Research interest in Additive Manufacturing (AM) as an enabling technology for customizable parts is rapidly expanding. While much AM research focus is on high performance feedstocks and process optimization to obtain parts with improved mechanical properties, interest in the environmental applications of AM has recently increased. The lower cost and greater accessibility AM is leading to novel environmental research solutions in wastewater treatment and toxicity reduction by capitalizing on the increased affordability and accessibility of 3D printing (3DP) technologies for customizable, high surface area structures. The novelty and focus of this dissertation is exploration of Material Extrusion (MatEx) based Fused Filament Fabrication (FFF) of filled polymer composites as a disruptive technology enabler for deployable and retrievable structures in environmental media for adsorption, destruction and toxicity reduction of harmful chemicals. This dissertation addresses research questions that generally answer, "why AM for environmental applications?". The inherent layer-by-layer design provides larger surface area structures for interaction with contaminated media. Polylactic acid (PLA) was selected due to its green sources and biocompatibility relative to synthetic polymers and its wide processing window allowing shear thinning and "printability" despite the elevated viscosity and modulus of highly filled composites. The filler selected for contaminant adsorption was microporous zeolite, which has affinity for ammonia, radionuclides and Per- and Polyfluorinated Substances (PFAS). The filler selected for contaminant destruction was photocatalytic TiO2 nanoparticles which can degrade organic chemicals, harmful algal bloom toxins and PFAS. A preliminary research hurdle was overcome by demonstrating that immobilization of zeolite and TiO2 in a PLA binder matrix did not prevent adsorption or free radical release, respectively. The first major research objective involved investigation of high surface area printed PLA-zeolite geometries with different zeolite loadings and found that while ammonia was reduced, there were diminishing returns with increased loading in terms of mass standardized adsorptive performance due to insufficiently exposed zeolite. The research solution leveraged AM print process parameters to increase the macroporosity of the printed composite structure to create voids and channels allowing water infiltration and chemical adsorption to zeolite. Faster printing of larger roadways generated macrostructural voids that were maintained by extrusion at lower temperature for rapid solidification. The second research objective involved compounding different loadings and dispersion states of TiO2 in PLA to demonstrate immobilization of TiO2 closer to UV-light penetration water improves photocatalysis. Higher 32% w/w TiO2 loadings were heavily agglomerated and more difficult to print process due to high viscosity, rapid liquid-solid transition (G'>G") and particle network recovery during printer retractions, leading to nozzle clogging. Lower 20% w/w loading was more conducive to larger production printing due to lower viscosity, longer viscosity recovery times for retractions and thus generally a wider processing window. While altering twin screw processing parameters reduced TiO2 agglomerates in filaments, leading to increases in crystallinity (due to seeding effects and chain scission) and lower viscosity recovery, photocatalytic performance was not significantly improved. Evidence presented showed that larger particle agglomerates were more toward the inside of printed surfaces and thus less available to UV-light irradiation. This location of larger particles is supported by previous theoretical and empirical investigations showing larger particles migrate at a faster velocity away from the outer walls of confined extrudates within non-Newtonian flow fields due to normal forces, leaving more smaller particles toward outer surfaces. This research provided novel contributions to the environmental and AM research communities and pioneered a convergence of these fields into an interdisciplinary community of practice focused on better characterization and processing in environmental applications to improve structure-environmental property relationships. Future research should build on these findings to enhance performance through multi-functional materials that adsorb and destroy contaminants. The reactive surface area should be further increased through by high surface area designs and print parameter optimized porous structures providing a continuum of meso- to