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1.
Crystallization behaviour of isotactic polypropylene/linear low density polyethylene (iPP/LLDPE) blends has been investigated by optical microscopy and DSC. Crystallization of iPP depends upon blend composition and thermal history. When blended with LLDPE, the crystallization temperature of iPP, Tc, decreased slightly. Crystallinity did not change in the range 0-80wt% LLDPE; there were only slight changes in the crystalline structure, but LLDPE seemed to resist forming the β type of spherulites. Below 80 wt% of LLDPE, iPP was a continuous phase. The iPP spherulite growth rate was almost constant; however, overall crystallization decreased due to decreasing primary nuclei density.  相似文献   

2.
The phase morphology and structure of thermoplastic elastomers obtained from isotactic polypropylene (iPP) and ethylene—propylene random copolymer (EPR) blends by means of the dynamic curing of EPR rubbery component carried out during its melt mixing with iPP in a Banbury mixer at 180°C were investigated. Samples obtained by compression molding and by using isothermal crystallization conditions of the iPP phase were analyzed by means of differential scanning calorimetry, of optical, scanning, and transmission electron microscopy, and of wide-angle and small-angle X-ray diffraction. The influence of cooling below the melting point and of EPR molecular structure on the kinetic and thermodynamic parameters related to crystallization process of the iPP phase was also studied. It was found that the process of dynamic curing of the EPR component dramatically affects the development of the phase morphology and structure in the material. As a matter of fact, the blend containing the uncured EPR is characterized by the presence of iPP domains randomly distributed in the EPR rubbery matrix, whereas in the blend containing the cured EPR the iPP phase becomes the continuous phase crystallizing in a structure that resembles a cobweb tending to surround the EPR cured particles; moreover such an iPP cobweb appears to be contituted by row structures of stacked lamellae. It was found that the addition of EPR phase interferes dramatically with the crystallization process of the iPP, thus inducing drastic modification in its intrinsic morphology (size, neatness, regularity of spherulites, inner structure of spherulites, etc.). Such interference was found to be comparatively stronger when the iPP phase crystallizes in presence of cured EPR. The elastic behavior of the thermoplastic elastomer material was accounted for by applying the “leaf spring model” to the morphology and structure of the iPP phase crystallized in presence of cured EPR. © 1994 John Wiley & Sons, Inc.  相似文献   

3.
The influence of stereochemical composition of the radial growth rate of spherulites, the nucleation density, the overall rate of crystallization and the thermal behaviour of fractions of iPP samples synthesized with different catalyst systems (low, high and very high yield) was investigated. The study used 13C n.m.r., differential scanning calorimetry (d.s.c.) and optical microscopy. The 13C n.m.r. analysis showed that due to the presence of catalytic sites with different stereoregulating capability the catalyst system produces polypropylene with different stereoregularity. It was found that the growth rate of spherulites and the overall rate of crystallization are strictly related to the stereochemical structure of the polypropylene. Moreover, for the low yield iPP, phenomena of secondary crystallization were observed by Avrami analysis of the overall kinetics. Values of the equilibrium melting temperature (Tm), energy of nucleation (Δø1) and surface free energy of folding (σe) of iPP lamellar crystals have been determined according to the kinetic theory of polymer crystallization. The values of such thermodynamic quantities as well as the thermal behaviour of various iPP are strongly dependent upon the amount and distribution of configurational irregularities existing along the chains and upon the molecular mass distribution.  相似文献   

4.
This study mainly focuses on the formation of isotactic polypropylene (iPP) blend morphologies with microspheres and distinct bead–string spherulites. iPP microspheres have been prepared by a simple and convenient strategy through either an isothermal or a nonisothermal crystallization process based on the macrophase‐separated structure in molten state of iPP/olefin block copolymer (OBC) blend. The dimension of the iPP spheres can be adjusted easily from about 1 µm to >10 µm by controlling the compatibility and annealing conditions. It was found that any of the following three parameters, the molecular structure of OBC (particularly the octene content), molecular weight of iPP, and annealing condition can be rescaled with others in controlling the dimension of the iPP microspheres. The mechanism of the formation of iPP microspheres was studied in detail. Surprisingly, the typical spinodal decomposition morphology with interconnected or thin sheet structure is the precursor of these microspheres. During the subsequent annealing process, it breaks up and further coarsens into spherical structure. In addition, distinct spherulites with a bead–string substructure have been obtained during the isothermal crystallization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40863.  相似文献   

