Submicro- and Nano-Structured Porous Materials for Production of High-Intensity Exotic Radioactive Ion Beams

ISOLDE, the CERN Isotope Separator On-line DEvice is a unique source of low energy beams of radioactive isotopes - atomic nuclei that have too many or too few neutrons to be stable. The facility is like a small 'chemical factory', giving the possibility of changing one element to another, by selecting the atomic mass of the required isotope beam in the mass separator, rather as the 'alchemists' once imagined. It produces a total of more than 1000 different isotopes from helium to radium, with half-lives down to milliseconds, by impinging a 1.4 GeV proton beam from the Proton Synchrotron Booster (PSB) onto special targets, yielding a wide variety of atomic fragments. Different components then extract the nuclei and separate them according to mass. The post-accelerator REX (Radioactive beam EXperiment) at ISOLDE accelerates the radioactive beams up to 3 MeV/u for many experiments. A wide international user radioactive ion beam (RIB) community investigates fundamental aspects of nuclear physics, particle and atomic physics, solid-state physics, materials science, astrophysics, biophysics and medicine. However, there are still a number of radioactive isotopes which are not accessible for experimental physics, either because it has been impossible to produce the element of interest, too low yields (number of isotopes per second measured in the beam line) are obtained or due to the higher post-acceleration energies required for the user's experiments. The aim of this thesis was to synthesize oxide and carbide porous materials, to be used as thick targets to increase the intensity of exotic RIBs. This was done by the evaluation of their radioactive isotope release properties and of their stability under irradiation conditions at high temperatures. This thesis is focused on the study of the chemical and physical processes occurring in the target system where the isotopes are produced, before these enter the ion-source system, are mass-separated and are sent to the user beam lines. The products formed in nuclear reactions between a proton beam and the target must, at a first step, diffuse from the interior of the target out to the surface and evaporate from it. Minimum delay times for the diffusion process can be realized by achieving the shortest diffusion lengths of highly-permeable, low-density, open-structure targets and by operating at the highest possible temperature so that release times are minimized and commensurate with the half-life of the isotopes of interest. Whereas until now target materials with micro-scale structures have been synthesized and used for RIB production, new porous submicro- and nano-structured materials offer the advantage of having lower diffusion activation energy of atoms and thus larger diffusion coefficient than the corresponding bulk counterpart, thanks to the increase of surface to volume ratio of these materials. The potential of this phenomenon for isotope mass separation online (ISOL) targets and many other applications is an evident drop of temperature to maintain a fast diffusion process, and higher release efficiency for the production of intense exotic isotope beams. In Chapter 1 the ISOL technique and the RIB production issues are introduced, followed by a review of recent progresses on target materials to increase yield production in the principal existing and next-generation ISOL and In-Flight facilities worldwide. Chapter 2 gives the theoretical fundamentals of diffusion and effusion in solid materials, and addresses specifically diffusion, effusion and release properties of ISOL targets. The study presented in Chapter 3 consists in the evaluation of release properties in different polycrystalline silicon carbide samples. The diffusion coefficients for Be, Na, Mg and F isotopes were extracted from off-line release measurements done at ISOLDE. The full characterization of the release time structure inherent to the physical and chemical processes of the ISOL RIB production on a submicrometric SiC target material (target SiC #334) used at ISOLDE, was made. This