材料是很重要的。最后,列举了PVDF及其它材料的压电常数,热释电系数和介电常数,以供读者参考。     

Extrusion of poly(vinylidene fluoride) recycled filaments: Effect of the processing cycles on the degree of crystallinity and electroactive phase content

This study analyses the possibility of reprocessing used poly(vinylidene fluoride), PVDF, maintaining the main properties critical for its use in piezoelectric sensor/actuator applications. The influence of multiple reprocessing cycles of PVDF on crystallinity and ß-phase content fundamental for its electroactive behaviour, was studied. Nine reprocessing cycles were completed and it was found that the material preserved the characteristics required for its use as piezoelectric polymer without significant degradation.     

聚偏氟乙烯-Nafion共混膜的制备及阻醇质子导电性能研究

直接甲醇燃料电池 (Ｄｉｒｅｃｔｍｅｔｈａｎｏｌｆｕｅｌｃｅｌｌ,ＭＤＦＣ)以高效、清洁和燃料储运方便等优点成为一类极具发展潜力的新型动力源 .但目前ＤＭＦＣ中普通使用的全氟磺酸膜 (如ＮａｆｉｏｎＴＭ 系列膜 )阻醇性能太差 ,导致大量甲醇从阳极穿过膜直接透到阴极 ,造成燃料的浪费和电池整体性能的下降 .据文献报道 ,即使甲醇浓度低到 1ｍｏｌ Ｌ ,也有近40 %的醇透过膜 .缺乏高性能的阻醇质子导电聚合物电解质膜是制约ＤＭＦＣ发展的瓶颈之一 .已有一些研究人员致力于新型膜材料的开发 ,如有人研制了聚苯并咪唑膜[1] 及各种掺杂…     

PVDF亲水复合膜的制备及表征

聚偏氟乙烯(PVDF)膜材料存在强疏水性的缺陷,亲水化改性是解决该问题的主要途径。以PVDF为基膜材料、聚乙烯醇(PVA)为共混材料、N,N-二甲基乙酰胺(DMAc)为溶剂,采用相转化法制备PVDF/PVA复合膜。考察了复合膜的PVDF/PVA共混比、固含量、低分子化合物添加剂、聚合物添加剂等非溶剂添加剂对复合膜接触角的影响。结果表明,当PVDF/PVA共混比为7/3,固含量为13%时,制备的复合膜接触角为22.92°;当添加剂为无水氯化锂、纳米二氧化硅、聚乙烯吡咯烷酮(PVP)时,复合膜接触角分别从53.12°、30.51°和41.89°都降低到了0°,亲水性提高,其中纳米二氧化硅作为添加剂时复合膜亲水性最好;当添加剂为丙三醇、PMMA、PEG时,复合膜接触角都增大,亲水性变差。     

Crystallization behavior and electroactive properties of PVDF,P(VDF-TrFE) and their blend films

PVDF, poly(vinylidene fluoride), as a semi-crystalline polymer, has interesting electroactive properties but usual melt and solution processing techniques result in its thermodynamically favored non-polar α-phase. By comparison, poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), PT for short, directly crystallizes in the polar β-phase under the same conditions as PVDF. In this study, blend thin films comprising PVDF and P(VDF-TrFE) were prepared by solvent casting method. The difference in the crystallization behavior is comprehensively investigated between the polymers: PVDF, P(VDF-TrFE), and the resulting blend films. It is found that replacement of the fluoride atom in TrFE monomer induces a strong steric hindrance that may alter the crystallization process to become more favorable for nucleation of the PVDF β-phase. To figure out the effect of TrFE content on the crystallization behavior and electroactive properties, films with different blend ratios of PVDF and P(VDF-TrFE) were prepared. We found that the PVDF films exhibit higher crystallization activation energy (ΔE) as PT content increases. The atomic force microscopy (AFM) in the piezoresponse force microscopy (PFM) mode illustrated that P5T5 films with equal contents of PVDF and P(VDF-TrFE) induced the highest d₃₃ values.     

NMR study of the tie-chain length distribution in oriented polymers

Wide-line NMR has been used in an investigation of noncrystalline (amorphous) regions in oriented semicrystalline polymers. Nylon 6 was chosen as a model material. The tie-chain length distribution function, the fraction of tie chains in the total number of chains in the crystallite cross section, and the relative number of taut tie chains have been determined. The data on the tie-chain length distribution are used in discussing specific features of vitrification of the amorphous regions in oriented polymers and in prediction macroscopic mechanical properties.     

