Studies on multilayer film coextrusion I. The rheology of flat film coextrusion

Multilayer flat film coextrusion was studied, both experimentally and theoretically. For the experimental study, a sheet-forming die with a feedblock was designed, and plastic films of three and five layers were coextruded. The die was provided with three pressure transducers in the axial direction in order to determine the pressure gradient in the die, allowing the determination of the reduction in pressure drop when different combinations of two polymer melts were coextruded. Polymers used for coextrusion were: (1) low density polyethylene and ethylene-vinyl acetate; (2) low density-polyethylene and high density polyethylene; (3) low density polyethylene and polystyrene. For the theoretical study, the z-component of the equations of motion for steady fully-developed flow were solved using a power law non-Newtonian model, Comparisons were made between the experimental and the theoretically predicted volumetric flow rates. Predictions of the velocity distributions, shear rate profiles, and shear stress distributions were made as functions of the processing conditions and the rheological properties of the individual polymers concerned.     

Studies on multilayer film coextrusion II. Interfacial instability in flat film coextrusion

An experimental study was carried out to investigate the phenomenon of interfacial instability in multilayer flat-film coextrusion. For the study, a sheet-forming die with a feed block was used to coextrude three-and five-layer flat films. Polymers coextruded were: (a) low-density polyethylene with polystyrene, and (b) high-density polyethylene with polystyrene. It was observed that, for a given polymer system, there is a critical value of wall shear stress at which an irregular (i.e., unstable) interface between the layers sets in, giving rise to a pattern similar to that usually found in a wood panel. Once the instability sets in, the severity of interfacial instability is found to depend on both the total volumetric flow rate (hence wall shear stress) of the combined streams and the ratio of the individual layer thicknesses. An attempt is made to correlate the critical conditions for the onset of interfacial instability in terms of the layer thickness ratio, and the viscosity and elasticity ratios of the two polymers being coextruded.     

Analysis of isothermal two-layer blown film coextrusion

The mechanics of a bicomponent two-layer blown film coextrusion is studied theoretically. As a first step for the modeling of this complex process, we adopt a simple system in which the flow is assumed to be isothermal and the two layers are a Newtonian and an upper-convected Maxwell fluid (UCM), respectively. The two fluids are chosen to investigate the relative influence of viscous and viscoelastic forces on the flow mechanics of the process. For a given total flow rate, blow-up ratio, freeze-line height, and film gage, the radius and the melt thickness profiles of the blown film are determined numerically for various values of the flow rate ratio of the two fluids. When the relaxation time of the UCM layer is small, the flow mechanics including the shape of the bubble (or the radius profile) is not much different from that of a Newtonian single-layer flow. With increasing relaxation time, the viscoelasticity effect of the UCM layer becomes more and more pronounced and eventually dominates the bubble dynamics even though its layer thickness may be smaller than that of the Newtonian layer.     

Studies on blown film extrusion. III. Bubble instability

An experimental study has been carried out to investigate flow instabilities in blown film extrusion. Two types of flow instabilities were observed, depending on whether a bubble was under uniaxial or biaxial stretching. Under biaxial stretching, the phenomenon of a surface wave-type instability was observed, yielding wavy bubble shapes which very much resembled water waves at the free surface. Under uniaxial stretching, another type of instability, frequently referred to as draw resonance, was observed. It was also observed that, once draw resonance occurs, the amplitude and frequency of bubble diameter pulsing increased with stretch ratio. Quantitative information was obtained from a series of motion pictures taken of bubble diameter in both types of flow instability. It was observed further that an increase in extrusion melt temperature enhanced the severity of bubble instability.     

