Cold pressed Hemp (Cannabis sativa L) seed oil, which contains a favorable ratio of omega-6/omega-3 and a considerable amount of vitamin E, is a high nutrition value product with various health benefits. However, the presence of a large amount of chlorophyll makes the oil highly susceptible to photo-oxidation and limits its applications. Chlorophyll and other pigments in edible oils are commonly reduced through oil bleaching process. The objective of this study was to reduce the chlorophyll content in cold pressed hemp seed oil using ultrasonic bleaching and evaluate the impacts on carotene content, peroxide value, conjugated diene, total phenolic content and oxidative stability. The bleaching efficiency increased significantly as the ultrasound power (0 to 60% pressure amplitude) and concentration of bleaching clay (20 to 40 g/kg) increased. At 20% ultrasound power, the chlorophyll reduction (%) of different clays was found to be 99.4% (industrial clay) > 97.8% (activated bentonite) > 82.7% (sepiolite) > 47.1% (non-activated bentonite). Ultrasonic bleaching significantly reduced (p<0.05) the total chlorophyll content, total carotene content and primary oxidation products of hemp seed oil. During accelerated oxidation tests (40 and 60 ℃), the developments of peroxide value and conjugated diene were significantly (p<0.05) slower for hemp seed oil treated with ultrasonic bleaching compared to the control oil. Enhanced oxidative stability was observed in hemp seed oil after ultrasonic bleaching. In addition, another objective of this study was to evaluate the impacts of solvent and heat treatment on phenolic profile and antioxidant activity of cold pressed canola and hemp meals. For canola meal, a solvent-mixture of aqueous methanol (70%) and aqueous acetone (70%) in a ratio of 1:1 (v/v) extracted (p<0.05) slightly higher total phenolic content (11.3 mg SAE/g), while aqueous methanol (70%) extracts exhibited higher DPPH scavenging effect (40.4%). For hemp meal, aqueous acetone (80%) extracts exhibited higher total phenolic content (6.0 mg GAE/g) and DPPH scavenging effect (12.5%). Total phenolic content and antioxidant activity in canola meal extracts were significantly higher (p<0.05) than those in hemp meal extracts. After heat treatments at temperature from 140 to 180 ℃, canola and hemp meal extracts showed equal or lower total phenolic content and DPPH scavenging effect. / May 2017

Les bétons de chanvre associent un granulat végétal issu du chanvre, appelé « chènevotte », et une matrice minérale. Ce sont des matériaux isolants répondant particulièrement bien aux nouvelles problématiques environnementales du secteur du bâtiment. Pourtant, leur développement est freiné par d'occasionnels désordres de mise en œuvre et des propriétés mécaniques relativement faibles qui pourraient résulter d'interactions complexes développées entre la chènevotte et le liant. Dans ce contexte, l'objectif des travaux a été de préciser la nature de ces interactions et d'identifier par quels mécanismes celles-ci peuvent modifier la prise du liant et les propriétés finales du matériau. Pour cela, l'évolution de mélanges de matières premières (chènevottes et liants) de natures différentes a été étudiée par des techniques de biochimie, de spectroscopie, de physico-chimie et de mécanique. Cette approche multi-échelle a ainsi permis de mettre en évidence le puissant pouvoir retardateur des produits extraits de la chènevotte sur la prise des liants hydrauliques. Ce retard peut conduire à une absence totale de prise du liant, lorsque celui-ci est couplé à des phénomènes de dégradation de la chènevotte, de migration de ces produits dans la matrice et d'évaporation d'eau. En outre, il a été démontré que les caractéristiques de la chènevotte (composition chimique), la nature du liant (ciment pur ou additionné de chaux), ainsi que les conditions de cure (présence ou non de CO2) sont des facteurs pouvant moduler les effets délétères sur la prise et les propriétés mécaniques du matériau formé. Ils constituent donc des paramètres potentiels d'optimisation des bétons de chanvre. / The hemp concretes, combine a plant aggregate, called “shiv” with a mineral binder. They are insulating materials particularly suited to face the new environmental problems of the building sector. However, their development is hampered by the occasional implementation problems and their relatively low mechanical properties that could result from complex interactions between the shiv and the binder. In this context, the objective of the presented work was to clarify the nature of these interactions and to identify the mechanisms by which they can impact the setting of the binder and the final properties of the material. To do so, the evolution of mixtures of the initial components (shiv and binders) differing by their nature was studied by biochemical, spectroscopic, physical chemistry and mechanical techniques. This multi-scale approach enabled us to highlight the powerful set retarding action of shiv-extractable products on hydraulic binders. This delay can even lead to a total failure of the binder setting when this one is coupled to simultaneous degradation of the hemp aggregate, migration of the formed products in the matrix and water evaporation. Finally, it has been demonstrated that the characteristics of the shiv (chemical composition), the nature of the binder (pure cement or lime added), and the curing conditions (presence or absence of CO2) represent factors that may modulate the deleterious effects on the setting and the mechanical properties of the formed material. They hence constitute potential parameters for the optimization of hemp concretes.

