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.     

Characterisation of injected EPBC plaques using the essential work of fracture (EWF) method

The influence of processing induced morphology, thickness and ethylene content (EC) of different ethylene-propylene block copolymers on fracture properties has been studied using the essential work of fracture (EWF) method. To analyse the influence of EC, four different materials were chosen with 0, 5.5, 7.8, and 8.4% in weight EC. Each material was injected in three different thicknesses (1, 2 and 3 mm). The resulting plaques were tested using the EWF method in both main orientations; the melt flow direction and transverse to melt flow direction. Different fracture behaviours have been observed, some of them preventing the applicability of the EWF method. Polarised light microscopy observations have revealed the existence of a skin/core structure, which is reduced with an increase in thickness and EC.     

An essential work of fracture study of the toughness of thermoset polyester coatings

The fracture toughness of a range of thermoset polyester paints with different cross-link densities has been studied, using the essential work of fracture (EWF) method. The glass transition temperature, T_g, of each of the materials was measured using differential scanning calorimetry, and found to lie between 8 and 46 °C. EWF tests were performed on the paint films at a range of temperatures around the measured glass transition temperature of each material. The essential work of fracture, w_e, at T_g was found to decrease with increasing cross-link density from around 20 kJ/m² at a cross-link density of 0.4 × 10⁻³ mol/cm³ to around 5 kJ/m² for cross-link densities of approximately 1 × 10⁻³ mol/cm³ or higher. A maximum in the essential work of fracture was observed at around T_g when w_e was plotted versus temperature, which could be attributed to the effect of an α-relaxation at a molecular level. The polyesters were found to be visco-elastic, and the applicability of the EWF test to the study of these visco-elastic thermoset materials is discussed.     

Orientation characteristics of LLDPE blown films and their implications on Elmendorf tear performance

The orientation features of several linear low-density polyethylene (LLDPE) blown films were characterized and significant insights into the morphological origin of Elmendorf tear resistance were developed. The orientation features of all the LLDPE blown films investigated were described in terms of the Keller–Machin “row” structure. The machine direction (MD) tear resistance was observed to be higher when the non-crystalline chains were closer to equi-biaxial in the plane of the film. Further, the transverse direction (TD) tear resistance was observed to be high when the crystalline lamellae were minimally curved and oriented closer to the film TD. These results indicated that deformations in the interlamellar region and the stresses borne along the lamellar long axes play important roles in distinguishing the MD and TD tear resistances, respectively, of LLDPE blown films.     

Effects of molecular structure on the essential work of fracture of amorphous copolyesters at various deformation rates

The fracture behavior of amorphous copolyesters with different molecular structure was studied with double edge notched tensile loaded specimens (DENT) using the essential work of fracture (EWF) approach. Various deformation rates ranging from 1 to 1000 mm/min were employed. Amorphous poly(ethylene terephthalate) (aPET) exhibited considerably higher specific essential and non-essential work of fracture than the copolyesters containing either cyclohexylenedimethylene (aPET-C) or neopentyl glycols (aPET-N). At high deformation rates, ductile/brittle fracture transition was observed with aPET-C and aPET-N, while aPET always fractured in ductile mode within the entire deformation rate range. These phenomena were ascribed to the different molecular flexibility and entanglement density of the copolyesters. The specific EWF of the aPET as a function of deformation rate went through a minimum. The initial decrease in toughness was caused by the hampered segmental mobility due to the increased deformation rate. The subsequent increase in toughness was attributed to the adiabatic heating induced temperature rise in the process and plastic zones. Strain-induced crystallization of the aPET was observed at ν=500 and 1000 mm/min, which may also contribute to the increase of the specific EWF.     

