La corrosion à haute température d'alliages métalliques représente un processus d’endommagement critique dans de nombreux domaines industriels. Le suivi en service de la dégradation des équipements opérant sous une atmosphère agressive à haute température devient un objectif majeur pour les industriels. Grâce à sa sensibilité et à son caractère non destructif, l'émission acoustique constitue une méthode intéressante pour suivre l’évolution de la détérioration des matériaux soumis à des formes sévères de corrosion comme le metal dusting pour les alliages de fer ou de nickel en pétrochimie. Notre étude a montré que les transformations irréversibles des matériaux telles que la fissuration peuvent être détectées grâce aux signaux acoustiques émis pendant la corrosion. Un couplage innovant a été développé associant l'émission acoustique in situ avec la thermogravimétrie. Dans un premier temps, ce couplage nous a permis d’étudier et d’approfondir nos connaissances de la corrosion à 900 °C sous atmosphère oxydante d’un alliage de zirconium. Les phénomènes comme la diffusion de l’oxygène dans la zircone ne sont pas émissifs ; par contre les mécanismes de dégradation irréversibles, comme l'initiation et la propagation des fissures dans la couche de zircone, sont décelables dès leur apparition. Dans un second temps, lors de l’étude de la carburation du fer pur ou du fer pré-Oxydé, nous avons démontré que la corrosion par metal dusting qui comporte une étape d’insertion des atomes de carbone dans la matrice de fer est détectable grâce à l’émission acoustique. Il est donc envisageable de suivre ce type de dégradation au moyen de l’émission acoustique lorsqu’il affecte les équipements industriels. / High temperature corrosion of metallic alloys can cause damage to chemical and petrochemical industrial equipment. On line monitoring of the behaviour of components, which operate under corrosive atmosphere at high temperature, has become an important challenge. In order to quantify the level of damage of materials affected by corrosion, acoustic emission seems to be an interesting method due to its sensitivity and its non-Destructive aspect. Based on bibliographic supports, we have developed an experimental device combining thermogravimetric analysis with acoustic emission in order to simultaneously record the sample mass variations and the acoustic signals mainly due to the degradation of materials such as cracks formation during oxidation of metal at high temperature for example.First of all, we have studied Zircaloy-4 corrosion behavior at 900 °C under oxidant gas by means of this innovative equipment. We have demonstrated the feasibility of such a coupling method; mass measurements are not disrupted by acoustic emission chain connected to the thermobalance. Irreversible mechanisms, as cracks initiation and propagation, generate acoustic emission bursts. Analysis of the burst waveforms and of the oxidized sample cross sections allows us to attribute the acoustic events to corrosion or cooling processes. Secondary, metal dusting of pure iron at 650 °C under highly carburising gases (i-C4H10 + H2) was studied. Iron bulk degradation caused by graphite deposition and insertion has been detected using acoustic emission. This result lets us think that this technique can be adapted to monitoring of industrial equipment.

This work is focused on oxide scale failure and characteristics created in high temperature – supercritical processes. The presence of high temperature corrosion in supercritical processes is minimalised by selection of the right material. For this work was selected material X10CrMoVNb9-1, where formulas of present oxidation scales are Fe2O3, Fe3O4 and FeCr2O4. Each oxidation scale has its own mechanical properties thus it is important to notice scale arrangement, thickness and geometry. Oxide scale mechanical properties, scale failure mechanisms and oxidation scale growth is evaluated in this work. Tension and pressure oxide scale failure are determined by critical values, which are mentioned in this work. Thanks to these values there was possibility to verify the authenticity of the finite element model. Oxidation scales created in heat exchangers are badly accessible thus it is difficult to observe them or remove them mechanically. Tube finite element model with oxidation scales was created in this work. There are simulations of scales on selected steel in supercritical conditions (pressure 24 MPa, temperature 500 °C). Simulation and analytic results are compared. Failure operative conditions are searched for scale FeCr2O4 until its compleate delamination and separation from metal. Aim of this work is to create an oxidation scale model with a possibility of futher use.

