Morphology,crystallization, and thermal behavior of isotactic polypropylene/propylene‐g‐styrene blends

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     

Isotactic polypropylene/ethylene‐co‐propylene blends: Influence of the copolymer microstructure on rheology,morphology, and properties of injection‐molded samples

Meltrheological behavior, phase morphology, and impact properties of isotactic‐polypropylene (iPP)‐based blends containing ethylene–propylene copolymer (EPR) synthesized by means of a titanium‐based catalyst with very high stereospecific activity (EPR_Ti) were compared to those of iPP/EPR blends containing EPR copolymers synthesized by using a traditional vanadium‐based catalyst (EPR_V). The samples of EPR copolymers were synthesized ad hoc. They were characterized by comparable propylene content, average molecular masses, and molecular mass distribution in order to assess the effects of distribution of composition and sequence lengths of the structural units on the structure–properties correlations established in the melt and in the solid state while studying different iPP/EPR pairs.^1–5 Differential scanning calorimetry, (DSC), wide‐angle X‐ray spectroscopy (WAXS), small‐angle X‐ray (SAXS), and scanning electron microscopy (SEM) investigations showed that the EPR_Ti chain is characterized by the presence of long ethylenic sequences with constitutional and configurational regularity required for crystallization of the polyethylene (PE) phase occurring, whereas a microstructure typical of a random ethylene–propylene copolymer was exhibited by the EPR_V copolymer. The different intra‐ and intermolecular homogeneity shown by such EPR phases was found to affect their melt rheological behavior at the temperatures of 200 and 250°C; all the EPR_Ti dynamic–viscoelastic properties resulting were lower than that shown by the EPR_V copolymer. As far as the melt rheological behavior of the iPP/EPR_V and iPP/EPR_Ti blends was concerned, both the iPP/EPR pairs are to be classified as “negative deviation blends” with G′ and G" values higher than that shown by the plain components. The extent of the observed deviation in the viscosity values and of the increase in the amounts of stored and dissipated energy shown by such iPP/EPR pairs was found to be dependent on copolymer microstructure, being larger for the melts containing the EPR_Ti copolymer. The application of the Cross–Bueche equation also confirmed that, in absence of shear, the melt phase viscosity ratio is the main factor in determining the viscosity of iPP/EPR blends and their viscoelastic parameters. The general correlation established between EPR dispersion degree (range of particle size and number‐average particle size), as determined in injection‐molded samples, and melt phase viscosity ratio (μ) was ratified; the type of dependence of EPR size upon μ value was in qualitative agreement with the prediction of the Taylor–Tomotika theory. Contrary to expectation,^1–5 for test temperature close to iPP T_g, EPR_V particles ranging in size between 0.75 and 1.25 μm resulted and were more effective than EPR_Ti particles, ranging in size between 0.25 and 0.75 μm, in promoting multiple craze formation. Also taking into account the SAXS results, revealed that the molecular superstructure (i.e., crystalline lamellar thickness and amorphous interlayer) of the iPP matrix is unaffected by both the presence of EPR_Ti and EPR_V phase. The above finding was related to the ethylenic crystallinity degree shown by the EPR_Ti copolymer. In particular, such a degree of crystallinity was supposed to deteriorate toughening by decreasing the tie molecules density in the EPR_Ti domains, notwithstanding the beneficial effect of the ethylenic lamellar buildup. For test temperature close to room temperature, the ductile behavior exhibited by the iPP/EPR_Ti blends was accounted for by a predominant shear yielding fracture mechanism probably promoted by a high concentration of interlamellar tie molecules among iPP crystallites in agreement with DSC results. Nonisothermal crystallization experiments showed, in fact, that the crystallization peak of the iPP phase from iPP/EPR_Ti melt is shifted to higher temperatures noticeably, thus indicating a material characterized by a comparatively higher number of spherulites per unit value grown at lower apparent undercooling values. Accordingly, WAXS analysis revealed comparatively higher iPP crystal growth in the directions perpendicular to the crystallographic planes (110) and (040) of the iPP. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 701–719, 1999     

