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Rubbers are widely used as main sealing materials for containers for low and intermediate level radioactive waste and as additional component to metal seals in spent fuel and high active waste containers. According to appropriate guidelines and regulations safe enclosure of the radioactive container contents has to be guaranteed for long storage periods as well as down to temperatures of -40 °C for transportation. Therefore the understanding of seal behavior is of high importance.
In this paper we focus on the behavior of elastomer seals at low temperatures with regard to poten-tial decrease of leak-tightness. In addition, changes in material properties due to aging effects over long periods of time and their influence on the seal performance is investigated.
It is known that material properties of rubbers are strongly temperature dependent. At low tempera-tures this is caused by the rubber-glass transition (abbr. glass transition). During continuous cool-ing, the material changes from rubber-like entropy-elastic to stiff energy-elastic behavior, that al-lows nearly no strain or retraction due to the glass transition. Hence rubbers are normally used above their glass transition but the minimum working temperature limit is not defined precisely.
Aging of elastomer seals is important, as possible dynamic loads may have to be considered during the whole interim storage period (so far approved in Germany for up to 40 years) and for transporta-tion after storage.
For the investigations, fluorocarbon (FKM) and ethylene-propylene-diene (EPDM) rubbers were selected as they are often used in radioactive waste containers. Some materials were purchased from a commercial seal producer and some materials were compounded and cured at BAM. The elastom-ers where studied by several thermo-analytical methods and compression set to characterize the material behavior at low temperatures. Additionally component tests were performed to determine the breakdown temperature of the sealing function of complete elastomer O-rings.
Rubbers are widely used as main sealing materials for Containers for low and intermediate level radioactive waste and as additional component to metal seals in spent fuel and high active waste containers. The save enclosure of the radioactive container inventory has to be guaranteed according to legislation and appropriate guidelines for long term storage periods as well as down to temperatures of -40 °C for transportation. Therefore the understanding of failure mechanisms that lead to leakage at low temperatures is necessary to ensure a proper material choice which is certainly also influenced by additional factors as e.g. the aging behavior.
To achieve the required tightness levels of Containers for low and intermediate level radioactive wastes rubbers are widely applied as main sealing materials. The save encapsulation of the radioactive Container contents has to be guaranteed according to legislation and appropriate guidelines for long storage periods as well as down to temperatures of-40 °C during transportation.
Therefore the understanding of failure mechanisms that lead to leakage at low temperatures is of high importance.
It is known that the material properties of rubbers are strongly influenced by temperature. At low temperatures this is caused by the rubber-glass transition (abbr. glass transition). During continuous cooling the material changes from rubber-like entropy-elastic to stiff energy-elastic behaviour, that allows nearly no strain or retraction. Therefore, rubbers are normally used above their glass transition but the minimum working temperature limit is not defrned precisely, what can cause problems during application. The temperature ränge where full functionality is possible is strongly dependent on the application conditions and the material.
For this investigation mainly ethylene propylene diene (EPDM) and fluorocarbon rubbers (FKM) were selected as they are often used for radioactive waste Containers.
Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) are typically used for the determination of the temperature ränge of the glass transition process. The standardized compression set measurement according to ISO 815 is common for investigation of rubber sealing materials as the test simulates the seal behaviour after release. To reduce the test time of the Standard tests a faster technique giving the same information was developed.
Additionally, the breakdown temperature of the sealing function of complete O-ring seals is measured in a component test Setup to compare it with the results of the other tests. The experimental Setup is capable of measuring the leakage rate at low temperatures by the pressure rise method.
A model was developed that allows calculating the minimum working temperature limit of a seal by combining the results of the applied methods.
O-rings made of HNBR, EPDM and FKM were aged in the compressed and uncompressed state at 150 °C, 125 °C, 100 °C, 75 °C, 60 °C and 23 °C for aging times of up to five years. Hardness was measured and increased with aging time and temperature for HNBR and EPDM, but it remained practically constant for FKM. Indenter modulus measurements were performed on the lateral O-ring surface (that was free of DLO effects) to assess an influence of the compression during aging, but none was detected. The equilibrium compression set (CS) exhibited faster and stronger degradation than hardness and was used for lifetime predictions using the time-temperature superposition (TTS) principle. With an end-of-lifetime criterion of 70 % CS, lifetimes of 4.5 years, 50 years and 526 years at 75 °C were estimated for HNBR, EPDM and FKM, respectively. The activation energies derived from an Arrhenius plot of the shift factors from the TTS were 85 kJ/mol, 99 kJ/mol and 78 kJ/mol for HNBR, EPDM and FKM, respectively, revealing that a higher activation energy does not necessarily mean that the material has a higher lifetime at lower temperatures. Furthermore, the measured lifetime of EPDM O-rings at 100 °C (5 years) was compared to that predicted on the basis of the lifetime at 150 °C as well as 125 °C using the corresponding shift factors. The error of the prediction was only ± 4 %. However, this precise prediction could only be achieved using the five-year long-term aging data. When using only data from aging times up to 0.5 years and 2 years, the lifetime of EPDM O-rings at 100 °C was underestimated by 31 % and 22 %, respectively.
