Microcellular foam of polymer blends of HDPE/PP and their composites with wood fiber

In this study, the effects of batch processing conditions (foaming time and temperature) and blend composition as well as the effect of incorporating wood fiber into the blends on the crystallinity, sorption behavior of CO₂, void fraction, and cellular morphology of microcellular foamed high‐density polyethylene (HDPE)/polypropylene (PP) blends and their composites with wood fiber were studied. Blending decreased the crystallinity of HDPE and PP and facilitated microcellular foam production in blend materials. The void fraction was strongly dependent on the processing conditions and on blend composition. Foamed samples with a high void fraction were not always microcellular. The addition of wood fiber inhibited microcellular foaming. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2842–2850, 2003     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

Cocontinuous phase morphology of asymmetric compositions of polypropylene/high‐density polyethylene blend by the addition of clay

A novel method of developing cocontinuous morphology in 75/25 and 80/20 w/w polypropylene/high density polyethylene (PP/HDPE) blends in the presence of small amount (0.5 phr) of organoclay has been reported. SEM study indicated a reduction in average domain sizes (D) of disperse HDPE when PP, HDPE, and the organoclay were melt‐blended simultaneously at 200°C. However, when the two‐sequential heating protocol was employed, (that is, the organoclay was first intercalated by HDPE chains at 150°C, followed by melt blending of PP at 200°C), very interestingly a cocontinuous morphology was found even for very asymmetric blend compositions. WAXD study revealed the intercalation of both PP and HDPE chains inside the clay galleries, when PP/HDPE and clay were melt‐mixed together at 200°C. However, when the two‐sequential heating protocol was used the organoclay platelets were selectively intercalated by the HDPE chains. Addition of SEPS in the blend decreased the D of HDPE domains in both the blending methods. Thus, the observed cocontinuous morphology in asymmetric composition of PP/HDPE blend in presence of clay is because of the barrier effect of the clay platelets in the HDPE phase that restrict the phase inversion into the domain/matrix morphology. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improved compatibility of high‐density polyethylene/poly(ethylene terephthalate) blend by the use of blocked isocyanate group

The blocked isocyanate group (BHI) was synthesized to improve the storage stability of HI (2‐hydroxyethyl methacrylate combined with isophorone diisocyanate) and characterized by Fourier transform infrared spectroscopy (FTIR). High‐density polyethylene grafted with the blocked isocyanate group (HDPE‐g‐BHI) was used as a reactive compatibilizer for an immiscible high‐density polyethylene/poly(ethylene terephthalate) (HDPE/PET) blend. A possible reactive compatibilization mechanism is that regenerated isocyanate groups of HDPE functionalized by BHI react with the hydroxyl and carboxyl groups of PET during melt blending. The HDPE‐g‐BHI/PET blend showed the smaller size of a dispersed phase compared to the HDPE/PET blend, indicating improved compatibility between HDPE and PET. This increased compatibility was due to the formation of an in situ graft copolymer, which was confirmed by dynamic mechanical analysis. Differential scanning calorimetry (DSC) analysis represented that there were few changes in the crystallinity for the continuous PET phase of the HDPE‐g‐BHI/PET blends, compared with those of the HDPE/PET blends at the same composition. Tensile strengths and elongations at the break of the HDPE‐g‐BHI/PET blends were greater than those of the HDPE/PET blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1017–1024, 2000     

Microcellular foaming of PE/PP blends

Three different polyethylene/polypropylene (PE/PP) blends were microcellular foamed and their crystallinities and melt strengths were investigated. The relationship between crystallinity, melt strength, and cellular structure was studied. Experimental results showed that the three blends had similar variation patterns in respect of crystallinity, melt strength, and cellular structure, and these variation patterns were correlative for each blend. For all blends, the melt strength and PP melting point initially heightened and then lowered, the PP crystallinity first decreased, and then increased as the PE content increased. At PE content of 30%, the melt strength and PP melting point were highest and the PP crystallinity was least. The blend with lower PP crystallinity and higher melt strength had better cellular structure and broader microcellular foaming temperature range. So, three blends had best cellular structure at PE content of 30%. Furthermore, when compared with PE/homopolymer (hPP) blend, the PE/copolymer PP (cPP) blend had higher melt strength, better cellular structure, and wider microcellular foaming temperature range, so it was more suited to be microcellular foamed. Whereas LDPE/cPP blend had the broadest microcellular foaming temperature range because of its highest melt strength within three blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4149–4159, 2007     

