Embora a ablação a laser venha sendo bastante utilizada em materiais em geral, pouco é entendido sobre o comportamento deste processo perto de uma interface separando dois materiais distintos. Neste contexto, o principal objetivo deste trabalho foi realizar um estudo macroscópico e microscópico dos processos que envolvem a ablação a laser em regime de femtossegundos em materiais homogêneos e estruturados. No caso de materiais estruturados, o estudo focou-se em uma situação de interface, na qual ocorrem mudanças nas propriedades de ablação. Baseado nos resultados, nós pretendemos obter subsídios científicos para entender as aplicações da ablação em regime de pulsos ultracurtos para estruturas estratificadas, tais como de dentes, ossos, interface resina-dente, dente-metal, e outras. Diferentes técnicas experimentais foram idealizadas para determinar a progressão da ablação dentro do material e obter dados extraídos da superfície. Utilizando luz espalhada de uma fonte externa, o processo de ablação foi temporalmente monitorado, permitindo determinar a velocidade de ablação em materiais transparentes, assim como perfis típicos de ablação nestes materiais. Em um segundo experimento, nosso estudo permitiu quantificar a variação da geometria de ablação perto de uma interface separando dois materiais distintos. Nossos dados foram suficientes para prever a ocorrência de uma descontinuidade no perfil da ablação entre dois meios: resina A e resina B, mostrando uma repentina descontinuidade do diâmetro da cavidade ablacionada. Adicionalmente, foi realizada uma análise dos aspectos morfológicos de diferentes tecidos biológicos irradiados e nosso estudo mostrou a eficiência da ablação utilizando laser de femtossegundos no processamento de tecidos duros e a possibilidade de utilizar esses sistemas sem causar danos térmicos e mecânicos nos tecidos remanescentes. Finalmente nós aplicamos a microperfuração a laser para produzir micro-poros na superfície de tecidos biológicos (fígados), melhorando a penetração do medicamento ALA e a aumentando a profundidade de tratamento. / Although laser ablation has been long used in general materials, little is known regarding the behavior of theses process near an interface separating two distinct materials. In this context, the main aim of this work was to perform a microscopic and macroscopic study of the processes that include femtosecond laser ablation in homogeneous and/or structured materials. In the case of structured materials, the study focused on an interface situation, in which sudden changes occurred in the properties. Based on the results, we aimed to obtain scientific subsidies to understand the application of ultrashort pulses to stratified structures, such as teeth, bones, resin-teeth or metal-teeth interface, and others. Distinct experimental techniques were used to determinate the ablation progression into the materials and to obtain data extracted from their surface. By using the scattered light from an external source, the ablation process was monitored temporally, allowing to determine the velocity of ablation in transparent materials, besides determining the typical profiles of ablated cavities in these materials. In a second experiment, our study allowed quantifying the overall variation in the ablation geometry that takes place on the interface of two different materials. Our data were sufficient to predict the occurrence of a discontinuity in the ablation profile on the interface between two media: resin A and resin B, showing a sudden discontinuity of the ablated cavity diameter. In addition, an analysis of the morphological aspects of different biological tissues irradiated by femtosecond laser pulses was performed and a comparative study showed the ablation efficiency of the femtosecond lasers in hard tissues processing and the possibility of using these systems with no thermal and mechanic damage. Finally, we applied a laser micromachining producing micro-pores on the tissue surface, improving the ALA penetration and increasing the treatment depth.

In order to investigate the thermal stress and expansion as well as the associated strain effect on material properties caused by high temperature and large temperature gradient, a two-way thermo-mechanical coupling solver is developed. This solver integrates a new structural response module to the Kentucky Aerothermodynamics and Thermal response System (KATS) framework. The structural solver uses a finite volume approach to solve either hyperbolic equations for transient solid mechanics, or elliptic equations for static solid mechanics. Then, based on the same framework, a quasi-static approach is used to couple the structural response and thermal response to estimate the thermal expansion and stress within Thermal Protection System (TPS) materials. To better capture the thermal expansion and study its impacts on material properties such as conductivity and porosity, a moving mesh scheme is also developed and incorporated into the solver. Grid deformation is transferred among different modules in the form of variations of geometric parameters and strain effects. By doing so, a bi-direction information loop is formed to accomplish the two-way strong thermo-mechanical coupling. Results revealed that the thermal stress experienced during atmospheric re-entry concentrates in a banded area at the edge of the pyrolysis zone and its magnitude can be large enough to cause the failure of the TPS. In addition, thermal expansion causes the whole structure to deform and the changes in material properties. Results also indicated that the impacts coming from structural response should not be ignored in thermal response.

