Effect of diatomite/polyethylene glycol binary processing aids on the rheology of a metallocene linear low‐density polyethylene

Flow performance of metallocene linear low‐density polyethylene (mLLDPE) containing small amounts of polyethylene glycol (PEG) diatomite and diatomite/PEG binary processing aids respectively was investigated. The mLLDPE melt viscosity is increased by the addition of diatomite, but is decreased by addition of PEG or the diatomite/PEG binary processing aids. It was also found that the viscosity reduction of mLLDPE with the addition of diatomite/PEG binary processing aid was significantly greater than that obtained with the addition of only PEG. The flow curves of mLLDPE containing diatomite/PEG binary processing aid show extremely lower value and stronger dependence on shear rate than the others. It is suggested that the rheological improvement of mLLDPE with diatomite/PEG binary processing aids resulted not entirely from the wall slip promoted by PEG; the intrinsic structure may have changed under the application of shear flow. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1546–1552, 2004     

Use of purified and modified bentonites in linear low‐density polyethylene/organoclay/compatibilizer nanocomposites

Polyethylene‐based ternary nanocomposites were prepared with different clay structures, obtained by the modification of purified Resadiye bentonite as the reinforcement, a random terpolymer of ethylene, butyl acrylate, and maleic anhydride with the trade name Lotader3210 as the compatibilizer, and linear low‐density polyethylene (LLDPE) as the polymer matrix in an intensive batch mixer. The quaternary ammonium/phosphonium salts used for the modification of bentonite were dimethyldioctadecyl ammonium (DMDA) chloride (Cl), tetrakisdecyl ammonium (TKA) bromide (Br), and tributylhexadecyl phosphonium (TBHP) Br. The effects of the physical properties and structure of the organoclay on the clay dispersion were studied at different clay contents (2 and 5 wt %) and at a compatibilizer/organoclay ratio of 2.5. The extent of organoclay dispersion was determined by X‐ray diffraction (XRD) and was verified by transmission electron microscopy (TEM), mechanical testing, and rheological analysis. XRD analysis showed that the nanocomposite with the organoclay DMDA contained intercalated silicate layers, as also verified by TEM. The TEM analysis of the nanocomposites with TBHP exhibited intercalated/partially exfoliated clay dispersion. TKA, with a crowded alkyl environment, sheltered and hindered the intercalation of polymer chains through the silicate layers. In comparison to pure LLDPE, nanocomposites with a 33–41% higher Young's modulus, 16–9% higher tensile strength, and 75–144% higher elongation at break were produced with DMDA and TBHP, respectively (at 5 wt % organoclay). The storage modulus increased by 807–1393%, and the dynamic viscosity increased by 196–339% with respect to pure LLDPE at low frequencies for the samples with DMDA and TBHP (at 5 wt % organoclay). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Melt strength of linear low‐density polyethylene/low‐density polyethylene blends

Linear low‐density polyethylenes and low‐density polyethylenes of various compositions were melt‐blended with a batch mixer. The blends were characterized by their melt strengths and other rheological properties. A simple method for measuring melt strength is presented. The melt strength of a blend may vary according to the additive rule or deviate from the additive rule by showing a synergistic or antagonistic effect. This article reports our investigation of the parameters controlling variations of the melt strength of a blend. The reciprocal of the melt strength of a blend correlates well with the reciprocal of the zero‐shear viscosity and the reciprocal of the relaxation time of the melt. An empirical equation relating the maximum increment (or decrement) of the melt strength to the melt indices of the blend components is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1408–1418, 2002     

Synthesis of reactor blend of linear and branched polyethylene using metallocene/Ni‐diimine binary catalyst system in a single reactor

