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1.
Blends of isotactic polypropylene and polyamide‐6/clay nanocomposites (iPP/NPA6) were prepared with an internal batch mixer. A high content of the β‐crystalline form of isotactic polypropylene (β‐iPP) was observed in the injection‐molded samples of the iPP/NPA6 blends, whereas the content of β‐iPP in the iPP/PA6 blends and the iPP/clay composite was low and similar to that of neat iPP. Quiescent melt crystallization was studied by means of wide‐angle X‐ray diffraction, differential scanning calorimetry, and polarized optical microscopy. We found that the significant β‐iPP is not formed during quiescent melt crystallization regardless of whether the sample used was the iPP/NPA6 blend or an NPA6 fiber/iPP composite. Further characterization of the injection‐molded iPP/NPA6 revealed a shear‐induced skin–core distribution of β‐iPP and the formation of β‐iPP in the iPP/NPA6 blends is related to the shear flow field during cavity‐filling. In the presence of clay, the deformation ability of the NPA6 domain is decreased, as evidenced by rheological and morphological studies. It is reasonable that the enhanced relative shear, caused by low deformability of the NPA6 domain in the iPP matrix, is responsible for β‐iPP formation in the iPP/NPA6 blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3428–3438, 2004  相似文献   

2.
The structure–property relationships of isotactic polypropylene (iPP)/styrenic block copolymer blends filled with talc were examined by optical and scanning electron microscopy, wide‐angle X‐ray diffraction, and tensile‐ and impact strength measurements. The composites were analyzed as a function of the poly(styrene‐b‐ethylene‐co‐propylene) diblock copolymer (SEP) and the poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer (SBS) content in the range from 0 to 20 vol % as elastomeric components and with 12 vol % of aminosilane surface‐treated talc as a filler. Talc crystals incorporated in the iPP matrix accommodated mostly plane‐parallel to the surface of the samples and strongly affected the crystallization process of the iPP matrix. The SBS block copolymer disoriented plane‐parallel talc crystals more significantly than the SEP block copolymer. The mechanical properties depended on the final phase morphology of the investigated iPP blends and composites and supermolecular structure of the iPP matrix because of the interactivity between their components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1255–1264, 2004  相似文献   

3.
The temperature dependence of the mean size of local free volumes in an amorphous atactic (aPP) and a semicrystalline syndiotactic polypropylene (sPP), and an amorphous ethylene‐propylene copolymer (E‐co‐P48) has been studied. Pressure‐volume‐temperature (PVT) experiments were performed for aPP, from which the hole fraction h of the Simha‐Somcynsky theory and the number density of holes were estimated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3089–3093, 2003  相似文献   

4.
The structure, morphology, and isothermal and nonisothermal crystallization of isotactic polypropylene/low‐molecular‐mass hydrocarbon resin blends (iPP/HR) (up to 20% in weight of HR) have been studied, using optical and electron microscopy, wide‐ and small‐angle X‐ray and differential scanning calorimetry. New structures and morphologies can be activated, using appropriate preparation and crystallization conditions and blend composition. For every composition and crystallization condition, iPP crystallizes in α‐form, with a spherulitic morphology. The size of iPP spherulites increases with resin content, whereas the long period decreases. In the range of crystallization temperatures investigated, HR modifies the birefringence of iPP spherulites, favoring the formation of radial lamellae and changing the ratio between tangential and radial lamellae. Spherulitic radial growth rates, overall crystallization rates, and melting temperatures are strongly affected by resin, monotonically decreasing with resin content. This confirms miscibility in the melt between the two components of the blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3368–3379, 2004  相似文献   

5.
This article reports the use of a binary single‐site catalyst system for synthesizing comb‐branched polypropylene samples having isotactic polypropylene (iPP) backbones and atactic polypropylene (aPP) side chains from propylene feedstock. This catalyst system consisted of the bisiminepyridine iron catalyst {[2‐ArN?C(Me)]2C5H3N}FeCl2 [Ar = 2,6‐C6H3(Me)2] ( 1 ) and the zirconocene catalyst rac‐Me2Si(2‐MeBenz[e]Ind)2ZrCl2 ( 2 ). The former in situ generated 1‐propenyl‐ended aPP macromonomer, whereas the latter incorporated the macromonomer into the copolymer. The effects of reaction conditions, such as the catalyst addition procedure and the ratio of 1 / 2 on the branching frequency, were examined. Copolymer samples having a branching density up to 8.6 aPP side chains per 1000 iPP monomer units were obtained. The branched copolymers were characterized by 13C NMR and differential scanning calorimetry. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1152–1159, 2003  相似文献   

