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The physical and chemical effects of diesel and biodiesel fuels on two high-density polyethylene (PE-HD) types were investigated. Both semi-crystalline PE-HD are common thermoplastic materials for container and storage tank applications. Biodiesel, a composition of unsaturated fatty acid esters from renewable resources, was chosen as it is regarded a possible green alternative to fossil fuels. The study aims at identifying significant differences between biodiesel and conventional diesel fuels based on the differences in the chemical nature of the two. The physical effects of the fuels on the polymer at first comprises the sorption behavior, i.e. kinetics and final equilibrium concentration. Not only are both fuels absorbed by the amorphous phase of the semi-crystalline PE-HD, they also induce a plasticization effect that modifies the molecular mobility and therefore also the characteristic yielding properties, manifest in the obtained stress-strain curves. The chemical effects related to degradation phenomena is investigated by a long-term storage scenario using partially immersed tensile test specimens in diesel and biodiesel. We were able to confirm the proposed co-oxidation mechanism by Richaud et al. for polyethylene-unsaturated penetrant systems on a larger scale based on practical tensile tests. One of the investigated polyethylene grades subjected to tensile drawing showed a significant loss of plastic deformation and the onset of premature failure after 150 days of storage in biodiesel. Further biodiesel storage showed a systematically reduced elongation at break before necking. None of these effects were observed in diesel. Oxidation of fuels and polymer after progressing storage times were analyzed by the evolution of carbonyl species in FT-IR/ATR spectroscopy.
PE-HD as a polymeric fuel storage tank material: Photooxidation, fuel sorption and long-term storage
(2018)
High-density polyethylene (PE-HD) is a commodity thermoplastic polymer which is typically used for packing of dangerous goods. Its good resistance against photooxidation, fuels, chemicals and other environmental factors in addition to low production costs makes PE-HD attractive for fuel storage applications. Typical engine fuels stored in polymer tanks are petrol, diesel and biodiesel that receives increasing attention as proper alternative to fossil fuels. One of the major problems with biodiesel is its susceptibility to oxidize due to its chemical composition of unsaturated fatty acids which also can cause polymer degradation.
The aim of this study is to investigate the influence of different environmental factors, UV radiation and commonly stored fuels, on the mechanical, physical and chemical properties of two types of PE-HD polymers (stabilized and non-stabilized). The influence on the mechanical properties was tested by Charpy and tensile tests, chemical and physical properties were evaluated by Fourier-transform infrared spectroscopy (FTIR) and by dynamical mechanical analysis (DMA) tests. Samples were characterized after varying exposure time of UV radiation and after fully and partially immersion in biodiesel. In addition, similar experiments were conducted using diesel for comparison.
Environmental Stress Cracking (ESC) and Slow Crack Growth (SCG) of PE-HD induced by external fluids
(2020)
High-density polyethylene (PE-HD) is widely used as a packaging material. Typical applications are pipes and containers for storage and transport of dangerous goods. For these applications, the understanding of the craze-crack damage mechanisms slow crack growth (SCG) and environmental stress cracking (ESC) is of importance. Since these mechanisms are considered to be the major causes of failure, their understanding is essential for inspection and release of those materials.
A well-established test method for the assessment of these damage mechanisms is the full-notch creep test (FNCT). It is used in this study for a detailed investigation of crack propagation phenomena in PE-HD container materials under the influence of different fluids such as air, water and aqueous detergent solutions (Arkopal N 100) as well as biodiesel and diesel. Based on the results of the FNCT, a classification scheme of different fluids is proposed, which allows for an assignment of the respective damage mechanisms. Hereby, it is differentiated between (i) inert, (ii) purely surface-active and (iii) additionally sorptive, bulk-active fluids with respect to SCG. If the test fluid changes the intrinsic properties (at the surface or in the bulk), the damage mechanism is addressed to ESC behavior.
In FNCT investigations, stress, temperature and specimen geometry were varied systematically. In addition to the time to failure as common measure for the resistance of a PE-HD type against crack propagation, specimen elongation was considered in detail.
Several imaging techniques were applied for fracture surface analysis of specimens tested in FNCT to gain novel information on SCG and ESC behavior. From height profiles obtained by laser scanning microscopy (LSM) and information on surface structures from scanning electron microscopy (SEM), indicators for the differentiation of the crack propagation mechanisms could be derived. Based on the LSM data, an algorithm for the distinction between ductile shear deformation and brittle crack growth as dominating failure mechanism was developed. Imaging techniques were also used for determination of crack propagation rates, which were related to time-resolved FNCT elongation data. From the time-resolved determination of crack lengths of partly damaged FNCT specimens, an increasing length of craze zone with a progressively propagating crack was revealed for the first time. This relation of crack and craze zones was specified by fracture mechanical considerations.
Characteristics of environmental stress cracking of PE-HD induced by biodiesel and diesel fuels
(2024)
In the context of the increasing effect of carbon dioxide emissions on the global climate biodiesel produced from renewable sources has emerged as a promising contender replacing fossil fuels, especially in long-range transport vehicles, using existing engines and infrastructure.
High-density polyethylene is one of the prevailing materials for pipe and container applications for storage and transport of such fuels, both, from fossil and renewable resources. The contact with the respective fuels raises questions concerning material compatibility as biodiesel exhibits significant differences compared to conventional diesel fuel affecting its sorption and plasticization behavior in polyethylene. In this study, its behavior with respect to environmental stress cracking, considered one of the most frequent damage mechanisms leading to failure of polymer parts and packaging, was evaluated using the well-established Full Notch Creep Test. This
approach allows for a detailed fracture surface analysis using imaging techniques, such as optical and laser scanning microscopy, as well as infrared spectroscopy. Comparing the environmental stress cracking behavior in standard surfactant solutions with that in biodiesel and diesel, respective crack propagation rates, showing different levels of acceleration, were determined and details of the underlying mechanisms could be revealed.
Furthermore, the specific infrared absorption of the biodiesel’s ester functionality allows its semi-quantitative determination on the fracture surface of the tested specimens after failure. Thus, a preferred uptake of sorptive fluids in the fracture zone due to local morphological changes of the polyethylene could be directly evidenced by infrared spectroscopy.