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Characterisation of degradation and determination of end-of-lifetime criterion for O-ring seals
(2017)
The ageing of polymers, including 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 occurence of critical failure is desired.
In order to investigate the degradation of material properties and to determine the lifetime of elastomers used as seals, an ageing programme was started with hydrogenated acrylonitrile butadiene rubber (HNBR), ethylene propylene diene rubber (EPDM) and fluorocarbon rubber (FKM) [1-3]. Both O-ring seals (uncompressed and compressed by 25 %) with a cord diameter of 10 mm as well as sheets with a thickness of 2 mm were aged at 75 °C, 100 °C, 125 °C and 150 °C for up to two years. The changes of material properties during ageing were characterised for each material using the sheets by means of e.g. dynamic-mechanical analysis and tensile tests, while sealing properties such as compression stress relaxation (CSR), compression set (CS) and leakage rate were determined on O-rings. The experimental results indicate that while material properties, CSR and CS show considerable degradation effects, the static leakage rate stays constant or even decreases before failure occurs quite suddenly at advanced degradation levels. This reveals that static leakage rate has only limited sensitivity for the degradation of the seal material.
Our approach to determine a suitable end of lifetime criterion, which involves a partial decompression of the seal during the leakage test, is presented and discussed.
Characterisation of degradation and determination of end-of-lifetime criterion for O-ring seals
(2017)
The ageing of polymers, including 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. in automotive, piping or container applications, a long lifetime or at least a timely exchange of a seal before occurrence of critical failure is desired.
In order to investigate the degradation of material properties and to determine the lifetime of elastomers used as seals, an ageing programme was started with hydrogenated acrylonitrile butadiene rubber (HNBR), ethylene propylene diene rubber (EPDM) and fluorocarbon rubber (FKM) [1-3]. Both O-ring seals (uncompressed and compressed by 25 %) with a cord diameter of 10 mm as well as sheets with a thickness of 2 mm were aged at 75 °C, 100 °C, 125 °C and 150 °C for up to two years. The changes of material properties during ageing were characterised for each material using samples from the sheets by means of e.g. Dynamic Mechanical Analysis and tensile tests, while sealing properties such as leakage rate were determined on O-rings. The experimental results indicate that while material properties show considerable degradation effects, the static leakage rate stays constant or even decreases before failure occurs quite suddenly at advanced degradation levels. This reveals that static leakage rate has only limited sensitivity for the degradation of the seal material.
Our approach to determine a suitable end of lifetime criterion, which involves a partial decompression of the seal during the leakage test, is presented and discussed.
Due to their simple and reliable application, elastomers are used for many tasks. Many fields of application like transport, aviation and process technology, entail low temperatures where proper functionality of the employed seals has to be ensured. Therefore, understanding the low temperature behavior of elastomeric seals is important for safe seal operation to restrict the temperature application range.
For all areas of application, the question of seal lifetime is also important for replacement or maintenance intervals. The lifetime is especially important in applications that allow no seal replacement. Since the seal can determine the lifetime of storage in such cases, reliable lifetime estimation is necessary for these applications, and requires an extensive knowledge of the specific aging behavior.
Due to delays in the siting procedure to establish a deep geological repository for spent nuclear fuel and high level radioactive waste as well as in construction of the already licensed Konrad repository for low and intermediate level radioactive waste, extended periods of interim storage become more relevant in Germany. BAM is involved in most of the cask licensing procedures and especially responsible for the evaluation of cask-related long-term safety issues.
The long-term performance of elastomer seals for lid systems of transport and storage casks, whether used as auxiliary seals in spent fuel casks or as primary seals for low and intermediate level waste packages, is an important issue in this context. The polymeric structure of these seals causes a complex mechanical behavior with time-dependent sealing force reduction.
The results of a comprehensive purpose-designed test program consisting of basic compression and tension tests as well as relaxation tests on unaged specimens of representative types of elastomers (fluorocarbon rubber (FKM) and ethylene propylene diene rubber (EPDM)) at different temperatures and strain rates are presented. They were used to identify the constitutive behavior and to obtain parameters for finite element material models provided by the computer code ABAQUS®. After estimating the influence of uncertainties such as Poisson’s ratio and friction coefficient by sensitivity analyses, the chosen parameters had to prove their suitability for the finite element simulation of the specimen tests themselves.
Based on this preliminary work the simulation of a specific laboratory test configuration containing a typical elastomer seal with circular cross section is presented. The chosen finite element material model and the implemented parameters had to show that they are able to represent not only the specimen behavior under predominantly uniaxial load but also the more complex stress states in real components. Deviations between the measured and calculated results are pointed out and discussed.
For the consideration of long-term effects in the simulation of elastomer behavior, test results of aged specimens are needed. First information about a new test program, started recently and planned to provide these data, are given.
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.
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.
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.
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.
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.
In this work, we focus on the behaviour of elastomer seals at low temperatures with regard to potential decrease of leak-tightness or catastrophic seal failure of O-ring rubber seals. This is required as material properties of rubbers are strongly temperature dependent but their temperature application range is not always clearly defined.
Based on previous investigations which considered the physical material properties and the seal behaviour under purely static conditions we widen the focus on the sealing performance after a fast partial relief of compressed seals and additional materials.
For the investigations, different typical rubber seal materials were used as e.g. fluorocarbon (FKM), ethylene propylene diene (EPDM) and hydrogenated acrylonitrile-butadiene (HNBR) rubber.
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.
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.
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.
