The durability of thermal barrier coatings (TBCs) affects the life of the hot section engine components on which they are applied. Fatigue is the general failure mechanism for such components and is responsible for most unexpected failures; therefore it is desirable to develop lifetime approximation models to ensure reliability and durability. In this study, we first examined the microstructural degradation of air plasma sprayed ZrO2-8wt.%Y2O3 TBCs with a low-pressure plasma sprayed CoNiCrAlY bond coat on an IN 738LC superalloy substrate. The durability of TBCs were assessed through furnace thermal cyclic tests carried out in air at 1100°C with a 1-, 10-, and 50-hour dwell period, preceded by a 10-minute heat-up and followed by a 10-minute forced-air-quench. Failure mechanisms of the TBCs were thoroughly investigated through materials characterization techniques including: X-Ray Diffraction, Scanning Electron Microscopy, and Energy Dispersive X-Ray Spectroscopy. Quantitative microstructural analyses were then carried out to document the growth of the thermally grown oxide (TGO) scale, the depletion of the Al-rich β-NiAl phase in the bond coat, and the population and growth of micro-cracks near the YSZ/bond coat interface. Trends in the TGO growth and the β-phase depletion in the bond coat followed those of diffusion-controlled processes—parabolic growth of the TGO and exponential depletion of the β-phase. Formation and propagation of cracks within the YSZ resulted in complete spallation of the YSZ topcoat from the bond-coated superalloy substrate. Evolution in these microstructural features was correlated to the lifetime of TBCs, which showed cracking within the YSZ to be the cause of failure; thus a lifetime iv approximation model was developed, via modification of Paris Law, based on the experimental data. The model predicted the TBC lifetime within 10% of the experimental lifetime.

Lead and cadmium frequently occur together as contaminants in polluted environments such as roadsides, urban areas, mines, and smelters. Few studies have been conducted to examine the possible interactive effects these metals may have on reproduction of wild species. The first part of this study was directed toward examining the effects of low level dietary lead and cadmium on reproduction in Peromyscus Jeucopus. Two laboratory studies were conducted. Treatment with combinations of 0, 1 or 4 μ/g lead acetate and/or cadmium chloride was found to have no effect on overall health or reproductive ability of white-footed mice. In a second, experiment mice were treated with combinations of 0 or 10 μg/g lead acetate and/or cadmium' chloride. Treatment was continued through three generations of mice (P1, Fl, F2); progeny of the P1 were paired with nonrelatives in the same group and continued on the same treatment. Percentage-of pairs producing at least one litter in a ten week period was reduced in mice receiving both lead and cadmium. By the F2 generation only one of ten pairs produced offspring. There were minor variations in litter parameters (# pups/litter, birth weight, weanling weight and viability of litters) measured for the three generations; however, treatment did not appear to greatly affect litters in those pairs which had litters. In the P1 generation kidney weights were lower in mice receiving lead and epididymidis weight was higher in mice receiving cadmium. Mice (P1) receiving cadmium and lead had lower numbers of spermatozoa/mg testis. Lead content of carcass, liver and kidneys was analyzed in mice from the P1 generation. The second part of this study examined the persistence of lead in the environment after the source of contamination has been removed. Short-tailed shrews (Blarina brevicauda) trapped in an orchard with a history of lead arsenate use had higher whole body lead concentrations than individuals of the same species trapped in a control orchard. Within the treated orchard lead concentrations in pine voles (Microtus pinetorum) were significantly higher than concentrations in short-tailed shrews. / Master of Science

La technologie de projection plasma sous basse pression a attiré l’attention de nombreux chercheurs comme une nouvelle technique qui permet d’établir un pont entre la projection thermique conventionnelle et le dépôt physique en phase vapeur. Ainsi, cette technologie étend les limites de projection thermique classique et augmente également la vitesse de croissance des dépôts par rapport aux procédés PVD ou CVD classiques. Cette technique peut évaporer totalement ou partiellement les poudres injectées et mener à la réalisation de revêtements à microstructure colonnaire et/ou plus denses, difficiles à réaliser avec des procédés de projection thermique conventionnels. La projection plasma de suspension a été effectuée pour la première fois sous basse pression. L’injection axiale de suspension avec une torche tri-cathodes permet d’augmenter l’échange enthalpique entre le jet de plasma et les poudres après l’évaporation du solvant. La spectroscopie à l’émission optique (OES) a été utilisée pour estimer la température électronique et vérifier l’existence de phase vapeur d’YSZ dans le jet de plasma. Finalement, des revêtements plus denses furent réalisés (comparés à ceux préparés par projection plasma de suspension à pression atmosphérique présentant des particules fondues, agglomérées