Delayed Hydride Cracking in Irradiated and Unirradiated Zircaloy-2 Cladding

Zirconium alloys used in the nuclear industry are exposed to extreme conditions undergoing high levels of irradiation damage and corrosion. Zircaloy-2 is used as nuclear fuel cladding in boiling water reactors and for the encapsulation of the spallation target in the neutron source SINQ at the Paul Scherrer Institute. As a result of oxidation, hydrogen is produced and partially taken up into the zirconium matrix. As the hydrogen reaches the solubility limit, it precipitates in the form of a zirconium hydride. A number of deleterious effects of hydrides have been extensively studied, including the embrittlement of the material and a unique cracking phenomenon, namely delayed hydride cracking (DHC). DHC occurs as hydrogen in solid solution diffuses towards locations of higher tensile stress, where it subsequently precipitates as the local solvus limit is reached. Once the hydride grows to a critical size, it fractures, which can continue to propagate in repeated steps by the same mechanism.Several studies have been performed in order to understand properties of DHC based on parameters like, alloy type, cracking temperature, hydrogen content, and cracking direction. The most important mechanical properties include the fracture toughness and cracking velocity, which governs the material failure conditions. Crystallographic properties have been investigated in order to understand how complex hydride precipitation develops within the context of DHC conditions. In this project, radial DHC is explored in irradiated and unirradiated thin-walled Zircaloy-2 nuclear fuel cladding with and without an inner liner, in addition to spallation target rod material. A unique three-point bending test, applicable also for irradiated samples in the hotlab, was developed to induce a consistent radially propagating outside-in crack. Results have provided insight into the effects of the inner liner on cracking velocity, showing correlations with the hydrogen depletion. The combined DHC and creep mechanisms, which cannot be decoupled, is coined as âcreep-delayed hydride crackingâ. As the initiating conditions for DHC are of great technical importance, the threshold stress intensity factor has been investigated, under ideal DHC conditions, where a minimum value occurs around 6 MPaâm. Quantitative analysis of the hydrogen distribution around the tip of an arrested DHC crack tip has been performed with neutron radiography at the SINQ. Trends show that the hydrogen concentration around the crack tip increases with temperature resulting likely from the larger hydrogen diffusion, and that the liner reduces the hydrogen available for DHC. Crystallographic analysis has provided insight on the hydride phases responsible for DHC with synchrotron micro X-ray diffraction, performed at the Swiss Light Source at PSI. The results directly suggest that the Î³-hydride is a stable phase precipitated at low temperatures. Testing of irradiated material provided insight into the crack initiation of DHC as a result of the strongly irregular outer surface generated from the oxidation. The propagation pattern is highly irregular compared to the unirradiated material due to the embrittled nature of the cladding from irradiation damage.

Decreasing the Stability of Borohydride with Ionic Liquids for Hydrogen Storage and Carbon Dioxide Conversion