Modeling the atmospheric entry of spacecraft is challenging because of the large number of physical phenomena that occur during the process. In order to study thermal protection systems, engineers rely on high fidelity solvers to provide accurate predictions of both the thermochemical environment surrounding the heat shield, and its material response. Therefore, it is necessary to guarantee that the numerical models are correctly implemented and thoroughly validated. In recent years, a high-fidelity modeling tool has been developed at the University of Kentucky for the purpose of studying atmospheric entry. The objective of this work is to verify and validate this code. The verification consists of the development of an automated regression testing utility. It is intended to both aid code developers in the debugging process, as well as verify the correct implementation of the numerical models as these are developed. The validation process will be performed through comparison to relevant ablation experiments, namely arc-jet tests. Two modules of the code are used: fluid dynamics, and material response. First the fluid dynamics module is verified against both computational and experimental data on two distinct arc-jet tests. The material response module is then validated against arc-jet test data using PICA.

The dissertation is split into two parts. The first part will be focused on changes in material properties found at the nanoscale, as miscibility and electronic structure can change significantly with size. The formation of classically-immiscible bimetallic nanoparticles (BNPs) becomes favorable at the nanoscale and novel catalytic properties can emerge from the bimetallic alloying. The formation of alloyed and non-alloyed BNPs is achieved through pulse laser ablation (PLA) and a significant increase in catalytic activity is observed for both. Recently discovered, the increased activity in the non-alloyed BNPs, deemed multicomponent photocatalysis, is examined and the proposed mechanism discussed. The second part of the talk will focus on thermal barrier coatings (TBCs), which are advanced, multi-layered coatings used to protect materials in high temperature environments. MCrAlY (M=Ni, Co) bond coats deposited via atmospheric plasma spray (APS) are intrinsically rough and initially the roughness provides a high surface area platform for the mechanical interlocking of the yttria stabilized zirconia (YSZ) top coat, which provides the bulk of the thermal insulation. After high temperature exposure, a protective oxide scale forms at the top coat/bond coat interface however the convex asperities of the bond coat can grow non-α-Al2O3 type oxides that can be detrimental for coating lifetime. A surface modification technique that removes the asperities while leaving intact the concavities is used to examine the role that roughness distribution has on 1100°C APS coating lifetime. Lastly, recent work validating a modelling strategy for evaluating 900°C TBC lifetimes, which can typically surpass 25 kh, is presented. Differences in coating-substrate interdiffusion behavior over 5-20 kh of 900°C exposure are discussed and reproduced with Thermo- Calc/DICTRA for three superalloys (1483, 247, X4) deposited with high velocity oxy fuel (HVOF) NiCoCrAlY coatings.

Use the contrast-enhanced ultrasound in the monitoring of the effect of liver tumors treatment by radiofrequency ablation. Summary High quality imaging is crucial for the treatment of liver tumors by the percutaneous radiofrequency ablation. Imaging methods are used for planning, navigation of the intervention and monitoring after treatment. An early detection of residual tumor tissue or recurrence affect significantly the quality of life and life expectancy of the patients. Contrast enhanced ultrasound (CEUS) seems to be a suitable method for monitoring the locoregional treatment mainly because zero radiation impact on patient and allows the highly accurate real-time assessment of vascularization. The aim of my work was to verify the ability of CEUS to detect residual tumor tissue or tumor recurrence in the field of changes after radiofrequency ablation. We evaluated the group of 73 patients, who were treated by radiofrequency ablation (RFA) for liver cancer. CEUS reached in our group the overal sensitivity 77.27 %, and in the group of colorectal cancer metastases 83.33 %. We compared CEUS with results of computed tomography (CT), which is the most commonly used method for monitoring the treatment. CEUS and CT results are similar. Based on this study, the CEUS appears to be a suitable method for monitoring...

