Proton spin-lattice and spin-spin relaxation times in annealed poly(ethylene terephthalate)

Proton spin-lattice, T₁, and spin-spin, T₂, relaxation times of poly(ethylene terephthalate) film annealed at various temperatures were measured using a broad line pulse spectrometer. The value of T₁ is closely related to the crystallinity of the sample and only one T₁ was observed for each sample, indicating that the spin diffusion is effectively operating. Even in the amorphous sample there are some nuclear spins, the motion of which is strongly restricted.     

Correlation of thermally stimulated current and blow molding condition in poly(ethylene terephthalate) bottles

Thermally stimulated current (TSC) was used to study molecular relaxations in polyethylene terephthalate (PET) bottles. Unstretched PET film, which was used as a model for the bottle preform, exhibited two peaks at 77 and 90°C that correspond to the α and ρ relaxation processes, respectively. The bottles exhibited only the ρ relaxation, which is located within the temperature range for blow molding PET bottles. The α peak is associated with the main glass transition temperature (T_g) and the ρ peak may be associated with a second T_g. The second T_g is attributed to a “constrained state,” which shows dipolar behavior. Heat‐shrinkage behavior was examined at 90°C. The maximum TSC (I_m) of the ρ peak decreased with increasing heat set temperature, and with decreasing shrinkage. Bottles blown at 113°C showed a lower I_m and shrinkage than those blown at 103°C for equivalent heat set temperatures. The higher blowing temperature allowed a higher stretch speed that produced higher crystallinity bottles with self‐heat generation during rapid deformation. A relationship between the shrinkage mechanism and the dipole relaxation was proposed.     

Dielectric relaxation spectroscopy of poly(ethylene terephthalate)

Contour maps of dielectric loss tangent within the ranges 0.1 Hz to 3 MHz and ?175 °C to +190 °C are presented for a commercial poly(ethylene terephthalate) (PET) in two initial states of crystallinity. Individual absorption regions resemble those for poly(butylene terephthalate) and are attributed to carbonyl‐driven α‐ and β‐relaxation processes and to Maxwell–Wagner–Sillars polarizations. Possible causes are considered for the asymmetry and structure apparent in the α‐peak of partially crystalline PET. © 2001 Society of Chemical Industry     

Enthalpy relaxation in poly(ethylene terephthalate) and related polyesters

Enthalpic relaxation data are presented on poly(ethylene terephthalate), poly(ethylene naphthalate) and their copolymers. Analysis of these data allows the determination of the amount of energy absorbed at the glass transition, Q_t, and the location of the enthalpic recovery peak, T_max, as a function of the time of ageing of the samples. Ageing measurements were carried out for periods of up to 2016 h and at temperatures between 40 °C and 110 °C, depending upon the chemical composition of the system being investigated. The enthalpic relaxation rates are influenced by the chemical structure and reflect the effects of local order pinning the chains and influencing the rate of enthalpic recovery. © 2000 Society of Chemical Industry     

Glass transition and structural relaxation in semi-crystalline poly(ethylene terephthalate): a DSC study

The aim of this work is to determine the relaxation times of the cooperative conformational rearrangements of the amorphous phase in semi-crystalline poly(ethylene terephthalate) (PET) and compare them with those calculated in amorphous PET. Samples of nearly amorphous polymer were prepared by quenching and samples with different crystallinity fractions were prepared from the amorphous one using cold crystallisation to different temperatures. The differential scanning calorimetry (DSC) thermograms measured on samples rapidly cooled from temperatures immediately above the glass transition show a single glass transition which is much broader in the case of high-crystallinity samples than in the amorphous or low-crystallinity PET. To clarify this behaviour, the samples were subjected to annealing at different temperatures and for different periods prior to the DSC measuring heating scan. The thermograms measured in samples with low crystallinity clearly show the existence of two amorphous phases with different conformational mobility, these are called Phases I and II. Phase I contains polymer chains with a mobility similar to that in the purely amorphous polymer, while Phase II shows a much more restricted mobility, probably corresponding to conformational changes within the intraspherulitic regions. The model simulation allows to determine the temperature dependence of Phase II relaxation times, which are independent from the crystallinity fraction in the sample and around two decades longer than those of the amorphous polymer at the same temperature.     

