The interaction of water vapor with the surface and bulk of poly(imidesiloxane) copolymers has been characterized in an attempt to determine the important factors in the copolymer's resistance to water ingression. The multi-block copolymers were synthesized from benzophenone tetracarboxylic dianhydride, bisaniline P and pre-formed amine-terminated poly(dimethylsiloxane) oligomers, with phthalic anhydride as an end-capping agent. Similar copolymers had been previously shown to have reduced water sorption, increased surface hydrophobicity, and increased adhesive durability in hot/wet environments. Inverse gas chromatography was used to conduct surface energetics studies on copolymers of different siloxane concentration and a polyirnide homopolymer. Free energies of specific interaction of water vapor, ΔG_sp°, with the polymer surfaces were found to decrease with the incorporation of siloxane into the polyirnide. The dispersive components of the solid surface free energy of the siloxane- containing copolymers were equal within error to that of pure poly(dimethylsiloxane), indicating a PDMS-rich, hydrophobic surface. The ΔG_sp° of the copolymers were not significantly different, suggesting that the copolymer surfaces were very similar. This indicated a minimum weight percent of siloxane incorporation required to maximize the copolymer's surface water resistance. The minimum amount for the studied system was at most ten percent. Diffusion coefficients of water vapor in the polyimide and copolymers were determined from gravimetric sorption experiments. Higher levels of siloxane incorporation caused a definite increase in the diffusion coefficient, indicating a decreased resistance to water ingression. The increase in diffusion was found to be influenced by siloxane block length and was interpreted in terms of morphological and free volume theories. The diffusion coefficient of a 10 weight percent PDMS copolymer, however, was found to be the same within error as the polyimide diffusion oefficient. The incorporation of siloxane into polyimides has been shown to increase water resistance due to the hydrophobicity of the siloxane-rich surface. However, high siloxane contents also increased the rate of water ingression in the bulk of the polymer. Increased water resistance of the surface may be achieved at lower siloxane concentrations without increasing diffusive (or decreasing mechanical) properties to undesirable levels. / Ph. D.

Drought conditions and wildfires can induce soil water repellency. Precipitation shifts are expected to exacerbate drought and wildfire in regions such as the southeastern United States, making it critical to understand how repellency affects water exchange processes in soil. The objectives of this dissertation were to 1) quantify the water vapor sorption dynamics of two clay minerals in which water repellency was induced; 2) identify if and for how long wildfires in humid hardwood forests induce water repellency, 3) evaluate if organic carbon content and hydrophobic functional groups explain actual and potential soil water repellency; and 4) understand how vertical position (i.e., depth) of water repellent layers affect infiltration processes. To meet these objectives, a laboratory test was first conducted examining water vapor sorption processes in water-repellent clay minerals. Next, a field study occurred in two forests that experienced wildfires in late 2016: Mount Pleasant Wildfire Refuge, Virginia, and Chimney Rock State Park, North Carolina, United States. Measurements include water drop penetration time, soil water content, and tension infiltration. Complimentary laboratory tests quantified potential soil water repellency, soil organic carbon content and hydrophobic functional groups. Results showed that water repellency inhibited water vapor condensation because of altered mineral surface potentials and decreased surface areas. Burned hardwood forest soils presented water repellency for > 1 year, though laboratory measurements presented different trends than in situ measurements. Total organic carbon content and hydrophobic functional groups correlated with soil water repellency measured in the laboratory but not the field. Soil water content was lower in burned than unburned soils, and negatively correlated with water repellency. Water repellency in the surface layers significantly reduced relative water infiltration rates, whereas subsurface water repellency did not, and water repellency persisted longer in sites with surface compared to subsurface water repellency. Finally, while the wildfires increased the occurrence of water repellency, they did not alter the underlying relationship between relative infiltration and surface water repellency. Altogether, this study provided new insight into water repellency effects on water partitioning at soil-atmosphere interfaces, and presented evidence of soil and hydrological changes induced by wildfires in humid hardwood forests. / PHD / Rising temperatures and shifting precipitation patterns that result from global climate change have the potential to induce long-term droughts, which may induce soil water repellency, as can wildfires that become more prevalent and damaging. Water repellency can alter the physical, chemical, and hydraulic properties of soil. These alterations may drive soil erosional processes and increase the mobility of surface-bound pollutants with the potential to reduce water quality and degrade down-gradient aquatic ecosystems. Thus, it is critical to understand how water repellency affects water movement in and through soils. Despite several decades of research towards this topic, some critical questions still remain. For example, how does water repellent soil influence water characteristics in the vapor phase (which is increasingly important under drought conditions)? Do wildfires in humid hardwood forests cause soil water repellency? If so, how long does water repellency persist? Do water repellency measurements using field and laboratory techniques correspond to one another? How does the depth of water repellent soil layer(s) affect water movement? In order to solve this questions, several tests were conducted in both field and laboratory. The field experiments