Universität Stuttgart
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Item Open Access Genetisch modifizierte Biotemplate zur Erzeugung von Zr-basierten Nanomaterialien(2019) Eisele, Rahel; Bill, Joachim (Prof. Dr.)In Biomineralisationsprozessen aus der belebten Natur scheiden sich anorganische Materialien auf organischen Templaten (Biomakromoleküle) ab. Funktionelle Gruppen der Makromoleküle steuern dabei die Abscheidung aus einer wässrigen Lösung sowie die Strukturierung des anorganischen Materials. Dabei sind spezifische Wechselwirkungen zwischen dem organischen Templat und dem anorganischen Material von Bedeutung. Die Materialbildung findet unter Umgebungsbedingungen in wässrigen Systemen statt. Für technisch interessante Materialien wie Zirkoniumdioxid (ZrO2) stellt die energieeffiziente Herstellung präziser Nanostrukturen eine technische Herausforderung dar. Daher wurden im Rahmen dieser Arbeit die Prinzipien der Biomineralisation auf die Herstellung von Zirkonium-basiertem Material (ZrbM) übertragen. Hierzu gehörte die Materialbildung durch Mineralisation aus einer ZrOCl2-Lösung sowie eine gezielte Mineralisation auf bioorganischen M13-Bakteriophagentemplaten. Um die „biologische Spezifität“ in Biomineralisationsprozessen auf die Bildung von ZrbM zu übertragen, wurden Peptide mittels Phagen-Display identifiziert, die spezifisch an ZrO2 binden. Mittels genetischer Modifikation wurden diese ZrO2 Bindepeptide auf der Phagenoberfläche präsentiert. Hierdurch wurde eine hohe Bindepeptiddichte und damit viele Interaktionspunkte zum anorganischen Material erzielt. Bevor der Einfluss dieser Bindepeptide auf die Mineralisation von ZrbM untersucht werden konnte, wurde zunächst der Partikelbildungs- und Partikelwachstumsprozess von ZrbM in einer ZrOCl2-Lösung und einem Ethanol-Wasser Lösungsmittelgemisch bei verschiedenen System- und Prozessparametern beschrieben. Auf Grundlage dieser Ergebnisse wurde eine Mineralisationslösung etabliert mit der der Einfluss der Bindepeptide - präsentiert auf der Phagenoberfläche - auf die Mineralisation von ZrbM untersucht werden konnte. Die Bindepeptide zeigten einen deutlichen Einfluss auf die Mineralisation von ZrbM. Im Vergleich zu Bakteriophagen ohne Bindepeptid wurde mit den genetisch modifizierten Bakteriophagen eine deutlich höhere Abscheiderate erzielt. Dieser Einfluss der Bindepeptide wurde auf Hydroxygruppen in Serineinheiten zurückgeführt. Diese führen zum einen zu einer starken Anziehung von molekularen Zr-Spezies an das Biotemplat. Zum anderen induzieren die Hydroxygruppen die heterogene Keimbildung von ZrbM durch Kondensationsreaktionen zwischen dem Biotemplat und molekularen Zr-Spezies. Somit ist es nun möglich genetisch kontrolliert Zr-basierte Nanomaterialien zu mineralisieren. Im Rahmen dieser Arbeit gelang es nicht nur einzelne Phagen zu mineralisieren, sondern auch dünne homogene Schichten aus ZrbM. Diese ZrbM-Schichten wurden im letzten Teil dieser Arbeit vergleichend zu Phagenschichten und SiO2-Schichten auf die Adhäsion von Staphylococcus aureus (S. aureus) getestet. S. aureus ist ein pathogenes Bakterium, welches zur Bildung von Biofilmen, zum Beispiel auf Implantaten, und dadurch zu einem Implantatverlust bis hin zu lebensbedrohlichen Komplikationen führen kann. Die Biofilmbildung kann effektiv unterbunden werden, indem die Bakterienadhäsion auf Oberflächen verhindert wird. Daher wurde im Rahmen dieser Arbeit untersucht, ob bestimmte chemische Oberflächen, das heißt bestimmte Materialien oder auch bestimmte funktionelle Gruppen, die Bakterienadhäsion unterdrücken können. Die Untersuchung der Bakterienadhäsion auf den verschiedenen Oberflächen ergab, dass auf der Phagenschicht im Vergleich zur SiO2-Schicht und einer Schicht aus ZrbM eine sehr geringe Bakterienadhäsion vorlag. Untersuchungen verschiedener Einflussfaktoren auf die Bakterienadhäsion zeigten, dass die Bakterienadhäsion an der SiO2-Schicht und der ZrbM-Schicht durch die Oberflächenrauigkeit, die Hydrophobizität und die Oberflächenladung beeinflusst werden kann. Bei der Phagenschicht korrelierten weder die Oberflächenladung, noch die Oberflächenrauigkeit und die Hydrophobizität im Vergleich zu den anorganischen Materialoberflächen mit der Bakterienadhäsion. Dies ließ darauf schließen, dass die geringe Bakterienadhäsion auf der Phagenschicht auf die biochemische Zusammensetzung der Hüllproteine, vor allem auf die Abwesenheit spezifischer Bindedomänen (Ligand-Rezeptor-Wechselwirkungen), zurückzuführen ist.Item Open Access Growth of oxide materials with Ruddlesden-Popper- and garnet-type structures via the optical float zone