Morphology,structure, and rheological property of linear low‐density polyethylene grafted with acrylic acid

The chain structure, spherulite morphology, and rheological property of LLDPE‐g‐AA were studied by using electronspray mass spectroscopy, ¹³C–NMR, and rheometer. Experimental evidence proved that AA monomers grafted onto the LLDPE backbone formed multiunit AA branch chains. It was found that AA branch chains could hinder movement of the LLDPE main chain during crystallization. Spherulites of LLDPE became more anomalous because of the presence of AA branch chains. Rheological behavior showed that AA branch chains could act as an inner plasticizer at the temperature range of 170–200°C, which made LLDPE‐g‐AA easy to further process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2538–2544, 2001     

Crystallization of low‐density polyethylene‐ and linear low‐density polyethylene‐rich blends

The crystallization of a series of low‐density polyethylene (LDPE)‐ and linear low‐density polyethylene (LLDPE)‐rich blends was examined using differential scanning calorimetry (DSC). DSC analysis after continuous slow cooling showed a broadening of the LLDPE melt peak and subsequent increase in the area of a second lower‐temperature peak with increasing concentration of LDPE. Melt endotherms following stepwise crystallization (thermal fractionation) detailed the effect of the addition of LDPE to LLDPE, showing a nonlinear broadening in the melting distribution of lamellae, across the temperature range 80–140°C, with increasing concentration of LDPE. An increase in the population of crystallites melting in the region between 110 and 120°C, a region where as a pure component LDPE does not melt, was observed. A decrease in the crystallite population over the temperature range where LDPE exhibits its primary melting peaks (90–110°C) was noted, indicating that a proportion of the lamellae in this temperature range (attributed to either LDPE or LLDPE) were shifted to a higher melt temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1009–1016, 2000     

Effect of blending high‐pressure low‐density polyethylene on the crystallization kinetics of linear low‐density polyethylene

It is well known that the addition of a small amount of high‐pressure low‐density polyethylene (HP‐LDPE) to linear low‐density polyethylene (LLDPE) can improve the optical properties of LLDPE, and LLDPE/HP‐LDPE blend is widely applied to various uses in the field of film. The optical haziness of polyethylene blown films, as a result of surface irregularities, is thought to be as a consequence of the different crystallization mechanisms. However, not much effort has been directed toward understanding the effect of HP‐LDPE blending on the overall crystallization kinetics (k) of LLDPE including nucleation rate (n) and crystal lateral growth rate (v). In this study, we investigated the effect of blending 20% HP‐LDPE on the crystallization kinetics of LLDPE polymerized by Ziegler‐Natta catalyst with comonomer of 1‐butene. Furthermore, by combining depolarized light intensity measurement (DLIM) and small‐angle laser light scattering (SALLS), we have established a methodology to estimate the lateral growth rate at lower crystallization temperatures, in which direct measurement of lateral growth by polarized optical microscopy (POM) is impossible due to the formation of extremely small spherulites. This investigation revealed that HP‐LDPE blending leads to enhanced nucleation rate, reduced crystal lateral growth rate, and a slight increase in the overall crystallization kinetics of pure LLDPE. From the estimated crystal lateral growth rate, it was found that the suppression in v from HP‐LDPE blending is larger at lower temperatures than at higher temperatures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of the compatibilization of linear low‐density polyethylene‐g‐acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low‐density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low‐density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method. For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE‐g‐AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE‐g‐AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE‐g‐AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/LLDPE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE‐g‐AA decreased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1059–1066, 2002; DOI 10.1002/app.10399     

Morphology and rheological properties of compatibilized low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch blends

Morphology and rheological properties of low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch (LDPE/LLDPE/TPS) blends are experimentally investigated and theoretically analyzed using rheological models. Blending of LDPE/LLDPE (70/30 wt/wt) with 5–20 wt % of TPS and 3 wt % of PE‐grafted maleic anhydride (PE‐g‐MA) as a compatibilizer is performed in a twin‐screw extruder. Scanning electron micrographs show a fairly good dispersion of TPS in PE matrices in the presence of PE‐g‐MA. However, as the TPS content increases, the starch particle size increases. X‐ray diffraction patterns exhibit that with increase in TPS content, the intensity of the crystallization peaks slightly decreases and consequently crystal sizes of the blends decrease. The rheological analyses indicate that TPS can increase the elasticity and viscosity of the blends. With increasing the amount of TPS, starch particles interactions intensify and as a result the blend interface become weaker which are confirmed by relaxation time spectra and the prediction results of emulsion Palierne and Gramespacher‐Meissner models. It is demonstrated that there is a better agreement between experimental rheological data and Coran model than the emulsion models. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44719.     