et de la condensation de vapeur. Des tests de nano-indentation instrumentée ont été effectués sur la surface polie des dépôts réalisés. Les résultats montrent des valeurs de 5,8 GPa pour la dureté et 114,5 GPa pour le module d’élasticité, augmentant de 61% et 31%, respectivement, en comparaison avec les valeurs obtenues par SPS sous atmosphère ambiante. Les essais de projection de poudre YSZ agglomérée ont été réalisés avec une torche F4-VB dans le but de synthétiser une phase vapeur d’YSZ. On observe que les dépôts peuvent se former derrière les échantillons en céramique, sans vis-à-vis du plasma, par condensation de vapeur. En face de cette torche, des revêtements composites ont été obtenus par un mélange de poudres fondues et condensation de vapeur, simultanément. Cependant la quantité de phase vapeur est très faible dans le jet de plasma. Pour comprimer ce jet sous basse pression et afin d’améliorer l’échange d’enthalpie entre le jet de plasma et les poudres injectées, une buse rallongée a été mise en place sur la torche F4-VB. Les revêtements présentent ainsi une microstructure plus dense. Ceci est attribué à la haute vitesse des particules fondues vers le substrat suite à l’utilisation de la buse modifiée. Ce type de revêtement montre une valeur maximale de microdureté Vickers de 1273 Hv100 g. Par ailleurs, la réalisation de dépôts de carbures a été effectuée. Les résultats montrent la possibilité de former des carbures par projection plasma sous basse pression. Les revêtements composites (TiC/Ti) sont déposés par projection plasma réactif sous basse pression en utilisant le méthane comme gaz porteur. La température électronique Te calculée est d’environ 6200 K selon les résultats d’OES, ce qui est supérieur à la température d’ébullition du Ti et de TiC. Le revêtement de Ti pur présente une microstructure dense alors que TiC/Ti présente une microstructure lamellaire. Cependant, la quantité de TiC dans les revêtements est d’environ 20 vol.%. La microdureté Vickers, effectuée sur surface polie, a tendance à diminuer de 846±152 à 773±86 Hv100 g avec l’augmentation de la distance de projection. / As a new technology, the very low pressure plasma spraying has attracted attentions of many researchers, making it possible to establish a bridge between the conventional atmospheric plasma spraying (APS) and the vapor deposition (PVD or CVD). As a result, this new technology enlarges the limitation of APS and increases the deposition rate in comparison with the PVD or CVD. It is possible to evaporate partially the injected material and even evaporate completely and finally realize the columnar or dense coatings from the vapor or the mixture of vapor and liquid. The suspension plasma spraying is performed for the first time at low pressure. Taking consideration of the configuration of the three-cathode torch, the axial injection of the suspension is conducted which can increase the enthalpy change between the plasma jet and the sprayed material. The data of optical emission spectroscopy (OES) could be used to calculate the electron temperature and verify the existence of vapor of YSZ in the plasma jet. Finally, the dense coating was prepared by suspension plasma spraying at low pressure, which is composed of the melted particles, the agglomerated particles and the vapor deposition. The test of nano-indentation is conducted on the polished surface. It shows a value of 5.8 GPa for the microhardness and 114.5 GPa for the elastic modulus, increasing 61% and 31%, respectively, compared with the values obtained by SPS in the ambient atmosphere. In this study, another torch F4-VB is also conducted even of it has a low power in compared with that of O3CP torch. The powder feed rate is reduced to about 1.5 g·min-1 to achieve the vapor of YSZ taking the low power input of the torch into consideration. The columnar structure coating is realized from vapor deposition out of line of sight of projection upon the ceramic tubes. The composite structure coating is deposited by the mixture of melted particles and the vapor deposition simultaneously in front of this torch. But the quantity of vapor of YSZ is low in plasma jet. In order to compress the larger plasma jet and then improve the enthalpy change between the plasma jet and sprayed particles, an extended nozzle is prepared. It shows that the coating has a dense structure, which can be attributed to higher velocity of the melted powders. The coating shows a maximum value of microhardness Vickers up to 1273 Hv100 g. The composite coating of TiC/ Ti is realized by reactive plasma spraying using the methane as the carrier gas. The electron temperature Te is calculated to be 6200 K, which is over the boiling point of TiC and Ti. The coating Ti shows a dense structure and the composite coating TiC/Ti shows a lamellar structure. But the quantity of TiC in the composite coating is very low, about 20 vol.%. The Vickers microhardness is performed on the polished surface. It shows a decreasing tendency from 846 ± 152 to 773 ± 86 Hv100g with the increase of spraying distance. The tribological test is also implemented showing a high value of the coefficient of friction of 0.78 to 0.85, which can lead to a high abrasion. In order to synthesize a larger quantity of TiC in the composite coating, a higher power input torch should be put into action in the future.