For many sealing applications rubbers are applied due to their special material properties and easy use. In many applications, e.g. in aviation, traffic or process technology the material can be exposed to low temperatures during Operation. Therefore it is important to know the material behaviour at those low temperatures to determine the temperature range that allows a safe Operation of the seal. As rubbers are used as main sealing materials for Containers for low and intermediate level radioactive waste and as additional component to metal seals in spent fuel and high active waste Containers, a comprehensive elastomer investigation program is run at BAM. This program comprises investigations of elastomer overall performance, durability, influence of gamma irradiation and low temperature behaviour.
In this paper we focus on the behaviour of elastomer seals at low temperatures with regard to potential decrease of leak-tightness as material properties of rubbers are strongly temperature dependent. But additionally to the investigation presented in the past which considered the material properties of new materials and the seal behaviour under purely static conditions [1, 2] we now focus on irradiated materials and on the sealing performance after a fast partial release of the compressed seal.
For the investigations different materials were used, e.g. fluorocarbon (FKM) and ethylenepropylene-diene (EPDM) rubber. To determine the effect of gamma irradiation some samples were irradiated and studied by several thermo-analytical methods and compression set. For the investigation of the seal performance under non static conditions we decided to design a new measurement setup which allows for a small flange deflection and simultaneous leakage rate measurement at low temperatures.
For many sealing applications rubbers are applied due to their special material properties and easy use. In many applications as e.g. in aviation, traffic or process technology the material can be exposed to low temperatures during operation. Therefore it is important to know the material behaviour at those low temperatures to determine the temperature range that allows a safe operation of the seal. As rubbers are used as main sealing materials for containers for low and intermediate level radioactive waste and as additional component to metal seals in spent fuel and high acitve waste containers, a comprehensive elastomer investigation program is run at BAM. This program comprises investigations of elastomer overall performance, durability, influence of gamma irradiation and low temperature behaviour.
In this paper we focus on the behaviour of elastomer seals below ambient temperatures after a fast partial release. Despite the primarily static application conditions of many seals their behaviour after partial compression release is of interest with regard to potential decrease of leak-tightness.
For this investigation a special setup was designed which allows the partial release of compressed seal systems at different temperatures accompanied by leakage rate measurements.
The results for FKM seals are presented and discussed.
In many fields the function of seal materials is required at low temperatures. Therefore the understanding of failure mechanisms at low temperatures is of high importance. In some applications elastomeric seals are used in environments with increased irradiation backgrounds, as e.g. in containers for radioactive waste. This paper reports on the influence of gamma irradiation on the low temperature properties of different fluorocarbon rubber (FKM) materials.
The samples were irradiated with gamma doses of up to 600 kGy and the induced changes of material properties were tested by methods sensitive to the rubber-glass transition, like DSC and DMA. Additionally, compression set measurements were performed to give information about recovery behaviour at low temperatures.
At BAM, which is the federal institute for materials research and testing in Germany, it is one of our tasks to evaluate the safety of casks designed for transport and/or storage of radioactive material. This includes assessment of elastomeric seals applied in the containers. Besides examining the low-temperature behaviour and irradiation effects of elastomeric seals, it is our goal to evaluate the service lifetime of the seals with regard to the requirements for long-term safety (40 years and more) of the containers. Therefore, we started an accelerated ageing programme with selected rubbers often used for seals (HNBR, EPDM and FKM) which are aged at four different temperatures (75 °C, 100 °C, 125 °C and 150 °C) up to 1 year. In order to assess sealability, O-rings are aged in compression by 25 % (corresponding to the compression during service) between plates as well as in flanges that allow leakage rate measurements. For comparison, uncompressed O-rings are aged as well. Further methods characterising seal performance are compression stress relaxation (CSR) reflecting the loss of sealing force of a compressed seal over time, and compression set (CS) which represents the recovery behaviour of a seal after release from compression. Additionally, hardness is measured for information about the change of mechanical properties. The experimental results indicate that while hardness, CSR and CS show considerable degradation effects, the leakage rate stays constant or even decreases until shrinkage and the loss of resilience of the aged seal leads to the formation of a leakage path. This indicates that static leakage rate, which is the only available direct seal performance criterion, has only limited sensitivity for the degradation of the seal material.