5.
Huihui Li  Dujin Wang 《Polymer》2004,45(23):8059-8065
The supermolecular structures of iPP fiber/matrix composites as a function of crystallization temperature were studied by means of optical microscopy. The results show that, even though partial melting of the iPP fibers is in favor of initiating the β-iPP crystal growth, the interfacial morphology of iPP single-polymer composites induced by its own fiber depends strongly on the crystallization temperature. It was found that transcrystalline structures of negative radial βIII-iPP or banded βIV-iPP can be produced within the crystallization temperature range 105-137 °C, while transcrystallization zone of pure negative radial αII-iPP crystals is observed at higher crystallization temperature, e.g. 141 °C. On the other hand, the surrounding iPP spherulites grown from the bulk are composed of α-iPP in the whole crystallization temperature range. However, the optical character of the spherulites is controlled by the thermal condition.  相似文献   

6.
Isothermal crystallization of isotactic polypropylene (iPP)/organic montmorillonite (OMMT) binary nanocomposite and iPP/OMMT/poly(ethylene-co-octene) (PEOc) ternary nanocomposites has been investigated by polarized optical microscopy (POM), rheometry and scanning electron microscopy (SEM). At the stage of nucleation the heterogeneous nucleation effect of OMMT was much greater than the concentration fluctuation assisted nucleation effect in the ternary nanocomposite. Besides, PEOc played a role of inhibitor of OMMT nucleation agents at the nucleation stage because many of OMMT layers were distributed around PEOc-rich domains. At stage II of the crystal growth process, the entanglement effect of PEOc greatly affected the rheological response (storage modulus (G′) and its growth rate) due to the long side chains of PEOc component. In stage III of the growth process, OMMT layers and the entanglement of PEOc chains limited the motion of polypropylene chains. So the growth rate of G′ was slowed down. During the shrinkage and cooling process after isothermal crystallization, some fibril links between the spherulites, consisting of PEOc chains and iPP chains, were formed from the amorphous phases surrounding the spherulites.  相似文献   

7.
The crystallization, the morphology and the thermal behaviour of thin films of isotactic polypropylene (iPP) blended with elastomers such as random ethylene-propylene copolymers (EPM) with different ethylene content and polyisobutylene (PiB) were investigated by means of optical microscopy, differential scanning calorimetry and wide angle X-ray diffractometry. During crystallization EPM copolymers are ejected on the surface of the film forming droplet-like domains. A different morphology is observed in iPP/PiB blends. For these mixtures the elastomers separate from the iPP phase forming spherical domains that are incorporated in the iPP intraspherulitic regions. Both EPM and PiB elastomers act as nucleant agents for iPP spherulites. This nucleation efficiency is strongly dependent on the chemical structure and molecular mass of the elastomers. The addition of EPM causes an elevation of the observed and equilibrium melting temperature of iPP. This unusual effect may be accounted for by assuming that the elastomers are able to extract selectively the more defective molecules of iPP. The depression of the growth rate of spherulites and the observed and equilibrium melting temperature of iPP, noted in iPP/PiB blends, suggests that these two polymers have a certain degree of compatibility in the melt.  相似文献   

8.
Blends of isotactic polypropylene with amorphous and slightly crystalline ethylene-propylene-diene terpolymer (EPDM), prepared by solution blending, have been investigated by optical microscopy and differential scanning calorimetry. Nucleation and crystallization kinetic parameters, such as nucleation rates, nucleation half times, Avrami-exponents and spherulitic growth rates, have been determined. It has been found that the dispersion of crystalline EPDM in iPP is different from that of amorphous EPDM. Both EPDMs are incorporated into the spherulites, causing a decrease of the maximum growth rate of the iPP spherulites. The surface free energy of the iPP crystals is diminished on adding EPDM to iPP and is accompanied by a higher secondary nucleation rate. From the decrease observed in the Avrami exponent with increasing EPDM concentration in the blend, it has been concluded that nucleation becomes predominantly heterogeneous, as there is a proportional increase in the interfacial area between the two components.  相似文献   

