Content: Polyacrylate as film-forming materials has been widely used in leather finishing, but its compactness significantly obstructs the hygienic property of upper leather. Therefore, considerable efforts have been made to endow polyacrylate with required properties. In this study, we demonstrated a facile and rapid sonochemical process to synthesis the flower-like ZnO nanostructures. The related morphology and structure of product were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Meanwhile, flower-like ZnO were introduced into the polyacrylate matrix by physical blending method, whose morphology, latex stability, water vapor permeability and water resistance were measured. The results showed that flower-like ZnO assembled by ellipsoid-like nanorods with the length of about 600 nm was successfully fabricated. The sizes of flower-like ZnO were 1.2 μm. According to SEM images, flower-like ZnO evenly dispersed were observed in composite matrix. Compared with pure polyacrylate, polyacrylate/flower-like ZnO composites exhibited the superior stability. Meanwhile, its water vapor permeability and water resistancewere increased by 52.91% and 53.13%, severally. The reason for this is that ZnO with rough structure can increase voids in polyacrylate film and thus improving hygienic property of polyacrylate film. Additionally, the hydrophilic groups on surface of ZnO can product the crosslinking with polyacrylate chains, which contributed to the enhancement of water resistance. Thus, a promising coating with hygienic property and water resistance for leather finishing agent was approved. Take-Away: 1. Polyacrylate/flower-like ZnO composites exhibited excellent hygienic property. 2. This composite coating achieves simultaneous enhancement in water vapor permeability and water resistance. 3. The morphology of ZnO can effect the properties of polyacrylate.

Content: In order to solve the negative impact of coating on water vapor permeability of leather and overcome the poor water resistance of polyacrylate leather finishing agent, it was proposed that the mesoporous SiO2 spheres with hollow structure instead of traditional surfactant were introduced into polyacrylate by Pickering emulsion polymerization. It was expected to increase the water vapor permeability of polyacrylate film by increasing the path and shortening the route of water vapor molecules through the film, and improve the water resistance of film by avoiding the use of surfactant. Hence, stable Pickering emulsion stabilized by mesoporous hollow SiO2 spheres was prepared and its stability was investigated by Turbiscan Lab in this paper. Water vapor permeability, water uptake and mechanical property of polyacrylate film were also studied. Compared with emulsion stabilized by surfactant, Pickering emulsion indicated excellent stability with lower TSI value of 0.5. Contrasted with polyacrylate film with SDS, the introduction of mesoporous hollow SiO2 spheres can improve the water vapor permeability of polyacrylate film. Meanwhile, water absorption measurements showed that the water absorption ratio of the film with mesoporous hollow SiO2 spheres decreased from 112.34 to 40.84%, possessing the ideal ability to water resistance of polyacrylate film. Its film with mesoporous hollow SiO2 spheres also revealed increases of up to 188% in tensile strength and 41.15% in elongation at break. This study can provide a theoretical foundation for designing and synthesizing leather finishing agent with excellent stability, water vapor permeability and water resistance synchronously. Take-Away: 1. Mesoporous hollow SiO2 spheres stabilized Pickering emulsion exhibits outstanding stability. 2. The introduction of mesoporous hollow SiO2 spheres can improve the water vapor permeability of polyacrylate membrane. 3. Polyacrylate membrane shows excellent water resistance.

Thermal insulation materials made from natural fibrous materials, such as cellulose fibers, have advantages over others from a sustainability point of view. However, cellulosic materials are generally prone to mold and absorb moisture, and these have negative effects on the insulation properties, the durability of insulation materials, and interior air quality. In this thesis, cellulose-fiber-based insulation foams were prepared from bleached chemithermomechanical softwood pulp, and these foams showed promising thermal insulation properties and fungal resistance. Hydrophobic extractives were isolated from birch (Betula verrucosa) outer bark and used to improve the water resistance of the foams, which were impregnated in solutions of extractives and then dried. The modified foams showed greater water resistance, and the modification had no negative effects on the thermal insulation, fungal resistance, and compressive strength of the foams. Another potential problem with low density cellulosic thermal insulation materials is their poor reaction-to-fire properties. Cellulose-fiber-based insulation foams were prepared from formulations containing bleached chemithermomechanical softwood pulp and commercial fire retardants to improve the reaction of the foams to fire. Single-flame source test results showed that the foams containing 20% expandable graphite (20% EG) or 25% synergetic (25% SY) fire retardant had significantly improved reaction-to-fire properties and passed class E, which reflected that they can resist a small flame attack without substantial flame spreading for a short period according to EN 13501-1. Compared with the reference without any fire retardant, the peak heat release rate (Peak-HRR) of the 20% EG and 25% SY decreased by 62% and 39% respectively when the samples were subjected to a radiance heat flow of 25 kW m-2 in a Cone Calorimeter. The thesis demonstrates that it is possible to produce cellulose-fiber-based insulation materials with improved properties in terms of fungal, improved water resistance and reaction-to-fire properties. / <p>QC 20170428</p> / Energy-efficient cellulosic insulation products/panels for green building solutions