De par ses propriétés thermomécaniques proches des polyoléfines, le poly(butylene succinate)est l’un des polymères biosourcés les plus attractifs pour la substitution de matériaux pétro-sourcés pour des applications automobiles. L’incorporation de fibres de chanvre, via une étape d’extrusion,renforce la matrice et permet de tendre vers les propriétés cibles exigées par les cahiers des charges automobiles pour les applications visées dans cette étude. Afin d’améliorer les propriétés thermomécaniques de ce matériau, trois sujets ont été développés dans cette étude :1- Qualification de l’interface PBS / fibres de chanvre : via une nouvelle méthodologie basée sur l’analyse de la contribution effective des fibres sur la contrainte (CFC) durant une sollicitation mécanique, il est montré que les liaisons hydrogène formées entre le PBSet la fibre influent fortement sur les mécanismes de transfert de charge. Couplée au modèle de Bowyer et Bader, cette approche permet d’identifier les mécanismes d’endommagement de l’interface et de quantifier la contrainte interfaciale (τchanvre/PBS=25,2MPa).2 - Signification du ratio L/D d’une fibre naturelle : au cours des procédés de mises en oeuvre (extrusion et injection), la morphologie d’une fibre végétale évolue et apparait complexe due à la structure branchée engendrée par la fibrillation. A partir d’une nouvelleméthodologie d’analyse d’images spécifiquement développée, il est montré que la fibrillation contribue au renforcement de la matrice au même titre que le défibrage.3 -Synthèse de PBS-co-amides : afin de couvrir les contraintes thermomécaniques exigées,l’introduction de groupements amide dans le PBS est étudiée pour augmenter le point de fusion du polymère. Afin de contourner notamment la réaction parasite de cyclisation entre l’acide succinique et les amines, une stratégie de synthèses multi-étapes de monomères et de poly(ester-amide) est étudiée permettant d’obtenir un PEA de faible masse molaire dont le point de fusion atteint 172°C. / With its thermomechanical properties closed to polyolefins, poly(butylene succinate) is one ofthe most interesting bio-based polymers for substitution of oil-based polymers for automotive applications. Addition of hemp fibers, through an extrusion process step, reinforces matrix and enables to fit with the targeted technical profile required by automotive specifications. In order to improve thermomechanical properties, three main topics have been investigated in this study:1 - PBS / hemp fibers interface qualification: through a new methodology based on the analysis of the effective fiber contribution on stress during mechanical solicitation, it was shown that hydrogen bonds between PBS and fibers play a major role in load transfer.Combined with the Bowyer and Bader model, this approach enables to highlight interface damages and to determine the interfacial shear strength (τhemp/PBS=25,2 MPa)2 - Meaning of natural fiber L/D ratio: during processes (extrusion and injection), vegetal fiber morphology changes and becomes complex due to the fibrillated structure. With anew developed image analysis tool, it was shown that fibrillation contributes to matrix einforcement as well as defibering.3 - Synthesis of PBS-co-amide: to reach the targeted thermomechanical performances,introduction of amide groups into PBS was studied to increase the melting point. In order to avoid the cyclic imide formation between succinic acid and amines, synthesis of monomers and poly(ester amide) were studied through a multistep strategy, enabling to get low molecular weight PEA with melting temperature around 172°C.

Face à la nécessité de trouver des alternatives aux ressources d’origine fossile et de limiter les impacts environnementaux de l’activité humaine, un important effort de recherche est actuellement en cours pour favoriser et accroître l’utilisation de produits issus de ressources renouvelables, comme les fibres végétales, dans la conception de pièces industrielles. Toutefois, de nombreux verrous scientifiques et technologiques restent encore à lever avant de pouvoir valoriser de façon fiable et durable ces fibres dans un contexte technique exigeant tel que celui du secteur l’automobile. Ainsi, l’amélioration de la qualité de l’interface fibres végétales / matrice polymère est un enjeu de taille car elle constitue une condition permettant de satisfaire les performances mécaniques requises telles que la rigidité, la résistance ou la tenue au choc. Dans ce contexte, l’objectif de la thèse a été le développement de fibres courtes de chanvre à propriétés de surface maitrisées et ciblées. Des solutions de fonctionnalisation de surface applicables par des procédés industrialisables ont été développées dans le but d’incorporer ces fibres dans une matrice polypropylène (PP). Les fibres de chanvre ont ainsi été traitées selon différentes stratégies de fonctionnalisation incluant l’utilisant du polypropylène greffé anhydride maléique (PP-g-MA), d’organosilanes, d’un acide aminé, d’isocyanates et d’un polyuréthane. Deux procédés de traitement à faible impact environnemental ont été comparés : le sprayage direct des fibres par les molécules de fonctionnalisation et l’incorporation de ces molécules par extrusion réactive. Les traitements en extrusion réactive se sont montrés plus efficaces que ceux réalisés par sprayage dans le cas du PP-g-MA. Trois voies de fonctionnalisation se sont avérées pertinentes au regard des propriétés mécaniques visées  : i) l’utilisation de PP-g-MA seul en extrusion réactive ; ii) la fonctionnalisation par sprayage d’un aminosilane ou d’un acide aminé couplée à l’incorporation du PP-g-MA en extrusion réactive. S’appuyant sur le développement de moyens expérimentaux et d’analyses spécifiques, l’étude du comportement au choc des biocomposites a montré que les composites renforcés fibres de chanvre permettent d’absorber d’avantage d’énergie que les composites PP / verre (à taux volumique de renfort identique) pour une longueur de fissuration similaire. Une modélisation par éléments finis du comportement au choc des composites étudiés est également proposée. / Due to the necessity to find alternatives to fossil resources and to reduce the environmental impacts of human activity, a major research effort is currently ongoing in order to develop and increase the use of biobased products from renewable resources, such as natural fibers, in the design of industrial parts. However, many scientific and technological