Theses and Dissertations at Montana State University (MSU)

Permanent URI for this collectionhttps://scholarworks.montana.edu/handle/1/733

Browse

Search Results

Now showing 1 - 10 of 30

Condensation of chromium vapor, generated in high-temperature (>800°C) environments, and interactions with aluminosilicate surfaces
(Montana State University - Bozeman, College of Engineering, 2024) van Leeuwen, Travis Kent; Chairperson, Graduate Committee: Paul E. Gannon; This is a manuscript style paper that includes co-authored chapters.
This work represents a collection of research and reporting with the goal of improving fundamental understanding of chromium (Cr) vapor reactive condensation, relevant in many high-temperature (>800°C) process environments where Cr-containing alloys are used. While reactive evaporation of Cr from stainless steels used in high-temperature solid oxide electrochemical systems is well-documented, the dynamics of Cr condensation onto surrounding interfaces during complex and dynamic system operation is less understood. Understanding these interactions during operation is critical for improving system performance and safeguarding environmental, health and safety, as some condensed species contain hexavalent chromium (Cr(VI)), a known carcinogen. A series of studies were designed and conducted to investigate the condensation pathways of Cr vapors within representative high-temperature system environments, simulating extreme conditions for Cr evaporation and downstream aluminosilicate fibers used in high-temperature insulation. The first study focuses on the influence of water vapor concentration in the gaseous environment on reactive Cr condensation and speciation onto aluminosilicate fibers. The second study explores the effects of alkaline oxide additives in aluminosilicate fibers on Cr condensation and speciation. The third study investigates the effects of presence of alkaline oxides within the Cr vapor source on reactive evaporation and condensation of Cr vapors onto downstream aluminosilicate fibers. To accomplish the specific objectives of these studies, Cr vapors, produced by high-temperature (>800°C) air exposures of trivalent chromium (Cr(III)) oxide (Cr 2O 3) (chromia) powder with variable moisture content, were condensed onto various ceramic materials (aluminosilicate fibers) downstream at lower temperatures (100-500°C). Total condensed Cr and ratios of oxidation states were measured using inductively coupled plasma optical emission spectroscopy (ICP-OES) and diphenyl carbazide (DPC) colorimetric/direct UV-VIS spectrophotometric analyses, respectively. Results indicate presence of both Cr(III) and Cr(VI) species condensed on all samples investigated. Total Cr and ratio of Cr(VI) to total Cr detected was significantly more on those containing alkaline oxides and at higher atmospheric water vapor concentration, while the presence of alkaline oxides in the Cr vapor source (Cr 2O 3) decreased the evaporation and amount of Cr/Cr(VI) condensed on the samples downstream. Computational thermodynamic equilibrium modelling helps explain experimental results showing the relative stability of alkaline-chromate compounds.
Operando optical and quantitative electrochemical studies of solid oxide fuel cell anode degradation and regeneration
(Montana State University - Bozeman, College of Letters & Science, 2022) Pomeroy, Elias Deen; Chairperson, Graduate Committee: Robert Walker; This is a manuscript style paper that includes co-authored chapters.
Solid Oxide Fuel Cells (SOFCs) are high temperature (600-1000 °C) devices that can generate electricity with extremely high efficiencies from a wide variety of fuels, including H 2, CH 4, Biogas, and crushed coal. Unfortunately, the SOFC anodes are highly sensitive to gas phase contaminants, including sulfur and carbon containing fuels. Sulfur is ubiquitous in all carbon containing fuels, with concentrations as low as a few parts per million to as high as 1% by mass. At all concentrations sulfur substantially decreases SOFC performance. Conventional models propose that sulfur decreases fuel cell performance by blocking anode active sites, preventing electrochemical reactions, and reducing surface area for heterogeneous catalysis. Carbon containing fuels can rapidly degrade SOFCs due to graphitic carbon formation. Graphite blocks active sites on the anode, causes damage within the anode microstructure, and removes electrocatalytic material via metal dusting. Studies presented in this work used operando optical techniques and quantitative electrochemistry to study degradation and remediation of SOFC anodes. First, since typical electrochemical techniques infer microstructural changes rather than directly measuring surface area, a traditional electrochemical technique, chronocoulometry (CC), was adapted to SOFCs for the first time to measure the electrochemically active area of the anode. This technique showed that active area is temperature dependent, and that sulfur participates in electrochemical