Thèses sur le sujet « Thermo-wood »

This research concentrates on the recyclability of two wood plastic composites (WPCs) - wood flour/HDPE and wood flour/PLA composites. Two different filler loadings (30 and 50 wt%) were considered for each polymer composite. Each composite formulation contained 3 wt% of a coupling agent, and was individually recycled up to six times by extrusion process. Samples for mechanical and thermo-mechanical tests were prepared by injection molding. All test results were statistically analyzed with a confidence level of 95%. Additional tests such as fiber length measurement, GPC, DSC, TGA, FTIR, and SEM were also performed at specific reprocessing cycles. After reprocessing six times, all formulations showed lower relative decrease in most stiffness properties but higher relative increase in most strain properties. In strength properties, both HDPE composites showed lower relative decrease after reprocessed six times; however, higher and lower filler PLA composites showed sharp decrease reprocessed at second and six times respectively.

Les anciennes peintures sur bois représentent une part importante du patrimoine culturel européen. Depuis longtemps, il est connu que les conditions de stockage peuvent entraîner des dégradations et endommagements aux panneaux. Une bonne compréhension de l'état actuel des peintures sur bois ainsi que la prédiction de leur comportement dans diverses conditions climatiques est essentielle pour mieux les conserver et les restaurer. De telles analyses peuvent être faites par le biais de la modélisation numérique. Cependant, la modélisation numérique est efficace que si les paramètres des matériaux sont équivalents à ceux de la réalité. Dans ce travail, les modifications mécaniques, physiques et chimiques qui se produisent au cours du vieillissement naturel ont été étudiées pour le bois et les couches de peintures. Les possibilités d'accélérer le vieillissement par des traitements thermo-hydrique ont été appliquées avec succès au bois. Une loi de vieillissement du bois a été trouvée pour la résistance radiale et la luminosité de la couleur. Malheureusement, une tel loi n'a pas été trouvé pour les couches de peinture. Ensuite, un modèle numérique tridimensionnel sur le comportement hygroscopique et mécanique des panneaux peints a été développé. La comparaison entre ce modèle et des expériences sont en bon accord. Finalement, une analyse de risques sur une ancienne peinture a montré que des fluctuations d'humidité relative normales ne devraient pas promouvoir de dommages dans le support en bois, mais la fissuration de la couche picturale est possible
Ancient wood panel paintings represent an important part of the European cultural heritage. Since long time it is known that the storing condition can degrade and damage them. Understanding of the actual state of old panel paintings and the prediction of their behaviour under various climatic conditions is essential to better conserve and restore them. Such analysis could be done by numerical modelling. However, numerical modelling can achieved good predictions only if the materials parameters are adequately determined. In this work, the mechanical, physical and chemical modifications occurring during natural aging have been investigated for wood and paint layers. The possibility to accelerate the aging with thermo-hydro treatments has been successfully applied to wood. A wood aging law has been found for the radial strength and the lightness. Unfortunately, no such law has been found for the paint layers. The hygroscopic and mechanical behaviour of panel paintings has been then simulated in 3D by finite element method model including time dependent behaviour. The comparison between the model and experiments shows good agreement. Finally, risk analysis on an old painting shows that normal climate fluctuation should not promote cracks in the wooden support but the cracking of the ground layer is possible

Les bétons végétaux, composés de particules végétales et d'un liant minéral ou organique, constituent une solution à explorer pour limiter l'impact environnemental du bâtiment. Utilisés principalement pour leurs performances thermiques, ces matériaux suscitent l'intérêt de plusieurs organismes de recherche ainsi que de plusieurs entreprises industrielles. La généralisation de leur utilisation dans la construction ne sera pas possible sans résoudre certains problèmes liés à leurs techniques de mise en œuvre, à leur certification et à leur durabilité. Le présent travail a pour objectif de contribuer à la caractérisation de ces matériaux complexes. Il s'agit en particulier d'étudier les comportements mécanique, thermique et hydromécanique du béton de granulats de bois. La stratégie utilisée consiste à combiner l'expérience et la modélisation pour mieux comprendre les mécanismes mis en jeu. Le module de Young et la résistance en compression ont été mesurés expérimentalement à l'aide de la technique de corrélation d'images numériques. L'évolution de ces propriétés dépend des conditions de conservation, de la durée de séchage ainsi que de la teneur en ciment. En raison de l'orientation aléatoire des granulats de bois, le comportement mécanique du béton est isotrope. Un modèle d'homogénéisation basé sur le schéma autocohérent a été développé pour prédire le module de Young du béton et ses résultats sont très satisfaisants. Les mesures de la conductivité thermique montrent que celle-ci reste