The application of the essential work of fracture methodology to the plane strain fracture of ABS 3-point bend specimens

The applicability of the EWF methodology to 3-point bend (SEB) specimens under conditions other than plane stress has been assessed experimentally. Different fracture conditions, pure plane strain and plane strain/plane stress transition, were obtained by varying the specimen thickness and testing temperature (20 and 80 °C). Post-mortem fracture surfaces appeared always completely stress-whitened, indicating ductile fracture. The load-line displacement plots are similar over a well-defined range of ligament lengths for which the application of the EWF methodology was in principle possible. Nevertheless, in experiments conducted at room temperature, crack growth was observed to initiate before maximum load and complete ligament yielding. This behaviour was confirmed through plastic collapse analyses. A critical ligament length was found, over which the total specific work of fracture was dominated by edge effects. Below this critical ligament length, EWF methodology was still applicable and it was possible to extrapolate reliable w_Ie values.     

Plane stress fracture toughness of physically aged plasticized PETG as assessed by the essential work of fracture (EWF) method

The plane stress fracture toughness of amorphous copolyester (PETG) sheets plasticized by various amount of neopentylglycol dibenzoate (NPGDB in 0, 5, 10 and 20 wt%) was studied in as-received (AR) and rejuvenated (RJ) states by adopting the essential work of fracture (EWF) method. EWF tests were performed on deeply double-edge notched tensile loaded (DDEN-T) specimens at various deformation rates (2,10 and 100 mm/min) at room temperature. It was established that physical aging strongly affected the EWF terms. The specific yielding-related EWF increased with increasing deformation rate and decreased with increasing plasticizer content. The specific non-essential work and its necking-related constituent, which changed parallel to each other, remained constant up to 10 wt% NPGDB content and decreased afterwards. The plastic zone in the DDEN-T specimens was formed by cold drawing which is governed by the entanglement structure. This was demonstrated by the shape recovery of the plastic zone in the broken DDEN-T specimens after heating them above the T_g of the related PETG compound.     

Physical properties of polyethylene/silicate nanocomposite blown films

Maleated polyethylene/silicate nanocomposite and maleated polyethylene/SiO₂ blown films were prepared by melt extrusion. The silicate and SiO₂ significantly affected the physical properties of the films. The former films showed higher tensile strength than the latter films. This high reinforcement effect seemed to be attributable to the strong interaction between the matrix and silicate as well as the uniform dispersion of silicate layers in the polymer matrix. The addition of silicate beyond a certain content gave a worse Elmendorf tear strength than SiO₂. The silicate did not increase the falling dart impact strength at all. The worst Elmendorf strength apparently originated from the orientation of anisotropic silicate rather than the orientation of lamellae of the polymer matrix, and the silicate made the films more brittle. The well‐dispersed silicate layers in the polymer matrix gave almost the same optical properties as the pure polymer despite the increase in the silicate content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2131–2136, 2003     

A comprehensive investigation of the origins of surface roughness and haze in polyethylene blown films

In an earlier publication we showed that the optical haze properties of blown and cast polyethylene (PE) films were adversely affected (i.e., haze increased) as a result of enhanced surface roughness caused by the formation of distinct optically anisotropic “spherulitic‐like” superstructures. In this report we have found that for a very wide variety of PE blown films, the total haze percent exhibited a complex parabolic relationship with the logarithm of the recoverable shear strain parameter, γ_∞. At low values of γ_∞, superstructures were developed (as discussed in our previous report) that increased surface roughness and hence total haze. As γ_∞ increased, such superstructures were either significantly diminished in size or altogether absent, giving rise instead to an oriented, row‐nucleated, stacked lamella texture that decreased surface roughness and hence total haze. However, at even higher γ_∞ values, representing highly melt elastic behavior, fine‐scale surface roughness due to high melt elastic instabilities was induced, thereby increasing surface roughness and consequently total haze as well. It was demonstrated in this work that two PE resins could exhibit the same level of total haze as a consequence of two completely different mechanisms or origins. Furthermore, we believe that this is the first time that both very low and very high melt elasticity have been shown as primary causative factors in yielding high haze in PE blown films, albeit for fundamentally very different reasons. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2396–2411, 2002     

Effect of the specimen dimensions and the test speed on the fracture toughness of iPP by the essential work of fracture (EWF) method

