聚偏氟乙烯的等离子体处理和ESR研究

在外部电极电容耦合反应装置中对聚偏氟乙烯(PVF₂)表面进行等离子体放电处理,测量了等离子体处理后PVF₂凝胶量、剪切强度和表面接触角等参量值的变化,另外,用ESR技术对等离子体处理生成的自由基进行研究,指出等离子体作用后表面分子不饱和链的增加和自由基引发的交联反应与表面粘接性能的改善有关.     

聚偏氟乙烯的等离子体处理和ESR研究

在外部电极电容耦合反应装置中对聚偏氟乙烯(PVF₂)表面进行等离子体放电处理,测量了等离子体处理后PVF₂凝胶量、剪切强度和表面接触角等参量值的变化,另外,用ESR技术对等离子体处理生成的自由基进行研究,指出等离子体作用后表面分子不饱和链的增加和自由基引发的交联反应与表面粘接性能的改善有关.     

聚偏氟乙烯分子链旋转时势能的变化

计算了聚偏氟乙烯分子链旋转时势能的变化.结果显示,当中心分子链旋转而其它链静止不动时,计算得到的势能曲线有4个很高的势垒,这些势垒来源于中心分子链和最近邻分子链中的氟原子对的“空间位阻”效应.这一结果与“六阱势”模型预言的势能变化存在准六度对称性相矛盾.计算结果表明,如果中心分子链和周围分子链同步旋转,势垒高度将极大地降低.另外,极化反转时晶格常数发生变化.最后得到的势垒高度约为7.5kJ/mol.与室温下的分子势运动的能量（约2.5kJ/mol）相比,这样的“浅”势阱不足以锁定分子偶极矩形成稳定的自发极 关键词：     

时间分辨傅里叶变换红外光谱法研究聚偏氟乙烯的晶变

本文用时间分辨傅里叶变换红外光谱（ＴＲ－ＦＴＩＲＳ）法研究了聚偏氟乙烯（ＰＶＤＦ）的晶型转变，并认５０８ｃｍ＾－１峰的增强和５２８ｃｍ＾－１峰的减弱表示ａ晶型向β晶型的转变，瞬变的初期时间约５ｍｓ，在晶型转变中伴随有“磁滞回线”的非线性效应。     

基于弛豫型铁电三元共聚物聚(偏氟乙烯-三氟乙烯-氯代偏氟乙烯)热释电性能的能量采集研究

研究了利用弛豫型铁电三元聚合物薄膜P(VDF-TrFE-CFE)的热释电性质,以温度波动作为初始能量形式进行热电能量的采集。由于该聚合物薄膜在发生由温度变化诱导的纳米极性区极化机制转换时,介电常数表现出明显的非线性变化,所以可以结合Ericsson循环实现热电能量采集。实验结果显示,最佳能量采集温度区间为20~-20℃,利用不同温度下的单极性电滞回线进行Ericsson循环模拟,两种模拟方式分别实现能量采集最大值和最小值,并从微观角度给出了两种模式的解释。同时研究了温度波动和外加电场对能量采集的影响。在外加电场100 kV·mm^-1、温度波动为40℃的情况下,能量采集值达到3483 mJ·cm^-3。与单晶材料相比,能量采集值提高了10倍。当工作温度降低至室温时,材料具有柔性,在能量采集方面具有应用潜力。     

聚(偏氟乙烯-三氟乙烯)纳米薄膜极化反转与疲劳特性

采用旋涂法制备了厚度为140 nm的聚(偏氟乙烯-三氟乙烯)[P(VDF-TrFE)]纳米薄膜, 研究了不同退火温度以及环境相对湿度对薄膜的极化反转和疲劳性能的影响. 运用X射线衍射仪、扫描电子显微镜和傅里叶变换红外光谱仪等测试技术对薄膜的微结构进行了表征. 实验结果表明, 通过不同温度的退火处理, P(VDF-TrFE)铁电薄膜的结晶度随着退火温度的升高而不断提高, 并且一定的温度范围内的退火处理可以提高薄膜的极化性能; 此外, P(VDF-TrFE) 铁电薄膜性能还表现出一定的环境湿度的敏感特性, 这与薄膜的物理性能和结构特点密切相关; P(VDF-TrFE)铁电薄膜在不同的环境湿度条件下 表现出较好的电学特性, 其漏电流均保持在10 ^-7A/cm² 的较低水平. 本工作揭示了再退火过程对薄膜的极化反转速度和疲劳恢复特性的影响, 并结合薄膜二次疲劳结果, 探讨了薄膜可逆的内部疲劳恢复特性机理.     