9.
The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007  相似文献   

10.
Isothermal radial growth rates (G) of isotactic polypropylene (iPP) spherulites in immiscible blends with a polyethylene based ionomer (1) partially neutralized with Zn+2, (2) completely acidified, and (3) completely esterified have been determined at crystallization temperatures between 118 and 124°C by time-lapse photomicroscopy. In these blends iPP spherulites grow with increased G as compared to that of pure iPP. This behavior is attributed to increases in the rate of transport, due to limited miscibility induced by mechanical mixing. However, subtle differences in the melting behavior suggest that changes in Spherulite morphology may also be a contributing factor.  相似文献   

11.
The supermolecular structure of binary isotactic polypropylene/poly(styrene‐b‐butadiene‐h‐styrene) (iPP/SBS) and isotactic polypropylene/atactic polystyrene (iPP/aPS) compression molded blends and that of ternary iPP/aPS/SBS blends were studied by optical microscopy, scanning and transmission electron microscopy, wide‐angle X‐ray diffraction and differential scanning calorimetry. Nucleation, crystal growth, solidification and blend phase morphology are affected by the addition of amorphous components (SBS and aPS). As a compatiblizer in immiscible iPP/aPS blends, SBS formed interfacial layer between dispersed honeycomb‐like aPS/SBS particles and the iPP matrix, thus influencing the crystallization process in iPP. The amount of SBS and aPS, and compatibilizing efficiency of SBS, determine the size of dispersed aPS, SBS, and aPS/SBS particles and, consequently, the final blend phase morphologies: well‐developed spherulitic morphology, cross‐hatched structure with blocks of sandwich lamellae and co‐continuous morphology. The analysis of the relationship between the size of spherulites and dispersed particles gave the criterion relation, which showed that, in the case of a well‐developed spherulitization, the spherulites should be about fourteen times larger than the incorporated dispersed particles; i.e. to be large enough to engulf dispersed inclusions without considerable disturbing of the spherulitic structure.  相似文献   

12.
A series of isotactic polypropylene/poly(propylene-1-octene) (iPP/PPOc) in-reactor alloys were synthesized by a one-step polymerization process, using Metallocene/Ziegler–Natta hybrid catalyst. The alloys were characterized by FT-IR, DSC, optical microscopy and SEM. The results suggested that the spherical morphology was maintained during one-step polymerization process, which provided a potential application for one-step polyolefin in-reactor alloys. A characteristic “shell–core” structure of the nascent alloy particles was observed for the first time. This phenomenon may be due to the difference between the homopolymerization and copolymerization rate at different active centers. It was also found that the majority of the elastomers in the matrix were homogeneously distributed in the alloys. The introduction of the relatively long 1-octene branches could effectively reduce the crystal size and the crystallinity of the obtained iPP/PPOc alloys and made it possible to vary their rigidity and elasticity in a wide range. The crystallization kinetics of the alloys with pure iPP was also investigated. With the increase of elastomer content, an increase of nucleation density (the nuclei number per unit area) and the decrease of crystal perfection could be clearly observed. In comparison with pure PP, the overall crystallization rates and the growth rates of the spherulites of the alloys decreased obviously. These results indicated that the growth rate of the spherulites was the decisive step for the overall crystallization rate in this case, which can be explained on the basis of dilution effect and obstruction effect on the mobility of PP chains in the propylene–octene copolymer. Investigation of the mechanical properties indicated that notched Izod impact strength of iPP/PPOc alloys have obviously increased in comparison with that of pure iPP. The improvement of impact strength can be mainly attributed to the increase of random copolymer content. Based on the understanding of microstructure and phase morphology, the correlation between morphological structure and mechanical properties has been established.  相似文献   

13.
Calcium salts of suberic (Ca‐Sub) and pimelic (Ca‐Pim) acids were synthesized and implemented as in different grades of isotactic polypropylene (iPP). Propylene homopolymer, as well as random and block copolymers containing these additives, crystallized iPP into pure or nearly pure β modification in the isothermal and nonisothermal crystallization experiments. Recently, Ca‐Sub proved to be the most effective β‐nucleating agent of iPP. The Ca‐Sub nucleating agent widens the upper crystallization temperature range of pure β‐iPP formation up to 140°C. In this study the effect of the these additives on the crystallization, melting characteristics, and structure of the PP were studied. The degree of crystallinity of β‐iPP was markedly higher than that of α‐iPP. A widening in the melting peak of the samples crystallized in a high temperature range was first observed and discussed in regard to literature results of the same phenomenon for α‐iPP. The morphology of the β‐iPP samples was revealed by scanning electron microscopy. Independent of the type of polymer or nucleating agent, hedritic structures were found in the early stages of growth of the β‐spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2357–2368, 1999  相似文献   