microporosity as confirmed by chemical flux and mass transfer studies for additional AM technologies (e.g., Direct Ink Write). / Doctor of Philosophy / Engineers and hobbies alike have great interest in Additive Manufacturing (AM), or 3D Printing, to customize parts and new designs. More recently, environmental scientists and engineers have turned to 3D printing to solve environmental problems due to the lower cost and user-friendliness of desktop machines. This research dissertation focuses on how 3D printing can allow for iterative improvements in customizable, high surface area structures to reduce chemical concentrations in water by either adsorbing or destroying the chemicals. Water is clearly a critical resource for ecosystems, recreation and drinking supplies as national security, human and ecosystem health are tied to clean water. This research addresses why 3D printing is interesting and effective for environmental solutions. Briefly the layer-by-layer design provides larger surface area structures for interaction with contaminated media. The common 3D printer feedstock Polylactic Acid (PLA) was selected since it is non-toxic and can be relatively easy to print even if modified by adding rigid filler particles for research. Micron-scale (zeolite) and nano-scale (Titanium Dioxide) particles were mixed with the polymer to make printable filaments to adsorb and destroy contaminants, respectively. This research demonstrated the proof-of-concept by removing ammonia, methylene blue dye and a harmful algal toxin from water. The materials produced are also applicable to both conventional organic pollutants and emerging contaminants of concern in the popular news such as Per- and Polyfluorinated Substances (PFAS), which were used as flame retardants and non-stick surfaces. This research ties the material properties of the experimental micro- and nano-composite filaments to how the materials extrude and solidify during 3D printing and how well the resulting printed structures work for reducing contaminant levels in water. Altering the parameters and conditions at which these materials are processed and 3D printed can significantly change their structure, density, porosity and distribution of particles and in turn increase effectiveness. The results provide new contributions to both the environmental and AM research communities and pioneers interdisciplinary collaborative ideas for these different subject matter experts to work together to better understand how handling and processing of these materials can improve their performance in environmental applications. New work should leverage the ideas and principles presented here to further improve performance, ease of production and scale-up of multifunctional material structures for multiple classes of chemicals that are of concern in surface and drinking water.

Density functional theory (DFT) has become the most widely used first-principles computational method to simulate different atomic, molecular, and solid phase systems based on electron density assumptions. The complexity of describing a many-body system has been significantly reduced in DFT. However, it also brings in potential error when dealing with a system that involves the interactions between metallic and non-metallic species. DFT tends to overly-delocalize the electrons in metallic species and sometimes results in the overestimation of reaction energy, metallic properties in insulators, and predicts relative surface stabilities incorrectly in some instances. There are two approaches to overcoming the failure of DFT using standard exchange-correlation functionals: One can either use a higher level of theory (and thus incur a greater computational cost) or one can apply an efficient correction scheme. However, inaccurate corrections and improper calculation models can also lead to more errors. In the beginning of this dissertation, we introduce the correction methods we developed to accurately model the structure and electron density in material surfaces; then we apply the new methods in surface reactivity studies under experimental conditions to rationalize and solve real life problems. We first investigate the post-DFT correction method in predicting the chemisorption energy (Echem) of a NO molecule on transition metal surfaces. We show that DFT systematically enhances back-donation in NO/metal chemistorption from the metal d-band to NO 2π* orbital, and relate the back-donation charge transfer to the promotion of an electron from the 5σ orbital to the 2π* orbital in the gas-phase NO G2Σ-←X2Π excitation. We establish linear relationships between