constante en conditions endogènes. La modélisation de cette propriété par le schéma autocohérent conduit à des résultats cohérents avec les mesures expérimentales. En conditions de dessiccation, la conductivité thermique dépend linéairement de la densité du béton. L'évolution de la conductivité thermique des granulats de bois et de la pâte de ciment au cours du séchage a été modélisée grâce au schéma de Mori-Tanaka. Ces évolutions ont été intégrées dans le modèle autocohérent qui fournit ainsi des résultats satisfaisants, mais qui pourrait être amélioré si l'on disposait des courbes de sorption/désorption des constituants du béton. Les variations dimensionnelles du béton au cours du temps dépendent des conditions de conservation, mais pas de la direction de mesure, ni de la teneur en ciment. Un modèle reposant sur une combinaison des déformations induites par la désorption de l'eau par des constituants et le transfert d'humidité entre ceux-ci a été proposé et a permis de capturer les tendances des déformations du béton sauf au jeune âge. À l'échelle locale, l'étude a montré que les déformations du béton sont du même ordre de grandeur que celles de la pâte de ciment. Elle a aussi mis en évidence un endommagement partiel de l'interface granulat/liant qui mériterait à être pris en compte dans la modélisation
Environmentally-friendly concretes, made up of plant-based particles and mineral or organic binder, are solutions worth exploring to reduce the environmental impact of buildings. Mainly used for their thermal performance, these materials have aroused interest of many research organisations and industrial companies. Their widespread use in construction is not possible without resolving some technical problems related to their implementation, certification and durability. This work aims to contribute to characterize these complex materials, in particular to study the mechanical, thermal and hydromechanical behaviors of wood-aggregate concrete. Modeling and experiments have been used to understand the complex mechanisms involved. The Young's modulus and the compressive strength were experimentally measured using digital image correlation. The evolution of these properties depends on the conditions of storage, the drying time and the cement content. Because of the random orientation of the wood aggregates, the material exhibits isotropic behavior. A homogenization model based on a self-consistent scheme was developed to predict the Young's modulus. The results were satisfactory. Measurements show that thermal conductivity remains constant under sealed conditions. The modeling of this property with the self-consistent scheme gives results consistent with experimental measurements. In desiccation conditions, the thermal conductivity depends linearly on the density of concrete. The evolution of the thermal conductivity of the wood aggregates and the cement paste during drying was modeled with the Mori-Tanaka scheme. These evolutions were integrated into the self-consistent model, which yielded satisfactory results, but could be improved if sorption/desorption curves of the phases were available. The macroscopic dimensional variations of the wood-aggregate concretes depended on the storage conditions, but not on the measurement direction, nor on the cement content. A model based on the combination of the strains induced by the desorption of water from the phases and the moisture transfer between them was proposed. It allowed us to capture the trends of the strains of our concrete except at early age. At a local scale, the study showed that the strains of concrete were close to those of the cement paste. The study also shed light on a significant damage of the aggregate/binder interfaces, which would deserve to be taken into account into the modeling

Dans le contexte du développement durable qui a vu l’introduction de la directive produits biocides BPD 98/8/CE, l’étude des méthodes innovantes de préservation du bois comme le traitement thermique revêt une importance prépondérante. Le traitement thermique du bois permet d’améliorer ses propriétés de résistance biologique, de stabilité dimensionnelle ainsi que son aspect esthétique, sans ajout de produit chimique. Les études actuelles sur la problématique de la qualité du bois traité thermiquement se focalisent sur les caractéristiques finales du bois déjà traité, l’influence des conditions de traitement ou encore l’effet essence. Les propriétés intrinsèques du bois avant le traitement ne sont pas encore prises en compte. Les propriétés du bois telles que la densité ou la composition chimique étant variables principalement sous l’effet de l’activité humaine comme la sylviculture, l’objectif de cette thèse était d’évaluer l’impact de cette variabilité chez le chêne sessile (Quercus petraea Liebll.) et le sapin (Abies alba Mill) sur leur modification par voie thermique. Un scanner et un micro-densitomètre à rayons X ont été utilisés pour caractériser la variation de la densité des échantillons de planches et des cernes de croissance provenant des arbres étudiés. Des traitements thermiques ont été réalisés dans un four pilote à conduction sous vide de type macro-thermobalance et un analyseur thermogravimétrique (ATG). Des analyses chimiques ont été également réalisées. Les résultats montrent qu’en prenant la perte de masse due à la dégradation thermique du bois comme réponse, les types de tissus du bois et la composition chimique influencent