Thesis (Ph.D.)--Duquesne University, 2006. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references and abstracts.

abstract: The partitioning of available solar energy into different fluxes at the Earth's surface is important in determining different physical processes, such as turbulent transport, subsurface hydrology, land-atmospheric interactions, etc. Direct measurements of these turbulent fluxes were carried out using eddy-covariance (EC) towers. However, the distribution of EC towers is sparse due to relatively high cost and practical difficulties in logistics and deployment. As a result, data is temporally and spatially limited and is inadequate to be used for researches at large scales, such as regional and global climate modeling. Besides field measurements, an alternative way is to estimate turbulent fluxes based on the intrinsic relations between surface energy budget components, largely through thermodynamic equilibrium. These relations, referred as relative efficiency, have been included in several models to estimate the magnitude of turbulent fluxes in surface energy budgets such as latent heat and sensible heat. In this study, three theoretical models based on the lumped heat transfer model, the linear stability analysis and the maximum entropy principle respectively, were investigated. Model predictions of relative efficiencies were compared with turbulent flux data over different land covers, viz. lake, grassland and suburban surfaces. Similar results were observed over lake and suburban surface but significant deviation is found over vegetation surface. The relative efficiency of outgoing longwave radiation is found to be orders of magnitude deviated from theoretic predictions. Meanwhile, results show that energy partitioning process is influenced by the surface water availability to a great extent. The study provides insight into what property is determining energy partitioning process over different land covers and gives suggestion for future models. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2012

O controle da temperatura de transformação de fase gama-alfa da alumina pelo uso de aditivos iônicos tem sido alvo de diversos estudos nas ultimas décadas. No entanto, os efeitos destes aditivos são usualmente explicados considerando apenas parâmetros cinéticos e de difusão e a conseqüência destas impurezas nas energias dos polimorfos e nas energias de superfície são geralmente desconsideradas. Neste trabalho, o efeito termodinâmico do Zr, Mg e Mn na transformação gama-alfa é estudado para pós de Al2O3 preparados pelo método do precursor polimérico. Microcalorimetria de adsorção acoplada com calorimetria de dissolução de alta temperatura mostraram que os íons Zr diminuem a energia de superfície do gama-Al2O3, aumentando a estabilidade da fase de transição, que é fortemente dependente desta energia. Utilizando as mesmas técnicas, mostrou-se que o íon Mg aumenta a estabilidade termodinâmica do g-Al2O3, também aumentando a temperatura de transformação. O efeito do Mg, no entanto, foi também relacionado a efeitos cinéticos tais como a diminuição de difusão pela rede. A ação do íon Mn na diminuição da temperatura de transformação foi sugerida como fortemente relacionada a parâmetros de difusão. Vacâncias geradas pela substituição de Al3+ por Mn4+ seriam responsáveis pelo aumento do processo difusional atômico pela rede, fazendo com que o sistema atinja o tamanho crítico pré-determinado para esta reação em temperaturas mais baixas. Estas importantes conclusões abrem novas perspectivas no estudo da ação de aditivos em processos de alta temperatura, que devem ser avaliados considerando ambos efeitos termodinâmico e difusional. / The control of the gamma-alpha alumina transformation temperature using ionic additives has been the subject of several studies in the past decades. In this sense, the influence of these additives is usually explained considering only kinetic and diffusional parameters. Effects of these impurities on energetics of polymorphism and surface energies are usually disregarded. In this work, the thermodynamic effect of Zr, Mg and Mn on the gamma-alpha transformation is reported on Al2O3 powders prepared by the polymeric precursor method. Adsorption microcalorimetry coupled with high temperature oxide melt solution calorimetry showed that Zr ions dramatically decrease the surface energy of gamma-Al2O3, increasing the stability of the transition phase as which has been described to have its stability considerably related to the surface energy. By the same techniques, Mg was shown to increase the thermodynamic stability of g-alumina, also increasing the transformation temperature. The role of Mg on the control of the transformation temperature, however, was also related to kinetic factors, such as the bulk diffusion decreasing. The effect of Mn on decreasing the transformation temperature, however, was considered to be almost completely related to diffusion parameters, and vacancies generated by the substitution of Al3+ by Mn4+ would be responsible for the increase in bulk diffusion, allowing the system to reach a pre-determined critical particle size at lower temperatures. These important conclusions opened new perspectives in the role of additives in the high-temperature processes that should now on be evaluated from both thermodynamic effects and kinetics viewpoints.