Echem and ΔEG←X and formulate an Echem correction scheme to the (111) surfaces of Pt, Pd, Rh and Ir. As a precursor to further optimization of DFT corrections on transition metal oxide surfaces, we systematically compare the alumina (α-Al2O3) and hematite (α-Fe2O3) (0001) surfaces to study how the atomic positions treatment during geometry optimizations would affect the electronic structure and modeled reactivity, since they are often reported to have a minimal effect. Our results suggest that both can vary significantly in quantitative and qualitative ways between partially constrained or fully relaxed slab models. We continue to use the α-Fe2O3 (0001) surfaces to optimize the Hubbard U method implemented in DFT that determines the Coulomb repulsion correction (Ud) to localize Fe d-electrons. It successfully restores the insulating properties of bulk hematite, but underestimates the stability of the oxygen-terminated surface. It is mainly due to the fact that all the chemically distinct surface Fe atoms were treated the same way. Here we develop a linear response technique to derive specific Ud values for all Fe atoms in several slab geometries. We also find that in a strongly correlated system, the O p-orbitals also need the Hubbard correction (Up) to accurately predict the structural and electronic properties of bulk hematite. Our results show that the site-specific Ud, combined with Up as Ud+p, is crucial in obtaining theoretical results for surface stability that are congruent with the experimental literature results of α-Fe2O3 (0001) surface structure. Besides methodology development, we continue to apply our specific Ud+p method in the engineered application of the Chemical Looping Combustion (CLC) process in which transition metal oxides play the role of oxidizing fuel molecules for full CO2 capture. Current molecular dynamic studies use partially constrained surface models to simulate the CH4 reaction on hematite surfaces without the detailed comparison of the early stage adsorption products. Here we use hematite (α-Fe2O3) and magnetite (Fe3O4) surfaces as analogous to systematically study the early adsorption products of CH4. Our results show that the reaction favors the homolytic pathway on O-terminated surface, and that as a reduced form of hematite, the magnetite surface also shows excellent reactivity on CH4 dissociation. Knowing how to simulate DFT surface model properly we continue to enrich our theoretical methods for more complicated systems under aqueous conditions. We focus on various structures of the lithium-ion battery material, LiCoO2 (LCO) (001) surface, involving hydroxyl groups. We assess the relative stabilities of different surface configurations using a thermodynamic framework, and a second approach using a surface-solvent ion exchange model. We find that for both models the –CoO–H1/2 surface is the most stable structure near the O-rich limit, which corresponds to ambient conditions. We also found that this surface has nonequivalent surface geometry with the stoichiometric –CoO–Li1/2 surface, leading to distinct band structures and surface charge distributions. We go on to probe how those differences affect the surface reactivity in phosphate anion adsorption. All of the work presented in this dissertation reveals the importance of accurately modeled material structures in theoretical studies to achieve correct physical properties and surface reactivity predictions. We hope our DFT correction schemes can continue to contribute to future surface studies and experimental measurements, and to enlighten new ideas in future DFT methodology improvements.

No description available.

Στην συγκεκριμένη διατριβή διερευνήθηκαν οι συνθήκες γένεσης του μικροκρυσταλλικού μαγνησίτη στις περιοχές Βάβδου και Γερακινής-Ορμύλιας της Χαλκιδικής. Η πετρογραφική μελέτη του μαγνησίτη και των ξενιστών του αποκάλυψαν δύο δομές δημιουργίας του μαγνησίτη: in situ εξαλλοίωση μέσα σε μανδυακά πετρώματα ξενιστές και ex situ αποθέσεις μέσα στους μανδυακούς σχηματισμούς. Επιπλέον, πιθανά υπάρχει στενή σχέση μεταξύ της κοιτασματογένεσης του μαγνησίτη και των περιβαλλόντων πυριτιωμένων πετρωμάτων (λιστβανίτες). Επίσης, οι γεωχημικές παρατηρήσεις συγχρόνως με τις ορυκτοχημικές αναλύσεις, δίνουν νέα στοιχεία όσον αφορά στην γένεση του κοιτάσματος. Παράλληλα, έγινε εργαστηριακή παραγωγή καυστικής μαγνησίας και παράχθησαν, με προσθήκη αυτής συγχρόνως με χρήση ερυθράς ιλύς και τέφρας πυθμένα, νέα κεραμικά υψηλού πορώδους. Τα αποτελέσματα υπήρξαν ιδιαίτερα ικανοποιητικά, καθώς παρατηρήθηκε ότι με προσθήκη μαγνησίας σε μικρό ποσοστό βελτιώνονται οι φυσικομηχανικές ιδιότητές