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Eingeladener Vortrag
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Use of Corrosion Resistant High-Alloyed Metallic Materials for Transport Tanks of Dangerous Goods
(2005)
In Germany the BAM-List Requirements for Tanks for the Transport of Dangerous
Goods is the basis for substance-related prototype approvals for tank containers designed for
the carriage of dangerous goods. Such approval is undertaken by the Federal Institute for
Materials Research and Testing (BAM). Compatibility evaluations of selected metallic
material groups as well as of polymeric gasket and lining materials under the influence of
dangerous goods and water-polluting substances are published in section 5 of the BAM-List.
According to the relevant regulations for rail, road and sea transportation a compulsory
internal inspection after certain intervals is required. The required corrosion resistance
depends on the length of the inspection interval.
There is a large number of dangerous goods with a high corrosivity to metals, where the standard
steels are not corrosion resistant. Chemical companies, transportation providers and tank
producers need tanks made of corrosion-resistant materials in order to protect the tank shell
and prevent contamination of high-value cargo as well as the environment. One solution is to
line the tank with a polymeric material, an alternative solution to corrosion problems is the
application of high-alloyed materials.
Only a narrow limited number of corrosion test results of these high-alloyed materials under
the influence of corrosive dangerous goods are available. In order to change this situation and
include the superaustenitic steels X1NiCrMoCuN25-20-7 (Alloy 926), X1NiCrMoCu32-28-7
(Alloy 31) and the nickel-based alloy NiCr23Mo16Al (Alloy 59) in the BAM-List, BAM,
IKS Dresden and ThyssenKrupp VDM started an comprehensive test program with welded
specimens made. The program comprises corrosion resistance evaluations of the high-alloyed
materials in substances representing 12 major groups of corrosive dangerous goods (e.g.
inorganic halogenides, organic acidic halogenides, halogenic carbonic acids, chlorosilanes,
chlorates, perchlorates, chlorites, hypochlorites and hydrogen sulphates).
The test results, presented in this paper, will be included in the upcoming 8th edition of the
BAM-List and therefore available for the costumer.
Use of Corrosion Resistant High-Alloyed Metallic Materials for Transport Tanks of Dangerous Goods
(2005)
Transportation of dangerous goods are worldwide regulated in the rules or standards e.g. in the recommendations on the Transport of Dangerous Goods of the United Nations, in the Accord Européen Relatif au Transport International des Marchandises Dangereuses par Route (ADR) etc. Addi-tional to these international regulations also national regulations and stan-dards e.g. Gefahrgutverordnung Straße und Eisenbahn (GGVSE) in Ger-many are bases for the transport of hazardous materials. For the material properties of tanks in the BAM-List Requirements for Tanks for the Transport of Dangerous Goods specifications for the sub-stance prototype approval for tank materials are listed. Further compati-bility evaluations of selected metallic material groups as well as of poly-meric gasket and lining materials under the influence of dangerous goods are published in the List. There are a large number of highly corrosive dangerous goods listed, in which conventional steels are not resistant. Chemical companies, transportation providers and tank producers need tanks made of corrosion-resistant materials (corrosion retardant materi-als) in order to protect the tank shell. The application of high-alloyed stainless steels and nickel alloys as there are alloy 926 (1.4529; X1NiCrMoCuN25-20-7), alloy 31 (1.4562;X1NiCrMoCu31-27-7) and Nickel-Chromium-Molybdenum Alloy 59 (2.4605; NiCr23Mo16Al) is an al-ternative solution compared with the lining of the tanks with a polymeric material. Due to the limited number of corrosion test results with welded test sam-ples of these high-alloyed materials under the influence of corrosive dan-gerous goods BAM, Institute for Corrosion Protection (IKS) Dresden and ThyssenKrupp VDM have been performing a comprehensive test program since 2002. The program comprised corrosion resistance evaluations of the three high-alloyed materials exposed to substances representing cor-rosive dangerous goods such as inorganic halogenides, organic acidic halogenides, sulfonic acids and nitrating acids.
Use of higher-alloyed metallic materials and duplex steels for transport tanks of dangerous goods
(2011)
Compatibility evaluations of selected metallic materials under the influence of dangerous goods are published in the BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” as basis for substance-related prototype approvals for tank Containers designed for the carriage of dangerous goods.
