Phase structure of impact-modified polypropylene blends

A morphological study of polypropylene/ethylene-propylene-diene terpolymer (PP/EPDM) and polypropylene (PP)/polyolefin thermoplastic rubber blends was conducted. Dispersion of the impact modifier in the blend was investigated by transmission and scanning electron microscopy (TEM and SEM). It was established that number-average particle size ($\text{D}\text{?}{}_{\mathrm{n}}$) of the EPDM impact modifier increased with its melt viscosity. The differences in melt viscosities of the blended components were characterized by the phase viscosity ratio (μ). The course of $\text{D}\text{?}{}_{\mathrm{n}}$ vs. log μ function was qualitatively in agreement with the Rayleigh—Taylor—Tomotika theory. Accordingly, high degree of dispersion of the impact modifier can be achieved if melt viscosities of the blended components are very closely matched, i.e. if $\text{μ ? 1}$. It was concluded from SEM results that, below an impact modifier content of 20%, the modifier formed the dispersed phase in the continuous PP matrix. In blends containing 50% of impact modifier, the latter may also form continuous phase depending on its type and μ value beside the still continuous PP phase (co-continuous network structure).     

Morphology and mechanical properties of injection-molded specimens of two-phase polymer blends

An experimental study was carried out to investigate the moldability of polymer blends which form two phases in the molten state and the effect of mixing on the morphology and mechanical porperties of molded specimens. Blends of polystyrene with polypropylene and blends of polystyrene with high-density polyethylene were used for this study. A plunger-type injection molding machine (Van Dorn) was employed for molding specimens. To improve the mixing performance of the plunger machine, a Static Mixer (Kenics Corp., Super Nozzle) was installed between the heating cylinder and the sprue. A number of different molding conditions (injection pressure, temperature, injection time, cooling time) were varied, and molded specimens were collected under each molding condition. The specimens were used for studying the degree of dispersion in the blends and for determining the mechanical properties. A differential thermal analysis (DTA) experiment was also carried out to determine the degree of dispersion of the blends in molded specimens. It was found that a linear correlation exists between the blend composition and thermal spectra area of the blends tested.     

Properties and morphology of some injection-molded polycarbonate-styrene acrylonitrile copolymer blends

A series of blends was prepared with broad concentration ranges of polycarbonate (PC) and styrene-acrylonitrile copolymers (SAN) containing 5.5 and 30 weight percent acrylonitrile (AN). These blends were then injection molded, and their properties were measured and correlated with the morphologies of the blends (as determined by transmission electron microscopy). The toughness properties were shown to be discontinuous and very sensitive to composition of the continuous phase in the blends. The dart impact toughness remained high up to 30–40 weight percent SAN and dropped rapidly above this SAN concentration. The notched Izod toughness fell off rapidly at 10 weight percent SAN and greater. The strength and modulus had a more linear dependence on composition. Results of studies of the T_g by differential scanning calorimetry (DSC) show the presence of two phases over the entire concentration and a small solubility of each phase in the other. The heat distortion temperature under load (DTUL) of the blends approximated a linear additivity curve for the components. As expected, the blends had much better clarity where the refractive indexes more nearly match (in the case of the 5.5 percent AN copolymer).     

Dynamic mechanical properties and morphology of polypropylene/maleated polypropylene blends

The dynamic mechanical properties of both homopolypropylene (PPVC)/Maleated Poly-propylene (PP-g-MA) and ethylene-propylene block copolymer (PPSC)/Maleated Poly-propylene (PP-g-MA) blends have been studied by using a dynamic mechanical thermal analyzer (PL-DMTA MKII) over a wide temperature range, covering a frequency zone from 0.3 to 30 Hz. With increasing content of PP-g-MA, α relaxation of both blends gradually shift to a lower temperature and the apparent activation energy ΔE_α increases. In PPVC/PP-g-MA blends, β relaxation shifts to a higher temperature as the content of PP-g-MA increases from 0 to 20 wt % and then change unobviously for further varying content of PP-g-MA from 20 to 35 wt %. On the contrary, in the PPSC/PP-g-MA blends β₁ relaxation, the apparent activation energy ΔE_β1 and β₂ relaxation are almost unchanged with blend composition, while ΔE_β2 increases with an increase of PP-g-MA content. In the composition range studied, storage modulus É value for PPSC/PP-g-MA blends decreases progressively between β₂ and α relaxation with increasing temperature, but in the region the increment for PPVC/PP-g-MA blends is independent of temperature. The flexural properties of PPVC/PP-g-MA blend show more obvious improvement on PP than one of PPSC/PP-g-MA blends. Scanning electron micrographs of fracture surfaces of the blends clearly demonstrate two-phase morphology, viz. the discrete particles homogeneously disperse in the continous phase, the main difference in the morphology between both blends is that the interaction between the particles and the continuous phase is stronger for for PPVC/PP-g-MA than for PPSC/PP-g-MA blend. By the correlation of the morphology with dynamic and mechanical properties of the blends, the variation of the relaxation behavior and mechanical properties with the componenet structure, blend composition, vibration frequency, and as well as the features observed in these variation are reasonably interpreted. © 1996 John Wiley & Sons, Inc.     

