Multifunctional drug delivery systems incorporated with stimuli-sensitive drug release, magnetic nanoparticles and magnetic resonance (MR) T2 contrast agents is attracting increasing attention recently. In this thesis, works on polymer nanospheres response to temperature change, superparamagnetic iron oxide nanoparticles (SPION)/polymeric composite materials for MR imaging contrast agents are summarized. A “shell-in-shell” polymeric structure has been constructed through a “modified double-emulsion method”. Thermosensitive inner shell is comprised of poly(N-isopropylacrylamide) which undergoes phase transition at body temperature. Such a feature could facilitate drug release at an elevated temperature upon administration. Furthermore, the dual-shell structure is covered by a layer of gold nanoparticles. According to the cytotoxicity tests, the biocompatibility is shown to be enhanced due to the layer of gold. SPION have been prepared using a high temperature decomposition method. Particle growth of SPION is monitored by transmission electron microscope and synchrotron X-ray diffraction. Poly(L,L-lactide)@SPION (PLLA@SPION) composite particles have been prepared through surface-initiated ring-opening polymerization which has been developed in our lab. For biomedical applications, it is essential to transfer the particles to physiological solutions from organic solutions. Phase transfer of SPION has been carried out by utilizing small molecules. Stability at the neutral pH is of large concern for such transfer systems. A novel phase transfer agent, Pluronic F127 (PF127), a triblock copolymer has been applied and the stability of the aqueous PF127@oleic acid (OA)@SPION solution has been greatly enhanced over a broad pH range. Most interestingly, PF127@OA@SPION show remarkable efficacy as T2 contrast agents as indicated by relaxometric measurements compared with commercially available products. / QC 20101115

The global transition to renewable energy sources is placing high demands on the development of effective energy storage methods, the most prevalent being batteries. Dual-ion batteries are a new battery technology that takes advantage of the simultaneous intercalation of both cations and anions. Dual-ion batteries can be made from environmentally friendly materials such as organic compounds or conductive polymers that are made up of highly abundant elements. These often have a lower cell voltage than metal-based batteries, allowing water-based electrolytes to be used without decomposing. This master’s thesis presents the synthesis, and electrochemical testing of a nanofibrous polyaniline cathode. It also presents the synthesis and electrochemical testing of two anodes being and graphene-enhanced polyimide, and perylene tetracarboxylic diimide (PTCDI). Aqueous ammonium sulfate of 1 M or 3 M concentration is used as electrolyte. A novel full-cell dual-ion battery is also constructed using polyaniline and PTCDI as electrodes. The addition of graphene to polyimide results in changes in morphology with decreased pore size and increased surface area for supposed improved reaction kinetics with the electrolyte. The electrochemical testing of this anode is however not successful. The polyaniline cathode has an early charge/discharge capacity of 184.5/85.2 mAh/g that decreases to 40.4/45.8 mAh/g after 100 cycles. The PTCDI anode has an early charge/discharge capacity of 80.2/87.3 mAh/g but cannot be evaluated after a few cycles due to electrolyte decomposition. For this reason, the electrolyte dependence on ammonium sulfate concentration is also investigated. An increase in molarity from 1 M to 3 M leads to increased stability of the electrolyte. The polyaniline//PTCDI full-cell has a voltage of 1.2 V and shows an early charge/discharge capacity of 17.6/11.9 mAh/g that decreases to 9.1/7.2 mAh/g after 100 cycles where the efficiency stabilizes at 80%.

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.

In this study a sample of particles in a size region of 0.05-10 μm were run through a centrifugation process with the ambition to make it monodisperse. The product requirements were stated as follows, particles within the size range of 2 to 3.8 μm should be isolated and separated from the sample with a D90/D10 < 1.4 where the D90/D50/D10 values should be approximately 3.8 μm/2.5 μm/2 μm. It was found that two layers of sucrose with a 50/50 volume distribution of 45w% sucrose solution and 60w% sucrose solution respectively, was the most efficient density gradient arrangement for separation of this particular sample. The optimal time and RPM combination was found to be 5 min 3000 RPM with a fast acceleration and slower deceleration, ratio 9:6. Two centrifugation rounds on the same sample improved D90/D10 drastically. The effect of centrifugation rounds on D90/D10 was not investigated further than 3 rounds, however this would be a good starting point for further studies. The upscaled test runs indicated a positive result, i.e. the yields with respect to both mass and purity were reproducible. It is worth mentioning that the upscale was only in the volume, sample load volume and surface area factors. The gradient height or particle travel distance remained the same.

