Rheological properties of polypropylenes with different molecular weight distribution characteristics

Relationships between the rheological properties and the molecular weight distribution of two polypropylene series with different molecular weight distribution characteristics were studied. The end correction coefficient in capillary flow is determined by the molecular weight M_w and the molecular weight distribution M_w/M_n, and is higher as both characteristic values are larger. The die swell ratio at a constant shear rate depends on M_w, M_w/M_n, and M_z/M_w, and is higher as the three characteristic values are larger. The critical shear rate at which a melt fracture begins to occurs depends on the molecular weight M_w and the molecular weight distribution M_z/M_w, and is proportional to M_z/M_w² in a log–log plot. The critical shear stress does not depend on the molecular weight, and is higher as M_z/M_w is higher. The zero‐shear viscosity is determined by a molecular weight of slightly higher order than M_w, and the characteristic relaxation time is determined by M_z. The storage modulus at a constant loss modulus scarcely depends on the molecular weight, and is higher as the molecular weight distribution M_w/M_n is higher. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2128–2141, 2002     

Study on thermal expansion in injection‐molded isotactic polypropylene and thermoplastic elastomer blends

The linear thermal expansion coefficients (CLTEs) along flow direction (FD) for the injection‐molded blends composed of isotactic polypropylene (iPP) and various ethylenic thermoplastic elastomers (TPEs) were investigated using a thermo‐mechanical analyzer. The iPP/TPE blends with higher comonomer contents in the TPE showed extremely low CLTE. TEM observation revealed that the array of the TPE whose MFR was adjusted to be higher than the iPP matrix was in lamella‐like sheet stacked normal to normal direction (ND) with being elongated along both FD and transverse‐to‐flow direction. At higher magnification of TEM, the iPP lamellae in the blend with higher comonomer contents in the TPE deeply penetrated into the TPE phase as a consequence of the faster iPP crystallization before the completion of the phase‐separation. Hence, the location of the iPP amorphous chains would change depending on the comonomer contents in the TPE; in the case of the iPP/TPE blend with higher comonomer contents, large amount of the iPP amorphous chains would be trapped inside the TPE phase because of incomplete phase‐separation arrested by faster crystallization. Therefore, the extremely low CLTE for the iPP/TPE blend with higher comonomer contents was accounted for by the simultaneous suppression of the thermal expansions from both the TPE phase and the iPP amorphous chains trapped inside the TPE by rigid iPP crystalline lamellae connecting in parallel with the TPE phase. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Combined effect of shear and nucleating agent on the multilayered structure of injection‐molded bar of isotactic polypropylene

Molten polymers are usually exposed to varying levels of shear flow and temperature gradient in most processing operations. Many studies have revealed that the crystallization and morphology are significantly affected under shear. A so‐called “skin‐core” structure is usually formed in injection‐molded semicrystalline polymers such as isotactic polypropylene (iPP) or polyethylene (PE). In addition, the presence of nucleating agent has great effect on the multilayered structure formed during injection molding. To further understand the morphological development in injection‐molded products with nucleating agent, iPP with and without dibenzylidene sorbitol (DBS) were molded via both dynamic packing injection molding (DPIM) and conventional injection molding. The structure of these injection‐molded bars was investigated layer by layer via SEM, DSC, and 2 days‐WAXD. The results indicated that the addition of DBS had similar effect on the crystal size and its distribution as shear, although the later decreased the crystal size more obviously. The combination of shear and DBS lead to the formation of smaller spherulites with more uniform size distribution in the injection‐molded bars of iPP. A high value of c‐axis orientation degree in the whole range from the skin to the area near the core center was obtained in the samples molded via DPIM with or without DBS, while in samples obtained via conventional injection molding, the orientation degree decreased gradually from the skin to the core and the decreasing trend became more obvious as the concentration of DBS increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of crystallization and interface formation mechanism on mechanical properties of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate

A previous study has shown that the adhesion between the film and substrate of film‐insert injection‐molded poly(propylene) (PP) film/PP substrate was evident with the increases in barrel temperature and injection holding pressure. In this second part of the research work, the crystallinity at the interfacial region (i.e., region between the film and the injected substrate) was extensively studied using FTIR imaging, polarized light microscopy, and DSC in an attempt to determine the level of influence that crystallinity has on the interface and bulk mechanical properties. Consequently, a more thorough and clearer picture of the influence of the inserted film on the interfacial crystallinity and subsequently the substrate mechanical properties, such as peel strength and impact strength, has been revealed. The initial proposition that crystallinity could enhance film–substrate interfacial bonding has been confirmed, judging from the higher peel strength with increasing crystallinity at the interfacial region. Nevertheless, the change in crystallinity was not only confined to the interfacial region. With the film acting as heat‐transfer inhibitor between the injected resin and the mold wall, the total crystal structure of the substrate was substantially altered, which subsequently affected the bulk mechanical properties. The lower impact strength of film‐insert injection‐molded samples compared to that of samples without film inserts provided evidence of how the film could impart inferior properties to the substrate. The difference in cooling rate between the substrate and film might also cause other defects such as warpage and/or residual stress build‐up within the product. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 294–301, 2005     

Melting and crystallization behaviors of injection‐molded polypropylene

The melting and crystallization behaviors of the skin layer in an injection‐molded isotactic polypropylene (PP) have been studied, mainly in comparison with those of the core layer and subsidiarily in comparison with those of a compression‐molded PP and a nucleator (talc)–added PP. The skin layer contains about 5% crystals, which have a high melting point of up to 184°C. They thermally vanish by melting once. The subsequent melting history will scarcely affect the melting behaviors. On the other hand, crystallization behaviors are strongly affected by the melting history. The skin layer crystallizes in a wide temperature range at high temperature. This tendency weakens with increasing melting temperature, approaching a constant and that of the core layer above 230°C, which suggests that the memory effect of the residual structure of PP vanishes by melting above 230°C. In explaining these experimental results, it is assumed that the residual structure substance is a melt orientation of molecular chains that works as crystallization nuclei and that the vanishing of the residual structure is nothing but a relaxation of the melt orientation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1751–1762, 2000     

Morphology and mechanical properties of injection‐molded ultrahigh molecular weight polyethylene/polypropylene blends and comparison with compression molding

The mechanical properties and morphology of UHMWPE/PP(80/20) blend molded by injection and compression‐molding were investigated comparatively. The results showed that the injection‐molded part had obviously higher Young's modulus and yield strength, and much lower elongation at break and impact strength, than compression‐molded one. A skin‐core structure was formed during injection molding in which UHMWPE particles elongated highly in the skin and the orientation was much weakened in the core. In the compression‐molded part, the phase morphology was isotropic from the skin to the core section. The difference in consolidation degree between two molded parts that the compression molded part consolidated better than the injection one was also clearly shown. In addition, compositional analysis revealed that there was more PP in the skin than core for the injection‐molded part, whereas opposite case occurred to the compression‐molded one. All these factors together accounted for the different behavior in mechanical properties for two molded parts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of high molecular weight component on the hierarchical crystalline structures of injection‐molded bars of polyethylene

A small amount of high molecular weight molecules can have a dramatic influence on the flow‐induced crystallization kinetics and orientation of polymers. To elucidate the effects of the high molecular weight component under a real processing process, we prepared model blends in which high density polyethylene with a high molecular weight and wide molecular weight distribution was blended with a metallocene polyethylene with a low molecular weight and very narrow molecular weight distribution. To enhance the shear strength, gas‐assisted injection molding was utilized in producing the molded bars. The hierarchical structures and orientation behavior of the molded bars were intensively explored by using scanning electron microscopy and two‐dimensional wide‐angle X‐ray diffraction, focusing on effects of the high molecular weight component on the formation of the shish kebab structure. It was found that there exists a critical concentration of high molecular weight component for the formation of a shish kebab structure. The threshold was about 5.5–7.0 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. Moreover, the rheological properties of molten polyethylene melts were studied by dynamic rheological measurements and a critical characteristic relaxation time for shish kebab formation was obtained under the processing conditions adopted in this research. © 2013 Society of Chemical Industry     