Morphology of a melt crystallized iPP/HDPE/hydrogenated hydrocarbon resin blend

The structure, phase structure, morphology, crystallization and melting behavior of isotactic polypropylene (iPP) blended with a master batch (MB), formed by high density polyethylene and hydrogenated hydrocarbon resin (iPP/MB), have been in details investigated by using X-ray diffraction, optical microscopy and differential scanning calorimetry. It was found that the structure and morphology depend on crystallization conditions. A new family of α spherulites of iPP (type I spherulites) can be activated using appropriate crystallization conditions. Nucleation of these spherulites has been explained by using the approach of nucleus migration in polymer blends. Type I spherulites present specific morphological, kinetic and thermal behaviors. In particular it was found that the growth rate of type I spherulites, at a given T_c, is higher than the growth rate of spherulites grown from plain iPP.     

Rheological and calorimetric evidences of the fractionated crystallization of iPP dispersed in ethylene/α-olefin copolymers

In this work, the melt crystallization of immiscible blends of isotactic polypropylene (iPP) and branched polyethylenes (PE) was followed by oscillatory shear measurements during controlled cooling. All the blends contained 20% iPP finely dispersed in several ethylene/α-olefin copolymer matrices (with and without a nucleating agent) with densities ranging from 0.88 to 0.92 g/cm³ (linear low, very low, and ultra low density polyethylenes: LLDPE, VLDPE, and ULDPE). The rheological results were compared with parallel differential scanning calorimetry (DSC) measurements at the same cooling rate. During preliminary evaluations of the neat resins, no effect was found of the variation of the frequency of oscillation or the applied shear strain on their crystallization (at least in the range explored in this work). In the case of the blends, when the iPP crystallized in a fractionated fashion, only one sudden increase in the storage modulus (G′) was observed during cooling due to the partial coincident crystallization of both iPP and the PE matrix. In the presence of a nucleating agent, an almost complete separation between the crystallization of both components in the blend was achieved and two increases in G′ were clearly observed upon cooling. A close match between the dynamic crystallization kinetics obtained by DSC and torsion rheometry was demonstrated by a direct comparison between calorimetrically measured solid conversion and G′ during cooling from the melt. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2481–2493, 1997     

Effects of SBS on phase morphology of iPP/aPS blends

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.     

Effect of N,N′‐diphenyl adipamide on the formation of the β‐crystalline form in isotactic polypropylene

The polymorphic compositions and mechanical properties of isotactic polypropylene (iPP) samples nucleated by a selective β‐nucleating agent [N,N′‐diphenyl adipamide (DPA)] were investigated with wide‐angle X‐ray diffraction, polarized light microscopy, scanning electron microscopy, and mechanical tests. It was found that β‐phase crystals emerged with the addition of DPA, and the relative proportion of the β‐crystalline form reached the maximum value of 0.97 with the addition of 0.1 wt % DPA. The curved lamellae in the β spherulites were like flowers. The β spherulites were etched more easily than α spherulites because amorphous regions were distributed inside the β spherulites. The Izod notched impact strength increased sharply with the addition of DPA and attained the maximum value of 7.30 kJ/m² (the value of blank iPP was 3.13 kJ/m²) with the addition of 0.1 wt % DPA. An analysis of the misfit factors between DPA and β‐iPP showed that β‐iPP could epitaxially crystallize on the DPA crystal well. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of composition,crystallization conditions and melt phase structure on solid morphology,kinetics of crystallization and thermal behavior of binary polymer/polymer blends

