Institut für Integrierte Naturwissenschaften, Abt. Chemie
Refine
Year of publication
Document Type
- Doctoral Thesis (22)
- Article (3)
Keywords
- Aluminiumorthophosphat (1)
- Arzneimittel (1)
- Bauxit (1)
- Biotransformation (1)
- Bororthophosphat (1)
- Cloud Point Extraction (1)
- Depth Profile (1)
- Ecotoxicity (1)
- Environmental organic chemistry (1)
- Environmental samples (1)
The title compound, [Fe(C5H5)(C21H24NO2)], which is produced by the oxidation of 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole, crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The central heterocyclic pyrrole ring system subtends dihedral angles of 13.7 (2)° with respect to the attached cyclopentadienyl ring and of 43.6 (7)° with the major component of the disordered phenyl group bound to the N atom. The 4-tert-butylphenyl group, as well as the non-substituted Cp ring are disordered with s.o.f. values of 0.589 (16) and 0.411 (16), respectively. In the crystal, molecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O—H···O hydrogen bonds between the hydroxy substituent and the carbonyl O atom of the adjacent molecule.
X-ray computed tomography (XRT) is a three-dimensional (3D), non-destructive, and reproducible investigation method capable of visualizing and examining internal and external structures of components independent of the material and geometry. In this work, XRT with its unique abilities complements conventionally utilized examination methods for the investigation of microstructure weakening induced by hydrogen corrosion and furthermore provides a new approach to corrosion research. The motivation for this is the current inevitable transformation to hydrogen-based steel production. Refractories of the system Al2O3-SiO2 are significant as lining materials. Two exemplary material types A and B, which differ mainly in their Al2O3:SiO2 ratio, are examined here using XRT. Identical samples of the two materials are measured, analyzed, and then compared before and after hydrogen attack. In this context, hydrogen corrosion-induced porosity and its spatial distribution and morphology are investigated. The results show that sample B has an higher resistance to hydrogen-induced attack than sample A. Furthermore, the 3D-representation revealed a differential porosity increase within the microstructure.
Nanoparticles are sensitive and robust systems; they are particularly reactive due to their large surface area and have properties that the bulk material does not have. At the same time, the production of nanoparticles is challenging, because even with the same parameters and conditions, the parameters can vary slightly from run to run. In order to avoid this, this work aims to develop a continuous synthesis in the microjet reactor for nanoceria. The aim is to obtain monodisperse nanoparticles that can be used in biosensors.
This work focuses on two precipitation syntheses with the intermediate steps of cerium carbonate and cerium hydroxide, as well as a microemulsion synthesis for the production of nanoceria. The cerium oxide nanoparticles are compared using different characterisation and application methods. The synthesised nanoparticles will be characterised with respect to their size, stability, chemical composition and catalytic capabilities, by electron microscopy, X-ray diffraction, Raman spectroscopy and photoelectron spectroscopy.
The biosensor systems to evaluate the nanoceria are designed to detect histamine and glucose or hydrogen peroxide, which are resulting from the oxidation of histamine and glucose. Hydrogen peroxide and glucose are detected by an electrochemical sensor and histamine by a colorimetric sensor system.
Organic binder mixtures and process additives have been used in refractory materials for a long time due to their property-improving effect. Coal tar pitches in particular can contain thousands of chemical compounds, of which especially polycyclic aromatic hydrocarbons (PAHs) are known to be carcinogenic and mutagenic and thus pose a risk to both the environment and human health. However, despite intensive research, the exact structure of these carbon mixtures is still not fully clarified. This is becoming an increasing problem, especially with regard to more stringent legal requirements arising from REACH, the European Chemicals Regulation for the Registration, Evaluation, Authorization and Restriction of Chemicals. Furthermore, the knowledge of the structural and chemical composition is also of great importance for optimal processing of the carbon mixtures to high-quality technical products. In the present work, an analytical strategy for the investigation of complex carbon mixtures containing PAHs is developed. Due to their complexity, a combination of different methods is used, including elemental analysis, solvent extraction, thermogravimetry, differential thermal analysis, raman and infrared spectroscopy as well as high-resolution mass spectrometry. In addition, a procedure for the evaluation of mass spectrometric data based on multivariate statistical methods such as hierarchical cluster analysis and principal component analysis is developed. The application of the developed analytical strategy to various industrially used carbon-based binder mixtures allowed the elucidation of characteristic properties, including aromaticity, molecular mass distribution, degree of alkylation and elemental composition. It was also shown that combining high-resolution time-of-flight mass spectrometry with multivariate statistical data analysis is a fast and effective tool for the classification of complex binder mixtures and the identification of characteristic molecular structures. In addition, the analytical strategy was applied to manufactured refractory products. Despite the small amount of the contained organic phase, characteristic structural features of each sample could be identified and extracted, which enabled an unambiguous classification of the refractory products.
