聚偏氟乙烯共混体系的压电性及其分子运动——Ⅱ.PVDF与 P(VDF-HFE)以及PVDF与P(VDF-TFE)的共混体系

本文研究了 PVDF-P(VDF-HFE)以及 PVDF-P(VDF-TFE)共混体系的压电、介电、力学松弛谱。其松弛转变过程基本与 PVDF 的相似。α,β,γ压电松弛峰分别位于40～120℃,-40℃,-85℃附近。实验结果表明后一体系的压电性大于前一体系的。同时,PVDF-P(VDF-TFE)的压电性也大于PVDF-PMMA 共混体系的。选择第二组分时,以介电常数高,模量小而本身又具有压电性的,更有助于共混薄膜压电性的提高。在同样的极化条件下,经拉伸的 P(VDF-TFE)薄膜,其压电性大于未经拉伸的薄膜,这表明分子的取向对薄膜的压电性也有影响。TSC 表明,42℃的松弛峰与晶区表面捕获的空间电荷有关,对压电性也有一定的贡献。     

聚偏氟乙烯共混体系的压电性及其分子运动II.PVDF与P(VDF-HFE)以及PVDF与P(VDF-TFE)的共混体系

本文研究了PVDF-P(VDF-HFE)以及PVDF-P(VDF-TFE)共混体系的压电、介电、力学松弛谱。其松弛转变过程基本与PVDF的相似。α,βγ压电松弛峰分别位于40～120℃,-40℃,-85℃附近。实验结果表明后一体系压电性大于前一体系的。同时,PVDF-P(VDF-TFE)的压电性也大于PVDF-PMMA共混体系的。选择第二组分时,以介电常数高、模量小而本身又具有压电性的,更有助于共混薄膜压电性的提高。在同样的极化条件下,经拉伸的P(VDF-TFE)薄膜,其压电性大于未经拉伸的薄膜,这表明分子的取向对薄膜的压电性也有影响。TSC表明, 42℃的松弛峰与晶区表面捕获的空间电荷有关,对压电性也有一定的贡献。     

聚偏氟乙烯共混体系的压电性及其分子运动

聚偏氧乙烯(PVDF)的压电效应近年来引起了人们的极大兴趣,为了探索PVDF共混体系中第二组分对薄膜压电性能的影响及开发新的压电材料,我们研究了PVDF的三个共混体系的压电性及其分子运动。这三个共混体系是: 1.PVDF+PMMA(聚甲基丙烯酸甲酯);2.PVDF+F₂₆(偏氟乙烯-全氟丙烯共聚物),3. PVDF+F₂₄(偏氟乙烯-四氟乙烯共聚物)。     

聚偏氟乙烯共混体系的压电性及其分子运动

聚偏氟乙烯(PVDF)的压电效应近年来引起了人们的极大兴趣,用它制成的各种换能器已得到了广泛应用,关于它的压电性及其分子运动已有报道。为了探索PVDF共混体系中第二组分对薄膜压电性能的影响及开发新的压电材料,我们研究了PVDF的三个共混体系的压电性及其分子运动。这三个共混体系是:     

相分离对聚偏氟乙烯/聚甲基丙烯酸甲酯共混物的力学与耐紫外老化性能的影响

采用熔融共混法制备聚偏氟乙烯/聚甲基丙烯酸甲酯( PVDF/PMMA)共混物,考察其力学性能、耐紫外老化性能、熔体动态流变、结晶与热分解行为.PMMA含量(wPMMA)为10 wt％时,共混物形成均相结构,力学与耐老化性能最好.wPMMA≥20 wt％时,PMMA形成球状聚集体,共混物力学性能与耐候性显著降低.PMMA的存在可提高PVDF的结晶度,降低熔融温度,但不改变PVDF晶体结构.     

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.     

聚偏氟乙烯/左旋聚乳酸的相容性及其共混膜的结构和性能研究

动态力学分析(DMA)、溶度参数法、聚合物混合焓法对聚偏氟乙烯(PVDF)和左旋聚乳酸(PLLA)的相容性分析结果显示,随着共混体系中PLLA的增加,PVDF和PLLA之间的相容性变差。扫描电镜(SEM)、广角X-射线衍射(WAXD)和拉伸实验对共混膜中PVDF/PLLA配比对其微观结构和力学性能影响的分析结果显示,随PLLA含量从10%增加到50%,共混膜由均匀致密结构变为存在缝隙的多孔结构,共混膜结晶度增加,断裂伸长率下降,断裂强度先增加后下降,在PLLA含量为40%时,强度达到最大。     

聚偏氟乙烯膜的改性研究进展

主要介绍了聚偏氟乙烯(PVDF)膜在近年来改性方法的最新研究进展,从辐照改性、等离子体改性、共混改性和化学改性等几方面进行了详细介绍,简要介绍了PVDF膜作为离子交换膜的一些最新应用.     