6.
The effect of compatibility on phase morphology and orientation of isotactic polypropylene (iPP) blends under shear stress was investigated via dynamic packing injection molding (DPIM). The compatibility of iPP blended with other polymers, namely, atactic polypropylene (aPP), octane-ethylene copolymer (POE), ethylene-propylene-diene rubber (EPDM) and poly(ethylene-co-vinyl acetate) (EVA), have first been studied using dynamic mechanical analysis (DMA). These blends were subjected to DPIM, which relies on the application of shear stress fields to the melt/solid interfaces during the packing stage by means of hydraulically actuated pistons. The phase morphology, orientation and mechanical properties of the injection-molded samples were characterized by SEM, 2D WAXS and Instron. For incompatible iPP/EVA blends, a much elongated and deformed EVA particles and a higher degree of iPP chain orientation were observed under the effect of shear. However, for compatible iPP/aPP blends, a less deformed and elongated aPP particles and less oriented iPP chains were deduced. It can be concluded that the compatibility between the components decreases the deformation and orientation in the polymer blends. This is most likely due to the hindering effect, resulting from the molecular entanglement and interaction in the compatible system.  相似文献   

7.
The conformational and dynamic properties of polypropylene (PP) for both pure melts and blends with different chain tacticity were investigated by Monte Carlo simulation of isotactic (iPP), atactic (aPP) and syndiotactic (sPP) polypropylenes. The simulation of coarse-grained PP models was performed on a high coordination lattice incorporating short- and long-range intramolecular interactions from the rotational isomeric state (RIS) model and Lennard-Jones (LJ) potential function of propane pairs, respectively. The dynamics of chains in binary PP/PP mixture were investigated with the composition of C150H302 with different chain taciticity. The diffusion rates of PP with different stereochemistry are generally in the order as: iPP 〉 aPP 〉〉 sPP. For PP/PP blends with 50:50 wt% binary mixtures, immiscibility was observed when sPP was introduced into the mixtures. The diffusion rate of iPP and aPP became slower after mixing, while sPP diffuses significantly faster in the binary mixtures. The mobility of PP chains depends on both intramolecular (molecular size and chain stiffness) and intermolecular (chain packing) interactions. The effect of intramolecular contribution is greater than that of intermolecular contribution for iPP and aPP chains in binary mixtures. For sPP chain, intermolecular interaction has greater influence on the dynamics than intramolecular contribution.  相似文献   

8.
The surface compositions and morphologies of melt‐quenched blends of isotactic polypropylene (iPP) with aspecific poly(ethylene‐co‐propylene) rubber (aEPR) were characterized by atomic force microscopy, optical microscopy, and X‐ray photoelectron spectroscopy. The surface morphologies and compositions formed in the melt are frozen‐in by crystallization of the iPP component and, depending on the processing conditions, are enriched in iPP or aEPR or contain a phase‐separated mix of iPP and aEPR. Enrichment of iPP is observed for blends melted in open air, in agreement with earlier work showing the high surface activity of atactic polypropylene at open interfaces. Surface segregation of iPP is suppressed at confined interfaces. Blends melt‐pressed between hydrophilic and hydrophobic substrates have phase‐separated iPP and aEPR domains present at the surface, which grow in size as the melt time increases. Surface enrichment of aEPR is observed after exposing melt‐pressed blends to n‐hexane vapor, which preferentially solvates aEPR and draws it to the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 421–432, 2004  相似文献   

9.
The in situ microfibrillar blend of poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) was fabricated through a slit die extrusion, hot stretch, and quenching process. The morphological observation indicates that while the unstretched blend appears to be a common incompatible morphology, the hot stretched blends present PET in situ fibers whose characteristics, such as diameter and aspect ratio, are dependent on the hot stretching ratio (HSR). When the HSR is low, the elongated dispersed phase particles are not uniform at all. As the HSR is increased to 16.1, well‐defined PET microfibers were generated in situ, whose diameter is rather uniform and is around 0.6 ~ 0.9 μm. The presence of the PET phase shows significant nucleation ability for crystallization of iPP. Higher HSR corresponds to faster crystallization of the iPP matrix, while as HSR is high up to a certain level, its variation has little influence on the onset and maximum crystallization temperatures of the iPP matrix during cooling from melt. Optical microscopy observation reveals that transcrystalline layers form in the microfibrillar blend, in which the PET microfibers play as the center row nuclei. In the as‐stretched microfibrillar blends, small‐angle X‐ray scattering measurements show that matrix iPP lamellar crystals have the same orientation as PET lamella. The long period of lamellar crystals of iPP is not affected by the presence of PET micofibers. Wide‐angle X‐ray scattering reveals that the β phase of iPP is obtained in the as‐stretched blends, whose concentration increases with the increase of the HSR. This suggests that finer PET microfibers can promote the occurrence of the β phase. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4095–4106, 2004  相似文献   