The work presented here pertains to investigations on gas-on-liquid type of impinging injectors with a generic approach with prospective applications in several areas, and at places with particular emphasis on cryogenic or semi-cryogenic liquid propellant rockets. In such rockets, one of the components arrives at the injector in a gaseous phase after passing through the regenerative coolant passages or a preceding combustion stage. Most often, the injectors in such systems are of shear coaxial type. The shear coaxial injectors suffer from several disadvantages like complexity in design, manufacture and quality control. Adoption of impinging jet configuration can alleviate these problems in addition to providing further benefits in terms of cost, robustness in high temperature environment and manifolding. However, there is very little literature on gas-on-liquid injectors either in this context or in any other Even for the simplest form of impinging injectors such as like-on-like doublets, literature provides no conclusive direction at describing a spray from the theoretical models of physical mechanisms. Empirical approach is still the prime mode of obtaining a proper understanding of the phenomena. Steady state spray characterization includes mainly of describing the spatial distribution of liquid mass and drop size distribution as a function of geometric and injection parameters. The parameters that are likely to have an impact on spray characteristics are orifice diameter, ratio of orifice length to diameter, pre-impingement length of individual jets, inter orifice distance, impingement angle, jet velocity and condition of the jet just before impingement. The gas-on- liquid configuration is likely to experience some qualitative changes because of the expansion of the gas jet. The degree to which each one of the above variables influences the drop size and mass distribution having implication to combustion performance forms the core theme of the thesis. A dedicated experimental facility has been built, calibrated and deployed exhaustively. While spray drop size measurement is done largely by a laser diffraction instrument, some of the cases warranted an image processing technique. Two different image processing algorithms are developed in-house for this purpose. The granulometric image processing method developed earlier in the group for cryogenic sprays is modified and its applicability to gas-on-liquid impinging sprays are verified. Another technique based on the Hough transform which is feature extraction technique for extracting quantitative information has also been developed and used for gas-on-liquid impinging injectors. A comparative study of conventional liquid-on-liquid doublet with gas-on-liquid impinging injectors are first made to establish the importance of studying gas-on-liquid impinging injectors. The study identifies the similarities and differences between the two types and highlights the features that make such injectors attractive as replacements to coaxial configuration. Spray structure, drop-size mass distributions are quantified for the purpose of comparison. This is followed by a parametric study of the gas-on-liquid impinging injectors carried out using identified control variables. Though momentum ratio appeared to be a suitable parameter to describe the spray at any given impingement angle, the variations due to impingement angle had to be factored in. It was found that normal gas momentum to liquid mass is an apt parameter to generalize the spray characteristics. It was also found that using identical nozzles for desired mass ratio could lead to rather large deflection of the spray which may not be acceptable in combustion chamber design. One way of overcoming this is to work with unequal orifice sizes for gas and liquid. It was found that using smaller gas orifice for a given liquid orifice resulted in lower SMD (Sauter Mean Diameter of the spray) for constant gas and liquid mass flow rates. This is attributable to the high dynamic pressure of gas in the case of smaller gas orifices for the same mass flow rate. The impinging liquid jets with unequal momentum in the doublet configuration would result in non-uniform mass and mixture ratio distribution within the combustion chamber which may have to operate under varying conditions of mass flow rates and/or mixture ratio. The symmetrical arrangement of triplet configuration can eliminate this problem at the same time generating finely atomized spray and a homogeneous mixture ratio. In view of the scanty literature available in this field, the atomization characteristics of the spray generated by liquid centered triplet jets are examined in detail. It was found that as in the case of gas-on-liquid impinging doublets, normal gas momentum to liquid mass is an ideal parameter in describing the spray. Variants of this configuration are studied recently for many other applications too. As done in the case of doublets, efforts have also been made to compare gas centered triplet to liquid-liquid triplet. It was found that the trend of SMD of gas centered triplet is different from that of liquid-liquid triplets, thus pointing to a different mechanism in play. The SMD in the case of liquid-liquid triplets decreases monotonically with increasing specific normal momentum. It is to be noted that specific normal momentum is an ideal parameter for describing the spray characteristics of liquid-liquid triplets and doublets. In the case of gas centered triplet the SMD first increases and then decreases with specific normal momentum, the inversion point depends on the gas mass flow rate for a constant specific normal momentum. The thesis concludes with a summary of the major observations of spray structures for all the above injector configurations and quantifies the parametric dependencies that would be of use to engineering design

