Aerosol Partikel interagieren mit solarer und terrestrischer Strahlung durch Absorption und Streuung. Zusätzlich bilden und modifizieren sie die Eigenschaften von Wolken da sie das Potential besitzen als Wolkenkondensationskeim (CCN) fungieren zu können und stellen somit eine wichtige Komponente im Klimasystem dar. Die Eigenschaften von Partikeln und CCN müssen genaustens bekannt sein um deren Einfluss in Klima- und Strahlungsmodellen akurat berücksichtigen zu können. Ziel dieser Arbeit ist die Charakterisierung der Partikeleigenschaften in Regionen, welche das Klima maßgeblich beeinflussen, wie die Arktis und die Antarktis. Im Rahmen dieser Arbeit wurden 2 Datensätze aufgenommen, welche helfen das Verständnis über Partikel und CCN im Frühjar und Sommer in der Arktis und Antarktis zu verbessern. Es wurden jeweils die Gesamt- und die CCN-Anzahlkonzentration (NCN, NCCN), die Anzahlgrößenverteilung (PNSD) und der Hygroskopizitätsparameter (k) der Partikel bestimmt. Die Herkunft der vermessenen Partikel wurde mit Rückwärtstrajektorien ermittelt sowie weitere Analysen bezüglich der Verweilzeiten durchgeführt. Beide Datensätze zeigen, dass eine starke Abhängigkeit der Partikel- und CCN-Eigenschaften vom Luftmassenursprung vorliegt. Zeigen arktische PNSDs nur eine Akkumulationsmode, konnte diese auf gealtertes Aerosol mit einem eurasischen Ursprung zurückgeführt werden. Kommt eine zweite Mode mit kleineren Partikeln hinzu, wurde der Nord-Pazifische Raum als Ursprung bestimmt. In der Antarktis wurde besonders für NCN und NCCN eine starke Abhängigkeit vom Luftmassenursprung gefunden. Dabei konnten mit der Anwendung des Dispersionsmodells NAME Antarktische Hintergrundkonzentrationen ermittelt werden. Weiterhin wurde gefunden, dass Antarktische Aerosolpartikel mit einem k von 1 hygroscopischer als das Arktische ist, für welches ein k von 0,19 bestimmt wurde. Zusätzlich durchgeführte Flugzeugmessungen über Tuktoyaktuk (Arktis) zeigen, dass die Messungen am Boden auch repräsentativ für die Grenzschicht sind. Die Schichten über der Grenzschicht scheinen jedoch von dieser entkoppelt zu sein und es wird vermutet, dass der Ursprung der Partikel in größeren Höhen in niedrigeren geographischen Breiten liegt.:Contents List of Abbreviations iii List of Symbols v 1. Introduction 1 2. Experimental 9 2.1. Measured Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 2.1.1. Total Particle Number Concentration . . . . . . . . . . . . . . . 9 2.1.2. Particle Number Size Distribution . . . . . . . . . . . . . . . . . 10 2.1.3. Total Concentration of Cloud Condensation Nuclei . . . . . . . . 15 2.2. Determination of the CCN hygroscopicity . . . . . . . . . . . . . . . . . 16 2.2.1. Köhler theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.2. The hygroscopicity parameter k and the critical diameter dcrit . . 18 2.3. Determination of the Air Mass Origin . . . . . . . . . . . . . . . . . . . 20 2.3.1. The NAME Dispersion Model . . . . . . . . . . . . . . . . . . . 20 2.3.2. Potential Source Contribution Function . . . . . . . . . . . . . . 22 3. Results and Discussion 25 3.1. Measurements of aerosol and CCN properties in the Mackenzie River delta (Canadian Arctic) during Spring-Summer transition in May 2014 . . 25 3.1.1. Campaign overview . . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.2. Overview of NCN, NCCN and PNSD data for the entire measurement period . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 3.1.3. Identification of air mass origins and potential source regions . . . 32 3.1.4. PNSD of the three periods . . . . . . . . . . . . . . . . . . . . . 35 3.1.5. Critical diameter dcrit and hygroscopicity parameter k . . . . . . 38 3.1.6. Comparison of height resolved airborne and ground based PNSDs 41 3.2. Measurements of aerosol and CCN properties at the Princess Elisabeth Antarctica Research Station during three austral summers . . . . . . . . . 45 3.2.1. Campaign overview . . . . . . . . . . . . . . . . . . . . . . . . 45 3.2.2. Total Particle and CCN number concentrations and regional analysis of the NAME model footprints . . . . . . . . . . . . . . . . 50 3.2.3. PSCF results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 3.2.4. Hygroscopicity . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 4. Summary, Conclusions and Outlook 65 A. Appendix 71 A.1. SS calibration of the CCNC . . . . . . . . . . . . . . . . . . . . . . . . . 71 A.2. Error Analysis with Monte Carlo Simulation . . . . . . . . . . . . . . . . 73 B List of Figures vii C List of Tables viii Bibliography xi / Atmospheric aerosol particles interact with solar and terrestrial radiation by absorption and scattering. Further, they have the potential to act as cloud condensation nuclei (CCN) and to form and modify the radiative properties of clouds and thus are an important component in the Earth’s climate system. An accurate knowledge about the aerosol particle and CCN properties is very important for accurate climate and radiation models. The objective of this thesis is the characterization of aerosol particles in regions that are key regulators of the Earth’s climate. The Arctic and the Antarctic are such regions. Hence, in the framework of this doctoral thesis two data sets were recorded, that help gaining further knowledge about the spring and summer time aerosol particles and CCN in the Arctic and Antarctic region. For both, the Arctic and the Antarctic aerosol population, the CCN and the total particle number concentration (NCCN, NCN), the particle number size distribution (PNSD) and the hygroscopicity parameter k were determined. The history of the measured air masses was explored using back trajectories and residence time analysis. For both examined regions, a strong