At BAM, which is the federal institute for materials research and testing in Germany, it is one of our tasks to evaluate the safety of casks designed for transport and/or storage of radioactive material. This includes the assessment of the service lifetime of elastomeric seals that are part of the container lid system with regard to the requirements for long-term safety (40 years and more) of the containers. Therefore, we started an accelerated ageing programme with selected rubbers often used for seals (HNBR, EPDM and FKM) which are aged at four different temperatures (75 °C, 100 °C, 125 °C and 150 °C) up to 1.5 years. In order to assess sealability, O-rings are aged in compression by 25 % (corresponding to the compression during service) between plates as well as in flanges that allow leakage rate measurements. For comparison, uncompressed O-rings are aged as well. Further methods characterising seal performance are compression stress relaxation (CSR) reflecting the loss of sealing force of a compressed seal over time, and compression set (CS) which represents the recovery behaviour of a seal after release from compression. Additionally, hardness is measured for information about the change of mechanical properties. The experimental results indicate that while hardness, CSR and CS show considerable degradation effects, the leakage rate stays relatively constant or even decreases until shrinkage combined with the loss of resilience of the aged seal leads to leakage. This demonstrates that static leakage rate, which is the only available direct seal performance criterion, has only limited sensitivity towards the degradation of the seal material. CS data is extrapolated using time-temperature shifts and Arrhenius graphs. An exemplary CS of 50 % would be reached after approx. 1.2, 17 and 29 years at 60 °C for HNBR, EPDM and FKM respectively.
The indication-oriented Dental Bone Graft Substitutes (DBGS) selection, the correct bone defects classification, and appropriate treatment planning are very crucial for obtaining successful clinical results. However, hydrophilic, viscoelastic, and physicochemical properties’ influence on the DBGS regenerative potential has poorly been studied. For that reason, we investigated the dimensional changes and molecular mobility by Dynamic Mechanical Analysis (DMA) of xenograft (cerabone®), synthetic (maxresorb®), and allograft (maxgraft®, Puros®) blocks in a wet and dry state. While no significant differences could be seen in dry state, cerabone® and maxresorb® blocks showed a slight height decrease in wet state, whereas both maxgraft® and Puros® had an almost identical height increase. In addition, cerabone® and maxresorb® blocks remained highly rigid and their damping behaviour was not influenced by the water. On the other hand, both maxgraft® and Puros® had a strong increase in their molecular mobility with different damping behaviour profiles during the wet state. A high-speed microscopical imaging system was used to analyze the hydrophilicity in several naturally derived (cerabone®, Bio-Oss®, NuOss®, SIC® nature graft) and synthetic DBGS granules (maxresorb®, BoneCeramic®, NanoBone®, Ceros®). The highest level of hydrophilicity was detected in cerabone® and maxresorb®, while Bio-Oss® and BoneCeramic® had the lowest level of hydrophilicity among both naturally derived and synthetic DBGS groups. Deviations among the DBGS were also addressed via physicochemical differences recorded by Micro Computed Tomography, Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, X-ray powder Diffractometry, and Thermogravimetric Analysis. Such DBGS variations could influence the volume stability at the grafting site, handling as well as the speed of vascularization and bone regeneration. Therefore, this study initiates a new insight into the DBGS differences and their importance for successful clinical results.
For many sealing applications low temperature performance is required. The overall understanding of the relevant influences on low temperature performance of rubber seals are summarized and the currently running investigations described.
The correlation of the physical material properties with seal performance is studied. This includes as well purely static sealing applications as the performance during/after fast partial relief of seals at low temperatures.
Fourier-Spektroskopische Untersuchungen von hochmolekularem Polyethylen (HMW-PE) und ultrahochmolekularem Polyethylen (UHMW-PE) im Mittleren - und Fernen Infrarotbereich können Veränderungen der molekularen Strukturen nachweisen, die durch Co60 γ-Strahlung und Rekristallisationsprozesse initiiert werden. UHMW-PE und HMW-PE sind im gewählten IR-Bereich unterscheidbar. Die integrale Absorption der B1u – Gitterschwingungen im Fernen Infrarotbereich (THz-Bereich) ermöglichen die quantitative Beschreibung des Kristallinitätsgrades und dessen Abbau. Die Bildung ungesättigter Vinylengruppen und der Abbau ungesättigter Methylengruppen können im Mittleren Infrarotbereich nachgewiesen werden.
To improve the predictive capability of long-term stress relaxation of elastomers during thermo-oxidative ageing, a method to separate reversible and irreversible processes was adopted.
The separation is performed through the analysis of compression set after tempering. On the Basis of this separation, a numerical model for long-term stress relaxation during homogeneous ageing is proposed. The model consists of an additive contribution of physical and chemical relaxation.
Computer simulations of compression stress relaxation were performed for long ageing times and the results were validated with the Arrhenius treatment, the kinetic study and the time-temperature superposition technique based on experimental data. For chemical relaxation, two decay functions are introduced each with an activation energy and a degradative process. The first process with the lower activation energy dominates at lower ageing times, while the second one with the higher activation energy at longer ageing times. A degradation-rate based model for the evolution of each process and ist contribution to the total system during homogeneous ageing is proposed. The main advantage of the model is the possibility to quickly validate the interpolation at lower temperatures within the range of slower chemical processes without forcing a straight-line extrapolation.