Adhesion promoters are traditionally used to improve the durability between an adhesive or any other organic phase, such as a sealant or a paint, and a metallic substrate. There are many different types of molecules which will act as adhesion promoters, but one class which has attracted considerable attention is that based on the organosilanes, such as y-aminotriethoxysilane, or y-glycidoxypropyl trimethoxysilane. Applications of such adhesion promoters are to be found in sealants, rubbers, primers in packaging and primers for coatings and adhesives. Organosilanes as adhesion promoters are widely used in industry, and until recently have been included in adhesive formulations in an empirical way, because it has been observed that the adhesive properties and hydrolytic stability can be improved. However recent work is leading to an understanding of how the silane molecules specifically interact with metallic and inorganic substrates. Little is known at the present time regarding the mode of operation of such molecules when applied to polymeric substrates. The purpose of the current work was to probe interaction of these molecules with low energy polymer substrates, for example, poly(methyl methacrylate) (PMMA) and poly(ethylene terephalate) (PET), using surface analysis techniques. Two factors which have been identified as controlling the adsorption of the organosilanes onto low energy substrates are the solution chemistry and the surface energy of the polymer. Both have been investigated extensively within this project. The latter was identified by means of investigating a series of substrates, with increasing polar contribution towards the surface free energy. The highest polar component was displayed by corona treated PET, which also displayed the highest levels of adsorption of organosilanes. Investigation of the adsorbed layer of the organosilane on the corona discharge treated PET has led to an understanding of the mechanism of the interaction of the molecules with all of the low energy substrates, and models for such interactions are proposed on the basis of spectroscopic observations.

A thin film is a material that is many orders of magnitude thinner than it is long or wide. They are commonly found in many forms and have been adapted to a wide variety of uses. The art of origami uses thin films(sheets of paper) and precise folding to create complex, three-dimensional shapes out of flat, quasi two-dimensional sheets, and has emerged as a unique way to solve problems in engineering and science. As technology and devices are scaled to smaller sizes new understanding of origami methods are required to work at these small scales. The interactions between thin films and liquids, substrates that films exist on, and other thin films is the focus of this dissertation. Capillary interactions are used to manipulate and fold thin films that are too thin to be actuated with hands or everyday tools. The relation between the macroscopic and the microscopic interactions at the point where the capillary liquid and the film meet is explored. We show how films can be manipulated by capillary drops and how exactly the force is applied to the film. The adhesive interactions of the film were studied as a method of precisely placing folds for elastic film origami. The capillary peel of a film from a substrate drove folds to desired locations. Adhesion of a film to itself was used to lock these bends in place in lieu of the permanent creases commonly used in plastic systems such as paper. The combination of these two methods enabled the creation of stable, multi-step origami systems from reusable elastic films. This research culminates in the discussion of fundamentally new origami-like designs that rely only on adhesion of the film to itself, which we call kuttsukugami (sticky+paper from Japanese). This new form allows for the creation of shapes that are nearly impossible to create with traditional origami methods such as loops, tubes, and cones. Advances made in capillary and adhesive thin film studies allow for kuttsukugami shapes to be scaled down to microscopic sizes for a huge array of applications including drug delivery, thin electronics, encapsulation, and more.