The skin-core morphology and structure–property relationships in injection-molded polypropylene

Tensile bars of an isotactic propylene homopolymer and an ethylene–propylene copolymer were prepared by injection molding under a variety of melt temperatures and injection pressures. The effects of these processing variables on morphology and crystalline orientation were studied using optical microscopy and x-ray diffraction. Microscopy of microtomed thin sections of the tensile bars revealed the presence of three distinct crystalline zones, namely, a highly oriented nonspherulitic skin, a row or shear-nucleated spherulitic intermediate layer, and a typically spherulitic core. The thickness of the oriented skin layer is a function of the polymer melt temperature and varies inversely with temperature. The thickness of the intermediate layer varies with injection pressure, but in a complex manner. Preferred crystallite orientation in the skin and intermediate layers exerts profound effects on mechanical properties. Tensile yield strength, impact strength, and shrinkage increase with increasing combined thickness of the two oriented outer layers.     

Shear-induced epitaxial crystallization in injection-molded bars of high-density polyethylene/isotactic polypropylene blends

As a continuation of our previous works on exploring shear-induced epitaxial crystallization of polyolefin blends during practical molding processing [Na et al. Polymer 2005; 46, 819 and 5258], the present study focused on the importance of molecular weight on the formation of epitaxial structure in injection-molded bars of high-density polyethylene (HDPE)/isotactic polypropylene (iPP) blends. By choosing two kinds of HDPE and two kinds of iPP with high molecular weight or low molecular weight, four blends with different molecular weight combinations can be designed. After making the blends via melt mixing, the injection-molded bars were prepared in a so-called dynamic packing injection molding equipment where repeated shearing was imposed on the melts during the solidification stage. Crystal structure and orientation were estimated mainly through 2D-WAXD. Our results indicated that an appropriate matching of low molecular weight HDPE and high molecular weight iPP was more favorable for epitaxial crystallization than other component matches. The effects of orientation and epitaxy on the re-crystallization behaviors of polyolefin blends have been elucidated in detail through PLM experiments. Moreover, epitaxy has been proved to play a positive effect in determining the ultimate mechanical properties of injection-molded bars.     

Plywood-like structures of injection-molded polypropylene

N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide, a commercial nucleating agent, can dissolve into molten polypropylene (PP) and self-organize into needle-like crystals when the melt temperature reaches 260°C. As temperature decreases, PP molecules crystallize on the surface of the needle-like crystals with their c-axis perpendicular to the long axis of the crystal. Under a flow field in injection molding, PP chains are parallel or perpendicular to the flow direction at different depths owing to the difference in crystallization kinetics and applied shear rate in the melt, forming a plywood-like material. This unique structure can simultaneously improve the toughness and strength of plastic parts. Herein, we present a novel method of producing high-performance plastic articles based on general plastics by manipulating their morphology and structure.     

Tensile properties and morphology of blends of polyethylene and polypropylene

The tensile behavior of blends of linear polyethylene (PE) and isotactic polypropylene (PP) was examined in relation to their morphology. Yield stress increases monotonically with increasing PP content, while true ultimate strength is much lower in all blends than in the pure polymers as a result of early fracture. The blends fail at low elongation because of their two-phase structure, consisting of interpenetrating networks or of islands of PE in a PP matrix, as shown by scanning electron microscopy of fracture surfaces and transmission electron microscopy of thin films. While spherulites in PP are very large (～100 μm in diameter), addition of 10% or more of PE drastically reduces their average size. This, together with the profusion of intercrystalline links introduced by PE, may be associated with maximization of tensile modulus in blends containing ～80% PP. Introduction of special nucleating agents to PP reduces average spherulite size and is accompanied by slight improvements in modulus. Thin films of blends strained in the electron microscope neck and fibrillate in their PE regions, but fracture cleanly with little fibrillation in areas of PP.     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

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     

Dynamic mechanical properties and morphology of polypropylene block copolymers and polypropylene/elastomer blends

