Effects of thermal treatment on biaxially oriented poly (ethylene terephthalate). III. Creep behavior following various thermal histories

Elongational creep measurements were carried out on a biaxially oriented poly (ethylene terephthalate) (PET) film parallel to, orthogonal to, and at 45° to the principal optic axis. Measurements made after various thermal treatments which were intended to stabilize the physical state of the PET were shown to be ineffective. Samples were annealed at 140°C for 12 days and aged at 95°C for over 24 days before measurement without success. Thermal cycling between 41 and 91°C which was also employed to stabilize the mechanical response also failed. Significant deceleration of the creep rate caused by densification of amorphous regions of the samples during storage below the glass temperature T_g is illustrated. Because of physical aging below T_g and morphological changes occurring above T_g during the various thermal treatments and histories, time-scale shift factors were found to be not unique.     

Effect of heating and aging on microstructure of polyester-polyamide copolymer

Polyester-polyamide (PET/PA) copolymers offer a wide range of possible applications where both dimensional stability and good impact resistance can be achieved from their synergism. In order to ensure these properties for long-term use, however, problems of phase separation, volume change, and chemical reequilibration on heating or aging must be identified and overcome. Wide-angle x-ray diffraction (WAXD), small-angle x-ray scattering (SAXS), and thermal analysis were employed to follow the microstructure of a 70:30 PET/PA copolymer with several different processing histories as a function of heat history and both short-term and long-term aging. Heating the copolymer, as received, above the melting temperature of PET caused phase mixing. The effect of heating on crystallinity depended on starting crystallinity. Holding the copolymer at 50°C, just below the glass transition temperature of PET, caused phase separation in samples which had been annealed for 30 min at 150°C. On long-term aging samples gave evidence of phase mixing. The results indicate highly nonequilibrium structure in the material, regardless of the original processing.     

Effect of previous thermal history on physical aging of amorphous poly (ethylene terephthalate)

Physical aging of amorphous PET, at aging temperatures (T_a) of 40 and 60°C and different aging times (t_a), has been studied by DSC using two kinds of samples with different thermal history: Liquid-Nitrogen-Quenched samples (LNQ) and DSC cooled samples at a controlled cooling rate of 60 K/min (CC). At T_a = 40°C, a sub-T_g peak appears in LNQ samples but is not clearly observed in the CC samples. At T_g = 60°C, a superposed peak to T_g is observed in both kinds of samples. This different behaviour can be explained considering the distribution of relaxation times in the polymer.     

Preparation,Homogeneity and Stability of Polar Pesticides in Freeze-Dried Water Interlaboratory Exercise

Abstract

An interlaboratory exercise was carried out to improve the state of the art of some polar pesticide determination in water (atrazine, simazine, carbaryl, propanil, linuron, fenamiphos and permethrin). The preparation, the homogeneity and the stability of freeze-dried water samples containing the above pesticides was studied. The final concentration of each pesticide in water was in the 50–80 μg.^?1 range with a salt content of 2.5 g.l^?1 of NaCl. After the lyophilization the residue was reho-mogenised, filled into amber glass bottles and stored at -20 °C and +20 °C. Every three months, one sample was analysed to verify the stability of the residue.

All pesticides were determined by high performance liquid chromatography with diode-array detection (HPLC-DAD) except permethrin which was determined by gas chromatography with electron capture detection (GC-ECD).

The results obtained show that the atrazine, carbaryl, propanil, linuron and fenamiphos samples were homogeneously distributed, whereas simazine and permethrin were not. With respect to the stability over three months, all pesticides were stable at ?20 °C. Atrazine, simazine, carbaryl, propanil and linuron are also stable for the maximum storage time at +20 °C but the concentration of fenamiphos decreased by about 70% after one month.

The results obtained in the interlaboratory study by the participants were in good agreement for many of the pesticides.     

