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BAM is the federal institute for materials research and testing in Germany. One of our tasks is to evaluate the safety of casks designed for transport and/or storage of radioactive waste. As elastomeric seals are used in the containers as safety-relevant parts, it is our goal to be able to evaluate the service lifetime of the seals with regard to the requirements for long-term safety (40 years and more) of the containers. For this reason, an accelerated ageing programme with selected rubbers often used for seals (HNBR, EPDM and FKM) was started. Ageing was performed at four different temperatures (75 °C, 100 °C, 125 °C and 150 °C) for up to 2 years. For assessing properties related to the sealability, O-rings were aged in compression by 25 % (corresponding to the compression during service) between plates. For comparison, uncompressed O-rings were aged as well. The aged materials were characterized with conventional polymer analysis methods such as hardness and tensile tests, but also with more seal-specific methods such as compression stress relaxation (CSR, reflecting the loss of sealing force of a compressed seal over time), and compression set (CS, representing the recovery behaviour of a seal after release from compression). CS is chosen as the property for lifetime prediction as it is both sensitive to degradation and related to the seal performance. CS data is extrapolated to 60 °C, which yields lifetimes of approximately 5 years for HNBR and 64 years for EPDM for a criterion of 85 % CS respectively, and approx. 40 years for FKM for a criterion of 65 % CS (the highest value measured so far).
HNBR, EPDM and FKM O-rings were aged uncompressed and compressed at 75 °C, 100 °C, 125 °C and 150 °C for up to 1 year. HNBR exhibited the strongest ageing effects with high increases of hardness and glass transition temperature. Furthermore, heterogeneous ageing caused by diffusion-limited oxidation effects had a significant influence for HNBR at ageing temperatures of 125 °C and 150 °C. EPDM showed similar property changes as HNBR, but less pronounced. FKM displayed only minor ageing effects. O-rings aged in compression exhibited considerable compression set (CS). CS data was used for a time-temperature shift and resulting master curve construction. Leakage rate measurements showed that O-rings can remain leak tight under static conditions even if material properties have already deteriorated strongly.
Elastomer seals are widely used as barrier seals in containers for low and intermediate level radioactive waste. In addition, they are also used in waste fuel storage and transportation casks as auxiliary seals. Depending on the area of use, the rubber materials have to demonstrate proper sealing performance with respect to mechanical, thermal and environmental conditions as well as irradiation during the entire operation period. A fundamental understanding of the structure property relationship and their changes during aging can help to evaluate the long-term sealing performance.
In the present study, specific materials are investigated to study the structure-property and seal performance-correlation. Fluoro-elastomer (FKM), silicone rubber (VMQ) and ethylene propylene diene rubber (EPDM) were chosen as base rubbers. Comparable mechanical properties for these seals, especially in terms of a comparable compression behavior were achieved by careful control of base rubber formulation, i.e., by opting for the right filler and its concentration, amount of crosslinking chemicals, and with the assistance of process oils. Moreover, with the same rubber, similar mechanical properties were achieved by varying the filler concentration and crosslinking degree, which shall enable to correlate the particular influence on the structure property dependency of the seals in detail. The materials are investigated under pristine and aged conditions to evaluate the influence of aging, e.g. on the stress relaxation or recovery behavior. These values appear to be suitable parameters to judge the expected sealing performance.
Due to the electrically conducting nature of some fillers used to reinforce rubbers (such as carbon blacks, carbon nanotubes (CNTs), Graphene, etc.) it is possible to obtain current information about mechanical and visco-elastic properties by monitoring the electrical conductivity or resistivity. A simple relation that relates electrical resistance with mechanical stress was derived and the stress values were theoretically predicted from the electrical resistance values, which showed good correlation with experimental results.
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.
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.
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.
Elastomers show a high versatility which makes them ideal materials for sealing applications in various fields. Especially under changing application conditions the high recovery potential of this class of material is beneficial to compensate temperature or pressure fluctuation, and geometrical changes resulting from mechanical loads in e.g. accident conditions. Out of these reasons elastomers are also used in containers for low and intermediate level radioactive waste and for spent fuel transportation casks. In cask designed for low and intermediate level waste elastomer seals can act as primary seal responsible for the containment function whereas in spent fuel storage and transportation casks (dual purpose casks (DPC)) elastomer seals are used as auxiliary seals to allow leakage rate measurements of metal barrier seals. An inherent prerequisite for this kind of application is the long time-scale of operation without or with limited possibility of seal replacement. In Germany an interim storage license for DPC`s is typically issued for 40 years, a timeframe which might increase in future due to challenges of the final repository siting procedure. For low and intermediate level waste, also long time periods are required before final disposal can be achieved. Therefore, the performance of elastomer seals over extended time periods is, as for other applications, of high importance.
A typical approach to ensure long-term functionality is to perform accelerated aging tests to calculate an estimated lifetime by assuming e.g. Arrhenius like equations for the time-temperature relationship. This approach requires a suitable end of life criterion considering the application of interest. This often can represent a challenge on its own.
As BAM is involved in most of the cask licensing procedures and especially responsible for the evaluation of cask-related long-term safety issues we initiated several test programs for investigating the behavior of elastomer seals. Experiments concerning the low temperature performance down to -40°C and the influence of gamma irradiation have been started first. Currently the thermal aging behavior of elastomer seals, which is the topic of this contribution, is examined.
For our aging investigations we use a broad approach to first determine the property changes in different elastomer materials due to thermo-oxidative aging at elevated temperatures and secondly we test how the typical methods of lifetime extrapolation can be applied to these results. This approach enables us to detect and exclude undesired side effects which very often influence lifetime estimations. In this contribution, our recent results are discussed.
Ein wesentliches sicherheitstechnisches Kriterium für Transport und Lagerbehälter ist das Langzeitverhalten von verschraubten Deckel-Dichtsystemen unter Verwendung von Metall- und Elastomerdichtungen sowie von im Behälterkörper integrierten Polyethylenen zur Neutronen¬abschirmung.
Die ordnungsgemäße Funktion der Metalldichtungen ist Voraussetzung für die Einhaltung der geforderten Dichtheit des Deckelsystems, während die Elastomerdichtungen für die Messung der Leckagerate an den Metalldichtungen benötigt werden. Darüber hinaus kommen Elastomer-dichtungen als Primärdichtungen in Behältern für radioaktive Abfälle mit vernachlässigbarer Wärmeentwicklung zum Einsatz.
Zur Bewertung des Dichtungsverhaltens sind die alterungsabhängige verbleibende Rückstellkraft für die Metall- und Elastomerdichtungen sowie die sog. nutzbare Rückfederung bei Metalldichtungen von entscheidender Bedeutung. Für Elastomerdichtungen ist zusätzlich eine radiologisch bedingte Materialdegradation zu bewerten.
In Bezug auf das Alterungsverhalten von Polyethylen zur Neutronenabschirmung sind neben zeit- und temperaturabhängigen Materialveränderungen insbesondere auch durch Gammastrahlung induzierte Degradationseffekte wie Wasserstoffabspaltung, Vernetzung und Abbau der Polymer¬moleküle zu berücksichtigen. Über die eigentliche Bewertung der Abschirmeigenschaften hinaus sind somit zusätzlich Auswirkungen von Degradationsprodukten auf andere Behälterkomponenten zu diskutieren.
Die an der BAM im Fachbereich 3.4 Sicherheit von Lagerbahältern durchgeführten und aktuell laufenden Untersuchungen werden vorgestellt und diskutiert.