method: investigations of scintillation, optical, and magnetic properties, and post-growth modifications of single crystals via topochemical routes(2025) Yilmaz, Hasan; Clemens, Oliver (Prof. Dr.)With the continuous progress in materials science, the global market demand for high-performance functional materials, especially those with customized optical and magnetic properties, has increased significantly due to their critical role in next-generation technologies such as photonic devices, data storage systems, quantum computing, and biomedical applications. With this motivation, this dissertation is focused on the growth of high-quality oxide single crystals with Ruddlesden-Popper (RP) and garnet-type structures using the optical floating zone (OFZ) method and the detailed investigation of their scintillation, optical and magnetic properties. Furthermore, the use of chemical doping and post-growth topochemical modifications as strategies to modify material properties and stabilise metastable structures is also covered. With these approaches, we can classify this study into two parts: optical and magnetic properties. In the first part of this work, RP-type n = 1 LaSrGaO4 (LSGO) and Garnet-type Gd3In2Ga3O12 (GIGG) single crystals doped with different Rare Earths (RE) including Eu, Sm, Ho, Nd have been grown via OFZ method to investigate their luminescence, decay time kinetics and scintillation properties. To compare the scintillation behaviour, a well-known commercial scintillator, Gd2.98Ce0.02Al2Ga3O12 (0.02Ce:GAGG) single crystal, was synthesised and characterised using the same methods. This limits deviations in scintillation properties caused by different synthesis methods. Powder X-ray diffraction (XRD) and Single Crystal X-ray diffraction (SC-XRD) measurements together with Rietveld analysis confirmed phase purity and crystallinity, while Scanning Electron Microscopy (SEM-EDX) and backscatter electron imaging (BSE) confirmed the homogeneous distribution of the dopants. In addition to these analytical methods, Photoluminescence Spectroscopy (PL) and luminescence decay measurements have demonstrated that these RE-doped single crystals have strong emission, which is related to the low phonon energy of their host lattices. However, scintillation measurements under 137Cs gamma-ray point source excitation resulted in a limited gamma ray response. This response was significantly weaker than observed for the well-known commercial scintillator 0.02Ce:GAGG. Inefficient absorption of high-energy excitation or inadequate energy transfer to the activator ions in these materials are responsible for this relatively low scintillation performance. The second part of the thesis is focused on bilayer Ruddlesden-Popper nickelates. Single crystals of Sr3Ni2-xAlxO7-δ (SNAO) and its Y-substituted modification YᵧSr3-yNi2-xAlxO7-δ (YSNAO) have been grown by using strategically chemical substitutions and high oxygen pressure conditions to stabilize the RP phase. XRD and SC-XRD analysis confirmed the existence of the n = 2 RP-type structure by doping with Al, while thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) indicated successful oxygen incorporation and corresponding changes in the Ni oxidation state. Magnetic susceptibility measurements (SQUID magnetometry) have demonstrated the antiferromagnetic ordering transitions in these doped nickelate single crystals, and transport measurements have shown enhanced electrical conductivity compared to the undoped parent compound. In addition, a topochemical fluorination process has been investigated as a post-growth modification for n = 1 RP-type La2NiO4+δ single crystals. Fluorine has been introduced into the crystal lattice at moderate temperatures using polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and CuF2 as fluorination reagent. PTFE has been found to be the most effective fluorinating agent, resulting in partially fluorinated La2NiO4+δ with a diffusion-limited penetration pattern. EDX and EDX-mapping analyses have demonstrated an inhomogeneous F distribution, indicating that fluorine incorporation is limited by diffusion kinetics. This inhomogeneity should be carefully considered in future structural and functional analyses as it may affect the accurate characterisation of intrinsic properties in fluorinated crystals. In summary, the results of this thesis demonstrate the flexibility of the optical floating zone technique for the growth of high-quality functional oxides and show how structural stability, and functional properties can be modified using specific chemical doping approaches. To optimise