Le travail de recherche présenté dans cette thèse s’est orienté vers l’élaboration de matériaux avancés et la conception de polymères/composites biosourcés. Ce dernier sujet a été entrepris à travers la combinaison de différentes matières premières biosourcées qui sont connues comme ayant un grand potentiel de substitution des monomères pétrosourcés. Tout d’abord, un travail fondamental a été exécuté en combinant l’huile de lin epoxydée (ELO) avec des dérivés d’anhydrides d’acides comme agents de réticulation, afin de relier la réactivité chimique de polymérisation à la structure du réseau formé et aux propriétés thermomécaniques. Afin de devenir économiquement viable, les bio-raffineries doivent urgemment valoriser les sous-produits issus de la conversion de la biomasse. Fort de ce constat, une deuxième étude sur l’incorporation et la copolymérisation d’une quantité importante d’humins (résidu hétérogène obtenu durant la conversion des sucres en hydroxymethylfurfural (HMF)) avec de l’alcool furfurylique (FA) a été réalisée avec succès afin de créer de nouvelles résines thermodures. Une autre voie proposée consiste en la combinaison de ELO et de FA à travers une polymérisation cationique, dans l’idée de créer de nouvelles résines totalement biosourcées, générant ainsi une gamme de matériaux aux propriétés mécaniques modulables. / The research work presented in this thesis was oriented on advanced thermoset materials and also on the conception of bio-based polymers and composites. This last topic has been investigated by the combination of different bio-based raw materials which are well-known to have a great potential to substitute the petroleum monomers. Firstly, a fundamental work has been done on the combination of epoxidized linseed oil (ELO) and anhydrides as cross-linkers, which links the polymerization reactivity with the network structure and thermomechanical properties. For being economically realistic, the bio-refineries are urged to valorize the sidestream products issued from biomass conversion. In that respect, a second study investigated successfully the incorporation and copolymerization of an important amount of humins (heterogeneous residues obtained during the sugar conversion into hydroxymethylfurfural (HMF)) with furfuryl alcohol (FA) in order to create new resins. Another proposed combination, focused on ELO and FA cationic copolymerization with the purpose to create new fully bio-based resins with tailored mechanical properties. Concerning the elaboration of advanced polymers and composites, a reflection around the hierarchically organized natural materials has been achieved in order to adapt the self-organization and structuration concepts to polymeric network.

Currently, the major sources of fuel, energy, and chemicals are nonrenewable fossil resources such as petroleum, natural gas, and coal. Additionally, petroleum is used for the production of most transportation fuels and for the production of about 95% of organic chemicals. However, the production and use of non-renewable fossil fuels are unsustainable. For economic and environmental sustainability, there is a need to search for new and/or renewable resources and technologies for energy, fuels, and chemicals production that have the potential of effectively substituting fossil resources. In this context, lignocellulosic biomass is one of the candidates that meet these requirements due to its abundance and renewability. Lignocellulosic biomass-derived sugars can be chemically converted into 5-(hydroxymethyl)furfural (HMF), a versatile platform chemical that can used to generate intermediates for the production of biofuels and chemicals. In this dissertation novel catalytic processes for converting monosaccharides into HMF are described. In chapter one, a literature review of the significance of HMF and the chemical intermediates derived from HMF is presented. The chapter also describes some of recent developments in the catalytic production of HMF from lignocellulosic sugars using homogeneous and heterogeneous catalysts. Chapter two discusses the catalytic activity of dimethylaluminum complexes bearing (aminomethyl)phenolate ligands that I developed for converting glucose to HMF in ionic liquids. A systematic study on the effects of modification of the aluminum ancillary ligands on the efficiency of glucose conversion is presented. High HMF yield were obtained with substitution of an aryl substituent on the amino groups of the (aminomethyl)phenolate ligands. In an effort to improve HMF yield, the effects of modifying the ligands on the phenolate moiety of the (aminomethyl)phenolate ligands were investigated in chapter three. Using bulky ortho-phenoxide substituents achieved high HMF yields. The selectivity for HMF production with respect to fructose dehydration was also discussed, together with spectroscopic characterization of the polymeric humins produced from the dehydration reactions. In chapter four a study of the structural differences of poor vs. effective dimethylaluminum complexes bearing (aminomethyl)phenolate ligands is described. Insights from this study shows that different precatalyst intermediate could be formed depending on the aluminum complex used, which in turn affects HMF selectivity of dehydration reactions. The isomerization of glucose to fructose using aluminum complexes in N-methyl-2-pyrrolidone (NMP) is discussed in chapter five. Using NMR spectroscopy on isotopically labeled glucose, a mechanism for glucose isomerization to fructose is presented. Finally, chapter six gives a summary and describes potential future directions for the research detailed in this dissertation.

