Measurement and modelling of the film casting process: 2. Temperature distribution along draw direction

In the case film process a polymer melt is extruded through a slit die, stretched in air and cooled on a chill roll. During the path in air the melt cools and a reduction of both thickness and width takes place; obviously, temperature distribution, thickness and width reductions are function of draw ratio and stretching distance.Temperature distribution along the draw direction was measured as function of flow rate during film casting experiments performed with an iPP resin. A non-contacting method of measurement, based on a narrow-band IR pyrometer, was adopted.A good qualitative agreement is shown between experimental temperature data and predictions of a model accounting of radiation emissivity dependence upon film thickness. Differences are consistent with discrepancies of film thickness evolution along draw direction, indeed the model slightly over predicts both film thickness reduction and, parallel, temperature decrease along the draw direction.     

Effect of uniaxial stretching on the structural and dielectric properties of melt cast Nylon 11 films

In this study, the effect of processing on the structural and dielectric properties of Nylon 11 melt cast film was studied. Capacitor grade thin films were cast using a film extruder and stretched uniaxially and real-time mechano-optical data were acquired at temperatures ranging from solid state all the way to partially molten state. These studies were supplemented with offline WAXS, SAXS, and DSC to develop a complete understanding of processing induced structural changes and their relation to dielectric properties. When stretched in the solid-state, preferential crystalline and amorphous chain orientation levels increased as a function of strain while the long spacing remained constant due to lamellar slippage. Processing in the partially molten state led to the formation of new lamellae with larger long spacings. It was also observed that the dielectric properties of Nylon 11 were strongly dependent on the crystallinity and crystal phase, with higher crystallinity of the α′ phase giving higher electrical breakdown strength. When films were stretched to 3X solid and partially molten states, together with crystallinity, the breakdown strength is increased, while the dielectric constant and loss decrease. Since crystalline regions are stiffer, they form effective barriers to hot carriers, retarding the electric breakdown.     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of semicrystalline polymers

A novel approach to predict anisotropic shrinkage of semicrystalline polymers in injection moldings was proposed using flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from amorphous and crystalline contributions. The amorphous contribution was based on the frozen‐in and intrinsic amorphous birefringence, whereas the crystalline contribution was based on the crystalline orientation function, which was determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with temperature‐ and crystallinity‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs on polypropylene of various molecular weights were carried out by varying the packing time, flow rate, melt temperature, and mold temperature. The anisotropic shrinkage of the moldings was measured. Comparison of the experimental and simulated results indicated a good predictive capability of the proposed approach. POLYM. ENG. SCI., 46:712–728, 2006. © 2006 Society of Plastics Engineers     

The thermomechanical environment and the microstructure of an injection moulded polypropylene copolymer

The microstructure of an injection moulding propylene copolymer is varied through systematic changes on the processing conditions (melt and mould temperatures and injection flow rate). The skin-core structure was characterised by several experimental techniques. The skin ratio was assessed by polarised light microscopy. The morphological features of the skin layer (level of crystalline phase orientation, degree of crystallinity, β-phase content and double texture) were evaluated by wide-angle X-ray diffraction. The core features (degree of crystallinity and lamella thickness) were assessed by differential scanning calorimetry. The thermomechanical environment imposed during processing was characterised by mould filling simulations. The thermal and shear stress levels were evaluated by a cooling index and the wall shear stress. The results show the relationship between these and the microstructural features. The microstructure development is then interpreted considering the constrictions imposed during processing, being assessed by thermomechanical indices. Furthermore, the direct connections between these indices and the degree of crystallinity of the core and the level of orientation of the skin are verified.     

涤纶FDY熔融纺丝模拟研究

基于熔融纺丝动力学模型及理论,建立了涤纶全拉伸丝(FDY)熔融纺丝模型。在已知工艺参数条件下,模拟了丝条温度、速度、取向和结晶在纺程上的变化。结果表明:在纺程200,700,800,1 300,1 500 cm处,模拟值与实测值误差均小于10%,该模型可用于实际生产的模拟;根据模型,获得了热辊温度及速度对涤纶FDY的取向及结晶的定量关系;随着GR1速度降低和GR1温度提高,纤维的取向度和结晶度升高;随着GR2速度增加和GR2温度提高,纤维的取向度越大,结晶度越高。     

Flow‐induced crystallization during isotactic polypropylene film casting

In this work, a previously proposed model for flow‐induced crystallization of polymers was slightly modified and successfully applied in describing film casting experiments performed working with isotactic polypropylene. In this process, the melt experiences flowing conditions, during the cooling. The effect of flow on crystallization kinetics was accounted for by the entropic increase of melting point because of the orientation effect of the flow. The orientation of the macromolecules was described by means of a nonlinear dumbbell model, and the entropic shift was calculated on the basis of the rubber elasticity theory. The flow‐induced crystallization model, using reasonable values for relaxation time, was proved able to quantitatively predict the enhancement effect of the flow as an increase of spherulite nuclei density and growth rate, in presence of low‐level flows (Deborah number <1–10). The morphology changes due to higher level of flow (fine grained, fibrils, shish‐kebab) were not predicted by this approach. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Preparation and Characterization of high‐strength poly(ether ether ketone) films

