Effective design of liquid fuel injection systems is a function of good understanding of liquid breakup mechanisms. A transient liquid breakup model is developed on the classical interfacial breakup theory by modifying the classical linear perturbation process to include time-dependent base and perturbed flow parameters. The non-isothermal condition on liquid jet instability and breakup is theoretically modelled; with the particular consideration of a spatially variation of surface tension along the liquid-gas interface. The model combines the classical interface hydrodynamic instability and breakup theory and heat-transfer through semi-infinite medium. Analytical liquid breakup model, which combines transient and non-isothermal effects on liquid jet breakup, is suggested. The suggested model could be simplified to the transient breakup model and the non-isothermal breakup model equivalents. A novel mechanistic model, which is based on a simple momentum balance between the injected jet and the aerodynamic drag force, is suggested for breakup length. A new model, which combines energy criterion and dual-timescale for turbulent shear in droplet dispersion, is suggested for droplet breakup criteria on the basis of critical Webber number. All developed models showed good predictions of available experimental data, and established empirical correlation, within the operational conditions of contemporary ICEs, specifically diesel engines. Continued research in these areas could benefit the development of the next generation of liquid fuel injectors and combustors – by accounting for transient effects and non-isothermal conditions in liquid jet breakup, and turbulent shear in droplet breakup.

Nanoparticles are promising platforms for biomedical applications ranging from diagnostic tools to therapeutic delivery agents. During the course of these applications, nanoparticles are exposed to a complex mixture of extracellular serum proteins that nonspecifically adsorb onto the surface. The resulting protein layer, or protein "corona," creates an interface between nanoparticles and the biological environment. Protecting the nanoparticle surface can reduce protein adsorption, but complete inhibition remains a challenge. As a result, the corona, rather than the nanoparticle itself, mediates the cellular response to the nanoparticle. The following dissertation describes the fundamental characterization of the cellular binding of charged nanoparticles, interactions of protein-nanoparticle complexes with cellular receptors, and the structural and thermodynamic properties of adsorbed corona proteins.

The tumor suppressor protein, p53, is mutated or dysregulated in nearly all human cancers(1). The amino terminal domains are essential for transcriptional activation in stressed cells and play a vital role in cell cycle regulation, apoptosis and senescence. The transactivation (TAD) and proline rich domains in this region are dynamic and intrinsically disordered; lacking stable secondary or tertiary structure. This region contains multiple binding sites; arguably, the most significant of these is for p53's negative regulator, the E3 ligase, MDM2. An important, but less understood interaction involving the single stranded DNA binding protein, RPA70A, is hypothesized to be involved in maintaining genome integrity(2-4). Additionally, the amino terminus contains an important single nucleotide polymorphism that has demonstrated different affinity for MDM2 and is of significant biological importance in the induction of apoptosis (5). Isothermal titration calorimetry (ITC) and nuclear magnetic resonance (NMR) spectroscopy were employed to investigate how the thermodynamics and the inherent flexibility of the amino terminus of p53 play a role in complex formation with the MDM2 or RPA70 proteins. Understanding the structure, dynamics, and function of p53 is paramount in the fight against cancer.