Molecular motions in poly(vinyl acetate) revisited. A thermally stimulated current study

The dipolar relaxation mechanisms in poly(vinyl acetate) have been studied in detail using the technique of thermally stimulated currents. The papers published in the literature about this subject are very contradictory, particularly with respect to the assignment of the observed discharges to the corresponding motions at the molecular level. This work aims at clarifying these problems. We detected and characterised three different relaxation mechanisms: (1) a low temperature one (around ?140°C) which was attributed to local internal rotations in the acetate side-groups; (2) a relaxation whose maximum occurs at 42°C, which corresponds to the glass transition relaxation, and shows a compensation behaviour; (3) an upper glass transition relaxation whose maximum appears at 87°C and was attributed to a liquid-liquid transition. These assignments have been made on the basis of the analysis of the behaviour of the samples when submitted to different thermal and electrical treatments.     

Solvent effects on microwave dielectric relaxation in poly(ethylene glycols)

This paper reports the results of a systematic study of microwave dielectric relaxation times of poly(ethylene glycols), average molecular weight 200–9000, in dilute solutions of benzene at 9·83GHz. These results are compared with the values of relaxation times obtained earlier in carbon tetrachloride solutions. This shows that the average relaxation times τ₀ and the relaxation time corresponding to segmental reorientation τ₁ are influenced by the solvent environment. The variation in chain flexibility in these polymers with the increase in degree of polymerization and formation of intra- and inter-molecular hydrogen bonding in benzene and carbon tetrachloride solutions is discussed with the help of relaxation data. The relaxation time τ₂ corresponding to group rotations has been determined. It is found that the τ₂ value is independent of solvent environment and degree of polymerization, and may be attributed to the rotation of chain −OH end-groups around the C−O bonds in dynamic equilibrium, with the formation of a five-membered ring due to intra-molecular hydrogen bonding at the end of the chain. © 1998 SCI.     

Dielectric properties of low molecular weight poly(ethylene glycol)s

This paper reports the measured values of dielectric permittivity ε′ and dielectric loss ε″ of ethylene glycol, diethylene glycol and poly(ethylene glycol)s of average molecular weight 200, 300, 400 and 600 g mol⁻¹ in the pure liquid state. The measurements have been carried out in the frequency range 200 MHz to 20 GHz at four different temperatures of 25, 35, 45 and 55 °C. The complex plane plots (ε″ versus ε′) of these molecules are Cole–Cole arcs. The static dielectric constant ε₀, high‐frequency limiting dielectric constant ε_∞, average relaxation time τ₀ and distribution parameter α have been determined from these plots. The value of the Kirkwood correlation factor g and the dielectric rate free energy of activation ΔF have also been evaluated. The dependence of relaxation time on molecular size and viscosity has been discussed. A comparison has also been made with the dielectric behaviour of these molecules in dilute solutions of non‐polar solvents, which were carried out earlier in this laboratory. The influences of intermolecular hydrogen bonding and molecular chain coiling on the dielectric relaxation of these molecules have been recognized. © 2000 Society of Chemical Industry     

Thermally stimulated current study on flexible siloxane-modified epoxy sheets

Copolymers prepared from the epoxy resin of ALBIFLEX and PMPS oligomer were evaluated with IR, ¹H-and ¹³C NMRs for structural determinations. The flexible epoxy resin as a model compound was examined by TSC with variations on the operational parameters t_p and V_p. Transitions denoted as T_g,δ, T_g,γ, T_g,β, T_g,α and T_g,ρ in increasing order of temperature were observed for these copolymers. As an example, ESAF-7430 copolymer showed these transitions at −138, −84, 26, 87, and 110 °C, respectively. Each transition except the T_g,ρ at 110 °C, has been correlated to a segment in the copolymeric structure. The result indicates that TSC provides clear molecular transitions at the temperature of the transition. The molecular transition of the grafted PMPS-siloxane segment in an epoxy matrix appeared at the −45 °C region as a broad, nearly flat peak as it filled the concave part of the TSC curve of the unmodified resin. The flexibility that the modified copolymers retained may be attributed to these sub-T_g transitions as observed in the TSC spectrum.     