sa thermo-dégradation. Que ce soit chez Quercus petraea ou chez Abies alba, le bois de printemps était plus sensible au traitement thermique que son voisin de bois d’été. De plus, les portions radiales du tronc, du bois juvénile à l’aubier en passant par le bois mature, se dégradaient suivant des cinétiques différentes. En conclusion, la variation de la microstructure et la composition chimique de ces bois influencent leur cinétique globale de thermo-dégradation. La sylviculture impacte cette différence intraspécifique de cinétique de dégradation à l’échelle intra- et interarbre. En effet, dans le cas du sapin pectiné, une gestion très dynamique des forêts dans le but de stimuler la croissance rapide des arbres qui produisent de gros bois contenant des cernes très larges, est source de variation dans la structure anatomique et la composition chimique à l’intérieur des arbres en comparaison aux petits bois à croissance lente plus homogènes. Toutes ces analyses ont pour objectif final de comprendre le lien entre les propriétés initiales du bois et les modifications thermiques intervenant au cours du traitement afin d’apporter une information utile aux industriels lors du choix des pièces de bois destinées au traitement thermique en vue d’une amélioration de la qualité du bois traité thermiquement
In the context of sustainable development which has seen the introduction of the biocides directive BPD 98/8/CE in the EU, innovative wood preservation practices such as Heat Treatment (HT) become relevant. Wood HT, also termed wood thermal modification, is a physical modification technology by which wood is heated at around 200 °C in an inert atmosphere. The main purpose of the treatment is to improve the biological durability and dimensional stability of wood. Current studies on thermally modified wood (TMW) quality are focusing on treated material, on treatment conditions or on species effect on the end-product characteristics. Relatively little is known about the effect of intrinsic wood properties on its thermal modification. As wood properties vary especially under the influence of human activities through sylviculture, this thesis studied the effect of European oak and silver fir wood density and chemical composition on their thermal modification kinetic. An X rays computed tomography (CT) and densitometer were used to characterize wood samples. Boards were heat-treated by conduction under vacuum using a pilot furnace, whereas sawdust samples underwent thermo-gravimetric analysis under nitrogen. The analysis allowed finding intra- and interspecific variations, especially within growth rings and along radial direction (from pith to bark). Forest management impacted heat modification kinetic of the studied samples, especially in silver fir where fast grown wood was more sensitive to treatment. The finding will be used as additional information to the wood industry which will account for homogeneity of loadings destined to heat treatment

Dans cette étude, l’amélioration des propriétés physiques et de sa durabilité aux agents de dégradation biologique du hêtre européen (Fagus sylvatica) a été réalisée au moyen de différents traitements. Les premiers types de traitements sont basés sur l'imprégnation de dérivés vinyliques de glycérol ou de polyglycérol en tant qu'additif suivi d’une étape de modification thermique réalisée dans un réacteur ouvert (OHT) ou fermé (HPS). Le deuxième type de traitement repose sur la poly-estérification in situ du sorbitol et de l'acide citrique à différentes concentrations et températures de durcissement en système ouvert. Diverses propriétés de durabilité physique, chimique, mécanique et biologique des bois modifiés ont été évaluées. Les résultats montrent que certains traitements peuvent améliorer de manière significative les propriétés de durabilité physique et biologique du bois contre les agents de pourriture blanche, brune et molle et surtout vis-à-vis de l’attaque des termites comparativement au bois non traité ou modifié thermiquement uniquement
In this study, improvement of physical and biological durability properties of European beech (Fagus sylvatica) has been performed through different bulking impregnation treatments. The first modification was based on the impregnation of vinylic derivatives of glycerol or polyglycerol as additive followed with different thermal modification conditions in the opened system (OHT) or in the closed system (HPS). The second modification was based on the in-situ polyesterification of sorbitol and citric acid at different concentrations and curing temperatures in the opened system. Various physical, chemical, mechanical, and biological durability properties of the modified woods were evaluated, including certain properties during modification. The results have disclosed that certain treatments can improve significantly physical and biological durability properties of wood against decay (white rot, brown rot, and soft rot fungi) and termites attacks in comparison to untreated wood or thermally modified woods