Catalyst deactivation in single catalyst pellets and in an isothermal catalytic fixed bed reactor have been analytically studied. The work reported here is unlike the vast majority of previous theoretical analyses which are numerical. This thesis deals with two types of deactivation - parallel and series mechanisms in which respectively, reactant and product are directly responsible for poisoning. For the single particle studies, the principal analytical tools used are based on singular perturbation theory. Use of these techniques in the temporal domain depends crucially on the smallness of the ratio of the deactivation rate constant to that of the main reaction. Depending on the range of Thiele modulus, whether small, intermediate or large, three different techniques are used in the spatial domain. First, when the Thiele modulus is small, a lumping technique due to Frank-Kamentskii (1955) is used to replace the Laplacian operator by a suitable constant. This reduces the coupled partial differential equations to ordinary ones. Main chemical kinetics of n-th order and of Michaelis-Menten type are investigated. Second, when the Thiele modulus is very large, matched asymptotic expansions in the spatial domain are used. The analysis is based on the smallness of the inverse Thiele modulus, 1/phi2. A moving reaction zone of thickness 0(1/phi) is found to separate the dead shell from the active core of the catalyst pellet. The catalyst activity profile exhibits a sharp change within the reaction zone and the structure of this profile is found to be self-preserving during the period of its propagation. Solutions are obtained for three different geometries - planar, cylindrical and spherical. The large Thiele modulus results obtained here are found to be more accurate than the shell-model solutions of Masamune and Smith (1966) (except for a slab geometry, when they are identical). Finally, for an intermediate range of Thiele modulus, finite Sturm-Liouville integral transforms along with the concept of an effective average are successfully applied. The approach taken is novel, and although not rigorously justifiable, it leads to results of suprising accuracy. The versatility of the technique is demonstrated by application to various non-linear problems which posess exact solutions and remarkable agreement is found. The finite-cylindrical catalyst pellet is also investigated using a double-integral transform in the spatial domain and it is shown that for small Thiele modulus, the infinite cylinder and slab results are good approximations to finite length cylinders with small and large ratio, R/L, respectively. The analytical solutions reported in this thesis agree well with the known numerical results of others (Masamune and Smith, 1966; Khang and Levenspiel, 1973 and Lamba and Dudukovic, 1978). The parametric - dependence of these solutions is explicit and numerical results can be easily obtained from them by hand calculation. All the single pellet results are brought together in the final chapter and used to analyze the performance of isothermal fixed-bed reactors undergoing poisoning. Such effects as external mass transfer resistance, pellet shape and chemical kinetic type are included in the analysis, which embraces the entire range of Thiele modulus.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 220-225).

This work was dedicated to quantify and distinguish the radio- and chemitoxic effects of environmentally relevant low doses of uranium on the metabolism of microorganisms and multicellular organisms by a modern and highly sensitive microcalorimetry. In such low-dose regime, lethality is low or absent. Therefore, quantitative assays based on survival curves cannot be employed, particularly for multicellular organisms. Even in the case of microbial growth, where individual cells may be killed by particle radiation, classical toxicity assessments based on colony counting are not only extremely time-consuming but also highly error-prone. Therefore, measuring the metabolic activity of the organism under such kinds of conditions would give an extremely valuable quantitative measure of viability that is based on life cell monitoring, rather than determining lethality at higher doses and extrapolating it to the low dose regime. The basic concept is simple as it relies on the metabolic heat produced by an organism during development, growth or replication as an inevitable byproduct of all biochemical processes. A metabolic effect in this concept is defined as a change in heat production over time in the presence of a stressor, such as a heavy metal. This approach appeared to be particular versatile for the low dose regime. Thus, the thesis attempted in this case to measure the enthalpy production of a bacterial population as a whole to derive novel toxicity concepts. In the following chapters, an introduction about the properties of ionizing radiation will be briefly presented, in addition to a review about the isothermal calorimetry and its application in studying the bacterial growth. Later in chapter 2, the effect of uranium on the metabolic activity of three different bacterial strains isolated form a uranium mining waste pile together with a reference strain that is genetically related to them will be investigated. Due to the lack of published dedicated calibration techniques for the interpretation of heat production of bacterial cells under the conditions of calorimetric recordings, additional experiments, thorough investigations of the effects of experimental conditions, have been carried out in order to guide the interpretation of calorimetric results. In chapter 3, the differentiation between chemi- and radiotoxicity of uranium has been addressed by isotope exchange, which was a key effort in this thesis as it opens new experimental approaches in radioecology. In chapter 4, through investigating the role of the tripeptide glutathione (GSH) in detoxifying uranium, it will be shown to which degree the intrinsically unspecific signal provided by metabolic heat can be related to highly specific metabolic pathways of an organism, when combined with genetic engineering. The demonstration of gaining molecule-specific information by life metabolic monitoring was another experimental challenge of this thesis and provides proof of principle that can be extended to many organisms. Finally in chapter 5, an attempt has been undertaken to establish a minimal food chain, in order to study the effects of the exposure of a multicellular organism to uranium through its diet.