This work reports the synthesis of a series of reactor blends of linear and branched polyethylene materials using a combination of [1,4‐bis(2,6‐diisopropylphenyl) acenaphthene diimine nickel(II) dibromide] ( 1 )/MMAO, known as an active catalyst for the production of branched polyethylene, and [rac‐ethylenebis(indenyl) zirconium dichloride] ( 2 )/MMAO, which is active for the production of linear polyethylene. The polymerization runs were performed at various levels of temperature, pressure, and catalyst 2 molar fractions. At 5°C, there was very low influence of catalyst 2 molar fraction on the overall catalyst activity. However, at 30°C and 50°C, the overall catalyst activity increased linearly with catalyst 2 molar fraction. The same linear dependency was also found for the polymerization reactions carried out at 60°C and 100°C. At various levels of temperature and ethylene pressure, higher melting temperature and crystallinity were observed with an increase in catalyst 2 molar fraction. At 60°C and 100 psig, the DSC thermograms of the polymers produced with 1 / 2 /MMAO exhibited two distinct peaks with melting temperatures closely corresponding to the melting temperatures of the polymers produced with the individual catalysts, 1 /MMAO and 2 /MMAO. The GPCV analysis of all polyethylene samples showed monomodal molecular weight distributions with low polydispersities. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2212–2217, 2005     

Effects of ultrasonic oscillations on processing behavior and mechanical properties of metallocene‐catalyzed linear low‐density polyethylene/low‐density polyethylene blends

The influences of ultrasonic oscillations on rheological behavior and mechanical properties of metallocene‐catalyzed linear low‐density polyethylene (mLLDPE)/low‐density polyethylene (LDPE) blends were investigated. The experimental results showed that the presence of ultrasonic oscillations can increase the extrusion productivity of mLLDPE/LDPE blends and decrease their die pressure and melt viscosity during extrusion. Incorporation of LDPE increases the critical shear rate for sharkskin formation of extrudate, crystallinity, and mechanical properties of mLLDPE. The processing behavior and mechanical properties of mLLDPE/LDPE blends were further improved in the presence of ultrasonic oscillations during extrusion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2522–2527, 2004     

Preparation and characterization of linear low‐density polyethylene/low‐density polyethylene/TiO2 membranes

Because of their special functions, the application of nanoscale powders has recently attracted both industrial and theoretical interest. In this study, nanoscale TiO₂, which exhibited a special UV absorption and consequent antibacterial function, was added to a low‐density polyethylene/linear low‐density polyethylene hybrid by melt compounding to yield functional composite membranes. TiO₂ exhibited an apparent induced nucleation effect on the crystallization of polyethylene, and the size of the crystallites decreased while the number increaed with the introduction of TiO₂; however, the crystallinity of polyethylene changed little. Also, TiO₂ exhibited an ideal dispersion in the membrane with an average size less than 100 nm, and this excellent dispersion provided the membranes extra UV absorption; moreover, the transparency of the membranes was maintained to satisfy common requirements. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 216–221, 2005     

Recycled milk pouch and virgin low‐density polyethylene/linear low‐density polyethylene based coir fiber composites

The viability of the thermomechanical recycling of postconsumer milk pouches [a 50 : 50 low‐density polyethylene/linear low‐density polyethylene (LDPE–LLDPE) blend] and their use as polymeric matrices for coir‐fiber‐reinforced composites were investigated. The mechanical, thermal, morphological, and water absorption properties of recycled milk pouch polymer/coir fiber composites with different treated and untreated fiber contents were evaluated and compared with those of virgin LDPE–LLDPE/coir fiber composites. The water absorption of the composites measured at three different temperatures (25, 45, and 75°C) was found to follow Fickian diffusion. The mechanical properties of the composites significantly deteriorated after water absorption. The recycled polymer/coir fiber composites showed inferior mechanical performances and thermooxidative stability (oxidation induction time and oxidation temperature) in comparison with those observed for virgin polymer/fiber composites. However, a small quantity of a coupling agent (2 wt %) significantly improved all the mechanical, thermal, and moisture‐resistance properties of both types of composites. The overall mechanical performances of the composites containing recycled and virgin polymer matrices were correlated by the phase morphology, as observed with scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Quantitative analysis of cloisite 93A infused into linear low‐density polyethylene and maleated linear low‐density polyethylene in a supercritical carbon dioxide medium

