Degradation von Werkstoffen
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Abstract Hydrogenated nitrile butadiene rubber (HNBR) elastomer was thermo-oxidatively aged at different temperatures up to 150 °C. Fourier transform infrared spectroscopy (FTIR), compression stress relaxation (CSR) and international rubber hardness degree (IRHD) microhardness were used to characterise the chemo-mechanical changes of HNBR O-rings during thermo-oxidative ageing. FTIR shows the development of carbonyl, methyl and ester groups but the nitrile content was not affected by ageing. The effect of sample geometry during CSR was investigated. CSR data were converted through integrated kinetic laws. The conversion has proven its sensibility to detect heterogeneous ageing. This was confirmed by the IRHD measure-ments across the section of O-rings. The influence of compression during ageing was assessed through IRHD measurements across the section of compressed and uncom-pressed aged O-rings. The DLO effect was more pronounced in compressed O-rings. By applying the model of Wise et al., theoretical IRHD and oxidation profiles were determined on the basis of IRHD experimental data of compressed O-rings. Good agreements between the experimental and the theoretical IRHD profiles in the core region were obtained. However, near the edge, the theoretical IRHD values were overestimated.
The storage of spent fuel and high level radioactive waste in Germany is performed in interim storage containers with double lid systems. The lids are bolted and equipped with metal seals (e.g. Helicoflex®) to ensure the safe enclosure of the inventory. The used metal seals have a layered structure consisting of three components as can be seen schematically in the cross-sectional view in Fig. 1.
In the center a helical spring is positioned that is surrounded by two C-shaped jackets and is mainly responsible for generation of the required restoring force. The inner jacket is made of stainless steel and homogenizes the restoring force of the helical spring. The outer jacket is made of silver or aluminium which both are soft metals in comparison to the contact partners (lid and container body). During bolting of the lid to the container body the seal is compressed. The generated restoring force of the helical spring causes a plastic deformation of the outer jacket and adapts to the surfaces of the lid and the container body. Hence, leakage paths are closed and the sealing function is generated.
Typical durations for existing interim storage licenses in Germany are 40 years, but it can be expected that they have to be extended to longer periods as a final repository will not be available before the end of the running licence periods. This extension of license periods requires a solid understanding of the long-term behaviour of the seals under storage conditions. To meet this challenge long-term investigations have been started at Bundesanstalt für Materialforschung und –prüfung (BAM) in 2009. These tests focus on seals assembled in test flanges which are stored at temperatures ranging from room temperature to 150 °C for accelerated ageing. The aged seals are tested repeatedly after certain ageing steps and the leakage rate as indicator for sealing performance, the remaining seal force, and the useable resilience upon decompression are determined.
In the poster an update on the performed investigations in respect to earlier publications (Grelle et al. 2019, Goral et al. 2023) will be given and the implications of the results for resilient long term safety will be presented. Additionally, a focus will be laid on the currently planned further investigations and the question “What is additionally needed for evaluation of an interim storage period extension in regard to the used metal seals?” will be addressed.
Overview of ongoing research and future prospects on polyethylene neutron shielding materials at bam
(2023)
The extension of the interim storage period of radioactive waste before disposal will cause additional challenges for the nuclear waste management in Germany, so that an extensive knowledge of the long-term performance of casks, including their components and inventories, will be required for future extended storage licenses.
Ultra-high and high molecular weight polyethylenes ((U)HMW-PE) are used for neutron shielding purposes in casks for storage and transport of spent fuel and high-level waste due to their extremely high hydrogen content. During their service life of several decades as cask components, the PE materials are exposed to neutron and gamma radiation from the radioactive inventory of the casks, mechanical assembling stresses and temperature. All these combined effects affect the material properties of such components which in turn may be crucial for some possible accident scenarios.