Guadua angustifolia Kunth (Guadua) is a bamboo species native to South and Central America that has been widely used for structural applications in small and large-scale buildings, bridges and temporary structures. Currently, its structural use is regulated within seismic resistant building codes in countries such as Peru and Colombia. Nevertheless, Guadua remains a material for vernacular construction associated with high levels of manual labour and structural unpredictability. Guadua buildings are limited to two storeys due to the overall flexibility of the slender and hollow culms and its connection systems. Its axial specific stiffness is comparable to that of steel and hardwoods, but unlike wood, Guadua’s hollow structure and lack of ray cells render it prone to buckling along the grain and to transverse crushing. As a result, Guadua’s mainstream use in construction and transformation into standard sizes or engineered Guadua products is scarce. Therefore, this work focussed on the development of standardised flat industrial structural products from Guadua devising replicable manufacturing technologies and engineering methods to measure and predict their mechanical behaviour. Cross-laminated Guadua panels were developed using thermohydro-mechanically modified and laminated flat Guadua strips glued with a high performance resin. Guadua was subjected to thermo-hydro-mechanical (THM) treatments that modified its microstructure and mechanical properties. THM treatment was applied to Guadua with the aim of tackling the difficulties in the fabrication of standardised construction materials and to gain a uniform fibre content profile that facilitated prediction of mechanical properties for structural design. Densified homogenous flat Guadua strips (FGS) were obtained. Elastic properties of FGS were determined in tension, compression and shear using small-clear specimens. These properties were used to predict the structural behaviour of G-XLam panels comprised of three and five layers (G-XLam3 and G-XLam5) by numerical methods. The panels were assumed as multi-layered systems composed of contiguous lamellas with orthotropic axes orientated at 0º and 90º. A finite element (FE) model was developed, and successfully simulated the response of G-XLam3 & 5 panels virtually loaded with the same boundary conditions as the following experimental tests on full-scale panels. G-XLam3 and G-XLam5 were manufactured and their mechanical properties evaluated by testing large specimens in compression, shear and bending. Results from numerical, FE predictions and mechanical testing demonstrated comparable results. Finally, design and manufacturing aspects of the G-XLam panels were discussed and examples of their architectural and structural use in construction applications such as mid-rise buildings, grid shells and vaults are presented. Overall, this research studies THM treatments applied to Guadua in order to produce standardised engineered Guadua products (EGP), and provides guidelines for manufacturing, testing, and for the structural analysis and design with G-XLam panels. These factors are of key importance for the use of Guadua as a mainstream material in construction.

In this research we are following the thermo-chemical degradation of wood in the absence of oxygen. The objectives are to evaluate the influence of heating rates on pyrolysis products obtained from wood pyrolysis and to evaluate the influence of acid pre-treatment on pyrolysis products. Depending on the wood heating rates, pyrolysis can be categorized as Flash pyrolysis, Fast pyrolysis, and Slow pyrolysis. We have evaluated the volatile products obtained at different heating rates and the volatile products obtained from sulfuric acid pre-treatment by using gas chromatography- mass spectrometry (GC-MS). We have also performed thermo-gravimetric analysis (TGA) of raw wood samples and sulfuric acid pre-treated wood samples of Yellow Pine to determine the changes in weight in relation to change in temperature. Our results indicated that by using the Flash, Fast, and Slow heating rates, the overall volatile products obtained from wood pyrolysis (i.e. the overall list of all the compounds obtained from different temperature ranges in wood pyrolysis by using different heating rates) were the same, but the volatile products obtained at different temperature ranges like Room temperature-300°C, 300°C - 400°C, and 400°C -500°C in Flash, Fast, and Slow pyrolysis were different. Most of the volatile products obtained from the pyrolysis of untreated wood were phenols. Our results also indicated that the pretreatment of wood with sulfuric acid alters the charcoal properties and releases gaseous products including furan derivatives that are useful as fuels or fuel additives. The sulfuric acid (10%) pretreatment of wood followed by slow pyrolysis produced maximum yield of charcoal, indicated by the lowest mass % decrease of 58.234. The production of furan derivatives increased by using sulfuric acid pre-treatment, which is a good improvement for the production of Furanics, the furan based biofuels. The furan based biofuels are of increasing research interest because of their significant advantages over the first generation biofuels. The thermogravimetric analysis (TGA) results indicated that the acid pre-treatment altered the decomposition rate of pyrolysis and lowered the onset of temperature for decomposition. The use of thermal degradation of plants for creating chemicals and fuels is seeing renewed interest across the globe as it is considered carbon-neutral and it uses a renewable feedstock. The information obtained from this research work will also be valued by industries, such as charcoal and activated carbon producers, which currently perform biomass pyrolysis, by allowing them to form approaches that optimize their energy use and minimize waste.

