Durch Biotemplating mit bakteriellen Oberflächenproteinen, sogenannten S-Layer Proteinen können Metallcluster mit einer definierten Größe und Verteilung auf verschiedensten Oberflächen abgeschieden werden. Damit eröffnet sich die Möglichkeit der gezielten Präparation heterogener Katalysatoren. Mit der Kalorimetrie sollen die katalytischen Eigenschaften von mit Platin belegten S-Layer Präparationen am Beispiel der Kohlenmonoxidoxidation vorgestellt werden. Es werden geträgerte Katalysatoren und katalytisch aktive Schichten untersucht. Der Fokus liegt bei den Katalysatorschüttungen auf der Charakterisierung der katalytischen Eigenschaften und resultierend daraus auf einer Optimierung der Präparation. Für die Untersuchungen der katalytisch aktiven Schichten muss im Unterschied zu den Katalysatorschüttungen eine neuartige miniaturisierte Anordnung auf der Basis von Pt 1000 Widerstandsthermometern entwickelt werden. Dabei werden auch Parameter, die für eine spätere sensorische Applikation von Bedeutung sind, untersucht.

Die vorliegende Arbeit befasst sich mit experimentellen Untersuchungen zur physikalisch-chemischen und strukturellen Charakterisierung von neuartigen supramolekularen Kristalleinschlussverbindungen am Beispiel der Clathrate der Wirtverbindung 2,2’-bis(9-hydroxy-9-fluorenyl)biphenyl mit Aceton (polar) sowie Chloroform (unpolar). Durch die Kombination von Röntgenstrukturanalysen mit systematischen Messungen thermodynamischer Größen wie Löslichkeit, Einschluss-, Zersetzungs-, Lösungs- und Kristallisationsenthalpien konnten neue Erkenntnisse bezüglich der Struktur-Eigenschaftsbeziehungen sowie zur Rolle der Wirt-Gast Wechselwirkungen in den existierenden Einschlussverbindungen abgeleitet werden. Die Einschlussbildung bzw. Kristallisation verläuft für alle untersuchten Clathratphasen exotherm. Dies bedeutet, dass die Einschlussverbindungen gegenüber dem reinem Wirt energetisch stark begünstigt sind. Der bestimmende Beitrag hierfür resultiert aus der Bildung eines optimal gepackten Kristallgitters, während spezifische Wirt-Gast Wechselwirkungen nur eine untergeordnete Rolle spielen. Das Zersetzungsverhalten der verschiedenen Clathratphasen kann widerspruchsfrei aus der Packungsstruktur der Kristalle erklärt werden.

