Caractérisation et modification des lignines industrielles

Les lignines sont des polymères naturels et renouvelables. C’est le polymère le plus abondant sur la terre après la cellulose. De nos jours, les lignines sont sous-exploitées et seulement 2 % de la lignine est valorisée par an, leur application capital restant comme combustible dans les industries papetières pour la production d'énergie. Au Québec, 130 000 tonnes de liqueur noire contenant de la lignine pourraient être extraites par an afin de les valoriser, sans perturber la production dans ces industries papetières. Sa valorisation pourrait contribuer à créer de nouveaux produits à valeur ajoutée tels que les biocomposites avec une matrice de polyéthylène, polystyrène recyclé ou encore le bois. Ces nouveaux produits de ces industries pourraient améliorer la situation économique dans ce domaine, mais aussi pourraient apporter de nouvelles connaissances dans le domaine des écomatériaux tout en contribuant à la diminution des gaz à effet de serre en favorisant le produit naturel contre le produit de synthèse. Les structures des lignines diffèrent selon certains paramètres (origine, le processus d'isolation ...). Dans ce projet, deux lignines Kraft seront précipitées à partir de liqueur noire de deux industries papetières québécoises en utilisant du dioxyde de carbone comme réactif. Ces lignines seront purifiées et comparées analytiquement à d’autres lignines; une lignine Kraft commerciale, une lignine pyrolytique et une lignine Protobind Soda 2400. Connaissant la structure des lignines, il sera plus facile de les modifier. Les lignines Kraft ont été estérifiées avec l'anhydride maléique et l'anhydride succinique et comparée aux lignines non modifiées par plusieurs techniques d'analyse telles que FT-IR, TGA, DSC, RMN. Les lignines Wayagamack maléatées et non maléatées ont été incorporées dans un biocomposite de polystyrène recyclé et les propriétés mécaniques et thermiques ainsi que la morphologie ont été étudiées. Les composites avec la lignine non modifié ont montré de bonnes propriétés mécaniques et thermiques par rapport au composite avec la lignine maléate où la lignine maléatée était pourtant compatible avec le polystyrène recyclé. Les lignines Windsor non estérifiée et succinate ont été utilisées en tant que liant dans un panneau de bois et leurs propriétés mécaniques ont également été étudiées. Les résultats ont montré les meilleures propriétés mécaniques pour le panneau de bois contenant de la lignine Kraft non modifié. Les réactions de condensation de la lignine Kraft au cours de la compression à chaud du panneau améliorerait la solidité du panneau contrairement à des réactions d'estérification qui pourraient avoir lieu entre la lignine estérifié et les hydroxyles de bois. Mots clés : Liqueur noire, Lignine, Procédé Kraft, Estérification, Caractérisation, Composite, Valorisation, polystyrène, bois.Lignins are renewable and natural polymers. It is the most abundant polymer on the earth after cellulose. Nowadays, lignins are not fully exploited and only 2% of lignin is valorised per year, their principal application remaining as a combustible in pulp industries for energy production. In Quebec, 130000 tons of black liquor containing lignin could be available from Kraft industry, per year, in order to valorise them, without disturbing the mill production. Its valorisation could contribute to create new value added products like bio composites with a matrix of polyethylene, recycled polystyrene or even wood. These new products of these industries could improve the economic situation in this field, but also could bring new knowledge in the eco materials field, in contributing of the decrease of greenhouse gases in favoring the natural product against the synthetic product. Lignin structure is different depending on several parameters (origin, isolation process…). In this project, two Kraft lignins will be precipitated from black liquor of two Quebecoise paper industries using carbon dioxide as the reagent. These lignins will be purified and compared analytically to others lignins; one Kraft softwood commercial lignin, one pyrolytic lignin and one Soda lignin Protobind 2400. With the knowledge of the Kraft lignin structure, it will be easier to modify these lignins. The esterified Kraft lignins with maleic anhydride and succinic anhydride will be compared to the unmodified lignin according to several analytical technical as FT-IR, TGA, DSC, NMR. Maleated and non modified Wayagamack lignins were incorporated in biocomposite of recycled polystyrene and the mechanical and thermal properties and the morphology were studied. The composite with non modified lignin showed good mechanical and thermal properties compared to the composite with maleated lignin where the maleated lignin was still compatible with the recycled polystyrene The Windsor succinated and non modified lignin were used as a binder in a wood panel and their properties were also studied. The results showed the best mechanical properties for the wood panel containing non modified Kraft lignin. Condensation reactions of Kraft lignin during the hot-pressing of the panel improve the solidity of the panel unlike esterification reactions that could take place between esterified lignin and the wood hydroxyls. Key words: Black liquor, Lignin, Kraft process, Characterisation, Esterification, Composite, Valorization, Polystyrene, Wood