14.
R. Alamo  J.G. Fatou  J. Guzmán 《Polymer》1982,23(3):379-384
The morphology and growth rates of crystallized molecular weight fractions of poly(1,3-dioxolane) covering the range Mn = 8 800 to 120 000 have been studied by polarized light microscopy. Two different supermolecular structures, dependent on molecular weight and crystallization temperature have been found. Spherulites are formed after rapid crystallization and a more disordered morphology is formed at the lowest undercoolings but there is a temperature region where both forms are observed. The disordered form appears first and a consecutive spherulitic growth takes place. The crystallization kinetics were analysed over the temperature range 10°C to 36°C. At crystallization temperatures lower than 15°–18°C, the growth rate is linear and only spherulites are found. In the temperature range from 18°C to 36°C a well defined break is observed in the growth rate but the spherulitic growth rate is always higher than that of the irregular form. The growth rate temperature coefficient was studied and the usual plots are not linear in the whole range of crystallization temperatures. For the high crystallization temperature region, the slope is about twice as great as the low crystallization temperature slope. This is the region where regular spherulites are formed. The comparison between dilatometric and growth rate data has shown that the overall rate and growth rate temperature coefficients are the same.  相似文献   

15.
Crystallization behaviors and kinetics of iPP in an in-situ prepared isotactic polypropylene/graphene (iPP/G) composites were studied in this paper. In samples used in this study, the graphene fillers were well dispersed, and the interfacial adhesion exhibited enhanced features between graphene and iPP components. The thermal stability of the composites was improved by about 100 °C compared to the pristine iPP. It was found that the crystallization morphology, crystallization rate and kinetics of the iPP/G composites were significantly influenced by the presence of graphene. The nucleation and epitaxial growth of iPP on the graphene surface were observed and studied in detail. It was observed that the nucleation of iPP favored to occur at the wrinkles and edges due to the good match of the lattice parameters and the weak spatial hindrance compared to the smooth surface. Numerous nuclei epitaxially formed and the size of the crystals was very small. The schematic diagram was also proposed for the nucleation and growth process of iPP on the graphene surface in the iPP/G composites. Meanwhile, the overall crystallization kinetics and crystals growth were analyzed through Avrami equation. The obtained Avrami index n decreased with the graphene loadings and was close to 2 for the iPP/G composites, which implied that the growth of iPP in the composites was in two-dimension. And this was caused by the structure of graphene and the spatial confinement effect of graphene platelets in the iPP/G composites.  相似文献   

16.
Optical microscopy, differential scanning calorimetry, and small angle X‐ray scattering techniques were used to study the influence of the crystallization conditions on morphology and thermal behavior of samples of binary blends constituted of isotactic polypropylene (iPP) and a novel graft copolymer of unsaturated propylene with styrene (uPP‐g‐PS) isothermally crystallized from melt, at relatively low undercooling, in a range of crystallization temperatures of the iPP phase. It was shown that, irrespective of composition, no fall in the crystallinity index of the iPP phase was observed. Notwithstanding, spherulitic texture and thermal behavior of the iPP phase in the iPP/uPP‐g‐PS materials were strongly modified by the presence of copolymer. Surprisingly, iPP spherulites crystallized from the blends showed size and regularity higher than that exhibited by plain iPP spherulites. Moreover, the amount of amorphous material located in the interspherulitic amorphous regions decreased with increasing crystallization temperature, and for a given crystallization temperature, with increasing uPP‐g‐PS content. Also, relevant thermodynamic parameters, related to the crystallization process of the iPP phase from iPP/uPP‐g‐PS melts, were found, composition dependent. The equilibrium melting temperature and the surface free energy of folding of the iPP lamellar crystals grown in the presence of uPP‐g‐PS content up to 5% (wt/wt) were, in fact, respectively slightly lower and higher than that found for the lamellar crystals of plain iPP. By further increase of the copolymer content, both the equilibrium melting temperature and surface free energy of folding values were, on the contrary, depressed dramatically. The obtained results were accounted for by assuming that the iPP crystallization process from iPP/uPP‐g‐PS melts could occur through molecular fractionation inducing a combination of morphological and thermodynamic effects. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2286–2298, 2001  相似文献   