As usinas sucroalcooleiras aproveitam apenas a fração colmo da planta para a produção de açúcar e etanol restando o bagaço da cana-de-açúcar, composto das frações fibra e medula, é em grande parte usado para geração de energia elétrica. O resíduo agrícola da cana RAC, constituído pelas folhas, palha, e a ponteira da cana de açúcar são cortados durante a colheita e devolvidos ao campo para adubar o solo contribuindo para a lavoura da cana-de-açúcar. Os painéis hardboards são produzidos a partir da aplicação de calor e pressão a um colchão de fibras ou serragem de madeira, sendo aplicados como pisos na construção civil e como pranchetas e fundo de gavetas na indústria moveleira. Assim, a proposta desse trabalho foi o estudo da utilização dos materiais provenientes da cultura de cana-de-açúcar, em particular a fração medula do bagaço de cana-de-açúcar e do RAC para produção de hardboard (sem a utilização de adesivos) e particleboards (com a adição de resina fenol-formaldeído). Adicionalmente, estudou-se a adição da humina resultante de processos de hidrólise ácida do bagaço de cana-de-açúcar como coadjuvante na produção de painéis de medula de cana-de-açúcar. A utilização da resina fenol-formaldeído foi estudada no intervalo de 10% a 33%, sendo os melhores resultados obtidos quando do uso de 25% de resina, que apresentou tensão máxima de 29,9 MPa em ensaio de tração. Definido esse valor, realizou-se o estudo do efeito da quantidade de humina no intervalo de 12,5% a 75%, o qual revelou que a humina leva à produção de materiais frágeis com redução do desempenho mecânico. As frações RAC foram empregadas para a produção de amostras com teor de resina fenol-formaldeído igual a 25%. Todos os corpos de prova produzidos foram analisados por ensaios de tração (MOR e MOE), análise térmica, microscopia eletrônica de varredura (MEV) e análise dinâmico mecânica. A produção de hardboards a partir da fração medula do bagaço de cana-de-açúcar, nas condições empregadas neste estudo preliminar, resultou em materiais com baixo desempenho mecânico, revelado pelos resultados dos ensaios de tração que indicou tensão máxima de 4,7 MPa. Entretanto, a mesma matéria prima quando misturada com resina fenol-formaldeído resultou na produção de particleboards que, apesar da dispersão pouca efetiva da resina, apresentaram um melhor desempenho mecânico (tensão máxima no intervalo de 29,9 a 11,3 MPa). Finalmente, os materiais obtidos com as frações RAC da cana-de-açúcar e resina FF mostraram-se mais homogêneos e com desempenho mecânico igual ou superior (tensão máxima no intervalo de 36,1 a 27,7 MPa) aos observados para os materiais obtidos com Pinus sp (tensão máxima de 27,7 MPa). / Sugar and ethanol mills use only the stem fraction of sugarcane for the production of sugar and ethanol. The sugarcane bagasse, composed of fiber and pith fractions, is largely used to generate electricity. The sugarcane agricultural residues - RAC, made up of leaves, straw and the tip of sugarcane are cut during harvest and returned to the field to fertilize the soil. Hardboard panels are produced from the application of heat and pressure to a fiber or sawdust mat. Its commercial application includes floors in construction and clipboards and bottom drawers in the furniture industry. Thus the purpose of this work was to study the use of materials from sugarcane culture, in particular the core fraction of bagasse sugarcane and the sugarcane trash for the production of hardboard (without the use of adhesives) and particleboards (with the addition of phenol formaldehyde resin). In addition, he studied the addition of the resulting humin acid hydrolysis process of sugarcane bagasse as an adjunct in the production of sugarcane pith panels. The use of phenol formaldehyde resin was studied in the range of 10% to 33%, with best results obtained when using 25% resin, which had maximum stress of 29.9 MPa in tensile testing. Once established, the study of the effect of the amount of humin was held in the range of 12.5% to 75%, which revealed that the humin leads to the production of brittle materials with reduced mechanical performance. Sugarcane trash fractions were used for production of resin samples with phenol formaldehyde content equal to 25%. All produced samples were analyzed by tensile tests (MOR and MOE), thermal analysis, scanning electron microscopy (SEM) and dynamic mechanical analysis. The production of hardboards from the marrow fraction of sugarcane bagasse, under the conditions employed in this preliminary study, resulted in materials with low mechanical performance, revealed the results of tensile tests indicated that maximum voltage of 4.7 MPa. However, the same raw material when mixed with phenol-formaldehyde resin resulted in the production of particleboards that despite the low effective dispersion of the resin, had a better mechanical performance (maximum stress in the range from 29.9 to 11.3 MPa). Finally, materials obtained from the fractions of RAC sugarcane and PF resin proved to be more homogeneous and with equal or higher mechanical performance (maximum stress in the range from 36.1 to 27.7 MPa) to that observed for materials obtained with Pinus sp (maximum stress of 27.7 MPa).

