Optical properties of blown and cast polyethylene films: Surface versus bulk structural considerations

In this article we report on some surprising, and we believe new, findings regarding the factors affecting the optical properties (haze) of polyethylene blown and cast films. A comprehensive investigation of blown and cast films made from conventional Ziegler‐Natta catalyzed linear low density polyethylene (LLDPE) as well as metallocene‐catalyzed LLDPE (mLLDPE) resins was conducted. The large majority of the contribution to the total haze in the blown and cast films was observed to come from the surface roughness of the films, with the bulk (internal) contribution being relatively minor. Using a variety of analysis and characterization methods, including atomic force microscopy, small angle light scattering, and wide angle X‐ray scattering, we determined that the surface roughness in these films was a result of the development of distinct spherulitic‐like superstructures formed during the blown or cast film processing. Furthermore, these superstructures were observed only in the mLLDPE blown films, and not in the LLDPE blown films processed at similar conditions. Analysis of the rheological and molecular characteristics of these various mLLDPE and LLDPE resins revealed that the mLLDPE resins exhibited considerably lower molecular weight, narrower molecular weight distribution, lower zero shear viscosity, and lower melt elasticity compared with the LLDPE resins of similar melt index. These observations support our general finding and primary conclusion from this work that in polyethylene blown and cast films made using typical processing conditions, the optical haze properties are adversely affected because of enhanced surface roughness caused by the formation of spherulitic‐like superstructures in polymer melts that possess fast relaxing and low melt elasticity rheological characteristics. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2845–2864, 2000     

Influence of molecular architecture and melt rheological characteristic on the optical properties of LDPE blown films

A systematic investigation on the origin of the haze of LDPE blown films was conducted, aiming to correlate the film haze with the molecular architecture and melt rheological properties. First of all, the haze measurement indicated that the surface haze, rather than the bulk haze, is the dominating factor for the total haze of the investigated films. No spherulitic crystals or other superstructures were observed for the LDPE blown films, implying that the crystallites formed in the film-blowing process are too small to be responsible for the optical haze. Rheological study revealed that the surface roughness was originated from the irregular flow of LDPE melt during the extrusion process. NMR, GPC and parallel-plate rheology were applied to study the molecular architecture of the LDPE resins. It was found that the LDPE sample with higher haze value exhibits distinctly larger portion of higher molecular weight component, broader molar mass distribution, significantly higher side chain branch density.     

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.     

Formulating of a novel polyolefin hazy film and the origins of haze thereof

A novel and thin polyolefin hazy film with high haze (>75%), low gloss, and high light transmittance was prepared by the blending polyethylene (PE) with polypropylene (PP) rather than the reverse applying measurements which improved clarity, although Chen and Lue et al. (Annual Technical Conference Proceedings of SPE (2004), pp 2117–2121 and 2140–2143) employed blending to reduce haze. This study also presents the low melt flow rate, high density PE1 blending with PP1, and the blending ratio of 50/50 (wt/wt), are the key factors to prepare the novel polyolefin hazy film. The major origin of total haze of the hazy film was explored. It is found that surface haze is the overwhelming majority of total haze, which is opposite to earlier works about the source of total haze of the films prepared from polymer blend. That rough surface textures was the intrinsic source yielding surface haze, and also huge surface roughness degree (Ra) was the reason of the excellent haze properties in the hazy film, was confirmed based on haze measurement, surface topology images and Ra data from haze instrument, optical microscopy, and atomic force microscope, respectively.     

Haze of polyethylene films—effects of material parameters and clarifying agents

Effects of material parameters on the haze of blown films were analyzed. Four linearlow‐density polyethylenes (two metallocene grades and two Ziegler‐Natta grades) were studied in combination with three additives (two sorbitol‐based clarifying agents and a low‐molecular‐weight long‐chain branched polyethylene). One of the sorbitol‐based additives reduced the haze of both the metallocene materials in this study, but did not have any positive effect on the two Ziegler‐Natta materials. The variation in haze among the four base materials was directly related to the root‐mean‐square surface roughness (σ). When considering all 16 material/additive combinations, the link between haze and surface topography was not a simple σ‐haze relationship, but the haze was correlated with the average distance between adjacent surface profile peaks, the average slope, and the power spectral density at high lateral frequencies. Both of the mechanisms referred to in the literature, extrusion‐induced haze and crystallization‐induced haze, were probably active for the films in this study.     

