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Changes in fuel composition and the introduction of alternative fuels often create problems of corrosion and degradation in materials. The objective of this research was to determine the corrosion behaviour of commercial metallic tank materials (unalloyed steels, austenitic CrNi- and CrNiMo-steels, aluminium and its alloys) in fuels and heating oil with admixtures of biogenic sources, such as gasoline with addition of ethanol (E10, E85), pure biodiesel and heating oil with 10 % biodiesel (B10).
Metallic tank materials were evaluated as resistant in a liquid if the annual corrosion rate due to uniform corrosion did not exceed 0.1 mm/year, and localized corrosion effects in the form of pitting corrosion, stress corrosion cracking and crevice corrosion did not occur.
The corrosion rates of the tank materials after exposure to E10, E85, non-aged and two-year aged pure biodiesel, and non-aged and one-year aged heating oil B10 for four weeks at 50 °C, according to DIN 50905/4, were well below the limit of 0.1 mm/year. For the unalloyed steels, the formation of rust was observed independently of the biofuels amount of ageing. U-bend specimens made of unalloyed steel were not damaged in form of stress corrosion cracking in all test fuels at this test temperature.
Ziel dieser Untersuchungen war die Bewertung der Beständigkeit häufig eingesetzter Dichtungswerkstoffe, wie FKM, FVMQ, VMQ, EPDM, CR, CSM, IIR, PA, NBR und PUR in Kraftstoffen und Heizöl mit und ohne biogene Zusätze bei 20 °C, 40 °C und 70 °C. E10, E85, Dieselkraftstoff mit max. 5 % Biodiesel, ungealtertes und 2 Jahre gealtertes B10 (Heizöl mit 10 % Biodiesel), reiner Dieselkraftstoff, Heizöl und Kraftstoff Super plus zählten zu den Testsubstanzen. Masse, Zugfestigkeit und Bruchdehnung wurden von den Prüfkörpern vor und nach der 84-tägigen Auslagerung in den Kraftstoffen und Heizöl bestimmt. Die visuelle Begutachtung einiger Elastomerprüfkörper zeigte eindeutig die hohe Quellung bis zur partiellen Auflösung. Die Shore-Härte A und D (für PA) der Prüfkörper wurden vor und nach der 42-tägigen Auslagerung in den Kraftstoffen bestimmt. In den internationalen Normen wird zur Bewertung der Beständigkeit von Elastomeren kein Grenzwert der Reduzierung der Zugeigenschaften und der Shore-Härte definiert. Deshalb wurde für die Beständigkeitsbewertung ein Grenzwert von 15 % festgelegt. Zusammenfassend kann die Aussage getroffen werden, dass die Beständigkeit der Fluorpolymere FKM und FVMQ in den Kraftstoffen und Heizöl mit und ohne biogene Zusätze die beste ist.
Changes in fuel composition and the introduction of alternative fuels often create problems of corrosion and degradation in materials. The objective of this research was to determine the corrosion behaviour of commercial metallic tank materials (unalloyed steels, austenitic CrNi- and CrNiMo-steels, aluminium and its alloys) in fuels and heating oil with admixtures of biogenic sources, such as gasoline with addition of ethanol (E10, E85), pure biodiesel and heating oil with 10 % biodiesel (B10).
Metallic tank materials were evaluated as resistant in a liquid if the annual corrosion rate due to uniform corrosion did not exceed 0.1 mm/year, and localized corrosion effects in the form of pitting corrosion, stress corrosion cracking and crevice corrosion did not occur.
The corrosion rates of the tank materials after exposure to E10, E85, non-aged and two-year aged pure biodiesel, and non-aged and one-year aged heating oil B10 for four weeks at 50 °C, according to DIN 50905/4, were well below the limit of 0.1 mm/year. For the unalloyed steels, the formation of rust was observed independently of the biofuels amount of ageing. U-bend specimens made of unalloyed steel were not damaged in form of stress corrosion cracking in all test fuels at this test temperature.
Die Bewertung der Werkstoffbeständigkeit ist von großer Bedeutung bei Änderung der Zusammensetzung der Kraftstoffe und des Heizöls, insbesondere die Frage nach der Beständigkeit der Dichtungswerkstoffe bei Zusätzen von Bioethanol und Biodiesel (Rapsölfettsäuremethylester).
Vorhergehende Untersuchungen (Messungen der Veränderungen der Masse, der Zugeigenschaften und der Härte) bezogen sich auf die Bewertung der Beständigkeit häufig verwendeter Dichtungswerkstoffe wie FKM, FVMQ, VMQ, EPDM, CR, CSM, IIR, PA, NBR und PUR in Kraftstoffen und Heizöl mit 10 % Biodiesel (nicht gealtert und bis zu 5 Jahre gealtert) unter statischen Bedingungen.
