No description available.

No description available.

This work addresses biogenic formaldehyde (CH₂O) generated by wood during the manufacture of non-structural wood-based composites, from which CH₂O emissions are regulated. The target for regulation has been anthropogenic CH₂O released from hydrolytically unstable amino resins like urea-formaldehyde. However, current regulations (the Formaldehyde Standards for Composite Wood Products Act, signed into law in 2010 and implemented in 2016) restrict allowable emissions to such low levels that biogenic CH₂O may affect regulation compliance. The industry has met the latest regulations with new amino resin technologies. Nevertheless persistent anecdotal reports suggest that biogenic CH₂O complicates regulation compliance. This work represents an industry/university cooperation to seek a more thorough understanding of biogenic CH₂O, to begin documentation of biogenic CH₂O levels in wood, and to study the conditions and chemical mechanisms of its formation. Efforts began by establishing CH₂O analysis using the fluorimetric acetylacetone determination. A custom 12-liter chamber with controlled temperature and relative humidity, and "ultrapure" nitrogen (N₂) ventilation was created to measure CH₂O emissions from flakes sampled from four Virginia pine (Pinus virginiana) trees. Emissions from never-heated specimens varied significantly among the four trees, ranging from 0.02 – 0.19 µg CH₂O/m³g dry wood. Heating (200°C, 1 hour), followed by chamber equilibration, resulted in significantly increased emissions on the order of 50%. Sequential heating, followed by chamber equilibration (in other words, heat/equilibrate/measure emission/repeat), resulted in declining emissions suggesting that a finite chemical source of CH₂O was being depleted by the sequential heat treatment. Flake specimens were stored in the open laboratory, and over 2-3 months laboratory storage, initially high emitting specimens gradually emitted less CH₂O, and initially low emitters gradually emitted more CH₂O. Concerns over laboratory contamination were perhaps allayed when background levels of laboratory CH₂O were determined to be similar to the background levels in the ultrapure N₂ used to ventilate the chamber. Measurement of emissions was abandoned, and thereafter a simple water extraction technique (~ 94% CH₂O recovery) was used to measure the CH₂O content of never-heated and heated wood specimens, where the difference was identified as CH₂O generated due to heating. Increment cores from living Virginia pine (Pinus virginiana), yellow-poplar (Liriodendron tulipifera), and radiata pine (Pinus radiata) trees were used to measure CH₂O content and CH₂O generation due to heating (200°C, 10 min). Significant variations within and between trees of the same species were observed. Tissue types (juvenile/mature, heartwood/sapwood) sometimes correlated to higher CH₂O contents and greater heat-generation potential; but sometimes not depending upon species. Heating increased CH₂O levels 3-60 fold. Heating with high moisture levels caused greater CH₂O generation than for dry specimens. This moisture effect and a separate serendipitous observation suggested that CH₂O generation is acid catalyzed. Radiata pine generated extraordinarily high CH₂O levels when heated, far exceeding the other two species. It was suggested that pine extractives might catalyze CH₂O generation, perhaps in lignin. Pinus virginiana wood was heated (200°C, 10 or 60 