In the Swedish concept for final disposal of spent nuclear fuel, referred to as KBS-3, a three-layered protection system is used. The system consists of a copper canister holding the spent nuclear fuel deposited 500 meters in a repository built in groundwater saturated granitic rock. The copper canisters are placed in deposition holes, buffered and backfilled by bentonite clay. One of the challenges associated with this system is the long-term exposure of the engineered barriers i.e. the canister including the spent fuel and the cast iron insert as well as the bentonite buffer to ionizing radiation. The possible effects of radiation on the materials in the engineered barriers have been studied not only by the Swedish Nuclear Fuel and Waste Co (SKB), but also by academia nationally and internationally. In this work, literature studies have been carried out to investigate whether all possible/potential effects of ionizing radiation from the spent nuclear fuel on the engineered barriers have been considered by SKB. Apart from a general summary of the relevant issues in chapter one, regions within the KBS-3 design where enhanced radiation may occur have been identified and the related radiation induced processes have been summarized in chapter two. These issues include effects of water-radiolysis on the spent fuel, the cast-iron insert and other ferrous materials, the copper shell and the bentonite buffer. Three types of possible damages have been identified: the microstructural defects in the ferrous materials by direct radiation, the radiation-induced microstructural alterations of the spent fuel and the bentonite and radiation-induced oxidation i.e. dissolution of the fuel and corrosion of the ferrous metals and the copper. The relevant SKB documents have been identified (in chapter 3) to be the SR-Site main report, the underlying Process reports and reports of FUD-programs. Apart from these documents, other SKB technical reports and open literature are used as basis for assessing whether all the issues mentioned in chapter two of this study have been considered by SKB.  According to the assessment, most of the significant issues mentioned in chapter two have been mentioned and discussed in the identified SKB documents. In the main safety assessment, i.e. the SR-Site project, the significance of most of the radiation processes has been based on dose levels expected at the different regions within the KBS-3 design. Irrespective of the assessments in SR-Site though, the current understanding of the relevant issues and plans for future research efforts summarized in FUD-programs reflect the research developments. However, the recent developments in understanding of radiation-induced effects on montmorillonite and the corrosion of copper in argon atmosphere need to be given due importance in coming FUD-programs. A separate investigation of radiation effects on FSW-joints may contribute to removal of the remaining uncertainties. In addition, mechanism involved in radiation-induced fuel dissolution and copper corrosion may require more research efforts than those planned. / Det svenska konceptet för slutförvar av använt kärnbränsle, KBS-3, består av tre barriärer som är tänkt att skydda omgivningen mot joniserande strålning från använt kärnbränsle. Systemet består av specialtillverkade kopparkapslar som innehåller det använda kärnbränslet. Kapslarna förvaras i deponeringshål 500 meter ner i berggrunden och är inneslutna i bentonitlera. En av frågeställningarna associerade med djupt geologiskt förvar av kärnbränsle är hur de konstruerade barriärna, alltså kopparhöljen som omsluter gjutjärninsatsen och det använda kärnbränslet samt bentonitleran, kan påverkas av joniserande strålning från det använda kärnbränslet. Möjliga strålningseffekter på de skyddande barriärna har studerats nationellt och internationellt. Syftet med denna studie var att utvärdera huruvida SKB har i sina säkerhetsanalyser av slutförvaret tagit tillräcklig hänsyn till effekter av joniserande strålning på de konstruerade barriärna. Studien består av tre kapitel där kapitel 1 utgör en generell sammanfattning av frågeställningar kopplade till KBS-3 barriärer. I kapitel 2 har områden i och omkring de konstruerade barriärna där joniserande strålning från använt kärnbränsle kan förekomma identifierats och möjliga strålningsinducerade processer i