influence of the air mass origin on the aerosol particle and CCN properties was found. The PNSDs measured in the Arctic were found to be mono-modal showing an accumulation mode which most likely contains well aged particles that have an Eurasian origin. Bi-modal PNSDs with an additional mode of smaller particles were found to originate from the Northern Pacific. In the Antarctic the air mass origin was found to significantly influence NCCN and NCN. With the application of the NAME dispersion model Antarctic continental background concentrations could be determined. With k values of 1 the Antarctic aerosol was found to be much more hygroscopic than the Arctic aerosol, for which a k of 0.19 was determined. Additional Arctic aircraft measurements show that ground based measurements are representative for the Arctic boundary layer. However particles above the boundary layer seem to be decoupled from lower layers and were believed to be advected from lower latitudes in different height layers and mixed down in the lower Arctic troposphere.:Contents List of Abbreviations iii List of Symbols v 1. Introduction 1 2. Experimental 9 2.1. Measured Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 2.1.1. Total Particle Number Concentration . . . . . . . . . . . . . . . 9 2.1.2. Particle Number Size Distribution . . . . . . . . . . . . . . . . . 10 2.1.3. Total Concentration of Cloud Condensation Nuclei . . . . . . . . 15 2.2. Determination of the CCN hygroscopicity . . . . . . . . . . . . . . . . . 16 2.2.1. Köhler theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.2. The hygroscopicity parameter k and the critical diameter dcrit . . 18 2.3. Determination of the Air Mass Origin . . . . . . . . . . . . . . . . . . . 20 2.3.1. The NAME Dispersion Model . . . . . . . . . . . . . . . . . . . 20 2.3.2. Potential Source Contribution Function . . . . . . . . . . . . . . 22 3. Results and Discussion 25 3.1. Measurements of aerosol and CCN properties in the Mackenzie River delta (Canadian Arctic) during Spring-Summer transition in May 2014 . . 25 3.1.1. Campaign overview . . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.2. Overview of NCN, NCCN and PNSD data for the entire measurement period . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 3.1.3. Identification of air mass origins and potential source regions . . . 32 3.1.4. PNSD of the three periods . . . . . . . . . . . . . . . . . . . . . 35 3.1.5. Critical diameter dcrit and hygroscopicity parameter k . . . . . . 38 3.1.6. Comparison of height resolved airborne and ground based PNSDs 41 3.2. Measurements of aerosol and CCN properties at the Princess Elisabeth Antarctica Research Station during three austral summers . . . . . . . . . 45 3.2.1. Campaign overview . . . . . . . . . . . . . . . . . . . . . . . . 45 3.2.2. Total Particle and CCN number concentrations and regional analysis of the NAME model footprints . . . . . . . . . . . . . . . . 50 3.2.3. PSCF results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 3.2.4. Hygroscopicity . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 4. Summary, Conclusions and Outlook 65 A. Appendix 71 A.1. SS calibration of the CCNC . . . . . . . . . . . . . . . . . . . . . . . . . 71 A.2. Error Analysis with Monte Carlo Simulation . . . . . . . . . . . . . . . . 73 B List of Figures vii C List of Tables viii Bibliography xi

It is well known that atmospheric aerosols provide the sites for forming cloud droplets, and can affect the Earth's radiation budget through their interactions with clouds. The ability of aerosols to act as cloud condensation nuclei is a strong function of their chemical composition and size. The compositional complexity of aerosol prohibits their explicit treatment in atmospheric models of aerosol-cloud interactions. Nevertheless, the cumulative impact of organics on CCN activity is still required, as carbonaceous material can constitute up to 90% of the total aerosol, 10-70% of which is water soluble. Therefore it is necessary to characterize the water soluble organic carbon fraction by CCN activation, droplet growth kinetics, and surface tension measurements. In this thesis, we investigate the water soluble properties, such as surface tension, solubility, and molecular weight, of laboratory and ambient aerosols and their effect on CCN formation. A mechanism called Curvature Enhanced Solubility is proposed and shown to explain the apparent increased solubility of organics. A new method, called Köhler Theory Analysis, which is completely new, fast, and uses minimal amount of sample was developed to infer the molar volume (or molar mass) of organics. Due to the success of the technique in predicting the molar volume of laboratory samples, it was applied to aerosols collected in Mexico City. Additionally the surface tension, CCN activity, and droplet growth kinetics of these urban polluted aerosols were investigated. Studies performed for the water soluble components showed that the aerosols in Mexico City have surfactants present, can readily become CCN, and have growth similar to ammonium sulfate. Finally, aerosols from three different polluted sources, urban, bovine, and ship emissions, were collected and characterized. The data assembled was used to predict CCN concentrations and access our understanding of the system. From these analyses, it was evident that knowledge of the chemical composition and mixing state of the aerosol is necessary to achieve agreement between observations and predictions. The data obtained in this thesis can be introduced and used as constraints in aerosol-cloud interaction parameterizations developed for global climate models, which could lead to improvements in the indirect effect of aerosols.