The relation between the dynamic mechanical properties and the morphology of polypropylene (PP) block copolymers and polypropylene/elastomer blends was studied by dynamic mechanical analysis (DMA), light- and electron microscopy. The latter techniques contributed to an improvement in assignments of relaxation transitions in the DMA spectra. It was established that PP block copolymers had multiphase structure since the ethylene/propylene rubber phase (EPR) formed in the copolymerization contained polyethylene (PE) domains. An identical morphology was found in the case of PP/polyolefin thermoplastic rubber (TPO) blends. Impact modification of PP by styrene/butadiene block copolymers led to a multiphase structure, too, due to the polystyrene (PS) domains aggregated in the soft rubbery polybutadiene phase. In the semicrystalline polyolefinic and in the amorphous styrene/butadienebased thermoplastic rubbers, PE crystallites and PS do mains acted as nodes of the physical network structure, respectively. PP/EPDM/TPO ternary blends developed for replacing high-density PE showed very high dispersion of the modifiers as compared to that of PP block copolymers. This fine dispersion of the impact modifier is a basic regulating factor of impact energy dissipation in the form of shear yielding and crazing.     

Phase morphology of injection-molded blends of nylon-6 and polyethylene and comparison with compression molding

An experimental study is presented of the development of phase morphology in injection and compression molding of 80/20 and 60/40 nylon-6/polyethylene blends and its evolution during annealing. The phase morphology of the compression-molded part is isotropic, while that of both screw and ram injection-molded parts is both heterogeneous and anisotropic through the cross section. In the injection-molded parts, the morphology exhibits its greatest level of isotropy in the core and becomes increasingly anisotropic approaching the mold wall (through the thinnest cross section); i.e., the 2 direction. There is an intermediate position of maximum anisotropy. Sections made in various directions indicate that the dispersed phase forms platelets oriented in the plane of the machine and width directions. The position of maximum anisotropy seems to represent a frozen layer thickness that increases with decreasing mold temperature and with decreasing injection rate into the mold. Annealing studies show coalescence in both compression- and injection-molded bars. The greatest coalescence occurs in the injection-molded parts near the positions of greatest anisotropy of morphology. This suggests that coalescence is associated with collisions between dispersed phase globules as their sphericity increases.     

Fabrication and morphology development of isotactic polypropylene nanofibers from isotactic polypropylene/polylactide blends

The excellent characteristics of polymeric nanofibers with diameters less than 1 μm such as the enormous specific surface result in a dramatic increase in a variety of functional applications. In this article, polymer blends of isotactic polypropylene (iPP) and polylactide (PLA) were fabricated through a twin‐screw extruder. The extrudates were prepared at various processing conditions and the iPP nanofibers were obtained by removal of the PLA matrix from the drawn samples. The influences of drawing ratio, the processing temperature, and the blend ratio of iPP/PLA on the morphology development of iPP phase were investigated by scanning electron microscopy. It was found that the uniformed iPP nanofibers with averaged diameters less than 500 nm were fabricated by the suitable processing parameters. Otherwise, the processing immiscibility and rheological behavior of iPP/PLA blends were studied by means of dynamic mechanical analysis and capillary rheometer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of talc orientation and non-isothermal crystallization rate on crystal orientation of polypropylene in injection-molded polypropylene/ethylene-propylene rubber/talc blends

The effects of talc orientation and non-isothermal crystallization rate on the crystal orientation of polypropylene in the injection-molded PP/EPR/Talc blends were studied by using AFM, DSC, SEM and XRD. Polypropylene was transcrystallized on the talc surface and the polypropylene crystal was oriented perpendicular to the talc surface. Therefore, the crystal orientation was affected by the talc orientation. At the surface of injection-molded specimens, the crystal orientation increased with decreasing the molecular weight of EPRs and increasing the talc content. Because talc particles were nearly oriented parallel to the flow direction in the skin layer of the specimens, the crystal orientation was amplified by the increased crystallization rate. The non-isothermal crystallization behavior of PP/EPR/Talc blends was investigated in terms of the molecular weight of EPRs and the talc content. Non-isothermal crystallization rate increased with decreasing the molecular weight of EPRs due to the plasticizing effect of EPRs and increasing the content of talc which acts as nucleating agent.     

The phase inversion and morphology of nylon 1010/polypropylene blends

Noncompatibilized and compatibilized blends of nylon 1010/PP blends having five different viscosity ratios were prepared by melt extrusion. Glycidyl methacrylate-grafted-polypro-pylene (PP-g-GMA) was used as the compatibilizer to enbance the adhesion between the two polymers and to stabilize the blend morphology. The effect of the viscosity ratio on the morphology of nylon 1010/polypropylene blends was investigated, with primary attention to the phase-inversion behavior and the average particle size of the dispersed phase. The relationship between the mechanical properties and the phase-inversion composition was investigated as well. Investigation of the morphology of the blends by microscopy indicated that the smaller the viscosity ratio (ηpp/ηpa) the smaller was the polypropylene concentration at which the phase inversion took place and polypropylene became the continuous phase. The compatibilizer induced a sharp reduction of particle size, but did not have a major effect on the phase-inversion point. An improvement in the mechanical properties was found when nylon 1010 provided the matrix phase. © 1996 John Wiley & Sons, Inc.     