occurred within forested hillslopes that underwent varying degrees of burning during widespread wildfires that affected the Southeastern United States in late 2016. Choosing two forested locations, we measured actual water repellency, soil moisture, and infiltration in burned and unburned sites after wildfire, and took loose samples for laboratory tests. In the lab, we tested potential water repellency on air-dried soil samples, soil organic carbon content and hydrophobic substance percentage. We also conducted water vapor sorption experiments to quantify water vapor exchange in two types of water repellent minerals: kaolinite and montmorillonite. The results showed that water repellency can affect water exchange between the subsurface and the atmosphere, by both limiting water vapor sorption and reducing liquid water infiltration. Soil organic matter and composition correlate well with potential water repellency measured in the laboratory, though less so with actual water repellency measured in the field. Instead, soil water content provided a high and inverse correlation with actual water repellency. Finally, water infiltration rates were influenced by the vertical position (depth) of water repellent layers, with water repellency at the soil surface causing much reduced initial infiltration rates compared to water-repellent layers in the subsurface.

La composition isotopique de l’eau (dO18 et dD) est couramment utilisée pour étudier le cycle de l’eau actuel et passé ainsi que ses variations. Alors que dans les zones polaires, cet outil géochimique représente les fondements de la reconstitution des climats polaires passés, de multiples questions demeurent quant aux facteurs pilotant la composition isotopique de l’eau dans les tropiques.Afin de répondre à ces questions, le présent travail de thèse a porté sur la réalisation de mesures en continu de la composition isotopique de la vapeur d’eau sur l’île de La Réunion (océan Indien), ainsi que sur l’évaluation du potentiel de ces mesures pour la compréhension des processus atmosphériques humides prévalant sur cette zone géographique. L’implantation d’un spectromètre laser à l’Observatoire Atmosphérique du Maïdo nous a permis d’obtenir une chronique de trois ans de mesures.Dans un premier temps, les différentes variabilités temporelles que présentent nos mesures ont été étudiées. Les enregistrements ne montrent aucune cyclicité saisonnière sur la composition isotopique de la vapeur d’eau. Elles indiquent en revanche une forte cyclicité diurne, ainsi qu’une variabilité synoptique associée à des évènements cycloniques.Dans un second temps, nous montrons que cette cyclicité diurne résulte de phénomènes de mouvement de couche limite atmosphérique, avec une vapeur marine qui atteint l’Observatoire durant la journée, alors que des masses d’air en provenance de la troposphère libre y parviennent durant la nuit. La présence de certaines nuits significativement plus appauvries en dO18 et dD reflète (1) une modification de la circulation atmosphérique régionale avec un renforcement des subsidences au niveau de La Réunion, lié à la position du Jet Subtropical durant l’hiver austral, et (2) tantôt une intensification de la subsidence au niveau de La Réunion, tantôt des processus de condensation locaux ou régionaux durant l’été austral.Enfin, l’étude des phénomènes cycloniques indique qu’au cours de ces périodes, un fort appauvrissement de la composition isotopique de la vapeur est observé. Celui-ci survient 2 à 3 jours avant et perdure jusqu’à 3 jours après le passage du système. Durant cette période, l’évolution de la composition isotopique de la vapeur d’eau présente une sous-structure. On note (1) un appauvrissement isotopique qui est fonction de la distance au centre du système, (2) un enrichissement isotopique au niveau du mur du système, et (3) des évolutions abruptes de la composition isotopique de la vapeur d’eau dans les bandes précipitantes dues à des processus de mélange, de condensation et/ou de recharge. / The isotopic composition of water vapor (dO18 and dD) is commonly used to study present and past water cycle and its varations. If this geochemical tool has been widely used to study past polar climates, many questions remain about the factors governing the isotopic composition of water in the tropics.The goal of this thesis is (1) to monitor the isotopic composition of water vapor in Reunion island (Indian Ocean), and (2) to evaluate the potential of theses measurements for understanding humid climate processes. We have set up a laser spectrometer at the Maïdo Atmospheric Observatory, allowing us to obtain a three-year chronicle of measurements.First, we analyze the temporal variability in our measurements. The isotopic composition of water vapor does not record any seasonal cyclicity. On the other hand, a strong diurnal cycle is visible, as well as a synoptic variability associated with cyclonic events.We then focus on the diurnal cycle. We show that it results from atmospheric boundary layer motions, with a marine vapor reaching the Observatory during the day, and air masses originating from the free troposphere reaching the Observatory during the night. During some nights, vapor is significantly more depleted in dO18 and dD. During the austral winter, this phenomenon is due to a modification of the regional atmospheric circulation causing a reinforcement of subsidences at Reunion Island, related to the position of the Subtropical Jet. During the austral summer, this phenomenon is sometimes due to an intensification of the subsidence at Reunion Island, and at other times to local or regional condensation processes.Finally, we focus on cyclonic events. During these periods, a strong isotopic depletion of the vapor is observed. We show that this depletion occurs 2 to 3 days before the system and continues until 3 days after. During this period, the evolution of the isotopic composition of the water vapor has a substructure. We note (1) an isotopic depletion that is a function of the distance to the center of the system, (2) an isotopic enrichment at the system wall, and (3) an abrupt evolutions of the isotopic composition of the water vapor in the rainbands due to mixing, condensation and/or recycling processes.