Thesis (MScAgric)--University of Stellenbosch, 2005. / ENGLISH ABSTRACT: Various studies revealed that Botrytis cinerea, the causal pathogen of Botrytis bunch rot, is mostly associated with pedicels, rachises, laterals and berry bases, and not with berry skins as previously understood. Provided that sufficient coverage of inner bunch parts was achieved, laboratory studies have shown that fungicides can effectively reduce the amount of B. cinerea at the various positions in bunches, and prevent infection and symptom expression at all growth stages. The same efficacy was, however, not achieved with the same fungicides when using conventional spraying methods in vineyards. Poor disease control on fruit and leaves in vineyards is attributed to inappropriate timing of fungicide applications and/or insufficient coverage of susceptible tissue. Previously, spray coverage evaluations in South Africa were based on the use of water-sensitive cards. A variety of other methods have been used to assess spray coverage in vineyards, but none of these methods could assess spray deposits on a very small, three-dimensional area of interest such as the susceptible grape bunch parts. The methods were furthermore dependent on human objectivity, which lacks quantitative measuring and speed of measurement. Suitable technology to determine spray coverage on susceptible bunch parts is, therefore, not available. The aim of this study was to develop a protocol to visualise and quantify spray deposits in grape bunches, specifically on the inner bunch parts and to use the protocol to determine the effect of different levels of spray cover on artificially inoculated B. cinerea grape bunches, in order to facilitate future determination of minimum effective coverage levels for effective B. cinerea control. A spray coverage assessment protocol using fluorometry, photomicrography and digital image analyses was developed to measure spray coverage on susceptible grape bunch parts. Among several fluorescent pigments tested, a yellow fluorescent pigment (SARDI Fluorescent Pigment) from Australia was selected on the basis of its small particle size (2.45 - 4.90 μm). Bunches were sprayed at pea size and bunch closure with different volumes of a mixture of fenhexamid and the yellow fluorescent pigment. Sprayed parts from bunches were illuminated under black light (UV-A light in the 365 nm region) and visualised under a stereo microscope at 20 x magnification. Photos of the berry skin, pedicel and rachis were taken with a digital camera (Nikon DMX 1200). Image analysis of photos was done with Image- Pro Discovery version 4.5 for Windows (Media Cybernetics) software. The total area of deposited pigment in selected areas of interest (AOI) was calculated. The percentage area covered was subsequently calculated for each AOI. Good correlation was evident between the parameters, sum of objects and percentage area covered. Bunch parts at pea size generally had higher coverage values than at bunch closure. Spray applications earlier in the season would therefore result in higher and more effective spray coverage of the susceptible bunch parts. Similar deposition trends were observed on the inner bunch parts (pedicel and rachis). These were, however, significantly different from berry skins, which had significantly higher levels of spray deposits than the inner bunch parts. The variance component analysis indicated that the highest variance was observed for berries and bunches, and substantially less for image readings. For the same accuracy, means for percentage coverage values of at least 10 bunches per treatment (1 part per bunch and 3 readings per part) will be sufficient. In order to determine the biological efficacy of different levels of spray coverage on B. cinerea incidence on grape bunches, bunches were sprayed at pea size and bunch closure with different volumes of a mixture of fenhexamid and a yellow fluorescent pigment and the percentage fluorescent pigment coverage on pedicels was determine. Bunches were subsequently dusted with dry airborne conidia of B. cinerea in a settling tower and incubated for 24 h at high relative humidity (98%). Infection was determined by estimating the amount of B. cinerea infections occurring on sprayed bunch parts with isolations on to paraquat and Kerssies mediums. Linear regressions for the part x stage combinations of percentage B. cinerea incidence on different bunch parts were fitted on mean coverage levels. An increase in spray cover caused linear reductions in levels of B. cinerea on susceptible bunch parts. Higher B. cinerea incidences were recorded at pea size. Furthermore, higher B. cinerea incidences were found on paraquat medium for both