Spherulitic crystallization behavior of linear low‐density polyethylene

In this study the crystallization behavior of linear low‐density polyethylenes (LLDPEs) (ethylene‐α‐olefin copolymers) was studied by polarized light microscopy. A modified Hoffman‐Lauritzen (MHL) expression is proposed whereby the equilibrium melting temperature, T (T), is replaced with the melting temperature of the crystal stem is replaced with the maximum possible stem length, T. It successfully describes the crystalline spherulitic growth kinetics for both homogeneous and heterogeneous LLDPEs. In addition to regimes III and II, another regime (IM) was found in the high crystallization temperature range. Linear growth behavior of crystalline spherulites was observed in regime III, and nonlinear growth behavior was found in regimes II and IM. The basal surface free energy can be estimated from the short chain branching polydispersity (SCBP) for LLDPEs with excluded comonomers. Polym. Eng. Sci. 45:74–83, 2005. © 2004 Society of Plastics Engineers.     

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     

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     

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     

Capillary flow of low‐density polyethylene

The capillary flow of a commercial low‐density polyethylene (LDPE) melt was studied both experimentally and numerically. The excess pressure drop due to entry (Bagley correction), the compressibility, the effect of pressure on viscosity, and the possible slip effects on the capillary data analysis have been examined. Using a series of capillary dies having different diameters, D, and length‐to‐diameter L/D ratios, a full rheological characterization has been carried out, and the experimental data have been fitted both with a viscous model (Carreau‐Yasuda) and a viscoelastic one (the Kaye—Bernstein, Kearsley, Zapas/Papanastasiou, Scriven, Macosko, or K‐BKZ/PSM model). Particular emphasis has been given on the pressure‐dependence of viscosity, with a pressure‐dependent coefficient β_p. For the viscous model, the viscosity is a function of both temperature and pressure. For the viscoelastic K‐BKZ model, the time‐temperature shifting concept has been used for the non‐isothermal calculations, while the time–pressure shifting concept has been used to shift the relaxation moduli for the pressure‐dependence effect. It was found that only the viscoelastic simulations were capable of reproducing the experimental data well, while any viscous modeling always underestimates the pressures, especially at the higher apparent shear rates and L/D ratios. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Degradation of polyethylene during extrusion. II. Degradation of low‐density polyethylene,linear low‐density polyethylene,and high‐density polyethylene in film extrusion

The degradation of different polyethylenes—low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and high‐density polyethylene (HDPE)—with and without antioxidants and at different oxygen concentrations in the polymer granulates, have been studied in extrusion coating processing. The degradation was followed by online rheometry, size exclusion chromatography, surface oxidation index measurements, and gas chromatography–mass spectrometry. The degradations start in the extruder where primary radicals are formed, which are subject to the auto‐oxidation when oxygen is present. In the extruder, crosslinking or chain scissions reactions are dominating at low and high melt temperatures, respectively, for LDPE, and chain scission is overall dominating for the more linear LLDPE and HDPE resins. Additives such as antioxidants react with primary radicals formed in the melt. Degradation taking place in the film between the die orifice, and the quenching point is mainly related to the exposure time to air oxygen. Melt temperatures above 280°C give a dominating surface oxidation, which increases with the exposure time to air between die orifice and quenching too. A number of degradation products were identified—for example, aldehydes and organic acids—which were present in homologous series. The total amount of aldehydes and acids for each number of chain carbon atoms were appeared in the order of C5>C4>C6>C7?C2 for LDPE, C5>C6>C4>C7?C2 for LLDPE, and C5>C6>C7>C4?C2 for HDPE. The total amounts of oxidized compounds presented in the films were related to the processing conditions. Polymer melts exposed to oxygen at the highest temperatures and longest times showed the presence dialdehydes, in addition to the aldehydes and acids. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1525–1537, 2004     

Nonisothermal crystallization kinetics of ethylene–butene copolymer/low‐density polyethylene blends

Nonisothermal crystallization kinetics of the blends of three ethylene–butene copolymers with LDPE was studied using differential scanning calorimetry (DSC) and kinetic parameters such as the Avrami exponent and the kinetic crystallization rate (Z_c) were determined. It was found that the pure components and the blends have similar Avrami exponents, indicating the same crystallization mechanism. However, the crystallization rate of the blends was greatly influenced by LDPE. The Z_c of all the blends first increases with increasing LDPE content in the blends and reaches its maximum, then descends as the LDPE content further increases. The crystallization rate also depends on the short‐chain branching distribution (SCBD) of the ethylene–butene copolymers. The Z_c of the pure component with a broad SCBD is smaller, but its blends have a larger crystallization rate due to losing highly branched fractions after blending with LDPE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 123–129, 2001     

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     

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 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     

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     

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     

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.     