Structure and adhesion properties of linear low‐density polyethylene powders grafted with acrylic acid via ultraviolet light

The structure and adhesion properties of linear low‐density polyethylene (LLDPE) powder grafted with acrylic acid (AA) via ultraviolet light (UV) were studied by Fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), and water contact angle, peel strength, and graft degree measurements. The results show that the chemically inert LLDPE powder can be graft‐copolymerized with AA via this photografting method. The graft degree increases with the ultraviolet irradiation time. The hydrophilicity of the grafted LLDPE powder and the peel strength of high‐density polyethylene (HDPE)/steel joint with the grafted LLDPE powder used as hot‐melt adhesive are improved considerably, as compared to that with the ungrafted LLDPE powder. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2549–2553, 2006     

Thermal fractionation and crystallization enhancement of silane‐grafted water‐crosslinked low‐density polyethylene

Thermal fractionations performed using differential scanning calorimetry (DSC) to characterize the heterogeneities in molecular structures of low‐density polyethylene (LDPE), silane‐grafted LDPE (G‐LDPE), and silane‐grafted water‐crosslinked LDPE with gel fractions of 30 and 70 wt % are reported. In regular DSC analyses, LDPE, G‐LDPE, and the low gel fraction of crosslinked samples (30 wt %) give one broad endothermic peak at ～110 °C, whereas the high gel fraction of crosslinked samples (70 wt %) give overlapped multiple endothermic peaks in a much broader temperature range. After thermally fractionated in the range 60–145 °C, LDPE, G‐LDPE, and the low gel fraction samples give five to six endothermic peaks in the low‐temperature range, whereas the high gel fraction samples give nine peaks, with three additional peaks appearing in the high‐temperature range. These multiple peaks correspond to fractions of different molecular structures, with the additional peaks for the high gel fraction samples corresponding to the fraction of molecular segments with low or no branching. This fraction of molecular segments is increasingly extruded out of the gel region with increasing gel fraction by crosslinking and leads to an enhancement of crystallization of the sample. This crystallization enhancement behavior is also demonstrated by the X‐ray diffraction data and polarized optical micrographs. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 591–599, 2001     

Thermo‐rheological properties and miscibility of linear low‐density polyethylene‐silsesquioxane nanocomposites

The influence of octakis(n‐hexadecyldimethylsiloxy)octasilsesquioxane (hdPOSS) on rheological and thermal properties of linear low‐density polyethylene was investigated. Rheological evaluations realized by two different measuring techniques (rotational and extensional rheometry) allowed to obtain a wide range of information concerning an influence of silsesquioxanes on rheological properties of polymeric matrix. The studies were complemented with Differential Scanning Calorimetry measurements. In order to evaluate the miscibility of thermoplastic matrix and hybrid organic‐inorganic nanosized filler, rheological investigations, Dynamic Mechanical Thermal Analysis and Scanning Electron Microscopy were applied. Simultaneously, based on the rheological and thermal investigations, the mechanism of interactions between polymeric matrix and silsesquioxanes was considered. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42825.     

Effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on thermal properties,morphology, and tensile properties of low‐density polyethylene (LDPE) and corn starch blends

The effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the thermal properties, morphology, and tensile properties of blends of low‐density polyethylene (LDPE) and corn starch were studied with a differential scanning calorimeter (DSC), scanning electron microscope (SEM), and Instron Universal Testing Machine, respectively. Corn starch–LDPE blends with different starch content and with or without the addition of PE‐g‐MA were prepared with a lab‐scale twin‐screw extruder. The crystallization temperature of LDPE–corn starch–PE‐g‐MA blends was similar to that of pure LDPE but higher than that of LDPE–corn starch blends. The interfacial properties between corn starch and LDPE were improved after PE‐g‐MA addition, as evidenced by the structure morphology revealed by SEM. The tensile strength and elongation at break of corn starch–LDPE–PE‐g‐MA blends were greater than those of LDPE–corn starch blends, and their differences became more pronounced at higher starch contents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2904–2911, 2003     

Thermal properties and morphology of recycled poly(ethylene terephthalate)/maleic anhydride grafted linear low‐density polyethylene blends