F�r die Therapie und Prophylaxe von Fischkrankheiten stehen nur wenige geeignete und zugelassene Medikamente zur Verf�gung. Daher kommt der Suche nach wirksamen und f�r Tier, Verbraucher und Umwelt sicheren Alternativen in der Fischhaltung eine besondere Bedeutung zu. �ber positive Effekte beim oralen Einsatz von Huminstoffen an landwirtschaftlichen Nutztieren, Zootieren und Heimtieren liegen eine Vielzahl von Berichten vor. Deshalb sollten in der vorliegenden Studie Huminstoffe (HS) in der �u�erlichen Anwendung bei Zierfischen und in der oralen Verabreichung �ber das Futter bei Nutzfischen n�her untersucht werden. Dazu wurden zwei Versuche (B I: Dauer 4 Tage; B II: Dauer 12 Tage) an Goldfischen (Carassius auratus) unter teichwirtschaftlichen Bedingungen, zwei Aufzuchtversuche (F I: Kv bis K3, Dauer: 1.000 Tage: F II: K0 bis K1, Dauer: 150 Tage) an Karpfen (Cyprinus carpio) in der Teichwirtschaft und ein Aufzuchtversuch (F III: vorgestreckte Brut bis 30 g Lebendmasse, 166 Tage) an Regenbogenforellen (Oncorhynchus mykiss) unter Laborbedingungen durchgef�hrt. Als Versuchsparameter dienten Mortalit�t und Morbidit�t, Wachstum und Futteraufwand in den Aufzuchtversuchen, pathologisch anatomische (einschlie�lich histologischer Befunde in B I und F II), parasitologische, bakteriologische und virologische Kriterien. Die Wasserqualit�t wurde regelm��ig ermittelt. In den Versuchen B I und B II wurde eine 10%ige Na-Humat-L�sung (HS vom Typ WH 67 SNa der Fa. Pharmawerk Weinb�hla) dem H�lterungswasser so zugesetzt, dass eine Na-Humat-Konzentration von 10 mg L-1 entstand. Zweij�hrige, multifaktoriell erkrankte Goldfische (B I: N=2 x 322, B II: N=2 x 100) wurden dem Na-Humat-Bad t�glich f�r die Dauer einer Stunde (B I) bzw. von 1,5 bis 2 Stunden (B II) ausgesetzt. Die HS-Badehandlungen f�hrten in beiden Versuchen zu einer Senkung der Verluste (Mortalit�tsrate in B I: 0,6 versus 4,7 %, p<0,0005; B II: 8 versus 16 %, p<0,05). Bei Versuchsende war in den Versuchsgruppen (Na-Humat-Bad) der Gesundheitszustand, beurteilt nach �u�erlich sichtbaren Ver�nderungen an Haut, Flossen und Kiemen, deutlich verbessert (B I: p<1�10-16; B II: p<0,001). So waren (Signifikanzangaben nur f�r B II) vor allem H�morrhagien der Haut und der Flossen (p<0,05), Flossenrand- und Kiemennekrosen (p<0,05) sowie akute Kiemenentz�ndungen (p<0,02) verringert. Die Badebehandlungen bewirkten weiter eine geringere Auspr�gung integument�rer Mykosen der Haut, Flossen und Kiemen durch Pilze der Gattung Saprolegnia (p<0,05). Der Befall von Haut und Kiemen mit vorrangig protozo�ren Ektoparasiten konnte insgesamt ebenso vermindert werden (p<0,01) wie der Befall der Kiemen mit Ichthyophthirius sp. (p<0,05). Aus der beobachteten Milderung von Krankheitssymptomen umweltbedingter, bakterieller, ektoparasit�rer und mykotischer Genese nach Na-Humat-B�dern bei Goldfischen kann auf einen gewebeprotektiven, antiphlogistischen, antimykotischen und antiparasit�ren Effekt der Na-Humat-Behandlung geschlossen werden. In der Aufzucht von Karpfen (F I) und Regenbogenforellen (F III) wurden dem Futter 5 % Humocarb, formuliert� (HS vom Typ WH 67 A), im Karpfenversuch F II 5 % Cellu-Ligno-Karbon-Isolat (HS vom Typ WH 67 G, beide Produkte: Fa. Pharmawerk Weinb�hla) zugesetzt. In F I und F III wurde ein gleiches pelletiertes Alleinfutter f�r Forellen, in F II ein pelletiertes Alleinfutter f�r Karpfen eingesetzt. In Versuch F I (Besatzdichte der beiden Teiche (0,2 ha) jeweils 35.000 Kv ha-1) wiesen die Karpfen der Versuchs- gegen�ber der Kontrollgruppe h�here mittlere K�rpermassen auf. Der Unterschied zwischen den Gruppen bewegte sich mit einer Ausnahme (zu geringer Stichprobenumfang) zwischen p<0,05 (65 versus 45 g, 114. Tag) und p<0,0001 (1.146 versus 855 g, Versuchsende 1000. Tag). Der um die HS-Aufnahme bereinigte Futteraufwand des ersten Versuchsjahres war durch HS um 34 % verbessert. Die Futterquotienten in der zweiten und dritten Aufzuchtperiode waren durch die subjektive Futterzumessung (Nichtber�cksichtigung zwischenzeitlicher Verluste) verf�lscht. In Versuch F II (Besatzdichten der 2 x 3 Teiche (0,25 ha) 20.000, 30.000 bzw. 40.000 K0 ha-1) erhielten die Br�tlinge �ber die ersten zwei Wochen kein zus�tzliches Futter (nur Naturnahrung), anschlie�end wurde Weizenschrot zugef�ttert, erst ab dem 63. Tag das Versuchs- bzw. Kontrollfutter f�r 87 Tage. Bei Versuchsende war in den Gruppen der h�chsten Besatzdichte die Mortalit�t durch HS um ca. 20 % verringert (p<0,0001). Die Abfischungsmassen waren bei geringer Besatzdichte ann�hernd gleich, bei mittlerer Besatzdichte war die Kontrollgruppe, bei h�chster Besatzdichte die Versuchsgruppe favorisiert (statistische Pr�fung wegen des Fehlens von Einzeldaten nicht m�glich). Der um die HS-Aufnahme bereinigte Futteraufwand war in den HS-Gruppen bei geringer bzw. h�chster Besatzdichte um 5 bzw. 17 % verringert. In beiden Versuchen, F I und F II, wurde eine deutliche Verringerung des Gehaltes der inneren Organe Leber, Niere und Milz an fakultativ pathogenen Aeromonas- und Pseudomonas spp. nachgewiesen (p<0,05). Bei der Aufzucht von Regenbogenforellen (F III; N=2 x 25) trugen die durch den HS-Zusatz bedingten Ver�nderungen der Konsistenz von Futter und Kot zur Verminderung einer starken Belagbildung (Bewuchs aus Algen und anderen Mikroorganismen) sowie zur Vermeidung von Wassertr�bungen in den Aquarien, insbesondere bei h�heren Temperaturen, bei. Signifikante Unterschiede in den Kenndaten von Wachstum und Futteraufwand wurden nicht beobachtet. Insgesamt gesehen erscheint aber der Zusatz von 5 % HS zum Futter als zu hoch gew�hlt, da sich der Futteraufwand in den HS-Gruppen bei Ber�cksichtigung der Gesamtfuttermenge (einschlie�lich des 5%igen HS-Zusatzes) �berwiegend ung�nstiger gestaltete. Die Effekte der oralen Applikation von 5 % HS im Futter sind damit weit weniger augenf�llig als nach �u�erlicher Anwendung. Die zootechnischen Parameter waren �berwiegend mehr oder weniger unver�ndert; allein in Versuch F I war die K�rpermasse in der HS-Gruppen im Versuchsverlauf (Stichproben und Abfischung) in der Regel signifikant h�her als in der Kontrollgruppe. Von k�nftiger Bedeutung f�r die Aquarienhaltung von Fischen (und m�glicherweise in Klein- und Zierteichen) k�nnte die beobachtete Wasserkl�rung und die Verminderung einer Belagbildung aus Algen und anderen Mikroorganismen sein. Eine intestinale Wirkung der HS wird insoweit unterstellt, als in beiden Karpfenversuchen die inneren Organe einen verminderten Befall an beweglichen Aeromonaden und Pseudomonaden aufwiesen. / Prophylactic and therapeutic use of brown coal-derived humic substances of the type WH 67 in finfish and ornamental fish farming On the market, there is a limited number of suitable and approved drugs available for therapy and prophylaxis of fish diseases. The