Anisotropy and dimensional stability of biaxially oriented poly(ethylene terephthalate) films

Anisotropy in mechanical properties, expansion coefficients, and long-term shrinkage of PET films was determined. The films ranged in thickness from 0.92 to 14 mils. Young's modulus, ultimate strength, ultimate elongation, and coefficient of thermal expansion were strongly anisotropic. This anisotropy was related to orientation in the films. Yield stress and coefficient of hygroscopic expansion were more nearly isotropic. In general, the thin films showed more anistropy than the thick films due to better in-plane orientation in the thin films.     

Morphology and barrier mechanism of biaxially oriented poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

To improve the barrier properties of poly(ethylene terephthalate) (PET), PET/poly(ethylene 2,6‐naphthalate) (PEN) blends with different concentrations of PEN were prepared and were then processed into biaxially oriented PET/PEN films. The air permeability of bioriented films of pure PET, pure PEN, and PET/PEN blends were tested by the differential pressure method. The morphology of the blends was studied by scanning electron microscopy (SEM) observation of the impact fracture surfaces of extruded PET/PEN samples, and the morphology of the films was also investigated by SEM. The results of the study indicated that PEN could effectively improve the barrier properties of PET, and the barrier properties of the PET/PEN blends improved with increasing PEN concentration. When the PEN concentration was equal to or less than 30%, as in this study, the PET/PEN blends were phase‐separated; that is, PET formed the continuous phase, whereas PEN formed a dispersed phase of particles, and the interface was firmly integrated because of transesterification. After the PET/PEN blends were bioriented, the PET matrix contained a PEN microstructure consisting of parallel and extended, separate layers. This multilayer microstructure was characterized by microcontinuity, which resulted in improved barrier properties because air permeation was delayed as the air had to detour around the PEN layer structure. At a constant PEN concentration, the more extended the PEN layers were, the better the barrier properties were of the PET/PEN blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1309–1316, 2006     

The crystallization of oriented poly(ethylene terephthalate)

The rate of crystallization of oriented poly(ethylene terephthalate) has been measured at 100°, 120° and 150°C using carefully prepared amorphous fibre samples. The samples were held to length during crystallization so that shrinkage did not occur, and the course of crystallization was followed by measuring the changes in density and boiling water shrinkage of the samples. The results show that the rate of crystallization is strongly dependent on the degree of orientation. Nucleation and initial growth of crystallites occur in times of the order of milliseconds at 120°C in samples of birefringence 0.08 compared with times of several minutes in isotropic material. It was found that crystallization in oriented material cannot be described by the Avrami equation.     

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.     

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.     

Dielectric relaxation spectroscopy of poly(ethylene terephthalate)

Contour maps of dielectric loss tangent within the ranges 0.1 Hz to 3 MHz and ?175 °C to +190 °C are presented for a commercial poly(ethylene terephthalate) (PET) in two initial states of crystallinity. Individual absorption regions resemble those for poly(butylene terephthalate) and are attributed to carbonyl‐driven α‐ and β‐relaxation processes and to Maxwell–Wagner–Sillars polarizations. Possible causes are considered for the asymmetry and structure apparent in the α‐peak of partially crystalline PET. © 2001 Society of Chemical Industry     

Crystallization behavior of poly(ethylene terephthalate)

The crystallization behavior of poly(ethylene terephthalate) (PET) was studied by the methods of small angle light scattering, depolarized light intensity and density measurements. Spherulite growth rates and the overall rates of crystallization were determined at various temperatures. A detailed analysis of the crystallization course has been made with special emphasis on the early stages of crystallization. The results indicate that a significant amount of crystallization takes place in the extraspherulitie material during isothermal crystallization.     

Rheological and mechanical relaxation behavior of a thermally crosslinkable poly(ethylene terephthalate)

A novel terephthalic acid derivative based on benzocyclobutene, XTA, has been used as a comonomer in the preparation of thermally crosslinkable poly(ethylene terephthalate) copolymers. We have examined the rheological properties of a series of such polymers containing varying monomer percentages of the XTA comonomer: 0, 1, 5, 10, and 20. Incorporation of XTA into PET is found to cause dramatic changes in the temperature and time dependence of the rheological material functions, all indicating that the rate of crosslinking between chains in the melt increases as the XTA percentage is increased. The impact of thermal crosslinking on mechanical properties is also examined using dynamic mechanical analysis (DMA) on samples molded at a selected crosslinking temperature for times yielding varying levels of crosslinking extent. DMA results show that the activation energy of the β mechanical relaxation increases significantly, indicating the importance of torsional mobility of the aromatic ring of PET.     

Long‐term stress relaxation behavior of predrawn poly(ethylene terephthalate)

Research has been carried out with the aim of better understanding the relevant properties of materials to be used in a new self‐healing cementitious composite material system. In a previous study, the buildup of stress in a heat‐activated restrained predrawn poly(ethylene terephthalate) (PET) specimen was investigated. In the current study, the long‐term stress relaxation behavior of such a restrained specimen has been explored so that its potential for use in the new material system can be better understood. The work includes an experimental study in which the stress in a number of PET specimens, restrained against longitudinal shrinkage, was measured during the initial heat activation and cooling phases, and then monitored for a further 6 months. These data were used to quantify the stress relaxation of the specimen and to inform the development of a new one‐dimensional numerical model to simulate the thermomechanical behavior of this material. This model is shown to be able to reproduce the observed short‐ and long‐term experimental behavior with good accuracy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41208.     