The investigation of methyl phenyl silicone resin/epoxy resin using epoxy-polysiloxane as compatibilizer

Styrene–butadiene rubber was subjected to long-term thermal aging treatment at 80 °C with aging period up to 180 days. The degradation kinetics of the aged sample was analyzed by thermogravimetric analysis. Multiple heating rate experiments were carried out in nonisothermal conditions and three isoconversional model-free methods (Friedman; Kissinger–Akahira–Sunose; Li and Tang methods) were employed. The results showed that the temperature for 5 % mass loss increased, whereas the maximum mass loss temperature decreased after aging. Activation energies (E _a) derived from the three methods were found to be dependent on conversion degree (α). E _a increased with increasing α in the whole range of conversion for samples aged for 0, 60, and 120 days, while the aged samples displayed higher E _a values. However, samples aged for 180 days showed declining E _a versus α. The changes on the degradation kinetics were associated with the modification on the chemical structure after thermal aging.     

Comportement Thermique du Polypropylene au Cours du Vieillissement

Several samples of polypropylene were studied by thermal analysis. The photo-oxidation and the aging of polypropylene films showed a mass loss more than 7% in heating from 20 to 220°C (5°C min-1), cooling to 20°C and reheating to 220°C. The authors observed also a decrease of the melting and crystallization temperatures. The non aged samples or these ones with preservatives are thermo-oxidised and presented an exothermic peak at about 200°C in DTA heating. The DTA-TG simultaneous apparatus is very useful in the study of polypropylene oxidation by making comparative trials according to a well definite procedure. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of copolymeric poly(diethylene glycol) terephthalate on the thermal stability of poly(ethylene terephthalate)

Copolymers of poly(ethylene terephthalate) (PET) containing 1–24% poly(diethylene glycol)terephthalate (PDEGT) were prepared and characterized by infrared spectra. The energy and entropy of activation for the thermal degradation were measured for these copolymers and for the PDEGT. These activation energies and energies and entropies were found to decrease steadily with increasing diethylene glycol content. From these measurements the mechanism of degradation of PDEGT was found to be different from that of PET. Fibers prepared from seven different copolymeric compositions were heat-aged at 121°C and 204°C for 24 hr. From the changes observed in intrinsic viscosity, per cent ether, hydroxyl and carboxyl endgroups during heat aging it became apparent that the mechanisms for decomposition are operative below melt temperatures and can rapidly destroy such copolymers.     

Experimental study on ballistic behaviour of an aluminised AP/HTPB propellant during accelerated aging

The chemical stability of a propellant and its influence on the ballistic properties during aging is a subject of interest. The effect of aging on ballistic properties, viz., ignition delay, burning rate, and heat of combustion for an aluminised ammonium perchlorate–hydroxyl-terminated polybutadiene (AP/HTPB) composite propellant during accelerated aging were investigated. Samples of composite propellants were aged at 60 and 70 °C at relative humidity of 50% in a climatic chamber. The propellant samples were tested with pressurized nitrogen gas environment for ignition delay measurement. Test results indicate that aging does not have any appreciable effect on ignition delay. The change in ignition delay time is less than 3% within the scatter of the data. Experiment results indicate that burn rate do affect with pressure but aging does not have much effect on burn rate. It was also observed that the burning rate at low pressures did not undergo significant changes during the aging period. The most significant of all the ballistic properties of this propellant is the burning rate exponent which increased by about 10% during the aging period.     

Changes of mechanical properties in cold-crystallized syndiotactic polypropylene during aging

Many semicrystalline polymers undergo a process of aging when they are stored at temperatures higher than their glass-transition temperature (T _g). Syndiotactic polypropylene was quenched from the melt to −40 °C, crystallized from the glassy state at 20 or 40 °C and stored at the respective temperature for different aging times up to 7200 h. A significant increase in the tensile modulus and stress at yield and a decrease in strain at yield were observed for both aging temperatures. Differential scanning calorimetry (DSC) scans of aged material showed an endothermic annealing peak 15–30 °C above the previous aging temperature, the maximum temperature and enthalpic content of which increased with aging time. The position and the shape of the melting peak were not affected by aging. Scans of the storage modulus obtained from dynamic mechanical analyser measurements indicated a softening process starting at about 20 °C above the aging temperature and correlating with the annealing peak detected by DSC. Density measurements and wide-angle X-ray scattering investigations revealed that neither the crystallinity increased significantly nor did the crystal structure change. So the observed property changes induced by aging are attributed to microstructural changes within the amorphous phase. Furthermore, it could be shown by annealing experiments carried out at 60 °C, that aging above T _g is, analogous to aging below T _g (physical aging), a thermoreversible process. Received: 18 September 2000 Accepted: 2 January 2001     