High‐strength poly(ether ether ketone) (PEEK) films were prepared through melt extrusion followed by stretching. The tensile strength, orientation, and crystallization behaviors of PEEK films were characterized by universal testing machine, thermomechanical analysis, wide‐angle X‐ray diffraction, and differential scanning calorimetry. The results indicated that the tensile strength of PEEK films mainly depended on the stretching rate (ν), stretching temperature (T), and stretching ratio (λ_L). Moreover, the tensile strength of the stretched PEEK film (333 MPa) was almost four times higher than that of the unstretched PEEK film (87 MPa) under an optimized condition. This is attributed to a synergistic effect of orientation and crystallization in the stretching process, and the influence of orientation is stronger than that of the crystallization on the improvement of the tensile strength of PEEK films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40172.     

Amorphous orientation and its relationship to processing stages of blended polypropylene/polyethylene fibers

Changes in the molecular orientation, melting behavior, and percent crystallinity of the individual components in a fibrous blend of isotactic polypropylene (iPP) and high-density polyethylene (HDPE) that occur during the melt extrusion process were examined using wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The crystalline orientation of each component was found using Wilchinsky's treatment of uniaxial orientation and described by the Hermans–Stein orientation parameter. The amorphous orientation was found by resolving the X-ray diffraction pattern in steps of the azimuthal angle into its iPP and HDPE crystalline and amorphous reflections. The utility of DSC and WAXD analyses to capture the effects of small differences in processing, and the use of these results as fingerprints of a particular manufacturing process were demonstrated. Major increases in the melting temperatures, percent crystallinities, and molecular orientations of the iPP and HDPE components occurred during the main stretching stage of the melt extrusion process. The annealing stage was found to have little to no effect on the melting behavior and molecular orientation of these components. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of cast film fabrication variables on structure development and key stretch film properties

The properties of films produced by the cast or blown film processes can be altered by varying the fabrication parameters. An experimental design is used to determine the effect of cast film fabrication variables on the performance of LLDPE stretch films. A three-variable Box–Behnken designed experiment was conducted to study the effects of air gap, melt temperature, and line speed on the key cast stretch film properties. In addition, the differences in molecular orientation in the films were studied using optical birefringence and shrinkage methods. The key film properties are correlated with the fabrication conditions using a statistical analysis program. The results of this study are explained in terms of web tensile stresses before solidification and the degree of molecular orientation developed in the film due to the stresses. © 1994 John Wiley & Sons, Inc.     

The specification of orientation and its development in polymer processing

A critical review of the specification of orientation and its development in polymer-processing operations is presented. Orientation may in general be specified by orientation distribution functions, but is most conveniently expressed in terms of orientation factors which are second moments of the distribution. The Hermans orientation factor represents polymer-chain orientation for systems with fiber symmetry (uniaxial orientation) and the Hermans-Stein orientation factors express uniaxial orientation for each of the crystallographic axes of crystalline polymers. Biaxial orientation is, however, developed in tubular film extrusion, blowmolding and, indeed, all processing operations other than fiber formation. Orientation factors developed previously by the authors express biaxial orientation in terms of the angles between the machine and transverse directions and the polymer chain axis or crystallographic axes. In flowing polymer melts, the Rheo-Optical Law, which relates birefringence and stress, represents a relationship between polymer-chain orientation and stress. In vitrified polymeric glasses (e.g. polystyrene), the orientation factors are related linearly to the stress field at vitrification. This has been shown experimentally for melt spinning and tubular film extrusion. The results of studies of blowmolding and injection molding are consistent with this. The crystalline orientation factors have also been found to be determined by the stress field at solidification in melt spinning and tubular film extrusion.     

Modeling and simulation of fiber‐reinforced polymer mold‐filling with phase change

A gas‐solid‐liquid three‐phase model for the simulation of fiber‐reinforced composites mold‐filling with phase change is established. The influence of fluid flow on the fibers is described by Newton's law of motion, and the influence of fibers on fluid flow is described by the momentum exchange source term in the model. A revised enthalpy method that can be used for both the melt and air in the mold cavity is proposed to describe the phase change during the mold‐filling. The finite‐volume method on a non‐staggered grid coupled with a level set method for viscoelastic‐Newtonian fluid flow is used to solve the model. The “frozen skin” layers are simulated successfully. Information regarding the fiber transformation and orientation is obtained in the mold‐filling process. The results show that fibers in the cavity are divided into five layers during the mold‐filling process, which is in accordance with experimental studies. Fibers have disturbance on these physical quantities, and the disturbance increases as the slenderness ratio increases. During mold‐filling process with two injection inlets, fiber orientation around the weld line area is in accordance with the experimental results. At the same time, single fiber's trajectory in the cavity, and physical quantities such as velocity, pressure, temperature, and stresses distributions in the cavity at end of mold‐filling process are also obtained. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42881.     

