This study aims to find how density affects the reduction extent and reduction rate. H2-CO gas mixture is used as reducing agent. Five groups of different density pellets were reduced at four different temperatures. Light optical microscope (LOM) and scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-EDS) used to detect completely and partially reduced pellets to investigate how density affects the reduction mechanisms. Results illustrate that density affects reduction extent and reduction rate a lot. However, when reaction temperature is 1123 K, density has less influenc on reduction extent. The carbon deposition occurred for high density pellets at 973 K and 1023 K. The reduction process cannot be described by a single rate controlling step. Reduced layer is denser compared with unreduced layer. Reaction at initial stages goes much faster than later stages.

Since the beginning of the Industrial Revolution, the global energy consumption has been continuously increasing, supplied mainly by coal, oil and natural gases. Unfortunately, this consumption is linked to the emission of greenhouse gasses such as CO2 to the atmosphere. For this reason, it is extremely important to look for sustainable and renewable energy sources in order to replace the commonly used fossil fuels. Within the different types of renewable energy sources, solar energy holds by far the largest potential capacity. In this respect, artificial photosynthesis is a promising technology not only to harvest solar energy, but also as a means of storage by producing energy-rich chemical fuels such as H2 from water. The main components of photoelectrochemical water splitting devices are the semiconductor light absorber photoelectrodes and the electrolyte. Chapter 1 reviews the fundamental aspects of photoelectrochemical water splitting and overviews the physics and electrochemistry of semiconductor materials. The second chapter describes the methodologies and techniques employed throughout the thesis. The experimental results are reported from Chapter 3 to 8, focusing on the development and further optimization of two photoelectrodes, concretely hematite and cupric oxide, besides the design and fabrication of tandem cells for standalone water splitting. In the case of hematite photoanodes, the main efforts have focused on its doping to enhance carrier density and mobility as a way of diminishing recombination. The major drawback present in cupric oxide photoelectrodes is their instability against photocorrosion, for this reason, research has focused on protecting them, both by impregnation and adsorption methodologies. Finally, a tandem cell composed by a hematite photoanode and a cupric oxide photocathode was developed. It is worth noting that a polymer electrolyte membrane (PEM) was employed as to facilitate upscaling and diminish the corrosion observed employing the typical acidic or basic liquid electrolytes.

<p> An Experimental investigation has been conducted to determine the effects on degree of reduction and efficiency of utilization of gases of changes in the levels of several variables when reducing fixed beds of commercial hematite pellets. The effects on reduction behaviour of changes in the levels of reducing gas composition and flow rate, and reaction temperature, were determined by graphical and numerical techniques.</p> / Thesis / Master of Engineering (MEngr)

The Leveäniemi iron oxide apatite (IOA) deposit, mined by LKAB, is located in Norrbotten, northern Sweden. The deposit has a partially more complex mineralogy than the neighbouring and more famous IOA deposits of Kiirunavaara and Malmberget. The Leveäniemi deposit contains comparatively more ore containing both magnetite and hematite but also maghemite and with slightly different trace element chemistry of the iron oxide minerals. Hematite is currently not considered a valuable mineral in the Svappavaara mineral processing and in the magnetite concentrate titanium and vanadium are considered to be penalty elements. Ore samples were collected from selected drill cores and from these polished thin sections were prepared that were investigated by optical microscopy, EPMA, and FE-SEM-EDS. Investigations focused on iron oxide mineralogy and mineral chemistry with special consideration to titanium and vanadium as those elements are considered deleterious in subsequent blast furnace or direct reduction processes. Investigations revealed that magnetite is the predominant mineral with secondary hematite being the second most abundant iron oxide mineral. In the investigated samples vanadium concentration in magnetite ranges from 0.12 to 0.32% V2O3 with higher concentrations in the southern part of the deposit. No such conclusions regarding spatial distribution could be done for titanium. Furthermore, the investigations indicated that alteration from primary magnetite to secondary hematite does not significantly affect the trace element chemistry of the minerals. Titanium in iron oxides occurs as either inclusions or lamellae of titanium oxide minerals. Vanadium in iron oxides occur as a substitution element and does not occur in stochiometric vanadium minerals. It is considered unfeasible to lower the content of these deleterious elements by physical separation methods. / Leveäniemi är en järnoxid-apatitfyndighet (IOA) i Norrbotten som bryts av LKAB. Fyndigheten har en delvis mer komplex mineralogi än de närliggande och mer kända IOA-fyndigheterna Kiirunavaara och Malmberget. Leveäniemifyndigheten innehåller jämförelsevis mer malm innehållande både magnetit och hematit men även maghemit samt med något annorlunda spårämneskemi i järnoxidmineralen. Hematit anses inte i nuläget vara ett värdemineral i Svappavaaras malmförädling och i magnetitekoncentratet anses titan och vanadin utgöra straffelement. Malmprov togs från utvalda borrkärnor och från dessa tillverkades polerade tunnslip som undersöktes med optisk mikroskopering, EPMA och FE-SEM-EDS. Undersökningarna var fokuserade på järnoxidernas mineralogi och mineralkemi med speciellt fokus på titan och vanadin då grundämnena anses vara skadliga i efterföljande masugns- eller direktreduktionsprocesser. Undersökningarna visade att magnetit är det dominerade mineralet med sekundär hematit som det näst vanligaste förekommande järnoxidsmineralet. I de undersökta proven varierade vanadinhalten från 0,12% till 0,32% V2O3 med högre halter i fyndigheten södra delar. Inga liknande slutsatser angående rumsliga fördelningen av titan kunde göras. Vidare så indikerade undersökningarna att omvandling från primär magnetit till sekundär hematit inte nämnvärt påverkar spårämneskemin i mineralen. Titan i järnoxider förekommer antingen som inneslutning eller lameller av titanoxidsmineral. Vanadin i järnoxider förekommer som ett substitutionselement och förekommer inte som stökiometriska vanadinmineral. Det anses inte vara tekniskt eller ekonomiskt möjligt att sänka halterna av dessa skadliga grundämnen med hjälp av fysiska separationsmetoder.