Hydrophobicity of hemp shiv treated with sol-gel coatings

This is the first time sol-gel technology is used in the treatment of hemp shiv to develop sustainable thermal insulation building materials. The impact on the hydrophobicity of hemp shiv by depositing functionalised sol-gel coatings using hexadecyltrimethoxysilane (HDTMS) has been investigated. Bio-based materials have tendency to absorb large amounts of water due to their hydrophilic nature and highly porous structure. In this work, the influence of catalysts, solvent dilution and HDTMS loading in the silica sols on the hydrophobicity of hemp shiv surface has been reported. The hydrophobicity of sol-gel coated hemp shiv increased significantly when using acid catalysed sols which provided water contact angles of up to 118° at 1% HDTMS loading. Ethanol diluted sol-gel coatings enhanced the surface roughness of the hemp shiv by 36% as observed under 3D optical profilometer. The XPS results revealed that the surface chemical composition of the hemp shiv was altered by the sol-gel coating, blocking the hydroxyl sites responsible for hydrophilicity

Hydrophobic Sol-Gel Coatings on Bio-Based Materials - Influence of Catalyst and Solvent Concentration

The impact of depositing sol-gel coatings on the hydrophobicity of a bio-based material was investigated in this study. Bio-based materials have tendency to absorb large amounts of water due to their highly porous structure and presence of hydrophilic hydroxyl groups in their structure. For this purpose, two sets of silica sols were prepared to study the influence of catalysts and solvent concentration on the hydrophobicity of hemp shiv. The first set of silica sols were prepared using different acidic (hydrochloric acid and nitric acid) and basic (sodium hydroxide and ammonium hydroxide) catalysts while keeping the concentration of precursors and solvents constant. The hydrophobicity of sol-gel coated hemp shiv increased significantly when using acid catalysed sols resulting in water contact angles of up to 100° using sessile drop method.Therefore, the next set of silica sols were prepared with acidic catalysts using higher concentration of solvent. Hemp shiv coated with ethanol diluted sols showed better hydrophobicity when compared to undiluted sols. This difference in hydrophobicity can be attributed to the change in surface roughness. It was found that silica sols containing higher concentration of solvent provide a uniform coating layer covering the hemp shiv entirely. In contrast, undiluted sol coatings developed minor cracks on the hemp shiv surface as observed under 3D optical profilometer. Therefore, the use of diluted hydrophobic silica sols offers potential for treatment of extremely hydrophilic bio-based materials by sol-gel technology. For practical application of coatings on bio-based materials, diluted silica sols are of interest due to longer shelf life, reduced cost and lower environmental impact of precursors.<br/