Studies on the kinetics of orientation and crystallization of nylon‐66 during high‐speed melt spinning

A new way of applying on‐line experimental data and basic theory to study the mechanism of orientation of a high‐speed melt spinning process is described. The relationship of birefringence and stress for Nylon‐66 was developed to understand the phenomena in the spinning line. The value of birefringence along the spinning line was calculated by various models to predict the orientation change. By comparison of the model prediction and on‐line experimental birefringence, a suitable mechanical model to simulate the change of the profiles along the spinning line was chosen, and the structural development mechanism is discussed. The results show that the orientation mechanism of high‐speed melt spinning of Nylon‐66 is determined by deformation and deformation rate along the spinning line. For Nylon‐66, molecular and crystal orientations develop independently and are controlled by the rotation of crystals and chain segments in the deformation field. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3157–3163, 2001     

Formation and characterization of cast and biaxially stretched poly(butylene terephthalate) film

An experimental study of structure development in cast film exhibited only α-form crystallites and relatively low crystallinities (X_c = 3.5–14%), while biaxially stretched films showed a mixed character of both α- and β-form crystallites with crystallinities of 20–30%. Crystal perfection increases with uniaxial deformation. Biaxiality causes a decrease both in crystal perfection and crystallinity of the films. Annealing increases crystallinity. The orientation of the films has been determined by refractive indices and WAXS pole figures. Polymer chains orient rapidly to the machine direction (MD) with uniaxial stretching. Increasing biaxiality causes an increase in population of TD-oriented crystals. The planarity of the film increases with simultaneous transverse stretching. The phenyl rings orient into the plane of the film. Annealing further increased the orientation of the films.     

Toward a viscoelastic modeling of anisotropic shrinkage in injection molding of amorphous polymers

A novel approach to predict anisotropic shrinkage of amorphous polymers in injection moldings was proposed using the PVT equation of state, frozen‐in molecular orientation, and elastic recovery that was not frozen during the process. The anisotropic thermal expansion and compressibility affected by frozen‐in molecular orientation were introduced to determine the anisotropy of the length and width shrinkages. Molecular orientation calculations were based on the frozen‐in birefringence determined from frozen‐in stresses by using the stress‐optical rule. To model frozen‐in stresses during the molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐ and pressure‐dependent relaxation time and viscosity. Contribution of elastic recovery that was not frozen during the molding process and calculated from the constitutive equation was used to determine anisotropic shrinkage. Anisotropic shrinkages in moldings were measured at various packing pressures, packing times, melt temperatures, and injection speeds. The experimental results of frozen‐in birefringence and anisotropic shrinkage were compared with the simulated data. Experimental and calculated results indicate that shrinkage is highest in the thickness direction, lowest in the width direction, and intermediate in the flow direction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2300–2313, 2005     

Thermomechanical analysis and modeling of the extrusion coating process

During the extrusion coating process, a polymer film is extruded through a flat die, stretched in air, and then coated on a substrate (steel sheet in our case) in a laminator consisting of a chill roll and a flexible pressure roll. The nip, i.e. the area formed by the contact between the pressure and the chill rolls, constitutes the heart of the extrusion coating process. Indeed, in this region, some of the most critical properties, such as adhesion, barrier properties, optical properties, are achieved or lost. In this article, we first present an experimental investigation of the coating step, which enables to characterize the leading thermomechanical phenomena. It is shown that there is no polymer macroscopic flow in the nip, but a local flow within the asperities of the steel substrate surface. This microscopic flow, at the interface between the film and the substrate, is slowed by strong cooling conditions in the nip. Several models are then proposed, giving access to the temperature profile through polymer thickness and substrate, the pressure distribution in the nip as well as the behavior of the polymer melt in the nip at the interface with the substrate. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Preparation of biaxially oriented polyamide 6/polyketone/graphene oxide films with enhanced barrier and mechanical behaviors

