Isothermal and nonisothermal melt-crystallization kinetics of syndiotactic polystyrene

Analyses of the isothermal and nonisothermal melt kinetics for syndiotactic polystyrene have been performed with differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The regime II-->III transition, at a crystallization temperature of 239degrees, is found. The values of the nucleation parameter K-g for regimes II and III are estimated. The lateral-surface free energy, sigma = 3.24 erg cm(-2), the fold-surface free energy, sigma(e) = 52.3 +/- 4.2 erg cm(-2), and the average work of chain folding, q = 4.49 +/- 0.38 kcal/mol, are determined with the (040) plane assumed to be the growth plane. The observed crystallization characteristics of syndiotactic polystyrene are compared with those of isotactic polystyrene. The activation energies of isothermal and nonisothermal melt crystallization are determined to be DeltaE = -830.7 kJ/mol and DeltaE = -315.9 kJ/mol, respectively.

Dynamic mechanical studies of the sulfonated butyl rubber ionomers and their blends

Dynamic mechanical properties of sulfonated butyl rubber ionomers neutralized with different amine or metallic ion (zinc or barium) and their blends with polypropylene (PP), high-density polyethylene (HDPE), or styrene-butadiene-styrene (SBS) triblock copolymer were studied using viscoelastometry. The results showed that glass transition temperatures of ion pair-containing matrix and ionic domains (T-g1 and T-g2, respectively) of amine-neutralized ionomers were lower than those of ionomers neutralized with metallic ions, and the temperature range of the rubbery plateau on the storage modulus plot for amine-neutralized ionomers was narrower. The modulus of the rubbery plateau for amine-neutralized ionomers was lower than that of ionomers neutralized with zinc or barium ion. With increasing size of the amine, the temperature range for the rubbery plateau decreased, and the height of the loss peak at higher temperature increased. Dynamic mechanical properties of blends of the zinc ionomer with PP or HDPE showed that, with decreasing ionomer content, the T-m of PP or HDPE increased and T-g1 decreased, whereas T-g2 or the upper loss peak temperature changed only slightly. The T-g1 for the blend with SBS also decreased with decreasing ionomer content. The decrease of T-g1 is attributed to the enhanced compatibilization of the matrix of the ionomer-containing ion pairs with amorphous regions of PP or HDPE or the continuous phase of SBS due to the formation of thermoplastic interpenetrating polymer networks by ionic domains and crystalline or glassy domains.

Morphology, crystallization behaviors, and mechanical properties of PA1010/HIPS and PA1010/HIPS-g-MA blends

The binary blends of polyamide 1010 (PA1010) with the high-impact polystyrene (HIPS)/maleic anhydride (MA) graft copolymer (HIPS-g-MA) and with HIPS were prepared using a wide composition range. Different blend morphologies were observed by scanning electron microscopy according to the nature and content of PA1010 used. Compared with the PA1010/HIPS binary blends, the domain sizes of dispersed-phase particles in PA1010/HIPS-g-MA blends were much smaller than that in PA1010/HIPS blends at the same compositions. It was found that the tensile properties of PA1010/HIPS-g-MA blends were obviously better than that of PA 1010/HIPS blends. Wide-angle xray diffraction analyses were performed to confirm that the number of hydrogen bonds in the PA1010 phase decreased in the blends of PA1010/HIPS-g-MA. These behaviors could be attributed to the chemical interactions between the two components and good dispersion in PA1010/HIPS-g-MA blends.

Influence of intermolecular entanglements on the glass transition and structural relaxation behaviors of macromolecules. 2. Polystyrene and phenolphthalein poly(ether sulfone)

The effect of entanglements on the glass transition and structural relaxation behaviors has been studied for polystyrene (PS) and phenolphthalein poly(ether sulfone) (PES-C) samples by fast evaporation of the solution of concentrations varying from above the overlapping concentration to far below it, and compared to the results we have studied previously in PC. It has been found that for all the polymers we have studied, in the concentrated solution region, the T-g of the samples obtained from solution are independent of the change of concentration and are very close to that of normal bulk samples, whereas in the dilute solution region the T-g of the samples decrease with the logarithm of decreasing concentration. The critical concentrations that divide the two distinct regions for the three polymers are 0.9% g/mL for PC, 0.1% g/mL for PS, and 1% g/mL for PES-C. The decrease of T-g of the samples is interpreted by the decrease of intermolecular entanglements as the isolation of polymer chains, and the entanglement of polymer chains restrained the mobility of the segments. The structural relaxation behavior of the polymers is also found to be different from that of normal bulk samples. The enthalpies of single-chain samples are lower than that of the bulk ones, which correspond to the lower glass transition temperature; the peaks are lower and broader, and the relaxed enthalpy is much lower as compared to that of bulk samples. In the three polymers we have studied, the influence of change of entanglements on both the decrease in glass transition temperature and relaxed enthalpy is the most significant for PS and the least for PES-C. It is indicated that the interactions in the flexible polymers are weak; thus, the restraint of the entanglements on the mobility of the segments plays a more important role in the flexible polymers, and the change of entanglement in the flexible polymers has a more significant influence on the physical properties.