acase@tulane.edu

A primary motivation for this research comes from the need to improve the ability of polymer-matrix composites to withstand lightning strikes. In particular, we are concerned with lightning strike damage in composite wind turbine blades. The direct effects of lightning strike on polymer-matrix composites often include rapid temperature rise, melting or burning at the lightning attachment points, and mechanical damage due to lightning-induced magnetic force and acoustic shock wave. The lightning strike damage accumulation problem is essentially multiphysic. The lightning plasma channel discharges an electric current up to 200 kA, inducing a severe heat flux at the surface of the composite structure, as well as generating Joule heating through the composite structure. The resulting electro-thermo-mechanical response of the composite structure may include matrix degradation and decomposition, delamination, and fiber breakage and sublimation, thus leading to catastrophic failure. The existing studies related to the lightning strike damage in composites ignored the lightning channel radius expansion during the initial lightning discharge and lacked adequate treatment of material phase transitions. These assumptions significantly simplify the mathematical treatment of the problem and affect the predictive capabilities of the models. Another common feature of these limited studies is that they all focused on carbon-fiber-reinforced polymer-matrix (CFRP) composites, which are electrically conductive. In the present thesis, the thermal responses and thermal ablations in a non-conductive glass-fiber-reinforced polymer-matrix (GFRP) composite wind turbine blade and in a conductive CFRP composite wind turbine blade are studied, respectively. In the case of non-conductive GFRP composite wind turbine blade, prior to the thermal response and thermal ablation analysis, a finite element analysis is performed to calculate the electric field due to lightning stepped leader to estimate the dielectric breakdown of the non-conductive composite wind turbine blade. The estimation of dielectric breakdown is used to determine whether Joule heating needs to be included in the problem formulation. To predict the thermal response and thermal ablation in the composite structure due to lightning strike, a physics-based model describing surface interaction between the lightning channel and the composite structure has been developed. The model consists of: (i) spatial and temporal evolution of the lightning channel as a function of the electric current waveform; (ii) temporary and spatially non-uniform heat flux and current density (in the case of electrically conductive CFRP composite or if dielectric breakdown occurs in the case of non-conductive GFRP composite) generated at the composite structure; and (iii) nonlinear transient heat transfer problem formulation for layered anisotropic composites that includes the moving boundary of the expanding lightning channel and the phase transition moving boundary associated with instantaneous material removal due to sublimation. The model has been employed to investigate the thermal responses and thermal ablations in a GFRP composite laminated panel used in a Sandia 100-meter all-glass baseline wind turbine blade (SNL 100-00) and a typical CFRP composite laminated panel subjected to lightning strike. The temperature-dependent directional material properties for both the GFRP and CFRP composites have been determined in this thesis using a micromechanics approach based on the experimental data for fibers and resin. An integrated Matlab-ABAQUS numerical procedure features the aforementioned aspects (i), (ii), and (iii) of the developed model. The obtained results include the evolution of temperature fields in the composite laminated panel and the progressive shape change of the composite laminated panel due to thermal ablation. The predictions of thermal ablation in the CFRP composite laminated panel are validated by reported experimental results.

Modern observations of planktic foraminifera from sediment trap studies help to constrain the regional ecology of paleoceanographically valuable species. Results from a weekly-resolved sediment trap time series (2008–2014) in the northern Gulf of Mexico demonstrate that 92% of Globorotalia truncatulinoides flux occurs in winter (January, February, and March), and that encrusted and non-encrusted individuals represent calcification in distinct depth habitats. We use individual foraminiferal analysis (IFA) of G. truncatulinoides tests to investigate differences in the elemental (Mg/Ca) and isotopic composition (18O and 13C) of the encrusted and non-encrusted ontogenetic forms of G. truncatulinoides, and to estimate their calcification depth in the northern Gulf of Mexico. We estimate that non-encrusted and encrusted G. truncatulinoides have mean calcification depths of 66 ± 9 meters and 379 ± 76 meters, respectively. We validate the Mg/Ca-calcification temperature relationship for G. truncatulinoides and demonstrate that the 18O and Mg/Ca of the non-encrusted form is a suitable proxy for winter surface mixed layer conditions in the Gulf of Mexico. Care should be taken not to combine encrusted and non-encrusted individuals of G. truncatulinoides for down core paleoceanographic studies.