Thesis (PhD)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: In this study, the use of surfactants, plate-like clays, organophilic molecules and side-chain crystallinity was investigated for their impact on the transport mechanisms of water vapour through polymer films. A model polymer latex, poly(styrene-co-butyl acrylate), was prepared using miniemulsion polymerization. Three different types of surfactants, sodium dodecyl benzene sulfonate (SDBS, an anionic surfactant), octyl phenol ethoxylate (OPE, a nonionic surfactant) and dodecyl ammonium- 3-butenoate (DA3B, a reactive surfactant) were used to stabilize the latex. Films were prepared from the resultant latices and their water vapour sorption behaviour determined across a water vapour partial pressure range of 0.1 to 0.9. Sigmoidal kinetic behaviour was seen for all three films, with the DA3B stabilized film exhibiting high diffusion coefficients compared to films stabilized with SDBS and OPE. The thermodynamic behaviour of the films differed and was dependent on the reactivity of the surfactant. SDBS and OPE stabilized films exhibited Flory- Huggins behaviour, while the DA3B stabilized film followed Henry’s Law. Despite significant differences in terms of these properties, the permeability coefficients were similar for the three films across the water vapour partial pressure range evaluated. The impact of sodium montmorillonite (Na-MMT) clay and an organophilic modifier, 2- acrylamido-2-methylpropanesulfonic acid (AMPS), on the water vapour sorption properties of poly(styrene-co-butyl acrylate) was evaluated. These polymer clay nanocomposites (PCNs) were synthesized using miniemulsion polymerization. The resultant latex films were characterized and used for water vapour sorption analyses. It was shown that complete exfoliation of the Na-MMT was necessary to minimize the equilibrium water vapour uptake. Even when Na-MMT was completely exfoliated, the amount of water vapour sorbed by the PCN was high and this was attributed to the hydrophilic nature of the clay. Using a least squares regression fit, good correlation was obtained between the experimental isotherms and the sorption behaviour predicted by the Dual Mode Sorption model which was originally developed for polymers in their glassy state. The impact of side chain crystallinity on the water vapour sorption properties of poly(methyl methacrylate-co-octadecyl acrylate) was evaluated. These random copolymers containing increasing amounts of octadecyl acrylate, and therefore increasing degrees of crystallinity, were synthesized using solvent polymerization. Although it could be expected that side chain crystallinity would be the main contributing factor resulting in a reduction in the diffusion coefficient, it was shown that the methyl group on the á- carbon of the vinyl group in the methacrylate reduced the diffusion to a greater extent through the increased stiffness of the polymer backbone. This was also reflected in poly(methyl methacrylate-co-octadecyl acrylate) having a greater activation energy for diffusion compared to polyoctadecyl acrylate. / AFRIKAANSE OPSOMMING: In hierdie studie is die gebruik van sepe, plaatagtige kleie, organofiliese molekules en sykettingkristalliniteit ondersoek ten opsigte van die impak op transportmeganismes van waterdamp deur polimeerfilms. ‘n Model polimeerlateks, polistireen-ko-butielakrilaat, is voorberei deur miniemulsiepolimerisasie. Drie verskillende tipes sepe, natriumdodekielbenseensulfonaat (NDBS, ‘n anioniese seep), oktielfenoletoksilaat (OFE, ‘n nie-ioniese seep) en dodekielammonium-3-butenoaat (DA3B, ‘n reaktiewe seep) is gebruik om die lateks te stabiliseer. Films is van die resultante lateks voorberei en hul waterdampsorpsie –eienskappe oor die parsiële waterdampdrukreeks van 0.1 tot 0.9 bepaal. Sigmodale kinetiese gedrag is vir al drie films waargeneem, met die DA3B gestabiliseerde film wat hoër diffusiekoëffisiënte toon in vergelyking met die films wat met NDBS en OFE gestabiliseer is. Die termodinamiese gedrag van die films het verskil en was afhanklik van die reaktiwiteit van die seep. NDBS en OFE gestabiliseerde films het Flory-Huggins gedrag getoon, terwyl