search for alternatives which are both effective and safe for animals, consumers and environment is therefore of special importance. There are numerous reports on positive effects of orally administered humic substances (HS) on agricultural livestock, zoo animals and pets. Therefore, the present study aimed on effects of HS for both external treatment of ornamental fish and oral application on culture fish via feed. Two experiments on goldfish (Carassius auratus) (exp. B I: 4 days; exp. B II: 12 days), and on common carp (Cyprinus carpio) (exp. F I: 1,000 days, fry to 3-year-old fish ; exp. F II: 150 days, fry to young-of-the-year size) were carried out under pond culture conditions. Additionally, one experiment on rainbow trout (Oncorhynchus mykiss) was carried out in the laboratory (exp. F III: 166 days, fingerlings up to 30 g body weight). The following parameters were examined: mortality, morbidity, growth, feed conversion ratio (exp. F I, F II, F III only), pathologic anatomical criteria (including histological examination of fish from B I and F II), parasitological investigation, bacteriological and virological state. Water quality was regularly examined as well. In the experiments B I and B II, a 10% sodium-humate solution (type WH 67 SNa, Pharmawerk Weinb�hla) was mixed into the water until a sodium-humate concentration of 10 mg L-1 was reached. Two-year old, multifactorially diseased goldfish (B I: N= 2 x 322; B II: N= 2 x 100) were daily exposed to this water for a period of one (B I) and 1.5-2 (B II) hours, respectively. In both experiments the treatment of fish reduced in mortality (B I: 0.6 vs. 4.7 %, p<0.0005; B II: 8 vs. 16 %, p<0.05). Moreover, at the end of the experiments the sodium-humate treated fish showed a significantly improved health state (B I: p<10-16; B II: p<0.001) as indicated by externally visible changes of the skin, fins and gills. Specifically, reductions in haemorrhage of skin and fins (B II: p <0.05), and fin and gill necroses (B II: p<0.05), and gill inflammations (B II: p<0.02) were noted. Additionally, the sodium-humate treatment reduced integumental mucoses of skin, fins and gills (p<0.05) caused by Saprolegnia sp. The infection of skin and gills with protozoan parasites was reduced (p<0.01) as well. Ichthyophthirius sp. infections of the gills dropped significantly (p<0.05) in the treated fish groups as compared to the controls. Due to the observed mitigation of disease symptoms of environmental, bacterial, parasitic and fungal origin after a sodium-humate bath treatment of goldfish, a tissue protective, antiphlogistic, antimycotic and antiparasitic effect of sodium-humate can be concluded. For rearing of carp (F I) and rainbow trout (F III), 5 % Humocarb, formuliert� (type WH 67 A, Pharmawerk Weinb�hla) was mixed among the feed, while for the experiment F II 5 % Cellu-Ligno-Carbon-Isolat (type WH 67 G, Pharmawerk Weinb�hla) was added. In F I and F III a complete feed for trout was applied whereas for F II a complete feed for carp was used. In experiment F I (stocking density of both ponds 35,000 carp fry per ha) test fish revealed a higher mean body weight compared to the controls. With one exception (sample size to small), the difference between the groups was either significant (day 114: 65 vs. 45 g, p<0.05) or highly significant (day 1000: 1,146 versus 855 g, p<0.0001). The feed conversion ratio of the first experimental year (expurgated by HS-uptake) improved by 34 % due to HS application. Feed conversion ratio of the second and third year were falsified because of subjective feeding (which does not consider occurring losses). In experiment F II (stocking density of the 2 x 3 ponds (0,25 ha) were 20,000, 30,000 and 40,000 individuals per ha, respectively) no additional feed was given to the hatched fry during the first two weeks so that all the fish lived on natural feed items. Afterwards, bruised wheat grain was given until from day 63 either test or control feed was applied for a total of 87 days. At the end of the experiment, at the highest stocking density the mortality was significantly (p<0.0001) decreased by 20% in the test group supplied with HS. At low stocking density the total weight of fish at harvest was not different between the test and control group. However, at medium stocking density the average body weight was higher in the control whereas reverse conditions were observed at the highest stocking density (due to a loss of data no statistical analysis was possible). The feed conversion ratio (expurgated by the uptake of humic substances) was decreased in the test groups of low (5 %) and high (17 %) density. In both experiments (F I and F II) significantly reduced infections of the internal organs liver, kidney and spleen with potentially pathogenic Aeromonas and Pseudomonas spp. were detected. In the rainbow trout rearing (F III; N = 2 x 25), the HS-caused changes in consistency of feed and faeces impaired the formation of heavy algal films and large microorganism populations, and contributed to less turbid water turbidity in the aquaria, particularly at high temperatures. Significant differences in growth and feed conversion ratio could not be observed. In general, the addition of 5 % HS to the feed is regarded as being too high because the total amount of feed given (inclusive 5 % HS) is considered. The feed conversion ratio was higher in most of the HS-groups. Effects of oral application of 5 % HS in feed were thus less obvious than the bath treatment. Zootechnical parameters, in general, did not change. Merely in experiment F I the body weight of the HS-groups was significantly higher than that of the controls. In aquaria and small ponds used for ornamental fish breeding the observed cleaning of water and reduced formation of algal films and microorganism populations caused by HS could be of future importance. Intestinal effects of HS are assumed as internal organs revealed a reduced infection with both motile aeromonads and pseudomonads.

