This master's thesis deals with growth of germanium nanowires using different catalyst particles. The emphasis is mainly layed on fabrication of specific alloyed catalyst consisting of (AgGa). In the first part of the thesis are mentioned two most common concepts of nanowire growth and the importance of phase diagrams for their interpretation. Method for production of alloyed catalyst is demonstrated and experiments focused on the growth of germanium nanowires using this catalyst were performed. Moreover, method for modification of germanium surface via anisotropic etching is demonstrated as well. Such etched structures are suitable for nanowire growth with the help of different kinds of catalyst particles or for the growth of nanowires made of various materials.

Metal-Organic Frameworks (MOFs) are an important class of materials that are gaining increasing relevance for many fields including energy storage, CO2 capture, photovoltaics, and catalysis. MOF mediated synthesis (MOFMS) is the decomposition of a MOF to form an amorphous carbon material decorated with metal nanoparticles. MOF thin films are an area where MOFMS has not been thoroughly explored, yet they are likely to be industrially relevant due to their potential application as highly dispersed, sinter resistant supported catalysts. In this work, we have developed a method for the growth of copper- and zinc-based MOF thin films on silicon- and aluminum- based wafers. A series of decomposition processes have allowed us to determine which variables can be used to design the final nanoparticle decorated product. These variables include oxygen/nitrogen ratios, the impact of water in atmospheric decomposition, substrate composition, and reduction under hydrogen. A high degree of control over the final thin film product is achieved, with the ability to make a carbon supported CuO structure with features between 1-5 nm, or CuO nanoparticles ranging from 10-500 nm, as well as finely tuned carbon/Cu ratios. Partially reduced Cu nanoparticles were obtained and used in the dehydrogenation of ethanol and methanol. Finally, alloyed nanoparticles were obtained through the growth and decomposition of Cu/Zn mixed-metal MOFs. Understanding the growth and decomposition variables as applied to supported MOF-thin films will enable development of next generation nanomaterials for use in catalysis.

Darbe analizuojamas abrazyvinio dilimo mechanizmas. Nustatomi šiems procesams didžiausią įtaką turintys veiksniai. Analizuojama abrazyvinių dalelių formos ir jų abrazyvumo vertinimo metodika. Apžvelgiami abrazyvinio dilimo modeliai. Abrazyvinių dalelių veikiami darbinių dalių paviršiai intensyviai dyla, todėl atsižvelgiant į jų darbo sąlygas būtina tinkamai parinkti jų savybes – kietumą, stiprumą bei sudėtį (legiravimą). Šių paviršių atnaujinimui ir sustiprinimui dažnai racionalu naudoti įvairios sudėties apvirinamus sluoksnius. Šio darbo tikslas – ištirti apvirintų kietųjų sluoksnių abrazyvinio dilimo ypatybes. Taip pat, ištirti lydinių abrazyvinio dilimo įtaką dylančio paviršiaus mikrogeometriniams parametrams. Atliktais tyrimais nustatyta legiruojančių elementų įtaka apvirintų sluoksnių abrazyviniam dilimui. Nustatyta optimali apvirinto sluoksnio sudėtis abrazyvinio dilimo sumažinimui. Tai pat nustatyta, kad termiškai apdirbtų plienų ir apvirintų sluoksnių dilimo atvejais nudilimas turi ryšį su paviršiaus parametru SPQP. Tuo remiantis, matuojant paviršiaus profilį, galima prognozuoti nudilimo dydį. / There is analysis of abrasive wear mechanism in this work. The most important factors in these processes were established. There are analysed technique of abrasive particles properties and abrasive wear models. Surfaces witch are under the abrasive sway wear very fast. Considering to working conditions of these surfaces it is necessarily to choose there properties – hardness, strength and composition. For renovation and fortify of these surfaces it is often rational hard facing. The aim of this work was to estimate the influence of alloying elements content to abrasive wear. And estimate the abrasive wear influence to micro geometry of wearing surface. The influence of alloying elements to abrasive wear was estimated. To decrease abrasive wear the optimal chromium content in the arc welded alloy was investigated. Clear influence of heat treated steels and arc welded alloys abrasive wear on surface profile quality parameter SPQP is estimated. Considering with that we can measure surface profile and predict the wear rates.

The goal of the thesis was research in the field of structure and properties of low alloyed steels used in low temperature environment. Work was focused on heat treatment and chemical composition of the steel and their impact to hardness and impact energy values. Chemical composition and heat treatment of steel was proposed on the basis of achieved results.