die DA3B gestabiliseerde film Henry se Wet gevolg het. Ten spyte van die beduidende verskille ten opsigte van hierdie eienskappe was die permitiewe koëffisiënte soortgelyk vir die drie films regoor die parsiële waterdampdrukreeks wat vir die evaluasie gebruik is. Die impak van natriummontmorilloniet (Na-MMT) klei en ‘n organofiliese modifiseerder, 2- akrielamido-2-metielpropaansulfoonsuur (AMPS), op die waterdampsorpsie-eienskappe van polistireen-ko-butielakrilaat is geevalueer. Hierdie polimeer-klei-nanosaamgesteldemateriale (PKNe) is gesintetiseer deur van miniemulsiepolimerisasie gebruik te maak. Die resultante lateksfilms is gekarakteriseer en gebruik vir waterdampsorpsie analises. Daar is getoon dat algehele afskilfering van die Na-MMT nodig was om die ewewigswaterdampopname te minimaliseer. Selfs wanneer Na-MMT algeheel afgeskilfer was, was die hoeveelheid waterdamp gesorbeer deur die PKN hoog en kan dit toegeskryf word aan die hidrofiliese karakter van die klei. Deur ‘n kleinste-kwadrate-regressie passing te doen, is ‘n goeie korrelasie verkry tussen die eksperimentele isoterme en die sorpsie gedrag voorspel deur die Dubbelmodussorpsiemodel wat oorspronklik ontwikkel is vir polimere in hul glasagtige toestand. Die impak van sykettingkristalliniteit op die waterdampsorpsie-eienskappe van poli(metielmetakrilaat-ko-oktadekielakrilaat) is ondersoek. Hierdie ewekansige kopolimere wat toenemende hoeveelhede oktadekielakrilaat, en dus toenemende grade van kristalliniteit bevat, is gesintetiseer deur van oplossingspolimerisasie gebruik te maak. Alhoewel dit te wagte was dat sykettingkristalliniteit die hoofbydraende faktor is in die redusering van die diffusiekoeffisiente, is daar getoon dat die metielgroep aan die α-koolstof van die vinielgroep in die metakrilaat die diffusie tot 'n groter mate gereduseer het deur toenemende styfheid van die polimeerrugraat. Dit is ook gereflekteer deur poli(metielmetakrilaat-ko-oktadekielakrilaat) wat 'n groter aktiveringsenergie vir diffusie het in vergelyking met polioktadekielakrilaat.

Darbe atlikta literatūros analizė šių procesų: (i) vykstančių vandens garų plazmoje; (ii) titano dangų oksidacija vandens garų plazmoje ir (iii) titano dioksido fotokatalitinės ir hidrofilinės savybės. TiO2 dangos buvo gautos po titano dangų ekspozicijos H2O garų plazmoje. Tyrimai parodė, kad TiO2 danga vandens garų plazmos aplinkoje formuoja elektrocheminį elementą. Darbe tirtos plazma aktyvuotos vandens skaldymo reakcijos. Parodyta, kad susidarę protonai pernešami per kietą TiO2 elektrolitą, o elektronai migruoja per plazmoje susiformavusią išorinę grandinę. Proceso metu dangos paviršinis sluoksnis formuojasi į TiO2–SiO2 kompozitą. Nors procesai vyksta žemoje temperatūroje, gauti rezultatai parodė masės pernešimo reiškinius, būdingus aukštoms temperatūroms. Pateikti nagrinėtų procesų mechanizmai. Darbo metu bandinių eksperimentinė analizė atlikta elektroninės dispersinės spektroskopijos (EDS), rentgeno spindulių difrakcijos (RSD), Auger elektroninės spektroskopijos (AES), skenuojančio elektroninio mikroskopo (SEM), optinės mikroskopijos ir kontaktinio profilometro metodais. / Processes in water vapor plasma, titania film oxidation in water vapor plasma and titanium dioxide photocatalytic and hydrophilic properties are discussed in this paper. Titatium dioxide thin films were obtained after titanium thin film exposure in water vapor plasma. Specimen together with H2O plasma forms electrochemical cell. In plasma film surface is activated and photocatalytic water splitting reactions occurs. Generated hydrogen ions are transported through solid titanium electrolyte and electrons are conducted to an external circuit via plasma. Titanium dioxide films surfaces are converted into composited composed of TiO2 and SiO2. Although oxidation process occurs in room temperature results showed mass transfer processes which occurs in high temperature. Specimens were analysed by electron dispersion spectroscopy (EDS), (X-ray diffraction (XRD), Auger electron spectroscopy (AES), glow discharge optical emission spectroscopy (GDOES), scanning electron microscopy (SEM), optical microscopy and nanoprofilometer methods.

