The stability of Haynes 230 and Hastelloy C-276 nickel alloys exposed to high temperature molten salt with trace contaminants (i.e., water and oxygen) is found to be acceptable for using these metals to house anaerobic MgCl2-KCl and NaCl-KCl-ZnCl2 molten salts at 800oC. The corrosion rate determined by gravimetric tests range from -98 µm/year to 20. 13 µm/year at 800˚C. The corrosion rate is estimated to be 16.14 µm/year for Haynes 230 and 10.03 µm/year for Hastelloy C-276 based on the weight loss and surface area of the coupons when the coupons of Haynes 230 and Hastelloy C-276 alloys are immersed in molten MgCl2-KCl salt in sealed quartz containers and left in an oven at a temperature of 800˚C up to 16 days. The corrosion rate is estimated to be -20.46 µm/year for Haynes 230 and -7.36 µm/year for Hastelloy C-276 based on the weight loss and surface area of the coupons when the alloys are immersed in molten NaCl-KCl-ZnCl2 salt in sealed quartz containers and left in an oven at 800˚C up to 56 days. The corrosion rate of the alloys are well below the DOE requirement of 50 µm/year for the alloys in molten chloride salts to be considered acceptably stable. Ultimate tensile strength (UTS) after immersion of Haynes 230 and Hastelloy C-276 in molten salt ranged from 634 MPa to 860 MPa. The UTS of Haynes 230 is estimated to be 642 MPa after exposure to NaCl-KCl-ZnCl2 for 4 weeks at 800˚c and 841 MPa after exposure to MgCl2-KCl for 4 weeks at 800˚c compared to an untreated sample which achieved a UTS of 851 MPa. Likewise, the UTS of Hastelloy C-276 is estimated to be 692 MPa after exposure to NaCl-KCl-ZnCl2 for 4 weeks at 800˚c and 842 MPa after exposure to MgCl2-KCl for 4 weeks at 800˚c compared to an untreated sample which achieved a UTS of 830 MPa. Molten chloride salts, such as NaCl-KCl-ZnCl2 and KCl-MgCl2, are pretreated by heating and bubbling dry Argon gas in the salt in order to remove oxygen and water and thereby reduce the corrosion of metal containers of molten salt. Monitoring the relative humidity and percent oxygen of the exhaust gas during the sparging of dry Argon at 240 sccm into 150 g of molten chloride salt at 500˚C for NaCl-KCl-ZnCl2 and 700˚C for KCl-MgCl2 allows an estimation time to reach a low level of oxygen and water in the salt and to estimate the amount of oxygen and water removed. Results show water is more difficult to remove than oxygen from the salt. Ten minutes of sparging with dry argon brings oxygen content of exhuast gas to<0.1% O2. Approximately fifty minutes of sparging leaves the exhaust gas only containing<0.7% RH. The total moles of oxygen removed from the salts are estimated to be 0.0043 moles for molten NaCl-KCl-ZnCl2 and 0.0076 moles for KCl-MgCl2. The total moles of water removed from the NaCl-KCl-ZnCl2 salt is estimated to be 0.016108379 moles and 0.002321214 moles from molten KCl-MgCl2.

