Correlations between processing parameters,morphology, and properties of blown films of linear low‐density polyethylene/low‐density polyethylene blends. I. Crystalline biaxial orientation by IR and mechanical properties

The change of the processing parameters of a blown film operation alters the mechanical and optical properties of the films. This work studied the influence of some of these parameters on the properties of blown films made of blends of linear low‐density polyethylene (LLDPE) and LDPE. Correlations between the crystalline biaxial orientations of these films and the mechanical properties were found. The crystalline biaxial orientation was measured by IR following the Krishnaswamy approach. The a axis of the unit cell was oriented along the machine direction (MD) at all LDPE concentrations, and it was not affected by the blow‐up ratio (BUR). In contrast, the b axis changed its orientation from orthogonal to MD to along the transverse direction (TD), and it was affected by the BUR. Finally, the c axis changed its orientation from equiplanar between the MD and TD to along the thickness of the film, and it was influenced by the BUR. The decrease of the tensile mechanical properties along the MD with the increase in the amount of LDPE in the blends was attributed to the tilting of the c axis toward the film thickness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3161–3167, 2006     

Correlation between different microstructural parameters and tensile modulus of various polyethylene blown films

The objective in this study is to establish a model for the prediction of tensile properties using various types of polyethylene films (LLDPE, HDPE, and LDPE). A series of blown films were produced by varying three process parameters: take‐up ratio, blow‐up ratio, and frost line height. The tensile properties of the resulting films were investigated in relation to their microstructural characteristics. The microstructural parameters were determined by differential scanning calorimetry, wide angle X‐ray diffraction (WAXD) pole figures, SAXS (small angle X‐ray diffraction), and birefringence measurements. The orientation parameters of the films were measured by WAXD and birefringence. They were determined for both crystalline and amorphous phases. The crystalline content, lamellar thickness, and crystal sizes were obtained from DSC and WAXD. The SAXS technique was used to find the average length of the crystalline and amorphous layers. A model for the tensile modulus is proposed and correlated to some structural parameters including crystallinity, orientation factors for crystalline c‐axis and amorphous phase, lamellar thickness, crystal size, the average length of the crystal layer, and long spacing period. The measured modulus and the calculated one were compared and a reasonable agreement was found between them for all series of films. POLYM. ENG. SCI., 47:1430–1440, 2007. © 2007 Society of Plastics Engineers     

Real‐time Raman spectroscopic measurement of crystallization kinetics and its effect on the morphology and properties of polyolefin blown films

The nonisothermal crystallization half‐time (t_0.5), defined as the time taken for a polymer film to reach half of its equilibrium crystallinity, was estimated from Raman spectroscopic measurements of crystallinity during blown film extrusion of a linear low‐density polyethylene (LLDPE) and an isotactic polypropylene (i‐PP). The crystalline a‐ and c‐axis orientation of LLDPE and i‐PP films, respectively, increased with decreasing crystallization half‐time. The transverse direction tensile modulus and tear strengths for LLDPE films also increased with decreasing half‐time. However, for i‐PP films, only the transverse direction tear strength increased with decreasing t_0.5, while the machine direction properties did not show a significant dependence on half‐time. Our real‐time Raman spectroscopy studies provide experimental evidence to theories proposed in the literature 1 - 3 with regards to the influence of the nonisothermal crystallization process (along the film axis) on the imparted final film structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1740–1747, 2005     

Orientation and crystalline morphology of blow molded polyethylene bottles

A study was carried out of the development of orientation during processing of conventional blow molded bottles made from low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE). The level of molecular orientation was found to be relatively low in all of the polyethylene bottles examined; it increased with increasing inflation pressure and decreasing extrusion temperature. Pole figures for the HDPE bottles indicated a slight a-axis orientation toward the circumferential direction of the bottle. The b-axes, which correspond to the lamellar growth direction, tend to be parallel to the bottle thickness direction. A comparison was made of the structure developed in blow molded bottles and blown films. The results for both films and bottles indicate that crystallization during processing involves both an increase in level of molecular orientation and an increased tendency toward biaxiality. Based on pole figures and small angle X-ray scattering patterns, a morphological model for HDPE blow molded bottles is proposed.     

