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- Vortrag (89)
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- Tensile properties (15)
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- 3 Gefahrgutumschließungen; Energiespeicher (27)
- 3.2 Gefahrguttanks und Unfallmechanik (27)
- 7 Bauwerkssicherheit (9)
- 7.6 Korrosion und Korrosionsschutz (9)
- 1 Analytische Chemie; Referenzmaterialien (3)
- 1.4 Prozessanalytik (3)
- 2 Prozess- und Anlagensicherheit (3)
- 2.1 Sicherheit von Energieträgern (3)
- 8 Zerstörungsfreie Prüfung (3)
- 8.1 Sensorik, mess- und prüftechnische Verfahren (3)
Eingeladener Vortrag
- nein (89)
The material parameters melt flow rate (MFR), density (D), notched impact strength (NIS) at –30°C, stress crack resistance [determined with the Full Notch Creep Test (FNCT)] and resistance to oxidative degradation (Ox) have been selected for a comparison of polyethylene grades in the European standard EN 15507. These parameters have a relationship with design type tests of packagings for the transport of dangerous goods.
This paper presents the results of additional investigations to determine the impact of the pre-storage time of jerricans with 55% nitric acid at 40°C and 23°C on the marginal drop heights in drop tests at –18°C, on the MFR and on the tensile properties. Jerricans made of different polyethylene grades were pre-stored with 55% nitric acid for 21, 42 and 84 days at 40°C and for six months at 23°C.
The tests showed that the NIS values at –30°C of polyethylene grades were not comparable with marginal drop heights determined in drop tests at –18°C.
Pre-damage with 55% nitric acid for 21 days at 40°C led to an increase in the marginal drop heights of the jerricans. Altering the test regulations by increasing pre-storage time with 55% nitric acid to 42 days would be an alternative.
The test results demonstrated clearly that pre-storage of the jerricans for six months at 23°C caused a higher increase in the MFR and lower marginal drop heights for the jerricans when compared with pre-stored jerricans for 21 days at 40°C.
The chemical industry has expressed great interest in using polyethylene terephthalate (PET) as material for packagings for the transport of dangerous goods. Due to the high strength and stiffness of PET, the wall thickness and weight of packagings can be reduced. This is a relevant cost factor. PET is a semi-crystalline thermoplast which is produced by polycondensation of terephthalic acid and ethylene glycol.
According to the European dangerous goods regulations RID and ADR, samples of PET design types of packagings for dangerous goods must be pre-stored with the original filling good for six months at 23°C, before the design type tests can be carried out. For packagings made of polyethylene (PE) tests to prove the stress cracking resistance by using laboratory methods are possible to reduce time and costs. Therefore, standard liquids, simulating the different types of damaging effects on PE are defined in RID and ADR. However, there is no information and research available about the damaging mechanisms on PET in comparison to PE, especially regarding to stress cracking resistance and test methods.
The aim of this work is to compare the stress cracking resistance of PE and PET with the Full Notch Creep Test (FNCT), which was developed by chemical industry and is described in the standards EN ISO 16101 and EN 15507. It was investigated whether testing specimens made of PE and PET with a full coplanar notch around the middle of the specimens show weakening after the impact of a tensile force in a wetting solution (Lutensol® FSA 10) at 50°C in a test device on the basis of the FNCT.
The test results confirmed the suitability of the method for eight PE grades. Unfortunately, this method couldn’t be used for PET because the specimens broke during notching. In addition the molding of the sheets and the following temper process for twelve hours are very time-consuming, and the specimens broke during notching due to the high brittleness of PET.
Another possibility to provide evidence of stress cracking resistance of PE packagings is laid down in BAM’s Dangerous Goods Rule BAM-GGR 015. This test was carried out with PE and PET bottles to compare both materials. Therefore 1l test bottles were filled with a 5% wetting solution and mounted with a clamping tool for 28 days at 40°C. Tensile test specimens were cut out afterwards from the middle of the bottles in the deformed areas. Tensile strength and breaking elongation of PE specimens were determined in comparison to the PET specimens. The tensile properties of the PET specimens couldn’t be determined due to the strength and the stiffness of the material.