Anthropogenic emission of greenhouse gases has long been suspected to contribute to global warming and climate change. Most greenhouse gases are emitted in a mixture, so efficient methods and materials to separate and capture the gases are in demand in order to reduce emissions. A promising material group for this purpose is metal-organic frameworks (MOFs). This class of material have the ability to selectively adsorb green house gases due to its high porosity and high surface area. Zeolitic imidazolate frameworks (ZIFs) are a subclass of MOFs that are topologically similar to zeolites and are known for their good chemical and thermal stability.   The aim of this project was to investigate if the greenhouse gas (i.e. CO2 and SF6) capture performance of ZIFs could be improved and tuned using a mixed-linker approach with seven different imidazolate-based organic linkers of different sizes or with various functional groups. As well as to investigate the processability of MOFs using 3D printing. ZIFs composed of different ratios of 2-methylimidazolate as base linker and a second linker of imidazolate, benzimidazolate, 2-aminobenzimidazolate, 5,6-dimethylbenzimidazolate, and 4,5-dichloroimidazolate were succesfully made. The materials were all found to be crystalline, however, mixed-linker ZIFs containing 2-aminobenzimidazole, 5,6-dimethylbenzimidazole and dichloroimidazole were observed to contain more than a single phase. All samples showed to be somewhat porous towards CO2 and SF6, and there seem to be a trend where a low % of a bulkier linker (eg. bIm, ambIm) resulted in a higher uptake of SF6 whereas a high % resulted in a higher uptake of CO2. For dcIm it was the other way around, a low % showed a higher uptake for CO2  whereas a high % showed a higher uptake for SF6. For CO2, the ZIF containing 80% benzimidazolate showed the highest uptake of 9.81 wt%. For SF6, the 25% 4,5-dichloroimidazolate showed the highest uptake of 17.73 wt%. Furthermore, direct ink writing (DIW) 3D printing was also successfully utilized to process and structure a Mn-based MOF using carbopol as binder. The printed structure was found to have similar properties to the pristine MOF in regards to crystallinity and porosity.

Fem metoder har använts för att modifiera barrvedslignin med syftet att öka reaktiviteten av ligninet mot epoxidgrupper. Ligninprover analyserades med NMR och FTIR medan reaktivitet var mätt genom reometri. Metoder som ökade mängden karboxylsyragrupper på ligninet minskade ligninets reaktivitet. Modifikation av lignin med resorcinol minskade reaktiviteten medan modifikation med fenol ökade reaktivitet mot epoxidgrupper. / Five different methods were used to modify softwood kraft lignin with the goal of increasing the reactivity of lignin towards epoxide groups. Lignin samples were characterized with NMR and FTIR while reactivity was measured through rheometry. Methods that increased carboxylic acid content in lignin decreased reactivity. Lignin modification with resorcinol decreased reactivity while lignin modified with phenol increased reactivity.

The increasing energy demand requires a transition from fossil fuels to renewable resources. Lithium-ion batteries (LIBs) offer a promising solution as efficient energy storage devices. However, the aluminum current collector (CC) in LIBs is susceptible to anodic dissolution above 3 V vs. Li+/Li in commercial carbonate liquid electrolytes, compromising the battery performance. In this study, various approaches were explored to mitigate anodic dissolution in LiFSI EC:DEC at high voltages of the aluminum CC in LIBs, employing cyclic voltammetry (CV) and scanning electron microscopy (SEM). It was found that boiling the Al foil in water in an air atmosphere to increase the thickness of the surface Al2O3 layer improved the anodic stability and offered enhanced protection against proton attack (due to the oxidation of the carbonate solvent at high voltage). However, increasing the LiFSI electrolyte concentration to 2 M did not increase the anodic stability due to the absence of a passivating AlF3 layer. Notably, in 4 M LiFSI, impurity-induced high F- concentration facilitated the formation of a passivating AlF3 layer, resulting in improved anodic stability. Moreover, specific volume ratios of LiFSI EC:DEC and 1 M LiPF6 EC:DEC (1:1) (LP40) yielded the F- concentration necessary for forming a passivating AlF3 layer and significantly enhanced the anodic stability. On the other hand, carbon-coating the Al foil did not show significant improvements regarding the anodic stability. It was found that the corrosion was time-dependent at a low scan rate, a drastic anodic dissolution of the aluminum was seen at higher temperatures, and the corrosion also became more pronounced. At room temperature, carbon-coated Al foils exhibited increased stability.

In today’s fast adjustment to renewable energy, new battery technologies are needed to meetthe ever-growing demands of energy storage. Cheaper and easier to produce materials areneeded, as well as materials with a lower environmental impact. One new and interestingtechnology is the dual-ion battery, and more specifically the aluminum dual-ion battery. Thisbattery uses cheap and abundant aluminum together with a graphitic cathode to work. However,a lot of research today uses expensive and sophisticated cathode materials to make this type ofbattery work. Therefore, this thesis focuses on creating a cheap and easy to produce graphitecathode material through the phase inversion method for the use in aluminum dual-ionbatteries, that is also freestanding for better energy density. Graphene is also used as anadditive to improve the electrical conductivity of the material, and the material is later tested in afull cell with the typical ionc liquid electrolyte EMImCL/AlCl4.Through phase inversion, a freestanding graphite cathode is produced with 8 wt% PVDF binderand 0.4 wt% graphene. The material has a porous structure and an enhanced electricalconductivity with the graphene added. Through CV cycling and symmetric Al-Al tests the batteryreactions are shown to work. However, when cycling the cell with a constant current there areproblems, probably coming from some sort of soft shorting or side reactions. It is revealed thatapart from the expected reactions, Ni dissolution from the contact tabs also takes place, andmay cause problems. Further tests are needed to validate if this material works. However,because no new active materials have been introduced to the battery chemistry, it is reasonableto believe that the battery will work with some small changes.Tek nisk-naturvetensk apliga fak ulteten, Upps ala universitet. Utgiv nings ort U pps al a/Vis by . H andledare: Anwar Ahniy az , Äm nesgranskar e: D aniel Brandell, Ex aminator: Lena Klintberg