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     

Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermostimulative shape‐memory effect of reactive compatibilized high‐density polyethylene/poly(ethylene terephthalate) blends by an ethylene–butyl acrylate–glycidyl methacrylate terpolymer

High‐density polyethylene (HDPE)/poly(ethylene terephthalate) (PET) blends were prepared by means of melt extrusion with ethylene–butyl acrylate–glycidyl methacrylate terpolymer (EBAGMA) as a reactive compatibilizer. The effects of the EBAGMA and PET contents, recovery temperature, and stretch ratio on the thermostimulative shape‐memory behavior of the blends were studied. The results show that the addition of EBAGMA to the HDPE/PET blends obviously improved the compatibility and the shape‐memory effects of the blends. The response temperature was determined by the melting point of HDPE, and the shape‐recovery ratio of the 90/10/5 HDPE/PET/EBAGMA blend reached nearly 100%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrical resistivity of carbon black filled high‐density polyethylene composites

The electrical resistivity of high‐density polyethylene (HDPE) loaded with carbon black (CB) blends was evaluated as a function of the blending time and the melt index of HDPE. The relationship between the positive temperature coefficient effect and the room temperature volume resistivity was investigated. The positive temperature coefficient effect and reproducibility were improved significantly when the blending time of HDPE and CB was comparatively long. The effects of ⁶⁰Co γ‐ray and electron beam irradiation on the positive and negative temperature coefficient behavior of the blends were studied. The effect of thermal aging on the volume resistivity was studied to ascertain the structural stability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2440–2446, 2002     

Blends of high‐density polyethylene with solid silicone additive

Silicone masterbatch (SMB) is a pelletized formulation containing 50% of an ultrahigh molecular‐weight polydimethylsiloxane dispersed in polyethylene. This SMB is designed to be used as an additive in polyethylene‐compatible systems to impart benefits such as processing improvement and modification of surface characteristics. In this work, binary blends of high‐density polyethylene (HDPE) and SMB were prepared by melt‐mixing technique to study the influence of this masterbatch on the processing and mechanical properties of HDPE. Ternary blends were also prepared by the addition of silane‐grafted polyethylene (HDPE‐VTES) as compatibilizer. The blends were analyzed by melting flow rate (MFR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and tensile tests. Data of final torque and MFR showed that SMB improved the processability of pure HDPE. DSC results showed differences in crystalline behavior between binary and ternary blends. In the former, the degree of crystallinity increased up to 10 wt % of SMB content; beyond this concentration, it decreased. In ternary blends, a reverse behavior was observed. The morphologic study showed silicone particles uniformly distributed in HDPE matrix. With high SMB concentration, the addition of HDPE‐VTES significantly reduced the size of silicone particles. In the range of SMB composition studied, the mechanical properties of blends lower slightly compared to pure HDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2347–2354, 2002     

Effect of interfacial stress on the crystalline structure of the matrix and the mechanical properties of high‐density polyethylene/CaCO3 blends