CANUTO, Holivânia Maria Pereira. Mamão (Carica papaya L.) liofilizado em pó: avaliação das características físicas, físico-químicas e higroscópicas. 2011. 77f. : Dissertação (mestrado) - Universidade Federal do Ceará, Centro de Ciências Agrárias, Departamento de Tecnologia de Alimentos, Fortaleza-CE, 2011 / Submitted by Nádja Goes (nmoraissoares@gmail.com) on 2016-06-09T13:45:39Z No. of bitstreams: 1 2011_dis_hmpcanuto.pdf: 3222547 bytes, checksum: 5970f45552fd506d0aec8afe39dd20b2 (MD5) / Approved for entry into archive by Nádja Goes (nmoraissoares@gmail.com) on 2016-06-09T13:46:00Z (GMT) No. of bitstreams: 1 2011_dis_hmpcanuto.pdf: 3222547 bytes, checksum: 5970f45552fd506d0aec8afe39dd20b2 (MD5) / Made available in DSpace on 2016-06-09T13:46:00Z (GMT). No. of bitstreams: 1 2011_dis_hmpcanuto.pdf: 3222547 bytes, checksum: 5970f45552fd506d0aec8afe39dd20b2 (MD5) Previous issue date: 2011 / Papaya (Carica papaya L.) is a tropical fruit known and appreciated worldwide. Their sensory and nutritional characteristics contribute to the wide acceptability of this fruit. However, in the post-harvest loss is high due to its highly perishable. In this context, the lyophilization appears as a promising process for dehydration of papaya, because is a drying process that contributes to preserve the vitamin and mineral components of food. In this work, was applied the lyophilization process in Formosa papaya pulp, being used for two of the three trials studied the adjuvant lyophilization maltodextrin. Was evaluated the stability of food powders obtained through of the study of the physical, physico-chemical and hygroscopic characteristics. The lyophilization significantly reduced the carotenoid contents of the pulps. The high sugar contents of the pulps were kept until the end of the storage the powders obtained after lyophilization. The increase in concentration of the adjuvant resulted in higher retention of vitamin C during storage, as well as reduced the hygroscopicity in papaya lyophilized powders, resulting in increased stability of the water activity and maintenance of humidity levels. Therefore, showed the relevance of maltodextrin as an adjuvant to lyophilization of the pulp of Formosa papaya, providing food powders more viable, including increasing the shelf life of these products. / O mamão (Carica papaya L.) é uma fruta tropical conhecida e apreciada mundialmente. Suas características sensoriais e nutricionais contribuem para a grande aceitabilidade desta fruta. Contudo, no período pós-colheita ocorrem elevadas perdas devido a sua alta perecibilidade. Nesse contexto, a liofilização surge como um processo promissor na desidratação de mamão, pois é um processo de secagem que contribui para preservar os componentes minerais e vitamínicos do alimento. Neste trabalho, aplicou-se o processo de liofilização em polpa de mamão Formosa, sendo utilizado para dois dentre os três ensaios estudados o adjuvante de liofilização maltodextrina. Foi avaliada a estabilidade dos pós alimentícios obtidos através do estudo das características físicas, físico-químicas e higroscópicas. A liofilização reduziu significativamente os teores de carotenóides das polpas. Já os elevados teores de açúcares das polpas foram conservados até o final do armazenamento dos pós obtidos após a liofilização. O aumento da concentração do adjuvante propiciou maior retenção de vitamina C durante o armazenamento, assim como reduziu a higroscopicidade nos pós de mamão liofilizado, resultando em maior estabilidade da atividade de água e manutenção dos níveis de umidade. Portanto, evidenciou-se a relevância da maltodextrina como adjuvante do processo de liofilização da polpa de mamão Formosa, fornecendo pós alimentícios mais viáveis, incluindo o aumento da vida de prateleira desses produtos.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study investigated the effect of thermal treatment technique, used in two treatment conditions: treated wood in an autoclave and after conditioning, subject to the treatment under electric heater (combination), and treated wood by using only electric kiln (oven) on mechanical, hygroscopic and biological properties of Pinus taeda L. and Eucalyptus grandis W. Hill ex Maiden woods, comparing them with the results obtained for the untreated wood. For that three trees with 25 years, were deployed for each species from which it drew the first two logs for making the samples used in the evaluations. In the combination treatment these parts were subjected to thermo treatment by autoclaving at 130°C/ ± 3°C and pressure of 2 kgf/ cm² for 3 hours and after a conditioning period, subjected to electric heat in an oven at 160°C/ ± 1°C for the same period, already parts for just treatment in oven were exposed the last condition. The physical properties consisted in the evaluation of weight loss and specific weight assigned to treatment, equilibrium moisture content, rate of water absorption, effectiveness of water repellency, anti swelling efficiency, tangential, radial, and volumetric swelling and coefficient of anisotropy, the mechanical properties consisted in evaluating the modulus of elasticity and rupture in bending, maximum resistance to compression parallel, Janka hardness, impact resistance, and finally to the biological was employed accelerated decay test in the laboratory using white rot fungi and brown. The effect of heat treatment employed in the two methodologies resulted in different effects than expected with regard to the mechanical and biological. The results indicated that heat treatments used were effective in reducing the hygroscopicity and increased dimensional stability of both species, the best results for the combination method. To provide the mechanical properties of different effects, reaching an increase of resistance to certain properties and for durability of biological parts, treatments favored decay fungi employees, more pronounced effect for the combined method. / A