There is a request of the tank manufacturing industry and transportation Companies to incorporate additional materials into the BAM-List, especially corrosion-resistant materials because of the large number of corrosive dangerous goods. One solution to solve corrosion Problems is to line the tank with a polymer, an alternative solution is the application of high-alloyed stainless steels and nickel-based alloys as there are 1.4529 (XINiCrMoCu 25-20-7, alloy 926), 1.4562 (X1NiCrMoCu32-28-7, alloy 31) and 2.4605 (NiCr23Mo16AI, alloy 59).
There is an interest to use cost-efficient steels with high strength values and concomitant adequate corrosion resistance such as duplex steel 1.4362 (X2CrNiN23-4).
This steel grade was originally developed as a substitute for the austenitic grades 1.4404 (X2CrNiMo17-12-2) and 1.4571 (X6CrNiMoTi17-12-2). Due to the lower content of the alloy elements nickel and molybdenum this duplex steel is a cost-efficient alternative to molybdenum containing austenite.
Due to the limited number of corrosion test results with welded test samples of these high-alloyed materials and the duplex steel under the influence of corrosive dangerous goods a comprehensive test Programme was performed with these materials in Cooperation with ThyssenKrupp VDM and Deutsche Edelstahlwerke GmbH. It can be concluded from the test results that the superaustenitic steels 1.4529 and 1.4562 as well as the nickel-based alloy 2.4605 are a really good alternative as tank materials for the transport of dangerous goods in comparison to the lining of the tanks. The nickel-based alloy 2.4605 shows the best resistance and is suitable as material for tanks transporting all tested corrosive substances. One exception is the temperature limit during the transport of hydrochloric acid.
The superaustenit 1.4562 is a resistant material with a wide ränge of application. Exceptions for use are: ammonium bifluoride, brine, 34 % calcium Chloride solution, hydrochloric acid, perchloric acid, 90 % 2-chloropropionic acid, nitrating acid with nitric acid content > 50 % and molten monochloroacetic acid. The alloy is limited suitable for allyl Chloride, aluminum Chloride, copper (II) -Chloride and ferric Chloride. The superaustenit 1.4529 showed the lowest resistance compared to the other two materials. This steel is not resistant in hydrochloric acid, perchloric acid, sodium Chlorite and sodium hypochlorite. The application is limited in the concentration ränge of aqueous Solutions of aluminum Chloride, copper (II) Chloride and ferric Chloride. Due to the reduced alloying content of the duplex steel 1.4362 (X2CrNiN23-4) compared to the austenitic CrNiMo-steels, a lower resistance especially in acidic media like formic, acetic or sulfuric acid was observed. Within the more than 7.000 substances contained in the BAM-List there is a large amount of dangerous goods such as hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, and inorganic alkaline substances which have a large transport volume and do not corrode the duplex steel 1.4362 (X2CrNiN23-4).
The test results are included in the actual 11th edition of the BAM-List and therefore available for the costumer.
In Germany the “BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” is the basis for substance-related prototype approvals for tank Containers undertaken by the BAM1 - Federal Institute for Materials Research and Testing. Compatibility evaluations of selected metallic materials as well as of polymeric gasket and lining materials under the influence of approximately 7200 dangerous goods have been published in the BAM-List since 1989.
The ferritic Steel UNS S44400 (X2CrMoTil8-10, 1.4521) was originally developed as alternative for the austenitic grade AISI316L (X2CrNiMo 17-12-2, 1.4404). Due to its characteristic profile this Steel was qualified for applications requiring high strength values at concomitant adequate corrosion resistance. Because of the lack of Nickel this Steel is a cost-efficient alternative to the Ni-containing austenites. No corrosion test results of UNS S44400 under the influence of dangerous goods were published in the BAM-List so far. Only data on the behavior of AISI 316L are listed. Therefore test specimens of this Steel were exposed to selected corrosive substances in order to compare both steels.