Conventional yttria stabilized zirconia (YSZ) are widely used in the gas turbine to protect the substrate material from high temperature. But the common YSZ top coatings have limitations at higher temperature (above 1200 ℃) due to significant phase transformation and intensified sintering effect. Among the list of pyrochlores, gadolinium zirconate offer very attractive properties like low thermal conductivity, high thermal expansion coefficient and CMAS resistance. However, a lower fracture toughness than YSZ and tendency to react with alumina (thermal grown oxide) can lead to lower lifetime. Therefore, multi-layered thermal barrier coating approach was attempted and compared with single layer system. Single layer (YSZ) was processed by suspension plasma spraying (SPS). Double layer coating system comprising of YSZ as the bottom ceramic layer and gadolinium zir-conate as the top ceramic coat was processed by SPS. Also, a triple layer coating system with denser gadolinium zirconate on top of double layer system, was sprayed. Denser gado-linium zirchonate acts as the sealing layer and arrest the CMAS penetration. Isothermal oxidation performance of the sprayed coating systems including bare substrate and sub-strate with bond coat were investigated for a time period of 10hr, 50hr and 100hr at 1150℃ in air environment. Weight gain was observed in all the systems investigated. Microstruc-tural analysis was carried out using optical microscopy, SEM/EDS. Phase analysis was done using X-ray diffraction (XRD). Porosity measurement was made by water impregna-tion method. It was observed that multi-layered thermal barrier coating systems of YSZ/GZ and YSZ/GZ/GZ(dense) showed lower weight gain and TGO thickness than the single layer YSZ for all exposure time (10hr, 50hr & 100hr). The triple layer system had lower weight gain and TGO thickness compared to double layer system due to lower po-rosity content. Also, from the porosity measurement data, it could be seen that sintering effect is more dominant at 10 hr. of oxidation for all the coatings systems.

abstract: Alkali-activated aluminosilicates, commonly known as "geopolymers", are being increasingly studied as a potential replacement for Portland cement. These binders use an alkaline activator, typically alkali silicates, alkali hydroxides or a combination of both along with a silica-and-alumina rich material, such as fly ash or slag, to form a final product with properties comparable to or better than those of ordinary Portland cement. The kinetics of alkali activation is highly dependent on the chemical composition of the binder material and the activator concentration. The influence of binder composition (slag, fly ash or both), different levels of alkalinity, expressed using the ratios of Na2O-to-binders (n) and activator SiO2-to-Na2O ratios (Ms), on the early age behavior in sodium silicate solution (waterglass) activated fly ash-slag blended systems is discussed in this thesis. Optimal binder composition and the n values are selected based on the setting times. Higher activator alkalinity (n value) is required when the amount of slag in the fly ash-slag blended mixtures is reduced. Isothermal calorimetry is performed to evaluate the early age hydration process and to understand the reaction kinetics of the alkali activated systems. The differences in the calorimetric signatures between waterglass activated slag and fly ash-slag blends facilitate an understanding of the impact of the binder composition on the reaction rates. Kinetic modeling is used to quantify the differences in reaction kinetics using the Exponential as well as the Knudsen method. The influence of temperature on the reaction kinetics of activated slag and fly ash-slag blends based on the hydration parameters are discussed. Very high compressive strengths can be obtained both at early ages as well as later ages (more than 70 MPa) with waterglass activated slag mortars. Compressive strength decreases with the increase in the fly ash content. A qualitative evidence of leaching is presented through the electrical conductivity changes in the saturating solution. The impact of leaching and the strength loss is found to be generally higher for the mixtures made using a higher activator Ms and a higher n value. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) is used to obtain information about the reaction products. / Dissertation/Thesis / M.S. Civil Engineering 2012

