L'objectif de la thèse a été d'explorer différentes voies de dispersion de charges graphitiques dans des élastomères de type polyisoprène dans le but d'améliorer les propriétés mécaniques et barrière. Pour augmenter les interactions entre le graphite et l'élastomère et donc diminuer les interactions entre charges, les charges graphitiques ont été modifiées chimiquement. Le graphite a été préalablement oxydé pour obtenir du graphite oxydé (GO) contenant des groupements époxyde, hydroxyle et acide carboxylique, susceptibles de servir comme sites d'ancrage de molécules et de chaînes polymères. Afin d'améliorer la compatibilité du GO avec la matrice polyisoprène, des amines et des alkoxysilanes ainsi que des chaînes polyisoprène ont été greffées sur le GO. Des taux de greffage variant de 4 à 50 % en poids ont été obtenus selon la technique de fonctionnalisation utilisée. Une expansion thermique du GO a aussi été étudiée et a conduit à la formation d'une structure graphitique poreuse. Des composites polyisoprène contenant 15 pce de ces charges graphitiques modifiées ont ensuite été préparés et ont montré une diminution de la perméabilité à l'air (-70 % pour les composites graphite traité thermiquement, par rapport à ceux chargés uniquement en noir de carbone) ainsi qu'une amélioration des propriétés mécaniques. Enfin, l'utilisation de liquides ioniques comme agents dispersants a été étudiée. Des composites caoutchouc-graphite avec 1 % en poids de liquides ioniques ont montré un renforcement plus élevé (+ 25 % pour la contrainte à 300 % d'élongation) tout en conservant un allongement à la rupture similaire par rapport à des composites contenant uniquement du noir de carbone / The aim of this study was the investigation of various dispersion methods for graphite-based fillers in elastomers such as polyisoprene, to enhance mechanical and barrier properties. To increase graphite-rubber interactions and so decrease filler-filler aggregation, graphite-based fillers have been chemically modified. Graphite was previously oxidized into graphite oxide (GO), bearing epoxide, hydroxyl and carboxylic acid groups, which could further act as anchor sites for molecules and polymer chains. To increase the compatibility between GO and the polymeric matrix, amines and alkoxysilanes, as well as polymer chains, were grafted on GO. Grafting contents between 4-50 wt% were obtained, depending on the functionalization technique which was used. A thermal modification path of GO was also investigated and led to the formation of porous graphite structure. Polyisoprene composites containing 15 phr of these graphite-based fillers were prepared and showed decreased air permeability (-70 % for composites containing thermally-treated graphite filler, as compared to those containing carbon black only) as well as enhanced tensile properties. Finally, the use of ionic liquids as dispersing agents was investigated. Natural rubber – graphite composites with 1 wt% of ionic liquid displayed enhanced reinforcement (+ 25 % for the stress at 300 % strain) while maintaining similar strain at break to composites containing carbon black only

Indiana University Purdue University Indianapolis / Human papillomaviruses (HPV) are the etiologic agents of most cervical dysplasia and all cervical carcinoma. Integration of high risk HPV into the human genome is thought to be a critical event in the progression from cervical dysplasia to invasive cervical carcinoma. The ability to use molecular assays in the detection and evaluation of HPV integration is essential in informing clinical models for early intervention and therapies. We therefore sought to determine the feasibility of real time-PCR (RT-PCR) as a molecular tool in detecting the physical state, episomal versus integration of HPV 16 and 18 DNA in cervical cancers. Tyramide amplified fluorescent DNA in situ hybridization (FISH) was used to look for evidence of HPV 16/18 integration using formalin-fixed, paraffin-embedded sections of cervical carcinomas. RT-PCR used the ratio of the E2 and E6 genes as a surrogate for determining the physical state of HPV 16 and 18 in 35 infected tissues. Results of RT-PCR showed that 16 cervical specimens (45.7%) contained episomal HPV, 17 cervical samples (48.6%) harbored the integrated form of HPV DNA, and 2 samples (5.7 %) contained both integrated and episomal forms of HPV. Results of the two assays were compared in 25 cervical carcinomas. For 13 of the 25 cervical samples there was an agreement in determining the physical state of HPV. RT-PCR, using the E2/E6 ratio as an assay for HPV integration appears to be promising and may prove to be an essential clinical method in the future.

No description available.

Higher alcohol synthesis (HAS) from syngas or biomass-derived syngas is an important process for the production of oxygenate fuels, fuel additives and other intermediates for valueded chemical feedstock to produce medicine, cosmetics, lubricants, detergents, and polyesters. Chapter I reviews biomass to liquid fuels technology, higher alcohols being used as alternative fuels and fuel additives, the historical perspective and commercial status of higher alcohols, the catalyst system and the reaction mechanism for HAS from syngas. Chapter II discusses the Zn-Mn promoted Cu-Fe based catalyst that was synthesized by the co-precipitation method. The reaction temperature has been tested to study the influence on the catalytic performance. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbon was also very high. Cu was the active site for alcohol synthesis, iron carbide was the active site for olefin and paraffin synthesis. The reaction mechanism of HAS from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Chapter III documents the three-dimensionally ordered macroporous (3DOM) Cu-Fe catalyst developed using a glyoxylate route colloidal crystal template method. The high intrinsic activity was ascribed to three factors. First, the unique ordered structure has a large pore size and interconnected macroporous tunnels of the catalyst with a large accessible surface area to improve the catalytic activity. Second, a high density of uniformly distributed defective Cu0 and Fe5C2 nanoparticles derived from the glyoxylate route helps to provide abundant, active, and stable dual sites. Third, atomic steps on the Cu surface, induced by planar defects and lattice strain, serve as high-activity oxygenation sites. Active Fe5C2 chain-growth sites intimately surround the defective and strained form of the Cu surface, which results in a synergetic effect between the active and stable Cu–FexCy dual site for HAS. In Chapter IV, in situ ambient pressure x-ray photoelectron spectroscopy and in situ synchrotron powder diffraction were applied to identify the active site of 3DOM Cu-Fe catalyst for HAS. The results show that after syngas pretreatment of the 3DOM Cu-Fe catalyst, Cu0 is the active oxygenation site for alcohol synthesis, and Fe5C2 is the active site for carbon chain growth.