Properties of recycled Poly(ethylene terephthalate) were greatly improved. Recycled PET was blended with LLDPE‐g‐MA by low‐temperature solid‐state extrusion. Mechanical properties of the blends were affected obviously by the added LLDPE‐g‐MA. Elongation at break reaches 352.8% when the blend contains 10 wt % LLDPE‐g‐MA. Crystallization behavior of PET phase was affected by LLDPE‐g‐MA content. Crystallinity of PET decreased with the increase of LLDPE‐g‐MA content. FTIR testified that maleic anhydride group in LLDPE‐g‐MA reacted with the end hydroxyl groups of PET and PET‐co‐LLDPE‐g‐MA copolymers were in situ synthesized. SEM micrographs display that LLDPE‐g‐MA phase and PET phase are incompatible and the compatibility of the blends can be improved by the forming of PET‐co‐LLDPE‐g‐MA copolymer. LLDPE‐g‐MA content was less, the LLDPE‐g‐MA phase dispersed in PET matrix fine. With the increase of LLDPE‐g‐MA content, the morphology of dispersed LLDPE‐g‐MA phase changed from spherule to cigar bar, then to irregular spherule. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Kinetics of thermal degradation of nanometer calcium carbonate/linear low‐density polyethylene nanocomposites

To improve the thermal properties of linear low‐density polyethylene (LLDPE), the CaCO₃/LLDPE nanocomposites were prepared from nanometer calcium carbonate (nano‐CaCO₃) and LLDPE by melt‐blending method. A series of testing methods such as thermogravimetry analysis (TGA), differential thermogravimetry analysis, Kim‐Park method, and Flynn‐Wall‐Ozawa method were used to characterize the thermal property of CaCO₃/LLDPE nanocomposites. The results showed that the CaCO₃/LLDPE nanocomposites have only one‐stage thermal degradation process. The initial thermal degradation temperature T₀ increasing with nano‐CaDO₃ content, and stability of LLDPE change better. The thermal degradation activation energy (E_a) is different for different nano‐CaCO₃ content. When the mass fraction of nano‐CaCO₃ in nanocomposites is up to 10 wt %, the nanocomposite has the highest thermal degradation E_a, which is higher (28 kJ/mol) than pure LLDPE. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of cross‐linked LLDPE/PP blend (LLDPE‐PP) as compatibilizer on morphology,crystallization behavior and mechanical property of LLDPE/PP blends

Moderate cross‐linked blend (LLDPE‐PP) of linear low‐density polyethylene (LLDPE) and polypropylene (PP) with benzoyl peroxide (BPO) were prepared by the reactive melt mixing in HAAKE mixer. Effect of LLDPE‐PP as compatibilizer on the morphology, crystallization behavior and mechanical properties of LLDPE/PP (87/13) blends were studied using scanning electron microscopy (SEM), polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and mechanical testing machines. The results showed that LLDPE‐PP not only improved the interfacial adhesion between the LLDPE and PP but also acted as selective nucleating agent for crystal modification of PP. In the blends, the sizes of LLDPE and PP spherulites became smaller, and their melting enthalpies reduced in the presence of LLDPE‐PP. Furthermore, the mechanical properties of LLDPE/PP blends were improved with the addition of LLDPE‐PP, and when the concentration of LLDPE‐PP was 2 phr, the ternary blend had the best mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Crystalline morphology at the interface between polyethylene‐grafted glass and polyethylene

Adhesion measurements performed on a polyethylene (PE)‐grafted‐glass interface showed that the structure of the PE free chains (matrix) was an important parameter. The fracture energy was higher for interfaces prepared from a linear matrix, such as high‐density polyethylene (HDPE), than for those from a branched PE [low‐density polyethylene (LDPE)]. Therefore, the microstructure of the grafted PE/PE matrix interface or interphase was investigated as a function of the molar masses of the connectors and the structure (linear or branched) of the free PE matrix chains. As the grafted chains were linear, a cocrystalline structure with free chains of the HDPE matrix was generated. PE connecting chains led to a low capacity for cocrystallization with LDPE. Cocrystallization was studied with blends based on functionalized PE chains and PE matrices. These blends were assumed to be miscible, as substantiated by a single differential scanning calorimetry (DSC) peak. The DSC analyses were confirmed by wide‐angle X‐ray scattering, which revealed a crystalline orientation of the chains in the interphase, that is, in the vicinity of the glass surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 214–229, 2003     

Blend of high‐density polyethylene and a linear low‐density polyethylene with compositional‐invariant mechanical properties

This article presents the tensile properties and morphological characteristics of binary blends of the high‐density polyethylene (HDPE) and a linear low‐density polyethylene (LLDPE). Two constituents were melt blended in a single‐screw extruder. Injection‐molded specimens were evaluated for their mechanical properties by employing a Universal tensile tester and the morphological characteristics evaluated by using a differential scanning calorimeter and X‐ray diffractometer. It is interesting to observe that the mechanical properties remained invariant in the 10–90% LLDPE content. More specifically, the yield and breaking stresses of these blends are around 80% of the corresponding values of HDPE. The yield elongation and elongation‐at‐break are around 65% to corresponding values of HDPE and the modulus is 50% away. Furthermore, the melting endotherms and the crystallization exotherms of these blends are singlet in nature. They cluster around the corresponding thermal traces of HDPE. This singlet characteristic in thermal traces entails cocrystallization between these two constituting components. The clustering of thermal traces of blends near HDPE meant HDPE‐type of crystallites were formed. Being nearly similar crystallites of blends to that of HDPE indicates nearness in mechanical properties are observed. The X‐ray diffraction data also corroborate these observations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2604–2608, 2002     