Linear low‐density polyethylene (LLDPE) is a widely used polymer that can benefit from the enhanced barrier, thermal, and mechanical properties offered by nanoclay fillers. However, optimal property enhancement requires complete exfoliation and uniform dispersion, both of which are difficult to achieve with nanoclay fillers. Supercritical carbon dioxide (scCO₂) processing is an inexpensive and environmentally benign method for exfoliating and dispersing clays into polymers. In a scCO₂ medium under controlled environments, the organically modified clay Cloisite 93A was infused into LLDPE and maleated linear low‐density polyethylene (LLDPE‐g‐MA). Upon microscopic inspection, it was evident that clay infusion was achieved near the surface of the polymer pellet, but no clay found its way into the interior of the pellet. In this article, we describe an analytical method for determining the amount of nanoclay infused into a polymer matrix via Fourier transform infrared analysis. Using this method, we determined the weight percentage of Cloisite 93A infused into LLDPE and LLDPE‐g‐MA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of polyethylene using ultrasonic energy with a metallocene catalyst

Ethylene polymer was synthesized by the treatment of a metallocene catalyst Zr(CP)₂Cl₂ solution with ultrasonic energy. Ultrasonic energy irradiation was used to change the polymer structure of the formed polymer. Different ultrasonic energy irradiation times were applied to the metallocene catalyst solution. The ultrasonic energy had an effect on the average molecular weight, molecular weight distribution, and polymer productivity. A lower average molecular weight and a narrower molecular weight distribution were produced with a longer ultrasonic irradiation time. The polymer productivity was almost constant when the metallocene catalyst was treated with ultrasonic energy. Finer polyethylene particles were produced with longer ultrasonic irradiation times. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 756–759, 2006     

The role of polymerizable organophilic clay during preparing polyethylene nanocomposite via filling polymerization

Effect of polymerizable montmorillonites (P‐MMTs) on the morphology of polyethylene/montmorillonites (PE/MMTs) nanocomposites during filling polymerization was studied. The microstructure analysis showed that the P‐MMTs were more exfoliatable than nonpolymerizable MMTs in the preparation of PE/MMTs nanocomposites. By examining the influence of the polymerization condition on the microstructure of the resultant nanocomposites, it was confirmed that the shear force formed by the mechanical stirring was the driving force of the exfoliation dispersion of MMT sheets during the filling polymerization. Comparatively, the shear force on MMT sheets might be increased due to strong interaction between PE chains linked to the surface of P‐MMTs and the solvents molecules, which is the reason that polymerizable clay is more exfoliatable than nonpolymerizable clay. The copolymerization between polymerizable modifier and ethylene was confirmed by NMR measurements. Furthermore, the morphology of the resultant nanocomposites was influenced by the concentration of the dispersed P‐MMTs. The degree of exfoliation of the resultant nanocomposites at a relatively low concentration was higher than that at a high concentration. This is because of the multiscale organization of the organoclay dispersed in the organic medium. High exfoliation degree of MMTs and improved interaction between PE matrix and P‐MMTs in PE/P‐MMTs nanocomposites led to significant improvements in mechanical properties and barrier properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of branch content,comonomer type,and crosshead speed on the mechanical properties of metallocene linear low‐density polyethylenes

The effects of branch content (BC) and comonomer type on the mechanical properties of metallocene linear low‐density polyethylene (m‐LLDPEs) were studied by means of a stress–strain experiment at room temperature. A total of 16 samples with different BCs and comonomer types were used. In addition, the effect of crosshead speed on the mechanical properties of m‐LLDPEs with different BCs was examined. The degree of crystallinity (X_t) of these copolymers was determined by differential scanning calorimetry. In addition, Ziegler–Natta linear low‐density polyethylenes (ZN‐LLDPEs) were also studied for comparison purposes. The increase in BC of m‐LLDPEs decreased X_t and the modulus. However, the ZN‐LLDPEs showed higher small‐strain properties but lower ultimate properties than the m‐LLDPEs with similar weight‐average molecular weights and BCs. In comparison with low‐BC resins, m‐LLDPEs with high BCs exhibited a stronger strain hardening during the stress–strain experiments. Strain hardening was modeled by a modified Avrami equation, and the order of the mechanically induced crystal growth was in the range of 1–2, which suggested athermal nucleation. The crosshead speed was varied in the range 10–500 mm/min. For low‐BC m‐LLDPEs, there existed a narrow crosshead speed window within which the maxima in modulus and ultimate properties were observed. The location of the maxima were independent of BC. The effect of the crosshead speed on the mechanical properties of the m‐LLDPEs was a strong function of BC. However, highly branched m‐LLDPE in this experiment showed a weak dependence on the crosshead speed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5019–5033, 2006     