dessa områden sammanfattats. Tre typer av möjliga strålningsinducerade skador har identifierats: 1) strålningsinducerade mikrostrukturella defekter i metaller som förekommer i systemet, 2) strålningsinducerade mikrostrukturella förändringar i använt kärnbränsle och i bentonitleran samt 3) strålningsinducerad oxidation, dvs. upplösning av det använda kärnbränslet och korrosion av metaller som förekommer i systemet. SKB-dokumenten som identifierats (i kapital 3) som relevanta för utvärderingen i denna studie är följande: Säkerhetsanalysen (SR-Site), tekniska rapporter som ligger till grund för SR-Site och FUD-programmen. Enligt bedömningen i denna studie har SKB tagit hänsyn till de flesta relevanta frågeställningarna kopplade till strålningsinducerade effekterna på de konstruerade barriärna. I SR-Site har de flesta bedömningar relaterade till och om signifikansen hos de strålningsinducerade processerna baserats på doser och dosrater som förväntas förekomma i och omkring de konstruerade barriärna. Oavsett bedömningarna i SR-Site har dock de mest relevanta frågeställningarna tagits upp i FUD-programmen och framtida forskningsinsatser i enlighet med det som av SKB har uttryckts som behov av en utökad processförståelse. Dessa frågeställningar reflekterar väl de mest signifikanta utvecklingarna som rapporterats i öppna vetenskapliga studier om strålningsinducerade processer som kan förekomma i ett djupt geologiskt förvar för använt kärnbränsle. De senaste rapporterade observationerna om strålningseffekter på montmorillonit och kopperkorrosion i argonatmosfär måste dock tas upp och diskuteras i de kommande FUD-programmen. Separata studier av strålningseffekter på koppardelar som har behandlats med FSW-teknik rekommenderas. För att uppnå en bättre och djupare förståelse för de förekommande mekanismerna i strålningsinducerad upplösning av använt kärnbränsle krävs sannolikt mera forskningsinsatser än de planerade.

The purpose of this lab was to investigate the printability of cellulose nanofiber/carbon nanotubes, their functions as actuators, and to compare these properties with MXene/nano cellulose gels. Data on MXene/nano cellulose gel was obtained from previous research made by Hamedi labs. Data on carbon nanotubes were collected through experiments evaluating different concentrations and sonication times to yield a gel with high conductivity and viscosity. While it was concluded that both gels could be printed into 2D or 3D shapes, the latter failed to maintain its structure over time due to issues with drying. However, it was found that only 2D MXene/CNF could be used as a reversible actuator. / Syftet med laborationen var att undersöka 3D skrivningsförmågan för nanocellulosa/ kolnanorör samt samt deras förmåga att fungera att svälla elektroniskt. Vidare jämfördes dessa egenskaper med MXene/nanocellulosageler. Data på MXene/nanocellulosa insamlades från tidigare experiment gjorda av Hamedi labs. Data på kolnanorör insamlades genom en rad experiment, vilka utvärderade olika koncentrationer och sonikeringstider för att producera geler med hög konduktivitet och viskositet. Slutsatsen blev att båda gelerna kunde 3D printas, men endast MXene/nanocellulosageler kunde användas för elektronisk svällning och avsvällning. Inga geler kunde göras till 3D strukturer.

This report explores simultaneous crystallization in multicomponent solutions to intensification of metal recovery in lithium-ion batteries. The main focus is to evaluate and compare the efficiency of sodium hydroxide and sodium carbonate as precipitating agents in recovering cobalt, nickel, manganese and lithium. To be able to do this, 15 different metal systems were precipitated with these two precipitating agents at 8 and 12 molar equivalent. The samples were then analyzed through ICP-OES, XRD, gravimetric analysis, and SEM-EDX. The results showed that the precipitation efficiency of the transition metals cobalt, nickel and manganese, in all the system was 98% or more. Lithium precipitated only with carbonate. In the system with four metals and 12 molar equivalents carbonate lithium 78% was precipitated. The results indicate that higher concentration of carbonate leads to higher precipitation efficiency. A way to likely reach a higher effective concentration is to first neutralize the solution with sodium hydroxide and then precipitate it with carbonate.