Clinical wavefront-guided corneal ablation has been now the most technologically advanced method to reduce the dependence of glasses and contact lenses. It has the potential not only to eliminate spherocylindrical errors but also to reduce higher-order aberrations (HOA). Recent statistics show that more than 96% of the patients who received laser in situ keratomileusis (LASIK) treatment reported their satisfaction about the improvement on vision, six months after the surgery. However, there are still patients complaining that their vision performance did not achieve the expectation or was even worse than before surgery. The reasons causing the unexpected post-surgical outcome include undercorrection, overcorrection, induced HOA, and other postoperative diseases, most of which are caused by inaccurate ablation besides other pathological factors. Therefore, to find out the method to optimize the LASIK procedures and provide a higher surgical precision has become increasingly important. A proper method to calculate ablation profile and an effective way to control the laser beam size and shape are key aspects in this research to resolve the problem. Here in this Master of Philosophy degree thesis, the author has performed a meticulous study on the existing methods of ablation profile calculation and investigated the efficiency of wavefront only ablation by a computer simulation applying real patient data. Finally, the concept of a refractive surgery system with dynamical beam shaping function is sketched, which can theoretically overcome the disadvantages of traditional procedures with a finite laser beam size.

Bio-microdevices are miniaturised devices based on biologically derived components (e.g., DNA, proteins, and cells) combined or integrated with microfabricated substrates. These devices are of interest for numerous applications, ranging from drug discovery, to environmental monitoring, to tissue engineering. Before a bio-microdevice can be fully developed, specific fabrication issues need to be addressed. One of the most important is the spatial immobilization of selected biomolecules in specific micro-areas of the device. Among the biomolecules of interest, the controlled immobilization of proteins to surfaces is particularly challenging due to the complexity of these macromolecules and their tendency to lose bioactivity during the immobilization step. The present Thesis reports on three novel micropatterning techniques for the spatial immobilization of proteins with bioactivity retention and improved read-out of the resulting micropatterns. The technologies developed are based on three different micropatterning approaches, namely 1) direct-writing UV laser microablation (proLAB), 2) a novel microcontact printing method (�CPTA) and 3) a replica molding method combined with bead selfassembly (BeadMicroArray). The first two technologies, proLAB and �CPTA, are an implementation of existing techniques (laser ablation and �CP, respectively), whereas the third, i.e., the BeadMicroArray, is a totally new technique and type of patterning platform. 'ProLAB' is a technology that uses a micro-dissection tool equipped with a UV laser (the LaserScissors�) for ablating a substrate made of a layer of ablatable material, gold, deposited over a thin polymer layer. The latter layer is transparent to the laser but favours protein adsorption. In the present work microchannels were chosen as the structure of interest with the aim of arranging them in 'bar-codes', so to create an 'information-addressable' microarray. This platform was fabricated and its application to specific antigen binding demonstrated. The second technique that was developed is a microstamping method which exploits the instability of a high-aspect ratio rubber stamp fabricated via soft-lithography. The technique is denominated microcontact printing trapping air (�CPTA) since the collapsing of a rubber stamp made of an array of micro-pillars over a plane glass surface resulted in the formation of a large air gap around the entire array. The method can be successfully employed for printing micro-arrays of proteins, maintaining biological activity. The technique was compared with robotic spotting and found that microarrays obtained with the �CPTA method were more homogeneous and had a higher signal-tonoise ratio. The third technique developed, the BeadMicroArray, introduces a totally new platform for the spatial addressable immobilization of proteins. It combines replica molding with microbead self-assembling, resulting in a platform where diagnostic beads are entrapped at the tip of micropillars arranged in a microarray format. The fabrication of the BeadMicroArray involves depositing functional microbeads in an array of V-shaped wells using spin coating. The deposition is totally random, and conditions were optimised to fill about half the array during spin coating. After replica molding, the resulting polymer mold contains pyramid-shaped posts with beads entrapped at the very tip of the post. Thanks to the fabrication mode involved, every BeadMicroArray fabricated contains a unique geometric code, therefore assigning a specific code to each microarray. In the present work it was demonstrated that the functionality of the beads after replica molding remains intact, and that proteins can be selectively immobilized on the beads, for instance via biorecognition. The platform showed a remarkable level of selectively which, together with an efficient blocking towards protein non-specific adsorption, lead to a read-out characterized by a very good signal-to-noise. Also, after recognition, a code was clearly visible, therefore showing the encoding capacity of this unique microarray.