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Thesis (Ph. D.)--University of Washington, 1992. / Vita. Includes bibliographical references (leaves [247]-251).

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1985. / Vita. Abstract. Includes bibliographical references (leaves 142-148). Also available via the Internet.

Lors de leur stockage ou de leur exposition, les objets du patrimoine sont soumis à des processus physico-chimiques d’altération liés à leur environnement et en particulier à l’action de polluants primaires (e.g. dioxyde de soufre, oxydes d’azote), secondaires (ozone) ou de composés organiques volatils (COVs). Il a été démontré que ces gaz/vapeurs se comportent comme des agents d’hydrolyse et d’oxydation. L’acide acétique fait partie des COVs ayant un impact considérable et reconnu dans la conservation des objets du patrimoine en particulier des films photographiques. En vue de lutter contre ses effets délétères, ce projet de thèse s’est focalisé sur la conception de nouveaux matériaux poreux hybrides multifonctionnels appelés « Metal-Organic Frameworks » (MOFs) pour la capture sélective de l’acide acétique en présence d’humidité (40% humidité relative) et à température ambiante. Les remarquables propriétés d’adsorption (sensibilité, sélectivité et capacité) et la grande versatilité des MOFs (balance hydrophile/hydrophobe, taille/forme des pores,…) ont été utilisés pour préconcentrer de façon sélective l’acide acétique en milieu humide. Les matériaux les plus performants ont ensuite été préparés sous forme de nanoparticules pour l’élaboration de films minces de qualité optique afin d’en étudier les propriétés d’adsorption et de co-adsorption (acide acétique/eau) par ellipsométrie. L’incorporation de nanoparticules métalliques plasmoniques a ensuite été effectuée afin de concevoir un capteur colorimétrique. L’objectif final de ce travail est de concevoir un nouveau type d’adsorbant caractérisé par une capacité et une sélectivité d’adsorption élevée et dont on pourrait aisément déterminer le niveau de saturation en acide acétique afin d’anticiper son remplacement et ainsi assurer la préservation des objets stockés et exposés dans les musées. / During their storage or their exhibition, the cultural heritage objects undergo physicochemical alteration processes related to their environment and in particular to the action of primary (e.g. sulfur dioxide, nitric oxides), secondary (ozone) pollutants or Volatile Organic Compounds (VOCs). It has been demonstrated that these gases/vapors are involved in hydrolysis and oxidation reactions. Among the most common VOCs encountered in museums, Acetic acid has a significant and recognized role in the deterioration of cultural heritage objects such as photographic films. In order to face this issue, this Ph.D. thesis focused on the design of new porous multifunctional hybrid materials denoted « Metal-Organic Frameworks » (MOFs) for the selective capture of acetic acid in the presence of moisture (40% relative humidity) and at room temperature. The remarkable adsorption properties (sensitivity, selectivity and capacity) and the great versatility of MOFs (hydrophicity/hydrophobicity balance, size/shape of pores,…) were used to preconcentrate selectively the acetic acid in humid conditions. The most performing materials were then prepared as nanoparticles and then used for the elaboration of high optical quality thin films in order to study the coadsorption (acetic acid/water) properties of MOFs by ellipsometry. The incorporation of plasmonic metal nanoparticles was then carried out in order to design a colorimetric sensor. The final objective is to devise a novel type of adsorbent that integrates a high VOC adsorption capacity and selectivity under humid conditions and an easy on-line monitoring of their saturation capacityin order to anticipate its replacement and therefore ensure the preservation of the stored and exhibited objects in museums.

A new methodology has been developed to model the viscoelastic behavior of solids using a general spectrum function. Not all materials can be modeled using simple Kelvin-Voigt (K-V) or Maxwell elements where the viscoelastic parameters are constants. There is a need for a general spectrum function that can be used to model the Lame' functions which constitute all properties of interest. Thus far, there is no method like the one presented in this study that can determine the moduli of viscoelastic materials. This study develops a methodology by which the time dependent properties of homogeneous and non-homogeneous materials may be modeled. Once the Lame' functions are determined, the Principle of Correspondence is applied to the elastic equations to determine the necessary properties. In uniaxial tension the time dependent strain, modulus, Poisson's ratio, and compliance are determined. The time dependent deflection is determined for beams in flexure. Where applicable, parameters determined from the analytical model are compared to the available experimental data. Good agreements are found between the analytical and experimental data sets.

The dynamic nuclear polarization of hydrogen nuclei by the solid effect in single crystals of samarium doped lanthanum magnesium nitrate (Sm:LMN) has been studied theoretically and experimentally. The equations of evolution governing the dynamic nuclear polarization by the solid effect have been derived in detail using the spin temperature theory and the complete expression for the steady-state enhancement of the nuclear polarization has been calculated. For well-resolved solid effect transitions at microwave frequencies Ï ~ Ï _e ± Ï _n, the expression for the steady-state enhancement differs from the expression obtained by the rate equation approach by small terms which become zero at Ï ~ Ï _e ± Ï _n Experimental enhancements of the proton polarization were obtained for eight crystals at 9.2 GHz and liquid helium temperatures. The samarium concentration ranged from 0.1 percent to 1.1 percent as determined by X-ray fluorescence. A peak enhancement of 181 was measured for a 1.1 percent Sm:LMN crystal at 3.0^" K. The maximum enhancements extrapolated with the theory using the experimental data for peak enhancement versus microwave power and correcting for leakage, agree with the ideal enhancement (24O in this experiment) within experimental error for three of the crystals. The calculated satellite separation was within 6 percent of the measured separation for each of the enhancement curves and the peak positive and negative enhancements were equal for all but two of the crystals. The nuclear spin"lattice relaxation time was measured for one of the crystals between l.6^" K and 4.2^" K. To account for nuclear spin"lattice relaxation, spin diffusion theory in the rapid airrusion limit was incorporated into the results of the spin temperature theory of the solid effect. The experimental results indicate that the spin temperature theory is a quantitatively correct approach for the description of dynamic nuclear polarization by the solid effect for well"resolved solid effect transitions. / Ph. D.

This thesis elucidates fundamental reactions that can control concentrations of arsenic and phosphate in water sources. High levels of arsenic or phosphorus have significant implications for the environment-- arsenic is extremely toxic to humans while phosphorus can cause eutrophication. Initial work focused on arsenic solids that might exert geochemical control on soluble arsenic. Formation of proposed iron, barium, copper and zinc-arsenic solids were systematically examined under realistic environmental conditions. Thermodynamically favored copper, ferrous and barium solids did not form under circumstances of significance to drinking water sources. However, sorption of arsenic to iron, zinc and copper solids was discovered to be very significant, depending on the pH and solids age. Given the established importance of sorption in arsenic and phosphate chemistry, two key constituents (silica and sulfide) implicated in mobilization of sorbed arsenic or phosphate were examined in detail. The addition of silica, which competes with arsenate or phosphate for sorption sites on Al(OH)3 and Fe(OH)3 hydroxides, caused release of 0-30% sorbed As and P at pHs between 7.0 and 8.5. Reaction of sulfide with Fe(OH)3 led to instantaneous release of 50-95% of sorbed As and P through a reductive dissolution mechanism. This instantaneous release was slowly reversed as orpiment (As2S3) and vivianite [Fe3(PO4)2] slowly precipitated, but under other circumstances, these solids would not be expected to form. Modeling results suggest that arsenic and phosphate concentrations could either increase or decrease in response to reaction between Fe(OH)3 and sulfides, thereby reconciling literature reports that seemed to contradict one another. / Master of Science