Water vapour content and transport over southern Africa and adjacent oceans are examined. Early summer rainfall over the northern and central interior of South Africa tends to be associated with baroclinic controls whereas late-summer rainfall is barotropic in origin. This is reflected in the northwesterly water vapour transport from an Atlantic Ocean source by middle and upper tropospheric westerly waves in early summer. A thermally indirect Ferrel cell, indicated-from energetics, COpIU1nSthe· temperate nature of the early-summer atmosphere over southern Africa. Late summer water vapour transport, in contrast, is strongly from the tropics, with' a reduced eddy component, indicating an important tropical control on late SUmmerrainfall especially in terms of fluctuations in the position of the ascending limb of .the Walker cell Over southern Africa. The Hadley cell is of importance to the late summer rainfall in that dry (wet) years are associated with an anomalous cell OVereastern (central) South Africa such that low level vapour transport is southerly (northerly). The anticyclone over the eastern parts of southern Africa, coupled with. a trough over the interior (especially at the 700 hPa pressure level), is important for the introduction of water vapour over the subcontinent in wet and dry years and for tropical-temperate trough case studies. Water vapour source regions differ from early summer (Atlantic Ocean) to late summer (Indian Ocean), which reflects the temperate. control on early and the tropical control on late summer circulation. The convergence of water vapour over southern Africa in wet years and during tropical-temperate troughs is not only important for cloud formation and precipitation, but also for latent heat release associated with convergent water vapour. Diabatic heating decreases the stability of the tropical atmosphere thereby resulting in increased vertical motion. It also forces an anomalous Badley circulation during wet late summers and tropical-temperate trough .cases as a result of complex energy transformations. Heating increases eddy available potential energy which is converted to zonal available potential energy by a thermally indirect circulation found in the tropics. The zonal potential energy is then converted to kinetic energy by the thermally direct Badley cell. Water vapour and its variations are thus important for the precipitation, heating and SUbsequent energy of the subtropical southern African atmosphere, / GR 2017

L'altimétrie spatiale contribue majoritairement à la compréhension de la circulation océanique régionale et globale. Elle permet aujourd'hui de fournir une cartographie de la topographie océanique à des échelles spatiales et temporelles de plus en plus fines. Le passage du signal radar à travers la vapeur d'eau de l'atmosphère implique un retard de l'onde, qui nécessite d'être corrigé : c'est la correction troposphérique humide. Des méthodes statistiques sont actuellement utilisées pour estimer la correction troposphérique humide. Elles permettent d'inverser des mesures de températures de brillance fournies par un radiomètre couplé à l'altimètre sur une mission altimétrique, à deux ou trois fréquences proches de la bande d'absorption de la vapeur d'eau, à 22.235 GHz. Bien que ces algorithmes permettent d'estimer cette correction avec de faibles incertitudes en plein océan, des améliorations sont nécessaires pour réduire les erreurs dans les zones océaniques complexes, comme les régions d'upwelling, et sur les surfaces hétérogènes, comme en régions côtières, sur glace de mer, ou sur les eaux continentales. A ces fins, une approche variationnelle uni-dimensionnelle (1D-Var) est développée dans cette thèse. Elle permet de tenir compte de la physique de l'atmosphère et des variations de la surface dans l'environnement des mesures, pour estimer la correction troposphérique de manière globale, sur différents types de surface, dans le contexte des missions altimétriques actuelles, et futures, dont les technologies instrumentales évoluent. Une analyse fine des caractéristiques de l'approche 1D-Var, et de ses performances, permet de montrer l'apport et l'impact des différents paramètres en jeu sur les variables atmosphériques restituées, et la correction troposphérique humide estimée. Les performances du 1D-Var ainsi que ses limites sont évaluées pour l'estimation la correction troposphérique humide en plein océan, en conditions de ciel clair. L'apport des mesures de températures de brillance aux hautes fréquences, typiques des missions altimétriques futures, est également analysé. Leur potentiel est exploité dans le cadre de l'estimation de la correction troposphérique humide dans les régions côtières, où les mesures de