Studies on wire coating extrusion. II. The rheology of wire coating coextrusion

An experimental and theoretical study of wire coating coextrusion through a pressure-type die was carried out. For the experimental study, the wire coating apparatus employed was the same as that described in Part I of this series (14), except for the newly constructed coextrusion die. The die was provided with three melt pressure transducers along the axial direction, which permitted us to determine the pressure gradient in the die. It was found that a reduction in pressure gradient was realized when a lower viscosity polymer was coextruded with a high viscosity polymer. The materials used for the coextrusion were combinations of low-density polyethylene, high-density polyethylene, polystyrene, and two different commercially available thermoplastic rubbers (UniRoyal TPR-1900 and Shell Kraton G 2701). The use of a high shrinking (crystalline) polymer inside a low shrinking (amorphous) polymer was found to give rise to distorted coatings (non-circular cross section of the coated wire). The interface between the coextruded layers was examined under a magnifying lens, and it was found that under certain processing conditions, the interface was highly irregular. Experimental correlations were obtained to explain the onset of an unstable interface in terms of the rheological properties of the individual components being coextruded, and of the processing variables. It was found that interfacial instability occurs when the shear stress and the viscosity ratio (also elasticity ratio) of the two components at the interface exceed certain critical values. For the theoretical study, using a power-law model, the equations of motion were solved numerically to predict the volumetric flow rate as functions of the pressure gradient in the die and the rheological properties of the polymers being coextruded. Solution of the system of equations permitted us to predict the velocity profile and shear stress distributions of two molten polymers inside a pressure-type wire coating coextrusion die. Comparisons were made between the experimental and theoretically predicted volumetric flow rates. The comparison was found to be reasonably good with certain systems. The discrepancy between the experimentally obtained and the theoretically predicted volumetric flow rates was attributed to interface migration and interfacial instability.     

Numerical modeling of multilayer film coextrusion with experimental validation

Computational fluid dynamics (CFD) using a finite volume technique and the volume of fluid method of interface tracking is used to model the production of polyester‐based multilayered films via coextrusion. Experimental methods encompass both overall flow validation and secondary layer thickness validation. The interpretation of frozen die plugs and layer thickness measurements of unstretched cast films using chloroform washing are used for overall flow validation. For secondary layer thickness validation, layer thickness measurements via both white light interferometry and chloroform washing of stretched final film samples are presented. Good agreement between CFD results and both die plug structures and layer thicknesses from chloroform washing of cast film is observed. When investigating final film samples, there is a good agreement between CFD and white light interferometry, based on individual layer thickness calculations. However, the layer thicknesses from chloroform washing of final films are lower than those obtained from both CFD and white light interferometry. This is attributed to partial crystallization of the thinner polymer at the interface after stretching and heating the film. POLYM. ENG. SCI., 55:1829–1842, 2015. © 2014 The Authors. Polymer Engineering & Science published by Wiley Periodicals, Inc. on behalf of Society of Plastics Engineers     

LLDPE‐based mono‐ and multilayer blown films: Property enhancement through coextrusion

In this study we investigated the performance of multilayer coextruded linear low‐density polyethylene (LLDPE) blown films. Five‐layer films were compared with monolayer dry‐blended films, and the effects of layer composition and layout on the end‐use properties of the coextruded films were highlighted. Three different LLDPEs were used: a conventional Ziegler‐Natta LLDPE gas phase butene copolymer, an advanced Ziegler‐Natta LLDPE solution octene copolymer, and a single‐site LLDPE solution octene copolymer. Numerous five‐layer coextruded structures comprising the single‐site resin and the other two Ziegler‐Natta resins were produced. The coextruded structures composed of the LLDPE butene and the single‐site resin yielded improved end‐use properties relative to the monolayer‐blended films. This result was ascribed to the presence of interfacial transcrystalline layers. Also, blends of the single‐site LLDPE and the advanced Ziegler‐Natta LLDPE octene resins within selected layers of coextruded films showed slightly enhanced tear resistance. Finally, it was found that haze was significantly reduced when the outside layers were composed of the single‐site resin. POLYM. ENG. SCI., 45:1222–1230, 2005. © 2005 Society of Plastics Engineers     

Studies on blown film extrusion. I. Experimental determination of elongational viscosity