聚偏氟乙烯β相全反式结构链的第一性原理计算

用紧束缚的Hartree-Fock自洽场方法对聚偏氟乙烯(PVDF)β相的全反式结构链进行了第一性原理计算.在结构方面,计算得出,相邻F原子对平均距离为0264nm 相邻H原子对平均距离为0255nm 和F原子相连的C原子的平均距离为0.260nm 和H原子相连的C原子的平均距离为0.257nm.电偶极矩方面,计算得出单体的平均电偶极矩为3.98×10-30C·m(三个单体的链) 4.40×10-30C·m(六个单体的链) 4.44×10-30C·m(十一个单体的链).结构和电偶极矩的计算值与实验值基本符合.最后预测了全反式链的振动模式 关键词： 聚偏氟乙烯β相全反式结构链 Hartree-Fock自洽场方法     

不同制备条件对聚偏氟乙烯纳米线生长的影响

为提高铁电聚合物聚偏氟乙烯(PVDF)的压电性能,利用纳米限域效应,采用模板直接浸润法,将多孔氧化铝(AAO)模板在不同浓度的PVDF的DMF溶液中自然浸润,并添加聚乙烯吡咯烷酮(PVP)作为表面修饰剂,制备了一维材料PVDF纳米线。分别研究了浸润温度、溶液浓度及表面修饰剂等因素对PVDF纳米线生长过程的影响。通过FTIR、SEM、XRD等对样品的形貌结构及性能进行了表征,进一步讨论了AAO模板中PVDF纳米线的生长机制。结果表明:模板法生长的PVDF纳米线形貌主要受溶液浓度的影响,并且当浓度为0.10 g/m L时形貌较优,其平均长度为50μm,平均直径为180 nm,与AAO模板孔径尺寸相当;表面修饰剂PVP可在一定程度上防止纳米线团聚并且优化其尺寸均一性;AAO模板中生长的PVDF纳米线由于纳米限域效应优先向β晶相结晶,并且在生长过程中PVDF并未参与任何化学反应。     

聚偏氟乙烯对高速气流的响应——二级轻气炮分流系统特性的测量

 本文介绍了一种适合于测量高速气流的聚偏氟乙烯（PVF₂）压力传感器，这种传感器适用于测量各种小空间、非平面状样品表面对高速气流的响应。我们还研制了一套能可靠测得聚偏氟乙烯对高速气流响应的触发系统，它具有触发灵敏，使用可靠等优点。利用上述技术已成功地测得了二级轻气炮分流系统的分流效果，研究表明，采用多级分流后能使高速气流对靶的作用减弱90%，并且只需三块分流板即可满足实验要求。     

聚偏氟乙烯添加剂提高CsPbBr3钙钛矿太阳能电池性能

全无机CsPbBr₃钙钛矿太阳能电池因其优良的特性而受到广泛关注,但是钙钛矿层具有带隙宽、结晶性较差、表面缺陷较多和水分稳定性差等缺点,严重制约了全无机CsPbBr₃钙钛矿太阳能电池性能的提高和商业化发展.本文以无空穴传输层的碳基CsPbBr₃钙钛矿太阳能电池作为控制组,在PbBr₂前躯液中引入具有丰富疏水F离子的聚偏氟乙烯(polyvinylideine fluoride,PVDF)作为添加剂,调节CsPbBr₃钙钛矿薄膜的生长过程,改善晶体结构和薄膜形态,降低缺陷密度及非辐射复合几率.结果表明,PVDF处理后钙钛矿器件的光伏性能得到了显著改善,光电转换效率提高至8.17%.并且在无封装条件下保存1400 h后,光电转换效率仍可保持90%以上.这表明适量添加PVDF可以有效提高CsPbBr₃薄膜质量及器件性能.本工作对进一步拓展CsPbBr₃钙钛矿太阳能电池的优化设计思路具有重要意义.     

Poly(vinylidene fluoride) Crystallization Behavior and Membrane Structure Formation Via Thermally Induced Phase Separation with Benzophenone Diluent

Microporous poly(vinylidene fluoride) (PVDF) membranes were prepared by thermally induced phase separation (TIPS) at different quenching temperatures with benzophenone as the diluent. The crystallization behavior and crystal structure of PVDF in PVDF/benzophenone systems were investigated by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). The different PVDF concentrations had a remarkable effect on PVDF crystallization behavior and resulted in different membrane structures. Spherulitic structures were vague when the PVDF/benzophenone solution was quenched to ?8°C; however, discernable spherulitic structures were obtained when quenched to 34 and 49°C. Additionally, two phase separation mechanisms (solid–solid (S–S) and solid–liquid (S–L) phase separation) were observed during membrane preparation. It was revealed by scanning electron microscopy (SEM) that microporous membranes had more discernable spherulitic structures formed by S–L phase separation than by S–S phase separation, which induced macrovoids and irregular pores on the fracture surfaces of membranes.     