Thermal analyses of polymers. XIII. Crystalline character of the 70°c transition of poly(ethylene terephthalate)

The abrupt changes in the linear expansion and dilatometric measurements of poly-(ethylene terephthalate) near 70°C indicate that the transition may be first order. DTA and DSC data show the normal heat capacity change at 70°C, while annealing for for 30 min. at 110°C induces further molecular order. Rapid quenching of PET after heating to 120°C yields an amorphous sample and measurement by depolarized light transmission as the sample is reheated shows rapid crystallization occurring near 80°C. With the occurrence of shrinkage near 68°C and apparent recrystallization at slow heating rates by depolarized light analyses, further support is added to the first-order character of this phase transition. Isothermal annealing for short times at temperatures between 50°C and 80°C produces further increases in molecular order. Cyclic and linear PET oligomers do not contribute to the occurrence of the 70°C transition.     

A method for determination of acetaldehyde in bottled waters and the effect of time and temperature on concentrations

ABSTRACT

Solid phase extraction (SPE) technique followed by gas chromatography (GC) coupled with flame ionisation detector was evaluated for the analysis of acetaldehyde concentration in water contained in polyethylene terephthalate (PET) bottles. Fifteen fresh samples of 1.5 L of different brands were collected from the local market and stored in the laboratory under controlled temperatures at 20°C, 30°C and 40°C. The samples were analysed at regular intervals of time. The acetaldehyde determined in these samples was found in the range of 9.88–139.44 µg/L. Moreover, the level of acetaldehyde was found to increase with increase in temperature and storage time. Furthermore, the results indicate that the proposed method is very simple, low cost and efficient for the determination and recovery of trace amount of acetaldehyde in bottled water.     

Determination of alachlor, metolachlor, and their acidic metabolites in soils by microwave-assisted extraction (MAE) combined with solid phase extraction (SPE) coupled with GC-MS and HPLC-UV analysis

A well-validated analytical method based on microwave-assisted extraction (MAE) and SPE is presented for the combined analysis of alachlor, alachlor-oxanilic acid (OXA), alachlor-ethanesulfonic acid (ESA), metolachlor, metolachlor-OXA, metolachlor-ESA residues in soils. Extraction of solutes by soil sample was carried out by MAE for 20 min at 100 degrees C in the presence of 50 mL solution (methanol/water 50:50), the extract was subsequently passed through C18 cartidges and fractionated into two fractions, the first with parent compounds (PCs) analyzed with GC-MS and the second one containing the metabolites analyzed with HPLC. For the SPE step, various types of sorbents (Environmental C18, tC18, Supelclean ENVI-carb, and LiChrolut EN) have been used, and their respective advantages and disadvantages are discussed. After the method optimization, average recovery values of all solutes were > 71% in the 50-500 microg/kg fortification range with RSD <10%. The LOQ and LOD were 10-50 and 5-10 microg/kg, respectively. The method was validated with two types of soils (1 and 2.4% organic matter) and in fresh (12 h aging), intermediate (1 wk aging), and aged (1 month aging) spiked samples. Moreover, residue levels determined after field application of alachlor or metolachlor were higher when soils were processed using this method than with a comparison method based on an overnight flask shaking (FS) of soil suspension.     

Aging and cold crystallization of melt‐extruded poly(trimethylene terephthalate) films