Effect of Supercritical Carbon Dioxide Conditions on PVDF/PVP Microcellular Foams

Supercritical carbon dioxide (ScCO₂) was used as a physical foaming agent to prepare poly(vinylidene f luoride)/poly(N-vinyl pyrrolidone) (PVDF/PVP) microstructure material. The effects of foaming conditions including saturation pressure, foaming temperature and foaming time on PVDF/PVP foams morphology, thermal and electrical behavior were systematically investigated by scanning electron microscope, differential scanning calorimeter and broadband dielectric spectrometer. Small cell and low cell density were achieved at low pressure of 12 MPa, as increasing saturation pressure, the average cell size increased first, and then decreased. The competition between the cell growth and cell nucleation played an important role in average cell size, which was directly related to ScCO₂ processing conditions. With increasing foaming temperature, cell size was increased and cell density was decreased, in a nearly linear manner. The variation of foaming time was considered to be closely related to the time for cells to grow. Thus, the results revealed that the average cell size enhanced with extending foaming time. The thermal properties of PVDF/PVP composites are slightly inf luenced by foaming parameters, and the dielectric constant of PVDF/PVP composite foams decreased with increasing volume expansion ratio.     

Influence of Ce addition on the catalytic behavior of alumina-supported Cu-Co catalysts in NO reduction with CO

Polyvinylidene difluoride (PVDF) is one of the most widely used piezoelectric materials in micro-electromechanical systems (MEMS) and nano-electromechanical systems (NEMS) due to its excellent properties. Its applications range from biological to electric devices, such as an artificial hip joint, a microgripper, and a force sensor. It is critical to understand friction, adhesion, and wear mechanisms of this material. In this study, effect of piezoelectricity and lubricant with electric field on tribological properties was investigated, using poled and unpoled PVDF. To understand the tribological properties at nano- and macroscales, scale effect was also studied using an AFM and a tribometer. Relevant mechanisms are discussed.     

Preparation and electric property of PA/PVDF blend for energy storage material

This paper selected typical polar polymers which are polyvinylidene fluoride (PVDF) and polyamide (PA) to prepare PA/PVDF blend for energy storage material. Three kinds of PA (PA6, PA66 and PA11) with representative characters were chosen as the main research polymers for blending with PVDF. The electrical properties of three kinds of all-polymeric blends were tested and the microstructure was characterized by X-ray diffractometer (XRD), Fourier transform infrared instrument (FTIR), Scanning electron microscope (SEM) and Differential scanning calorimetry (DSC). Our finding suggests that the created high-ε polymeric blends represent a novel type of material that is easy to process. In addition, the dielectric constant and breakdown strength of PA/PVDFs are relatively high so that it can be applied to electronic components.     

Electrospun Nylon6 Nanofibrous Membrane as SPE Adsorbent for the Enrichment and Determination of Three Estrogens in Environmental Water Samples

In this paper, electrospun Nylon6 nanofibrous membrane was firstly used as adsorbent for solid membrane extraction (SME). The membrane was arranged as a disk in a home-made device, three estrogens-estradiol (E2), ethinylestradiol (EE2) and estrone (E1) in environmental water were extracted and then determined by liquid chromatography–ultraviolet detector (LC–UV). The important parameters affecting extraction efficiency were completely studied and optimized. The experimental results showed that only 1.5 mg Nylon6 nanofibrous membrane could make the maximum sample loading volume up to 50 mL and the target analytes were adsorbed effectively. Under the optimized conditions, the limits of detection (LOD) for E2, EE2, E1 were up to 0.05, 0.08, 0.17 ng mL^?1 respectively and the repeatabilities (RSD%) of intra-membrane and inter-membrane were below 6.0% about spiked samples. The proposed method was subsequently applied to studying water samples from river, rain, pond and tap. Satisfactory spiked recoveries in the range of 85.3–95.9% at 0.25 ng mL^?1 spiked level for the three estrogens were obtained. A comparison with commercial nylon microporous membrane and octadecylsilica (ODS) cartridges was also carried out. All the results showed that electrospun Nylon6 nanofibrous membrane, as a new adsorbent material has great potential for the enrichment of steroid estrogens in the water samples with satisfactory recovery and repeatability.     