A series of high‐density polyethylene (HDPE)/CaCO₃ blends were prepared with different kinds of coupling agents, with CaCO₃ particles of different sizes, and with matrixes of different molecular weights during the melt‐mixing of HDPE and CaCO₃ particles. The mechanical properties of these blends and their dependence on the interfacial adhesion and matrix crystalline structure were studied. The results showed that the Charpy notched impact strength of these blends could be significantly improved with an increase in the interfacial adhesion or matrix molecular weight or a decrease in the CaCO₃ particle size. When a CaCO₃ surface was treated with a compounded coupling agent, the impact strength of the HDPE/CaCO₃(60/40) blend was 62.0 kJ/m², 2.3 times higher than that of unimproved HDPE; its Young's modulus was 2070 MPa, 1.07 times higher than that of unimproved HDPE. The heat distortion temperature of this blend was also obviously improved. The improvement of the mechanical properties and the occurrence of the brittle–tough transition of these blends were the results of a crystallization effect induced by the interfacial stress. When the interfacial adhesion was higher and the CaCO₃ content was greater than 30%, the interfacial stress produced from matrix shrinkage in the blend molding process could strain‐induce crystallization of the matrix, leading to an increase in the matrix crystallinity and the formation of an extended‐chain (or microfibrillar) crystal network. The increase in the critical ligament thickness with an increasing matrix molecular weight was attributed to the strain‐induced areas becoming wider, the extended‐chain crystal layers becoming thicker, and the interparticle distance that formed the extended‐chain crystal network structure becoming larger with a higher matrix molecular weight. The formation of the extended‐chain crystal network and the increase in the matrix crystallinity were also the main reasons that Young's modulus and the heat distortion temperature of this blend were improved. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2120–2129, 2003     

Modification of recycled high‐density polyethylene by low‐density and linear‐low‐density polyethylenes

The present study investigated mixed polyolefin compositions with the major component being a post‐consumer, milk bottle grade high‐density polyethylene (HDPE) for use in large‐scale injection moldings. Both rheological and mechanical properties of the developed blends are benchmarked against those shown by a currently used HDPE injection molding grade, in order to find a potential composition for its replacement. Possibility of such replacement via modification of recycled high‐density polyethylene (reHDPE) by low‐density polyethylene (LDPE) and linear‐low‐density polyethylene (LLDPE) is discussed. Overall, mechanical and rheological data showed that LDPE is a better modifier for reHDPE than LLDPE. Mechanical properties of reHDPE/LLDPE blends were lower than additive, thus demonstrating the lack of compatibility between the blend components in the solid state. Mechanical properties of reHDPE/LDPE blends were either equal to or higher than calculated from linear additivity. Capillary rheological measurements showed that values of apparent viscosity for LLDPE blends were very similar to those of the more viscous parent in the blend, whereas apparent viscosities of reHDPE/LDPE blends depended neither on concentration nor on type (viscosity) of LDPE. Further rheological and thermal studies on reHDPE/LDPE blends indicated that the blend constituents were partially miscible in the melt and cocrystallized in the solid state.     

Thermal and mechanical properties of uncrosslinked and chemically crosslinked polyethylene/ethylene vinyl acetate copolymer blends

Uncrosslinked and chemically crosslinked binary blends of low‐ and high‐density polyethylene (PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt‐mixing process using 0–3 wt % tert‐butyl cumyl peroxide (BCUP). The uncrosslinked blends revealed two distinct unchanged melting peaks corresponding to the individual components of the blends, but with a reduced overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced compatibility between EVA and polyethylene, with LDPE being more compatible than HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the addition of BCUP, and only the corresponding PE melting point was observed at a lowered temperature. But blended with 40% EVA, two peaks still existed with a slight shift toward lower temperatures. Changes of mechanical properties with blending ratio, crosslinking, and temperature had been dominated by the extent of crystallinity, crosslinking degree, and morphology of the blend. A good correlation was observed between elongation‐at‐break and morphological properties. The blends with higher level of compatibility showed less deviation from the additive rule of mixtures. The deviation became more pronounced for HDPE/EVA blends in the phase inversion region, while an opposite trend was observed for LDPE/EVA blends with co‐continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3261–3270, 2007     