碳纳米管的加入对聚偏氟乙烯/丙烯酸酯共混物形状记忆性能的影响

利用聚偏氟乙烯(PVDF)微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物(PVDF/ACM)共混材料。为提高其形状回复应力,又将碳纳米管(CNT)引入该共混体系中,系统研究了PVDF/ACM/CNT三元体系纳米复合材料的制备、结构及性能。结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,加入质量分数为4%的CNT,材料在25℃时的储能模量由2000 MPa提高至3130 MPa。     

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.     

Miscibility and crystallization behavior in blends of poly(methyl methacrylate) and poly(vinylidene fluoride): Effect of star‐like topology of poly(methyl methacrylate) chain

A tetraarmed star‐shaped poly(methyl methacrylate) (s‐PMMA) was synthesized via atom transfer radical polymerization with 2‐bromoisobutyryl pentaerythritol as the initiator. For comparison, a linear PMMA with the identical molecular weight (l‐PMMA) was also prepared. The blends of the two PMMA samples with poly (vinylidene fluoride) (PVDF) were prepared to investigate the effect of macromolecular topological structure on miscibility and crystallization behavior of the binary blends. The behavior of single and composition‐dependent glass transition temperatures was found for the blends of s‐PMMA with PVDF, indicating that the s‐PMMA is miscible with PVDF in the amorphous state just like l‐PMMA. The miscibility was further evidenced by the depression of equilibrium melting points. It is found that the blends of s‐PMMA and PVDF displayed the larger k value of Gordon–Taylor equation than the blends of l‐PMMA and PVDF blends. According to the depression of equilibrium melting points, the intermolecular parameters for the two blends were estimated. It is noted that the s‐PMMA/PVDF blends displayed the lower interaction parameter than l‐PMMA/PVDF blends. The isothermal crystallization kinetics shows that the crystallization of PVDF in the blends containing s‐PMMA is faster than that in the blends containing the linear PMMA. The surface‐folding free energy of PVDF chains in the blends containing s‐PMMA is significantly lower than those in the blends containing l‐PMMA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2580–2593, 2007     

Thermal and mechanical behavior of amorphous and semi-crystalline poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Various PVDF/PMMA (poly(vinylidene fluoride)/poly(methyl methacrylate)) blends were selected for mechanical testing in compression. At low PVDF content (less than 50/50 w/w), the blends remain amorphous and PVDF and PMMA are fully miscible. In PVDF-richer blends, PVDF crystallizes in part, leading to a PMMA-enriched homogeneous amorphous phase. In this study, the degree of crystallinity was set at equilibrium by appropriate annealing of the samples before testing. Mechanical analysis was focused on the low deformation range, and especially on the yield region. Depending on the test temperature and blend composition, three types of response were identified, depending on whether plastic deformation is influenced: 1) by the PMMA secondary relaxation motions, 2) by the PVDF/PMMA glass transition motions, or 3) by the crystallite-constrained PVDF chains.     

Ba0.6Sr0.4TiO3/聚偏氟乙烯-聚甲基丙烯酸甲酯复合材料的制备及其介电性能

采用流延热压工艺制备Ba_0.6Sr_0.4TiO₃(BST)/聚偏氟乙烯(PVDF)?聚甲基丙烯酸甲酯(PMMA)复合薄膜,研究了PMMA含量对复合材料微观组织结构和介电性能的影响规律。结果表明,BST相能够均匀分散在聚合物基体中,归因于PMMA与PVDF良好的相容性,2种聚合物之间的界面不分明;随着PMMA含量的增加,复合材料的介电常数先降低后升高,耐击穿强度和介电可调性先增加后减少。PMMA含量(体积分数)为15%的BST/PVDF?PMMA₁₅复合材料的综合性能最佳:介电常数为23.2,介电损耗为0.07,耐击穿强度为1412 kV·cm^-1,在550 kV·cm^-1偏压场下,介电可调性为26.2%。     

