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     

Correlations between processing parameters,morphology, and properties of blown films of LLDPE/LDPE blends,part 2: Crystalline and amorphous biaxial orientation by WAXD pole figures

The biaxial molecular orientation of blown films made of blends of linear low density polyethylene (LLDPE) with low density polyethylene (LDPE) was characterized by two different methods: complete pole figures obtained by wide angle X‐rays diffraction (WAXD) and polarized infrared spectroscopy (IR) using the Krishnaswamy approach. The molecular orientation of the blends amorphous phase was also evaluated by polarized IR. The crystallinity of the blown films was determined by WAXD. A good correlation between the X‐ray pole figures and the polarized IR results was obtained. At all blends compositions, it was shown that the a‐axis of the polyethylene orthorhombic cell was preferentially oriented along the machine direction, the orientation degree along this direction increasing with the increase of the LDPE amount in the blends. The b‐axis changed its preferential orientation from film thickness in the 100/0 LLDPE/LDPE film to along the transverse direction with increasing LDPE in the blends. The c‐axis changed its orientation from orthogonal to normal direction in the 100/0 LLDPE/LDPE film to along the film thickness with increasing LDPE in the blends. Polarized IR characterization showed a negligible orientation of the amorphous phase. The amount of crystallinity was dependent on blend composition decreasing with the increase of LDPE content in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2760–2767, 2006     

Rice bran‐filled biodegradable low‐density polyethylene films: Development and characterization for packaging applications

Rice bran was incorporated into low‐density polyethylene (LDPE) at different concentrations by compounding in a twin‐screw extruder and blown into films of uniform thickness. The rice bran incorporation influenced physical, mechanical, barrier, optical, thermal properties, and biodegradation of LDPE. The mechanical and optical properties decreased as the percentage of rice bran increased. The effect of rice bran on the morphology of LDPE blends was examined using scanning electron microscopy. Oxygen transmission rate and water vapor transmission rate increased with the increased content of rice bran. Addition of rice bran did not alter the melting temperature (T_m) of the blends; however the thermal stability decreased, while glass transition temperature (T_g) increased. Kinetics of thermal degradation was also investigated and the activation energy for thermal degradation indicated that for up to 10% filler addition, the dispersion and interfacial adhesion of rice bran particles in LDPE was good. Aerobic biodegradation tests using municipal sewage sludge and biodegradation studies using specific microorganism (Streptomyces species) revealed that the films are biodegradable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4514–4522, 2006     

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.     

In situ fibre‐reinforced composite films of poly(lactic acid)/low‐density polyethylene blends: effects of composition on morphology,transport and mechanical properties

This study aimed to investigate the effects of blend composition on packaging‐related properties of poly(lactic acid) (PLA) and low density polyethylene (LDPE) blown films. Blend films with PLA contents of 5–20 wt% were produced and compared. Scanning electron micrographs of cross‐sectional cryofractured surfaces of the blend films revealed that in situ fibre‐reinforced composites were obtained. Viscosity ratio of the polymer components of ca 1 confirmed that fibre formation was favourable for this blend system. PLA microdomains were dispersed throughout the film in forms of long fibres (length‐to‐diameter ratio > 100) and ribbons. The number of fibres and ribbons increased with an increase of PLA content. Critical content of PLA was found to be 20 wt% for effective improvement of both moduli and gas barrier properties. Incorporation of poly[ethylene‐co‐(methyl acrylate)] compatibilizer showed minimal effect on PLA structure. However, it did improve moduli and O₂ barrier properties when sufficient amount (1.5 pph) was used in 10 wt% PLA/LDPE. In short, flow behaviour, ratio of polymer components and degree of compatibility together played intricate roles in the morphology and hence mechanical and transport properties of PLA/LDPE immiscible blends. © 2017 Society of Chemical Industry     

Structure,mechanical, and electrical properties of high‐density polyethylene/multi‐walled carbon nanotube composites processed by compression molding and blown film extrusion

The structure and properties of melt mixed high‐density polyethylene/multi‐walled carbon nanotube (HDPE/MWCNT) composites processed by compression molding and blown film extrusion were investigated to assess the influence of processing route on properties. The addition of MWCNTs leads to a more elastic response during deformations that result in a more uniform thickness distribution in the blown films. Blown film composites exhibit better mechanical properties due to the enhanced orientation and disentanglement of MWCNTs. At a blow up ratio (BUR) of 3 the breaking strength and elongation in the machine direction of the film with 4 wt % MWCNTs are 239% and 1054% higher than those of compression molded (CM) samples. Resistivity of the composite films increases significantly with increasing BURs due to the destruction of conductive pathways. These pathways can be recovered partially using an appropriate annealing process. At 8 wt % MWCNTs, there is a sufficient density of nanotubes to maintain a robust network even at high BURs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42665.     

