Structure and properties of biaxially stretched poly(ethylene terephthalate) sheets

Huge numbers of PET (poly[ethylene terephthalate]) bottles are produced in the world. Especially in Japan, the number of hot-fillable PET bottles used is extremely large and is still increasing. This type of bottle is generally manufactured by the heat-set method using hot molds after stretch-blow molding. Herein, we examined how the PET sheet stretching condition affects the PET heat-shrinkage behavior at 85°C, which is the hot-filling temperature. Sheets stretched at a higher temperature and higher speed had higher thermal stability for a wider range of draw ratios. This is because those sheets have a higher crystallinity and relaxed amorphous regions. The higher stretch speed gives the sheet a higher crystallinity with self heat generation during rapid deformation. A higher stretch temperature makes the molecular segments relaxed.     

Structure formation in stretched sheets of poly(butylene terephthalate)

Crystalline and amorphous sheets of poly(butylene terephthalate) (PBT) were drawn in the temperature range of 20–150°C. The molecular orientation and the relative amount of α- and β-form crystals in the stretched sheets were studied by wide-angle X-ray diffraction (WAXD) and density measurements. When crystalline PBT sheets are drawn at lower temperatures, α-form crystals are partially transformed into β-form crystals. Both α- and β-form crystals are formed by drawing amorphous PBT sheets. The relative amount of α- and β-form crystals is much more sensitive to drawing temperature than to draw ratio. The α-form crystallinity is higher at higher drawing temperature and increases slightly with increasing draw ratio. The second moments of orientation functions of α- and β-form crystals increase with increasing draw ratio, and the increase of the orientation function is suppressed at higher draw ratio. The orientation function of α-form crystals is higher than that of β-form crystals in a same sample.     

Effect of initial take-up speed on properties and structure of as-spun and drawn/heat-set poly(ethylene terephthalate) filaments

The effect of initial take-up speed on the properties and structure of both as-spun and drawn/heat-set poly(ethylene terephthalate) filaments was characterized through measurements of birefringence, percent crystallinity, tensile properties, high temperature shrinkage, loss tangent temperature dependence, DSC melting behavior, and wide-angle (WAXS) and small-angle X-ray scattering (SAXS). While a steady trend toward improved as-spun filament orientation and tensile properties occurred with increasing initial take-up speed, the reduced drawability of these more structured precursor filaments resulted in corresponding drawn/heat-set filaments that were of relatively lower overall orientation and tensile strength. The observed trends in tenacity, initial modulus, and high temperature shrinkage of the drawn/heat-set filaments appeared to be well correlated with the extent and distribution of amorphous phase rigidity as perceived through inferences made from the loss tangent temperature dependence. The WAXS patterns of the drawn/heat-set samples indicated that these filaments all possess a well-developed and highly oriented crystalline structure. Application of a simple two phase model allowed the determination of an amorphous orientation factor, which for the drawn/heat-set filaments was generally found to decrease as the draw ratio imposed in order to achieve comparable levels of elongation to break decreased. The SAXS patterns of the drawn/heat-set filaments indicated that comparable long period spacings exist in all cases and that a transition from a four-point pattern to a two-point bar-shaped pattern occurred when the precursor filament possessed some significant amount of as-spun crystallinity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2115–2131, 1998     

Evolution of hot strain induced crystalline texture of poly(ethylene terephthalate) films

Differential scanning calorimetry, birefringence and X-ray poles figure analysis were used to characterize the evolution of the strain induced crystalline texture of poly(ethylene terephthalate) films. The films are initially wholly amorphous and drawn above the glass transition temperature. For a critical draw ratio, a crystalline phase appears with a weak crystalline fiber texture. For the highest draw ratio we observe that the texture is better defined, and the drawing tends to align the crystallites with the draw direction and to increase slightly the degree of crystallinity. For the highly drawn sample an extra texture is also observed.     