Results of an investigation on the morphology, the crystallization and the thermal behavior of several binary crystallizable blends are reported. The composition, molecular mass and crystallization conditions strongly influence the crystallization and the thermal behavior as well as the overall morphology of crystallizable binary blends. Quantities such as nucleation density (N), radial growth rate (G) of spherulites, overall rate of crystallization (K), and equilibrium melting temperature (T_m) are strongly dependent upon composition, crystallization conditions, and molecular mass of components. The type of dependence is to be related to the physical state of the melt, which, at the crystallization temperature, is in equilibrium with or coexists with the developing solid phase. In the ease of compatible blends such as poly(ethylene oxide)/poly(methyl methacrylate) the depression observed for G and T_m is mainly to be attributed to the diluent effect of the non-crystallizable component. For such a blend it is found that, after crystallization, the non-crystallizable component is trapped in intralamellar regions increasing the distance between adjacent lamellae. Depression of G, in the case of incompatible blends such as isotactic polypropylene/rubbers is mainly accounted for by rejection and deformation of rubber drops. The coexistence during crystallization of different processes such as molecular fractionation and segregation, preferential inclusion or dissolution of molecules with lower molecular mass and/or high degree of steric disorder of the crystallizable component in the phase rich in non-crystallizable component and vice versa may explain some minima observed in the plots of T and T^m, vs. composition in the case of blends semicompatible in the melt. It was found that the addition of a second non-crystallizable component causes drastic variations on some morphological and structural quantities of the semicrystalline matrix (isotactic polypropylene or nylon 6) such as the shape, dimensions, and regularity of spherulites and interspherulite boundary regions and lamella and interlamella thickness. In some cases the formation of new boundary lines connecting occluded particles are also observed. Such phenomena may have great importance on crack propagation and on impact behavior as well as on the tensile mechanical properties of binary blends characterized by a semicrystalline polymer component with a relatively high T^g and a rubber-like component with a lower T^g.     

The effect of propylene–ethylene copolymers with different comonomer content on melting and crystallization behavior of polypropylene

The effect of propylene–ethylene copolymers (PEc) with different ethylene‐unit contents on melting and crystallization behaviors of isotactic‐polypropylene (iPP) were investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). The results show that the addition of PEc decreases significantly crystallization temperature (T_c) of iPP, but slightly affects melting temperature (T_m). With increasing the ethylene‐unit content of the propylene–ethylene copolymers, the decrease in crystallization temperature of iPP is smaller. The PLM results show that the spherulite growth rate decreases with increasing crystallization temperature for iPP and iPP/PEc blends. The higher the ethylene‐unit content of the copolymers is, the lower the spherulite growth rate (G) of iPP/PEc blends is. The influence of the PEc on nucleation rate constant (K_g) and fold surface energy (σ_e) of iPP was examined by nucleation theory of Hoffman and Lauritzen. The results show that both K_g and σ_e of iPP/PE20(80/20) and iPP/PE23(80/20) blends are higher than those of iPP, demonstrating that the overall crystallization rate of iPP/PEc blends decreased as compared to that of iPP, resulting from the decrease of the nucleation rate and the spherulite growth rate of iPP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Isotactic polypropylene/polymethylmethacrylate blends: Effects of addition of propylene-graft-methylmethacrylate copolymer