Photobiodegradation of low‐density polyethylene/banana starch films

The effects of the starch content, photosensitizer content, and compatibilizer on the photobiodegradability of low‐density polyethylene (LDPE) and banana starch polymer blend films were investigated. The compatibilizer and photosensitizer used in the films were PE‐graft‐maleic anhydride (PE‐g‐MA) and benzophenone, respectively. Dried banana starch at 0–20% (w/w) of LDPE, benzophenone at 0–1% (w/w) of LDPE, and PE‐g‐MA at 10% (w/w) of banana starch were added to LDPE. The photodegradation of the blend films was performed with outdoor exposure. The progress of the photodegradation was followed by determining the carbonyl index derived from Fourier transform IR measurements and the changes in tensile properties. Biodegradation of the blend films was investigated by a soil burial test. The biodegradation process was followed by measuring the changes in the physical appearance, weight loss, and tensile properties of the films. The results showed that both photo‐ and biodegradation rates increased with increasing amounts of banana starch, whereas the tensile properties of the films decreased. The blends with higher amounts of benzophenone showed higher rates of photodegradation, although their biodegradation rates were reduced with an increase in benzophenone content. The addition of PE‐g‐MA into polymer blends led to an increase in the tensile properties whereas the photobiodegradation was slightly decreased compared to the films without PE‐g‐MA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2725–2736, 2006     

Low‐density polyethylene/plasticized tapioca starch blends with the low‐density polyethylene functionalized with maleate ester: Mechanical and thermal properties

In this study, the mechanical and thermal properties of low‐density polyethylene (LDPE)/thermoplastic tapioca starch blends were determined with LDPE‐g‐dibutyl maleate as the compatibilizer. Mechanical testing for the evaluation of the impact strength and tensile properties was carried our as per standard ASTM methods. Thermogravimetric analysis and differential scanning calorimetry were also used to assess the thermal degradation of the blends. Scanning electron micrographs were used to analyze fracture and blend morphologies. The results show significant improvement in the mechanical properties due to the addition of the compatibilizer, which effectively linked the two immiscible blend components. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1109–1120, 2006     

Multiple shape memory effects of trans‐1,4‐polyisoprene and low‐density polyethylene blends

A novel series of shape memory blends of trans‐1,4‐polyisoprene (TPI) and low‐density polyethylene (LDPE) were prepared using a simple physical blending method. The mechanical, thermal and shape memory properties of the blends were studied and schemes proposed to explain their dual and triple shape memory behaviors. It was found that the microstructures played an important role in the shape memory process. In TPI/LDPE blends, both the TPI crosslinking network and LDPE crystalline regions could work as fixed domains, while crystalline regions of LDPE or TPI could act as reversible domains. The shape memory behaviors were determined by the components of the fixed and reversible domains. When the blend ratio of TPI/LDPE was 50/50, the blends showed excellent dual and triple shape memory properties with both high shape fixity ratio and shape recovery ratio. © 2017 Society of Chemical Industry     

Molecular,rheological, and crystalline properties of low‐density polyethylene in blown film extrusion

The molecular weight and its distribution, degree of long chain branching and cooling rate strongly influence crystallinity during processing, which in turn determines the processability and the ultimate properties of the blown film. Generally a decrease in the number of branches and molecular weight of the polymer and the cooling rate results in an increase of the crystallinity. Length of the main chain and extent of branching in low‐density polyethylene (LDPE) are also factors that affect melt rheology and film crystallinity. Long chain branched polyethylene is suitable in the blown film process due to its better melt strength for bubble stability. The objective of this article is to describe the effect of molecular properties (e.g. molecular weight and its distribution, degree of long chain branching etc) of LDPE on film crystallinity at different cooling rates of blown film extrusion. Two different grades of LDPE were selected to investigate molecular characteristics, crystallinity, and rheology. The resins were processed in a blown film extrusion pilot plant using four different cooling rates. Molecular, rheological, and crystalline properties of the resins were key parameters considered in this study. POLYM. ENG. SCI., 47:1983–1991, 2007. © 2007 Society of Plastics Engineers     

Effects of the biaxial orientation on the mechanical and optical properties and shrinkage of polyamide 6-66–montmorillonite–nanosilica nanocomposite films

Polyamide 6–66 (PA6-66)–montmorillonite (MMT)–nanosilica (NS) nanocomposite films were fabricated through a cast film process and then biaxially stretched on a laboratory stretcher. Uniaxial or biaxial stretching induced the elongated conformation of MMT and NS. The b axis of the α crystals and the amorphous phase were revealed to align along the machine direction (MD) after stretching, with the uniaxial orientation playing a more significant role. Furthermore, the crystallinity of PA6-66 stretching increased with the stretching ratio. Uniaxial stretching gave rise to a significantly enhanced tensile strength along the MD, whereas it slightly decreased the mechanical properties along the transverse direction (TD). In contrast, the films subjected to biaxial stretching exhibited more balanced mechanical properties. Uniaxial and biaxial stretching led to decreased transmittance and increased haze in the PA6-66–MMT–NS films; this could have been due to the elongated nanostructure of the two nanofillers, which inhibited the transmission and facilitated the scattering of visible light. The thermal shrinkage of the films increased with increasing stretching ratio, and the biaxially oriented films presented nearly equal shrinkage in the MD and TD. The addition of nanofillers decreased the shrinkage attributed to the mobility inhibition of the polymer chains during heating. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47504.     