We analyzed the thermal crystallization, glass‐transition behavior, and mechanical properties of melt‐extruded poly(trimethylene terephthalate) (PTT) films to investigate their physical aging and annealing effects. The physical aging and annealing of PTT films had an influence on the glass‐transition temperature, recrystallization behavior, and mechanical properties. When samples were aged at an ambient temperature, the crystallization temperature decreased largely within 5 h, the heat of crystallization increased, and the breaking stress and breaking elongation increased. The glass‐transition temperature of annealed samples, which was obtained from differential scanning calorimetry and dynamic mechanical measurements, increased with increasing annealing temperature below 80 °C but decreased above that temperature. In addition, the glass‐transition temperature and modulus of annealed samples were largely affected by the annealing time; in particular, they increased sharply within 1 h on annealing at 50 °C. Consequently, the change in the glass‐transition temperature on annealing was ascribed to the fact that the molecular constraint due to recrystallization and the mobility of rigid amorphous PTT chains competed with each other, being dependent on the annealing temperature. The mechanical properties of aged samples were closely related to their cold‐crystallization behavior. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1920–1927, 2001     

Formation of hybrid nano-crystals in organic–inorganic films from a basic sol

Organic–inorganic films containing hybrid nanocrystals have been prepared by sol–gel processing in controlled conditions. We have systematically changed the temperature and the aging time of a precursor sol containing an organically modified alkoxide bearing an epoxy group, 3-glycidoxypropyltrimethoxysilane, to obtain a controlled crystallization of hybrid layered structures in hybrid films. The precursor sol has been aged at different temperatures, from 5 to 60 °C, and for 1, 2 or 3 days; the films have been deposited from the aged sol and immediately after characterized by X-ray diffraction, Fourier transform infrared spectroscopy and Raman spectroscopy. We have observed that the formation of the hybrid crystals can be obtained only when at least 50% of the epoxies are opened and a larger silica condensation is achieved. These conditions are reached after aging at 60 °C for 1 day, or at longer aging times when the sol is aged at lower temperatures. Transmission electron microscopy and optical polarized images have confirmed the formation of the hybrid crystals.     

Changes in light scattering from poly(ethylene terephthalate) and nylon 6 films upon stretching in relation to the deformation mechanism

Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65–75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the H_v eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the V_v cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.     

Evaluation of the Effect of Plasma Treatment Frequency on the Activation of Polymer Particles

This study investigates the influence of treatment frequency (1–150 kHz) on the atmospheric plasma activation of both silicone and polyethylene terephthalate (PET) particles. These polymer particles with diameters in the range 3–5 mm, were treated using either helium or helium/oxygen gas mixtures, in a barrel atmospheric plasma system. The level of polymer particles activation was monitored using water contact angle measurements. The effect of plasma treatment frequency on barrel heating was monitored using an infrared thermographic camera, the maximum barrel temperature after 15 min treatment was found to be 98 °C at a frequency of 130 kHz. Optical emission spectroscopy was used as a diagnostic tool to monitor changes in atomic and molecular species spectral intensity with experimental conditions, as well as a change in electron energy distribution function. Electrical characterisation studies demonstrated an increase in plasma power with increasing frequency, in the range investigated. X-ray photoelectron spectroscopy analysis indicate an increase of oxygen content on polymer surfaces after plasma treatment. For silicone particles, the minimum polymer water contact angle was obtained by using a frequency of 130 kHz. After 15 min treatment time, the water contact angle decreased from 141° to 11°. While for PET particles the optimum treatment frequency was found to be 70 kHz, resulting in a water contact angle decreased from 94° to 32°. This lower frequency was used due to the partial melting of the PET (Tg of 80 °C), when treated at the higher frequency.     

TSDC and DSC Study of Effects of Physical Aging on Polybutylene Terephthalate (PBT)

The impact of the physical aging process on the electrical and thermal properties of semicrystalline polybutylene terephthalate (PBT) was investigated by means of thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC). The TSDC technique was used to study the relaxation modes of PBT in the temperature range ?50° to + 120°C. The obtained spectra revealed two peaks located at temperature maxima of 45° and 93°C. The peak appearing at 45°C corresponds to the dielectric manifestation of the glass transition phenomenon (α-relaxation). The aim of this work is to study the effect of physical aging on this relaxation. The recording of TSDC peaks of aged PBT at different temperatures for different times revealed a reduction in their intensities and their shift towards higher temperatures when the aging becomes significant. This result can be explained by the diminution of molecular chain mobility, which is directly related to the area under the peak representing the polarization of the sample. This result was confirmed by DSC measurements, which revealed the growth and the shift of the peak, which is superimposed on the jump of the heat capacity, located around 38°C and characteristic of the glass transition, towards higher temperatures where aging becomes significant.     

