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 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).     

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     

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     

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     

Nonisothermal crystallization,melting behavior,and morphology of PP/EPPE blends

Nonisothermal crystallization, melting behavior, and morphology of polypropylene (PP)/Easy processing polyethylene (EPPE) blends were studied by differential scanning alorimetry (DSC) and scanning electron microscope (SEM). The results showed that PP and EPPE are miscible, and there is no obvious phase separation in microphotographs of the blends. The modified Avrami analysis, Ozawa equation, and also Mo Z.S. method were used to analyze the nonisothermal crystallization kinetics of the blends. Values of Avrami exponent indicated the crystallization nucleation of the blends is homogeneous, the growth of spherulites is tridimensional, and crystallization mechanism of PP is not affected much by EPPE. The crystallization activation energy was estimated by Kissinger method. The result obtained from modified Avrami analysis, Mo Z.S. method, and Kissinger methods were well agreed. The addition of minor EPPE phase favored to decrease the overall crystallization rate of PP, showing some dilution effect of EPPE on PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Melting behavior and isothermal crystallization kinetics of nylon 11/EVOH/dicumyl peroxide blends

Nylon 11/ethylene‐vinyl alcohol/dicumyl peroxide (DCP) blends were prepared using a single‐screw extruder. The melting behavior and isothermal crystallization kinetics were investigated using differential scanning calorimetry. The reorganization of nylon 11 crystals is strongly hindered owing to cocrosslinking phenomena. The analysis of the crystallization kinetics demonstrated that the Avrami equation well described the isothermal crystallization process of the primary stage. The spherulites growth kinetics parameters and fold surface free energy were also evaluated. The experimental results confirmed that the presence of DCP increased the crystallization rate. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

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     

动态硫化对三元乙丙橡胶/聚丙烯共混体系等温结晶行为和形态结构的影响

研究了三元乙丙橡胶/聚丙烯(EPDM/PP)共混物和动态硫化EPDM/PP热塑性弹性体(TPV)的等温结晶行为及形态结构,并用Avrami方程对其进行等温结晶动力学分析。结果表明,EPDM/PP共混物和EPDM/PP TPV的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV比共混物的Avrami指数小,半结晶时间短,结晶速率常数大;EPDM/PP共混物为双连续相结构,而EPDM/PP TPV是以硫化的细小橡胶颗粒为分散相、PP为连续相的"海-岛"结构,橡胶颗粒尺寸约为0.5μm。     

Isothermal crystallization behavior of polypropylene catalloys

The isothermal crystallization behavior of polypropylene (PP) catalloys and neat PP were studied with differential scanning calorimetry and polarized optical microscopy (POM). The crystallization kinetics of the samples were described with the well‐known Avrami equation. The crystallization rate depended remarkably on the content of the ethylene component in the PP catalloys. The crystallization half‐time increased obviously with the increase of the ethylene component in the PP catalloys. We also observed by POM that in isothermal crystallization, there were many more nuclei in the PP catalloys than that in neat PP and with an increase of the ethylene component, the average size of the spherulites decreased obviously. Even when ethylene content was as high as 27%, the crystallization rate still increased apparently, and this was quite different from common PP melting blends, in which the crystallization rate decreased when the ethylene content was relatively high because of the obstruction effect of dispersed droplets to the spherulite growth of the PP matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 877–882, 2004     

Thermal properties and crystallization behavior of polyolefin ternary blends

Crystallization behaviors, spherulite growth and structure, and the crystallization kinetics of polypropylene (PP)/ethylene‐α‐olefln copolymer (mPE)/high‐density polyethylene (HDPE) ternary blends and of mPE/HDPE binary blends have been studied using polarizing optical micrography (POM) and differential scanning calorimetry (DSC). In mPE/HDPE blends, large pendant groups of mPE disturbed spherulite growth of HDPE, leading to a different crystallite morphology and isothermal kinetics. Non‐isothermal properties, morphology, and isothermal crystallization kinetics of PP in ternary blends were significantly influenced by the composition and crystallization behavior of the mPE/HDPE binary blends as well as the crystallization condition. Polym. Eng. Sci. 44:1858–1865, 2004. © 2004 Society of Plastics Engineers.     

Isothermal crystallization kinetics and melting behavior of polyamide 11/silica nanocomposites prepared by in situ melt polymerization

Polyamide 11 (PA 11)/silica nanocomposites were prepared via in situ melt polymerization by the dispersion of hydrophobic silica in 11‐aminoundecanoic acid monomer. Their isothermal crystallization process and melting behaviors were analyzed by differential scanning calorimetry. The isothermal crystallization kinetics was analyzed by the Avrami equation. The obtained data showed that the model of nucleation and growth of PA 11 was not affected after the incorporation of silica and was a mixture with two‐dimensional, circular, three‐dimensional growth with thermal nucleation. Double and single melting peaks were observed depending on the crystallization temperature. The equilibrium melting point of samples was evaluated, and the spherulites growth kinetics parameters and fold surface free energy were further calculated according to the classical theories. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