Hydrophobicity of Hemp Shiv treated with Sol-gel Coatings

This is the first time sol-gel technology is used in the treatment of hemp shiv to develop sustainable thermal insulation building materials. The impact on the hydrophobicity of hemp shiv by depositing functionalised sol-gel coatings using hexadecyltrimethoxysilane (HDTMS) has been investigated. Bio-based materials have tendency to absorb large amounts of water due to their hydrophilic nature and highly porous structure. In this work, the influence of catalysts, solvent dilution and HDTMS loading in the silica sols on the hydrophobicity of hemp shiv surface has been reported. The hydrophobicity of sol-gel coated hemp shiv increased significantly when using acid catalysed sols which provided water contact angles of up to 118° at 1% HDTMS loading. Ethanol diluted sol-gel coatings enhanced the surface roughness of the hemp shiv by 36% as observed under 3D optical profilometer. The XPS results revealed that the surface chemical composition of the hemp shiv was altered by the sol-gel coating, blocking the hydroxyl sites responsible for hydrophilicity

Development of novel building composites based on hemp and multi-functional silica matrix

This study focuses on the development of novel bio-composites using a silica matrix that provides dual functionality: as a hydrophobic surface treatment and as a binder for hemp-shiv. The hydrophilic nature of hemp shiv, a plant based aggregate, results in composites having poor interfacial adhesion, weak mechanical properties and long drying times. In this work, sol-gel process has been utilised to manufacture durable low density hemp based composites. Morphological characterisation by scanning electron microscopy (SEM) showed that hemp shiv was embedded well in the matrix. Detailed chemical analysis using x-ray photoelectron spectroscopy (XPS) and gas chromatography-mass spectrometry (GC-MS) indicate the presence of water soluble and ethanol soluble extractives leached from the hemp shiv which are incorporated into the silica matrix inducing the binding effect. The composites were water resistant and showed good mechanical performance having the potential to develop novel thermal insulation building materials

Using individual-based bioenergetic models to predict the aggregate effects of disturbance on populations : a case study with beaked whales and Navy sonar

Funding: This research was supported by the Office of Naval Research (https://www.onr.navy.mil/) grant N0001419WX00431 and N000142012045: “Integrating information on displacement caused by mid-frequency active sonar and measurements of prey field into a population consequences of disturbance model for beaked whales” awarded to Dave Moretti, ND, SW, JH, LT, KB-B, AdR & VH. Funding support for tagging was provided by the US Navy's Office of Naval Research and Living Marine Resources program, the Chief of Naval Operations' Energy and Environmental Readiness Division and the NOAA Fisheries Ocean Acoustics Program.Anthropogenic activities can lead to changes in animal behavior. Predicting population consequences of these behavioral changes requires integrating short-term individual responses into models that forecast population dynamics across multiple generations. This is especially challenging for long-lived animals, because of the different time scales involved. Beaked whales are a group of deep-diving odontocete whales that respond behaviorally when exposed to military mid-frequency active sonar (MFAS), but the effect of these nonlethal responses on beaked whale populations is unknown. Population consequences of aggregate exposure to MFAS was assessed for two beaked whale populations that are regularly present on U.S. Navy training ranges where MFAS is frequently used. Our approach integrates a wide range of data sources, including telemetry data, information on spatial variation in habitat quality, passive acoustic data on the temporal pattern of sonar use and its relationship to beaked whale foraging activity, into an individual-based model with a dynamic bioenergetic module that governs individual life history. The predicted effect of disturbance from MFAS on population abundance ranged between population extinction to a slight increase in population abundance. These effects were driven by the interaction between the temporal pattern of MFAS use, baseline movement patterns, the spatial distribution of prey, the nature of beaked whale behavioral response to MFAS and the top-down impact of whale foraging on prey abundance. Based on these findings, we provide recommendations for monitoring of marine mammal populations and highlight key uncertainties to help guide future directions for assessing population impacts of nonlethal disturbance for these and other long-lived animals.Publisher PDFPeer reviewe