Blown-film extrusion experiments were carried out to investigate the elongational flow behavior of viscoelastic polymer melts at different melt temperatures. Materials chosen for study were high-density polyethylene, lowdensity polyethylene, and polypropylene. In the study, isothermal blown-film extrusion experiments were carried out in which the molten blown film traveled upward through a heated chamber of about 13 in. in length maintained at the same temperature as the melt. Axial tension was measured at the take-up roller, the axial profiles of bubble diameter were determined by a photographic technique, and, from the samples collected, the variation in the film thickness along the axial direction was found. These measurements were used later to determine the elongational viscosity, using the force balance equations. It was found, in the experiment, that a careful control of the pressure difference across the thin film permitted one to maintain the bubble diameter constant, and, therefore, depending on the choice of the extrusion conditions, either a uniaxial or biaxial elongational flow was made possible. The experimental results show that, depending on the materials, elongation rate, and melt temperature tested, the elongational viscosity may decrease or increase with elongation rate, and may also stay constant independent of elongation rate. It was observed that the data of elongational viscosity obtained under uniaxial stretching in blown film extrusion is consistent with the data of elongational viscosity obtained earlier by use of the melt-spinning operation.     

Studies on blown film extrusion. II. Analysis of the deformation and heat transfer processes

Having investigated the elongational flow behavior of polymer melts (part I of this series), we have carried out both theoretical and experimental studies in order to better understand the deformation and heat transfer processes involved in blown film extrusion. For the experimental study, nonisothermal experiments were carried out, using high-density and low-density polyethylenes. Measurements were taken of the axial tension, bubble diameter, and film thickness at a series of extrusion conditions (i.e., flow rate, pressure difference across the film, and take-up speed). For the theoretical study, an analysis was carried out to simulate the blown-film extrusion process, by setting up the force- and energy-balance equations on the blown bubble moving upward. The approach taken in the theoretical study may be considered as an extension of the earlier work by Pearson and Petrie who considered the isothermal operation of Newtonian fluids. In the present study, However, we have considered the nonisothermal operation of power law fluids, whose rheological parameters were determined by an independent experimental study an described in part I of this series. Four highly nonlinear differential equations were solved numerically with the aid of the CDC 360 digital computer, using the fourth-order Runge-Kutta method. The mathematical model predicts the bubble shape, temperature profile, and film thickness as a function of the distance along the machine axis. Comparison is made of the experimentally observed bubble shapes with the theoretically predicted ones, showing a reasonable agreement.     

Countercurrent cooling of blown film

Presently used methods for the external cooling of blown film involve the use of an air ring located at the base of the bubble that blows air upward along the surface of the bubble. The air is heated as it rises, while the film is cooling and moving in the same direction. This is an example of cocurrent heat exchange, and the result is the accumulation of heated air around the upper portion of the bubble, which interferes with the cooling in this region. While rapid initial cooling is required to maintain bubble stability, we have explored the possibility of using countercurrent cooling for the upper region of the bubble. A standard air ring is mounted at the base of the bubble, and a circular shroud surrounds the bubble above this air ring. All the heated air is collected in an upper chamber surrounding the shroud and is exhausted by means of a secondary blower. The proposed scheme was found to increase heat transfer in the upper regions of the bubble and to permit the ducting of all heated air away from the film line.     

The development of surface texture in blown polypropylene film

The reorganization processes that give rise to surface fibrillation in blown polypropylene film are described in some detail with the aid of numerous photomicrographs. A relationship between stalk surface morphology and degree of surface roughness is noted.     

Two-dimensional multilayer coextrusion flow in a flat coat-hanger die. Part I: Modeling

The multilayer stratified flow of several polymers in a flat coat-hanger die was modeled using a finite element method. The problem was formulated using the lubrication approximation theory. A solution procedure in decoupling pressure and streamlines was developed. This new method is very powerful in comparison with more classical approaches, permitting the solution of flow problems involving a great number of layers in a complex industrial geometry. It allows us to obtain, among other things, pressure field, streamlines, residence times, and the values of the interface positions in the whole die.     