Biaxial orientation in LLDPE films: Comparison of infrared spectroscopy,X‐ray pole figures,and birefringence techniques

In this study, linear low‐density polyethylene films were produced using different processes (film blowing and biaxial orientation) and processing conditions. The orientation of the films was characterized in terms of their biaxial crystalline, amorphous, and global orientation factors using birefringence, tilted incidence polarized Fourier Transform Infrared Spectroscopy (FTIR), and X‐ray diffraction pole figures. Evaluation of a simplified FTIR procedure without the use of the tilted method for the determination of crystalline orientation factors proposed in the literature is also evaluated and assessed. The results indicate that FTIR overestimate the crystalline orientation factors, particularly for the crystalline a‐axis. Significant discrepancies are also observed for the b‐axis orientation, which may be due to an overlap of the amorphous phase contribution. Those differences are larger for films with low orientation, such as blown films. Amorphous phase orientation from FTIR depends on the band used and is not necessarily in agreement with that determined from the combination of X‐ray and birefringence. The simplified FTIR procedure is proven to be inadequate in the case of linear low‐density polyethylene blown films studied having a random lamellar crystalline morphology. POLYM. ENG. SCI. 46:1182–1189, 2006. © 2006 Society of Plastics Engineers.     

Oriented structure and anisotropy properties of polymer blown films: HDPE, LLDPE and LDPE

Different types of polyethylene blown films (HDPE, LDPE, LLDPE) differ significantly in the ratio between machine and transverse direction tear resistance. In this paper, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) blown films at different draw-down ratios are studied, and the relation between crystalline structure and anisotropy of blown film properties is investigated. The crystalline morphology and orientation of HDPE, LDPE, LLDPE blown films were probed using microscopy and infrared trichroism. Significant differences in crystalline morphology were found: at medium DDR HDPE developed a row-nucleated type morphology without lamellar twisting, LDPE showed rod-like crystalline morphology and turned out to the row-nucleated structure with twisted lamellae at high draw-down ratio (DDR), while a spherulite-like superstructure was observed for LLDPEs at all processing conditions. They also showed quite different orientation characteristics corresponding to different morphologies. The morphologies and orientation structure for LDPE, LLDPE and HDPE are related to the stress applied (DDR) and their relaxations in the flow-induced crystallization process, which determine the amount of fibrillar nuclei available at the time of crystallization and therefore, the final crystalline morphology. These structure differences are shown to translate into different ratios of machine and transverse direction tear and tensile strengths.     

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     

Mechanical properties,stress‐relaxation,and orientation of double bubble biaxially oriented polyethylene films

Biaxially oriented linear low density polyethylene (LLDPE) films were produced using the double bubble process with different machine direction (MD) orientation levels and the same transverse direction (TD) blow‐up ratio. Their mechanical behavior was characterized in terms of the tensile strength and tear resistance. The viscoelastic behavior of oriented films was studied using dynamic‐mechanical thermal analysis (DMTA). The microstructure and orientation were characterized using microscopy, X‐ray diffraction pole figures, and birefringence. The results indicate that MD ultimate tensile strength increases and the TD one decreases with MD stretching ratio. Tear propagation resistance, in general, remained mainly constant in TD and decreased in MD, as the draw ratio was increased. The morphology analyses exhibit a typical biaxial lamellar structure for all samples with different lamellar dimensions. Orientation of c‐axis in crystalline phase, molecular chain in amorphous phase along MD increased with draw ratio. In most crystals, a‐axis was located in the normal direction (ND) and the b‐axis in the ND–TD plane. A good correlation was observed between c‐axis orientation factor and MD mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3545–3553, 2006     

Effect of clay on mechanical and gas barrier properties of blown film LDPE/clay nanocomposites

