In situ WAXS/SAXS structural evolution study during uniaxial stretching of poly(ethylene terephthalate) nanocomposites in the solid state: Poly(ethylene terephthalate)/titanium dioxide and poly(ethylene terephthalate)/silica nanocomposites

This work reports an in situ WAXS and SAXS investigation, under X‐ray synchrotron source radiation, on the structural evolution during solid‐state uniaxial deformation of poly(ethylene terephthalate) (PET) nanocomposites with 0.3 wt % of 3D nanoparticles [nanotitanium dioxide (TiO₂) and nanosilica (SiO₂)]. Good dispersion and average agglomerate sizes of nanoparticles of about 80 nm for both nanocomposites were revealed by transmission electron microscopic characterization. The influence of the nanofillers on the deformation‐induced phase's formation and their evolution along the stretching process were compared with respect to the neat PET. WAXS results indicated that the structural evolution of all samples passes through three main stages, with evolution of amorphous phase into mesophase, a rapid increase of molecular orientation, and the formation of a periodical mesophase (PM). The incorporation of the nanofillers promoted a higher fraction, and an earlier formation, of PM during stretching when compared with pure PET. Furthermore, the presence of TiO₂ nanoparticles in the PET matrix resulted in the earliest formation and the highest amount of PM and the retardation of crack growth and bigger voids when compared with PET/SiO₂ nanocomposite. A multiscale structural evolution mechanism is proposed to interpret these results. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39752.     

Dynamic thermomechanical and tensile properties of chain-extended poly(ethylene terephthalate)

A series of chemically modified poly(ethylene terephthalate) (PET) samples was received after chain extension of a virgin sample at different reaction times with a new diepoxide as chain extender. These samples showed different intrinsic viscosity and degrees of branching or crosslinking. The effect of this differentiation on thermal properties was studied by dynamic mechanical thermal analysis and the determined T_g values were found to be in good agreement with those obtained by differential scanning calorimetry and thermomechanical analysis. Also, the branching or crosslinking exhibited significant improvement in tensile mechanical properties, which were studied, and the results are discussed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 797–803, 1998     

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.     

Molar mass of poly (ethylene terephthalate) (PET) during ultimate uniaxial drawing

The changes of the average molar mass M_w, M_n, M_z, and molar mass distributions during multistep uniaxial drawing of poly(ethylene terephthalate) (PET) to achieve ultimate mechanical properties have been studied in detail by means of size exclusion chromatography (SEC) with triple detection: concentration, viscosimetry, and light scattering, using HFIP as solvent. An increase in molar mass of PET due to post‐polycondensation and/or transesterfication during drawing at a high temperature of 160 to 230°C was found. Moreover, drawing leads to crystallization and large orientation in the amorphous phase, which results in lower molecular mobility and prevents a further growth in chain length. Crazing under extreme drawing conditions occurs and affects a decrease in molar mass.     

A structural study of the tensile drawing behaviour of poly(ethylene terephthalate)

A study of single-stage and two-stage drawing of poly(ethylene terephthalate) has been undertaken. Measurements of the modulus of the drawn films were combined with a range of structural measurements, including refractive index, X-ray diffraction and infra-red spectroscopy. The development of molecular orientation during drawing is discussed in terms of the deformation of a molecular network, and reasons for the differences between single stage and two-stage drawing are proposed. The relationships between different measures of molecular orientation are considered with the aim of obtaining an understanding of the factors which influence the modulus values. It appears that the modulus relates primarily to the molecular chains which are in the extended trans conformation, irrespective of crystallinity.     

Heterogeneous blends of recycled poly(ethylene terephthalate) with impact modifiers: phase structure and tensile creep

Several types of photomicrographs have concurrently shown that impact modifiers (IMs) form particles (on a micrometre scale) which are evenly dispersed in a recycled poly(ethylene terephthalate) (PET) matrix; their adhesion to the latter is high enough that fracture surfaces (produced in liquid nitrogen) do not follow the interface. An essential part of the tensile creep of PET corresponds to the elastic time‐independent component; the time‐dependent component is rather limited, even if relatively high stresses are applied. Thus, the tensile compliance of PET is virtually independent of the applied stress, which indicates linear viscoelastic behaviour. The compliance of PET/IM blends (93/7, 90/10, 85/15 (by weight)) grows with the IM content and its time‐dependence becomes more visible. The effects of the two types of IM used in this study seem to be practically identical from the viewpoint of dimensional stability of the blends. The logarithm of compliance grows with the logarithm of time faster than linearly, and this tendency becomes more apparent with increasing fraction of IM. Even if the strain‐induced free volume is taken into account, a noticeable upswing of the compliance for longer creep periods (t > 1000 min) is evident. This cannot be interpreted as a consequence of the flow, because the recovery following the creep has proved the complete reversibility of the previous deformation. A simple empirical equation is proposed, which provides a plausible prediction of the creep behaviour of PET with dispersed impact modifiers. Copyright © 2004 Society of Chemical Industry     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Flame-retardant poly(ethylene terephthalate)