températures de brillance sont contaminées par la présence de terre dans le signal. Enfin, une analyse des estimations des émissivités de surface, et de leurs variations sur la glace de mer, est proposée dans le cadre d'une étude préliminaire à l'estimation de la correction troposphérique humide, aux interfaces complexes mer/glace de mer, dans les régions polaires. / Space altimetry is one of the major contributors to the understanding of regional and global oceanic circulation. It currently enables to provide a map of ocean topography at higher temporal and spacial scales. A propagation delay of the altimeter signal along its path through atmospheric water vapor needs to be accounted for, and corresponds to the wet tropospheric correction. Statistical methods are currently used to estimate wet tropospheric correction. These methods are fed by brightness temperature measurements provided by a radiometer coupled to the altimeter, at two or three frequencies close to the water vapor absorption line, at 22.235 GHz. While these algorithms provide wet tropospheric correction with low uncertainties over open ocean, improvements are still needed to reduce higher uncertainties in complex oceanic areas, such as upwelling regions, and over heterogeneous surfaces, as coastal regions, sea ice or inland waters. To this end, a one-dimensional variational approach (1D-Var) is developed in the frame of this thesis. This approach accounts for atmospheric and surface variability in the surroundings of the measurements, to provide wet tropospheric correction estimates at a global scale, over various surfaces, in the context of both current and future altimetry missions, with improved instrumental technologies. We first analyze the characteristics of the 1D-Var approach and evaluate its performances. The contribution and impact of the different input parameters on retrieved atmospheric variables and wet tropospheric correction are shown through this analysis. The potential and limits of the 1D-Var approach to retrieve wet tropospheric correction over open ocean, for clear sky conditions, are evaluated. The contribution of high frequencies, typical to future altimetry missions, is also analyzed. It is fully exploited to retrieve wet tropospheric correction over coastal areas, where land contamination occurs within brightness temperature measurements. A preliminary analysis of surface emissivity estimates and their variability over sea ice is also undertaken, in the frame of the 1D-Var estimation of wet tropospheric correction over sea ice/open sea transition surfaces, in polar areas.

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No. of bitstreams: 2 Dissertação Itallo Conrado PDF.pdf: 1385053 bytes, checksum: 2683757eec44901652cc4f8c98297b4d (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2013-03-05 / This study aimed to assess the age of the breeder broiler and the machine type incubation on hatching parameters, the window hatch, embriodiagnosis and physical quality newborn chicks. We also evaluated the technique for measuring the conductance of the eggshell fragments using bark and also the correlation of the conductance values with parameters of incubation. In Experiment 1 was used in DBC design, and using DIC for embriodiagnosis. In a 2x3 factorial - multi-stage machines (MS) or single (SS) and ages of breeder (29w, 35w and 59w). In experiment 2 was randomized in DBC. In a 3x3 factorial scheme - region of the eggshell (blunt end, equator, pointy end) and ages of breeder (29w, 35w and 59w). The variables were subjected to analysis of variance and means were compared by quantitative and qualitative Tukey test (5%) and Kruskal-Wallis (5%) respectively, although the data for embriodiagnosis were subjected to Fisher's exact test (5%). In experiment 1 there was no interaction between treatments (P> 0.05), verifying, however, differences (P <0.05) for some of the results. The machine did not influence incubate the eggs hatch (P> 0.05). Arrays with older age (59w) had higher rates of infertility (6.84%) and lower hatching rates (88.26%). The early embryonic mortality (0-4 d) was higher (5.47%) in the eggs of breeders 59w. The hatch window was lower (P <0.05) for eggs incubated in SS. The weight of the eggs hatched followed the age pattern, influencing the weights of newborns. The chicks from SS machines had higher birth weight, weight and net weight of the shipment (P <0.05). Chicks from the SS had higher quality physical scores and length. For the results of experiment 2 there was no interaction between the treatments for conductance or shell thickness (P> 0.05). The breeders aged influenced conductance being greater in eggs from breeders of 59w (0.323 mg d1-1 torr), the region of the