presente pesquisa objetivou investigar o efeito da técnica de retificação térmica, empregada sob duas condições de tratamento: madeira tratada em autoclave e após condicionamento, submetida ao tratamento em estufa (combinação), e madeira tratada pelo uso de estufa elétrica apenas (estufa), nas propriedades mecânicas, higroscópicas e biológicas das madeiras de Pinus taeda L. e Eucalyptus grandis W. Hill ex Maiden, comparando-as com os resultados obtidos para a madeira sem tratamento. Para tanto, foram amostradas três árvores com 25 anos, para cada espécie, de onde se extraíram as duas primeiras toras, para confecção dos corpos de prova utilizados nas avaliações. No tratamento de combinação, as peças foram submetidas a termorretificação em autoclave a 130ºC/±3°C e pressão de 2 kgf/cm², por 3 horas e, após um período de condicionamento, submetidas ao calor em estufa elétrica a 160°C/±1°C, pelo mesmo período; já as peças destinadas apenas ao tratamento em estufa foram submetidas a última condição. As propriedades físicas consistiram na avaliação da perda de peso e massa específica, atribuída ao tratamento, umidade de equilíbrio, taxa de absorção de água, efetividade de repelência à água, eficiência anti inchamento, inchamento tangencial, radial, volumétrico e coeficiente de anisotropia; as propriedades mecânicas consistiram na avaliação do módulo de elasticidade e ruptura em flexão estática, resistência máxima à compressão paralela, dureza de Janka, resistência ao impacto; por fim, para as propriedades biológicas, empregou-se o ensaio de apodrecimento acelerado em laboratório, utilizando fungos de podridão branca e parda. O efeito do tratamento térmico empregado sob as duas metodologias, provocaram resultados diferentes do esperado, no que se refere as propriedades mecânicas e biológicas. Os resultados obtidos indicaram que os tratamentos térmicos empregados, foram eficientes na redução da higroscopicidade e aumento da estabilidade dimensional de ambas as espécies, com os melhores resultados obtidos pelo método de combinação. Para as propriedades mecânicas, os tratamentos térmicos promoveram efeitos diversos, chegando a um incremento da resistência para certas propriedades e, em relação à durabilidade biológica das peças, os tratamentos favoreceram o apodrecimento aos fungos empregados, efeito mais pronunciado para o método combinado.

Cette thèse est consacrée à l’étude de l’évolution des propriétés physico-chimiques d’un panache d’aérosols désertiques nord africains au cours de son transport vers l’Europe du Nord. Cet épisode de mai 2008 est considéré comme l’évènement de transport d’aérosols désertiques le plus important de ces cinq dernières années observé sur le continent européen. La propagation de ce panache a été étudiée en combinant des moyens d’observation (sols, aéroportées, spatiales) au modèle de recherche Méso-NH. L’analyse des processus de dépôt a révélée que les quantités éliminées de l’atmosphère par dépôt sec et humide représentent respectivement 7 et 40 % de la quantité émise. Les valeurs d’épaisseur optique mesurées à 440 nm sur l’Europe variaient de 0.1 à 0.8, avec un maximum proche de 1 au-dessus des Pays-Bas. Au-dessus de cette région, les aérosols désertiques sont principalement situés entre 2.5 et 5.2 km d’altitude, mais aussi proche de la surface. La concentration en aérosols désertiques au sein de ces deux couches a été estimée respectivement à 350 et 450 ��g.m-3. Néanmoins, les mesures réalisées ne présentaient pas les caractéristiques optiques habituellement associées à la présence d’aérosols désertiques. En particulier, la présence d’une importante dépendance spectrale a été observée le 30 mai à proximité de Cabauw. L’exploitation des simulations ont permis de montrer que cela résultait d’une efficacité de lessivage plus importante du mode grossier. La présence d’aérosols désertiques coïncide avec une augmentation de la concentration des noyaux de condensation (CCN). Nos résultats suggèrent que le mélange entre le panache et les aérosols de pollution d’origine anthropique a conduit à une augmentation des capacités hygroscopiques des aérosols désertiques. Ce travail de recherche confirme ainsi que les conditions physico-chimiques de l'atmosphère régissent le cycle de vie des aérosols. / This thesis focuses on the evolution of the dust physical and chemical properties through a case of long-range transport of Saharan dust over Northern Europe. This episode of May 2008 is considered as the strongest event of Saharan dust transport to Europe observed since these last five years. This spread of dust is investigated by combining observations (ground-based, airborne, satellite) and the meso-scale model Méso-NH.The analysis of the removal processes reveals that the amounts lost by dry and wet deposition represent 7 and 40 % the total dust emitted respectively. The observed aerosol optical thickness ranged from 0.1 to 0.8 at the wavelength of 440 nm, with a maximum value close to 1 is found over the Netherlands. Over that site, the dust layer was mainly located between 2.5 and 5.2 km, moreover dust was also present at 0.5 km. The concentration of dust inside these two layers is estimated to 350 and 450 ��g.m-3 respectively. Nevertheless, the usual optical characteristics of Saharan dust were not observed. In particular, the scattering coefficient measurements revealed a strong spectral dependence observed during the 30th May, close to Cabauw. The analysis of the numerical experiements revealed that this was due to high precipitation scavenging efficiency for the coarse mode. The presence of Saharan dust coincides with an increase of the cloud condensation nuclei (CCN) concentration. Our results suggest that the mixing processes between the Saharan dust and anthropogenic particles have led to an increase of the Saharan dust hygroscopic properties. Thus, this thesis confirms that physical and chemical conditions of the atmosphere govern the life cycle of dust.