Studies of optical haze and surface morphology of blown polyethylene films using atomic force microscopy

Atomic force microscopy (AFM) has been used to examine the inner and outer surfaces of commercial blown polyethylene films. When this technique has been used, direct-space images of surface lamellae have been obtained, and the surface roughness determined. The haziness of the films has been measured, both in the as-produced state and when coated with suitable oil. Thus, both surface and bulk contributions to the apparent turbidity have been estimated. The aim of this study has been to correlate in turn the haziness, roughness, and surface morphology. Results obtained showed that the haze is related primarily to the surface roughness and can be reduced by lowering the frost line. AFM images unveiled lamellar features that were oriented predominantly in the transverse direction. The observed wide-angle X-ray diffraction (WAXD) intensities were consistent with an a-axis type of orientation.     

Formation of hydrophilic starch coatings on polyethylene films

Thin starch coatings were deposited onto polyethylene (PE) film surfaces when PE films were immersed in 1% jet cooked starch solutions and the hot solutions were allowed to cool. Normal cornstarch, waxy cornstarch, high amylose cornstarch, and solvent‐extracted normal cornstarch (to remove native lipid) were used in these experiments. Amounts of adsorbed starch varied from about 0.03–0.05 mg per cm² of PE, and these starch coatings imparted hydrophilic properties to film surfaces, as evidenced by contact angle measurements. Although starch could be removed by gently rubbing water‐wet PE surfaces, air‐dried coatings were more firmly attached, and did not separate from the PE surface when films were bent or flexed. SEM images of starch‐coated film surfaces showed that starch was deposited as particles less than 1 μm in diameter, and also as aggregates of these submicron particles. Despite the fact that some starch samples contained only very small amounts of amylose and native lipid, surface‐deposited starch in all experiments contained 90–100% amylose; and exhibited the same V_h X‐ray diffraction pattern, indicative of helical inclusion complex formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1781–1788, 2002; DOI 10.1002/app.10589     

TiO2‐kaolin‐PE composite film: A study based on photocatalytic degradation and biodegradation

A novel photodegradable and biodegradable polyethylene (PE) film was prepared through a melt blending technique, where nano‐TiO₂ and common kaolin were used as the photocatalyst and biodegradable promoter showing improved degradable efficiency of the waste PE. The photo‐degradation of the composite film was investigated by weight loss monitoring, attenuated total reflection–fourier transformed infrared spectroscopy (ATR–FTIR), and scanning electron microscopy. The aerobic biodegradation of the residue films after photodegradation was investigated by analysis of evolved carbon dioxide of films in aquatic test systems according to the international standards (ISO 14852, 1999). The results showed that the weight loss of as‐prepared photo‐ and biodegradable composite film reached 26.8% after 240 h of UV light irradiation. The big cavities formed not only on the film surface but also inside the bulk film, together with the chalking phenomenon taking place. The biodegradation results revealed that the addition of kaolin enhanced the degradation of UV‐light treated TiO₂‐PE films. The prepared PE based composite films showed promising application as novel photo‐biodegradable environment‐harmless materials. In addition, a degradation mechanism for this composite film was also discussed. POLYM. COMPOS., 37:2353–2359, 2016. © 2015 Society of Plastics Engineers     

Crystallization and orientation development in fiber and film processing of polypropylenes of varying stereoregular form and tacticity

