Stellar population synthesis is a tool for modelling galaxies and their spectral energy distributions. By combining the spectra of every star within a galaxy, it becomes possible to form the spectrum of the galaxy as a whole. This requires a large collection of stellar spectra which, ideally, contains spectra for every kind of star in the model galaxy. To contribute to the development of stellar population synthesis and model atmospheres, I examine two such collections of stars, the MARCS and ATLAS9 theoretical stellar libraries. I compare 18 spectra of model stars for which both libraries have performed calculations. Stars with three different temperatures were chosen (8000K, 4500K and 3500K). For each temperature, three values of metallicity and two values of effective gravity were chosen. I find a mismatch in the spectra of the medium and low temperature model stars (4500K and 3500K), in addition, a difference in molecular features (~7000Å) is found in the 3500K low metallicity models ([Me/H]=-2.5). I conclude that this difference is caused by missing molecular opacities for the calcium hydride (CaH) molecule in the ATLAS9 library. Four possible causes of the overall mismatch are discussed: the temperature structure of the models; the geometry of the models; and partition functions used for the calculation of the models. I conclude that none of these four sources could produce the mismatch. This leaves room for further investigation into the cause of the mismatch.

Les déchets issus de l’industrie vinicole française sont traditionnellement traités et valorisés en distilleries. Ce travail porte sur l’étude de la valorisation à échelle industrielle d’un des résidus ultimes des distilleries : le marc de raisin épuisé. Les marcs issus de différents bassins de productions français ont été caractérisés chimiquement, principalement par leur taux de tannins condensés et de sucres. Les conditions d’extraction des tannins condensés ont été optimisées en laboratoire puis le procédé a été transféré à l’échelle industrielle. Plusieurs extractions ont été menées dans trois distilleries partenaires et l’analyse chimique (en termes de polyphénols, de tannins condensés, de sucres et de matières inorganiques) des différentes fractions isolées a été réalisée. Des extraits industriels ont permis la fabrication du premier panneau de particules dont l’adhésif est constitué à 80 % de tannins de marcs de raisins et renforcé à l’aide d’une résine synthétique satisfaisant à la norme européenne de cohésion interne. Ces extraits industriels ont également partiellement substitué une résine phénol-formaldéhyde pour la production de panneaux de particules. Différents post-traitements ont été réalisés sur les extraits de marcs afin d’en augmenter la réactivité chimique vis-à-vis d’agents de réticulation. Une filtration à un seuil de coupure de 1 µm a entrainé une légère amélioration des performances adhésives, alors qu’une hydrolyse acide de l’extrait les a dégradées. Un procédé d’ultrafiltration des extraits à 5 kDa ou 1 kDa a permis d’obtenir des extraits beaucoup plus réactifs et ouvre des perspectives pour la production d’adhésifs biosourcés pour le bois / Wastes from the French wine industry are traditionally treated and upgraded in distilleries. This work deals with the study of an industrial-scale valorization of a final waste from distilleries: the spent grape pomace. Pomace from different French production areas were chemically characterized, in terms of condensed tannins and polysaccharides. An extraction process of condensed tannins has been optimized in laboratory and was then transferred to an industrial scale. Several extractions were carried out in three partner distilleries and chemical analysis (in terms of polyphenols, condensed tannins, sugars and inorganics) of the different isolated fractions were performed. Industrial extracts were used for the elaboration of the first particleboard whose adhesive constituted by 80% of grape pomace tannins and strengthened with a synthetic resin to satisfy the European standard for internal bond. These industrial extracts were also used to partially substitute a phenol-formaldehyde resin for the production of particleboards. Different post-treatments were performed on the pomace extracts in order to increase their chemical reactivity toward cross linking agents. Filtration with a cut-off of 1 µm led to a slight improvement in adhesive performances, whereas acid hydrolysis of the extract have degraded it. An ultrafiltration process of the extracts at 5 kDa or at 1 kDa enabled to get much more reactive extracts and opened up prospects for the production of bio-based adhesives for wood