Poly(vinylidene fluoride) (PVDF)/potassium sodium niobate (KNN)–based nanofibrous web: A unique nanogenerator for renewable energy harvesting and investigating the role of KNN nanostructures

In the recent era, finding renewable energy sources that are environmentally benign the main focus of scientific community around the globe. There is a plenty of renewable energy sources that are currently being researched such as solar power, thermal energy, wind energy, salinity gradients, and kinetic energy. Polymer‐ceramic–based nanocomposite piezoelectric material is known for quite some time for energy harvesting, but the real challenge lies as it requires very high loading of the ceramic part to obtain the required property and thus almost makes the system nonflexible. Developed material needs to be poled later on to use it as an electric energy generator from ambient mechanical movement. This current study is the first time attempt to produce a simple yet unique lightweight energy harvester using polyvinylidene fluoride (PVDF)/potassium sodium niobate (KNN) nanostructures–based nanocomposite flexible fibrous web where the material is in situ poled during its production using an electrospinning setup. At the beginning, various parameters were identified to synthesize and modulate KNN as nanostructural materials having higher aspect ratio, which is intended to provide a unique connection between KNN once these are embedded within the fibrous matrix. The incorporated KNN nanostructure having higher aspect ratio was also found to act as a beta nucleating agent in PVDF matrix and enhances the β‐phase crystal into the resultant fibrous web, which in turn increases the piezoelectric energy‐harvesting capacity manifold as compared with bare PVDF fibrous web. The in situ alignment of the nanostructured KNN (with a minimum loading, 5% only) into the fibrous nanocomposite is another achievement to obtain higher output. X‐ray diffraction and Fourier transform infrared analysis confirmed the mixture of α‐ and β‐crystalline phase of pure PVDF, which gets converted into β phase once KNN nanostructures are incorporated inside the nanofibrous web. An output voltage of 1.9 V was obtained from PVDF/KNN nanocomposite–based web, which is significantly higher (38 times) than generated voltage (50 mV) from the pure PVDF nanoweb without any subsequent poling operation.     

Determination of phthalate esters in water samples using Nylon6 nanofibers mat-based solid-phase extraction coupled to liquid chromatography

A new method was developed for simultaneous determination of five phthalate esters by a combination of mat-based solid-phase extraction (SPE) with high-performance liquid chromatography. The mat is composed of Nylon6 nanofibers. Dimethyl phthalate (DMP), diethl phthalate (DEP), di-n-butyl phthalate (DBP), di-(2-ethylhexyl) phthalate (DEHP) and dioctyl phthalate (DOP) were successfully separated on a RP-C18 column. Under optimized conditions, the detection limits found for DMP, DEP, DBP, DEHP and DOP were 3, 2, 6, 10 and 33 pg mL^?1, respectively. The method was applied to the analysis of various water samples. Spiked samples gave recoveries in the range from 86.9 to 101.9%, with relative standard deviations below 7.0%. A comparison of Nylon6 nanofibers mat as sorbents, and C18 cartridges and other kinds of SPE sorbents was carried out with respect to recovery, sensitivity, and reproducibility. The results indicated that the Nylon mat is a viable material for the enrichment and determination of phthalate esters in environmental water samples.     

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。     

尼龙1012的Brill转变

作为一类重要的结晶性聚合物 ,尼龙在加热或冷却过程中的晶型转变 [1,2 ]一直为人们所关注 .其中对尼龙 66的晶型转变研究得最多 [3～ 6 ] .在加热过程中尼龙 66室温下三斜的α晶型转变为高温下的假六方晶型 ,尼龙 66的这一晶型转变称为 Brill转变 [3] .在变温 X射线衍射测试中可明显观察到 Brill转变 :室温下α晶型的两个强的衍射峰随温度升高逐渐靠近 ,并在某一温度下合并为一个峰 ,这一温度称为 Brill转变温度 .近年来研究表明 ,许多脂肪族的尼龙升温时均表现出 Brill转变 ,并且 Brill转变温度随尼龙结晶条件及其结构的不同而不同 [7…     

Facile Spray-Coating for Fabrication of Superhydrophobic SiO2/PVDF Nanocomposite Coating on Paper Surface

A facile and low-cost superhydrophobic nanocomposite coating on paper surface was fabricated through one-step simply spraying dispersion, using hydrophobic silica nanoparticles as a filter (SiNPs) and polyvinylidene fluoride (PVDF) as a film-forming material. Hydrophobic SiNPs were fabricated via co-hydropholysis and condensation of TEOS and long-chain alkyl silane based on a simple sol-gel process, and the surface chemical structure of SiNPs was characterized by Fourier transform infrared (FTIR) spectra. The wettability and morphology of the coating surface were measured by contact angle (CA) measurement and scanning electron microscope, respectively. The influence of the mass ratio of hydrophobic SiNPs to PVDF (M(SiNPs:PVDF)) on the superhydrophobicity of paper surface was studied. The results showed that when M(SiNPs:PVDF) was 3:1, the water CA was 156.0 ± 1.0° for the nanocomposite coating with micro/nano-hierarchical structure on paper surface. Further, such superhydrophobic nanocomposite coatings on paper surface showed little adhesive property with water. In addition, the prepared superhydrophobic nanocomposite coating could be applied in other substrates, such as wood, aluminum sheet, stainless steel, polytetrafluoroethylene (PTFE), etc.     

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.