Binary blends of polyethers with fatty acids: A thermal characterization of the phase transitions

A series of binary blends of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and polytetrahydrofuran (PTHF), characterized by similar average molecular weights, with selected fatty acids (capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid) were prepared by melt mixing. Differential scanning calorimetry was applied to characterize the phase transitions of melting and crystallization, and a synergistic effect was found to occur for PEO/fatty acid blends, as evidenced by the values of the enthalpy of the phase transition. This effect was probably due to hydrogen bonding between PEO and the fatty (carboxylic) acids, which facilitated the formation of crystalline structures; an analysis of IR spectroscopy data showed a shift in the absorption bands of OH groups. The morphology development of the PEO/carboxylic acid blends, as observed with polarizing light microscopy, could be described as spherulitic growth with spontaneous selection of the lamellar thickness. The textures of the individual fibrils, consisting of stacks of several tens of lamellae corresponding to PPO and PTHF, were less regular than the texture of PEO and showed large macroscopic heterogeneity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 861–870, 2003     

熔体温度对气体辅助注射成型PC／PE共混物形态的影响

分别在低温（200℃）和高温（270℃）下制备了聚碳酸酯／聚乙烯（PC／PE）共混物的气体辅助注射成型制品，通过扫描电镜对PC相不同部位的形态观察，发现分散相PC的形变和分布受成型温度的影响比较大。在低温成型时，分散相PC从表层到气道都有变形，而在高温成型时，分散相PC在气道部位几乎没有变形。在形态分析的基础上，探讨了温度对气体辅助注射成型共混物形态的形成和分布的影响机理。     

Effects of substituted aromatic heterocyclic phosphate salts on properties,crystallization, and melting behaviors of isotactic polypropylene

Nucleation effects of 2,2′‐methylene‐bis (4,6‐di‐tert‐butylphenyl) phosphate metal salts as a nucleating agent for isotactic polypropylene (iPP) were investigated with differential scanning calorimeter and polarized optical microscope, and their effects on mechanical, optical, and heat resistance properties of iPP were also studied. The results showed that monovalent metal salts of substituted aromatic heterocyclic phosphate such as sodium salt, lithium salt, and potassium salt had a good performance. With 0.2 wt % of sodium salt, lithium salt, or potassium salt incorporated into iPP, the crystallization peak temperature of iPP could be increased by 13.5, 13.6, and 15.0°C, respectively; the mass fraction of crystallinity of iPP could be increased by about 5%; and crystallization rate was enhanced increasingly. Meanwhile the tensile strength and flexural modulus of iPP could be increased by about 10 and 30%, respectively, and the clarity and heat distortion temperature of iPP could also be improved significantly. But bivalent and trivalent metal salts of substituted aromatic heterocyclic phosphate had little effect on properties of iPP. Meanwhile the morphology study showed that the addition of monovalent sodium salt could decrease the spherulite size of iPP significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4868–4874, 2006     

On the issue of urea phase connectivity in formulations based on molded flexible polyurethane foams

Lithium chloride was added to systematically alter the phase separation behavior, and hence, the nature of urea phase connectivity, in a series of plaques based on molded flexible polyurethane foam formulations. The plaques prepared were found to possess varied levels of urea phase connectivity that was examined at different length scales using several characterization techniques. SAXS, TEM, and t‐AFM were used to show that addition of LiCl systematically reduced the formation of the urea aggregate structures typically observed in flexible polyurethane foam formulations and thus led to a loss in urea phase connectivity at the macrolevel. SAXS, DSC, and DMA revealed that formulations with and without LiCl exhibited similar interdomain spacings and soft segment glass transitions, suggesting that incorporation of LiCl did not prevent the plaques from undergoing partial microphase separation. WAXS demonstrated that addition of LiCl led to a loss in the local ordering of the hard segments within the microdomains, i.e., it led to a reduction of microlevel connectivity or the regularity in segmental packing of the urea phase. High‐magnification t‐AFM images showed that increasing the LiCl content dispersed the urea component more homogeneously and in a more uniform manner in the polyol matrix, and thus altered the connectivity of the urea phase at the microdomain level. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2956–2967, 2002     

New catalyst systems for the polymerization of acetylene

The catalytic activities of WCI₆Ph₄Sn, MoCl₅Ph₄Sn and tetrabenzyltitanium were examined in the polymerization of acetylene. The structure, morphology and electrical conductivity of the doped and non doped polyacetylene were also studied.     

