Iodine-transfer polymerization and CuAAC “click” chemistry: A versatile approach toward poly(vinylidene fluoride)-based amphiphilic triblock terpolymers

This study presents the synthesis and properties of linear PVDF-based amphiphilic triblock terpolymers with PS and PEO, [PVDF-b-PS-b-PEO], by adopting a procedure that involves: (a) iodine-transfer polymerization (ITP) of VDF with 1-iodoperfluorohexane (C₆F₁₃I) serving as chain-transfer agent (CTA) to afford C₆F₁₃-PVDF-I, (b) ITP of styrene with the C₆F₁₃-PVDF-I macromolecular-CTA to obtain C₆F₁₃-PVDF-b-PS-I diblock copolymer, (c) end-group exchange from iodo- to azido-group by nucleophilic substitution reaction with NaN_3, and (d) copper-catalyzed azide-alkyne cycloaddition (CuAAC) with alkyne-terminated PEO to achieve C₆F₁₃-PVDF-b-PS-b-PEO triblock terpolymers. The ¹H and ¹⁹F NMR spectroscopy confirmed the presence of all blocks, while gel permeation chromatography traces showed the living nature of ITP technique. The self-assembly of these terpolymers was investigated in films (atomic force microscopy and DSC), as well as in aqueous and organic solvents (DLS). The analysis of crystalline phases based on the FTIR spectroscopy indicated the conversion of PVDF α-phase into α + β-phases and β + γ-phases upon the incorporation of PS and PEO blocks, respectively. The synthesized amphiphilic copolymers were evaluated (fluorescence spectroscopy) as carriers of small hydrophobic molecules in water. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 163–171     

Thermal properties and structure of electrospun blends of PVDF with a fluorinated copolymer

We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322     

High Dielectric Poly(vinylidene fluoride)-Based Polymer Enables Uniform Lithium-Ion Transport in Solid-State Ionogel Electrolytes

Ionic liquids (ILs)-incorporated solid-state polymer electrolytes (iono-SPEs) have high ionic conductivities but show non-uniform Li⁺ transport in different phases. This work greatly promotes Li⁺ transport in polymer phases by employing a poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE), PTC] as the framework of ILs to prepare iono-SPEs. Unlike PVDF, PTC with suitable polarity shows weaker adsorption energy on IL cations, reducing their possibility of occupying Li⁺-hopping sites. The significantly higher dielectric constant of PTC than PVDF facilitates the dissociation of Li-anions clusters. These two factors motivate Li⁺ transport along PTC chains, narrowing the difference in Li⁺ transport among varied phases. The LiFePO₄/PTC iono-SPE/Li cells cycle steadily with capacity retention of 91.5 % after 1000 cycles at 1 C and 25 °C. This work paves a new way to induce uniform Li⁺ flux in iono-SPEs through polarity and dielectric design of polymer matrix.     

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.     

PVDF应力测量技术及在混凝土冲击实验中的应用

介绍了使用PVDF(polyvinylidene fluoride,聚偏二氟乙烯)应力计的应力直接测量技术。在SHPB装置上进行自制PVDF应力计动态压电系数的标定实验,分析了应力集中、横向泊松效应、摩擦效应对PVDF应力计信号及动态压电系数的影响。用PVDF应力计进行了混凝土的冲击压缩实验。利用混凝土前后端面PVDF应力计信号分析了实验过程中混凝土试样的应力均匀性。与应变计直测应变技术相结合得到了混凝土的动态应力-应变关系。     

Predicting Polymorphism of Electrospun Polyvinylidene Fluoride Membranes by Their Morphologies

Although electrospinning of polyvinylidene fluoride (PVDF) has been studied for more than 10 years, the crystalline phase differentiation of the electrospun mats is still normally through the combination of different characterization techniques, and the relationship between polymorphism and morphology of the fibers in electrospun PVDF membranes has never been reported. Here, we show their close relationships by conducting room-temperature electrospinning experiments on various polymer/solvent systems. The electrospun membranes full of bead-free fibers have a very high fraction of β-phase, F(β), over 90%, and high orientation, whereas the membranes comprising beads and/or a large number of beaded fibers most often result in a low fraction of β-phase (F(β) normally below 50%) and low orientation. On the other hand, electrospun membranes consisting of both bead-free fibers and a very limited number of beaded fibers showed a medium high fraction of β-phase, F(β) more than 70% but less than 90%. These findings suggest the feasibility of intuitively predicting the crystalline phase of electrospun PVDF membranes directly by their morphologies, which is obviously simple, inexpensive and convenient for future investigations.     

Co-continuity interval in immiscible polymer blends by dynamic mechanical spectroscopy in the molten and solid state

The work focuses on the detection of the co-continuity window in immiscible polymer blends. The purpose of the paper is to describe how rheological techniques can help to evaluate the composition range of the co-continuous morphology through the study of a particular system: PEO/PVDF-HFP. First, the blends were characterized by selective dissolution experiments and SEM observations. Then the ability of dynamic mechanical spectroscopy to detect the co-continuity was investigated in the melt and in the solid state. The evolution of the storage modulus of molten blends with their composition at a constant low frequency gives information about the co-continuity interval, especially as far as the onset of the continuity of the PEO phase is concerned. Then the immiscibility of the polymers and the continuity of PVDF-HFP as a function of blend composition have been highlighted by means of dynamic mechanical spectrometry below the melting point of PVDF-HFP. Comparison with results from classical methods shows fair agreement.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

PVDF压电薄膜在应力波测量中的应用

综合介绍了PVDF压力传感器的测试原理、动态标定实验，并采用定制的PVDF压力传感器测量了不同类型分层介质在冲击载荷作用下的压力衰减，说明了PVDF压力传感器在压力测量中有着很好的前景．     

PVDF在动态应变测量中的应用

研究了用PVDF压电薄膜进行动态应变测量的原理和方法,在单向应变块上对两种PVDF应变片的应变电荷常数进行了标定,并对一维应力杆中的应变波形进行了测量。实验给出了较好的测量精度。研究结果表明,PVDF应变片在动态应变测量中具有很好的应用潜力。     

用PVDF实时测量激光诱导的冲击波压力

本文用自己研制的ＰＶＤＦ（ｐｏｌｙｖｅｎｙｌｉｄｅｎｆｌｕｏｒｉｄｅ）压电传感器测量了０．２ｍｍ厚铝和２．０８ｍｍ厚Ｔ３００／环氧复合材料中激光诱导的冲击波压力，首次获得了这些材料中激光冲击波压力的时间演化波形。实验在中国科大强激光实验室的ＹＡＧ脉冲激光器上进行，激光波长１．０６μｍ，脉宽３３ｎｓ，靶面平均功率密度为１０９Ｗ／ｃｍ２量级。从所得数据估计了表面入射压力，其值与已有结果符合良好。实验结果证实，ＰＶＤＦ压电传感器频响高，量程宽，多次使用重复性好，可有效应用于激光冲击波压力的实时测量