Nonisothermal crystallization,melting behavior,and morphology of polypropylene/metallocene‐catalyzed polyethylene blends

The nonisothermal crystallization, melting behavior, and morphology of blends of polypropylene (PP) and a metallocene‐catalyzed polyethylene (mPE) elastomer were studied with differential scanning calorimetry, scanning electron microscopy, polarized optical microscopy, and X‐ray diffraction. The results showed that PP and mPE were partially miscible and could form some cocrystallization, although the extent was very small. A modified Avrami analysis and the Mo method were used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was homogeneous, the growth of the spherulites was three‐dimensional, and the crystallization mechanism of PP was not affected by mPE. The crystallization activation energy was estimated with the Kissinger method. Interesting results were obtained with the modified Avrami analysis and Mo and Kissinger methods, and the conclusions were in good agreement. The addition of less mPE increased the overall crystallization rate of PP. The relationship between the composition and morphology of the blends was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1203–1210, 2004     

Nonisothermal crystallization,melting behavior,and morphology of polypropylene/linear bimodal polyethylene blends

The nonisothermal crystallization, melting behavior, and morphology of isotactic polypropylene (PP)/linear bimodal polyethylene (LBPE) blends were studied with differential scanning calorimetry, scanning electron microscopy, and polarized optical microscopy. The results showed that PP and LBPE were miscible to a certain extent, and there was no obvious phase separation in the blends. The modified Avrami analysis, Ozawa equation, and Mo method were used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was homogeneous, the growth of spherulites was three‐dimensional, and the crystallization mechanism of PP was not affected much by LBPE. The crystallization activation energy was estimated by the Kissinger method. The results obtained with the modified Avrami analysis, Mo method, and Kissinger method agreed well. The addition of a minor LBPE phase favored an increase in the overall crystallization rate of PP, showing some dilution effect of LBPE on PP. The PP spherulites decreased obviously with increasing content of LBPE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melting behavior,isothermal and nonisothermal crystallization kinetics of PP/mLLDPE blends

Melting behavior, nonisothermal crystallization and isothermal crystallization kinetics of polypropylene (PP) with metallocene‐catalyzed linear low density polyethylene (mLLDPE) were studied by differential scanning calorimetry (DSC). The results show that PP and mLLDPE were partially miscible. The Avrami analysis was applied to analyze the nonisothermal and isothermal crystallization kinetics of the blends, the Mo Z.S. method was used to take a comparison in nonisothermal kinetics. Values of Avrami exponent indicate the crystallization nucleations of both pure PP and PP in the blends were heterogeneous, the growth of spherulites is tridimensional and the spherulites in the blends were more perfect than that in pure PP. The crystallization activation energy was estimated by Kissinger method and Arrhenius equation and the two methods draw similar results. The mLLDPE increased the crystallization rate of PP in nonisothermal crystallization process and decreased it in isothermal process. The results from nonisothermal crystallization and isothermal crystallization kinetics were not consistent because the two processes were completely different. Addition of minor mLLDPE phase favors to increase the overall crystallinity of PP, showing the mLLDPE entered the PP crystals. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melting,nonisothermal crystallization behavior and morphology of polypropylene/random ethylene—propylene copolymer blends

The melting, nonisothermal crystallization behavior and morphology of blends of polypropylene (PP) with random ethylene–propylene copolymer (PP‐R) were studied by differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and X‐ray diffraction. The results showed that PP and PP‐R were very miscible and cocrystallizable. Modified Avrami analysis was used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was heterogeneous, the growth of the spherulites was tridimensional, and the crystallization mechanism of PP was not affected by PP‐R. The crystallization activation energy was estimated using the Kissinger method. An interesting result was obtained with the modified Avrami analysis and the Kissinger method, whose conclusions were in good agreement. The addition of a minor PP‐R phase favored an increase in the overall crystallization rate of PP. Maximum enhancing effect wass found to occur with a PP‐R content of 20 wt %. The relationship between the composition and the morphology of the blends is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 670–678, 2006     

