Rapid structural changes that take place during constrained annealing of biaxially stretched pet films

The aim of this work is to study the structural changes that take place during the heat setting of simultaneously and sequentially biaxially stretched polyethylene terephthalate films. The rate of structural rearrangement, as detected by real‐time birefringence and off‐line Raman spectroscopy, DSC thermal analysis and X‐rays, was found to be dependent on the state of the orientation and crystallinity attained by the samples during the stretching step. This suggested that the annealing behavior can be categorized into three regimes according to the birefringence behavior of the samples. At low deformations, the films not crystallized by strain exhibit complete birefringence relaxation without showing any sign of crystallization. The intermediate ratio samples that were stretched to the onset of the strain‐induced crystallization exhibited the highest levels of birefringence increase after a short relaxation. The samples stretched well above the onset of the strain‐induced crystallization exhibited intermediate level of birefringence and crystallinity increase. Therefore, the classification of the three regimes was found to be related to the onset of the strain‐induced crystallization during the stretching step. POLYM. ENG. SCI., 57:550–562, 2017. © 2016 Society of Plastics Engineers     

Relationship between biaxial orientation and oxygen permeability of polypropylene film

Biaxially oriented polypropylene (BOPP) films were produced by simultaneous and sequential biaxial stretching to various balanced and unbalanced draw ratios. The BOPP films were characterized in terms of density, crystallinity, refractive index, oxygen permeability and dynamic mechanical relaxation behavior. It was found that the density and crystallinity of BOPP films decreased as the area draw ratio increased. Sequential stretching led to a slightly lower density than simultaneous stretching to the same draw ratio. Moreover, sequential stretching produced lower orientation in the first stretch direction and higher orientation in the second stretch direction compared to simultaneous stretching. The study confirmed the generality of a one-to-one correlation between the oxygen permeability of BOPP films and the mobility of amorphous tie chains as measured by the intensity of the dynamic mechanical β-relaxation. Moreover, the study established the correlation for commercially important sequentially drawn BOPP films with an unbalanced draw ratio. Finally, the chain mobility in the stretch direction was found to depend on the final stress during stretching.     

Strain-induced crystallization of poly(ethylene terephthalate)

The fabrication of poly(ethylene terephthalate), PET, into fibers, films, and containers usually involves molecular orientation caused by molecular strain, which may lead to stress- or strain-induced crystallization (SIC). The SIC of PET was studied by the methods of birefringence, density, thermal analysis, light scattering, and wide-angle X-ray. The development of crystallinity is discussed in relation to the rate of crystallization, the residual degree of orientation, and stress relaxation. The experimental procedure involves stretching samples at temperatures above the glass transition temperature, Tg, to a given extension ratio and at a specific strain rate of an Instron machine. At the end of stretching, the sample is annealed in the stretched state and at the stretching temperature for various periods of time, after which the sample is quickly quenched to room temperature for subsequent measurements. During stretching, the stress strain and the stress relaxation curves are recorded. The results indicate that the SIC of annealed, stretched PET can proceed in three different paths depending on the residual degree of orientation. At a low degree of residual orientation, as indicated by the birefringence value, annealing of stretched PET leads only to molecular relaxation, resulting in a decrease of birefringence. At intermediate orientation levels, annealing causes an initial decrease in birefringence followed by a gradual increase and finally a leveling off of birefringence after a fairly long period of time. At higher orientation levels, annealing causes a rapid increase in birefringence before leveling off. The interpretation of the above results is made using the measurements of light scattering, differential scanning calorimetry, and wide-angle X-ray. The rate of the SIC of PET is also discussed in terms of specific data analysis.     

Origin of stress and birefringence generation at hot-stretching of poly(methyl methacrylate) containing low-molecular-weight compound

The simultaneous measurements of stress and birefringence during hot-stretching, and after the cessation of stretching, were performed using a miscible blend of poly(methyl methacrylate) (PMMA) and 10 wt% of 4-cyano-4′-pentylbiphenyl (which is commonly known as 5CB). The birefringence of the blend exhibited anomalous behavior during stretching, that is, it initially decreased, then rapidly increased to a positive value. A concave curve with a minimum birefringence was prominent at low temperatures, during which PMMA determined birefringence. After passing the yield point, which corresponded to the minimum birefringence, the birefringence increased in proportion to the applied stress. That is to say, the stress-optical coefficient remained constant. In this region, the 5CB molecules oriented themselves with the PMMA chains, that is, there was nematic interaction. After stretching ceased, the stress initially decreased rapidly; during this period, the stress-optical coefficient was determined mainly by the deformation of PMMA, that is, glassy component. Subsequently, the orientation relaxation of 5CB, which occurred with the orientation relaxation of PMMA chains in the stage with a long time region, determined the birefringence. These results demonstrated that nematic interaction does not occur when inelastic deformation is governed.     

