Isothermal and non-isothermal crystallization kinetics of syndiotactic polypropelene

Isothermal and non-isothermal crystallization kinetics of a syndiotactic polypropylene(sPP) sample synthesized by new metallocene catalyst at different annealing temperatures and different cooling rates have been investigated by using differential scanning calorimetry(DSC) and density analysis. The equilibrium melting temperature( T-m(0)) is 158 degrees C by Hoffman-Weeks method. The equilibrium heat of fusion(Delta H-m(0)) is 88J/g in terms of the density analysis and DSC methods. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 5.2erg/cm(2) and sigma(e) = 69erg/cm(2), respectively. The work of chain folding is determined to be q = 33.75kJ/mol. Modified Avrami equation and Ozawa equation can be used to describe the non-isothermal crystallization behavior. And a new and convenient approach by combining the Avrami equation and Ozawa equation in a same crystallinity is used to describe the non-isothermal behavior as well. The crystallization activation energies are evaluated to be 73.7kJ/mol and 73.1kJ/mol for isothermal crystallization and non-isothermal crystallization, respectively. The Avrami exponent n is 1.5 similar to 1.6 for isothermal crystallization procedure, while the Avrami exponent n,is 2.5 similar to 3.5 for non-isothermal crystallization procedure. This indicated the difference of nucleation and growth between the two procedures.

Processible nanostructured materials with electrical conductivity and magnetic susceptibility: Preparation and properties of maghemite polyaniline nanocomposite films

We here present a versatile process for the preparation of maghemite/polyaniline (gamma-Fe2O3/ PAn) nanocomposite films with macroscopic processibility, electrical conductivity, and magnetic susceptibility. The gamma-Fe2O3 nanoparticles are coated and the PAn chains are doped by anionic surfactants of omega-methoxypoly(ethylene glycol) phosphate (PEOPA), 4-dodecylbenzenesulfonic acid (DBSA), and 10-camphorsulfonic acid (CSA). Both the coated gamma-Fe2O3 and the doped PAn are soluble in common organic solvents, and casting of the homogeneous solutions gives free-standing nanocomposite films with gamma-Fe2O3 contents up to similar to 50 wt %. The morphology of the gamma-Fe2O3 nanoparticles are characterized by transmission electron microscopy, UV-vis spectroscopy, and X-ray diffractometry. The gamma-Fe2O3/PAn films prepared from chloroform/m-cresol solutions of DBSA-coated gamma-Fe2O3 and CSA-doped PAn are conductive (sigma = 82-237 S/cm) and superpapamagnetic, exhibiting no hysteresis at room temperature. The zero-field-cooled magnetization experiment reveals that the nanocomposite containing 20.8 wt % gamma-Fe2O3 has a blocking temperature (T-b) in the temperature region of 63-83 K.

In-situ microscopic Fourier transform infrared spectroelectrochemistry of redox mechanism for electroactive species in polyelectrolyte

Studies for the development of the in-situ microscopic FTIR spectroelectrochemistry (MFTIRS) have been carried out in polyethylene glycol(PEG) polyelectrolyte, Redox reaction mechanisms of various electroactive substances involving inorganic salt, organic compound and inorganic polymeric particles have been studied.

The characterization of the interfacial reaction in polyamide 1010 poly(propylene)-graft-(glycidylmethacrylate) blends

Binary blends of polyamide 1010/poly(propylene) and polyamide 1010 (PA1010)/poly(propylene)-graft-(glycidyl methacrylate) (PP-g-GMA) were prepared. The epoxy groups in PP-g-GMA react with the amino end-groups in PA1010, thus a PA1010-graft-PP copolymer is formed and acts as a compatibilizer between PA1010 and PP-g-GMA. The reaction was confirmed by electron spectroscopy for chemical analysis (ESCA) and attenuated total reflection (ATR)-FTIR spectroscopic analysis, and also evaluated by the stability of the suspension obtained by dissolving the blends in formic acid and by the morphologies of the blends.

In-situ microscopic FTIR spectroelectrochemical study of the reduction of K3Fe(CN)(6) in polymer electrolyte

Cyclic voltammetry and in-situ microscopic FTIR spectroelectrochemistry were used for the electrochemical and vibrational characterizations of the reduction process of K3Fe (CN)(6) in polyethylene glycol(PEG) with LiClO4 as supporting electrolyte at a Pt microelectrode. The rate of electron transfer is a function of the concentration of the supporting electrolyte. The redox potentials and cyclic voltammetric currents vary with Li/O molar ratio. The bl-situ spectroelectrochemistry shows that the infrared spectra are influenced by the concentration of LiClO4. The bridging cyanide groups with a structure Fe-I-C drop N ... Fe-I-C drop N are formed during the reduction process of K3Fe (CN)(6). There may be an activated complex between the Lif cation and the complex anion.