Effects of the chemical foaming agents,injection parameters,and melt‐flow index on the microstructure and mechanical properties of microcellular injection‐molded wood‐fiber/polypropylene composites

Wood‐fiber‐reinforced plastic profiles are growing rapidly in nonstructural wood‐replacement applications. Most manufacturers are evaluating new alternative foamed composites, which are lighter and more like wood. Foamed wood composites accept screws and nails better than their nonfoamed counterparts, and they have other advantages as well. For example, internal pressures created by foaming give better surface definition and sharper contours and corners than nonfoamed profiles have. In this study, the microfoaming of polypropylene (PP) containing hardwood fiber was performed with an injection‐molding process. The effects of different chemical foaming agents (endothermic, exothermic, and endothermic/exothermic), injection parameters (the mold temperature, front flow speed, and filling quantity), and different types of PP (different melt‐flow indices) on the density, microvoid content, physicomechanical properties, surface roughness, and microcell classification of microfoamed PP/wood‐fiber composites were studied. A maleic anhydride/polypropylene copolymer (MAH‐PP) compatibilizer was used with the intention of improving the mechanical properties of microfoamed composites. The microcell classification (from light microscopy) and scanning electron micrographs showed that an exothermic chemical foaming agent produced the best performance with respect to the cell size, diameter, and distance. The polymer melt‐flow index and the variation of the injection parameters affected the properties and microstructure of the microfoamed composites. The density of the microfoamed hardwood‐fiber/PP (with a high melt‐flow index) composites was reduced by approximately 30% and decreased to 0.718 g/cm³ with an exothermic chemical foaming agent. Tensile and flexural tests were performed on the foamed composites to determine the dependence of the mechanical properties on the density and microvoid content of the foamed specimens, and these properties were compared with those of nonfoamed composites. MAH‐PP improved the physicomechanical properties up to 80%. With an increase in the mold temperature (80–110°C), the surface roughness was reduced by nearly 70% for the foamed composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1090–1096, 2005     

Optical properties of injection‐molded polystyrene scintillators. I. Processing and optical properties

Scintillating tiles for the Tilecal/Atlas calorimeter can be produced by injection molding, an alternative to mold casting via in situ polymerization. This new production method, which leads to a much faster production rate, introduces a number of additional variables that affect the optical yield of the scintillators and that have not yet been reported in the literature. In this work, the effect of processing‐induced orientation on the optical properties of the scintillators is analyzed and discussed. For this purpose, the birefringence across the thickness of the scintillator has been measured. The variations of the birefringence may be correlated with the orientation and, therefore, related to the optical performance, that is, the average light output and its nonuniformity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2706–2713, 2003     

Studies of Injection‐Moulded Isotactic Poly(propylene) by Synchrotron WAXD/SAXS: Effects of Nucleating Agent on Morphological Distribution

The morphological distribution of injection‐moulded isotactic poly(propylene) (iPP) plates in the presence of nucleating agents was extensively investigated using synchrotron radiation. The commercial PP compound was injection‐moulded under a variety of different conditions in order to explore the effects of shear flow and temperature on the morphology and morphological distribution. The iPP structures obtained were characterized using the degree of crystallinity, α‐phase orientation index, β‐phase index, long spacing of lamellae, and the thickness of both crystalline and amorphous lamellae. These parameters were plotted as a function of position through the plate depth for the injection‐moulding conditions. Unlike relatively pure iPP, the distributions of crystallinity and α‐phase orientation index in this commercial iPP are independent of position through the plate depth. The “skin‐core” structure that is generally found for injection‐moulded iPP is not present because of the addition of nucleating agents. The β‐phase of iPP has the same distribution through the plate depth as that expected for iPP without nucleating agents. Additionally, the lamellar dimension is found to be independent of position through the plate depth and the fraction of noncrystalline materials residing outside the lamellar stacks can be up to about 30%. The results indicate that the properties of different injection‐moulded iPP grades should be investigated individually.