hurdles have yet to be removed so as to promote these products before we can reliably and durably use these fibers in a demanding technical context as in automotive sector. Thus, improving the quality of the interface between natural fibers and polymer matrix is a major challenge, since it constitutes a condition for satisfying the required mechanical performances, such as stiffness, tensile or impact strengths. In this context, the thesis objective was to develop short hemp fibers with controlled and targeted surface properties. Surface-functionalization solutions have been developed, to be used by industrial processes, with the aim of incorporating these fibers in a polypropylene (PP) matrix. Therefore, hemp fibers have been treated according to various functionalization strategies including the use of grafted polypropylene maleic anhydride (PP-g-MA), organosilanes, an amino acid, isocyanates and a polyurethane. Two treatments processes, with low environmental impact, were compared: the direct spraying of functionalization molecules on fibers and reactive extrusion incorporation of these molecules. Reactive extrusion treatments were more efficient than those performed by spraying in the case of PP-g-MA. Three functionalization lanes have been found to be relevant regarding the mechanical properties targeted: i) using PP-g-MA alone in reactive extrusion; ii) spraying-functionalization of an aminosilane or of an amino acid coupled with the incorporation of PP-g-MA into the reactive extrusion. Based on the development of experimental means and specific analyzes, the study of the impact behavior of biocomposites has shown that hemp fiber reinforced composites allow to absorb more energy than PP / glass composites (at identical reinforcing volume rate) for a similar crack length. Also, a finite element modeling of the impact behavior of the studied composites is propounded.

Limitações nas reservas de combustíveis fósseis e a crescente concentração de gases de efeito estufa na atmosfera tem aumentado o interesse para incrementar a participação da cana-de-açúcar como fonte de biomassa para geração de energia renovável. O uso dos resíduos de colheita da cana-de-açúcar para produção de eletricidade e etanol de segunda geração foi intensificado nos últimos anos, sem haver conhecimento claro das implicações da retirada total ou parcial da palha na produtividade da cultura e qualidade do solo a médio e longo prazo. O objetivo deste estudo foi avaliar a produtividade da cana-de-açúcar, os atributos químicos e os estoques de C e N no solo sob níveis de remoção de palha em áreas com e sem rotação com crotalária. Os parâmetros produtivos da cana-de-açúcar foram avaliados em áreas experimentais localizadas em Quirinópolis/GO, Chapadão do Céu/GO, Iracemápolis/SP e Quatá/SP, enquanto os atributos químicos e os estoques de C e N do solo foram avaliados em Quirinópolis/GO e Quatá/SP, locais com solos de textura argilosa e arenosa, respectivamente. Em cada local, foram instalados dois experimentos, um com rotação com crotalária e outro sem rotação com crotalária (pousio) na renovação do canavial. Após a colheita da cana-planta, foram instalados os tratamentos de soqueira referentes aos níveis de 0, 50 e 100% de manutenção de palha. Os parâmetros produtivos foram avaliados nos dois anos seguintes, enquanto os efeitos no solo foram avaliados no final do segundo ciclo agrícola. A manutenção de palha aumentou a produtividade de colmos em três áreas (Quirinópolis/GO, Chapadão do Céu/GO e Quatá/SP) e reduziu a produtividade em um local (Iracemápolis/SP).O efeito benéfico da rotação com crotalária foi menos persistente no tempo do que a manutenção da palha. Os atributos químicos do solo foram mais influenciados pelos tratamentos no solo argiloso do que no solo arenoso. No solo argiloso, a interação da rotação com crotalária e manutenção da palha aumentou os teores de Mg e o V%, e reduziu a acidez potencial do solo. A rotação aumentou os teores de P, K nos dois solos estudados e a CTC no solo argiloso. A rotação com crotalária não afetou os estoques de C e N, enquanto que a manutenção de palha favoreceu o acumulo de C nos dois tipos de solo. / The limited fossil reserves and the growing concentration of greenhouse gases in the atmosphere, have augmented the interest for a greater participation of sugarcane as a source of biomass for renewable energy generation. The use of sugarcane harvest residues for the production of electricity and second generation ethanol has been intensifying in recent years, without having a clear understanding of the implications of total or partial removal of the straw on the crop productivity and soil quality in the medium and long term. The objective of this study was to evaluate sugarcane productivity, soil chemical attributes and C and N stocks in the soil under straw removal levels in areas with and without sunn hemp rotation. The productivity parameters of sugarcane were evaluated in experimental areas located in Quirinópolis / GO, Chapadão do Céu / GO, Iracemápolis / SP and Quatá / SP, while the chemical attributes and the soil C and N stocks were studied in Quirinópolis / GO and Quatá / SP, places with clay and sandy soils respectively. In each site, two experiments were installed, one with sunn hemp rotation and the other without sunn hemp (fallow) in the renovation of the cane field. After harvesting of the cane-plant, were installed the ratooning treatments referring to the levels of 0, 50 and 100% of straw maintenance were installed. The productive parameters were evaluated in the following two years, while the effects on the soil were evaluated at the end of the second agricultural cycle. The straw retention increased the yield of stalks in three areas (Quirinópolis / GO, Chapadão do Céu / GO and Quatá / SP) and reduced productivity in one place (Iracemápolis / SP). The beneficial effect of rotation with sunn hemp was less persistent in the time than the maintenance of the straw. The chemical attributes of the soil were more influenced by treatments in the clay soil than in the sandy soil. In the clay soil, the rotation interaction with crotalaria and straw maintenance increased the Mg and %BS, and reduced the potential acidity of the soil. The rotation increased the P, K content in the two studied soils and the CEC in the clay soil. Sunn hemp rotation did not affect soil C and N stocks, and maintenance of straw favored C accumulation in both types of soil.