Since the discovery in 1977 that conjugated polymers can be doped to achieve almost metallic electronic conduction, the research field of conducting polymers has escalated, with applications such as light emitting diodes, solar cells, thin film transistors, electrochemical transistors, logic circuits and sensors. The materials can be chemically modified during their synthesis in order to tailor the desired mechanical, electronic and optical properties of the final product. Polymers are also generally possible to process from solution, and regular roll-to-roll printing techniques can therefore be used for manufacturing of electronic components on flexible substrates like plastic or paper. On top of that, the nature of conjugated polymers enables the creation of devices with novel properties, which are not possible to achieve by using inorganic materials such as silicon. The work presented in this thesis mainly focuses on devices that utilize two rather unique properties of conducting polymers. Conducting polymers are generally electrochromic, i.e. they change color upon electrochemical oxidation or reduction, and can therefore be used as both conductor and pixel element in simple organic displays. As a result of the electrochemical reaction, some polymers also alter their surface properties and have proven to be suitable materials for organic electronic wettability switches. Control of surface wettability has applications in such diverse areas as printing techniques, micro-fluidics and biomaterials. The aim of the thesis is to briefly describe the physical and chemical background of the materials used in organic electronic devices. Topics include molecular properties and doping of conjugated polymers, electrochromism, surface tension etc. This slightly theoretical part is followed by a more detailed explanation of device design, functionality and characterization. Finally, a glance into future projects will also be presented. / <p>ISRN/Report code: LiU-TEK-LIC-2005:50</p>

Elektrokemisk korrosionsanalys av legeringar är en essentiell del av den större materialanalysen som måste utföras när en legerings lämplighet för en viss applikation evalueras. Nickelbaserade legeringar är kända för sin utmärkta korrosionsresistans, och de Ni-Cr-Mo-baserade legeringarna 59, 625, och 718 är också så kallade superlegeringar. Superlegeringar karaktäriseras med att legeringarna behåller sina mekaniska, termiska, och korrosion egenskaper även vid temperaturer nära smältpunkten. Den elektrokemiska korrosionsanalysen av legeringarna 59, 625, och 718 utfördes med OCP, cyklisk polarisation, samt EIS. Experimenten utfördes i en tre-elektrod elektrokemisk cell med en Ag/AgCl referenselektrod och en platina motelektrod, så väl som en Gamry Reference 600+ potentiostat. Detta arbete framhäver vikten att utföra cyklisk polarisation i korrosionsanalysen eftersom metod kan upptäcka viktiga skillnader mellan till synes liknande legeringar, vilket kunde ses vid jämförelsen av legering 718 med 625 och 59. EIS visas också vara en kraftfull analytisk verktyg genom sin förmåga att approximera verkliga elektrokemiska system genom att använda elektriska kretsar, så väl som EIS:s förmåga att användas som ett komplementärt analytiskt verktyg för att assistera i interpretationen av cyklisk polarisationsdata. / Electrochemical corrosion analysis of alloys forms an essential part of the larger material analysis procedure that needs to be performed when evaluating the feasibility of an alloy for a certain application. Nickel-based alloys are known for having excellent corrosion resistance, and the Ni-Cr-Mo-based alloys 59, 625, and 718 are also known as superalloys. Superalloys are characterized by the alloy maintaining its mechanical, thermal, and corrosion properties even at temperatures close to the melting point. The electrochemical corrosion analysis of alloys 59, 625, and 718 was performed with OCP, cyclic polarization, and EIS. The experiments made use of a three-electrode electrochemical cell with an Ag/AgCl reference electrode and a platinum counter electrode, as well as a Gamry Reference 600+ potentiostat. This work highlights the importance of performing cyclic polarization in the corrosion analysis since the method can reveal important differences in seemingly similar alloys, which was seen when comparing alloy 718 with 625 and 59. EIS is also shown to be a powerful analytical tool through the method's ability to approximate real electrochemical systems using electrical circuits, as well as the ability of EIS to be used as a complementary analytical tool to assist in interpreting cyclic polarization data.

