Crazing behaviour in oriented poly(ethylene terephthalate)

A study has been made of the two types of crazes formed in oriented sheets of poly(ethylene terephthalate). The crazes have been termed tensile crazes and shear crazes. The tensile crazes formed parallel to the initial draw direction (IDD) whereas the shear crazes formed in a direction close to that of the deformation bands observed when the material yields.The possibility of applying a yield criterion to shear craze formation has been examined and there appears to be fairly good agreement between theory and experiment. Measurements of crazing stress on the tensile crazes indicated that the criterion for tensile craze formation is not purely dependent on the component of stress normal to the extended chains.It is concluded that the two types of crazes are formed by two quite different mechanisms, although the exact nature of these mechanisms is still uncertain.     

Structural changes during photodegradation of poly(ethylene terephthalate)

An investigation has been conducted into the effects of photodegradation on the structure of poly(ethylene terephthalate) (PET). Films, with and without ultraviolet absorbers and prepared by biaxial orientation after extrusion, have been exposed in the laboratory for periods of up to 1020 hours. The samples were investigated by differential scanning calorimetry (DSC), X-ray diffraction and size exclusion chromatography. The appearance of a cold crystallization peak during DSC heating scans was noted for exposed samples and this was considered to be a result of released molecules in the amorphous region that could rearrange into a crystalline phase. From X-ray analysis, a loss of crystalline orientation was observed after degradation and an interpretation was given based on relaxation in the mesophase region. In samples containing the photostabilizer additive the magnitude of changes in structure was lower, possibly due to segregation effects during film production making the non-crystalline region relatively immune to degradation effects.     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) nanocomposites

This article reports the nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nanocomposites. The non-isothermal crystallization behaviors of PET and the nanocomposite samples are studied by differential scanning calorimetry (DSC). Various models, namely the Avrami method, the Ozawa method, and the combined Avrami-Ozawa method, are applied to describe the kinetics of the non-isothermal crystallization. The combined Avrami and Ozawa models proposed by Liu and Mo also fit with the experimental data. Different kinetic parameters determined from these models prove that in nanocomposite samples intercalated silicate particles are efficient to start crystallization earlier by nucleation, however, the crystal growth decrease in nanocomposites due to the intercalation of polymer chains in the silicate galleries. Polarized optical microscopy (POM) observations also support the DSC results. The activation energies for crystallization has been estimated on the basis of three models such as Augis-Bennett, Kissinger and Takhor methods follow the trend PET/2C20A < PET/1.3C20A < PET, indicating incorporation of organoclay enhance the crystallization by offering large surface area.     

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.     

Viscoelastic properties of poly(butylene terephthalate)/poly(ethylene naphthalate) blends

Melt blends of poly(butylene terephalate) (PBT) and poly(ethylene naphthalate) (PEN) with 30 and 60 wt% PEN were prepared using a single screw extruder and an injection moulding machine. Stress relaxation tests for the specimens of PBT/PEN blends and the homopolymers were carried out using an Instron testing machine in an Instron environmental chamber. The Taguchi method of experimental design analysed how different levels of temperature, PEN content and initial stress affected the relaxation behaviour of PBT/PEN blends and homopolymers. From the response tables and analyses of main and interaction effects, it was shown that the most significant factor was temperature, followed by PEN content and then the initial stress. Consequently, high temperature, low PEN content and high initial stress speeded up stress relaxation rate of specimens. Interaction effects between factors were insignificant. To fit the relaxation curves of the PBT/PEN blends and the homopolymers at different temperatures, PEN contents and the initial stresses, four different equations were attempted with Matlab™, which determined the coefficients of these functions using the experimental data of stress change with time. The simulated curves from the most suitable function among them were shown using the calculated coefficients to predict the relaxation behaviour of PBT/PEN blends (50% PEN) at temperatures of 30 and 60°C with an initial stress of 7 MPa.     