We investigated the crystallization and orientation development in melt spinning and tubular blown film extrusion of several different types of polypropylenes, including conventional high tacticity isotactic polypropylenes (iPP) and metallocene catalyst low tacticity iPPs and syndiotactic polypropylenes (sPP). The fiber and film samples were characterized by wide‐angle X‐ray diffraction (WAXD), birefringence and differential scanning calorimetry (DSC). In melt spinning iPP, we found that the mesomorphic structure of iPP is more readily formed in lower tacticity fibers, and significant amounts of hexagonal β‐form crystals are found in low tacticity iPP fibers spun at high draw‐down ratios. Low tacticity iPP fibers exhibited a significant decrease in the crystalline chain‐axis orientation at high draw‐down ratios, resulting from increased epitaxially branched lamellae. Melt‐spun sPP fibers exhibit Form I helical structure at low spinning speeds and Form III zigzag all trans structure at high spinning speeds. We found that the level of spinline stress is the governing factor for this structural change. Melt‐spun sPP fibers exhibit much higher chain‐axis (c‐axis) orientation factors (f_c) and lower birefringence than iPP fibers spun at the same spinline stresses. In tubular blown sPP films, the a‐axis of Form I unit cell tends to orient perpendicular to the film surface, while the b‐axis of monoclinic α unit cell does so in iPP blown films.     

The Rheology of Wetting By Polymer Melts

Theoretically, the rate of capillary penetration of a polymer melt into a slit, a model for a surface irregularity, has been shown to depend on γcosθ/η) where γ refers to the surface tension of the liquid, η its viscosity and θ a time-dependent contact angle. Analytical expressions relating the depth of penetration with time have been experimentally verified by observations of the penetration of molten polyethylene and poly-(ethylene-vinyl acetate) into aluminum channels. Values of η, calculated from the observed data, agree closely with independent determinations of this material parameter. A theoretical treatment has also been developed which describes the velocity of spreading of a liquid drop over a flat surface. Flow equations for the flow of free films were adapted for this purpose. The spreading velocity is predicted to depend on the product of three factors (1) a scaling factor, (γ/η1R_o), where R_o is the initial radius of curvature, (2) cosθ_∞. (l-cosθ/cosθ_∞) where θ_∞ refers to the equilibrium value of θ, and (3) geometric terms. After demonstrating that a drop of molten polymer may be treated as a spherical cap, the predicted dependence of spreading rate on drop size, cosθ_∞ (nature of the substrate) and the scaling factor was experimentally verified. Some discrepancies noted at long times and high temperatures are discussed.     

Polyethylene grafted maleic anhydride to improve wettability of liquid on polyethylene films

Blends of linear low density polyethylene (LLDPE) and LLDPE grafted maleic anhydride (LLDPE‐g‐MA) were prepared by melt mixing. The surface of cast films with different contents and types of maleated PE were characterized through contact angle and wetting tension measurements, as well as attenuated total reflection IR spectroscopy. The tensile properties and light transmission of extruded films, as well as the performance of these films compared with commercial “antifog” films, for greenhouses were determined. The carbonyl polar groups on the surface of LLDPE/LLDPE‐g‐MA blends increased, and the equilibrium contact angles of water and dimethylformamide decreased when the content of maleated PE increased. Films made with these blends showed a noticeable reduction in water drop formation as the MA content was increased and when using LLDPE‐g‐MA of lower molecular weight. The light transmission through these films under condensation was improved when using increased contents of MA, which promotes better wetting of the water on the surface. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1802–1808, 2001     

Evaluation of biocompatibility of the surface of polyethylene films modified with various water soluble polymers using Ar plasma‐post polymerization technique

Surface modified polyethylene (g‐PE), PMPC‐g‐PE, PGEMA‐g‐PE, PNIPAAm‐g‐PE and PHPMA‐g‐PE films with the water soluble polymers such as poly[2‐(methacryloyloxy)ethyl phosphorylcholine] (PMPC), poly[2‐(glucosyloxy)ethyl methacrylate] (PGEMA), poly(N‐isopropylacrylamide) (PNIPAAm) and poly[N‐(2‐hydroxypropyl) methacrylamide] (PHPMA) were prepared by graft copolymerization using an Ar plasma‐post polymerization technique. The surface of the g‐PE films was characterized by means of X‐ray photoelectron spectroscopy and the grafting percentage of PMPC, PNIPAAm and PHPMA was found to be 5.31, 2.83, and 3.40% for the corresponding g‐PE film. Biocompatibility of the g‐PE films was evaluated by the adsorption of serum proteins and the Michaelis constant (K_m) for the enzymatic reaction of thrombin with synthetic substrate S‐2238 in the presence of g‐PE film. The biocompatibility of water soluble polymers such as PMPC, polyoxyethylene (POE), PGEMA, PNIPAAm and PHPMA was also evaluated by the same enzymatic reaction of thrombin with S‐2238 in their polymer solutions. The K_m values in the presence of water soluble polymers was found to decrease in the order PMPC > POE > PGEMA > PNIPAAm > PHPMA. As a conclusion, PMPC‐g‐PE film exhibited the most biocompatibility among g‐PE films because its surface adsorbed less protein than those of the untreated PE and other g‐PE films and it showed the largest K_m for the enzymatic reaction.     