Les sulfates de calcium sont des matériaux économiques et écologiques. Pourtant leur utilisation dans le domaine de la construction est assez limitée du fait de leur sensibilité à l’eau. La capacité des ciments alumineux (CAC) à diminuer la sensibilité à l’eau des sulfates de calcium ainsi que les mécanismes d’insensibilisation ont été étudiés. L’insensibilisation à l’eau des sulfates de calcium a été réalisée par ajout de faibles quantités de ciment alumineux (≤ 30%). Quatre sulfates de calcium de nature différente : gypse, hémi-hydrate α et β, anhydrite synthétique ont été étudiés. L’étude des mécanismes d’insensibilisation à l’eau des sulfates de calcium par ajout du ciment Fondu, menée à différentes analyses de la microstructure : IR, DRX, ATD-TG, MEB, a mis en évidence deux approches : la formation de l’ettringite insoluble et la formation du gel d’AH3 qui colle les grains de sulfate de calcium soluble. La nature des phases cristallochimiques du ciment alumineux a des influences sur les caractéristiques mécaniques, la sensibilité à l’eau ainsi que la durabilité des mélanges [sulfate de calcium / CAC]. L’étude des mélanges [anhydrite synthétique / laitier / CAC] offrent des perspectives intéressantes notamment concernant le développement des liants à faible empreinte CO2. / Calcium sulphate materials are economical and ecological. But their use in the construction is quite limited because of their sensibility to water. The capacity of aluminate cement (CAC) to decrease the water sensibility of calcium sulphate and the mechanisms of insensibilisation were investigated. Waterproofing of gypsum base materials was carried out by addition of small amounts of aluminate cement (≤ 30%). Different nature of calcium sulphates : gypsum, hemihydrate α and β, synthetic anhydrite was studied. The study of mechanisms of insensibilisation to water of calcium sulphate by adding cement Fondu, with different analysis of microstructure : IR, DRX, ATD-TG, MEB, revealed two approaches : formation of ettringite insoluble and formation of gel AH3 that stick soluble grains of calcium sulphate. The nature of phases of aluminate cement has influences on the mechanical properties, sensibility to water and durability of mixtures [calcium sulphate / CAC]. The studies of mixtures [synthetic anhydrite / slag / CAC] offer interesting perspectives for the development of binders with low imprint CO2.

The diploma thesis deals with technology for the implementation and use of asphalt concrete for very thin layers (BBTM) with use of asphalt binder of high-polymer modification (HiMA). Further, there are described selected and performed functional tests. Thesis also contains design of a mixture for bituminous concrete type targeted for very thin layers with different types of binders. After a suitable design of the mixture, laboratory tests were carried out (stiffness modulus, resistance to permanent deformation, low temperature characteristics, water resistance and particle loss). The output of this work is a set of measured values and processed results with their interpretation.