Bauxite is, among other raw materials, an important material for the production of refractories. However, the availability of refractory raw material grades is limited worldwide. As high iron contents have a negative influence on the temperature resistance of the refractory material produced, a maximum iron oxide content of 2 wt.-% in the bauxite is acceptable. This means that only native raw materials from a few deposits can be used. In order to counteract the problem of too high iron oxide contents in natural bauxites, the possibility of processing bauxite for the refractory industry by using an acid leaching process was to be investigated within the scope of this work. In previous studies on this topic, some investigations on iron leaching have already been carried out on individual bauxites. However, the resulting bauxite composition was mostly neglected in its entirety and only the influences of individual leaching parameters on the leaching result were investigated independently. Moreover, the results and procedures generated are not generally valid and cannot be transferred to bauxites of other chemical or mineralogical compositions.
In order to clarify the open questions in the processing of natural bauxites, leaching tests with hydrochloric acid were carried out on five different bauxites within this work. By using computerized statistical design of experiments, an individual model was generated for each bauxite to predict the optimal factor settings. The factors investigated were acid concentration, solid-acid ratio, leaching temperature, leaching time and grain fraction. The general planning method for bauxite processing developed in this context contains all necessary factors, useful factor settings and the effects to be considered during planning and evaluation. It could be shown that, based on this planning method, a significant, individual model can be created for each of the bauxites investigated, which predicts the optimal leaching settings for the corresponding bauxite. Furthermore, it was found that the transfer of an already created model to another bauxite of similar composition is possible. Based on the results obtained from the leaching tests and model fittings, in combination with further results on the structural analysis of the bauxites, insights into the leachability of various aluminium and iron minerals from bauxite could be gained.
To develop a sustainable acid leaching process, the possibility of regenerating the contaminated acid produced was also tested as an example. It was shown that liquid-liquid extraction can extract more than 99 % of the iron present in the solution and that the regenerated acid can then be reused for the leaching process.
X-ray computer tomography (XRT) is a three-dimensional, nondestructive, and thus reproducible examination method that allows for the investigation of internal and external structures of objects. Due to its characteristics, the XRT technique has increasingly established itself as an alternative examination method and is also applied in the field of mineral processing. Within this work, XRT is used to investigate the influence of hydrochloric acid leaching of iron-rich bauxites on grain composition. Acid leaching is a promising method for the beneficiation of iron-rich bauxites for refractories. Many studies have already established that leaching with hydrochloric acid can reduce the Fe₂O₃ content in bauxites. However, apart from the influence of the leaching process on the composition of the bauxites, aspects such as the influence of the acid on the exact grain constitution or the porosity behavior have rarely been considered so far. To address these open questions, XRT analysis was used to examine and characterize various bauxites. By comparing identical grains before and after leaching, it was observed that in gibbsite bauxites the acid penetration is deeper, and the volume decreases significantly. In diasporic and boehmitic bauxites, clear leaching edges can be seen in which the iron content has been reduced.
The present study deals with the synthesis of N-phenacylpyridinium salts and their use as photoinitiators for epoxy resins. The use and suitability of phenacyl salts as photoinitiators for epoxy resins has already been described in previous studies. The individual impact of the specific components on the rate constants of epoxy reaction has not been investigated in detail. Based on the structure of N-phenacylpyridinium salt the substances described in the present study were varied due to the exchange of counter ion and different substituents. Investigating the impact of the specific substituent with focus on the reaction of epoxy groups there is a dependence found for three main factors. First, depending on whether to use a phenyl or methyl group as substituent there was found an impact on the process of photolysis. Furthermore, concerning the dependences on the pyridine derivative and the counter ion, it was found that pyridine derivatives with electron withdrawing groups and counter ions, which can build strong acids, accelerate the rate constants of the epoxy reaction. Vice versa, pyridine derivatives with electron donating groups and counter ions, which can form weaker acids, decrease the rate constants.
