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     

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     

Crosslinking of high‐density polyethylene in the presence of organic peroxides

The crosslinking efficiency of various commercially available organic peroxides (dicumyl peroxide, O,O‐t‐butyl O‐2‐ethylhexylperoxycarbonate, t‐butyl peroxybenzoate, t‐butyl 3,5,5‐trimethylperoxyhexanoate, and t‐butyl 2‐ethylperoxyhexanoate) was tested on high‐density polyethylene (HDPE) in its molten state. The variations of the concentrations of the peroxides versus the crosslinking extent were plotted for these peroxides, and the values were compared. Dicumyl peroxide was found to be the best crosslinking agent for HDPE. The efficiency of the HDPE crosslinking with each peroxy derivative was analyzed on the basis of the behavior of the radicals generated from it. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 75–81, 2004     

Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Time–temperature superposition principle applied to a kenaf‐fiber/high‐density polyethylene composite

The time–temperature superposition principle was applied to the viscoelastic properties of a kenaf‐fiber/high‐density polyethylene (HDPE) composite, and its validity was tested. With a composite of 50% kenaf fibers, 48% HDPE, and 2% compatibilizer, frequency scans from a dynamic mechanical analyzer were performed in the range of 0.1–10 Hz at five different temperatures. Twelve‐minute creep tests were also performed at the same temperatures. Creep data were modeled with a simple two‐parameter power‐law model. Frequency isotherms were shifted horizontally and vertically along the frequency axis, and master curves were constructed. The resulting master curves were compared with an extrapolated creep model and a 24‐h creep test. The results indicated that the composite material was thermorheologically complex, and a single horizontal shift was not adequate to predict the long‐term performance of the material. This information will be useful for the eventual development of an engineering methodology for creep necessary for the design of structural building products from these composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1995–2004, 2005     

Bi‐axial self‐reinforcement of high‐density polyethylene induced by high‐molecular weight polyethylene through dynamic packing injection molding

Previously, bi‐axial self‐reinforcement of high‐density polyethylene (HDPE) was achieved through a uni‐axial shear stress field introduced by dynamic packing injection molding technology. Here, further improvement of tensile strength along the flow direction (MD) was achieved by blending a small amount of high‐molecular‐weight polyethylene (HMWPE) with HDPE, while the tensile strength along the transverse direction (TD) still substantially exceeded that of conventional moldings. Tensile strengths in both flow and transverse directions were considerably enhanced, with improvements from 23 MPa to 76 MPa in MD and from 23 MPa to 31 MPa in TD. The effect of HMWPE content and molding parameters on tensile properties was also investigated. The tensile strength along MD was highly dependent on HMWPE content, oscillating cycle, mold temperature, melt temperature and packing pressure, while that along TD was insensitive to composition and processing parameters within the selected design space. According to the stress–strain curves, samples with HMWPE produced by dynamic packing injection molding had a special tensile failure mode in MD, different from both typical plastic and brittle failure modes. There were no yielding and necking phenomena, which are characteristic during tensile testing of plastic materials, but there was still a considerably higher elongation compared to those of brittle materials. However, in TD, all dynamic injection molding samples exhibited plastic failure as did typical conventional injection molding samples. Copyright © 2006 Society of Chemical Industry     

Ultraviolet weathering of photostabilized wood‐flour‐filled high‐density polyethylene composites

Wood‐plastic composites are being increasingly examined for nonstructural or semistructural building applications. As outdoor applications become more widespread, durability becomes an issue. Ultraviolet exposure can lead to photodegradation, which results in a change in appearance and/or mechanical properties. Photodegradation can be slowed through the addition of photostabilizers. In this study, we examined the performance of wood flour/high‐density polyethylene composites after accelerated weathering. Two 2⁴ factorial experimental designs were used to determine the effects of two hindered amine light stabilizers, an ultraviolet absorber, a colorant, and their interactions on the photostabilization of high‐density polyethyl‐ ene blends and wood flour/high‐density polyethylene composites. Color change and flexural properties were determined after 250, 500, 1000, and 2000 h of accelerated weathering. The results indicate that both the colorant and ultraviolet absorber were more effective photostabilizers for wood flour/high‐density polyethylene composites than the hindered amine light stabilizers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2609–2617, 2003     

Solid‐state compaction and drawing of nascent reactor powders of ultra‐high‐molecular‐weight polyethylene

The continuous production of ultra‐high‐molecular‐weight polyethylene (UHMWPE) filaments was studied by the direct roll forming of nascent reactor powders followed by subsequent multistage orientation drawing below their melting points. The UHMWPE reactor powders used in this study were prepared by the polymerization of ethylene in the presence of soluble magnesium complexes, and they exhibited high yield even at low reaction temperatures. The unique, microporous powder morphology contributed to the successful compaction of the UHMWPE powders into coherent tapes below their melting temperatures. The small‐angle X‐ray scattering study of the compacted tapes revealed that folded‐chain crystals with a relatively long‐range order were formed during the compaction and were transformed into extended‐chain crystals as the draw ratio increased. Our results also reveal that the drawability and tensile and thermal properties of the filaments depended sensitively on both the polymerization and solid‐state processing conditions. The fiber drawn to a total draw ratio of 90 in the study had a tensile strength of 2.5 GPa and a tensile modulus of 130 GPa. Finally, the solid‐state drawn UHMWPE filaments were treated with O₂ plasma, and the enhancement of the interfacial shear strength by the surface treatment is presented. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 718–730, 2005     