stages, than on Kerrsies medium. The information gathered from this study will be used to facilitate future determination of minimum effective coverage levels for effective B. cinerea control in grape bunches. In these validation experiments, the results clearly showed that the protocol can be used to determine the effect of different levels of spray coverage on B. cinerea incidence and that an increase in spray coverage will decrease B. cinerea incidence. The information gathered from this study will be used to facilitate future determination of minimum effective coverage levels for effective B. cinerea control in grape bunches and subsequently be used as benchmarks to evaluate spray application in vineyards. / AFRIKAANSE OPSOMMING: Vaalvrot by wingerde word veroorsaak deur Botrytis cinerea. Verskeie studies het getoon/gewys dat die oorsaaklike patogeen meestal geassosieer word met die pedisel, ragis, laterale en die korrelbasis, en nie met die korrelskil soos voorheen beweer nie. Laboratorium studies het getoon dat swamdoders wel effektief is om B. cinerea by alle trosdele te verminder en simptoomontwikkeling te voorkom tydens alle groeistadia, mits die binne-trosdele voldoende spuit bedekking ontvang het. Dieselfde effektiwiteit is egter nie gevind in wingerde met konvensionele spuittegnieke nie. Onvoldoende siektebeheer van vrugte en blare van wingerde kan toegeskryf word aan verkeerde spuit skedulering en/of swak spuitbedekking van vatbare gasheerweefsel. Evaluering van spuitbedekking is voorheen in Suid Afrika deur middel van water-sensitiewe papier gedoen. Verskeie ander metodes is al gebruik om spuitbedekking te evalueer in wingerde, maar nie een van hierdie metodes kan gebruik word om spuitbedekking op ’n baie klein, drie-dimensionele oppervlak, soos die vatbare trosdele, te evalueer nie. Verder was die tegnieke afhanklik van menslike objektiwiteit, en gevolglik ontbreek kwantitatiewe meting en metingspoed. Daar is dus nie geskikte tegnologie vir die evaluering van spuitbedekking op vatbare trosdele nie. Die doel van hierdie studie was die ontwikkeling van ‘n protokol vir die visualisering en kwantifisering van spuitbedekking op spesifiek die binne-tros dele en om die protokol dan te gebruik om die effek van verskillende vlakke van spuitbedekking op B. cinereageinokuleerde druiwetrosse te bepaal, Protokol vir evaluasie van spuitbedekking op vatbare druifdele is ontwikkel deur gebruik te maak van fluorometrie, fotomikrografie en digitale beeldanalise. Van die verskillende fluoresensie pigmente wat getoets is, is ‘n geel flouresensie pigment (SARDI Flourescent Pigment) van Australië gekies op grond van sy klein partikelgrootte (2.45 - 4.90 μm). Druiwetrosse is gespuit tydens ertjie- en trostoemaakstadia met verskillende volumes van ’n mengsel van fenheksamied en die geel fluorosensie pigment. Die gespuite druifdele is dan verlig onder swartlig buise (UV-A lig in die 365 nm spektrum) en gevisualiseer deur ’n stereo mikroskoop by 20x vergroting. Foto’s van die korrelskil, pedisel en ragis is met ‘n digitale kamera (Nikon DMX 1200) geneem. Beeldanalise is gedoen met ImagePro Discovery weergawe 4.5 vir Windows (Media Cybernetics) sagteware. Die totale area neerslag van die pigment is in geselekteerde areas bereken. Die presentasie area bedek is bereken vir elkeen van hierdie areas. Goeie korrelasie is gevind tussen die parameters aantal fluoresserende partikels en die persentasie bedekte area. Trosdele tydens ertjie-stadium het in die algemeen hoër waardes gehad as by trostoemaak. Dit blyk dus dat spuittoediening vroeg in die seisoen meer effektief sal wees vir die bedekking van vatbare trosdele. Soortgelyke bedekkings patrone is gevind by die binne trosdele (pedisel en ragis). Dit het egter betekenisvol verskil van die korrelskil, wat betekenisvol meer spuitbedekking as die binne trosdele gehad het. ’n Variasie komponent analise het getoon dat die meeste variasie gevind is tussen korrels en trosse, en heelwat minder vir die beeld analise lesings. Om dieselfde akkuraatheid te behou, is ten minste 10 trosse per behandeling (1 deel per tros en 3 lesings per deel) nodig. Vir die bepaling van biologiese effektiwiteit van verskillende vlakke van spuitbedekking op B. cinerea voorkoms op druiwe, is druiwe gespuit tydens ertjie- en trostoemaak-stadia met verskillende volumes van ’n mengsel van fenheksamied en die geel fluorosensie pigment. Die persentasie fluoresensie pigment is bepaal op die pedisels. Trosse is vervolgens geinokuleer met droë luggedraagde konidia van B. cinerea in ’n inokulasietoring en geïnkubeer vir 24 h by hoë relatiewe humiditeit (98%). Die voorkoms van B. cinerea infeksie op gespuite tros dele is bepaal deur middel van isolasies op paraquat en Kerssies medium. Liniêre regressies vir trosdeel x stadium kombinasies van persentasie B. cinerea voorkoms op verskillende trosdele is gepas vir gemiddelde bedekkings waardes. ’n Verhoging in spuit bedekking het ‘n liniêre vermindering van B. cinerea voorkoms op vatbare trosdele veroorsaak. Verder is hoër vlakke van B. cinerea op paraquat medium as op Kerssies medium vir beide die groeistadia gevind. Die kennis wat verkry is uit hierdie studie sal gebruik word om minimum effektiewe spuitbedekkingsvlakke vir die beheer van B. cinerea op druiwetrosse te bepaal.