Processing–structure–property relationships in poly(ethylene terephthalate) blown film

An investigation was undertaken to establish processing–structure–property relationships in poly(ethylene terephthalate) (PET) blown film. For the study, a commercial grade of PET was used to fabricate the film specimens by means of a tubular film blowing process. In this process, the stretch temperature was accurately controlled by an oven. The annealing treatment of the oriented specimens involved clamping the sample in an aluminum frame and then putting the clamped sample in an oven, controlled at a temperature between the glass transition temperature (70°C) and the melting point (255°C) of PET, for a specified annealing period. The structure of the blown film samples was characterized by density, bulk birefringence, flat plate wide-angle X-ray scattering, and pole figure analysis. The processing variables, namely, takeup ratio, blowup ratio, and stretch temperature were found to significantly affect the bulk birefringence and density of the oriented PET blown film samples. It was found that both the bulk birefringence and density of the specimens increased upon annealing at an elevated temperature. Both the crystalline and amorphous orientation functions were calculated from the data of bulk birefringence, density, and the pole figure analysis. Compared to the amorphous orientation functions, the crystalline orientation functions were found to be relatively insensitive to the processing variables. It was concluded that equibiaxially oriented PET films can be produced via a tubular film blowing process by judiciously controlling the processing and annealing conditions. It has also been observed that the tensile stress-at-break of equibiaxially oriented PET film increases with decreasing stretch temperature and increasing annealing temperature.     

Comparative study on development of structural hierarchy in constrained annealed simultaneous and sequential biaxially stretched polylactic acid films

Structural evolution during constrained annealing of PLA films biaxially stretched in simultaneous and sequential biaxial stretching was compared. Annealing of simultaneous biaxially stretched films yields films with in-plane isotropy with (100) crystallographic planes parallel to the surface. The first stage of sequential stretching where the films are stretched in Uniaxial constrained mode was found to yield films exhibiting transverse isotropy. The transverse stretching of these films lead to formation of a distinct second population of chains primarily oriented in transverse direction, generating bimodal orientation texture. When the extent of stretching in two directions are balanced, constrained annealed samples were found to exhibit uniplanar axial (100)[001] texture with the primary chain axial direction now switched to transverse direction. Two new superstructures, along [110] and [100] respectively were discovered in annealed PLA films.     

Orientation in amorphous polymers I. Preparation and testing of oriented samples

Orientation effects in amorphous polystyrene are studied using a uniaxial stretching experiment. The rheological properties of the polymer are determined from an analysis of creep data obtained from the tensile apparatus, and oriented polymer samples are prepared at different extension ratios and rates of stretching. From birefringence and tensile strength measurements on oriented samples of polystyrene, it is shown that the tensile strength is not a unique function of the birefringence. It is proposed that the tensile strength may depend not only on the average orientation, as reflected by the birefringence, but on which portion of the relaxation spectrum is preferentially oriented.     

Kinetics of rapid structural changes during heat setting of preoriented PEEK/PEI blend films as followed by spectral birefringence technique

The influence of composition and preorientation on the development of structural hierarchy during heat setting of PEEK/PEI films was investigated using on-line birefringence, and off-line wide-angle and small-angle X-ray scattering, infrared dichroism and thermal analysis techniques. When the PEEK/PEI blends are drawn to deformation levels below the onset of strain hardening, the subsequent heat setting at high temperature starts with a large relaxation process followed by a fast crystallization and a long-term slow structural rearrangement stages. When the films are predrawn beyond a critical structural level (crystallinity and orientation), the initial relaxation stage disappears. This signifies that beyond a critical structural order a long-range physical network, where the nodes consist of crystallized domains and chain—self and cross-entanglements—are formed. This physical network allows the entropy driven shrinkage stresses to be maintained that results in the development of oriented crystalline phase. The addition of non-crystallizable PEI chains was found to retard the formation of this ‘network structure’ resulting in lower orientation levels.     