The fracture parameters of an isotactic polypropylene are studied by the essential work of fracture method. The influence of the specimen height, width and thickness and the effect of the test speed are investigated. Results show that this method is very useful for studying the plane‐stress fracture of this kind of materials in form of films and sheets. Varying the width (30 to 60 mm) and the test speed (2 to 100 mm/min) has no relevant influence, whereas the results are only length independent in a range from 40 to 100 mm. The influence of the thickness is very high, obtaining an important decrease of the specific essential work as the thickness is increased in a range from 38 to 2500 μm. This result is justified with the fracture surfaces obtained, observed by SEM, in which an evolution of the fracture behavior is seen as a function of thickness (38, 100, 500, 1000, 2500 μm). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 177–187, 1999     

Preparation of HDPE/UHMWPE/MMWPE blends by two-step processing way and properties of blown films

Summary Blends of high density polyethylene (HDPE) and ultra high molecular weight polyethylene (UHMWPE) were prepared by two-step processing way. Middle molecular weight polyethylene (MMWPE) as a fluidity modifier and compatilizer was added into UHMWPE in the first step, and then modified UHMWPE and HDPE were blending extruded to prepare the HDPE/UHMWPE/MMWPE blends used for blown films. The mechanical test of the blown films revealed that when the content of MMWPE in modified UHMWPE was 40wt% and the content of UHMWPE in the blends was 20 wt%, the film had the optimal mechanical properties. The tensile strength and tear strength of the film increased by 50% and 21%, respectively, compared with those of pure HDPE film. Rheological curves indicated that the melt torque and the apparent viscosity of the HDPE/UHMWPE/MMWPE blends made by two-step processing way both greatly reduced than other blends. The results from DSC suggested that the blends by two-step processing way may form more stable and perfect co-crystallization. PLM (polarized light microscopy) and SEM micrographs revealed that two-step processing way can improve the surface morphology of the films and make the dispersion of UHMWPE particles in HDPE increase.     

Effect of annealing on fracture behavior of poly(propylene‐block‐ethylene) using essential work of fracture analysis

The influence of annealing conditions on the fracture behavior of poly(propylene‐block‐ethylene) sheets was investigated by means of the essential work of fracture method, and was complemented by the study of the effect of annealing on crystal structure, using differential scanning calorimetry. It was shown that both the crystal perfection degree and crystallinity could be improved substantially as annealing temperature (Ta) increased, while the prolonged annealing time at 80°C mainly resulted in the improvement of crystallinity. The reasons for an increase in the specific essential work of fracture and a decrease in the specific plastic work item as crystal perfection degree and crystallinity grew are discussed. The displacement to failure of double edge notched tension specimens decreased gradually with increasing T_a, and the double‐plastic zone could be observed in all specimens. In addition, a novel method to aid the accurate measurement of intense stress‐whitening outer plastic zone height by adjustment of illumination conditions is proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3438–3446, 2007     

Effect of processing parameters on essential work of fracture toughness of LLDPE blown films

Blown film process is one of the most attractive processes for producing low‐cost, high‐performance polyolefin films. In this study, mode‐I essential work of fracture (EWF) analysis and Elmendorf tear test were performed on m‐LLDPE films to investigate how different processing conditions influence blown film EWF and tear properties. After the EWF test, the film was carefully characterized, especially within the necked zone. Effects of frost‐line height, draw down ratio, blow‐up ratio, and haze‐zone region on the EWF parameters of the films were determined. Correlation between the EWF parameters and the films' Elmendorf tear properties was also made. The usefulness of the EWF test for investigating ductile polymeric blown films fracture performance is discussed. POLYM. COMPOS., 55:2403–2413, 2015. © 2015 Society of Plastics Engineers     

Effect of raster angle on the fracture properties of additively manufactured ABS via essential work of fracture