Polyedrisk oligomer silsesquioxane (POSS) är molekyler som har en inorganisk ryggrad med organiska grupper fa ̈sta utan på. Själva kåren har en bur liknande form och har en hög termisk stabilitet tack vare kisel (Si) och syre (O) som den består av. Det organiska grupperna som kan fästas på kåren kan variera för att få en molekyl som är anpassad för det material den ska blandas in i, tillexempel polyvinylklorid (PVC). POSS molekylerna kan blandas in i material antigen fysiskt eller kemiskt beroende på vilka organiska grupper molekylen består av. Tack vare den termiska stabiliteten POSS är på en intressant molekyl att använda som ett alternativt flamskyddsmedel till existerande flamskyddsmedel.  Det olika POSS materialen var producerade med lite olika reaktions parametrar och var gjorda av Funzionano AS i Norge, Porsgrunn. Materialet har bevarat olika lång tid men det olika POSS materialen har också olika funktionella grupper. Provet med namn SF458 211122 var också adderat till PVC materialet för att se om det påverkade PVC:s termiska egenskaper.  Syftet med detta master arbete är att kolla om tiden proverna bevaras, olika funktionella grupper och om olika reaktions parametrar kommer påverka det termiska egenskaperna. Dessa parametrar utforskas genom att använda analys instrumenten TGA/DSC och DSC. Men också för att se om POSS förbättrar PVC:s termiska egenskaper.  Resultaten visar att 3 av det 4 olika SF458 proverna hade liknande glasstransaktions temperaturer (Tg) som är runt 27 °C även om det förvarats olika lång tid. 1 av det 4 olika SF458 hade högre Tg vilket kan bero p ̊a att den syntesen hade andra reaktions förhållanden i sista reaktions steget bland annat. Smältpunkten och mängden prov kvar efter TGA analyserna kan påverkas av förvaringstiden eller reaktions förhållandena. För att få fram vad som påverkar vad måste mer forskning göras. / Polyhedral oligomeric silsesquioxane (POSS) are molecules with an inorganic backbone which has organics groups attached to the backbone. The backbone is like a cage and the functional groups are arms that goes out from the cage. The inorganic backbone does so the molecule has high thermal stability and the functional groups make it possible to tailor the molecule so it can be easier to physical or chemical blend it into a material, like thermoplastics. The thermal properties of POSS make it to an interesting alternative as a flame retardant since it is also not has hazardous as other common flame retardants.  The different POSS material have been synthesised with some different reaction parameters and were prepared by Funzionano AS in Norway, Porsgrunn. The material have been stored for different times but also the cage have different functional groups attached to it. POSS named SF458 211122 were also physically incorporated to polyvinyl chloride (PVC) to see if it have any effect on the thermal properties.  The aim of the study is to see if the time of storage, different functional groups and different synthesis parameters affect the thermal properties of the POSS material by using DSC and TGA/DSC instruments. But also to see if the thermal properties of PVC is improved when POSS is physically added.  The results showed that 3 of 4 of the different SF458 samples had similar glass transition temperatures (Tg), around 27 °C so the time of storage does not affect that property. Since 1 of the 4 samples had a higher Tg is probably due to other synthesis conditions. The affect in melting point and amount of residue can be effected by either the time of storage or the parameters for the synthesis. So, further research needs to be done.