CH3Br and CH3Cl (methyl halides) are the most abundant natural vectors of bromine and chlorine into the stratosphere and play an important role in stratospheric ozone destruction. The current knowledge of their respective natural sources is incomplete leading to large uncertainties in their global budgets. Beside the issue of quantification, characterisation of possible sources is needed to assist modelling of future environmental change impacts on these sources and hence the stratosphere. This study describes measurements conducted at two temperate salt marsh and three temperate forest sites in Scotland, and one tropical rainforest site in Malaysian Borneo to quantify and characterise natural methyl halide producing processes in these respective ecosystems. Measurements were conducted with static enclosure techniques, and methyl halide fluxes were calculated from the concentration difference between blank/background and afterenclosure samples. Methyl halide concentrations were determined via oxygen-doped GCECD with a custom-built pre-concentration unit. External factors such as photosyntheticallyactive radiation (PAR), total solar radiation, air temperature, soil temperature, internal chamber temperature and soil moisture were recorded in parallel to the enclosures to determine possible dependencies. Salt marsh studies were carried out at Heckie’s Hole in East Lothian, and Hollands Farmin East Dumfriesshire for 2 years. The study subjects were salt marsh plants that were enclosed during daylight hours in transparent enclosures for 10min each at 2–4 week intervals throughout the year. Parallel to this monitoring programme, systematic manipulation experiments and diurnal studies were carried out to learn more about the possible influence of potential drivers such as sunlight and temperature. Mean annual net fluxes ( standard deviation (sd)) were 300 44 ngm-2 h-1 for CH3Br and 660 270 ngm-2 h-1 for CH3Cl, with fluxes of both gases following a diurnal as well as an annual cycle, being lowest during winter nights and highest during summer days. A possible link between variations of daytime fluxes over the course of a year and changes in temperature was found. CH3Cl and CH3Br fluxes were positively correlated to each other and average fluxes of CH3Cl were linked to dry mass of certain species such as Puccinellia maritima, Aster tripolium, Juncus gerardi and Plantago maritima as found at the different measurement locations. No link between methyl halide fluxes and total halogen content or halogen concentration of the enclosed vegetation was found. Work in temperate forests was carried out for over one year at Fir Links, a mixed beech/ sycamore forest in East Lothian, and on one occasion each in Griffin Forest, a sitka spruce plantation in Perthshire, and finally the Hermitage of Braid, a mixed woodland park in Edinburgh. The study subject was leaf and needle litter which was enclosed in opaque 12 L containers for 10min–24h. During enclosure, internal chamber temperature was recorded, and leaf/needle litter water content was determined after enclosure. Combined average CH3Br and CH3Cl fluxes from temperate forest litter were 4.3 10-3 ngg-1 h-1 and 0.91 ngg-1 h-1, respectively. Average fluxes measured from leaf and needle litter were comparable in magnitude and CH3Br and CH3Cl were positively correlated. However no correlation of methyl halide fluxes to either temperature or litter water content was observed. Work at Danum Valley inMalaysian Borneo focused on flux measurements from both trees and leaf litter in a tropical dipterocarp forest. Fluxes from tropical trees were measured with transparent branch chambers at 20min enclosure times whilst methyl halide fluxes from leaf litter were measured with opaque 12 L containers at 24h enclosure times. Mean CH3Br and CH3Cl fluxes from branch enclosures were 0.53 ngg-1 h-1 and 27 ngg-1 h-1, respectively, and CH3Br and CH3Cl fluxes from tropical leaf litter were 1.4 10-3 ngg-1 h-1 and 2.3 ngg-1 h-1 respectively. Again fluxes of CH3Br and CH3Cl were positively correlated but no direct environmental driver for flux variations was found. The magnitude of methyl halide fluxes was species specific with individuals of the genus Shorea generally producing large amounts of methyl halide. Tropical rainforests were confirmed to be potentially the largest single natural source of CH3Cl. Global estimates were derived from extrapolating measured fluxes from the respective global land cover areas. These estimates suggest that the ecosystems examined in this study could account for over 1/3 of global CH3Cl production and up to 13%of global CH3Br production in nature. The ratio of CH3Br to CH3Cl emissions for these ecosystems is likely to be dependent on the abundance of bromine in the plant material with higher bromine content boosting CH3Br production and suppressing CH3Cl production. For this reason salt marshes are only a very minor source of CH3Cl.