Blown film extrusion of poly(lactic acid) without melt strength enhancers

Processing strategies were developed to manufacture poly(lactic acid) (PLA) blown films without melt strength enhancers (MSEs). The effects of processing temperature on PLA's melt properties (shear and elongational viscosities), PLA grades, and other processing conditions [ratio of take‐up roller to extruder's rotational screw speeds or processing speed ratio (PSR) and internal air pressures] on film's blow‐up ratio were examined. Experimental results indicate that extrusion‐blown amorphous and semicrystalline PLA films can be successfully manufactured without MSEs by controlling melt rheology through processing temperature and other extrusion processing conditions. PLA processed at lower extrusion temperature had higher melt viscosities, which favored the formation of stable films depending on the PSR and internal air pressure used. Inappropriate control of PSR and internal air pressure led to unstable films with various processing defects such as melt sag, bubble dancing, or draw resonance, irrespective of the lower extrusion processing temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45212.     

Effects in Surface Free Energy of Sputter-Deposited VNx Films

Vanadium nitride (VN _x ) thin films have attracted much attention for semiconductor integrated circuit (IC) packaging molding dies, and forming tools due to their excellent hardness and, thermal stability. VN _x thin films with VN_0.45, VN_0.83, VN_1.22, VN_1.73, VN_2.06 were prepared using a radio frequency (RF) sputter technique. The experimental results showed that the contact angle at 20°C increases with increasing nitrogen content of the VN _x films, to 101.4° corresponding to VN_1.73 and then decreased. In addition, the contact angles decreased with increasing surface temperature, because an increase of the surface temperature disrupts the hydrogen bonds between water and the films and the water gradually vaporizes. The total surface fee energy (SFE) at 20°C decreased with nitrogen content of the VN _x films to 29.8 mN/m (VN_1.73) and then increased. This is because a larger contact angle means weaker hydrogen bonding which results in a lower SFE. The polar SFE component had the same trend as the total SFE, but the dispersive SFE component had the opposite trend. The polar SFE component is also lower than the dispersive SFE component. This is because hydrogen bonds are polar. The total SFE, dispersive SFE and polar SFE of the VN _x films all decrease with increasing surface temperature. This is because with increasing temperature, water evaporates from the surface, disrupting hydrogen bonds and hence increasing surface entropy. The film roughness has an obvious effect on the SFE and there is tendency for the SFE to increase with increasing film surface roughness. As a result the SFE and surface roughness can be expressed in terms of a simple ratio function.     

Effects of clay dispersion on the foam morphology of LDPE/clay nanocomposites

Intercalated and exfoliated low‐density polyethylene (LDPE)/clay nanocomposites were prepared by melt blending with and without a maleated polyethylene (PE‐g‐MAn) as the coupling agent. Their morphology was examined and confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of clay content and dispersion on the cell morphology of nanocomposite foams during extrusion foaming process were also thoroughly investigated, especially with a small amount of clay of 0.05–1.0 wt%. This research shows the optimum clay content for achieving microcellular PE/clay nanocomposite foams blown with supercritical CO₂. It is found that < 0.1 wt% of clay addition can produce the microcellular foam structure with a cell density of > 10⁹ cells/cm³ and a cell size of ～ 5 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2129–2134, 2007     

Evaluation of the tear properties of polyethylene blown films using the essential work of fracture concept