17.
The deformation behavior of isotactic polypropylene (iPP) spherulites with uniaxial stretching was investigated at different drawing temperatures via in situ polarized optical microscope (POM) observation. The iPP spherulites were prepared by two procedures: cooled to the room temperature from melt and annealed at 135, 140, and 145°C for 3 h. It was found that the crystallization conditions dominate the crystalline morphology and even the tensile properties of iPP. For iPP which crystallized during cooling progress, the spherulites were imperfect and the boundaries of the spherulites were diffuse, displaying good toughness at various drawing temperatures. For iPP annealed at high temperatures displayed the brittle fracture‐modes and the crack happened between spherulites, which due to the large and perfective spherulites have thick lamellas and weak connection at interspherulitic boundary. The shape and size of the iPP spherulites formed at 140 and 145°C are affected with uniaxial stretching till to the fracture of the samples at different drawing temperatures. The spherulites obtained at 135°C are deformed along the drawing direction at 100°C but not affected at low drawing temperatures, indicating the toughness increased with the increase of the drawing temperatures. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

18.
The morphology and thermal properties of isothermal crystallized binary blends of poly(propylene-co-ethylene) copolymer (PP-co-PE) and isotactic polypropylene (iPP) with low molecular weight polyethylene (PE) were studied with differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). In PP-co-PE/PE binary blends, however, the connected PE acted as a phase separating agent to promote phase separation for PP-co-PE/PE binary blends during crystallization. Therefore, the thermal properties of PP-co-PE/PE presented double melting peaks of PE and a single melting temperature of PP during melting trace; on the other hand, at cooling trace, the connected PE promoted crystallization rate because of enhanced segmental mobility of PP-co-PE during crystallization. At isothermal crystallization temperature between the melting points of iPP and PE, the binary blend was a crystalline/amorphous system resulting in persistent remarkable molten PE separated domains in the broken iPP spherulite. And then, when temperature was quenched to room temperature, the melted PE separated domains were crystallized that presented a crystalline/crystalline system and formed the intra-spherulite segregation morphology: these PE separated domains/droplet crystals contained mixed diluent PE with connected PE components. On the other hand, in the iPP/PE binary blends, the thermal properties showed only single melting peaks for both PE and iPP. Moreover, the glass transition temperature of iPP shifted to lower temperature with increasing PE content, implying that the diluent PE molecules were miscible with iPP to form two interfibrillar segregation morphologies: iPP-rich and PE-rich spherulites. In this work, therefore, we considered that the connected PE in PP-co-PE functioned as an effective phase separating agent for PP and diluent PE may be due to the miscibility between connected PE and diluent PE larger than that between PP and dispersed PE.  相似文献   

19.
Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-Tm component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-Tm component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.  相似文献   

20.
The correlation between crystalline morphology development and tensile properties of isotactic polypropylene (iPP) and its blend with poly(ethylene-co-octene) (PEOc) was investigated to study the ductile-brittle transition (DBT) in fracture modes. The sample processing strategy and the scientific observations have never been reported previously. The samples were first isothermally crystallized at 130 °C, 123 °C or 115 °C for a wide range of crystallization times, and then quenched to 35 °C for characterization. It was found that the crystallization conditions including crystallization temperature and time governed the crystalline morphology and even the tensile properties of iPP and the iPP/PEOc (80/20) blend. The lower the crystallization temperature, the shorter the crystallization time was needed for the occurrence of DBT, and the sharper the transition would be. The addition of the elastomer component delayed the DBT occurrence for the iPP/PEOc blend in terms of the crystallization time, owing to the fact that the existence of PEOc domains between the iPP lamellar stack regions or at the iPP spherulitic boundaries enhanced the ductility of the blend. The X-ray diffraction results displayed the oriented and destroyed crystalline structure characterizing the ductile fracture, while unoriented structure describing the brittle failure. The DBT is closely related to the crystal perfection, and factors such as the crystallization temperature and time and the compositions have been proven to be significant variables in determining the DBT occurrence.  相似文献   

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