The preparation of a certified reference material of polar pesticides in freeze-dried water (CRM 606)

The preparation of a certified reference material of polar pesticides in freeze-dried water is described. The pesticides selected were atrazine, simazine, carbaryl, propanil, linuron, fenamiphos and permethrin which were added to 6000 litres of tap water at 50–80 μg · L^–1 (200–320 μg · L^–1 for permethrin) level in presence of NaCl (2.5 g · L^–1) prior lyophilization. After the freeze-drying process the residue was rehomogenized, filled into amber glass bottles and stored at –20?°C, +4?°C and +20?°C. All pesticides were determined by HPLC/diode array detector, except permethrin which was determined by GC/ECD. The results obtained for atrazine, simazine, carbaryl, propanil, linuron and fenamiphos showed no within- or between-bottle inhomogeneity, however the material was non-homogeneous for permethrin and therefore this was withdrawn from further studies. With respect to the stability for over one year, all pesticides were stable at –20?°C. At +4?°C all pesticides were stable for at least 9 months and at +20?°C the stability was demonstrated only during the first month of storage. The content (mass fractions) of atrazine, simazine, carbaryl, propanil and linuron in freeze-dried water (CRM 606) was certified by an interlaboratory testing and a certification campaign.     

Uniaxial ratcheting behavior of hygrothermal aging anisotropic conductive adhesive film

A series of uniaxial ratcheting experiments on anisotropic conductive adhesive film (ACF) were conducted under stress-control at elevated temperature using a DMA-Q800. The ratcheting behavior of ACF specimens with different hygrothermal aging times was investigated at room temperature and 120 °C. The effects of loading rate, mean stress and stress amplitude on the ratcheting behavior of unaged and aged specimens were compared. The results show that the ratcheting strains of aged specimens are smaller than those of unaged specimens under the same experimental conditions. The cycling stability of aged specimens is increased by hygrothermal aging. At room temperature, with the increase of aging time, the ratcheting strains of aged specimens increase with hygrothermal aging time when it is less than or equal to 96 h but, however, decrease when it exceeds 96 h. At 120 °C the ratcheting strains of ACF only decrease with the increase of hygrothermal aging time. Additionally, the effects of loading rate, mean stress and stress amplitude on the ratcheting behavior of unaged and aged ACF are different and their effects are weakened by hygrothermal aging.     

Physical aging studies in epoxy resins. I. Kinetics of the enthalpy relaxation process in a fully cured epoxy resin

The physical aging of an epoxy resin based on diglycidyl ether of bisphenol-A cured by a hardener derived from phthalic anhydride has been studied by differential scanning calorimetry. The isothermal curing of the epoxy resin was carried out in one step at 130°C for 8 h, obtaining a fully cured resin whose glass transition was at 98.9°C. Samples were aged at temperatures between 50 and 100°C for periods of time from 15 min to a maximum of 1680 h. The extent of physical aging has been measured by the area of the endothermic peak which appears below and within the glass transition region. The enthalpy relaxation was found to increase gradually with aging time to a limiting value where structural equilibrium is reached. However, this structural equilibrium was reached experimentally only at an aging temperature of T_g-10°C. The kinetics of enthalpy relaxation was analysed in terms of the effective relaxation time τ_eff. The rate of relaxation of the system given by 1/τ_eff decreases as the system approaches equilibrium, as the enthalpy relaxation tends to its limiting value. Single phenomenological approaches were applied to enthalpy relaxation data. Assuming a separate dependence of temperature and structure on τ, three characteristic parameters of the enthalpic relaxation process were obtained (In A = ?333, E_H = 1020 kJ/mol, C = 2.1 g/J). Comparisons with experimental data show some discrepancies at aging temperatures of 50 and 60°C, where sub-T_g peaks appears. These discrepancies probably arise from the fact that the model assumes a single relaxation time. A better fit to aging data was obtained when a Williams-Watts function was applied. The values of the nonexponential parameter β were slightly dependent on temperature, and the characteristic time was found to decrease with temperature. © 1994 John Wiley & Sons, Inc.