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     

Rheological behavior and mechanical properties of high‐density polyethylene blends with different molecular weights

The dynamic rheological and mechanical properties of the binary blends of two conventional high‐density polyethylenes [HDPEs; low molecular weight (LMW) and high molecular weight (HMW)] with distinct different weight‐average molecular weights were studied. The rheological results show that the rheological behavior of the blends departed from classical linear viscoelastic theory because of the polydispersity of the HDPEs that we used. Plots of the logarithm of the zero shear viscosity fitted by the Cross model versus the blend composition, Cole–Cole plots, Han curves, and master curves of the storage and loss moduli indicated the LMW/HMW blends of different compositions were miscible in the melt state. The tensile yield strength of the blends generally followed the linear additivity rule, whereas the elongation at break and impact strength were lower than those predicted by linear additivity; this suggested the incompatibility of the blends in solid state. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties of high‐density polyethylene filled with waste crosslinked foam

Crosslinked polyethylene foam is widely used in packaging and as an insulation material. Finely ground waste of such crosslinked foam mesh size 7 or particle size less than 2815 μm is used as a filler in high‐density polyethylene (HDPE) of two different grades (7.5 and 21 MFI). Mechanical, thermal, and morphological properties of filled composites is studied experimentally. Waste foam powder concentration was varied up to 40% by weight basis. Impact strength of base HDPE increased by a factor of six. The overall changes in mechanical properties are similar to the crosslinking effect. It is believed that waste foam particles act as a point of entanglement with different chains of polyethylene. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 110–114, 2004     

Effect of stabilization on creep crack growth in high‐density polyethylene

Polyolefins, particularly polyethylene, are known to fail via crack initiation and crack propagation when exposed to multiaxial long‐term static stresses at elevated temperatures. Using concepts of linear elastic fracture mechanics, this article describes and discusses the effects of stabilization on the kinetics of creep crack growth (CCG) in high‐density polyethylene (PE‐HD) and the failure micromechanisms involved. As for the influence of stabilization, six PE‐HD formulations (two polymer types, each with three stabilizer systems) were investigated. CCG initiation times and CCG rates were determined at 60 and 80°C in distilled water as functions of the crack tip stress field characterized by the stress intensity factor. Although no influence of the stabilizer type was found in either polymer type for CCG initiation times and CCG rates at high crack speeds, significant effects of the added stabilizer type and concentration were detected for low CCG rates. The observed phenomena were explained in terms of local aging processes in the immediate vicinity of the crack tip, which were controlled by the presence and content of various stabilizers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3191–3207, 2003     

Time–temperature dependence of the electrical resistivity of high‐density polyethylene/carbon black composites

Several carbon blacks with surface areas from 105 to 1353 m²/g were used to produce composites through melt compounding with a high‐density polyethylene matrix. The electrical behavior of the obtained composites was investigated by the measurement of their resistivity as a function of the carbon black content and type at various temperatures and times during isothermal annealing treatments. The percolation threshold markedly decreased as the carbon black surface area increased, reaching a minimum value of 1.8 vol % for the carbon black with a surface area of 1353 m²/g. The resistivity passed through a maximum as the test temperature increased. Moreover, the analysis of the experimental data evidenced that the host high‐density polyethylene matrix and the conductive carbon black network rearranged during the isothermal thermal treatments, causing a resistivity decrease. This rearrangement became less and less important as the carbon black surface area increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Modeling the oxidative degradation of ultra‐high‐molecular‐weight polyethylene

Understanding the sequence of reactions that occur in ultra‐high‐molecular‐weight polyethylene (UHMWPE) following ⁶⁰Co γ irradiation has been the focus of numerous experimental studies. In the study reported here, we have incorporated recent experimental findings into a mathematical model for UHMWPE oxidation. Simulation results for shelf aging and accelerated aging are presented. It is shown that very reasonable simulations of shelf‐aging and accelerated‐aging data can be obtained. It is also shown that simulations of shelf aging in reduced oxygen environments predict that the subsurface peaks of ketones will be shifted to the exterior surface. In vivo aging can be simulated if we assume that the oxygen level in the synovial fluid is about one‐eighth that of atmospheric levels. Some reduced irradiation doses are predicted to significantly reduce the ketone formation for shelf‐aging periods of up to 10 years. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 814–826, 2003     

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     

Surface chemistry and mechanical property changes of wood‐flour/high‐density‐polyethylene composites after accelerated weathering