Low density polyethylene (LDPE)/clay nanocomposites, which can be used in packaging industries, were prepared by melt‐mix organoclay with polymer matrix (LDPE) and compatibilizer, polyethylene grafted maleic anhydride (PEMA). The pristine clay was first modified with alkylammonium salt surfactant, before melt‐mixed in twin screw extruder attached to blown‐film set. D‐spacing of clay and thermal behavior of nanocomposites were characterized by Wide‐Angle X‐ray Diffraction (WAXD) and differential scanning calorimetry (DSC), respectively. WAXD pattern confirmed the increase in PEMA contents exhibited better dispersion of clay in nanocomposites. Moreover, DSC was reported the increased PEMA contents caused the decrease in degree of crystallinity. Mechanical properties of blown film specimens were tested in two directions of tensile tests: in transverse tests (TD tests) and in machine direction tests (MD tests). Tensile modulus and tensile strength at yield were improved when clay contents increased because of the reinforcing behavior of clay on both TD and MD tests. Tensile modulus of 7 wt % of clay in nanocomposite was 100% increasing from neat LDPE in TD tests and 17% increasing in MD tests. However, elongation at yield decreased when increased in clay loading. Oxygen permeability tests of LDPE/clay nanocomposites also decreased by 24% as the clay content increased to 7 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Investigation of processing-structure-properties relationships in polyethylene blown films

Molecular orientation imparted during film fabrication is known to have a major effect on mechanical and thermal properties of both glassy and semicrystalline polymers. A three-variable Box-Behnken designed experiment was used to study the effects of die gap, die land length, and blowup ratio (BUR) on key linear low density polyethylene (LLDPE) blown film properties at constant final film thickness. In addition, differences in molecular orientation in the films were studied using optical birefringence and shrinkage methods. Measured key film properties were correlated to processing conditions and to measured molecular orientation. Die land length had no significant effect on film structure and properties. All LLDPE films exhibited about 70 to 80% shrinkage in the machine direction (MD) but expanded in the cross direction (CD). Most films exhibited negative in-plane birefringence. MD Elmendorf tear was found to be inversely related to drawdown ratio and MD shrinkage, suggesting that MD tear is dependent primarily on amorphous chain extension and hence, amorphous segments orientation for LLDPE blown films. Dart impact strength of the films was shown to be related to MD shrinkage and to the induced surface roughness due to varying die gap. In a separate study, blown films of three high pressure LDPEs were fabricated under nearly identical conditions. No correlation was found between birefringence and shrinkage data on the LDPE blown films.     

Structure and Morphology Development in Films of mLLDPE/LDPE Blends During Blowing

Summary: In this work the analysis of the structure orientation, morphology, relaxation time and optical properties of blown films of mLLDPE, LDPE and their blends were performed by using WAXD, SALS, AFM, DSC and rheological and haze tests. For mLLDPE film, the crystals do not present “a”‐axis orientation along the machine direction; a distinct spherulite like superstructure is seen. The film surface is very rough. The values of bulk and surface haze are higher than LDPE and blends, whereas the relaxation time is lower. For LDPE film the (110) planes are parallel and at same time twisted with respect to the layer of the film with the “a”‐axis well oriented along the machine direction. No spherulite superstructure is observed and the surface of the film is more regular. High values of relaxation time are observed. The surface haze is the predominant contribution to the total haze. For the blend films no clear and distinct spherulite structures are observed. The orientation degree increases with composition never approaching that of LDPE. The surface is very more regular and smooth than that of the pure polymers. The haze values are below the values of pure materials. It was underlined that bulk and surface morphology and orientation degree of the crystalline planes along the machine direction dictate the optical properties of the films. Moreover both orientation and morphology are defined by the PE molecular and melt rheology characteristics, processing conditions and blend composition.

Total, bulk and surface haze of mLLDPE/LDPE blend films as a function of composition.     

