Ionic transport in metal oxides is crucial for the functioning of a broad range of different components, such as heat resistant alloys designed for high temperature applications and oxide electrolytes in solid oxide fuel cells. This thesis presents results from in situ electrochemical studies of properties related to ionic transport in metal oxides that are important for their applications as protective oxides and ionic conductors. Heat resistant alloys of alumina-former type are known to form an adherent, slowly growing and protective aluminium oxide (Al2O3) scale that protects metals from chemical degradation at high temperature. In situ impedance spectroscopy was used to study highly pure and dense samples of a-alumina in the temperature range 400 – 1000 °C. It was shown that surface conduction on the sample could severely distort the measurement below 700 °C. The magnitude of the distortions appeared to be sensitive to the type of electrodes used. The use of a so-called guard electrode was shown to effectively block the surface conduction in the measurements. By varying the grain size of the sintered alpha-alumina samples, the influence of grain size on the overall conductivity of the a-alumina was studied. It was shown that the activation energy for conductivity increased as the grain size decreased. Molecular dynamics calculations were performed in order to elucidate whether Al- or O ions are dominant in the ionic conductivity of the alpha-alumina. Comparing the calculation and experimental results, the dominating charge carrier was suggested to be oxygen ions. Moreover, the ionic transport in thermally grown alumina-like oxide scales formed on a FeCrAl alloy was studied in situ by impedance spectroscopy between 600 and 1000 °C. It was shown that the properties of these scales differ largely from those of pure and dense alpha-alumina. Furthermore, the conductivity is mainly electronic, due to the multiphase/multilayer microstructure and substantial incorporation of species from the base metal. However, the diffusivity obtained from the ionic conductivity was in line with diffusion data in literature obtained by other methods such as thermogravimetry. Besides, the initial stage of oxidation of a number of Fe-, Ni- and Co-based alloys at temperatures between 500 and 800 °C was studied in situ by high temperature cyclic voltammetry, in which the oxygen activity was changed over a wide range. From the resulting voltammograms the redox reactions occurring on the alloy surface could be identified. It was concluded that the base metal oxidized readily on these alloys before a protective chromia- or alumina-like scale is formed. The base metal oxide is most likely incorporated into the more protective oxide. Further, the oxygen ionic conductivity of highly pure and fully dense yttria-stabilized zirconia produced by spark plasma sintering was studied by impedance spectroscopy. The aim was to evaluate intrinsic blocking effects on the ionic conduction associated with the space charge layer in the grain boundary region. It was observed that the ionic conductivity of the spark plasma sintered oxides is equal or slightly higher than what has been achieved by conventional sintering methods. In addition, it was shown that the specific grain boundary conductivity increases with decreasing grain size, which can be explained by a decreasing Schottky barrier height (i.e., decreasing blocking effect). The quantitative results from this work verify the space charge model describing the influence of grain size on the ionic conductivity of yttria-stabilized zirconia through dopant segregation and oxygen vacancy depletion along the grain boundaries. / QC 20100825

This Thesis is about the aging of FECRAL surface coatings. In this thesis various substrates have been investigated such as 16 Mo3, 304, 347, Sanicro 31, 800HT, Nikrothal 80 and Kanthal APMT. These substrates have been coated with different FeCrAl alloys, using two different coating methods spraying with (High Velocity Air Force) and welding with (Metal Inert Gas). The purpose of coating is to achieve specific properties of the layer without affecting the original properties of the substrate. Therefore, it is important to investigate the boundary layer between these two different materials to observe how the interdiffusion of different substances such as Cr, Al, Fe and C is affected, which is the purpose of this project. The method used to investigate this purpose was to expose these combinations in different temperatures and in different environments for different time intervals. Then, using LOM, SEM and EDS analysis, the change that the boundary layers have undergone is examined. Some calculations in DICTRA have also been performed to see if it was possible to find any connection between experimental data and simulation results. The result showed carburization of FeCrAl-coatings on 16Mo3 substrates which can lead to deterioration of mechanical properties in the substrates but also decreased corrosion resistance for the coated layers. The result has also shown that it is difficult to perform spraying for small cylindrical products. The reason for this may be the high powder dispersion and the expansion of certain products when spraying, which causes the layer to loosen due to the shrinkage followed by cooling. APMT sprayed with Nikrothal 80 has shown high porosity in the substrates and high interdiffusion of Fe and Ni. High Ni diffusion in low Al alloys such as K 198 may be a reason why the coated layer cannot optimally form the protective oxide. / Detta projekt handlar om åldring av FECRAL ytbeläggningar. I den här avhandlingen så har olika substrat blivit undersökta såsom 16Mo3, 304, 347, Sanicro 31, 800HT, Nikrothal 80 och Kanthal APMT. Dessa substrat har blivit belagda med olika FeCrAl legeringar, med hjälp av två olika beläggningsmetoder, påsprutning (High Velocity Air Force) och påsvetsning (Metal Inert Gas). Syftet med att materialet beläggs är att uppnå specifika egenskaper utan att påverka substratens ursprungliga egenskaper. Det är därför viktigt att undersöka gränsskiktet mellan dessa två olika material för att se hur interdiffusionen av olika element såsom Cr, Al, Fe och C påverkas av värmebehandling. Metoden som användes för att undersöka detta var att exponera dessa kombinationer i olika temperaturer och i olika miljöer för olika tidsintervall. Därefter med hjälp av LOM, SEM och EDS analys undersöktes förändringen som gränsskikten har genomgått. Några beräkningar i DICTRA har även utförts för att se om det var möjligt att hitta någon koppling mellan experimentella data och simuleringsresultatet. Resultaten visade att 16Mo3 kombinationer fått en tydlig hög uppkolning i skiktet vilket kan påverka mekaniska egenskaperna och korrosionbeständigheten under användning vid höga temperaturer. Resultatet har även visat att det är svårt att utföra påsprutning för små cylindriska produkter. Anledningen till detta kan vara hög pulverspridningen samt den termiska expansionen av vissa produkter vid påsprutning som leder till att skiktet kan lossna på grund av krympningen vid svalning. APMT påsprutad med Nikrothal 80 har visat hög porositet i substraten och hög interdiffusion av Fe, Al och Ni under exponering vid 1200°C. Hög uppblandning och diffusion av nickel för det FECRAL belagda skiktet med relativt låg halt av aluminium K 198 kan vara en anledning till att belagda skiktet inte kan forma en skyddande oxid på ett optimalt sätt.

