Calorimetric determination of the enthalpy change for the binding of methyl orange to poly(vinylpyrrolidone) in aqueous solution

Thermodynamic parameters have been determined for the interaction of methyl orange and poly(vinylpyrrolidone) in aqueous solutions containing tris, tris and hydrochloric acid, or water only. Enthalpy changes were determined by use of a flow microcalorimeter. Free energy changes were calculated from the results of equilbrium dialysis studies. The results are interpreted in terms of the behaviour of poly(vinylpyrrolidone) in these systems. Analysis of data shows that the hydrophobic interactions in the systems are in the order: tris > wateronly > tris-HC1.     

Mechanical properties of poly(ether-ether-ketone) for engineering applications

An outline of the characteristics of PEEK and the versatility of its compositional forms (micro and macro composites) are given to illustrate its wide potential for success in engineering applications. Although it is necessary to have particular tabulations of mechanical properties for engineering design, these are seldom available and consequently it is argued that an understanding of stiffness, toughness and strength properties are required to fully exploit available manufacturer's data and thus develop the full potential of PEEK and its composites. Stiffness characteristics are considered in terms of a modulus function which is dependent on time under load and temperature. In its composite forms, whether reinforced with short or continuous fibres, stiffness anistropy can be both considerable and complex, but some empirical ground-rules are apparent. For continuous fibre composites even in the form of complex lay-ups, it is also possible to attempt some stiffness prediction from certain pseudo-elastic constants. Toughness of PEEK and its composites is described in terms of both comparative and intrinsic properties. Instrumented falling weight impact data, particularly as a function of temperature enable some insight into ductile-brittle transitions for the unreinforced material, but crack initiation and crack propagation processes for the various fibre reinforced forms. Intrinsic toughness is described in terms of linear elastic fracture mechanics theory. Strength properties are described for static and dynamic loading configurations. In particular, PEEK and its composites are evaluated for increasing test severities for strength characteristics; stress concentration, loading form and test temperature are considered.     

Thermal degradation of cinnamoylated poly(vinyl alcohol)

Thermogravimetry and pyrolysis in combination with gas chromatography and infrared spectroscopy were the experimental techniques applied to the thermal degradation of cinnamoylated poly(vinyl alcohol) samples, constituted from vinyl alcohol-vinyl cinnamate photocrosslinkable copolymers. The thermal decomposition products include gases, liquids and solids. The gases are formed from saturated and unsaturated volatile hydrocarbons C₁? C₄, carbon monoxide and carbon dioxide. The liquid fraction includes aromatic hydrocarbons and some oxygenated organic compounds. The solid product identified in the greatest amount was cinnamic acid. The content in the thermal decomposition products varies considerably both with copolymer composition and temperature.     

Structure and properties of injection‐molded polypropylenes with different molecular weight distribution and tacticity characteristics

Two series of polypropylenes with different molecular weight distribution and tacticity characteristics were injection molded into flexural test specimens by varying cylinder temperature and the effects of the molecular weight distribution and tacticity on the structure and properties of the moldings were studied. Measured propertied were flexural modulus, flexural strength, heat distortion temperature, Izod impact strength, and mold shrinkage and structures studied were crystallinity, the thickness of skin layer, a*‐axis‐oriented component fraction and crystalline orientation functions. The relations between the structures and properties were also studied. It was found that the molecular weight distribution and tacticity characteristics affect the properties mainly through the molecular orientation and crystallinity, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2142–2156, 2002     

Alternating,all-trans polyenynes: Model compounds for poly(diacetylene)s with defined conjugation length

The syntheses of polyenynes as model compounds for poly(diacetylene)s (PDAs) are described. Variation of properties (UV–VIS, Raman, NMR and bond geometries) as a function of the chain length was investigated. After extrapolation to infinite chain length these data were compared to those for PDAs. From UV–VIS spectra a value of λ = 551 nm (2.25 eV) was calculated corresponding to the electronic transition of a single polyenyne chain. This energy is located at the low energy end of a yellow PDA solution spectrum. From Raman scattering v_(C?C) = 2108–2128 cm^?1 and v_(C?C) = 1505–1532 cm^?1 were calculated after extrapolation. Similarly sp-C¹³C NMR data yielded a shift of δ = 100 ppm. These data are almost identical to data known for yellow PDA solutions. Bond geometries are almost identical to those of poly(diacetylene)s and theoretical data.     