Nonisothermal crystallization behavior of glass‐bead‐filled polypropylene

The effects of the glass‐bead content and size on the nonisothermal crystallization behavior of polypropylene (PP)/glass‐bead blends were studied with differential scanning calorimetry. The degree of crystallinity decreased with the addition of glass bead, and the crystallization temperature of the blends was marginally higher than that of pure PP at various cooling rates. Furthermore, the half‐time for crystallization decreased with an increase in the glass‐bead content or particle size, implying the nucleating role of the glass beads. The nonisothermal crystallization data were analyzed with the methods of Avrami, Ozawa, and Mo. The validity of various kinetic models for the nonisothermal crystallization process of PP/glass‐bead blends was examined. The approach developed by Mo successfully described the nonisothermal crystallization behavior of PP and PP/glass‐bead blends. Finally, the activation energy for the nonisothermal crystallization of pure PP and PP/glass‐bead blends based on the Kissinger method was evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2026–2033, 2006     

Nonisothermal crystallization kinetics of poly(vinylidene fluoride) in a poly(vinylidene fluoride)/dibutyl phthalate/di(2‐ethylhexyl)phthalate system via thermally induced phase separation

The nonisothermal crystallization kinetics of poly(vinylidene fluoride) (PVDF) in PVDF/dibutyl phthalate (DBP)/di(2‐ethylhexyl)phthalate (DEHP) blends via thermally induced phase separation were investigated through differential scanning calorimetry measurements. The Ozawa approach failed to describe the crystallization behavior of PVDF in PVDF/DBP/DEHP blends, whereas the modified Avrami equation successfully described the nonisothermal crystallization process of PVDF. Two stages of crystallization were observed in this analysis, including primary crystallization and secondary crystallization. The influence of the cooling rate and DBP ratio in the diluent mixture on the crystallization mechanism and crystal structure was determined by this method. The Mo approach well explained the kinetics of primary crystallization. An analysis of these two methods indicated that the increase in the DBP ratio in the diluent mixture caused a decrease in the crystallization rate at the primary crystallization stage. The activation energy was determined according to the Kissinger method and also decreased with the DBP ratio in the diluent mixture increasing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melting behavior,isothermal and nonisothermal crystallization kinetics of EPPE/mLLDPE blends

Melting behavior and crystallization kinetics of easy processing polyethylene (EPPE) and the blends of EPPE/mLLDPE were studied using differential scanning calorimetry at various crystallization temperature and cooling rates. The Avrami analysis was employed to describe the isothermal and nonisothermal crystallization process of pure polymers and their blends, and a method developed by Mo was applied for comparison. Kinetic parameters such as the Avrami exponent (n), the kinetic crystallization rate constant (k and k_c), the peak temperatures (T_p), and the half-time of crystallization (t_1/2), etc. were determined. The appearance of double melting peaks and the double crystallization peaks of the polymers showed that the main chain and the branches crystallize seperately, but the main chains of two polymers can crystallize together and mLLDPE act as nuclei while EPPE crystallizes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonisothermal crystallization kinetics of polypropylene/polypropylene‐g‐polystyrene/polystyrene blends

The nonisothermal crystallization kinetics of polypropylene (PP), PP/polystyrene (PS), and PP/PP‐g‐PS/PS blends were investigated with differential scanning calorimetry at different cooling rates. The Jeziorny modified Avrami equation, Ozawa method, and Mo method were used to describe the crystallization kinetics for all of the samples. The kinetics parameters, including the half‐time of crystallization, the peak crystallization temperature, the Avrami exponent, the kinetic crystallization rate constant, the crystallization activation energy, and the F(T) and a parameters were determined. All of the results clearly indicate that the PP‐g‐PS copolymer accelerated the crystallization rate of the PP component in the PP/PP‐g‐PS/PS blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Non-isothermal crystallization kinetics and nucleation activity of hyperbranched polyester (HBPET) in recycled PET

The non-isothermal crystallization of pure recycled polyethylene terephthalate (RPET) and its blends with 3 and 5 wt% hyperbranched polyester (HBPET) were investigated by differential scanning calorimetry (DSC). The DSC curves demonstrate that the melt-crystallization temperatures of the blends are always higher than that of pure RPET regardless of the cooling rate. Their non-isothermal crystallization kinetics was further analyzed with modified Avrami equation, Ozawa equation and Mo method. The analysis reveals that the crystallization half-time (t _1/2) of the blends is shorter than pure RPET. The activation energy of crystallization of RPET was also determined according to Kissinger method and it is found to decrease remarkably in RPET-3 and RPET-5 blends. All the results indicate that HBPET serves as an effective nucleating agent for RPET.     

