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     

Mechanical,thermal, and structural characterization of poly(ethylene terephthalate) and poly(butylene terephthalate) blend systems by the addition of postconsumer poly(ethylene terephthalate)

The focus of this study was mainly on the use of scrap poly(ethylene terephthalate) (PET) in poly(butylene terephthalate)‐rich blend systems. A good combination of tensile and impact properties was observed in the newly formed blend system with scrap PET. The morphology depicted controlled and well‐dispersed phases. The thorough mixing of the constituents was observed in the thermal study. For this innovative blend system, an attempt to correlate the mechanical, thermal, structural, morphological properties and the chemistry of the blend system seemed to be technoeconomical. This study contributed to the recycling of waste material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Processing characteristics of poly(ethylene terephthalate): hydrolytic and thermal degradation

The effects of poly(ethylene terephthalate) (PET) resin moisture content and temperature exposure have been investigated in terms of material changes resulting from the injection moulding process. Two resins with initial carboxyl contents of 10 µeq/g PET and 20 µeq/g PET have been analysed. Preforms processed at different resin moisture contents and processing temperatures of 280, 290 and 300 °C were evaluated in terms of carboxyl end‐group concentration using a titration method. Intrinsic viscosities of the performs were also measured by solution viscosity. Mathematical models describing the relationships of carboxyl end‐group concentration and intrinsic viscosity to the processing conditions were generated from the experimental data. Carboxyl end‐groups formed were compared for both resins and shown to be dependent on initial carboxyl content in the resin. Reducing the initial carboxyl content in the resin has been shown to increase its hydrolytic stability. The hydrolytic effect on the overall molecular weight drop was separated from the thermal/thermal‐oxidative degradation and shown to be dependent on both the processing temperature and the resin moisture content. © 2002 Society of Chemical Industry     

Effect of macromolecular orientation on the structural relaxation mechanisms of poly(ethylene terephthalate)

In this work we used Dielectric Spectroscopy (DS) and Thermally Stimulated Depolarisation Currents (TSDC) analysis to obtain values of fragility indexes as defined in the ‘Strong-fragile’ glass former liquid concept. DS and TSDC measurements have been performed on a series of polyethylene terephthalate (PET) samples with various degrees of macromolecular orientations. These orientations have been obtained by means of uniaxial drawing performed above the glass transition temperature. Samples with draw ratios λ=1, λ=2 and λ=5 have been obtained. From TSDC measurements, the fragility index of the glassy state (m_g) can be obtained, while DS measurements allow to reach the fragility index value of the liquid-like state (m). Furthermore, for low draw ratio, the material is practically wholly amorphous and its liquid state can be classified as ‘fragile’ glass forming liquid while for semi-crystalline PET (draw ratio λ=5), it is shown the remaining amorphous phase becomes stronger (m varies from 170 to 60 and m_g varies from 81 to 21).     

Effect of radiation dose on the thermal degradation of poly(ethylene terephthalate) fabric

The effect of radiation dose (10–30 kGy) on the thermal decomposition of poly(ethylene terephthalate) was studied using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD) analysis. The TGA and DSC were carried out in a flowing nitrogen atmosphere at heating rates of 5 and 30°C/min for TGA and 10°C/min for DSC. The degradation process was composed of three overlapping stages. The second stage, at which a rapid degradation occurs, was studied in detail. The process was found to follow a second‐order kinetics and was independent of radiation dose or heating rate. The reaction rate constant (k) was found to depend on the heating rate and iradiation dose. The apparent activation energy (Q) and the logarithm of the preexponential rate constant (log A) were found to decrease linearly with the increase in dose at rates of 3.32 kJ mol^?1 kGy^?1 and 0.177 s^?1 kGy^?1 with intercepts of 249 kJ/mol and 12.26 s^?1 for Q and log A of unirradiated fabric, respectively. A direct relationship was found between the percentage decrease in Q and log A and the percentage decrease in the temperature corresponding to 50% conversion (T_50%) for samples irradiated at different doses. It was found that a decrease in T_50% by 1% resulted in a decrease in Q and log A by 1.855 and 2.1%, respectively. Changes in Q and log A resulting from radiation, mechanical and thermal treatments, or their combinations can be predicted from the shift in T_50%. The history of the fibers substantially affected the thermal properties. DSC and XRD studies revealed changes in the fabric crystallinity. DSC measurements indicated a linear increase in heat of fusion with dose increase at a rate of 0.855 kJ kg^?1 kGy^?1. XRD analysis confirmed structural changes, rearrangement by plane rotations, and formation of compact crystalline lattice with patterns characterizing irradiated samples. An attempt to explain the dependency of the apparent activation energy on dose was given. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3710–3720, 2004     