<p>Rechargeable lithium ion batteries (LIBs) are widely used in various daily life applications including electronic portable devices, cell phones, military applications, and electric vehicles throughout the world. The demand for building a safer and higher volumetric/gravimetric energy density LIBs has increased exponentially for electronic devices and electric vehicles. With the high energy density and longer cycle life, the LIBs are the most prominent energy storage system for electric vehicles. Researchers are further exploring for new materials with a high specific capacity, the MXene has been a promising new anode material for LIBs. The typical MXene material Ti₃C₂T_z has 447mAh/g theoretical capacity, which is higher than traditional graphite (372 mAh/g for LiC₆) based anode.</p> <p>Though LIBs are used in most of the portable energy storage devices, LIBs are still having thermal runaway safety concern, which is caused by three main reasons: mechanical, electrical, and thermal abuse. The thermal runaway is caused by the initiation of solid electrolyte interface (SEI) degradation above 80 °C on the anode surface, generating exothermic heat, and further increasing battery temperature. The SEI is a thin layer formed on anode due to electrolyte decomposition during first few charging cycles. Its degradation at low temperature generates heat inside the LIBs and triggers the thermal runaway. The thermal runaway follows SEI degradation, electrolyte reactions, polypropylene separator melting, cathode decomposition and finally leads to combustion. The thermal runaway mechanism of graphite, which is the most common and commercialized anode material of LIBs, has been studied for years. However, the thermal safety aspects of the new MXene material has not been investigated yet. </p> <p>In this thesis, we primarily used differential scanning calorimetry (DSC) and specially designed multi module calorimetry (MMC) to measure exothermic and endothermic heat generated at <a>Ti₃C₂T_z </a>anode, associated with multiple chemical reactions as the temperature increases. The <i>in-situ</i> MMC technique is employed to study the interactions and chemical reactions of all the components (separator, electrolyte, cathode and MXene anode) in the coin cell for the first time, while the <i>ex-situ</i> DSC is used to investigate the reactions happened on anode side, including electrolyte, PVDF binder, MXene, SEI and intercalated Li. Along with other <a>complementary </a>instruments and methods, the morphological, structural and compositional studies are carried out using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) surface area measurement and electrochemical measurement to support the thermal analysis. The electrochemical and thermal runaway mechanism of conventional graphitic anode is studied and used for comparison with MXeneanodes.</p> <p>The Ti₃C₂T_z thermal runaway is triggered by SEI decomposition around 120 °C analogous to conventional graphite. The thermal behavior of Ti₃C₂T_z anode is highly dependent on electrode material, surface area, lithiation states, surface morphology, structure and surface-terminating functional groups on Ti₃C₂T_z, which provides more active lithium sites for exothermic reactions with the electrolyte. Especially the terminal groups (-OH, -F, =O, etc.) from the etching process affect the lithium ion intercalation and thermal runaway mechanism. With annealing treatment, the surface-terminating functional groups are modified and can achieve less exothermic heat release. By normalizing the total heat generation by specific capacities of the anode materials, it is observed that Ti₃C₂T_z (2.68 J/mAh) generates slightly less exothermic heat than graphite (2.72 J/mAh) indicating slightly safer nature of Ti₃C₂T_z anode. The <i>in-situ</i> thermal analysis results on the Ti₃C₂T_z half-cell exhibited less total heat generation per mass (1.56 kJ/g) compared to graphite (1.59 kJ/g) half-cell. </p><br>

Fragment-screening by X-ray crystallography (XFS) is an expensive and low throughput fragment drug discovery screening method, and it requires a lot of optimization for each protein target. The advantages with this screening method are that it is very sensitive, it directly gives the three-dimensional structure of the protein-fragment complexes, and false positives are rarely obtained. The aim of this project was to help Sprint Bioscience assess if the advantages with XFS outweigh the disadvantages, and if this method should be used as a complement to their differential scanning fluorimetry (DSF) screening method. An XFS campaign was run using the oncoprotein vaccinia related kinase 1 (VRK1) as a target protein to evaluate this screening method. During the development of the XFS campaign, a diverse fragment library was created which consisted of 298 fragments that were all soluble in DMSO at 1 M concentration. The crystallization of the protein VRK1 was also optimized in this project to get a robust, high throughput crystallization set up which generated crystals that diffracted at higher resolution than 2.0 Å when they were not soaked with fragments. The soaking protocol was also optimized in order to reduce both the steps during the screening procedure and mechanical stress caused to the crystals during handling. Lastly, the created fragment library was used in screening VRK1 at 87.5 mM concentration with XFS. 23 fragment hits could be obtained from the X-ray crystallography screening campaign, and the mean resolution of the crystal structures of the protein-fragment complexes was 1.87Å. 11 of the 23 fragment hits were not identified as hits when they were screened against VRK1 using DSF. XFS was deemed as a suitable and efficient screening method to complement DSF since the hit rate was high and fragments hits could be obtained with this method that could not be obtained with DSF. However, in order to use this screening method a lot of time needs to be spent in optimizing the crystal system so it becomes suitable for fragment screening. Sprint Bioscience would therefore need to evaluate the cost/benefit ratio of using this screening method for each new project.

No description available.