Water pollution is a profound ecological concern, exerting detrimental effects on human well-being, ecological systems, and animal life. Among the emerging contaminants that critically influence water quality and have garnered substantial scientific interest in recent times are per- and polyfluoroalkyl substances (PFAS). It is crucial to investigate the de- velopment of an easy technique for PFAS detection and measurement that can be used for quick analysis. This thesis explores the possibility to use amine-functionalized mesoporous carbon as an adsorbent to develop a detection method based on sequential adsorption of per- and polyfluoroalkyl substances (PFAS) and a dye, Rose Bengal, onto the adsorbent. The hypothesis is that the concentration of non-adsorbed dye is dependent on the amount of PFAS present, making the color intensity of the remaining solution proportional to the PFAS concentration. Mesoporous carbon was chosen as the adsorbent due to their high specific surface area, providing a high adsorption capacity, and the potential to functionalize the surface with amine groups which will attract the PFAS. Rose Bengal was selected as a concentration indicator as it has been shown that it can be used as a proxy for PFAS. In this study, the most prevalent PFAS compounds, namely PFOA and PFOS, were investigated. Prior to testing, the adsorbent underwent characterization using diverse techniques to show the porosity and particle morphology. The adsorption experiments encompassed varying PFAS concentrations and a range of dye solutions to determine the detection range, the powder-to-solution ratio necessary for discernible differentiation, and the adsorption or saturation time for both PFAS and dye. This thesis concludes that it was not possible to detect neither PFOA nor PFOS in the range of 0.1 pg/mL to 1 μg/mL with the setup, even though Rose Bengal adsorption could be detected down to 0.6 μg/mL. It was further observed that amine-functionalized hard templated mesoporous carbon has a higher adsorption capacity compared to the soft templated material.

Metallic films are important in various applications, such as electric devices where it can act as contacts. In electrical devices, the substrate typically consists of silicon dioxide (SiO2) which is a temperature-sensitive substrate. Therefore, plasma enhanced chemical vapor deposition (PECVD) are better suited than thermally activated chemical vapor deposition (CVD). Depositing metallic films with PECVD demands co-reactants that act as reducing agents. However, these are not well-studied and do not always have the power enough to perform the reduction reaction for metals. Recently it has been concluded that electrons can act as reducing agents in the deposition of first row transition metallic films in a PECVD process. By supplying a positive bias to the substrate, the electrons got attracted to the surface of the substrate, which facilitated metal growth. The study concluded that metal growth only occurred at conductive -and semiconductive substrates and that the substrate bias and plasma power affected the metal growth. The process is however not well understood, which causes a knowledge gap, signifying that studies of the surface chemistry are needed. Here a new modified analytical method to study the surface chemistry in the newly developed process mentioned above is presented. The analytical method consists of an electrically modified quartz crystal microbalance (QCM) with gold electrodes as a conductive substrate. This allows the electron current to run through the QCM during the measurement. By supplying a DC-voltage to the front electrode it gets readily biased (negative and positive) and by placing a capacitor in the circuit, it connects the AC-circuit (oscillator circuit) and the DC-circuit (DC-voltage bias circuit). At the same time, it blocks the DC-current from going back to the oscillator but allows the high-frequency signal to pass from the QCM. The results in this thesis concluded that the QCM can be electrically modified to allow an electron flux to the QCM while using it as a substrate when electrons are used as reducing agents. Scanning electron microscopy (SEM) of a QCM crystal revealed that a 2 µm film had been deposited while SEM coupled with energy dispersive X-ray spectroscopy (EDS) showed that the film indeed contained iron. Further analysis was made by high-resolution X-ray photoelectron spectroscopy (HR-XPS) to find the elemental composition of the film, which revealed that the thin film contained 41 at.% iron. In addition, this study investigated if the QCM could be used to study CVD processes where electrons were used as reducing agents. The results indeed revealed that it is possible to study the surface chemistry where electrons are used as reducing agents with the electrically modified QCM to gain knowledge concerning film deposition. Initial results of the QCM showed that film growth could be studied when varying the plasma power between 5 W to 15 W and the QCM bias between -40 V to +40 V. The method generated easily accessible data concerning the process where electrons are used as reducing agents, which gained insight to the method that never has been disclosed before.