DSC studies on the crystallization characteristics of poly(ethylene terephthalate) for blow molding applications

The crystallization behavior of blow-molded PET bottles, which helps determine the product's transparency, was investigated by DSC dynamic cooling experiments that simulated the cooling that occurs in the injection blow-molding manufacturing process. Dynamic cooling crystallization of PET optimized the conditions for keeping crystallinity to a minimum during the production of PET bottles. The kinetic parameters of non-isothermal crystallization behavior were determined, which indicate that the competing processes of nucleation and the growth of PET spherulites during the cooling process are the controlling factors for the degree of crystallinity in the final product. In addition, DSC measurements were employed to obtain information on related aspects, such as the ease of crystallization from glassy and molten states and the crystallinity in the products. An Avrami equation was used for the calculations of the crystallization kinetic parameters.     

Synthesis and thermally stimulated current study of molecular relaxations of the grafted polymethylphenylsiloxane segment in thiodiphenol-modified epoxy resin

A series of grafted polymethylphenylsiloxane (PMPS) segments in thiodiphenyl-containing epoxy resin (ESTP) was prepared. The structure was evaluated by IR, ¹H-NMR, and ¹³C-NMR measurements. DSC measurements on the grafted ESTP epoxy resins showed a decreasing trend for T_g with increasing content of PMPS siloxane. The TSC measurements further confirmed this trend. This result suggests that the matrix of ESTP copolymer was less rigid with grafting of PMPS oligomer, due to the Si—O—C linkage at the opened glycidyl ether chain located approximately between the BPA and 4,4′-thiodiphenoxyl chains in the epoxy backbone. A new and broad sub-T_g transition appeared at −60°C in the TSC spectrum was observed for the cooperative motion of this siloxane moiety. All copolymers showed sub-T_g relaxations of γ- and δ-modes, observed at −100 and −130°C, respectively. These two relaxations may be attributed to the motions of BPA and the terminal groups in the epoxy matrix. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1523–1530, 1998     

Thermally stimulated depolarization effect in thiourea-formaldehyde condensate

A thiourea-formaldehyde condensate was synthesized in an acid medium and characterized by elemental analysis, infra-red spectroscopy, and thermal methods of analysis. The thermally stimulated depolarization effect was studied in samples polarized under different conditions. The results indicate two distinct transitions in the temperature ranges 94°–100°C and 122–126°C. The polarization-depolarization phenomena were correlated with the physicochemical changes occurring in the matrix. Depolarization kinetics data such as activation energy and relaxation times of the electrets are reported.     

Orientation studies of poly(ethylene terephthalate)

This paper discusses the results of a detailed study of the relationships between molecular orientation, physical properties, and molecular weight of polyethylene terephthalate (PET), and their dependence on orientation variables. The molecular weight range of the samples used in this study included weight average molecular weights, M_w, between 29,000 and 65,000 which correspond to inherent viscosities, I.V., from 0.5 to 0.9. The orientation temperatures investigated were between 80 and 120°C. The extent of molecular ordering imparted by the orientation process was studied by birefringence, density, light scattering, and depolarized light intensity techniques. The results show that the degree of molecular orientation and the physical properties are strongly dependent on strain rate, extension ratio, molecular weight, and orientation temperature. The mechanical and transport properties, of PET are directly related to the degree of orientation as measured by birefringence. It is found that at a comparable level of orientation, the mechanical properties are also dependent on molecular weight, whereas the transport properties are independent of molecular weight. The degree of orientation varies according to the molecular weight of PET and stretch temperature. It is shown that for the same stretch ratio and stretch speed, the birefringence decreases with increasing stretch temperature. The light scattering results indicate that biaxial orientation of PET can lead to strain-induced crystallization. The amount and form of the crystalline structures are dependent on strain rate and orientation temperature.     