Poly(ethylene terephthalate) containing hexabromobenzene, tricresyl phosphate, or a combination of triphenyl phosphate and hexabromobenzene, pentabromotoluene, or octabromobiphenyl was extruded or spun at 280°C into monofilaments or low-denier yarn, respectively. Only combinations of the phosphorus- and halogen-containing compounds resulted in flame-retardant poly(ethylene terephthalate) systems, without depreciating their degree of luster and color quality. The melting temperature, the reduced viscosity, and the thermal stability above 400°C of these flame-retardant systems were in most cases comparable to those of poly(ethylene terephthalate) itself. Phosphorus-bromine synergism was proposed with flame inhibition occurring mostly in the gas phase.     

Structural development of poly(ethylene terephthalate) during uniaxial stretching above the glass‐transition temperature: Study of the statistical influence of the stretching variables

In this article, we present an investigation of the structural development of poly(ethylene terephthalate) (PET) during uniaxial stretching above the glass‐transition temperature; this followed a statistical design of experiment approach to determine the influence of the stretching variables on the structural development. Amorphous PET was submitted to a stretching program with variations in the stretching temperature (T_st), stretching rate ( $\dot {\varepsilon}_{st}$ ), and stretching ratio (λ_st). Stretched samples were rapidly quenched and characterized by wide‐angle X‐ray scattering, optical birefringence, and differential scanning calorimetry. The relevance and influence of the stretching variables on the obtained parameters (phase fraction, phase orientation, and thermal parameters) were analyzed. The strain‐induced crystallinity was controlled by T_st, λ_st, and the interactions between them. Mesophase development was not dependant on T_st but on the interactions between $\dot {\varepsilon}_{st}$ and λ_st. The molecular orientation was proportionally dependent on T_st, λ_st, and their interactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Powdered poly(ethylene terephthalate)

The influence of the conditions of preparation on the properties of powdered poly(ethylene terephthalate) was followed from the point of view of its specific surface. The powdered poly(ethylene terephthalate) prepared by reprecipitation from the melt of 6-caprolactam has a porous and structured surface, and consequently, also a large specific surface in comparison with the powedered poly(ethylene terephthalate) prepared by mechanical milling. The specific surface value is influenced by the cooling rate of the initial homogeneous melt of poly(ethylene terephthalate)-6-caprolactam, by the concentration of poly(ethylene terephthalate) in this melt and by its molecular weight, by the water temperature at the extraction of 6-caprolactam from the tough mixed melt, by the drying temperature of the powdered poly(ethylene terephthalate), and by the content of residual 6-caprolactam in the powdered product. In the examined area, the specific surface value of the powdered poly(ethylene terephthalate) prepared by reprecipitation from the melt of 6-caprolactam ranged from 10 to 110 m²·g^?1.     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

Effect of ammonium salts on poly(ethylene terephthalate) materials

The study of the effect of solutions of ammonium salts of low concentrations on polyester fibre material showed that modification of the material with ammonia formed by thermal hydrolysis of ammonium salts differs from modification with ammonia obtained by the reaction of equimolar quantities of ammonium nitrate and sodium hydroxide and is similar to the process that takes place when ammonia is added to the working solution. Of the salts examined, ammonium fluoride in the concentration of 0.02–0.35 M at 130°C and 30-min process time is the most active modifying agent. In these conditions, ammonium fluoride and the products of its high-temperature hydrolysis — hydrogen fluoride and ammonia — have the strongest catalytic effect on hydrolysis of cyclic oligomers with formation of their linear form. On the whole, ammonium fluoride has a stronger modifying effect on polyester material than aqueous ammonia. __________ Translated from Khimicheskie Volokna, No. 1, pp. 17–21, January–February, 2007.     