Orientador: Marcelo Lancellotti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-23T12:42:44Z (GMT). No. of bitstreams: 1 Amstalden_MariaCeciliaKrahenbuhl_M.pdf: 4328649 bytes, checksum: efc5c151f8382e97f2def6576eb633b6 (MD5) Previous issue date: 2013 / Resumo: Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: Note: The complete abstract is available with the full electronic document / Mestrado / Fármacos, Medicamentos e Insumos para Saúde / Mestra em Biociências e Tecnologia de Produtos Bioativos

Heat of hydration is a property of Portland cement and a direct result of the chemical reaction between cement and water. The amount of heat released is dependent upon the cement mineralogical composition, curing temperature, water to cement ratio, and cement fineness. High temperature resulting from heat of hydration (thereon referred to as HOH) of cement can affect the hydration process, and consequently the kinetics of development of the mechanical properties of concrete. One of the main reasons triggering the interest in HOH of cement is its implication in thermal cracking of concrete. The high temperature gradient between the inner core and the outer surface of a concrete element is known to result in large tensile stresses that may exceed tensile strength, thus leading to early–age thermal cracking in mass concrete. This dissertation initially addresses accurately predicting the heat of HOH of Portland cement at seven days based on the heat flow data collected from isothermal calorimetry for a time interval of 0-84 h. This approach drastically reduces the time required to identify the seven day HOH of Portland cement. The second part of this study focuses on cement fineness and its critical role on the heat generated by Portland cement during hydration. Using a matrix of four commercially available Portland cements, representing a wide range of mineralogical composition, and subjecting each of the as-received cements to several grinding increments, a linear relationship was established between cement fineness and heat of hydration. The effect of cement fineness and mineralogical composition on HOH of Portland cement was then related through a mathematical expression to predict the HOH of Portland cement based on its mineralogical composition and fineness. Three expressions were proposed for the 1, 3 and 7 day HOH. The findings indicate that the equations developed, based on cement main phase composition and fineness, can be used to identify cements with high heat of HOH that may cause thermal cracking in mass concrete elements. Also, the equations can be used to correlate the HOH with the other properties of Portland cement for quality control and prediction of chemical and physical properties of manufactured Portland cement and concrete. Restrained shrinkage experiments results on mortar specimens prepared with cements of variable phase composition and fineness indicate that interaction of C3A and sulfate source is the prime phenomenon followed by cement fineness as the second main factor influencing concrete cracking. In order to minimize this effect, the third part of this study focused on studying alternatives that can lower the heat generated by concrete on hydration through the incorporation of nanomaterials; namely, graphene nanoparticles. The results indicate that incorporation of graphene a as replacement for Portland cement improves thermal diffusivity and electrical conductivity of the cement paste. Consequently, the use of graphene can trigger improvement of the thermal conductivity of concrete elements thus reducing the cracking potential of concrete. Measurements of HOH of graphene-cement paste, at w/c=0.5, using isothermal conduction calorimetry, indicate that incorporation of graphene up to 10% increases the length of the induction period while reduces the magnitude of the alite main hydration peak due to the filler effect. Furthermore, increasing the w/c ratio from 0.5 to 0.6 and graphene content from 1 % to 10% (as a partial replacement of cement) increases the 7 day HOH of Portland cement by 50 J/g. Isothermal conduction calorimetry heat flow curves show that incorporation of graphene particles up to 10% does not have significant effect on interaction of aluminates and sulfates sources since the time of occurrence of the C3A sulfate depletion peak is not affected by graphene substitution up to 10%. Full factorial statistical design and analysis conducted on compressive strength data of mortar specimens prepared at two w/c ratios, using cements of different finenesses and graphene content indicates that the quantity of graphene and the physical interaction due to variable w/c, graphene and cement fineness, have the smallest P-value among all the samples, representing the most significant impact on compressive strength of mortar samples. It appears that in graphene cement paste composites, addition of 1% graphene results in 21% reduction of Young’s modulus. Increasing the graphene content from 1% to 5% and/or 10% does not show significant effect on Young’s modulus. Similar trends can be observed in the hardness of graphene cement paste samples. In conclusion, partial replacement of Portland cement with graphene nanoparticles in concrete mixtures is a good alternative to lower the cracking potential in mass concrete elements.