Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

液相添加剂对PTCR陶瓷电性能的影响

液相添加剂ＡＳＴ（Ａｌ２Ｏ３＋ＳｉＯ２＋ＴｉＯ２）对ＢａＴｉＯ３陶瓷材料电性能的影响很大，随着Ａｌ２Ｏ３含量的增加，材料的电性能降低；ＳｉＯ２、ＴｉＯ２的物理特性对材料电性能影响较大；过量ＴｉＯ２对材料ＰＴＣ效应有重要影响，适当过量ＴｉＯ２含量，可得到性能优良的ＰＴＣＲ陶瓷。     

简并量子拍频三能级系统中的光场压缩效应

本文讨论了V-型简并量子拍频三能级原子与单模相干辐射场相互作用时的动力学行为，并研究了光场的压缩效应。     

Chemical synthesis and electric properties of the conducting copolymer of aniline and o‐aminophenol

A copolymer, poly(aniline‐co‐o‐aminophenol), was prepared chemically by using ammonium peroxydisulfate as an oxidant. The monomer concentration ratio of o‐aminophenol to aniline strongly influences the copolymerization rate and properties of the copolymer. The optimum composition of a mixture for the chemical copolymerization consisted of 0.3 M aniline, 0.021 M o‐aminophenol, 0.42 M ammonium peroxydisulfate, and 2 M H₂SO₄. The result of cyclic voltammograms in a potential region of ?0.20 to 0.80 V (vs.SCE) indicates that the electrochemical activity of the copolymer prepared under the optimum condition is similar to that of polyaniline in more acid solutions. However, the copolymer still holds the good electrochemical activity until pH 11.0. Therefore, the pH dependence of the electrochemical property of the copolymer is improved, compared with poly(aniline‐co‐o‐aminophenol) prepared electrochemically, and is much better than that of polyaniline. The spectra of IR and ¹H NMR confirm that o‐aminophenol units are included in the copolymer chain, which play a key role in extending the usable pH region of the copolymer. The visible spectra of the copolymers show that a high concentration ratio of o‐aminophenol to aniline in a mixture inhibits the chain growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5573–5582, 2007     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003     

Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003     

Influence of preparation methods on structure and properties of PA6/PA66 blends: A comparison of melt‐mixing and in situ blending

The blends composed of polyamide 6 (PA6) and polyamide 66 (PA66) were obtained using two different preparation methods, one of which was the melt‐mixing through a twin‐screw extruder and the subsequent injection molding; and the other, the in situ blending through anionic polymerization of ε‐caprolactam in the presence of PA66. For the former, there existed a remarkable improvement in toughness but a drastic drop in strength and modulus; however, for the latter, a reverse but less significant trend of mechanical properties change appeared. Various characterizations were conducted, including the analyses of crystalline morphology, crystallographic form, and crystallization and melting behaviors using polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively; observation of morphology of fractured surface with scanning electron microscope (SEM); measurement of glass transition through dynamic mechanical analysis (DMA); and the intermolecular interaction as well as the interchange reaction between the two components by Fourier transform infrared spectrometry (FT‐IR) and ¹³C solution NMR. The presence and absence of interchange reaction was verified for the in situ and melt‐mixed blends, respectively. It is believed that the transreaction resulted in a drop in glass transition temperature (T_g) for the in situ blends, contrary to an increase of T_g with increasing PA66 content for the melt‐mixed ones. And the two kinds of fabrication methods led to significant differences in the crystallographic form, spherulite size and crystalline content and perfection as well. Accordingly, it is attempted to explain the reasons for the opposite trends of changes in the mechanical properties for these two blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1176–1186, 2007     

Synthesis and optoelectronic properties of silole‐containing polyfluorenes with binary structures

2,5‐Bis(2‐bromofluorene‐7‐yl)silole was prepared by a modified one‐pot synthesis with a reverse addition procedure, from which novel silole‐containing polyfluorenes with binary random and alternating structures (silole contents between 4.5 and 25% and high M_w up to 509 kDa were successfully synthesized. The well‐defined repeating unit of the alternating copolymer comprises a terfluorene and a silole ring. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were examined. The different excitation energy transfers from fluorene to silole of the copolymers in solution and in the solid state were compared. The films of the copolymers showed silole‐dominant green emissions with high absolute PL quantum yields up to 83%. EL devices of the copolymers with a configuration of ITO/PEDOT/copolymer/Ba/Al displayed exclusive silole emissions peaked at around 543 nm and the highest EL efficiency was achieved with the alternating copolymer. Using the alternating copolymer and poly(9,9‐dioctylfluorene) as the blend‐type emissive layer, a maximum external quantum efficiency of 1.99% (four times to that of the neat film) was realized, which was a high efficiency so far reported for silole‐containing polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 756–767, 2007     

Insight into chain dimensions in PEO/water solutions

Small‐Angle Neutron Scattering has been performed from poly(ethylene oxide) in deuterated water at temperature ranging from 10 to 80 °C. A simple fitting model was used to obtain a correlation length and a Porod exponent. The correlation length L characterizes the average distance between entanglements in the semidilute region and is proportional to the individual coil sizes in the dilute region. L was found to increase with temperature in the semidilute region but it decreases with temperature in the dilute region. This decrease is the precursor to the single‐chain collapse which applies to very dilute polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2196–2200, 2007     

The effect of nanoparticle shape on polymer‐nanocomposite rheology and tensile strength

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007