As usinas sucroalcooleiras aproveitam apenas a fração colmo da planta para a produção de açúcar e etanol restando o bagaço da cana-de-açúcar, composto das frações fibra e medula, é em grande parte usado para geração de energia elétrica. O resíduo agrícola da cana RAC, constituído pelas folhas, palha, e a ponteira da cana de açúcar são cortados durante a colheita e devolvidos ao campo para adubar o solo contribuindo para a lavoura da cana-de-açúcar. Os painéis hardboards são produzidos a partir da aplicação de calor e pressão a um colchão de fibras ou serragem de madeira, sendo aplicados como pisos na construção civil e como pranchetas e fundo de gavetas na indústria moveleira. Assim, a proposta desse trabalho foi o estudo da utilização dos materiais provenientes da cultura de cana-de-açúcar, em particular a fração medula do bagaço de cana-de-açúcar e do RAC para produção de hardboard (sem a utilização de adesivos) e particleboards (com a adição de resina fenol-formaldeído). Adicionalmente, estudou-se a adição da humina resultante de processos de hidrólise ácida do bagaço de cana-de-açúcar como coadjuvante na produção de painéis de medula de cana-de-açúcar. A utilização da resina fenol-formaldeído foi estudada no intervalo de 10% a 33%, sendo os melhores resultados obtidos quando do uso de 25% de resina, que apresentou tensão máxima de 29,9 MPa em ensaio de tração. Definido esse valor, realizou-se o estudo do efeito da quantidade de humina no intervalo de 12,5% a 75%, o qual revelou que a humina leva à produção de materiais frágeis com redução do desempenho mecânico. As frações RAC foram empregadas para a produção de amostras com teor de resina fenol-formaldeído igual a 25%. Todos os corpos de prova produzidos foram analisados por ensaios de tração (MOR e MOE), análise térmica, microscopia eletrônica de varredura (MEV) e análise dinâmico mecânica. A produção de hardboards a partir da fração medula do bagaço de cana-de-açúcar, nas condições empregadas neste estudo preliminar, resultou em materiais com baixo desempenho mecânico, revelado pelos resultados dos ensaios de tração que indicou tensão máxima de 4,7 MPa. Entretanto, a mesma matéria prima quando misturada com resina fenol-formaldeído resultou na produção de particleboards que, apesar da dispersão pouca efetiva da resina, apresentaram um melhor desempenho mecânico (tensão máxima no intervalo de 29,9 a 11,3 MPa). Finalmente, os materiais obtidos com as frações RAC da cana-de-açúcar e resina FF mostraram-se mais homogêneos e com desempenho mecânico igual ou superior (tensão máxima no intervalo de 36,1 a 27,7 MPa) aos observados para os materiais obtidos com Pinus sp (tensão máxima de 27,7 MPa). / Sugar and ethanol mills use only the stem fraction of sugarcane for the production of sugar and ethanol. The sugarcane bagasse, composed of fiber and pith fractions, is largely used to generate electricity. The sugarcane agricultural residues - RAC, made up of leaves, straw and the tip of sugarcane are cut during harvest and returned to the field to fertilize the soil. Hardboard panels are produced from the application of heat and pressure to a fiber or sawdust mat. Its commercial application includes floors in construction and clipboards and bottom drawers in the furniture industry. Thus the purpose of this work was to study the use of materials from sugarcane culture, in particular the core fraction of bagasse sugarcane and the sugarcane trash for the production of hardboard (without the use of adhesives) and particleboards (with the addition of phenol formaldehyde resin). In addition, he studied the addition of the resulting humin acid hydrolysis process of sugarcane bagasse as an adjunct in the production of sugarcane pith panels. The use of phenol formaldehyde resin was studied in the range of 10% to 33%, with best results obtained when using 25% resin, which had maximum stress of 29.9 MPa in tensile testing. Once established, the study of the effect of the amount of humin was held in the range of 12.5% to 75%, which revealed that the humin leads to the production of brittle materials with reduced mechanical performance. Sugarcane trash fractions were used for production of resin samples with phenol formaldehyde content equal to 25%. All produced samples were analyzed by tensile tests (MOR and MOE), thermal analysis, scanning electron microscopy (SEM) and dynamic mechanical analysis. The production of hardboards from the marrow fraction of sugarcane bagasse, under the conditions employed in this preliminary study, resulted in materials with low mechanical performance, revealed the results of tensile tests indicated that maximum voltage of 4.7 MPa. However, the same raw material when mixed with phenol-formaldehyde resin resulted in the production of particleboards that despite the low effective dispersion of the resin, had a better mechanical performance (maximum stress in the range from 29.9 to 11.3 MPa). Finally, materials obtained from the fractions of RAC sugarcane and PF resin proved to be more homogeneous and with equal or higher mechanical performance (maximum stress in the range from 36.1 to 27.7 MPa) to that observed for materials obtained with Pinus sp (maximum stress of 27.7 MPa).

Dans un contexte de transition énergétique et de lutte contre le réchauffement climatique, la production d’éthanol de seconde génération semble une voie très prometteuse afin de réduire notre dépendance aux énergies fossiles. Il existe 3 étapes clés pour la production de ce nouveau biocarburant : le prétraitement qui permet de déstructurer la matrice lignocellulosique afin de rendre la cellulose plus accessible aux enzymes, l’hydrolyse enzymatique qui a pour but de produire des sucres fermentescibles et la fermentation qui permet de transformer ces sucres en éthanol. Actuellement, le prétraitement considéré comme le plus efficace, et principalement retenu par les industriels, est le prétraitement par explosion à la vapeur. Cependant, certains aspects comme les effets physicochimiques induits par le prétraitement ainsi que leurs impacts sur les caractéristiques de la biomasse prétraitée restent encore mal compris.Schématiquement, le prétraitement par explosion vapeur peut se décomposer en deux étapes : la première se rapproche d’une cuisson acide réalisée à 150-200°C durant 5 30 min et permet