Effect of the high‐density polyethylene melt index on the microcellular foaming of high‐density polyethylene/polypropylene blends

The effect of high‐density polyethylene (HDPE)/polypropylene (PP) blending on the crystallinity as a function of the HDPE melt index was studied. The melting temperature and total amount of crystallinity in the HDPE/PP blends were lower than those of the pure polymers, regardless of the blend composition and melt index. The effects of the melt index, blending, and foaming conditions (foaming temperature and foaming time) on the void fractions of HDPEs of various melt indices and HDPE/PP blends were also investigated. The void fraction was strongly dependent on the foaming time, foaming temperature, and blend composition as well as the melt index of HDPE. The void fraction of the foamed 30:70 HDPE/PP blend was always higher than that of the foamed 50:50 HDPE/PP blend, regardless of the melt index. The microcellular structure could be greatly improved with a suitable ratio of HDPE to PP and with foaming above the melting temperature for long enough; however, using high‐melt‐index HDPE in the HDPE/PP blends had a deleterious effect on both the void fraction and cell morphology of the blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 364–371, 2004     

Studies on blends of high‐density polyethylene and polypropylene produced by oscillating shear stress field

Tensile strength and morphology of blends of high‐density polyethylene (HDPE) and polypropylene (PP) obtained by oscillating packing injection molding were investigated via Universal Testing Machine, DSC, and SAXS. Tensile strength is greatly enhanced from 24.5 MPa to more than 90 MPa for pure HDPE and for blends with PP content less than 10 wt %. There exists a sharp decrease of tensile strength when PP content is more than 10 wt %. The shear‐induced morphologies with core in the center, oriented zone surrounding the core and skin layer are observed in the cross‐section areas of the samples. Interestingly, a sharp decrease of oriented zone is seen when PP content is more than 10 wt %, associated with the sharp decrease of tensile strength. DSC result shows double melting peaks with a high‐temperature melting peak that is not present in the endotherm obtained from the central core and obtained from the samples by static packing injection molding, which indicates the existence of shish‐kebab structure in the oriented zone. However, there is no difference of crystallinity between the samples by oscillating and by static packing injection molding. SAXS was used to analyze the complicated morphologies induced by shear stress, and results show that the crystal thickness could be greatly increased under shear stress. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 58–63, 2002     

Effect of die geometry on foaming behaviors of high‐melt‐strength polypropylene with CO2

This article reports on a systematic study that was conducted to investigate the effects of die geometry (i.e., pressure and pressure drop rate) on the cell nucleation and growth behaviors of noncrosslinked high‐melt‐strength (HMS) polypropylene (PP) foams blown with supercritical CO₂. The experimental results showed that the cellular morphologies of PP foams were sensitive to the die geometry. Furthermore, the initial expansion behavior of the foam extrudate at the die exit was recorded using a high‐speed CCD camera. This enabled us to achieve a more thorough understanding of the effect of die geometry on both the initial expansion behavior and the final cellular morphology of HMS PP foams. The effect of die temperature on cell morphology was also studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Characterization of the free volume in high‐impact polystyrene/polypropylene and high‐impact polystyrene/high‐density polyethylene blends probed by positron annihilation spectroscopy

The free‐volume properties of high‐impact polystyrene (HIPS)/polypropylene (PP) and HIPS/high‐density polyethylene (HDPE) blends were investigated by means of positron annihilation lifetime spectroscopy (PALS). The measured results show that the free‐volume holes in the semicrystalline polymers, such as PP and HDPE, were not large enough to accommodate the branched chains and the end groups of the macromolecular chains in HIPS to produce favorable interactions between the semicrystalline polymers and the HIPS polymer in these blends; thus immiscible blends were formed. The weak interaction between two dissimilar polymer molecules only took place in the regions between two amorphous phases. In addition, the observed negative deviations of the longest lifetime intensity and the free‐volume fraction were attributed to the influence of the interfacial polarization during PALS measurement. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1507–1514, 2003     