Crystallization and morphology of reactor-made blends of isotactic polypropylene and ethylene-propylene rubber

The crystallization and morphology of reactor-made blends of isotactic polypropylene (PP) with a large content of ethylene-propylene rubber (EPR) (i.e., > 50%) were investigated. In the blends, PP was found to form spherulites during the crystallization process, with the growth rate constant under isothermal conditions. For crystallization temperatures in the range of 118–152°C, the birefringence of the spherulites varied from negative to positive by decreasing crystallization temperature, while homopolypropylene (homo-PP), the same as used in the blends as a matrix, showed negative spherulites in the whole temperature range investigated (118–152°C). Both the spherulite growth rate and the overall crystallization rate were slower for the blends than for homo-PP. The density of the crystallization nuclei was lower in the blends than in the homo-PP. It was concluded that a large amount of EPR content in the reactor-made blends of PP retards and hinders the crystallization of the matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1007–1014, 1997     

Structure of skin layer in injection-molded polypropylene

The structure of skin layer in injection-molded polypropylen which displayed a clear two-phase structure of skin and core has been studied by means of wide-angle x-ray diffraction, small-angle x-ray scattering, melting behavior, density, dynamic viscoelasticity, and tensile test. In skin layer, the c-axis and a^*-axis were highly oriented to the machine direction (MD), and the plane of the lamellar structure of about 160 Å in thickness was in normal to MD. The density was about 0.907 g/cm³, which was nearly the same as that of core layer. Although the majority of crystallites melted in the same temperature range as in that of the core layer, there was about 5.3% higher temperature melting structure (T_m = 182°C). The dynamic tensile modulus E′ in MD decreased more slowly with increasing temperature than that of the core layer and held high modulus in the range of ca. 30°C, just above the temperature at which E′ of the core layer suddenly dropped. E′ in MD was higher than that in TD in the temperature range below 33°C, which was slightly higher than the primary absorption temperature, and the order reversed above 33°C. The tensile yield stress in MD was 1.5 times higher than that of the core layer. The skin layer in MD ruptured just after yielding and did not show necking. The tensile yield stress in TD was about half of that in MD about 0.7 times that of the core layer. The necking stress in TD was about 0.6 times that of the core layer. In general, a polypropylene melt crystallizes under a high shear stress in injection molding. From these facts, it was concluded that the skin layer is composed of so-called “shishkebab”-like main skeleton structures, whose axis is parallel to MD, piled epitaxially with a^*-axis-oriented imperfect lamellar substructure.     

The morphology of hyperbranched polymer compatibilized polypropylene/polyamide 6 blends

The influence of hyperbranched polymer grafted polypropylene (PP‐HBP) on the morphology of polypropylene (PP)/polyamide 6 (PA6) blends has been investigated. The final morphology was strongly influenced by the PP‐HBP compatibilizer concentration. At low concentrations, PP‐HBP acts as an emulsifying agent, reducing the size of the dispersed phase and preventing coalescence. This is due to the high reactivity and diffusitivity of PP‐HBP rapidly forming a high density of copolymers at the interface. Compared to the use of maleic anhydride grafted PP (PP‐MAH) at identical concentrations, PP‐HBP yielded a smaller dispersed phase particle size. Therefore, PP‐HBP allows the use of less compatibilizer to obtain identical morphologies. At higher compatibilizer concentrations, it has been shown that the PP‐HBP efficiently stabilizes the interface and inhibits both coalescence and breakup of the PA6 droplets. The high concentration of reactive sites and the ability of PP‐HBP to react with both chain‐ends of PA6 suggest that interfacial stabilization occurs because of the formation of a partly crosslinked interface. The interfacial stabilization effects generated by PP‐HBP should allow one to control the morphology of polymer blends in order to create specific functional morphologies.     

Ambient mechanical properties of impact-modified polyvinyl chloride and methyl methacrylate copolymer blends

The objectives of this study were to determine the compatibility of various blends of commercially available rigid, unplasticized, impact-modified polyvinyl chloride (UPVC) and methyl methacrylate (MMA) copolymers. The effects of acrylic type and loading level on compatibility were investigated. The resultant alloys or blends were subsequently evaluated for compatibility through examination of the following properties: processability, rigidity, strength, impact resistance, heat resistance, clarity, and ultra-violet aging. This report limits itself to the discussion of the ambient mechanical properties of rigidity, strength, and impact behavior.