shell being affected conductance region of the thin edge was lower (0.024 mg d-1 torr -1). The shell thickness was similar peel breeders derived from 29w or 35w, being higher (P <0.05) the thickness found in egg shells breeders 59w. The largest thickness found in the region of the pointy tip (P <0.05). There was an interaction (P <0.05) for the porosity of the eggshell conductance and bark. Regardless of age, the tip region has a higher number of large pores. Regarding age, the wide end regions of the equator and exhibit significant increases (P <0.05) pores. Weak correlations were found between the average conductance of the shell eggs and incubation parameters. Weak correlations were also observed between the average thickness of the eggshell and incubation parameters. There was a strong positive correlation (P <0.05) between the average porosity of the shell eggs and some parameters of incubation. It was concluded that both machines offer conditions for embryonic development without affecting the hatching rate, however the physical quality of the chicks was better in newborns chicks from the single stage machine. Yet, the technique using fragments of eggshell can be used to measure the conductance of the shell. The porosity of the eggshell was better correlated with parameters of incubation. / Objetivou-se avaliar a idade da matriz pesada e o tipo de máquina de incubação sobre os parâmetros de eclosão, a janela de nascimento, o embriodiagnóstico e a qualidade física dos pintos neonatos. Avaliou-se também a técnica de mensuração da condutância da casca dos ovos utilizando fragmentos de casca e ainda a correlação dos valores de condutância com parâmetros de incubação. No experimento 1 foi utilizado delineamento em DBC, sendo utilizando DIC para o embriodiagnóstico. Em esquema fatorial 2x3 - máquinas de estágio múltiplo (EM) ou único (EU) e idades da matriz pesada (29s, 35s e 59s). No experimento 2 delineamento foi em DBC. Em esquema fatorial 3x3 – região da casca do ovo (ponta larga, equador, ponta fina) e idades da matriz pesada (29s, 35s e 59s). As variáveis foram submetidas à análise de variância e as médias quantitativas e qualitativas comparadas pelo teste de Tukey (5%) e Kruskal-Wallis (5%) respectivamente, ainda os dados de embriodiagnóstico foram submetidos ao exato de Fisher (5%). No experimento 1 não houve interação entre os tratamentos (P>0,05), verificando-se, entretanto, diferenças (P<0,05) para alguns dos resultados. A máquina de incubar não influenciou a eclosão dos ovos (P>0,05). Matrizes com idade mais avançada (59s) tiveram maiores taxas de infertilidade (6,84%) e menores taxas de eclosão (88,26%). A mortalidade embrionária inicial (0-4 d) foi maior (5,47%) nos ovos de matrizes de 59s. A janela de eclosão foi menor (P<0,05) para os ovos incubados em EU. O peso dos ovos incubados seguiu o padrão etário, influenciando os pesos dos neonatos. Os pintos oriundos de máquinas EU tiveram maiores peso ao nascimento, peso na expedição e peso líquido (P<0,05). Pintos oriundos do EU tiveram maior escore de qualidade física e comprimento. Para os resultados do experimento 2 não houve interação entre a os tratamentos para condutância ou espessura da casca (P>0,05). A idade das matrizes influenciou a condutância sendo maior nos ovos oriundos de matrizes de 59s (0,323 mg d-1 torr-1), a região da casca afetou a condutância sendo que a região da ponta fina foi menor (0,024 mg d-1 torr-1). A espessura da casca foi similar em cascas oriundas de matrizes de 29s ou 35s, sendo superiores (P<0,05) a espessura encontrada nas cascas dos ovos de matrizes de 59s. A maior espessura foi encontrada na região da ponta fina (P<0,05). Houve interação (P<0,05) para a porosidade da casca dos ovos e a condutância da casca. Independente da idade, a região da ponta larga apresenta maior número de poros. Em relação à idade, as regiões da ponta larga e do equador apresentam aumentos significativos (P<0,05) de poros. Foram encontradas correlações fracas entre a condutância média da casca dos ovos e os parâmetros de incubação. Também foram encontradas correlações fracas entre a espessura média da casca do ovo e os parâmetros de incubação. Houve correlação positiva forte (P<0,05) entre a porosidade média da casca dos ovos e alguns parâmetros de incubação. Foi possível concluir que ambas as máquinas oferecem condições para o desenvolvimento embrionário sem afetar a taxa de eclosão, entretanto a qualidade física dos pintos neonatos foi melhor nos pintainhos oriundos da máquina de estágio único. Ainda, a técnica que utiliza os fragmentos de casca dos ovos pode ser utilizada para mensurar a condutância da casca. A porosidade da casca dos ovos foi mais bem correlacionada com os parâmetros de incubação.