Although wood–plastic composites have become more accepted and used in recent years and are promoted as low‐maintenance, high‐durability building products, they do experience a color change and a loss in mechanical properties with accelerated weathering. In this study, we attempted to characterize the modulus‐of‐elasticity (MOE) loss of photostabilized high‐density polyethylene (HDPE) and composites of wood flour and high‐density polyethylene (WF/HDPE) with accelerated weathering. We then examined how weathering changed the surface chemistry of the composites and looked at whether or not the surface changes were related to the MOE loss. By examining surface chemistry changes, we hoped to begin to understand what caused the weathering changes. The materials were left unstabilized or were stabilized with either an ultraviolet absorber or pigment. After 1000 and 2000 h of accelerated weathering, the samples were tested for MOE loss. Fourier transform infrared (FTIR) spectroscopy was employed to monitor carbonyl and vinyl group formation at the surface. Changes in the HDPE crystallinity were also determined with FTIR techniques. It was determined that structural changes in the samples (carbonyl group formation, terminal vinyl group formation, and crystallinity changes) could not be reliably used to predict changes in MOE with a simple linear relationship. This indicated that the effects of crosslinking, chain scission, and crystallinity changes due to ultraviolet exposure and interfacial degradation due to moisture exposure were interrelated factors for the weathering of HDPE and WF/HDPE composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2263–2273, 2004     

Nonisothermal bulk crystallization of high‐density polyethylene via a modified depolarized light microscopy technique: Further analysis

The quiescent nonisothermal bulk crystallization kinetics of high‐density polyethylene was investigated with a modified depolarized light microscopy technique, which allowed for studies at average cooling rates of approximately 5–2500 °C min^?1. All of the samples crystallized at a pseudoisothermal temperature (i.e., the plateau or crystallization temperature), despite the nonisothermal nature of the cooling conditions. The rate of the crystallization process increased monotonically with increasing the cooling rate and decreasing the crystallization temperature. Moreover, the apparent crystallinity content was a certain decreasing function with the cooling rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1009–1022, 2002     

Mechanical and thermal properties of high‐density polyethylene toughened with glass beads

Glass beads were used to improve the mechanical and thermal properties of high‐density polyethylene (HDPE). HDPE/glass‐bead blends were prepared in a Brabender‐like apparatus, and this was followed by press molding. Static tensile measurements showed that the modulus of the HDPE/glass‐bead blends increased considerably with increasing glass‐bead content, whereas the yield stress remained roughly unchanged at first and then decreased slowly with increasing glass‐bead content. Izod impact tests at room temperature revealed that the impact strength changed very slowly with increasing glass‐bead content up to a critical value; thereafter, it increased sharply with increasing glass‐bead content. That is, the Izod impact strength of the blends underwent a sharp transition with increasing glass‐bead content. It was calculated that the critical interparticle distance for the HDPE/glass‐bead blends at room temperature (25°C) was 2.5 μm. Scanning electron microscopy observations indicated that the high impact strength of the HDPE/glass‐bead blends resulted from the deformation of the HDPE matrix. Dynamic mechanical analyses and thermogravimetric measurements implied that the heat resistance and heat stability of the blends tended to increase considerably with increasing glass‐bead content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2102–2107, 2003     

Thermal and mechanical properties of linear low‐density polyethylene/low‐density polyethylene/wax ternary blends

The thermal and mechanical properties of uncrosslinked three‐component blends of linear low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and a hard, paraffinic Fischer–Tropsch wax were investigated. A decrease in the total crystallinity with an increase in both LDPE and wax contents was observed. It was also observed that experimental enthalpy values of LLDPE in the blends were generally higher than the theoretically expected values, whereas in the case of LDPE the theoretically expected values were higher than the experimental values. In the presence of higher wax content there was a good correlation between experimental and theoretically expected enthalpy values. The DSC results showed changes in peak temperature of melting, as well as peak width, with changing blend composition. Most of these changes are explained in terms of the preferred cocrystallization of wax with LLDPE. Young's modulus, yield stress, and stress at break decreased with increasing LDPE content, whereas elongation at yield increased. This is in line with the decreasing crystallinity and increasing amorphous content expected with increasing LDPE content. Deviations from this behavior for samples containing 10% wax and relatively low LDPE contents are explained in terms of lower tie chain fractions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1748–1755, 2005     

Study of the effect of branch content of octene‐based linear low‐density polyethylene on its melt miscibility with high‐density polyethylene by inverse gas chromatography

Inverse gas chromatography was used to measure Flory–Huggins interaction parameters (χ₂₃) for five binary blends consisting of high‐density polyethylene (HDPE) and octene‐based linear low‐density polyethylene (LLDPE) with different compositions at four elevated temperatures. The branch content of the LLDPE used in each pair of the blends ranged from 2 to 87 branches per 1000 backbone carbons. To obtain solvent‐independent χ₂₃, the data analysis approach recently proposed by Zhao and Choi (Polymer 2001, 42, 1075) was used. The results indicate that the higher the branch content of LLDPE, the higher the measured χ₂₃, signifying that HDPE/LLDPE blends with low branch content LLDPEs are relatively more miscible than those with high branch contents. In particular, when the branch content of LLDPE is higher than 50 branches per 1000 backbone carbons, phase separation may occur. This result is in good agreement with other researchers' results obtained from different techniques. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1927–1931, 2004