Due to the reduced alloy content a reduced corrosion resistance of the Steel UNS S44400 in acidic substances, such as formic acid, acetic acid and sulfuric acid, in comparison to the austenitic CrNiMosteels was expected but not observed. Tests in an alkaline medium showed sufficient resistance.
Alloy 59 (NiCr23Mo16Al) with a lot of chromium, molybdenum and nickel possesses excellent resistance not only to reducing but also oxidizing chemicals. Both the Nickel alloy 59 and the superaustenitic steel alloy 31 have already been used as shell materials for tank vehicles or tank containers. Use of these alloys allows the transport of a signifi-cantly more wider variety of chemicals and, especially, waste mixtures than the use of common aus-tenitic steels. Another advantage is the extension of test intervals of for transport tanks. In Germany the 'BAM-List – Requirements for Tanks for the Transport of Dangerous Goods' is the basis for substance-related prototype approvals for tank containers designed for the carriage of dangerous goods issued by the Federal Institute for Materials Research and Testing (BAM). Com-patibility evaluations of selected metallic material groups as well as polymeric gasket and lining materials under the influence of approximately 7000 dangerous goods and water-polluting sub-stances are published in the BAM-List. Alloy 59 belongs to the group of metallic materials in the BAM-List. Due to the large number of dangerous goods in the BAM-List BAM, IKS Dresden and ThyssenKrupp VDM performed a comprehensive corrosion test programme with welded specimens of the nickel alloy 59 and the superaustenitic steels alloy 926 and alloy 31 in the period 2002 - 2010. Especially In particular alloy 59 and alloy 31 were exposed to a large number of corrosive sub-stances such as various mixtures of both nitric acid/sulphuric acid and nitric acid/phosphoric acid at 55 °C. Other corrosive test substances were different organic and inorganic halogenides, peroxyace-tic acid and molten substances. In the case of molten chemicals such as monochloroacetic acid the test temperature was increased to more than 100 °C. The test results presented in this paper are al-ready included in the 10th edition of the BAM-List and, therefore, available to the customer.
Comparison of the corrosion resistance to dangerous goods of austenitic CrNiMo and duplex steels
(2014)
The “BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” is the basis in Germany for substance-related prototype approvals for tank Containers in Germany. Compatibility evaluations of selected metallic materials and polymeric materials under the influence of approximately 7200 dangerous goods have been published in the BAM-List since 1989. The austenitic CrNi- and CrNiMo-steels - UNS S30403, UNS S31600, UNSS31603 and UNS S31635 - are the materials mostly used worldwide for transport tanks. The duplex Steel UNS S31803 has been put on the BAMList due to the great interest of tank producers and transport Companies. Using UNS S31803 instead of 316L, the weight of the tanks can be reduced, and the list of transportable goods can be extended. The objective of these investigations was to compare the corrosion resistance of duplex Steel UNS S31803 and austenitic Steel UNS S31603. Therefore, test specimens of both steels were exposed to selected corrosive substances, such as formic acid, acetic acid, phosphoric acid, sulfuric acid, nitrating acid, monochloroacetic acid and trichloroacetone at 55 °C (30 °C, 70 °C). The test results have shown that the duplex Steel UNSS31803 is a good alternative to austenitic CrNiMo-steel UNS S31603 for tanks carrying corrosive dangerous goods.
Comparison of the Corrosion Resistance to Dangerous Goods of Austenitic CrNiMo and Duplex Steels
(2014)
In Germany the "BAM-List - Requirements for Tanks for the Transport of Dangerous Goods" is the basis for substance-related prototype approvals for tank Containers undertaken by the BAM - Federal Institute for Materials Research and Testing. Compatibility evaluations of selected metallic materials as well as of polymeric gasket and lining materials under the influence of approximately 7000 dangerous goods have been published in the BAM-List since 1989.
The duplex Steel 1.4362 (2304, UNS S32304) was originally developed as substitute for the austenitic grades 1.4404 (316L, UNS S31603) and 1.4571 (316Ti, UNS S31635). Due to its characteristic profile this Steel was qualified for applications requiring high strength values at concomitant adequate corrosion resistance. Because of its lower content of the alloy elements nickel and molybdenum this duplex Steel is a cost-efficient alternative to the molybdenum containing austenite. Only a limited number of corrosion test results of 1.4362 under the influence of dangerous goods published in the BAM-List were available. Therefore test specimens of this Steel were exposed to selected corrosive substances.