principalement l’hydrolyse des hémicelluloses, alors que la seconde est une détente explosive qui permet un éclatement mécanique du substrat rendant potentiellement la cellulose plus réactive à l’hydrolyse enzymatique. Globalement les effets de ce type de prétraitement sur la biomasse lignocellulosique sont aujourd’hui bien connus mais la compréhension des différents phénomènes physico-chimiques ayant lieu en son sein reste limitée. En effet le découplage de l’étape de cuisson et de l’étape de détente est délicat car, la température du réacteur (qui impacte principalement les réactions de cuisson) est directement liée à sa pression (qui impacte principalement la détente) par la thermodynamique des phases.Ce travail de thèse se propose donc de mieux appréhender l’ensemble des phénomènes physico-chimiques ayant lieu durant le prétraitement par explosion à la vapeur en s’appuyant notamment sur une discrimination expérimentale des phénomènes chimiques (réactions de dépolymérisation) et des phénomènes physiques (détente explosive) ainsi que sur une caractérisation multi-techniques et multi-échelles de la biomasse lignocellulosique obtenue après ce type de prétraitement. L’objectif est aussi de comprendre quelles sont les principales caractéristiques de la biomasse qui expliquent les différences de réactivité observées lors de l’étape d’hydrolyse enzymatique et d’expliquer l’impact du prétraitement par explosion à la vapeur sur les propriétés physicochimiques et donc sur la réactivité. / In a context of energy transition and climate change challenge, the production of second generation ethanol seems to be a very promising way to reduce our dependence on fossil fuels. There are 3 key steps for producing this new biofuel: pretreatment to decompose the lignocellulosic biomass and to make cellulose more accessible to enzyme attacks, enzymatic hydrolysis to produce fermentable sugars and fermentation to convert these sugars into ethanol. Currently, the pretreatment considered to be the most efficient, and mainly retained for industrialization, is the steam explosion pretreatment. However, some aspects such as the physicochemical effects induced by pretreatment and their impacts on the characteristics of pretreated biomass remain misunderstood.Schematically, the steam explosion pretreatment can be separated into two stages: the first is similar to an acid cooking carried out at 150-200°C during 5-30 min and allows mainly the hydrolysis of hemicelluloses, while the second is an explosive release which allows a mechanical bursting of the substrate potentially making the cellulose more reactive to enzymatic hydrolysis. As a whole, the effects of this type of pretreatment on lignocellulosic biomass are now well known, but the understanding of the different physicochemical phenomena occurring within it remains limited. Indeed, decoupling the cooking stage and the expansion stage is complicated because the reactor temperature (which mainly impacts the cooking reactions) is directly related to its pressure (which mainly impacts the explosive release) by the phase thermodynamics.This thesis work aims to better understand all the physicochemical phenomena occurring during a steam explosion pretreatment, based in particular on experimental discrimination of chemical phenomena (depolymerization reactions) and physical phenomena (explosive release) as well as on a multi-technical and multi-scale characterization of the lignocellulosic biomass obtained after this type of pretreatment. The objective is also to understand what are the main characteristics of biomass that explain the differences in reactivity observed during the enzymatic hydrolysis step and to explain the impact of the steam explosion pretreatment on the physicochemical properties and therefore the reactivity.

La laine de verre est un matériau utilisé pour l'isolation acoustique et thermique des habitations. Ce matériau est constitué à 95% de fibres de verre et à 5% d'un liant. Bien que ce dernier soit utilisé en quantité très faible dans la formulation du matériau, il est responsable de l'obtention de bonnes propriétés mécaniques en assurant, notamment, l'intégrité structurelle du panneau de laine de verre. Pour préparer ces liants, une résine et des additifs (huile, silicone et silane) sont utilisés. Depuis une cinquantaine d'années, les résines majoritairement utilisées pour la préparation de liant pour la fabrication de la laine de verre sont de type formo-phénolique. Bien que les propriétés mécaniques des panneaux de laine de verre obtenus avec cette résine soient bonnes, il a été nécessaire d'éliminer le formaldéhyde, composé Cancérigène-Mutagène-Reprotoxique, de la formulation. C'est pourquoi de nouvelles résines ont dû être développées. Ces développements ont permis de retenir une résine pH-compatible à base de saccharose et avec des propriétés mécaniques analogues à celles obtenues avec la résine formo-phénolique. Le but de cette thèse est donc d'accéder à une connaissance approfondie des mécanismes réactionnels mis en jeu dans la formation de cette résine pour pouvoir, in fine, en optimiser ses performances / Glass wool is a material used for the acoustic and thermal insulation of dwellings. This material contains 95% of glass fibers and 5% of binder. Although this binder is used in a very small quantity in the formulation, it provides the expected mechanical properties by ensuring the structural integrity of the glass wool panel. To prepare these binders, resin and additives (oil, silicone and silane) are used. For fifty years the resins mostly used for the preparation of glass wool’s binders were the formo-phenolic’s types. Although theses resins provide good mechanical properties of the glass wool panels, it was necessary to remove the formaldehyde, a Carcinogen-Mutagen-Reprotoxic compound, from the formulation. As a consequence, new resins were developed. These developments helped us to retain a pH-compatible resin based on sucrose with mechanical properties as good as formo-phenolic’s resin. So, the aim of this thesis is to investigate the whole chemistry’s mechanism involved in the formation of this resin in order to be able to increase its performance