Optical properties of simultaneous biaxially stretched poly(ethylene terephthalate) films

We offer a detailed study on the anisotropic optical properties in uni and simultaneous biaxially stretched Poly(ethylene terephthalate) (PET) films. Cast amorphous sheets of PET were stretched to a series of extension ratios in two mutually perpendicular directions at 80, 90, and 100°C. Additionally, 0selected films were subsequently “heat-set” by annealing with their width and lengths constrained. The principal refractive indices at sodium D wavelength of these, asstretched and heat-set films were obtained using a modified Abbe refractometer. The changes in the principal refractive indices with the processing history were correlated with the orientation of PET chains and phenyl plane normals, which were determined independently by wide angle X-ray (WAXS) pole figure technique.     

Deep drawability of biaxially rolled thermoplastic sheets

The deep drawability of biaxially cold-rolled thermoplastic sheets has been studied using polycarbonate, polyvinyl chloride, and acrylonitrile-butadiene-styrene polymers. Each polymer was rolled to two different reductions in thickness. The deep drawability of these rolled sheets was measured by determining the limiting draw ratio using a Swift cup test. Strain ratios were measured in three directions for each of the rolled sheets in order to determine the normal and planar anisotropy of the sheets. It has been determined that the drawability of a sheet can be correlated with the normal anisotropy of the sheet and it is the increase in normal anisotropy of a sheet which increases the drawability of the sheet. It has also been shown that lubrication increases the drawability due to a reduction in punch force.     

The effect of hot drawing on the properties of short fiber reinforced extruded sheets

The hot drawing of extruded composite sheets can be used to control the orientation of both matrix and reinforcing fibers. A study was made of the effect of draw ratio on the properties of an extruded polystyrene sheet containing 0 to 1 percent of short glass fibers. An increase in draw ratio resulted in an increase in fiber orientation. A model of a rigid fiber rotating in an elongational flow field was used to describe the effect of draw ratio on the final orientation distribution. An increase in draw ratio also caused an increase in the amount of fiber breakage. A shear-lag analysis was used to estimate the extent of damage as a function of draw ratio. It was also found that the mechanical properties were dependent upon both the draw ratio and fiber concentration.     

X‐ray pole figures to assess orientation in PVC sheets

A series of X‐ray pole figures were obtained from oriented and unoriented rigid polyvinyl chloride sheets. From these, information about crystallite orientation in uniaxially and biaxially drawn sheets stretched at 90°C was obtained. Uniaxial orientation produced two crystallite orientations with the extent of orientation increasing with draw ratio; for biaxial samples the chain direction (c) was distributed uniformly in the plane of the sheet, with the planar orientation improving as draw ratio increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 528–535, 2007     

Proton spin–lattice and spin–spin relaxation times in isotactic polypropylene. II. Effects of stretching ratio and temperature

Proton spin–lattice, T₁, and spin–spin, T₂, relaxation times of uniaxially stretched polypropylene film were measured at 40°C using a wide line pulse spectrometer operating at 19.8 MHz. T_1l, the longer T₁, increases almost linearly with increasing stretching ratio, and T_2a, T₂ of the amorphous region, decreases gradually as the stretching ratio is increased. These results can be interpreted in terms of the increased constraints to molecular motion in the amorphous region. The fraction of the rigid protons in the sample, F_c, increases with increasing stretching ratio, while the crystallinity calculated from the density, X_d, does not change largely. The difference between F_c and X_d, therefore, increases as the stretching ratio is increased. This indicates that the physical structure of the highly stretched sample is far from the ideal two-phase model. The influence of the stretching temperature was also investigated. There are only slight increases in T_1l and in F_c for the samples stretched in a temperature range from 80°C to 150°C, whereas the considerable increase in T_2a occurs. The most notable change introduced at a high temperature stretching is the increase in the chain mobility in the amorphous region.     

Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

The nanostructure of stretched and nonstretched PVDF samples was studied by small-angle X-ray scattering (SAXS). The crystallinity of the samples was determined by wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC), and crystalline phases by Fourier transform infrared spectroscopy (FTIR). The nanostructure can be described by a lamellar stacking of crystalline and amorphous layers, with a fairly well defined long period D and a diffuse-boundary in the interface between the crystalline and amorphous phases. The crystallinity of the stretched sample was found to be greater than that of the nonstretched sample. The long period D and the thicknesses of the crystalline lamellae T_c were found to be greater in the stretched sample than those in the nonstretched sample. The thickness of the diffuse-boundary was evaluated as being ∼ 1.4 nm in the nonstretched sample and 1.1 nm in the stretched sample. It was concluded that the growth of the thickness of the crystalline layer induced by the stretching process (stretch-induced crystallization) occurs partially at expense of the diffuse boundary and also by the coarsening of the structure with the stretching process, because of the diminution in the surface area to volume ratio observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure and physical properties of biaxially stretched polyethylene terephthalate sheets under different heat‐set and stretch conditions

The thermal shrinkage of heat‐set polyethylene terephthalate (PET) sheets at 85°C after stretching at low speed and low temperature was similar to that for sheets stretched at high speed and high temperature if the crystallinities of these sheets were the same. However, differences between other physical properties, such as yield strength, were observed, which may be due to differences in the amorphous phase. The sheets stretched at the higher temperature and higher speeds may have different structures in the molecular segments in the amorphous phase, more relaxed than in the sheets prepared at the lower speed and temperature.     

Novel impacts of glycol-modified poly(ethylene terephthalate)(PETG) to crystallization behavior of polyethylene naphthalate (PEN) within stretched miscible blends

For studied blends of amorphous glycol-modified poly(ethylene terephthalate) (PETG) and semicrystalline polyethylene naphthalate (PEN), melt miscibility is understood from the linear variation of a single glass transition temperature (T_g) over the entire composition range. The diluent effect of PETG component severely retarded the crystallization of PEN component within blends. Nevertheless, after being through isothermal stretching at 120 °C, crystallization was able to progress efficiently during heating in a continuous manner. Instead of being thermally relaxed back to amorphous state, parallel sliding motions of stretched PEN segments toward crystallization appear rather dominant. Within stretched blends, the PETG content emerged as a critical factor to the crystallinity increase of PEN fraction and the absence of lattice defect, instead of behaving as a diluent component. Furthermore, as being indicated by in-situ small-angle X-ray experiments, regular lamellar stacking gradually developed within stretched blends through heating, which indicates the involvement of thermally activated self-association of randomly distributed crystalline lamellae. With including a higher fraction of PETG component, these secondary ordering processes including lamellar thickening can be activated at lower temperature. Hence, the accompanied thermal relaxation of flexible PETG segment is inferred able to lubricate the sliding of stretched PEN segments in amorphous regions via lowering encountered frictional hindrance, and thus enhance both primary and secondary ordering processes within stretched blends.     

Preparation of high modulus polyethylene sheet by the roller-drawing method

The high density polyethylene (HDPE) sheets were drawn through a pair of heated rollers. The process, referred to as roller drawing, was found to be useful for producing high modulus and high strength HDPE sheets. The higher draw ratio could be obtained for the HDPE sheet with lower molecular weight and narrower molecular weight distribution. The Young's modulus and the breaking strength reached 43 GPa and 0.67 GPa, respectively, at the highest draw ratio. The measurements of wide-angle X-ray diffraction (WAXD) pole figures revealed that the crystallographic a-, b-, and c-axes were oriented to the normal direction (ND), the traverse direction (TD), and the drawing direction (DD), respectively. The small-angle X-ray scattering (SAXS) of the roller-drawn HDPE sheets with draw ratio higher than 7 exhibited two intensity maxima on the meridian, suggesting the presence of the two-phase structure in which crystalline and amorphous regions are stacked alternately along DD. The relationship between mechanical properties and microstructure was discussed on the basis of the concept of the formation of amorphous tie molecules in the interfibrillar and intercrystallite regions.     

