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     

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     

提高太安堆积密度的结晶工艺研究

以季戊四醇经浓硝酸酯化后的粗制太安为原料，在溶课题上重结晶得精制成品太安，讨论了不同溶剂，结晶速度，结晶溶液pH值对太安堆积密度的影响。     

Studies on crystallization behaviors and crystal morphology of polyamide 66/clay nanocomposites

X‐ray diffraction methods, DSC thermal analysis, and polarized light microscopy (PLM) were used to investigate the structural changes of nylon 66/clay nanocomposites. PA 66/clay nanocomposites were prepared by the method of melt intercalation. The results indicate that the addition of the intercalated organo‐montmorillonite (OMMT) can induce generation of the β‐form crystal of PA 66 and substantially affect the arrangement of molecules in the α‐form crystal, although the crystallinity scarcely changes. Also, the DSC results indicate that the addition of OMMT in the PA 66 matrix leads to increases of crystallization temperatures and the full width at half maximum (FWHM) of the exothermic peaks. Moreover, the viscosity factor is the main influence on FWHM of the exothermic peaks of PA 66/clay nanocomposites. The results of nonisothermal crystallization kinetics show that OMMT has the effect of heterogeneous nucleation and leads to the decrease of the size of the spherocrystal. The heterogeneous nucleation effects of OMMTs influence the mechanism of crystallization and the growth mode of PA 66 crystals. PLM photographs verify that the size of spherocrystal is decreased and visually confirm the theory of crystallization kinetics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 756–763, 2005     

Solid‐state polymerization of poly(ethylene terephthalate). I. Experimental study of the reaction kinetics and properties

The solid‐state polymerization (SSP) reaction kinetics of poly(ethylene terephthalate) were investigated in connection with the initial precursor intrinsic viscosity (IV; molecular weight). Evaluations were performed with otherwise equivalent precursors melt‐polymerized to IVs of 0.50, 0.56, and 0.64 dL/g. The changes in the molecular weight and other properties were monitored as functions of the reaction times at solid‐state temperatures of 160–230°C. Precursors with higher initial molecular weights exhibited higher rates of SSP than those with lower initial values, as discussed in connection with the levels of crystallinity and the carboxyl and hydroxyl end‐group composition. Activation energies decreased at temperatures above 200°C, and this indicated a change in the SSP reaction mechanism. At temperatures of 200–230°C, similar activation energies were required for the polymerization of all three precursors. Lower temperature polymerizations, from 160 to 200°C, required higher activation energies for all precursors, with the 0.50‐IV material requirement almost twice as high as that calculated for the higher IV precursors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 197–212, 2003     

麝香体系结晶分离研究

研究了根据酮麝香、1,3-二甲基-2,4-二硝基-5-叔丁基苯晶体生长速度的不同,从对二者均达到饱和的溶液中分离得到1,3-二甲基-2,4-二硝基-5-叔丁基苯晶体的过程,计算了晶体生长速度并进行了实验验证。     

Crystallographic Texture Development in Bismuth Sodium Titanate Prepared by Reactive-Templated Grain Growth Method

Bi_0.5Na_0.5TiO₃ (BNT) and 0.94Bi_0.5Na_0.5TiO₃·0.06BaTiO₃ (BNT–BT) bulk ceramics with extensive 〈100〉 texture were prepared by the reactive-templated grain growth method, using platelike Bi₄Ti₃O₁₂ (BIT) particles as templates for BNT. Calcined compacts were composed of matrix grains with random orientation and 〈100〉-oriented grains transformed from aligned BIT particles, and the texture developed by the growth of oriented grains during sintering. Ceramics with extensive texture were obtained by using the starting mixture containing the maximum concentration of platelike BIT to form the maximum volume fraction of oriented grains.     

Influence of the cross‐sectional shape on the structure and properties of polyester fibers

The effects of the fiber cross‐sectional shape on the structure and properties of polyester fibers were investigated. Fully drawn yarn (FDY) polyester fibers (167 dtex and 48 filaments) were produced under the same spinning conditions used in a spinning plant. The only difference between the fibers was their cross‐sectional shapes. Four different cross‐sectional shapes were chosen for the experimental work: round, hollow‐round, trilobal, and hollow‐trilobal. The crystallinity and values of the maximum stress, maximum strain, modulus, yield stress, shrinkage in boiling water, and unevenness of the fibers were determined. The difference in the cross‐sectional shapes influenced the modulus, maximum strain, yield stress, and shrinkage in boiling water. No effects on the crystallinity and maximum stress were observed. The results suggested that the hollow fibers had higher amorphous orientation than the full fibers. The hollow‐round fiber had the highest unevenness value. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2615–2621, 2007     

Role of heat transfer and thermal conductivity in the crystallization behavior of polypropylene‐containing additives: A phenomenological model

The thermal conductivity of a filler and the thermal conductivity of a composite made from that filler influence the heat‐transfer process during melt processing. The heat‐transfer process from the melt to the mold wall becomes an important factor in developing the skin–core morphology. These aspects were examined in this study. The thermal conductivity of polypropylene–filler composites was estimated with a standard model for various fillers such as calcium carbonate, talc, silica, wollastonite, mica, and carbon fibers. The rate of cooling under given conditions, including the melting temperature, mold wall temperature, mass of the composite, and filler content, was estimated with standard heat‐transfer equations. The time to attain the crystallization temperature for polypropylene was evaluated with a regression method with differential temperature steps. The crystallization curves were experimentally determined for the different fillers, and from them, the induction period for the onset of crystallization was estimated. These observations were correlated with the expected trends from the aforementioned formalism. The excellent fit of the curves showed that in all these cases, the thermal conductivity of the filler and composite played a dominant role in controlling the onset of the crystallization process. However, the nucleation effects became important in the later stages after the crystallization temperature was attained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2994–2999, 2003     

Band Gap Modification of Diamond Photonic Crystals by Changing the Volume Fraction of the Dielectric Lattice

Photonic crystals with a diamond structure of epoxy lattices in which TiO₂-based ceramic particles are dispersed were fabricated by stereolithography. The periodicity of the lattice was designed to reflect electromagnetic waves in the gigahertz range. The volume fraction (β) of the dielectric lattice medium was modified from 14% to 33% by changing the rod diameter of the lattice. The photonic band gap was observed along Γ-L 〈111〉, Γ-X 〈100〉, and Γ-K 〈110〉 directions and the complete photonic band gap was formed at over β= 20%. The width of the forbidden gap increased gradually when the β increased over 14%, and reached 2.4 GHz at β= 33%. These results agreed with the band calculation using the plane wave expansion method.