聚醚砜中空纤维的成形条件对其宏观结构的影响

主要讨论了纺速、填充液压力、凝固浴浓度和拉伸率成形条件的设置对中空纤维的宏观结构的影响 ,为设计具有合理的宏观结构的中空纤维膜提供参考     

交联型聚醚聚氨酯的表征、力学性能及其碱金属盐络合物的导电性能

采用三羟甲基丙烷（ＴＭＰ）作交联剂与聚乙二醇（ＰＥＯ－１５４０）和甲苯二异氰酸酯（ＴＤＩ）反应，得到了具有较好力学性能的交联型聚醚聚氨酯（ＰＥＵ），该聚合物与ＬｉＣｌＯ４的结合物具有较高的室温电导率（σ３０℃＝１．８７×１０￣（－４）Ｓ／ｃｍ）。采用全反射红外光谱（ＡＴＲ－ＩＲ）对聚合物的结构进行了表征。对聚合物的组成、不同ＴＤＩ类型及络合盐浓度对聚合物力学性能及其络合物电导率的影响进行了探讨。低度交联聚合物的络合物，其电导率与温度的关系符合建立在自由体积理论上的ＶＴＦ方程，表明络合物中离子的传导主要是在无定形区域进行，与自由体积有关。     

Preparation and properties of poly(ethylene oxide) star polymers

Poly(ethylene oxide) (PEO) star polymers were prepared by anionic polymerization of methacryloyl chloride and glyceryl trimethacrylate with sec‐butyllithium in cyclohexane. The ensuing polymers were grafted with poly(ethylene glycol) of molecular weight 400. The final product was washed with methylene chloride and analyzed with infrared spectroscopy, differential scanning calorimetry, and thermogravimetry. Star polymers of PEO were also prepared by anionic polymerization of glycidol with sec‐butyllithium in cyclohexane. The initiator was chosen so as to yield a polymer of 10,000 molecular weight. The resulting polymers were analyzed by nuclear magnetic resonance, infrared spectroscopy, and thermogravimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 322–327, 2003     

Flow of solutions of hydroxypropyl guar-poly(ethylene oxide) mixtures through a porous medium

Summary In flow through porous media, solutions of poly(ethylene oxide) (PEO) exhibit extension thickening, whereas hydroxypropyl guar (HPG) solutions are shear-thinning at high concentrations. The results show that the extension-thickening exhibited by PEO solutions becomes less critical with increasing flow rate as the concentration of HPG in the solution is increased. At high concentrations of HPG, the presence of PEO inhibits the shear-thinning behaviour, without increasing the apparent viscosity of the solution. The presence of HPG reduces the rate and extent of degradation of PEO in the flowing solution.     

Effects of α‐form or β‐form nuclei on polymorphic crystalline morphology of poly(butylene adipate)

The effects of α‐form and β‐form nuclei on polymorphic morphology of poly(butylene adipate) (PBA) upon recrystallization from the molten state up to various T_max values were examined by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and polarized light microscopy (PLM). In this study, PBA with complex melting and polymorphism behaviour was used as a model for examining different types and extents of residual nuclei. As the PBA initially containing the sole α‐crystal was brought to a molten state of various T_max, the extents of trace α‐form crystal nuclei varied and were dependent on T_max. Furthermore, it did not matter whether, initially, the PBA contained α‐ or β‐form crystals (or both) because only a single type of α‐nuclei could be left upon treatment to the molten liquid state at T_max. Therefore, only the α‐crystal in PBA had ‘memory capacity’ in the molten liquid state while the β‐crystal did not. This was so because the latter had been completely transformed into the solid state prior to being heated into a liquid. PBA crystallized before α‐nuclei could be packed into α‐crystal, regardless of the crystallization temperature (T_c). For recrystallization from molten PBA without any nuclei, the crystalline polymorphism was correspondingly influenced by T_c. Copyright © 2005 Society of Chemical Industry