reactions, decreasing performance with sluggish oxidation kinetics, rather than simply blocking active sites. Carbon monoxide, on the other hand, decreased the number of active sites, rather than participating in electrochemical reactions, either by blocking active sites or forming carbon. Then, a comparative study was undertaken of different methodologies of carbon remediation, comparing electrochemical oxidation, molecular oxygen, and steam as methods to remove graphite accumulated on SOFC anodes. This study found that with all methods, CO 2 played a key role in removing carbon, that both electrochemical oxidation and steam removed carbon more globally than oxygen, and that imaging the entire cell is critical for understanding the complex, spatially and temporally heterogeneous chemistry occurring across SOFC anodes. Finally, sulfur was employed to passivate SOFC anodes operating on dry methane, significantly reducing carbon formation with only slight decreases in electrochemical performance.
Temperature dependent second harmonic generation studies of materials used in energy conversion applications
(Montana State University - Bozeman, College of Engineering, 2022) McNally, Marshall Traver; Chairperson, Graduate Committee: Robert Walker; This is a manuscript style paper that includes co-authored chapters.
Materials in energy conversion devices often undergo a variety of degradation mechanisms. Solid oxide fuel cell cathodes materials, for example, are subject to surface compositional changes due to material segregation. The extreme operating conditions in these energy conversion devices requires the development of an operando technique that is surface and material specific to accurately probe these degradation mechanisms. Second harmonic generation (SHG) is a surface specific technique that probes the electronic structure of a material using the 2nd order polarizability. Using well characterized materials like Au, Si and NiO, we began investigating how high temperatures (260 °C) and atmospheric composition affected the surface electronic structures. To do this, a custom sample chamber dubbed TROPICS was designed and built to achieve temperature, atmospheric compositional and eventually, electrochemical control. We found that gold's SH intensity was enhanced (3.5 times) when O 2 was present in the atmosphere but this enhancement disappeared at high temperatures. Using data from titrating O 2 into a N 2 atmosphere, we concluded that a monolayer of O 2 was forming on the gold surface, providing backbonding opportunities for gold's free electrons into the partially filled O 2 pi* orbitals. Similar behavior was seen in N-type Si which also showed SH enhancement at room temperature. However, P-type and undoped Si showed no such atmospheric dependent behavior. SHG experiments done with NiO showed decoupled behavior in the electronic structure recovery between the bulk and surface. After heating to 260 °C, the SH signal did not return to pre-heating intensities but required ~60 and ~90 minutes in N 2 and air respectively. The difference in recovery time between N 2 and air could be attributed to interactions between the still paramagnetic NiO electrons and the partially filled O 2 pi* orbitals.
Operando optical studies of next generation anode materials in high temperature solid oxide fuel cells
(Montana State University - Bozeman, College of Letters & Science, 2020) Welander, Martha Maria; Chairperson, Graduate Committee: Robert Walker; Marley S. Zachariasen, Clay D. Hunt, Stephen W. Sofie and Robert A. Walker were co-authors of the article, 'Operando studies of redox resiliance in alt enhanced NIO-YSZ SOFC anodes' in the journal 'Journal of the electrochemical society' which is contained within this dissertation.; Marley S. Zachariasen, Stephen W. Sofie and Robert A. Walker were co-authors of the article, 'Enhancing Ni-YSZ anode resilience to environmental redox stress with aluminum titanate secondary phases' in the journal 'ACS applied energy materials' which is contained within this dissertation.; Marley S. Zachariasen, Stephen W. Sofie and Robert A. Walker were co-authors of the article, 'Mitigating carbon formation with Al 2TiO 5 enhanced solid oxide fuel cell anodes' in the journal 'The journal of physical chemistry C' which is contained within this dissertation.; Daniel B. Drasbaek, Marie L. Traulsem Bhaskar R. Sudireddy, Peter Holtappels and Robert A. Walker were co-authors of the article, 'What does carbon tolerant really mean? Operando vibrational studies of carbon accumulation on novel solid ocide fuel cell anodes prepared by infiltration' submitted to the journal 'RSC physical chemistry chemical physics' which is contained within this dissertation.; Disseration contains an article of which Martha Maria Welander is not the main author.
