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Biodiesel (FAME) from rapeseed is an environmentally friendly alternative to common fossil fuels. It is also suitable to serve as blending component to fuels like heating oil. If the fuel composition is changed, materials compatibility must be guaranteed. Adding polar biodiesel to nonpolar heating oil, changes the blend’s solvency and might cause swelling, extraction and solvation of polymers. The objective of this research was to investigate the compatibility of polymeric materials, which are commonly used for components in middle distillate facilities, along with blends of heating oil and 20 % biodiesel (B20). For this propose, ACM, HNBR, FKM, PE, PA 6, POM, PUR and PVC were exposed to heating oil and B20 for 42 and 84 days at 40 °C. In addition, the polymers HNBR, FKM, PA, POM and PVC were also exposed at 70 °C. Furthermore, the resistance of polymers in eight-year aged B10 at 40 °C was evaluated. Ageing of biodiesel increases acidity which might propagate polymer corrosion. The materials were evaluated as resistant, if the loss in tensile properties (tensile strength and elongation at break) and Shore hardness remained under 15 % compared to the initial unexposed material values. For investigations under compressed conditions, the compression set was determined for specimens of ACM, FKM and HNBR after exposure in heating oil B0 and B20 for 3,7,14, 28, 56 and 90 days at 40 °C according to ISO 815-1. It was found that the resistance in B20 at 40 °C was given for all tested polymers except PUR. In the 8 years aged B10, PUR and POM were not compatible and ACM just conditionally compatible. At 70 °C, FKM and PVC were resistant in B20, whereas HNBR and PA 6 were not compatible. Swelling occurred for the elastomers ACM, HNBR and PUR.
Biodiesel (FAME) from rapeseed is an environmentally friendly alternative to common fossil fuels. It is also suitable to serve as blending component to fuels like heating oil. If the fuel composition is changed, materials compatibility must be guaranteed. Adding polar biodiesel to nonpolar heating oil, changes the blend’s solvency and might cause swelling, extraction and solvation of polymers.
The objective of this research was to investigate the compatibility of polymeric materials, which are commonly used for components in middle distillate facilities, along with blends of heating oil and 20 % biodiesel (B20). For this propose, ACM, HNBR, FKM, PE, PA 6, POM, PUR and PVC were exposed to heating oil and B20 for 42 and 84 days at 40 °C. In addition, the polymers HNBR, FKM, PA, POM and PVC were also exposed at 70 °C. Furthermore, the resistance of polymers in eight-year aged B10 at 40 °C was evaluated. Ageing of biodiesel increases acidity which might propagate polymer corrosion.
The materials were evaluated as resistant, if the loss in tensile properties (tensile strength and elongation at break) and Shore hardness remained under 15 % compared to the initial unexposed material values. For investigations under compressed conditions, the compression set was determined for specimens of ACM, FKM and HNBR after exposure in heating oil B0 and B20 for 3,7,14, 28, 56 and 90 days at 40 °C according to ISO 815-1.
It was found that the resistance in B20 at 40 °C was given for all tested polymers except PUR. In the 8 years aged B10, PUR and POM were not compatible and ACM just conditionally compatible. At 70 °C, FKM and PVC were resistant in B20, whereas HNBR and PA 6 were not compatible. Swelling occurred for the elastomers ACM, HNBR and PUR.
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.
Für Bauteile (Komponenten) von Versorgungsanlagen für flüssige Brenn- und Kraftstoffe muss die Beständigkeit der metallenen Werkstoffe und Polymere nachgewiesen werden. Im Anwendungsfall von Heizöl mit 20 % biogenen Anteilen in Form von Rapsölfettsäuremethylester (FAME, Biodiesel) ist es für eine konservative Beurteilung des Korrosionssystems Werkstoff/Medium/Umgebung wichtig, die Alterungseffekte des Mediums einzubeziehen.
Entwicklung eines Prüfverfahrens für die Untersuchung der Beständigkeit von metallenen Werkstoffen und Polymeren in Heizöl und Heizöl-FAME-Blends, das für eine Vorauswahl der Werkstoffe und zum Nachweis der Beständigkeit im Hinblick auf die bauaufsichtlichen Zulassungsverfahren geeignet ist.
In Europe biodiesel gained from rapeseeds are considered as an alternative to common fossil fuels due to its environmental performance and its independence from import of raw materials. Biodiesel is also suitable to serve as blending component to heating oil. In that case, it must be considered that changes of fuel composition might cause material degradation.
The objective of this research was to investigate the resistance of metallic materials exposed to heating oil, heating oil blend B20 with 20 % biodiesel and pure biodiesel. Furthermore, the resistance of metals to eight-year aged B10 and six-year aged pure biodiesel was evaluated. Ageing of biodiesel forms acids and water which might propagate metal corrosion. The investigated metals (aluminium, unalloyed steel, austenitic CrNi-steel, copper, die cast zinc and brass) are commonly used for components in middle distillate facilities.
According to DIN 50905-4 the immersed metals were exposed in a climate chamber at 50°C for 4 weeks. The metallic materials were evaluated as resistant if the annual corrosion rate due to uniform corrosion remained under 0.1 mm/year and no localized corrosion in the form of pitting occurred.
The corrosion rates of the exposed materials stayed far below the limit of 0.1 mm/year for all tested fuels. An exception was die cast zinc ZP0410 in eight-year aged B10; a corrosion rate up to 0.3 mm/year due to uniform corrosion was measured. In no case localized corrosion occurred. Copper and brass caused discolouration of biodiesel from yellow to green.
In conclusion, the tested metallic materials were resistant in heating oil, heating oil blend B20 and pure biodiesel at 50 °C. Even the metals exposed to six-year aged biodiesel and eight-year aged B10 showed no uniform or localized corrosion; except for zinc, which was not resistant in eight-year aged B10.
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.
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 %.
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.
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.
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.