A novel graft copolymer of unsaturated propylene with methyl methacrylate (uPP-g-PMMA) was added to binary blends of isotactic polypropylene (iPP) and atactic poly(methyl methacrylate) (aPMMA) with a view to using such a copolymer as a compatibilizer for iPP/aPMMA materials. Optical microscopy (OM), scanning electron microscopy, wide angle X-ray scattering (WAXS), and small angle X-ray scattering (SAXS) techniques showed that, contrary to expectation, the uPP-g-PMMA addition does not provide iPP/aPMMA compatibilized materials, irrespective of composition. As a matter of fact the degree of dispersion of the minor component achieved following the addition of uPP-g-PMMA copolymer remained quite comparable to that exhibited by binary blends of iPP and aPMMA with no relevant evidence of adhesion or interconnection between the phases. On the other hand the crystalline texture was deeply modified by the copolymer presence. With increasing uPP-g-PMMA content (w/w) the iPP spherulites were found to become more open and coarse and the dimensions and number per unit area of the amorphous interspherulitic contact regions were found to increase. According to such OM results the copolymer uncrystallizable sequences were assumed to be mainly located in interfibrillar and interspherulitic amorphous contact regions. SAXS analysis demonstrated that the phase structure developed in the iPP/aPMMA/uPP-g-PMMA blends is characterized by values of the long period increasing linearly with increasing copolymer content (w/w). Assuming a two phase model for the iPP spherulite fibrillae, constituted of alternating parallel crystalline lamellae and amorphous layers, the lamellar structure of the iPP phase in the ternary blends is characterized by crystalline lamellar thickness (L_c) and an interlamellar amorphous layer (L_a) higher than that shown by plain iPP and L_c and L_a values both increased with increasing uPP-g-PMMA content (w/w). Such SAXS results have been accounted for by assuming that a cocrystallization phenomenon between propylenic sequences of the uPP-g-PMMA copolymer and iPP occurs. The development of the iPP lamellar structure in the iPP/aPMMA/uPP-g-PMMA blends was thus modeled hypothesizing that during such a cocrystallization process copolymer PMMA chains with comparatively lower molecular mass remain entrapped into the iPP interlamellar amorphous layer forming their own domains. Moreover, evidence of strong correlations between the crystallization process of the uPP-g-PMMA copolymer and the iPP crystallization process was shown also by differential scanning calorimetry and WAXS experiments. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2377–2393, 1997     

Preparation and properties of dynamically vulcanised blends of isobutylene–isoprene rubber and isotactic polypropylene

Abstract

Dynamic vulcanisation was employed to prepare blends of isobutylene–isoprene rubber (IIR) and isotactic polypropylene (iPP) with superior properties. The preparation technology, the effects of the presence of IIR on the crystallisation properties of iPP and the mechanical properties of the IIR/iPP thermoplastic vulcanisates (TPVs) were investigated. It was revealed that, under regular shearing at 180°C, dynamic vulcanisation for 10 min produced IIR/iPP TPVs of excellent properties; while degradation occurred when the duration of vulcanisation was extended to 15 min. Incorporation of IIR into iPP dramatically reduced the size of the iPP spherulites, and thus decreased the melting temperature and the degree of crystallinity of the iPP. When the IIR content was 50 wt-%, maximally balanced mechanical properties of IIR/iPP TPVs were obtained with a Charpy impact strength of 53·6 kJ m^?2 and a tensile strength of 31·3 MPa.     

Crystallization behaviour of isotactic polypropylene/linear low density polyethylene blends

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, T_c, 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.     

Isotactic polypropylene/polystyrene blends: Effects of the addition of a graft copolymer of propylene with styrene