Due to the reduced alloy content a reduced corrosion resistance of the duplex Steel 1.4362 in acidic substances, such as formic acid, acetic acid and sulfuric acid, in comparison to the austenitic CrNiMosteels was observed. Tests in the alkaline medium showed a sufficient resistance.
In der DIN 6601 - Beständigkeit der Werkstoffe von Behältern/Tanks aus Stahl gegenüber Flüssigkeiten (Positiv-Flüssigkeitsliste) ist die Beständigkeit unlegierter Stähle, austenitischer CrNi- und CrNiMo-Stähle gegenüber den reinen Ottokraftstoffen bewertet. Mit der verstärkten Verwendung bioethanol- und biodieselhaltiger Kraftstoffe und Heizöl stellt sich auch die Frage nach der Beständigkeit der handelsüblichen Tank- und Behälterwerkstoffe sowie der Dichtungswerkstoffe unter dem Einfluss dieser Medien.
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.
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.
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.
Im Vorhaben wurde eine forcierte Prüfmethode zur Bestimmung der Beständigkeit von metallenen Werkstoffen gegenüber Brennstoffen aus Mitteldestillaten und Gemischen aus Mitteldestillat und paraffinischen Kohlenwasserstoffen, die jeweils Fettsäuremethylester (FAME) als biogene Komponente enthalten, entwickelt. Bei der Prüfmethode werden Prüfkörper des jeweiligen Werkstoffes in speziellen Prüfmedien ausgelagert. Die Zusammensetzung von zwei Prüfmedien wurde im Vorhaben erarbeitet. Diese Prüfmedien erfassen die Effekte der Alterung des FAME, die zu erwarten sind, wenn der Brennstoff länger als 2 Jahre im Feld lagert. Sie decken den Bereich bis 20 % (V/V) FAME-Anteil ab. Die Auslagerung kann bei geringem Aufwand unter Atmosphärendruck durchgeführt werden.
Die Eignung einer Auswahl von metallenen Werkstoffen und Polymerwerkstoffen, die für Versorgungsanlagen für Mitteldestillat relevant sind, wurde durch Auslagerung in folgenden nicht gealterten Brennstoffen bestimmt: Heizöl EL schwefelarm (B0), Heizöl EL schwefelarm mit 20 % (V/V) FAME (B20), FAME (B100) und hydriertes Pflanzenöl (HVO). Die Werkstoffe wurden auch in einem 1 Jahr gealterten B20 und einem 8 Jahre gealtertem B10 ausgelagert. Die Temperatur bei der Auslagerung betrug 50 °C für die metallenen Werkstoffe und 40 °C und 70 °C für die Polymerwerkstoffe. Die Ergebnisse der Beständigkeitsbewertung wurden in Beständigkeitslisten zusammengefasst. Die mit B20 erhaltenen Bewertungen gelten generell für Gemische aus Heizöl EL schwefelarm und FAME mit einem FAME-Gehalt bis 20 % (V/V). Sie sind auch auf Gemische aus Dieselkraftstoff und FAME mit einem FAME-Gehalt bis 20 %(V/V) übertragbar.
Die forcierte Prüfmethode kann insbesondere KMUs bei der Weiterentwicklung von bestehenden Produkten und der Entwicklung von neuen Produkten als ein kostengünstiger Schnelltest zur Überprüfung der Werkstoff- und Bauteilbeständigkeit gegenüber Mitteldestillaten mit hohem FAME-Anteil dienen. Sie kann für die Hersteller die Sicherheit erhöhen, dass Bauteile die Freigabeprüfungen der Bauaufsicht bestehen, wobei die Freigabe jedoch nur für Deutschland gültig ist.
Die Erkenntnisse des Forschungsvorhabens können in eine harmonisierte Europäische Norm für alternative Brenn- und Kraftstoffe einfließen. Diese ist für die Bauteilhersteller die Voraussetzung für die Erschließung des europäischen Marktes.