Finite strain behavior of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG)

Uniaxial and plane strain compression experiments are conducted on amorphous poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG) over a wide range of temperatures (25-110 °C) and strain rates (.005-1.0 s⁻¹). The stress-strain behavior of each material is presented and the results for the two materials are found to be remarkably similar over the investigated range of rates, temperatures, and strain levels. Below the glass transition temperature (θ_g=80 °C), the materials exhibit a distinct yield stress, followed by strain softening then moderate strain hardening at moderate strain levels and dramatic strain hardening at large strains. Above the glass transition temperature, the stress-strain curves exhibit the classic trends of a rubbery material during loading, albeit with a strong temperature and time dependence. Instead of a distinct yield stress, the curve transitions gradually, or rolls over, to flow. As in the sub-θ_g range, this is followed by moderate strain hardening and stiffening, and subsequent dramatic hardening. The exhibition of dramatic hardening in PETG, a copolymer of PET which does not undergo strain-induced crystallization, indicates that crystallization may not be the source of the dramatic hardening and stiffening in PET and, instead molecular orientation is the primary hardening and stiffening mechanism in both PET and PETG. Indeed, it is only in cases of deformation which result in highly uniaxial network orientation that the stress-strain behavior of PET differs significantly from that of PETG, suggesting the influence of a meso-ordered structure or crystallization in these instances. During unloading, PETG exhibits extensive elastic recovery, whereas PET exhibits relatively little recovery, suggesting that crystallization occurs (or continues to develop) after active loading ceases and unloading has commenced, locking in much of the deformation in PET.     

X-ray low-angle scattering from oriented poly(ethylene terephthalate) films

Low-angle x-ray scattering data are used to deduce the morphology of oriented polymeric films. Generally, the structural models proposed to explain these patterns have been extrapolations of observations made from solution-grown polymer single crystals or from highly crystalline bulk polymers. These models and explanations may not be applicable broadly to oriented systems having only modest amounts of crystallinity or to those generated from precursor states that are grossly different. Poly(ethylene terephthalate) (PET) was chosen as a model polymer system for study. A systematic series of uniaxially and biaxially deformed films were produced from this polymer, made from the initially glassy or crystalline states. The low-angle x-ray scattering patterns generated from these films were studied as a function of (a) the sequence of deformation, (b) the precursor structure, (c) molecular orientation, and (d) the direction of observation. Optical diffraction and model structures were used to aid in the interpretation of the morphology produced. At least three different-sized domains are developed upon deformation, ranging from that of the unit cell (about 10 Å) to large laminar domains of average size 2,000 Å × 10,000 Å. This structure is shown to be substantially different from that developed in an oriented polyethylene film.     

Anisotropy of dielectric relaxation in poly(ethylene terephthalate) fibres

Dielectric measurements have been made on poly(ethylene terephthalate) (PET) fibres in the frequency range 0.5–10 kHz in temperature range ?120°?+30° C with the applied electric field parallel and perpendicular to the fibre axis. Considerable directional anisotropy was observed in the β-relaxation process, which was independent of frequency. The observed dielectric anisotropy has been related to the structural parameters thus leading to a value 〈cos²ψ〉 = 0.21, where ψ is the angle between the dipole moment vector responsible for this relaxation and the molecular chain axis. Activation energy for this process in PET fibres (9 kcal/mol) was lower than that reported for PET films and extruded rods.     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Raman spectroscopy of stressed samples of oriented poly(ethylene terephthalate)

Measurements of the shift and change of shape of the 1616 cm⁻¹ Raman scattering peak of two moderately oriented samples of poly(ethylene terephthalate) (PET) under tensile loads of up to 0.2 GPa are reported, together with the corresponding strains. To obtain reproducible results load cycling procedures were adopted similar to those established for the study of viscoelastic behaviour. The Raman scattering was observed with polarized incident and scattered light, with the polarization directions either both parallel or both perpendicular to the draw direction in the samples. The results showed that for both samples the Raman shift was linearly related to the applied stress below the yield point. Up to the yield point very little change of line width was observed but above the yield point the width increased significantly. Differences in both widths and shifts were observed for the two polarization directions at the same stress level. The results are discussed in terms of the usual assumptions that the shift of the line gives a measure of the average stress in those chains which predominantly contribute to the peak and that the width and shape of the line give information about the spread of stresses. It is concluded that the technique can give useful information about the molecular stress distribution in thick samples of moderately oriented PET under load, including information about the different stress distributions on chains at different angles to the draw direction.     

