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- ItemComparative study of sculptured metallic thin films deposited by oblique angle deposition at different temperatures(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2018) Liedtke, Susann; Grüner, Christoph; Gerlach, Jürgen W.; Rauschenbach, BerndMetals with a wide range of melting points are deposited by electron beam evaporation under oblique deposition geometry on thermally oxidized Si substrates. During deposition the sample holder is cooled down to 77 K. It is observed that all obliquely deposited metals grow as tilted, high aspect ratio columns and hence with a similar morphology. A comparison of such columns with those deposited at room temperature (300 K) reveals that shadowing dominates the growth process for columns deposited at 77 K, while the impact of surface diffusion is significantly increased at elevated substrate temperatures. Furthermore, it is discussed how the incidence angle of the incoming particle flux and the substrate temperature affect the columnar tilt angles and the porosity of the sculptured thin films. Exemplarily for tilted Al columns deposited at 77 K and at 300 K, in-plane pole figure measurements are carried out. A tendency to form a biaxial texture as well as a change in the crystalline structure depending on the substrate temperature is found for those films.
- ItemElectron beam-induced immobilization of laccase on porous supports for waste water treatment applications(Basel : MDPI AG, 2014) Jahangiri, E.; Reichelt, S.; Thomas, I.; Hausmann, K.; Schlosser, D.; Schulze, A.The versatile oxidase enzyme laccase was immobilized on porous supports such as polymer membranes and cryogels with a view of using such biocatalysts in bioreactors aiming at the degradation of environmental pollutants in wastewater. Besides a large surface area for supporting the biocatalyst, the aforementioned porous systems also offer the possibility for simultaneous filtration applications in wastewater treatment. Herein a "green" water-based, initiator-free, and straightforward route to highly reactive membrane and cryogel-based bioreactors is presented, where laccase was immobilized onto the porous polymer supports using a water-based electron beam-initiated grafting reaction. In a second approach, the laccase redox mediators 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and syringaldehyde were cross-linked instead of the enzyme via electron irradiation in a frozen aqueous poly(acrylate) mixture in a one pot set-up, yielding a mechanical stable macroporous cryogel with interconnected pores ranging from 10 to 50 μm in size. The membranes as well as the cryogels were characterized regarding their morphology, chemical composition, and catalytic activity. The reactivity towards waste-water pollutants was demonstrated by the degradation of the model compound bisphenol A (BPA). Both membrane- and cryogel-immobilized laccase remained highly active after electron beam irradiation. Apparent specific BPA removal rates were higher for cryogel-than for membrane-immobilized and free laccase, whereas membrane-immobilized laccase was more stable with respect to maintenance of enzymatic activity and prevention of enzyme leakage from the carrier than cryogel-immobilized laccase. Cryogel-immobilized redox mediators remained functional in accelerating the laccase-catalyzed BPA degradation, and especially ABTS was found to act more efficiently in immobilized than in freely dissolved state.
- ItemPorosity estimation of a geothermal carbonate reservoir in the German Molasse Basin based on seismic amplitude inversion(Berlin ; Heidelberg [u.a.] : SpringerOpen, 2022) Wadas, Sonja Halina; von Hartmann, HartwigThe Molasse Basin is one of the most promising areas for deep geothermal exploitation in Germany and the target horizon is the aquifer in the Upper Jurassic carbonates. Carbonate deposits can be very heterogeneous even over a small area due to diagenetic processes and varying depositional environments. The preferential targets for geothermal exploitation in carbonate deposits are fault zones, reef facies and karstified areas, since they are expected to act as hydraulically permeable zones due to high porosity and high permeability. Therefore, identifying these structures and characterizing, e.g., their internal porosity distribution are of high importance. This can be accomplished using 3D reflection seismic data. Besides structural information, 3D seismic surveys provide important reservoir properties, such as acoustic impedance, from which a porosity model can be derived. In our study area in Munich we carried out a seismic amplitude inversion to get an acoustic impedance model of the Upper Jurassic carbonate reservoir using a 3D seismic data set, a corresponding structural geological model, and logging data from six wells at the ‘Schäftlarnstraße’ geothermal site. The impedance model and porosity logs were than used to calculate a porosity model. The model shows a wide porosity range from 0 to 20% for the entire reservoir zone and the lithology along the wells reveals that dolomitic limestone has the highest porosities and calcareous dolomite has the lowest porosities. The study area is cut by a large W–E striking fault, the Munich Fault, and the footwall north of it shows higher porosities and more intense karstification than the hanging wall to the south. Considering the entire study area, an increase in porosity from east to west is observed. Furthermore, we identified a complex porosity distribution in reef buildups and pinnacle reefs. The reef cores have mostly low porosities of, e.g., < 3% and the highest porosities of up to 7 to 14% are observed at the reef caps and on the reef slopes. The reef slopes show a characteristic interfingering of the reef facies with the surrounding bedded facies, which indicates a syn-sedimentary reef development with slightly varying build up growth rates. We also assessed the reservoir quality with regard to porosity distribution and determined areas with moderate to good quality for geothermal exploitation by defining porosity evaluation levels. The porosity evaluation maps show that the carbonate rocks of Berriasian to Malm ζ1 are preferential targets for exploitation, especially in the footwall of the Munich Fault and to the west of the hanging wall, because these areas are characterized by high porosities due to intense karstification of bedded and massive facies, although the latter is mainly restricted to reef caps and reef slopes.