The determined rate constants and the formulation of substances discussed in the present thesis in an adhesive formulation show the suitability of selected substances as photoinitiators for the polymerization of epoxy resins.
Speziell in Anwendungen mit intensiver Temperatur- und Korrosionsbeanspruchung finden vermehrt Phosphate als sogenannte chemische Binder für Hochleistungskeramiken Verwendung. Konkret ist die Summe der Reaktionsverläufe während des Bindemechanismus in Folge einer thermisch-induzierten Aushärtung und somit die Wirkungsweise von Phosphatbindern prinzipiell innerhalb der Fachliteratur nicht eindeutig untersucht. Innerhalb dieser Arbeit wurden aufbauend auf einer umfangreichen strukturanalytischen Prüfungsanordnung (Festkörper-NMR, RBA, REM-EDX) einer exemplarischen phosphatgebundenen Al₂O₃-MgAl₂O₄-Hochtemperaturkeramikzusammensetzung unter Einbeziehung verschiedenartiger anorganischer Phosphate grundlegende Bindemechanismen charakterisiert. Mechanisch-physikochemische Eigenschaftsuntersuchungen (STA, Dilatometrie, DMA, KBF) deckten zudem den Einfluss der eingesetzten Phosphate auf die Eigenschaftsentwicklungen der Feuerfestkeramiken bezüglich des Abbindeverhaltens, der Biegefestigkeit sowie der thermischen Längenänderung auf, welche mit Strukturänderungen korreliert wurden. Es wurde gezeigt, dass sich Bindemechanismen bei Verwendung von Phosphaten temperaturgeleitet (20 °C ≤ T ≤ 1500 °C) grundsätzlich aus zwei parallel ablaufenden Reaktionsabfolgen zusammensetzen, wobei die sich entwickelnden Phosphatphasen innerhalb der Keramikmasse quantitativ und qualitativ bezüglich ihrer Bindewirkung bewertet wurden. Zum einen wurde die Bildung eines festigkeitssteigernden Bindenetzwerks aus Aluminiumphosphaten meist amorpher Struktur identifiziert und charakterisiert. Dieses bindungsfördernde, dreidimensionale Aluminiumphosphatnetzwerk baut sich innerhalb der Initialisierungs- und Vernetzungsphasen temperaturgeleitet kontinuierlich über multiple Vernetzungsreaktionen homogen auf. Zum anderen werden Reaktionsabfolgen durch parallel ablaufende Strukturumwandlungen nicht aktiv-bindender Phosphatspezies wie Magnesium-, Calcium- oder Zirkoniumphosphate ergänzt, welche lediglich thermische Umwandlungsreaktionen der Ausgangsphosphate darstellen. Vermehrt bei T > 800 °C geht das phosphatische Bindenetzwerk Festkörperreaktionen mit MgAl₂O₄ unter Ausbildung und Agglomeration von Magnesium-Orthophosphat-Sinterstrukturen ein. Die Bildung dieser niedrigschmelzenden Hochtemperaturphasen führt zu einem teilweisen Bruch des Bindenetzwerks.
SUMMARY
Buildings and infrastructures characterize the appearance of our cultural landscapes and provide essential services for the human society. However, they inevitably impact the natural environment e.g. by the structural change of habitats. Additionally, they potentially cause further negative environmental impacts due to the release of chemical substances from construction materials. Galvanic anodes and organic coatings regularly used for corrosion protection of steel structures are building materials of particular importance for the transport infrastructure. In direct contact with a water body or indirectly via the runoff after rainfall, numerous chemicals can be released into the environment and pose a risk to aquatic organisms. Up to now, there is no uniform investigation and evaluation approach for the assessment of the environmental compatibility of building products. Furthermore, galvanic anodes and organic coatings pose particular challenges for their ecotoxicological characterization due to their composition. Therefore, the objective of the presented thesis was the ecotoxicological assessment of emissions from galvanic anodes and protective coatings as well as the development of standardized assessment procedures for these materials.
The possible environmental hazard posed by the use of anodes on offshore installations was investigated on three trophic levels. To ensure a realistic and reliable evaluation, the experiments were carried out in natural seawater and under natural pH conditions. Moreover, the anode material and its main components zinc and aluminum were exposed while simulating a worst-case scenario. The anode material examined caused a weak inhibition of algae growth; no acute toxicity was observed on the luminescent bacteria and amphipods. However, an increase of aluminum and indium levels in the crustacean species was found. On the basis of these results, no direct threat has been identified for marine organisms from the use of galvanic aluminum anodes. However, an accumulation of metals in crustaceans and a resulting entry into the marine food web cannot be excluded.