超支化聚酯共混聚合物等温结晶动力学研究

采用三羟甲基丙烷、2,2-二羟甲基丙酸、对甲苯磺酸反应制备第2～5代超支化聚酯(HBP),将其按质量分数10%分别与聚丙烯(PP)和聚甲醛(POM)共混,用差示扫描量热法(DSC)研究了共混物的等温结晶动力学。结果表明,用Avrami方程描述PP/HBP和POM/HBP的结晶动力学较理想。在PP中,HBP主要起成核作用;在POM中,HBP主要起稀释作用;第2代HBP成核作用最弱,稀释作用最强,第5代HBP稀释作用最小。     

Kinetics of isothermal and non‐isothermal crystallization of poly(butylene terephthalate)/ liquid crystalline polymer blends

The melting behavior and isothermal and non‐isothermal crystallization kinetics of poly(butylene terephthalate) (PBT)/thermotropic liquid crystalline polymer (LCP), Vectra A950 (VA) blends were studied by using differential scanning calorimetry. Isothermal crystallization experiments were performed at crystallization temperatures (T_c), of 190, 195, 200 and 205°C from the melt (300°C) and analyzed based on the Avrami equation. The values of the Avrami exponent indicate that the PBT crystallization process in PBT/VA blends is governed by three‐dimensional morphology growth preceded by heterogeneous nucleation. The overall crystallization rate of PBT in the melt blends is enhanced by the presence of VA. However, the degree of PBT crystallinily remains almost the same. The analysis of the melting behavior of these blends indicates that the stability and the reorganization process of PBT crystals in blends are dependent on the blend compositions and the thermal history. The fold surface interfacial energy of PBT in blends is more modified than in pure PBT. Analysis of the crystallization data shows that crystallization occurs in Regime II across the temperature range 190°C‐205°C. A kinetic treatment based on the combination of Avrami and Ozawa equations, known as Liu's approach, describes the non‐isothermal crystallization. It is observed that at a given cooling rate the VA blending increases the overall crystallization rate of PBT.     

Miscibility,Mechanical and Thermal Properties of Melt-Mixed Poly(trimethylene terephthalate)/Polypropylene Blends

This study examined the miscibility, mechanical and thermal properties of melt-mixed blends of PTT(poly(trimethylene terephthalate)) with PP(isotatic polypropylene). DMA and SEM results indicated that the PTT/PP blends are immiscible. Revealed from TGA analyses, the blends with a higher PP content showed a higher degradation temperature. A complex melting behavior was observed for the blends. The isothermal crystallization kinetics of the blends was analyzed from 200°C to 210°C using the Avrami equation. The WAXD results showed that the crystal structure of PTT remained unchanged in the blends. Nevertheless, the PP rich blends possessed lower tensile strength and higher elongation at break.     

Dramatic influence of compatibility on crystallization behavior and morphology of polypropylene in NBR/PP thermoplastic vulcanizates

In this study, the isothermal/nonisothermal crystallization behavior of polypropylene (PP) in acrylonitrile butadiene rubber (NBR)/PP thermoplastic vulcanizates (TPVs) prepared with three different processing methods, the compatibility effect therein, and the mechanism involved were studied. We concluded that the vulcanized NBR particles in TPVs act as heterogeneous nucleation centers and increase the number of nuclei. The crystallization rate of PP thereby increases and the growth of PP spherulites is restrained because of the isolation of vulcanized NBR particles. Since the addition of compatibilizer improves the compatibility of NBR and PP, the smaller and uniformly dispersed NBR particles are obtained, resulting in more and smaller PP crystals as well as higher crystallization rate, compared with Ultra-fine fully vulcanized NBR particles (UFNBR)/PP TPV and NBR/PP TPV without compatibilization. The isothermal crystallization kinetics of PP in TPVs obeys the Avrami equation, whereas the nonisothermal crystallization kinetics is well described by the equation of Mo et al.     

动态硫化EPDM/PP热塑性弹性体等温结晶行为研究

采用差示扫描量热仪（DSC）对比研究了聚丙烯（PP）和动态硫化三元乙丙橡胶/聚丙烯热塑性弹性体（EPDM/PPTPV）的等温结晶行为,并用Avrami方程对其进行等温结晶动力学分析。结果表明,在相同的结晶温度下,EPDM/PPTPV比PP结晶更快。2种试样的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV的Avrami指数n比PP的低,半结晶时间t_1/2比PP的低,结晶速率常数k比PP的高。     

Isothermal crystallization and spherulite nucleation in blends of polypropylene with metallocene‐prepared polyethylene

The isothermal crystallization behavior and morphology of a polypropylene (PP)‐based copolymer, a metallocene‐prepared linear low‐density polyethylene (M‐LLDPE) and their three 10/90, 30/70 and 50/50 M‐LLDPE/PP blends have been investigated. The PP and M‐LLDPE contained 5 ethylene and 3.3 mol% hexene‐1 as a comonomer, respectively. Isothermal crystallization studies revealed a different temperature‐dependence on crystallization for M‐LLDPE, PP and their blends and the crystallization half‐life for the M‐LLDPE was higher than either PP or the blends at a certain temperature. The PP‐rich blends also showed a quite similar crystallization rate to that of PP. Investigations on the variation of spherulite growth rate of PP in the blends at different temperatures revealed no significant change and was quite independent of the amount of M‐LLDPE being employed. The morphology studies revealed that the nucleation densities of the PP spherulites decreased by introducing M‐LLDPE into PP and the M‐LLDPE remained as discrete droplets dispersed throughout the PP spherulites. The results obtained were consistent with no miscibility between the two components. Copyright © 2005 Society of Chemical Industry