A novel graft copolymer of unsaturated propylene with styrene (uPP-g-PS) was added to binary blends of isotactic polypropylene (iPP) and atactic polystyrene (aPS) with a view to using such a copolymer as compatibilizer for iPP/aPS materials. Differential scanning calorimetry, optical microscopy, scanning electron microscopy (SEM), wide angle X-ray scattering, and small angle X-ray scattering (SAXS) techniques have been carried out to investigate the phase morphology and structure developed in solution-cast samples of iPP/aPS/uPP-g-PS ternary blends. It was found that the uPP-g-PS addition can provide iPP/aPS-compatibilized materials and that the extent of the achieved compatibilization is composition-dependent. Blends of iPP and aPS exhibited a coarse domain morphology that is characteristic of immiscible polymer systems. By adding 2% (wt/wt) of uPP-g-PS copolymer a very broad particle-size distribution was obtained, even though the particles appeared coated by a smooth interfacial layer, as expected according to a core–shell interfacial model. With increasing uPP-g-PS content (5% wt/wt), a finer dispersion degree of particles, together with morphological evidence of interfacial adhesion, was found. With further increase of uPP-g-PS amount (10% wt/wt) the material showed such a homogeneous texture that neither domains of dispersed phase nor holes could be clearly detected by SEM. The type of interface developed in such iPP/aPS/uPP-g-PS blends was accounted for by an interfacial interpenetration model. The iPP crystalline texture, size, neatness, and regularity of iPP spherulites crystallized from iPP/aPS/uPP-g-PS blends were found to decrease when the copolymer content was slightly increased. Assuming, for the iPP spherulite fibrillae, a two-phase model constituted by alternating parallel crystalline lamellae and amorphous layers, it was shown by SAXS that the phase structure generated in iPP/aPS/uPP-g-PS blends is characterized by crystalline lamellar thickness (L_c) and interlamellar amorphous layer thickness (L_a) higher than that shown by plain iPP; the higher the copolymer content, the higher the L_c and L_a. It should be remarked that considerably larger increases have been found in L_a values. Such SAXS results have been accounted for by assuming that a cocrystallization phenomenon between propylenic sequences of the uPP-g-PS copolymer and iPP occurs and that during such a process PS chains grafted into copolymer sequences remain entrapped in iPP interlamellar amorphous layers, where they form their own separate domains. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1539–1553, 1997     

Crystallization kinetics and tensile modulus of blends of metallocene short‐chain branched polyethylene with conventional polyolefins

In this study, blends of metallocene short‐chain branched polyethylene (SCBPE) with low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), polystyrene (PS), ethylene–propylene–diene monomer (EPDM), and isotactic polypropylene (iPP) were prepared in weight proportions of 80 and 20, respectively. The crystallization behaviors of these blends were studied with polarized light microscopy (PLM) and differential scanning calorimetry. PLM showed that SCBPE/LDPE, SCBPE/HDPE, and SCBPE/EPDM formed band spherulites whose band widths and sizes were both smaller than that of pure SCBPE. No spherulites were observed, but tiny crystallites were observed in the completely immiscible SCBPE/PS, and the crystallites in SCBPE/iPP became smaller; only irregular spherulites were seen. The crystallization kinetics and mechanical properties of SCBPE were greatly affected by the second polyolefin but in different way, depending on the phase behavior and the moduli of the second components. SCBPE may be phase‐miscible in the melt with LDPE, HDPE, and EPDM but phase‐separated during crystallization. A big change in the crystal morphology and crystallization kinetics existed in the SCBPE/iPP blend. The mechanical properties of the blends were also researched with dynamic mechanical analysis (DMA). DMA results showed that the tensile modulus of the blends had nothing to do with the phase behavior but only depended on the modulus of the second component. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1816–1823;2005     

Morphology and mechanical behavior of isotactic polypropylene (iPP)/syndiotactic polypropylene (sPP) blends and fibers

The crystallization morphologies and mechanical behaviors of iPP/sPP blends and the corresponding fibers were investigated in the present work. For all the investigated iPP/sPP blends, the starting crystallization temperature of sPP during cooling process was significantly increased with increasing iPP content. The iPP/sPP blends are strongly immiscible at the conventional melt processing temperatures, in consistence with the literature results. As isothermally crystallized at 130 °C, sPP still keeps melt state, while iPP component is able to crystallize and the spherulites become imperfect accompanied by decreasing of the crystallite size as sPP content increases. The addition of sPP decreases the crystallinity of iPP/sPP blends and fibers. The storage modulus, E′, of the iPP/sPP blends is higher than that of sPP homopolymer in the temperature range from −90 to 100 °C. The iPP/sPP fibers can be prepared favorably by melt-spinning. As sPP content exceeds 70%, the elastic recovery of the iPP/sPP fibers is approximately equal to that of sPP homopolymer fiber. The drawability of the as-spun fiber of iPP/sPP (50/50) is better than that of sPP fiber, which improves the fiber processing performance and enhances the mechanical properties of the final product. The drawn fiber of sPP presents good elastic behavior within the range of 50% deformation, whereas the elastic property of the iPP/sPP (50/50) fiber slightly decreases, but still much better than that of iPP fiber.     

