E. V. Stepanov

Oxygen barrier properties of crystallized and talc-filled poly(ethylene terephthalate)

The improvement in oxygen barrier properties of poly(ethylene terephthalate) (PET) by incorporation of an impermeable phase such as crystallinity or talc platelets was examined. Crystallinity was induced by crystallization from the glassy state (cold crystallization). Microlayering was used to create talc-filled structures with controlled layer architecture. The reduction of permeability in crystallized and talc-filled PET was well described by Nielsens model. Changes in permeability of crystalline PET could not be ascribed to the filler effect of crystallites only. Our data on solubility, obtained on the basis of measurements of the oxygen transport coefficients, confirmed a previous finding that the amorphous phase density of PET decreases upon crystallization. The data were amenable to interpretation by free volume theory. Talc-filled materials processed by different methods showed the same permeability; however, much better mechanical properties were achieved by microlayering.

Oxygen-barrier properties of oriented and heat-set poly(ethylene terephthalate)

The improvement in the oxygen-barrier properties of poly(ethylene terephthalate) (PET) by orientation and heat setting was examined. Orientation was carried out at 65 °C by constrained uniaxial stretching to a draw ratio of about 4. Heat setting was performed at temperatures from 90 to 160 °C with the specimen taut. Orientation decreased the permeability of PET to almost one-third that of the unoriented, amorphous polymer because of decreases in both the diffusion coefficient and the solubility coefficient. The proposed two-phase model for oriented PET consisted of a permeable isotropic amorphous phase (density = 1.335 g/cm3) with ethylene linkages predominately in the gauche conformation and an impermeable oriented phase (density = 1.38 g/cm3) with ethylene linkages that had transformed from the gauche conformation to the trans conformation during stretching. Chain segments in the trans conformation did not possess crystalline order; instead, they were viewed as forming an ordered amorphous phase. Crystallization by heat setting above the glass-transition temperature did not dramatically affect the permeability. However, a decrease in the diffusion coefficient, offset by an increase in the solubility coefficient, indicated that crystallization affected the barrier properties of the permeable amorphous phase. Analysis of the barrier data, assuming a two-phase model with variable density for both the permeable and impermeable phases, revealed that the impermeable phase density increased during crystallization, approaching a value of 1.476 g/cm3. This value is consistent with previous measurements of the density of the defective crystalline phase in PET. The density of the permeable amorphous phase decreased concurrently to about 1.325 g/cm3, indicating the appearance of additional free volume.

Correlation of fatigue and creep slow crack growth in a medium density polyethylene pipe material

The relationship between slow crack propagation in creep and fatigue in a medium density polyethylene pipe material was studied by increasing the R-ratio (defined as the ratio of minimum to maximum stress in the fatigue loading cycle) from 0.1 to 1.0 (creep). The study included characterization of the effects of R-ratio and temperature (21 to 80°C) on the mechanism and kinetics of slow crack propagation. With increasing R-ratio and decreasing temperature, the fracture mode changed from stepwise crack propagation, i.e. crack growth by the sequential formation and breakdown of a craze zone, to a “quasi-continuous” mode of crack growth through the preexisting craze. Despite the change in fracture mode, the damage zone, as characterized by the length of the main craze, shear crazes, and crack tip opening displacement, followed the same dependence on loading parameters, and crack growth rate followed the same kinetics. Crack growth rate (da/dt) was related to the maximum stress intensity factor KI, max and R-ratio by a power law relationship (da/dt) = B′K4I, max(1 + R)−6. Alternatively, crack growth rate was expressed as (da/dt) = B′KI4(t)Tβ(∈) with a creep contribution B‹KI4(t)›T, calculated by averaging the known dependence of creep crack growth rate on stress intensity factor KI over the period T of the sinusoidal loading curve, and a fatigue acceleration factor β(∈) that depended on strain rate only. The correlation in crack growth kinetics allowed for extrapolation to creep fracture from short-term fatigue testing. The temperature dependence of crack growth rate was contained in the prefactors B and B′. A change in slope of the Arrhenius plot of B′ at 55°C indicated that at least two mechanisms contributed to crack propagation, each dominating in a different temperature region. This implied that a simple extrapolation to ambient temperature creep fracture from elevated temperature tests might not be reliable.

Effect of strain rate on stepwise fatigue and creep slow crack growth in high density polyethylene

The effects of frequency and R-ratio (the ratio of minimum to maximum stress in the fatigue loading cycle) on the kinetics of step-wise crack propagation in fatigue and creep of high density polyethylene (HDPE) was characterized. Stepwise crack growth was observed over the entire range of frequency and R-ratio examined. A model relating crack growth rate to stress intensity factor parameters and applied strain rate was proposed by considering the total crack growth rate to consist of contributions from creep and fatigue loading components. The creep contribution in a fatigue test was calculated from the sinusoidal loading curve and the known dependence of creep crack growth on stress intensity factor in polyethylene. At a very low frequency of 0.01 Hz, fatigue crack growth rate was found to be completely controlled by creep processes. Comparison of the frequency and R-ratio tests revealed that the fatigue loading component depended on strain rate. Therefore, crack growth rate could be modeled with a creep contribution that depended only on the stress intensity factor parameters and a fatigue contribution that depended on strain rate.