Improving polypropylene microcellular foaming through blending and the addition of nano‐calcium carbonate

This article reports an attempt to improve polypropylene (PP) microcellular foaming through the blending of PP with high‐density polyethylene (HDPE) as a minor component and the incorporation of nano‐calcium carbonate (nano‐CaCO₃) into PP and its blends with HDPE. Three HDPEs were selected to form three blends with a viscosity ratio less than, close to, or greater than unity. Two concentrations of nano‐CaCO₃, 5 and 20 wt %, were used. The blends and nanocomposites were prepared with a twin‐screw extruder. The foaming was carried out by a batch process with supercritical carbon dioxide as a blowing agent. The online shear viscosity during compounding and the dynamic rheological properties of some samples used for foaming were measured. The cell structure of the foams was examined with scanning electron microscopy (SEM), and the morphological parameters of some foams were calculated from SEM micrographs. The rheological properties of samples were used to explain the resulting cell structure. The results showed that the blend with a viscosity ratio close to unity produced a microcellular foam with the minimum mean cell diameter (0.7 μm) and maximum cell density (1.17 × 10¹¹ cells/cm³) among the three blends. A foamed PP/nano‐CaCO₃ composite with 5 wt % nano‐CaCO₃ exhibited the largest cell density (8.4 × 10¹¹ cells/cm³). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Bubble growth in the microcellular foaming of CO2/polypropylene solutions

This article is concerned with bubble growth dynamics in the CO₂/polypropylene microcellular foaming process. The effect of the melt strength on the bubble growth was thoroughly investigated in theory for the first time. The theoretical results indicate that enhanced melt strength effectively restrains the bubble growth and stabilizes the bubble oscillation. Higher melt strength leads to lower bubble growth rate, shorter growth time, and smaller ultimate bubble size. Compared to the melt strength, the viscoelasticity and the gas pressure have less effect on the microcellular foaming process. The bubble growth varies a little as the viscoelasticity is varied. The bubble oscillation and growth rate are enhanced with increasing gas pressure, which leads to the augmentation of the bubble size. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Effect of long‐chain branches of polypropylene on rheological properties and foam‐extrusion performances

The effect of modifying polypropylene by the addition of long‐chain branches on the rheological properties and performance of foam extrusion was studied. Three polypropylenes, two long‐chain‐branched polypropylenes and a linear polypropylene, were compared in this study. The modification was performed with a reactive‐extrusion process with the addition of a multifunctional monomer and peroxide. The rheological properties were measured with a parallel‐plate and elongational rheometer to characterize the branching degree. The change from a linear structure to a long‐chain‐branched nonlinear structure increased the melt strength and elasticity of polypropylene. Also, there was a significant improvement in the melt tension and sag resistance for branched polypropylenes. Foaming extrusion was performed, and the effect of the process variables on the foam density was analyzed with Taguchi's experimental design method. For this study, an L₁₈(2¹3⁵) orthogonal array was used on six parameters at two or three levels of variation. The considered parameters were the polypropylene type, the blowing agent type, the blowing agent content, the die temperature, the screw speed (rpm), and the capillary die length/diameter ratio. As a result, the most significant factor that influenced the foam density was the degree of long‐chain branching of polypropylene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1793–1800, 2005     

Morphology and mechanical properties of polypropylene/high‐impact polystyrene blends from postconsumer plastic waste