Les marcs de raisin issus de la viniculture constituent un gisement de ressource naturelle abondant, sous valorisé et riche en polyphénols. Une méthode d?extraction de ces tannins condensés a été développée et optimisée en vue d'une application en adhésif pour les produits dérivés du bois. Les tannins ont été caractérisés par Résonance Magnétique Nucléaire, spectroscopie Infra Rouge (FTIR), spectrométrie de masse (MALDI TOF) et Analyse Thermomécanique (TMA). Des panneaux de particules ont été fabriqués à l'aide des colles élaborées en laboratoire et testés suivant les normes françaises en vigueur, plusieurs dépassent largement les valeurs seuils / The extraction of condensed tannins from grape pomace was examined using water medium in the presence of different bases as catalyst (NaOH, Na2CO3, NaHCO3 and Na2SO3). Two different extraction processes and the influence of 4 parameters (i.e., temperature, reaction time, chemical reagents and concentration of the chemical reagents) on the tannin extracts yields and properties were studied. The tannin fractions were characterized by Fourier transform-infrared spectroscopy, thermogravimetric analysis, carbon nuclear magnetic resonance spectroscopy and matrix assisted laser desorption ionization time of flight mass spectrometry ( MALDI-TOF ). It was demonstrated that it is possible to extract reactive tannins from grape pomace in basic medium. The tannin extracts obtained by precipitation in acidic conditions display a high phenolic content (Stiasny number higher 95%) but low water solubility and low reactivity toward formaldehyde because of the formation of catechinic acid phlobatannins during the acidification step. The tannins extracts obtained by lyophilization of the liquid, despite of their lower phenolic contents, displayed promising properties for adhesive applications. The optimum temperature of the extraction process was 100 °C, reaction time was 120 min; the best concentration of reagent was 10% (w/w). It was also shown that addition of sulphite ions during the extraction step improved the process :y the introduction of a sulfonic group through sulfitation increased both tannin solubility and reactivity as a result from the opening of the heterocyclic ring during extraction The structure of grape pomace sulfited tannin extracts did not present noticeable discrepancy exception of the ratio of the opening pyran ring which was different as a function of the catalyst used. The opening of pyran ring during the tannins extraction seem to be more important by using Na2CO3 and NaHCO3 than when using NaOH. The FT-IR bands assigned to aromatic ring vibration and carbonyl groups were stronger and no bands attributed to sulfited groups were tested detected in acidified tannins compared to lyophilized tannins. The TG2 results showed that the weight lost of these tannin extracts mainly composed of two steps. The first step starts from room temperature to 200 °C. It is attributed to the mass lost of water and some easy-degraded small low molecules. The secondly steps which is the mainly degradation step of tannin extract samples from 200 to 400 °C. The results from 13C-NMR showed that condensed tannin extracts from grape pomace were consistent with dominant procyanidin units with a minor amount of prodelphinidin units that are linked together by a C4-C8 bond. Relatively low carbonhydrate and high catechinc acid content was observed in acidified tannins compared to lyophilized tannins. It was shown by MADI-TOF experiments that grape pomace tannin extracts are mainly composed of flavoinoid oligomers up to 6 repeating units in lyophilized tannins and 10 repeating units in acidified tannins respectively, with dominant procyanidin units. A small proportion of substitution with glucose and gallic acid was detected in procyanidin units of polyflavonoid oligomers. The degree of polymerization of acidified tannins is higher than lyophilized tannins. Two different formulations (nonfortified tannin adhesive and fortified with addition of 20% of polymeric 4, 4'-diphenyl methane diisocyanate (p-MDI)) were used to press one layer wood particle board. It was shown that the nature of the extraction reagent (NaOH, Na2CO3 or NaHCO3) greatly impacts the properties of the resins and the mechanical properties of the panel internal bonding strengths. The particleboards bonded by the tannins extracted using Na2CO3 as catalyst give the best performance and were good enough to pass relevant international standard specifications for interior grade panels. Formaldehyde emission of these panels was below the European Norm requirements (<= 6.5 mg/ 100g panel)

