The major part of the present work, deals with the reduction kinetics of Cu2O powder and a Cu2O-WO3 powder mixture by hydrogen gas, studied by ThermoGravimetric Analysis (TGA). The reduction experiments were carried out both isothermally and non-isothermally on thin powder beds over different temperature intervals. During the experiments, the reductant gas flow rate was kept just above the starvation rate for the reaction to ensure that chemical reaction was the rate-controlling step. The activation energy for the reactions was evaluated from isothermal as well as non-isothermal reduction experiments. In the case of the reduction of Cu2O, the impact of the stability of the copper oxide on the activation energy for hydrogen reduction under identical experimental conditions is discussed. A closer investigation of additions of Ni or NiO to Cu2O did not have a perceptible effect on the kinetics of reduction. In the case of the reduction of the Cu2O-WO3 mixture, the reaction mechanism was found to be affected in the temperature range 923-973 K, which is attributed to the reaction/transformation in the starting oxide mixture. At lower temperatures, Cu2O was found to be preferentially reduced in the early stages, followed by the reduction of the tungsten oxide. At higher temperatures, the reduction kinetics was strongly affected by the formation of a complex oxide from the starting materials. It was found that the Cu2O-WO3 mixture underwent a reaction/transformation which could explain the observed kinetic behavior. The composition and microstructures of both the starting material and the reaction products were analyzed by X-ray diffraction (XRD) as well as by microprobe analysis. vi Kinetic studies of reduction indicated that, the mechanism changes significantly at 923 K and the product formed had unusual properties. The structural studies performed by XRD indicated that, at 923 K, Cu dissolved in W forming a metastable solid solution, in amorphous/nanocrystalline state. The samples produced at higher as well as lower temperatures, on the other hand, showed the presence two phases, pure W and pure Cu. The SEM results were in conformity with the XRD analysis and confirmed the formation of W/Cu alloy. TEM analysis results confirmed the above observations and showed that the particle sizes was about 20 nm. The structure of the W/Cu alloy produced in the present work was compared with those for pure copper produced from Cu2O produced by hydrogen reduction under similar conditions. It indicated that the presence of W hinders the coalescence of Cu particles and the alloy retains its nano-grain structure. The present results open up an interesting process route towards the production of intermetallic phases and composite materials under optimized conditions. / QC 20101222

Nowadays due to large demand for clean and defect-free steels, several techniques based on different characteristics of particles are applied to investigate the steel cleanness. Outokumpu Stainless AB in Avesta has performed extensive work in this field by applying several methods, which all of them have specific advantages and limitations. However, it is necessary to find an accurate technique to investigate real properties of inclusions in duplex stainless steels. For routine analytical methods, calibration and parameters adjustment can be followed by help of these investigation results. The aim of present work is to apply automated INCA-Feature method for controlling cleanness of LDX 6112 duplex stainless steels after electrolytic extractions (EE) as a reference method. Three methods of investigations, INCA-Feature on polished samples as two-dimensional and on film-filter as three-dimensional and EE as three-dimensional analyses, were compared. The results of comparison between running INCA-Feature on polished samples and film filters show an acceptable agreement which proves the possibility of performing EE on this steel grade and using INCA-Feature for investigating this as a fast method. These methods are compared statistically and quantitative results are reported in details.

Articular cartilage is a specialized connective soft tissue that resides onthe ends of long-bones, transfers the load smoothly between the bones in diarthrodialjoints by providing almost frictionless, wear resistant sliding surfacesduring joint articulation. Focal chondral or osteochondral defects in articularcartilage are common and show limited capacity for biological repair. Furthermore,changes in the bio-mechanical forces at the defect site may makethe tissue more susceptible to continued degeneration. Alternatively, the contouredfocal resurfacing metal implant can be used to treat such full thicknesscartilage defects. Physiological and biomechanical studies on animal modelswith metal implant have shown good clinical outcomes. However, the mechanicalbehavior of cartilage surrounding the implant is not clearly known withrespect to the joint function after treating such defects with metal implantsand also to improve the implant design. We developed a simple 3-dimensionalfinite element model by approximating one of the condyles of the sheep kneejoint. Parametric study was conducted in the simulations to verify differentprofiles for the implant, positioning of the implant with respect to cartilagesurface, defect size and to show the mechanical sealing effect due to the wedgeshape of the implant. We found the maximal deformations, contact pressuresand stresses which constitute the mechanical behavior of cartilages. We alsoconfirmed that using a metal implant to fill the full thickness chondral defectsis more beneficial than to leave the defect untreated from mechanical point ofview. The implant should be positioned slightly sunk into the cartilage basedon the defect size, in order to avoid damage to the opposing surface. The largerthe defect size, the closer the implant should be to the flush. We also simulatedthe time dependent behavior of the cartilages. In all the simulations, a staticaxial loading was considered. The wedge shape of the implant provided themechanical sealing of the cartilage surrounding the implant. The determineddeformations in the cartilages immediately surrounding the implant are instrumentalin predicting the sticking-up of the implant into the joint cavity whichmay damage opposing soft tissues. / <p>QC 20101125</p>