The compatibilizing effect of the triblock copolymer poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) on the morphological and mechanical properties of virgin and recycled polypropylene (PP)/high‐impact polystyrene (HIPS) blends was studied, with the properties optimized for rigid composite films. The components of the blend were obtained from municipal plastic waste, PP being acquired from mineral water bottles (PP_b) and HIPS from disposable cups. These materials were preground, washed only with water, dried with hot air, and ground again (PP_b) or agglutinated (HIPS). Blends with three different weight ratios of PP_b and HIPS (6:1, 6:2, and 6:3) were prepared, and three different concentrations of SEBS (5, 6, and 7 wt %) were used for investigations of its compatibilizing effect. Scanning electron microscopy showed that SEBS reduced the diameter of dispersed HIPS particles in the globular and fibril shapes and improved the adhesion between the disperse phase and the matrix. However, SEBS interactions with PP_b and HIPS influenced the mechanical properties of the compatibilized PP_b/HIPS/SEBS blends. An adequate composition of PP/HIPS, for both virgin and recycled blends, for applications in composite films with characteristics similar to those of synthetic paper was obtained with a minimal amount of SEBS and a maximal HIPS/PP ratio in the range of concentrations studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2861–2867, 2003     

Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

Very high modulus high‐density polyethylene and high‐modulus polypropylene obtained by solid‐state roll drawing

This article describes results obtained with a process developed for rolling and drawing simultaneously polymer profiles in the solid state. Solid‐state roll drawing has the advantage of being continuous, which allows relatively high production rates and the generation of high deformation ratios with some degree of biaxial orientation. The roll‐drawing process allows the extent of biaxial orientation to be controlled by the adjustment of the tension and compression loads applied to the polymers, in particular semicrystalline thermoplastics. Some experimental results obtained with a four‐station roll‐drawing apparatus are presented, particularly on high‐density polyethylene (HDPE) and polypropylene. The effect of process parameters, such as the gap between the rolls and tension, are discussed. Aspects discussed also include relaxation; structure development in terms of orientation and crystallinity as a function of draw ratio (λ); λ as a function of process parameters; and finally, mechanical and thermal properties as a function of λ. Moduli as high as 25 GPa in the longitudinal direction and about 4 GPa in the transverse direction were obtained with successively rolled, initially thick, HDPE profiles. © 2006 Government of Canada. Exclusive worldwide publication right in the article have been transferred to Wiley Periodicals, Inc. J Appl Polym Sci 102: 3391–3399, 2006     

A study on the onset surface melt fracture of polypropylene materials with foaming additives

The melt fracture behaviors of linear and branched polypropylene resins with foaming additives were investigated. The effects of branching, processing temperature, additives, and blowing agent on the surface melt fracture of polypropylene materials were thoroughly studied. A CCD camera was installed at the die exit to precisely observe the onset of surface melt fracture of extruded foams. The critical wall shear stress was determined for various linear and branched polypropylene resins using a capillary die. It was found that the branching required to foam polypropylene resins also promotes melt fracture: the critical shear stress was decreased by 0.0175 MPa with an increase of 0.1 n/1000c in long‐chain branching. It was also observed that the dissolved blowing agent (butane) significantly suppressed the melt fracture of both linear and branched polypropylene resins. On the other hand, a noticeable increase in the critical shear stress of branched polypropylene materials was observed with the nucleating agent (talc) and the aging modifier (glycerol mono stearate), whereas almost negligible effect of the additives on the critical shear stress was observed for linear polypropylene materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of recycled polypropylene on polypropylene/high‐density polyethylene blends

The effect of recycled PP on incompatible blends of virgin polypropylene (PP) and high‐density polyethylene (HDPE) was studied. Recycled PP from urban solid waste was extracted with methyl ethyl ketone and the compatibilizing action of the product before and after extraction was examined. The characterization of the recycled PP was performed by FTIR, NMR, and DSC analyses. Mechanical properties of the blends were evaluated. The results showed partial compatibility of the blend components, reflected in the improvement of the tensile strength and elongation. Best results were achieved by the addition of extracted recycled PP on the 50/50 PP/HDPE blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1305–1311, 2001     

Fundamental foaming mechanisms governing the volume expansion of extruded polypropylene foams