Baigiamajame magistro darbe nagrinėjamos vibromechaniškai veikiamų perlydymo metu purkštinių NiCrBSi dangų savybės. Dangos pailgina mašinų, metalinių gaminių bei konstrukcijų eksploatacinį resursą, taupo medţiagas, apsaugo metalus nuo korozijos, agresyvios aplinkos poveikio. Terminis purškimas – vienas populiauriausių dangų dengimo būdų. Darbe pateikta terminio purškimo technologijų, purkštinių dangų savybių tyrimo metodų bei vibromechaninio apdorojimo taikymo apžvalga. Dangų purškimui bei perlydymui naudotas robotizuotas stendas. Atlikti dangos mikrostruktūros, porėtumo, kietumo, mikrokietumo bei atsparumo dilimui tyrimai, suformuluotos darbo išvados. Darbą sudaro šešios dalys: įvadas, literatūros analizė, eksperimentiniai tyrimai, tyrimų rezultatai, išvados, literatūros sąrašas. Darbo apimtis – 62 p. teksto be priedų, 24 iliustr., 15 lent., 35 bibliografiniai šaltiniai. / In the final master thesis the research of vibromechanical treatment of thermal sprayed NiCrBSi coatings during refuse process is completed. Coatings prolong machines, metal products and constructions worktime, save materials and protect metals from corrosion and impact of aggressive environment. Thermal spraying is one of the most common covering method. Review of thermal spraying techniques, methods of thermal sprayed coating properties analysis and application of vibromechanical treatment is given. Robot was used for covering and refusing the coating. Coatings microstructure, porosity, hardness, microhardness and wear test analysis were done. Conclusions are formulated. Structure: introduction, literature review, experimental researches, results, conclusions, references. Thesis consist of 62 p. text without appendixes, 31 pictures, 15 tables, 35 bibliographical entries.

Doctor of Philosophy / Department of History / James E. Sherow / This dissertation contributes to the environmental, agricultural, and technological history of the modern United States by examining pesticide use and the debates surrounding them in the Great Plains from the 1940s to the 1980s. Specifically, it addresses the relationships among aerial sprayers, farmers, agriculturalists, and grassroots concepts of toxicity that emerged from mid-century technological and environmental changes. It argues that pesticides as well as a variety of weeds and insects actively transformed the tools, attitudes, and regulatory policies of their users. Historians of agricultural chemical use in America have focused on the political debates over DDT, the social activism against pesticides that Rachel Carson inspired with her best-selling book Silent Spring (1962), the growth in federal regulatory policy in the 1970s, and the contentious reactions by the chemical and agricultural industries. This study offers a new, ground-level history of pesticides by showing how aerial sprayers, farmers, and agriculturalists developed custom chemical applications and conceptualized toxicity as each related to the technological and environmental changes in the region. Drawing on multiple sources, including agricultural experiment station reports, scientific studies, government documents, farm journals, landowner and aerial spray pilot correspondence, and oral histories, this study explores how local producers changed with their chemicals, spray planes, and pests to develop an environmental ethos that understood toxicity as a synthetic and natural danger. Although opposition to pesticides became central to modern environmentalism, debates around pesticides‘ effectiveness and dangers did not come only from activists or government regulators. Beginning just after World War II, landowners and spray pilots in the fields and rural airstrips of the Great Plains took the hazards of agricultural chemicals seriously, critiquing how and why pesticides were used for decades after. By viewing chemicals, spray planes, and pests, as well as landowners, pilots, and agriculturalists as equal forces in the regional transformation of farming landscapes, this dissertation highlights a new history of pesticides, agriculture, and the environment. Farmers and custom applicators did not simply follow the economic goals of agribusiness. Nor did they dismiss the dangers of pesticides. Rather, they constructed their own standards of injury and environmental risk that stressed accuracy, regulation, and a reasonable certainty of safety—a result of the equally transformational influences of chemicals, pests, and the region. This study finally offers new insights into the creation of national chemical policy and the regulatory debates over pesticides during the 1960s and 1970s.