Solid oxide fuel cells (SOFCs) are high temperature energy conversion devices capable of efficient and sustainable energy production. Because of the need to electrochemically reduce molecular oxygen and the relatively high activation energy required for oxide ions to diffuse through the dense, solid-state electrolyte, SOFCs typically operate at temperatures > or = 500 °C. High operating temperatures endow SOFCs with many advantages, including fuel flexibility and high conversion efficiencies, distinguishing them from other types of fuel cells. However, high temperatures also present challenges related to the stability of the electrode materials, accelerating cell degradation and limiting the development and integration of SOFCs into large scale power production strategies. These mechanisms are the result of fundamental changes in material properties that remain poorly described and difficult to predict. Studies presented in this work utilized operando Raman spectroscopy and electrochemical measurements to directly correlate material changes with changes in cell performance under various operating conditions. Research focused on developing and characterizing new electro-catalytic materials having improved conversion efficiencies and mechanical resilience to thermal and chemical stress. Because current state of the art SOFC Ni-YSZ cermet anodes are sensitive to oxidation, the first two studies investigated the effects of adding small amounts of Al 2TiO 5 to Ni-YSZ anodes and the impact of resulting secondary (2°) phases that formed on SOFC tolerance to electrochemical and environmental reduction and oxidation (redox) cycling. Results show that Al 2TiO 5 helps improve tolerance to both types of redox cycling by maintaining electrode-electrolyte connectivity and minimizing catalyst coarsening. The third study illustrates how this same dopant improved anode carbon tolerance when operating with hydrocarbon fuels. Because excessive carbon accumulation on SOFC anodes can lead to rapid cell failure, ways to improve carbon tolerance was further explored in the last two studies. These studies investigate the effect of decoupling the electro-catalytic and the electronically conductive phases of the anode under pure methane and biogas-surrogate environments. Collectively, the studies described in this dissertation provide insight into the materials-specific mechanisms responsible for limiting degradation of doped and functionally decoupled anodes to help guide the design of new SOFC electrode materials.
Aluminate spinels for use as catalyst enhancement of solid oxide fuel cells
(Montana State University - Bozeman, College of Engineering, 2019) Zachariasen, Marley Sarria; Chairperson, Graduate Committee: Stephen W. Sofie
The growing necessity to find clean, efficient power sources has led to the advancement of technology in various fields of renewable energy. The field of electrochemical energy conversion, better known has Hydrogen Fuel Cell energy, has shown promise in replacing fossil fuels. This technology is fuel flexible, emits no harmful products, and generates power at efficiencies double or triple that of the Carnot combustion cycle widely used in automotive propulsion and large scale combustion power generation. However, the power production is limited by the short life expectancy of the components used to convert the chemical energy of the fuel into an electrical current. Two mechanisms work simultaneously during fuel cell operation to degrade the anodic electrode of the cell. The coarsening of the catalyst metal particles reduces the total active area of the anode while contaminants from the fuel deposit on the anodes remaining active areas, blocking fuel from the locations where the reaction takes place. Recent studies have shown that doping the industry standard fuel cell anode, Ni/YSZ, with a compound known as Aluminum Titanate (ALT) increases the overall resiliency of the cell. When heat-treated, ALT disassociates in to aluminum and titanium oxides which are then able to go into solution with the material components of the anode. These new secondary phases were shown to increase the strength and overall power output of the cell while decreasing the rate at which the catalyst coarsens. The electrochemical enhancements were attributed to the aluminum based secondary phase, known as nickel aluminate, a spinel structured compound which undergoes unusual reduction and catalytic transport kinetics. This work assesses the viability of transferring these enhancement effects to various other cermet anode systems by individually exchanging the ceramic ion conductor and metal electrocatalyst. The electrochemical performance and degradation, as well as mechanical properties, were evaluated for Ni/GDC anodes doped with ALT and alumina. In addition, synthesis and reduction behavior of cobalt and copper aluminate spinels were analyzed for similarities with nickel aluminate.
Investigation of the mechanical properties of aluminum titanate (Al 2TiO 5) doped NI-YSZ solid oxide fuel cell anodes