It has been historically assumed that most of the uncertainty associated with the aerosol indirect effect on climate can be attributed to the unpredictability of updrafts. We assess the sensitivity of cloud droplet number density to realistic variations in aerosol chemical properties and to variable updraft velocities using a 1-dimensional cloud parcel model. The results suggest that aerosol chemical variability may be as important to the aerosol indirect effect as the effect of unresolved cloud dynamics, especially in polluted environments. We next used a continuous flow streamwise thermal gradient Cloud Condesnation Nuclei counter (CCNc) to study the water-uptake properties of the ambient aerosol, by exposing an aerosol sample to a controlled water vapor supersaturation and counting the resulting number of droplets. The heat transfer properties and droplet growth within the CCNc were first modeled and experimentally characterized. We describe results from the MIRAGE field campaign at a ground-based site during March, 2006. Size-resolved CCN activation spectra and hygroscopic growth factor distributions of the ambient aerosol in Mexico City were obtained, and an analytical technique was developed to quantify a probability distribution of solute volume fractions for the CCN, as well as the aerosol mixing-state. The CCN were shown to be much less CCN active than ammonium sulfate, with water uptake properties more consistent with low molecular weight organic compounds. We also describe results from the GoMACCS field study, an airborne field campaign in Houston, Texas during August-September, 2006. GoMACCS tested our ability to predict CCN for highly polluted conditions with limited chemical information. Assuming the particles were composed purely of ammonium sulfate, CCN closure was obtained with a 10% overprediction bias on average for CCN concentrations ranging from less than 100 cm-3 to over 10,000 cm-3, but with on average 50% variability. Assuming measured concentrations of organics to be internally mixed and insoluble tended to reduce the overprediction bias for less polluted conditions, but led to underprediction bias in the most polluted conditions. Comparing the two campaigns, it is clear that the chemistry of the particles plays an important role in our ability to predict CCN concentrations.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study aims to investigate chemical, physical, mechanical and surface properties of Eucalyptus grandis and Eucalyptus cloeziana wood subjected to different treatments of freezing and heat. To achieve this, six trees for each specie were used to prepare sample for each mechanical test. The samples were subjected to six thermal treatments. Freezing treatment was performed in a horizontal freezer at -22 ± 2°C for 72 hours, while heat treatment was performed using an oven with force air circulation at 180 and 200 ± 1°C for 3.5 hours. Sampling to perform chemical, physical and surface tests were obtained from samples used in mechanical characterization of wood. Chemical changes were evaluated quantitatively through wet process and qualitatively through infrared spectroscopy (ATR-IR). Physical properties evaluated were: weight loss, specific gravity, equilibrium moisture content, dimensional stability and hygroscopicity of wood. Mechanical evaluation was performed through static bending, impact strength, compression parallel to fibers and Janka hardness. Color and wettability of wood were evaluated using colorimetry and contact angle techniques, respectively. The main findings showed that freezing slightly affected the chemical properties of wood, in which the main changes were found in heat treatments, mainly at 200°C. Freezing improve in weight and equilibrium moisture content of wood, while heat treatment caused weight loss and decrease of equilibrium moisture content of wood. Both heat treatments improved dimensional stability of wood, however when freezing and heat was performed in a combination, they did not showed the best results. Regarding the hygroscopicity of wood, results obtained in heat treatment at 200°C should be highlighted. On the other hand, freezing treatment increased absorption of water. In general, freezing reduced mechanical properties of wood. Heat treatments increased stiffness at static bending and strength at compression parallel to fibers of wood however was responsible for reduction in other mechanical properties. Color of wood was affected mainly for heat treatments, in which a darkening of surface was observed and quantified by decrease of parameter L*. Wettability of wood slightly decreased after heat treatments. Influence of freezing on wettability of wood was related to the natural characteristic of wood from species studied because they did not showed a defined tendency. Therefore, it is believed that treatments performed in this study changed significantly the technological properties of wood. / O presente estudo teve como objetivos investigar as propriedades químicas, físicas, mecânicas e superficiais da madeira de Eucalyptus grandis e Eucalyptus cloeziana submetida a diferentes tratamentos de congelamento e termorretificação. Para tanto, foram confeccionados, a partir de seis árvores de cada espécie, corpos de prova para cada ensaio mecânico. Os corpos de prova foram submetidos a seis tratamentos térmicos. O congelamento foi realizado em um