F�r die Therapie und Prophylaxe von Fischkrankheiten stehen nur wenige geeignete und zugelassene Medikamente zur Verf�gung. Daher kommt der Suche nach wirksamen und f�r Tier, Verbraucher und Umwelt sicheren Alternativen in der Fischhaltung eine besondere Bedeutung zu. �ber positive Effekte beim oralen Einsatz von Huminstoffen an landwirtschaftlichen Nutztieren, Zootieren und Heimtieren liegen eine Vielzahl von Berichten vor. Deshalb sollten in der vorliegenden Studie Huminstoffe (HS) in der �u�erlichen Anwendung bei Zierfischen und in der oralen Verabreichung �ber das Futter bei Nutzfischen n�her untersucht werden. Dazu wurden zwei Versuche (B I: Dauer 4 Tage; B II: Dauer 12 Tage) an Goldfischen (Carassius auratus) unter teichwirtschaftlichen Bedingungen, zwei Aufzuchtversuche (F I: Kv bis K3, Dauer: 1.000 Tage: F II: K0 bis K1, Dauer: 150 Tage) an Karpfen (Cyprinus carpio) in der Teichwirtschaft und ein Aufzuchtversuch (F III: vorgestreckte Brut bis 30 g Lebendmasse, 166 Tage) an Regenbogenforellen (Oncorhynchus mykiss) unter Laborbedingungen durchgef�hrt. Als Versuchsparameter dienten Mortalit�t und Morbidit�t, Wachstum und Futteraufwand in den Aufzuchtversuchen, pathologisch anatomische (einschlie�lich histologischer Befunde in B I und F II), parasitologische, bakteriologische und virologische Kriterien. Die Wasserqualit�t wurde regelm��ig ermittelt. In den Versuchen B I und B II wurde eine 10%ige Na-Humat-L�sung (HS vom Typ WH 67 SNa der Fa. Pharmawerk Weinb�hla) dem H�lterungswasser so zugesetzt, dass eine Na-Humat-Konzentration von 10 mg L-1 entstand. Zweij�hrige, multifaktoriell erkrankte Goldfische (B I: N=2 x 322, B II: N=2 x 100) wurden dem Na-Humat-Bad t�glich f�r die Dauer einer Stunde (B I) bzw. von 1,5 bis 2 Stunden (B II) ausgesetzt. Die HS-Badehandlungen f�hrten in beiden Versuchen zu einer Senkung der Verluste (Mortalit�tsrate in B I: 0,6 versus 4,7 %, p<0,0005; B II: 8 versus 16 %, p<0,05). Bei Versuchsende war in den Versuchsgruppen (Na-Humat-Bad) der Gesundheitszustand, beurteilt nach �u�erlich sichtbaren Ver�nderungen an Haut, Flossen und Kiemen, deutlich verbessert (B I: p<1�10-16; B II: p<0,001). So waren (Signifikanzangaben nur f�r B II) vor allem H�morrhagien der Haut und der Flossen (p<0,05), Flossenrand- und Kiemennekrosen (p<0,05) sowie akute Kiemenentz�ndungen (p<0,02) verringert. Die Badebehandlungen bewirkten weiter eine geringere Auspr�gung integument�rer Mykosen der Haut, Flossen und Kiemen durch Pilze der Gattung Saprolegnia (p<0,05). Der Befall von Haut und Kiemen mit vorrangig protozo�ren Ektoparasiten konnte insgesamt ebenso vermindert werden (p<0,01) wie der Befall der Kiemen mit Ichthyophthirius sp. (p<0,05). Aus der beobachteten Milderung von Krankheitssymptomen umweltbedingter, bakterieller, ektoparasit�rer und mykotischer Genese nach Na-Humat-B�dern bei Goldfischen kann auf einen gewebeprotektiven, antiphlogistischen, antimykotischen und antiparasit�ren Effekt der Na-Humat-Behandlung geschlossen werden. In der Aufzucht von Karpfen (F I) und Regenbogenforellen (F III) wurden dem Futter 5 % Humocarb, formuliert� (HS vom Typ WH 67 A), im Karpfenversuch F II 5 % Cellu-Ligno-Karbon-Isolat (HS vom Typ WH 67 G, beide Produkte: Fa. Pharmawerk Weinb�hla) zugesetzt. In F I und F III wurde ein gleiches pelletiertes Alleinfutter f�r Forellen, in F II ein pelletiertes Alleinfutter f�r Karpfen eingesetzt. In Versuch F I (Besatzdichte der beiden Teiche (0,2 ha) jeweils 35.000 Kv ha-1) wiesen die Karpfen der Versuchs- gegen�ber der Kontrollgruppe h�here mittlere K�rpermassen auf. Der Unterschied zwischen den Gruppen bewegte sich mit einer Ausnahme (zu geringer Stichprobenumfang) zwischen p<0,05 (65 versus 45 g, 114. Tag) und p<0,0001 (1.146 versus 855 g, Versuchsende 1000. Tag). Der um die HS-Aufnahme bereinigte Futteraufwand des ersten Versuchsjahres war durch HS um 34 % verbessert. Die Futterquotienten in der zweiten und dritten Aufzuchtperiode waren durch die subjektive Futterzumessung (Nichtber�cksichtigung zwischenzeitlicher Verluste) verf�lscht. In Versuch F II (Besatzdichten der 2 x 3 Teiche (0,25 ha) 20.000, 30.000 bzw. 40.000 K0 ha-1) erhielten die Br�tlinge �ber die ersten zwei Wochen kein zus�tzliches Futter (nur Naturnahrung), anschlie�end wurde Weizenschrot zugef�ttert, erst ab dem 63. Tag das Versuchs- bzw. Kontrollfutter f�r 87 Tage. Bei Versuchsende war in den Gruppen der h�chsten Besatzdichte die Mortalit�t durch HS um ca. 20 % verringert (p<0,0001). Die Abfischungsmassen waren bei geringer Besatzdichte ann�hernd gleich, bei mittlerer Besatzdichte war die Kontrollgruppe, bei h�chster Besatzdichte die Versuchsgruppe favorisiert (statistische Pr�fung wegen des Fehlens von Einzeldaten nicht m�glich). Der um die HS-Aufnahme bereinigte Futteraufwand war in den HS-Gruppen bei geringer bzw. h�chster Besatzdichte um 5 bzw. 17 % verringert. In beiden Versuchen, F I und F II, wurde eine deutliche Verringerung des Gehaltes der inneren Organe Leber, Niere und Milz an fakultativ pathogenen Aeromonas- und Pseudomonas spp. nachgewiesen (p<0,05). Bei der Aufzucht von Regenbogenforellen (F III; N=2 x 25) trugen die durch den HS-Zusatz bedingten Ver�nderungen der Konsistenz von Futter und Kot zur Verminderung einer starken Belagbildung (Bewuchs aus Algen und anderen Mikroorganismen) sowie zur Vermeidung von Wassertr�bungen in den Aquarien, insbesondere bei h�heren Temperaturen, bei. Signifikante Unterschiede in den Kenndaten von Wachstum und Futteraufwand wurden nicht beobachtet. Insgesamt gesehen erscheint aber der Zusatz von 5 % HS zum Futter als zu hoch gew�hlt, da sich der Futteraufwand in den HS-Gruppen bei Ber�cksichtigung der Gesamtfuttermenge (einschlie�lich des 5%igen HS-Zusatzes) �berwiegend ung�nstiger gestaltete. Die Effekte der oralen Applikation von 5 % HS im Futter sind damit weit weniger augenf�llig als nach �u�erlicher Anwendung. Die zootechnischen Parameter waren �berwiegend mehr oder weniger unver�ndert; allein in Versuch F I war die K�rpermasse in der HS-Gruppen im Versuchsverlauf (Stichproben und Abfischung) in der Regel signifikant h�her als in der Kontrollgruppe. Von k�nftiger Bedeutung f�r die Aquarienhaltung von Fischen (und m�glicherweise in Klein- und Zierteichen) k�nnte die beobachtete Wasserkl�rung und die Verminderung einer Belagbildung aus Algen und anderen Mikroorganismen sein. Eine intestinale Wirkung der HS wird insoweit unterstellt, als in beiden Karpfenversuchen die inneren Organe einen