Combined processing of polypropylene film by coextrusion and zone-annealing

In order to improve the mechanical properties of polypropylene film, a new processing combining extrusion and zone-annealing has been applied. It was found that there are suitable conditions for each step in the combined processing. When the coextrusion draw ratio was low, the total draw ratio and modulus could be increased by the zone-annealing subsequently done. The highest modulus was obtained when the film was coextruded at extrusion draw ratio 4 and then zone-annealed at 120°C under 7 kg/mm². The value was 12 GPa in Young's modulus or 17 GPa in dynamic modulus. The peak temperature of α_c dynamic dispersion for the combinedly processed film was 109°C, which is higher by 10°C than that for the as-coextruded film. Four drawing methods were compared in dynamic viscoelasticity. These methods are the coextrusion, zone-drawing/zone-annealing, two-step coextrusion, and the combined processing by coextrusion and zone-annealing. The highest dynamic modulus for each method was arranged in the above order. The combined processing indicated the most effective improvement in mechanical properties, because it is believed that lamellae in the original film were broken by cooperating interaction of shear stress, compression, and tension on coextrusion and then the superstructure with a high crystallinity and a high molecular orientation was formed on zone-annealing.     

Effect of wall slip on blown film thickness distribution

One of the most important materials for blown film is high‐density polyethylene (HDPE) with wide molecular weight distribution. First, we computed a wall stress at the entrance of a spiral groove in a particular die during blown film processing on a particular condition, to which a similar condition is widely utilized in a film works. The computed value is about 170 kPa, while the HDPE melt slips at die wall at stresses above approximately 50 kPa. The stress of 170 kPa is sufficiently large for the slip occurrence of the melt. Then, we investigated the effects of wall slip and melt visosity on film thickness distribution in the circumferential direction; the distribution tends to decrease with decreasing wall slip and melt viscosity. This tendency is explained by considering flow distribution in a spiral mandrel die and polymer melt flow characteristics.     

Studies on structural foam processing I. The rheology of foam extrusion

An experimental study was carried out to investigate the flow behavior of gas-charged molten polymers in foam extrusion. For the study, a rectangular slit die with glass windows was constructed to permit visual observations, from the direction perpendicular to flow, of the dynamic behavior of gas bubbles when a gas-charged molten polymer flows between two parallel planes. Pictures were taken of gas bubbles in the flow channel with the aid of a camera attached to a microscope, and these were later used to determine the position at which gas bubbles start to grow. Using three melt pressure transducers mounted on the short side of the rectangular slot, pressure distributions were measured along the longitudinal centerline of the die. The polymeric materials used were high-density polyethylene and polystyrene, and the chemical blowing agents used were a proprietary hydrazide which generates nitrogen, and sodium bicarbonate which generates carbon dioxide. It was observed that the gas-charged molten polymer shows a curved pressure profile as the melt approaches the die exit, whereas the polymer without a blowing agent shows a linear pressure profile. The visual observations of the bubble growth in the flow channel, together with the pressure measurements, permitted us to determine the bubble inflation pressure, often referred to as the critical pressure for bubble inflation. It was found that the critical pressure decreases with increasing melt extrusion temperature, and increases with increasing blowing agent concentration. It was also found that the bulk viscosity of gas-charged molten polymers decreases with increasing blowing agent concentration and with increasing melt temperature. A general remark is made concerning the precaution one should take when an Instron rheometer is used for determining the bulk viscosity of gas-charged molten polymers.     