In the case of very thin materials such as blown films, the applied stress state in front of the crack tip is normally a plane stress condition, and the deformation around the crack tip due to the remote stress is very large. However, current standard test methods for quantifying the fracture toughness of thin films, such as the Elmendorf tear test, cannot explain or represent the tear characteristics accurately. The common way of interpreting the test results from the Elmendorf tear test is to develop an empirical correlation and then compare the average values. In this paper, essential work of fracture (EWF) tests for five commercial polyethylene (PE) blown films have been conducted, and the fundamentals of their tear properties based on fracture mechanics have been studied. The results from the EWF test are interpreted based on two important parameters, i.e., the essential work of fracture (W_e) and the non-essential work of fracture (W_p). Further, the relationship between these parameters and the current standard Elmendorf tear test is shown.     

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     

Mathematical and computational modeling of heat transfer and deformation in film blowing process

The blown‐film extrusion process was investigated both experimentally and theoretically. In experimental study, nonisothermal experiments were conducted using low‐density polyethylene. Rheological parameters were studied, considering the polymer melt as a power law fluid in nonisothermal conditions. Axial tension, bubble diameter, and film thickness at a variety of film extrusion conditions, that is, different flow rate, pressure difference across the film, and take‐up speeds were measured. In theoretical study, an analysis was employed to simulate the blown‐film extrusion process by setting up the force‐ and energy‐balance equations on the film bubble moving upward. Four nonlinear complex differential equations were integrated numerically, using an iterative backward shooting method and the fifth‐order Runge‐kutta technique. The program written, based on a mathematical model, predicts the bubble shape, temperature profile, and film thickness as a function of the distance along the machine axis. Furthermore, the model evaluates the elongational viscosity of LDPE in biaxial tension in terms of distance from die axis and take‐up speed. In this simulation, the total stress components in machine and the transverse directions were computed from the die exit up to the freeze line, the knowledge of which is necessary for evaluation of the elastic memory build up in heat‐shrinkable films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2115–2123, 2002     

Controlling the surface wettability of poly(sulfone) films by UV‐assisted treatment: benefits in relation to plasma treatment

Hydrophilic and superhydrophilic surfaces of poly(sulfone) (PSU) thin films were prepared by UV irradiation in the presence of O₂ or acrylic acid (AA) vapor. Treated surfaces were then investigated by water contact angle measurements, Fourier transformed IR spectroscopy in attenuated total reflectance mode (FTIR‐ATR), X‐ray photoelectron spectroscopy (XPS), near‐edge X‐ray absorption fine structure (NEXAFS) and AFM. Water contact angle values of treated PSU films using either O₂ or AA vapor as the reactive atmosphere reached about 6° after more than 120 min of irradiation. FTIR‐ATR, XPS and NEXAFS analysis showed incorporation of oxygenated groups onto the surface that led to its hydrophilic characteristics. In addition, when AA vapor was used as the reactive atmosphere, a photopolymerization process of poly(acrylic acid) onto the surface of the PSU was observed. AFM analysis showed a very low level of roughness after the treatments. A comparison of UV‐assisted surface modifications of PSU films with traditional plasma treatments showed excellent qualitative agreement between the two techniques. Our results show that UV‐assisted treatments in the presence of AA vapor or O₂ are efficient ways of controlling the surface wettability and functionalities grafted on the surface of PSU films. This treatment can be considered as a permanent dry grafting method that resists aging and uses a simple experimental setup. © 2012 Society of Chemical Industry     

Room temperature sputtering deposition of high-haze Ga-doped ZnO transparent conductive thin films on self-textured bio-based poly(ethylene 2, 5-furandicarboxylate) substrates

In this work, bio-based poly(ethylene 2,5-furandicarboxylate) (PEF) films were prepared by drop-casting method and used as substrates for depositing Ga-doped ZnO (GZO) transparent conductive thin films. Results showed that the 300-nm GZO thin films deposited on PEF substrates exhibited haze values above 65% at 550 nm without post-treatment. The high haze value was because of the large surface roughness of PEF films. The total optical transmittance and electrical properties of GZO thin films on PEF were comparable to those of GZO thin films on PET. The present study provides a simple way for the sputtering deposition of high-haze transparent conductive thin films on flexible substrates.