[pt] Esta dissertação apresenta os resultados obtidos no processo de remediação de uma área contaminada por cromo hexavalente por meio da técnica de remediação química in situ (ISCR). A área de estudo localiza-se na cidade do Rio de Janeiro e foi ocupada por uma fábrica de vidros por cerca de quarenta anos e comprada para construção de condomínios residenciais. A área de estudo passou um processo de gerenciamento ambiental que contemplou diversos estudos ambientais para aquisição de dados e delimitar a contaminação, horizontal e verticalmente. O teste de bancada realizado com o reagente químico polissulfeto de cálcio demonstrou ser eficiente para reduzir as concentrações de cromo hexavalente em solo e água subterrânea. Com base nos dados adquiridos neste teste foi possível calcular a dose de injeção do polissulfeto de cálcio. Foram realizados setenta pontos de sondagem, pela técnica direct push, para injetar duzentos e cinquenta e dois mil e trinta litros de solução de polissulfeto de cálcio e água, sendo aproximadamente três mil e quinhentos litros por ponto de injeção. Os resultados após a injeção demonstraram que o polissulfeto de cálcio conseguiu remover o cromo hexavalente que estava adsorvido ao solo e reduziu a concentração de cromo hexavalente na água subterrânea entre quarenta e seis e sessenta e sete e noventa e nove e noventa e cinco por cento , após dezenove meses da injeção. Dessa forma, comprovou a eficiência deste reagente químico para remediação de áreas contaminadas por cromo hexavalente, assim como foi observado nos artigos técnicos de estudos de casos nos Estados Unidos e Europa. / [en] This dissertation presents the results obtained in the remediation process remediation of a contaminated area by hexavalent chromium applying the technology in situ chemical remediation (ISCR). The study area is located in the Rio de Janeiro city and was occupied by a glass factory for forty years and purchased for construction of residential condominiums. This dissertation presents the results obtained in the remediation process remediation of a contaminated area by hexavalent chromium applying the technology in situ chemical remediation (ISCR). The study area is located in the Rio de Janeiro city and was occupied by a glass factory for forty years and purchased for construction of residential condominiums. Chromium is an important metal for the industry and is used in various products and processes, such as electroplating, leather treatment, pulp, wood preservation, and refractory manufacturing. The trivalent chromium is essential from a nutritional point of view, non-toxic and poorly absorbed in the body, acting in the maintenance of some functions. Cr(III) is the most common being found and occurs naturally, since the element Cr(VI) can occur naturally, but in low concentrations, if the groundwater has geochemical conditions the Cr (III) can be oxidize to Cr (VI). The hexavalent chromium is the most dangerous valence state and, according to ATSDR (two thousand and twelve), have greater mobility in the groundwater, being carcinogenic by inhalation of high doses of soluble chromate salts. The mobility of hexavalent chromium is high in soil and groundwater because it is not adsorbed by the soil in that valence state, on the other hand when it is in trivalent form is strongly adsorbed by the soil, forming insoluble precipitates, having low mobility in soil and groundwater. The hexavalent chromium remediation by in situ chemical reduction using calcium polysulfide has been the subject of several field studies documented in the literature, both for soil and groundwater from the Chromite Ore Processing Residue (COPR) (Storch, et al., two thousand and two; Graham, et al., two thousand and six ; Charboneau, et al., two thousand and six ; Wazne, et al., two thousand seven a; Wazne, et al., two thousand seven b; Chrysochoou, et al., two thousand and ten ; Chrysochoou & Ting, two thousand and eleven ; Pakzadeh & Batista, two thousand and eleven ; Chrysochoou, et al., two thousand and twelve ). Calcium polysulfide is a fertilizer to soil and commercially available and has been used in some remediation studies cases for reducing hexavalent chromium in soil and groundwater. Being commercially available and used as fertilizer, it is a relatively cheap chemical reagent in comparison with other chemical compounds exclusively developed for this purpose. The stoichiometric demand and the chemical kinetics of the reduction of Cr (VI) by the calcium polysulfide in aqueous solution was studied by Graham et al. (two thousand and six) from the chromite ore processing residue (COPR). With this study it was reported that a molar ratio of a point sixty-six is required (close to the theoretical value of one point five) and a first-order kinetics with an initial concentration of twenty-six eight point mg/L and pH of the CPS solution around eleven point five, with the presence of oxygen. Thus, the hexavalent chromium is reduced to chromium hydroxide, slightly water soluble compound which is precipitated to the soil. The trivalent chromium has low solubility, toxicity, mobility, reactivity and is considered stable. There are various application techniques of chemical reagents in the underground environment, and choosing the most appropriate method for each area depends on the type of contaminant, geological environment, groundwater and surface interference, depth, thickness and size of the contaminated area. As described by Suthersan (mil novecentos ninety-six), the injection of chemical reagents has to achieve two objectives: (one) creating and maintaining an ideal redox environment and other parameters such as pH, presence or absence of dissolved oxygen, etc.; and (two) the delivery and distribution of the necessary reagents for a homogeneous way throughout the injection area, both horizontally and vertically. Thus, it is essential that the conceptual model of the study area is very