Microporous membranes of isotactic poly(4‐methyl‐1‐pentene) from a melt‐extrusion process. II. Effects of thermal annealing and stretching on porosity

A two‐part study utilizing isotactic poly(4‐methyl‐1‐pentene) (PMP) was undertaken to investigate a three‐stage process (melt‐extrusion/annealing/uniaxial stretching) (MEAUS) utilized to produce microporous films. In this report, the thermal‐annealing (second stage) and subsequent uniaxial‐stretching (third stage) results of selected PMP films from three resins, labeled A, B, and C, are discussed. From sequential analysis of the effect each stage had on the resulting microporosity, it was discovered that the melt‐extruded precursor morphology and orientation, as a consequence of the first‐stage extrusion parameters and resin characteristics, were crucial to controlling the membrane permeability. The annealing parameters were also critical, where a temperature of 205°C applied for 20 min under no tension was the optimum annealing condition for producing highly microporous PMP films upon stretching. For the conditions studied, the stretching parameters that were found to be the optimum for producing the desired characteristics in the final film were cold‐ and hot‐stretch temperatures of 70 and 180°C, respectively. The cold‐ and hot‐stretch extension levels concluded to be the best were a cold‐stretch extension of 80%, followed by hot stretching to 90%, and, thus, a total overall extension level of 170% for the processing window studied. However, these results were only with respect to resin A films, while resin B and C samples could not be produced into microporous films via the MEAUS process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1076–1100, 2002; DOI 10.1002/app.10395     

Evolution of phase behavior and orientation in uniaxially deformed polylactic acid films

The development of crystalline structure and orientation during uniaxial stretching of cast amorphous linear and branched lactic acid films were investigated in the rubbery temperature ranges that spans between glass transition temperature and cold crystallization temperature. This material exhibited almost ideal stress‐strain behavior in the temperature range 65–80°C. Because of its strain crystallizability, films with uniform thickness can be obtained at high deformation levels as a result of self‐leveling. Branching was found to retard this self‐leveling through its slightly detrimental effect on the strain hardening. Upon stretching the material undergoes rapid orientation in the amorphous state and beyond a critical level very sharp and highly oriented β crystalline form chains with ?3/1 helix. If the temperature is at or below Tg, with additional stretching, the films were found to revert to a highly oriented amorphous state through the destruction of the crystalline domains. At higher temperatures, further stretching results in continuation of improvement in crystalline order.     

Mechano optical behavior of polyethylene terephthalate films during simultaneous biaxial stretching: Real time measurements with an instrumented system

We present an experimental study of real time true stress–strain–birefringence measurements to elucidate the sequence of structural mechanisms that occur during simultaneous biaxial stretching of PET films from amorphous precursors in rubbery state. Stress–birefringence relationship, wide angle X-ray diffraction, Raman spectroscopy and DSC thermal analysis were used to identify the stages of the mechano-optical behavior of the films during stretching, and to identify their structural origins. The measurements revealed four regimes for the relationship between the stress and birefringence. In the first regime the stress has a linear relationship with birefringence where the linear stress optical rule holds and the stress optical constant for PET is 5.8 GPa⁻¹ (5800 Brewster). In the second regime, the relationship is also nearly linear with a steeper positive slope, and in the third regime the relationship is nonlinear. At very high stretching rates, a fourth stage could be seen, where the stress increases while the birefringence reaches a plateau. This stage is reached when the polymer chains attain their finite extensibilities. This stage was not observed if low rates of stretching employed, where high relaxation movements dominate the orientation effects. The deviation from the initial linear stress optical rule coincides with the onset of the stress-induced crystallization as revealed by the off line measurements. This transition was found to be rate dependent and increased rate delays this transition to higher stresses.     

Microporous membranes of polyoxymethylene from a melt‐extrusion process: (II) Effects of thermal annealing and stretching on porosity

A two‐part study utilizing polyoxymethylene (POM) was undertaken to investigate a three‐stage process (melt‐extrusion/annealing/uniaxial‐stretching) utilized to produce microporous films. In this report, the thermal annealing (second stage) and subsequent uniaxial‐stretching (third stage) results of selected POM films from two commercial resins, labeled D & F, are discussed. Specifically, the annealing and uniaxial stretching effects on film morphology, orientation, and other pertinent film properties are addressed. Additionally, sequential analysis was performed regarding the influence each stage had on the resulting microporosity. It was found that the melt‐extruded precursor morphology and orientation, as a consequence of the first stage extrusion parameters and resin characteristics, are crucial to controlling the membrane permeability. The annealing parameters were also deemed critical, where a temperature of 145°C applied for 20 min under no tension was the optimum annealing condition for producing a highly microporous film upon stretching. For the conditions studied, the stretching parameters that were found to be optimum for producing the desired characteristics in the final film were a cold temperature of 50°C and hot stretch temperature of 100°C. The optimum extension levels were concluded to be 90% for both the cold and hot stretch steps, and thus a total overall extension level of 180%. However, these results were only with respect to resin F films. Because the resin D melt‐extruded precursors possessed twisted lamellar morphologies and relatively low crystal orientation, their samples could not be produced into microporous films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1762–1780, 2002; DOI 10.1002/app.10587     

