Geometrical bowing and molecular orientation angle in biaxially stretched poly(ethylene terephthalate) films

The aim of this study was to investigate in greater detail the occurrence of geometrical bowing and the average molecular orientation direction in biaxially stretched and annealed film webs and to determine possible causes for these effects at a morphological level. This involved studying the temperature‐dependent behavior of annealed and nonannealed film webs and determining the geometrical bowing and average molecular orientation direction across the working width of the film. The average molecular orientation direction was measured offline using a polarimeter and also online using a novel online orientation sensor. It was shown that the geometrical bowing correlates directly with the amount of film shrinkage in machine direction which occurs during annealing in the transverse direction orienter. In addition, a possible explanation is given for the greater increase in the molecular orientation angle at the film edges compared with the geometrical bowing. Good agreement was found between online and offline measurement of the molecular orientation angle. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

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.     

Phase morphology and mechanical properties of blends of poly(p-phenylene sulfide) and polyamides

An experimental study of the blending, thermal transitions, phase morphology, and mechanical properties of poly(p-phenylene sulfide) (PPS)/polyamide blends is presented. Nylon-6, rubber modified nylon-6, nylon-66, nylon-11, nylon-12, and two partially aromatic amorphous polyamides were included in the study. Generally, blends of PPS with aromatic amorphous polyamides exhibit better mechanical properties than those with aliphatic polyamides. The blends with nylon-12 exhibit the best characteristics among the aliphatic polyamides.     

Processing characteristics,structure development,and properties of uni and biaxially stretched poly(ethylene 2,6 naphthalate) (PEN) films

Poly(ethylene 2,6, naphthalene dicarboxilate), PEN, is very similar to poly(ethylene terephthalate), PET, in its chemical structure and was, therefore, expected to exhibit similar processing characteristics. We, however, observed a few problems during stretching of PEN, the most important of which was necking behavior at 145°C, which is between T_g (117°C) and T^cc (195°C). This is usually observed in PET only when it is stretched close to or below T_g. At temperatures between T_g and T_cc (cold crystallization temperature) PET stretches rather uniformly. The temperature window for film stretching appears to be rather wide, but our results indicate that this is not the case. Films stretched to high stretch ratios become uniform due to propagation and final disappearance of necks as a result of stress hardening. Our attempts at stretching these films at higher temperatures indicated that necking is eliminated, but so is stress induced crystallization, which causes stress hardening (unless high stretching rates are employed). The presence of stress hardening is essential for obtaining high quality, uniform films of these polymers. In addition, at high temperatures thermally activated crystallization which starts dominating the structure development, detrimentally affects the general appearance of the films. In brief, the PEN films we investigated have a narrower processing window than was anticipated based on their thermal behavior alone. At elevated temperatures the films are sensitive to the rate of stretching even more than typical PET processed at comparable conditions. The uniformity of the films depends on the stretch ratio, stretching mode, ratio(s) and rates and temperature. WAXS studies on the films indicate that the macromolecules packed into the low temperature crystal modification. In addition, WAXS pole figure studies suggest that naphthalene planes preferentially orient parallel to the film surface during biaxial stretching. The biaxially stretched films were observed to exhibit a bimodal chain orientation as evidenced by pole figure analysis of the (010) planes.     

Electronic structure of poly(p-phenylene sulfide)

The electronic structure of poly(p-phenylene sulfide) (PPS) was studied through steady state photocurrent spectra and temperature dependence of dark conductivity for undoped film, by changes in the in situ optical absorption and ESR spectra under photoirradiation, and optical absorption spectra for doped film. The charge carriers in the undoped state are electronic since the photoconductivity is large and the kink point in the temperature dependence of dark conductivity is higher than the glass transition temperature. A sharp peak near the absorption edge in the photocurrent spectrum of undoped PPS is caused by the diffusion of photocarriers in a sheet with high surface recombination under conditions of low applied field. The in situ optical absorption and ESR spectra of SO₃-doped PPS were similar to those of di-p-tolyl sulfide (a monomer unit of PPS) and the formation of sulfur-centered radical cations was suggested rather than bipolaron states. The stable conduction of SO₃-doped PPS after exposure to atmosphere was analyzed by the classical Lorentz model and the existence of nearly free carriers within subchains was suggested. Their conductivity and mobility were estimated to be 2 S/cm and 3.6 cm²/Vs, respectively. Inter-chain conduction appears to be very low.     

聚苯硫醚热氧化处理研究

研究了聚苯硫醚在空气环境下经过热处理的合成化学改性.采用高温凝胶渗透色谱、光电子能谱、热失重、红外光谱和高压毛细管流变技术对聚苯硫醚进行表征.结果表明:低相对分子质量的聚苯硫醚和高相对分子质量的聚苯硫醚经过热处理,相对分子质量都会大幅提高;聚苯硫醚经过热处理过程会同时发生氧化反应、氧化交联反应、热交联反应和链增长反应.     