detailed, so there is no doubt in the choice of chemical reagent application methodology. Although there are numerous laboratory studies on hexavalent chromium remediation using calcium polysulfide, there are few reports in the literature on the field application, especially case studies in Brazil, therefore, this case study becomes a demonstration applying calcium polysulfide as a remediation technique for hexavalent chrome, with geochemical data, which are important for monitoring chemical reduction. This case study shows the effectiveness, dosage and concentration of the study area, and may apply to other hexavalent chromium remediation projects. Materials and Methods A former glass factory (the Site ) operated in the North Zone of Rio de Janeiro / RJ, Brazil from the mid-thousand nine hundred and fifty s to two thousand and five. A portion of the facility was used to store raw material to produce glass, including arsenic oxide, and another portion of the Site was used to conduct industrial plating using hexavalent chromium (Cr(VI)) in the glass molds. In two thousand and nine, the Site was purchased for mixed use redevelopment, demanding an environmental assessment and subsequent remediation. Between two thousand and nine and two thousand and twelve several phases of site investigation was conducted. The results of the investigation indicated that Cr(VI) was present in soil at concentrations up to approximately twenty one mg/kg and in groundwater at concentrations up to approximately thirty mg/L. These concentrations exceeded regulatory criteria of three hundred mg/Kg for soil and zero point zero five mg/L for groundwater. A phased remedial approach was developed consisting of the following: (a) excavation and off-site disposal of two and four hundred ton of Cr(VI) impacted soil from the source area, performed in the unsaturated and saturated zone soils in the Cr(VI) source area; (b) post-excavation monitoring of the groundwater conditions; and (c) groundwater treatment following the excavation program. Hexavalent chromium concentrations in groundwater decreased significantly following the excavation, however, additional reduction of concentrations of Cr(VI) contaminant in groundwater was required. Then was designed and implemented a set of bench-scale treatability tests in order to evaluate groundwater remediation alternatives. Several proprietary and non-proprietary reductants for co-treatment of Cr(VI) were evaluated. Calcium polysulfide were selected to treat Cr(VI). To reduce residual Cr(VI) concentrations in the groundwater plume located downgradient of the former excavated source area, dois e seven hundred cubic meters were targeted for active treatment. The groundwater remediation approach consisted of the injection of thirty liters of CPS (twenty nine percent) diluted in two hundred and twenty liters of water, yielding a total of two hundred and fifty liters of solution injected using direct push technology into seventy two locations. Groundwater Monitoring As part of chemical reagent injection stage was performed the baseline monitoring with collection of soil and groundwater samples. The soil sampling was performed by direct push technique using PVC liner with two inches in diameter, to analyze the total and hexavalent chromium concentrations. Six months after the injection were installed sixteen monitoring wells, eight shallow wells (five meters) and eight deep wells (nine meters) spread upstream, side, middle and downstream of the injection area. Groundwater geochemical parameters (i.e., temperature, total solids dissolved, specific conductance, pH, oxidation-reduction potential, and temperature) were measured at the time groundwater samples were collected. Groundwater samples were collected and analyzed for total and dissolved chromium, hexavalent chromium, iron, arsenic, manganese, calcium, sulfate, and sulfide. Samples were field-filtered with disposable zero point forty-five μm polyethylene filter capsules prior to collecting samples for dissolved metals. Results and Discussion Dose calculations for the reduction of hexavalent chromium have been performed with the data obtained in the bench-scale treatability test and resulted in a stoichiometric demand of four mlCPS/kg soil to the treatment of the study area. Therefore thirty liters of solution was used containing twenty-nine percent calcium polysulfide and approximately two hundred and twenty two liters to perform their mixture, totaling two hundred and fifty-two thousand and thirty liters of solution. For solution injection were performed seventy two soil borings with eight point five meters deep, and the product was injected range between two point five and eightpoint five meters. The depth of injection was from two point five mbgl covered any change in water level due to seasonal variation. In each soil boring was injected chemical reagent solution comprised four hundred and seventeen liters of calcium polysulfide diluted in tree and eighty-three liters of water for a total volume of tree and a half liters of solution injected per point. The comparative analysis results of the third monitoring campaign ( eighteen months post-injection) with the baseline campaign (september/two thousand and twelve) indicated reduction of hexavalent chromium concentrations between forty-six point sixty-seven and ninety-nine and ninety-five percent. Regarding the second monitoring campaign (twelve months post-injection), the hexavalent chromium concentrations reduced between twenty-three point ninety-nine and ninety nine point seventy-nine percent in five of the fifteen monitoring wells that were sampled. In three of the fifteen monitoring wells the hexavalent chromium concentrations remained below the quantitation limit used by the analytical laboratory method. There was no increase in hexavalent chromium concentration, compared the results of the third and second monitoring campaign. The evaluation of the Eh