Elastomers are widely used as the main sealing materials in Containers for low- and intermediate-level radioactive waste and as an additional component fo metal seals in spent-fuel and high-level waste containers. According to appropriate guidelines and regulations, safe enclosure of the radioactive container contents has to be guaranteed for lengthy storage periods of at least 40 years. Therefore, the understanding of seal ageing behaviour is of high importance and has to be considered with regard to possible dynamic events taking place during transport after storage. An accelerated ageing approach for compressed seals is presented, as well as some first results.
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.
In Germany, for the transport and storage of spent nuclear fuel, casks with double closure lid systems are used, which are equipped with Helicoflex® metal seals. The original interim storage period for these casks was planned to be 40 years. However, recent political developments indicate that a storage time of more than 80 years might be necessary. Therefore, the current storage licenses have to be renewed in due course, which requires extended knowledge of the long-term behaviour of all cask components.
At the Bundesanstalt für Materialforschung und -prüfung (BAM), metal seals have been investigated after ageing at temperatures between room temperature and 150 °C for up to 7 years. At regular intervals the seals have been tested for leakage rate as well as for their mechanical behaviour. From these tests pronounced influence of ageing could be shown which results in the decrease of the seal force and the useable resilience. The main reason attributed to these performance changes is the increasing permanent deformation of the outer layer of the seal due to creep. So far, an explicit analytical description of the long-term behaviour that could be used for predictions exceeding the tested ageing times and temperatures was not suitable.
In addition to the component tests that were already conducted, a comprehensive investigation programme has been started to describe the mechanical behaviour of the individual seal components.
The individual seal components are tested regarding different material characteristics including creep, deformation and microstructural properties. The comparability of the material characterization is ensured by comparing the basic raw material of the specimen with the actual component material.
Furthermore, detailed investigations of the time and temperature dependent deformation behaviour are realized by ageing seal segments at multiple temperatures for different periods of time and employing standardized tests.
By analysing the acquired data in combination with the ongoing long-term component tests a dataset for analytical prediction of the long-term behaviour of the seals is intended for an extended period of time under a certain temperature regime.
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...
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 Bundesanstalt für Materialforschung und –Prüfung (BAM) runs an investigation program on the long-term behavior of multi-component metal seals. Such seals are used in a wide area of applications including transport and storage casks for spent nuclear fuel and high level radioactive waste.
The seal function is mainly based on the compression of the inner helical spring, which generates the necessary seal force to keep the sealing surfaces in close contact. This in turn leads to a plastic deformation of the outer jacket of the seal, comprised of highly ductile aluminum or silver that adapts to the sealing surfaces of cask body and bolted lid, thus providing high Level leak tightness. In Germany, those casks are licensed for Interim storage periods of up to 40 years or more if extended Interim storage would become necessary before a final repository is available. Thus, the sealing performance has to be evaluated, including factors like elevated temperature due to decay heat or mechanical loads due to transport under normal as well as accident conditions. Long-term investigations at BAM have been running over the last nine years to identify and evaluate the seal performance by measuring the remaining seal force, the useable resilience and the leakage rate after various time intervals at temperatures ranging from room temperature up
to 150 °C. It was found that the seal force and useable resilience decrease with time and temperature, caused by creep deformation of the outer jacket. In order to obtain an analytical description for the seal behavior and to achieve more information on the material behavior under application conditions a comprehensive investigation program with Focus on aluminum as outer jacket material was launched. The program includes material investigations such as compression and tension creep tests with representative basic materials. An additional test setup allows for the continuous measurement of the remaining seal force at temperatures of up to 150 °C. Furthermore, seal segments are compressed and stored in heating chambers, thus producing segments at different stages of the aging process. The segments are investigated regarding the development of the contact area width, jacket thickness and microstructural changes. This data will be used to develop material models and an analytical description of the time and temperature dependent long-term sealing behavior. This paper explains the current status of gained test results and modelling approaches and closes with an outlook to the future Project plans.
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.
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.
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.
In this work, we focus on the behaviour of elastomer seals at low temperatures with regard to potential decrease of leak-tightness or catastrophic seal failure of O-ring rubber seals. This is required as material properties of rubbers are strongly temperature dependent but their temperature application range is not always clearly defined.
Based on previous investigations which considered the physical material properties and the seal behaviour under purely static conditions we widen the focus on the sealing performance after a fast partial relief of compressed seals and additional materials.
For the investigations, different typical rubber seal materials were used as e.g. fluorocarbon (FKM), ethylene propylene diene (EPDM) and hydrogenated acrylonitrile-butadiene (HNBR) rubber.
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.
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.
In Germany spent nuclear fuel is stored and transported in casks that possess bolted lid systems equipped with double jacket metal seals of Helicoflex® type in order to enable safe enclosure of the radioactive inventory. A dry interim storage period of 40 years was planned and the casks are licensed for that time span. However, due to political reasons and delayed disposal projects this time span is expected to increase significantly. It is therefore necessary to evaluate the long-term sealing behavior of the casks exceeding 40 years of operating time. In this paper, we discuss our approach to investigate the aging behavior of such metal seals, and to predict the long-term sealing behavior.
Accelerated aging component tests with seals are performed at temperatures up to 150°C to investigate the course of seal force, useable resilience and leakage rate. Even though these tests have already shown a significant decrease in seal force and useable resilience after aging times of less than 1 year, for most seals the leakage rate stayed better than the specified value. However, observation of the leakage rate has to be continued to determine the aging effect on the seal properties. As a main influence on the seal long-term behavior the increasing permanent deformation of the outer jacket has been recognized. It is made of aluminum or silver which means that the temperatures that are relevant for the aforementioned application in casks lead to creep deformation.