Hydrogel composites based on linear low‐density polyethylene‐g‐poly (acrylic acid)/Kaolin or halloysite nanotubes

Two series of superabsorbent hydrogel composites were prepared using waste linear low‐density polyethylene, acrylic acid, and two types of clays including kaolin and halloysite nanotube (HNT) through emulsion polymerization. The effects of the clay content on Water absorbency were investigated to obtain a high swelling capacity. The prepared samples were characterized using FTIR, SEM, thermogravimetric analysis, XRD, solid‐state ¹³C Nuclear Magnetic Resonance spectroscopy, and ²⁹Si NMR. SEM characterization of the samples showed that the hydrogel composites have more pores and a higher swelling ratio than the clay‐free hydrogels. The hydrogel composite containing kaolin had higher water absorbency compared to the hydrogel composites with HNT. The swelling behavior of the hydrogel composite was investigated in various saline solutions. The hydrogel composite containing 5 wt % kaolin had the highest water absorbency (760 g/g in distilled water). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40101.     

Experimental estimation of gas‐transport properties of linear low‐density polyethylene membranes by an integral permeation method

In recent years, we have investigated gas‐transport phenomena in coextruded linear low‐density polyethylene (LLDPE) membranes. For the most part, coextruded LLDPE membranes were investigated because of their excellent mechanical properties, which explain their extensive use in the packaging industry. Because of the small thickness of coextruded LLDPE membranes, significant errors can be involved in the determination of the diffusion coefficient of gases in the membranes by the time‐lag method. To obtain more precise transport parameters for LLDPE membranes, we determined the permeability and diffusion coefficients for O₂, CO₂, He, and N₂ from 298 to 348 K by employing an alternative method recently developed. The results indicate that the procedure used in this study for determining the diffusivity of gases in membranes was precise and more efficient than a method based on the evaluation of the time‐lag parameter. With respect to permeability, the coefficients obtained in this work agree satisfactorily with those obtained by the time‐lag method. In general, the permeability and diffusivity results are in satisfactory agreement with the literature values reported for semicrystalline polyethylene membranes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3013–3021, 2001     

Natural weather,soil burial and sea water ageing of low‐density polyethylene: Effect of starch/linear low‐density polyethylene masterbatch

Degradation of the blends of low‐density polyethylene (LDPE) with a starch‐based additive namely, polystarch N was studied under various environmental conditions such as natural weather, soil and sea water in Saudi Arabia. Stress–strain properties and thermal behavior were investigated for the LDPE and LDPE/polystarch N blend having 40% (w/w) of polystarch N. Environmental ageing resulted in the reduction of percentage of elongation and crystallinity for the blend. Rheological studies and scanning electron microscope photomicrographs of the polymer samples retrieved after ageing showed that addition of polystarch N enhanced the degradation of LDPE. This is ascribed to high extent of chain scission and leaching out of starch present in polystarch N, which was corroborated by the results of morphology and Fourier transform infrared spectroscopy analyses. In the case of underground soil ageing, microbes present in the soil consume the starch in the blend, thus accelerating the degradation process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization behavior of glass bead‐filled low‐density polyethylene composites

The effects of the filler content and the filler size on the crystallization and melting behavior of glass bead‐filled low‐density polyethylene (LDPE) composites have been studied by means of a differential scanning calorimeter (DSC). It is found that the values of melting enthalpy (ΔH_c) and degree of crystallinity (x_c) of the composites increase nonlinearly with increasing the volume fraction of glass beads, ϕ_f, when ϕ_f is greater than 5%; the crystallization temperatures (T_c) and the melting temperatures (T_m) of the composites are slightly higher than those of the pure LDPE; the effects of glass bead size on x_c, T_c, and T_m are insignificant at lower filler content; but the x_c for the LDPE filled with smaller glass beads is obviously greater than that of the filled system with bigger ones at higher ϕ_f. It suggests that small particles are more beneficial to increase in crystallinity of the composites than big ones, especially at higher filler content. In addition, the influence of the filler surface pretreated with a silane coupling agent on the crystallization behavior are not too outstanding at lower inclusion concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 687–692, 1999