and pH values measured in the monitoring campaigns showed that the pH value was in the acidic range (about four ) and after removal of contaminated soil with hexavalent chromium pH raised to between five and six, after the chemical reagent injection pH increased to the basic range (above seven point five). In the second and third campaign the pH reduced to acid range (below six point five), which can be regarded as the pH value of the area background. The Eh has inversely proportional behavior, increasing between the first and third campaign, and in the third campaign the measured values are in the ranges considered as moderately reducing (hundred to four hundred mV) and oxidizer (> four hundred mV). The pH variation also showed a relationship between increased concentrations of calcium, iron, manganese and sulfate (in some monitoring wells). There were also reductions in hexavalent chromium concentrations in monitoring wells. Conclusion This case study indicates that the use of different remediation techniques when applied together (excavation and chemical reduction), reducing the time required for remediation of a contaminated site without impacting the final cost of remediation. The chemical reduction of hexavalent chromium using calcium polysulfide was effective to reduce the concentration to less than the quantification limit of the analytical method used. Therefore, as presented it is necessary to carry out several studies to detail the hexavalent chromium concentration in the site, as well as understand the geochemistry of groundwater and performing bench-scale tests to evaluate the effectiveness of the chemical reagent in the site study hydrogeological environment and calculate the required dose. The treatability test with calcium polysulfide demonstrated the feasibility of using this chemical reagent by In Situ Chemical Reduction (ISCR) to reduce the hexavalent chrome concentration in soil and groundwater. The test resulted in a stoichiometric demand of four mlCPS /kg soil to the treatment of the study area. Soil samples collected six months after injection showed that the calcium polysulfide could desorb hexavalent chromium from the soil, since, contaminant concentrations were not detected in the samples. neteen months after the injection of the chemical reagent the groundwater concentrations of hexavalent chromium reduced from forty-six point sixty-seven to ninety-nine and ninety-five percent in relation to baseline campaign. And, of the fifteen monitoring wells in just three wells hexavalent chromium concentrations were detected. This demonstrates the effectiveness of using calcium polysulfide to remediate hexavalent chromium in soil and groundwater, confirming the studies by Storch et al. (two thousand and two), Graham et al (two thousand and six), Charboneau et al. ( two thousand and six), Wazne et al. (two thousand and seven a), Wazne et al. (two thousand and seven b), Chrysochoou et al. (two thousand and ten), Chrysochoou & Ting (two thousand and eleven), Pakzadeh & Batista (two thousand and eleven), Chrysochoou et al (2012) in several areas in United States and Europe.

Aerosol particles directly influence the radiative transfer within the atmosphere by scattering and absorption of solar radiation and indirectly in their role as cloud condensation nuclei (CCN). The influence is subject to uncertainties, which can be reduced by a better understanding of their vertical distribution. The vertical aerosol distribution can be determined by airborne in-situ measurements, e.g., helicopter-borne probes, and ground-based remote sensing methods, e.g., lidar. Using algorithms with underlying assumptions and simplifications, physical and optical aerosol properties can be retrieved from lidar measurements. These derived aerosol properties, such as the CCN number concentration (NCCN), can be validated using direct in-situ measurements. In addition, the optical properties underlying the retrieval algorithms can be validated using Mie theory-based modeling. However, here the ambient humidity of the aerosol must be considered since the hygroscopic growth of the aerosol particles changes their optical properties. In the frame of this dissertation, three peer-reviewed scientific papers were published. The goals were to validate lidar-retrieval-based aerosol properties like NCCN, identify sources of uncertainty in Mie theory-based validation studies, and improve the quality of in-situ measurements, such as those of the aerosol particle light absorption coefficient conducted with filter-based absorption photometers. To this end, a Mie theory-based model was developed to calculate aerosol particles' optical properties in the dry and ambient states. The model input parameters were determined with sophisticated instrumentation deployed on the ground and within airborne measurement platforms during three conducted field campaigns. Lidar-based NCCN and the model were compared with corresponding direct in-situ measurements of aerosol optical and microphysical properties with satisfactory results. Sources of deviations concerning the modeled aerosol particle light absorption were identified; among others, the assumed aerosol mixing state and the consideration of light-absorbing organic aerosol components are key parameters. In addition, the representation of aerosol hygroscopicity in the model was investigated based on different measurement techniques. Possible further sources of uncertainty regarding the comparison with aerosol optical properties measured by lidar were discussed. Regarding the aerosol particle light extinction-to-backscatter ratio, also known as the lidar ratio, the dependence on the ambient relative humidity is shown for the first time by employing in-situ measurements and the developed Mie model. A corresponding parameterization was determined. Previous theoretical considerations from other studies were qualitatively confirmed. In addition, the lidar ratio