The master´s thesis deals with steam boiler design that burns contaminated wood with output 55 tons of steam per hour, steam pressure 4,2 MPa and temperature 423 °C. First two chapters focuses on stoichiometry and calculation of heat losses and boiler efficiency. Great part of thesis constitutes of thermal and dimensional calculations of every heat transfer surface. Some specific boiler parts are described considering special fuel properties. Final chapters contain pressure losses calculation of flue gas and heated medium for pumps and fans design. Drawing is also part of the work which is included as an attachment.

Due to coming emission legislations, the temperature is expected to increase in heavy-duty diesel engines, specifically in the hot-end of the exhaust system affecting components, such as exhaust- and turbo manifolds. Since the current material in the turbo manifold, a ductile cast iron named SiMo51, is operating close to its limits there is a need for material development in order to maintain a high durability of these components. When designing for increased life, many material properties need to be considered, for example, creep-, corrosion- and fatigue resistance. Among these, the present work focuses on the latter two up to 800°C improving the current material by additions of Cr, for corrosion resistance, and Ni, for mechanical properties. The results show improved high-temperature corrosion resistance in air from 0.5 and 1wt% Cr additions resulting in improved barrier layer at the oxide/metal interface. However, during oxidation in exhaust-gases, which is a much more demanding environment compared to air, such improvement could not be observed. Addition of 1wt% Ni was found to increase the fatigue life up to 250°C, resulting from solution strengthening of the ferritic matrix. However, Ni was also found to increase the oxidation rates, as no continuous SiO2-barrier layers were formed in the presence of Ni. Since none of the tested alloys showed improved material properties in exhaust gases at high temperature, it is suggested that the way of improving performance of exhaust manifolds is to move towards austenitic ductile cast irons or cast stainless steels. One alloy showing good high-temperature oxidation properties in exhaust atmospheres is an austenitic cast stainless steel named HK30. This alloy formed adherent oxide scales during oxidation at 900°C in gas mixtures of 5%O2-10%H2O-85%N2 and 5%CO2-10%H2O-85%N2 and in air. In the two latter atmospheres, compact scales of (Cr, Mn)-spinel and Cr2O3 were formed whereas in the atmosphere containing 5%O2 and 10%H2O, the scales were more porous due to increased Fe-oxide formation. Despite the formation of a protective, i.e. compact and adherent, oxide scale on HK30, exposure to exhaust-gas condensate showed a detrimental effect in form of oxide spallation and metal release. Thus, proving the importance of taking exhaust-gas condensation, which may occur during cold-start or upon cooling of the engine, into account when selecting a new material for exhaust manifolds. / <p>QC 20130508</p>