- ItemProbability of success studies for geothermal projects in clastic reservoirs: From subsurface data to geological risk analysis(Amsterdam [u.a.] : Elsevier Science, 2020) Schumacher, Sandra; Pierau, Roberto; Wirth, WolfgangIn the realisation of a geothermal project, an important step is the quantification of the geological risk of a well not achieving the economically necessary cut-off values with respect to temperature and flowrate/drawdown. In this paper, we present a new method for calculating this risk via a probability of success study by using all available types of hydraulic data, including porosity values derived from core samples or borehole logs. This method has been developed for geothermal projects in fluvial sandstones of the North German Basin but can be applied to any clastic, not fracture-dominated reservoir worldwide. © 2019 The Authors
- ItemGeometry-Driven Cell Organization Determines Tissue Growths in Scaffold Pores: Consequences for Fibronectin Organization(San Francisco, CA : Public Library of Science, 2013) Joly, P.; Duda, G.N.; Schöne, M.; Welzel, P.B.; Freudenberg, U.; Werner, C.; Petersen, A.To heal tissue defects, cells have to bridge gaps and generate new extracellular matrix (ECM). Macroporous scaffolds are frequently used to support the process of defect filling and thus foster tissue regeneration. Such biomaterials contain micro-voids (pores) that the cells fill with their own ECM over time. There is only limited knowledge on how pore geometry influences cell organization and matrix production, even though it is highly relevant for scaffold design. This study hypothesized that 1) a simple geometric description predicts cellular organization during pore filling at the cell level and that 2) pore closure results in a reorganization of ECM. Scaffolds with a broad distribution of pore sizes (macroporous starPEG-heparin cryogel) were used as a model system and seeded with primary fibroblasts. The strategies of cells to fill pores could be explained by a simple geometrical model considering cells as tensioned chords. The model matched qualitatively as well as quantitatively by means of cell number vs. open cross-sectional area for all pore sizes. The correlation between ECM location and cell position was higher when the pores were not filled with tissue (Pearson's coefficient ρ = 0.45±0.01) and reduced once the pores were closed (ρ = 0.26±0.04) indicating a reorganization of the cell/ECM network. Scaffold pore size directed the time required for pore closure and furthermore impacted the organization of the fibronectin matrix. Understanding how cells fill micro-voids will help to design biomaterial scaffolds that support the endogenous healing process and thus allow a fast filling of tissue defects.
- ItemNano- to millimeter scale morphology of connected and isolated porosity in the permo-triassic khuff formation of Oman(Basel : MDPI AG, 2020) Smodej, Jörg; Lemmens, Laurent; Reuning, Lars; Hiller, Thomas; Klitzsch, Norbert; Claes, Steven; Kukla, Peter A.Carbonate reservoirs form important exploration targets for the oil and gas industry in many parts of the world. This study aims to differentiate and quantify pore types and their relation to petrophysical properties in the Permo-Triassic Khuff Formation, a major carbonate reservoir in Oman. For that purpose, we have employed a number of laboratory techniques to test their applicability for the characterization of respective rock types. Consequently, a workflow has been established utilizing a combined analysis of petrographic and petrophysical methods which provide the best results for pore-system characterization. Micro-computed tomography (μCT) analysis allows a representative 3D assessment of total porosity, pore connectivity, and effective porosity of the ooid-shoal facies but it cannot resolve the full pore-size spectrum of the highly microporous mud-/wackestone facies. In order to resolve the smallest pores, combined mercury injection capillary pressure (MICP), nuclear magnetic resonance (NMR), and BIB (broad ion beam)-SEM analyses allow covering a large pore size range from millimeter to nanometer scale. Combining these techniques, three different rock types with clearly discernible pore networks can be defined. Moldic porosity in combination with intercrystalline porosity results in the highest effective porosities and permeabilities in shoal facies. In back-shoal facies, dolomitization leads to low total porosity but well-connected and heterogeneously distributed vuggy and intercrystalline pores which improves permeability. Micro- and nanopores are present in all analyzed samples but their contribution to effective porosity depends on the textural context. Our results confirm that each individual rock type requires the application of appropriate laboratory techniques. Additionally, we observe a strong correlation between the inverse formation resistivity factor and permeability suggesting that pore connectivity is the dominating factor for permeability but not pore size. In the future, this relationship should be further investigated as it could potentially be used to predict permeability from wireline resistivity measured in the flushed zone close to the borehole wall. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemSulfonated covalent triazine-based frameworks as catalysts for the hydrolysis of cellobiose to glucose(London : RSC Publishing, 2018) Artz, Jens; Delidovich, Irina; Pilaski, Moritz; Niemeier, Johannes; Kübber, Britta Maria; Rahimi, Khosrow; Palkovits, ReginaCovalent triazine-based frameworks (CTFs) were synthesized in large scale from various monomers. The materials were post-synthetically modified with acid functionalities via gas-phase sulfonation. Acid capacities of up to 0.83 mmol g−1 at sulfonation degrees of up to 10.7 mol% were achieved. Sulfonated CTFs exhibit high specific surface area and porosity as well as excellent thermal stability under aerobic conditions (>300 °C). Successful functionalization was verified investigating catalytic activity in the acid-catalyzed hydrolysis of cellobiose to glucose at 150 °C in H2O. Catalytic activity is mostly affected by porosity, indicating that mesoporosity is beneficial for hydrolysis of cellobiose. Like other sulfonated materials, S-CTFs show low stability under hydrothermal reaction conditions. Recycling of the catalyst is challenging and significant amounts of sulfur leached out of the materials. Nevertheless, gas-phase sulfonation opens a path to tailored solid acids for application in various reactions. S-CTFs form the basis for multi-functional catalysts, containing basic coordination sites for metal catalysts, tunable structural parameters and surface acidity within one sole system.