freezer horizontal sob condições de temperatura e tempo de -22 ± 2°C durante 72 horas, enquanto que a termorretificação foi realizada em uma estufa laboratorial com circulação de ar forçada, à 180 e 200 ± 1°C durante 3,5 horas. A amostragem para realização dos ensaios químicos, físicos e superficiais foram provenientes dos corpos de prova utilizados na caracterização mecânica da madeira. As modificações químicas foram avaliadas quantitativamente em ensaios via úmida e qualitativamente por espectroscopia no infravermelho (ATR-IR). As propriedades físicas avaliadas foram a perda de massa e massa específica, teor de umidade de equilíbrio, estabilidade dimensional e higroscopicidade da madeira. Para avaliação das propriedades mecânicas foram realizados ensaios de flexão estática, flexão dinâmica, compressão paralela e dureza Janka. Também foram avaliadas a colorimetria e molhabilidade da madeira, por meio das técnicas de colorimetria e ângulo de contato. Os principais resultados encontrados mostraram que o congelamento pouco afetou as propriedades químicas da madeira, sendo as principais alterações oriundas do processo de termorretificação, principalmente a 200°C. O congelamento causou acréscimos na massa e no teor de umidade de equilíbrio da madeira, enquanto que a termorretificação ocasionou a perda de massa e redução do teor de umidade de equilíbrio. Os dois tratamentos térmicos causaram melhoria na estabilidade dimensional, entretanto, quando combinados, não apresentaram os melhores resultados. Para a higroscopicidade destacam-se os resultados obtidos na termorretificação a 200°C, por outro lado, o congelamento aumentou a absorção de água. De maneira geral, o congelamento causou redução nas propriedades mecânicas da madeira. A termorretificação causou aumento na rigidez a flexão estática e resistência a compressão paralela e redução nas demais propriedades mecânicas. A coloração da madeira foi afetada principalmente pela termorretificação, em que ocorreu um escurecimento superficial, quantificado pelo decréscimo do parâmetro de claridade L*. A molhabilidade da madeira diminuiu sensivelmente após a realização dos tratamentos de termorretificação. A influência do congelamento sobre a molhabilidade foi atribuída a características naturais da madeira das espécies estudadas, sem apresentar tendência definida. Dessa forma, verificou-se que os tratamentos realizados alteraram significativamente as propriedades tecnológicas da madeira.

Dans le contexte actuel, les communautés scientifiques et politiques sont centrées sur les différentes manières de mieux préserver et utiliser les ressources naturelles de notre planète. Dans le but de réduire la consommation des matières issues du pétrole, et de développer de nouveaux produits et procédés industriels plus propres, l’industrie des fragrances et des arômes cherche aujourd’hui à développer de nouveaux matériaux bio-sourcés pour protéger leurs molécules volatiles odorantes. Dans ce travail de thèse, les maltodextrines ont été choisies comme composé majoritaire, les protéines de pois et un amidon modifié ont été sélectionnés comme additifs compatibilisants pour la composition des matrices d’agromatériaux. L’incorporation des molécules volatiles odorantes, ainsi que l’élaboration des matrices encapsulantes ont été réalisées en une seule étape, grâce à la technologie d’extrusion bi-vis à basse température. Les caractéristiques physicochimiques, thermiques et morphologiques de ces nouvelles matrices enrobantes ont été analysées, de même que la détermination de leur efficacité d’encapsulation et du profil de libération du principe actif. Les différentes investigations menées ont permis de mieux comprendre l’impact des formulations et de l’incorporation des molécules volatiles odorantes sur les paramètres opératoires. Les interactions entre la matrice enrobante et le principe actif ont également été étudiées. Les conditions d’extrusion établies, ainsi que les caractéristiques de ces nouvelles matrices encapsulantes, s’avèrent être pertinentes pour le domaine de la parfumerie. / Nowadays, scientific and political communities are focused on ways to better preserve and manage the natural resources of our planet. In order to reduce consumption of fossil resources, and to develop more environmentally friendly industrial processes, the industry of flavors and fragrances became interested in developing new bio-based encapsulating materials. In the present work, maltodextrins have been chosen as main component of the matrix, and pea protein isolate and a modified starch were selected as compatibilizing additives. The incorporation of volatile odorant compounds and the elaboration of the new bio-based delivery systems were performed, all in one single step, by low temperature twin-screw extrusion. The physicochemical, thermal and morphological properties of these matrices were studied, as well as the encapsulation efficiency and the release profile of the active compounds. These investigations have led to a better understanding of the impact of the formulations and of the incorporation of the active compound on the process parameters. The interactions between the wall and the encapsulated materials were also analyzed. The characteristics of the new bio-based delivery systems and the established extrusion process conditions were found to be very promising to be employed in the field of perfumery.

