Because of global warming the energy production development has progressed towards more renewable energy sources. Biomass has great potential in this matter and pellet is already a big market that has increased seven times the past decade. A periodically strained woodchip resource market and statements of short supply in the future has got actors exploring opportunities with other commodities. Grasses such as Canary grass has shown great potential in this matter and in this study a wetland grass is tested as an additive, 0,5, 1,0, 1,5, and 1,9%, with spruce woodchips. The test production series was performed at a production unit located at the department of environmental and energy system at Karlstad University, Karlstad. Quality was controlled accordingly to the European standard and parameters such as energy consumption, moisture content, mechanical durability and bulk density was tested. For comparison, a sample with only spruce wood chips was produced, and a sample containing 1% of a commonly used additive, potato starch. The results showed that a decrease in energy consumption with 14% when 2% wetland grass was added, part of the decline may be due to the increased production flow compared with the reference sample. The positive effects on decrease in energy consumption, that 1% potato starch results in, is equal to reults from 1% wetlandgrass. This indicates lubricating properties in wetlandgrass. This is attributed to that herbaceous plants have a high content of extracts such as waxes and that they cause less friction in the press. Tests also showed that pellet with wetland grass did not qualify the European standard in terms of mechanical durability. Extracts can form a weak boundary layer in the pellet and cause this. A possible trend shows a better mechanical durability with more grass in pellets. The presence of different size of particles can be a reason. Moisture content qualifies according to the European standard but is below optimum 8%. This despite to relatively high moisture content in the mixer. Higher moisture content in the press would certainly result in a generally higher quality. Suggestions for future studies are to produce pellets with greater distribution on the wetland grass added, to easier interpret a connection. Also examine the extracts behavior with different moisture content. For a sustainable development accordingly renewable energy it is important to ensure the future commodity market for pellets. Further studies should be performed to help the development of alternative raw materials in conjunction with pellet production. / Den globala uppvärmningen är en påverkande faktor gällande dagens energiutveckling. Europeiska unionens krav på mer förnyelsebar energi är därtill en anledning till det ökade intresset för bioenergi. Pelletsmarknaden har sjufaldigt ökat globalt det senaste decenniet med tidvis ansträngd resursmarknad som följd. Träspån anses komma bli en bristvara i framtiden och aktörer ser sig redan om efter alternativa råvaror. Olika typer av gräs som till exempel rörflen har visat sig ha stor potential. I denna studie testas ett våtmarksgräs som additiv i bränslepellets, med 0,5, 1, 1,5, och 1,9% inblandning. Pelletsproduktion samt tester gjordes i pilotanläggningen på Karlstads universitet, avdelningen för miljö-, och energisystem.  Energiförbrukning, fukthalt, hållfasthet och bulkdensitet är några av de variabler som testades. Pellets med våtmarksgräs jämfördes med ett referensprov med endast granspån samt ett prov med ett vanligt förekommande additiv (potatisstärkelse 1%). Kvalitén på pellets bedömdes utifrån den europeiska standarden. Resultatet visade att den specifika elförbrukningen minskade med 14% när 2% våtmarksgräs adderades, en del av den minskningen kan bero på det ökade produktionsflödet jämfört med referensprovet. De positiva effekter på specifik elförbrukning som 1% potatisstärkelse resulterade i, visade våtmarksgräs 1% liknande effekt. Detta indikerar smörjande egenskaper hos våtmarksgräset. En orsak kan vara den höga halt extrakt, såsom vaxer, som många örtartade växter består av. Dessa har i tidigare studier setts minska friktionen i pressen vilket reducerar elförbrukningen. Pellets med våtmarksgräs som additiv klarade inte de Europeiska kraven på hållfasthet. En låg fukthalt och närvaron av extrakt kan ha medfört svaga gränslager i pellets och därmed påverkat hållfastheten negativt. En svag trend visade på förbättring av hållfastheten vid högre andelar våtmarksgräs. Den varierande storleken på partiklar som sampelleteras kan ha bidragit till detta. Fukthalten är godkänd enligt den europeiska standarden men under det optimala 8%. Detta trots en relativt hög uppmätt fukthalt innan pressen. En högre fukthalt i samband med pressning hade troligen höjt kvaliteten generellt. Förslag till vidare studier är att utföra tester med större variation på mängden våtmarksgräs, för att få ett tydligare resultat. Extraktivens beteende i samband med andra varierande parametrar som exempelvis fukthalt, borde studeras närmare för att kunna bedöma våtmarksgräsets möjligheter som additiv. För en hållbar utveckling av förnybar energi är det viktigt att säkerställa den framtida råvarumarknaden för pellets. Fortsatta studier bör göras för att bidra till utvecklingen av alternativa råvaror i samband med pelletsproduktion.