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

Compatibilization of the partially miscible poly(vinylidene fluoride) (PVDF)/poly(styrene-co-acrylonitrile) (SAN) pair by a third homopolymer, i.e., poly(methyl methacrylate) (PMMA), was investigated in relation to cross section morphology, crystallization behaviors and hydrophilicity of the polyblends. Scanning electron microscopy showed a more regular and homogeneous morphology when more than 15 wt.% PMMA was incorporated. The samples presented only α phase regardless of PMMA content in the blend. As the PMMA content increased in the blends, the interactions between each component were enhanced, and the crystallization of PVDF was limited, leading to a decreasing of the crystallinity and the crystallite thickness. Besides, the hydrophilicity of PVDF was further improved by PMMA addition. The sample containing 15 wt.% PMMA showed a more hydrophilic property due to the more polar part of surface tension induced by PMMA addition. Observed from the cross section of the blends, the miscibility of partially miscible PVDF/SAN blends were efficiently improved by PMMA incorporation.     

Studies of ESR Nitroxide probe mobility in polymer blends

We report studies of the temperature-dependence of the ESR spectrum of the nitroxide spin radical 4-(2-bromoacetamide)-2,2,6,6 tetramethyl-1-oxyl piperidine (BRAMO) dispersed in poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), and PVDF/PMMA and PVAC/PMMA blends of varying composition. In PVDF/PMMA blends which show a single composition-dependent T_g, the mobility of BRAMO is identical to that in pure PMMA. On the other hand, in PVAC/PMMA blends, the mobility of BRAMO corresponds to that in pure PVAC. The results suggest that (1) BRAMO selectively binds to polymers based on hydrogen bonding affinity, (2) the spin probe is sensitive to segmental motions on a length scale shorter than those which give rise to the glass transition, and (3) compatible polymer blends are heterogeneous on the length scale of the BRAMO probe (ca. 8.3 Å).     

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.     

Thermorheological complexity of poly(methyl methacrylate)/poly(vinylidene fluoride) miscible polymer blend: Terminal and segmental levels

Oscillatory shear rheometry data for a miscible blend of 20 wt % poly(vinylidene fluoride) (PVDF) in poly(methyl methacrylate) (PMMA) shows breakdown of time–temperature superposition for this blend. A comparison between glass transition temperature which PMMA chains sense in the blend and effective glass transition temperature of this component indicates that, the Lodge–McLeish model can describe terminal dynamics of PMMA. In addition, terminal dynamics of PVDF chains in the blend is similar to that of its pure state in agreement with the mentioned model. At segmental level, dynamic mechanical thermal analysis of four wholly amorphous blends suggests that cooperativity of molecular motions decreases upon addition of 30 and 40 wt % PVDF to PMMA. This behavior has been confirmed via calculation of degree of fragility which presumably is attributed to strong tendency of PVDF chains to self‐association rather than inter‐association with PMMA chains according to the FTIR results. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2860–2870, 2007     

Hydrophilic modification of poly(vinylidene fluoride) (PVDF) by in situ polymerization of methyl methacrylate (MMA) monomer

The hydrophilicity of poly(vinylidene fluoride) (PVDF) was first improved by in situ polymerization of polar monomer in PVDF solution. Methyl methacrylate was adopted as the reaction monomer, and the polymerization occurred in a solution of PVDF in N,N-dimethylformamide. PVDF/poly(methyl methacrylate) (PMMA) blend was obtained after in situ polymerization. The relative hydrophilicity of the in situ blend was characterized by contact angle measurement. At the same time, the hydrophilicity of the PVDF/PMMA blends prepared by solution blending was compared with that of the in situ blend. The contact angle measurements indicated that in situ polymerization has a stronger modifying effect on the hydrophilicity of PVDF than solution blending.     

PMMA/PVDF共混对PVDF的β相构型影响的研究

采用溶液法制备了不同含量的聚甲基丙烯酸甲酯/聚偏二氟乙烯(PMMA/PVDF)共混薄膜,利用傅立叶变换红外光谱(FTIR)、X射线衍射谱(XRD)、和差热分析法(DSC)对共混薄膜的结晶行为进行了分析。结果表明,共混物中PMMA的含量对PVDF的β相构型有明显影响:PMMA/PVDF=30/70共混物中β相含量最高。为提高PVDF薄膜的铁电性能提供了新的研究方法。