min) while dry or after aqueous/acid or base pretreatment in order to reveal mechanisms of formaldehyde (CH₂O) generation. Among wood structural polymers, lignin was the overwhelming source of biogenic CH₂O, consistent with prior reports. The effects of wood extractives are mentioned below. The selection of acid catalyst strongly affected CH₂O generation as predicted in the acidolysis literature of lignin model compounds and isolated lignins. Lignin methoxyl cleavage was also observed, but was considered an unlikely source of thermochemical CH₂O. Alkaline pretreatments suppressed CH₂O generation. Regarding wood-based composite manufacture, the implications are that lignin reactions can be manipulated during hot-pressing. Potential benefits include reduced product emissions, and/or novel crosslinking strategies using biogenic CH₂O. Heat generation of CH₂O in Virginia pine and radiata pine was substantially reduced by extractives removal, but there was no such effect in yellow-poplar wood. Results suggested that pine extractives promote CH₂O generation by catalyzing or otherwise promoting C2 cleavage (acidolysis) in lignin. Thioacidolysis demonstrated that pine lignin reactions were strongly dependent upon the presence or absence of the extractives. When present, pine extractives seemed to promote C2 cleavage (CH₂O generation), but otherwise reduced the overall extent of lignin degradation. When pine extractives were removed, lignin suffered substantial degradation, but apparently less C2 cleavage since CH₂O generation was reduced. In contrast, thioacidolysis showed that yellow-poplar extractives appeared to promote lignin degradation, but extractives removal had no detectable impact on CH₂O generation. Implications exist for biorefinery research because it was shown that lignin reactions can be strongly affected by wood extractives. Two dimensional, proton-carbon, correlation NMR spectroscopy (2D NMR), and solvent submersion dynamic mechanical analysis (DMA) was used to investigate wood changes caused by heating in the presence or absence of external acid catalysis. 2D NMR was relatively insensitive to fine lignin changes that were detected using thioacidolysis. 2D NMR was effective for observing lignin changes under more extreme heating conditions, and evidence was found for lignin crosslinking reactions that probably occurred through substitution into lignin aromatic rings. DMA showed that most heating conditions caused an increase in the lignin glass transition temperature (Tg), consistent with heat-induced lignin crosslinking. Under one experimental condition of wood heating, DMA showed a reduction in the lignin glass transition temperature (Tg). This suggested that lignin cleavage without subsequent repolymerization might be promoted by carefully controlled conditions, and this has implications for biorefinery research where lignin repolymerization can be problematic. Finally, this work strongly supported the hypothesis that lignin generates CH₂O through well-known acidolysis pathways where CH₂O is borne from the lignin gamma-methylol group. Therefore, it was predicted that upon heating corn (Zea mays L.) stalk should generate less CH₂O than wood because corn stalk lignins exhibit a high degree of coumaric acid esterfication at the gamma-methylol group. This hypothesis was perhaps verified- it was found that in 4 out of 6 experimental heating conditions that corn stalk generated significantly less CH₂O than Virginia pine. / Ph. D.

