Cooperative relaxations in semicrystalline fluoropolymers studied by thermally stimulated currents and ac dielectric

Semicrystalline fluoropolymers including poly(tetrafluoroethylene) (PTFE), a 8 mol % hexafluoropropylene (HFP)/92% TFE random copolymer (FEP), and poly(vinyl fluoride) (PVF) were studied using thermally stimulated current depolarization (TSC), ac dielectric, and other thermal analysis techniques. The TSC thermal sampling (TS) technique is emphasized here for the detection of broad and weak “cooperative” relaxations with all three of the polymers studied exhibiting two cooperative (i.e., relatively high apparent activation energy) transitions. The well-studied low-temperature γ relaxation in PTFE at ca. −100°C is characterized by this method as well as the γ relaxation in the less crystalline FEP sample. Higher temperature cooperative glass transitions, associated with constrained noncrystalline regions, are found at ca. 100°C in PTFE and ca. 80°C in FEP at TSC frequencies. Comparisons with relaxation studies of linear polyethylene are made, and the effects of crystallinity on the various transitions are discussed. The unique characterization by the TSC-TS technique in the detection of multiple “cooperative” relaxations, even in the case of overlapping transitions, is emphasized here. An example is the low-temperature relaxation in FEP. Two cooperative transitions were detected in PVF. The higher temperature one at ca. 45°C is the glass transition, as is well known in the literature. More information is needed to confirm the molecular origin and the effects of crystallinity and chemical structure on the low-temperature cooperative transition in PVF. © 1996 John Wiley & Sons, Inc.     

制备方法对AgInO2结构及光催化性能的影响

以离子交换法和"氟化异丙烯膜袋"水热法分别制备了AgInO2,利用XRD、低温氮吸附-脱附、SEM、紫外-可见漫反射光谱(UV-Vis diffuse reflection spectroscopy,DRS)和XPS对不同方法所得到的AgInO2进行了表征;以罗丹明B(RhB)和甲基橙(MO)为目标物,在可见光下考察了2种催化剂的光催化性能。结果表明,利用"氟化异丙烯膜袋"水热法制备的样品由于具有更好的结晶度,且在可见光区有更强的吸收,从而表现出了更好的可见光光催化活性(3 h降解RhB达94%。7 h降解MO达83%)。     

Strongly nonlinear beats in the dynamics of an elastic system with a strong local stiffness nonlinearity: Analysis and identification

We consider a linear cantilever beam attached to ground through a strongly nonlinear stiffness at its free boundary, and study its dynamics computationally by the assumed-modes method. The nonlinear stiffness of this system has no linear component, so it is essentially nonlinear and nonlinearizable. We find that the strong nonlinearity mostly affects the lower-frequency bending modes and gives rise to strongly nonlinear beat phenomena. Analysis of these beats proves that they are caused by internal resonance interactions of nonlinear normal modes (NNMs) of the system. These internal resonances are not of the classical type since they occur between bending modes whose linearized natural frequencies are not necessarily related by rational ratios; rather, they are due to the strong energy-dependence of the frequency of oscillation of the corresponding NNMs of the beam (arising from the strong local stiffness nonlinearity) and occur at energy ranges where the frequencies of these NNMs are rationally related. Nonlinear effects start at a different energy level for each mode. Lower modes are influenced at lower energies due to larger modal displacements than higher modes and thus, at certain energy levels, the NNMs become rationally related, which results in internal resonance. The internal resonances of NNMs are studied using a reduced order model of the beam system. Then, a nonlinear system identification method is developed, capable of identifying this type of strongly nonlinear modal interactions. It is based on an adaptive step-by-step application of empirical mode decomposition (EMD) to the measured time series, which makes it valid for multi-frequency beating signals. Our work extends an earlier nonlinear system identification approach developed for nearly mono-frequency (monochromatic) signals. The extended system identification method is applied to the identification of the strongly nonlinear dynamics of the considered cantilever beam with the local strong nonlinear stiffness at its free end.     

Frequency–energy plots of steady-state solutions for forced and damped systems,and vibration isolation by nonlinear mode localization

We study the structure of the periodic steady-state solutions of forced and damped strongly nonlinear coupled oscillators in the frequency–energy domain by constructing forced and damped frequency – energy plots (FEPs). Specifically, we analyze the steady periodic responses of a two degree-of-freedom system consisting of a grounded forced linear damped oscillator weakly coupled to a strongly nonlinear attachment under condition of 1:1 resonance. By performing complexification/averaging analysis we develop analytical approximations for strongly nonlinear steady-state responses. As an application, we examine vibration isolation of a harmonically forced linear oscillator by transferring and confining the steady-state vibration energy to the weakly coupled strongly nonlinear attachment, thereby drastically reducing its steady-state response. By comparing the nonlinear steady-state response of the linear oscillator to its corresponding frequency response function in the absence of a nonlinear attachment we demonstrate the efficacy of drastic vibration reduction through steady-state nonlinear targeted energy transfer. Hence, our study has practical implications for the effective passive vibration isolation of forced oscillators.     

聚全氟乙丙烯中空纤维膜研究

以聚全氟乙丙烯(FEP)为成膜聚合物,复合无机粒子为成孔剂,邻苯二甲酸二辛酯(DOP)为稀释剂,采用熔融纺丝工艺制备得到FEP中空纤维膜.分析和讨论了不同成膜体系对FEP中空纤维膜热性能、动态力学性能和力学性能的影响,并对膜的纯水通量和孔径分布进行表征.用扫描电子显微镜(SEM)观察了膜的横断面和表面形貌.结果表明,所得FEP中空纤维膜为由溶出微孔和界面微孔组成的海绵状孔结构.随着成孔剂含量的增加,成孔剂在成膜体系中分散程度变差,容易发生团聚,最终导致膜孔径变大,孔径分布变宽.成孔剂和稀释剂对FEP中空纤维膜的热性能和动态力学性能影响较小.当FEP含量增加到70 wt％时,膜表面容易形成一层致密层,降低了膜的通透性.