10.
This study describes the morphology and nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) in situ micro‐fiber‐reinforced blends (MRB) obtained via slit‐extrusion, hot‐stretching quenching. For comparison purposes, neat PP and PET/PP common blends are also included. Morphological observation indicated that the well‐defined microfibers are in situ generated by the slit‐extrusion, hot‐stretching quenching process. Neat iPP and PET/iPP common blends showed the normal spherulite morphology, whereas the PET/iPP microfibrillar blend had typical transcrystallites at 1 wt % PET concentration. The nonisothermal crystallization kinetics of three samples were investigated with differential scanning calorimetry (DSC). Applying the theories proposed by Jeziorny, Ozawa, and Liu to analyze the crystallization kinetics of neat PP and PET/PP common and microfibrillar blends, agreement was found between our experimental results and Liu's prediction. The increases of crystallization temperature and crystallization rate during the nonisothermal crystallization process indicated that PET in situ microfibers have significant nucleation ability for the crystallization of a PP matrix phase. The crystallization peaks in the DSC curves of the three materials examined widened and shifted to lower temperature when the cooling rate was increased. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 374–385, 2004  相似文献   

11.
Several blends, covering the entire range of compositions, of a metallocenic ethylene‐1‐octene copolymer (CEO) with a multiphasic block copolymer, propylene‐b‐(ethylene‐co‐propylene) (CPE) [composed of semicrystalline isotactic polypropylene (iPP) and amorphous ethylene‐co‐propylene segments], have been prepared and analyzed by differential scanning calorimetry, X‐ray diffraction, optical microscopy, stress‐strain and microhardness measurements, and dynamic mechanical thermal analysis. The results show that for high CEO contents, the crystallization of the iPP component is inhibited and slowed down in such a way that it crystallizes at much lower temperatures, simultaneously with the crystallization of the CEO crystals. The mechanical results suggest very clearly the toughening effect of CEO as its content increases in the blends, although it is accompanied by a decrease in stiffness. The analysis of the viscoelastic relaxations displays, first, the glass transition of the amorphous blocks of CPE appearing at around 223 K, which is responsible for the initial toughening of the plain CPE copolymer in relation to iPP homopolymer. Moreover, the additional toughening due to the addition of CEO in the blends is explained by the presence of the β relaxation of CEO that appears at about 223 K. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1869–1880, 2002  相似文献   

12.
In previous studies, we found that Young's moduli of quenched isotactic polypropylene/high‐density polyethylene (iPP/HDPE) exceeded the upper bound, calculated from the Voigt model, with the moduli of the quenched homopolymers as those of the two components. We suggested that this might be due to crystallization, as the components crystallized at higher temperatures in the blend than on their own. We repeated the same set of measurements, this time on iPP/HDPE blends that were cooled slowly. We also examined crystallization at various rates of cooling with differential scanning calorimetry. At slow cooling rates, the HDPE and iPP components in the blends crystallize at lower temperatures than in the pure homopolymers, suggesting that the presence of one component inhibits rather than promotes the crystallization of the other. Electron microscopy of slowly cooled blends revealed very different interfacial morphologies depending on whether the HDPE or the iPP crystallizes first. Young's moduli of most of the blends lie on the upper bound; however, some blends with co‐continuous morphologies fall well below the lower bound. The mechanical properties are discussed in terms of the interfacial morphology, the crystallization behavior, and the large‐scale phase separation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1384–1392, 2003  相似文献   

