Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

Scaling laws and internal structure for characterizing electrospun poly[(R)-3-hydroxybutyrate] fibers

Using chloroform/dimethylformamide (CF/DMF) co-solvent, electrospinning of poly[(R)-3-hydroxybutyrate] (PHB) solutions was carried out at ambient temperature. The effects of the applied voltage (V), flow-rate (Q), and solution viscoelastic properties on the Taylor cone, electrified jet, and fiber morphology were investigated. In addition, the electric field developed by the needle-plate electrode configuration was calculated using a finite element analysis to reveal the tip-to-collector (H) effect. Among the processing parameters (V, Q and H), it was found that Q played a key role in determining the jet diameter (d_j) and electrospun fiber diameter (d_f), and scaling laws existed between them, i.e., d_j-Q^0.61 and d_f-Q^0.33. The diameter reduction ratios of D_o/d_j (D_o is the needle diameter) and d_j/d_f were measured as 50-120 and 5-10, respectively; it suggested that major jet stretching took place in the straight electrified jet region, and further chain orientation could be gained by the subsequent process of jet whipping. By changing PHB concentrations from 5 to 15 wt%, the solution viscosity (η_o) was increased from 100 to 4900 cP, whereas the surface tension and solution conductivity remained unchanged; it provided a good model solution to exclusively reveal the η_o effect on the electrospinning process. Our results showed that the η_o-dependence of d_j and d_f also followed simple scaling laws: d_j-η_o^0.06, and d_f-η_o^0.39, with a prefactor depending on the processing variables, mainly the flow-rate. Regardless of the PHB concentrations used, the obtained PHB fibers showed a similar crystallinity fraction of ca. 0.63 and possession of major α-crystals together with a small amount of β-crystals with zigzag chain conformation.     

Morphological changes in poly(?-caprolactone) in dense carbon dioxide

Morphological changes that take place in poly(?-caprolactone) upon exposure to carbon dioxide at high pressures have been explored as a function of pressure and temperature. SEM and DSC results point to a competition between CO₂-modulated crystallization and pressure-induced phase separation which leads to unique morphologies. At 293 K, exposure to CO₂ at pressures up to 45 MPa leads to recrystallization resulting in higher level of crystallinity and higher melting temperatures. Highest crystallinity levels along with distinct crystal morphology were observed after exposure to CO₂ at 308 K and 21 MPa. At a higher pressure at this temperature (308 K/34 MPa) polymer undergoes melting, and foaming is achieved during depressurization prior to solidification. At 323 K, the polymer is found to display unique crystal morphology with concave crystal geometry as well as porous domains. The results are discussed in terms of the crystallization and phase separation paths that are followed during exposure to CO₂ and the depressurization stages.     

乳状液膜法制备草酸稀土

系统研究了在乳状液膜内水相直接制备草酸稀土的方法，讨论了内水相草酸浓度、表面活性剂浓度、载体浓度、外水相酸度和外水相稀土浓度对迁移率的影响，找到了制备草酸稀土的最佳条件，草酸稀土经灼烧所得的氧化物含ＲＥ２Ｏ３〉９９．５％，与萃取法相比，此方法具有成本低、能耗少、污染程度低的特点，具有工业化前景。     

Determination of the solubility parameter of poly(ethylene oxide) at 25°C by gas-liquid chromatography

The solubility parameter of poly(ethylene oxide) at 25°C has been determined using the method developed by DiPaola-Baranyi and Guillet, by the extrapolation of the values of the interaction parameter χ, at high temperatures, ranging from 70°–90°, 90°–110° and 110°–130°C down to 25°C. The values of the solubility parameter obtained, depending on the temperature ranges employed, are 9.8, 9.9 and 10.1, respectively.     

淀粉丙烯酸接枝共聚吸水性树脂的研究进展

基于淀粉丙烯酸接枝共聚作为吸水性树脂具有环保和可生物降解的优良特性 ,目前 ,人们普遍关注的是如何提高其吸水性 ,抗温性 ,控制水份释放 ,压力下保水 ,以及电解液的吸收等。这些特性的改进将使产品的用途更为广泛 ,可以预见 ,淀粉丙烯酸接枝共聚作为吸水性树脂具有广阔的应用和发展前景。     

Degree of crosslinking and mechanical properties of crosslinked poly(vinyl alcohol) beads for use in solid-phase organic synthesis

The limited swellability in polar media of the commonly used polystyrene/divinylbenzene (PS-DVB) support materials for solid-phase organic synthesis has led to the development of novel, highly swellable hydrophilic gels designed for use in aqueous or polar media. Poly(vinyl alcohol) beads crosslinked with epichlorohydrin (PVA-EP) were prepared by a two-step inverse-suspension polymerization method. While it is known that the morphology of the resulting beads can be controlled by the ratio of EP versus PVA as well as by the pre-crosslinking time, the actual degree of crosslinking of the beads and their mechanical properties remain unknown. It is therefore the purpose of this study to evaluate the actual degree of crosslinking of beads prepared with different quantities of crosslinker in the feed by spectroscopic (Raman, nuclear magnetic resonance) and chemical (functional group loading) methods. The mechanical properties of these swollen PVA-EP beads will be evaluated by single-bead unconfined compression in solvents such as water, N,N-dimethylformamide (DMF), and tetrahydrofuran (THF) and compared to model PS-DVB beads commonly used for solid phase synthesis.     

Synthesis of tertiary poly(amido-amine)s with amido- and amino-groups randomly arranged along the macromolecular chain

A new synthesis of poly(amido-amine)s from bis (secondary amine)s and acryloyl chloride has been studied, leading to polymers in which the amido- and amino-groups are randomly arranged along the macromolecular chain. A poly(amido-amine) based on piperazine, chosen as the mother compound, has been fully characterized by ¹³C n.m.r. as well as by identification and quantitative evaluation of its hydrolysis products.     

Poly(N-vinyl-2-pyrrolidone) hydrogel production by ultraviolet radiation: new methodologies to accelerate crosslinking

Poly(N-vinyl-2-pyrrolidone) hydrogels produced by high-energy radiation relies on water radiolysis as a primary process leading to crosslinks. Conversely, ultraviolet direct irradiation into PVP leads to crosslinking trough pyrrolidinone moiety photolysis. However, this process showed to be rather inefficient. This work describes the crosslinking of poly(N-vinyl-2-pyrrolidone) based on hydrogen peroxide photolysis, therefore mimicking water radiolysis, using UV-C (e.g. low pressure Hg lamp) or UV-A radiation sources. The process efficiency and the properties of the hydrogel formed are discussed and compared with other methods of hydrogel production.