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Langzeitversuche über 10 Jahre an Federkern-Metalldichtungen mit Aluminium- bzw. Silberummantelungen
(2023)
Federunterstützte Metalldichtungen mit Aluminium(Al)- oder Silber(Ag)-Ummantelung werden u.a. in Behältern für Wärme entwickelnde radioaktive Abfälle eingesetzt, da diese Dichtungen eine sehr gute Dichtheit gewährleisten sowie Langlebigkeit und Beständigkeit gegenüber erhöhten Temperaturen und radioaktiver Strahlung aufweisen. Auch wenn die Sicherheit solcher Behälter und der verwendeten Dichtungen vielfach belegt wurde, sind sie Gegenstand andauernder Forschung, etwa im Hinblick auf eine absehbar benötigte verlängerte Zwischenlagerdauer. Aus diesem Grund werden an der Bundesanstalt für Materialforschung und -prüfung (BAM) im Fachbereich 3.4 „Sicherheit von Lagerbehältern“ seit über 20 Jahren Versuche an solchen Metalldichtungen durchgeführt. Dabei sollen zusätzliche Erkenntnisse hinsichtlich der Sicherheitsreserven der Dichtungen in unterstellten Störfallszenarien (axiale Bewegung des Deckelsystems bzw. Aufweitung der Nutgeometrie) und insbesondere detailliertere Erkenntnisse zum Langzeitverhalten gewonnen werden.
The investigation of the long-term performance of sealing systems employed in containers for radioactive waste and spent nuclear fuel is one research focus area for division 3.4 “Safety of Storage Containers” at the Bundesanstalt für Materialforschung und -prüfung (BAM). Our investigations comprise investigations on metallic and elastomeric seals and covers experimental investigations to get a database on the component/material behaviour, work on analytical descriptions and numerical analysis. Our aim is to understand the long-term behaviour of the sealing systems for evaluation of their performance during possible extended interim storage and subsequent transportation.
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 casks 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 the 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 timetemperature 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 extended. The results show that lifetime estimation based on single material properties can be misleading and therefore a combination of several methods is recommended.
At BAM, which is a 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 casks. Besides examining the low-temperature behaviour and irradiation effects of elastomeric seals, it is our goal to estimate 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 five years. In order to assess sealability, O-rings were 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 were 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, material properties such as hardness, elastic modulus, glass transition temperature and viscoelastic loss factor as well as relaxation and recovery behaviour are examined in order to understand the underlying ageing mechanisms in each material. For obtaining 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, resulting in distorted bulk properties such as compression stress relaxation and compression set. However, if DLO-affected data is excluded, extrapolations of CS data are possible using time-temperature shifts and Arrhenius graphs.
For selecting an appropriate end-of-lifetime criterion, leakage rate measurements were performed, since leakage rate is the only characteristic directly correlated to the performance of the sealing system. A significant increase in leakage rate was considered as the end of the lifetime. However, the O-rings remained leak tight under static conditions and even exhibited an improved, i.e. decreased leakage rate while other properties already indicated strong deterioration. These tests were extended by seal tests with fast partial decompression.
Overall an update will be given on the current investigations and results and the planned activities.
Aging of elastomer O-rings and PE neutron shielding materials for radioactive waste containers
(2021)
Our institution BAM in Berlin, Germany is concerned with research and testing of materials in the context of safety in chemistry and technology. Our working group is involved in the licensing procedures of casks for radioactive waste. Besides, we’re doing research on aging and lifetime prediction of elastomer O-rings and investigate degradation and thermal expansion of PE neutron shielding materials.
Elastomeric O-ring seals are used in a wide range of applications due to their excellent elasticity. However, like all polymers, elastomers degrade under the influence of e.g. time, temperature, oxygen, radiation and mechanical stress. Especially in applications where a replacement of seals after a certain time is hard or almost impossible, it is important to know the seal lifetime. Therefore, an extensive ageing programme with elastomers made of EPDM, HNBR and other materials was started with the aim of determining suitable methods for accelerated ageing and lifetime prediction.