Properties of thin films of isotactic polypropylene blended with polyisobutylene and ethylene-propylene-diene terpolymer rubbers

An experimental study was carried out to investigate the kinetic, morphological and thermodynamic properties of thin films of isotactic polypropylene (iPP) blended with several elastomers such as ethylene-propylene-diene terpolymer (EPDM) and three samples of polyisobutylene (PIB) with different molecular masses. The addition of the rubber to iPP causes drastic modifications in the morphology, nucleation density, spherulite growth rate and thermal behaviour of iPP. Such modifications depend strongly on the chemical and molecular mass of the added elastomer and on the composition of the blend. All the elastomers studied seem to act as nucleating agents for the iPP spherulites. The addition of PIB to iPP results in a reduction of the spherulite growth rate G, whereas the addition of EPDM does not seem to have a great influence. For the iPP/PIB_HM iPP/PIB_MM and iPP/EPDM blends a depression of the equilibrium melting temperature T_m, with respect to that of pure iPP, is observed. This depression is increased for the blend containing 20% rubber. This effect is probably related to phenomena of partial miscibility in the melt and to the coexistence of processes such as molecular fractionation and preferential dissolution of the more defective molecules.     

Effects of EPDM and wollastonite on structure of isotactic polypropylene blends and composites

Polypropylene blends and composites with 5, 10, and 15 vol % of EPDM and 2, 4, and 6 vol % of untreated and treated wollastonite filler were examined by applying different techniques. Elastomeric ethylene/propylene/diene terpolymer (EPDM) component and wollastonite influenced the crystallization process of isotactic polypropylene (iPP) matrix in different ways. The nucleation of hexagonal β‐iPP, the increase of overall degree of crystallinity, and crystallite size of iPP were more strongly affected by wollastonite than the addition of EPDM was. Both ingredients also differently influenced the orientation of α‐form crystals in iPP matrix. Wollastonite increased the number of a*‐axis‐oriented α‐iPP lamellae plan parallel to the sample surface, whereas the addition of EPDM reoriented the lamellae. The orientation parameters of ternary composites exhibited intermediate values between those for binary systems because of the effects of both components. EPDM elastomer considerably affected well‐developed spherulitization of iPP, increasing the spherulite size. Contrary to EPDM, because of nucleating ability or crystal habit, wollastonite caused significantly smaller iPP spherulites. Small spherulites in ternary iPP/EPDM/wollastonite composites indicated that the wollastonite filler (even in smallest amounts) exclusively determined the morphology of ternary composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4072–4081, 2004     

Experimental verification on UCST phase diagrams and miscibility in binary blends of isotactic, syndiotactic, and atactic polypropylenes

Issues in blends of polymers of the same chemical repeat unit but with different tacticities were addressed by investigating on the phase behavior and interaction strength of binary blends of three polypropylenes of different tacticities, i.e., isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), and atactic polypropylene (aPP) using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Although blends of polypropylenes have been widely studied in the past, there are still on-going debates on true phase behavior (miscibility vs. upper critical solution temperature (UCST) or immiscibility). Except for several earlier theoretical predictions based on the Flory-Huggins mean field theories, UCST behavior had not been experimentally proven for blends of sPP/iPP or aPP/sPP, owing to interference from PP crystallinity. In addition, interaction strength of the blends of different tactic polypropylenes is yet to be established. Using the method of equilibrium melting points, the Flory-Huggins interaction parameter of the aPP/iPP blend was shown to possess a significantly negative value (χ₁₂ = −0.21), which proves that the blend is indeed miscible in the melted amorphous as well as semicrystalline states as previously reported in the literature. However, the interaction parameters for the sPP/iPP and aPP/sPP blends were found to be nearly zero (χ₁₂ = −0.02 and −0.0071, respectively, at T = 150-180 °C), indicating that the interactions in two blends are weak and that the corresponding phase behavior for them borders on immiscibility at ambient temperature. This study also utilized novel approaches in constructing UCST phase diagrams by separating the amorphous phase domains from the crystalline spherulites, yielding data plausible for experimentally determining the UCST in iPP/sPP blend vs. aPP/sPP blend.     