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Den ökade efterfrågan på pellets har fört med sig högre krav på pelletkvalité och detta har lett till att forskningen i Sverige har övergått från att studera möjliga bränslen till att studera pelletkvalité, ofta med fokus på mekanisk hållfasthet. För att pröva den mekaniska hållfastheten så finns olika standardmetoder såsom tumling enligt ISO 17831-1:2015, som är europeisk standard, och lignotest. Standardmetoderna kräver en större mängd pellets och kan inte användas för att pröva pellets från en singelpelletpress, vilket är ett mycket vanligt sätt att producera nya pelletsammansättningar. En singelpelletpress tillverkar en pellet åt gången och för att prediktera mekaniska hållfastheten finns många olika metoder, till exempel dropp- och hårdhetstest. Det är idag oklart hur väl metoderna för att pröva pellets från en singelpelletpress predikterar mekaniska hållfastheten och det finns en begränsad mängd forskning som undersöker korrelationen med standardmetoderna. Äldre forskning visar på en positiv linjär korrelation medan nyare forskning visar att korrelationen även beror på pelletens sammansättning. Det finns också studier som använder nya sätt att pröva enstaka pellets. En ny studie tumlar pellets tillsammans med plastpellets, men inga jämförelser med andra metoder utförs. En annan studie prövade tumling samt lignotest för en pellet åt gången och jämförde med tumling enligt ISO 17831-1:2015. Den studien visade ett R2 på 0.83 respektive 0.94 för pellets med en mekanisk hållfasthet över 90%.  En metod som korrelerar med standardmetoderna skulle mycket tydligare indikera hur en pellet från en singelpelletpress skulle prestera i större produktionsskala. Om metoden även utnyttjar redan tillgänglig teknik finns möjligheten för en bred användning, likt en standardmetod, som skulle underlätta jämförelser mellan olika studier och samarbeten mellan forskningsinstitut.  I detta arbete undersöks validiteten av att tumla enstaka pellets tillsammans med plastpellets. Plast- och singelpelletsmixen som innehöll 3, 10 och 20 pellets, resterande del (upp till 500g ±10g) plastpellets, tumlades för 6 olika sorters pellets. Standardavvikelse, relativ standardavvikelse samt medelvärdet av mekaniska hållfastheten bestämdes och den linjära regressionen med tumling enligt ISO 17831-1:2015 undersöktes. För samma pelletsorter genomfördes dropptest och hårdhetstest där den linjära regressionen med tumling enligt ISO 17831-1:2015 även gjordes för hårdhetstestet. Resultaten visar att tumling med plast- och singelpelletmix fungerar som alternativ metod till ISO 17831-1:2015 för pellets med en mekanisk hållfasthet över 92,45%, där mycket tillförlitligt resultat fås för 3 eller fler tumlade pellets över 96,62% mekanisk hållfasthet där 8 av 9 uppmätta standardavvikelser var under 1 %. För hela det prövade kvalitetsintervallet visades en korrelation (R2) med standardmetoden på 0,88-0,98 och ett R2 nära 1 för pellets med en mekanisk hållfasthet över 95 %. Dropptestet gav ingen information om pelletens mekaniska hållfasthet och bedömdes inte som en lämplig metod. Hårdhetstestet visade en hög relativ standardavvikelse mellan 19-40 % och en korrelation (R2) med standardmetoden på 0,78. Tumling med plast- och singelpelletmix hade både lägre standardavvikelse och högre korrelation med standardmetoden som visar att det är en bättre metod för att prediktera mekaniska hållfastheten för enstaka pellets än hårdhetstest. / The increased demand of pellets has led to higher demand on pellet quality causing a shift in Swedish research from studying possible fuels to studying pellet quality, often with a focus on mechanical durability. To test the mechanical durability there are various standard methods such as tumbling according to ISO 17831-1:2015, which is the European standard, and lignotest. The standard methods require a large amount of pellets and can´t be used to test pellets from a single-pellets press, a common way to produce new pellet compositions. A single-pellet press produces one pellet at a time and to predict the mechanical durability there are different methods, such as drop and hardness tests. Today it´s unclear how well the methods for testing pellets from a single-pellets press predicts the mechanical durability and there are a limited amount of research that examines the correlation with the standard methods. Earlier research shows a positive linear correlation while a recent publish study showed that the correlation also depends on the composition of the pellet. However, also new ways to test individual pellets has recently bin published, where single pellets were tumbled together with plastic pellets, but no comparisons with other methods were made. Another study tried tumbling and lignotest for one pellet at a time and compared with ISO 17831-1:2015. The study showed an R2 of 0,83 and 0,94 respectively for pellets with a mechanical durability above 90% A method that correlates with the standard methods would indicate how a pellet from a single-pellet press would preform on a larger production scale. If the method also uses already known technology there is the possibility of a broad use, similar to a standard method, wich would facilitate comparisons between different studies and collaborations between research institutes.   