The reaction kinetics of Iroko and Mahogany were studied using TGA. The pyrolysis process was achieved using six different heating rates of 2,5,8,12,15 and 20˚C. A 15˚C/min heating rate was used for gasification in steam at different temperatures while varying the concentrations of nitrogen and steam in the process. The kinetic parameters, activation energy and pre exponential factor, were obtained by implementing two chosen kinetic models. These models are: Friedman’s Iso-conversional Method, Flynn-Wall-Ozawa Method (FWO). There were substantial differences in the values of the kinetic triplets found from the experiments. Due to the substantial differences in the values, it was not the best way to perform this kind of analysis (which is the traditional way) but instead to use pure regression analysis; but using it for the whole data set (that means for all heating rates) and minimize the difference with experimental data.

Cette étude porte sur la production des bio-huiles à partir de la pyrolyse de bois de hêtre et celui du pin représentant respectivement les bois durs et les bois tendres. Afin de répondre à la problématique liée à la séparation des composés chimique de valeur ajoutée de la bio-huile,une étude a été effectuée sur la faisabilité d’une pré-séparation des constituants chimiques de la bio-huile à l’aide d’une pyrolyse étagée en température dans un réacteur en lit fixe de sorte à cibler la thermo-décomposition sélective des macro-composants de la biomasse (hémicellulose, cellulose et lignine). L’identification du couple macro-composant – marqueur de la décomposition est réalisée à partir du bilan en macro-composant dans le solide résiduel et l’identification par GC/MS des constituants contenus dans la bio-huile produite. Les résultats de cette partie ont montré la possibilité de la pré-séparation des fractions de dérivés de furane et des produits phénoliques, cependant le gain en sélectivité se fait au détriment du rendement total de la bio-huile. La deuxième partie de ce travail concerne l’étude de la production de la bio-huile dans les conditions de pyrolyse rapide dans un réacteur gaz/solide.Afin d’établir une relation entre les conditions opératoires de pyrolyse et la composition des bio-huiles, un outil permettant la comparaison pertinente des testes expérimentaux a été élaboré. Les expériences ont montré que le rendement de et la composition de l’huile de pyrolyse dépend essentiellement de : la nature du bois, la vitesse de chauffe et le temps de séjours effectif des particules de bois dans le réacteur
This research study is concerned in the production of bio-oils from the pyrolysis of beech and pines wood representing the hard and soft wood, respectively. In order to resolve the problems related to the separation of high added value molecules from the bio-oil, a study was held out on the feasibility of the pre-separation of the chemical components of bio-oil using of a staged pyrolysis temperature in a fixed bed reactor in order to target selective thermal decomposition of macro-components of biomass (hemicellulose, cellulose and lignin). The identification of macro-component couples - marker of decomposition is made from the balance macro-component in the residual solid and identification by GC / MS of the chemical components contained in the produced bio-oil. The results of this part have shown the possibility of the pre-separation of furans and phenolic derivatives, despite of the gain in selectivity at the expense of overall yield of bio-oil. The second part of this work (concerns with the study of the production of bio-oil in fast pyrolysis conditions in a gas / solid reactor. To establish a relationship between the operating conditions and chemical composition of pyrolysis bio-oil, a tool for meaningfull comparison of experiments was developed. Experiments have shown that the yield and composition of pyrolysis oil depends mainly on the composition of wood, the heating rate and the effective residence time of the wood particles into the reactor

Thermomechanical pulping (TMP) is a highly energy intensive process where most of the energy is used in therefining of chips to fibres. Various ways of reducing the energy consumption have earlier been studied, for examplechange of refiner pattern, addition of various chemicals, and also some biochemical implementation in the form of fungus and enzymes. This study includes pre-trials with the enzymes pectin lyase and pectin esterase,multipectinase, xylanase, and mannanase. The results are studied via a reducing sugar assay, an enzymatic assayusing spectrophotometry, and capillary zone electrophoresis. The study also includes results from a pilot scalerefining with multipectinase, xylanase, and mannanase, performed with a wing refiner at Helsinki University.Reductions of energy consumption in TMP by pre-treatment of Norwegian spruce chips are investigated and apotential reduction of energy consumption of 6 % is indicated.