Isothermal crystallization behavior of metallocene‐catalyzed isotactic polypropylene

Isothermal crystallization behavior of isotactic polypropylene (iPP) synthesized using metallocene catalyst was investigated in this work. The isotacticity of the polypropylene was characterized by ¹³C‐NMR spectroscopy. It was found that the melting temperature (T_m) of the iPP is 123.51°C and the crystallization temperature (T_c) is 93°C. The iPP synthesized in this work did not show a general increase of T_m with an increase of crystallization temperature T_c, due to the short crystallization time of 20 min and low molecular weight (number average molecular weight = 6,300). The iPP showed a tendency of increasing heat of fusion (ΔH_f) with decreasing crystallization temperature. All the spherulites of iPP samples showed negative birefringence. For the iPP sample crystallized at the highest T_c (= 123°C, just below T_m), the spherulite showed a pronounced Maltese Cross and a continuous sheaf‐like texture aligning radially, which suggests that R‐lamellaes are dominant in this spherulite. The crystalline structure of the iPP was also investigated by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 231–237, 2005     

Correlation of miscibility and mechanical properties of polypropylene/olefin block copolymers: Effect of chain composition

This study examines the miscibility and mechanical properties of isotactic polypropylene (iPP) and olefin block copolymer (OBC) blends (70/30 wt %). The blends exhibit phase-separated morphology. The OBC domain size decreases with increasing the 1-octene content in the soft segment. The crystallization, melting behavior, and the long spacing of the iPP component in the blends are nearly the same as those of neat iPP, while the T_g of the iPP component shifts slightly to lower temperature. “Blocky” OBC is immiscible with iPP, while the soft segment rich polymers in OBC could be partially miscible with iPP. The impact strength of the blends is greatly increased with increasing the 1-octene content in the OBC soft segment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Miscibility in crystalline polymer blends: Isotactic polypropylene and linear low‐density polyethylene

The phase behavior and the crystallization kinetics of blends composed of isotactic polypropylene (iPP) and linear low‐density polyethylene (LLDPE) were investigated by differential scanning calorimetry. The phase behavior indicates the formation of separate crystals of iPP and LLDPE at each investigated blend composition. The crystallization trace reveals that iPP crystallizes in its normal range of temperatures (i.e., at temperatures higher than that of LLDPE), when its content in the blend is higher than 25% by weight. In the blend whose iPP content is as high as 25%, at least a portion of iPP crystallizes at temperatures lower than that of LLDPE. This behavior has been proposed by Bassett to be attributed to a change in the kind of nucleation from heterogeneous to homogeneous. From the Avrami analysis of the isothermal crystallization of iPP in the presence of molten LLDPE, n values close to 2 are always obtained. According to our previously proposed interpretation of the Avrami coefficient, it can be related to the crystallite fractal dimension, through d = n + 1, which gives values close to 3, according to the spherulitic observed morphology. The kinetics parameter, i.e., the half‐time of crystallization, and the kinetic constant k show that a decrease in the overall rate of crystallization of iPP occurs on blending. Optical microscopy photographs, taken during the cooling of the samples from the melt, confirm the above results and show increasingly less resolved spherulite texture on increasing LLDPE content in the blend. The diffusion parameters evaluated for the neat polymers and for the blends in dichloromethane, which give information on the miscibility in the amorphous state, show that the diffusional behavior of the blends is governed by iPP, suggesting a two‐phase amorphous state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3338–3346, 2003