Increasing awareness of environmental protection has made both governments and the industry aim for lowering carbon dioxide emissions. For the transport industry this means increasing engine efficiency, replacing fossil fuels with bio-based fuels or full electrification. For heavy-duty trucks, the first two options are currently the paths taken as short and mid-term solutions. These alternatives introduce new service conditions to the engines; namely higher combustion temperature and pressure, which will impose increased thermal and mechanical loads on the engine parts. In particular, the exhaust system parts must withstand constant thermal cycles in their normal operation. In heavy-duty trucks, exhaust systems are mostly manufactured from cast iron or cast steel. The usual materials, such as cast iron SiMo51 are reaching their maximum operating temperature, therefore new materials must come forward to fulfill new challenges. These materials oxidize at high temperatures forming different types of scales, which sometimes can act as protective barriers preventing their degradation. However, thermal cycles in the engine can impose new stresses and strains in these newly formed oxide scales, sometimes leading to spallation. A continuous spallation behavior in the exhaust systems is deleterious for the system, and the debris could also affect the downstream engine parts. This investigation focuses on the study of high temperature oxidation behavior of four iron-based candidate materials. Samples of two ductile cast irons and two austenitic stainless steels were exposed to thermal cycling in a simulated exhaust gas atmosphere at 850 °C, and to isothermal experiments at 850 °C and 900 °C in a stagnant air atmosphere. Additionally, the thermodynamics and kinetics were simulated using Thermo-Calc and Dictra software, respectively.  The results show that SiMo1000 grows a relatively thick iron-rich oxide layer with evidence of internal oxidation aided by the graphite shape exhibited by the alloy. The other cast iron Ni-Resist behaves better than SiMo1000, forming chromia and silica layers that prevent internal oxidation from occurring, although some spallation did occur in water containing atmospheres. 1.4832 behaved poorly compared to the other materials, entering into breakaway oxidation mode throughout all the exposures; therefore, it is not a material suited for high temperature service. HK30 was susceptible to water aided chromium evaporation but had a comparatively small mass change throughout the experiments; nonetheless, there was evidence of internal oxidation following interdendritic zones. Also casting defects were observed in these areas. Both might affect mechanical properties at high temperature. / Ökad miljömedvetenhet har gjort att både industri och politiker har satt upp mål för att sänka koldioxidutsläppen. För transportbranschen innebär detta till exempel ökad motoreffektivitet, att fossila bränslen ersätts med biobaserade bränslen eller full elektrifiering. För tunga lastbilar är de två första alternativen de som är aktuella på kort och medellång sikt. Dessa alternativ innebär nya förhållanden för motorn; nämligen högre förbränningstemperatur och -tryck, vilket kommer att öka termisk och mekanisk last på motorn. Detta är särskilt tydligt för avgassystemet, eftersom det utsätts för termisk cykling vid normal drift. Avgassystemet i en tung lastbil är oftast gjort i gjutjärn och ibland i gjutstål. Gjutjärnen, t ex segjärn SiMo51, börjar nu närma sig sin maximala driftstemperatur och nya material behöver introduceras. Vid höga temperaturer oxiderar dessa metalliska material och bildar olika typer av oxidskal. Beroende på sammansättningen på oxidskalet, kan det fungera som skydd för underliggande material. Termisk cykling kan ge spänningar i oxidskiktet som i sin tur kan ge flagning av skiktet. Om flagningen fortsätter kontinuerligt, förbrukas dels material, men flagorna kan också ge skador nedströms i avgassystemet. I detta arbete undersöks fyra järnbaserade kandidatmaterial avseende högtemperaturkorrosion. Prover av två gjutjärn och två austenitiska rostfria gjutstål exponerades dels isotermt vid 850 °C och 900 °C i stillastående luft, dels i experiment med termisk cykling i en simulerad flödande avgasatmosfär och varm temperatur 850 °C. Dessutom användes termodynamisk programvara (Thermo-Calc/DICTRA) för att simulera termodynamik och kinetik. Resultaten visar att SiMo1000 bildar ett relativt tjockt, järnrikt oxidskikt med viss inre oxidation som verkar följa grafitstråk i materialet. Det andra gjutjärnet, segjärnet Ni-Resist, beter sig bättre än SiMo1000 och bildar krom och kiseldioxidlager som förhindrar intern oxidation. Viss flagning observerades i den cykliska exponeringen. 1.4832 visade ett sämre beteende än de andra materialen och bildade inget skyddande oxidskikt, utan visade kontinuerlig massförlust i samtliga exponeringar. Detta material är därför inte lämpligt för de undersökta högtemperaturmiljöerna. HK30 visade låg massförlust i samtliga undersökningar med oxidation i interdendritiska områden. Även gjutfel som t ex porer observerades idessa områden. Båda kan påverka materialets mekaniska egenskaper vid dessa temperaturer.

Additive manufacturing (AM) techniques are being studied for their application in the aerospace industry. Numerous benefits come from the already in shape final piece, which needs reduced amount of prime material for its production and can have its shape numerically optimized for weight reduction. Austenitic stainless steels (AuSS) are widely used in aerospace and their manufacturing through AM is a popular research topic in order to accelerate their effective incorporation in air-crafts and spaceships. The special microstructures of AM has been observed with characterization techniques. The present work studies the high temperature stability of three AuSS (316L, MOD-316 and 21-6-9) considering two approaches; surface corrosion and microstructure evolution. First, for high temperature corrosion, thermogravimetric analysis has been performed from 850°C to 1150°C. From the results, kinetic analysis were performed and the activation energy was extracted from Arrhenius fits. Two mechanism were found for alloy 316L (first 435.41 kJ/mol and second 593.24 kJ/mol) and MOD-316 (first 740.01 kJ/mol and second 495.58 kJ/mol). Further SEM observations on the scales have shown Ni diffusion through the chromia scale in MOD-316 alloy, which could explain the higher oxidation rates at 1150°C. Alloy 21-6-9 has the best passivation behaviour with an activation energy of 190.47 kJ/mol. Secondly, long heat treatment (HT) at 725°C in air atmosphere has been performed, for 24 and 240h. Samples were initially as-built or annealed (900°C for 1h), to compare the effect of the HT on the microstructure evolution and precipitates formation. LOM observation showed preferable nucleation in grain boundaries (GB), an increment of the number of precipitates and a growth towards elongated shapes following GB with increased time. It was also observed a reduction in precipitates number with the annealing HT for all the alloys. XRD, SEM and EDS analysis has been carried out to identify the structure and composition of the precipitates. Various chromium, tungsten, copper, molybdenum and niobium carbides and oxides have been found in MOD-316. Higher porosity is observed in 21-6-9, that presented mainly chromium oxides, carbides and nitrides in GB and surrounding the AM defects. / SeSSA