The effect of physical ageing on the properties of poly(ethylene terephthalate)

Physical ageing rates of poly(ethylene terephthalate) have been measured, and ageing is interpreted to be associated with the conventional glass formation process, which occurs at a more rapid rate at higher temperatures. Ageing is accompanied by a marked change in mechanical properties, increased tensile yield stress and drawing stress, more localized yielding of the polymer and a marked decrease in impact strength. The fracture results have been attributed to the increased yield stress and a change in contribution of plane stress and plane strain conditions in the samples. Fracture surfaces show evidence of mixed modes of fracture.     

Mechanical properties in torsion for poly(butylene terephthalate) and a poly(ether ester) based on poly(ethylene glycol) and poly(butylene terephthalate)

The torsional behavior of poly(ether ester) (PEE) thermoplastic elastomer, based on poly(ethylene glycol) (PEG) and poly(butylene terephthalate) (PBT) was studied and compared with that of PBT itself. Two types of experiments were performed: (1) stress relaxation in torsion, and (2) measurement of intermittent couple-twist responses. It was shown that the relaxation of the torsional couple M could be represented as a sum of several exponential terms in the time, rather than as a simple exponential function. This sum might be called a Prony series on the analogy of the usual stress relaxation which occurs after stretching a sample to a certain deformation and holding it constant. The intermittent couple-twist experiments were carried out by analogy with similar experiments in elongation. For PEE the couple rises steadily with the twist, whereas for PBT it rises abruptly and remains constant within the experimental error for high twists. The residual twist, however, showed a similar trend for both PEE and PBT. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 495–502, 1998     

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     

Environmental stress cracking resistance of blow moded poly(ethylene terephthalate) containers

A method is developed for determining the environmental stress cracking resistance (ESCR) of blow molded poly(ethylene terephthalate) (PET) containers. By this method, the internal chamber of a container is presurized in 68.9 kPa (10 psi) increments while the outside of the base is being exposed to an environmental stress cracking (ESC) agent. The base of the container is examined after each 68.9 kPa of pressurization if crazing has occurred. The process is continued until a threshold value of craze initiation pressure (CIP) can be determined. Low CIP for the type of containers tested generally corresponds to a high rate of field failures. The method does not only gage the susceptibility of different types of one-piece PET containers to ESC but also provides helpful information to improve the container designs.     

Anisotropy of dielectric relaxation in poly(ethylene terephthalate) fibres

Dielectric measurements have been made on poly(ethylene terephthalate) (PET) fibres in the frequency range 0.5–10 kHz in temperature range ?120°?+30° C with the applied electric field parallel and perpendicular to the fibre axis. Considerable directional anisotropy was observed in the β-relaxation process, which was independent of frequency. The observed dielectric anisotropy has been related to the structural parameters thus leading to a value 〈cos²ψ〉 = 0.21, where ψ is the angle between the dipole moment vector responsible for this relaxation and the molecular chain axis. Activation energy for this process in PET fibres (9 kcal/mol) was lower than that reported for PET films and extruded rods.     

Stress relaxation behavior of biaxially oriented poly(ethylene terephthalate)

The stress relaxation behavior of biaxially oriented semicrystalline poly(ethylene terephthalate) was studied by thermomechanical analysis. Experimental techniques were developed for thin films. Relaxation moduli were measured as a function of stress, time, and temperature. The relaxation modulus was shown to be independent of stress over the range tested. Rate of loss of the relaxation modulus was found to be a nonlinear function of time and temperature up to about 100°C, encompassing the T_g for the polymer. Over the temperature range of 100–120°C it was primarily temperature-dependent. An empirical time—temperature superposition showed that significant losses in modulus can occur at very short times. At temperatures above the T_g these losses can result in significantly reduced film physical properties.