Enthalpy relaxation in poly(ethylene terephthalate) and related polyesters

Enthalpic relaxation data are presented on poly(ethylene terephthalate), poly(ethylene naphthalate) and their copolymers. Analysis of these data allows the determination of the amount of energy absorbed at the glass transition, Q_t, and the location of the enthalpic recovery peak, T_max, as a function of the time of ageing of the samples. Ageing measurements were carried out for periods of up to 2016 h and at temperatures between 40 °C and 110 °C, depending upon the chemical composition of the system being investigated. The enthalpic relaxation rates are influenced by the chemical structure and reflect the effects of local order pinning the chains and influencing the rate of enthalpic recovery. © 2000 Society of Chemical Industry     

聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)等温结晶行为研究

以对苯二甲酸(PTA)、乙二醇(EG)、异山梨醇(ISB)为原料,通过直接熔融缩聚法合成聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)(PEIT)共聚酯。利用差示扫描量热法(DSC)研究了共聚酯的结晶行为,采用Avrami方程分析了共聚酯的等温结晶动力学。结果表明,PEIT共聚酯结晶行为受共聚组成和结晶温度影响。随着ISB用量的增加或结晶温度的降低,共聚酯半结晶周期t1/2增加、结晶速率变慢;ISB摩尔分数超过20%,共聚酯无法结晶。     

Polarized internal reflectance spectroscopic studies of oriented poly(ethylene terephthalate)

Polarized internal reflectance spectroscopy (IRS) has been used to evaluate molecular orientation and crystallinity of poly(ethylene terephthalate) film surfaces. Measurements were taken using samples stretched in both uniaxial and biaxial modes. All bands of interest were normalized with a reference band near 1410 cm^?1, resulting from phenylene ring vibrations. Normalization was performed in order to overcome problems with sample contact and effective thickness. Results obtained using bands representing trans and gauche rotational isomers, present, respectively, at 1340 and 1370 cm^?1, have been related to data acquired using density and birefringence techniques. The polarized IRS technique discussed is well suited for investigations of polymer orientation and crystallinity, since it avoids limitations related to sample thickness and clarity imposed by polarized transmission infrared spectroscopy. Parameters such as orientation functions, attenuation indices, dichroic ratios, and structural factors have been determined from data collected in each of the three spatial directions. Results are correlated with corresponding density, birefringence, and refractive index values and are found to give good agreement with these methods. © 1994 John Wiley & Sons, Inc.     

Micromechanical behavior of impact modified poly(ethylene terephthalate)

The micromechanical behavior of poly(ethylene terephthalate), PET, modified with a metallocene polyolefin copolymer (mPE) was investigated. Uniaxial deformation tests were performed using a tensile stage in a scanning electron microscope. This technique allowed the identification of the main deformation mechanisms that are associated with energy dissipation and toughness improvement. The poly(ethylene terephthalate) was blended with 5 wt% mPE by single‐screw extrusion. Films with thicknesses ranging from 200 to 500 μm were produced. Observation of the surfaces of the films during uniaxial deformation revealed the sequence of events leading to the full yielding of the matrix. In the early stages of deformation, the particles deform together with the matrix. As the deformation is increased, cavitation inside the particles occurs and fibrillation at the particle/matrix interface is observed, as well as the onset of shear banding. In order to study the effect of interfacial adhesion of the deformation mechanisms, the PET/mPE blends were compatibilized by grafting with glycidyl methacrylate (GMA). The reduction of the particle size was significant, which is indicative of the efficiency of GMA grafting in this type of blend. In this case, the particles were difficult to detect on the surface. Cavitation and shear banding occurred simultaneously. A similar behavior was observed in the case of oriented blends.     

Nanoindentation and nanoscratch testing of uniaxially and biaxially drawn poly(ethylene terephthalate) film

Nanoindentation and nanoscratch testing have revealed large differences in nanomechanical behaviour on uniaxially and biaxially drawn poly(ethylene terephthalate) films. Differences can be ascribed to the processing history of the film. The biaxial material exhibited significantly higher hardness and elastic modulus than the uniaxial film, presumably due to increased crystallinity from the second draw. The biaxially drawn material was also less susceptible to creep deformation. The plasticity index, the ratio of the dissipated energy to the total indentation energy, was greater on the uniaxial film, indicating that it exhibits less plastic deformation than the biaxially stretched film. The differences in processing also affected the resistance of the films to nanoscratching wear. The wear resistance of the films correlated with the ratio of the hardness to the modulus.     

Cold-drawing behavior of naturally aged poly(ethylene terephthalate)

The cold-drawing behavior of naturally aged poly(ethylene terephthalate) (PET) is investigated and an attempt is made to compare the mechanical behavior of unaged commercial PET and material which has been naturally aged for 11 years. Mechanical, viscometric, DSC and IR measurements are applied. The previously observed unusual ability of fresh PET bristles to be cold drawn up to 15:1 is not achieved for the naturally aged material. This fact is related to chemical cross-linking occurring on the surface of bristles after drawing and thermal treatment. The cross-linked skin is unsoluble, infusible, and uncrystallizable. The natural aging defeats the ability of PET to respond to external treatments which would otherwise change the internal structure. Such a “stabilization” of material properties is a result of the transformation, during natural aging, of the original physical network into a chemical network consisting of covalent bonds.