L'utilisation de matériaux isolants à base de granulats végétaux est en plein essor notamment pour la réhabilitation du bâti ancien, améliorant ainsi le confort des habitants. Ces matériaux possèdent des propriétés thermiques, hydriques et acoustiques appréciables. Cependant, leur développement est encore limité par le manque d'information sur l'évolution de leurs performances à long terme. Ainsi, l’objectif de cette étude est d’évaluer l’évolution des propriétés fonctionnelles du béton de chanvre, en identifiant les mécanismes de vieillissement lorsque le matériau est exposé à différents types d'environnements. Pour cela, deux bétons de chanvre formulés avec une même chènevotte et deux liants de nature chimique différente sont retenus. L’approche utilisée dans cette étude est pluridisciplinaire (chimique, physico-chimique, microbiologique, microstructurale, acoustique, thermique et mécanique) et multi échelle. L'étude des propriétés chimiques et microstructurales permet de comprendre les variations des propriétés fonctionnelles. Dans un premier temps, la caractérisation initiale des deux formulations a permis de mettre en évidence l’absence d’influence de la nature du liant sur les propriétés fonctionnelles des isolants, ce qui peut être en partie expliqué par des microstructures similaires. Une faible résistance mécanique des matériaux, liée à l'inhibition de la prise des liants en raison de leurs interactions avec les molécules extraites de la chènevotte, a également été mise en évidence. Dans un second temps, les bétons de chanvre ainsi que la chènevotte brute sont soumis à un vieillissement accéléré en imposant des cycles d’humidification/séchage pendant deux ans. Les modifications des performances des matériaux à différentes échéances sont comparées à celles d'échantillons de référence placés à 50% d’humidité relative et une température constante contrôlée. Dans les conditions de référence, aucune variation de propriétés n'est observée. Pour le vieillissement accéléré, les variations de propriétés mises en évidence sont induites par différents paramètres. Dans le cas de la chènevotte brute, l’action des microorganismes et l’adsorption d’eau entrainent une perte de masse et l'ouverture des porosités à l'origine des variations des propriétés acoustiques et hydriques. Pour le béton de chanvre, aucun développement fongique n’est observé en surface du matériau. En revanche, l’action de microorganismes est bien visible à l’intérieur des granulats végétaux, et des mécanismes supplémentaires sont identifiés : les réactions d'hydratation et de carbonatation au sein du liant ainsi que la minéralisation de la chènevotte entrainent des variations de propriétés thermiques, acoustiques et hydriques en modifiant la microstructure des bétons de chanvre. En conclusion, l’absence de variations des propriétés des bétons de chanvre dans les conditions de référence laisse penser que dans un bâtiment réel, leurs propriétés peuvent être stables dans le temps, les pathologies observées étant alors liées à une mise en œuvre défaillante. Pour aller plus loin, les résultats obtenus lors de ce travail devront être validés par une étude in situ qui permettrait d’estimer la durée de vie de ces matériaux / The use of insulating materials based on plant aggregates is growing quickly, especially for the rehabilitation of old buildings, thus improving the comfort of residents. These materials have significant thermal, hydric and acoustic properties. However, their development is still limited by the lack of information on the evolution of their long-term performances. Thus, the objective of this study is to evaluate the evolution of the functional properties of hemp concretes, by identifying the aging mechanisms when the material is exposed to different types of environments. For this aim, two hemp concretes formulated with one type of hemp and two binders with different chemical nature are retained. The approach of this study is multidisciplinary (chemical, physico-chemical, microbiological, microstructural, acoustic, thermal and mechanical) and multi-scale. The study of chemical and microstructural properties allows the understanding of the variations of functional properties. Firstly, the initial characterization of the both hemp concretes made it possible to demonstrate the absence of impact of the nature of the binder on the functional properties of the insulators, which can be partly explained by their similar microstructure. A weak mechanical resistance of the materials was also highlighted, related to the inhibition of the setting of the binders because of their interactions with the molecules extracted from the shiv. Secondly, hemp concretes and bulk shiv hemp are subjected to an accelerated aging by imposing cycles of humidification / drying during two years. The modifications of the material performances at different time scales are compared to reference samples stored at 50% of relative humidity and a constant controlled temperature. Under reference conditions, no variation in properties is observed. For accelerated aging, the variations of properties highlighted are induced by several parameters. In the case of bulk shiv, the action of microorganisms and the adsorption of water lead to a loss of mass and to the opening of porosities, leading to variations in acoustic properties. For hemp concretes, no fungal development is observed on the surface of the material. On the other hand, the action of microorganisms is clearly visible inside the plant aggregates, and additional mechanisms are identified: the hydration and carbonation reactions within the binder as well as the mineralization of the vegetal particles cause variations in thermal, acoustic and hydric properties by modifying the microstructure of hemp concretes.In conclusion, the absence of variations in the properties of hemp concretes in the reference conditions suggests that in a real building, their properties can be stable over time, the observed pathologies then being due to a faulty implementation. To go further, the results obtained during this work have to be validated by an in-situ study to be able to estimate the lifetime of these materials