Dans le cadre de la pulvérisation agricole, la diminution de la quantité des intrants est devenue une étape cruciale, et ce notamment en viticulture. La pulvérisation de précision en viticulture implique cependant une maitrise conjointe du matériel utilisé, des produits et de la répartition de ces produits sur le feuillage. Dans ce contexte, nombreuses sont les recherches menées sur l’optimisation d’utilisation des produits phytosanitaires, leur objectif final étant de réduire de manière significative la quantité d’intrants dans la culture. Cependant, peu de travaux ont été effectués sur l’étude du comportement des produits directement sur le feuillage, ce qui constitue donc l’objectif de cette thèse. La première partie de ce travail est consacrée particulièrement à l’analyse de l’état de la surface foliaire, en se focalisant spécifiquement sur l’étude de la rugosité de surface de la feuille qui constitue un paramètre essentiel dans le processus d’adhésion du produit pulvérisé sur la feuille. L’analyse de la surface de la feuille est réalisée en déterminant les caractéristiques texturales extraites d’images microscopiques. Un nouvel indicateur de rugosité est proposé ainsi que, des paramètres spatiaux et fréquentiels sont utilisés pour estimer et la rugosité de la feuille. Ces paramètres permettent ensuite la caractérisation de l’homogénéité de la surface et la détection des nervures/poils au niveau de la surface de la feuille. Cette partie représente une base fondamentale pour mieux comprendre le comportement des gouttelettes pulvérisées sur la feuille de vigne. La deuxième partie de ce travail de thèse est consacrée à des études expérimentales, qui ont pour but de définir et construire des modèles statistiques permettant d’estimer la quantité de produit restant sur la feuille ou la surface occupée par les gouttes. Ces modèles prennent en considération différents paramètres de pulvérisation, tels que la taille de la goutte et sa vitesse, la tension superficielle du produit, l’angle d’inclinaison et la rugosité de la surface de la feuille. Ces modèlespourraient être vus comme des outils de décision communs pour optimiser la quantité du produit pulvérisé et l’estimation du produit restant sur la feuille, et comme un outil d’aide pour optimiser les bancs d’essais et de tests de la qualité de la pulvérisation. / In the context of agricultural spraying, reducing the amount of input became a crucial step particularly in viticulture. The development of spraying precision in this domain needs the mastery of the use of spray equipment, product and distribution of these products on the foliage. In this area, many research have been done, their main goal being to optimize the use of plant product protection and to reduce significantly the input quantity inside the culture. However, few research has been done on the behavior of the product directly on the foliage which constitutes finally the main goal of this thesis. The first part of this report deals particularly with the analysis of leaf surface state by focusing precisely on the leaf surface roughness, one of the main parameters in product adhesion process. A leaf surface analysis is performed by determining the textural features extracted from microscopic images. A new roughness indicator is proposed and, spatial and frequency parameters were used to estimate and characterize the leaf roughness. These parameters allow both the characterization of surface homogeneity and the detection of the presence of rib/hair on the leaf surface. Indeed, this part represents a fundamental basis for understanding the spray droplet behavior on the vine leaf. The second part of this thesis deals with experimental studies which aim to define and to create statistical models to estimate the amount of product remaining on the leaf surface or the surface occupied by droplets. These models consider different spray parameters, such as droplet size and velocity, surface tension of the product, slope angle and roughness of the leaf. These models could be seen as aid-decision tools to optimize the amount of spray and the estimated product remaining on the leaf.

Orientador: Dagoberto Martins / Banca: Mario Sergio Tomazela / Banca: Sidnei Roberto de Marchi / Banca: Fernando Tadeu de Carvalho / Banca: Eduardo A. Lemus Erasmo / Resumo: O objetivo deste trabalho foi avaliar a deposição proporcionada por diferentes pontas e volumes de calda de pulverização sobre a cultura do milho e duas espécies de plantas daninhas presentes na linha e entrelinha da cultura em duas épocas de aplicação. O estudo em campo foi conduzido na Faculdade de Ciências Agronômica - FCA/UNESP, campus de Botucatu/SP, e as análises laboratoriais foram realizadas no Núcleo de Pesquisas Avançadas em Matologia / FCA. O milho foi semeado em espaçamento de 0,8 m, com 7 plantas/m. Sementes de Euphorbia heterophylla e Brachiaria plantaginea, foram semeadas e em média obteve-se 222,1 e 164,3 plantas/mø, respectivamente. Os tratamentos foram constituídos de duas pontas (DG 11002VS, TX08) e dois volumes de pulverização (100 e 200 Lha-1). Aos 13 dias após a germinação do milho realizou a primeira aplicação, pulverizando uma calda com corante alimentício azul brilhante FDC-1, a uma concentração de 3000 ppm. Para tal, foi utilizado um pulverizador costal pressurizado a CO2 com pressão constante de 30 l/polø, equipado com uma barra de pulverização com quatro bicos. Após a aplicação, coletaram-se 20 plantas daninhas de ambas as espécies presentes na linha e entrelinha do milho, e em seguida coletaram-se 20 plantas de milho. As plantas coletadas foram colocadas em sacos plásticos nos quais as plantas daninhas foram lavadas com 35,7 ml e o milho com 100 ml de água destilada. Após a lavagem as plantas foram colocadas em sacos de papel e levadas para estufa de ventilação forçada para secagem. Aos 26 dias após o início da germinação do milho realizouse segunda aplicação, com procedimentos idênticos ao da primeira, com exceção para coleta e lavagem. As plantas de milho foram divididas em ápice e base e a quantidade de água de lavagem, nesta ocasião, foi de 100 ml para as plantas daninhas e 300 ml para o milho... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The objective of this reseach was to evaluate the deposition of different nozzles and spraying volumes on maize crop and two species of weed in the line and space between lines at two application times. The field trial was carried in the Faculdade de Ciências Agronômica - FCA/UNESP, campus of Botucatu/SP, and the laboratories analyses had been carried through in the Núcleo de Pesquisas Avançadas em Matologia from FCA. The maize was sown in space of 0,8 m, with 7 plants/m. Seeds of Euphorbia heterophylla and Brachiaria plantaginea had been sown and in 164.3 average it got 222.1 plants/mø, respectively. The treatments had been constituted of two nozzles (DG 11002VS, TX08) and two spraying volumes (100 and 200 Lha-1). After 13 days the germination carried through the first application, spraying with brilliant blue FDC-1 tracer solution (3000 ppm). It was used a back pack sprayer pressurized by CO2 at 30 l/polø, equipped with spraying bar with four nozzles. After the application, were collected 20 plants of both weeds and crop in the line and space between lines of the maize. The collected had been put in plastic bags in which the weed had been washed with 35,7 ml and the maize with 100 ml of distilled water. After the plants had been put in bags of paper to drying. After 26 days the germination beginning of the maize carried through the second spraying, with identical procedures to the first one, with exception for the maize plants, which had been divided in apice and base and, the amount of water, with the tracing but in two case had been 100 ml to weed and 300 ml to the maize. The samples obtained were analyzed through spectrophotometer at wavelength of 630 nm. Just to determine the tracer concentration. The plants stadium influenced the spraying drift. In the crop, the spraying deposition was depended of the stadium, type of nozzles and volume of application... (Complete abstract, click electronic access below) / Doutor

Neste trabalho, estudou-se a viabilidade da aplicação de revestimentos de ferro fundido branco multicomponente (FFBMC) pelo processo de aspersão térmica por chama hipersônica (HVOF). A melhor condição de aspersão, variando-se a vazão e razão dos gases oxigênio e propano, a distância de aspersão e a granulometria do pó, foi utilizada para aplicação dos revestimentos em substratos de aço e de FFBMC com e sem preaquecimento. Caracterizaramse os revestimentos de FFBMC em relação ao teor de carbono, temperatura final, espessura, porosidade, dureza, aderência, perda de massa, coeficiente de atrito e mecanismo de desgaste abrasivo. Os revestimentos com menor porosidade e maior dureza foram aqueles depositados com razão oxigênio/propano de 4,6, 200 mm de distância de aspersão e granulometria entre 20 e 45 μm. Com esses parâmetros obtiveram-se revestimentos com aderência de 84 MPa, em substratos de aço sem preaquecimento e temperatura final de 200 °C, sendo que o fator mais importante no valor da aderência foi a temperatura final do revestimento. Além disso, a perda de massa foi semelhante aos valores obtidos para amostras de FFBMC fundidas, temperadas e revenidas. Os fatores responsáveis por estes valores foram a eliminação da austenita retida e a sinterização das partículas do revestimento quando as amostras foram temperadas e revenidas. O mecanismo de desgaste predominante foi o microcorte associado à fratura das lamelas próximas das partículas não fundidas, poros de aspersão e dos vazios formados no processo de desgaste. Considerando os níveis de aderência e perda de massa obtidas neste trabalho é viável a aplicação de FFBM por aspersão térmica HVOF. / In this work, the viability of the application of multicomponent white cast iron coatings was studied using high velocity oxygen fuel thermal spray process. The best spray condition, varying the oxygen and propane flow rate, the oxygen/propane ratio, the spraying distance and the powder size, was used for the application of coatings in steel and multicomponent white cast iron substrates with and without preheating. Carbon content, final temperature, thickness, porosity, hardness, adherence, mass loss, friction coefficient and abrasive wear mechanism of the coatings were characterized. The coatings that presented lower porosity and greater hardness were those deposited with oxygen/propane ratio of 4.6, spraying distance of 200 mm and powder size between 20 and 45 μm. With these parameters, coatings with adherence of 84 MPa in steel substrate, without preheating and final temperature of 200 °C, were obtained. The final temperature was identified as the most important factor for the adherence value. Moreover, the coating mass loss was similar to the multi-component white cast iron substrate tempered and annealed. The factors responsible for the high adherence and lower mass loss were the elimination of the retained austenite and the sintering of particles of the coating when the samples were tempered and annealed. The predominant wear mechanism was microcutting associated with the fracture of the lamellae near to unmelted particles, pores of spraying process and the voids formed in the wear process. Considering the levels of adherence and mass loss verified in this work, the application of multicomponent white cast iron coatings using high velocity oxygen fuel thermal spray process is viable.