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24000号 / エネ博第436号 / 新制||エネ||82(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 野平 俊之, 教授 萩原 理加, 教授 佐川 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

A breed-and-burn molten salt reactor (BBMSR) concept is proposed to address the Generation IV fuel cycle sustainability objective in a once-through cycle with low enrichment and no reprocessing. The BBMSR uses separate fuel and coolant molten salts, with the fuel contained in assemblies of individual tubes that can be shuffled and reclad periodically to enable high burnup. In this dual-salt configuration, the BBMSR may overcome several limitations of previous breed-and-burn (B$\&$B) designs to achieve high uranium utilisation with a simple, passively safe design. A central challenge in design of the BBMSR fuel is balancing the neutronic requirement of large fuel volume fraction for B$\&$B mode with the thermal-hydraulic requirements for safe and economically competitive reactor operation. Natural convection of liquid fuel within the tubes aids heat transfer to the coolant, and a systematic approach is developed to efficiently model this complex effect. Computational fluid dynamics modelling is performed to characterise the unique physics of the system and produce a new heat transfer correlation, which is used alongside established correlations in a numerical model. A design framework is built around this numerical model to iteratively search for the limiting power density of a given fuel and channel geometry, applying several defined temperature and operational constraints. It is found that the trade-offs between power density, core pressure drop, and pumping power are lessened by directing the flow of coolant downwards through the channel. Fuel configurations that satisfy both neutronic and thermal-hydraulic objectives are identified for natural, 5$\%$ enriched, and 20$\%$ enriched uranium feed fuel. B$\&$B operation is achievable in the natural and 5$\%$ enriched versions, with power densities of 73 W/cm$^3$ and 86 W/cm$^3$, and theoretical uranium utilisations of 300 $\mathrm{MWd/kgU_{NAT}}$ and 25.5 $\mathrm{MWd/kgU_{NAT}}$, respectively. Using 20$\%$ enriched feed fuel relaxes neutronic constraints so a wider range of fuel configurations can be considered, but there is a strong inverse correlation between power density and uranium utilisation. The fuel design study demonstrates the flexibility of the BBMSR concept to operate along a spectrum of modes ranging from high fuel utilisation at moderate power density using natural uranium feed fuel, to high power density and moderate utilisation using 20$\%$ uranium enrichment.

Concentrating Solar Power (CSP) is one of the most promising renewable energybased electricity generation technologies to deal with the increasing demand of power consumption and environmental sustainability. With the aim of achieving the 2020 SunShot cost target for CSP of 60 USD/MWh, the United States Department of Energy presented, in May 2018, the Gen3 CSP initiative. In particular, the CSP Gen3 Liquid-Phase Pathway proposes to design a CSP system adopting liquid sodium as Heat Transfer Fluid (HTF) in the receiver, advanced high-temperature molten chloride salt as storage fluid and supercritical CO2 (sCO2) Brayton cycle as power cycle. Within this framework, the aim of this master thesis was to design the sodium-chloride salt Heat Exchanger (HX) by developing both a heat exchanger model and a sodiumsalt-sCO2 system model. To pursue these purposes, a completely new Modelica-based HX model was developed and added to the SolarTherm library. Furthermore, as an extension of earlier models, the sodium-salt-sCO2 CSP system (NaSaltsCO2System) was implemented in SolarTherm, by incorporating the HX model and linking it with other new and existing component models. As for the HX, a general model was developed for shell and tube heat exchangers, based on the TEMA guidelines, with the possibility of being customized in terms of media