The use of renewable wood-based fuel has been increasing in the last few decades because it is said to be carbon neutral. However, wood-based fuel, and especially used wood (also known as recycled wood or waste wood), is more corrosive than virgin wood (forest fuel), because of higher amounts of chlorine and heavy metals. These elements increase the corrosion problems at the furnace walls where the oxygen level is low. Corrosion mechanisms are usually investigated at the superheaters where the temperature of the material and the oxygen level is higher than at the furnace walls.  Much less work has been performed on furnace wall corrosion in wood or used wood fired boilers, which is the reason for this project.    Tests are also mostly performed under simplified conditions in laboratories, making the results easier to interpret.  In power plants the interpretation is more complicated. Difficulties in the study of corrosion processes are caused by several factors such as deposit composition, flue gas composition, boiler design, and combustion characteristics and so on. Therefore, the laboratory tests should be a complement to the field test ones. This doctoral project involved in-situ testing at the furnace wall of power boilers and may thus contribute to fill the gap. The base material for furnace walls is a low alloy steel, usually 16Mo3, and the tubes may be coated or uncoated. Therefore tests were performed both on 16Mo3 and more highly alloyed materials suitable for protective coatings. Different types of samples exposed in used-wood fired boilers were analysed by different techniques such as LOM (light optical microscopy), XRD (X-ray diffraction), SEM (scanning electron microscopy), EDS (energy dispersive spectroscopy), WDS (wavelength dispersive spectroscopy), FIB (focused ion beam) and GD-OES (glow discharge optical emission spectroscopy). The corrosion rate was measured. The environment was also thermodynamically modelled by TC (Thermo-Calc ®). The results showed that 16Mo3 in the furnace wall region is attacked by HCl, leading to the formation of iron chloride and a simultaneous oxidation of the iron chloride. The iron chloride layer appeared to reach a steady state thickness.   Long term exposures showed that A 625 (nickel chromium alloy) and Kanthal APMT (iron-chromium-aluminium alloy) had the lowest corrosion rate (about 25-30% of the rate for 16Mo3), closely followed by 310S (stainless steel), making these alloys suitable for coating materials. It was found that the different alloys were attacked by different species, although they were exposed in the boiler at the same time in the same place. The dominant corrosion process in the A 625 samples seemed to be by a potassium-lead combination, while lead did not attack the APMT samples. Potassium attacked the alumina layer in the APMT samples, leading to the formation of a low-protective aluminate and chlorine was found to attack the base material.  The results showed that stainless steels are attacked by both mechanisms (Cl- induced attack and K-Pb combination). Decreasing the temperature of the furnace walls of a waste wood fired boiler could decrease the corrosion rate of 16Mo3. However, this low corrosion rate corresponds to a low final steam pressure of the power plant, which in not beneficial for the electrical efficiency. The short term testing results showed that co-firing of sewage sludge with used wood can lead to a reduction in the deposition of K and Cl on the furnace wall during short term testing. This led to corrosion reduction of furnace wall materials and coatings. The alkali chlorides could react with the aluminosilicates in the sludge and be converted to alkali silicates. The chromia layer in A 625 and alumina in APMT were maintained with the addition of sludge. / Förnybara träbaserade bränslen har ökat i användning under de senaste decennierna, eftersom det är koldioxidneutrala. Emellertid är träbaserade bränslen, och i synnerhet använt trä (även känt som återvunnet trä, returträ eller träavfall), mer korrosivt än skogsbränsle, på grund av högre halter klor och tungmetaller. Dessa ökar korrosionsproblemen på eldstadsväggarna, särskilt på platser där syrehalten är låg. Korrosionsmekanismer undersöks vanligtvis på överhettare dvs. på områden där materialets temperatur och syrenivån är högre än vid eldstadsväggarna. Färre arbeten har utförts på eldstadskorrosion i returträ pannor, vilket är motiveringen till detta projekt. Normalt sätt så görs endast i laboratorietester där resultaten är lättare att tolka. I kraftverk är tolkningen mer komplicerad. Undersökningar av korrosionsprocesser försvåras av flera faktorer såsom