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A dissertation is presented on the bioreduction of hematite (&#945;-Fe2O3) nanoparticles. The study shows that an alternative extracellular electron transfer mechanism other than the classical 'direct-contact' mechanism may be simultaneously employed by Shewanella oneidensis MR-1 during solid-phase metal reduction. This conclusion is supported by analysis of the bioreduction kinetics of hematite nanoparticles coupled with microscopic investigations of cell-mineral interactions. The reduction kinetics of metal-oxide nanoparticles were examined to determine how S. oneidensis utilizes these environmentally-relevant solid-phase electron acceptors. Nanoparticles involved in geochemical reactions show different properties relative to larger particles of the same phase, and their reactivity is predicted to change as a function of size. To demonstrate these size-dependent effects, the surface area normalized reduction rates of hematite nanoparticles by S. oneidensis MR-1 with lactate as the sole electron donor were measured. As evident from whole cell TEM analysis, the mode of nanoparticle adhesion to cells is different between the more aggregated, pseudo-hexagonal to irregular shaped 11 nm, 12 nm, 99 nm and the less aggregated 30 nm and 43 nm rhombohedral particles. The 11 nm, 12 nm and 99 nm particles show less cell contact and coverage than the 30 nm and 43 nm particles but still show significant rates of reduction. This leads to the provisional speculation that S. oneidensis MR-1 employs a pathway of indirect electron transfer in conjunction with the direct-contact pathway, and the relative importance of the mechanism employed depends upon aggregation level and the shape of the particles or crystal faces exposed. In accord with the proposed increase in electronic band-gap for hematite nanoparticles, the smallest particles (11 nm) exhibit one order of magnitude decrease in reduction when compared with larger (99 nm) particles, and the 12 nm rates fall in between these two. This effect may also be due to the passivation of the mineral and cell surfaces by Fe(II), or decreasing solubility due to decrease in size. / Ph. D.

Scanning tunneling microscopy (STM) images and scanning tunneling spectroscopy (STS) spectra of galena (PbS) and hematite (a-Fe203) were calculated using ab-initio methods in order to interpret experimental images and spectra that were taken in previous studies. These calculations have helped to understand which states of the mineral surfaces were imaged depending on the bias voltage and tip-sample separation. The computational results also gave insight in electron transfer processes that take place during surface adsorption/oxidation/reduction processes. In this context, different oxidation (using O₂ and ferric iron as oxidants) and gold adsorption/reduction mechanisms on galena were evaluated at an atomic level. On hematite, the main emphasis was determining the differences in the local electronic structure of specific sites above the surface and the electronic structure of the bulk. Hereby, step sites turned out to have an increased local density of states at certain electron binding energies that are absent on flat surfaces. states can explain the highly increased reactivity of step sites as compared to terraces. X-ray photoelectron spectra (XPS) were calculated to compare the photoelectron peaks of the calculated specific surface structures (that do not have a bulk equivalent) with experimentally obtained XPS spectra. Most of the calculated peak chemical shifts coincided with those that were found in experiments and that were previously interpreted in terms of known bulk structures. Therefore, it can be inferred that the conventional way of interpreting XPS spectra might be incomplete if specific surface structures are neglected. In order to understand step velocities on a gypsum (010) surface, step energies of different step directions were calculated using an ab-initio approach. An approximately linear relationship was found between the calculated step energies and the experimentally determined step velocities. / Ph. D.

This investigation is focused on the understanding of mechanical and chemical reaction behaviors of stoichiometric mixtures of nano- and micro-scale aluminum and hematite (Fe2O3) powders dispersed in epoxy. Epoxy-cast Al+Fe2O3 thermite composites are an example of a structural energetic material that can simultaneously release energy while providing structural strength. The structural and energetic response of this material system is investigated by characterizing the mechanical behavior under high-strain rate and shock loading conditions. The mechanical response and reaction behavior are closely interlinked through deformation characteristics. It is, therefore, desirable to understand the deformation behavior up to and beyond failure and establish the necessary stress and strain states required for initiating chemical reactions. The composite s behavior has been altered by changing two main processing parameters; the reactants particle size and the relative volume fraction of the epoxy matrix. This study also establishes processing techniques necessary for incorporating nanometric-scale reactants into energetic material systems. The mechanochemical behavior of epoxy-cast Al+Fe2O3 composites and the influence of epoxy volume fraction have been evaluated for a variety of loading conditions over a broad range of strain rates, which include low-strain rate or quasistatic loading experiments (10-4 to 10-2 1/s), medium-strain rate Charpy and Taylor impacts (103 to 104 1/s), and high-strain rate parallel-plate impacts (105 to 106 1/s). In general, structural strength and toughness have been observed to improve as the volume fraction of epoxy decreases, regardless of the loading strain rate regime explored. Hugoniot experiments show damage occurring at approximately the same critical impact stress for compositions prepared with significantly different volume fractions of the epoxy binder phase. Additionally, Taylor impact experiments have indicated evidence for strain-induced chemical reactions, which subject the composite to large shear accompanied by temperature increase and associated softening, preceding these reactions. Overall, the work aims to establish an understanding of the microstructural influence on mechanical behavior and chemical reactivity exhibited by epoxy-cast Al+Fe2O3 materials when exposed to high stress and high-strain loading conditions. The understanding of fundamental aspects and the results of impact experiment measurements provide information needed for the design of structural energetic materials.