Les biocomposites sont des matériaux renforcés de fibres issues de ressources renouvelables. Ces matériaux sont une solution alternative aux composites renforcés de fibres de verre ou de carbone. En effet, leur légèreté et leurs propriétés mécaniques intéressantes leur confèrent un intérêt grandissant dans les secteurs tels que la construction (terrasse, meubles de jardin) ou l’automobile (panneaux de porte, tableaux de bord). Toutefois, les milieux humides, la température et le rayonnement UV sont des paramètres pouvant compromettre la stabilité physico-chimique des biocomposites. L’objectif principal de cette thèse a été d’évaluer la durabilité des biocomposites sous leurs conditions d’usage principales. Pour cela, ces matériaux ont été exposés pendant une année à l’extérieur (lames de terrasse) et sous vitre pare-brise (tableaux de bord). Les résultats ont montré que, bien que la performance mécanique des biocomposites ait été affectée, celle-ci n’a pas été grandement influencée par le type d’exposition. Par contre, les différences de variations de couleur et de cristallinité différant entre les deux expositions suggèrent des mécanismes de dégradation différents et très dépendants des conditions d’usage.Puisque les biocomposites peuvent être utilisés dans des environnements clos tels que les habitacles d’automobile, ils peuvent être également des sources de polluants dans l’air intérieur. L’étude des émissions de composés organiques volatils (COV) par les biocomposites au cours de leur vieillissement sous vitre pare-brise, a permis de générer des données nécessaires à l’évaluation de l’impact sur la qualité de l’air intérieur de véhicule de ces nouveaux matériaux. Cependant, l’augmentation drastique de la concentration de surface en COV au cours du vieillissement suggère que l’exposition a fortement affecté les biocomposites à cause de la sensibilité des composants structurant les fibres végétales face aux conditions d’exposition.La compréhension des mécanismes de dégradation peut s’effectuer à travers l’interprétation des liens de causalité entre les propriétés mécaniques et de microstructure, les émissions de COV, et l’apparence visuelle. Un traitement statistique par analyse en composantes principales (ACP) a ainsi permis de dégager les relations entre les paramètres quantitatifs.Le vieillissement naturel nécessite souvent une durée d’exposition longue pour apercevoir une dégradation effective des matériaux. De ce fait, le vieillissement accéléré en enceinte de laboratoire est de plus en plus réalisé en industrie permettant un gain de temps. Afin de vérifier la représentativité des mécanismes de dégradation en environnement extérieur par l’enceinte, une étude comparative entre le vieillissement naturel extérieur et un vieillissement accéléré en enceinte a été menée. / Biocomposites are fiber-reinforced materials from renewable resources. These materials are an alternative to fiberglass or carbon reinforced composites. Indeed, their lightweight and interesting mechanical properties give them a growing interest in sectors such as building (decking, garden furniture) or automobile (door panels, dashboards). However, humidity, temperature and UV radiation are parameters that can compromise the physicochemical stability of biocomposites.The main objective of this thesis is to assess the biocomposites durability in their main conditions of use. For this purpose, these materials have been exposed for one year outdoors (deck boards) and under windshield glass (dashboards). The results showed that the mechanical performance of biocomposites was affected and greatly influenced by the type of exposure. On the other hand, the differences in color and crystallinity variations that differ between the two exposures suggest different degradation mechanisms that are very dependent on the conditions of use.Since biocomposites can be used in environments such as the passenger cabin, they can also be sources of pollutants in indoor air. The study of emissions of volatile organic compounds (VOCs) by biocomposites during their ageing under windshield glass allowed generating data necessary for the evaluation of the impact on the car indoor air quality of these new materials. However, the drastic increase of VOCs surface concentration during exposure suggests that weathering strongly affected biocomposites due to the sensitivity of the structural components of plant fibers to exposure conditions.Understanding of the degradation mechanisms can be carried out through the interpretation of the causal links between mechanical and microstructural properties, VOC emissions and visual appearance. Statistical treatment by Principal Component Analysis (PCA) revealed the links and relationships existing between the quantitative parameters.Natural weathering often requires long time of exposure for an efficient perception of the materials degradation. Thus, accelerated ageing in laboratory is more and more carried out in industry for time saving. In order to verify the representativeness of the degradation mechanisms occurring during exterior weathering by weathering chambers, a comparative study between the exterior aging and the artificial aging was carried out.