panndesign, förbränningsegenskaper, rökgassammansättning, beläggningskemi och så vidare. Därför bör laboratorietester kompletteras med fältförsök. Detta doktorandprojekt kan således bidra till att fylla denna brist. Eldstadsväggarna är uppbyggda av flera rör som svetsas samman och de består vanligtvis av 16Mo3 stål. Rören kan vara belagda eller obelagda. Tester har därför genomförts på 16Mo3 samt på höglegerade material vilka är lämpliga som skyddande beläggningar. Olika typer av prov som exponerats i förbränningspannor av returträ analyserades med olika tekniker såsom SEM (svepelektronmikroskopi), EDS (energidispersiv spektroskopi), WDS (våglängd dispersiv spektroskopi), FIB (fokuserad jonstråle) LOM (ljusoptisk mikroskopi), XRD (röntgendiffraktion), och GD-OES (glimurladdning med optisk emissionsspektroskopi). Miljön samt korrosionsprocesser har modellerats termodynamiskt med mjukvaran TC (Termo-Calc®). Resultaten visade att 16Mo3 i eldstadsväggen angrips av väteklorid, vilket leder till bildning av järnklorid och en samtidig oxidation av järnkloriden. Järnkloridskiktet verkade nå ett stationärt tillstånd vad avser tjocklek. Sex veckors prov visade att A 625 (nickelkromlegering) och Kanthal APMT (järnkromaluminiumlegering) hade den lägsta korrosionshastigheten (ca 25-30% av korrosionshastigheten för 16Mo3), följt av 310S (rostfritt stål). Vi har funnit att de olika legeringarna angrips genom olika mekanismer, även om de var exponerade i pannan samtidigt på samma plats. Den dominerande korrosionsmekanismen för legeringen A 625 verkar i huvudsak bero på kalium och bly, medan bly inte attackerar Kanthal APMT. Kalium angriper aluminiumoxidskiktet på Kanthal APMT, vilket leder till bildning av icke-skyddande aluminat medan klor i sin tur attackerar basmaterialet. Resultaten visar att rostfritt stål attackeras genom klor-inducerad korrosion samt kalium och bly i kombination. Reducering av temperaturen kan minska korrosionshastigheten hos 16Mo3. Men denna lägre korrosionshastighet motsvarar ett lågt slutligt ångtryck hos kraftverket, vilket inte är fördelaktigt för elverkningsgraden. De kortare exponeringarna visade att samtidig förbränning av avloppsslam med returträ kan leda till minskad avsättning av kalium och klor i form av alkaliklorider på eldstadsväggarna. Detta ledde till korrosionsminskning av alla studerade material. Dessa alkaliklorider skulle kunna reagera med aluminiumsilikaterna från slammet och omvandlas till alkalisilikater. Detta verkar minska den alkali-inducerade korrosionen på A 625, APMT och 310S. Den aluminiumoxid som bildades på APMT och det kromoxidskikt som bildades på A 625 upprätthölls med tillsats av slam. / <p>QC 20151015</p>

FeCrAl alloys are being investigated as candidate materials for replacing zirconium based alloys as nuclear reactor fuel cladding because of their superior high temperature oxidation resistance in steam environments. Unirradiated FeCrAl as well as Fe²⁺ ion irradiated FeCrAl to a peak dose of 20DPA were mechanically tested and compared against each other. Nanohardness tests were performed on both the unirradiated and irradiated conditions and it was found that the irradiated alloy was about 1GPa harder than its unirradiated counterpart. TEM <i>in situ</i> tensile tests were performed using the Bruker push to pull device alongside a PI95 Picoindenter on single crystals with grain orientations 001, 011 and 111. The unirradiated 001 grains tended to fail without yielding in a brittle manner while the irradiated 001 grain yielded and reached an ultimate tensile strength before failure. The unirradiated 011 grains behaved in a mixed manner, where one failed without yielding and one slipped many times before failing. The irradiated 011 grain yielded and failed quickly thereafter. The unirradiated 111 grain yielded, slipped and twinned before failing and both irradiated 111 grains slipped. Two general trends were observed. One, each unirradiated single grain was stronger than its irradiated counterpart. This trend is indicative of the ion irradiated microstructure facilitating bulklike mechanical behavior in the irradiated samples whereas the unirradiated samples exhibited mechanical size effects due to either the total lack of preexisting defects or the ability for existing defects to escape easily to the surface of the sample resulting in a pristine, defect free sample. Two, regardless of irradiation condition, the 001 grain orientation was brittle, the 011 grain orientation deformed in a mixed brittle/ductile manner and the 111 grain orientation was ductile through all tests. These results are indicative of the geometry of the BCC crystal structure and the slip system involving these orientations.