was determined for the first time based on airborne in-situ measurements for the light of wavelength 1064 nm. Also, employing a laboratory study, the influence of rapid changes in relative humidity on filter-based absorption photometers was quantified. Surprisingly, an opposite effect was observed for two different filter materials. First approaches to correct the observed humidity effect were provided using two parameterizations. The findings are crucial, especially in environments with low aerosol particle light absorption, because the effect can exceed the measured values. The results of this work are an important contribution to the improvement, interpretation, and application of the vertical measurement of aerosol properties.:List of Figures I List of Tables I List of Acronyms II List of Symbols IV 1 Introduction 1 2 Theoretical background 5 2.1 Aerosol particles 5 2.1.1 Microphysical properties 5 2.1.2 Aerosol optical properties 8 2.1.3 Aerosol particles under humidified conditions 11 2.2 Lidar theory 11 2.3 Filter-based aerosol particle light absorption measurements and eBC mass concentration 15 2.4 Mie theory 17 3 Methodology 19 3.1 Measurement site 19 3.2 Mie-model 20 3.3 Field campaign instrumentation 20 3.3.1 Aerosol microphysical properties 22 3.3.2 Aerosol Hygroscopicity and complex refractive index 22 3.3.3 Aerosol optical properties 24 3.4 Filter-based particle light absorption measurements and RH 24 4 Results and Discussion 27 4.1 First publication 27 4.1.1 Re-usage of parts of Master thesis 27 4.1.2 Helicopter-borne observations of continental background aerosol in combination with remote sensing and ground-based measurements 27 4.2 Second publication 57 4.2.1 The effect of rapid relative humidity changes on filter-based aerosol-particle light-absorption measurements: uncertainties and correction schemes 57 4.3 Third publication 75 4.3.1 Measurement report: Comparison of airborne, in situ measured, lidar-based, and modeled aerosol optical properties in the central European background – identifying sources of deviations 75 4.3.2 Supplementary material of “Measurement report: Comparison of airborne, in situ measured, lidar-based, and modeled aerosol optical properties in the central European background – identifying sources of deviations” 105 5 Summary, Conclusions, and Outlook 117 Appendix A 121 Bibliography 123 Acknowledgments i Declaration of Independence iii / Aerosolpartikel beeinflussen den Strahlungstransport in der Atmosphäre durch Streuung und Absorption von solarer Strahlung direkt und indirekt in ihrer Wirkung als Wolkenkondensationskerne (CCN, cloud condensation nuclei). Der Einfluss ist mit Unsicherheiten behaftet, welche unter anderem durch ein besseres Verständnis über deren vertikale Verteilung reduziert werden kann. Die vertikale Verteilung der Aerosole kann mittels luftgetragener in-situ Messungen, z.B. mit helikoptergetragenen Sonden, und bodengebundener Fernerkundungsmethoden, z.B. Lidar, bestimmt werden. Mittels verschiedener Algorithmen, denen jedoch diverse Annahmen und Vereinfachungen zu Grunde liegen, können aus Lidarmessungen mikrophysikalische und optische Aerosoleigenschaften abgeleitet werden. Mittels direkter Messungen können diese abgeleiteten Aerosoleigenschaften, wie z.B. die CCN Anzahlkonzentration (NCCN), überprüft werden. Zudem können die, den Ableitungsalgorithmen zu Grunde liegenden, optischen Eigenschaften mittels Mie-Theorie basierter Modellierung validiert werden. Die Umgebungsfeuchte des Aerosols muss dabei jedoch berücksichtig werden, da auf Grund des hygroskopischen Wachstums die optischen Eigenschaften von Aerosolpartikeln verändert werden. Im Rahmen dieser Dissertation wurden drei begutachteten wissenschaftlichen Artikel publiziert. Die Ziele waren aus Lidarretrievals abgeleitete Aerosolgrößen wie z.B. NCCN zu validieren, Unsicherheitsquellen in Mie-Theorie basierten Validierungsstudien zu identifizieren und die Qualität von in-situ Messungen, wie z.B. die des Lichtabsorptionskoeffizienten von Aerosolpartikeln mittels filterbasierter Absorptionsphotometern, zu steigern. Dazu wurde ein Mie-Theorie basiertes Model entwickelt, welches die optischen Eigenschaften von Aerosolpartikeln im trockenen und Umgebungszustand berechnen kann. Dessen Eingangsparameter wurden mit hochqualitativen Messungen am Boden und in der Luft während dreier Feldkampagnen ermittelt. Korrespondierende in-situ Messungen am Boden und in der Luft verifizierten neben Lidar-basierten NCCN die Modelqualität mit zufriedenstellendem Resultat. Bezüglich der Aerosolpartikellichtabsorption konnte die Wichtigkeit des angenommen Aerosolmischungszustandes und der Berücksichtigung von lichtabsorbierenden organischen Aerosolkomponenten identifiziert werden. Zudem wurde die Repräsentierung der Aerosolhygroskopizität im Model auf Grundlage von verschiedenen Messtechniken untersucht. Mögliche weitere Unsicherheitsquellen bezüglich des Vergleiches mit den von Lidar gemessenen optischen Aerosoleigenschaften wurden diskutiert. Bezüglich des Lichtextinktions-zu-Rückstreuverhältnisses von Aerosolpartikeln, auch Lidarverhältnis (LR), konnte erstmals mit in-situ Messungen und dem entwickelten Mie-Model die Abhängigkeit dieses Parameters gegenüber der relativen Umgebungsfeuchte gezeigt und parametrisiert werden. Theoretische Betrachtungen aus vorherigen Studien wurden qualitativ bestätigt. Auf Basis von luftgetragenen in-situ Messungen konnte erstmalig das LR für Licht der Wellenlänge 1064 nm bestimmt werden. Mittels einer Laborstudie konnte der Einfluss von schnellen Änderungen der relativen Feuchte auf filterbasierte Absorptionsphotometer quantifiziert werden. Überraschenderweise zeigten zwei verschieden Filtermaterialen ein gegensätzlicher Effekt. Erste Ansätze zu der Korrektur des Feuchteeffekts wurden mit zwei Parametrisierungen geliefert. Gerade in Umgebungen mit niedriger Lichtabsorption durch Aerosol kann dies wichtig sein, da der Effekt die Messwerte