聚酯热稳定性的研究

在合成聚酯试验之后,利用聚合试验装置搅拌器扭矩变化来表征聚酯加工过程中的热稳定性,比热失重法更接近聚酯加工过程,比粘度降法减少了干扰因素。研究结果表明:稳定剂种类、添加量和调配方式等均影响聚酯的热稳定性。     

Environmental aging and stress-cracking of poly(ethylene terephthalate)

The environmental stress-cracking behavior of poly(ethylene terephthalate), PET, has been studied by exposing PET sheet samples to a stress-cracking liquid, at constant stress, for various periods of time. Samples evaluated are of equivalent molecular weights but vary in copolymer concentrations. The characterization of exposed samples includes examination of craze formation and density changes, measurement of tensile mechanical properties, and evaluation of changes in their enthalpies of relaxation by differential scanning calorimetry, DSC. Data analysis includes the correlation between the number of crazes formed as a function of exposure time and the nature of tensile failure. The relationship between measured enthalpy of relaxation and brittle vs. ductile failure is also established. Among the conclusions to be discussed are: (1) Samples with large numbers of crazes do not necessarily exhibit brittle failure during tensile evaluation; and (2) Brittle failure may be associated with crazing, but it must be caused by other factors.     

Physical aging studies of semicrystalline poly(ethylene terephthalate)

Physical aging of semicrystalline poly(ethylene terephthalate) has been investigated as a function of crystalline content. Stress–strain, stress relaxation, and differential scanning calorimetry experiments were used to monitor the physical aging process. Both the overall extent and the rate of physical aging in this material decrease with increasing crystallinity. Several possible reasons for this behavior are advanced and discussed. It was also found that the drawing behavior of amorphous PET changes significantly as physical aging progresses. Specifically, for samples aged and then elongated, the extent of localized deformation (necking) and associated strain-induced crystallization was greater for samples aged for longer periods of time.     

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     

Estimation of intrinsic birefringence of poly(ethylene terephthalate) crystal

The intrinsic birefringence of poly(ethylene terephthalate) crystal has been estimated by means of the Orito method using experimental data and using theoretical calculation. The experimental estimation was performed on the basis of the assumption of a two-phase model consisting of crystalline and amorphous phases and the additivity of birefringence contributions — that total birefringence is equal to the sum of the orientation contributions from crystalline and amorphous phases, and of form birefringence. The value experimentally extrapolated by the Orito method is approx. 0.24. On the other hand, the theoretical calculation was carried out in the usual way using the values of bond polarizabilities according to Bunn and the atomic arrangements within the crystal according to Daubeny et al. The calculated value is 0.251. The difference between two results is also discussed.     