Future directions in research on beaked whales

Until the 1990s, beaked whales were one of the least understood groups of large mammals. Information on northern bottlenose whales (Hyperoodon ampullatus) and Baird’s beaked whales (Berardius bairdii) was available from data collected during whaling, however, little information existed on the smaller species other than occasional data gleaned from beach-cast animals. Recent research advances have been plentiful. Increasing global survey effort, together with morphometric and genetic analyses have shown at least 22 species in this group. Longitudinal field studies of at least four species (H. ampullatus, B. bairdii, Ziphius cavirostris, Mesoplodon densirostris) have become established over the last three decades. Several long-term studies support photo-identification catalogs providing insights into life history, social structure and population size. Tag-based efforts looking at diving, movements and acoustics have provided detail on individual behavior as well as population structure and ranges. Passive acoustic monitoring has allowed long-term and seasonal monitoring of populations. Genetic studies have uncovered cryptic species and revealed contrasting patterns of genetic diversity and connectivity amongst the few species examined. Conservation concern for these species was sparked by mass strandings coincident with military mid-frequency sonar use. Fat and gas emboli have been symptomatic indicators of mortalities related to sonar exposure, suggesting that their vulnerability stems from the physiological exertion of extreme diving for medium-sized whales. Behavioral response experiments have now shown that beaked whales appear to cease foraging and delay their return to foraging and/or leave the area in association with exposure to mid-frequency signals at low acoustic levels. Future priorities for these species will be to (1) continue field-studies to better understand smaller-scale habitat use, vital rates and social structure; (2) develop better detection methods for larger-scale survey work; (3) improve methodology for monitoring energetics, individual body condition and health; (4) develop tools to better understand physiology; (5) use recent genetic advances with improved sample databanks to re-examine global and local beaked whale relationships; (6) further quantify anthropogenic impacts (both sonar and other noise) and their population consequences (7) apply acquired data for realistic mitigation of sonar and other anthropogenic impacts for beaked whale conservation.Publisher PDFPeer reviewe

Improvement of white spruce wood dimensional stability by organosilanes sol‐gel impregnation and heat treatment

Wood is a living material with a dimensional stability problem. White spruce wood is a Canadian non‐permeable wood that is used for siding applications. To improve this property, white spruce wood was treated with organosilanes sol‐gel treatment with different moisture content (oven dried, air dried, and green wood). No major morphological changes were observed after treatment. However, organosilanes were impregnated into the cell wall without densifying the wood and without modifying the wood structure. Si‐O‐C chemical bonds between organosilanes and wood and Si‐O‐Si bonds were confirmed by FTIR and NMR, showing the condensation of organosilanes. The green wood (41% moisture content) showed only 26% dimensional stability due to the presence of too much water for organosilanes treatment. With a moisture content of 14%–18% (oven dried or air dried wood), the treatment was adapted to obtain the best improvement in dimensional stability of 35% and a 25% reduction of water vapor sorption. Finally, impregnation with organosilanes combined with the appropriate heat treatment improved the dimensional stability of white spruce wood by up to 35%. This treated Canadian wood could be an interesting option to validate for siding application in Canada

Effect of a Thermal Catalyst on Organosilanes Treatment to Improve Durability and Stability of Canadian Wood

The demand for exterior wood siding is stagnating in North America due in part to perceptions of low durability and the need for frequent maintenance. One way to address these concerns is to modify the wood to improve its physical properties, while maintaining its appearance. In this study, white spruce was treated with organosilanes and a combination of aluminum treatments followed by a thermal treatment to improve the dimensional stability and the wood durability. Anti-swelling efficiency (ASE), leaching and decay tests were performed on the treated Canadian wood species. The quantity of hydroxyls available after treatment was evaluated by water vapor sorption. The results showed that the treatment improved the dimensional stability up to 50%. Available hydroxyls decreased by as much as 37%. The organosilanes treatment was resistant to leaching, while the aluminum was observed to leach. Organosilanes in combination with aluminum showed brown rot resistance. The addition of aluminum to the organosilanes treatment did not have effect on dimensional stability but it had a great impact on the brown rot resistance