A flexible nanofibrous PVDF-BaTiO3 composite material is prepared for impact sensing and biomechanical energy harvesting applications. Dielectric polyvinylidene fluoride (PVDF) and barium titanate (BaTiO3)-PVDF nanofibrous composites were made using the electrospinning process based on a design of experiments approach. The ultrasonication process was optimized using a 2k factorial DoE approach to disperse BaTiO3 particles in PVDF solution in DMF. Scanning electron microscopy was used to characterize the microstructure of the fabricated mesh. The FT-IR and Raman analysis were carried out to investigate the crystal structure of the prepared mesh. Surface morphology contribution to the adhesive property of the composite was explained through contact angle measurements. The capacitance of the prepared PVDF- BaTiO3 nanofibrous mesh was a more than 40% increase over the pure PVDF nanofibers. A comparative study of dielectric relaxation, thermodynamics properties and impact analysis of electrospun polyvinylidene fluoride (PVDF) and 3% BaTiO3-PVDF nanofibrous composite are presented. The frequency dependent dielectric properties revealed micro structural features of the composite material. The dielectric relaxation behavior is further supported by complex impedance analysis and Nyquist plots. The temperature dependence of electric modulus shows Arrhenius type behavior. The observed non-Debye dielectric relaxation in electric loss modulus follows a thermally activated process which can be attributed to a small polaron hopping effect. The particle induced crystallization is supported with thermodynamic properties from differential scanning calorimetric (DSC) measurements. The observed increase in piezoelectric response by impact analysis was attributed to the interfacial interaction between PVDF and BaTiO3. The interfacial polarization between PVDF and BaTiO3 was studied using density functional theory calculations and atomic charge density analysis. The results obtained indicates that electrospinning offers a potential way to produce nanofibers with desired crystalline nature which was not observed in molded samples. In addition, BaTiO3 can be used to increase the capacitance, desired surface characteristics of the PVDF nanofibers which can find potential application as flexible piezoelectric sensor mimicking biological skin for use in impact sensing and energy harvesting applications.

This diploma thesis is focused on issues concerning the stability of selected vegetable oils which are used in cosmetic industry. The stability of eight oils without additives were determined by a differential scanning calorimeter. In the first phase, the temperatures of oil degradation were determined for different rates of heating, i.e. nonisothermal stabilities. They were consequetly used to calculate isothermal stabilities alias induction periods. The calculation of induction periods was completed by using integral isoconversional methods, which applied four different temperature functions. One of the temperature functions corresponded to Arrhenius equation while the others to non-Arrhenius functions. The confrontation of induction periods under standart conditions showed that an optimal temperature function to calculate oil stabilities is one of the non-Arrhenius functions in exponential form. We can state that all oils are degraded by similar, if not the same, mechanism. The specified stabilities, in periods of months, have proved the importance of using stabilizers and other additives in the commercial and technological use of vegetable oils.

The formation of liquid films is a widely known problem in aluminium heat exchanger materials. The phenomenon results in decreased brazeability along with severely deteriorated mechanical properties which might cause assembly collapse. In addition, low-melting-point elements like tin, bismuth and lead are thought to promote grain boundary sliding which is the main deformation mechanism during brazing. Their melting characteristics are not adequately reported in literature. It is therefore of great importance to examine the behaviour of these elements.The main objectives with this work is melting range determination of fin heat exchanger materials, melting detection of low-melting-point elements and calculation of tin, bismuth and lead solid-solubility in aluminium. This work does also involve distribution analysis of such elements in aluminium matrix after heat treatment.These investigations require development of a differential scanning calorimetry (DSC) technique that is applicable for analysis of aluminium fin heat exchanger material containing low-melting-point elements on ppm level. Optimization of the technique includes parameter control; like heating rate, sample mass, reproducibility and choice of crucible material. Laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) is additionally used in order to analyse solid solubility and distribution of low-melting-point elements in aluminium after heat treatment.The developed DSC technique shows a sensitivity limit in the range of 260-600 ppm. It means that it is not possible to detect melting of phases within and below that range. Solid solubility of tin was calculated for the three heat treatment temperatures, 400°C, 500°C and 625°C. Same procedure was applied on bismuth and lead. However, calculated values did not agree with Thermo-Calc. The distribution analysis indicate an exudation of trace elements i.e. diffusion toward surface during heat treatment.In conclusion, more knowledge regarding liquid films in aluminium fin heat exchanger material was obtained. Future work should be to further optimize the DSC technique for trace element analysis for concentrations below 100 ppm. The LA-ICP-MS technique is likely to improve experimentally unverified binary phase diagrams like Al-Bi, Al-Pb and Al-Sn phase diagrams. It can also be used to study exudation behaviour of liquid films.