Nowdays biofuels are becoming a good alternative for petroleum fuels due to environmental issues like high carbon dioxide emission and increasing vehicles population, together with the high price and fast depletion of petroleum oils. This project aims to investigate the corrosive effects of wood Pyrolysis oil on a special grade of nitrogen alloyed tooling steels to be used for injector nozzles in Diesel engines, where high stress and strain encounter high acidity and corrosivity of the Pyrolysis oil and cause breakdown over short periods. Vanax 35 and Vanax 75 manufactured in Uddeholm are two types of powder metallurgy high nitrogen alloyed martensitic stainless steel with a high combination of hardness (over 56HRC), low friction properties, wear resistance, anti-galling and corrosion properties. In this work, the newly developed Vanax material together with the tool steels Elmax and AISI O1 were tempered at various temperatures from 200°Cto 500°C. The tempered steels were then exposed in pyrolysis oil at 4 different temperatures, 20°C, 70°C, 95°Cand 130°C. The materials were investigated by means of corrosion rate measurements, microscopy (LOM, SEM, confocal) and Thermo-Calc calculations. The corrosion rate measurement proved that Vanax tempered at lower ranges (200°C, 400°Cand 450°C) showed the best corrosion resistance while higher tempering temperatures such as 500°C, Elmax and AISI O1 tempered at 200°Csuffered a great deal of general corrosion attack. Thermo-Calc calculations showed the formation of a hard phase, VN as primary nitrides instead of primary chromium carbides at austenizing temperature for the Vanax group. Higher amount of chromium is dissolved in solid solution in Vanax at austenizing temperature hence the martensite matrix has, after quenching, a higher chromium content that helps passivation. The loss in corrosion properties at higher tempering temperatures was due to the formation of CrN secondary phase at around 400˚C which reduces the chromium content of the martensite matrix. The results of light optical and confocal microscopy showed the presence of pits when tempering at 400˚C and 450˚C. No pits were observed at 200˚C. Elmax was not passivated at all which resulted in general corrosion attacks, due to a high chromium loss from the austenite solid solution at the austenizing procedure temperature and also the tempering temperatures. The chromium depletion from the austenite can be explained by a high carbon and a low nitrogen content in the composition which resulted in formation of a high amount of Cr7C3.

The landfilling of slag obtained from the high alloyed Electric Arc Furnace (EAF) steel making process, constitutes an environmental treat for society as well as an economical problem for the companies producing it, due to the costs related to waste management practices. Conventional methods of slag recycling are abundantly used among the steelmaking business, but due to their particular physical properties, high- alloyed EAF slags cannot be properly valorized. Moreover, the pickling process that high-alloyed EAF steels undergo to, generates acidic wastewaters, that need to be collected and neutralized, before they can be recirculated into the natural water streams. For such a task, steel mills currently utilize slaked lime (a Ca rich mineral) to raise the pH and to remove any metal particles dissolved into the wastewaters. Slag contains high amount of Ca; therefore, it has already been tested as a slaked lime replacement. In fact, previous studies conducted at the Material Science and Engineering department at KTH Royal Institute of Technology showed, on a laboratory scale, that slag has the potential to replace lime for the neutralization and purification of the acidic wastewaters. This Master’s thesis project aims at upscaling the volumes of wastewaters to be tested, about 70 to 90 folds of the one from previous research, bridging the gap between laboratory tests and the industrial scale. The thesis is divided into three tranches, a first part where a water-salt solution conductivity trials were carried out, to model the behavior or slag dispersion in the acidic wastewaters. After the results obtained from the conductivity trials, neutralization trials with slag and the lime product currently in use by the company, were carried out at the neutralization plant in Outokumpu Stainless, Avesta (Sweden). The neutralization trials were carried out with 70 and 90 liters of acidic wastewaters and in order to perform the trials on site, the slag sample was dried and later sieved to a particle size of less than 350μm. Moreover, data was analyzed and compared to previous studies in order to have a clearer understanding regarding the neutralization efficiency of the slag, especially whether or not the technology would had worked on upscaled volumes. Additionally, the project checked if it was possible to find a generalized relationship between the mass of slag and volume of wastewaters required for the neutralization process. Slag demonstrated to be able to buffer the pH to the target values of 9, while also showing an almost linear trend compared to previous studies. The reaction progress between slag, lime, and the acidic wastewaters was also analyzed. / Deponering av slagg som erhållits från den höglegerade ljusbågsugn (EAF) stålframställningsprocessen utgör en miljömässig behandling för samhället och ettekonomiskt problem för de företag som producerar den på grund av kostnaderna för avfallshantering. Konventionella metoder för återvinning av slagg används i storutsträckning bland stålindustrin, men på grund av deras speciella fysiska egenskaper kan höglegerade EAF-slaggen inte värderas ordentligt. Dessutom produceras sura avloppsvatten av betningsprocessen som höglegerade EAF-stål genomgår som sedan måste samlas in och neutraliseras innan de kan återcirkuleras i det naturliga vattnet. För en sådan uppgift använder stålfabriker för närvarande släckt kalk (ett Ca-rikt mineral) för att höja pH-värdet och för att avlägsna alla metallpartiklar som löses upp i avloppsvattnet. Slaggen innehåller hög mängd Ca och därför har den testats som en ersättning till släckt kalk. Tidigare studier utförda vid avdelningen materialvetenskap och teknik vid Kungliga Tekniska Högskola visade på laboratorieskala att slagg har potential att ersätta kalk för neutralisering och rening av sura avloppsvatten. Detta examensarbete syftar till att skala upp volymerna av avloppsvattnet som ska testas till cirka 70–90 gånger av den från tidigare forskning, och därav fylla ut bryggan mellan laboratorietester och industriell skala. Avhandlingen är uppdelad i tre delar, Första delen innehåller försök på ledningsförmåga i en vatten-saltlösning som genomfördes för att modellera beteende eller slaggspridning i sura avloppsvatten. Efter de resultat som erhållits från konduktivitetsmätningarna genomfördes neutraliseringsförsök med slagg och kalk som för närvarande används av företaget vid neutraliseringsanläggningen i Outokumpu Stainless, Avesta (Sverige). Neutraliseringsförsöken genomfördes med 70 och 90 liter sura avloppsvatten och för att utföra experimenten på plats torkades slagg provet och siktades senare till en partikelstorlek på mindre än 350 μm. Dessutom analyserades data och jämfördes med tidigare studier för att få en tydligare förståelse för slaggens neutraliseringseffektivitet, särskilt huruvida tekniken skulle ha fungerat på större volymer, och även om det också var möjligt att hitta ett generaliserat samband mellan mängden slagg och volym avloppsvatten som krävs för neutraliseringsprocessen. Slagget visade sig kunna buffra pH till målvärdena 9, samtidigt som den visade en nästan linjär trend jämfört med tidigare studier. Reaktionsförloppet mellan slaggkalk och de sura avloppsvattnen analyserades också.