NONISOTHERMAL CRYSTALLIZATION KINETICS AND MECHANICAL PROPERTIES OF PP/NANO-SiO2 COMPOSITES

The nonisothermal crystallization kinetics of polypropylene (PP)/nano-SiO₂ composites was studied by means of differential scanning calorimetry (DSC). The modified Avrami theories by Jeziorny, Ozawa, and Mo were used to analyze the data of DSC. The results showed that both the Jeziorny and Mo methods could describe this system very well, but the Ozawa analysis failed. The activation energy was evaluated by the Kissinger method. It was found that the crystallization activation energy of PP was higher than that of PP/nano-SiO₂ composites. The determined results of mechanical properties showed that the addition of nano-SiO₂ increased the mechanical properties of the PP. Micrographs of Polarized optical micrograph (POM) further demonstrated that nano-SiO₂ could toughen the PP.     

聚丙烯/超高相对分子质量聚乙烯共混物的结晶动力学及发泡性能研究

采用差示扫描量热仪（DSC）对含有不同含量超高分子量聚乙烯（UHMWPE）的聚丙烯进行测试和表征,采用Ozawa方法、莫志深方法和Kissinger方法分析了该体系的非等温结晶动力学。利用自行研制的超临界流体挤出发泡实验装置,对含有UHMWPE的PP进行了超临界二氧化碳挤出发泡实验研究。结果表明：超高分子量聚乙烯的加入降低了PP的结晶活化能,含有UHMWPE的PP在较高的温度下开始结晶,且由于超高分子量聚乙烯大分子链的存在,与聚丙烯分子链发生缠结,阻碍聚丙烯分子链排入晶格,降低了结晶速率,结晶温区拓宽,有利于聚丙烯挤出发泡成型;加入UHMWPE后,PP的发泡效果明显改善,泡孔平均直径减小,泡孔尺寸分布更加均匀,PE-UHMW的含量为5份时,表观密度达到0.038g/cm-3。     

Non-isothermal crystallization kinetic and compatibility of PTT/PP blends by using maleic anhydride grafted polypropylene as compatibilizer

The crystallization behaviors, non-isothermal crystallization kinetics, and the morphology of poly(trimethylene terephthalate)/Polypropylene (PTT/PP) blends using a maleic anhydride grafted polypropylene (PP-g-MAH) as a compatibilizer were investigated by differential scanning calorimeter (DSC) and scanning electron microscope (SEM), respectively. The results suggested that the blends exhibited different crystallization and melting behaviors due to different content of PP-g-MAH. All of the DSC curves of the blends exhibited two exothermic peaks and endothermic peaks. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization process. The results suggested that the crystallization rate of PTT component was increased, whereas, that of PP component was retarded with the introduction of PP-g-MAH. The effective activation energy was calculated by differential iso-conversional method developed by Vyazovkin. The SEM result suggested that the introduction of PP-g-MAH greatly improved the compatibility between PTT and PP, and decreased the size of dispersed particles.     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Melting behavior and isothermal crystallization kinetics of PP/mLLDPE blends

The melting/crystallization behavior and isothermal crystallization kinetics of polypropylene (PP)/metallocene-catalyzed linear low density polyethylene (mLLDPE) blends were studied with differential scanning calorimetry (DSC). The results showed that PP and mLLDPE are partially miscible and interactions mainly exist between the mLLDPE chains and the PE segments in PP molecules. The isothermal crystallization kinetics of the blends was described with the Avrami equation. Values of the Avrami exponent indicated that crystallization nucleation of the blends is heterogeneous, the growth of spherulites is almost three-dimensional, and the crystallization mechanism of PP is not affected much by mLLDPE. The Avrami exponents of the blends are higher than that of pure PP, showing that the mLLDPE helps PP to form perfect spherulites. The crystallization rates of PP are decreased by mLLDPE because the crystallization temperature of PP was decreased by addition of mLLDPE and consequently the supercooling of the PP was correspondingly lower. The crystallization activation energy was estimated by the Friedman equation, and the result showed that the activation energy increased by a small degree by addition of mLLDPE, but changed little with increasing content of mLLDPE in the blends. The nucleation constant (K _g) was determined by the Hoffman–Lauritzen theory. Supported by the Science Foundation of Hebei University (2006Q13).     