Characterization of an amorphous surface layer on blown polyolefin film

This study concerned an amorphous surface layer on blown polyethylene film with a composition different from that of the bulk. The surface layer was characterized by gentle probing with an atomic force microscope. The demonstration of an amorphous layer uniformly covering the surface of a blown Ziegler–Natta‐catalyzed polyethylene (znPE) film reproduced previous reports. Removing the surface layer by solvent washing confirmed the hypothesis that the layer consisted of lower molecular weight, higher branch content fractions. A blown film of znPE blended with up to 30 wt % impact‐modified high‐melt‐strength polypropylene (hmsPP) also exhibited an amorphous surface layer. In thin films, it was advantageous for the mobile, amorphous fractions of ethylene–propylene rubber (EPR) to locate at the surface rather than at the phase interface. The amorphous EPR tended to segregate into pools on the film surface, and this pointed to a substantial difference between the amorphous surface layers on the znPE and hmsPP/znPE blend films. Surface enrichment best described the compositional gradient that resulted from the concentration of lower molecular weight, higher branch content chains at the surface of the znPE film. Surface segregation was more appropriate for the emergence of EPR fractions as a separate phase on the surface of the hmsPP blend film. Films blown from a blend of a Ziegler–Natta‐catalyzed polyethylene and a metallocene‐catalyzed polyethylene (zn/mPE) and its blend with hmsPP reproduced the primary features of surface enrichment and surface segregation. Some differences between the znPE and zn/mPE films were attributed to the metallocene constituent of zn/mPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3625–3635, 2002     

X-ray diffraction orientation studies on blown polyethylene films. III. High-stress crystallization orientation

X-Ray diffraction orientation measurements have been made on a wide range of films blown from three high-density polyethylenes, to determine more precisely the conditions which lead to the high-stress crystallization type of orientation. The most extensive measurements relate to films from Hostalen GM 9955F; the results show that there is a very wide range of orientational behavior. Under very low-stress conditions there is almost pure a-axis orientation; with very high stress there is substantial c-axis orientation, both with reference to the machine direction. Commercial blowing conditions give rather high stress and the a axis is inclined at 60° to 70° to the machine direction in the sheet-normal—machine-direction plane. Calcium stearate, used to improve the surface finish, increases the stress for a given set of machine conditions and, of these, a high draw ratio and a low extrusion temperature are most effective in promoting high-stress crystallization. The less extensive results for an experimental Rigidex grade and Shell LPPE 040 fit into this overall pattern; for a given set of blowing conditions they have lower stress than the Hostalen polymer. Commercial blowing conditions give an a-axis inclination of about 45°.     

Studies on wire coating extrusion. I. The rheology of wire coating extrusion

Wire coating extrusion was studied, both experimentally and theoretically, using a pressure-type die. For the experimental study, a wire coating apparatus of laboratory scale was constructed, consisting of a pay-off device, extruder, cross-head and pressure-type die, cooling trough, and take-up device. The materials used were low- and high-density polyethylenes and thermoplastic rubber. The following measurements were taken during the experiments: (1) the axial pressure profiles in the die, (2) melt flow rate, and (3) take-up speed. The measurements were then used to determine the effect of the rheological properties of the polymers on the performance of the wire coating operation. It was found that a reduction in axial pressure gradient and a reduction in the recoverable elastic strain of a molten polymer at the die exit can be realized as the speed of the wire is increased. For the theoretical study, using a power-law model, the equations of motion were solved numerically to predict the volumetric flow rate as functions of the pressure gradient in the die and the rheological properties of the polymer being extruded. Solution of the system equations permitted us to predict the velocity profile and shear stress distributions of a molten polymer inside a pressure-type wire coating die.     

Orientation of LCP blown film with rotating dies

Liquid crystal polymers (LCPs) have been commercially available for over 10 years, but their use has been limited almost entirely to injection molded parts, totaling only about 7.5 million kg per year. Much larger volume uses of LCP in film, tube, pipe and extruded parts have not been exploited because of uncontrolled orientation in LCP. This paper explains how shear and elongation forces, controlled by rotating extrusion dies, orient LCP film, tube and other extruded parts. Applications to electronic, medical and high barrier packaging markets are discussed.     

Rheological properties of blown film low-density polyethylene resins

Three blown-film-grade low-density-polyethylene (LDPE) resins were studied using different rheological techniques. Eccentric rotating disks (ERD), cone-plate viscometry, capillary rheometry, annular die extrusion, and non-isothermal stretching of a filament were used. The viscoelasticity of the melts was found to play a dominant role in the observed behavior. Extrudate appearance in annular flow, melt strength, and extensibility are affected by melt elasticity. A correlation was found between the maximum draw ratio of a filament stretched under non-isothermal conditions and minimum film thickness.