For further investigation of seal behavior a comprehensive research program concerning the material characteristics and aging behavior of the individual seal components, with an emphasis on the outer jacket material, has been launched. The aim is to get a better understanding of the time and temperature dependent creep mechanisms and deformation. The examinations are separated into tests on seal segments and tests on standardized specimen.
In order to be able to study the aging process, seal segments are compressed in flanges and stored at temperatures ranging from room temperature to 150°C. After defined time intervals the segments are analyzed by using standardized tests including structure investigation and creep tests. The results are compared with the behavior of the specimen basic raw material. This is done to ensure comparability of the thin jacket material and additional sheet material used for standardized tests. Thus, the prediction of component changes after different aging times at different temperatures can be made. As a result forecasts on the long term seal behavior are intended.
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.
Optical and thermal analysis of PVB encapsulant polymer functionalized with luminescent organic dyes
(2018)
This work focused on the technology of luminescent down shift (LDS), with a primary aim to identify and investigate a methodology to introduce the luminescent organic dye into PVB polymer encapsulant as emergent material for photovoltaic application. For this goal, we propose to study the feasibility to implement the LDS functionality and to identify suitability of available luminescent to be incorporated into the host polymer encapsulant material. The first step to this direction was through a comprehensive optical study of Violet 570 (V) organic dye in ethanol solvent. The methodology and experimental conditions such as laboratory polymer preparation and luminescence dye concentration were presented. Also, the emergent polymer encapsulant sheets were characterized by using optical and thermal analysis techniques. The absorption spectrum of the prepared PVB material shifts towards longer wavelengths, with increasing organic dye concentration.
Low temperature performance of rubber seals - Influence of crystallite formation on seal performance
(2018)
Rubbers are widely used as sealing materials in various applications. In many fields the function of seal materials at low temperatures is necessary. Therefore, the understanding of failure mechanisms that lead to leakage at low temperatures is of high importance.
It is known that rubbers possess strongly temperature dependent material properties. At low temperatures high changes in the material properties are observed which can be caused by the rubber-glass transition (abbr. glass transition) or for some rubbers also by partial crystallisation at lower temperatures. During continuous cooling the material changes during rubber-glass transition from rubber-like entropy-elastic behaviour to stiff energy-elastic behaviour. In case of (thermal-) crystallisation the formed crystallites act as additional (physical) crosslinks within the material but the molecules in the amorphous phase can still behave like a rubber. Hence, rubbers are normally used above rubber-glass transition and (thermal-) crystallization temperature but the minimum working temperature limit is heavily depending on the application conditions. Therefore, the lower operation temperature limit of rubber seals is under investigation.
In the past we have investigated material properties and sealing behaviour of rubber seals at low temperatures. As the initial work was dedicated to purely static sealing conditions we started to investigate the effect of a small partial release of rubber seals at low temperatures to study the influence of dynamic events on leak tightness. In addition, other groups report on the influence of counterpart surface and adhesion.
In this contribution we focus on the difference between purely amorphous elastomers and elastomers which become partially crystalline at low temperatures. The influence of partial crystallization on the low temperature performance of rubber seals is discussed.
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.
In Germany, spent nuclear fuel and high active waste from reprocessing is stored in transport and storage containers with double lid systems that are equipped with metal seals completing the primary sealing barrier. The tasks of the Bundesanstalt für Materialforschung und -prüfung (BAM) within the interim storage licensing procedures ruled by the German Atomic Energy Act include the long-term safety evaluation of the container design regarding the permanently safe enclosure of the inventory. In order to generate a knowledge base for the safety evaluation, research regarding the long-term behavior of the critical components is performed. So far, the containers are licensed for an interim storage period of 40 years. However, due to significant delays in establishing a final repository, the required time span for interim storage is expected to increase significantly. Thus, a widespread investigation program is run to gain systematic data on the long-term behavior of the seals and to develop prediction models.
Long-term seal investigations consider the development of their restoring seal force, their useable resilience and their achievable leakage rate caused by aging at temperatures ranging from room temperature up to 150 °C. This year, the total time span of the tests reaches 10 years. Furthermore, seal segments are aged at the selected temperatures for up to 300 days. From these segments additional information on the sealing behavior, changes of the seal contact and the material behavior is gained.
This contribution deals with the current results of the long-term seal investigations at BAM. Furthermore, insights of the more in-depth component and material investigations of the metal seals with focus on the seal contact development are discussed and the ongoing work aiming for an analytical description of the thermo-mechanical aging effects on metal seals are presented.
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.
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.
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 investigation of the long-term performance of sealing systems employed in containers of 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. The behaviour of metallic seals, which are employed in interim storage casks for spent nuclear fuel and high active waste, over time is of high importance for ensuring safe enclosure. Therefore, investigations on these systems were started at BAM to get a general understanding of the relevant processes. Our investigations comprise investigations on different parameters which influence the seal Performance and the main part is focussed on the time and temperature dependent behaviour. Our aim is to understand the longterm behaviour of the sealing systems for evaluation of their performance during possible extended interim storage and subsequent transportation. In this contribution an overview of the performed tests and their respective results is given. A focus lies on a comparison between seals with large torus diameter in comparison to small diameters.
Understanding the failure mechanisms that lead to leakage of rubber seals at low temperatures is important. Rubber properties are highly temperature dependent. Changes in behaviour at low temperatures can result from the rubber-glass transition and for some rubbers by partial crystallisation. Experimental results on the low temperature behaviour of different rubber seals were discussed to help understand seal failure processes.