Revealing the prior austenite grain boundaries from a martensitic structure is well known to be very difficult and dependent on the chemical composition and the thermomechanical processing of the steel. In the present study, four different chemical etching reagents and additional thermal etching have been conducted for thermomechanical simulated tool steels Orvar Supreme and Stavax ESR. The etching results have been characterized using light optical microscopy and electron backscattered diffraction. The obtained results show that saturated aqueous picric acid, oxalic and sodium bisulfite based acid reveals prior austenite grain boundaries well for Orvar Supreme. For Stavax ESR, only aqueous CrO3-NaOH-picric acid provides good results in revealing the prior austenite grain boundaries. Thermal etching shows good potential and if conducted properly, thermal etching is a good alternative to the chemical reagents from a health- and environmental perspective.

Today, the world faces an energy source transformation that is difficult to grasp. To convert to a green energy society, carbon, oil, and natural gas must faze out as fuels during the upcoming decades. Hydrogen gas has received a lot of attention in recent years regarding the challenges in the energy sector, not only because of its multifunctionality as a fuel but also because it is a great energy carrier. The largest part of the green hydrogen gas produced in the future will be made in locations with great possibilities to produce hydrogen gas from solar energy. This means that a huge amount of this will need to be transported (and stored correctly during transportation) to countries with an increased industrial need for hydrogen but with insufficient production of hydrogen. The report will cover two different ways of transporting hydrogen gas. The first one is intermodal transport of tubes (hydrogen gas) or tanks (cryogenic hydrogen), and the second one is through pipelines. The report will also investigate two different ways of storing hydrogen, as a cryogenic liquid or as a compressed gas. The report will also investigate the production of intermodal commodities for compressed hydrogen gas where a material selection will be made to optimise the possibilities to store and transport hydrogen gas. The material selection analysis showed that a duplex stainless steel was the best material for hydrogen gas tubes. From the result, it is clear that compressed hydrogen gas in tube containers is the cheapest transport method with respect to both Operational Expenses (OpEx) and Capital Investment Expenses (CapEx). / Idag står världen inför en energiomställning med stora hinder. För att ställa om till ett samhälle med grön energi står det klart att kol, olja och naturgas måste fasas ut som bränslen under de kommande decennierna. Vätgas har fått mycket uppmärksamhet under de senaste åren när det gäller utmaningarna inom energisektorn, inte bara på grund av dess multifunktionalitet som bränsle utan också för att det är en utmärkt energibärare. Den största delen av den gröna vätgas som produceras i framtiden kommer att tillverkas på platser med stora möjligheter att producera vätgas från solenergi. Detta innebär att en enorm mängd av detta kommer att behöva transporteras (och lagras korrekt under transporten) till länder med ett ökat industriellt behov av vätgas men med otillräcklig produktion av vätgas. Rapporten kommer att omfatta två olika sätt att transportera vätgas. Det första är intermodal transport av tuber (vätgas) eller tankar (kryogen vätgas), och det andra är genom rörledningar. Rapporten kommer också att undersöka två olika sätt att lagra vätgas, som en kryogen vätska eller som en komprimerad gas. Rapporten kommer också att undersöka produktionen av intermodala råvaror för komprimerad vätgas där ett materialval kommer att göras för att optimera möjligheterna att lagra och transportera vätgas. Materialvalsanalysen visade att duplex rostfritt stål var det bästa materialet för vätgastuber. Av resultatet framgår det tydligt att komprimerad vätgas i rörbehållare är den billigaste transportmetoden med avseende på både Operational Expenses (OpEx) och Capital Investment Expenses (CapEx).