Loris Giovanni Lombardo

The world needs to move from a fossil fuel to a renewable energy based society. With the increasing electricity production from wind and PV, short and long term energy storage are becoming one of challenge of the 21st century. While batteries are the preferred method for short term storage, another technology is required for seasonal storage. Hydrogen is a valuable energy carrier owning its high energy density (122 kJ/g). However, compact and safe storage of H2 is challenging. The current solution is to compress hydrogen up to 700 bar for mobile application (fuel cell cars), and metal hydrides for stationary application. Material-based H2 storage avoids using high-pressure cylinder. Complex hydrides are especially attractive for solid-state H2 storage due to their high gravimetric and volumetric hydrogen density. Sodium borohydride (NaBH4) contains 10.6 mass% of H2, but high temperatures are needed to release H2 (505 Â°C) and the reaction is not reversible under moderate conditions. To apply complex hydrides in real applications, they must be modified to improve the kinetics and thermodynamics of H2 desorption. Several possibilities exist such as confinement into scaffolds, catalyst addition, or combination of several hydrides to modify the dehydrogenation pathway. The stability of complex hydrides is determined by the localization of the charge on the central atom of the complex. Therefore, in this thesis the interaction of highly polar or ionic compounds with complex hydrides were investigated. We combine NaBH4 with a special class of organic salts: ionic liquids (IL). Considering their chemical and thermal stability, IL are attractive additive. Using organic additives instead of expensive metal catalysts is another advantage. Two different techniques were employed to combine the IL and NaBH4. The first one consists of mechanochemically milling them to create an interaction between BH4- and IL. The second one is to directly synthesized IL borohydrides ([IL][BH4]) by metathesis reaction. Different ILs, such as vinylbenzyltrimethylammonium chloride ([VBTMA][Cl]), 1-butyl-3-methylimidazolium chloride ([bmim][Cl]), and 1-ethyl-1-methylpyrrolidinium bromide ([EMPY][Br]) were tested. [bmim][BH4] was able to release H2 below 100 Â°C. The hydrogen content ranges between 2.4 mass% and 2.9 mass%. The second challenge of this century is the CO2 problematic. Atmospheric CO2 concentration linearly increases, leading to greenhouse effect. Carbon capture and sequestration (CCS) and utilization (CCU) are primordial research topic to stabilize the CO2 emission. Hydrides are primary reducing agents, thus reduction of CO2 can be accomplished with them. Direct CO2 reduction at ambient conditions is challenging for classical borohydrides. With our [IL][BH4], gaseous CO2 can be captured and reduced under ambient conditions (1 bar, RT). Three CO2 bounds with boron to give triformatoborohydride ([HB(OCHO)3]â. Dilute CO2 (6 vol%) can be used as well. The reaction was followed in real time with a magnetic suspended balance (MSB). Further, CO2 reduction happened when air is used as a carbon dioxide source. Formic acid can be obtained by adding HCl. Thus, ionic liquid borohydrides have great potential as a CO2 absorber and reducer to alternative fuels. In short, we applied ionic liquid to destabilized borohydrides. The resulting materials exhibited potential for solid-state hydrogen storage, as well as CO2 capture and transformation.

EPFL2021

Water-soluble (eta(6)-arene)ruthenium(II)-phosphine complexes and their catalytic activity in the hydrogenation of bicarbonate in aqueous solution

Gabor Laurenczy

The reactions of (eta(6)-C6H6)RuCl2 and (eta(6)-p-cymene)RuCl2 With hydrogen in the presence of the water-soluble phosphines tppts (meta-trisulfonated triphenylphosphine) and pta (1,3,5-triaza-7-phosphaadamantane) afforded as the main species (eta(6)- C6H6)RuH(tppts)(2), (eta(6)-C6H6)RuH(pta)(2), (eta(6)-p-cymene)RuH(tppts)(2) and (eta(6)-p-cymene)RuH(pta)(2). This latter complex was also formed in the reaction of [(eta(6)-p-cymene)RuCl2(pta)] and hydrogen with a redistribution of pta. In addition, prolonged hydrogenation at elevated temperatures and in the presence of excess of pta led to the formation of the arene-free [RuH(pta)(4)CI], RuH(pta)(4)(H2O), [RuH2(pta)(4)] and RuH(pta)(5) complexes. Ru-hydrides, such as (eta6-arene)RuH(L)(2), catalyzed the hydrogenation of bicarbonate to formate in aqueous solutions at p(H-2) = 100 bar, T = 50-70 degreesC. (C) 2004 Elsevier B.V. All rights reserved.