[pt] Este trabalho tem como objetivo estudar a expansão térmica extrínseca e intrínseca do Al2-xInxW3O12, suas transições de fase e higroscopicidade para as fases: x = 0,2; 0,4; 0,7 e 1. Os pós foram obtidos pelo método de co-precipitação. Esta técnica permite a produção de materiais cerâmicos avançados por meio de reações químicas suaves em temperaturas relativamente baixas usando em solução aquosa. A família Al2-xInxW3O12 faz parte do que se pode classificar como cerâmicas termomióticas (do grego thermo para calor e mio para contração) e pertence à família A2M3O12 (A = cátion trivalente, M = cátion hexavalente), com expansão térmica negativa ou quase zero. Este fato torna esta cerâmica uma candidata potencial em aplicações que requerem materiais com alta resistência ao choque térmico. Na literatura, encontramos poucos estudos sistemáticos que relatam parâmetros de interesse no sistema Al2-xInxW3O12, como os coeficientes de expansão térmica (CET) e suas transições de fase. Portanto, o presente trabalho tem como objetivo determinar os coeficientes de expansão intrínsecos (determinados por difração de raios X que é relativa às variações nos parâmetros de rede do material) e o coeficiente de expansão extrínseco (obtido por dilatometria que leva em consideração a variação intrínseca e também extrínseca, dimensões do material, estas últimas relacionadas a defeitos microestruturais) do sistema Al2-xInxW3O12, temperaturas de transição de fase (monoclínica e ortorrômbica) na faixa de x = 0,2 a x = 1. Além disso, este estudo pretende relatar a higroscopicidade deste sistema (usando termogravimetria). Os resultados mostraram que o Al2-xInxW3O12 adotou uma estrutura ortorrômbica em temperatura ambiente para as composições x = 0,2; 0,4; 0,7 e uma estrutura monoclínica para a composição x = 1. Na fase x = 1, uma transição de fase monoclínica para ortorrômbica ocorreu perto de 200 oC. Finalmente, o sistema Al2-xInxW3O12 apresentou baixa higroscopicidade nas quatro fases estudadas. / [en] The Al2-xInxW3O12 family is part of thermomiotic ceramics (from the Greek thermo for heat and mio for contraction) and belongs to the A2M3O12 family (A = trivalent cation, M = hexavalent cation), wich can show negative or near zero thermal expansion. This fact makes this ceramic a potential candidate in applications that require materials with high resistance to thermal shock. In the literature, we found few systematic studies that report parameters of interest in Al2-xInxW3O12 system such as the coefficients of thermal expansion (CTE) and its phase transitions. Therefore, the present work aims to determine the intrinsic coefficients of expansion (determined by X-ray diffraction that is relative to variations in the material s lattice parameters) and the extrinsic coefficient of expansion (obtained by dilatometry which takes into account intrinsic and also extrinsic variations in dimension, these later related to microstructural defects) of Al2-xInxW3O12, phase transition temperatures (monoclinic to orthorhombic) in the range between x = 0.2 to x = 1. In addition, this study intends to report hygroscopicity of this system (using thermogravimetry). The results showed that Al2-xInxW3O12 adopted an orthorhombic structure at room temperature (RT) for x = 0.2; 0.4; 0.7 compositions and monoclinic structure for x = 1 composition. In x = 1 phase, a monoclinic to orthorhombic phase transition occurred close to 200 oC. Finally, the Al2-xInxW3O12 system presented low hygroscopicity in all four studied phases.