Aufgrund ihrer einfachen und zuverlässigen Anwendung werden Elastomere für viele Dichtungsaufgaben eingesetzt. In vielen Anwendungsbereichen, wie z.B. Verkehr, Luftfahrt und Verfahrenstechnik, können während des Einsatzes tiefe Temperaturen auftreten, bei denen die Funktionsfähigkeit der Dichtung erhalten bleiben muss. Daher ist die Untersuchung des Verhaltens von Elastomerdichtungen bei tiefen Temperaturen wichtig, um ihren Temperatureinsatzbereich nach unten abzugrenzen und dadurch einen verlässlichen Betrieb zu sichern. Ziel dieser Arbeit ist es, den sicheren Einschluss von gefährlichen Gütern unter verschiedenen Umgebungsbedingungen und über lange Zeiten zu ermöglichen bzw. die Materialauswahl entsprechend zu steuern.
Über die in der Technik weit verbreitete typisierte Harnstoffformmasse UF 131.5, ein Aminoplast, wird berichtet, dass sie im Zuge der thermisch aktivierten Vernetzungsreaktion wegen "Überhärtung" mangelhafte Eigenschaften annimmt. Zur Verifizierung dieses Effektes werden mithilfe der Ultraschall-Prozesskontrolle gezielt Proben unterschiedlicher Aushärtegrade hergestellt. Sie werden mit verschiedenen Methoden, wie der "Kochprobe" und der Thermoanalyse, charakterisiert und auf ihre Materialeigenschaften untersucht. Dabei zeigt sich ein deutlicher Einfluss der Härtezeit auf die Glasübergangstemperatur der Formmasse. In den mechanischen Eigenschaften ist eine Veränderung allerdings nur in der Schlagzähigkeit festzustellen, die sich mit steigender Härtezeit sogar wesentlich verbessert.
Einfluss der Alterung auf dichtungsrelevante Eigenschaften von FKM-, VMQ- und EPDM-Elastomeren
(2017)
Da Elastomere in vielfältigen Dichtungsanwendungen eingesetzt werden und dabei teilweise großen Einfluss auf die Funktionsfähigkeit und Sicherheit haben, ist der Einfluss der Alterung auf dichtungsrelevante Eigenschaften relevant. Eine strukturierte Untersuchung des Einflusses von verschiedenen Mischungsrezepturen auf die Bauteileigenschaften, das Alterungsverhalten und die Funktion wird vorgestellt.
Seals used in containers for dangerous goods need to maintain leak tightness for several decades. For investigating the change in seal material properties during aging, a comprehensive aging program on both uncompressed and compressed EPDM and HNBR seals was started. In order to obtain results closely related to practical conditions, O-rings with a full-scale cord diameter of 10 mm were aged. However, this set-up can lead to heterogeneous aging caused by diffusion-limited oxidation (DLO) effects. These effects depend on material, dimensions, time and temperature. Heterogeneous aging results in distorted bulk properties such as compression stress relaxation and compression set (CS) suggesting that HNBR has better performance than EPDM at 150 °C but which is not the case at 100 °C. The presence of heterogeneous material properties was shown by hardness measurements across the seal cross-section. If DLO-affected data is excluded, extrapolations of CS data are possible using time-temperature shifts and Arrhenius graphs. Exemplary CS values of 50 % and 80 % would be reached after approx. 10 years and 29 years, respectively for HNBR and after approx. 400 years and 1100 years, respectively for EPDM.
High and ultra-high molecular weight polyethylenes were gamma-irradiated with doses up to 600 kGy. The changes in the material properties were analysed using DSC, DMA, IR spectroscopy, as well as measurements of density and insoluble content. The irradiation led to an increase of the degree of crystallinity because of chain scissions during irradiation, leading to shorter and thus more mobile chains. Both the plateau value of the shear modulus G′ and the insoluble content increased with Irradiation dose, indicating the formation of additional crosslinks. Furthermore, IR spectroscopy revealed irradiation induced oxidation and the formation of double bonds, indicating that some of the hydrogen atoms responsible for the neutron shielding capability have been released.
Editorial
(2019)
Dear Readers, a new year started for all of us (as I write these lines, possibly it was already some time ago when these lines are finally available) and this is the time for the so-called New Year’s resolutions. Setting goals and changing our behavior as well in a private as in a professional context.
For Scientists the resolutions may comprise tasks like finalizing a longago started publication, picking up the loose ends of an application for funding or just bringing the running projects in a greater structure.
Epoxy carbon-fibre prepreg, Hexcel Type 6376 HTS, was investigated using Dynamic Mechanical Analysis (DMA). The DMA characteristic parameters are storage modulus E', loss modulus E' and loss factor tanδ. These parameters are ideally suited to observe the vitrification, referred to as glass transition, resulting from the cross-linking reaction. Detection of the cure state may also be achieved by determining the momentary glass transition temperature of partially cured samples. The consequent use of a multi-frequency measuring regime was used to derive the apparent activation energy for the glass transition process. Different temperature programs were also applied to monitor the curing process directly, as well as to investigate the different states of incomplete cure reached in preceding curing steps. The intention was to provide better understanding of the consequences of an interrupted autoclave curing process and to use DMA to detect the cure state achieved. With DMA, the continuation of an incomplete curing process also can be monitored. DMA measurements up to 300 °C showed, furthermore, that the final glass transition temperature was reduced by thermal degradation at high temperatures.