τους. Κεραμικά υψηλού πορώδους είναι κατάλληλα για χρήση σε φίλτρα και σε απορροφητικά υλικά. Τέλος, προτείνεται νέος τρόπος αξιοποίησης στείρων υλικών μαγνησίτη από τις εξορυκτικές διεργασίες, καθώς αποδεικνύεται ότι ο μαγνησίτης έχει πολύ θετικά αποτελέσματα με προσθήκη του σε οξινισμένα ύδατα, δίνοντας νέες προοπτικές αξιοποίησης του σε περιβαλλοντικές εφαρμογές. Το πειραματικό σκέλος της δοκιμής σε οξινισμένα νερά, πραγματοποιήθηκε σε σύγκριση με πετρώματα που χρησιμοποιούνται για την αντιμετώπιση όξινων απορροών μεταλλείων. / In the present thesis, the microcrystalline magnesite from Central Chalkidiki (Vavdos and Gerakini areas) are investigated in order to clarify the conditions of its genesis. Petrographic study of the magnesite and its host rocks revealed two types of formation: a) in situ alteration in the mantle host rocks, due to metasomatic process, and b) ex situ deposit within mantle formations, related to hydrothermal fluids. Furthermore, petrographic observations suggest a close association between the genesis of the microcrystalline magnesite with the surrounding high silica-carbonate rocks, also termed as listwaenites. Moreover, scanning electron microscopy (S.E.M.) observations along with geochemical analysis provide new evidence for the formation of the magnesite. Caustic magnesia produced in the laboratory was mixed with red mud and bottom ash from industrial wastes, in order to make new, high porosity ceramics. It was observed that the addition of small amounts of caustic magnesia improved the physicomechanical properties of the briquettes. High porosity ceramics are suitable for their use in filters and absorbent materials for environmental applications. Finally, a new way for utilizing waste materials from magnesite mining processes in the disposal of acidified waters is proposed. Addition of magnesite improved the alkalinity of high acidic waters, offering new perspectives for environmental applications. The experimental results from magnesite were compared with similar results from other rocks used to treat acid mine drainage.

Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / For solar environmental remediation, a new generation of nanosized (< 10 nm) titanium dioxide photocatalysts codoped with metals and nonmetals, or metals only were prepared by the xero-gel and aero-gel methods. For silver or cobalt-based xero-gel titanium dioxide photocatalysts, photoactivities tests revealed that codoping of titanium dioxide with a metal (1% Ag or 2% Co) and nonmetals (carbon and sulfur) is necessary to achieve high-activities for acetaldehyde degradation under visible light (wavelength > 420 nm). It was concluded that high visible-light-activities for acetaldehyde degradation over codoped titanium dioxide were attributed to an interplay of anatase crystallinity, high-surface area, reduced band-gap (< 3.0 eV), uniform dispersion of doped metal ions, and suppressed recombination rate of photogenerated electron-hole pairs. Moreover, the nature and amount of codoped metals play a significant role in visible-light-induced photocatalysis. Metals (Al, Ga, and In) doped/codoped titanium dioxide photocatalysts were prepared by the aero-gel method. The photocatalytic studies showed that activities of metal doped/codoped photocatalysts under UV light (wavelength < 400 nm) were found to be dependent on pollutants. Indium demonstrated beneficial effects in both textural and photocatalytic properties. Gallium and indium codoped titanium dioxide photocatalysts displayed even better performance in the CO oxidation reaction under UV light. Notably, titanium dioxide codoped with Ga, In, and Pt, exhibited unique photoactivities for the CO oxidation under both UV and visible light irradiation, indicating that this system could have promise for the water-gas shift reaction for hydrogen production. Silver-based nanostructured titanium dioxide samples were developed for killing human pathogens (Escherichia coli cells and Bacillus subtilis spores). Biocidal tests revealed that silver, carbon, and sulfur codoped titanium dioxide nanoparticles (< 10 nm) possess very strong antimicrobial actions on both E. coli (logarithmic kill > 8) and B. subtilis spores (logarithmic kill > 5) for 30 minute exposures in dark conditions compared with Degussa P25. It was believed that the carbon and sulfur codoped titanium dioxide support and Ag species acted synergistically during deactivation of both E. coli and B. subtilis spores. Thus, titanium dioxide codoped with silver, carbon, sulfur can serve as a multifunctional generic biocide and a visible- light-active photocatalyst.