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. Ein Schwerpunkt wird bei den metallenen Werkstoffen auf der Erprobung von Messmethoden liegen, mit denen sich in kurzer Versuchszeit ein Korrosionsangriff detektieren lässt.
Die untersuchten Werkstoffe Aluminium, Stahl 1.0037, 1.4301, Kupfer, Messing (CuZn40Pb) und Zink (ZP0410) sind in B0, B20, B100 und in 6 Jahre altem B100 beständig.
Auch in einem Jahr alten B20 und in einem Jahr alten B100 sind die Werkstoffe beständig.
Bei Kupfer blieb die Korrosionsrate in der Flüssigphase sowohl in B20 (0 μ m/ a) als auch in B100 (4 μ m/ a) nach einem Jahr unverändert. Für das 6 Jahre alte B100 stieg die Korrosionsrate des Kupfers an (16 μ m/a). Im Gegensatz dazu sank bei Messing die Korrosionsrate in der Flüssigphase mit dem Alter des Brennstoffs, nach einem Jahr für B20 von 4 μ m/ a auf 1 μ m/a und für B100 von 36 μ m/ a auf 6 μ m/ a, im 6 Jahre alten B100 lag die Korrosionsrate des Messings bei 0 μ m/ a.
In 8 Jahre altem B10 trat bei Zink in der Flüssigphase Flächenkorrosion auf, es ist in dem Medium demnach nicht beständig. Messing zeigte örtliche Korrosion in der Gasphase, es ist folglich unbeständig und für den Einsatz in stark gealterten B10 nicht geeignet.
Aluminium, 1.0037, 1.4301 und Kupfer sind in dem 8 Jahre alten B10 beständig.
Die Änderung der Zugfestigkeit und der Reißdehnung von ACM, HNBR und FKM in Heizöl, B20 und gealterten B10 beträgt < 15 %. Diese Werkstoffe sind in Heizöl, B20 und in gealterten B10 unter Berücksichtigung des von der BAM zur Beurteilung der Beständigkeit festgelegten Grenzwertes von 15 % bei 40 °C als beständig zu bewerten.
PUR ist bei 40 °C nicht beständig in B20 und in gealtertem B10. Bei 70 °C ist HNBR nicht in B20 beständig aufgrund der Verringerung der Zugfestigkeit (40 %) und der Reißdehnung (50 %). FKM ist bei 70 °C in Heizöl und in B20 beständig.
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-Biodiesel-Blends, das für eine Vorauswahl der Werkstoffe und zum Nachweis der Beständigkeit im Hinblick auf die bauaufsichtlichen Zulassungsverfahren geeignet ist. Ein Schwerpunkt wird bei den metallenen Werkstoffen auf der Erprobung von Messmethoden liegen, mit denen sich in kurzer Versuchszeit ein Korrosionsangriff detektieren lässt.
Biodiesel is viewed as a major source of energy. In areas such as the European Un-ion, where 80 % of the oil-based fuel is imported, there is also the desire to reduce dependence on external oil supplies.
Materials compatibility is a major concern whenever the fuel composition is changed. The question arises of whether polymeric materials are resistant to heating oil with 20 % biodiesel (B20) in comparison to pure heating oil.
The polarity of biodiesel increases its solvency and facilitates permeation and extrac-tion. Solvation, swelling and/or extraction lead to changes in the physical properties. Extraction alters the fuel chemistry. These chemical changes could also accelerate the degradation (hydrolysis and oxidation) of the polymeric material with the loss of additives and stabilizers.
Exposure tests to determine the resistance of polymers frequently used for compo-nents in middle distillate facilities, such as ACM, FKM, HNBR, PA, PE, POM, PUR and PVC in heating oil and a blend of heating oil and 20 % biodiesel (B20) were al-ready performed.
The objective of this research was to determine the resistance of these polymers in 8-year aged heating oil blend B10 and 1-year aged blend B20 at 40 °C.
Mass, tensile strength, breaking elongation and Shore hardness A (D) of the test specimens were determined before and after exposure for 84 (42) days in the test fuels under static conditions.
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 deter-mined for the evaluation of the compatibility.
A significant reduction in Shore hardness was determined after exposure of ACM and PUR test specimens in 1-year aged B20.