(Montana State University - Bozeman, College of Engineering, 2019) McCleary, Madisen Wynn; Chairperson, Graduate Committee: Roberta Amendola; Roberta Amendola was a co-author of the article, 'Effect of aluminum titanate (Al 2TiO 5) doping on the mechanical performance of solid oxide fuel cell Ni-YSZ anode' in the journal 'Fuel Cells' which is contained within this thesis.; Roberta Amendola was a co-author of the article, 'Investigation of the kinetics of the solid-state reduction process of undoped and aluminum titanate (Al 2TiO 5) doped NiO-YSZ anodes for solid oxide fuel cells' in the journal 'Ceramics international' which is contained within this thesis.; Roberta Amendola, Stephen Walsh and Benjamin McHugh were co-authors of the article, 'Analysis of the mechanical strength and failure mode of undoped and aluminum titanate (Al 2TiO 5, ALT) doped-Ni-YSZ solid oxide fuel cell anodes under uniaxial and biaxial strength testing conditions' submitted to the journal 'Materialia' which is contained within this thesis.; Roberta Amendola and Benjamin McHugh were co-authors of the article, 'Effect of redox cycling on the mechanical performance of undoped and aluminum titanate (Al 2TiO 5, ALT) doped NiO-YSZ solid oxide fuel cell anodes' which is contained within this thesis.; Roberta Amendola was a co-author of the article, 'Mechanical performance of aluminum titanate (Al 2TiO 5, ALT) doped NiO-YSZ SOFC half cells' which is contained within this thesis.
Recently, there has been growing interest in anode supported Solid Oxide Fuel Cells (SOFCs) because of improved single cell performance. In these systems, the anode layer is the thickest and provides the mechanical strength of the stack. Nickel-yttria stabilized zirconia (Ni-YSZ) composites are widely used as anode material but, in contrast to the vast amount of data available on their electrochemical properties, little data on the mechanical performance exists. This dissertation work focuses on the use of secondary materials added to traditional Ni-YSZ anodes to enhance SOFC anode mechanical performance. Small amounts of, aluminum titanate (Al2TiO5, ALT), added to the NiO-YSZ system during the manufacturing process, results in a material that is over 50% stronger than the native Ni-YSZ. Samples with different geometries have been fabricated and tested in uniaxial and biaxial strength testing apparatuses. Advanced microscopy techniques and Weibull statistical analyses have been used to properly characterize the mechanical performance, the failure mechanism and to elucidate chemical compositions. This work has found that the enhanced strength resulting from ALT is related to the development of secondary phases: Al2O3 reacts with NiO to form NiAl2O4 while TiO2 preferentially reacts with YSZ to form a solid YSZ framework defined as the 'rough phase' that add stiffness to the system and persists upon reduction. The mechanical behavior of reduced samples has been related to the partial reduction of NiAl2O4 which results in the formation of Ni nanoparticles within an Al2O3 matrix ('small particle phase'). This phase is characterized by a high strength interface while adding ductility and crack deflection ability to the system. ALT was also found responsible for changing the Ni-YSZ system failure mechanism from an intergranular to a transgranular fashion indicating the material toughness increased. During cyclic operational testing, ALT has potential for mechanical stabilization through porosity development with secondary phase formation. Testing of ALT anodes with YSZ electrolyte material showed increased strength over similar native assemblies. This dissertation work lays the foundation for future research into the effects of ALT doping on the SOFC system and how this material could be tailored for even further increases in strength.
Fabrication and assessment of anode supported SOFCS doped with aluminum titanate via electrochemical and non-destructive micro-indentation testing
(Montana State University - Bozeman, College of Engineering, 2019) Kent, John Parker; Chairperson, Graduate Committee: Stephen W. Sofie
Ceramic-metal (cermet) composites are the most promising electrochemical anodes for commercial implementation in solid oxide fuel cells (SOFC). Recent advances at MSU in cermet formulations utilizing aluminum titanate (ALT) dopants in nickel oxide (NiO)-yttria stabilized zirconia (YSZ) anodes has shown substantial performance gains in degradation rates as well as mechanical behavior when evaluated in low power density electrolyte supported cell (ESC) geometries and bulk anode forms through modulus of rupture and equibiaxial flexure. The benefits associated with ALT are due to the formation of secondary phases of nickel aluminate and zirconium titanate in NiO-YSZ cermets that form during processing. Cermet modulus of rupture studies are rigorous, can span multiple months, and requiring hundreds of samples when studying the effects of both thermal and redox cycling on SOFC anodes to achieve statistically significant results. The use of non-destructive methods such as micro-indentation to examine the strength and toughness of doped and differently processed cermet anodes can rapidly speed up the analysis of