scintillation performance in novel garnet-type hosts and to improve the magnetic and electronic behaviour of RP-type nickelates, the combined approach of crystal growth and post-growth modification could provide an additional parameter for material modification.Item Open Access Microstructural changes and intermetallic compound formation in metallic bilayers(Stuttgart : Max-Planck-Institut für Intelligente Systeme (ehemals Max-Planck-Institut für Metallforschung), 2016) Rossi, Paul J.; Mittemeijer, Eric Jan (Prof. Dr. Ir.)This thesis investigates interdiffusion and intermetallic compound (IMC) formation, as well as their effects on the microstructure, in metallic thin-film bilayers. The investigation focuses on bilayers based on the Ag-Sn and Ag-In binary systems, which are technologically important as basis for lead free solders. Due to the enhanced diffusional mechanisms in these systems, diffusion occurs readily even at room and low temperatures. The proceeding interdiffusion eventually leads to IMC formation in the bilayers, allowing for the investigation of the kinetics of IMC formation and the associated microstructural changes at room and low temperatures. The combination of the properties special to thin films with the diffusional mechanisms in the binary Ag-Sn and Ag-In systems leads to interesting effects, such as the dependence of IMC formation on the stacking sequence in the bilayers. The obtained experimental results for both systems could be explained using thermodynamic and kinetic models. Experimental characterization of the bilayers mainly relied on X-ray diffraction (XRD) and electron microscopy. In order to investigate the effect of the deposition process on IMC formation and the microstructure of the bilayers, different physical vapor deposition (PVD) techniques, especially thermal evaporation and magnetron sputtering, were used for the preparation of the bilayers. During investigation of the Ag-Sn system it was found that ambiguity exists among the published crystal structures of the Ag3Sn IMC. Therefore, the crystal structure of Ag3Sn has been reinvestigated using high-resolution XRD in connection with Rietveld refinements.Item Open Access Nano-analysis of surface reaction kinetics of automotive exhaust gas catalyst(2025) Lee, Yoonhee; Schmitz, Guido (Prof. Dr. Dr. h.c.)This study aims to advance our comprehension of the reaction kinetics occurring in nano-sized noble metal catalysts. Advanced microscopy techniques were employed to investigate the precise details of oxidation and diffusion behavior at different temperatures. In particular, atom probe tomography (APT), a highly sophisticated characterization technique, was utilized to obtain accurate and detailed information regarding these processes. By employing this microscopy technique, a comprehensive analysis of the reaction kinetics of nano-sized noble metal catalysts could be achieved, contributing to the development of more efficient catalysts for automotive applications. Noble metal nanoparticles such as Pt, Pd, and PtPd exhibit distinct oxidation behaviors during NO conversion. Understanding the alterations in the catalyst surface is crucial, as it has a direct effect on the performance of the catalytic converter. For this study, wires were utilized made of pure Pt, pure Pd, and PtPd alloy to create sharp tip samples through electrochemical polishing or FIB annular milling. The hemispherical shape of the tip apex serves as a model for the nanosized catalyst surface. The tips were oxidized in the reaction chamber and investigated by APT. The effective oxide thicknesses were determined and compared to the NO conversion rates measured using a Flat Bed Reactor (FBR). Additionally, experimental results of studying the interdiffusion behavior of the Pt-Pd binary system at various temperatures are presented and discussed. To achieve this purpose, the samples were prepared and examined with two different methods, depending on the heating temperatures. For the temperature range between 673 and 973 K, the samples made of nano-sized multiple layers were investigated using APT. For the temperature range between 1073 and 1243 K micro-sized Pt/Pd diffusion couples were annealed and analyzed using energy dispersive X-ray spectroscopy (EDX). The interdiffusion coefficients for both methods were determined by representing them as Fourier series and the Boltzmann-Matano method, respectively. The latter study was conducted in collaboration with the department of Materials design. Consequently, the interdiffusion coefficients were compared with the results of density functional