2004

Porosity in Aluminum Alloys

Milan Felberbaum

Porosity is one of the major defects in castings because it reduces the mechanical properties of a cast piece [1]. Porosity formation results from the effect of two concomitant mechanisms, namely solidification shrinkage and segregation/precipitation of gases [1]. A model for the prediction of microporosity, macroporosity and pipe shrinkage during the solidification of alloys has been developed at the Computational Materials Laboratory (LSMX-EPFL) [2]. This model has then been improved by taking into account the effect of various alloying elements and gases on porosity formation [3, 4, 5]. However, the modeling of two physical phenomena still needed to be improved: (i) the curvature influence and (ii) the hydrogen diffusion influence on the growth of pores. The effect of pinching, i.e. the pores are forced by the growing solid network to adopt a complex non spherical shape, induces curvature restriction to the pores. This pinching effect can be a limiting factor for the growth of pores and is too simply modeled in the model of Péquet et al. [2]. Several other pinching models exist, but a rigorous experimental study to validate either one of these models is needed. Additionally, Carlson et al. [6] have recently shown that hydrogen diffusion might also be a limiting factor for the growth of pores. In the model of Péquet et al. [2], this effect was not taken into account. This thesis is mainly aimed to (i) provide experimental results that specifically validate the pinching model developed by Couturier et al. [4], (ii) investigate the influence of hydrogen diffusion on the growth of pores and (iii) provide a new model that takes into account the pinching effect and the hydrogen diffusion influence on the growth of pores. At first, pores formed in aluminum-copper (Al-Cu) samples (cast under controlled conditions) have been analyzed using high resolution X-ray tomography. The influence of the alloy inoculant, copper content, cooling rate and initial hydrogen content on the morphology of pores has been investigated. The results show that the curvature of micropores pinched in either non-inoculated or inoculated Al-4.5wt%Cu alloys can be fairly well approximated to that of cylinders. The results also show that the pinching model must be function of (i) the volume fraction of the primary phase gα and (ii) the secondary dendrite arm spacing λ2. However, the influence of the initial hydrogen content appears to be negligible. The pinching model developed by Couturier et al. [4] accounts for these observations and their relation fits fairly well the average mean curvature value of our experimental data. A new model has been developed to calculate an effective hydrogen diffusion coefficient De(gs), that is a function of the volume fraction of solid only. For that purpose, in-situ X-ray tomography has been performed on Al-Cu alloys. For each volume fraction of solid 0.6 ≤ gs ≤ 0.9, a representative volume element of the microstructure has been obtained from the tomography data. Solid and liquid voxels being assimilated to solid and liquid nodes respectively, a hydrogen diffusion equation has then been solved numerically. Calculations have been run until steady-state was reached in order to deduce De(gs) and the simulation results were successfully compared with a new theory based on effective-medium approximations. Both approaches lead to the main conclusion that hydrogen diffusion through the solid phase cannot be neglected, unlike it is assumed in the model of Carlson et al. [6]. Next, using the pinching model of Couturier et al. [4] and the obtained De(gs), a new volume-averaged model has been developed in order to simulate the growth of pores limited by (i) the curvature of the pore phase and (ii) the diffusion of hydrogen. The results show that, although hydrogen diffusion can be a limiting factor for the growth of pores, the pinching effect has a much larger influence. Accordingly, any model for porosity prediction should carefully take into account the influence of curvature and hydrogen diffusion on the growth of pores. In order to ripen this study at a refined scale, a 2D phase-field model has been developed to describe the complex shape of a pore formed within interdendritic liquid channels [7]. The influence of the solid, which can force the pore to adopt a non-spherical shape, is taken into account through the geometry of the domain and appropriate boundary conditions. This model accounts for curvature influence and hydrogen diffusion in the liquid, two of the main aspects governing the growth kinetics of a pore. However, the model still needs to be combined with a description of the liquid flow induced by the pore growth. Basically, this model should serve as a sound basis for further developments that might lead to more sophisticated pinching models. Finally, an experimental study has been conducted in order to track the inoculant influence on the shape of pipe shrinkage. Simultaneously, pipe shrinkage calculations (using the model of Péquet et al. [2]) were performed in order to track the influence of the gs,c parameter on the shape of the pipe shrinkage. This gs,c parameter corresponds to the critical volume fraction of solid at which mass feeding stops. Comparisons between experimental and simulation results show that the gs,c parameter should be set equal to 0.6 or 0.1 for a casting simulation of an inoculated or non-inoculated alloy, respectively.