The ability to fabricate structures and engineer materials on the nanoscale leads to the development of new devices and the study of exciting phenomena. Nanostructures attached to the surface of a substrate, in a manner that renders them immobile, have numerous potential applications in a diverse number of areas. Substrate-supported nanostructures can be fabricated using numerous modalities; however the easiest and most inexpensive technique to create a large area of randomly distributed particles is by the technique of thermal dewetting. In this process a metastable thin film is deposited at room temperature and heated, causing the film to lower its surface energy by agglomerating into droplet-like nanostructures. The main drawbacks of nanostructure fabrication via this technique are the substantial size distributions realized and the lack of control over nanostructure placement. In this doctoral dissertation, a new pathway for imposing order onto the thermal dewetting process and for manipulating the size, placement, shape and composition of preformed templates is described. It sees the confinement of substrate-supported thin films or nanostructure templates by the free surface of a metal film or a second substrate surface. Confining the templates in this manner and heating them to elevated temperatures leads to changes in the characteristics of the nanostructures formed. Three different modalities are demonstrated which alters the preformed structures by: (i) subtracting atoms from the templates, (ii) adding atoms to the template or (iii) simultaneously adding and subtracting atoms. The ability to carry out such processes depends on the choice of the confining surface and the nanostructured templates used. A subtractive process occurs when an electroformed nickel mesh is placed in conformal contact with a continuous gold film while it dewets, resulting in the formation of a periodic array of gold microstructures on an oxide substrate surface. When heated the gold beneath the grid selectively attaches to it due to the surface energy gradient which drives gold from the low surface energy oxide surface to the higher surface energy nickel mesh. With this process being confined to areas adjacent to and in contact with the grid surface the film ruptures at well-defined locations to form isolated islands of gold and subsequently, a periodic array of microstructures. The process can be carried out on substrates of different crystallographic orientations leading to nanostructures which are formed epitaxially and have orientations based on underlying substrate orientations. The process can be extended by placing a metallic foil of Pt or Ni over preformed templates, in which case a reduction in the size of the initial structures is observed. Placing a foil on structures with random placement and a wide size distribution results, not only in a size reduction, but also a narrowed size distribution. Additive processes are carried out by using materials which possess high vapor pressures much below the sublimation temperature of the template materials. In this case a germanium substrate was used as a source of germanium adatoms while gold or silver nanostructures were used as heterogeneous nucleation sites. At elevated temperatures the adatoms collect in sufficient quantities to transform each site into a liquid alloy which, upon cooling, phase separates into elemental components sharing a common interface and, hence, resulting in the formation of heterodimers and hollowed metal nanocrescents upon etching away the Ge. A process which combined aspects of the additive and subtractive process was carried out by using a metallic foil with a high vapor pressure and higher surface energy than the substrate surface (in this case Pd foil). This process resulted in the initial preformed gold templates being annihilated and replaced by nanostructures of palladium, thereby altering their chemical composition. The assembly process relies on the concurrent sublimation of palladium and gold which results in the complete transfer of the templated gold from the substrate to the foil, but not before the templates act as heterogeneous nucleation sites for palladium adatoms arriving to the substrate surface. Thus, the process is not only subtractive, but also additive due to the addition of palladium and removal of gold. / Mechanical Engineering

Well-defined central functionalized asymmetric tri-block copolymers (CFABC) were designed as a new type of polymer brush surface modifier, with a short central functionalized block that can form chemical bonds with a suitable substrate surface. A combination of sequential living anionic polymerization and polymer modification reactions were used for the synthesis of two CFABCs: PS-b-poly(4-hydroxystyrene)-b-PMMA and PS-b-poly(4-urethanopropyl triethoxysilylstyrene)-b-PMMA. GPC and NMR characterization indicated that the block copolymers possessed controlled molecular weights and narrow molecular weight distributions. CFABC polymer brushes were successfully prepared by chemically grafting PS-b-poly(4-urethanopropyl triethoxysilylstyrene)-b-PMMA onto silicon wafer surfaces. AFM, XPS and ellipsometry were used to confirm the CFABC polymer brush structures and thickness. The surface properties of CFABC polymer brush modified silicon wafer substrates subjected to different environmental parameters were studied. Reversibly switchable surface energies were observed when the polymer brush modified surfaces were exposed to solvents with different polarities. The phenomenon was attributed to the chain configuration auto-adjustment in the polymer brush systems. The same mechanism was also used to explain the enhanced adhesion capability between the modified surfaces and different polymer materials (PS and PMMA). Phase behaviors of polymer thin films on unmodified and CFABC polymer brush modified silicon wafer surfaces were also studied. For thin films of polymer blends, PS blend PS-co-PMMA, the effects of film thickness, chemical composition and temperature on the phase separation mechanism were investigated. The phase behavior in thin films of triblock copolymers with or without central functionalities were compared to reveal the role of the central functionalized groups in controlling film structures. Finally, the presence of CFABC polymer brush at the interface between PS-b-PMMA diblock copolymer thin film and silicon wafer substrate was found to decrease the characteristic lamellar thickness in the thin film. A mechanism of tilted chain configurations in the thin film due to the interactions with the CFABC polymer brushes was proposed. / Ph. D.