mechanical properties including the mechanical support characteristics of higher power density anode supported cell (ASC) geometries targeted by industrial SOFC developers. The aim of this study was to examine non-destructive micro-indentation testing in evaluating cermet anode materials in both oxidized and reduced state in direct contrast with traditional destructive methods. Extending the current state of ALT anode doping by utilizing these rapid assessment methods, this work examines mechanical properties degradation and fracture toughness under multiple thermal and redox cycles. Additionally, this work details the framework for cell fabrication methods that were developed to process ASCs with state of the art 5 micrometer electrolytes for the first evaluation of ALT doping of SOFCs in this high power cell configuration.
Reactive evaporation of chromium from stainless steel and the reactive condensation of chromium vapor species on ceramic surfaces
(Montana State University - Bozeman, College of Engineering, 2018) Tatar, Gregory Steven; Chairperson, Graduate Committee: Paul E. Gannon
Stainless steels are often used in high temperature (greater than or equal to 500°C) applications such as solid oxide fuel cells (SOFCs), combustion engine exhaust systems, and various power/chemical plant process equipment. At high temperatures and in oxidizing conditions, chromium containing oxides, such as chromia (Cr2O 3), form protective surface layers on the underlying stainless steel. Reactive evaporation of these surface layers, however, may form volatile chromium species such as CrO 2 (OH) 2 and CrO 3, compromise the protection of stainless steels, and cause deleterious downstream effects. Such effects include SOFC performance degradation and hazardous materials generation. This study focuses on both the reactive evaporation and reactive condensation processes and their dependencies on materials and environmental conditions. First, the corrosion behaviors of stainless steels were investigated in a variety of exposure conditions and then the nature of chromium vapor condensation was investigated on ceramic surfaces under various conditions. Ferritic stainless steel samples (T409) were examined after 700°C exposures (94 h) to dry or wet air or nitrogen, and with or without contacting aluminosilicate fibers. Surface compositions and structures were characterized using field emission scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray diffraction. The fibers had a substantial impact on corrosion behaviors; likely serving as a mass transport barrier for corrosive gas species. Observed corrosion behaviors under these different environments and their potential mechanisms are presented and discussed. Additionally, quantification of chromium content on fibers was performed using inductively coupled plasma mass spectroscopy. Fibers were observed to collect chromium in dry/moist air consistent with the formation of CrO 3 and CrO 2(OH) 2, respectively, and their subsequent reactive condensation. To better understand the reactive condensation of volatile chromium species onto various ceramic surfaces, volatile chromium species were generated from chromium containing sources at 500-900°C and flowed past samples of aluminosilicate fibers, alumina, mica, and quartz wool at temperatures ranging from 100-900°C for 24-150 hours. The ceramic surfaces were characterized using x-ray photoelectron spectroscopy. Analysis of Cr 2p 3/2 peak positions revealed the influence of temperature, material, and exposure time on the oxidation states of surface chromium compounds, and extent of chromium deposition. Potential mechanisms are proposed to help explain the observed trends.
Chlorine induced degradation of SOFCS operating on carbon containing fuels
(Montana State University - Bozeman, College of Letters & Science, 2017) Reeping, Kyle Wyatt; Chairperson, Graduate Committee: Robert Walker; Robert A. Walker was a co-author of the article, 'In operando vibrational raman studies of chlorine contamination in solid oxide fuel cells' in the journal 'The journal of the Electrochemical Society' which is contained within this thesis.; John D. Kirtley, Jessie M. Bohn, Daniel A. Steinhurst, Jeffrey C. Owrutsky and Robert A. Walker were co-authors of the article, 'Chlorine-induced degradation in solid oxide fuel cells identified by optical methods' in the journal 'The journal of physical chemistry C' which is contained within this thesis.; Jessie, M. Bohn and Robert A. Walker were co-authors of the article, 'Chlorine-induced degradation in SOFCS operating with biogas' in the journal 'Sustainable energy and fuels' which is contained within this thesis.; Jessie, M. Bohn and Robert A. Walker were co-authors of the article, 'The palliative effect of H 2 on SOFCS operating on contaminated carbon containing fuels' submitted to the journal 'The journal of power sources' which is contained within this thesis.