The increasing application of additive manufacturing (AM) technology across various sectors has sparked significant interest in characterizing 3D-printed components. An essential aspect of achieving fracture-resistant designs is gaining a comprehensive understanding of the fracture behavior exhibited by these components. While most studies have focused on linear-elastic fracture mechanics (LEFM), there is a lack of comprehensive studies on the post-yield fracture behavior (PYFM) of 3D-printed components. As a result, this study aims to fill this gap by investigating the impact of raster angle, a critical parameter influencing fracture properties and often leading to premature failures, on the fracture properties of fused deposition modeling (FDM) 3D printed acrylonitrile butadiene styrene (ABS) using essential work of fracture (EWF). Outcomes showed that by changing lay-ups from [90]₅ to [0]₅, the value of w_e or elastic work increased by nearly 306%. Further, the maximum and minimum values of the plastic work (βw_p) were for [45/−45/45/−45/45] and [90]₅ lay-ups, in order. By changing lay-ups from [90]₅ to [45/−45/45/−45/45], the value of βw_p increased by approximately 216%. In addition, the fractured surfaces of tested samples are also analyzed to provide insights into the dominant failure mechanisms for different raster angles.     

Fracture characterization of recycled high density polyethylene/nanoclay composites using the essential work of fracture concept

The effect of nanoclay on the plane‐strain fracture behavior of pristine High density polyethylene (HDPE) and recycled HDPE blends was studied using the essential work of fracture (EWF) concept. The failure mode of EWF tested specimens was found to be associated with the specific non‐EWF (β_Bw_p,B). Adding 6‐wt% of nanoclay to pristine HDPE and 2‐wt% to recycle‐blends greatly decreased the β_Bw_p,B values and led to a transition from ductile to brittle failure mode. A fractographic study revealed that the difference in failure modes was caused by the changes in micro and macro morphologies, which could be related with the specific EWF (w_e,B). In the ductile failure, w_e,B is governed by the fibril size; adding nanoclay and recycled HDPE to pristine HDPE decreased the fibril size and subsequently lowered the w_e,B value. In the brittle failure, the w_e,B value was enhanced by creating a rough fracture surface. Adding nanoclay to pristine HDPE, a steadily decrease in w_e,B was measured until 4‐wt% after which the change was insignificant. Conversely, nanoclay content more than 2‐wt% in recycle‐blends greatly decreased the w_e,B value. A transition map was constructed to illustrate the potential failure mode and the associated fracture morphology based on the tested material compositions. POLYM. ENG. SCI., 56:222–232, 2016. © 2015 Society of Plastics Engineers     

Effect of processing conditions on the orientation and properties of polyethylene blown film

The amorphous and crystallite orientation in a number of films produced from characterised grades of high density polyethylene has been examined and some tensile properties measured. The films were produced under commercial production conditions with various blow ratios, freeze line heights and thicknesses. Orientation was assessed using optical and X-ray methods. The relative contributions of the crystallite and amorphous components were calculated for a limited number of the films produced. Amongst the properties measured the ultimate tensile strength and elongation at break appeared to be the most variable. Birefringence was more affected by variation in blow ratio and film thickness than by freeze height changes. Attempts have been made to correlate these variations with crystallite and amorphous orientation as well as the individual behaviour of the polyethylene grades. In carrying out this correlation it became clear that the films could not generally be described by established low or high stress models of crystallite orientation. For these films produced on full-scale commercial equipment it appears that transcrystallisation behaviour is frequently observed, with a tendency towards the low stress model.     

Rheological,mechanical, optical,and transport properties of blown films of polyamide 6/residual monomer/montmorillonite nanocomposites