Morphology‐related packetlike space‐charge behavior in linear low‐density polyethylene doped with Al2O3 nanoparticles

Packetlike space‐charge behavior and the isothermal decay processes of the injected charge in neat linear low‐density polyethylene (LLDPE) and LLDPE doped with Al₂O₃ nanoparticles were investigated by the pressure wave propagation method. The 1‐mm sheet samples, sandwiched by semiconductive electrodes, were submitted to 40 kV/mm of direct current field at various temperatures for 3 h. The charge‐injecting rate and the apparent mobility of packetlike space charge under direct‐current stress were compared among the samples subjected to different blending processes with or without nanoparticles. The slight doping concentration showed a significant influence on the space‐charge dynamics, with a lower injecting rate and apparent mobility for higher doped samples. The isothermal decay processes of the injected charge indicated trap‐modulated features. The phenomena were considered to be related to the changing morphology of the matrix material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonlinear viscoelastic model for the prediction of double yielding in a linear low‐density polyethylene film

Tensile testing and tensile creep experiments for linear low‐density polyethylene in a thin‐film form were examined and analyzed in terms of a nonlinear viscoelastic model. The proposed model, based on two distinct thermally activated rate processes (Eyring models), was proved to describe the double‐yield‐point tensile behavior of the material tested. The required model parameters were evaluated from the corresponding creep‐strain curves, and this revealed the relationship between the main aspects of the inelastic behavior of polymers, that is, the monotonic loading and creep response. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3519–3527, 2004     

Mechanical and antibacterial properties of modified nano‐ZnO/high‐density polyethylene composite films with a low doped content of nano‐ZnO

Nano‐ZnO/high‐density polyethylene (HDPE) composite films were prepared via melt blending and a hot compression‐molding process. The properties, including ultraviolet absorption, mechanical and antibacterial properties of the films, and plasticizing behavior of the composites, were investigated. The results show that the absorbance in the ultraviolet region of the HDPE films was enhanced after the addition of modified nano‐ZnO to the HDPE matrix. Also, we found that improvement in the HDPE films of the tensile strength and elongation at break was achieved by the incorporation of modified ZnO nanoparticles up to 0.5 wt % in contrast with the original nano‐ZnO/HDPE composite films. Antibacterial testing was carried out via plate counting, and the results indicate that the HDPE films doped with modified ZnO nanoparticles showed favorable antibacterial activity, especially for Staphylococcus aureus. However, the low doped content of modified nano‐ZnO in the HDPE matrix made the balance torque of the composites increase slightly. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of linear low‐density polyethylene/sepiolite nanocomposites

Linear low‐density polyethylene (LLDPE)/sepiolite nanocomposites were prepared by melt blending using unmodified and silane‐modified sepiolite. Two methods were used to modify sepiolite: modification before heat mixing (ex situ) and modification during heat mixing (in situ). The X‐ray diffraction results showed that the position of the main peak of sepiolite remained unchanged during modification step. Infrared spectra showed new peaks confirming the development of new bonds in modified sepiolite and nanocomposites. SEM micrographs revealed the presence of sepiolite fibers embedded in polymer matrix. Thermogravimetric analysis showed that nanocomposites exhibited higher onset degradation temperature than LLDPE. In addition, in situ modified sepiolite nanocomposites exhibited higher thermal stability than ex situ modified sepiolite nanocomposites. The ultimate tensile strength and modulus of the nanocomposites were improved; whereas elongation at break was reduced. The higher crystallization temperature of some nanocomposite formulations revealed a heterogeneous nucleation effect of sepiolite. This can be exploited for the shortening of cycle time during processing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of linear low density polyethylene (LLDPE) by in situ copolymerization with novel cobalt and zirconium catalysts