For many sealing applications rubber O-rings are applied due to their special properties and easy use. In many applications as e.g. in aviation, traffic or process technology the material can be exposed to a variety of conditions during operation as e.g. low temperatures, elevated temperatures and different media. Therefore, it is important to know the material behaviour and the seal performance under those conditions. Additionally ageing of seals is an important factor which has an influence on the long term reliability.
In this contribution we would like to discuss different aspects affecting the seal performance, lifetime estimation and address open questions which should be addressed to come to a deeper understanding of these seals commonly understood as typical machine elements.
Results of running investigations at the Bundesanstalt für Materialforschung und -prüfung (BAM), Division 3.4 “Safety of Storage Containers” are presented and discussed.
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.
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.
Monitoring the vulcanization of elastomers: Comparison of curemeter and ultrasonic online control
(2009)
The vulcanization of elastomeric materials has a high impact on the properties of the final product. Therefore, it is important to monitor and control this crosslinking process. A common technique to attain the necessary curing time is the use of a curemeter in accordance with ISO 6502 in order to determine the time for full cure of a sample with a standardized geometry. Based on this result and a lot of practical experience, the required curing time for a given product geometry is estimated. Within the scope of this work, a new analysis technique will be compared with the standard procedure. The ultrasonic online control employs ultrasound waves to measure the changes in material properties caused by vulcanization. For this study, a natural rubber compound with a conventional curing system was investigated by both techniques. It was found that the results of the ultrasonic technique show good agreement with the results of the curemeter.
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.
Two types of commercially applied Ethylene/Vinyl Acetate Copolymers (EVA) for encapsulation of photovoltaic modules were investigated by the thermal analysis methods of Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) in the temperature range from -150 °C to 200 °C. Glass transition, crystal melting and cross-linking were analyzed. The aims of the investigations were to gain more information for incoming goods control and to get information about the whole temperature dependent material properties in the investigated temperature range, starting at very low temperatures up to the crosslinking temperature region.
Die Messung des dynamischen Speichermoduls mit der Dynamisch-Mechanischen-Analyse ermöglicht einen schnellen Überblick über das temperaturabhängige Verhalten von elastomeren Dichtungsmaterialien. Ein direkter Rückschluss von der so ermittelten Glasübergangstemperatur Tg auf die Versagenstemperatur einer Dichtung ist aber ohne zusätzliche Messungen bisher nicht möglich.
Mit den Ergebnissen des Druckverformungsrestes DVR und des DVRDMA ist eine ge-nauere Beschreibung der Tieftemperatureigenschaften und dadurch der Funktion von elastomeren Dichtungsmaterialien möglich. Messungen ergeben beispielsweise, dass sich das EPDM bei einer Temperatur von -40 °C laut der Dynamisch Mechanischen Analyse noch im gummielastischen Bereich befindet. Die DVRDMA-Werte zeigen eine Rückstellung um mehr als 40 % der Ausgangsdeformation in wenigen Minuten.
Mit derart detailliert bestimmten Eigenschaften lassen sich Rückschlüsse auf einsatzspezifische Anforderungen wie z. B. die Dichtwirkung in Abhängigkeit von Betriebstemperatur und mechanischer Belastungsgeschwindigkeit ziehen, so dass je nach Einsatzbedingungen für die Dichtungen eine geeignete Materialauswahl getrof-fen werden kann.
Ultra high molecular weight polyethylene (UHMW-PE) - due to its high hydrogen content - is used as neutron shielding material in casks for storage and transport of radioactive materials. Besides this, UHMW-PE - as a high-performance polymer - has been used for several years in medical technology due to its excellent slip and wear properties. Due to the special properties of UHMW-PE which result basically from its extreme chain lengths and its high degree of crystallinity, it is predestinated for the aforementioned applications.
In both cases, irradiation and its impact on the molecular structure of polyethylene play an important role. In the first case, irradiation exists as a by-product of inserting the radioactive material in the cask. Hence PE has to withstand any type of degradation affecting safety relevant aspects to be applicable for long term radiation shielding purposes for instance over a period of 40 years. In the second case irradiation is applied deliberately for purposes such as sterilization and crosslinking, leading to partial improvement of the mechanical properties (e.g. fracture toughness, crack propagation resistance, wear resistance) and better Chemical stability.
Specifically concerning their use in the field of medical technology, different types of UHMW-PE have been objects of numerous publications. It is generally accepted that two parallel and competitive processes, based on chain scission and reactions of Ccentered radicals and molecular fragments, occur in PE as a consequence of radiation: radical recombination accounts for crosslinking, together with some disproportionation, formation of low molecular weight fragments, and recrystallization. Furthermore, formation of oxygenated structures in the presence of traces of oxygen is an antagonist of the C-centered radicals. Radiation induced scission preferentially takes place in the amorphous phase and noncrystalline surface of the crystals. It is followed by folding of molecular fragments, crystallinity growth and increased perfection in the crystal lamellae [4, 5]. Chain scission results in shorter polymer molecules, fewer entanglements, and consequently, increased molecular mobility.
The scope of our investigation comprises an estimation of the radiation and thermal impact on the molecular and supra molecular structure of the two types of PE used for neutron shielding cask components. A further point which is worth to explore is to what extent these changes are detectable by thermo-analytical (TA) methods, such as Differential Scanning Calorimetry (DSC), Thermo Mechanical Analysis (TMA), Dynamic Mechanical Analysis (DMA) and Thermogravimetry (TG). Additionally FT-IR and solubility measurements have been performed.