theory (DFT) simulations.Item Open Access Design of nanostructured vanadium pentoxide scaffolds inspired by natural cuttlebone(2018) Knöller, Andrea; Bill, Joachim (Prof. Dr.)Item Metadata only Internal precipitation of nitrides in iron-based alloys(Stuttgart : Max-Planck-Institut für Intelligente Systeme (ehemals Max-Planck-Institut für Metallforschung), 2016) Steiner, Tobias; Mittemeijer, Eric J. (Prof. Dr. Ir.)X‐ray diffraction has become a standard method of microstructural analysis. However, in systems with a complex microstructure, the interpretation of the measured diffractograms may not be very straightforward. The influence of the precipitation of fine alloying element nitrides and the changes in precipitation morphology that occur upon continued nitriding on the shape and position of XRD peaks have been identified. The thus obtained quantitative model has been applied to a variety of precipitation systems and in general good agreement of predicted values and experimental results is found. The precipitation of finely distributed alloying element nitrides is the main strengthening mechanism in the diffusion zone of nitrided parts. Various alloying elements having an affinity for N show considerably different nitriding behavior. Cr shows a strong N‐affinity and therefore readily precipitates in the presence of N. However, Mo has a weak strength of interaction with N and reacts only slowly. In order to better understand the nitriding behavior of nitrided steels containing both Cr and Mo, the nitriding behavior of ternary Fe‐Cr‐Mo model alloys is investigated. The complex precipitation sequence of ternary mixed Cr-Mo-nitrides has been identified and the role of the Cr/Mo-ratio of the alloy is exposed. X‐ray diffraction has become a standard method of microstructural analysis. However, in systems with a complex microstructure, the interpretation of the measured diffractograms may not be very straightforward. The influence of the precipitation of fine alloying element nitrides and the changes in precipitation morphology that occur upon continued nitriding on the shape and position of XRD peaks have been identified. The thus obtained quantitative model has been applied to a variety of precipitation systems and in general good agreement of predicted values and experimental results is found.Item Open Access Template controlled mineralization of functional ZnO thin films(2017) Blumenstein, Nina; Bill, Joachim (Prof. Dr.)In this thesis, the influence of different organic templates on the bioinspired deposition of ZnO thin films is investigated. Depending on the polarity of the templates, the growth and the properties of the films can be influenced. On a non-polar template, film growth is inhibited whereas homogeneous films grow on polar templates. Additionally, it was shown that on a template with high polarity a crystallographic texture is observed. This leads to a macroscopically measurable piezoelectric response of these samples. In the last part of this work, the incorporation of Al, Ga and In into the ZnO films was investigated. Measurements showed a blue shift of the UV photoluminescence emission and an improved electrical conductivity with increasing doping content.Item Open Access Interaction of carbon and nitrogen in iron(Stuttgart : Max-Planck-Institut für Intelligente Systeme (ehemals Max-Planck-Institut für Metallforschung), 2016) Göhring, Holger; Mittemeijer, Eric Jan (Prof. Dr. Ir.)Item Open Access Aluminum-induced crystallization of semiconductor thin films(2015) Qu, Fei; Schmitz, Guido (Prof. Dr.)Thin film materials of the semiconductors, such as silicon (Si), germanium (Ge) or their alloys, are turning into the most promising functional materials in the energy technology. However, the morphologies of these semiconductor thin films must be varied to be suitable for the different applications, e.g. a large-grained layer as the seed layer of thin film solar cells, a porous structure for anode materials of high energy rechargeable lithium (Li) ion batteries. Due to the collective interdiffusion process during the aluminum (Al)-induced crystallization, in this thesis, the suitable morphologies are achieved for the corresponding applications under the different fabrication conditions. A large-grained Si layer can be formed by the crystallization of Si in a porous Al layer, which is obtained by applying a bias voltage. Since the Al grain boundaries are contaminated by e.g. oxygen (O), the diffusion of Si in the Al grain boundaries is retarded. It can lead to a reduction of the nucleation density of Si. At a certain high temperature, a