Mitt i Europas växande beroende av extern antimonproduktion har Europeiska kommissionen konsekvent betonat ett växande gap mellan utbud och efterfrågan sedan 2014. Som svar på denna utmaning riktade sig denna studie mot sekundära antimonkällor från underutnyttjade rester av guld, koppar och blymalm, som för närvarande utgör ett miljöproblem. Genom noggranna experiment, fastställde vi att optimal antimonurlakning uppnås vid 120 °C inom 2 timmar med en 250 g/L Na2S och 60 g/L NaOH-blandning. Detta tillvägagångssätt accentuerar selektiv extraktion, förbättrar antimonåtervinningen och minimerar kopparinterferens. En innovativ aspekt av denna studie var användandet utav mikrovågsassisterad urlakning, vilket visar fördelar i både utvinningseffektivitet och bevarande av mineralstrukturer jämfört med traditionella metoder. Våra resultat stöds av flera analytiska verktyg och ger en första förståelse, även om detaljerna kring mikrovågsassisterad urlakning och dess skalbarhet motiverar ytterligare utforskning. Denna studie introducerar en metod för urlakning av antimon från koppargruvavfall och föreslår ett motsvarande återvinningssystem som kan vara ekonomiskt lönsamt. Sådana ansträngningar kan ge ett blygsamt bidrag till att lindra den nuvarande situationen. / Amid Europe's growing reliance on external antimony production, the European Commission has consistently emphasized an expanding supply-demand gap since 2014. Responding to this challenge, our research targeted secondary antimony sources from underutilized residues of gold, copper, and lead ore processing, which currently pose environmental concerns. Through meticulous experimentation, we determined that optimal antimony leaching is achieved at 120°C within 2 hours, using a 250 g/L Na2S and 60 g/L NaOH mixture. This approach accentuates selective extraction, enhancing antimony recovery and minimizing copper interference. An innovative facet of this study was the adoption of microwave-assisted leaching, demonstrating advantages in both extraction efficiency and mineral structure conservation over traditional methods. Our results, backed by multiple analytical tools, provide an initial understanding, though areas like the specifics of microwave-assisted leaching and its scalability warrant further exploration. This study introduces a method for leaching antimony from copper mining waste and suggests a corresponding recycling system that may be economically viable. Such endeavors might offer a modest contribution to alleviating the present situation.

The mining of sulphidic ore to extract metals such as zinc and copper produces huge quantities of waste material. The weathering and oxidation of the waste produces what is commonly known as Acid Mine Drainage (AMD), a dilute sulphuric acid rich in Fe(II) and heavy metals. This thesis serves to summarise five papers reporting how the precipitation of Fe(III) phases can attenuate the contamination of heavy metals by adsorption processes. Schwertmannite (Fe8O8(OH)6SO4) is a common Fe(III) mineral precipitating in AMD environments at pH 3-4. The stability and surface chemistry of this mineral was investigated. It was shown that the stability depended strongly on pH and temperature, an increase in either promoted transformation to goethite (α-FeOOH). Two pH dependent surface species of SO42- were detected with infrared (ATR-FTIR) spectroscopy. The adsorption of Cu(II), Pb(II) and Zn(II) to schwertmannite occurred at lower pH than to goethite, whereas Cd(II) adsorption occurred in a similar pH range on both schwertmannite and goethite. Extended x-ray absorption fine structure (EXAFS) spectroscopy suggests two surface species for Cu(II) and Cd(II) at the schwertmannite surface. Cu(II) adsorbs monodentately and Cd(II) bridging bidentately to adsorbed SO42-. Both metal ions also adsorb in a bridging bidentate mode to the surface hydroxyl groups. At pH 7.5 up to 2.7 μmol Cd(II) m-2 could be adsorbed to schwertmannite, indicating a large adsorption capacity for this mineral. The acid-base properties of two NOM samples were characterised and could be well described as diprotic acids below pH 6. The adsorption of NOM to schwertmannite and goethite was very similar and adsorption occured in a very wide pH range. High concentrations of NOM increased the adsorption of Cu(II) to goethite at low pH whereas a slight decrease was noted at low concentrations of NOM. No effect was detected in the schwertmannite system. The formation of Fe(III) phases from precipitation of AMD was shown to be very pH dependent. At pH 5.5 a mixture of minerals, including schwertmannite, formed whereas at pH 7 only lepidocrocite (γ-FeOOH) formed. The concentration of Zn(II) in AMD could by adsorption/coprecipitation be reduced to environmentally acceptable levels.