Uniaxial deformation of overstretched polyethylene: In-situ synchrotron small angle X-ray scattering study

Synchrotron small angle X-ray scattering was used to study the deformation mechanism of high-density polyethylene that was stretched beyond the natural draw ratio. New insight into the cooperative deformational behavior being mediated via slippage of micro-fibrils was gained. The scattering data confirm on the one hand the model proposed by Peterlin on the static structure of oriented polyethylene being composed of oriented fibrils, which are built by bundles of micro-fibrils. On the other hand it was found that deformation is mediated by the slippage of the micro-fibrils and not the slippage of the fibrils. In the micro-fibrils, the polymer chains are highly oriented both in the crystalline and in the amorphous regions. When stretching beyond the natural draw ratio mainly slippage of micro-fibrils past each other takes place. The thickness of the interlamellar amorphous layers increases only slightly. The coupling force between micro-fibrils increases during stretching due to inter-microfibrillar polymer segments being stretched taut thus increasingly impeding further sliding of the micro-fibrils leading finally to slippage of the fibrils.     

Orientation of amorphous poly(ethylene terephthalate) by tensile drawing,roll-drawing,and die-drawing

Orientation of initially amorphous poly(ethylene terephthalate) films and sheets was carried out by means of tensile drawing in a tensile tester, roll-drawing using a series of four rolling stations, and by die-drawing. The drawing temperature was 80 and 90°C and drawing rate ranged from 2 to 20 cm/min in the different processes. Crystallinity was observed to increase with draw ratio for all these processes. The onset of crystallinity development depends on the drawing rate. The glass transition temperature was essentially constant and crystallization temperature decreased with increasing draw ratio. The trans conformers content was observed to increase with draw ratio at the expense of the gauche conformers for the three processes. The orientation of the trans conformers increases readily from the beginning of draw and saturates rapidly. The orientation of the gauche conformers was negligible. Some differences are observed for the behavior of the 1020 and 730 cm^?1 benzene ring bands, which may be due to differences in the benzene ring configuration at the surface as a result of different deformation mechanisms for the die and roll-drawing. However, further investigations to elucidate this hypothesis are needed. The mechanical properties obtained in the longitudinal direction increased for all the processes. In the transverse direction, the roll and die-drawing processes induced a decrease in modulus and strength with increasing draw ratio, similar to that observed for uniaxial orientation. This indicates that these processes are mainly uniaxial, despite the plane strain nature of the deformation.     

Effect of postdrawing on the permeability of gases in blown polyethylene film

The effect of orientation on the structure and transport properties of high-density polyethylene film has been studied. Microstructure was characterized using small-angle light scattering, birefringence, and wide-angle x-ray scattering. Water vapor and oxygen transmission rates were determined as a function of film draw ratio. The object of the present work is to correlate the effects of postprocessing conditions on the transport properties and morphology of linear polyethylene. High-density spherulitic polyethylene films were produced by blown film extrusion and subsequently oriented by longitudinal stretching in a postoperation. Various degrees of orientation were imparted to the films, with percent crystallinity, sample orientation and transport properties measured as a function of draw ratio. For the postoriented films, results indicate there was no significant change in percent crystallinity with increasing draw ratio although water vapor and oxygen permeability decreased substantially. This is attributed to the increased orientation of the crystalline and amorphous regions and rod-like and microfibril structure formation brought about by the drawing process. Lower processing temperatures result in increased orientation which improves the vapor barrier properties.     