A adoção da rotação de culturas com leguminosas em áreas de implantação e reforma de canaviais é uma estratégia promissora para recuperação e manutenção da fertilidade do solo, e tem potencial no aproveitamento do N para as soqueiras. A análise mais detalhada do comportamento do N no solo durante o ano agrícola e dos parâmetros de produção em locais que possuem solo e clima contrastantes, permitem aprimorar o manejo da adubação nitrogenada da cana-de-açúcar. As hipóteses deste trabalho são (1) a rotação de culturas irá aumentar a disponibilidade de N no solo, a qual suprirá parte da demanda do N das soqueiras subsequentes e (2) a rotação de culturas promoverá redução da resposta das soqueiras à adubação nitrogenada. Objetivou-se avaliar o efeito da rotação de culturas nas transformações do N no solo (N mineral, N-ISNT e N e C da biomassa microbiana) e na produtividade da primeira soqueira. Os experimentos foram instalados em quatro regiões representativas de cultivo de cana-de-açúcar na região Centro Sul do Brasil: Quatá/SP (Local A); Iracemápolis/SP (Local B); Chapadão do Céu/GO (Local C) e Quirinópolis/GO (Local D). Em cada local, foi instalado um experimento em esquema de parcelas subdivididas no delineamento blocos ao acaso com quatro repetições, em áreas submetidas (com rotação) ou não (sem rotação) ao plantio de leguminosa do gênero crotalária. Após a colheita da cana planta, foram implantados os seguintes tratamentos: 60, 120 e 180 kg ha-1 de N e um controle (sem N), aplicados superficialmente sobre a palhada. Foram realizadas três amostragens para determinação do conteúdo de N mineral, N-ISNT e C e N da biomassa microbiana. Entre 150 a 180 dias após a colheita da cana-planta, foram realizadas avaliações de perfilhamento e índice SPAD. Na colheita, avaliou-se matéria seca da parte aérea, produtividade e atributos tecnológicos. Os resultados demonstraram que a mineralização dos resíduos da crotalária influenciaram a dinâmica do C e N e os reservatórios de N no perfil do solo ao longo do ciclo da primeira soqueira, com destaque para o solo de textura média (Local A). Apesar da rotação de culturas ter modificado o conteúdo de N mineral, N-ISNT, e aumentado o perfilhamento e índice SPAD no local A, somente nos solos argilosos (Locais C e D), a rotação aumentou a produtividade da soqueira. A hipótese de que a rotação de culturas reduz a demanda de fertilizantes nitrogenados não foi aceita; houve resposta à adubação nitrogenada nos quatro locais, independentemente da rotação de culturas. Porém, a rotação demonstrou potencial em aumentar a produção de biomassa com manutenção da dose de N. Esta pesquisa demonstrou a viabilidade de rotação de culturas em solos argilosos com elevado conteúdo de C e N total, com potencial de aumentar a produtividade do canavial, porém sem reduzir a demanda de adubação nitrogenada. / The adoption of crop rotation with sugarcane is a promising strategy for the recovery and maintenance of soil fertility, and it shows potential in the use of N to the sugarcane ratoon. A more detailed analysis of the transformations N in soil during the agricultural year and production parameters in sites that have contrasting soil texture and climate, allows to improve management of N fertilization for sugarcane. The hypothesis of this work are (1) crop rotation will increase soil N availability, which will satisfy part of N requirements of sugarcane ratoon and (2) crop rotation will reduce the sugarcane ratoon response to N fertilization. The objective was to evaluate the effects of sunn hemp rotation in the transformations of N in soil (mineral N content, ISNT-N and microbial biomass C and N) and sugarcane ratoon yield. The field trials were installed in four representative regions of cultivation of sugarcane in Brazil: Quatá/SP (Site A); Iracemápolis/SP (Site B); Chapadão do Céu/GO (Site C) e Quirinópolis/GO (Site D). At each site, a field trial was installed in split plot in a randomized block experimental design with four replications, in areas sowed (rotation) and not sowed (no rotation) with sunn hemp. After the harvest of cane-plant, the following treatments were applied: 60, 120 and 180 kg ha-1 of N and a control (without N) over the straw. Three sampling were performed to determine the soil inorganic N content, ISNT-N, C and N of microbial biomass. Between 150 to 180 days after the harvest of the cane-plant, tillering was counted and SPAD index was measured. At harvest of the sugarcane ratoon, biometric parameters, yield and quality parameters were evaluated. The results showed that mineralization of residues of sunn hemp influenced the dynamics of C and N and N content in the soil profile throughout the cycle of the sugarcane ratoon, with emphasis on medium-textured soil (Site A). Despite crop rotation has modified mineral N stocks, ISNT-N, and increased tillering and SPAD index in site A, crop rotation only increased the sugarcane ratoon yield on clay soils (Sites C and D). The hypothesis that crop rotation reduces N-fertilizer requirement was not accepted; there was response to N fertilization in four sites, regardless of crop rotation. However, the rotation showed potential in increase biomass production with maintenance of N rate. This research demonstrated the viability of crop rotation in clay soils with high total C and N content, with potential to increase sugarcane yield, but without reducing N-fertilizer requirement.