Uniplanar orientation of poly(p-phenylene terephthalamide) crystal in thin film and its effect on mechanical properties

The uniplanar orientation of poly(p-phenylene terephthalamide) (PPTA) crystal was investigated by x-ray and infrared measurements. Thin PPTA films 3–15 μm thick were prepared by coagulating a sulfuric acid solution of PPTA with various coagulants. Two types of uniplanar orientation were observed, depending on the coagulant used. Thin film coagulated with water exhibits (0k0) uniplanar orientation and film coagulated with other coagulants such as methanol, ethanol, and acetone exhibits (h00) uniplanar orientation. These (h00) and (0k0) uniplanar orientations are formed with crystal modifications I and II, respectively. The (0k0) uniplanar orientation transforms to (h00) upon annealing, accompanying crystal transformation from modification II to modifications I. These uniplanar orientations may result from anisotropic crystal growth due to polymer–coagulant interaction along the hydrogen bond direction. The effect of these uniplanar orientations on the mechanical properties was also examined. The thin film having the (0k0) uniplanar orientation shows ductile fracture, whereas the one having the (h00) uniplanar orientation shows brittle fracture upon tensile deformation. These results are explained on the basis of the direction of the uniplanar orientation of the hydrogen-bonded sheet.     

Surface modification and bonding of poly(p-phenylene sulfide)

It is demonstrated that both chemical oxidation, e.g. by using acetic acid/hydrogen peroxide or chromosulfuric acid, and plasma treatment of poly(p-phenylene sulfide) (PPS) surfaces introduce polar groups. The changes of the surface chemistry are detected by FTIR spectroscopy, X-ray photoelectron spectroscopy, and contact angle measurements. The increased polarity is partially responsible for better adhesion as verified by lap shear measurements using acrylic adhesive. Another important contribution to the improved adhesion originates from increased surface roughness after surface modification as measured by atomic force microscopy. This effect is very pronounced for PPS surfaces treated with chromosulfuric acid.     

Process for the formation of biaxially oriented films of poly(p-phenylene terephthalamide) from liquid crystalline solutions

A new process for making equal biaxially oriented films from liquid crystalline solutions of poly(p-phenylene terephthalamide) (PPD-T) is described. The process involves extruding solutions of PPD-T/H₂SO₄ through an annular die and over an oil-coated mandrel into a coagulation bath. The films were studied using wide angle X-ray diffraction (WAXS) and scanning electron microscopy (SEM). Tensile stress–strain properties were obtained on samples cut at various directions in the plane of the film. Biaxially oriented films which possess equal properties in the various directions in the plane of the film were produced. Moduli of 2.3 × 10⁹ Pa and tensile strengths of 9.6 × 10⁷ Pa were obtained in the plane of the film. Films with unequal biaxial orientation were also produced. These tend to have higher modulus/tensile strength in the direction of major orientation, the machine direction (up to 8.3 × 10⁹ Pa/2.5 × 10⁸ Pa), but become brittle in the transverse direction.     

The crystallinity of poly(phenylene sulfide) and its effect on polymer properties

The crystallinity and crystallizability of poly(phenylene sulfide) have been examined by a number of common techniques. Several provided qualitative information, but only one, x-ray diffraction, was considered sufficiently reliable and reproducible to allow quantitative comparisons. Based on x-ray measurements, an approximate degree of crystallinity, termed crystallinity index (C_i), could be readily assigned. According to this method, virgin polymer possesses significant crystallinity (C_i ≈ 65%). Curing (crosslinking) the resin below its melting point did not change the crystallinity but did affect the crystallizability. Lightly cured resin suitable for molding and film extrusion was easily quenched from the melt to give amorphous polymer. The amorphous samples crystallized rapidly when heated to temperatures > 121°C (250°F). At mold temperatures below 93°C (200°F), moldings with very low surface crystallinity were produced. Annealing (204°C, 400°F) caused rapid crystallization of such moldings, and changes in crystallinity were correlated with observed changes in physical properties. The resin crystallizes so rapidly that these quenched moldings possessed a crystallinity gradient, the internal crystallinity being substantially greater. At high mold temperatures (121–204°C, 250–400°F), moldings very similar to fully annealed specimens were obtained.     

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.     

Small angle and wide angle x-ray pole figure studies on simultaneous biaxially stretched poly(ethylene terephthalate) (PET) films

Biaxially oriented poly(ethylene terephthalate) (PET) films have been characterized by small angle and wide angle x-ray scattering. The films were studied at various rotational angles to the impinging beam and orientations relative to axes in three directions in the film were obtained. Pole figures were developed for both the major small angle scattering peak and wide angle diffraction peaks. These are used to interpret structural changes in the films associated with various degrees of biaxial stretching and subsequent constrained annealing.     