verminderten Befall an beweglichen Aeromonaden und Pseudomonaden aufwiesen. / Prophylactic and therapeutic use of brown coal-derived humic substances of the type WH 67 in finfish and ornamental fish farming On the market, there is a limited number of suitable and approved drugs available for therapy and prophylaxis of fish diseases. The search for alternatives which are both effective and safe for animals, consumers and environment is therefore of special importance. There are numerous reports on positive effects of orally administered humic substances (HS) on agricultural livestock, zoo animals and pets. Therefore, the present study aimed on effects of HS for both external treatment of ornamental fish and oral application on culture fish via feed. Two experiments on goldfish (Carassius auratus) (exp. B I: 4 days; exp. B II: 12 days), and on common carp (Cyprinus carpio) (exp. F I: 1,000 days, fry to 3-year-old fish ; exp. F II: 150 days, fry to young-of-the-year size) were carried out under pond culture conditions. Additionally, one experiment on rainbow trout (Oncorhynchus mykiss) was carried out in the laboratory (exp. F III: 166 days, fingerlings up to 30 g body weight). The following parameters were examined: mortality, morbidity, growth, feed conversion ratio (exp. F I, F II, F III only), pathologic anatomical criteria (including histological examination of fish from B I and F II), parasitological investigation, bacteriological and virological state. Water quality was regularly examined as well. In the experiments B I and B II, a 10% sodium-humate solution (type WH 67 SNa, Pharmawerk Weinb�hla) was mixed into the water until a sodium-humate concentration of 10 mg L-1 was reached. Two-year old, multifactorially diseased goldfish (B I: N= 2 x 322; B II: N= 2 x 100) were daily exposed to this water for a period of one (B I) and 1.5-2 (B II) hours, respectively. In both experiments the treatment of fish reduced in mortality (B I: 0.6 vs. 4.7 %, p<0.0005; B II: 8 vs. 16 %, p<0.05). Moreover, at the end of the experiments the sodium-humate treated fish showed a significantly improved health state (B I: p<10-16; B II: p<0.001) as indicated by externally visible changes of the skin, fins and gills. Specifically, reductions in haemorrhage of skin and fins (B II: p <0.05), and fin and gill necroses (B II: p<0.05), and gill inflammations (B II: p<0.02) were noted. Additionally, the sodium-humate treatment reduced integumental mucoses of skin, fins and gills (p<0.05) caused by Saprolegnia sp. The infection of skin and gills with protozoan parasites was reduced (p<0.01) as well. Ichthyophthirius sp. infections of the gills dropped significantly (p<0.05) in the treated fish groups as compared to the controls. Due to the observed mitigation of disease symptoms of environmental, bacterial, parasitic and fungal origin after a sodium-humate bath treatment of goldfish, a tissue protective, antiphlogistic, antimycotic and antiparasitic effect of sodium-humate can be concluded. For rearing of carp (F I) and rainbow trout (F III), 5 % Humocarb, formuliert� (type WH 67 A, Pharmawerk Weinb�hla) was mixed among the feed, while for the experiment F II 5 % Cellu-Ligno-Carbon-Isolat (type WH 67 G, Pharmawerk Weinb�hla) was added. In F I and F III a complete feed for trout was applied whereas for F II a complete feed for carp was used. In experiment F I (stocking density of both ponds 35,000 carp fry per ha) test fish revealed a higher mean body weight compared to the controls. With one exception (sample size to small), the difference between the groups was either significant (day 114: 65 vs. 45 g, p<0.05) or highly significant (day 1000: 1,146 versus 855 g, p<0.0001). The feed conversion ratio of the first experimental year (expurgated by HS-uptake) improved by 34 % due to HS application. Feed conversion ratio of the second and third year were falsified because of subjective feeding (which does not consider occurring losses). In experiment F II (stocking density of the 2 x 3 ponds (0,25 ha) were 20,000, 30,000 and 40,000 individuals per ha, respectively) no additional feed was given to the hatched fry during the first two weeks so that all the fish lived on natural feed items. Afterwards, bruised wheat grain was given until from day 63 either test or control feed was applied for a total of 87 days. At the end of the experiment, at the highest stocking density the mortality was significantly (p<0.0001) decreased by 20% in the test group supplied with HS. At low stocking density the total weight of fish at harvest was not different between the test and control group. However, at medium stocking density the average body weight was higher in the control whereas reverse conditions were observed at the highest stocking density (due to a loss of data no statistical analysis was possible). The feed conversion ratio (expurgated by the uptake of humic substances) was decreased in the test groups of low (5 %) and high (17 %) density. In both experiments (F I and F II) significantly reduced infections of the internal organs liver, kidney and spleen with potentially pathogenic Aeromonas and Pseudomonas spp. were detected. In the rainbow trout rearing (F III; N = 2 x 25), the HS-caused changes in consistency of feed and faeces impaired the formation of heavy algal films and large microorganism populations, and contributed to less turbid water turbidity in the aquaria, particularly at high temperatures. Significant differences in growth and feed conversion ratio could not be observed. In general, the addition of 5 % HS to the feed is regarded as being too high because the total amount of feed given (inclusive 5 % HS) is considered. The feed conversion ratio was higher in most of the HS-groups. Effects of oral application of 5 % HS in feed were thus less obvious than the bath treatment. Zootechnical parameters, in general, did not change. Merely in experiment F I the body weight of the HS-groups was significantly higher than that of the controls. In aquaria and small ponds used for ornamental fish breeding the observed cleaning of water and reduced formation of algal films and microorganism populations caused by HS could be of future importance. Intestinal effects of HS are assumed as internal organs revealed a reduced infection with both motile aeromonads and pseudomonads.