Exfoliated nanocomposites of polyamide 6 (PA6) with residual monomer and an organically treated montmorillonite (3 and 5 wt %) were produced by twin‐screw extrusion. The composites had their steady state, dynamic, and transient rheological properties measured by parallel‐plates rheometry; their exfoliation level was characterized by wide angle X‐rays diffraction (WAXD) and transmission electron microscopy (TEM). The characterization showed as follows: (i) the nanoclay's lamellas were well dispersed and distributed thru the PA6, (ii) the postpolymerization of the residual monomer produced more branched chains than linear ones in the pure PA6, (iii) the nanoclay's lamellas acted as entanglement points in the nanocomposites, and (iv) the molecular weight of the PA6 in the nanocomposites decreased. Blown films of the nanocomposites were produced by single screw extrusion; the die pressure during the film blowing of the nanocomposites strongly decreased. The tensile mechanical properties of the blown films were also measured. Along the machine direction (MD), the best mechanical properties were obtained with the 5 wt % nanocomposite, whereas along the transverse direction (TD), the 3 wt % nanocomposite had the best behavior. The glass transition temperature (T_g) of the blown films was measured by dynamic mechanical thermal analyses (DMTA). The 5 wt % nanocomposite had the highest T_g of all the films. The optical properties were measured by spectrophotometry; the nanoclay decreased the films' haze, but the level of transmittance was not affected. The water vapor and oxygen permeability rates of the nanocomposites films were found to be lower than in the pure PA6 blown film as a result of a tortuosity effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Observation and understanding of the tear mechanism of polyethylene blown films at variable loading angles

Tear is a key physical property of polyethylene (PE) blown films. There are many variables that affect the overall tear property, such as tear path and plastic deformation wake. In this study, five blown PE films are prepared and tested by the Elmendorf tear test at five sampling angles, i.e. 0 (MD), 30, 45, 60, and 90 (CD) degrees. Statistical analysis is carried out on the tear values and the variation of the tear data is investigated based on the observation of the tear samples. The mechanism of severely curved crack, i.e. J‐tear, is also studied to understand the tear property variation of blown PE films. In addition, the relationship between tear values and tensile toughness in perpendicular direction is investigated to understand the role of a process zone lying in front of a crack tip during tear. POLYM. ENG. SCI., 54:1038–1046, 2014. © 2013 Society of Plastics Engineers     

Morphological considerations on the mechanical properties of blown high-density polyethylene films

Blown films having a broad range of morphologies were prepared from high-density polyethylenes (HDPE) with unimodal and bimodal molecular weight distribution under several processing conditions, and the effect of their morphological features on the dart drop impact resistance, Elmendorf tear strength, and tensile properties of the films has been studied. The organization of lamellar stacks seems to play a critical role on the mechanical properties of the blown HDPE films. The dart drop impact resistance of the blown HDPE films is highly dependent on the presence of the network structure of lamellar stacks and the level of the intraconnectivity and interconnectivity of lamellar stacks. The coherent orientation of lamellar stacks leads to significant anisotropy of tear and tensile properties. © 1997 John Wiley & Sons, Inc.     

Structure and properties of starch/poly(ethylene-co-vinyl alcohol) blown films

Blends of native corn starch and poly(ethylene-co-vinyl alcohol) (EVOH), with starch: EVOH ratios of 1 : 1 (SE-50) and 2 : 1 (SE-67A, SE-67B), were processed into blown films. SE-67A had a higher glycerol and water content and was processed at 5°C higher than was SE-67B. The films were conditioned to various moisture contents by equilibrating at a constant relative humidity and by oven drying at 41°C. Equilibrium moisture content, which ranged from 2 to 11%, increased with increasing starch content at a given relative humidity. Mechanical properties depended strongly on starch and moisture content as well as on processing history. The extension to break of SE-50 was only about one-third that of EVOH, while that of the 2 : 1 blends was even lower. SE-67A exhibited a higher extension to break, lower tensile strength and modulus, and greater moisture sensitivity than those of SE-67B. Differential scanning calorimetry and dynamic mechanical analysis revealed evidence of interactions between starch and EVOH, probably indicative of extensive intermixing but not necessarily miscibility. Scanning electron micrographs of fracture surfaces revealed extensive differences in texture with microcracking in SE-50 and SE-67A. The combination of the analytical results provide a basis for explaining many aspects of the mechanical behavior including the marked difference in properties between SE-67A and SE-67B. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2613–2622, 1997