In this study, the validity of tumbling individual pellets together with plastic pellets is investigated. The plastic and single-pellet mix containing 3, 10 and 20 pellets, the remaining part (up to 500 ±10g) plastic pellets, was tumbled with 6 different types of pellets. Standard deviation, relative standard deviation and the mean value of the mechanical durability were determined and the linear regression with tumbling according to ISO 17831-1:2015 was examined. For the same pellet varieties, drop and hardness tests where preformed, where the linear regression with ISO 17831-1:2015 was also examined for the hardness test.   The results show that tumbling with plastic and single-pellet mix works as an alternative method to ISO 17831-1:2015 for pellets with a mechanical durability above 92,45 %, where very reliable results was obtained for 3 or more tumbled pellets above 96.62 % mechanical durability where 8 out of 9 standard deviations measured below 1%. For the entire tested quality range, a correlation (R2) was shown with ISO 17831-1:2015 of 0.88-0.98 and an R2 close to 1 for pellets with a mechanical durability over 95 %. The drop test did not provide any information on the mechanical durability of the pellet and was not considered an appropriate method. The hardness test showed a high relative standard deviation between 19-40 % and a correlation (R2) with ISO 17831-1:2015 of 0.78. Tumbling plastic and single-pellet mix had both lower standard deviation and higher correlation with the standard method ISO 17831-1:2015 which shows that it is the superior method for predicting the mechanical durability of individual pellets over hardness test.

In this dissertation, the effect of temperature and humidity on the viscoelastic and fracture properties of proton exchange membranes (PEM) used in fuel cell applications was studied. Understanding and accurately modeling the linear and nonlinear viscoelastic constitutive properties of a PEM are important for making hygrothermal stress predictions in the cyclic temperature and humidity environment of operating fuel cells. In this study, Nafion® NRE 211, Gore-Select® 57, and Ion Power® N111-IP were characterized under various humidity and temperature conditions. These membranes were subjected to a nominal strain in a dynamic mechanical analyzer (DMA), and their stress relaxation behavior was characterized over a period of time. Hygral master curves were constructed noting hygral shift factors, followed by thermal shifts to construct a hygrothermal master curve. This process was reversed (thermal shifts followed by hygral shifts) and was seen to yield a similar hygrothermal master curve. Longer term stress relaxation tests were conducted to validate the hygrothermal master curve. The Prony series coefficients determined based on the hygrothermal stress relaxation master curves were utilized in a linear viscoelastic stress model. The nonlinear viscoelastic behavior of the membranes was characterized by conducting creep tests on uniaxial tensile specimens at various constant stress conditions and evaluating the resulting isochronal stress-strain plots. The nonlinearity was found to be induced at relatively moderate stress/strain levels under dry conditions. To capture the nonlinearity, the well known Schapery model was used. To calculate the nonlinear parameters defined in the Schapery model, creep/recovery tests at various stress levels and temperatures were performed. A one-dimensional Schapery model was developed and then validated using various experiments. The fracture properties were studied by cutting membranes using a sharp knife mounted on a specially designed fixture. Again, various temperature and humidity conditions were used, and the fracture energy of the membranes was recorded as a function of cutting rate. Fracture energy master curves with respect to reduced cutting rates were constructed to get some idea about the intrinsic fracture energy of the membrane. The shift factors obtained from the fracture tests were found to match with those obtained from the stress relaxation experiments, suggesting that the knife cutting process is viscoelastic in nature. The rate and temperature dependence for these fracture energies are consistent with the rate, temperature, and moisture dependence of the relaxation modulus, suggesting the usefulness of a viscoelastic framework for examining and modeling durability of fuel cell membranes. The intrinsic fracture energy was initially thought to be a differentiating factor, which would separate various membranes tested in this study from one another. However, it was later found that all the membranes tested showed similar values at lower cutting rates, but showed significant variation at higher reduced cutting rates, and thus was thought to be a more meaningful region to differentiate the membranes for durability understanding. While the preceding work was undertaken to characterize as-received commercial PEMs, it is possible to modify material properties through treatment processes including thermal annealing and water treatment. The transient and dynamic viscoelastic properties of water-treated Nafion membranes revealed unusual behavior. Such unusual properties might have originated from irreversible morphological changes in PEM. Besides the constitutive viscoelastic properties, another set of properties useful for the stress modeling is the hygral strain induced as a function of relative humidity (RH) The effect of pretreatment on hygral strains induced as a function of RH was also investigated. These studies suggest that pretreatment significantly changes the mechanical properties of proton exchange membranes. / Ph. D.

