Methodologies for Obtaining Reliable Indicators for the Environmental Stress Cracking Resistance of Polyethylene

Environmental stress cracking (ESC) is one of the main, and probably the most common, failure mechanisms involved in polymer fractures. This type of failure is critically important as it occurs suddenly, without any visible pre-fracture deformation. Such failure can be catastrophic and costly in cases where structural integrity is required. In polyethylene (PE), ESC occurs through a slow crack growth mechanism. Cracks initiate from stress-concentrated imperfections, propagate through the bulk of PE, and ultimately result in a brittle fracture. In order to predict the environmental stress cracking resistance (ESCR) of PE, it is necessary to fully understand the molecular structure of the resin. In this thesis, attempts were made to find relationships between molecular structure characteristics and material responses, mainly inter-lamellar entanglements and strain hardening behaviour of PE resins, through mechanical and rheological experiments. Inter-lamellar entanglements are believed to be the main factor controlling slow crack growth of PE. Extent of entanglements and entanglement efficiency were investigated by monitoring the strain hardening behaviour of PE resins in the solid state through a uniaxial tensile test, and in the melt state, through extensional rheometry. ESCR is usually assessed by unreliable and time consuming testing methods such as the notch constant load test (NCLT) on notched PE specimens in the presence of an aggressive fluid and elevated temperatures. In this thesis, a practical, yet reliable, tensile test was developed for the evaluation and prediction of ESCR. The developed test offers a more reliable and consistent ESCR picture without the drawbacks of the subjective notching process and presence of aggressive fluids. Through this test, a factor called “corrected hardening stiffness (cHS)” was developed, which can easily be used for a relative ranking of ESCR of different PE resins. Studies were next extended to the melt state via shear and extensional rheometry. Through studies in the shear mode, a molecular weight-normalized average characteristic relaxation time (λN) was found to be efficient in predicting the extent of chain entanglements in resins. This provided a potential melt indicator for a relative measure of ESCR, for linear low density polyethylene (LLDPE), with different short chain branching levels. Extensional studies were conducted to evaluate the strain hardening behaviour in the melt state. An inverse correlatio