In our studies we focused on the UHMW-PE material GUR 4120 which was y irradiated at RT and compared to the untreated material.
The special properties of high molecular weight polyethylene (HMW-PE) and ultra high molecular
weight polyethylene (UHMW-PE) result basically from their extreme chain lengths and their high
degree of crystallinity. As high-performance polymers, they are used for a variety of applications.
UHMW-PE in particular is often utilized for endoprothesis (due to its excellent slip and wear
properties) and due to its high hydrogen content as a neutron moderator in casks for storage and
transport of radioactive materials.
To prepare the material for instance for its use as a total joint replacement, it is exposed to radiation
for several reasons, such as sterilization and crosslinking, leading to partial improvement of the
mechanical properties (e.g. fracture toughness, crack propagation resistance, wear resistance) and
better chemical stability.
To be applicable for long term radiation shielding purposes for instance over a period of 40 years,
PE has to withstand any type of degradation affecting safety relevant aspects.
The scope of our investigation comprises an estimation of the radiation impact on the molecular and
supra molecular structure of two types of PE and to what extent these changes are detectable by
thermo-analytical (TA) methods, such as Differential Scanning Calorimetry (DSC), Thermo
Mechanical Analysis (TMA), Dynamic Mechanical Analysis (DMA) and Thermo Gravimetric
Analysis (TGA). Additionally FT-IR spectroscopy as well as density and gas sorption
measurements were carried out.
Due to the poor solubility of HMW-PE and UHMW-PE, some classical analytical techniques are
not applicable. But TA-methods represent a feasible approach to detect structural and
morphological features of these materials as well as changes caused by external influences, such as
thermal treatment and/or irradiation. With the combination of the applied TA-techniques it is
possible to distinguish between crosslinking and degradation.
Partial discharges may cause damage to electrical insulation of high voltage equipment. They initiate elastic waves in the insulating material, e.g. in the stress cone of an outdoor termination. Localisation of the origin of such elastic waves can help to predict serious damaging processes in the electrical insulation. In order to measure and evaluate the wave propagation effects in typical multilayered elastomeric structures, knowledge of the material properties is required. The propagating velocity and the attenuation of longitudinal waves are important parameters. Values for these quantities found in the literature were not appropriate. Therefore, for cross-linked polyethylene (XLPE) and cured liquid silicone rubber (LSR), the longitudinal wave velocity and the attenuation were evaluated in the temperature interval from -20°C to 50°C and in the frequency range from 200 kHz to 600 kHz using a two-sample ultrasound technique. The loss factor was determined from these measured quantities. Additionally, low frequency Dynamic Mechanical Thermal Analysis (DMTA) was applied to investigate LSR and XLPE in a temperature interval between -100 and 50°C and to check qualitatively the ultrasound data.
Elastomer seals are widely used as barrier seals in containers for low and intermediate level radioactive waste and in some countries for spent fuel transportation casks. Depending on the area of use, the rubber materials have to demonstrate proper sealing performance with regard to mechanical, thermal and environmental conditions as well as irradiation during the entire operation period.
In Germany the low and intermediate level radioactive waste is planned to be disposed in the Konrad repository in standardized containers. Many of these containers use an elastomer seal between lid and container body. Depending on the radiactive inventory and a possible containment of the waste in inner barrels and/or concrete structures, such containers may require a specific leak tightness. In such cases, specified leakage rates are shall not be exceeded by the the seals to keep potential activity releases from the inventories well below defined limits.
Generally, all waste containers have to fulfill the waste acceptance criteria for the Konrad repository as defined by the reports BfS SE-IB-29/08 and SE-IB-30/08. From these criteria several requirements for seal performance are derived. The seals have to:
- ensure full functionality until final container disposal,
- maintain its function in case of a thermal or mechanical accident,
- ensure encapsulation also at -20 °C.
This combination of requirements is challenging especially as a seal exchange, which is typical for many other applications, is hardly possible and thus a sound understanding of how to perform safety evaluation of containers is required. Therefore BAM has initiated investigations on elastomer seal behaviour. This work focuses on low temperature behaviour and sealing performance concerning static conditions as well as partial loss of compression and ageing of elastomer seals. Concerning ageing, property changes caused by long-term thermooxidative conditions as well as gamma irradiation are investigated.
This contribution presents an overview and explanation of the aims of the ongoing research and gives an update of the most relevant results.
Elastomer seals are widely used as barrier seals in containers for low and intermediate level radioactive waste and in some countries for spent fuel transportation casks. Depending on the area of use, the rubber materials have to demonstrate proper sealing performance with regard to mechanical, thermal and environmental conditions as well as irradiation during the entire operation period.
In Germany the low and intermediate level radioactive waste is planned to be disposed in the Konrad repository in standardized containers. Many of these containers use an elastomer seal between lid and container body. Depending on the radiactive inventory and a possible containment of the waste in inner barrels and/or concrete structures, such containers may require a specific leak tightness. In such cases, specified leakage rates are shall not be exceeded by the the seals to keep potential activity releases from the inventories well below defined limits.
Generally, all waste containers have to fulfill the waste acceptance criteria for the Konrad repository as defined by the reports BfS SE-IB-29/08 and SE-IB-30/08. From these criteria several requirements for seal performance are derived. The seals have to:
- ensure full functionality until final container disposal,
- maintain its function in case of a thermal or mechanical accident,
- ensure encapsulation also at -20 °C.