Development of nanofibrous morphology in LDPE/LLDPE/PP blends and its effect on mechanical properties of blend films

Nanofibrous morphology has been observed in ternary blends of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and isotactic polypropylene (PP) when these were melt‐extruded via slit die followed by hot stretching. The morphology was dependent on the concentration of the component polymers in ternary blend LDPE/LLDPE/PP. The films were characterized by wide angle X‐ray diffraction (XRD), scanning electron microscopy (SEM), and testing of mechanical properties. The XRD patterns reveal that the β phase of PP is obtained in the as‐stretched nanofibrillar composites, whose concentration decreases with the increase of LLDPE concentration. The presence of PP nanofibrils shows significant nucleation ability for crystallization of LDPE/LLDPE blend. The SEM observations of etched samples show an isotropic blend of LDPE and LLDPE reinforced with more or less randomly distributed and well‐defined nanofibrils of PP, which were generated in situ. The tensile modulus and strength of LDPE/LLDPE/PP blends were significantly enhanced in the machine direction than in the transverse direction with increasing LLDPE concentration. The ultimate elongation increased with increasing LLDPE concentration, and there was a critical LLDPE concentration above which it increased considerably. There was a dramatic increase in the falling dart impact strength for films obtained by blow extrusion of these blends. These impressive mechanical properties of extruded samples can be explained on the basis of the formation of PP nanofibrils with high aspect ratio (at least 10), which imparted reinforcement to the LDPE/LLDPE blend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Orientation and property correlations for LLDPE blown films

The orientation and property correlations of biaxially oriented polyethylene (PE) blown films have been studied. A linear low density polyethylene (LLDPE) (DOWLEX ? 2045A) was used to fabricate films at different conditions with blow up ratio, die gap, and frost line height as the variables. The White‐Spruiell orientation factors of crystal unit cells, amorphous chains, and Herman's orientation factors of lamellae were determined from wide‐angle X‐ray diffraction pole figure, birefringence, and small angle X‐ray scattering (SAXS). A general orientation pattern with the crystal unit cell a‐axis preferentially oriented to MD, b‐axis to TD, lamellae stacking along the MD, and amorphous chains preferentially to the MD has been found for all films in this study. A correlation between the orientation of each element of the morphology hierarchy has been revealed. Key mechanical properties including dart impact and Elmendorf tear strength in both MD and TD have been determined. Good correlation has been found among these properties. Most importantly, these properties have excellent correlation to the orientation. These correlations have been linked to underlying morphology and microdeformation mechanisms. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 898–907, 2006     

LLDPE／LDPE薄膜加工改性剂PPA

以LLDPE/LDPE共混树脂为基料,添加加工改性剂氟弹性体PPA,采用挤出吹塑成型加工薄膜制品。以LLDPE/LDPE质量比为1/2作空白样。按每克试样总量中含500μg PPA的比例添加PPA,当共混物中LLDPE含量为1/3时,挤出机电流下降,薄膜的透光率增加,雾度降低;LLDPE含量为60％时,挤出机电流未变而产量提高,薄膜的透光率和雾度变化不大;继续增加LLDPE比例时,挤出机电流和雾度增加。薄膜的拉伸性能随LLDPE比例增大显著提高,且纵横向的取向度变小。     

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     

Co‐crystallization in ternary polyethylene blends: tie crystal formation and mechanical properties improvement

Understanding the co‐crystallization behavior of ternary polyethylene (PE) blends is a challenging task. Herein, in addition to co‐crystallization behavior, the rheological and mechanical properties of melt compounded high density polyethylene (HDPE)/low density polyethylene (LDPE)/Zeigler ? Natta linear low density polyethylene (ZN‐LLDPE) blends have been studied in detail. The HDPE content of the blends was kept constant at 40 wt% and the LDPE/ZN‐LLDPE ratio was varied from 0.5 to 2. Rheological measurements confirmed the melt miscibility of the entire blends. Study of the crystalline structure of the blends using DSC, wide angle X‐ray scattering, small angle X‐ray scattering and field emission SEM techniques revealed the formation of two distinct co‐crystals in the blends. Fine LDPE/ZN‐LLDPE co‐crystals, named tie crystals, dispersed within the amorphous gallery between the coarse HDPE/ZN‐LLDPE co‐crystals were characterized for the first time in this study. It is shown that the tie crystals strengthen the amorphous gallery and play a major role in the mechanical performance of the blend.© 2016 Society of Chemical Industry     