Wood extractives from softwood species include resin acids, fatty acids and triglycerides. Their water repellency, adhesive properties and biological activity make them useful in manufacturing, agriculture and medicine with broader applications expected to be developed in the future with a shift toward renewable resources. These wood extractives can be problematic in paper manufacture as they cause deposits on machinery and in the paper products, which requires higher levels of maintenance, limits water recycling, increases wastewater toxicity and can reduce product quality. Current methods for addressing these problems in thermo-mechanical pulp (TMP) and paper mills include treatment of wood to reduce extractives content prior to pulping, tighter control of processes to prevent formation of deposits, and the use of additives to fix extractives into the paper product. None of these methods allow for recovery of the valuable wood extractives. This thesis presents flotation as a viable method for recovery of wood extractives from TMP process water in pulp and paper mills. While flotation of wood extractives has been studied previously, it is not well understood in terms of the mechanism of flotation or its dependence on different variables. Furthermore, most published research relates to extractives from Norway spruce (Picea abies) which is a common plantation species in the northern hemisphere. By contrast, there are relatively few studies relating to Radiata pine (Pinus radiata) which is common in the southern hemisphere and contains a different composition of extractives. The studies presented here investigate flotation of extractives from Pinus radiata TMP process water. Optimal flotation of wood extractives was achieved using 80 mg/L of added cationic surfactant dodecyltrimethylammonium bromide (DTAB) at pH 5 and 60 °C. This treatment reduced the extractives concentration by 95% and returned 90% of the water volume for recirculation. The effects of different variables on flotation were studied and the results used to identify possible mechanisms of flotation. The most influential variables were the type of surfactant added, pH, and ionic strength. Flotation mechanisms proposed to explain the results included colloidal flotation, flotation of dissolved extractives as either surfactants or as complexes with DTAB, and entrainment of fibres. Colloidal flotation appeared to depend on electrostatic attraction between air bubbles and wood extractive colloids which occurred either at low pH or with addition of a cationic surfactant. The efficiency of colloidal flotation was reduced by increased ionic strength, explained by compression of the electrical double layers around air bubbles and colloids by the electrolyte. Dissolved wood polymers also reduced colloidal flotation efficiency, presumably by inhibition of bubble-colloid attachment by steric hindrance. Flotation of dissolved extractives was proposed to occur at higher pH levels due to adsorption of resin and fatty acid anions on bubble surfaces by either surfactant adsorption or complex formation with DTAB. Fibre-bound extractives could be floated by physical entrainment of fibres in the froth. Methods for recovery of extractives and DTAB from froth generated by the flotation treatment were also investigated. Maximum recovery of extractives was achieved by solvent extraction with a 60:40 mixture of ethyl acetate and heptane at pH 6 which recovered 88% of resin acids, 75% of fatty acids and 10% of triglycerides. Evidence of complex formation between wood extractives and DTAB was found which could explain the limited recovery of both extractives and DTAB from the froth. Flotation is shown to be an effective laboratory method for removal and recovery of wood extractives from TMP process waters, that could be implemented in industry using existing machinery. The most effective surfactant additives have been identified as well as the most important process parameters and conditions that affect flotation efficiency. The influence of these variables on flotation has provided insight into the mechanisms of flotation to enable better control of flotation processes. Implementation of a flotation process for wood extractives recovery would reduce problems related to wood extractives and provide a valuable by-product. These benefits may offset the costs to make implementation feasible.