In conclusion the only way to provide information about the stress cracking resistance of PET was to perform stacking tests. 1l bottles made of PE and PET were filled with a 5% wetting solution and stored with a stacking load for 28 days at 40°C according to EN ISO 16495. Design types of PE and PET both passed the stacking tests.
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)
For the characterization and the comparison of polyethylene grades used for the manufacture of packaging and intermediate bulk container, the following parameters are required: melt flow rate (MFR), density (D), low-temperature notched impact strength, full notch creep test (FNCT) and increase of MFR by molecular degradation (resistance to oxidative degradation). The relationship between these material parameters determined on the basis of specimens prepared from compression-moulded sheets of polyethylene grades and the test behaviour of packaging has been investigated in several tests. The environmental stress crack resistance determined by FNCT represents the impacts from the stacking tests performed with standard liquid wetting solution (without pre-storage) and with normal butyl-acetate-saturated wetting solution (pre-storage with normal butyl acetate). Resistance to molecular degradation by the determination of MFR increase is related to the impacts in drop tests and stacking tests performed after pre-storage for 21 days with standard liquid 55% nitric acid at 40°C. The low-temperature impact strength is directly comparable with the impacts in drop tests at -18°C performed without pre-storage and after pre-storage with 55% nitric acid. A partly good relationship was found between the test results and the material parameters. Conditioning the design types with 55% nitric acid for 21 days causes an increase in the marginal drop heights of the design types in drop tests at -18°C when compared with design types without pre-storage. Post-cross-linking of the grades increases stiffness because of the acidic influence.
Materials compatibility is a major concern whenever the fuel composition is changed in a fuel system. Therefore 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), N8R (acrylonitrile-butadiene rubber) and PUR (polyester urethane rubber) were exposed to E1 0, diese I fuel with 5% biodiesel, non-aged and 2 year aged 810 (heating oil with 10% biodiesel), and for comparison to pure diese! fuel, standard heating oil and Super plus without bioethanol at 20 °C, 40 oc and 70 oc for 84 days. Mass, tensile strength and breaking elongation of the test specimens were determined before and after the exposure. 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 to 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.
The sealing materials FKM, EPDM, N8R, FMVQ, CSM and PA were evaluated on the basis of this threshold as resistant in E1 0 at 20 oc and 40 °C. FKM, FVMQ and PA were resistant at 40 oc , and none of the materials were resistant at 70 °C. FKM and FVMQ absorbed much less 810 and swelled less. CR, CSM, EPDM, IIR, N8R and VMQ were not resistant to 810 at all at 20 oc, 40 oc and 70 oc as the decrease in the tensile properties was significantly over 50%. FVMQ and PA could be evaluated as resistant in non-aged and two year aged 810 at 20 oc and 40 oc, whereas FKM was resistant up to 70 °C. FKM, PA and PUR were evaluated as resistant in standard heating oil and pure diese! fuel at temperatures up to 40°C, only FKM was resistant up to 70°C. FVMQ, FKM, N8R, VMQ, CR and IIR can be evaluated as resistant in premium grade fuel Super plus without ethanol at 20 oc. FKM, FVMQ, VMQ and IIR were still resistant at 40 °C. FKM and FVMQ were evaluated as resistant with restrictions at 70 °C.
ln 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 objective of this research was to determine the resistance of frequently used sealing materials such as FKM, FVMQ, VMQ, EPDM, CR, CSM, IIR, PA, NBR and PUR in fuels and heating oil with and without admixtures of biogenic sources such as E10, diesel fuel with 5 % biodiesel, non-aged and 2 year aged B10 (heating oil with 10 % biodiesel), pure diesel, standard heating oil and premium grade fuel Super plus 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.