Cette thèse se place dans le cadre de la Statistique des valeurs extrêmes. Elle y apporte trois contributions principales. L'estimation des quantiles extrêmes se fait dans la littérature en deux étapes. La première étape consiste à utiliser une approximation des quantiles basée sur la théorie des valeurs extrêmes. La deuxième étape consiste à estimer les paramètres inconnus de l'approximation en question, et ce en utilisant les valeurs les plus grandes du jeu de données. Cette décomposition mène à deux erreurs de nature différente, la première étant une erreur systémique de modèle, dite d'approximation ou encore d'extrapolation, la seconde consituant une erreur d'estimation aléatoire. La première contribution de cette thèse est l'étude théorique de cette erreur d'extrapolation mal connue.Cette étude est menée pour deux types d'estimateur différents, tous deux cas particuliers de l'approximation dite de la "loi de Pareto généralisée" : l'estimateur Exponential Tail dédié au domaine d'attraction de Gumbel et l'estimateur de Weissman dédié à celui de Fréchet.Nous montrons alors que l'erreur en question peut s'interpréter comme un reste d'ordre un d'un développement de Taylor. Des conditions nécessaires et suffisantes sont alors établies de telle sorte que l'erreur tende vers zéro quand la taille de l'échantillon augmente. De manière originale, ces conditions mènent à une division du domaine d'attraction de Gumbel en trois parties distinctes. En comparaison, l'erreur d'extrapolation associée à l'estimateur de Weissman présente un comportement unifié sur tout le domaine d'attraction de Fréchet. Des équivalents de l'erreur sont fournis et leur comportement est illustré numériquement. La deuxième contribution est la proposition d'un nouvel estimateur des quantiles extrêmes. Le problème est abordé dans le cadre du modèle ``log Weibull-tail'' généralisé, où le logarithme de l'inverse du taux de hasard cumulé est supposé à variation régulière étendue. Après une discussion sur les conséquences de cette hypothèse, nous proposons un nouvel estimateur des quantiles extrêmes basé sur ce modèle. La normalité asymptotique dudit estimateur est alors établie et son comportement en pratique est évalué sur données réelles et simulées.La troisième contribution de cette thèse est la proposition d'outils permettant en pratique de quantifier les limites d'extrapolation d'un jeu de données. Dans cette optique, nous commençons par proposer des estimateurs des erreurs d'extrapolation associées aux approximations Exponential Tail et Weissman. Après avoir évalué les performances de ces estimateurs sur données simulées, nous estimons les limites d'extrapolation associées à deux jeux de données réelles constitués de mesures journalières de variables environnementales. Dépendant de l'aléa climatique considéré, nous montrons que ces limites sont plus ou moins contraignantes. / This thesis takes place in the extreme value statistics framework. It provides three main contributions to this area. The extreme quantile estimation is a two step approach. First, it consists in proposing an extreme value based quantile approximation. Then, estimators of the unknown quantities are plugged in the previous approximation leading to an extreme quantile estimator.The first contribution of this thesis is the study of this previous approximation error. These investigations are carried out using two different kind of estimators, both based on the well-known Generalized Pareto approximation: the Exponential Tail estimator dedicated to the Gumbel maximum domain of attraction and the Weissman estimator dedicated to the Fréchet one.It is shown that the extrapolation error can be interpreted as the remainder of a first order Taylor expansion. Necessary and sufficient conditions are then provided such that this error tends to zero as the sample size increases. Interestingly, in case of the so-called Exponential Tail estimator, these conditions lead to a subdivision of Gumbel maximum domain of attraction into three subsets. In constrast, the extrapolation error associated with Weissmanestimator has a common behavior over the whole Fréchet maximum domain of attraction. First order equivalents of the extrapolation error are thenderived and their accuracy is illustrated numerically.The second contribution is the proposition of a new extreme quantile estimator.The problem is addressed in the framework of the so-called ``log-Generalized Weibull tail limit'', where the logarithm of the inverse cumulative hazard rate function is supposed to be of extended regular variation. Based on this model, a new estimator of extreme quantiles is proposed. Its asymptotic normality is established and its behavior in practice is illustrated on both real and simulated data.The third contribution of this thesis is the proposition of new mathematical tools allowing the quantification of extrapolation limits associated with a real dataset. To this end, we propose estimators of extrapolation errors associated with the Exponentail Tail and the Weissman approximations. We then study on simulated data how these two estimators perform. We finally use these estimators on real datasets to show that, depending on the climatic phenomena,the extrapolation limits can be more or less stringent.