New cobalt catalysts {[2,6‐(CH₃C=NAr)₂C₅H₃N]CoCl₂} (Ar=2‐methyl‐4‐methoxyphenyl, 1 ) and (Ar=2,4‐dimethylphenyl,2) were synthesized and found to exhibit good selectivity for α‐olefins with methylaluminoxane (MAO) as co‐catalyst. With only ethylene as the feed monomer cobalt catalysts 1 or 2 can be coupled with zirconium catalyst Dichloro [rac‐ethylenebis(indenyl)]Zirconium (IV) rac‐EtInd₂ZrCl₂ ( 3 ) to produce linear low density polyethylene by in situ polymerization. Spectra of resulting materials exhibit ethyl, butyl and long‐chain branches in the backbone of polyethylene. The ratio of Co/Zr and Δt, which is defined as the interval between introductions of two catalysts into the reactor, influenced catalytic activity and the resulting materials greatly. Compatibility and complementary behaviour of different catalysts proved to be two most important factors for in situ copolymerization. Copyright © 2003 Society of Chemical Industry     

Statistical and kinetic approaches for linear low‐density polyethylene melting modeling

The aim of this study was to compare different models, either originating from literature or originally proposed in this study, for the interpretation of the melting behavior of polymers. In particular, these models, tested with a linear low‐density polyethylene widely used in rotational molding, are suitable for coupling with energy balances in the study of polymer processing. We obtained the experimental data from differential scanning calorimetry (DSC) dynamic scans, assuming that the endothermic flux was related to the rate of melting of the polymer. The studied models were able to predict the broad melting temperature range typically observed during polymer melting with either a statistical or a kinetic approach. The two different approaches were compared with experimental DSC data. The analysis of model performances with complex thermal programs showed that the statistical approach could provide a more realistic representation of polymer melting. These models were particularly suitable in rotational molding, where the lack of any flow and, hence, of any crystalline orientation leads to a degree of melting determined by the actual temperature of the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 289–295, 2003     

PE/OMMT nanocomposites catalyzed by the OMMT‐intercalated Et[Ind]2ZrCl2 in slurry polymerization: Effects of organic solvent on ethylene polymerization behaviors and the nanocomposite structures

In situ intercalative polymerization for ethylene monomers was carried out to produce PE‐based hybrids through a slurry polymerization method. In this approach, organic solvent for olefin polymerization was found to be one of the most significant factors for the dispersion of the OMMT‐intercalated Et[Ind]₂ZrCl₂ catalysts, which determines that whether olefin monomers polymerize is in a well‐defined confinement environment or not. Understanding the olefin polymerization occurring in between the nanoscale silicate layers of OMMT as well as the corresponding structure of OMMT in an organic polymerization solvent is a critical step toward tailoring and characterizing nanocomposites formed by OMMT in a polyolefin matrix. As we know, the Et[Ind]₂ZrCl₂ catalyst and MAO are both better dissolved in toluene than that in hexane because of the larger polarity of toluene. Thus, in hexane the active sites of the OMMT/Et[Ind]₂ZrCl₂ catalyst exist in the silicate layers of OMMT and the PE chains grow in the middle of them, while in toluene the active specimens are exposed in the gel formed by the OMMT‐intercalated catalyst with MAO, which cause that the PE chains propagated in the mixture liquids. Consequently, when hexane is selected as the polymerization solvent, the formed PE‐based nanocomposites have a good dispersion of OMMT and the nanofiller content (TGA measurement residue at 600°C) is thus higher (>7.0 wt %). However, in toluene, most of the silicate layers of OMMT are agglomerated in the PE matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011