Cette thèse porte sur la fonctionnalisation de fils en acier inoxydable via des revêtements colorés base titane, élaborés par pulvérisation cathodique avec un magnétron cylindrique. Ce travail s’intéresse à la caractérisation chimique, morpho-structurale et à l’évaluation de la durabilité mécano-chimique des fils revêtus.Premièrement, la vitesse de dépôt et la composition chimique des films sont déterminées dans des conditions statiques. Les hétérogénéités du plasma dans la cathode sont démontrées et reliées aux paramètres tels que la puissance, la pression et la polarisation d’anodes auxiliaires.Les dépôts monocouches de Ti, TiN et TiOx sont ensuite élaborés en continu. La relation entre la couleur du TiN et sa composition chimique est établie. La couleur dorée est obtenue pour des films stœchiométriques contenant peu d’oxygène (< 5 %at.). Les microstructures sont caractérisées par MET-ASTAR et des cartographies d’orientation sont dressées à l’échelle nanométrique. Tandis que les dépôts de TiN sont colonnaires avec une texturation selon <111>, les grains des films de Ti sont plutôt équiaxes et orientés selon <0001>. Pour une température d’élaboration de 650 °C, les éléments du substrat diffusent dans les films et mènent à la formation de phases de Laves. Les dépôts de TiOx, élaborés en mode métallique, présentent des couleurs d’interférence et une composition proche du monoxyde. Les surfaces revêtues de TiN ont une résistance à la corrosion élevée semblable à l’acier inoxydable 316L, contrairement aux fils revêtus de Ti et TiOx. La ténacité et l’énergie d’adhérence des revêtements sont déterminées par traction in-situ sous MEB : Ti et TiN sont particulièrement adhérents au substrat contrairement à TiOx.Enfin, les dépôts sont architecturés avec l’ajout d’un dépôt de titane entre le substrat et le revêtement céramique. Ainsi, l’adhérence du film Ti-TiOx est largement augmentée par rapport au monocouche TiOx (5 à 200 J/m2). Enfin, les études microstructurales et électrochimiques montrent qu’un paramètre clef de la résistance à la corrosion est la présence de porosité ouverte dans les revêtements. / This thesis treats of the functionalization of stainless steel wires with colored Ti-based coatings, grown by PVD with a cylindrical magnetron, their chemical and morpho-structural characterization, and the evaluation of the chemico-mechanical durability of the coated wires.First, the deposition rate and the chemical composition of the films are determined under static conditions. Cathode plasma heterogeneities are demonstrated and related to parameters such as power, pressure and polarization of auxiliary anodes.Then, Ti, TiN and TiOx monolayer coatings are grown continuously. The relationship between the color of TiN and its chemical composition is established and golden color is obtained for stoichiometric films with low oxygen content (<5% at.). Microstructures are studied with TEM-ASTAR and orientation maps are obtained with a nanometric resolution. While TiN coatings are columnar with <111> texture, Ti grains are rather equiaxed and <0001> oriented. With a 650 ° C substrate temperature, substrate elements diffuse into the films which results in Laves phase formation. TiOx is grown in metallic mode, presents interference colors and a composition close to monoxide. TiN coated surfaces display high corrosion resistance similar to 316L stainless steel, unlike Ti and TiOx coated wires. The toughness and the adhesion energy of the coatings are determined by SEM in-situ tensile tests: Ti and TiN are particularly adherent to the substrate in contrast to TiOx.Finally, coatings are architectured with the addition of a titanium interlayer between the substrate and the ceramic coating. Thus, Ti-TiOx film adhesion is greatly superior compared to the TiOx monolayer (5 to 200 J/m2). Finally, microstructural and electrochemical studies show that a key parameter of corrosion resistance is the presence of open porosity in the coatings.