Ce travail de thèse a été conduit dans le but d’élaborer des papiers résistants à l’eau liquide et ayant des propriétés antifongiques, ce par utilisation de composés biosourcés. Deux approches ont été proposées : soit une modification en surface par enduction, soit une modification des fibres de cellulose. Dans le cas de la modification en surface, deux formulations d’enductions ont été étudiées. La première, composée de chitosane et de carbonate de calcium précipité (PCC) modifié, a été utilisée pour limiter le développement de moisissures et améliorer la résistance des papiers à l’eau. La formulation incorporant 20 % de PCC modifié a montré un retard de croissance significatif de la souche fongique sélectionnée en tant que souche cible. La seconde formulation, destinée à améliorer la résistance à l’eau des papiers, par enduction d'un latex prévulcanisé d’hévéa, a montré de très bons résultats, conduisant à une réduction de près de 95 % de l’absorption d’eau liquide. Toutefois, une perte d’opacité des papiers a été observée après pénétration de l’eau dans le matériau. Par conséquent, une seconde approche a été proposée, basée sur la modification physico-chimique des fibres de cellulose. Un procédé d’hybridation a été utilisé, permettant l’adsorption d’acide stéarique sur le PCC synthétisé in situ à la surface des fibres de cellulose. Un compromis entre la rétention des charges, la résistance à l’eau et les propriétés mécaniques a pu être proposé. Après détermination des conditions optimales de mise à l’échelle industrielle du procédé d’hybridation, un essai industriel a pu être réalisé et a conduit à des résultats prometteurs. / The present work investigates the creation of water-resistant and antifungal papers by using biobased compounds. Two approaches were developed: A surface modification by coating or a cellulose fibre modification. For the coating approach, two formulations were studied. The first one, consisting in chitosan and modified precipitated calcium carbonate (PCC) was mainly used to limit the development of molds while improving paper water resistance. The formulation incorporating 20 % of modified PCC showed a significant increase of the lag phase of the target fungal strain. The second coating formulation, especially designed to improve papers water resistance by a coating layer of prevulcanized natural rubber latex, showed very positive results, leading to 95 % reduction of liquid water absorption but with a negative impact on the material opacity after water penetration. As a consequence, physico-chemical modification of cellulose fibre was investigated in a second approach. An hybridization process was used, leading to stearic acid adsorption on in situ PCC synthesized at the surface of cellulosic fibres. A compromise between fillers retention, water resistance and mechanical properties was found. After determination of optimal conditions carried out to an industrial scale up, an industrial pilot was performed and gave promising results.

Literature shows that production of cottonseed adhesives is feasible to develop an environmentally friendly and competitive bio-based wood adhesive. Defatted cottonseed and water-washed cottonseed meals were prepared from glandless cottonseed and were used in adhesive formulations to produce three-ply yellow poplar (Liriodendron tulipifera) plywood panels as the first objective. These two cottonseed meals were compared with the properties of plywood panels made with an adhesive formulated from a commercial soybean meal, as a control. Adhesive resins were prepared from each protein meal with sodium metabisulfite (Na2S2O5) and one of two polyamido-amine-epichlorohydrin (PAE) wet strength agents, and the plywood panels were produced by hot pressing for 7, 8.5 and 10 minutes at 135°C with a constant pressure of 1.241 MPa. Panels prepared from three protein meals had comparable shear strengths. The combinations of the two cottonseed preparations and the two wet strength agents produced panels with acceptable wet resistant properties, whereas the soybean meal only produced acceptable panels with one of the wet strength agents. Because the panels prepared from the two cottonseed meals had comparable properties, there appears to be no benefit to including a water-washing step to increase the meal’s protein level. The second objective of this research was to reduce the hot press time and develop cottonseed meals into adhesives to become comparable to commercial soybean-based adhesives. New cottonseed, water-washed cottonseed, and commercial in-house soybean meals were separately prepared with deionized water, sodium metabisulfite, and PAE to produce three-ply yellow poplar plywood panels. The panels were hot pressed for 4, 5, and 6 minutes at 135°C with a constant pressure of 1.241 MPa. Panels prepared from the three meals and commercial soybean plywood panels had comparable mechanical shear strengths and water resistance properties. Results indicated that press time, meal types, and interactions were statistically significant. Shear strength results indicate that cottonseed could be used alternatively to soybean. The new cottonseed panels were more resistant to delamination than soybean. The cottonseed meals showed great promise for applicability as a formaldehyde-free, bio-based, and environmentally friendly hardwood plywood wood-based adhesives product for use in interior type applications.