Enthalpy and Anisotropy Relaxation of Glass Fibers

Optical birefringence and calorimetric studies have been conducted with respect to structural relaxation of E-glass (a type of calcium–alumosilicate glass system) fibers. Upon fiber drawing, the liquid of E-glass is thermally hyperquenched and mechanically stretched. Hyperquenching (cooling rate >10⁶ K/min) leads to higher enthalpy state of liquids, and thereby, to a higher fictive temperature than normal quenching (20 K/min), whereas stretching results in structural anisotropy of glasses, i.e., a certain degree of preferred structural orientation (stretched network) along the axial direction of the fibers, which is quantified by the optical birefringence. Simultaneous relaxation of both anisotropy and excess enthalpy (relative to the enthalpy of a glass cooled at the standard rate of 20 K/min) upon static annealing and dynamic heating is observed, both of which can be described using the Kohlrausch function. However, there is a striking difference between the birefringence and the excess enthalpy relaxations. The birefringence decays much faster than does the excess enthalpy during annealing. These observations imply that the birefringence decay results from fast relaxation of the local structure, while the enthalpy relaxation results from slow relaxation of larger domains of the network.     

Oxygen permeability of biaxially oriented polypropylene films

The effect of thermal history on the oxygen permeability of biaxially oriented polypropylene (BOPP) films was investigated. Compression‐molded sheets prepared with different cooling rates were biaxially oriented at several temperatures in the range between the onset of melting and the peak melting temperature and at a strain rate similar to that encountered in a commercial film process. The stress response during stretching was found to depend on the residual crystallinity in the same way regardless of the thermal history of the compression‐molded sheet. Biaxial orientation reduced the oxygen permeability measured at 23°C; however, the reduction did not correlate with the amount of orientation as measured by birefringence or with the fraction of amorphous phase as determined by density. Rather, the decrease in permeability was attributed to reduced mobility of amorphous tie molecules. A single one‐to‐one correlation between the oxygen permeability and the intensity of the dynamic mechanical β‐relaxation was demonstrated for all the films used in the study. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Doubly oriented β-form films of poly(vinylidene fluoride)

PVDF sheets, rapidly quenched, were (1) two-step transversely stretched at various temperatures and (2) stretched at various temperatures, rolled at room temperature and then annealed. The orientation patterns of the β-form crystal (which contains the polar b-axis) in these films were analysed on the basis of X-ray diffraction photographs taken with flat and cylindrical cameras. In the case of (1), when both of the two-step transversely stretching temperatures were below 100°C, a doubly oriented film with the plar b-axis oriented parallel to the film surface was obtained. In the case of (2), when the stretching temperature was below 100°C, the sheets then rolled without annealing, another doubly oriented film with the polar b-axis preferentially oriented at 30° to the film surface was obtained. On the other hand, when these films were annealed above 100°C, or the stretching temperatures were above 100°C, orientation patterns in which the polar b-axis was partially rotated through 60° were obtained. The orientation mechanisms of these films are discussed using the measurements of the lattice spacings of the β-form crystal.     

The role of interlamellar chain entanglement in deformation-induced structure changes during uniaxial stretching of isotactic polypropylene

In-situ small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD) were carried out to investigate the deformation-induced structure changes of isotactic polypropylene (iPP) films during uniaxial stretching at varying temperatures (room temperature, 60 °C and 160 °C). From the WAXD data, mass fractions of amorphous, mesomorphic and crystal phases were estimated. Results indicate that at room temperature, the dominant structure change is the transformation of folded-chain crystal lamellae (monoclinic α-form) to oriented mesomorphic phase; while at high temperatures (>60 °C); the dominant change is the transformation of amorphous phase to oriented folded-chain crystal lamellae. This behavior may be explained by the relative strength between the interlamellar entangled network of amorphous chains, which probably directly influence the tie chain distribution, and the surrounding crystal lamellae. It appears that during stretching at low temperatures, the interlamellar entanglement network is strong and can cause lamellar fragmentation, resulting in the formation of oriented mesomorphic phase. In contrast, during stretching at high temperatures, the chain disentanglement process dominates, resulting in the relaxation of restrained tie chains and the formation of more folded-chain lamellae.     