Les pompes sèches primaires dédiées aux procédés de fabrication en microélectronique sont soumises à des environnements très corrosifs de plus en plus oxydants et halogénés (Cl2, F2 et O2). Or pour des raisons mécaniques et économiques, les parties fonctionnelles des pompes sont usinées dans la fonte à graphite sphéroïdale EN-GJS-500-7. La fonte est alors protégée par un dépôt de nickel-phosphore (NiP) chimique. Cette thèse, reprend des études classiques sur la cinétique et le mécanisme de nickelage d'une part, et sur l'optimisation des propriétés mécaniques et la résistance à la corrosion des couches de NiP d'autre part. Cependant, le caractère innovant de ce travail repose sur la réalisation de couches NiP sur un substrat en fonte à graphite sphéroïdale.L'étude de la cinétique de nickelage et la caractérisation morphologique des revêtements en fonction du temps de dépôt a montré l'influence de la nature chimique du substrat. Les sphères de graphite affleurantes à la surface du substrat n'étant pas catalyseur du nickel chimique, provoque des défauts dans le revêtement, dommageables pour la conformité du dépôt. Il a été montré qu'une polarisation cathodique de la surface du substrat pouvait, dans les premiers instants du dépôt, amorcer le nickelage à l'aplomb des sphères de graphite.Une relation entre la microstructure des dépôts en fonction des traitements thermiques subis et des propriétés mécaniques des couches de NiP a été mise une évidence. Les dépôts NiP amorphes présentent une faible dureté et un comportement ductile tandis que les dépôts cristallisés possèdent une dureté élevée et un comportement fragile. Ces dépôts ont une bonne tenue à la corrosion en milieux halogéné lorsqu'ils sont intacts. Actuellement, au niveau industriel, les dépôts les plus fragiles sont choisis, bien qu'ils présentent une résistance à la corrosion plus faible : en effet, la durée de vie des pompes est alors supérieure car les effets de grippage sont atténués.Mots-clés : nickel chimique, résistance à la corrosion, fonte à graphite sphéroïdale, caractérisation physico-chimique, couches minces, durabilité mécanique / Primary dry pumps dedicated to manufacturing processes in microelectronics are subjected to highly corrosive environments that are increasingly oxidizing and halogenous (Cl2, F2 and O2). However, for mechanical and economic reasons, the functional parts of the pumps are machined in EN-GJS-500-7 spheroidal graphite cast iron. The cast iron is consequently protected by a nickel-phosphorus chemical deposit. This thesis is based on classical studies on the kinetics and the nickel-plating mechanism on the one hand, and on the optimization of the mechanical properties and corrosion resistance of the NiP layers on the other hand. The innovative nature of this work is based on the production of NiP layers on a spheroidal graphite cast iron substrate.The study of the kinetics of nickel-plating as well as the morphological characterization of coatings as a function of the deposit time showed the influence of the chemical nature of the substrate. The flush graphite spheres on the surface of the substrate being not a catalyst for the chemical nickel, they can cause defects in the coating and a loss of compliance. It has been shown that a cathodic polarization of the surface of the substrate, in the first moments of the deposit, could initiate the nickel-plating right on the graphite spheres.A relationship exists between the microstructure of the deposits as a function of the thermal treatments undergone and the mechanical properties of the NiP layers. The amorphous NiP deposits have a low hardness and a ductile behavior while crystallized deposits have a high hardness and a brittle behavior. These deposits have a good resistance to corrosion in halogenated environments when they are intact. Actually, at the industrial level, the most brittle deposits are chosen, although they have a lower corrosion résistance: indeed, the service life of the pumps is higher because the seizing effect are minimized.Keywords: electroless nickel, resistance to corrosion, spheroidal graphite cast iron, physicochemical characterization, thin layers, mechanical durability

The diploma thesis is focused on the behaviour of natural and synthetic aggregates and their behaviour in polymer – cement composites, while being exposed to high temperature. The processes, happening in aggregates and mortar under the thermal load, were described in the theoretical part of the thesis same as the testing of heat effects on the aggregates and mortar. Further, the influence of high temperature on each component of concrete was described, followed by the suggestion of the appropriate components for concrete exposed to high temperature. Various aggregates were tested in the experimental part of the thesis. The basic physical and mechanical properties of aggregates were examined same as their mineralogical composition with using XRD, DTA and SEM methods. At the mortar, the influence of high temperature on the concrete density, compressive strength and tensile strength was defined. The gained knowledge was evaluated in the final part of the thesis