Brittle-tough transition in PP/EPDM blends: effects of interparticle distance and tensile deformation speed

The toughness of polypropylene (PP)/ethylene-propylene-diene monomer rubber (EPDM) blends containing various EPDM contents as a function of the tensile speed was studied. The toughness of the blends was determined from the tensile fracture energy of the side-edge notched samples. A sharp brittle-tough transition was observed in the fracture energy versus interparticle distance (ID) curves when the crosshead speed < 102.4 mm/min. It was observed that the brittle-ductile transition of PP/EPDM blend occurred either by reducing ID or by decreasing the tensile speed. The correlation between the critical interparticle distance and tensile deformation rate was compared with that between the critical interparticle distance and temperature for PP/EPDM blends. (C) 2000 Elsevier Science Ltd. All rights reserved.

Single crystal structure of form I syndiotactic poly(butene-1)

The structures of single crystals of syndiotactic poly(butene-1) in form I, produced by thin-film growth, are studied by transmission electron microscopy and electron diffraction. Bright-field electron microscopy observation shows that the single crystal exhibits a regular rectangular shape with the long axis along its crystallographic b-axis. Electron diffraction results indicate an isochiral C-centered packing of a-fold helical chains in an orthorhombic unit cell corresponding to the C222(1) space group, according to the model proposed in the literature. The differences with the polymorphic behavior of syndiotactic polypropylene concerning the formation and the stability of the isochiral mode of packing are outlined.

Influence of the size of ultrafine CaCO3 powder on PP crystallization

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD. The average sizes of the CaCO3 powders used were 0.1 mum (UC) and 0.5 mum (GC), respectively. The PP/CaCO3 composites at compositions of 1 phr and 10 phr were investigated. The results showed that the addition of CaCO3 reduced the supercooling, the rate of nucleation and the overall rate of crystallization (except for the 10 phr UC/PP sample). The crystallinity of PP was increased and the size distribution of the crystallites of alpha -PP; was: broadened. On the other hand,the crystallization rate of 10 phr UC/PP is 1.5 times higher than that of neat PP. It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity. The sizes of crystallites and the unit cell parameters of alpha -PP were varied by the addition of CaCO3. beta -PP was formed by addition of Ge and was not detected by addition of UC. The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.

Morphology, structure, and rheological property of linear low-density polyethylene grafted with acrylic acid

The chain structure, spherulite morphology, and theological property of LL-DPE-g-AA were studied by using electronspray mass spectroscopy, C-13-NMR, and rheometer. Experimental evidence proved that AA monomers grafted onto the LLDPE backbone formed multiunit AA branch chains. It was found that AA branch chains could hinder movement of the LLDPE main chain during crystallization. Spherulites of LLDPE became more anomalous because of the presence of AA branch chains. Rheological behavior showed that AA branch chains could act as an inner plasticizer at the temperature range of 170-200 degreesC, which made LLDPE-g-AA easy to further process. (C) 2001 John Wiley & Sons, Inc.

Efforts to decrease crosslinking extent of polyethylene in a reactive extrusion grafting process

Grafting of acrylic acid and glycidyl methacrylate onto low density polyethylene (LDPE) was performed by using a corotating twin-screw extruder. The effects of residence time and concentration of initiator and monomers on degree of grafting and gel content of grafting LDPE were studied systematically. Paraffin, styrene, p-benzoquinone, triphenyl phosphite, tetrachloromethane, and oleic acid were added to try to decrease the extent of crosslinking of LDPE. 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidinyloxy (4-hydroxyl-TEMPO) and dipentamethylenethiuram tetrasulfide were also tried to inhibit crosslinking reaction of LDPE during its extruding grafting process. It was found that p-benzoquinone, triphenyl phosphite and tetrachloromethane were good inhibitors for crosslinking of LDPE. (C) 2000 John Wiley & Sons, Inc.

Influence of entanglements an the glass transition and structural relaxation behaviors of macromolecules. 1. Polycarbonate

We obtained the single-chain polycarbonate sample, by a new fast evaporation method and found that the polycarbonate sample obtained by this method is completely amorphous, while the polycarbonate sample obtained by other methods all have a certain degree of crystallinity. The glass transition temperature (T-g) of the sample decreases with the decreasing of concentration when the concentration of the prepared solution is below the critical value. The critical concentration we obtained from the T-g dependence of concentration is 0.9% g/mL and is in accord with that obtained by viscometry and light scattering methods directly from the solution. The structural relaxation behavior is found also different from that of a normal bulk sample of polycarbonate. The enthalpic peak of the single-chain sample is lower: than that of the bulk one, which corresponds to the lower glass transition temperature. The peak of the single-chain sample is lower and broader, and the relaxed enthalpy is much lower compared with that of the bulk sample. These results have been explained in terms of the effect of entanglement on the mobility of the segments in polymer and the compact conformation in the single-chain sample.

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.

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.

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.

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.

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.