The environmental compatibility of organic coating systems was exemplarily evaluated using a selection of relevant products based on epoxy resins (EP) and polyurethanes. For this purpose, coated test plates were dynamically leached over 64 days. The eluates obtained were systematically analyzed for their ecotoxicological effects (acute toxicity to algae and luminescent bacteria, mutagenic and estrogenic effects) and their chemical composition. In particular, the EP-based coatings caused significant bacterial toxicity and estrogen-like effects. The continuously released 4-tert-butylphenol was identified as a main contributor to these effects and was quantified in concentrations exceeding the predicted no effect concentration for freshwater in all samples. Interestingly, the overall toxicity was not governed by the content of 4-tert-butylphenol in the products but rather by the release mechanism of this compound from the investigated polymers. This finding indicates that an optimization of the composition can result in the reduction of emissions and thus of environmental impacts - possibly due to a better polymerization of the compounds.
Coatings for corrosion protection are exposed to rain, changes in temperature and sun light leading to a weathering of the polymer. To determine the influence of light-induced aging on the ecotoxicity of top coatings, the emissions and associated adverse effects of UV-irradiated and untreated EP-based products were compared. To that end, the investigation of static leachates was focused on estrogenicity and bacterial toxicity, which were detected in the classic microtiter plate format and in combination with thin-layer plates. Both materials examined showed a significant decrease of the ecotoxicological effects after irradiation with a simultaneous reduction of the 4-tert-butylphenol emission. However, bisphenol A and various structural analogues were detected as photolytic degradation products of the polymers, which also contributed to the observed effects. In this context, the identification of bioactive compounds was supported by the successful combination of in-vitro bioassays with chemical analysis by means of an effect-directed analysis. The presented findings provide important information to assess the general suitability of top coatings based on epoxy resins.
Within the scope of the present study, an investigation concept was developed and successfully applied to a selection of relevant construction materials. The adaptation of single standard methods allowed an individual evaluation of these products. At the same time, the suitability of the ecotoxicological methods used for the investigation of materials of unknown and complex composition was confirmed and the basis for a systematic assessment of the environmental compatibility of corrosion protection products was created. Against the background of the European Construction Products Regulation, the chosen approach can facilitate the selection of environmentally friendly products and contributes to the optimization of individual formulations by the simple comparison of different building materials e.g. within a product group.
Modellbildung zum Abbindeverhalten von PCE-verflüssigten und CA-Zement-gebundenen Feuerbetonen
(2021)
Feuerbetone werden als Auskleidung in industriellen Hochtemperaturaggregaten, wie beispielsweise in der Eisen- und Stahlindustrie, eingesetzt. Nach dem Mischen und dem Gießen eines Feuerbetons in Formen bzw. Schalungen, muss dieser abbinden und eine ausreichende Festigkeit ausbilden. Die Kinetik der Abbindevorgänge und somit auch das Erhärtungsverhalten variiert dabei stark in Abhängigkeit der Zusammensetzung, vor allem hinsichtlich des Bindemittels und der Additive, des Feuerbetons. In der Praxis der Herstellung von Feuerbetonen kommt es häufig zu Beschädigungen der hergestellten Bauteile oder Auskleidungen durch das Fließen noch nicht ausreichend abgebundener Feuerbetone bzw. die Beschädigung von Ecken und Kanten während des Ausschalens oder Bauteilen reißen durch mechanische Belastung beim Umsetzen oder beim Transport. Diese Beschädigungen basieren auf Fehleinschätzungen zum Abbindefortschritt und der korrespondierenden Festigkeitsausprägung der Feuerbetone. Diese wiederum sind auf Lücken im Stand der Technik zurück zu führen.
Für PCE-verflüssigte und CA-Zement-gebundene Korund-Feuerbetonen mit einer Al₂O₃- und Al₂O₃-SiO₂-Matrix, werden die Defizite des Stands der Technik für diese Feuerbetonklasse identifiziert: Diese liegen im Bereich der Verflüssigungswirkung und des ersten Ansteifens der Feuerbetone, der Hydratation des CA-Zements in den Feuerbetonen und der Festigkeitsausprägung der Feuerbetone. Hieraus leitet sich ein entsprechender Forschungsbedarf ab.