Formaldehyde-based adhesives have been reported to be detrimental to health. Petrochemical-based adhesives are non-renewable, limited and costly. Therefore, the improvement of environmental-friendly adhesive from natural agricultural products has awakened noteworthy attention. A novel adhesive for wood application was successfully prepared with enhanced shear strength and water resistance. The Fourier transmform infrared spectra showed the surface functionalities of the functionalized carbon nanotubes (FCNTs) and soy protein isolate nanocomposite adhesive. The attachment of carboxylic functional group on the surface of the carbon nanotubes (CNTs) after purification contributed to the effective dispersion of the CNTs in the nanocomposite adhesive. Hence, enhanced properties of FCNTs were successfully transferred into the SPI/CNTs nanocomposite adhesive. These unique functionalities on FCNTs however, improved the mechanical properties of the adhesive. The shear strength and water resistance of SPI/FCNTs was higher than that of the SPI/CNTs. SEM images showed the homogenous dispersion of CNTs in the SPI/CNTs nanocomposite adhesive. The carbon nanotubes were distributed uniformly in the soy protein adhesive with no noticeable clusters at relatively reduced fractions of CNTs as shown in the SEM images, which resulted into better adhesion on wood surface. Mechanical (shear) mixing and ultrasonication with 30 minutes of shear mixing both showed an improved dispersion of CNTs in the soy protein matrix. However, ultrasonication method of dispersion showed higher tensile shear strength and water resistance than in mechanical (shear) mixing method. Thermogravimetric analysis of the samples also showed that the CNTs incorporated increases the thermal stability of the nanocomposite adhesive at higher loading fraction. Incorporation of CNTs into soy protein isolate adhesive improved both the shear strength and water resistance of the adhesive prepared at a relatively reduced concentration of 0.3%.The result showed that tensile shear strength of SPI/FCNTs adhesive was 0.8 MPa and 7.25MPa at dry and wet state respectively, while SPI/CNTs adhesive had 6.91 MPa and 5.48MPa at dry and wet state respectively. There was over 100% increase in shear strength both at dry and wet state compared to the pure SPI adhesive. The 19% decrease in value of the new adhesive developed compared to the minimum value of ≥10MPa of European standard for interior wood application may be attributed to the presence of metallic particles remaining after purification of CNTs. The presence of metallic particles will prevent the proper penetration of the adhesive into the wood substrate. The type of wood used in this study as well as the processing parameters could also result into lower value compared to the value of European standard. Therefore, optimization of the processing parameter as well as the conversion of carboxylic acid group on the surface of the CNTs into acyl chloride group may be employed in future investigation. However, the preparation of new nanocomposite adhesive from soy protein isolate will replace the formaldehyde and petrochemical adhesive in the market and be of useful application in the wood industry.
Civil and Chemical Engineering
M. Tech. (Chemical Engineering)

The present work focuses on the study of biomass gasification process for generating hydrogen rich synthetic gas with oxy-steam as reactants using experiments and modeling studies. Utilization of the syngas as a fuel in general applications like fuel cells, Fischer-Tropsch FT) process and production of various chemicals like DME, etc. are being considered to meet the demand for clean energy. This study comprises of experiments using an open top down draft reactor with oxygen and steam as reactants in the co-current configuration. Apart from the standard gasification performance evaluation; parametric study using equivalence ratio, steam-to-biomass ratio as major variables towards generation of syngas is addressed towards controlling H2/CO ratio. The gasification process is modeled as a packed bed reactor to predict the exit gas composition, propagation rate, bed temperature as a function of input reactants, temperature and mass flux with variation in thermo-physical properties of biomass. These results are compared with the present experiments as well as those in literature. Experiments are conducted using modified open top downdraft configuration reactor with lock hoppers and provision for oxy-steam injection, and the exit gas is connected to the cooling and cleaning system. The fully instrumented system is used to measure bed temperatures, steam and exit gas temperature, pressures at various locations, flow rates of fuel, reactants and product gas along with the gas composition. Preliminary investigations focused on using air as the reactant and towards establishing the packed bed performance by comparing with the experimental results from the literature and extended the study to O2-N2 mixtures. The study focuses on determining the propagation rate of the flame front in the packed bed reactor for various operating conditions. O2 is varied between 20-100% (vol.) in a mixture of O2-N2 to study the effect of O2 fraction on flame propagation rate and biomass conversion. With the increase in O2 fraction, the propagation rates are found to be very high and reaching over 10 mm/s, resulting in incomplete pyrolysis and poor biomass conversion. The flame propagation rate is found to vary with oxygen volume fraction as XO22.5, and stable operation is achieved with O2 fraction below 30%. Towards introducing H2O as a reactant for enhancing the hydrogen content in the syngas and also to reduce the propagation rates at higher ER, wet biomass is used. Stable operating conditions are achieved using wet biomass with moisture-to-biomass (H2O:Biomass) ratio