The electrical potential differences which arise across the length of capillary tubes containing 1 N perchloric acid and mercury drops are studied experimentally and theoretically for constant acceleration and different lengths of the drops of mercury. A relatively simple theory explains many features of the voltage on the experimental parameters. The results suggest that surface modes exist on the mercury drops which, in association with the Gibbs-Thompson effect, is the coupling between the mechanical and electrochemical phenomena. / Ph. D.

The bond performance and surface energy of hygro-thermal compression densified wood were studied using comparisons to hygro-thermally treated and control yellow-poplar (Liriodendron tulipifera). Bond performance was studied using opening mode double cantilever beam fracture testing and cyclic boiling of one half of all fracture samples. Phenol formaldehyde film (PF-film) and polymeric diphenylmethane diisocyanate (pMDI) were the two different adhesives used to bond fracture samples. Hygro-thermal samples bonded with PF-film had significantly higher fracture toughness than control samples, while no difference was found for densified samples. Densified samples bonded with pMDI had significantly higher fracture toughness than control samples while no change was seen for hygro-thermal samples. Boil cycling reduced fracture toughness of hygro-thermal fracture samples only, irrespective of adhesive type. Surface energy was studied using sessile drop contact angle measurement and the Chang model of acid-base, surface energy component calculation. Water, glycerol, formamide, ethylene glycol, and -Bromonapthalene were used as probe liquids. Densified and hygro-thermally treated yellow-poplar had significantly higher contact angles than control samples. The contact angle trends for densified and hygro-thermally treated wood were found to be the same. Total surface energy as well as the polar and acid components of surface energy decreased with hygro-thermal treatment. The dispersive and base components of surface energy increased with hygro-thermal treatment. / Master of Science

Calcified skeletons are produced within complex assemblages of proteins and polysaccharides whose roles in mineralization are not well understood. Researchers have long postulated that living organisms utilize the macromolecules of organic matrices to actively guide the formation of crystal structures. The timing and placement of the subsequent minerals that form are most easily controlled during nucleation; however, a physical and chemical picture of how organic functional group chemistry influences the initial stages of nucleation is not yet established. These processes are further complicated by the realization that carbonate biominerals can form by an amorphous to crystalline transformation process, which has prompted the question of how chemical signatures are recorded during mineralization. Investigations of mineralization processes such as the kinetics of nucleation and the transformation of amorphous calcium carbonate (ACC) to crystalline products are critical to building a better understanding of biomineral formation. Only from that fundamental basis can one begin to decipher changes in climate and seawater chemistry over geologic time and by recent anthropogenic effects. This dissertation presents the findings from experimental studies of the thermodynamics and kinetics of multiple mineral formation processes, including nucleation and transformation from an amorphous phase. The kinetics of calcite nucleation onto a suite of high-purity polysaccharide (PS) substrates were quantified under controlled conditions. Nucleation rates were measured as a function of 1) supersaturation extending above and below ACC solubility and 2) ionic strength extending to seawater salinity. These conditions decipher the chemical interactions between the PS substrate, calcite crystal, and solution. These investigations show the energy barrier to calcite formation is regulated by competing interfacial energies between the substrate, crystal, and liquid. The energy barriers to nucleation are PS-specific by a systematic relationship to PS charge density and substrate structure that is rooted in minimization of the competing substrate-crystal and substrate-liquid interfacial energies. The data also suggest ionic strength regulates nucleation barriers through substrate-liquid and crystal-liquid interfacial energetics. In a second experimental study, stable isotope labeling was used to directly probe the transformation pathway. Four processes were considered: dissolution-reprecipitation, solid-state, or combinations of these end member processes. Isotope measurements of calcite crystals that transform from ACC have signatures that are best explained by dissolution-reprecipitation. The extent of isotopic mixing correlates with the amount of ACC transferred and the time to transformation, suggesting the calcite crystals are recording the changing local solution environment during the transformation. These investigations into different mineralization mechanisms build a framework for how functional group chemistries of organic molecules regulate mineralization and the resulting isotopic and elemental signatures in the calcite. This may provide useful insights to interpreting chemical signatures of carbonate biominerals in fossil record and understanding ocean chemistry changes throughout geologic time. / Ph. D.