Cold pilgering is a challenging tube forming process in terms of modeling due to the complexity in kinematic of tools, friction condition and material behavior. The process development has mostly been based on simple formulas and costly full-scale tryouts. The aim in this study is to develop validated Finite element models of cold pilgering to increase the understanding of influence of the process parameters on the produced tubes. In the course of this thesis, three-dimensional mechanical and thermo-mechanical Finite element models of cold pilgering were developed. The commercial code MSC.Marc was used in the simulations. General 3D models are needed to be able to capture asymmetric deformation in cold pilgering. It was found that tool deflections together with elastic deformation of roll dies have considerable influence on the rolling force. Furthermore, the strain rate and temperature effects on the response of the material and thereby on the rolling force were evaluated.

The purpose of this work was to investigate ways to modify Silex sol-gel deposition of PZT (PbZrxTi(1-x)O3, Lead Zirconate Titanate) in order to improve its properties for energy harvesting applications. A number of methods to improve the figure of merit for energy harvesting (FOM= e312/ε), cause self-polarization, increase lifetime, reduce cost, increase throughput or simplify processing were tested. In order to create a barrier preventing lead diffusion into the substrate, a method to oxidize the bottom electrode’s Ti adhesion layer into TiO2 by RTA (Rapid Thermal Anneal) was tested. Oxidation was successfully achieved and was found to aid in self-polarization, thereby increasing the FOM for films without post-processing polarization. An extended lifetime is expected, but has not yet been confirmed by testing. A seed layer of a different material was tested and compared to a PZT-based seed layer. The new seed layer was found to give highly (100) crystalline PZT with improved self-polarized e31,f and FOM. The new seed layer was also found to be less sensitive to processing variations. Oxygen control during crystallization of the PZT was used in an attempt to generate PZT layers with oxygen vacancies. These hypoxic layers were intended to polarize the film, but were found to reduce the FOM and lead to partial delamination of the film due to stress. A different type of PZT sol-gel was tested as an alternative to the PZT sol-gel in use at Silex. The tested solution was found to result in PZT films with similar properties to those generated by the original type, but the tested type allowed for single layer thicknesses nearly three times thicker than the original type, thereby increasing the throughput and reducing manufacturing costs. / Arbetet undersöker metoder att modifiera Silex sol-gel deponeringsprocess för PZT (PbZrxTi(1-x)O3, blyzirconiumtitanat) i syfte att att förbättra dess egenskaper för energy harvesting. Ett antal metoder testades för att förbättra godhetstalet för energy harvesting ("figure of merit", FOM= e312/ε), åstadkomma självpolarisering, utöka livslängden, minska kostnader, öka produktionskapaciteten eller förenkla tillverkningsprocessen. En metod testades för att oxidera bottenelektrodens fästlager av Ti till TiO2 genom RTA (Rapid Thermal Anneal). Detta för att åstadkomma en barriär som förhindrar diffusion av bly in i substratet. Oxidering uppnåddes och mätningar visade en positiv inverkan på självpolariseringen, vilket ökade godhetstalet för energy harvesting i PZT-skikt utan efterbehandlingspolarisering. En utökad livslängd förväntas, men har ännu inte bekräftats via testning. Ett seedlager av ett annat material testades och jämfördes med ett PZT-baserat seedlager. Det nya seedlagret gav välkristalliserat (100) PZT med förbättrade värden för e31,f och godhetstal för energy harvesting. Det nya seedlagret var även mindre känsligt för processvariationer. Tester med begränsad syretillgång under kristallisering av PZT genomfördes för att generera PZT-lager med syrevakanser. Syftet med dessa hypoxiska PZT-lager var att polarisera materialet, men testerna resulterade i försämrat godhetstal för energy harvesting, samt partiell delaminering av PZT-skiktet orsakad av spänningar i materialet. Som alternativ till den PZT sol-gel som användes på Silex testades en annan typ av PZT sol-gel. Den testade sol-gelen resulterade i PZT-skikt med liknande materialegenskaper som hos den ursprungliga typen, men med möjlighet till nästan tre gånger så tjocka enskilda lager, vilket leder till ökad produktionskapacitet och minskade produktionskostnader.