<p>The mining of sulphidic ore to extract metals such as zinc and copper produces huge quantities of waste material. The weathering and oxidation of the waste produces what is commonly known as Acid Mine Drainage (AMD), a dilute sulphuric acid rich in Fe(II) and heavy metals. This thesis serves to summarise five papers reporting how the precipitation of Fe(III) phases can attenuate the contamination of heavy metals by adsorption processes. </p><p>Schwertmannite (Fe8O8(OH)6SO4) is a common Fe(III) mineral precipitating in AMD environments at pH 3-4. The stability and surface chemistry of this mineral was investigated. It was shown that the stability depended strongly on pH and temperature, an increase in either promoted transformation to goethite (α-FeOOH). Two pH dependent surface species of SO42- were detected with infrared (ATR-FTIR) spectroscopy.</p><p>The adsorption of Cu(II), Pb(II) and Zn(II) to schwertmannite occurred at lower pH than to goethite, whereas Cd(II) adsorption occurred in a similar pH range on both schwertmannite and goethite. Extended x-ray absorption fine structure (EXAFS) spectroscopy suggests two surface species for Cu(II) and Cd(II) at the schwertmannite surface. Cu(II) adsorbs monodentately and Cd(II) bridging bidentately to adsorbed SO42-. Both metal ions also adsorb in a bridging bidentate mode to the surface hydroxyl groups. At pH 7.5 up to 2.7 μmol Cd(II) m-2 could be adsorbed to schwertmannite, indicating a large adsorption capacity for this mineral.</p><p>The acid-base properties of two NOM samples were characterised and could be well described as diprotic acids below pH 6. The adsorption of NOM to schwertmannite and goethite was very similar and adsorption occured in a very wide pH range.</p><p>High concentrations of NOM increased the adsorption of Cu(II) to goethite at low pH whereas a slight decrease was noted at low concentrations of NOM. No effect was detected in the schwertmannite system. </p><p>The formation of Fe(III) phases from precipitation of AMD was shown to be very pH dependent. At pH 5.5 a mixture of minerals, including schwertmannite, formed whereas at pH 7 only lepidocrocite (γ-FeOOH) formed. The concentration of Zn(II) in AMD could by adsorption/coprecipitation be reduced to environmentally acceptable levels.</p>

<p>Diabetes mellitus is one of the most threatening epidemics of modern times with rapidly increasing incidence. Vanadium and peroxovanadium compounds have been shown to exert insulin–like actions and, in contrast to insulin, are orally applicable. However, problems with side–effects and toxicity remain. The exact mechanism(s) by which these compounds act are not yet fully known. Thus, a better understanding of the aqueous chemistry of vanadates and peroxovanadates in the presence of various (bio)ligands is needed.</p><p>The present thesis summarises six papers dealing mainly with aqueous speciation in different vanadate – and peroxovanadate – ligand systems of biological and medical relevance. Altogether, five ligands have been studied, including important blood constituents (lactate, citrate and phosphate), a potential drug candidate (picolinic acid), and a dipeptide (alanyl serine) to model the interaction of (peroxo)vanadate in the active site of enzymes. Since all five ligands have been studied both with vanadates and peroxovanadates, the number of systems described in the present work is eleven, including the vanadate – citrate – lactate mixed ligand system. The pH–independent formation constants have been determined for 33 ternary vanadate – ligand, 41 quaternary peroxovanadate – ligand and two vanadate – mixed ligand species in addition to the p<i>K</i>_a values of all five ligands. These constants have been used to model physiological conditions, and the biomedical relevance of the different species is discussed.</p><p>The studies have been performed at 25 ºC in the physiological medium of 0.150 M Na(Cl), i.e. the ionic strength of human blood. No buffers have been used, and wide pH–ranges have usually been covered. The applied experimental techniques comprise mostly ⁵¹V NMR and potentiometry, but ³¹P, ¹³C, ¹H and ¹⁴N NMR as well as EPR and ESI–MS have also been used to gain additional information. Multimethod data have been treated by the least–squares program LAKE and modelling has been carried out by the software package WinSGW.</p><p>Whenever possible, solution structures of the species have been proposed. In addition, simple biological tests have been carried out to determine the stability of the formed peroxovanadate complexes in the presence of human catalase. A brief comparison is given of the different vanadate – ligand and peroxovanadate – ligand systems with emphasis on observed trends and general features.</p>