Limitações nas reservas de combustíveis fósseis e a crescente concentração de gases de efeito estufa na atmosfera tem aumentado o interesse para incrementar a participação da cana-de-açúcar como fonte de biomassa para geração de energia renovável. O uso dos resíduos de colheita da cana-de-açúcar para produção de eletricidade e etanol de segunda geração foi intensificado nos últimos anos, sem haver conhecimento claro das implicações da retirada total ou parcial da palha na produtividade da cultura e qualidade do solo a médio e longo prazo. O objetivo deste estudo foi avaliar a produtividade da cana-de-açúcar, os atributos químicos e os estoques de C e N no solo sob níveis de remoção de palha em áreas com e sem rotação com crotalária. Os parâmetros produtivos da cana-de-açúcar foram avaliados em áreas experimentais localizadas em Quirinópolis/GO, Chapadão do Céu/GO, Iracemápolis/SP e Quatá/SP, enquanto os atributos químicos e os estoques de C e N do solo foram avaliados em Quirinópolis/GO e Quatá/SP, locais com solos de textura argilosa e arenosa, respectivamente. Em cada local, foram instalados dois experimentos, um com rotação com crotalária e outro sem rotação com crotalária (pousio) na renovação do canavial. Após a colheita da cana-planta, foram instalados os tratamentos de soqueira referentes aos níveis de 0, 50 e 100% de manutenção de palha. Os parâmetros produtivos foram avaliados nos dois anos seguintes, enquanto os efeitos no solo foram avaliados no final do segundo ciclo agrícola. A manutenção de palha aumentou a produtividade de colmos em três áreas (Quirinópolis/GO, Chapadão do Céu/GO e Quatá/SP) e reduziu a produtividade em um local (Iracemápolis/SP).O efeito benéfico da rotação com crotalária foi menos persistente no tempo do que a manutenção da palha. Os atributos químicos do solo foram mais influenciados pelos tratamentos no solo argiloso do que no solo arenoso. No solo argiloso, a interação da rotação com crotalária e manutenção da palha aumentou os teores de Mg e o V%, e reduziu a acidez potencial do solo. A rotação aumentou os teores de P, K nos dois solos estudados e a CTC no solo argiloso. A rotação com crotalária não afetou os estoques de C e N, enquanto que a manutenção de palha favoreceu o acumulo de C nos dois tipos de solo. / The limited fossil reserves and the growing concentration of greenhouse gases in the atmosphere, have augmented the interest for a greater participation of sugarcane as a source of biomass for renewable energy generation. The use of sugarcane harvest residues for the production of electricity and second generation ethanol has been intensifying in recent years, without having a clear understanding of the implications of total or partial removal of the straw on the crop productivity and soil quality in the medium and long term. The objective of this study was to evaluate sugarcane productivity, soil chemical attributes and C and N stocks in the soil under straw removal levels in areas with and without sunn hemp rotation. The productivity parameters of sugarcane were evaluated in experimental areas located in Quirinópolis / GO, Chapadão do Céu / GO, Iracemápolis / SP and Quatá / SP, while the chemical attributes and the soil C and N stocks were studied in Quirinópolis / GO and Quatá / SP, places with clay and sandy soils respectively. In each site, two experiments were installed, one with sunn hemp rotation and the other without sunn hemp (fallow) in the renovation of the cane field. After harvesting of the cane-plant, were installed the ratooning treatments referring to the levels of 0, 50 and 100% of straw maintenance were installed. The productive parameters were evaluated in the following two years, while the effects on the soil were evaluated at the end of the second agricultural cycle. The straw retention increased the yield of stalks in three areas (Quirinópolis / GO, Chapadão do Céu / GO and Quatá / SP) and reduced productivity in one place (Iracemápolis / SP). The beneficial effect of rotation with sunn hemp was less persistent in the time than the maintenance of the straw. The chemical attributes of the soil were more influenced by treatments in the clay soil than in the sandy soil. In the clay soil, the rotation interaction with crotalaria and straw maintenance increased the Mg and %BS, and reduced the potential acidity of the soil. The rotation increased the P, K content in the two studied soils and the CEC in the clay soil. Sunn hemp rotation did not affect soil C and N stocks, and maintenance of straw favored C accumulation in both types of soil.