Physical ageing studies in semicrystalline poly(ethylene terephthalate)

The physical ageing of semicrystalline poly(ethylene terephthalate) (c-PET) of different crystallinities and morphological structures was studied using differential scanning calorimetry. Samples of c-PET of crystallinity content _c = 0.12, crystallized at low temperatures (105 °C for 13 min), submitted to physical ageing in a temperature range between 50 and 65 °C for different periods of time, showed two endothermic peaks. The first peak (P₁) of higher intensity, appeared at a temperature close to the glass transition temperature, T _g, of the amorphous PET, and the other peak (P₂) of lower intensity, merged as a shoulder of the first one, at a higher temperature. These peaks have been attributed to the enthalpy relaxation process of two different amorphous regions: one amorphous phase outside the spherulitic structure (interspherulitic amorphous region) and another amorphous phase inside the spherulites (interlamellar amorphous region). The separation between P₁ and P₂ indicates that DSC, via enthalpy relaxation, is a good technique to detect the real double glass transition of the semicrystalline PET. However, the physical ageing of a semicrystalline PET of _c = 0.32, crystallized at 114 °C during 1 h, showed a main endothermic peak shifted to a higher temperature, which probably corresponds to the enthalpy relaxation of the more restricted interlamellar amorphous region, and a small endothermic peak at lower temperature which could be a reflection of the hindered interspherulitic amorphous region.     

Morphological instability of poly(ethylene terephthalate) cyclic oligomer crystals

The mechanism of formation of depressions and cavities in the middle of the basal faces of hexagonal plates of poly(ethylene terephthalate) oligomer single crystals upon growth during heat treatment is investigated. It is proposed that this effect is caused by two simultaneously occurring processes: supersaturation inhomogeneity in the centre of the plates and formation of the kinematic (shock) waves at the edges of the plates.     

长支链支化制备高熔体强度PET研究进展

主要介绍了采用多官能单体以及扩链/支化剂在PET主链上引入长支链的方法,论述了长支链结构对PET熔体强度、熔体流变行为和结晶行为的影响.     

Surface properties of poly(ethylene terephthalate) foils of different thicknesses

Surface properties of commercially available poly(ethylene terephthalate) (PET) foils of different thicknesses (3, 13, 23, 50, and 100 μm) were characterized using different analytical methods. Surface roughness and morphology were determined by atomic force microscopy, goniometry was used for determination of contact angle (wettability of surface) and electrokinetical analysis (zeta potential) for characterization of surface polarity and conductivity. X-ray photoelectron spectroscopy was used for characterization of PET surface chemistry. Infrared spectroscopy and differential scanning calorimetry (DSC) were used for determination of crystallinity portion. By DSC analysis, it was confirmed that the crystallinity portion depends on the foil thickness. Most important result of this study is that the surface properties of PET foils depend not only on the foil thickness but also on the foil side under study. This finding may be of importance for future experiments performed on PET foils and for their application in tissue engineering or microelectronics.     

Surface modification of poly(ethylene terephthalate) polymeric films for flexible electronics applications

The production of Flexible Electronic Devices (FEDs) by roll-to-roll large-scale manufacturing processes is a rapidly growing sector and the development of functional (inorganic and/or organic) thin layers onto flexible polymeric substrates represents one of the key issues for the low cost production of FEDs. However, the flexible substrates should meet advanced demands, as high optical transparency, high barrier properties and increased adhesion of the subsequent functional layers, which will have a major affect on their performance, efficiency and lifetime. Plasma treatment can be successfully employed for the improvement of the bonding structure and surface properties of flexible polymeric substrates. In this work, we report on the effect of Pulsed DC N⁺ ion bombardment using different ion energies, on the bonding structure, electronic and optical properties and surface nanotopography of Poly(Ethylene Terephthalate) (PET) substrates. For the investigation of the optical properties, we have used in-situ and real-time Spectroscopic Ellipsometry from the IR to Vis-farUV spectral region, in combination to advanced modeling procedures, whereas Atomic Force Microscopy has been employed for surface nanotopography investigation. As it has been found, the N⁺ bombardment leads to the appearance of new chemical bonds (C-N or C-O bonds in Φ-NH₂, Φ-NHR, C(O)-NHR, Φ-OH, or (CO)-OH), as well as partial disappearing of the C-O bond of ester group, on a surface layer of PET.     