Friction and Wear Behavior of Polyamide 66/Poly(vinylidene fluoride) Blends

The tribological performance of PA66 and PVDF blends was investigated by a block‐on ring sliding friction and wear tester. The appropriate amount of PVDF can decrease the friction coefficient and improve the wear resistance of PA66. Moreover, the appropriate amount of PA66 can improve the wear resistance of PVDF. SEM analysis shows that PVDF is noncompatible with PA66, and the blend presents a two‐phase structure. A smooth worn surface is a main reason for improving the frictional and wear properties of the PA66/PVDF blend. Besides, slight debris is an important factor in improving the wear resistance of the PA66/PVDF blend. FT‐IR analysis shows that the oxidation and degradation behavior of PVDF is effectively controlled in the PA66/PVDF blends. Therefore, the blend of PA66 and PVDF is a potential polymer material for tribological applications.     

Crystallization Behavior of Amorphous Poly(l-Lactide)

Amorphous poly(l-lactide) (PLLA) was annealed in two different ways: amorphous samples were heated at a given temperature to induce crystallization (one-step annealing); and amorphous samples were first crystallized at a low temperature and subsequently annealed at a higher temperature than the crystallization temperature. Samples thus prepared were measured by DSC. The original amorphous sample exhibited an exothermic peak at about 100°C (exothermic peak I), an exothermic peak just below the melting point (exothermic peak II), and an endothermic peak when it was melted. Exothermic peak I was caused by cold crystallization. When the melting points of PLLA samples, heat-treated in various ways, were plotted as a function of annealing temperature, there was discontinuity at about 120°C. From analyses of wide-angle X-ray diffraction patterns, it was found that when amorphous PLLA was crystallized at a temperature below 120°C, crystallites of the β-form formed, and when annealed at a temperature above 120°C, crystallites of the α-form grew. Thus, exothermic peak I was attributed to cold crystallization of the β-form, and peak II was caused by the phase transition of the β-form to a more stable form.     

Poly(vinylidene fluoride) membranes by an ultrasound assisted phase inversion method

Poly(vinylidene fluoride) (PVDF) membranes were prepared by an ultrasound assisted phase inversion process. The effect of ultrasonic intensity on the evolution of membrane morphology with and without the addition of pore former LiCl during precipitation process was comprehensively investigated. Besides the inter-diffusion between the solvent and nonsolvent, the ultrasonic cavitation was thought to have significant influences on phase inversion and the resultant membrane morphology. The mutual diffusion between water and solvent during the ultrasound assisted phase inversion process was measured. The crystalline structure was detected by wide angle X-ray diffractometer (WAXD). The thermal behavior was studied by differential scanning calorimeter (DSC). The mechanical strength, forward and reverse water flux, rejection to bovine serum albumin (BSA) and pepsin were also investigated. By the ultrasound assisted phase inversion method, ultra-filtration membrane was successfully prepared, which exhibited more preferable morphology, better mechanical property and more favorable permeability without sacrificing the rejection and thermal stability.     

Analysis of plasticizer influence in Poly(vinyl acetate)/Poly(vinylidene fluoride) polymer blend electrolyte

Gel polymer electrolyte based on poly(vinyl acetate) and poly(vinylidene fluoride) was prepared by solvent casting technique, in which the addition of plasticizers improves the conductivity of polymer membranes. The blend polymer electrolyte containing propylene carbonate (PC) exhibits the highest conductivity of 0.922?×?10^?2 S cm^?1 at room temperature because of the higher dielectric constant as compared to other plasticizers used in the present study. Material characterizations were done with the help of SEM and FT-IR techniques. The activation energy values were computed from ‘log σ?1/T’ Arrhenius plots.     