Effect of tensile strain rate on the mechanical properties of constrained-uniaxially and simultaneous-biaxially drawn poly(ethylene terephthalate) sheets

The dependency of the mechanical properties (Young's modulus, yield strength, breaking strain, and breaking energy) of preoriented poly(ethylene terephthalate) (PET) sheets on the tensile deformation speeds was examined and discussed in relation to changes of density and birefringence. The procedures for preorientation were constrained-uniaxially (CU) and simultaneous-biaxially (SB) drawings at 65°C. The performance characteristics of the present tensile testing at room temperature were obtained over a wide range of extension rates (1.7 × 10^?4?13.1 m/s = 0.29–2.3 × 10⁴%/s) without changing the mode of deformation and the shape of the test pieces. The CU drawn PET is strain-rate-independent and mechanically superior in structure in the preextended direction with draw ratio λ > 2.5. In the SB drawn PET such a structure comes into existence at λ > 3, which has, furthermore, no dependency on draw direction (mechanically isotropic). The draw ratio of the latter case corresponded to the birefringence (?Δn/d) of about 5 × 10^?2. These results imply a possibility of producing the strain rate (from low to impact speeds) independent, anisotropy-free, and mechanically superior molded products of PET if adequate extrusion or blow molding methods which induce multiaxial orientation with ?Δn/d > 5 × 10^?2 are developed.     

Structural formation of amorphous poly(ethylene terephthalate) during uniaxial deformation above glass temperature

An in situ study of structural formation of amorphous poly(ethylene terephthalate) (PET) during uniaxial deformation above its T_g (at 90 °C) was carried out by wide-angle X-ray diffraction (WAXD) with synchrotron radiations. Results indicate that the relationships between structure and mechanical property can be divided into three zones: I, II and III. In Zone I, oriented mesophase is induced by strain, where the applied load remains about constant but the amount of mesophase increases with strain. In Zone II, crystallization is initiated from the mesophase through nucleation and growth, where the load starts to increase marking the beginning of the strain-hardening region. The initial crystallites are defective but they form an effective three-dimensional network to enhance the mechanical property. The perfection of the crystal structure and the orientation of the crystals all increase with strain in this zone. In Zone III, the ratio between load and strain is about constant, while the stable crystal growth process takes place until the breaking of the sample. The sample damage is probably dominated by the chain pull-out mechanism from the crystal amorphous interface. The increase in molecular weight was found to enhance the overall mechanical properties such as the load to induce the mesophase and the ultimate tensile strength before breakage.     

Influence of temperature during overmolding on the tensile modulus of self-reinforced poly(ethylene terephthalate) insert

Self-reinforced polymer composites are thermoplastic materials for design of recyclable lightweight components. The combination of sheet forming and subsequent overmolding from these materials allows an efficient manufacturing process with function integration. This article investigates how temperature exposure during an overmolding cycle influences the tensile modulus, shrinkage, and warpage for an insert made from self-reinforced poly(ethylene terephthalate) (PET) when it is overmolded with polycarbonate (PC)/PET material. The temperature gradient that is induced by overmolding is simulated, and the results are validated through experiments. The results show that the insert reaches a temperature above the glass-transition temperature for the matrix material in the main part of the insert, which leads to relaxation of residual stresses and thereby a reduction of the tensile modulus up to 18% for the insert after overmolding. Even though overmolding is an efficient process, it requires thorough knowledge of how temperature influences the material when applied to self-reinforced composite materials. The study shows very interesting results, which can lead to new areas of applications for self-reinforced PET. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48334.     

Effect of recycling on the properties of poly(ethylene terephthalate) films

Different proportions of recycled poly(ethylene terephthalate) (PET) films were blended with virgin PET and evaluated for physicomechanical, chemical, thermal, optical and barrier properties. The safety evaluation of the films for food contact applications has also been carried out. The variations in properties, such as tensile behaviour, impact strength, tear resistance, burst strength, gloss, haze, barrier properties, crystallization temperature and melting temperature, are reported. © 2000 Society of Chemical Industry     

Effect of cryomilling on the thermal behaviors of poly(ethylene terephthalate)

We have studied the effect of cryomilling (high‐energy ball milling under cryogenic temperature) on the thermal behaviors of poly(ethylene terephthalate) (PET) by comparing with original PET and quenched PET. Cryomilling induced the amorphization of crystalline PET, but the thermal behaviors of amorphous PET obtained from cryomilling are significantly different to those of amorphous PET obtained from quenching. Unlike amorphous PET obtained from quenching, the heating curve of amorphous PET obtained from cryomilling shows no cold crystallization peak, but evidences are found that its cold crystallization occurs within a wide temperature range. In addition, the stability of amorphous PET obtained from cryomilling is higher than that of amorphous PET obtained from quenching. The difference is proved to be attributed to the stored energy in cryomilled PET. The hot crystallization behaviors of PET improve a lot after cryomilling, and the heat stability of cryomilled PET is also better than those of original PET during reheating. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001