An investigation of optical clarity and crystalline orientation in polyethylene tubular film

A study of the crystalline orientation, light transmission, and surface roughness of polyethylene tubular film prepared in our laboratories is presented. The present studies were primarily carried out on low-density (LDPE) and linear-low-density (LLDPE) polyethylene films. The optical properties of a few films of high-density polyethylene (HDPE) prepared for a previous study of morphology were characterized for comparison to the LDPE and LLDPE films. Wide angle X-ray diffraction and birefringence were used to characterize orientation. Both the LDPE and LLDPE films exhibited crystalline texture in which the b-axes tended to be perpendicular to the film surface and the a-axes had some tendency to align with the machine direction. The c-axes tended to be concentrated in the plane of the film with nearly equal biaxial orientation with respect to the machine and transverse directions. Little variation in the crystalline orientation was found with changes of process conditions in the range studied. Birefringence results indicate that the amorphous regions developed an orientation in which the chains tend to be normal to the film surface. The majority of light scattering from these films and a series of HDPE films was from the surface and not from the film interior. The transmission coefficient for the surface contribution was found to be a monotonic decreasing function of the standard deviation of the surface height obtained from surface profiles measured by profilometer. The surface asperites were largest for the HDPE and smallest for the LDPE samples. The intensity of both the surface and interior contributions to the scattering increased with increasing frostline height, i.e., a slower cooling rate. As draw-down ratio and blow-up ratio increase the scattering contribution from the film interior decreases but the contribution from the surface increases somewhat. These effects are discussed in terms of the changes in crystalline morphology and surface roughness produced by flow defects generated during extrusion.     

LLDPE/LDPE blends. I. Rheological,thermal, and mechanical properties

Structure and mechanical properties were studied for the binary blends of a linear low density polyethylene (LLDPE) (ethylene‐1‐hexene copolymer; density = 900 kg m⁻³) with narrow short chain branching distribution and a low density polyethylene (LDPE) which is characterized by the long chain branches. It was found by the rheological measurements that the LLDPE and the LDPE are miscible in the molten state. The steady‐state rheological properties of the blends can be predicted using oscillatory shear moduli. Furthermore, the crystallization temperature of LDPE is higher than that of the LLDPE and is found to act as a nucleating agent for the crystallization of the LLDPE. Consequently, the melting temperature, degree of crystallinity, and hardness of the blend increase rapidly with increases in the LDPE content in the blend, even though the amount of the LDPE in the blend is small. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3153–3159, 1999     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

Covulcanization of LLDPE/EMA blends using dicumyl peroxide

The effect of dicumyl peroxide (DCP) content on the gel fraction, mechanical, dynamic mechanical, and thermal properties of linear low‐density polyethylene (LLDPE)/ethylene‐co‐methyl acrylate (EMA) blends were studied. Gel content of the blends increases with increasing DCP content, and EMA is more prone to crosslinking than LLDPE. Wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) were used to study the effect of DCP crosslinking on percent crystallinity and crystalline structure of the blends and individual components. At lower level of DCP loading, crosslinking process does not have significant effect on the crystalline structure of the LLDPE, which was confirmed from the percent crystallinity and lattice distance value. However, at higher DCP content, percent crystallinity decreases significantly. At lower EMA concentration (<50%), percent crystallinity and lattice distance remain unchanged up to 2 wt % of DCP. For EMA contents of more than 50 wt %, increasing DCP content reduces the crystallinity of the blends and increases the lattice distance. The highest level of mechanical and dynamic mechanical properties was observed for 60/40 LLDPE/EMA blends at 2 wt % DCP. Addition of LLDPE‐g‐MA (3 wt %) as a compatibilizer enhances the properties of the vulcanizates. Blends crosslinked with DCP up to 0.3 wt % can easily be reprocessed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011