Für Elastomenwerkstoffe im Allgemeinen und im Bereich der Dichtungstechnik im Besonderen ist der Druckverformungsrest eine wichtige Kenngröße zur Beurteilung der Eignung eines Werkstoffs bzw. der Funktion eines Bauteils. Er ermöglicht eine Einschätzung des zeitabhängigen Rückstellverhaltens eines Werkstoffs nach Deformation. Dieses ist für Dichtungen von besonderer Bedeutung, da der Test deren Einbauzustand nachstellt.
Oft wird er, bei der Prüfung unter erhöhten Temperaturen, zur Beurteilung des Alterungsverhaltens verwendet und kann anhand eines definierten Versagenskriteriums zur Lebensdauerabschätzung eingesetzt werden. Bei tiefen Temperaturen dient er dazu, die limitierende Einsatztemperatur zu bestimmen. Dabei spielt eine Alterung im eigentlichen Sinne nur eine untergeordnete Rolle, wohl aber physikalische Effekte wie Tieftemperaturkristallisation und Glasübergang. Diese Effekte sind weit weniger durch lange Lagerzeiten beeinflusst als die eigentliche Alterung.
Die Versuchsdurchführung unterscheidet sich je nach angewandter Norm und kann einen deutlichen Einfluss auf den Druckverformungsrest haben. Alle standardisierten Methoden sind aufgrund der langen Lagerzeiten relativ langwierig und erfordern das regelmäßige Eingreifen durch den Prüfer. Zusätzlich sehen einige Methoden nur die Bestimmung eines einzelnen Wertes nach einer definierten Zeit vor.
Um die Messungen zu beschleunigen wurde eine Methode entwickelt, die automatisch die erforderlichen Messungen bei mehreren Temperaturen durchführt.
Dazu wird ein Prüfgerät der Dynamisch Mechanischen Analyse verwendet, das kontinuierlich die Deformation während eines frei programmierbaren Temperaturzyklus misst, wodurch eine sehr große Datenmenge verfügbar ist.
Ein Vergleich der neuen Methode mit den Ergebnissen des nach ISO 815 genormten Messprinzips ergibt eine gute Übereinstimmung. Ergebnisse der neuen Methode werden vorgestellt und die Vorzüge der kontinuierlichen Datenerfassung, z.B. für die Materialauswahl, diskutiert.
Die vorgestellten Ergebnisse beziehen sich zum großen Teil auf die in beschriebenen Untersuchungen und Ergebnisse.
Der Druckverformungsrest (DVR) stellt insbesondere für Dichtungsanwendungen eine wichtige Kenngröße zur Beurteilung der Eignung eines Elastomers dar. Er ermöglicht die Einschätzung des zeitabhängigen Rückstellverhaltens eines Werkstoffs nach Deformation. Neben der Prüfung bei erhöhten Temperaturen, zur Beurteilung des Alterungsverhaltens, lässt sich bei der Durchführung bei tiefen Temperaturen die limitierende Einsatztemperatur bestimmen. Die Versuchsdurchführung unterscheidet sich je nach angewandter Norm und kann einen deutlichen Einfluss auf den DVR-Wert haben. Um bei tiefen Temperaturen eine schnelle Aussage zu gestatten, ist eine im Vergleich zu genormten Methoden deutlich schneller durchzuführende, automatisierte Methode entwickelt und mit Standardmethoden verglichen worden. Durch kontinuierliche Messung des Druckverformungsrests kann die Kinetik der Materialrückstellung betrachtet und dadurch ein effizienter Materialvergleich und eine effiziente Materialauswahl ermöglicht werden. Compression set (CS) is especially for sealing applications an important parameter for material selection. It allows an assessment of the time dependent recovery after deformation.
In addition to testing at elevated temperatures which aims at the evaluation of the ageing behaviour, testing at low temperatures permits the determination of the low working temperature limit. The test procedure varies depending on the applied standard and can show a significant effect on the CS value. In order to allow a quick statement regarding low temperatures an automated procedure being significantly faster realisable in relation to the standardised methods has been developed and compared with standard procedures. Continuous measurement of the compression set allows evaluating the recovery kinetics and therefore an efficient comparison and selection of materials.
Discoloration Effects of High-Dose gamma-Irradiation and Long-Term Thermal Aging of (U) HMW-PE
(2017)
Two polyethylene types with ultra-high (UHMWPE) and high molecular weight (HMW-PE) used as neutron radiation shielding materials in casks for radioactive waste were irradiated with doses up to 600 kGy using a 60Co gammasource. Subsequently, thermal aging at 125∘C was applied for up to one year. Degradation effects in the materials were characterized using colorimetry, UV-Visspectroscopy, IR spectroscopy, and DSC. Both materials exhibited a yellowing upon irradiation.The discoloration of UHMW-PE disappeared again after thermal aging.Therefore, the yellowing is assumed to originate fromannealable color centers in the formof free radicals that are trapped in the crystalline regions of the polymer and recombine at elevated temperatures. For the antioxidantcontaining HMWPE, yellowing was observed after both irradiation and thermal aging. The color change was correlated mainly to decomposition products of the antioxidant in addition to trapped radicals as in UHMW-PE. Additionally, black spots appeared after thermal aging of HMW-PE.