Metal-organic frameworks are a new class of porous materials that have potential applications in gas storage, separations, catalysis, sensors, non-linear optics, displays and electroluminescent devices. They are synthesized in a "building-block" approach by self-assembly of metal or metal-oxide vertices interconnected by rigid linker molecules. The highly ordered nature of MOF materials and the ability to tailor the framework's chemical functionality by modifying the organic ligands give the materials great potential for high efficiency adsorbents. In particular, MOFs that selectively adsorb CO₂ over N₂, and CH₄ are very important because they have the potential to reduce carbon emissions from coal-fired power plants and substantially diminish the cost of natural gas production. Despite their importance, MOFs that show high selective gas adsorption behavior are not so common. Development of MOFs for gas adsorption applications has been hindered by the lack of fundamental understanding of the interactions between the host-guest systems. Knowledge of how adsorbates bind to the material, and if so where and through which interaction, as well as how different species in adsorbed mixture compete and interact with the adsorption sites is a prerequisite for considering MOFs for adsorptive gas separation applications. In this work, we seek to understand the role of structural features (such as pore sizes, open metal site, functionalized ligands, pore volume, electrostatics) on the adsorptive separation of CO₂, CO and N₂ in prototype MOFs with the help of molecular modeling studies (GCMC simulations). Our simulation results suggest that the suitable MOFs for CO₂ adsorption and separation should have small size, open metal site, or large pore volume with functionalized groups. Some of the experimental challenges in the MOF based adsorbents for CO₂ capture include designing MOFs with smaller pores with/without open metal sites. Constructing such type of porous MOFs can lead to greater CO₂ capacities and adsorption selectivities over mixtures of CH₄ or N₂. Therefore, in the second project, we focused on design and development of small pore MOFs with/without open metal sites for adsorptive separation of carbon dioxide from binary mixtures of methane and nitrogen. We have synthesized and characterized several new MOFs (single ligand and mixed ligand MOFs) using different characterization techniques like single-crystal X-ray diffraction, powder X-ray diffraction, TGA, BET, gravimetric adsorption and examined their applicability in CO₂/N₂ and CO₂/CH₄ mixture separations. Our findings from this study suggest that further, rational development of new MOF compounds for CO₂ capture applications should focus on enriching open metal sites, increasing the pore volume, and minimizing the size of large pores. Flue gas streams and natural gas streams containing CO₂ are often saturated by water and its presence greatly reduces the CO₂ adsorption capacities and selectivities. So, in the third project, we investigated the structural stability of the developed MOFs by measuring water vapor adsorption isotherms on them at different humid conditions to understand which type of coordination environment in MOFs can resist humid environments. The results of this study suggest that MOFs connected through nitrogen-bearing ligands show greater water stability than materials constructed solely through carboxylic acid groups.

Šio darbo literatūros apžvalgoje aptariami plazmos tipai, plazmos charakteristikos bei sąveika su medžiaga. Aptariama plazminės implantacijos technologija. Trumpai apibūdinama vandens garų plazma ir jos panaudojimas. Apžvelgiama titano oksido struktūra bei jo panaudojimas katalizatorių gamybai, kurie gali būti skirti skaldyti vandens molekules ir gaminti vandenilį. Darbe paaiškinamas magnetroninis nusodinimas bei jo privalumai. Darbo metu buvo oksiduojamas titanas vandens garų plazmoje. Titano oksidacija priklauso nuo daugybės plazmoje vykstančių procesų (adsorbcija, sulaikymas, vakansijų susidarymas ir pan.). Titano oksido panaudojimas yra labai platus dabartiniu metu. Aptariama šio eksperimento technologija bei atliekama oksiduotų titano dangų analizė. SEM, XRD, AES, GDOES analizės metodais buvo tiriama titano dangos oksidacija ir aiškinamas oksidacijos mechanizmas. / Types of plasma, characteristics and plasma interaction with solids are discussed in the literature review of this paper. Also, the plasma immersion ion implantation are described. Water vapour plasma are briefly discussed. Titanium oxide structure and it‘s usage for catalyst which could split water molecules are reviewed. Magnetron deposition are explained in this paper. The titanium film was oxidized by water vapour plasma on experiment. The oxidation of titanium depends on many processes in plasma (adsorption, trapping, formation of oxygen vacancies and etc.). Appliance of titanium oxide is very large in recent times. Experimental technology are discussed and plasma treated films are analysed. Titanium oxidation was analysed by SEM, XRD, AES, GDOES. Oxidation mechanism was explained in this paper.