The tensile strength of PUR test specimens in 1-year aged B20 was reduced by more than 50 %, and the breaking elongation by more than 30 %.
A decrease in breaking elongation was measured for POM test specimens after ex-posure to 1-year aged B20 by 25 % (limited resistance).
8-year aged B10 had a stronger effect than 1-year aged B20 on the polymers. ACM test specimens were softened by B10 resulting in a drop of Shore hardness by over 20 %. B10 reduced tensile strength and breaking elongation of PUR test specimens by over 50 %. In contrast, the breaking elongation of POM was increased by over 270 %.
It can be concluded that the polymers HNBR, FKM, PA6, PE and PVC are resistant in 1-year aged B20 whereas ACM and POM are limited resistant. PUR is not re-sistant.
HNBR, FKM, PA6, PE and PVC are resistant in 8-year aged B10, whereas PUR and POM are not resistant, and ACM just limited resistant.
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. Ein Schwerpunkt wird bei den metallenen Werkstoffen auf der Erprobung von Messmethoden liegen, mit denen sich in kurzer Versuchszeit ein Korrosionsangriff detektieren lässt.
Metallene Werkstoffe:
Weder örtliche Korrosion noch erhöhte Flächenkorrosion (Korrosionsrate:< 0,1 m/Jahr) sind bei den bisher geprüften Werkstoffen: Aluminium,
C-Stahl 1.0037, austenitischer CrNi-Stahl 1.4301, Kupfer und Messing in Heizöl und B20 (Heizöl mit 20% Biodiesel) aufgetreten. Diese Werkstoffe sind in den Prüfmedien Heizöl und B20 als beständig zu bewerten.
Es wurde keine signifikante Veränderung des pH-Wertes der Prüfmedien gemessen.
Polymere:
Massebestimmung:
Die Prüfkörper der Elastomere ACM, HNBR und PUR sowie in geringerem Maße PE neigten zur Quellung in Heizöl und B20 nach 42 d und 84 d Auslagerung; für PA 6, POM und PVC wurde keine Masseänderung gemessen. Die Masseänderung der Prüfkörper in Heizöl und B20 ist mit Ausnahme von PUR vergleichbar. Bei PE traten Verfärbungen durch die Brennstoffe auf.
Zugeigenschaften:
ACM, HNBR, PE und PVC sind in Heizöl und B20 beständig, da die Änderung der Zugfestigkeit und der Reißdehnung < 15 % beträgt. PA und POM sind bedingt beständig, da die Änderung der Zugfestigkeit und der Reißdehnung < 30% beträgt.
Heating oil storage tanks made of polyethylene grades have been on the market in Germany since the early 1970s. To ensure safety, their replacement is recommended by tank manufacturers after a period of 30 years. Polyethylene is subject to ageing by alteration of the properties during its life cycle. The degree of degradation and the nature of the process mainly depend on the chemical alteration of the polyethylene, the wall thickness of the tank and the environmental conditions. There are no data available on the long-term behaviour of the polyethylene grades, especially after a service life of more than 30 years.
The aim of this investigation was to find a suitable test method to determine the factual degree of damage in comparison to the uncontaminated polyethylene grades. Material data of the used polyethylene grades are available because the BAM was the competent authority for the tests and expert reports for the approval of these tanks until the middle of the 1990s. Therefore, tank sections from the bottom, the shell and the roof of 22 individual storage tanks produced of polyethylene grades A and B have been examined by Melt Flow Rate (MFR) and Attenuated Total Reflectance (ATR). Their service life was in the range between 20 and 41 years.
The MFR measurements of the tank sections showed differences in the values depending on the weight which was used (5 kg or 21.6 kg). An increase of the MFR was determined for the samples of polyethylene grade A, whereas a reduction of the MFR values was measured for most samples of polyethylene grade B. This grade is mainly subject to the internal ageing by cross-linkages, increased degree of branched molecules and loss of the plasticizer.
ATR analysis exhibits an absorption band at 909 cm‒1 predominantly in samples of polyethylene grade A indicating chain scission and concomitantly formed terminal vinyl groups. This absorption band can be used for the characterization of the ageing of the polyethylene grades.