Le développement d’un médicament pour une cible thérapeutique donnée passe par plusieurs étapes qui se résument en une étape de criblage, une phase préclinique et plusieurs phases cliniques. Ces étapes permettent de sélectionner une substance active et de démontrer son efficacité thérapeutique et sa sécurité toxicologique. Ces deux critères définissent la qualité du médicament qui, une fois démontrée, doit être garantie pendant toute sa durée de validité. La qualité est évaluée au moyen d’études de stabilité qui sont réalisées d’abord sur la matière première de la substance active au cours de la phase de pré-développement du médicament, ensuite sur le produit fini. La stabilité intrinsèque de la substance active concerne à la fois ses propriétés chimiques et ses propriétés physiques qui sont liées à la nature de la substance. L’étude de stabilité repose d’abord sur la caractérisation de ces propriétés, et ensuite sur l’étude de la sensibilité de la substance à l’égard des facteurs environnementaux pouvant modifier les propriétés intrinsèques de la substance. L’approche adoptée dans ce travail repose d’une part sur l’évaluation de la stabilité chimique c’est à dire de la réactivité chimique des substances à usage pharmaceutique au travers des études de pureté chimique et des études de dégradation forcée de ces substances en solution, et d’autre part, sur l’évaluation de la stabilité physique. Dans ce cadre, l’étude du polymorphisme cristallin revêt une grande importance, tout comme l’aptitude à la formation d’hydrates ou de solvates. Cette étude, basée sur la thermodynamique, consiste pour l’essentiel à construire un diagramme de phases pression-température permettant de définir les domaines de stabilité relative des différentes formes cristallines. Cinq substances actives, existant à l’état solide et entrant dans la composition de médicaments administrés par voie orale, ont été étudiées dans le cadre de ce travail. L’analyse chimique du tienoxolol, présentant un effet anti-hypertenseur, a montré qu’il est très sensible à l’hydrolyse et à l’oxydation. Sept produits de dégradation ont été identifiés pour ce produit dont un schéma probable de fragmentation a été établi. Des diagrammes de phases pression-température ont été construits pour le bicalutamide et le finastéride, médicaments du cancer de prostate, en utilisant une approche topologique basée simplement sur les données disponibles dans la littérature. Cette étude a montré que la relation thermodynamique (énantiotropie ou monotropie) entre les formes cristallines sous conditions ordinaires peut être modifiée en fonction de la température et de la pression. Ce résultat est important pour la production des médicaments car il montre comment une telle information peut être obtenue par des mesures simples et accessibles aux laboratoires de recherche industrielle, sans que ces derniers soient contraints d’expérimenter sous pression. La méthode topologique de construction de diagramme de phases a été validée ensuite en la comparant à une méthode expérimentale consistant à suivre, par analyse thermique, des transitions de phases en fonction de la pression. La méthode expérimentale a été appliquée à deux composés, la benzocaine, anesthésique local, et le chlorhydrate de cystéamine, médicament utilisé pour les cystinoses. Les deux formes étudiées de benzocaine présentent une relation énantiotrope qui se transforme en relation monotrope à haute pression. Une nouvelle forme cristalline (forme III) du chlorhydrate de cystéamine a été découverte au cours de ce travail. La relation thermodynamique entre cette forme III et la forme I est énantiotrope dans tout le domaine de température et de pression. De plus, le chlorhydrate de cystéamine, classé hygroscopique, a fait l’objet d’une étude quantitative de sa sensibilité à l’eau, montrant qu’il devient déliquescent sans formation préalable d’hydrate (...) / The development of a drug for a given therapeutic target requires several steps, which can be summarized by drug screening, a preclinical phase and a number of clinical phases. These steps allow the selection of an active substance and a verification of its therapeutic efficacy and toxicological safety. The latter two criteria define the quality of the drug, which once demonstrated, must be guaranteed throughout its shelf life. Quality is assessed through stability studies that are carried out with the raw material of the active substance (preformulation phase) and with the final product. The intrinsic stability of the active substance depends on its chemical and physical properties and their characterization is the core of the stability studies, which in addition consists of sensitivity studies of the active pharmaceutical ingredient (API) for environmental factors that can modify the intrinsic properties of the substance. The approach presented in this work is based on the one hand on the assessment of the chemical stability, i.e. the reactivity of APIs through chemical purity studies and forced degradation in solution, and on the other hand on the assessment of the physical stability. For the latter, crystalline polymorphism is of great importance, as is the ability of the API to form hydrates or solvates. The study of crystalline polymorphism is based on the construction of pressure-temperature phase diagrams in accordance with thermodynamic requirements leading to the stability condition domains of the different crystalline forms. The stability behavior of five APIs used or meant for oral applications has been studied as part of this work. The chemical analysis of tienoxolol, an antihypertensive drug, has demonstrated its sensitivity for hydrolysis and oxidation. Seven degradation products were identified and patterns of fragmentation have been established. Pressure-temperature phase diagrams have been constructed for bicalutamide and finasteride, drugs against prostate cancer, using a topological approach based on data available in the literature. The study demonstrates that the thermodynamic relationship (enantiotropy or monotropy) between crystalline forms under ordinary conditions can change depending on the pressure. This is important for drug development as it demonstrates how stability information can be obtained by standard laboratory measurements accessible to industrial research laboratories without the necessity to carry out experiments under pressure. The topological approach for the construction of phase diagrams has subsequently been validated by measuring transition temperatures as a function of pressure. Experiments have been carried out with benzocaine, a local anesthetic, and with cysteamine hydrochloride, a drug used against cystinosis. Two crystalline forms were observed in the case of benzocaine. They exhibit an enantiotropic relationship that becomes monotropic at high pressure. For cysteamine hydrochloride, a new crystalline form (form III) was discovered. The thermodynamic relationship between the new form III and the known form I is enantiotropic for the entire temperature and pressure range. Cysteamine hydrochloride’s sensitivity to water has been studied, as it is hygroscopic. It has been demonstrated that it becomes deliquescent in the presence of water and no trace of a hydrate has been found. Finally, a study combining thermal and chromatographic methods showed that, under the effect of temperature, cysteamine hydrochloride turns into cystamine in the solid as well as in the liquid state, The latter is known to be an important impurity of cysteamine hydrochloride. In conclusion, the approach developed in this work allowed to characterize the stability properties of a number of APIs and to determine the factors that may change these properties and influence the intrinsic stability (...)