Typical WAXS patterns of the sample S9 at different labeled distances from the surface. The patterns are vertically shifted for clarity.     

Measurement and numerical simulation of three‐dimensional fiber orientation states in injection‐molded short‐fiber‐reinforced plastics

To determine three‐dimensional fiber orientation states in injection‐molded short‐fiber composites, a confocal laser scanning microscope (CLSM) is used. Since the CLSM optically sections the specimen, more than two images of the cross sections on and below the surface of the composite can be obtained. Three‐dimensional fiber orientation states can be determined by using geometric parameters of fiber images obtained from two parallel cross sections. For experiments, carbon‐fiber‐reinforced polystyrene is examined by the CLSM and geometric parameters of fibers on each cross‐sectional plane are measured by an image analysis. In order to describe fiber orientation states compactly, orientation tensors are determined at different positions of the prepared specimen. Three‐dimensional orientation states are obtained without any difficulty by determining the out‐of‐plane angles utilizing fiber images on two parallel planes acquired by the CLSM. Orientation states are different at different positions and show the shell–core structure along the thickness of the specimen. Fiber orientation tensors are predicted by a numerical analysis and the numerically predicted orientation states show good agreement with measured ones. However, some differences are found at the end of cavity. They may result from the fountain flow effects, which are not considered in the numerical analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 500–509, 2003     

Controlled rheology of polypropylene: Modeling of molecular weight distributions

A mathematical model for the controlled degradation of polypropylene is presented in this article. A previous model of this process was extended to predict the whole molecular weight distribution of the modified resin. Probability generating functions were applied to transform the infinite set of mass balance equations of both polymer and radicals. The integration of the transformed set of equations yielded the probability generating function transforms. These transforms were then inverted with two different inversion algorithms, recovering the molecular weight distributions of the polymer. The model predictions were compared with our experimental data and other information taken from the literature. Good agreement was obtained. The approach presented here is also useful for other polymerization and postpolymerization processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1676–1685, 2003     

Characterization of molecular orientation in injection–stretch–blow‐molded poly(ethylene terephthalate) bottles by means of external reflection infrared spectroscopy

The molecular orientation at the outer surface of injection–stretch–blow‐molded bottles made from poly(ethylene terephthalate) was characterized and quantified by means of front‐surface reflection infrared spectroscopy based on a method developed previously. Results were obtained for two different bottle shapes (cylindrical and rectangular) molded at different injection mold temperatures (16, 38, and 60°C). For the cylindrical bottles, the preferred molecular chain orientation was found to be in the axial direction, with the Hermans orientation function near 0.3 for all three mold temperatures. For the less symmetrical rectangular bottles, a significant difference was observed between the large and small faces. For the large face, the orientation was mainly in the hoop direction; the Hermans orientation function was in the range of 0.3–0.5 and was essentially the same at all mold temperatures and positions along the bottle height. For the small face, on the other hand, the preferred orientation changed from the hoop direction near the bottom to the axial direction near the top, and the variation was more pronounced at lower mold temperatures. The utility of the front‐surface reflection technique was clearly demonstrated. It was also applied, with the use of an infrared microscope, to examine the orientation gradient across the wall thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1319–1327, 2007     

The relationship between mechanical properties and morphology of vibration‐injection‐molded polyethylene