Polyphosphazene/low‐density polyethylene blends: Miscibility and flame‐retardance studies

The effect of poly(dianilinephosphazene) (PDAP) on the processability, thermal behavior, crystallinity, morphology, mechanical properties, and flammability behavior of low‐density polyethylene (LDPE) was studied. Plasticorder traces of PDAP/LDPE blends implied good processability and miscibility. Thermogravimetric analysis showed that PDAP improved the thermal stability of LDPE. X‐ray diffraction results indicated that PDAP was a semicrystalline polymer, and the crystallinity of the blends decreased with increasing PDAP content. A new reflection at 2θ = 23.15° was found in wide‐angle X‐ray diffraction spectra of the blends, indicating that these two components interacted with one another. The scanning electron microscopy microstructures of the blends also supported these findings. Moreover, PDAP substantially enhanced the limited oxygen index and elongation at break of LDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 709–714, 2002     

ESR and FTIR studies on electron beam‐irradiated low‐density polyethylene blends

Low‐density polyethylene (LDPE) composites modified with a resin based on ethylene/methacrylic acid copolymer (surlyn) and/or citric acid were electron beam‐irradiated and investigated by electron spin resonance (ESR) at room temperature. ESR studies were carried out directly after irradiation and after various time intervals up to 72 h postirradiation. The irradiated samples showed the ESR spectrum of seven lines that was assigned to the formation of allyl radical. The nature and yield of the allyl radical of the different LDPE samples were analyzed as a function of time after irradiation. Also, the radical concentration, decay, decay rate, and kinetics of radical decay were evaluated. Fourier transform infrared (FTIR) analysis at a series of different temperatures upon cooling from room temperature to ?175°C and the reverse heating to +125°C was also carried out. The structural changes while cooling and heating of LDPE samples were investigated using FTIR spectrometry. The results showed that cooling of unirradiated LDPE samples to ?175°C results in a decrease of the intensities of IR bands. However, heating the samples from ?175°C up to +125°C led to a consequence increase in the intensities of the IR bands. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3461–3469, 2007     

Nonisothermal crystallization kinetics of linear bimodal–polyethylene (LBPE) and LBPE/low‐density polyethylene blends

Nonisothermal crystallization kinetics of linear bimodal–polyethylene (LBPE) and the blends of LBPE/low‐density polyethylene (LDPE) were studied using DSC at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of LBPE and LBPE/LDPE blends. The theory of Ozawa was also used to analyze the LBPE DSC data. Kinetic parameters such as, for example, the Avrami exponent (n), the kinetic crystallization rate constant (Z_c), the crystallization peak temperature (T_p), and the half‐time of crystallization (t_1/2) were determined at various scanning rates. The appearance of double melting peaks and double crystallization peaks in the heating and cooling DSC curves of LBPE/LDPE blends indicated that LBPE and LDPE could crystallize, respectively. As a result of these studies, the Z_c of LBPE increases with the increase of cooling rates and the T_p of LBPE for LBPE/LDPE blends first increases with increasing LBPE content in the blends and reaches its maximum, then decreases as the LBPE content further increases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2431–2437, 2003     

Melt electrospinning of low‐density polyethylene having a low‐melt flow index

Melt electrospinning is a cheaper, more environmentally friendly, and safer alternative to solution electrospinning. We have designed a novel melt spinning device which incorporates a reverse of the normal polarity, with the capillary grounded and the collector grid at positive potential. The apparatus is much simpler and more economical than conventional equipment because no syringe pump is required. Low‐density polyethylene (LDPE) with a low‐melt flow index of 2 g/10 min, which is not suitable for spinning using current commercial methods, was chosen to highlight the advantages of melt electrospinning in general, and our device in particular. The effects of varying the electrospinning parameters such as temperature, electrostatic field, spinning distance, and capillary inner diameter, have been studied. Although it was found that temperatures higher than normal processing temperatures had to be employed in our electrospinning system to reduce the viscosity of the polymer melt sufficiently, good quality fibers with smooth and even surfaces, most of which had diameters smaller than 15 μm, were electrospun successfully. It was observed that there was an optimum point for the spinning distance (14–15 cm) and the capillary inner diameter (0.4–0.6 mm) to get fine fiber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Non‐isothermal crystallization kinetics and segmental dynamics of high density polyethylene/butyl rubber blends

Non‐isothermal crystallization kinetics and dynamics of polymer blends are important to both theory and applications. In this work, we studied the morphology, crystal structure, non‐isothermal crystallization kinetics and dynamics of high density polyethylene/butyl rubber (HDPE/IIR) blends. The non‐isothermal crystallization kinetics is analyzed by Mo's model and the dynamics behavior is analyzed by a linear method. The results of morphology, non‐isothermal crystallization kinetics and dynamics show that the condensed structure of HDPE/IIR blends has a marked influence on their non‐isothermal crystallization kinetics and segmental dynamics. © 2015 Society of Chemical Industry     

Biodegradability and degrading microbes of low‐density polyethylene

This article is intended to establish a comprehensive interpretation of the noticeable differences in the dynamic mechanical behaviors of polypropylene/talc composites with and without modified interphases. The latter are discussed on the basis of different surface treatments applied to the reinforcement particles. To this end, a series of 75/25 (w/w) polypropylene/talc composites with and without interfacial modifications from the reinforcement side were evaluated by dynamic mechanical analysis. The proven capability of this technique analysis to follow the transitions and structural and morphological changes in organic polymers, which are largely influenced by the degree of compatibility between the components of heterogeneous materials based on polymers, was used in this study to check and discuss the kinds and efficiencies of different physisorption‐ and chemisorption‐based processes carried out on the surface of talc particles. We tackled this study by embracing the different relaxation phenomena taking place in the polymer matrix. To this end, five different temperature intervals were distinguished according to the relaxation phenomena taking place. Finally, a correlation between the parameters on the microscopic scale and others on the macroscopic scale appeared to emerge. Thus, the interfacial effects caused by the modified reinforcements could be determined by observations on either scale. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009