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     

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.     

Effect of starch on thermal,mechanical, and barrier properties of low density polyethylene film

Low‐density polyethylene (LDPE) with different quantities of starch was compounded using a twin screw extruder and blown into films by a Konar K, blow‐film machine. Mechanical properties, namely percent elongation, tensile, bursting, and tear strength, as well as barrier properties, such as water vapor and oxygen transmission rate, of the filled LDPE film were studied. Thermal properties of the films were studied using DSC and DMA. Master curves at reference temperature of 30°C were obtained using software linked to DMA. Incorporation of 1% starch in LDPE has marginally affected the thermal, barrier, and mechanical properties; however, that of 5% starch filled LDPE has affected the properties to a great extent. The mechanical properties, such as percent elongation, tensile, tear, bursting, and seal strength, decreased by 19.2, 33.6, 3.60, 10.8, and 22.12%, respectively. Similarly, water vapor and oxygen transmission rate increased to 32.5 and 18.3%, respectively. Other physical properties, namely migration and thermal properties, were also affected in 5% starch filled LDPE; however, the film can still be used as packaging material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3355–3364, 2006     

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     

Structure and properties of polypropylene/low‐density polyethylene blends grafted with itaconic acid in the course of reactive extrusion

This study was concerned with the structural features and mechanical properties of polypropylene (PP)/low‐density polyethylene (LDPE) blends, which after compounding were modified by the free‐radical grafting of itaconic acid (IA) to produce [PP/LDPE]‐g‐IA in the course of reactive extrusion. To analyze the structural features of the [PP/LDPE]‐g‐IA systems, differential scanning calorimetry and relaxation spectrometry techniques were used. The data were indicative of the incompatibility of PP and LDPE in the [PP/LDPE]‐g‐IA systems on the level of crystalline phases; however, favorable interactions were observed within the amorphous phases of the polymers. Because of these interactions, the crystallization temperature of PP increased by 5–11°C, and that of LDPE increased by 1.3–2.7°C. The rapprochement of their glass‐transition temperatures was observed. The single β‐relaxation peak for the [PP/LDPE]‐g‐IA systems showed that compatibility on the level of structural units was responsible for β relaxation in the homopolymers used. Variations in the ratios of the polymers in the [PP/LDPE]‐g‐IA systems led to both nonadditive and complex changes in the viscoelastic properties as well as mechanical characteristics for the composites. Additions of up to 5 wt % PP strengthened the [PP/LDPE]‐g‐IA blended systems between the glass‐transition temperatures of LDPE and PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1746–1754, 2006     

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     

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.     

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     

Influence of branching characteristics on thermal and mechanical properties of Ziegler–Natta and metallocene hexene linear low‐density polyethylene blends with low‐density polyethylene

The effect of the branch content (BC) and composition distribution (CD) of linear low‐density polyethylene (LLDPE) on the thermal and mechanical properties of its blends with LDPE were studied. All blends and pure resins were conditioned in a Haake PolyDrive blender at 190°C and in the presence of adequate amounts of antioxidant. Two metallocene LLDPEs (m‐LLDPE) and one Ziegler–Natta (ZN) hexene LLDPE were melt blended with the same LDPE. The effect of the BC was investigated by blending two hexene m‐LLDPEs of similar weight‐average molecular weights and molecular weight distributions but different BCs with the same LDPE. The effect of the CD was studied by using a ZN and an m‐LLDPE with similar weight‐average molecular weights, BCs, and comonomer type. Low‐BC m‐LLDPE blends showed separate crystallization whereas cocrystallization was observed in the high‐BC m‐LLDPE‐rich blends. However, ZN‐LLDPE/LDPE blends showed separate crystallization together with a third population of cocrystals. The influence of the crystallization behavior was reflected in the mechanical properties. The BC influenced the modulus, ultimate tensile strength, and toughness. The addition of a small amount of LDPE to a low‐BC m‐LLDPE resulted in a major improvement in the toughness, whereas the results for the high‐BC pair followed the additivity rule. ZN‐LLDPE blends with LDPE blends were found to be more compatible and exhibited superior mechanical properties compared to m‐LLDPE counterparts with the same weight‐average molecular weight and BC. All mechanical properties of ZN‐LLDPE blends follow the linear rule of mixtures. However, the CD had a stronger influence on the mechanical properties in comparison to the BC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2488–2498, 2005