collective diffusion process of Si in Al is activated. Consequently, a large-grained Si layer with (100) texture can be formed. By purposely interrupting the annealing of nanocrystalline Al/amorphous Si (a-Si) bilayers, a porous structure of the crystallized Si can be developed due to the incomplete intermixing of Si and Al. Due to the different dominant diffusion processes of Si in Al at the different annealing temperatures, the most Si diffuses along the different paths in the Al layer, such as triple junction, grain boundary and Al bulk. Therefore, it can develop the different morphologies of the porous Si layers after the selectively etching of Al. By introducing an amorphous Ge interlayer between the crystalline Al and amorphous Si layer, the Al grain boundaries are not essential for the crystallization of the amorphous Si in contrast to the case in Al/Si bilayer system. Si crystallizes continuously on the pre-crystallized Ge seeds which form initially at the original interface of crystalline Al and amorphous Ge. The thermodynamic models to interpret the fundamentals of these different crystallization behaviors of Si are established based on the change of the interface energy between the different phases of the whole system during the crystallization. Using the effective diffusivity, the dominant diffusion process of Si in Al can be investigated to explore the morphological dependence of the crystallized Si layer on the annealing conditions.Item Open Access Nitriding behavior of Ni and Ni-based binary alloys(2015) Fonovic, Matej; Mittemeijer, Eric J. (Prof. Dr. Ir.)Gaseous nitriding is a prominent thermochemical surface treatment process which can improve various properties of metallic materials such as mechanical, tribological and/or corrosion properties. This process is predominantly performed by applying NH3+H2 containing gas atmospheres serving as the nitrogen donating medium at temperatures between 673 K and 873 K (400 °C and 600 °C). NH3 decomposes at the surface of the metallic specimen and nitrogen diffuses into the surface adjacent region of the specimen whereas hydrogen remains in the gas atmosphere. One of the most important parameters characterizing a gaseous nitriding process is the so-called nitriding potential (rN) which determines the chemical potential of nitrogen provided by the gas phase. The nitriding potential is defined as where and are the partial pressures of the NH3 and H2 in the nitriding atmosphere. In contrast with nitriding of alpha-Fe where the nitriding potential is usually in the range between 0.01 and 1 atm-1/2, nitriding of Ni and Ni-based alloys requires employing nitriding potentials higher than 100 atm-1/2 and even up to infinity (nitriding in pure NH3 atmosphere). This behavior is compatible with decreased thermodynamic stability of the 3d-metal nitrides with increasing atomic number. Depending on the nitriding conditions (temperature, nitriding potential and treatment time), different phases are formed at the surface of the Ni-based alloys. By applying very high nitriding potential, formation of hexagonal Ni3N at the surface of the specimen (known as external nitriding) leads to the development of a compound layer, which may improve tribological properties. Underneath the Ni3N compound layer, two possibilities exist: (i) alloying element precipitation within the nitrided zone (known as internal nitriding) and/or (ii) development of metastable and precipitate-free microstructure known as expanded austenite or S-phase, which can enhance surface hardness, fatigue properties and corrosion properties.Nitriding of multicomponent Ni-based alloys is usually applied in the industry. Nevertheless, the understanding of nitriding is mostly based on phenomenological research and experience. Thereby there is still absence of complete understanding of nitriding of Ni-based alloys, which requires further detailed investigations. Since studying the nitrided multicomponent alloys is complicated, in this thesis fundamental investigations were performed on pure nickel and binary Ni-based model alloys.This thesis focuses on the nitriding behavior of pure nickel, which will result with an thermodynamic evaluation of the Ni-N system. Furthermore, deeper insights in the nitriding behavior of the binary Ni-based alloys is obtained upon nitriding Ni-4 wt.% Ti and Ni-2 wt.% Ti (Ni-5 at.% Ti and Ni-2.5 at.% Ti) alloys. Thereby, the development of large residual macrostresses parallel to the surface of the specimen is related with the N concentration gradient in the nitrided zone.
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