Dichtungsverhalten bei niedrigen Temperaturen - Untersuchung der unteren Temperatureinsatzgrenze
(2018)
Elastomere werden vielfach in Produkten eingesetzt, die bei verschiedenen Temperaturen verwendet werden. Dabei sind O-Ringe kostengünstige Dichtelemente, die allerdings für die Funktionsfähigkeit und Sicherheit eines Produkts entscheidend sind. Die untere Temperatureinsatzgrenze ist dabei durchaus relevant und aus wissenschaftlicher Sicht nicht allgemeingültig zu definieren, da diese einerseits durch die Änderungen der Materialeigenschaften im Zuge des Gummi-Glas-Übergangs definiert werden, die Temperaturlage dieses Übergangs jedoch sehr stark von den jeweiligen Einsatzbedingungen (z.B. Frequenz) abhängt. Dadurch ergeben sich große Unterschiede zwischen statischen und dynamischen Anwendungen. Verschiedene Untersuchungen sollen vorgestellt und interpretiert werden, um das Auditorium auf verschiedene Herausforderungen aufmerksam zu machen und Lösungsansätze vorzustellen...
Elastomere werden vielfach in Produkten eingesetzt, die bei verschiedenen Temperaturen verwendet werden. O-Ringe sind kostengünstige Dichtelemente, die allerdings für die Funktionsfähigkeit und Sicherheit eines Produkts entscheidend sein können. Die untere Temperatur-einsatzgrenze ist dabei relevant und aus wissenschaftlicher Sicht nicht allgemein gültig zu definieren, da diese einerseits durch die Änderungen der Materialeigenschaften im Zuge des Gummi-Glas-Übergangs definiert werden, die Temperaturlage dieses Übergangs jedoch sehr stark von den jeweiligen Einsatzbedingungen (z.B. Frequenz) abhängt. Dadurch ergeben sich große Unterschiede zwischen statischen und dynamischen Anwendungen.
Verschieden Untersuchungen sollen vorgestellt und interpretiert werden, um das Auditorium auf verschiedene Herausforderungen aufmerksam zu machen und Lösungsansätze vorzustellen.
Carbon-fibre prepregs have found widespread use in lightweight applications. They are based on a carbon-fibre fabric impregnated with reactive epoxy resin. Prepreg materials are generally pre-cured so that they have a higher molecular weight than typical resins in order to reduce resin flow, which facilitates storage and later processing properties.
The measurements were carried out using commercially available materials and follow the published DMA investigations of the same material. TMDSC was used to find the correlation between curing conditions, the degree of cure and glass transition temperature. TMDSC has the advantage over standard DSC that it enables better determination of the glass transition temperature, which is often accompanied by an exothermic curing reaction, and thus overshadowed. The influence of the amplitude of temperature modulation was tested in preliminary experiments. For non-cured material a glass transition temperature of approximately 0 °C was determined; whereas for the totally cured material it was approximately 230 °C. The changes in degree of cure, temperature of actual glass transition and post-reaction are given as a function of curing time at 180 °C. The correlation between actual glass transition temperature and degree of cure is derived.
In Germany spent nuclear fuel and high level radioactive waste is stored in interim storage containers with double lid systems. Those lids are equipped with metal seals (e.g. Helicoflex®) that ensure the safe enclosure of the inventory. The used metal seals consist of three components as can be seen in the cross-sectional view in Figure 1. The innermost part is a helical spring that is surrounded by an inner jacket made of stainless steel. The outer jacket that is made of a softer material which in case of assembly in the aforementioned storage containers is silver or aluminum (i.e. Al 99.5). During application the seal is compressed and due to the restoring force of the helical spring, the outer jacket is plastically deformed and adapts to the sealing surface. Hence, leakage paths are closed and the sealing function is generated. In Germany the above-mentioned containers are licensed for up to 40 years of interim storage, which in case extended storage becomes necessary before a final repository is available will have to be extended to even longer periods. Therefore, the evaluation of the long-term behavior of the seals is necessary, taking into account storage conditions, decay heat and possible mechanical loads as well.
At Bundesanstalt für Materialforschung und –prüfung (BAM) long-term investigations are being conducted in which seals are assembled in test flanges and aged at temperatures ranging from room temperature to 150°C for accelerated aging. The aged seals are tested semi-annually (after the first 6 months in which the seals are tested more frequently) regarding the sealing performance, the remaining seal force, and the useable resilience upon decompression. Results of these investigations have been published over the past years (e.g. Grelle, Wolff, Probst, Jaunich, & Völzke, 2017; Völzke, Wolff, Probst, Nagelschmidt, & Schulz, 2014). It was found that the seal force and the useable resilience decrease with time and temperature, which is in agreement with the result of other studies (Sassoulas et al., 2006; Wataru et al., 2016) as well. Geometry change of the outer jacket has been identified as the main reason for this seal behavior. At the prevailing operating temperatures and stresses the aluminum is subjected to creep deformation leading to a thinning of the outer jacket. Since the seal groove depth remains unchanged the helical spring expands, which in turn leads to a decrease of the generated spring and seal force.