<div>Several truck fires have occurred in recent years involving bridges with reinforced and prestressed concrete components. If the fire burns for a significant period of time (15 minutes or more), bridge inspectors and engineers must determine if the exposure to elevated temperature has reduced the strength and serviceability of the concrete components. Little guidance is available, however, correlating the results of field inspections with the actual condition of the reinforced/prestressed concrete elements. This dissertation presents the results of a research program conducted to develop rational guidance for inspectors and engineers to evaluate concrete bridge elements after a fire event and help them make informed decisions regarding the future status of the bridge. <br></div><div><br></div><div>The research program includes tests on portions of a reinforced concrete deck and three full-scaled AASHTO Type I prestressed girders acquired from a decommissioned highway bridge. In addition, six pretensioned concrete prismatic beam specimens with varying levels of prestress were fabricated and tested. The specimens had cross-sectional dimensions of 8 in. by 8 in. and were designed to simulate the bottom flanges of common I-shaped prestressed concrete bridge girders. The deck specimens and four (of the six) concrete beam specimens were subjected to elevated temperatures using radiation-based heaters. Two (of the six) prismatic specimens built in the laboratory were subjected to a hydrocarbon pool fire test conducted in the field for using approximately 135 gallons of kerosene. The concrete temperature profiles and the deformations of the specimens were measured using thermocouple trees and displacement transducers, respectively. Concrete samples were also cored and examined using various methods (DSC and SEM) to correlate microstructure degradation (microcracking, dehydration of C-S-H, decomposition of calcium hydroxide, etc.) with the measured temperatures through the depth of the specimens. <br></div><div><br></div><div>To evaluate the residual loading-carrying capacities of prestressed concrete girders after being subjected to fire, a hydrocarbon pool fire test was performed on two decommissioned AASHTO Type I girders in the field. Load tests were then conducted on the prestressed girders under both ambient and post-fire conditions. After structural testing, material tests were also conducted on concrete cores taken from the girders to evaluate the post-fire concrete microstructure alteration. Furthermore, three-dimensional finite element models were developed to predict the residual load-carrying capacities and overall structural responses of prestressed concrete bridge girders after being exposed to fire. Results from the numerical models generally agree favorably with experimental observations and provide insights into the behavior of the specimens. A parametric study was performed using the benchmarked finite element models to expand the database and establish design recommendations further. Capacity influence lines for load-carrying capacities and structural stiffness were developed and discussed.</div><div><br></div><div>Based on the results from this research, guidelines for the post-fire assessment of prestressed concrete bridges are included in this dissertation along with a step-by-step checklist. Bridge inspectors can infer the extent of damage to prestressed concrete bridge girders in the event of a fire and develop a post-fire assessment plan cognizant of the findings. In most cases, no more than 1.0 in. of the concrete from the exposed surface undergoes material damage / deterioration due to loss of CH, cracking, and spalling. The impact on the strength of prestressed concrete girders is relatively minor based on experimental results. Their initial stiffness, however, will likely be reduced. <br> </div><br>

Today, in the automotive industry, many of the interior parts in the car are made of ABS and PC/ABS polymeric blend. These materials are used in the areas for example: instrument panels, tunnel consoles and door panels. The extensive use of these materials means that it is important to gain in-depth knowledge about the materials,their properties; and also their behaviour when in contact with different chemicals andat different conditions.This study aims to address the potential problem of the polymers used in the interiorof the car - ABS and PC/ABS cracking due to environmental factors. This study proposes to introduce a low-cost test method to compare the polymeric materials and choose the best one for future purposes with the environmental circumstances in mind for materials to have a good service life.During the thesis project, ABS and PC/ABS samples were tested for environmental stress cracking to compare the strained materials against PEG 400 and an assemblyfluid chemical. These tests were conducted at three different temperature levels.Differential Scanning Calorimetry (DSC) was used to verify the polymeric materialsthat the samples were made of. Optical microscope and FTIR were employed to analyzethe samples for crazes / cracks and degradation of material, respectively.This thesis helped in establishing a good starting point for ESC testing of different materials for the organization. The test method was used to test the failure of material sin ESC. It was observed that the chemicals used for the testing were aggressive and accelerated the cracking process in the materials rapidly. Another observation of the tests was that high strain also caused the materials to fail quickly. While comparing the materials, PC/ABS polymer blend was more resistant than ABS materials to cracking when exposed to same strain level during the creep rupture test (test in absence ofchemicals acting as a reference test for ESC).