This combination of requirements is challenging especially as a seal exchange, which is typical for many other applications, is hardly possible and thus a sound understanding of how to perform safety evaluation of containers is required. Therefore BAM has initiated investigations on elastomer seal behaviour. This work focuses on low temperature behaviour and sealing performance concerning static conditions as well as partial loss of compression and ageing of elastomer seals. Concerning ageing, property changes caused by long-term thermooxidative conditions as well as gamma irradiation are investigated.
This contribution presents an overview and explanation of the aims of the ongoing research and gives an update of the most relevant results.
Elastomerdichtungen finden als Bauteil oder Maschinenelement vielseitige Verwendung. Jedoch war trotz ihrer zentralen Bedeutung die untere Temperaturgrenze, bis zu der solche Dichtungen eingesetzt werden können, bisher nicht tiefgehend verstanden. Dieser Umstand erschwert die entsprechende notwendige sicherheitsrelevante Beurteilung. Mit der vorliegenden Arbeit ist deshalb das Ziel verfolgt worden, dass Materialverhalten repräsentativer Elastomerwerkstoffe in Abhängigkeit von der Temperatur zu verstehen und daraus dann abzuleiten, bis zu welcher Temperatur eine daraus hergestellte Dichtung unter Berücksichtigung der jeweiligen Einsatzbedingungen ihre Funktion noch sicher erfüllen kann. Ausgehend von der in der Literatur beschriebenen Aussage, dass eine Dichtung auch unterhalb der „Glasübergangstemperatur“ funktionsfähig ist, wurde der Einfluss des Glas-Gummi-Übergangs auf das Dichtungsversagen untersucht. Zunächst wurden dazu die Glasübergangstemperaturen an einer Vielzahl von Elastomeren mit gebräuchlichen Verfahren bestimmt, um diese mit dem Verhalten der Dichtung vergleichen zu können. Weiterhin wurde im Rahmen der Arbeit eine neue Charakterisierungsmethode des Tieftemperaturverhaltens von Elastomeren entwickelt, die die bisher für Dichtungen eingesetzte Normprüfung des Druckverformungsrests nachstellt. Mit dieser Methode ist im Vergleich zur Normprüfung jedoch eine deutlich schnellere und automatisierbare Untersuchung des Materialverhaltens gegeben. Darüber hinaus ist durch eine modellgestützte Auswertung eine Extrapolation der Messdaten auf zusätzliche Temperaturen möglich, wodurch der experimentelle Aufwand weiter reduziert wird. Zur temperaturabhängigen Charakterisierung des Versagensvorgangs an realen Bauteilen wurde deren Dichtverhalten mittels eines dafür entwickelten Versuchsstandes untersucht. Die festgestellte Abhängigkeit der Versagenstemperatur vom Verpressgrad konnte unter Verwendung der Ergebnisse aller angewandten Charakterisierungsmethoden für die hier untersuchten statisch beanspruchten Dichtungen erklärt werden. Zudem lassen sich aus dem mit Hilfe des Zeit-Temperatur- Superpositionsprinzips gewonnenen Informationen zur Zeitabhängigkeit der Materialeigenschaften auch Aussagen zum Verhalten von dynamisch beanspruchten Dichtungen ableiten. Mit dem Ergebnis der Arbeit zum Verständnis des Verhaltens von Elastomerdichtungen bei tiefen Temperaturen wird die gezielte Beurteilung und Auswahl von sicherheitsrelevanten Dichtsystemen in Zukunft vereinfacht.
THz and Mid IR Fourier transform spectroscopy on polyethylene irradiated with Gamma- Co60 radiation
(2014)
THz and mid IR spectroscopy of high molecular PE (HMW) and ultra high molecular PE (UHMW) reveals modifications of the molecular structure induced by γ-Co60 radiation. UHMW-PE and HMW-PE can be distinguished. The integral absorption in the B1u THz-region can quantitatively describe the amorphization of crystallinity. The formation of trans vinylene unsaturations and the decay of vinyl can be followed by mid IR spectroscopy
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.
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.
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.
Due to delays in the site-selection procedure to establish a deep geological repository for spent nuclear fuel and high level waste and in construction of the already licensed Konrad-repository for low and intermediate level waste without heat generation, extended periods of interim storage become more relevant in Germany. BAM is involved in most of the cask licensing procedures and especially responsible for the evaluation of cask-related long-term safety issues.
The long-term performance of elastomer seals for lid Systems of transport and storage casks whether used as auxiliary seals in spent fuel caslcs or as primary seals for low and intermediate level waste packages is an important issue in this context (Jaunich, 2013; Jaunich, 2014; Kömmling, 2015). The polymeric structure of these seals causes a complex mechanical behaviour with time-dependent elasticity reduction and loss of elastic recovery.
The paper presents first results of a comprehensive test Programme consisting of several static and dynamic mechanical short- and long-term tests which have been carried out at BAM on specimens made of representative types of elastomers, fluorocarbon rubber (FKM) and ethylene propylene diene rubber (EPDM). The investigation of the test results used to identify material models and their Parameters as well as the development of two finite element models for the numerical Simulation of tension and compression tests using the finite element code ABAQUS® are described. The calculation results are presented in comparison to the test results. The influence of important material and test parameters was investigated and discussed in sensitivity analyses.
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.
The properties of the encapsulant are critical to the long-term performance of photovoltaic (PV) modules under the influence of sunlight including UV, elevated temperature, humidity and diffusion of oxygen. Encapsulation process represents about 40% of the whole PV module cost. The introduction of new non-EVA encapsulant material type “Low-Cost, High-Performance” should provide a solution to outdoor yellowing degradation problems. The emerging encapsulant materials exhibit a good compatibility with emerging PV solar cells for long term durability. This new generation of encapsulant materials has the advantage to improve the PV module performances and long term durability for specific climate like desert regions. This scientific contribution presents an overview of the different encapsulant materials currently on the market, the general requirements of the emerging encapsulant materials and characterizations techniques for degradation, diagnostic and reliability lifetime estimation in the framework of Algerian renewable energy strategy.