This degree project focused on examining new possible application of near-infrared (NIR) spectroscopy for quantitative and qualitative characterization of refuse derived fuel (RDF). Particularly, two possible applications were examined as part of the project. Firstly, use of NIR hyperspectral imaging for classification of common materials present in RDF. The classification was studied on artificial mixtures of materials commonly present in municipal solid waste and RDF. Data from hyperspectral camera was used as an input for machine learning models to train them, validate them, and test them. Three classification machine learning models were used in the project; partial least-square discriminant analysis (PLS-DA), support vector machine (SVM), and radial basis neural network (RBNN). Best results for classifying the materials into 11 distinct classes were reached for SVM (accuracy 94%), even though its high computational cost makes it not very suitable for real-time deployment. Second best result was reached for RBNN (91%) and the lowest accuracy was recorded for PLS-DA model (88%). On the other hand, the PLS-DA model was the fastest, being 10 times faster than the RBNN and 100 times faster than the SVM. NIR spectroscopy was concluded as a suitable method for identification of most common materials in RDF mix, except for incombustible materials like glass, metals, or ceramics. The second part of the project uncovered a potential in using NIR spectroscopy for identification of inorganic chlorine content in RDF. Experiments were performed on samples of textile impregnated with a water solution of kitchen salt representing NaCl as inorganic chlorine source. Results showed that contents of 0.2-1 wt.% of salt can be identified in absorbance spectra of the samples. Limitation appeared to be water content of the examined samples, as with too large amount of water in the sample, the influence of salt on NIR absorbance spectrum of water was too small to be recognized. / FUDIPO