Correlation of stepwise fatigue and creep slow crack growth in high density polyethylene

The kinetics and mechanism of slow crack growth in fatigue and creep of high density polyethylene were studied. The relationship between fatigue and creep was examined by varying the R-ratio (the minimum/maximum loads in the fatigue loading cycle) in the tensile mode such that loading ranged from mainly dynamic (R = 0.1) to static (R = 1.0, creep test). The stepwise crack propagation mechanism characteristic of long-term failures in polyethylene was observed for all loading conditions studied. Fatigue fracture kinetics allowed for extrapolation to the case of creep failure, which suggested that short-term fatigue testing can be used to predict long-term creep fracture properties. The size of the craze damage zone ahead of the arrested crack tip was controlled only by the mean stress, however the lifetime of the zone was determined by both the maximum stress and the mean stress. Crack growth rate was related to the maximum stress and the mean stress by a power law relationship, which described crack growth over the entire range of loading conditions studied.

Stepwise fatigue crack propagation in polyethylene resins of different molecular structure

Stepwise fatigue crack propagation in a range of polyethylene resins, some of which are candidates for use in pipes for natural gas distribution, was studied. Examination of the effect of molding conditions on fatigue crack propagation in a pipe resin indicated that fast cooling under pressure produced specimens with the same crack resistance as specimens taken from a pipe extruded from this resin. The mechanism of stepwise crack propagation in fatigue was the same as reported previously for creep loading. Observations of the region ahead of the arrested crack revealed a complex damage zone that consisted of a thick membrane at the crack tip followed by a main craze with subsidiary shear crazes that emerged from the crack tip at an angle to the main craze. The effects of molecular parameters, such as molecular weight, comonomer content, and branch distribution, on the kinetics of fatigue crack propagation were examined. Correlation of creep and fatigue crack resistance made it possible to relate fatigue fracture toughness to molecular parameters by invoking concepts of craze fibril stability developed for creep.

Study of polyethylene pipe resins by a fatigue test that simulates crack propagation in a real pipe

A fatigue test that simulates the step-wise crack propagation found in pipes in the field, and uses a standard compact-tension specimen, was employed to study and rank crack resistance of various pipe resins. The thermal history during compression moulding of the test specimens strongly affected fracture kinetics. It was found that crack-resistant properties of in-service pipe were best reproduced if compression-moulded plaques were fast cooled under load. This procedure was used to prepare specimens from candidate pipe resins for fatigue testing. The resins were compared in terms of discontinuous crack growth kinetics. The ranking based on resistance to fatigue crack propagation correlated with results of a standard PENT creep test. However, fatigue failure times were an order of magnitude less than the standard creep times. After comparing the initiation and failure times of the resins with detailed kinetics of step-wisse crack propagation, a simplified and rapid procedure is proposed which calls for evaluating only the first jump after initiation.

Solid state structure and melting behavior of interdiffused polyethylenes in microlayers

Gradient structures, produced by interdiffusion in microlayers of a high density polyethylene/linear low density polyethylene polymer pair that cocrystallizes isomorphically, were studied experimentally. Microlayers were taken into the melt for a period of time, and the compositional gradient was fixed by crystallization upon quenching. High specific interfacial area of microlayers offset the low diffusion mobility of polymeric chains so that the microlayer in the melt approached compositional homogeneity on a laboratory time scale. Taking advantage of the systematic change of the melting temperature with the blend composition, the compositional gradient was visualized by progressively melting the microlayer with increasing temperature. This made it possible to monitor the kinetics of interdiffusion without using a chemical label. The compositional profiles were analyzed with a diffusion model formulated for a polydisperse system. Diffusion coefficients for lightly branched and linear polyethylene chains, which correlated well with the data of previous studies, were obtained. It was found that the interlayer boundaries remained stationary during a characteristic time of interdiffusion of the component main fractions, and moved at long times as high molecular weight fractions became involved in interdiffusion. The moving boundary phenomenon was investigated with optical and atomic force microscopy and the development of crystalline morphology in the microscopic compositional gradient was described.

The damage zone ahead of the arrested crack in polyethylene resins

Formation and growth of the crack tip damage zone during slow stepwise crack propagation in polyethylene resins was studied experimentally. The study focused on the differences between the damage zone in high density polyethylene (HDPE), that represented traditional single-craze morphology, and the damage zone in more fracture resistant ethylene copolymers (MDPE) under plain strain conditions. It was shown that improved fracture resistance correlated with development of an epsilon-shaped damage zone that consisted of the central craze and an accompanying pair of hinge shear zones of comparable length. The shear zones emanated from the crack tip immediately above and below the central craze where highly stretched material formed a membrane that separated the crack tip from the cavitated material in the craze. The remarkable observation that the shear zones underwent crazing despite the presumably unfavorable stress-strain conditions was attributed to a dilatational stress component resulting from partial re-distribution of the load as the main craze opened. Microscopic analysis revealed differences in the crazed material between the single-craze (HDPE) and the epsilon-shaped (MDPE) morphology. An array of cellular cavities separated by walls of biaxially oriented material in the MDPE craze contrasted with the traditional structure of uniaxially stretched fibrils in the HDPE craze. The stepwise development and fracture of the damage zone was monitored in time, and the differences in kinetics of these processes between the two types of morphologies were characterized.

Correlation of fatigue crack propagation in polyethylene pipe specimens of different geometries

Correlation in mechanisms and kinetics of step-wise fatigue crack propagation in polyethylene pipe specimens of different geometries is studied experimentally. It is shown that crack propagation in a non-standard specimen cut from a real pipe and conserving the pipe geometry can be effectively simulated using a standard compact tension specimen. Good correlation in both kinetics of step-wise crack propagation and fractography between the specimens is achieved if experimental conditions are chosen to assure equal values of (a) stress intensity factor and (b) stress intensity factor gradient at the initial notch tips. These results extend previous technique of fatigue accelerating slow crack growth used to predict lifetime of polyethylene pipes.