The energy demands in the world is rapidly increasing and with this,  a supply nuclear  power  is  of  much  interest.    Nuclear  fuel  is  relatively  efficient  when comparing to power sources like wind­ and hydropower plants. Pellets are used as fuel by many plants however, its main concern is to find maximize cost efficiency and  minimize  fuel­waste.   Studying  how  to  get  the  pellets  to  be  as  optimal  as possible is of massive importance and in huge focus in order to match the worlds power demand. These  pellets  are  sintered  in  a  furnace  type  known  as  ”pusher­type”  furnaces that functions continuously and is incredibly efficient when it comes to its heat transfer capacity and high­performance output.  In this sintering process, a gas­ flow from the opposite side from the pellets interacts with the solid pellets in order to get the desired reaction. However, the turbulence and the nature of the multi­ phase flow problem causes many unknown interactions and the main focus is do create a theoretical model based on the process parameters to understand what is happening in the furnace. In this study, a simplified model of the inside of the furnace chamber was created in order to observe where and when in the furnace a dissociation from CO2 to CO + O2 would occur. Data given by Westinghouse was put into a mathematical model created in MATLAB and parameters given by the thermodynamic model was in turn put in to ANSYS, a program based on Computational Fluid Dynamics for a simulation. The simulation was considered a success when the gas­mix goes from 3% CO2 to 0.4%. The CFD of the model estimates this to happen at 250 seconds, where as the thermodynamic model predicts the exchange time to be about 200 seconds.   This study is a major first step in understanding the dynamics of the furnace. / Energibehovet i världen ökar snabbt och då blir ett stadigt tillförsel av kärnenergi mycket intressant.  Kärnbränsle är relativt effektivt jämfört med kraftkällor som vind­  och  vattenkraftverk.    Pellets  används  som  bränsle  av många  kraftverk och då blir det ett upphov att hitta maximal kostnadseffektivitet och minimera bränsleavfall.  Att forska fram till hur man gör pellets så optimala som möjligt är av enorm betydelse och i stort fokus för att matcha världens energi behov. Dessa pellets sintras i en ugnstyp som kallas ”pusher­type” ugnar som fungerar kontinuerligt och är otroligt effektiva när det gäller dess värmeöverförings-kapacitet och högpresterande effekt.  I denna sintringsprocess startar ett gasflöde från motsatt sida från pelletsen med de fasta pelletsen för att få den önskade reaktionen.  Det blir ett flerfasigt flödesproblem och orsakar många okända interaktioner och huvudfokus är att skapa en teoretisk modell baserad på processparametrarna för att förstå vad som händer i ugnen. I  denna  studie  gjordes  en  förenklad  modell  av  ugnskammarens  insida för  att observera var och när i ugnen en dissociation från CO2 till CO + O2 skulle inträffa. Data från Westinghouse placerades i en matematisk modell skapad i MATLAB och  parametrar  som  gavs  av  den  termodynamiska modellen  lades  i  sin  tur  till ANSYS, ett program baserat på Computational Fluid Dynamics för en simulering. Simuleringen ansågs vara färdig när gasblandningen går från 3% CO2 till 0,4%. CFD:n  för  modellen  uppskattar att  detta  händer  vid  250  sekunder,  där  den termodynamiska modellen förutspår utbytestiden till cirka 200 sekunder. Denna studie är ett stort första steg för att förstå ugnens dynamik.