last target development resulted in improvement of magnesium short-lived isotopes yields. This was the first demonstration of the successful use of a submicrometric porous material as an ISOL target material, which delivered unprecedented 8x104 21Mg ions per µC. In Chapter 4, the synthesis of porous submicro- and nano-structured alumina to be used as an ISOL target, was followed by materials characterization in terms of microstructure and related with selected isotope release properties. Whenever possible, the release mechanisms were explained or proposed. The approach is relevant for the study of microstructure effects in other solid porous oxide and carbide targets, for optimization of their release performance. Chapter 5 shows the results of the TARPIPE experiment, set up within the design study task of the foreseen ISOL-type European facility called EURISOL, to investigate proton irradiation damage on typical and novel ISOL target materials under continuous proton irradiation at high temperature (> 1273 K). Materials such as SiC, Al2O3, Y2O3, C and Ta in a variety of forms were irradiated at the 72 MeV proton irradiation station of injector 1 at PSI (Paul Scherrer Institute). The effects of radiation damage on these materials were evaluated from microstructure and chemical analyses before and after irradiation by visual inspection, gamma spectroscopy, scanning electronic microscopy and electron dispersive X-ray analysis on a case-by-case basis. The moderate structure evolution of the porous oxide and carbide samples tested confirms that these materials are good candidates for high-power solid targets to be used at the existing and next generation high-power ISOL facilities, such as TRIUMF (TRI-University Meson Facility) and EURISOL (EURopean Isotope Separator On-line). In Chapter 6, the development and testing of a composite high-power alumina target for neon isotope production associated to a cold FEBIAD ion-source exposed to unprecedented proton beam intensities is reported. A 0.5 GeV proton beam from TRIUMF was used up to 25 µA, a factor 10 with respect to the present oxide targets in operation. The yields obtained were compared to the ones delivered by using a 70 µA proton beam in SiC targets at this facility. The target performance in terms of diffusion properties was evaluated. A general conclusion and discussion are given in Chapter 7. The release studies obtained with irradiation and ion implantation techniques on prospective SiC and Al2O3 matrices resulted in the identification of alternative target matrices for fast radioisotope release; this was confirmed experimentally from Na and Mg elements release efficiency determined online for a SiC target. A high-power oxide/metal composite target made of micrometric structural length scale Al2O3 pellets and Nb foils was operated online at unprecedented beam power intensities. Composite targets made of Nb foils and submicro- and nano-structured porous Al2O3 are expected to further increase yields of exotic isotopes. This ISOL target concept can be applied in the future for many other refractory insulating ceramics by using gradient microstructures and/or different ceramic/metallic combinations. Special care has to be taken, in order to minimize the stress induced by a mismatch of the coefficient of thermal expansion in the different ceramic layers and/or the underlying metallic substrate. Micro- and nano-technology fabrication techniques can be used to tailor pore and grain size distribution in ceramic and metallic complex-shaped composite materials and to shape these in compacts, monoliths and fenestrated structures. A balance between large surface area and large macropore volume for optimum target radioisotope release performance must be achieved. The resulting target material must in addition be stable at high temperatures, have good thermo-mechanical resistance and high thermal conductivity under irradiation for long irradiation time. The understanding of isotope release mechanisms in different solid materials, including the porous and dense fast-ion conductors will contribute to the production of exotic RIB at unprecedented high-intensity.