Although the main reason for the change of seal parameters over time and temperature is known, a detailed characterization of the seal behavior and a reliable prediction of the parameter development for aging times that exceed the experimental time frame have not been possible, yet.
For deeper understanding of the aging processes, an Investigation program, which is covered in this contribution, is conducted at Bundesanstalt für Materialforschung und –prüfung (BAM) that focusses on the behavior of the aluminum jacket and its influence on the long-term sealing performance. The program investigates properties of material samples as well as the behavior of the seal as a component.
Original sheet material of the same aluminum that is used for manufacturing of the seals is investigated in compression creep tests. For this, a DMA (dynamic mechanical analysis) machine is employed (here used for static tests) that allows for a measurement of the specimens deformation under forces of up to 500 N. The advantage of this method is that the original material can be tested in the same shape as used for the seals which is 0.5 mm thick sheet material. For investigation of tensile creep standard specimens are used, that were machined from surrogate material of the same composition and annealing condition.
Furthermore, aluminum seals that are cut into smaller segments are assembled in flanges and placed in heating chambers at temperatures ranging from 23°C to 150°C. After different periods of time from 3 days to 300 days the segments are taken out of the flanges and are investigated, thus giving information on different states of aging. Measurements of the development of the seal contact width and the aluminum jacket thickness are done with an optical microscope. Further investigations on the segments will include metallography and hardness measurements.
From the detailed material and component behavior including the results of the long-term seal force and useable resilience investigations a better understanding of the overall seal behavior can be gained. The aim is to contribute to the development of material models and analytical approaches for the prediction of the sealing behavior in dependence of time and temperature.
Fracture mechanics approaches are increasingly applied for the characterization of epoxy resin and adhesive mechanical properties. Therefore, the fracture toughness and crack resistance under static load ISO 13586 [1] are often regarded as state of the art to analyse material improvements. However, experimental investigations on fatigue behaviour, thus the crack propagation according to ISO 15850 [2], seem to be much more sensitive to characterize the materials for in service loading conditions. Firstly, an efficient testing concept was developed at BAM. In this framework, the geometry for a modified single edge notched tensile specimen (SET) was developed in order to assure appropriate resolution in measuring the crack length via a CCD-camera [3]. In the next step, the influence of the cure temperature on the fracture-mechanical properties was investigated.
A Memorandum of Understanding (MOU) between Argonne National Laboratory (Argonne) and the German Bundesanstalt für Materialforschung und -prüfung (BAM) was signed in October 2014. Its objectives are to promote cooperation among scientists and specialists at Argonne and BAM and establish a framework for collaboration in advanced technologies associated with the back end of the nuclear fuel cycle. Collaborative activities involving Argonne and BAM may be implemented through the promotion of joint research activities and scientific workshops and conferences; exchange of technical information; and visits by scientists, specialists, and graduate, postgraduate, and Ph.D. students. The MOU was renewed in January 2020 for another five years. Highlights of the progress and achievements are provided in identified topical areas for collaboration on ageing management guidance, storage, transportation and disposal R&D, joint conference activities, and conclude with the benefits of the MOU in fostering Argonne and BAM collaboration.
Component and material investigations on metal seals for high level radioactive waste containers
(2018)
Long-term investigations performed at BAM look to extend the state of knowledge on safety-related components of interim storage containers. Metal seals act as the primary sealing barrier in the bolted double lid closure system of the containers. The behaviour of metal seals has been investigated for ageing times up to 8.5 years and for various temperatures. The main cause for reduction in useable resilience overtime was due to creep deformation of the outer jacket of the seal.
Component and material investigations on metal seals for high level radioactive waste containers
(2018)
In Germany casks for interim storage of spent nuclear fuel and high level radioactive waste are equipped with Helicoflex® metal seals as main sealing barrier of the double lid system. The long-term behaviour of those seals is investigated at Bundesanstalt für Materialforschung und –prüfung (BAM) in order to evaluate the safety function of the containment at different temperatures over storage periods of 40 years or more in case extended interim storage becomes necessary.
Long-term investigations have been done for ageing times of up to 8.5 years at temperatures ranging from room temperature to 150 °C. It was found that the seal force and useable resilience decrease over time, which is mainly caused by creep deformation of the aluminium (or silver) outer jacket of the seals. This effect becomes stronger with increasing temperature.
The ageing processes of the seal material and the overall seal behaviour is under investigation in order to derive analytical descriptions for the long-term seal performance. Thus, standardized tests on the basic seal materials, with focus on aluminium, and additional investigations on the seals as a component are conducted. The current investigations include compression and tension creep measurements as well as tensile testing. Furthermore, ageing of seal segments provides information on the development of the contact area width, jacket thickness and microstructural changes in dependence of time and temperature. The obtained data are used for the development of material models and an analytical approach to describe and predict the time and temperature dependent sealing behaviour in the long-term.
