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- Gamma irradiation (3)
- Polyethylene (3)
- HMW-PE (2)
- UHMW-PE (2)
- (U)HMW-PE (1)
- Absorption (1)
- B1uTHz-region (1)
- Cask for storage and transport of radioactive materials (1)
- Co-60 irradiation (1)
- Colour center (1)
Organisationseinheit der BAM
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.
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.
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
Fourier-Spektroskopische Untersuchungen von hochmolekularem Polyethylen (HMW-PE) und ultrahochmolekularem Polyethylen (UHMW-PE) im Mittleren - und Fernen Infrarotbereich können Veränderungen der molekularen Strukturen nachweisen, die durch Co60 γ-Strahlung und Rekristallisationsprozesse initiiert werden. UHMW-PE und HMW-PE sind im gewählten IR-Bereich unterscheidbar. Die integrale Absorption der B1u – Gitterschwingungen im Fernen Infrarotbereich (THz-Bereich) ermöglichen die quantitative Beschreibung des Kristallinitätsgrades und dessen Abbau. Die Bildung ungesättigter Vinylengruppen und der Abbau ungesättigter Methylengruppen können im Mittleren Infrarotbereich nachgewiesen werden.
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.
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.
Elastomers are widely used as the main sealing materials for containers for low and intermediate level radioactive waste and as an additional component to metal seals in spent fuel and high active waste containers. The safe encapsulation of the radioactive container inventory has to be guaranteed according to regulation and appropriate guidelines for long term storage periods as well as for temperatures as low as -40°C during transport. 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 elastomers are strongly temperature dependent. At low temperatures, this is caused by the rubber-glass transition (abbreviated: glass transition). During continuous cooling, the material changes from a rubber-like entropy elastic to a stiff energy elastic behaviour, which allows nearly no strain or retraction. Hence, rubbers are normally used above their glass transition, but the minimum working temperature limit is not defined precisely; this can cause problems during the above noted applications. Therefore, the lower operation temperature limit of elastomer seals must be determined in dependence of the material properties. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) are combined with standardised measurements to determine the compression set according to ISO 815. To reduce the test time of the standard tests, a faster technique than normally used was developed. Additionally, the breakdown temperature of the sealing function of complete O ring seals was measured in a component test set-up to compare it with the results of the other tests. The experimental set-up is capable of measuring the leakage rate at low temperatures by the pressure rise method. A fluorocarbon rubber (FKM) was selected for this investigation as it is often used for radioactive waste containers. The materials (seals and test sheets) were purchased from a commercial seal producer.
Rubbers are widely used as main sealing materials for containers for low and intermediate level radioactive waste and as additional component to metal seals in spent fuel and high active waste containers. The save encapsulation of the radioactive container inventory has to be guaranteed according to legislation and appropriate guidelines for long term storage periods as well as down to temperatures of -40 °C during transport.
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 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.
The results of Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) are combined with the results of standardized measurements as the compression set according to ISO 815. To reduce the test time of the standard tests a faster technique 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 fluorocarbon rubber (FKM) was selected for this investigation as it is often used for radioactive waste containers. Some materials (seals and test sheets) were purchased from a commercial seal producer and some materials were compounded and cured at BAM in form of rubber sheets.