Electron microscopy of high pressure crystallised poly (p-phenylene sulfide)

Abstract

High pressure crystallised poly (p-phenylene sulfide) (PPS) samples were investigated with wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The striation appearance, which is the most common feature of polymer extended chain crystals, was clearly observed. Poly (p-phenylene sulfide) extended chain crystals with a C-axis thickness around 10 μm were formed at high pressure. The DSC results showed that the melting temperature of high pressure crystallised PPS samples was up to 332·3°C, which was higher than the values of ideal PPS perfect crystals used by some researchers. Other morphologies formed at high pressure, including crystalbars and regular polygonal crystals of different characteristics, were also presented with the SEM measurements. The obtained PPS extended chain crystals may be used in the re-evaluation of certain parameters crucial to the processing of PPS products such as the equilibrium melting point and melting enthalpy of ideal crystal.     

Shrinkage behavior after the heat setting of biaxially stretched poly(ethylene 2,6‐naphthalate) films and bottles

Amorphous preforms of poly(ethylene 2,6‐naphthalate) (PEN) were biaxially drawn into bottles up to the desired volume under industrial conditions. These bottles were used to characterize the shrinkage behavior of the drawn bottles with or without heat treatment and to study structural variations during heat setting. During drawing, a rigid phase structure was induced, and the amount of the induced rigid phase structure was linearly related to the square root of the extra first strain invariant under equilibrium conditions. During the production of these bottles, this equilibrium was not attained because of high stretching conditions and rapid cooling after stretching. The structure after orientation contained a rigid amorphous phase and an oriented amorphous phase. The shrinkage behavior was a function of the temperature and time of heat setting. Long heat‐setting times, around 30 min, were used to characterize the possible structural variations of the oriented PEN after heat setting at equilibrium. Under the equilibrium conditions of heat setting, the start temperature of the shrinkage was directly related to the heat‐setting temperature and moved from 60°C without heat treatment up to a temperature of 255°C by a heat‐setting temperature of 255°C; this contrasted with poly(ethylene terephthalate) (PET), for which the start temperature of shrinkage was always around 80°C. For heat‐setting temperatures higher than 220°C, the structural variations changed rapidly as a function of the heat‐setting time, and the corresponding shrinkage of the heat‐set samples sank below 1% in a timescale of 30–60 s for a film thickness of 500 μm. The heat treatment of the oriented films taken out of the bottle walls with fixed ends stabilized the induced structures, and the shrinkage of these heat‐set films was zero for temperatures up to the heat‐setting temperature, between 220 and 265°C, if the heat‐setting time was sufficient. According to the results obtained, a heat‐setting time of 30 s, for a film thickness of 500 μm, was sufficient at a heat‐setting temperature of 255°C to stabilize the produced biaxially oriented PEN bottles and to take them out the mold without further shrinkage. During the drawing of PEN, two different types of rigid amorphous phases seemed to be induced, one with a mean shrinkage temperature of 151°C and another rigid amorphous phase, more temperature‐stable than the first one, that shrank in the temperature range of 200–310°C. During heat setting at high temperatures, a continuous transformation of the less stable phase into the very stable phase took place. The heat‐set method after blow molding is industrially possible with PEN, without the complicated process of subsequent cooling before the molds are opened, in contrast to PET. This constitutes a big advantage for the blow molding of PEN bottles and the production of oriented PEN films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1462–1473, 2003     

Effect of molecular weight and crystallinity on poly(lactic acid) mechanical properties

Several samples of poly(lactic acid) with different molecular weights and tacticity have been prepared, and some PLLA injection moulded specimens have been annealed to promote their crystallization. From the characterization data, poly(L -lactide) showed more interesting mechanical properties than poly(D, L -lactide), and its behavior significantly improves with crystallization. In fact, annealed specimens possess higher values of tensional and flexural modulus of elasticity, Izod impact strength, and heat resistance. The plateau region of flexural strength as a function of molecular weights appears around M_v = 35,000 for PDLLA and amorphous PLLA and at higher molecular weight, around M_v = 55,000, for crystalline PLLA. The study of temperature effect shows that at 56°C only crystalline PLLA still exhibits useful mechanical properties. © 1996 John Wiley & Sons, Inc.     

超支化聚苯硫醚与线性聚苯硫醚的对比表征

以2,4-二氯苯硫酚为原料,采用一步法合成超支化聚苯硫醚。笔者运用红外光谱、拉曼光谱、荧光光谱、示差扫描量热分析、热重分析、广角X-射线衍射、溶解实验等分析手段,对超支化聚苯硫醚和线性聚苯硫醚的基本性能进行了对比。由于两者结构上的差异,使得两者表现出不同的特性。超支化聚苯硫醚具有三取代苯结构,具有很强的荧光效应、完全的不结晶、溶于有机溶剂、热降解温度低于线性聚苯硫醚约60℃等特性。广角X-射线衍射谱图也和结晶、无定型线性聚苯硫醚有很大不同。