Nanofibres de carbone sur filtre métallique comme support catalytique structuré

Pascal Tribolet

The main objectives of this work are 2-fold : The development of a novel type of composite material based on carbon nanofibers supported on sintered metal fibers filters (CNF/SMF) and to explore the use of this material as a catalytic support for a model reaction: selective hydrogenation of acetylene. The advantages of this novel support are: Due to carbon nanofibers, it combines a graphitic structure with a high specific surface area without microporosity. Supported carbon nanofibers can be used in a fixed bed reactor without very high pressure drop. Combination of two materials with high thermal conductivity gives a composite which keeps this property. It is suitable for highly exo/endothermic reactions, diminishing temperature gradients in the catalytic bed. The synthesis of carbon nanofibers on SMF filters was carried out by ethane catalytic decomposition at 655°C directly on metallic filters. An oxidation of SMF followed by a reduction in H2 create surface roughness, leading to a larger area for CNF nucleation. The CNF formation mechanism includes several steps: it starts with carbon deposition on metallic surface followed by its diffusion into the metal leading to carbides formation. When the limit of carbon solubility is attained, a layer of carbon is formed on the surface of metallic fibers. High tension within the bulk metal leads to carbide dissociation and by phase separation to graphite formation, which pushes the metallic particles through the carbon layer. Nickel, stainless steel an Inconel (an alloy of mainly nickel, iron and chromium) filters were used. The latter gave the highest uniformity of the carbon nanofibers layer showing an excellent mechanical stability. In order to control carbon deposition on the filters, a formal kinetic analysis of the decomposition reaction was undertaken. Partial orders of 1 for ethane, -2 for hydrogen and an apparent activation energy of 235 kJ/mol were obtained. The observed kinetics suggests strongly that the C – C bond scission is the rate determining step and not carbon diffusion into the metal which is often reported in the literature. The synthesis procedures like time on stream and reaction temperature were optimized: 1 hour of a mixture C2H6:H2:Ar (3:17:80) decomposition over SMFInconel at 655°C lead to ∼6% of carbon, leading to a CNF layer of 1 µm thickness covering the metallic fibers entirely. This material presents a high specific surface area (22.2 m2/g) and a low pressure drop for the gas flowing through. The carbon nanofibers have a diameter between 20 and 50 nm and a crystalline structure with platelets morphology where the graphene layers are stacked one above the other. Their surface is composed almost exclusively of carbon and hydrogen. Amongst the multiple possible applications of this novel composite material, its use as a catalyst support was assessed. Selective hydrogenation of acetylene was carried out over palladium supported on CNF/SMF and compared with commercial supports (ACF, EGF and AGF). The activated carbon fibers cloth (ACF) led to a Pd activity at least twice as E-type glass fibers tissue (EGF) or EGF covered by an alumina layer (AGF). Reaction kinetics was studied for Pd/ACF, leading to acetylene and hydrogen partial orders of -0.5 and 2.4, respectively and apparent activation energy of 50 kJ/mol. The negative partial order for C2H2 suggests high adsorption strength of this compound compared to other reagents on palladium. This particularity allows Pd to be selective. Hydrogenations are known to be structure sensitive. Therefore the catalyst activity for the model reaction depends on Pd particle size. It increases for large particle sizes. The control of this parameter was a priority. Variations of the palladium precursor, of the support and catalyst treatment were carried out. Micro-wave plasma was used since it is fast and has low energy consumption allowing chemically modifying the carbon support surface and activating catalyst after impregnation. This controls not only palladium sintering, but also decomposes tetraaminopalladate more efficiently, resulting in a catalyst activity of one order of magnitude higher. In order to control the palladium deposition on CNF/SMFInconel composite, it is important to have surface functional groups. The activation of carbon nanofibers was carried out with a 4 hours treatment in a boiling aqueous solution of hydrogen peroxide. This led to an amount on surface oxygen containing groups, per mass of carbon, higher than in ACF. Palladium particle size on the composite was controlled by support activation, the use of several metal precursors or different loadings or by a thermal treatment in argon at 500°C. Optimisation of the procedure allowed to obtain in a controlled way an average palladium particle sizes between 3.6 and 25 nm. The activity and selectivity towards ethylene of Pd/CNF/SMFInconel were observed to be higher compared to palladium supported on activated carbon, alumina or barite. Graphitic nature of carbon nanofibers, leading to strong metal-support interaction, was accounted as responsible for these improvements. The high thermal conductivity of the composite CNF/SMF ensured good heat transfer released due to the exothermicity of the reaction and allowed to work close to isothermal conditions in the catalytic bed. Finally it can be concluded, that for the first time carbon nanofibers synthesis was carried out in one step on sintered metal fibers filters, resulting in a novel structured composite material combining different specific properties and having promising potential applications.