Morphology,nonisothermal crystallization behavior,and kinetics of poly(phenylene sulfide)/polycarbonate blend

The morphology and nonisothermal crystallization behavior of blends made of poly(phenylene sulfide) (PPS), with a amorphous polycarbonate (PC) were studied. The blend is found to be partially miscible by the dynamic mechanical thermal analysis (DMTA) and melt rheological measurements. The nonisothermal crystallization behavior of blend was studied by differential scanning calorimetry (DSC). The results show clearly that the crystallization temperatures of PPS component in the blend decrease with increasing of PC contents. The crystallization kinetics was then analyzed by Avrami, Jeziorny, and Ozawa methods. It can be concluded that the addition of PC decreases the PPS overall crystallization rate because of the higher viscosity of PC and/or partial miscibility of blend, despite of small heterogeneous nucleation effect by the PC phase and/or phase interface. The results of the activation energy obtained by Kissinger method further confirm that the amorphous PC in the partial miscible PPS/PC blend may act as a crystallization inhibitor of PPS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nonisothermal Crystallization Kinetics of Polypropylene/Polyethersulfone Blend

The nonisothermal crystallization kinetics of PP and PP/PES (80/20 wt%) blend was investigated by using differential scanning calorimetry (DSC). It was observed that the crystallization peak temperature (T_p) and the half time (t _1/2) of crystallization of PP/PES blend are slightly but consistently lower than those of PP at various cooling rates. The nonisothermal crystallization data were analyzed by using Avrami equation, Ozawa and Mo method. The validity of the different kinetics models to the nonisothermal crystallization process of two samples is discussed. The Mo method can successfully explain the overall nonisothermal crystallization process of PP and PP/PES blend. The activation energy (ΔE) for nonisothermal crystallization of PP and PP/PES blend is determined by using the Kissinger method. The result shows that the ΔE value of PP is slightly higher than that of PP/PES blend.     

Melting behavior,nonisothermal crystallization kinetics,and morphology of PP/nylon 11/EPDM‐g‐MAH blends

The melting behavior, nonisothermal crystallization behavior, and morphology of pure polypropylene (PP) and its blends were investigated by differential scanning calorimetry and polarized optical microscopy. The nonisothermal crystallization kinetics was analyzed using the Avrami equation modified by Jeziorny and the equation combining the Avrami and Ozawa method. The surface fold free energy and the effective activation energy for both PP and its blends were obtained by Hoffman‐Lauritzen theory and Vyazovkin's approach, respectively. The results showed that the presence of nylon 11 hindered the mobility of PP chains but accelerated the overall crystallization rate. The POM observation confirmed that the addition of nylon 11 decreased the spherulites size of PP matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology,crystallization and melting properties of isotactic polypropylene blended with lignin

The influence of lignin (L) on the thermal properties and kinetics of crystallization of isotactic polypropylene (PP) is reported in this article. PP blends containing 5 and 15 wt % of L were prepared by mixing the components in a screw mixer. An increase of the thermal degradation temperature of the blends was observed as a function of L content. The crystallization and thermal behavior of the pure PP and of the PP/L blends were analyzed by differential scanning calorimetry (DSC). Isothermal crystallization kinetics were described by means of the Avrami equation, which suggests a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation. The isothermal growth rate of PP spherulites was studied using a polarizing optical microscope. The enhancement of PP crystallization rate for the PP/L blends was observed and ascribed to the nucleating action of lignin particles. Non‐isothermal crystallization kinetics were applied, according to the results elaborated by Ziabicki and the method modified by Jeziorny. The kinetic crystallizability of the PP is not influenced by the L present in the blend. In the presence of L, PP can simultaneously crystallize in both the α and β crystalline forms, and the ratio between the α and β forms was determined by X‐ray diffraction analysis. Two melting peaks relative to the two crystalline form of PP were observed for the PP/L blends, for all isothermal crystallization temperatures investigated by means of DSC. The equilibrium melting temperature for α‐form of pure PP was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1435–1442, 2004     

Non-isothermal crystallization kinetics of poly(ethylene terephthalate)/mica composites

The non-isothermal crystallization kinetics of pure poly(ethylene terephthalate) (PET), PET/mica and PET/TiO₂-coated mica composites were investigated by differential scanning calorimetry with different theoretical models, including the modified Avrami method, Ozawa method and Mo method. The activation energies of non-isothermal crystallization were calculated by Kissinger method and Flynn–Wall–Ozawa method. The results show that the modified Avrami equation and Ozawa theory fail to describe the non-isothermal crystallization behavior of all composites, while the Mo model fits the experiment data fair well. It is also found that the mica and TiO₂-coated mica could act as heterogeneous nucleating agent and accelerate the crystallization rates of PET, and the effect of TiO₂-coated mica is stronger than that of mica. The result is further reinforced by calculating the effective activation energy of the non-isothermal crystallization process for all composites using the Kissinger method and the Flynn–Wall–Ozawa method.