This study investigated the natural durability of 8 and 60 year old Eucalyptus bosistoana (coast grey box). The sample’s heartwood compounds were extracted with an optimised extraction process and then incorporated into agar. Trametes versicolor (white rot) and Gloeophyllum trabeum (brown rot) fungi were grown upon these agars and their growth rate was used to assess the fungicidal abilities of the extracts. The extraction method of cell wall compounds was optimised. An Accelerated Solvent Extraction system (ASE) was used with the following settings: • 2 cycles per sample • 70°C extraction temperature • 50% rinse • 5 minute static time Ethanol was found to extract the compounds of the highest fungicidal activity. Ethanol was found to extract similar amounts to water (~13% of dry weight for a 60 year old sample), however analysis of both water and ethanol extracts with a FTIR spectrometer, found that they were of different chemical composition. A difference in fungicidal activity of extracts was found between the 8 year old and 60 year old samples. There was a large difference in the percentage of extracts present between the samples as well as the type of compounds present, shown by FTIR.

No description available.

Ph.D. / The main objective of this study was to investigate the presence, variations and the fate of lipophilic extractives during all the stages in the dissolving pulp production process. Lipophilic wood extractives which include fatty acids, sterols, hydrocarbons, steroid hydrocarbons and ketones are organic compounds present in the wood and dissolving pulp which are soluble in organic solvents. Their presence in wood and pulp has negative effects on both the pulping process and the quality of the produced dissolving pulp. Comparison of two Eucalyptus species (E. grandis and E. dunnii) at three different sites (Richmond, Umvoti and Ixopo in KwaZulu-Natal Province, South Africa) revealed that lipophilic extractives were higher in E. dunnii than in E. grandis in all the sampled sites and that the woods at the Ixopo site were found to have the highest amount of lipophilic extractives. The quantitative variation of lipophilic extractives in wood was found to be significantly affected by respective sites and tree species. The principal component analysis (PCA) model, which was used to correlate soil parameters and amount of lipophilic extractives in woods per each site, revealed that high amounts of lipophilic extractives were found in trees grown at sites with a high composition of clay soil and organic matter. Thus if the industry is to avoid the high levels of lipophilic extractives in wood, sandy sites should be the choice to grow the trees. Partial least squares (PLS) modelling revealed that sterols and saturated fatty acids significantly influence the quality parameters (Kappa number, viscosity, copper number, cellulose yield and retained carbohydrates) of dissolving pulp, whereas unsaturated fatty acids and unsaturated sterols in particular were found to positively correlate with the Kappa number, thus affecting its measurement.The main objective of this study was to investigate the presence, variations and the fate of lipophilic extractives during all the stages in the dissolving pulp production process. Lipophilic wood extractives which include fatty acids, sterols, hydrocarbons, steroid hydrocarbons and ketones are organic compounds present in the wood and dissolving pulp which are soluble in organic solvents. Their presence in wood and pulp has negative effects on both the pulping process and the quality of the produced dissolving pulp. Comparison of two Eucalyptus species (E. grandis and E. dunnii) at three different sites (Richmond, Umvoti and Ixopo in KwaZulu-Natal Province, South Africa) revealed that lipophilic extractives were higher in E. dunnii than in E. grandis in all the sampled sites and that the woods at the Ixopo site were found to have the highest amount of lipophilic extractives. The quantitative variation of lipophilic extractives in wood was found to be significantly affected by respective sites and tree species. The principal component analysis (PCA) model, which was used to correlate soil parameters and amount of lipophilic extractives in woods per each site, revealed that high amounts of lipophilic extractives were found in trees grown at sites with a high composition of clay soil and organic matter. Thus if the industry is to avoid the high levels of lipophilic extractives in wood, sandy sites should be the choice to grow the trees. Partial least squares (PLS) modelling revealed that sterols and saturated fatty acids significantly influence the quality parameters (Kappa number, viscosity, copper number, cellulose yield and retained carbohydrates) of dissolving pulp, whereas unsaturated fatty acids and unsaturated sterols in particular were found to positively correlate with the Kappa number, thus affecting its measurement. Viscosity of pulp which is an important quality parameter was also found to be positively influenced by sterol residues, whereas the reducing properties of pulp were found to be affected by sterols and saturated fatty acids with a carbon chain length of less than C20.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23525号 / 農博第2472号 / 新制||農||1087(附属図書館) / 学位論文||R3||N5356(農学部図書室) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 梅村 研二, 教授 矢野 浩之, 教授 仲村 匡司 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