13.
The influence of low contents of a liquid crystalline polymer on the crystallization and melting behavior of isotactic polypropylene (iPP) was investigated using electron and optical microscopy, differential scanning calorimetry, and X-ray diffraction. In pure iPP, the α modification was found, whereas for iPP/Vectra blends at Vectra concentration <5%, both α and β forms were observed. The amount of β phase varied from 0.23 to 0.16. Optical microscopy showed that Vectra was able to nucleate both α and β forms. Non-isothermal crystallization produces a material with a strong tendency for recrystallization of the α and β forms (αα′ and ββ′ recrystallization) leading to double endotherms for both crystalline forms in DSC thermograms. Melting thermograms after isothermal crystallization at low temperatures showed a similar behavior. At values of Tc > 119 °C for the α form and Tc > 125 °C for the β form, only one melting endotherm was observed because enough perfect crystals, not susceptible to recrystallization, were obtained. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1949–1959, 2004  相似文献   

14.
An amorphous 50/50 atactic polypropylene (aPP)/isotactic polypropylene (iPP) mixture at 125 degrees C was simulated using a second nearest neighbor diamond lattice and a three states rotational isometric state model. The result suggests that at the liquidlike density that corresponds to the atmospheric pressure, aPP prefers to interact with other aPP chains rather than with iPP chains. The result is consistent with the inference of Keith and Padden [J. Appl. Phys. 35, 1286 (1964)] that aPP and iPP will tend to separate from one another in their melt at 125 degrees C, before the onset of crystallization of iPP. The tendency for immiscibility of the amorphous aPP/iPP blend is likely attributed to the presence of short syndiotactic sequences in the aPP chains adopting all-trans conformations. The attractive intermolecular interaction of pairs of such subchains at 125 degrees C promotes the separation of aPP from iPP. This interaction is weakened at higher temperature, where aPP and iPP become miscible. The result also shows that miscibility of the blend increases with increasing pressure. However, the origin of the pressure effect is not clear.  相似文献   

15.
A general approach, based on the polymer reference interaction site model (PRISM) integral equation theory, suitable for characterizing arbitrarily complex polyolefin melts is described. We tested the method by calculating the melt structures of linear polyethylene (PE) and isotactic polypropylene (iPP) and the spinodal decomposition temperatures for PE/iPP blends. The computational expense of the PRISM calculation was reduced with a single‐site united atom model in which the polyolefin CH, CH2, and CH3 groups were approximated as chemically equivalent sites with spherically symmetric energetic interactions. The site–site interactions were defined by a potential function comprising a hard core with an attractive Lennard–Jones term. These energetic parameters were optimized with a central composite design strategy that enabled a simultaneous fit of experimental melt density and structure factor data. Values were obtained for PE and iPP individually and for common universal parameters that could potentially be used for all polyolefins. The rotational isomeric state–metropolis Monte Carlo (RMMC) technique was used to generate sets of conformers at specified temperatures covering the melt‐temperature range of the polymers. The characteristic ratio was used to assess the quality of the conformers and the RMMC method. Values of 9.68 for PE and 9.27 for iPP were obtained. The single‐chain structure factors calculated by the RMMC method were used to calculate the total structure factor for each melt. These were validated against published X‐ray diffraction results. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1803–1814, 2001  相似文献   

16.
The fracture behavior and deformation mechanisms of polypropylene modified by elastomeric metallocene‐catalyzed polyolefin blends were investigated under both static and dynamic loading conditions. The fracture toughness was evaluated with the J integral approach. The development of damage mechanisms was studied by the examination of fracture surfaces with scanning electron microscopy and by the examination of single‐edge, double‐notch, four‐point‐bending or low‐impact‐energy fractured samples with optical microscopy. In addition, tensile dilatometry measurements were carried out to determine the nature of the deformation micromechanisms. The fracture behavior and the size and shape of the damage zones were drastically influenced by the elastomeric particles and the imposed constraint. The role of the elastomeric particles was different, depending on the strain rate. Under impact loading, particle pullout and crazing were responsible for the increased fracture toughness of polypropylene. Under quasistatic loading, stable fracture growth was caused by particle cavitation, which promoted ductile tearing of polypropylene before failure continued in an unstable fashion via crazing. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1075–1089, 2004  相似文献   

17.
This article discusses the influence of two natural terpene resins (NTR), poly(α‐pinene) (PαP A115) and poly(d‐limonene) (PL C115), on morphology, miscibility, thermal, and dynamic‐mechanical properties of their blends with isotactic polypropylene (iPP). The NTR have interesting physical and chemical properties, and they are approved for food contact application. From the results of differential scanning calorimetry and dynamic‐mechanical thermal analysis it was deduced that both the resins were completely miscible with the amorphous iPP up to the composition investigated here (70/30 wt %). Scanning electron microscopy (SEM) analysis instead showed that the 70/30 iPP/PαP A115 blend and 80/20 and 70/30 iPP/PL C115 blends contained very small domains homogeneously distributed into the matrix. It is hypothesized that the domains are likely formed by the terpene‐rich phase, and the matrix by the iPP‐rich phase (besides the crystallized iPP phase). The iPP‐rich phase and the NTR‐rich phase would have the glass transition temperatures so close that they cannot be resolved by DSC and DMTA. Finally, for the iPP/PαP A115 system an upper critical solution temperature (UCST) is proposed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 867–878, 1999  相似文献   