No description available.

Le développement de systèmes mécaniques, toujours plus performants et légers, demande l’optimisation continue des matériaux utilisés ainsi que leurs traitements. Dans le domaine des transmissions de puissance, la nitruration gazeuse apporte une hausse significative des durées de vie en fatigue des pièces fortement sollicitées. Alors que le rôle des gradients de propriétés mécaniques générés sur la résistance en fatigue est reconnu, l’influence de cette microstructure nitrurée sur les mécanismes de plasticité ou de microplasticité menant à de l’endommagement puis à l’initiation d’une fissure reste relativement méconnue. Ce travail de thèse concerne exclusivement la nitruration de l’acier de nuance 33CrMoV12-9, particulièrement utilisée dans les roulements et engrenages des industries aéronautiques et navales. Les propriétés mécaniques liées aux phénomènes menant à l’initiation de fissures en fatigue à grand nombre de cycles ont, tout particulièrement, été étudiées. Les propriétés mécaniques, comme le module d’élasticité, la dureté, la limite d’élasticité ou encore les contraintes résiduelles sont déterminées à plusieurs échelles, de celles de la microstructure à celles plus macroscopiques. Des observations in-situ ou post-mortem des couches nitrurées sollicitées jusqu’à l’endommagement ayant pour but d’estimer l’influence de la microstructure sur les hétérogénéités de déformations, les phénomènes de microplasticité et les mécanismes d’endommagement correspondants n’ont pas permis d’identifier clairement des mécanismes d’initiations de fissures. Pour ces essais, une éprouvette nitrurée à cœur représentative de la couche nitrurée a été développée. Cet outil expérimental a permis d’effectuer des essais simples de sollicitations des microstructures et ainsi déterminer des caractéristiques élastiques, d’écrouissage et de tenue en fatigue. Enfin, il a été démontré que les propriétés mesurées comme le module d’élasticité dépendent de l’échelle d’observation, des moyens et des méthodes utilisés. / Design of high-performance and lighter mechanical systems needs a perpetual work on materials used. In the power transmission field, gaseous nitriding thermochemical treatment enhances significantly the life-cycle of the parts which are higher stressed on the surface. While the contribution of the mechanical property gradients due to the treatment on the fatigue life is well-known, the microstructure effects on the (micro-)plasticity mechanisms remains undetermined. This work concerns exclusively the nitrided 33CrMoV12-9 graded steel, used for gears and bearings in the naval and aeronautical industry. It aims particularly at defining mechanical properties linked to crack initiation mechanisms during high-cycle fatigue. Properties such as Young modulus, hardness, yield stress and fatigue limits are looked at several scales, from microstructural ones to hardened case one. In-situ and post-mortem investigation on loaded and damaged nitrided layers leads to estimating the microstructural influence on local deformations, microplasticity and damage but no particular mechanisms were found. Special fully-nitrided parts were designed to perform the experiments. This tool helps to carry out simple loadings and measure the strain-hardening curve and fatigue limits. Finally, it as been attested that measured properties depend on scales, means and methodology.