The cure behaviour of a specific ethylene vinyl acetate material as used for encapsulation of photovoltaic modules was analysed by rheometer, differential scanning calorimetry and Fourier transform infrared spectroscopy to test for a suitable replacement for the laborious determination of gel content. The results show that all applied methods are capable of describing the effects of the cross-linking process. Some provide results very similar to those yielded by analysis of the insoluble content, but the question remains as to whether indirect methods should be preferred over the direct measurement of physical properties, e.g. as performed by the curemeter. A material stored for one year was also tested to demonstrate the effect of extended storage on cure behaviour and how this is detected by different methods. This complements the other methods, which were clearly able to detect the different cure behaviour of the aged EVA, whereas determination of the gel content could not.
In technical applications, static seals are sometimes also subjected to dynamic loadings. Therefore, the leakage behaviour under dynamic conditions has to be evaluated as well. For this purpose, FKM elastomer seals have been tested by using newly designed equipment that allows for rapid partial release of the seal and simultaneous leakage rate measurement at a wide range of test temperatures. Furthermore, material characterisation was done by using Dynamic Mechanical Analysis, Differential Scanning Calorimetry and Compression Set. It was shown that, under static conditions, the leakage rate increased significantly during cooling at temperatures around 18 K lower than the glass transition range. On reheating, the seal’s functionality was restored in the high temperature region of the glass rubber transition. In the subsequent dynamic release tests, that comprised a reduction of the seal compression within 1 s from 25 % to 23 %, increased leakage rates were observed in the high temperature region of the glass transition range. It was shown that the temperature that is critical for increased leakage is significantly lower under static conditions compared to dynamic conditions. The obtained leakage rates for static tests and dynamic release tests at different temperatures were analysed with reference to results of the material characterisation.
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).
Rubber is widely used as sealing material in various applications. In many fields the function of seal materials at low temperatures is necessary.
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 temperature dependent. 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 behaviour to stiff energy-elastic behaviour, that allows 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, what can cause problems during application. Therefore the lower operation temperature limit of rubber seals should be determined in dependence of the material properties.
In the past we investigated the material properties and sealing behaviour of elastomeric seals at low temperatures. Additionally we started to study the effect of a small partial release of elastomer seals at low temperatures. To study the influence of dynamic events on seal performance and to enhance the understanding of occurring seal failure, a setup for a fast partial seal release was designed.
In this contribution we focus on the correlation of material properties and component behaviour under different application conditions. It is desired to widen the understanding of the process of seal failure at low temperature.
Rubber is widely used as sealing material in various applications. In many fields the function of seal materials at low temperatures is necessary. 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 temperature dependent. 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 behaviour to stiff energy-elastic behaviour, that allows 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, what can cause problems during application. Therefore the lower operation temperature limit of rubber seals should be determined in dependence of the material properties. In the past we investigated the material properties and sealing behaviour of elastomeric seals at low temperatures. Additionally we started to study the effect of a small partial release of elastomer seals at low temperatures. To study the influence of dynamic events on seal performance and to enhance the understanding of occurring seal failure, a setup for a fast partial seal release was designed. In this contribution we focus on the correlation of material properties and component behaviour under different application conditions. It is desired to widen the understanding of the process of seal failure at low temperature.
Thermoanalytische Charakterisierung von Ethylen-Vinylacetat-Copolymer (EVA) für Photovoltaikmodule
(2011)
Das Ziel der Untersuchungen war mit Hilfe von DSC und DMA EVA-Folien im Anlieferungszustand hinsichtlich der Lage der Glasübergangstemperatur, des Schmelzverhaltens und der Temperaturabhängigkeit der Vernetzungsreaktion zu charakterisieren. Auf dieser Basis sollte die Lieferstabilität im Sinne einer Wareneingangskontrolle auf eine messtechnische Basis gestellt werden. In einem 2. Schritt sollte die vernetzte Folie dahingehend charakterisiert werden, ob infolge der Vernetzung eine Änderung der
Today rubber is due to its unique property profile one of the most important materials for the production of bearings, dampers or also tires and tubes. In the production of rubber goods a chemical cross-linking reaction (vulcanisation) generates the final material properties. This process takes place during the shape giving of the rubber compound in the mould and can proceed for several minutes. The cross-linking process is influenced by the mixture of the basic polymer, the cross-linking agent, the influence of catalysts and inhibitors and especially the processing conditions. The quality of every ingredient, the reproducibility of the mixing ratio, the homogeneity of the mixture and the accurateness in temperature control can have a direct influence on the cross linking reaction. To control the quality of a rubber compound and verify the processing conditions in industry moving die rheometers, named curemeter, are involved in the production process. Starting from our experience in cure monitoring of thermosetting materials by measuring ultrasound velocity in the mould we extended the measuring principle to rubber vulcanisation monitoring. After first investigations using a compression mould we dealt here with on-line monitoring of vulcanisation in an injection moulding process which is one of the most used techniques in rubber industry.
In consideration of the influence of the curing reaction on the material properties of elastomers, it is very important to control the vulcanization process properly.
As shown previously [1], the effects of the vulcanization reaction of an elastomer can be monitored by use of ultrasonic sound waves. This technique has to a certain degree a high similarity to the standard curemeter test according to ISO 6502 but can be applied also inside a production tool.