18.
The low‐temperature mechanical behavior of semicrystalline polymer blends is investigated. Isotactic polypropylene (iPP) is blended with both Zeigler–Natta polyethylene (PE) and metallocene PE. Transmission electron microscopy (TEM) on failed tensile bars reveals that the predominate failure mode in the Zeigler–Natta blend is interfacial, while that in the metallocene blend is failure of the iPP matrix. The observed change in failure mode is accompanied by a 40% increase in both tensile toughness and elongation at −10 °C. We argue that crystallite anchoring of interfacially entangled chains is responsible for this dramatic property improvement in the metallocene blend. The interfacial width between PE and iPP melts is approximately 40 Å, allowing significant interfacial entanglement in both blends. TEM micrographs illustrate that the segregation of low molecular weight amorphous material in the Zeigler–Natta blend reduces the number and quality of crystallite anchors as compared with the metallocene blend. The contribution of anchored interfacial structure was further explored by introducing a block copolymer at the PE/iPP interface in the metallocene blend. Small‐angle X‐ray scattering (SAXS) experiments show the block copolymer dilutes the number of crystalline anchors, decoupling the interface. Increasing the interfacial coverage of the block copolymer reduces the number of anchored interfacial chains. At 2% block copolymer loading, the low‐temperature failure mode of the metallocene blend changes from iPP failure to interfacial failure, reducing the blend toughness and elongation to that of the Zeigler–Natta blend. This work demonstrates that anchored interfacial entanglements are a critical factor in designing semicrystalline blends with improved low‐temperature properties. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 108–121, 2000  相似文献   

19.
The residual stress of the iPP surface layer in Al/iPP/Al under the influence of microwave irradiation was investigated by thin film (TF)‐X‐ray diffraction (XRD). Depending on the irradiation time, we calculated the macro residual stress, micro stress, and lattice static distortion stress. The results show that the macroscopic residual tensile stress of irradiated iPP samples dropped from about 12 MPa to 4 MPa. D(300) (the β crystal phase) becomes larger from about 4 to 10 nm as the irradiation time increased, and the β‐form iPP becomes more perfect. However, for theα‐form phase, D(110) remains almost stable. Moreover, the microscopic distortion coefficient ε(300) that decreases from approximately 0.03 to 0.018, becomes smaller than ε(110) parallel to the irradiation time, so the microscopic stress of the β‐crystal is decreased. In addition, the lattice static distortion energy of the α‐form greatly increases from 2 to 6 MPa, but the lattice static distortion energy of the β‐crystals remains constant at about 1.5 MPa and is much smaller than that of the α‐crystals at the same irradiation time. These calculated results are in good agreement with that of the crystallinity and order parameter of the β‐crystals of the TF‐XRD. The lattice distortion energy is a major portion of the plastic deformation, therefore, it suggests that the lattice static distortion energy is the main cause of α → β crystalline transformation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3759–3765, 2004  相似文献   

20.
A new family of thermoplastic nanocomposites based on isotactic polypropylene (iPP) and inorganic fullerene‐like tungsten disulfide (IF‐WS2) has been successfully prepared. A very efficient dispersion of IF‐WS2 material was obtained by mixing in the melted polymer without using modifiers or surfactants. The addition of IF‐WS2 nanoparticles induces a remarkable enhancement of the thermal stability of iPP, as well as an increase in the crystallization rate of the matrix when compared with pure iPP. The nucleating efficiency of IF‐WS2 solid lubricant nanoparticles on the α‐phase of iPP reaches very high values (60–70%), the highest values observed hitherto for polypropylene nanocomposites. The incorporation of IF‐WS2 has also been observed to increase the size and stability of the crystals formed. The melting behavior of the nanocomposites indicates the formation of more perfect crystals as determined by differential scanning calorimetry and time‐resolved synchrotron X‐ray scattering experiments. The new nanocomposites show an increase in the storage modulus with respect to pure iPP measured by dynamic mechanical analysis. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2309–2321, 2007  相似文献   

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