übersteigen kann. Die Ergebnisse diese Arbeit sind ein wichtiger Beitrag zur Verbesserung, Interpretation und Anwendung vertikaler Messungen von Aerosoleigenschaften.:List of Figures I List of Tables I List of Acronyms II List of Symbols IV 1 Introduction 1 2 Theoretical background 5 2.1 Aerosol particles 5 2.1.1 Microphysical properties 5 2.1.2 Aerosol optical properties 8 2.1.3 Aerosol particles under humidified conditions 11 2.2 Lidar theory 11 2.3 Filter-based aerosol particle light absorption measurements and eBC mass concentration 15 2.4 Mie theory 17 3 Methodology 19 3.1 Measurement site 19 3.2 Mie-model 20 3.3 Field campaign instrumentation 20 3.3.1 Aerosol microphysical properties 22 3.3.2 Aerosol Hygroscopicity and complex refractive index 22 3.3.3 Aerosol optical properties 24 3.4 Filter-based particle light absorption measurements and RH 24 4 Results and Discussion 27 4.1 First publication 27 4.1.1 Re-usage of parts of Master thesis 27 4.1.2 Helicopter-borne observations of continental background aerosol in combination with remote sensing and ground-based measurements 27 4.2 Second publication 57 4.2.1 The effect of rapid relative humidity changes on filter-based aerosol-particle light-absorption measurements: uncertainties and correction schemes 57 4.3 Third publication 75 4.3.1 Measurement report: Comparison of airborne, in situ measured, lidar-based, and modeled aerosol optical properties in the central European background – identifying sources of deviations 75 4.3.2 Supplementary material of “Measurement report: Comparison of airborne, in situ measured, lidar-based, and modeled aerosol optical properties in the central European background – identifying sources of deviations” 105 5 Summary, Conclusions, and Outlook 117 Appendix A 121 Bibliography 123 Acknowledgments i Declaration of Independence iii

Ziel der vorliegenden Arbeit ist die Entwicklung eines neuartigen Ferti-gungsprozesses für hochfunktionalisierte Strukturbauteile in PFH-Technologie. Eigens für die Verarbeitung von FKV-Profilen wird das IHU/Spritzgießverfahren grundlegend analysiert und die einzelnen Pro-zessstufen durch den Einsatz geeigneter Prozessmedien und -parametrierungen modifiziert. Mit Hilfe umfangreicher analytischer und numerischer Berechnungen sowie erfolgreicher Umsetzung eines neuar-tigen Temperierungskonzeptes lassen sich erstmals FKV-Profile ohne den Einsatz von Barriereschichten, endkonturnah und reproduzierbar in seriellen Taktzeiten umformen. Zudem ist somit eine Funktionalisierung mittels Spritzgießen und ein gesamtheitliches Beherrschen des Hybrid-prozesses gegeben. Ein Vergleich der Verbindungsfestigkeiten mit hyb-riden Referenzbauteilen beweist, dass sich durch die stoffschlüssige Anbindung zeit- und kostenintensive Vorbehandlungen einsparen und gleichzeitig höhere Verbundqualitäten erzielen lassen. Um das PFH-Strukturbauteil mit montagegerechten Verbindungsschnittstellen zu werkstofflich andersgearteten Multimaterialstrukturen zu versehen, dient ein eigens entwickeltes prozesskomplementäres In-situ-Integrationsverfahren. Abschließend ist ein allgemeiner methodischer Ansatz für den technologischen Transfer und Adaption systematisch aufgeschlüsselt, sodass sich die einzelnen Entwicklungspfade nachvoll-ziehen lassen.:1 Einleitung 2 Zielsetzung 3 Stand der Wissenschaft und Technik 4 Anforderungen an einen faserverbund-gerechten IHU/Spritzgießprozess 5 Prozessentwicklung und Validierung 6 In-situ-Integrationsprozess für metallische Inserts 7 Konfiguration einer seriellen Fertigungstechnologie 8 Zusammenfassung und Ausblick Anhänge / The goal of this thesis is the development of a new production technol-ogy for highly functional lightweight structural parts. Therefor the hy-droforming supported overmolding process was chosen as a suiting manufacturing process. By usage of analytical and numerical calcula-tions as well as adapting a new kind of temperature distribution con-cept, the new Polymer-FRP-Hbyrid-Technology is enabled to manufac-ture frp-profile based structural components without the need for a barrier layer. The final product possesses its’s final shape already and has no need for further machining processes. A comparison with state-of-the-art metal-plastic-hybrid bonding systems shows a way higher value for the new technology due to the adhesive bond between the tape and injection molding polymer. Furthermore, the technology was enhanced with a process implemented insert joining process. Finally, a methodical approach for the technology transfer is presented.:1 Einleitung 2 Zielsetzung 3 Stand der Wissenschaft und Technik 4 Anforderungen an einen faserverbund-gerechten IHU/Spritzgießprozess 5 Prozessentwicklung und Validierung 6 In-situ-Integrationsprozess für metallische Inserts 7 Konfiguration einer seriellen Fertigungstechnologie 8 Zusammenfassung und Ausblick Anhänge

Three-dimensional volume data is routinely produced, at increasingly high spatial resolution, in computer simulations and image acquisition tasks. In-situ visualization, the visualization of an experiment or simulation while it is running, enables new modes of interaction, including simulation steering and experiment control. These can provide the scientist a deeper understanding of the underlying phenomena, but require interactive visualization with smooth viewpoint changes and zooming to convey depth perception and spatial understanding. As the size of the volume data increases, however, it is increasingly challenging to achieve interactive visualization with smooth viewpoint changes. This thesis presents an end-to-end solution for interactive in-situ visualization based on novel extensions proposed to the Volumetric Depth Image (VDI) representation. VDIs are view-dependent, compact representations of volume data than can be rendered faster than the original data. Novel methods are proposed in this thesis for generating VDIs on large data and for rendering them faster. Together, they