Zusammenfassend wird aufgrund der Ergebnisse der durchgeführten Untersuchungen die Aussage getroffen, dass die Fluorpolymere FKM und FVMQ die beständigsten Dichtungswerkstoffe in Biokraftstoffen und Heizöl B10 im Temperaturbereich bis 70 °C sind. In E10 und E85 kann keiner der Dichtungswerkstoffe bei 70 °C als beständig bewertet werden. Diese Erkenntnisse können vielen Wirtschaftszweigen ein Innovationspotential bieten und ihre Wettbewerbsfähigkeit steigern.
In der Bundesrepublik Deutschland werden über 400 Mio.t Gefahrgüter jährlich in Tankfahrzeugen, Aufsetztanks, Batteriefahrzeugen, Eisenbahnkesselwagen und Tankcontainern befördert, davon etwa 150 Millionen Tonnen im Straßengüterverkehr. Zu den Hauptschadensursachen zählt die Korrosion, wobei die gleichmäßige und ungleichmäßige Flächenkorrosion die Korrosionsart ist, die beim Chemikalientransport in Tanks am häufigsten auftritt. Viele Schäden durch Lochkorrosion entstehen beim Transport von chloridhaltigen Medien bei Anwesenheit von Feuchtigkeit.
Die BAM-Liste - Anforderungen an Tanks für die Beförderung gefährlicher Güter - ist Grundlage für die stoffbezogenen Baumusterzulassungen für Tankcontainer und ortsbewegliche Tanks zur Beförderung gefährlicher Güter durch die BAM seit der Herausgabe der 1. Auflage 1989. In die BAM-Liste wurden vorrangig solche gefährlichen Güter aufgenommen, die potenziell in Tanks befördert werden können. Die Beständigkeitsbewertungen gebräuchlicher metallischer Tankwerkstoffe und polymerer Dichtungs-, Beschichtungs- und Auskleidungswerkstoffe werden auch bei der Zulassung von Kesselwagen und Tankfahrzeugen als Erkenntnisquelle verwendet. Diese Daten sind aber unter sorgfältiger Überprüfung der Übertragbarkeit auch für andere praktische Anwendungen und unter Berücksichtigung der jeweiligen Praxisbedingungen auch als Ratgeber für Verpackungen, IBC, Lagerbehälter, Rohrleitungen usw. aus metallischen Werkstoffen anwendbar.
In den internationalen Gefahrgutverordnungen ADR, RID und IMDG-Code wird nach einer vorgegebenen Prüffrist eine innere Besichtigung der Tanks gefordert. Bei Tankcontainern beträgt diese Prüffrist im ADR/RID, Kap. 6.8 , fünf Jahre (bei der Beförderung von ortsbeweglichen Tanks nach ADR/RID, Kap. 6.7, und nach dem IMDG-Code 2½ Jahre) und bei Tankfahrzeugen sechs Jahre. Im RID wird für Eisenbahnkesselwagen eine Prüffrist von acht Jahren für die Innenbesichtigung vorgeschrieben. Für die Dauer der Prüfintervalle muss die Werkstoffbeständigkeit der Tankwerkstoffe gewährleistet sein.
Die BAM-Liste - Anforderungen an Tanks für die Beförderung gefährlicher Güter – mit den Beständigkeitsbewertungen metallischer und polymerer Werkstoffe ist Grundlage für die stoffbezogenen Baumusterzulassungen für Tankcontainer und ortsbewegliche Tanks zur Beförderung gefährlicher Güter durch die BAM seit der Herausgabe der 1. Auflage 1989. Diese Beständigkeitsbewertungen werden nicht nur bundesweit, sondern weltweit als Erkenntnisquelle genutzt. Für die Zulassung von Kesselwagen und Tankfahrzeugen werden diese Daten auch herangezogen. Die Werkstoffbeständigkeitsdaten und der damit verbundene Informationsservice der BAM haben mit Sicherheit dazu beigetragen, Leckagen von Tanks aufgrund des Einsatzes von Tanks/Kesselwagen aus einem gegenüber dem Füllgut unbeständigem Tankwerkstoff oder Dichtungswerkstoff zu vermeiden.
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.
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.