Identification of rheological and structural characteristics of foamable poly(ethylene terephthalate) by reactive extrusion

The reactivity and efficiency of five low molecular weight multifunctional anhydride and epoxy compounds as chemical modifiers of a bottle grade poly(ethylene terephthalate) (PET) resin were evaluated by reactive extrusion under controlled conditions. The two dianhydrides and the three epoxy compounds were used at concentrations based on stoichiometry derived from the measured carboxyl and hydroxyl end group contents of the base resin. Measures of melt viscosity, melt strength, intrinsic viscosity and carboxyl group content were used as criteria of the extent of the modification. Correlations of die pressure with extrudate swell during extrusion, and melt flow index (MFI) with melt strength by off‐line testing of the extrudates permitted the ranking of the modifiers according to their chain‐extending/branching efficiency. For some systems molecular weight increases (related to die pressure/MFI/intrinsic viscosity) accompanied by broadening of the molecular weight distribution (related to die swell/melt strength) were considered excessive. Extrusion foaming experiments with one particular dianhydride modifier that increased the intrinsic viscosity of the resin from 0.71 to 0.9 dl g^?1 indicate that production of low‐density foams by a process involving one‐step reactive modification/gas injection foaming is feasible, at conditions not significantly different from those employed in the simple reactive modification of the PET resin. The rheological and structural parameters determined in this work may be used as criteria to specify PET foamable compositions in terms of types and concentrations of modifiers. Copyright © 2004 Society of Chemical Industry     

Investigations on thermal and hydrolytic degradation of poly(ethylene terephthalate)

The thermal properties of poly(ethylene terephthalate) (PET) are sensitively affected by polycondensation catalysts and temperature. The kinetics of thermal degradation were investigated by determining the rates of formation of carboxyl groups on isothermal heating. Carboxyl groups in PET were not only a result of thermal exposure but they were also an influence on hydrolytic stability. The hydrolytic cleavage of polyester chains, i.e., the formation of carboxyl groups, was found to be an autocatalytic reaction.     

Effects of microcrystallinity and morphology on physical aging of poly(ethylene terephthalate)

Physical aging characteristics of poly(ethylene terephthalate) have been evaluated in relationship to volume fraction levels of crystallinity up to 25%. Changes in the enthalpies of relaxation, monitored at aging temperatures from 55 to 65°C, are found to give good fits with the Cowie‐Ferguson model. Overall equilibrium enthalpy of relaxation values decrease linearly with increased crystallinity. They increase with decreased aging temperature, providing extrapolated lower temperature results that are validated in terms of specific heat relationships. Activation energies for enthalpic relaxations are found to increase from 337 to 361 kJ/mole as crystallinity increases up to 25%. Overall relaxation endotherms are further resolved into contributions from interspherulitic and intraspherulitic amorphous regions. Interspherulitic, equilibrium enthalpies of relaxation decrease with increased levels of crystallinity, while intraspherulic values show corresponding increases. Characteristic relaxation times of the intraspherulic regions increase greatly, as levels of crystallinity increase; however, interspherulitic relaxation times decrease very slightly. Dynamic differential scanning calorimetry results show two glass transitions in the case of a 25% crystalline sample and a single transition for noncrystallized material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Structural and thermal properties of modified poly(ethylene terephthalate)

High-molecular-weight copolyesters based on ethylene glycol, tetraphthalic and 4,4′-biphenyl dicarboxylic acids containing up to 10.3 mole % of a second component were synthesized in the presence of homo- and heterogeneous catalysts. It was found that synthesis of these copolymers with a heterogeneous catalyst yields polymers with a higher molecular weight. The thermochemical properties of the copolyesters obtained were investigated. The thermostabilizing effect on addition of up to 10.3 mole % ethylene-4,4′-biphenyl dicarboxylic acid units to the PET polymer substrate was demonstrated. It was hypothesized that this modifier is a mesogen with respect to poly(ethylene terephthalate). Translated from Khimicheskie Volokna, No. 1, pp. 21-23, January-February, 2009.     

Effects of physical aging on thermomechanical behaviors of poly(ethylene terephthalate)-glycol (PETG)

ABSTRACT

A series of experiments are performed to investigate the effects of physical aging on thermomechanical properties of poly(ethylene terephthalate)-glycol (PETG). The DMA, DSC and XRD tests are used to characterize the change of dynamic property, heat capacity and microstructure with annealing treatments. The uniaxial tension tests together with the DIC technique are employed to describe the failure behaviors of PETG. The results show that the annealed polymers exhibit a larger maximum local strain and fail at a smaller displacement. The type and size of the geometry defects can also affect the strain localization and final failure behaviors of PETG.     