enable interactive in situ visualization with smooth viewpoint changes and zooming for large volume data. The generation of VDIs involves decomposing the volume rendering integral along rays into segments that store composited color and opacity, forming a representation much smaller than the volume data. This thesis introduces a technique to automatically determine the sensitivity parameter that governs the decomposition of rays, eliminating the need for manual parameter tuning in the generation of a VDI. Further, a method is proposed for sort-last parallel generation and compositing of VDIs on distributed computers, enabling their in situ generation with distributed numerical simulations. A low latency architecture is proposed for the sharing of data and hardware resources with a running simulation. The resulting VDI can be streamed for interactive visualization. A novel raycasting method is proposed for rendering VDIs. Properties of perspective projection are exploited to simplify the intersection of rays with the view-dependent segments contained within the VDI. Spatial smoothness in volume data is leveraged to minimize memory accesses. Benchmarks are performed showing that the method significantly outperforms existing methods for rendering the VDI, and achieves responsive frame rates for High Definition (HD) display resolutions near the viewpoint of generation. Further, a method is proposed to subsample the VDI for preview rendering, maintaining high frame rates even for large viewpoint deviations. The quality and performance of the approach are analyzed on multiple datasets, and the contributions are provided as extensions of established open-source tools. The thesis concludes with a discussion on the strengths, limitations, and future directions for the proposed approach.

Transparent trä biokompositer (TW) är en ny attraktiv klass av biokomposit. De är uppbyggda av delignifierat trä som impregnerats med en polymer med matchande brytningsindexet.  TW kan skräddarsys för inom ett brett spektrum av funktionella, optiska och mekaniska egenskaper. Eftersom de är biobaserade ses de dessutom som ett möjligt material som kan ersätta andra, mer miljöpåverkande material, inom olika sektorer, däribland byggnadsindustrin. Till skillnad från de funktionella egenskaperna har det mekaniska beteendet hos dessa biokompositer dock inte undersökts särskilt ingående. Syftet med denna avhandling är därför att utöka den nuvarande kunskapen om det mekaniska beteendet av dessa material genom att använda två olika mekanisk karakterisering metoder av TW och vanligt trä som referensmaterial. TW framställdes genom impregnering av delignifierade björkfaner med PMMA. Den mekaniska karakteriseringen utfördes med hjälp av olika metoder. Elastiska modulen och böjhållfastheten i tvärriktningen studerades med hjälp av fyrpunktsböjningprov. Resultaten visade en förbättring för båda egenskaperna jämfört med vanligt björkträ. Brottet vinkelrätt mot fibern (TR-systemet) undersöktes genom att utföra in situ fyrpunktsböjningstester på prover med en kant-spricka i ett svepelektronmikroskop för att observera hur sprickorna fortplantar sig i den komplexa mikrostrukturen. En anmärkningsvärd förbättring (cirka 175 procent) av brottsstyrkan konstaterades jämfört med vanligt trä. Dessutom användes DIC-teknik (digital image correlation) på fyrpunktsböjningstesterna, med kant-spricka, för att studera spänningsfältet under spricktillväxten, särskilt bildandet av brottprocesszonen (FPZ) runt sprickspetsen. Därefter föreslogs en ekvation som beskriver kohesionslagen för båda materialen baserat på experimentella observationer som i slutändan kan användas för sprickmekaniska simuleringar. Slutligen visades kort hur man kan använda de uppmätta mekaniska egenskaperna hos den nya TW för materialval för tekniska tillämpningar. / Transparent wood (TW) biocomposites are a new attractive class of materials. They are based on a delignified wood template impregnated by a refractive index-matching polymer.  TWs can be tailored in order to show a wide range of functional, optical, and mechanical properties. Moreover, being biobased, they are seen as a possible key material to replace more environmentally impactful materials in various sectors including the construction industry. However, unlike the functional properties, the mechanical behaviour of this class of materials has been poorly investigated. Therefore, in this thesis, the aim was to extend the current knowledge about the mechanical response of these materials by using a two-step mechanical characterization on TW and native wood as reference material. The analysed TW biocomposite was prepared by impregnation of delignified birch veneers by PMMA. The mechanical characterization was carried out using different techniques. The Young’s modulus and the flexural strength along the transverse direction were studied by four-point bending tests. The results showed an improvement for both properties compared to native birch wood. The fracture perpendicular to the grain (TR system) was investigated by performing in situ single-edge-notched four-point bending tests onto a scanning electron microscope to observe how the cracks propagate in this complex microstructure. A remarkable improvement (about 175 percent) in fracture toughness was found compared to the native wood. Furthermore, the in situ single-edge-notched four-point bending test was also applied, together with the digital image correlation (DIC) technique, to study the strain field during the crack growth, specifically the formation of the fracture process zone (FPZ) around the crack tip. Then, an equation describing the cohesive law was proposed for both materials based on experimental observations that can be ultimately used for fracture mechanics simulations. Finally, it was briefly shown how to make use of the measured mechanical properties of the novel TW for material selection for engineering applications.