At the Bundesanstalt für Materialforschung und -prüfung (BAM), the effects of high temperature exposure in combination with subsequent or previous irradiation were investigated with a comprehensive aging program including thermal aging at 125 °C for different aging periods up to 5 years and irradiation with doses ranging from 50 to 600 kGy.
This contribution provides an overview of the ongoing research related to the structural changes of (U)HMW-PE induced by gamma irradiation and high temperature exposure and focuses on current research perspectives at BAM with regard to the prediction of the dynamic behavior of the material during extended interim storage in case of an accident scenario. First results of the coupled effect of temperature, radiation and mechanical loading will be presented. The effect of microstructural changes induced by gamma irradiation and high temperature on the mechanical behavior of (U)HMW-PE will be assessed.
It is common practice in the application of finite element analysis to model compression set (CS) of elastomers during aging with two different material models according to the two-network theory of Tobolsky. The theory relies on the existence of two networks. The first one represents the original network after vulcanization and is sensitive to chain scission. The second network accounts for the formation of additional crosslinking during aging. Besides the use of user subroutines to describe the two-network model, an element overlay technique is also needed as the full set of both material behaviors did not exist for assignment to a single element. This element overlay technique is valuable for research and developmental purposes but makes extension to industrial usage quite challenging. Our goal is to simulate the CS of elastomers after long-term aging in a commercial finite element software with no need for extra subroutine codes or mesh superposition.
Ethylene propylene diene (EPDM) O-rings were aged in a compressed state at 75 °C, 100 °C, 125 °C and 150 °C for up to 183 days. Investigations of the experimental test results were used to identify material models and their parameters to develop a finite element model to simulate CS. The model was implemented in the finite element software ABAQUS/Standard® with a sequential temperature-displacement coupling.
Regarding the influence of temperature, the Arrhenius equation is adopted for the time-temperature relationship. The activation energy value that is required for the simulation is firstly determined from shifting the experimental CS results with the time-temperature superposition technique and plotting the shift factors in an Arrhenius diagram. The experiments were compared with the simulation results. Afterwards different activation energies were used in the simulation and discussed. A suitable choice of the activation energy value with regard to the reference temperature and the test temperature is presented. With the chosen activation energies, the match between numerical CS values after long-term aging and the experimental results was improved.
Recovery is an important measure for seal applications representing to which extent the elastomer regains its initial shape after deformation and release of an applied force. Compression set (CS) indicates the degree of recovery. Ethylene propylene diene rubber (EPDM) was aged at 75 ◦C, 100 ◦C, 125 ◦C and 150 ◦C for different ageing times up to five years and compression set measurements were performed at different times after disassembly and after additional tempering. Short- and long-term recovery up to one year after release for samples aged at 125 ◦C and 150 ◦C was also studied. To assess the curvature in the Arrhenius diagram that may occur due to non-sufficiently aged specimens, a degradation-rate based model was fitted to the CS data after tempering. For each ageing temperature, two decay fit functions were proposed, each with an activation energy and a corresponding degradative process. The influence of ageing on the leak-tightness after fast small partial release is investigated and estimated through the analysis of the shift factors from time temperature superposition (TTS) of CS measurements at different times after disassembly. Shift factors of CS measurement after 1 s and after additional tempering are in good agreement.
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.
During an extensive test programme at the Bundesanstalt für Materialforschung und prüfung, material property changes of EPDM O-rings were investigated at different ageing times and two ageing temperatures of 125∘C and 150∘C. To exclude possible diffusion-limited oxidation (DLO) effects that can distort the data, IRHD microhardness measurements were taken over the cross section of compressed O-rings. Continuous stress relaxation measurements were taken on samples free of DLO effects. The additional effect of physical processes to irreversible chemical ones during a long-term thermal exposure is quantified by the analysis of compression set measurements under various test conditions. By combining the different experimental methods, characteristic times relative to the degradation processes were determined. On the basis of experimental data, a microphysically motivated model that takes into account reversible and irreversible processes was developed. The parameter identification strategy of the material model is based on our experimental investigations on homogeneously aged elastomer O-rings. The simulated results are in good agreement with the experiments.