This paper introduces a novel melt vibration‐injection molding. The effect of mid‐frequency melt vibration on mechanical properties was introduced, and SEM, WAXD and DSC investigations had been employed to provide evidence for explaining the relationship between mechanical properties and morphology of vibration‐injection‐molded specimens. The results show that the effect of vibration frequency is very different from that of vibration pressure amplitude. At a given vibration pressure amplitude, the increase of vibration frequency is beneficial for obtaining preferential orientation, more perfect lamellae and enhanced mechanical properties. For a given vibration frequency, increase of vibration pressure amplitude is a pre‐requisite for the achievement of a large‐scale lamella, more pronounced orientation, increase of cyrstallinity and high strength of high‐density polyethylene, but part of the toughness is lost. Copyright © 2004 Society of Chemical Industry     

Effects of molecular weight and molecular weight distribution on creep properties of polypropylene homopolymer

The molecular weights of the industrial-grade isotactic polypropylene (i-PP) homopolymers samples were determined by the melt-state rheological method and effects of molecular weight and molecular weight distribution on solid and melt state creep properties were investigated in detail. The melt-state creep test results showed that the creep resistance of the samples increased by M_w due to the increased chain entanglements, while variations in the polydispersity index (PDI) values did not cause a considerable change in the creep strain values. Moreover, the solid-state creep test results showed that creep strain values increased by M_w and PDI due to the decreasing amount of crystalline structure in the polymer. The results also showed that the amount of crystalline segment was more effective than chain entanglements that were caused by long polymer chains on the creep resistance of the polymers. Modeling the solid-state viscoelastic structure of the samples by the Burger model revealed that the weight of the viscous strain in the total creep strain increased with M_w and PDI, which meant that the differences in the creep strain values of the samples would be more pronounced at extended periods of time.     

Properties of glass‐filled thermoplastic polyesters

The thermal, mechanical, and rheological properties of glass‐filled poly(propylene terephthalate) (GF PPT) were compared to glass‐filled poly(butylene terephthalate) (GF PBT). The impetus for this study was the recent commercial interest in PPT as a new glass‐reinforced thermoplastic for injection‐molding applications. This article represents the first systematic comparison of the properties of GF PPT and GF PBT in which differences in properties can be attributed solely to differences in the polyester matrices, that is, glass‐fiber size and composition, polymer melt viscosity, nucleant content and composition, polymerization catalyst composition and content, and processing conditions were kept constant. Under these controlled conditions, GF PPT showed marginally higher tensile and flexural properties and significantly lower impact strength compared to GF PBT. The crystallization behavior observed by cooling from the melt at a constant rate showed that GF PBT crystallized significantly faster than did GF PPT. Nucleation of GF PPT with either talc or sodium stearate increased the rate of crystallization, but not to the level of GF PBT. The slower crystallization rate of GF PPT was found to strongly affect thermomechanical properties of injection‐molded specimens. For example, increasing the polymer molecular weight and decreasing the mold temperature significantly increased the modulus drop associated with the glass transition. In contrast, the modulus–temperature response of GF PBT was just marginally influenced by the polymer molecular weight and was essentially independent of the mold temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 889–899, 1999     

Flow‐induced crystallization in the injection molding of polymers: A thermodynamic approach

The prediction of the crystallinity and microstructure that develop in injection molding is very important for satisfying the required specifications of molded products. A novel approach to the numerical simulation of the skin‐layer thickness and crystallinity in moldings of semicrystalline polymers is proposed. The approach is based on the calculation of the entropy reduction in the oriented melt and the elevated equilibrium melting temperature by means of a nonlinear viscoelastic constitutive equation. The elevation of the equilibrium melting temperature that results from the entropy reduction between the oriented and unoriented melts is used to determine the occurrence of flow‐induced crystallization. The crystallization rate enhanced by the flow effect is obtained by the inclusion of the elevated equilibrium melting temperature in the modified Hoffman–Lauritzen equation. Injection‐molding experiments at various processing conditions were carried out on polypropylenes of various molecular weights. The thickness of the highly oriented skin layer and the crystallinity in the moldings were measured. The measured data for the microstructures in the moldings agree well with the simulated results. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 502–523, 2005     