This article describes the fundamental foaming mechanisms that governed the volume expansion behavior of extruded polypropylene (PP) foams. A careful analysis of extended experimental results indicated that the final volume expansion ratio of the extruded PP foams blown with butane was governed by either the loss of the blowing agent or the crystallization of the polymer matrix. A charge coupling device (CCD) camera was installed at the die exit to carefully monitor the shape of the extruded PP foams. The CCD images were analyzed to illustrate both mechanisms, gas loss and crystallization, during foaming at various temperatures, and the maximum expansion ratio was achieved when the governing mechanism was changed from one to the other. In general, the gas loss mode was dominant at high temperatures and the crystallization mode was dominant at low temperatures. When the gas loss mode was dominant, the volume expansion ratio increased with decreasing temperature because of the reduced amount of gas lost. By contrast, when the crystallization mode was dominant, the expansion ratio increased with increasing temperature because of the delayed solidification of the polymer. The processing window variation with the butane concentration, the change in the temperature ranges for the two governing modes, and the sensitivity of melt temperature variations to the volume expansion ratio are discussed in detail on the basis of the obtained experimental results for both branched and linear PP materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2661–2668, 2004     

Structure and properties of polypropylene/low‐density polyethylene blends grafted with itaconic acid in the course of reactive extrusion

This study was concerned with the structural features and mechanical properties of polypropylene (PP)/low‐density polyethylene (LDPE) blends, which after compounding were modified by the free‐radical grafting of itaconic acid (IA) to produce [PP/LDPE]‐g‐IA in the course of reactive extrusion. To analyze the structural features of the [PP/LDPE]‐g‐IA systems, differential scanning calorimetry and relaxation spectrometry techniques were used. The data were indicative of the incompatibility of PP and LDPE in the [PP/LDPE]‐g‐IA systems on the level of crystalline phases; however, favorable interactions were observed within the amorphous phases of the polymers. Because of these interactions, the crystallization temperature of PP increased by 5–11°C, and that of LDPE increased by 1.3–2.7°C. The rapprochement of their glass‐transition temperatures was observed. The single β‐relaxation peak for the [PP/LDPE]‐g‐IA systems showed that compatibility on the level of structural units was responsible for β relaxation in the homopolymers used. Variations in the ratios of the polymers in the [PP/LDPE]‐g‐IA systems led to both nonadditive and complex changes in the viscoelastic properties as well as mechanical characteristics for the composites. Additions of up to 5 wt % PP strengthened the [PP/LDPE]‐g‐IA blended systems between the glass‐transition temperatures of LDPE and PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1746–1754, 2006     

PP/LDPE blends produced by reactive processing. I. Grafting efficiency and rheological and high‐elastic properties of [PP/LDPE]‐g‐IA melts

Itaconic acid (IA) was grafted onto polypropylene/low‐density polyethylene (PP/LDPE) blends. The ratio of polymeric components was varied from 100 : 0 to 0 : 100. The effect of the variation in the ratios of the components on grafting efficiency and concomitant side processes was studied. Grafting of IA (1 wt %) was initiated by 2,5‐dimethyl‐2,5‐di(tert‐butyl peroxy)‐hexane (0.3 wt %) and was carried out in an extruder reactor equipped with a dynamic mixer. An increase in the PP content of the blend led to a lower yield of the grafted product. With low concentrations of LDPE in the blend (up to 25 wt %), grafting efficiency was observed to increase, and this increase was greater in comparison with the additive rule. Between 25 and 99 wt % of LDPE in the blend, grafting efficiency rose monotonically with LDPE concentration. At or below an LDPE content of 25 wt %, the melt flow index (MFI) of [PP/LDPE]‐g‐IA would increase unlike with PP‐g‐IA systems. But a small quantity of PP (below 25 wt %) in the [PP/LDPE]‐g‐IA blends would result in a decreased MFI unlike with LDPE‐g‐IA. The dependence of swell index and melt strength on the ratio of polymeric components in [PP/LDPE]‐g‐IA blends also was investigated. ©2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5095–5104, 2006     

Polypropylene/polypropylene‐grafted acrylic acid copolymer/ethylene–Acrylic acid copolymer ternary blends for hydrophilic polypropylene