La technologie de l’électrolyse de la vapeur d’eau à haute température (EVHT) est unesolution alternative à la production d’hydrogène. Le principe est inversé à celui d’une pile àcombustible de type SOFC : on utilise la vapeur d’eau et de l’électricité afin de produire del’hydrogène. Une difficulté technique majeure repose sur la mise au point d’interconnecteursfonctionnant efficacement sur le long terme. Sur le plan électrique, l’interconnecteur doitprésenter une valeur de résistance de contact aux électrodes la plus faible possible, car elleaffecte directement le rendement de conversion électrochimique (eau en hydrogène) et peutpénaliser le procédé. Il ne doit donc pas présenter une cinétique d’oxydation élevée ni formerdes oxydes isolants électriquement. Sur le plan chimique, l’interconnecteur doit être résistantà l’oxydation sous atmosphère riche en oxygène côté anode et riche en vapeur d’eau côtécathode. De plus, le problème de la volatilisation des oxydes de chrome, qui peuvent diffuseret empoisonner les électrodes, déterminant ainsi une réduction de l’activité électrochimique etdes performances du « stack » sur des longues durées de fonctionnement, doit être réduit. Latempérature de fonctionnement comprise entre 700 et 900°C permet l’utilisationd’interconnecteurs métalliques, qui présentent l’avantage d’une mise en oeuvre plus facile etd’un coût plus faible par rapport aux interconnecteurs céramiques.Dans cette étude, deux matériaux ont été testés en tant qu’interconnecteurs pour lessystèmes EVHT : un acier ferritique chromino-formeur K41X et un alliage Fe-Ni-Co necontenant pas de chrome. Le comportement envers la corrosion à haute température et laconductivité électrique des deux alliages ont été évalués à 800°C sous un mélange 95%O2-5%H2O, pour le côté anodique, et 10%H2-90%H2O, pour le côté cathodique. Pour l’alliageK41X, l’effet de l’état initial de la surface des échantillons sur la nature des oxydes formés àhaute température sous mélange H2-H2O a été pris en compte, à travers une comparaison desalliages bruts de laminage avec des surfaces polies miroir. L’effet d’une pré-oxydation decourte durée à 800°C sur le comportement à haute température de l’alliage K41X brut deréception sous atmosphère H2-H2O a également été évalué. Mais, le travail le plus original decette étude a consisté à effectuer des essais de marquage à l’or et des marquages isotopiquessous mélange H216O-H218O, H2-D2O et D2-H2O. Ces tests ont permis d’étudier lesmécanismes responsables de la croissance de la couche de corrosion de l’alliage K41X brut deréception et poli miroir à 800°C sous atmosphère H2-H2O et d’évaluer le rôle de la vapeurd’eau et de l’hydrogène dans le mécanisme d’oxydation / The high temperature water vapour electrolysis offers a promising method for highlyefficient hydrogen production. It works as an inverse solid oxide fuel cell, using water vapourand electricity in order to produce hydrogen. A major technical difficulty related to hightemperature water vapour electrolysis (HTVE) is the development of interconnects workingefficiently on a long period. From the electrical point of view, the interconnect must have alow contact resistance with the electrodes. Indeed, it directly affects the electrochemicalconversion efficiency (water into hydrogen) and it can penalize the process. The interconnectmust present a slow oxidation kinetics and form as less as possible electrical insulatingoxides. From the chemical point of view, the interconnect has to be resistant against oxidationin an oxygen rich atmosphere (anode side) and water vapour rich atmosphere (cathode side).Moreover, the problem of the volatility of chromium oxide species, which might migrate andpoison the electrodes, leading to a decrease in their electrochemical activity and degradationof stack performance, over long-term operation, needs to be reduced. The operatingtemperature between 700°C and 900°C allows the use of metallic interconnects, which havehigher electrical and thermal conductivities, easier shaping and lower cost, with respect to theceramic materials.In this study, two materials were tested as interconnects for the HTVE systems: a ferriticchromia-forming alloy, the K41X, and a Fe-Ni-Co alloy, which does not contain chromium.High temperature corrosion behaviour and electrical conductivity were tested in both anode(95%O2-5%H2O) and cathode (10%H2-90%H2O) atmospheres at 800°C. Moreover, for theK41X alloy, the effect of the initial surface state of the samples on the chemical nature of theoxides formed at 800°C in H2-H2O atmosphere was evaluated, by comparing as received andmirror polished surfaces. The effect of a short-term air preoxidation at 800°C on the hightemperature behaviour of the K41X as received sample in H2-H2O atmosphere was tested.The most original part of this study consisted in the investigation of the oxidation mechanismsof both as received and mirror polished K41X samples at 800°C in H2-H2O atmosphere bymeans of marking experiments using Au and isotopes (H216O-H218O mixture). Moreover,marking tests using H2-D2O and D2-H2O were carried out, in order to further investigate therole of hydrogen and water vapour in the oxidation mechanism

The thesis deals with the modeling and prediction of corrosion of radiation tube snake in the heating furnace. Specifically it is focused on vertical cylindrical furnace which is included in the catalytic hydrocracking unit and serves for heating aggressive circulation gas which is the cause of high temperature corrosion. An important basis for the creation of computational models are available records about the operation of the furnace and about the corrosion and degradation mechanisms during the lifetime of the tube system in furnace. Such information enables the creation of a computational model which is based on the prediction of high-temperature corrosive damage of radiation tube snake. The computational model involving all relevant factors may serve as the basis for a predictive life management system of radiation snakes in the heating furnace.

While using iron castings behind temperature of 500 oC namely at cyclic heat straining, degradation of structure and breaching iron castings. For this purpose introduce cast iron with content of Si and Mo. Focusing on improvement of SiMo51 for increased high-temmperature corrosion-and fatigue life in exhaust-gas temperatures up to 800 oC. Thesis set up survey types alloys, properties, and way of casting production.