Elastomer seals are used in many industrial applications due to their excellent mechanical properties at a wide range of temperatures. Their high versatility and recovery potential under several load conditions make them well suitable for the application in containers designed for transport, storage and/or disposal of radioactive materials. In containers for low and intermediate level radioactive waste, elastomer seals are used as barrier seals, and as auxiliary seals in storage and transportation casks (dual purpose casks) for heat generating radioactive waste, such as spent fuel and high-level waste. While a seal exchange at defined intervals is typical in many conventional applications, it is impossible or at least hard to perform when principles of minimization of radiation exposure have to be considered and prohibit an unnecessary cask handling. An extensive knowledge of the change of the elastomer’s properties during aging and the availability of reliable end-of-lifetime criteria to guarantee the permanent safe enclosure of the radioactive material is mandatory. As BAM is involved in most of the national cask licensing procedures and in the evaluation of cask-related long-term safety issues, great efforts have been already made and are still planned to scientifically support this task.
Compression stress relaxation and compression set were identified as key indicators of elastomer long-term performance and quantitatively investigated in comprehensive test programs. Among other representative types of elastomers, specimens made from ethylene propylene diene rubber (EPDM) were tested before, during and after aging to capture the most important of their complex mechanical properties.
In the presented study, exemplary results were used to simulate the compression stress relaxation and the compression set of elastomer O-rings during aging. Regarding the influence of temperature, the time-temperature superposition principle is applied in the relaxation analysis of elastomer O-rings. The proposed model is implemented in the commercial finite element software ABAQUS/Standard® [1] with a sequential temperature displacement coupling. Numerical results match the experimental compression stress relaxation measurements well. The prediction of compression set values after long-term aging shows a relatively good agreement with the experimental results. Nevertheless, all input parameters derived from the specimen tests, additional assumptions concerning boundary conditions and modeling strategy are discussed with regard to the identified slight discrepancies.
The possibility to extend the finite element model to represent the O-ring seal’s ability to recover after a (fast) partial release is taken into account.
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.
Eine Aufgabe des Fachbereichs 3.4 Sicherheit von Lagerbehältern der Bundesanstalt für Materialforschung und -prüfung (BAM) ist es, die Sicherheit von Behältern zur Lagerung von radioaktivem Abfall mit vernachlässigbarer Wärmeentwicklung zu bewerten. Da solche Behälter vor der Entsorgung transportiert und gelagert werden, ist während dieser Zeit ein sicherer Einschluss des radioaktiven Inhalts von größter Bedeutung. Zur Abdichtung dieser Behälter sind Elastomer-O-Ringe weit verbreitet. Um für solche, wie auch für viele andere Anwendungen, eine Voraussage über die Lebensdauer dieser Komponenten treffen zu können, ist es unerlässlich zu verstehen, welchen Einfluss der durch Alterung hervorgerufene Abbau auf Dauer auf die Elastomerdichtungen hat. In einem Langzeittest wurden drei Kautschukarten (EPDM und FKM, die für die Anwendung relevant sind, und HNBR als Vergleich) über mehrere Jahre untersucht. Dabei wurden die Veränderungen der mechanischen Eigenschaften (z. B. Härte und Bruchdehnung) bei vier verschiedenen Alterungstemperaturen (75 °C, 100 °C, 125 °C und 150 °C) sowie das Dichtungsverhalten betrachtet. Um den Einfluss von Vernetzung und Kettenspaltung auf die beobachteten Alterungseffekte zu bestimmen, wurden Messungen zur kontinuierlichen und intermittierenden Druckspannungsrelaxation durchgeführt. Dadurch konnten Erkenntnisse über Kinetik und Mechanismus der Abbaureaktionen
gewonnen werden. Zur Einschätzung des Dichtungsverhaltens wurden Durckverformungsrest und Leckagerate gemessen. Die Ergebnisse zeigen, dass die O-Ringe unter statischen Bedingungen auch dann dicht halten, wenn die Werte für Druckverformungsrest, Druckspannungsrelaxation und mechanische Eigenschaften schon auf einen fortgeschrittenen Alterungsabbau hindeuten. Aus diesem Grund wurde ein modifizierter Dichtigkeitsversuch mit einer geringen und schnellen teilweisen Entlastung der Dichtung entwickelt, mit dessen Hilfe sich ein Lebensdauerkriterium bestimmen lässt, das eine Sicherheitsspanne für thermische Schrumpfung und Vibrationen beinhaltet.