Ziel der Untersuchungen war die Bewertung der Beständigkeit von Fluorkautschuk unter verpressten Bedingungen in Analogie zu den Einsatzbedingungen in der Praxis. Die Masse und der Druckverformungsrest von Prüfkörpern aus FKM wurden vor und nach der Auslagerung über einen Zeitraum von 3, 7, 14, 28, 56 und 90 Tagen in E10 (Kraftstoff mit max. 10 % Ethanol), E85 (Kraftstoff mit 85 % Ethanol), Biodiesel (Rapsölfettsäuremethylester), Super (Kraftstoff mit max. 5 % Ethanol), Dieselkraftstoff mit max. 5 % Biodiesel, Super Plus (Kraftstoff ohne Ethanolzusatz) und Heizöl mit 10 % Biodiesel (B10) bei 40 °C gemäß ISO 815-1 bestimmt. Die Druckverformungsrestprüfung zählt neben der Messung der Härte, der Dichte und der Zugeigenschaften zu den wichtigsten Grundprüfverfahren der Elastomerindustrie. Nach Ende der Auslagerung in den Kraftstoffen und der Aufhebung der Verpressung wur-de der Druckverformungsrest der Prüfkörper in regelmäßigen Zeitabständen bis zu einer Rücktrocknung > 90 Tage bestimmt. Zum Vergleich wurden Prüfkörper aus FKM ohne Kraftstoff oder Heizöl unter Verpressung bei 40 °C ausgelagert.
Die Masseänderung der Prüfkörper aus FKM betrug nach 90 Tagen Auslagerung in E10 9 %, in Super 8 %, in E85 4% und 0,6 % in Biodiesel. Die Erhöhung der Masse und die damit verbundene Quellung der Prüfkörper in E10 und Super mit 5 – 10% Ethanolzusatz hatte einen Einfluss auf den Druckverformungsrest, der sprunghaften Veränderungen unterlag im Vergleich zu den Werten nach Auslagerung in Biodiesel, Dieselkraftstoff und Heizöl B10 bei 40 °C. Zum Vergleich, unter statischen Bedingungen verringerte sich die Zugfestigkeit der Prüfkörper aus FKM nach Auslagerung in E10 bei 40 °C um 31 % und die Reißdehnung um 18 %.
Materials compatibility is a major concern whenever the fuel composition is changed. The question arises of whether sealing materials are resistant to fuels with bioethanol and biodiesel (rapeseed oil fatty acid methyl ester).
Previous research considered the resistance of frequently used sealing materials such as FKM (fluorocarbon rubber), FVMQ (methyl-fluoro-silicone rubber), VMQ (methyl-vinyl-silicone rubber), EPDM (ethylene-propylene-diene rubber), CR (chloroprene rubber), CSM (chlorosulfonated polyethylene), IIR (butyl rubber), PA (polyamides), NBR (acrylonitrile-butadiene rubber) and PUR (polyester urethane rubber) in fuels and heating oil with admixtures of biogenic substances such as biodiesel and B10 (heating oil with 10 % biodiesel) under purely static conditions.
The aim of this study was to evaluate the fluorocarbon rubber performance under compressed conditions. For the investigations, the mass and the compression set of the FKM test specimens were determined before and after exposure for 3, 7, 14, 28, 56 and 90 days in E10 (fuel with 10 % ethanol), E85 (fuel with 85 % ethanol), biodiesel (fatty acid methyl ester, FAME), Super (fuel with max. 5 % ethanol), diesel fuel with max. 5 % biodiesel, pure diesel fuel, Super Plus (fuel without ethanol) and heating oil with 10 % biodiesel (B10) at 40 °C according to ISO 815-1 “Rubber, vulcanized or thermoplastic - determination of compression set – Part 1: At ambient or elevated temperatures”. The compression set test belongs beside the determination of the Shore hardness, the density and the tensile properties to the basic test methods for elastomers. It was measured in regular time intervals up to a re-drying of more than 90 days after relaxation of test specimens. For comparison, FKM test specimens were exposed without fuel under compressed conditions at 40 °C.
The highest mass increase of FKM test specimens was measured after 90 days exposure in E10 by 9 %, followed by 8 % in Super fuel, by 4 % in E85 and by 0.6 % in biodiesel. Mass increase and swelling of the test specimens in E10 and Super fuel with max. 5 % ethanol had an influence on the compression set values which were subject to high fluctuations in comparison to the values obtained after exposure to other fuels such as biodiesel, diesel fuel and B10.
The results of the present work confirmed the higher swelling of the elastomers such as FKM in E10 obtained under static condition. It can be concluded on the basis of the mass increase and compression set values that FKM is resistant in all fuels under compressed conditions at 40 °C.