A adoção da rotação de culturas com leguminosas em áreas de implantação e reforma de canaviais é uma estratégia promissora para recuperação e manutenção da fertilidade do solo, e tem potencial no aproveitamento do N para as soqueiras. A análise mais detalhada do comportamento do N no solo durante o ano agrícola e dos parâmetros de produção em locais que possuem solo e clima contrastantes, permitem aprimorar o manejo da adubação nitrogenada da cana-de-açúcar. As hipóteses deste trabalho são (1) a rotação de culturas irá aumentar a disponibilidade de N no solo, a qual suprirá parte da demanda do N das soqueiras subsequentes e (2) a rotação de culturas promoverá redução da resposta das soqueiras à adubação nitrogenada. Objetivou-se avaliar o efeito da rotação de culturas nas transformações do N no solo (N mineral, N-ISNT e N e C da biomassa microbiana) e na produtividade da primeira soqueira. Os experimentos foram instalados em quatro regiões representativas de cultivo de cana-de-açúcar na região Centro Sul do Brasil: Quatá/SP (Local A); Iracemápolis/SP (Local B); Chapadão do Céu/GO (Local C) e Quirinópolis/GO (Local D). Em cada local, foi instalado um experimento em esquema de parcelas subdivididas no delineamento blocos ao acaso com quatro repetições, em áreas submetidas (com rotação) ou não (sem rotação) ao plantio de leguminosa do gênero crotalária. Após a colheita da cana planta, foram implantados os seguintes tratamentos: 60, 120 e 180 kg ha-1 de N e um controle (sem N), aplicados superficialmente sobre a palhada. Foram realizadas três amostragens para determinação do conteúdo de N mineral, N-ISNT e C e N da biomassa microbiana. Entre 150 a 180 dias após a colheita da cana-planta, foram realizadas avaliações de perfilhamento e índice SPAD. Na colheita, avaliou-se matéria seca da parte aérea, produtividade e atributos tecnológicos. Os resultados demonstraram que a mineralização dos resíduos da crotalária influenciaram a dinâmica do C e N e os reservatórios de N no perfil do solo ao longo do ciclo da primeira soqueira, com destaque para o solo de textura média (Local A). Apesar da rotação de culturas ter modificado o conteúdo de N mineral, N-ISNT, e aumentado o perfilhamento e índice SPAD no local A, somente nos solos argilosos (Locais C e D), a rotação aumentou a produtividade da soqueira. A hipótese de que a rotação de culturas reduz a demanda de fertilizantes nitrogenados não foi aceita; houve resposta à adubação nitrogenada nos quatro locais, independentemente da rotação de culturas. Porém, a rotação demonstrou potencial em aumentar a produção de biomassa com manutenção da dose de N. Esta pesquisa demonstrou a viabilidade de rotação de culturas em solos argilosos com elevado conteúdo de C e N total, com potencial de aumentar a produtividade do canavial, porém sem reduzir a demanda de adubação nitrogenada. / The adoption of crop rotation with sugarcane is a promising strategy for the recovery and maintenance of soil fertility, and it shows potential in the use of N to the sugarcane ratoon. A more detailed analysis of the transformations N in soil during the agricultural year and production parameters in sites that have contrasting soil texture and climate, allows to improve management of N fertilization for sugarcane. The hypothesis of this work are (1) crop rotation will increase soil N availability, which will satisfy part of N requirements of sugarcane ratoon and (2) crop rotation will reduce the sugarcane ratoon response to N fertilization. The objective was to evaluate the effects of sunn hemp rotation in the transformations of N in soil (mineral N content, ISNT-N and microbial biomass C and N) and sugarcane ratoon yield. The field trials were installed in four representative regions of cultivation of sugarcane in Brazil: Quatá/SP (Site A); Iracemápolis/SP (Site B); Chapadão do Céu/GO (Site C) e Quirinópolis/GO (Site D). At each site, a field trial was installed in split plot in a randomized block experimental design with four replications, in areas sowed (rotation) and not sowed (no rotation) with sunn hemp. After the harvest of cane-plant, the following treatments were applied: 60, 120 and 180 kg ha-1 of N and a control (without N) over the straw. Three sampling were performed to determine the soil inorganic N content, ISNT-N, C and N of microbial biomass. Between 150 to 180 days after the harvest of the cane-plant, tillering was counted and SPAD index was measured. At harvest of the sugarcane ratoon, biometric parameters, yield and quality parameters were evaluated. The results showed that mineralization of residues of sunn hemp influenced the dynamics of C and N and N content in the soil profile throughout the cycle of the sugarcane ratoon, with emphasis on medium-textured soil (Site A). Despite crop rotation has modified mineral N stocks, ISNT-N, and increased tillering and SPAD index in site A, crop rotation only increased the sugarcane ratoon yield on clay soils (Sites C and D). The hypothesis that crop rotation reduces N-fertilizer requirement was not accepted; there was response to N fertilization in four sites, regardless of crop rotation. However, the rotation showed potential in increase biomass production with maintenance of N rate. This research demonstrated the viability of crop rotation in clay soils with high total C and N content, with potential to increase sugarcane yield, but without reducing N-fertilizer requirement.