Ternary blends of polypropylene (PP), a polypropylene‐grafted acrylic acid copolymer (PP‐g‐AA), and an ethylene–acrylic acid copolymer (EAA) were prepared by melt blending. The surfaces of films with different contents of these three components were characterized with contact‐angle measurements. Scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the microstructure, melting and crystalline behavior, and thermal stability of the blends. The contact angles of the PP/PP‐g‐AA blends decreased monotonically with increasing PP‐g‐AA content. With the incorporation of EAA, the contact angles of the PP/PP‐g‐AA/EAA ternary blends decreased with increasing EAA content. When the concentration of EAA was higher than 15 wt %, the contact angles of the ternary blends began to increase. Scanning electron microscopy observations confirmed that PP‐g‐AA acted as a compatibilizer and improved the compatibility between PP and EAA in the ternary blends. Differential scanning calorimetry analysis suggested that acrylic acid moieties could act as nucleating agents for PP in the polymer blends. Thermogravimetric analysis and differential thermogravimetry confirmed the optimal blend ratio for the PP/PP‐g‐AA/EAA ternary blends was 70/15/15. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 436–442, 2006     

Nonisothermal crystallization,melting behavior,and morphology of polypropylene/metallocene‐catalyzed polyethylene blends

The nonisothermal crystallization, melting behavior, and morphology of blends of polypropylene (PP) and a metallocene‐catalyzed polyethylene (mPE) elastomer were studied with differential scanning calorimetry, scanning electron microscopy, polarized optical microscopy, and X‐ray diffraction. The results showed that PP and mPE were partially miscible and could form some cocrystallization, although the extent was very small. A modified Avrami analysis and the Mo method were used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was homogeneous, the growth of the spherulites was three‐dimensional, and the crystallization mechanism of PP was not affected by mPE. The crystallization activation energy was estimated with the Kissinger method. Interesting results were obtained with the modified Avrami analysis and Mo and Kissinger methods, and the conclusions were in good agreement. The addition of less mPE increased the overall crystallization rate of PP. The relationship between the composition and morphology of the blends was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1203–1210, 2004     

Nonisothermal crystallization kinetics of polypropylene/polypropylene‐g‐polystyrene/polystyrene blends

The nonisothermal crystallization kinetics of polypropylene (PP), PP/polystyrene (PS), and PP/PP‐g‐PS/PS blends were investigated with differential scanning calorimetry at different cooling rates. The Jeziorny modified Avrami equation, Ozawa method, and Mo method were used to describe the crystallization kinetics for all of the samples. The kinetics parameters, including the half‐time of crystallization, the peak crystallization temperature, the Avrami exponent, the kinetic crystallization rate constant, the crystallization activation energy, and the F(T) and a parameters were determined. All of the results clearly indicate that the PP‐g‐PS copolymer accelerated the crystallization rate of the PP component in the PP/PP‐g‐PS/PS blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel multimonomer‐grafted polypropylene preparation and application in polypropylene/poly(vinyl chloride) blends

A novel grafted polymer was prepared in one step through free‐radical melt grafting in a single‐screw extruder. It was shown that the addition of styrene (St) to the melt‐grafting system as a comonomer could significantly enhance the grafting degree of methyl methacrylate (MMA) onto polypropylene (PP) and reduce the degradation of the PP matrix by means of Fourier transform infrared and melt flow rate testing, respectively. Then, the potential of using multimonomer‐grafted PP, which was designated PP‐g‐(St‐co‐MMA), as the compatibilizer in PP/poly(vinyl chloride) (PVC) blends was also examined. In comparison with PP/PVC blends, the average size of the dispersed phase was greatly reduced in grafted polypropylene (gPP)/PVC blends because of the addition of the PP‐g‐(St‐co‐MMA) graft copolymer. The tensile strength of the gPP/PVC blends increased significantly, and the impact strength was unchanged from that of the pure PP/PVC blends. The results of differential scanning calorimetry and scanning electron microscopy suggested that the compatibility of the PP/PVC blends was improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008