The method for the determination of compression set values with a Dynamic Mechanical Analysis (DMA) setup at low temperatures, which was presented previously, allows a much faster and readily automated procedure than the standardized compression set test according to ISO 815-2. This method is applied to a series of different elastomeric materials that are commonly used for sealing applications. The results of the compression set test are compared with results from thermal analysis to allow an in depth comparison of the material behaviour at low temperatures.
Furthermore, a comparison between two EPDM materials is presented. These materials show very similar properties determined by thermo analytical methods such as Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) but differ clearly in their compression set behaviour. This comparison shows the importance and value of information of the compression set test in addition to thermal analysis to judge the behaviour of sealing materials and confirms the relevance of the new compression set test method for the investigation of low temperature properties of elastomers.
Elastomeric seals are essential components in the infrastructure which prevent leakage of gas and proper function of technical devices and are therefore highly safety relevant. For proper function a remaining resilience and tolerance to pressure changes is required.
The ageing of elastomers is an undesirable but inevitable process leading to a limited lifetime of rubber products such as seals. Independent of the application, as e.g. automotive, piping or container applications, a long lifetime or at least a timely exchange of a seal before occurrence of critical failure is desired.
Hydrogen is a key element for the energy turnaround and therefore the compatibility of seals with hydrogen is essential. In addition to the effect of hydrogen uptake and release, which might also cause destructive effects such as rapid gas decompression, ageing at high temperature under hydrogen atmosphere is of interest too. Most of the existing work is addressing the performance of new materials and comprises only very limited investigations concerning long-term use and the behaviour of aged materials in contact with hydrogen. As ageing can lead to substantial changes of material properties, it must be evaluated whether these changes are beneficial or deteriorating for the component function.
In this work we present and compare results of the characterisation of three sealing materials (EPDM, HNBR, FKM) after ageing at high temperature under hydrogen and air. Despite the common assumption that ageing under hydrogen atmosphere should be less severe for the material in comparison to air ageing, this is not the case for every material.
Elastomer seals are mounted as barrier seals in lid systems of containers designed for transport and disposal of negligible heat generating radioactive waste and as auxiliary seals in spent fuel storage and transportation casks (dual purpose casks (DPC)). When the behavior of mounted seals under normal and hypothetical accident conditions of disposal and transport is to be simulated, a comprehensive knowledge of their complex mechanical properties at every state of aging is necessary. In previous works, BAM’s efforts in experimental investigations on specimen artificially aged at different temperatures and times and the implementation of the found results in finite element material models were presented. Additionally, our approaches to reproduce the aging process itself and to extrapolate the results of artificially accelerated aging to longer times were presented. Numerical simulations have shown that the behavior of the seal during mounting and one-sided pressurizing and the resulting performance values such as leakage rate strongly depend on the coefficient of friction (COF) between flange and seal. The friction coefficient, in turn, depends on the aging state of the elastomer material as several publications suggest (see below).
Dynamic COF between an exemplary ethylene propylene diene rubber (EPDM) material and a stainless steel ball were determined by using a self-designed linear oscillation tribometer. Unaged and artificially aged EPDM specimen stored for 30 days and 100 days at a temperature of 150 °C were tested. A stainless steel ball (d=10 mm) is brought in contact with the specimen’s surface und loaded by normal forces of 2.5 N, 5 N, 10 N and 20 N. During a reciprocating movement of the EPDM sheet, the horizontal force/friction force is continuously measured, and the COF can be derived.
It is well known that friction is a complex phenomenon especially in soft materials. It cannot be excluded that the measured friction force is influenced by additional force components, resulting from the ball’s grooving through the elastomer’s surface. This force depends on the penetration depth of the ball and on the resistance of the elastomer in its different states of aging. The latter results from microstructural changes i.e., chain scission and additional crosslinking that occur during aging which in turn influence the softening or hardening of the material.
A finite element (FE) ABAQUS® model was developed to reproduce the measurement process. It should help to better understand the physical mechanisms and to quantify the percentage of measured forces resulting from real friction on the one hand and forces resulting from unintended side effects that could falsify the result on the other hand. The behavior of the elastomer in its different states of aging is reproduced by a FE material model already presented in previous works of BAM.
Rubbers are often used for seal applications due to their special material properties and easy use. In many applications the material is exposed to low temperatures during Operation. Therefore it is important to know the material behavior at low temperatures to determine the temperature ränge that allows a Safe Operation of the seal, e.g. in storage and transport Containers for radioactive materials.
The seal function of an elastomer is limited in temperature by the rubber-glass transition during which the material properties change from rubber-like to stiff and glass-like. For a given application this correlation is not trivial and therefore needs an in-depth investigation under consideration of the physical properties and the
application conditions.
In this work different analytical methods are used to characterize the material behavior at low temperature in the ränge of the glass-rubber-transition and are compared with the quality of Operation of a component which is here defined by the detected leakage rate.