adopted, constraints, boundary conditions, and correlations. The model performs an optimization in order to select the internal geometry configuration that optimizes a user-defined objective-function. By employing the implemented HX model in the NaSaltsCO2System, the sodium-salt heat exchanger was designed aiming at minimizing the Levelized Cost of Electricity (LCOE), providing a complete geometry description, and an estimation of the performances and costs. The resulting NaSaltsCO2System model was found to be robust and able to perform annual simulations that allowed to estimate the energy performances of the CSP plant, as well as the LCOE. Considering the sodium-salt-sCO2 CSP system characterized by a receiver capacity of 543 MWth, 12 hours of Thermal Energy Storage (TES), and a 100 MWe power block, the LCOE resulted equal to 72.66 USD/MWh. The sodium-salt HX design that minimizes the LCOE resulted in a single-shell/single tube pass configuration, with vertical alignment, characterized by an overall height of 15 m, and a shell diameter of 1.8 m. It represents the 3.2% of the total capital cost of the plant. An interesting system-level optimization was then carried out on the combined receiver-heat exchanger block. It regarded the variation of the Log Mean Temperature Difference (LMTD) of the HX and highlighted the possibility to drop the LCOE down to 68.54 USD/MWh. The techno-economic investigations and the sensitivity analysis showed the flexibility and robustness of the HX model, as well as the importance of the NaSaltsCO2System. The latter lays the groundwork to explore potential improvements of this new generation of CSP systems, which can play a fundamental role in the future global energy mix. / Termisk solkraft (CSP) är en av de mest lovande elproduktionsteknologierna baserade på förnybar energi. Den kan bidra till hanteringen av den ökande efterfrågan på energi och miljömässig hållbarhet. I syfte att uppnå 2020 SunShot-kostnadsmålet för CSP på 60 USD/MWh presenterade USA:s energidepartement Gen3 CSPinitiativet. I synnerhet föreslår CSP Gen Liquid-Phase Pathway att utforma ett CSPsystem som använder flytande natrium som värmeöverföringsvätska i mottagaren, smält kloridsalt med hög temperatur som lagringsvätska, samt superkritisk CO2 (sCO2) Brayton-cykel som kraftcykel. Syftet för detta examensarbete var att utforma natriumkloridsaltets primära värmeväxlare genom att utveckla både en värmeväxlarmodell (HX) modell och en natriumsalt-sCO2-systemmodell. För att fullfölja dessa syften utvecklades HX-modellen först, sedan implementerades natriumsalt-sCO2 CSP-systemet NaSaltsCO2System. Båda verktygen utvecklades med hjälp av Modelica som programmeringsspråk. De finns nu tillgängliga i det öppna SolarTherm-biblioteket. När det gäller HX utvecklades en allmän modell för skal- och rörvärmeväxlare med möjligheten att anpassas när det gäller antagna medium, begränsningar, gränsvillkor och korrelationer. Dessutom utförde modellen en optimering för att välja den interna geometri-konfigurationen som optimerar en användardefinierad objektiv-funktion. Genom att använda den implementerade HX-modellen i NaSaltsCO2System designades natriumsalt-värmeväxlaren, vilket gav en fullständig konfiguration-beskrivning och en uppskattning av prestanda och kostnader. Den utvecklade NaSaltsCO2System-modellen visade sig vara robust och kapabel till att utföra simuleringar på årsbasis. Detta gjorde det möjligt att uppskatta CSP-anläggningens energiprestanda samt LCOE. Det utvecklade natriumsalt-sCO2 CSP-systemet som känneteckna des av en mottagarkapacitet på 543 MWth, 12 timmars TES och ett 100 MWe power block, resulterade i en LCOE på 72.66 USD/MWh. Natrium-salt HX-konstruktionen som minimerade LCOE resulterade i en enskalig/enkel rörpassningskonfiguration, med vertikal inriktning, kännetecknad av en total höjd av 15 m och en skaldiameter på 1.8 m. Det motsvarade 3.2% av anläggningens totala kapitalkostnad. Den mest intressanta systemoptimeringen genomfördes på det kombinerade blocket bestående av mottagare och värmeväxlare. Den behandlade variationen av HX:s LMTD och framhöll möjligheten att sänka LCOE till 68.54 USD/MWh. De teknisk-ekonomiska undersökningarna och känslighetsanalysen visade flexibiliteten och robustheten i HX-modellen, liksom vikten av NaSaltsCO2Systemet. Den senare lägger grunden för att utforska potentiella förbättringar av denna nya generation av CSP-system, som kan spela en grundläggande roll i den framtida globala energimixen.