The sulfite pulping process is today practised in only a small number of pulp mills around the globe and the number of sulfite mills that use sodium as the base (cation) is less than five. However, due to the increasing interest in the wood based biorefinery concept, the benefits of sulfite pulping and especially the sodium based variety, has recently gained a lot of interest. It was therefore considered to be of high importance to further study the sodium based sulfite process to investigate if its benefits could be better utilized in the future in the production of dissolving pulps. Of specific interest was to investigate how the pulping conditions in the initial part of the cook (≥ 60 % pulp yield) should be performed in the best way. Thus, this thesis is focused on the initial phase of single stage sodium bisulfite cooking of either 100 % spruce or 100 % pine wood chips. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and cooking time were varied. Activation energies for different wood components were investigated as well as side reactions concerning the formation of thiosulfate and sulfate. / Single stage sodium bisulfite cooking was carried out on either spruce or pine wood chips to investigate the influence of several process parameters in the initial phase of such a cook i.e. between 100 % and 60 % pulp yield. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and time in the initial stage were varied. The influence of dissolved organics and inorganics components in the cooking liquor on the final pulp properties and side reactions were investigated. The impact of temperature and time on the pulp components were analyzed with respect to carbohydrates, lignin, extractives and thiosulfate. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation. It was found that if using a mill prepared cooking acid, this had a beneficial effect with respect to side reactions, better extractives removal and higher pH stability during the cook, compared to a corresponding cook with a lab prepared cooking acid. Cooking with mill prepared and lab prepared cooking acids showed the same behaviour with respect to delignification and carbohydrate degradation, but the lab acid experiments resulted in a higher thiosulfate formation during the cook. The cellulose yield was not affected at all during the initial phase of the sulfite cook verifying earlier results by other researchers. The temperature had an influence on both the delignification rate and the rate of hemicelluloses removal.  The corresponding activation energies were found to increase in the following order; cellulose, xylan, glucomannan and lignin. / <p>Artikel 1: "The Initial Phase of Sodium Bisulfite Pulping of Spruce: Part 1" ingick i avhandlingen som manuskript. Nu publicerad.</p>

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.

Há 27 anos foi criada a RESEX Chico Mendes, no Acre, conquista histórica para o movimento dos seringueiros. Desde a década de 1970, os seringueiros vinham resistindo contra a expropriação causada pelo avanço da fronteira agropecuária na Amazônia e faziam frente a um modelo específico de desenvolvimento econômico que era fruto da aliança entre o capital monopolista e o Estado. Como reivindicação popular, no I Encontro Nacional dos Seringueiros (1985) foi proposta uma outra lógica de reforma agrária que mais adiante ganharia o nome de Reserva Extrativista (RESEX), onde a territorialidade e a (re)produção da família seringueira seriam contempladas e aliadas à conservação ambiental. Neil Smith (2008) aponta que, a partir da crise capitalista dos anos 1970, início do período neoliberal, houve uma intensificação do movimento de captura da natureza como estratégia de acumulação. A institucionalização da RESEX, em 1990, está inserida nesse quadro global e também marca o começo da guinada neoliberal no Brasil. Observa-se um processo de captura da proposta gestada pelo movimento social dos seringueiros para a constituição e concretização de um outro projeto, que contemplaria os interesses do capital monopolista e de novos atores sociais, onde se enquadram as ONGs. Na presente pesquisa, buscaremos compreender a produção capitalista da natureza a partir da RESEX Chico Mendes (1990-2017), por meio da qual o Estado e o mercado incorporam - de maneira contraditória e conflituosa - relações de produção não capitalistas, redefinindo os usos, a apropriação da natureza e as territorialidades dos seringueiros. / Extractive Reserve Chico Mendes in Acre was created 27 years ago and considered a historic step towards the rubber tappers movement. Since the 1970\'s they had been resisting the expropriation starting from the agriculture frontier in the Brazilian Amazon Region which was part of specific economic development frame fruit of the link between monopolistic capital and the State. The first National Rubber Tappers Conference (1985) covered the popular motion and proposed a new concept of an agrarian reform which later on would be known as the Extractive Reserve (RESEX), in which the territoriality and the family social reproduction would be assisted together with environmental conservation. Neil Smith (2008) points out that the capitalist crisis of the 1970s mainly during the neoliberal showed an intensification of nature\'s takeover as an accumulation strategy. The institutionalization of RESEX in 1990 is inserted in this global picture and with the start of the pivotal neoliberal in Brazil. A process for the so called takeover proposal which was initially developed by the rubber tappers social movement was observed and the constitution and the materialization of another project which would assist the interests of the monopolist capital and of new social players such as NGOs. This present research aims to better understand the capitalist production of the nature through the constitution and materialization of RESEX Chico Mendes (1990-2017) whereby the State and the market both incorporate in contractionary and conflicting manner the non-capitalist production relations redefining its uses, the appropriation of nature and the rubber tappers territoriality.