Intrinsic birefringence of amorphous poly(bisphenol-A carbonate)

The birefringence of uniaxially oriented poly(bisphenol-A carbonate) (PC) samples stretched over a wide range of temperatures has been measured accurately with a combination of the compensator and the wedge methods. The Hermans' orientation function of anisotropic PC was calculated from the measured dichroic ratio of the infrared absorption band at 1364 cm^-1. Measurements using differential scanning calorimetry, X-ray diffraction, or infrared spectroscopy indicated no stress-induced crystallinity in stretched amorphous PC. At each state having a defined molecular orientation, samples stretched below the glass transition temperature (T_g) always exhibited excess birefringence and slightly higher density. This phenomenon is attributed to bond distortion during stretching, a result of the suppression of large-scale segmental motions of polymer chains below the T_g. The birefringence of samples stretched above the T_g arises exclusively from the orientation effect as a result of greater chain mobility. These measured birefringence values are proportional to Hermans' orientation functions, yielding a linear relationship which allows precise determination of the intrinsic birefringence of amorphous PC as 0.192 ± 0.006.     

Rheo-optical studies on the deformation mechanism of semicrystalline polymers: 2. Analyses of orientational and form birefringence of tubular-extruded poly(butene-1) films

Birefringence studies have been carried out to assess amorphous chain orientation of the ‘row-nucleated’ superstructure developed by crystallization from oriented melts. Birefringence, measured as a function of percentage elongation of film specimens subjected to stretching along the extrusion direction (the films are prepared by a tubular extrusion) and as a function of the refractive indices of the immersion liquid was separated into orientational and form birefringences. The orientational birefringence was further separated into the birefringence arising from crystal orientation and that from the amorphous chain orientation, utilizing orientation measurements made on crystals by wide-angle X-ray diffraction; the results indicate that the two contributions are comparable for a particular value of the intrinsic birefringence of the crystal Δ°_c = 0.0108, and the contribution of the amorphous tie chains is substantial. The form birefringence contributes negatively to the total birefringence and the negative contribution increases with increasing percentage elongation owing to the special morphology of the stacked lamellae and the decrease of interlamellar density with stretching. Its contribution to the total birefringence is initially minor (～6%) but increases with elongation until most of the total birefringence arises from the form birefringence. The form birefringence calculated using Franklin's theory shows a relatively good agreement with the experimental values, indicating that the deformation model involving a uniform interlamellar lowering of density is appropriate.     

Characterization of crystallinity,orientation, and mechanical properties in biaxially stretched poly(p-phenylene sulfide) films

In this paper, we describe the preparation and structural characterization of biaxially oriented poly(p-phenylene sulfide) (PPS) films. These films were prepared in a biaxial stretching machine at various stretching temperatures, rates, and stretching ratios. Selected samples were constrained annealed at elevated temperatures. The state of orientation was determined by wide angle X-ray diffraction (pole figure determination) and birefringence measurements. The results are expressed in terms of the biaxial orientation functions (?,?). Mechanical properties (tensile modulus, tensile strength, and elongation to break) were obtained as a function of processing conditions and direction in the plane of the films.     

Poly(ethylene terephthalate) nucleation as studied by shrinkage of film of low orientation level

Poly(ethylene terephthalate)s of weight average MW 74,000 and 30,000 have been uniaxially stretched, cooled under restraint, reheated, and shrunk unrestrained. Five stretch temperatures between 80 and 120°C and elongations up to 280 percent have been employed. Density and wide-angle X-ray diffraction results indicate conventional crystallization to have occurred only for the highly oriented samples, e.g., stretching above 200 percent at 90°C. The majority of stretching conditions studied produced only nucleated polymer. A sensitive, qualitative measure of nucleation is the degree of stretch imposed. Sufficiently high stretch temperature and low stretch rate lead to negligible nuclei formation. Nucleation in stretched, unshrunk films correlates with relatively high shrinkage, low orientation, low density and the absence of crystallinity until after the film has been shrunk. Crystallization on the other hand correlates with relatively high density, relatively low shrinkage and high orientation.