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At least 1,693 records · Page 94

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

D and D: Dismantling and Release of Large Components at the GNS Premises in Duisburg on the Example of a CASTOR S1 Container - 13536

There are a lot of metallic large components for the transport of radioactive waste in Germany. Some of these large components like for example the Castor S1 with 82 Mg are so old, that the transport via streets is not possible because the permission is not valid anymore. The application for a new permission is economically not reasonable. Out of this reason the large components need to be decontaminated and recycled to use them again in the economic cycle. Decontamination of large components by cleaning/removing the surface for example with beam technology is a very time-consuming release procedure. Manufacturing a specialized machine for decontamination and creation of a new surface was the intention of this project. The objective was to save interim storage and final repository volume and costs as well as developing a process that is nationally and internationally usable. 90% of the volume/mass of waste could be released and therefore possibly re-used. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigation of ruthenium dioxide formation mechanisms in containment glass synthesized by liquid feed

The presenting paper focuses on the structural configuration of ruthenium in vitreous matrices with the objective of obtaining more insight into ruthenium incorporation and solubilization mechanisms in borosilicate glasses. To determine the structural effect of an increasing RuO{sub 2} in a borosilicate glass, a series of glass samples were selected from a benchmark composition. {sup 11}B NMR shows that the borate network is influenced by the presence of RuO{sub 2} in the glass: the addition of 2% RuO{sub 2} in a borosilicate glass led to a significant rise of BO{sub 4}. RuO{sub 2} precipitated in the glass does not seem to be the cause of this modification because when RuO{sub 2} increase there is no further change of BO{sub 4} fraction. This effect can be therefore attributed to RuO{sub 2} dissolved in the glass. RuO{sub 2} is known to have a very low solubility in borosilicate glasses (50 to 2000 ppm depending on the temperature, sodium concentration and conditions of synthesis). The link between the ruthenium and the borated network is not yet clearly identified, however, assumptions can be made such as the formation of Ru-O-B when a sufficient quantity of Ru is add (> 400 ppm). Ruthenium could play the role of silicon in increasing the possibility of bridging bond formation with boron coordination number IV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Efficient Tool-Set for Modeling Containment Ventilation in Very Complex Facilities - 17215

The applicability of a multi-zone ventilation analysis program, CONTAM, to complex radioactive waste material handling or processing plants is evaluated. Validation results are based on simulations from three-dimensional multi-physics computational fluid dynamics. Insight into the application limits of CONTAM and conditions under which the use of higher fidelity tools are required are also discussed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Actinide Containment Safety Case in a TRU/HLW Repository in Salt - 16369

The safety case for the permanent isolation of actinides in a salt nuclear repository is discussed. The need for actinide and brine chemistry research is driven by the regulatory process that requires an accounting of low-probability 'worst case' scenarios to show that the release criteria are met under these unexpected conditions. An overview of the WIPP approach to establish the actinide source term, which is defined by the oxidation state distribution, solubility and tendency to form colloidal species, is presented for the key actinides. This approach is then discussed in the context of extending the salt repository concept to defense high level waste (HLW) and possibly spent fuel (SF) to identify key needs and gaps. It is an overall conclusion of this review that the WIPP serves as a good template for the HLW/SF case and the safety case can be readily extended to this repository concept with proper repository design and supporting experimental results. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Durability of Containers for the Disposal of Radioactive Waste - Swiss and Belgian R and D Studies - 19392

In this paper, we present a summary of the results from research and development (R and D) studies associated with the durability of steel-based disposal canisters for high-level waste (HLW) and spent nuclear fuel (SNF), focusing on experimental studies carried out in support of the Swiss and Belgian disposal programmes. We present the results of laboratory studies carried out for periods of the order of ten to twenty years, and compare them with more recent observations from in situ experiments carried out at the Mont Terri and Grimsel underground laboratories. For the Belgian programme, which is currently envisaging relatively high gamma dose rates outside the steel overpack, we also show the results of studies focusing on gamma radiation at dose rates compatible with those expected in the disposal system. These studies show how, in bentonite systems, corrosion rates decrease to values lower than 1 μm year{sup -1} after an initial period. In the case of cement-based systems, corrosion rates lower than 0.1 μm year{sup -1} are typically observed, with modest effects of gamma irradiation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Archaeal protein containing domain of unknown function 2193 undergoes oligomeric reconfiguration upon iron–sulfur cluster binding

Methanogenic archaea are particularly rich in iron–sulfur proteins, yet their roles remain largely enigmatic. Here, we characterized aMethanococcus voltae(Mvo) protein from the domain of unknown function (DUF) 2193 family, a group of proteins present primarily in archaea and characterized by a conserved cysteine‐rich C‐terminal motif.MvoDUF2193 was heterologously expressed and characterized by a range of spectroscopic and analytical methods. The results demonstrate thatMvoDUF2193 binds a single [4Fe–4S] cluster per subunit and that cluster occupancy regulates the transition from an apo tetramer to a [4Fe–4S] monomeric form. We hypothesize thatMvoDUF2193 serves a regulatory role in the cell, mediated by [Fe–S] cluster binding and changes in oligomeric state.

Biochemistry & Molecular Biology↗

Depressurization-Induced Fines Migration in Sediments Containing Methane Hydrate: X-Ray Computed Tomography Imaging Experiments

Depressurization of hydrate-bearing sediments (HBS) can cause the movement of fine particles, and in turn, such fines migration affects fluid flow and mechanical behavior of sediments, ultimately affecting long-term hydrocarbon production and wellbore stability. In this work, we investigate how and to what extent depressurization of HBS causes fines migration using X-ray computed tomography (CT) imaging. Methane hydrate was synthesized in sediments with 10% fines content (FC), composed of sands with silt and/or clay, and the hydrate-bearing samples were stepwisely depressurized while acquiring CT images. The CT images were analyzed to quantify the spatial changes in FC in the host sediment and thus to capture the fines migration during depressurization. It was found that the FC changes began occurring from the hydrate dissociation regions. This confirms that the multiphase flow caused by depressurization accompanies fines migration. Depressurization of HBS with a hydrate saturation of ~20–40% caused FC reduction from ~10% to ~6–9%, and the extent of fines migration differed with the particle sizes of the host sands and the types of fines. It was found that fines migration was more pronounced with coarse sands and with silty fines. Such observed level of FC reduction is estimated to increase sediment permeability by several factors based on the Kozeny-type permeability model. In conclusion, our results support the notion that the extent of fines migration and its effect on fluid flow behavior need to be assessed in consideration of physical properties of host sediment and fine particles to identify optimum depressurization strategies.

42 ENGINEERING↗