EPFL2006

On the relationship between the microstructure and the mechanical properties of an ODS ferritic/martensitic steel

Amuthan Ramar

In the quest of materials for the first wall of the future fusion reactor, it has been shown that oxide dispersion strengthened (ODS) ferritic / martensitic (F/M) steels appear to be promising candidates. The inherent good mechanical properties supported by a good thermal conductivity, swelling resistance and low radiation damage accumulation of the base material, such as EUROFER97, are further enhanced by the presence of a fine dispersion of nanometric oxide particles. They would allow in principle for a higher operating temperature of the fusion reactor, above 550°C, which improves its thermal efficiency. In effect, their strength remains higher than the base material at high temperatures. There are however limitations to their application in the reactor, which relate to the intimate link between the microstructure and the mechanical properties. These limitations, such as an increased ductile to brittle transition temperature above room temperature relative to the base material, come directly from the role played by the oxide particles but also from their indirect impact on the overall microstructure, stemming from the procedure of elaboration of these materials. In addition, there is a lack of knowledge on their response to irradiation, which, even though it appears to be promising with a reduced irradiation induced hardening, is not very well understood. In this work we have developed and evaluated ferritic/martensitic steel, EUROFER97, strengthened by a dispersion of yttria particles. (1) The powder metallurgical process used to obtain it was optimized, (2) the basic mechanisms of hardening were identified and (3) the impact of irradiation on its microstructure and mechanical properties were investigated. In order to understand the behaviour of this class of material other oxide dispersion strengthened (ODS) ferritic/martensitic steels based on EUROFER97 and model alloys were also investigated. For the elaboration of the ODS steel the powders of atomized EUROFER97 and yttria are ball milled in a planetary ball mill and the material is compacted by hot isostatic pressing (HIP). The mechanical properties are evaluated by uniaxial tensile test, Charpy test and micro-indentation while the microstructure is investigated by optical microscopy, scanning electron microscopy and transmission electron microscopy. The focused ion beam (FIB) technique is also used. In the study of the ball milling it appears that the optimal time is 20 hours, as the X-ray peak broadening, crystallite size and hardness of the particles remain unchanged at longer times. Yttria nanoparticles clusters are no more detectable by X-ray after 2 hrs of milling, which is attributed here to their incorporation in the matrix, as opposed to dissolution in the matrix as is often suggested in the open literature. HR-TEM performed on the yttria particles before and after incorporation in the steel by ball milling shows that the yttria maintain its bcc equilibrium structure throughout the process. This could suggest that they are not dissolved during ball milling. We have clarified this point by a cross sectional examination of the EUROFER97 ball milled particles with 0.3wt% of yttria in an FIB. By X-ray EDS analysis it shows nanometric regions reach in yttrium and oxygen, which are the yttria particles embedded in the EUROFER97 particles, proving that they are not dissolved by ball milling. The mechanism at the origin of the alloy compaction during HIP was elaborated. The alloy compaction was done through HIPing at 1150°C for 2.5 hrs at a pressure of 190 MPa. This condition is shown to provide the highest bulk density, to a value close to 99.9%. In the optimization process, it is found that temperature plays a larger role than pressure for alloy compaction. The compaction appears to be mainly due to diffusion. Also, it appears that the ball milled particle size plays a major role in the alloy compaction. It is shown that smaller particles size induces better compaction, provided that the densification proceeds through diffusion flow. This further suggests to terminate the ball milling process by 20 hrs as the particles size reaches its minimum. The impact of the ball milling process on the mechanical properties was evaluated. EUROFER97 with and without ball milling, with and without oxide addition presents an average density around 99.8%. In the as received state, casted EUROFER97, atomized EUROFER97, ball milled EUROFER97 and ODS Yttria present microstructure morphology typical of tempered martensite, whereas ODS Ti presents a nano sized grain microstructure with an average grain size of 200 nm. Ball milling and HIPping does have a slight influence up to 400°C, due to the higher dislocation density induced by ball milling relative to casted EUROFER97. It becomes negligible above 400°C, since both casted and ball milled EUROFER97 present similar hardness and microstructure. In ODS Yttria, yttria presents an average particle size of 25 nm. In ODS Ti, Y-Ti-O presents an average particle size of 7 nm. In the following the identification of the hardening mechanisms in ODS F/M steels. A new model was developed to quantify the collective hardening due to different obstacles, assuming that they provide independent hardening mechanisms. The model helped identifying the dominating source of hardening in ODS F/M steels. The base of the model is the dispersion barrier strengthening model, which is given by Δσsparticle or defects = Mαμb(Nd)1/2 for the hardening due small defects or oxide particles and is given by Δσd-d = Mαμb(ρ)1/2 for the hardening due to dislocations. In this approximation, the total hardening is then given by Δσtotal = {(Δσd-d)2 + (Δσparticle or defects)2}1/2 . The model is used to explain the hardening due to oxides, dislocations and irradiation induced defects. It appears that dispersed oxides is dominating hardness up to 800°C, while following a heat treatment at 1000°C it is the dislocations that then dominate the hardness. Deformation mechanisms were investigated using differential strain rate experiments. The activation parameters, i.e. the activation volume and activation energy, were calculated. It appears that there is a decrease in the activation volume from room temperature to 400°C, which is less than 3%. At about 500°C there is a sudden drop in the activation volume that reaches a minimum at 600°C. With further increase in temperature, there is a significant raise in the activation volume. This abrupt decrease between 400°C and 600°C hints at a change in dislocation-rate controlling mechanism, marking two regimes, a low temperature one and a high temperature one. In situ TEM observations show that at low temperature the deformation is mainly due to the formation of the Orowan loops around the particle. At high temperature the activation energy is about 3.4 eV for ODS, whereas it is 1.3 eV for EUROFER97. The calculated activation energy corresponds well to the one of dislocation climb mechanism. This indicates that at high temperature the yttria particles could be overcome by climb, while at low temperature they are overcome by the Orowan mechanism. The peculiar response of the yield stress to irradiation for this class of material was rationalized using the total hardening model we developed. At a dose of 2 dpa, irradiation induced defects are higher in number density than the dispersed yttria particles, which although they are weaker than the yttria particles they can explain the significant hardening observed in the material. Conversely, the shallow impact of irradiation on ODS F/M steels at low doses, relative to base F/M steels, is explained by the fact that the amount of dispersoid is found to be higher than the density of irradiation induced defects.