At the Bundesanstalt für Materialforschung und -prüfung (BAM) in Division 3.4 Safety of Storage Containers, one of our tasks is to evaluate the safety of containers designed for disposal of low and intermediate radioactive waste. As such containers might be transported before and stored until disposal, safe enclosure of the radioactive inventory is important for this time span. Elastomer O-rings are widely used as barrier seals in these containers. Thus, as for many other applications, an understanding of the practical effects of ageing degradation on elastomer seals during long-term exposure is mandatory for predicting the lifetime of such components. According to a long-term test programme on three kinds of rubbers (EPDM and FKM (relevant for application), HNBR (for comparison)), over several years we have studied the degradation and the change of mechanical properties (e.g. hardness, strain at break) at four different ageing temperatures (75 °C, 100 °C, 125 °C and 150 °C) as well as the change of sealing properties. Continuous and intermittent compression stress relaxation (CSR) measurements were performed in order to investigate the respective contribution of crosslinking and chain scission to the observed degradation effects. Thus, the degradation kinetics and mechanisms could be resolved more clearly. For assessing the seal performance, compression set (CS) and leakage rate measurements were conducted. The experimental results showed that the O-rings remained leak-tight under purely static conditions even when CSR, CS and mechanical properties already indicated far advanced degradation. For this reason, a modified leakage test involving a small and rapid partial decompression of the seal was developed that enabled determining an end-of-lifetime criterion for O-rings with a safety margin for thermal shrinkage and vibrations.
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.
Determining a suitable and reliable end-of-lifetime criterion for O-ring seals is an important issue for long-term seal applications. Therefore, seal failure of ethylene propylene diene rubber (EPDM) and hydrogenated nitrile butadiene rubber (HNBR) O-rings aged in the compressed state at 125 °C and at 150 °C for up to 1.5 years was analyzed and investigated under static conditions, using both non-lubricated and lubricated seals. Changes of the material properties were analyzed with dynamic-mechanical analysis and permeability experiments. Indenter modulus measurements were used to investigate DLO effects. It became clear that O-rings can remain leak-tight under static conditions even when material properties have already degraded considerably, especially when adhesion effects are encountered. As a feasible and reliable end-of-lifetime criterion for O-ring seals under static conditions should include a safety margin for slight dimensional changes, a modified leakage test involving a small and rapid partial decompression of the seal was introduced that enabled determining a more realistic but still conservative end-of-lifetime criterion for an EPDM seal.
Elastomers are susceptible to chemical ageing, i.e., scission and cross-linking, at high temperatures. This thermally driven ageing process affects their mechanical properties and leads to limited operating time. Continuous and intermittent stress Relaxation measurements were conducted on ethylene propylene diene rubber (EPDM) and hydrogenated nitrile butadiene rubber (HNBR) samples for different ageing times and an ageing temperature of 125 °C. The contributions of chain scission and cross-linking were analysed for both materials at different ageing states, elucidating the respective ageing mechanisms. Furthermore, compression set experiments were performed under various test conditions. Adopting the two-network model, compression set values were calculated and compared to the measured data. The additional effect of physical processes to scission and cross-linking during a long-term thermal exposure is quantified through the compression set analysis. The characteristic times relative to the degradation processes are also determined.
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.
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.
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.
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.