Improvement of Hardening Stiffness Test as an Indicator of Environmental Stress Cracking Resistance of Polyethylene

Long term mechanical behavior of polyethylene (PE) is of great importance especially in cases where structural integrity is required. In order to predict characteristics of the mechanical behavior of PE, it is necessary to fully understand the molecular structure of the employed resins. In this study, evaluation of several micromolecular properties of PE is conducted. These properties influence an important performance indicator of PE for structural applications, namely, the environmental stress cracking resistance (ESCR). ESCR in PE resins occurs through a slow crack growth mechanism under low applied stresses and long periods of time. This property 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 at elevated temperatures. In the work presented herein, relationships between molecular structure and material response characteristics, mainly between molecular weight properties and short chain branching content in relation to strain hardening behavior of PE resins, were investigated based on results from tensile experiments. Inter-lamellar entanglements are believed to be the main feature controlling slow crack growth of PE. Extent of entanglements and entanglement efficiency has been investigated by monitoring the strain hardening behavior of PE resins in solid state through a uniaxial tensile test. The hardening stiffness (HS) test for prediction of ESCR was refined and improved to cover a broader range of PE resins, along with easier sample preparation, and faster testing. The improved test offers a more reliable and consistent ESCR picture without the drawbacks of the subjective notching process and ad-hoc presence of aggressive fluids.     

Effect of Temperature on Environmental Stress Cracking Resistance and Crystal Structure of Polyethylene

Studies were conducted on the crystalline properties of different polyethylene resins to identify their influence on phase interconnectivity between amorphous and crystalline regions. This work offers a thorough investigation on the potential correlation between environmental stress cracking resistance (ESCR) and crystalline structure characteristics, namely, crystallinity, mean lamella thickness and its distribution, and lamella surface area (LSA). The initial objective of this work was to investigate an existing ambiguity in the literature with respect to the effect of the crystalline phase on ESCR. In addition, research was conducted to evaluate the degree of variability in the lamella surface area, as a measure of phase interconnectivity and ESCR, with processing temperature and post-process annealing. Annealing at various conditions, along with cooling at different rates, were employed to investigate the effect of temperature on LSA. It was observed that a clear correlation exists between crystalline phase properties and ESCR, given that the comparison is made between polymers with similar molecular weights. Annealing temperature and time were found to cause a general reduction in LSA, however, to varying degrees, according to the type of PE molecular structure (significant interactions exist between annealing conditions and polymer type). LSA showed a significant dependence on cooling rate, however, no interaction was found between cooling rate and type of PE molecular structure. Additionally, lamella surface areas obtained from quenching and air cooling were found to be almost the same.     

Strain hardening of high density polyethylene

The introduction of true stress strain measurements, at constant strain rate, has promoted the development of empirical or semiempirical models for large deformations in thermoplastics. One such theory, which proposes that the post yield deformation process can be represented by equations derived from the theories of rubber elasticity, has been successfully applied to several glassy polymers. Unexpectedly, it can also model the post yield deformation of many different grades of polyethylene, even when rubber theory is employed in the simplest Gaussian form. Strain hardening is then represented by the single strain hardening coefficient Gp. Examples are given of this equation, which can be modified to give the true engineering or nominal stress σ_n and then be differentiated to give dσ_n/dλ = Gp ? Y₀ / λ² + 2Gp / λ³, where Y₀ is the yield stress and λ the extension ratio. Negative values of this differential then predict the onset of necking in tension and positive values stabilization of the neck. The relation of Gp to molecular weight is then discussed using literature measurements for polyethylenes of differing molecular weight and similar molecular weight distributions. When these results are then plotted, a strong dependency of Gp on molecular weight is observed. Some implications of these measurements are then considered. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1090–1099, 2007     

Environmental stress cracking resistance of polyethylene: The use of CRYSTAF and SEC to establish structure–property relationships

Nineteen commercial high‐density polyethylene resins made with different polymerization processes and catalyst types were analyzed by high‐temperature size exclusion chromatography and crystallization analysis fractionation. The information obtained with these characterization techniques on the polymer chain structure was correlated to environmental stress cracking resistance. Environmental stress cracking resistance increases when the molecular weight and concentration of polymer chains that crystallize in trichlorobenzene between 75 and 85 °C increase. Polymer chains present in this crystallization range are assumed to act as tie molecules between crystal lamellae. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1267–1275, 2000