EPFL2008

Fluid-structure thermal coupling and ablation effects in atmospheric entry

Ojas Joshi

This thesis deals with the modelling of fundamental aspects of the mission engineering, the physics, and the constraints of atmospheric entry of space vehicles. The aim of this work is to formulate a coupled approach for the modelling and the simulation of thermal fluid-structure interaction in atmospheric entries, taking into account the thermochemical and physical response of the material composing the solid structure. Numerous missions that aim to explore planets, comets or regions outside our galaxy are planned for the next few years. During the phase of entry into the atmosphere of a planet or a moon, space vehicles encounter extreme heating conditions that can damage the structure and the on-board equipment. A Thermal Protection System (TPS) is hence installed to insulate the vehicle’s internal parts from high temperatures and heat fluxes. Ablative materials, which are composed of high-temperature resistant fibre porous structure filled with an organic matrix, are often used to manufacture heat shields of high speed entry vehicles. The hot gas around the spacecraft transfers energy fluxes to the vehicle through the fluid-structure interface. The solid then reacts, with part of the heat being conducted in the deeper layers of the material, and part being absorbed by physical and chemical transformations of the material itself. The organic phase of the ablative material evaporates – this process is called pyrolysis – and these gases are blown into the outer flow, creating thus a protective layer. Moreover, the surface of the TPS may react with the atmospheric gases, consuming in this way a fraction of the material. A model for these two phenomena and the thermal fluid-structure interaction is proposed in this thesis. Numerical simulations are one of the most widely used tools to design the TPS, and a detailed mathematical model allows to reduce margins in the sizing. Atmosphere gases and the spacecraft structure form two distinct systems that interact through the external surface of the TPS, and through which energy and mass exchanges occur. Many computational tools exist to simulate the physics of each of the two domains. A higher level of accuracy is however achieved if the problem is approached in a coupled fashion, where each system takes into account the thermophysical response of the other. An innovative coupling algorithm, which includes the direct evaluation of the surface chemistry, is presented in this thesis. Using this coupling procedure, numerical simulations of the TPS of a European Space Agency project are performed and key parameters for the sizing of the heat shield are evaluated and discussed.

EPFL2013