La principal motivación de esta investigación es la necesidad de conocer el impacto que ocasiona la escoria de acero en la resistencia a compresión y flexión del concreto cuando este sustituya al agregado fino en diferentes porcentajes. Asimismo, esta investigación brinda una opción viable para utilizar la escoria como agregado alternativo. Y así disminuir la demanda y dependencia que aún tenemos a los agregados naturales. Pues, su extracción descontrolada genera contaminación en ríos y playas. Además, estudios científicos demostraron que la extracción ocasiona enfermedades como la malaria debido a las piscinas de aguas estancadas que se forman. En la metodología se utilizó un diseño de investigación cuasi-experimental, la muestra censal fue de 45 probetas cilíndricas y 30 vigas rectangulares para los ensayos de compresión y flexión respectivamente, las variables en estudio fueron; VI=escoria de acero, VD=resistencia a la compresión y flexión, para la recolección de datos se utilizó guías de observación y para su análisis se utilizó la estadística descriptiva. Los resultados más relevantes fueron; el concreto tipo E30 alcanzo 394.89 kg/cm2 de resistencia a la compresión con respecto al concreto convencional lo cual es un incremento de 34.6% y que el concreto E40 alcanzo 71.86 kg/cm2 de resistencia a la flexión con respecto al concreto convencional lo cual es un incremento de 23.9%. Para ambos casos el diseño fue para un concreto de 280kg/cm2. Finalmente, se llega a la conclusión que la sustitución de escoria por agregado fino incrementa la resistencia a la compresión y flexión del concreto. / The main motivation of this research is the need to know the impact of steel slag on the compressive and flexural strength of concrete when it replaces fine aggregate in different percentages. Likewise, this research provides a viable option to use slag as an alternative aggregate. And thus reduce the demand and dependence we still have on natural aggregates. Because, its uncontrolled extraction generates pollution in rivers and beaches. In addition, scientific studies have shown that extraction causes diseases such as malaria due to the pools of stagnant water that are formed. In the methodology a quasi-experimental research design was used, the census sample was 45 cylindrical specimens and 30 rectangular beams for compression and flexural tests respectively, the variables under study were; VI=steel slag, VD=compressive and flexural strength, for data collection observation guides were used and for analysis descriptive statistics were used. The most relevant results were: concrete type E30 reached 394.89 kg/cm2 of compressive strength with respect to conventional concrete, which is an increase of 34.6%, and concrete type E40 reached 71.86 kg/cm2 of flexural strength with respect to conventional concrete, which is an increase of 23.9%. For both cases the design was for a concrete of 280kg/cm2. Finally, it is concluded that the replacement of slag with fine aggregate increases the compressive and flexural strength of the concrete. / Tesis

A rapidly growing topic of great interest is the adaptation of benchtop analytical instrumentation for use in outdoor harsh environments. Some of the areas that stand to benefit from field instrumentation development include government agencies involved with the preservation of the environment and institutions responsible for the safety of the general public. Detection systems are at the forefront of the miniaturization movement as the interest in analyte identification and quantitation appears to only be accessible through the use of analytical instrumentation. Mass spectrometry is a distinguished analytical technique known for its ability to detect the mass-to-charge (m/z) ratios of gas-phase ions of interest. Although these systems have been routinely limited to research lab-based analysis, there has been considerable development of miniaturized and portable mass spectrometry systems. Membrane Inlet Mass Spectrometry (MIMS) is becoming a common method of sample introduction that is subject to significant development. MIMS allows for minimal sample preparation, continuous sampling, and excludes complicated analyte introduction techniques. Sampling is accomplished using a semipermeable membrane that allows selective analyte passage into the vacuum of the mass spectrometer. MIMS is becoming the preeminent choice of homeland security and environmental monitoring applications with increasing opportunities for the future development of specialized systems. The steadfast development of miniaturized mass spectrometry systems with efficient operation capabilities for a variety of applications gives promise to the further development of MIMS technology as well as other analytical instrumentation.