In order to determine the lifetime of polymeric parts, the time-temperature superposition principle is commonly used to shift property changes obtained by accelerated ageing at higher temperatures to lower temperatures. If the shift factors yield a straight line in an Arrhenius diagram, a corresponding activation energy can be determined. However, we have found that the shift factors and thus the predicted lifetime depends on the test method that yielded the shifted data. For example, the shift factor between 125 °C and 150 °C ageing temperature was roughly the same (5/5/4.5 respectively) for hardness, density and maximum of loss factor tan measured on HNBR, but different for elongation at break (8) and compression set (2.2, excluding DLO-affected data). A possible explanation might be that while the different oxidation reactions proceed with a fixed activation energy, they have differing impact on the measured properties. For example, hardness is lowered by chain scission reactions, and increases by crosslinking reactions during ageing. As usually both chain scission and crosslinking reactions occur during ageing, the measured hardness increase reflects only the net effect of both reaction types. On the other hand, compression set is influenced additively by both reaction types: chain scission leads to an increase of the remaining deformation, as broken chains lose their recovery potential, and crosslinking reactions during ageing fix the compressed geometry, which also leads to less recovery. Thus, compression set reflects the total number of changes in the network and shows degradation effects much faster, which results in lower shift factors and lower activation energy. This phenomenon was observed for EPDM as well.
In order to verify our hypotheses and to gain further insights, temperature-dependent oxygen consumption measurements are currently being performed and results will be presented at the conference. The shift factors and activation energy determined by oxygen consumption measurements are expected to be close to the values for compression set.
At BAM, which is a 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 casks. One of the aims is to identify a suitable method for estimating 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) for up to five years. In order to assess sealability, O-rings were 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 were aged as well. In order to understand the underlying ageing mechanisms in each material, material properties such as hardness, density and tensile properties were examined. Additionally, compression set (CS), which represents the recovery behaviour of a seal after release from compression, is measured. For obtaining 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 ageing caused by diffusion-limited oxidation (DLO) effects especially for HNBR, resulting in distorted bulk properties such as compression set. However, if DLO-affected data is excluded, extrapolations of CS data are possible using time-temperature shifts.
For selecting an appropriate end-of-lifetime criterion, leakage rate measurements were performed, since leakage rate is the only characteristic directly correlated to the performance of the sealing system. A significant increase in leakage rate was considered as the end of the lifetime. However, the O-rings remained leak tight under static conditions even though material properties had already degraded strongly. For this reason, a modified, more demanding leakage test involving a fast small decompression of the seal was developed that allowed determining a more conservative end-of-lifetime criterion with a safety margin for EPDM seals. FKM, which is a very heat and oxidation resistant material, exhibited only little degradation, even though it had the smallest activation energy.
Safety of long term containment and storage of radioactive waste is an essential issue, which is increasingly gaining international attention. Extending interim storage beyond initial license periods is one of the major challenges worldwide.
BAM has been involved in all kinds of radioactive waste container safety evaluation for storage and transportation including their long term performance from the very beginning. Today, all work related to the safe management of radioactive waste is linked by the activity field “Nuclear Waste Management” within the Focus Area “Energy” at BAM and in conjunction with a research strategy and agenda. Most recently, the working group “Long Term Safety of Container Systems and Components” was established to launch and perform research projects related to safety issues concerning the extended interim storage of radioactive waste.
For example, within our project LaMEP, we investigate ageing effects of metal and elastomer seals as well as polymeric neutron shielding materials, which are container components that fulfil major safety functions. The results of the experiments help to understand the long term behaviour of these components. Likewise, our project BRUZL started at BAM in 2018 with the aim of developing a fracture mechanics approach to understand and describe a potential brittle failure mechanism of fuel cladding during long-term interim storage. BAM also contributes to the GRS project “Development of methods and models and international exchange for safety evaluation in the frame of interim storage of radioactive waste”. Additionally, BAM is involved in several international research programmes dealing with extended interim storage, such as the European Joint Programme on Radioactive Waste Management (EURAD), the Extended Storage Collaboration Program (ESCP) and IAEA Coordinated Research Projects.
The present contribution provides a comprehensive overview of BAM research activities contributing to national and international gap analyses and to filling knowledge gaps regarding the safe long term management of radioactive waste.
The thermal expansion of polymeric parts can be an issue in many applications where the available space is limited, or exact dimensions of the part are required. For this study, a device was designed and built that allowed measuring the thermal expansion simultaneously in all three spatial directions on cubic samples with real-scale dimensions (78 mm edge length). The results are shown between 25 °C and 125 °C for two PE materials, one HMWPE and one tempered UHMWPE, for non-irradiated samples as well as cubes that have been irradiated with 100 and 400 kGy. The results measured with the new device were very similar to those measured with conventional thermo-mechanical analysis equipment and to literature data of UHMWPE. The HMWPE material shows a much larger thermal expansion coefficient in one direction compared to the other two directions during the first heating due to frozen stresses from the pressing step during material manufacturing. These stresses are mostly released by the expansion during the first heating, so that the expansion during the second heating is more uniform. The overall volumetric expansion is the same for both heating runs. By contrast, the tempered UHMWPE material shows no significant difference between first and second heating run, as the stresses from processing could already relax in the tempering step. The irradiation treatment does not affect the values significantly for the given test set-up.
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.