Defining the physical structure and properties in novel monofilaments with potential for use as absorbable surgical sutures based on a lactide containing block terpolymer

Monofilaments of a block terpolymer of l-lactide, ?-caprolactone and glycolide have been melt spun for potential use as absorbable surgical sutures. As-spun fibres of the terpolymers produced by melt spinning were elastic, amorphous and isotropic. A two-stage process involving hot drawing was employed to enhance their mechanical properties. WAXS and SAXS results coupled with DSC demonstrated that hot drawing leads to an orientated amorphous matrix containing small highly aligned crystals. Hot drawing was carried out at a range of temperatures using the highest possible draw rate commensurate with maintaining continuity of the fibre. A novel WAXS analysis based on a spherical harmonic analysis allowed a separation of the scattering into three components: oriented crystalline, oriented amorphous, and an isotropic amorphous. There is a steady increase in the fraction of oriented crystalline material with increasing hot draw temperature, although the level of crystallinity is ultimately limited by the statistical nature of the terpolymer. The material shows highly promising potential properties for use as a monofilament suture.     

Mechanical properties of oriented poly(vinyl chloride)–poly(caprolactone) blends

Blends of poly(vinyl chloride) (PVC) with polycaprolactone (PCL) of different compositions were prepared from solutions in tetrahydrofuran (THF). The dried blends were stretched at different temperatures above the glass transition, and the birefringence and mechanical properties were studied. It is shown that the birefringence of PVC and the 75/25 PVC/PCL blend follows an affine deformation scheme with a decreasing number of segments with deformation. The 50/50 PVC/PCL blend shows a complex orientation behavior because of the presence of crystallinity in the PCL phase. The mechanical properties of the blends are shown to increase with orientation, and the aggregate model is acceptably followed by the amorphous oriented blends.     

Structure and properties of MDO stretched polypropylene

Two polypropylene cast films of different crystalline structures (one with coexisting small rows of lamellae and spherulites and the other with only a spherulitic structure) were prepared by extrusion. The produced cast films were uniaxially hot drawn at T = 120 °C using a machine direction orientation (MDO) unit and the changes in structure and morphology were examined and related to barrier as well as tear and puncture properties. Structural changes in terms of the degree of crystallinity and crystal size distribution, orientation of the amorphous and crystalline phases, and the deformation behavior at the crystal lattice and lamellae scales were investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), wide angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS), respectively. A significant effect of the original crystal morphology on the alignment of the amorphous and crystalline phases was observed from FTIR and WAXD. The results also revealed that the deformation behavior of the crystal structure was dependent on the draw ratio (DR). Our findings showed that by increasing DR the crystal lamellae first broke up and oriented along the drawing direction and then, at large DR, they were deformed and created a fibrillar structure. Morphological pictograms illustrating the effects of original morphology and draw ratio on the stretched film microstructure are proposed. The tear resistance along the machine direction (MD) decreased significantly with increasing DR whereas the puncture resistance increased drastically. Finally, the oxygen transmission rate (OTR) of the MDO stretched films could be correlated with the orientation parameters as well as the β-relaxation peak magnitude of the amorphous tie chains.     

Phthalonitrile end‐capped polyarylene ether nitrile: crystals embedded in matrix through crosslinking reaction

A novel single‐component composite based on phthalonitrile end‐capped polyarylene ether nitrile (PEN‐Ph) which undergoes a crosslinking reaction combined with crystallization behavior has been prepared successfully by hot compressing. The project focuses on studying the influence of the processing temperature and curing time on the crosslinking reaction and crystallization behavior. Differential scanning calorimetry analysis indicates that the crosslinking degree increases with an increase of processing temperature and curing time. In contrast, the crystallinity increases first and then decreases as the curing time increases, owing to the effect of the restriction of the crosslinking reaction on the crystallization behavior. Thermal polarizing microscope images provide direct evidence for crystal formation as a result of crosslinking reaction. Moreover, through comparative analysis of amorphous and crystallized PEN‐Ph sheets, the conclusion is drawn that the glass transition temperature and mechanical properties are affected by not only the degree of crosslinking but also by the crystallinity. © 2015 Society of Chemical Industry