Comparison of the molecular properties and morphology of polypropylenes irradiated under different atmospheres and after annealing

Electron‐beam irradiation, a well‐known way of generating long‐chain branching, was used to modify polypropylene. Samples were investigated with differential scanning calorimetry, polarized light microscopy, and size exclusion chromatography. Independently of the atmosphere, postannealing led to the deactivation of residual radicals and to the reduction of the nucleus density. In comparison with the initial polypropylene, the crystallization temperatures increased for nonannealed samples but decreased for annealed samples. Stable products were obtained only by irradiation in nitrogen followed by annealing. A reaction including free radicals with oxygen in the ambient atmosphere led to increasing molar mass degradation and the formation of long‐chain branching after storage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 634–639, 2006     

Evaluation of processing effects in injection‐molded amorphous and crystalline thermoplastics using an excimer laser

The ablation behavior of amorphous [polystyrene (PS), polycarbonate (PC)] and crystalline [PET, glass‐filled poly(butylene terephthalate) (PBT)] polymers by 248‐nm KrF excimer laser irradiation were investigated for different injection‐molding conditions, namely, injection flow rate, injection pressure, and mold temperature, as a possible method for evaluating processing effects in the specimens. For this purpose, dumbbell‐shaped samples were injection‐molded under different sets of processing conditions, and weight loss measurements were carried out for the different injection‐molding conditions. Some of the crystalline (PET) samples were annealed at different annealing times and temperatures. For PET, the weight loss decreased with increasing mold temperature and remained insensitive to injection flow rate. Annealing time and temperature significantly reduced weight loss in PET. For PBT, the weight loss due to laser ablation decreased with increasing material packing due to pressure, and it also showed some sensitivity to flow rate variation. The major effect was seen with glass‐filled PBT samples. The weight loss decreased drastically with increasing glass fiber content. Laser ablation allowed us to observe process‐induced fiber orientation by scanning electron microscopy in PBT samples. For PS and PC, the weight loss increased with increasing injection flow rate and mold temperature and decreased with increasing injection pressure. The position near the gate showed higher ablation than the position at the end for all the conditions. A decrease in the material orientation with injection speed and mold temperature led to an increase in the weight loss, whereas an increase in the injection pressure, and consequently orientation, led to a lower weight loss for PS and PC. Higher residual stress samples showed higher weight losses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

Structure development and interfacial interactions in high‐density polyethylene/hydroxyapatite (HDPE/HA) composites molded with preferred orientation

Composites of high‐density polyethylene (HDPE) filled with sintered and nonsintered hydroxyapatite (HA) powders, designated as HAs and HAns, respectively, were compounded by twin screw extrusion. Compounds with neoalkoxy titanate or zirconate coupling agents were also produced to improve interfacial interaction and filler dispersion in the composites. The composites were molded into tensile test bars using (i) conventional injection molding and (ii) shear‐controlled orientation in injection molding (SCORIM). This latter molding technique was used to deliberately induce a strong anisotropic character to the composites. The mechanical characterization included tensile testing and microhardness measurements. The morphology of the moldings was studied by both polarized light microscopy and scanning electron microscopy, and the structure developed was assessed by wide‐angle X‐ray diffraction. The reinforcing effect of HA particles was found to depend on the molding technique employed. The higher mechanical performance of SCORIM processed composites results from the much higher orientation of the matrix and, to a lesser extent, from the superior degree of filler dispersion compared with conventional moldings. The strong anisotropy of the SCORIM moldings is associated with a clear laminated morphology developed during shear application stage. The titanate and the zirconate coupling agents caused significant variations in the tensile test behavior, but their influence was strongly dependent on the molding technique employed. The application of shear associated with the use of coupling agents promotes the disruption of the HA agglomerates and improves mechanical performance. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2873–2886, 2002