between 0.6 to 1.1 (mass basis) and H2 yield up to 63 g/kg of dry biomass amounting to 33% volume fraction in the syngas. Identifying the limitation on the hydrogen yield and the criticality of achieving high quality gas; oxy-steam mixture is introduced as reactants with dry biomass as fuel. An electric boiler along with a superheater is used to generate superheated steam upto 700 K and pressure in the range of 0.4 MPa. Steam-to-biomass ratio (SBR) and ER is varied with towards generating hydrogen rich syngas with sustained continuous operation of oxy-steam gasification of dry biomass. The results are analysed with the variation of SBR for flame propagation rates, calorific value of product syngas, energy efficiency, H2 yield per kg of biomass and H2/CO ratio. Hydrogen yield of 104 g per kg of dry casuarina wood is achieved amounting to 50.5% volume fraction in dry syngas through oxy-steam gasification process compared to air gasification hydrogen yield of about 40 g per kg of fuel and 20% volume fraction. First and second law analysis for energy and exergy efficiency evaluation has been performed on the experimental results and compared with air gasification. Individual components of the energy input and output are analysed and discussed. H2 yield is found to increase with SBR with the reduction in energy density of syngas and also energy efficiency. Highest energy efficiency of 80.3% has been achieved at SBR of 0.75 (on molar basis) with H2 yield of 66 g/kg of biomass and LHV of 8.9 MJ/Nm3; whereas H2 yield of 104 g/kg of biomass is achieved at SBR of 2.7 with the lower efficiency of 65.6% and LHV of 7.4 MJ/Nm3. The energy density of the syngas achieved in the present study is roughly double compared to the LHV of typical product gas with air gasification. Elemental mass balance technique has been employed to identify carbon boundary at an SBR of 1.5. Controlling parameters for arriving at the desired H2/CO ratio in the product syngas have been identified. Optimum process parameters (ER and SBR) has been identified through experimental studies for sustained continuous oxy-steam gasification process, maximizing H2 yield, controlling the H2/CO ratio, high energy efficiency and high energy density in the product syngas. Increase in ER with SBR is required to compensate the reduction in O2 fraction in oxy-steam mixture and to maintain the desired bed temperature in the combustion zone. In the range of SBR of 0.75 to 2.7, ER requirement increases from 0.18 to 0.3. The sustained continuous operation is possible upto SBR of 1.5, till the carbon boundary is reached. Operating at high SBR is required for high H2 yield but sustained highest H2 yield is obtained as SBR of 1.5. H2/CO ratio in the syngas increases from 1.5 to 4 with the SBR and depending on the requirement of the downstream process (eg., FT synthesis), suitable SBR and ER combination is suggested. To obtain high energy density in syngas and high energy efficiency, operations at lower SBR is recommended. The modeling study is the extension of the work carried by Dasappa (1999) by incorporating wood pyrolysis model into the single particle and volatile combustion for the packed bed of particles. The packed bed reactor model comprises of array of single particles stacked in a vertical bed that deals with the detailed reaction rates along with the porous char spheres and thermo-physical phenomenon governed by the mass, species and energy conservation equations. Towards validating the pyrolysis and single particle conversion process, separate analysis and parametric study addressing the effects of thermo-physical parameters like particle size, density and thermal conductivity under varying conditions have been studied and compared with the available results from literature. It has been found that the devolatilisation time of particle (tc) follows closely the relationship with the particle diameter (d), thermal conductivity (k), density () and temperature (T) as: The complete combustion of a single particle flaming pyrolysis and char combustion has been studied and validated with the experimental results. For the reactor modeling, energy, mass and species conservation equations in the axial flow direction formulate the governing equations coupled to the detailed single particle analysis. Gas phase reactions involving combustion of volatiles and water gas shift reaction are solved in the packed bed. The model results are compared with the experimental results from wood gasification system with respect to the propagation rate, conversion times, exit gas composition and other bed parameters like conversion, peak bed temperatures, etc. The propagation rates compare well with experimental data over a range of oxygen concentration in the O2- N2 mixture, with a peak at 10 mm/s for 100 % O2. In the case of oxy-steam gasification of dry biomass, the results clearly suggest that the char conversion is an important component contributing to the bed movement and hence the overall effective propagation rate is an important parameter for co-current reactors. This is further analyzed using the carbon boundary points based on elemental balance technique. The model predictions for the exit gas composition from the oxy-steam gasification matches well with the experimental results over a wide range of equivalence ratio and steam to biomass ratio. The output gas composition and propagation rates are found to be a direct consequence of input mass flux and O2 fraction in oxy-steam mixture. The present study comprehensively addresses the oxy-steam gasification towards generating hydrogen rich syngas using experimental and model studies. The study also arrives at the parameters for design consideration towards operating an oxy-steam biomass gasification system. The following flow chart provides the overall aspects that are covered in the thesis chapter wise.