In this study, biaxially oriented polyamide 6/polyketone/graphene oxide (PA6/PK/GO) films were prepared by melt blending then simultaneously biaxially stretched process, with the aim of obtaining high barrier properties films and improvements in their mechanical properties. The oxygen transmission rate of biaxially oriented PA6/PK/GO film significantly decreased with addition of polyketone and GO. It is surprising that the biaxially oriented process can excellently improve the barrier properties of biaxially oriented PA6/PK/GO film. For example, there was 94.7% OTR reduction of the film containing 20 wt% PK and 0.08 wt% GO compared with PA6 film at a stretching ratio of 3.3 × 3.3. It is due to more tortuous permeation path of oxygen molecule owing to molecular orientation during biaxially stretching, and higher relative crystallinity with addition of GO. The tensile strength of film was remarkablly improved by stretching orientation and increase GO concentration. However, the elongation at break of film was considerably reduced by increase of stretching ratio. Although addition of GO may slightly improve the elongation at break of film at low stretching ratio, there was dramatic decline of elongation at break with increasing the content of GO at a stretching ratio of 3.3 × 3.3.     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of various polyesters

A novel approach to predict anisotropic shrinkage of slow crystallizing polymers in injection moldings was proposed, using the flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. In the present study, three different polyesters, polyethylene terephthalate, polybutylene terephthalate, and polyethylene‐2,6‐naphthalate (PEN), are used. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from the amorphous contribution based on the frozen‐in and intrinsic amorphous birefringence and crystalline contribution based on the crystalline orientation function determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs were carried out by varying the packing time, packing pressure, flow rate, melt and mold temperature, and anisotropic shrinkage of moldings were measured. The experimental results were compared with the simulated data and found in a fair agreement. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3526–3544, 2006     

热管纺丝工艺的模型研究

利用ＰＥＴ聚合物的本构方程，与热管和侧向冷却风有关的热传递机理以及纺丝运动学和非等温结晶动力学等建立了热管纺丝过程的数学模型。运用该数学模型进行了模拟计算，并得到了ＰＥＴ纤维热管纺丝线上的纺丝线张力、运行速度、温度、双折射、结晶度和直径沿纺程的梯度分布。于不同的工艺条件下在德国Ｂａｒｍａｇ公司生产的热管纺丝设备上纺制了ＴＣＳ－ＰＥＴ纤维，并分别测定了其卷绕丝的直径、双折射和结晶度。模拟计算得到的卷绕丝的双折射、结晶度和直径与实测结果吻合良好。     

Comonomer effect on the mechanical and morphological behavior on the calcite‐filled PP,CoPP, and TerPP

Comonomer effect on the mechanical and morphological behavior of the calcite (stearic acid coated calcium carbonate)‐filled polypropylene (PP), poly(propylene‐random‐ethylene) copolymer (CoPP), and poly(propylene‐co‐ethylene‐co‐1‐butene) terpolymer (TerPP) composites were investigated by using dumbbell bar and film specimens. The tensile properties of the calcite‐filled PP, CoPP, and TerPP composites exhibited lower values than those of the pure polymers (calcite‐unfilled polymers), whereas the complex viscosity of the calcite‐filled polymers exhibited slightly higher values than that of the pure polymers. Mechanical properties studied by using various strain rates and draw ratios rationalized in terms of comonomer units and contents in various PP systems. Morphological behavior of the specimens stretched at various strain rates and draw ratios was investigated by using SEM microphotographs and the mechanism of the formation of air holes was proposed. The air hole initiated from crack propagation and followed by dewetting between the calcite surface and the polymer interface in the weakened region. The crack propagated along the transverse direction; then the air hole developed parallel to the machine direction with fibril structure of the resin in PP and CoPP systems. However, TerPP composite exhibited no cracks in the beginning of the elongation, but the air hole was initiated due to dewetting; then its enlargement was exhibited by broken fibril structure of the resin. In the final stage of stretching, the air hole was dominated by merging of the neighboring air holes. Thus, different comonomer units, which are the small content of ethylene and 1‐butene in CoPP and TepPP, are responsible for these systems behaving in a different manner on the mechanical and morphological properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2041–2053, 2002     

A model for the two-layer blown film process with flow-enhanced crystallization

A 2-D model for non-isothermal bi-layer film blowing is developed based on the 1-D film blowing model of Henrichsen and McHugh [2007a. Analysis of film blowing with flow-enhanced crystallization: part 1. Steady-state behavior. International Polymer Processing XXII (2), 179-189] that accounts for viscoelasticity and flow-enhanced crystallization. Numerical results demonstrate the role of rheological, thermal, and crystallization properties on the development of crystallinity and stresses in a bi-layer system consisting of two crystallizable polymers. For a two-layer film consisting of the same materials, the evolution of the stress in an individual layer can be significantly different due to the temperature difference. Varying the material properties in a given layer, such as the plateau modulus and the maximum crystallization rate, not only leads to the corresponding responses in its own layer, but also influences stresses and crystallinity in the other layer through heat transfer between two layers. Results further demonstrate that stresses in the film after the frost line will be borne primarily by the layer that solidifies first, while the second, molten component will have a tendency to relax. The layer arrangement is also shown to have direct impact on the stresses and semi-crystalline phase orientation at the freeze point which will impact the final properties of the film.