Am Beispiel von zwei PCE-verflüssigten (PCE mit kurzer Hauptkette und langen Seitenketten sowie PCE mit langer Hauptkette und kurzen Seitenketten) und CA-Zement-gebundenen (70 % Al₂O₃) Feuerbetonen mit einer reaktivtonerde-basierten und einer reaktivtonerde-mikrosilika-basierten Matrix werden abbindekinetische Untersuchungen durchgeführt. Anhand verschiedener abbindekinetischer Messmethoden, wie Schallgeschwindigkeit oder elektrischer Leitfähigkeit, und einigen ergänzenden Messung, wie beispielsweise das ζ-Potential, wird der Abbindeverlauf der Feuerbetone untersucht und die Defizite aus dem Stand der Technik aufgeklärt.
Im Detail wurde der Stand der Technik um folgende Erkenntnisse ergänzt:
• Verflüssigung von Feuerbetonen mit PCE-Molekülen: Es wurde festgestellt, dass die Verflüssigungswirkung und das erste Ansteifen maßgeblich durch die Struktur der Verflüssigermoleküle hervorgerufen werden.
PCE-Moleküle mit langen Seitenketten verflüssigen eher sterisch. Durch die Vermittlung von Ca²⁺ aus dem CA-Zement wird die Adsorption der PCE-Moleküle verstärkt. Freie PCE-Moleküle können auf CAH-Phasen (Hydratationsprodukte) adsorbieren und somit die Fließfähigkeit des Feuerbetons für eine gewisse Zeit aufrechterhalten.
PCE-Moleküle mit kurzen Seitenketten verflüssigen elektrosterisch. Bei Lösung von Ca²⁺ aus dem CA-Zement kommt es zu einer Ca-PCE Gel-Bildung und einer korrespondierenden Koagulation der Feuerbetonmatrix und der Feuerbeton steift zeitnah nach dem Mischen an.
• Hydratation von CA-Zement: Die Hydratation von CA-Zement in den Feuerbetonen wird wesentlich durch die Länge der Seitenketten der PCE-Moleküle bzw. der Anwesenheit von Zitronensäure beeinflusst.
In Feuerbetonen die mit PCE-Molekülen mit langen Seitenketten verflüssigt wurden, kann der CA-Zement weitestgehend frei hydratisieren. Der CAH-Phasenanteil steigt in zwei Abschnitten, getrennt von einer dormanten Phase. Die dormante Phase der CA Zementhydratation wurde auf eine Lösungshemmung der Al-O-H-Passivierungsschicht auf dem CA-Zement bei mäßigem pH-Wert (pH = 12,3) zurückgeführt.
In Feuerbetonen die mit PCE-Molekülen mit kurze Seitenketten und Zitronensäure verflüssigt werden, wird die Hydratationsreaktion durch eine Ca-Citrat-PCE-Al(OH)₄-Gelbildung stark gehemmt. Es besteht die Vermutung, dass die Bindung von Ca²⁺ in dem Gel zum einen eine sehr ausgeprägte dormante Phase (pH < 12,3), mit einer schlechten Löslichkeit der Passivierungsschicht, bewirkt und zum anderen auch die Fällung von CAH-Phasen unterdrückt.
• Festigkeitsausprägung von CA-Zement-gebundenen Feuerbetonen:
Eine Koagulation bewirkt die erste Festigkeitssteigerung der Feuerbetone auf σB < 1 MPa. Im Anschluss findet die Hauptfestigkeitssteigerung auf Grund von Austrocknung durch Hydratation und Verdunstung statt. Der weitere Teil der Festigkeitssteigerung wird durch die Reduzierung der Porosität durch expansive CA-Zementhydratation und die hohe spezifische Oberfläche sowie deren weitere Erhöhung durch die CA-Zementhydratation bewirkt.
Aus den einzelnen abbindekinetischen Effekten können, zusammen mit dem Stand der Technik und den neuen Erkenntnissen, mikrostrukturelle Abbindemodelle und Modelle zur Festigkeitsentwicklung der Feuerbetone abgeleitet werden. In Folge kann für die zwei Feuerbetone zu jedem Zeitpunkt des Abbindens eine Aussage zum Abbindefortschritt und zur Festigkeitsausprägung getätigt werden. Einige der Abbindemechanismen und festigkeitsbildenden Mechanismen können auf andere Feuerbetonzusammensetzungen übertragen werden.