Dielectric Loss Suppression of Silver/Poly(vinylidene fluoride) Composite Films with Polydopamine

The preparation and dielectric properties of silver-polydopamine/poly(vinylidene fluoride) (Ag-PDOP/PVDF) composite films with suppressed dielectric loss are reported. The dielectric loss tangents of the composite films were found to be rather low similar to that of pure PVDF over the frequency range 100 Hz to 30 kHz, almost regardless of the Ag content, and even lower than that of pristine PVDF in the relatively high frequency region. The nanoscale structure comprised of Ag nanoparticles (Ag NPs), isolated by the PDOP coating and the PVDF matrix, hindered the formation of percolative networks, resulting in the decreased conduction loss in the composite films, even at a high filler loading. The strong interfacial interaction between the Ag@PDOP particles and the PVDF matrix also contributed to the restrained interfacial loss. Consequently, these composite films had higher permittivity and smaller dielectric loss than the PVDF matrix at relatively high frequencies, and would thus be attractive for physically small capacitor applications in electronics and electric power systems.     

The polymorphism of poly(vinylidene fluoride) IV. The structure of high-pressure-crystallized poly(vinylidene fluoride)

A detailed study of high-pressure-crystallized poly(vinylidene fluoride) has indicated that a mixture of low-melting phase II and high-melting phase I is present, rather than a new crystalline phase (phase III) as originally suggested.

The relative amounts of phase I and phase II resulting from crystallization under pressure are a function of pressure and the degree of supercooling. Pressure crystallization at 285°C and 5500 atm results in samples which were pure phase I with an increased melting point of 187°C.     

Preparation of Poly(vinylidene fluoride)/Poly(methyl methacrylate) Blend Microporous Membranes via the Thermally Induced Phase Separation Process

The thermally induced phase separation (TIPS) process was employed to prepare poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blend microporous membranes. The effect of PMMA content on the dynamic crystallization temperature of the PVDF/PMMA/sulfolane system was analyzed. The effects of PMMA weight fraction and cooling rate on the cross-sectional morphology, crystallinity, crystal structure, thermal stability, and porous structure of the resulting membranes were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a mercury porosimeter, respectively. The mechanical properties of the membranes were evaluated by tensile tests. It was found that solid–liquid phase separation occurred in the PVDF/PMMA/sulfolane system. Scanning electron microscopy revealed that either increasing PMMA weight fraction or decreasing cooling rate will lead to a macroscopical phase separation between PVDF and PMMA. PMMA weight fraction and cooling rate had some influence on the crystallinity, porous structure, and mechanical properties, but no influence on the polymer crystal structure of the membranes. PMMA weight fraction influenced thermal stability of the final membranes but cooling rate did not.     

Surface Effect of Two Different Calcium Fluoride Fillers on the Non-Isothermal Crystallization Behavior of Poly(ethylene Terephthalate)

Two different types of calcium fluoride (CaF₂) particles were incorporated into a poly(ethylene terephthalate) (PET) matrix, fine particles (～350 nm), and nanoparticles (～70 nm). Both of them were synthesized by a chemical precipitation method using triethanolamine (TEA) as stabilizer. To obtain the nanoparticles, a greater amount of TEA was added during the synthesis in order to limit their growth. Therefore, unlike the fine particles, nanoparticles contained a greater amount of the stabilizer. Once CaF₂ particles were obtained, the composite materials were prepared by melt-blending PET and particles at different filler loadings. The influence of both kinds of particles on the non-isothermal crystallization behavior of PET was investigated by using differential scanning calorimetry and field emission scanning electron microscopy. The Jeziorny-modified Avrami equation was applied to describe the kinetics of the non-isothermal crystallization, and several parameters were analyzed (half-crystallization time, Avrami exponent, and rate constant). According to the results, it is clear that CaF₂ particles act as nucleating agents, accelerating the crystallization rate of PET. However, the effect on the crystallization rate was more noticeable with the addition of the fine particles where the surface plays an important role for epitaxial crystallization, while the addition of the nanoparticles with an organic surface coating resulted in a crystallization behavior similar to the observed for PET.     

Effect of Benzoic Acid on the Crystallization Behavior of Poly(3-Hydroxybutyrate)

The effect of benzoic acid (BA) on the crystallization behavior of poly(3-hydroxybut yrate; PHB) was studied. A differential scanning calorimeter was used to monitor the crystallization kinetics and thermal behavior. During the crystallization process from the melt, the presence of BA led to a decrease of the crystallization temperature of PHB compared with that for pure PHB. From the depression of the melting and glass transition temperatures of PHB, it can be concluded that BA is miscible, and has a strong plasticization effect on PHB. Isothermal crystallization at 80°C results showed that the addition of BA caused a decrease in the overall crystallization rate of PHB. Polarized optical micrographs of PHB/BA showed that the nucleation density of PHB spherulites decreased with increasing weight percentage of BA.