采用复合分散剂制备高表观密度聚氯乙烯树脂

介绍了高醇解度、高粘度聚乙烯醇 6 35与分散能力较强的其它分散剂按一定配比复合后的使用情况 ,结果表明 :采用复合分散剂 ,可在保持PVC树脂具有适当孔隙率的前提下 ,提高其表观密度 ;采用KH2 0 /6 0SH5 0复合分散剂在 10L釜中制得的PVC树脂表观密度约为 0 .4 6g/mL ;采用 6 35 /B72或 6 35 /F5 0复合分散剂制得PVC树脂的表观密度可比采用通用分散体系提高 10 %～ 15 % ,且水油比减少 ,增塑剂吸收量提高。分析了影响树脂表观密度和颗粒形态的主要因素     

Crystallization of poly(3‐hydroxybutyrate) by exfoliated graphite nanoplatelets

Poly(3‐hydroxybutyrate) (PHB) has been shown to be efficiently nucleated by exfoliated graphite nanoplatelets (xGnP). The nucleating effect of xGnP was investigated using differential scanning calorimetry, optical microscopy and atomic force microscopy. Nonisothermal crystallization of PHB from the melt required lower activation energies for PHB containing 1 wt % and 3 wt % xGnP (?214 and ?102 kJ/mol respectively) than for pure PHB (?60 kJ/mol). A kinetic study of the PHB/xGnP crystallization employing a modified form of the Avrami equation revealed that the presence of xGnP increased the PHB crystallization temperature, as well as the crystallization rates, and generated smaller and more numerous spherulites. Optical microscopy and atomic force microscopy confirmed the incorporation of xGnP into the lamellar structure of the PHB spherulites and provided insight into the influence of xGnP on spherulite size and lamellae thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Use of laser scanning confocal microscopy for characterizing changes in film thickness and local surface morphology of UV-exposed polymer coatings

Laser scanning confocal microscopy (LSCM) has been used to characterize the changes in film thickness and local surface morphology of polymer coatings during the UV degradation process. With the noninvasive feature of LSCM, one can obtain thickness information directly and nondestructively at various exposure times without destroying the specimens or deriving the thickness values from IR measurement by assuming uniform film ablation. Two acrylic polymer coatings were chosen for the study, and the physical and chemical changes of the two systems at various exposure times were measured and analyzed. Those measurable physical changes caused by UV exposure include film ablation, formation of pits and other surface defects, and increases in surface roughness. It was found in both coatings that changes in measured film thickness by LSCM were not correlated linearly to the predicted thickness loss using the changes in the CH band obtained by the Fourier Transform Infrared (FTIR) spectroscopy measurements in the later degradation stages. This result suggested it was not a uniform film ablation process during the UV degradation. At later stages, where surface deformation became severe, surface roughness and profile information using LSCM were also proven to be useful for analyzing the surface degradation process Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2004 in Philadelphia, PA.     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002     

PMMA‐modified divinylester/styrene resins: Phase diagrams and morphologies

Binary and ternary experimental cloud‐point curves (CPCs) for systems formulated with a low molar mass synthesized divinylester (DVE) resin, styrene (St), and poly(methyl methacrylate) (PMMA) were determined. The CPCs results were analyzed with the Flory–Huggins (F‐H) thermodynamic model taking into account the polydispersity of the DVE and PMMA components, to calculate the different binary interaction parameters and their temperature dependences. The St‐DVE system is miscible in all the composition range and down to the crystallization temperature of the St; therefore, the interaction parameter expression reported for a higher molar mass DVE was adapted. The interaction parameters obtained were used to calculate the phase diagrams of the St‐PMMA and the DVE‐PMMA binary systems and that of the St‐DVE‐PMMA ternary system at three different temperatures. Quasiternary phase diagrams show liquid–liquid partial miscibility of the St‐PMMA and DVE‐PMMA pairs. At room temperature, the St‐DVE‐PMMA system is miscible at all compositions. Final morphologies of PMMA‐modified cured St‐DVE materials were generated by polymerization‐induced phase separation (PIPS) mechanism from initial homogeneous mixtures. SEM and TEM micrographs were obtained to analyze the generated final morphologies, which showed a direct correlation with the initial miscibility of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4539–4549, 2006