Crystallization and melting behavior of nylon 66 poly(ether imide) blends

Isothermal crystallization and melting behavior of nylon 66 and its blends with poly(ether imide) (PEI) were investigated by differential scanning calorimetry. Crystallization kinetics such as overall rate constant Z and index n were calculated according to Avrami approach. Crystallization in the blend was retarded with respect to that of pure nylon 66 by incorporation of PEI with high glass transition temperature (T-g). The lowest growth rate of the spherulites was observed in the blends containing 10 and 15 wt% fraction of PEI. A transition temperature where positively birefringent spherulites disappear and negative birefringent spherulites develop was measured by thermal analysis. The transition temperature increased with content of PEI in the blends. A suitable range of isothermally crystallization temperatures, 238.5-246 degrees C, is suggested For determining the equilibrium melting points by means of Hoffman-Weeks approach.

Epitaxial crystallization of sPP on the (100) lattice plane of HDPE crystals

Crystallization behavior of syndiotactic polypropylene(sPP) on the (100) lattice plane of high-density polyethylene(HDPE) crystals was studied by means of transmission electron microscopy and electron diffraction. The results indicate that sPP crystals can grow epitaxially on the (100) PE lattice plane with their chain directions +/-37 degrees apart from the chain direction of the HDPE substrate. The contact planes are (100) lattice planes for both polymers. This kind of epitaxy is explained in terms of parallel alignment of HDPE chains along the rows formed by the {CH3, CH2,CH3} groups in the (100) lattice plane of the sPP crystals. This implies that in the epitaxial crystallization of sPP with fiber oriented HDPE substrate, not only the (110) but also the (100) HDPE lattice planes can act as the oriented nucleation sites. Furthermore, according to the poor matching between HDPE chains in the (100) lattice plane and the {CH3, CH2, CH3} group rows in the (100) lattice plane of the sPP crystals, it is concluded that the geometric matching is not the only controlling factor for the occurrence of polymer epitaxy.

Tremolite-reinforced nylon 66 composites: Mechanical and rheological properties

The reinforcement effect of an acicular inorganic filler, tremolite, on nylon 66 was studied. The mechanical properties of tremolite-filled nylon 66 composites and the effect of the filler particle size on them were obtained. The dynamic mechanical properties and rheological properties of the composites were measured. Two treatments, silane and unsaturated polyester, were used to improve the interface between tremolite and the nylon matrix. The morphologies of the composites were investigated using SEM. (C) 1998 John Wiley & Sons, Inc.

Study on a comb-like polymer electrolyte based on the backbone of ethylene-maleic anhydride copolymer

A comb-like polymer host(CBPE) as polymer electrolyte was synthesized by reacting poly(ethylene glycol) monomethyl ether (PEGME) with ethylene-maleic anhydride copolymer(EMAC) and endcapping the residual carboxylic acid with methanol. The synthetic process was followed by IR and the amorphous product characterized by IR and elemental analysis. There were two peaks in the plot of the ionic conductivity against Li salt concentration. The plot of log sigma vs. 1/(T - T-0) may exhibit dual VTF behavior when using the glass transition temperature of PEO of side chain as T-0. The comb-like polymer is a white rubbery solid which dissolves in acetone. (C) 1998 Elsevier Science B.V. All rights reserved.

Novel morphology in ring-banded spherulites from single-phase mixtures of poly(epsilon-caprolactone) with poly(styrene-co-acrylonitrile)

Novel morphology of ring-banded spherulites in the surface of poly(epsilon-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends was discovered and studied by SEM and TEM. The ring-banded spherulites separate into those exhibiting a very dark contrast, of relatively regular bundles of lamellae and others appearing with a much brighter intensity, of a coarse and irregular aggregates of lamellae. The origin of the novel morphology is not due to different crystalline structures as in the case of isotactic polypropylene because only one crystal structure exists in PCL/SAN blends. The formation may reflect whether spherulites in PCL/SAN blends are nucleated at the bottom surface or at the top (free) surface.