Cette étude présente une dimension économique, sociale et environnementale très importante. Elle rentre dans le cadre du projet Franco-Marocain PHC Toubkal (Ecopama, Volubilis 2012). Son objectif majeur est de valoriser les écorces Marocaine d’Acacia mollissima par une extraction verte permettant l’obtention des produits réactifs, des tanins condensés, qui seront utilisés dans le collage des panneaux de contreplaqués. Trois méthodes d’extraction ont été étudiées. Deux sont conventionnelles, une macération et une infusion ; ces deux techniques d’extraction sont simples, peu coûteuses. La troisième est une extraction assistée par micro-ondes ; c’est une technique innovante, rapide et peu consommatrice en solvant. La méthodologie des plans d’expériences est utilisée dans cette étude pour déterminer les facteurs les plus significatifs pour l’amélioration du rendement d’extraction des tanins condensés, optimiser les conditions d’extractions, réduire la proportion de solvant utilisé ainsi que le temps d’extraction. L’impact des conditions d’extraction et des méthodes d’extraction sur la teneur des tanins condensés sont étudiés pour la première fois pour les écorces d’Acacia mollissima du Maroc. Les extraits ont été caractérisés par des dosages colorimétriques, par des analyses structurales et thermiques. Les trois méthodes d’extraction ont été comparées. La teneur des extractibles est affectée par la proportion de solvant utilisé et le temps d’extraction. L’extraction assistée par micro-onde présente des teneurs en tanins condensés supérieure à l’extraction par des méthodes conventionnelles mais la teneur en sucre extraits est aussi élevée. Des formulations de colles à base de tanin et de lignosulfonate ont été élaborées en utilisant l’hexamine comme durcisseur. La colle biosourcée et ses constituants ont été caractérisés par analyse thermogravimétrique (ATG), et par calorimétrie différentielle à balayage (DSC). Les propriétés thermomécaniques et mécaniques des colles élaborées sont évaluées. L’optimisation des conditions de pressage des panneaux de contreplaqués, ainsi que le ratio tanin-lignosulfonate glyoxalé, ont été réalisées. La résistance des panneaux à l’eau froide et chaude est améliorée par l’addition de la résine époxy aux formulations de colle. Les propriétés mécaniques des panneaux de contreplaqués encollés ont été évalués par des tests normatifs et ont été comparés à celle des résines synthétiques commerciales (urée formaldéhyde et phénol formaldéhyde). La qualité de collage des panneaux élaborés a été évaluée. Les différentes colles présentent des caractéristiques physiques et thermiques satisfaisantes et acceptables pour les industries de collage des panneaux de bois. Des panneaux de contreplaqués avec de bonnes performances mécaniques et une excellente résistance à l’eau froide et bouillante ont été fabriqués. Ces colles présentent une qualité de collage qui se rapproche de celle des résines phénol-formaldéhyde, et peuvent être utilisées avec succès, pour une application industrielle des panneaux de contreplaqués, en milieu sec, humide et extérieur. / This study has an important economical, social and environmental dimension. It was conducted within the framework Franco-Moroccan PHC Toubkal "Ecopama, Volubilis 2012". The desire to enhance Moroccan bark of Acacia mollissima by the use of green extraction and also to obtain reagent products, condensed tannins, was the main objective of this study. These tannins will be used in the bonding of plywood panels. Three extraction methods were studied. Two are conventional, maceration and infusion; witch is simple and cheap extraction method. The third is microwave assisted extraction which is a fast, innovative method using a small amount of solvent. The experimental design methodology was used to identify the significant factors to improve yield extraction of condensed tannins, to optimize extraction process, to reduce solvent proportion and time extraction. The impact of extraction conditions and extraction process were studied for the first time on condensed tannins contents extracted from Moroccan bark of Acacia mollissima. The extracts were characterized using colorimetric assays, structural and thermal analysis.The three types of extraction were compared. The extractibles contents were affected by solvent proportion and also time extraction. Microwave assisted extraction produced a higher condensed tannins than the conventional method but in the other hand the sugars extracted is more important. Tannin-lignosulfonate adhesives were produced using hexamine as a hardener. The biobased adhesive formulations and their compounds were compared using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and by determining the thermal and mechanical proprieties of the adhesives. Optimal tannin-glyoxalated lignosulfonates ratio and pressing conditions of plywood panels were measured. The resistance of plywood panels to the cold and hot water was improved by the addition of epoxy resin in adhesive formulations. Mechanical properties of plywood panels made with tannin-lignosulfonates-epoxy adhesives were evaluated using normative standard and compared to those of panels made with a commercial resins (urea formaldehyde and phenol formaldehyde). The bonding quality of plywood panels elaborated was evaluated. The various adhesives elaborated have satisfactory and acceptable physical and thermal characteristics for bonding panels used in wood industries. Plywood panels with good mechanical performance, good resistance to cold water and to boiling water, were produced. The bonding quality of the adhesives elaborated in laboratory scale presented approximate proprieties than the phenol-formaldehyde resins which can use with successfully in dry, wet and exterior industrial application of plywood panels.

The works deals with the possibilities of using non-standard fraction of fine crushed aggregate in route base layers. Goal of my thesis is research of using material from specific location. Theoretical part summarizes basic knowledge regarding bound mixtures and their normative requirements. Practical part of my thesis describes my various mixture design and following testing and determination of design properties by official and experimental tests. The conclusion summarizes the researched outputs and findings, which confirm the future possibilities of using this material in base layers.

The aim of bachelor thesis is to gain experience with the design mixtures of asphalt concrete for very thin layers. Familiarizing with the properties of these mixtures, as porosity, water resistance and resistance to permanent deformation. Comparing detected parameters with the requirements of standard EN 13108-2 and its National Annex.