- ItemA numerical sensitivity study of how permeability, porosity, geological structure, and hydraulic gradient control the lifetime of a geothermal reservoir(Göttingen : Copernicus Publ., 2019) Bauer, Johanna F.; Krumbholz, Michael; Luijendijk, Elco; Tanner, David C.Geothermal energy is an important and sustainable resource that has more potential than is currently utilized. Whether or not a deep geothermal resource can be exploited, mostly depends on, besides temperature, the utilizable reservoir volume over time, which in turn largely depends on petrophysical parameters. We show, using over 1000 (n=1027) 4-D finite-element models of a simple geothermal doublet, that the lifetime of a reservoir is a complex function of its geological parameters, their heterogeneity, and the background hydraulic gradient (BHG). In our models, we test the effects of porosity, permeability, and BHG in an isotropic medium. Furthermore, we simulate the effect of permeability contrast and anisotropy induced by layering, fractures, and a fault. We quantify the lifetime of the reservoir by measuring the time to thermal breakthrough, i.e. how many years pass before the temperature of the produced fluid falls below the 100 ∘C threshold. The results of our sensitivity study attest to the positive effect of high porosity; however, high permeability and BHG can combine to outperform the former. Particular configurations of all the parameters can cause either early thermal breakthrough or extreme longevity of the reservoir. For example, the presence of high-permeability fractures, e.g. in a fault damage zone, can provide initially high yields, but it channels fluid flow and therefore dramatically restricts the exploitable reservoir volume. We demonstrate that the magnitude and orientation of the BHG, provided permeability is sufficiently high, are the prime parameters that affect the lifetime of a reservoir. Our numerical experiments show also that BHGs (low and high) can be outperformed by comparatively small variations in permeability contrast (103) and fracture-induced permeability anisotropy (101) that thus strongly affect the performance of geothermal reservoirs.
- ItemPorosity and distribution of water in perlite from the island of Milos, Greece(Berlin : SpringerOpen, 2014) Kaufhold, Stephan; Reese, Anke; Schwiebacher, Werner; Dohrmann, Reiner; Grathoff, Georg H.; Warr, Laurence N.; Halisch, Matthias; Müller, Cornelia; Schwarz-Schampera, Ulrich; Ufer, KristianA perlite sample representative of an operating mine in Milos was investigated with respect to the type and spatial distribution of water. A set of different methods was used which finally provided a consistent view on the water at least in this perlite. Infrared spectroscopy showed the presence of different water species (molecular water and hydroxyl groups / strongly bound water). The presence of more than 0.5 mass% smectite, however, could be excluded considering the cation exchange capacity results. The dehydration measured by thermal analysis occurred over a wide range of temperatures hence confirming the infrared spectroscopical results. Both methods point to the existence of a continuous spectrum of water binding energies. The spatial distribution of water and/or pores was investigated using different methods (CT: computer tomography, FIB: scanning electron microscopy including focused ion beam technology, IRM: infrared microscopy). Computer tomography (CT) showed large macropores (20 – 100 μm) and additionally revealed a mottled microstructure of the silicate matrix with low density areas up to a few μm in diameter. Scanning electron microscopy (FIB) confirmed the presence of μm sized pores and IRM showed the filling of these pores with water. In summary, two types of pores were found. Airfilled 20 – 100 μm pores and μm-sized pores disseminated in the glass matrix containing at least some water. Porosity measurements indicate a total porosity of 26 Vol%, 11 Vol% corresponding to the μm-sized pores. It remains unsolved wether the water in the μm-sized pores entered after or throughout perlite formation. However, the pores are sealed and no indications of cracks were found which indicated a primary source of the water, i.e. water was probably entrapped by quenching of the lava. The water in these pores may be the main reason for the thermal expandability which results in the extraordinarily porous expanded perlite building materials.