Chlorine present in green and synthetic fuels such as biogas and syngas can accelerate degradation of solid oxide fuel cell (SOFC) nickel-based anodes. Chlorine contamination has been studied in SOFCs where H 2 was the primary fuel but little attention has focused on deleterious, cooperative effects that result from Cl-contamination in predominantly carbon-containing fuels. Experiments described in this work examine degradation mechanisms in SOFCs with Ni-YSZ cermet anodes operating with a biogas surrogate and exposed to 110 ppm Cl (delivered either as CH 3Cl or HCl). Operando Raman spectroscopy is used to directly observe the the anode's catalytic activity as evidenced by observable carbon accumulation, and electrochemical impedance and voltammetry measurements report on overall cell performance. Studies performed at 650 °C and 700 °C show that Cl suppresses carbon accumulation and causes slow but steady cell degradation. Prolonged exposure to Cl results in and irreversible device failure. These results differ markedly from recent reports of Cl contamination in SOFCs operating independently with H 2 and CH 4.
Sintering in ceramics and solid oxide fuel cells
(Montana State University - Bozeman, College of Engineering, 2017) Hunt, Clay Dale; Chairperson, Graduate Committee: Stephen W. Sofie; David Driscoll, Adam Weisenstein and Stephen W. Sofie were co-authors of the article, 'Nickel nitrate and molybdenum oxide as a yttria-stabilized zirconia sintering aid' in the journal 'Processing, properties, and design of advanced ceramics and composites' which is contained within this thesis.; Marley Zachariasen, David Driscoll and Stephen W. Sofie were co-authors of the article, 'Current degradation rate quantification of solid oxide fuel cells with and without aluminum titanate' which is contained within this thesis.; David Driscoll and Stephen W. Sofie were co-authors of the article, 'Constant rate of heating definition of the undefined function of density of the Wang and Raj equation for 8YSZ' which is contained within this thesis.; David Driscoll and Stephen W. Sofie were co-authors of the article, 'Constant rate of heating definition of undefined density function for 8YSZ with a sintering aid' which is contained within this thesis.; David Driscoll and Stephen W. Sofie were co-authors of the article, 'Constant temperature definition of the undefined density function for 8YSZ' which is contained within this thesis.; David Driscoll and Stephen W. Sofie were co-authors of the article, 'Constant temperature definition of the undefined density function of 8YSZ with a sintering aid' which is contained within this thesis.
Nature's propensity to minimize energy, and the change in energy with respect to position, drives diffusion. Diffusion is a means by which mass transport resulting in the bonding of the particles of a powder compact can be achieved without melting. This phenomenon occurs in powdered materials near their melting temperature, and is referred to as 'sintering'. Because of the extreme melting temperature of some materials, sintering might be the only practical means of processing. The complexity and subtlety of sintering ceramics motivated the evaluation of empirical data and existing sintering models. This project examined polycrystalline cubic-zirconia sintering with and without transition-metal oxide additions that change sintering behavior. This study was undertaken to determine how sintering aids affect the driving force, and activation energy, the energy barrier that must be overcome in order for an atom or ion to diffuse, of the densification occurring during sintering. Examination of commercially-available cubic-zirconia powder sintering behavior was undertaken with dilatometry, which allows monitoring of the length change a material undergoes as it sinters, and with scanning electron microscopy, which facilitates the study of sintered-sample microstructure. MATLAB algorithms quantifying sintering results were developed. Results from this work include proposed definitions of a 26-year-old undefined function of density factor in a well-accepted mathematical model of sintering. These findings suggest activation energy is not changing with density, as is suggested by recent published results. The first numerical integration of the studied sintering model has been performed. With these tools, a measure of the activation energy of densification of cubic-zirconia with and without the addition of cobalt-oxide as a sintering aid has been performed. The resulting MATLAB algorithms can be used in future sintering studies. It is concluded that sintering enhancement achieved with cobalt-oxide addition comes from reduction in activation energy of densification of cubic-zirconia. Further, it is suggested that the activation energy of densification does not change with material density. This conclusion is supported by the sensitivity of the numerical integration of the aforementioned sintering model to changes in activation energy.

Theses and Dissertations at Montana State University (MSU)

Browse

Filters

Settings

Sort By

Results per page

Search Results