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     

Adhesion of propylene–ethylene copolymers to high‐density polyethylene

The adhesion of some propylene–ethylene (P/E) copolymers to polypropylene (PP) and high density polyethylene (HDPE) was studied in order to compare them with other olefin copolymers as compatibilizers for PP/HDPE blends. A one‐dimensional model of the compatibilized blends was fabricated by layer‐multiplying coextrusion. The microlayered tapes consisted of many alternating layers of PP and HDPE with a thin tie‐layer inserted at each interface. The thickness of the tie‐layer varied from 0.1 to 15 μm, which included thicknesses comparable to those of the interfacial layer in a compatibilized blend. In the T‐peel test, the P/E copolymers delaminated at the HDPE interface. An elastomeric P/E with higher ethylene content exhibited substantially higher delamination toughness than a more thermoplastic P/E with lower ethylene content. Inspection of the crack‐tip damage zone revealed that a change from deformation of the entire tie‐layer to formation of a localized yielded zone was responsible. By treating the damage zone as an Irwin plastic zone, it was demonstrated that a critical stress controlled the delamination toughness. The temperature dependence of the delamination toughness was also measured. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Foam extrusion of high density polyethylene/wood‐flour composites using chemical foaming agents

A one‐way analysis of variance and thermal analysis were performed in this study to examine the influences of the contents, types (exothermic vs. endothermic), and forms (pure vs. masterbatch) of chemical foaming agents (CFAs), as well as the use of coupling agents, on the density reduction (or void fraction) and cell morphology of extrusion‐foamed neat high density polyethylene (HDPE) and HDPE/wood‐flour composites. The CFA types and forms did not affect the void fractions of both the neat HDPE and HDPE/wood‐flour composites. However, a gas containment limit was observed for neat HDPE foams whereas the average cell size achieved in the HDPE/wood‐flour composite foams remained insensitive to the CFA contents, irrespective of the foaming agent types. The experimental results indicated that the use of coupling agent in the formulation was required to achieve HDPE/wood‐flour composite foams with high void fraction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3139–3150, 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     

Melt miscibility and mechanical properties of metallocene linear low‐density polyethylene blends with high‐density polyethylene: influence of comonomer type

In this paper, the implications of melt miscibility on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)/high‐density polyethylene (HDPE) blends were assessed with respect to the influence of the comonomer type. The influence of the latter was examined by selecting one butene LLDPE and one octene LLDPE of very similar weight‐average molecular weight (M_w), molecular‐weight distribution (MWD) and branch content, keeping the comonomer type as the only primary molecular variable. Each of the two metallocene LLDPEs was melt‐blended with the same HDPE at 190 °C in a Haake melt‐blender. The rheological, thermal and mechanical properties were measured by the use of an ARES rheometer, differential scanning calorimeter and Instron machine, respectively. The rheological measurements, made over the linear viscoelastic range, suggested no significant influence of the branch type on the melt miscibility. The rheology results are in agreement with those obtained from previous transmission electron microscopy (TEM) and small‐angle neutron scattering (SANS) studies. The dynamic shear viscosity and total crystallinity of the metallocene (m)‐LLDPE blends with HDPE followed linear additivity. At small strains, the branch type has little or no influence on the melt miscibility and solid‐state properties of the blends. Even the large‐strain mechanical properties, such as tensile strength and elongation at break, were not influenced by the comonomer type. However, the ultimate tensile properties of the HDPE‐rich blends were poor. Incompatibility of the HDPE‐rich blends, as a result of the weak interfaces between the blend components, is suggested to develop at large strains. Copyright © 2005 Society of Chemical Industry     

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     

High‐density polyethylene/ultrahigh‐molecular‐weight polyethylene blend. I. The processing,thermal, and mechanical properties

Various blend ratios of high‐density polyethylene (HDPE) and ultrahigh‐molecular‐weight polyethylene (UHMWPE) were prepared with the objective of determining their suitability as biomaterials. Although the presence of HDPE in the blends enabled melt processing, the presence of UHMWPE helped to improve the toughness of the resulting blends. The processability of the blends was investigated with the Brabender torque, which was used as an indication of the optimum blend conditions. The blends were characterized with differential scanning calorimetry. The mechanical tests performed on the blends included tensile, flexural, and impact tests. A 50:50 (w/w) blend yielded optimum properties in terms of the processability and mechanical properties. The tensile property of the 50:50 blend was intermediate between those of HDPE and UHMWPE, but the strain at break increased 200% in comparison with that of both neat resins. The energy at break of the 50:50 blend revealed an improvement in the toughness. The fracture mechanism was also investigated with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 413–425, 2005