Ce travail de doctorat traite l’optimisation des méthodes d’extraction des composés phénoliques à partir des sous-produits de la viticulture et de la viniculture, à savoir les sarments de vigne et les marcs de raisins. Plusieurs technologies innovantes sont appliquées et comparées : l’extraction accélérée par solvant (EAS), les décharges électriques de haute-tension (DEHT), les ultrasons (US) et les champs électriques pulsés (CEP). Les extractions solide-liquide faites sur les sarments ont montré que, parmi les solvants étudiés, l’eau est le moins efficace. L’ajout de la β-cyclodextrine dans l’eau améliore le procédé d’extraction mais est moins efficace que les mélanges hydroéthanoliques. L’extraction en milieu alcalin donne le meilleur rendement en composés phénoliques. L’intensification de l’extraction des composés phénoliques des sarments est possible grâce aux nouvelles technologies d’extraction. L’efficacité des méthodes testées est la moindre avec les US, moyenne avec les CEP pour atteindre le meilleur rendement phénolique avec les DEHT. La filtrabilité de ces extraits est d’autant plus lente que leur composition est complexe. L’ultrafiltration membranaire permet une très bonne purification et concentration des composés phénoliques. L’étude des mécanismes d’action des DEHT a permis d’identifier les phénomènes favorisant l’extraction des composés phénoliques à partir des sarments. Un effet mécanique des DEHT, capable de fragmenter les sarments, est en majorité responsable de cette amélioration. Le procédé énergivore du broyage pourra alors être omis. Un effet électrique contribuant également à l’intensification du procédé d’extraction est démontré. La formation de peroxyde d’hydrogène durant le traitement par DEHT est quantifiée mais ne semble pas altérer les composés phénoliques qui sont des molécules à capacité antiradicalaire élevée. Quant aux études portées sur les marcs de raisins, la variation simultanée de plusieurs paramètres opératoires a permis l’optimisation de l’extraction aqueuse et hydroéthanolique des composés phénoliques en ayant recours à la méthodologie de surface de réponse (MSR). Le passage d’un milieu aqueux à un milieu hydroéthanolique a permis d’améliorer nettement le procédé d’extraction solide-liquide des composés phénoliques et l’utilisation de l’EAS a permis l’augmentation du rendement en composés phénoliques jusqu’à trois fois par rapport à l’optimum obtenu en milieu hydroéthanolique. / This study deals with the optimization of the extraction methods of phenolic compounds from viticulture and viniculture by-products, namely vine shoots and grape pomace. Several innovative technologies were tested and compared: high voltage electrical discharges (HVED), accelerated solvent extraction (ASE), ultrasounds (US) and pulsed electric fields (PEF). The solid-liquid extraction conducted on vine shoots showed that, amongst the studied solvents, water is the least effective. The addition of the β-cyclodextrin to water improves the extraction process but remains less effective than that with hydroethanolic mixtures. The extraction in alkaline medium gives the highest phenolic compound extraction yields. The intensification of phenolic compound extraction from vine shoots was possible thanks to new extraction technologies. The effectiveness of the tested methods was the least with US, followed by PEF to accomplish the highest phenolic yield with HVED. The filterability of the extracts was slower when their composition was complex, and the membrane technology allowed a good purification and concentration of phenolic compounds. The reason behind the high effectiveness of HVED was investigated. The action mechanisms of HVED were studied in details. A mechanical effect of HVED provoked vine shoots fragmentation and particle size reduction. This was the main phenomenon responsible for the intensification of the extraction process. It also suggested that a grinding pretreatment would not be necessary prior to HVED, which considerably diminishes the energy input of the overall process. The presence of a non-mechanical effect and its contribution in the efficiency of HVED were also shown. The formation of hydrogen peroxide during the treatment was observed. However it did not seem to alter vine shoot phenolic compounds since these demonstrated a high radical scavenging capacity. As for the studies conducted on grape pomace, the simultaneous variation of several operating parameters allowed the aqueous and hydroethanolic optimization of phenolic compound extraction from these byproducts by response surface methodology (RSM). The passage from an aqueous to a hydroethanolic medium clearly improved the solid-liquid extraction of phenolic compounds from grape pomace. The use of ASE further increased the phenolic compound yield up to three times as compared to the optimum obtained with a hydroethanolic solvent.