Metal  additive  manufacturing  technologies  are  widely  employed  in  the aerospace, automotive  and  medical  industries. Selective  laser  melting  is  a type  of  metal additive manufacturing process in which powders are consolidated layer by layer in a predefined pattern with the help of a laser beam to create a component.   Powder characteristics are critical in influencing the quality of the printed component.  Metal powders must be within a specific size range and have spherical morphology to exhibit good  flow  and  spread behaviour  during  the  additive  manufacturing  process.   It  is necessary to understand the flow behaviour to comprehend the powder’s performance during the  process.   The  study  investigates  the  effect  of  powder  characteristics like particle  shape,  particle  size  and  size  distribution  on  the  flow behaviour  of  steel powders.   Powder  characterisation  techniques  relevant  to the  powders  for  additive manufacturing application is identified and performed. Sieve analysis fails to incorporate the particle shape during the particle size estimation. Optical microscopy is not a robust method for determining the particle shape.  Flow behaviour of the powders was studied using flowmeter test, rheometric analysis and static angle of repose test.  Rheometric analysis is more sensitive to minor variations in the flow behaviour compared to flowmeter tests. The static angle of repose test fails to incorporate the stresses experienced by the powder during the process and can be used to get a rough estimate for the powder flow behaviour in terms of cohesion.  Of the seven steel powders examined, the same powder with flow time 12 [s/(50 g)] kept being ranked in the top three for all the flow tests. So this powder is recommended for use in additive manufacturing. In addition, one other powder that failed in flowmetertests was consistently placed towards the bottom of all tests. / Metalladditiv tillverkningsteknik används i stor utsträckning inom flyg­, fordons­, och medicinsk industri. Selektiv lasersmältning är en typ av metalladditiv tillverknings­ process där pulver konsolideras lager för lager i ett fördefinierat mönster med hjälp av en laserstråle för att skapa en komponent. Pulveregenskaper är avgörande för att påverka kvaliteten på den tryckta komponenten. Metallpulver måste ligga inom ett visst storleksintervall och ha en sfärisk morfologi för att uppvisa ett bra flödes­, och dispersionsbeteende under den additiva tillverkningsprocessen. Det är nödvändigt att förstå flödesbeteendet för att förstå pulvrets prestanda under processen. Studien undersöker effekten av pulveregenskaper som partikelform, partikelstorlek och storleksfördelning på flödesbeteendet hos stålpulver. Pulverkarakteriseringstekniker som är relevanta för pulvren för tillsatstillverkning identifieras och utförs. Siktanalysen misslyckas med att införliva partikelformen under partikelstorleksupp­ skattningen. Optisk mikroskopi är inte en robust metod för att bestämma partikelformen. Pulvrets flödesbeteende studerades med hjälp av flödesmätartest, reometrisk analys och statisk vinkel på vilotest. Reometrisk analys är mer känslig för mindre variationer i flödesbeteendet jämfört med flödesmätartester. Det statiska vilovinkeltestet misslyckas med att införliva de påfrestningar som pulvret upplever under processen och kan användas för att få en grov uppskattning av pulverflödesbeteendet i termer av kohesion. Av de sju stålpulver som undersöktes rankades samma pulver med flödestiden 12 [s/(50 g)] i topp tre för alla flödestester. Så detta pulver rekommenderas för användning i additiv tillverkning. Dessutom placerades ett annat pulver som misslyckades i flödesmätartester konsekvent mot botten av alla tester.

In this thesis, gas sensors based on on-chip hydrothermally grown 1-D zinc oxide (ZnO) nanostructures are presented, to improve the sensitivity, selectivity, and stability of the gas sensors. Metal-oxide-semiconductor (MOS) gas sensors are well-established tools for the monitoring of air quality indoors and outdoors. In recent years, the use of 1-D metal oxide nanostructures for sensing toxic gases, such as nitrogen dioxide, ammonia, and hydrogen, has gained significant attention. However, low-dimensional nanorod (NR) gas sensors can be enhanced further. Most works synthesize the NRs first and then transfer them onto electrodes to produce gas sensors, thereby resulting in large batch-to-batch difference. Therefore, in this thesis six studies on 1-D ZnO NR gas sensors were carried out. First, ultrathin secondary ZnO nanowires (NWs) were successfully grown on a silicon substrate. Second, an on-chip hydrothermally grown ZnO NR gas sensor was developed on a glass substrate. Its performance with regard to sensing nitrogen dioxide and three reductive gases, namely, ethanol, hydrogen, and ammonia, was tested. Third, three 1-D ZnO nanostructures, namely, ZnO NRs, dense ZnO NWs, and sparse ZnO NWs, were synthesized and tested toward nitrogen dioxide. Fourth, hydrothermally grown ZnO NRs, chemical vapor deposited ZnO NWs, and thermal deposited ZnO nanoparticles (NPs) were tested toward ethanol. Fifth, the effect of annealing on the sensitivity and stability of ZnO NR gas sensors was examined. Sixth, ZnO NRs were decorated with palladium oxide NPs and tested toward hydrogen at high temperature. The following conclusions can be drawn from the work in this thesis: 1) ZnO NWs can be obtained by using a precursor at low concentration, temperature of 90 °C, and long reaction time. 2) ZnO NR gas sensors have better selectivity to nitrogen dioxide compared with ethanol, ammonia, and hydrogen. 3) Sparse ZnO NWs are highly sensitive to nitrogen dioxide compared with dense ZnO NWs and ZnO NRs. 4) ZnO NPs have the highest sensitivity to ethanol compared with dense ZnO NWs and ZnO NRs. The sensitivity of the NPs is due to their small grain sizes and large surface areas. 5) ZnO NRs annealed at 600 °C have lower sensitivity toward nitrogen dioxide but higher long-term stability compared with those annealed at 400 °C. 6) When decorated with palladium oxide, both materials form alloy at a temperature higher than 350 °C and decrease the amount of ZnO, which is the sensing material toward hydrogen. Thus, controlling the amount of palladium oxide on ZnO NRs is necessary.