Under senare år har omfattande insatser gjorts för att främja mer hållbara flygtransporter i Europa. De konventionella tillverkningsmetoderna som används inom flyg- och rymdindustrin kräver betydande mängder råmaterial, vars utvinning, bearbetning och användning har negativa miljöeffekter. Därför finns det ett starkt incitament att utveckla nya, mer material-effektiva tillverkningsmetoder. Additiv tillverkning (AM), även känd som 3D-printining, har fördelen att direkt komma nära den slutliga formen på strukturer genom att lägga till material endast där det behövs, något som minimerar spill och förbättrar materialanvändningen. Dock utgör införandet av AM komponenter i säkerhetskritiska flyg- och rymdtillämpningar en betydande utmaning på grund av komplexiteten hos processerna. Denna komplexitet kan leda till tillverkningsvariationer som i sin tur kan resultera i defekter i de tillverkade strukturerna. Därför är framsteg inom automation genom utvecklingen av lösningar för övervakning och styrning under processens gång ett nödvändigt steg för att uppnå tillräcklig pålitlighet och repeterbarhet. Denna avhandling presenterar en utveckling av multisensorövervakning och styrning av Directed Energy Deposition (DED) med en laservärmekälla (LB). DED-LB är en avancerad teknik som möjliggör tillverkning av storskaliga metallkomponenter nära den slutliga formen. I detta arbete har lösningar undersökts för övervakning av DED-LB med tillsatspulver och tråd. För fallet med tillsatstråd kan denna kompletteras med resistiv förvärmning (så kallad hotwire), vilket ger möjlighet att ytterligare finjustera värmetillförseln och förbättra smältprocessen. För övervakningsändamål undersöktes tre olika in-situtekniker för processens stabilitet och varians. Maskinseende och elektriska givare användes för DED-LB med tillsatstråd (DED-LB/w), medan optisk spektroskopi användes för övervakning både av processen med tillsatspulver (DEDLB/p) samt med tråd. Ett multisensorsystem baserat på de tre teknologierna testades för DED-LB/w. Det kamerabaserade systemet gav tydliga indikationer på avvikelser från nominella processförhållanden. Spännings-och strömgivarnas signaler korrelerade med förändringar i processparametrar och återspeglade tydligt metallöverföringen. Spektrometersystemet indikerade förändringar relaterade till värmeöverföringen. Dessutom möjliggjorde analysen av erhållna spektra en detektering av förluster av viktiga legeringselement under DED-LB/p. Slutsatsen från resultaten understryker behovet av multisensorövervakning, eftersom det inte bara möjliggör detektering och skattning av processförändringar utan även en bättre förståelse av deras grundorsaker. Den presenterade ansatsen är ett viktigt bidrag i utvecklingen av ett framtida robust och feltolerant automatiskt styrsystem. / In recent years, an extensive effort has been made to leap European aviation towards more sustainable transportation. Conventional manufacturing methods used in aerospace industry require significant amounts of raw materials, whose extraction, processing, and utilization have adverse environmental impacts. Thus, there is a strong motivation to develop novel, more material efficient fabrication methods. Additive Manufacturing (AM), also known as 3D-printing, offers the advantage of manufacturing near-net-shape structures by adding material only where it is needed, minimizing waste, and improving material efficiency. However, introducing AM fabricated structures as components in safety-critical aerospace systems poses a significant challenge due to the inherent complexity of AM processes. This complexity can result in variations that may lead to defects or inconsistencies in the fabricated structures. Thus, increasing automation by developing in-process monitoring, and control solutions is the vital step to reach the necessary reliability and repeatability. This thesis presents development towards multi-sensor monitoring and control of Directed Energy Deposition (DED) using a Laser Beam (LB). DED-LB is an advanced technology that allows to manufacture large-scale, near-net-shape metallic parts. In this work, in-process monitoring solutions for DED-LB with feedstock powder and wire were investigated. The set-up of the latter was complemented by resistive pre-heating of the feedstock wire (hot-wire) which provided means of fine-tuning the heat input and improving metal fusion. Formonitoring purposes, three different in-situ techniques were investigated to monitor process stability and variability. Machine vision and electrical sensing were utilized during DED-LB with feedstock wire (DED-LB/w) depositions,while optical emission spectroscopy was used for monitoring processes with feedstock powder (DED-LB/p) as well as wire. A multi-sensorsystem based on the three sensing technologies was tested during DED-LB/w depositions. The vision system gave clear indications of variations from nominal conditions. Voltage and current sensors indications correlated to changes in process parameters and reflected well the metal transfer (liquid bridge) condition.The spectrometer system indicated well changes related to heat input. In addition, analysis of obtained spectra allowed to detect losses of vital alloying element during DED-LB/p. The main conclusion from the results underlines the need for simultaneous multi-sensor monitoring as it allows not only to detect and estimate process changes but also to better interpret their root causes. Such setup will positively enable a future robust, fault tolerant control system. / <p>Paper 3 is under acception but included in this thesis with CC BY-license.</p>