Influence of thermal aging on the electrical properties of poly(vinyl chloride)

This article reports on the study of the thermal aging of poly(vinyl chloride) (PVC) used in medium‐ and high‐voltage cables. It is shown that the thermal aging leads to the degradation of the material and to the modification of its electrical properties. The degradation is all the more important and faster as the temperature is high. This degradation is attributed to a progressive evaporation of the plasticizer at the beginning of aging and to a weight loss of stabilizer followed by a change in the color of polymer and a release of hydrochloric acid at more advanced stages of aging. It also results in a crosslinking of the material and a shrinking of samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4728–4733, 2006     

PET的紫外老化性能及机理研究

采用力学、紫外-可见光分析和热失质等测试手段研究了PET改性料的紫外老化性能及老化机理。结果表明:复合助剂的加入能显著提升体系的力学性能保持率,进而提升其紫外老化寿命,提升的幅度随复合助剂中耐紫外剂含量的增加而显著增加。DSC分析表明,随着复合助剂的引入和老化的进行,改性料结晶度增加。文中进一步讨论了PET改性料的紫外老化机理。紫外-可见光分析表明,紫外老化能产生醌类和双醌类物质,进而提升PET改性料的紫外吸收度。     

Mechanism of densification and crystal perfection of poly(ethylene terephthalate)

Amorphous poly(ethylene terephthalate) has been isothermally annealed in a wide range of temperatures from T_g to T_m. The effects of temperature and time of thermal treatment on density, melting curve and WAXS have been systematically explored. The results showed that densification and crystal perfection take place through a step mechanism involving partial melting and diffusion. The evaluation of the activation energies suggests that diffusion is the rate determining step in the low temperature range.     

Role of 2‐hydroxyethyl end group on the thermal degradation of poly(ethylene terephthalate) and reactive melt mixing of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

In an attempt to minimize the acetaldehyde formation at the processing temperatures (280–300°C) and the outer–inner transesterification reactions in the poly (ethylene terephthalate) (PET)–poly(ethylene naphthalate) (PEN) melt‐mixed blends, the hydroxyl chain ends of PET were capped using benzoyl chloride. The thermal characterization of the melt‐mixed PET–PEN blends at 300°C, as well as that of the corresponding homopolymers, was performed. Degradations were carried out under dynamic heating and isothermal conditions in both flowing nitrogen and static air atmosphere. The initial decomposition temperatures (T_i) were determined to draw useful information about the overall thermal stability of the studied compounds. Also, the glass transition temperature (T_g) was determined by finding data, indicating that the end‐capped copolymers showed a higher degradation stability compared to the unmodified PET and, when blended with PEN, seemed to be efficient in slowing the kinetic of transesterification leading to, for a finite time, the formation of block copolymers, as determined by ¹H‐NMR analysis. This is strong and direct evidence that the end‐capping of the ? OH chain ends influences the mechanism and the kinetic of transesterification. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Crystallization characteristics of weakly branched poly(ethylene terephthalate)

A series of branched poly(ethylene terephthalate) (BPET) samples were prepared from melt polycondensation by incorporation of various amount (0.4-1.2 mol%) of glycerol as a branching agent. These polymers were characterized by means of H¹ NMR, intrinsic viscosity. The general crystalline and melting behavior was investigated via DSC. It was found that the crystalline temperature T_cc from the melt shifted to high temperature and the T_hc from the glass got low for BPETs while the melting temperatures of BPETs kept almost unchanged. The kinetics of isothermal crystallization was studied by means of DSC and POM. It was found that the present branching accelerated the entire process of crystallization of BPETs, although prolonged the induced time. In addition, branching reduced nucleation sites; hence the number of nucleates for BPET got smaller. Therefore, more perfect geometric growth of crystallization and greater radius of spherulites could develop in BPET due to less truncation of spherulites.