A study on the diffusion of quinhydrone in polymer electrolyte

The diffusion coefficients (D) of quinhydrone were estimated in polymer electrolytes by using non-steady-state chronoamperometry and steady-state current voltammetry. The D values have been estimated in polyethylene glycol (PEG) containing different concentrations, and cations of supporting electrolytes, and in different solvents over a range of temperatures. The dependencies of electroactive probe diffusion coefficients on temperature, supporting electrolyte concentration and polymer chain length are discussed. The results show that D increases with increasing temperature and decreasing concentration of supporting electrolyte. The diffusion coefficient depends strongly on the length of polymer chain and decreases sharply with increasing polymer chain length. The contribution of electron self-exchange has been explored and it seems to be negligible here. (C) 1998 Elsevier Science S.A.

Compatibilization effect of graft copolymer on immiscible polymer blends: 1. LLDPE/SBS/LLDPE-g-PS systems

compatibilizing effect of graft copolymer, linear low density polyethylene-g-polystyrene (LLDPE-g-PS), on immiscible blends of LLDPE with styrene-butadiene-styrene triblock copolymer (SBS) has been investigated by means of C-13 CPMAS n.m.r. and d.s.c. techniques. The results indicate that LLDPE-g-PS is an effective compatibilizer for LLDPE/SBS blends. It was found that LLDPE-g-PS chains connect two immiscible components, LLDPE and SBS, through solubilization of chemically identical segments of LLDPE-g-PS into the amorphous region of LLDPE acid PS block domain of SBS, respectively. It was also found that LLDPE-g-PS chains connect the crystalline region of LLDPE by isomorphism, with serious effects on the supermolecular structure of LLDPE. The effect of LLDPE-g-PS on the supermolecular structure of LLDPE in the LLDPE/SBS blends obviously depends on the composition of the blends, but has little dependence on the PS grafting yields of LLDPE-g-PS. (C) 1998 Elsevier Science Ltd. All rights reserved.

Effects of the compatibilizer PP-g-GMA on morphology and mechanical properties of PP/PC blends

Effects of the compatibilizer polypropylene grafted with glycidyl methacrylate(PP-g-GMA) on the morphology, thermal, rheological and mechanical properties of polypropylene and polycarbonate blends (PP/PC) were studied. It was found that the addition of PP-g-GMA significantly changed their morphology. The mean size of domains reduced from 20 mu m to less than 5 mu m. The dispersed domain size is also strongly dependent upon the content of PP-g-GMA. The interfacial tension of PP/PC/PP-g-GMA (50/30/20) is only about one-tenth of PP/PC (70/30). The crystallization temperature of PP in PP/PC/PP-g-GMA is 5-8 degrees C higher than that of PP in PP/PC blends. Characterization studies based on mechanical properties, differential scanning calorimetry, rheology and morphological evidence obtained by using scanning electron microscopy support the hypothesis that an in-situ copolymer PP-g-PC was formed during the blending process. (C) 1997 Elsevier Science Ltd.

Thermal analysis of ethylene propylene copolymer-grafted-acrylic acid

The thermal properties of ethylene propylene copolymer-grafted-acrylic acid (EP-g-AA) were investigated by using differential scanning calorimetry (DSC). Compared with the ethylene propylene copolymer (EP), the peak values of the melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, the crystallization temperature (T-c) increased about 8-12 degrees C, and the melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of the ungrafted sample was 1.6-1.8, and that of grafted samples were all above 2, which indicated that the grafted monomer could become the crystal nuclei for the crystallization of propylene sequence. With increasing grafted monomer content, the crystallization rate of propylene sequence in grafted EP increased; it might be the result of rapid nucleation rate and crystal growth rate.

Morphology, mechanical properties and interfacial behaviour of PA1010/PP/PP-g-GMA ternary blends

Morphology, mechanical properties, and interfacial interaction of polyamide 1010/polypropylene (PA1010/ PP) blends compatibilized with polypropylene grafted with glycidyl methacrylate (PP-g-GMA) were studied. It was found that the size of the PP domains, tensile and impact strength of ternary blends, and adhesion fracture energy between two layers of PA1010 and PP were all significantly dependent on the PP-g-GMA contents in the PP layer. Correlations between morphology and related properties were sought. The improvements in properties have been attributed to chemical and physical interaction occurring between PA1010 and PP-g-GMA. (C) 1997 Elsevier Science Ltd.