So far, the method was only applied to the vulcanization of one compound at a given temperature and sample thickness. This is now complemented with measurements on another compound system at different temperatures and sample thicknesses.
The expected effects of temperature and thickness on the curing behaviour were found by use of the ultrasound online control.
A new method for the evaluation of the low temperature properties of rubber materials is presented. The method emulates the standardized compression set measurement, which is frequently used for sealing materials, but can be performed within a considerably shorter time. The results are compared with the standard test and found to be qualitatively the same. Slight differences are discussed on the basis of the differences in the measurement procedures. Further data evaluation is done by fitting functions to describe the material behaviour.
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.
Carbon fibre prepregs have found widespread application in lightweight constructions. They are based on a carbon-fibre fabric impregnated with reactive epoxy resin. DMA measurements under temperature conditions similar to an autoclave programme were carried out using commercially available prepreg material with a high glass transition temperature. The characteristic of the temperature programme was a dynamic heating segment at 1.5 K/min followed by a longer isothermal segment at 180 °C. The courses of the storage modulus E', loss modulus E'' and tanδ were recorded. The measuring frequency was varied between 1 Hz and 33.3 Hz. Gelation and vitrification are assigned. The influence of the measuring frequency on the time to vitrification and the correlation with DSC are discussed. The reaction does not end even after 10 h curing at 180 °C, which is interpreted as the slow cessation of the reaction caused by vitrification.
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.
Rubbers are widely used as sealing material in various applications. In many fieldsthefunction of seal materials at lowtemperatures is required. Therefore the understanding of faiiure mechanisms that lead to leakage at low temperatures is of high importance. Therefore the lower Operation temperature limit of rubber seals should be determined in dependence of the material properties.
The results of Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) are combined with results of standardized measurements as the compression set according to ISO 815. To reduce the test time of the Standard tests a faster and more efficient technique was developed and applied. In addition the breakdown temperature of the sealing function of O-ring seals at lowtemperatures is measured in a component test Setup in dependence of the material and the degree of compression.
Langzeituntersuchungen an Metalldichtungen mit innen liegendem Federkern und doppelter Ummantelung
(2013)
In Deutschland werden in Transport- und Lagerbehältern (TLB) wärmeentwickelnde radioaktive Abfälle gegenwärtig über einen Zeitraum von bis zu 40 Jahren zwischengelagert. Aufgrund der Situation der noch nicht abgeschlossenen Endlagersuche werden hier möglicherweise Verlängerungen in Betracht zu ziehen sein. Im Deckeldichtsystem der TLB werden in der Regel Metalldichtungen vom Typ Helicoflex® eines französischen Herstellers verwendet, die aus einem innen liegenden Spiralfederkern und zwei Ummantelungen bestehen. Die Ermittlung der Fliess- und Relaxationseigenschaften der Dichtungskomponenten über den vorgesehenen langen Betriebseitraum sind vor dem Hintergrund des Erhalte eines geforderten hohen Dichtniveaus ein wichtiger Untersuchungsgegenstand.
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.
Elastomere werden vielfach als Dichtungsmaterial für verschiedene Anwendungen eingesetzt.
In vielen Bereichen ist die Funktion der Dichtung auch bei tiefen Temperaturen erforderlich. Daher ist das Verständnis des Versagensmechanismus von großer Bedeutung.
Normalerweise werden Elastomere oberhalb ihres Glass-Gummi Umwandlungsbereiches eingesetzt, wobei die minimale Einsatztemperatur nicht exakt definiert ist. Daher ist es sinnvoll, diese untere Temperatureinsatzgrenze in Abhängigkeit von den Materialeigenschaften zu bestimmen. Hierfür werden die Ergebnisse der thermischen Analyse mit den Resultaten des Druckverformungsrests aus einer abgewandelten Messung mit der Dynamisch Mechanischen Analyse (DMA) kombiniert.
Weiterhin werden Ergebnisse von Bauteilversuchen vorgestellt und diskutiert.
Die vorgestellten Untersuchungen wurden zum großen Teil auf Untersuchungen im Rahmen der Dissertation von M. Jaunich durchgeführt.
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.
Due to their extreme high hydrogen contents, high molecular weight (HMW-) and ultra-high molecular weight (UHMW-) polyethylene (PE) are a comprehensible choice as neutron radiation shielding material in casks for storage and transport of radioactive materials. But as a direct consequence of inserting radioactive material in such casks, gamma radiation occurs. Hence, the impact of gamma radiation on the molecular structure of polyethylene has to be taken into consideration. Consequently, PE has to withstand any type of gamma radiation induced degradation affecting safety relevant aspects in order to be applicable for long term neutron radiation shielding purposes during the whole storage period (in Germany, for instance, up to 40 years). The scope of our investigation comprises an estimation of the impact of gamma radiation and temperature on the molecular and supra molecular structure of the two types of PE used as neutron radiation shielding cask components. A further point which is worth exploring is to what extent these changes are detectable by conventional analysis methods. Therefore, thermoanalytical measurements were performed such as differential scanning calorimetry (DSC), thermo mechanical analysis (TMA), dynamic mechanical analysis (DMA), and thermo gravimetric analysis (TGA). Additionally optical and weighing methods were applied. With those methods it is possible to detect structural changes in polyethylene induced by exposure to gamma radiation. The observed amounts of changes of the irradiated material are not safety relevant for the application of polyethylene as neutron radiation shielding material; moreover, some properties actually improve via irradiation.