Vid framställning av olika material är introduceringen av legeringselement ett betydelsefullt område. Vid framställning av stål kan egenskaperna för stålet optimeras genom att styra de kemiska reaktionerna som sker i samband med att stålet legeras. För legeringar av stål är låga halter av grundämnet bor av intresse. Tillsatser av bor vid ståltillverkningen har visats ge betydande förbättringar av olika materialegenskaper för stål. Ett känt problem är att bor uppvisar hög affinitet till flera andra grundämnen. Detta leder till att bor vid materialtillverkningen bildar ej önskvärda kemiska föreningar med dessa ämnen vilket leder till att borets bidrag till stålets egenskaper förloras i hög utsträckning.Med hjälp av termodynamiska beräkningsmodeller, såsom CALPHAD-metoden, går det att beräkna olika termodynamiska beskrivningar av kemiska föreningar. Dessa kan därefter sammanställas i databaser för framtida beräkningar. Genom att utföra utvärderingar och beräkningar på system av lägre grad, t.ex. binära system, kan i förlängningen mer komplexa beräkningar utföras på multikomponenta system som innehåller flera olika grundämnen. Databasen i detta projekt saknar en uppdaterad beskrivning av tillgänglig termodynamisk informationen för vissa borkarbider. Syftet med detta examensarbete var att utföra en utvärdering av stål mikrolegerat med bor och utföra en uppdatering av en databas med avseende på utvalda kemiska föreningar. Med programvaran Thermo-Calc har en termodynamisk utvärdering skett av Fe-B-C-systemet med avseende på de tidigare ej beskrivna borkarbiderna Fe3(B,C) och Fe23(B,C)6. Deframtagna beskrivningarna av föreningarna implementerades i databasen på ekvationsform och beräkningar utfördes för att påvisa pålitligheten i beskrivningarna. Resultaten från beräkningarna visades överensstämma väl med referenser i litteraturen. / When studying the production of different materials, the introduction of alloying elements is of great importance. The material properties of steels can be optimized through control of the different chemical reactions taking place in the production process. For different steel alloys, alloying with the element boron has shown an increased hardenability for the end products. One problem with boron is that it shows high affinity to several other elements. This can lead to boron forming different chemical compounds that are not desired and thus losing the contribution of boron to the hardenability effect. With the help of thermodynamic calculation models, such as the CALPHAD-method, it is now possible to calculate different kinds of thermodynamic descriptions for chemical compounds. These descriptions can be used in databases for future calculations. By making evaluations of thermodynamic systems of lower degrees, for example a binary system, one could perform more complex calculations of systems involving many elements and compounds. The database used in this project lacked an updated thermodynamic description of selected boron carbides. The purpose of this Master’s Thesis was to perform a thermodynamic evaluation of steel alloyed with small amounts of boron. Using the updated descriptions, the database was updated with the latest thermodynamic information regarding the chemical compounds of Fe3(C,B) and Fe23(C,B)6.A thermodynamic evaluation has been performed using the software Thermo-Calc for the boron carbides Fe3(C,B) and Fe23(C,B)6 in the ternary system Fe-B-C. These new descriptions were implemented in the database and through calculations validated against published articles and journals. The results from the calculations were shown to be satisfactory when comparing to other published results.

Le fonctionnement à haute température de certains composants des centrales nucléaires, provoque une dégradation de leurs propriétés à rupture. Cette dégradation provient essentiellement de l'activation de phénomènes thermodynamiques qui entraînent la ségrégation d'éléments aux joints des grains. L'objectif de ce travail est de proposer une modélisation multi-échelle permettant de relier la cinétique de cette ségrégation à l'évolution des propriétés à rupture du matériau. / The use of some PWR components at a relatively high temperature generates a drop of their fracture properties. This embrittlement is generally attributed to the segregation of some impurities at grains boundaries. This work aims at correlating the kinetics of this segregation to the embrittlement kinetics through a multi-scale approach, combining thermodynamical and micro-mechanical analysis.