Forensic analysis of poly(ethylene terephthalate) fibers by infrared spectroscopy

Poly(ethylene terephthalate) (PET) is one of the most commonly employed polymers in the textile industry. Its relevance as a source of evidence in the reconstruction of criminal cases is nevertheless very limited because the properties and morphologies of fibers from different producers tend to be very similar. By integrating bands, obtained on single fibers by infrared (IR) microscopy, associated with trans and gauche conformation and to the O-H end-groups of the molecules, a method is proposed that can discriminate otherwise similar PET fibers. The absorbancies at 1370 and at 846 cm(-1) relative, respectively, to the gauche and trans conformation, were measured and ratioed. The end-group content was evaluated by ratioing the absorbancies of the signals at 3440 and at 874 cm(-1). Relative standard deviation (R. S. D.) was 1% for repetitive analyses on the same location of the same single fiber. Precision was reduced if the ratios were measured along the length of a single fiber (R. S. D. = 3%) and even further when different fibers of the same sample were examined (R. S. D. varied from 2 to 10%). This simple method can greatly enhance the evidential value of PET fibers by subclassifying them, thus helping the Court to better assess their significance.     

Molecular orientation of poly(ethylene terephthalate) and poly(butylene terephthalate) probed by polarized Raman spectra: a parallel study

Poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) samples uniaxially drawn above Tg and beyond the yield point exhibit significant differences in their molecular orientation behavior as probed by polarized Raman spectra. The quasi-amorphous PET samples, drawn close to the Tg, manifest considerable molecular orientation development; however, when drawn above Tg + 30 degrees C, they exhibit significant molecular orientation relaxation. The semi-crystalline PBT samples maintain prominent molecular orientation even when drawn 110 degrees C above Tg. The drawing process, in PET samples, when resulting in molecular orientation, is accompanied by a gauche-trans transformation of the glycol linkage and a concurrent initiation of crystallinity development. In PBT specimens, it gives rise to a coexistence of alpha- and beta-type crystalline phases. Phase alpha is predominant at high draw temperatures, i.e., Tg + 110 degrees C, while phase beta dominates at low draw temperatures, i.e., Tg + 10 degrees C. PBT samples, with beta-phase predominance, left at relevant draw temperatures without stress, exhibit a beta-alpha phase change though no molecular orientation relaxation occurs. A note is made of the fact that complete molecular orientation analysis of PBT segments utilizing the depol method gives more reliable results than the simplified analysis assuming a cylindrical tensor for the 1614 cm(-1) symmetric stretch of the para-disubstituted benzene ring of PBT. In this context, segments of PBT specimens rich in alpha-phase exhibit higher molecular orientation than those with beta-phase predominance.     

Thermal effects on fracture of biaxial-oriented poly(ethylene terephthalate) (BOPET) film

The effect of temperature on the fracture behaviour of biaxial-oriented poly(ethylene terephthalate) (BOPET) film was studied using the Essential Work of Fracture (EWF) approach. Fracture tests were performed over the temperature range +25 to +160 °C at the speed of 5 mm/min using double edge notched tension (DENT) specimens. The length of the specimens was either along the machine direction (MD) (0°), transverse direction (TD) (90°) or at 45° to either MD or TD. Ductile tearing of the ligament region was noted over the entire temperature range in all three directions. A linear relationship was found between the specific total work of fracture and the ligament length at all test temperatures. Values of the specific essential work of fracture (w _e) in the MD and TD were similar and smaller than in the 45° direction. Within temperature range 25–140 °C, w _e showed little variation if any with respect to temperature. As expected, the Specific Non-Essential Work of Fracture (βw _p) was temperature dependent. This parameter increased with increasing temperature and reached a maximum around the glass transition temperature of BOPET (T _g ≈ 80 °C). The values of the maxima are respectively 16.15, 20.38 and 17.8 MJm⁻³ for the 0°, 45° and 90°.     

Orientation in poly(ethylene terephthalate) drawn by solid state coextrusion

The development of uniaxial orientation by solid-state extrusion at 60 to 90° C has been evaluated for both the amorphous and crystalline components of a polyethylene terephthalate). Analyses involved X-ray diffraction, birefringence and visable dichroism. The dichroism was evalulated from a host dye molecule. The initial PET film for draw was amorphous and isotropic. Orientation functions for the amorphous and the developed crystalline phases are reported at a series of draw ratios up to 4.4.     

Miscibility and melting properties of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting properties of binary crystalline blends of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) (PEN/PTT) have been investigated with differential scanning calorimetry (DSC). The glass transition and cold crystallization behaviors indicated that in PEN/PTT blends, there are two different amorphous phases and the PEN/PTT blends are immiscible in the amorphous state. The polymer–polymer interaction parameter, , calculated from equilibrium melting temperature depression of the PEN component was −1.791 × 10⁻⁵ (300 °C), revealing miscibility of PEN/PTT blends in the melt state.