The objective of this research was to determine the resistance of frequently used sealing materials such as FKM (fluorocarbon rubber), FVMQ (methyl-fluoro-silicone rubber), VMQ (methyl-vinyl-silicone rubber), EPDM (ethylene-propylene-diene rubber), CR (chloroprene rubber), CSM (chlorosulfonated polyethylene), IIR (butyl rubber), PA (polyamides), NBR (acrylonitrile-butadiene rubber) and PUR (polyester urethane rubber) in fuels and heating oil with admixtures of biogenic sources such as E10 (fuel with 10 % ethanol), E85 (fuel with 85 % ethanol), non-aged and aged biodiesel, diesel fuel with 5 % biodiesel, non-aged and aged B10 (heating oil with 10 % biodiesel) at 20 °C, 40 °C and 70 °C.
Mass, tensile strength and breaking elongation of the test specimens were determined before and after the exposure for 84 days in the fuels. The visual examination of some elastomer test specimens clearly showed the great volume increase until break or partial dissolution. Shore hardness A and D (for PA) were determined before and after exposure of the test specimens in the biofuels for 42 days.
There is not determined a threshold for the reduction in tensile properties and Shore hardness in the international standards. Therefore a threshold of 15 % was determined for the evaluation of the compatibility.
In summary, it can be therefore stated that the chemical resistance of the fluoropolymers FKM and FVMQ in fuels and biofuels is the best one.
The full-notch creep test (FNCT) is widely used to characterize the slow crack growth (SCG) behavior of polyolefin materials in “inert” media as well as effects of environmental stress cracking (ESC) in which the medium has decisive influence on damage mechanism and time to failure. The test is of greatest importance for pipe and blow molding types of polyethylene, high density (PE-HD). Usually the full-notch creep test is applied as a standardized testing method (ISO 16770) using a few universal liquid media, such as solutions of Arkopal N 100. In our study, selected relevant polyethylene, high density materials are investigated also in real media – practical formulations as well as representative pure chemicals – and influences of temperature and geometry of specimen and notch are explicitly addressed. Furthermore, the investigations comprise also the environmental stress cracking behavior of polyethylene, high density in media that are sorbed to a significant extent – examples are diesel and biodiesel – based on comparison with samples previously saturated with those media. Thus, also the underlying diffusion controlled sorption process has to be assessed before. The investigations were performed using a full-notch creep testing device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
The FNCT is widely used to characterize the slow crack growth (SCG) behavior of polyolefinic materials in “inert” media as well as effects of environmental stress cracking (ESC) in which the medium has decisive influence on damage mechanism and time to failure. The test is of greatest importance for pipe and blow molding types of PE-HD - especially for transport and packaging of dangerous goods but also for most other high-performance applications.
Usually the FNCT is applied as a standardized testing method (ISO 16770) using a few universal liquid media, such as solutions of Arkopal N 100.
In our study, selected relevant PE-HD materials are investigated also in real media – practical formulations as well as representative pure chemicals – and influences of temperature and geometry of specimen and notch are explicitly addressed. Furthermore, the investigations comprise also the ESC behavior of PE-HD in media that are sorbed to a significant extent – one example are fuels, such as diesel and biodiesel – based on comparison with samples previously saturated with those media. Thus, also the underlying diffusion controlled sorption process has to be assessed before.
The investigations were performed using a FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
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.
Due to the increasing demand for utilization and improvement of energy efficient materials, especially concerning requirements in lightweight construction and design, polyolefin materials are used extensively and in an increasingly broad range of applications.
Although loaded with stresses under yield stress, preformed voids, inhomogeneities or notches can possibly lead to damage and unexpected failure induced by liquid media in polyolefin materials. For PE-HD, slow crack growth (SCG) as well as environmental stress cracking (ESC) are relevant mechanisms of damage. SCG appears without influence of a surrounding medium or in “inert” media whereas ESC occurs in “active” media, which have decisive influence on damage mechanism and time to failure. To characterize the intrinsic resistance of the material against those damage mechanisms, the Full-Notch Creep Test (FNCT) is widely used and of paramount importance particularly for the assessment of pipe and blow molding types of PE-HD.
In this study, the FNCT – usually applied as a standardized testing method (ISO 16770) using a few universal model liquid media – is extended by investigations of selected relevant PE-HD materials with a variety of properties also in real media. Mainly topical fuels, customary in the market such as diesel and biodiesel are examined. Especially the influence of temperature, and the ESC behavior of PE-HD in media that are sorbed to a significant extent, are addressed. The underlying diffusion-controlled sorption process was assessed before comparing non-saturated specimens with samples previously saturated with sorbing media.
The investigations were performed using a novel FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
In addition to acquired results concerning time to failure and elongation behavior, imaging techniques, such as light microscopy (LM), laser scanning microscopy (LSM) and X-ray computed tomography (CT scan) were utilized to obtain data concerning crack propagation and media migration. Fracture surface analysis (LM, LSM) and quasi in-situ imaging (CT scan) via measurement in different load stages are considered explicitly. Correlations of elongation behavior and data derived from imaging analysis such as fracture plane roughness and height of areas of ductile deformation were obtained.