Historical masonry constructions are difficult to mimic in hygrothermal models. The material properties of the walls are often highly uncertain due to the natural origin of the aggregates and the ...various, manual production processes used through time. Therefore, sensitivity analyses based on probabilistic simulations are powerful tools to indicate the risks on damage in masonry constructions. Damage criteria for relevant pathologies such as frost damage, potential decay of wooden beam heads and mould growth at the interior surface are used. The assessment methods (Scatter plots, Classification trees and Sobol indices) are based on 1D Heat, Air and Moisture simulations, including realistic variations on climate parameters and wall properties. These methodologies are applied to probabilistic simulations in which a potential damage risk is expected in historic masonries. The application of interior insulation, the use of hydrophobic treatments, and the impact of potential water infiltrations through cracks are discussed. In most of these situations a high dependency of each of the damage criteria on the rain intensity, the trend of the moisture retention/liquid conductivity curve and the absorption coefficient is evident, but also additional insights are found. For example, the thermal impact of interior insulation is negligible compared to its reduction of the first phase drying potential towards the interior. For hydrophobic treatments, the risk for damage typically decreases, but in combination with a rain water infiltration rate above approximately 5% of the wind driven rain the risk on mould growth at the interior surface significantly increases.
Lipases are used in various sectors, as pharmaceutical, food or detergency industry. Their advantage versus classical chemical catalysts is that they exhibit a better selectivity and operate in ...milder reaction conditions. Theses enzymes can also be used in lipophilization reactions corresponding to the grafting of a lipophilic moiety to a hydrophilic one such as sugar, amino acids and proteins, or phenolic compounds. The major difficulty to overcome in such enzyme-catalyzed reaction resides in the fact that the two involved substrates greatly differ in term of polarity and solvent affinity. Therefore, several key parameters are to be considered in order to achieve the reaction in satisfactory kinetics and yields. The present review discusses the nature of such parameters (eg solvent nature, water activity, chemical modification of substrates) and illustrates their effect with examples of lipase-catalyzed lipophilization reactions of various sugar, amino acids or phenolic derivatives.
As a result of extensive research work performed on durability design and long-term performance of concrete structures in marine environments, new procedures for probability-based durability design ...have been shown to provide a more realistic basis for the analysis. This approach has been successfully applied to several new concrete structures, where requirements for a more controlled durability and service life have been specified.
It is commonly assumed that the dominant degradation mechanism for reinforced concrete structures in a marine environment is the corrosion of the reinforcement due to the presence of chlorides. A design approach based on the verification of the serviceability (durability) limit states has been suggested, examples of which are depassivation of reinforcement, cracking and spalling due to corrosion, and collapse due to cross section loss of reinforcement. With this design approach the probability of failure, i.e. the probability of not verifying the limit state, can be determined as a function of time.
In the present paper, a probability-based durability performance analysis is used in order to demonstrate the importance of the durability design approach of concrete structures in marine environments. In addition, the sensitivity of the various durability parameters affecting and controlling the durability of concrete structures in a marine environment is studied.
Results show that the potential of this approach to assist durability design decisions making process is great. Based on the procedure shown, it is possible to prolong the service life of structures while simultaneously optimizing the final design solution.
The topics focusing on functionalization of gold nanorods have been reviewed with a view toward their advanced uses. In most cases, as-prepared gold nanorods are hydrophilic and protected by ...surfactants, since anisotropic growth of gold nanorods by chemical, electrochemical, and photo-induced methods is carried out in aqueous media in the presence of surfactants and additives. Since solvophilicity of gold nanorods predominantly affects on their optical properties, the control of dispersity of gold nanorods in matrices has been performed, without loss of their optical characters, by surface modification and hybridization with small molecules or polymers. As a result of the functionalization procedure, the capability of self-assembly of gold nanorods has been improved. Furthermore, the examples of application using gold nanorods demonstrate that gold nanorod is a promising material.
Chitosan is a biopolymer derived from chitin in crustacean shells. Over the past decade it has been studied as an environmentally benign wood-protecting agent. It is assumed to act as a fungi-stat ...against a wide range of fungi and even as a fungicide at higher concentrations. This study investigated the properties of wood treated with modified chitosan of different molecular weights. Scots pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) samples were impregnated with two chitosan solutions differing in their average molecular weights. The chitosan solutions were depolymerized by nitrous acid to one solution of high molecular weight and one solution of low molecular weight with a concentration of 5% (w/v). The results show changes in sorption properties, antifungal properties, fire-retardant properties and mechanical properties of modified chitosan-treated wood. Heat-modified, chitosan-treated wood showed similar properties to chitosan-treated wood, except for brownish coloration, enhanced hydrophobation, and slightly reduced antifungal and fire-retardant properties. The modulus of rupture and hardness showed little or no change. The modulus of elasticity of the heat-modified, chitosan-treated wood increased by 27% compared with untreated wood.
New principles for the protection of wood: impregnation with water-borne resins Rapp, A.O; Peek, R.D. (Bundesforschungsanstalt fuer Holz- und Forstwissenschaft, Hamburg (Germany). Inst. fuer Holzbiologie und Holzschutz)
Document - the International Research Group on Wood Preservation (Sweden),
1995
95-40047
Conference Proceeding
Les fibres naturelles telles que le coton et le lin sont utilisées depuis longtemps dans l'industrie textile. De plus, elles prennent de plus en plus d'importance dans l'industrie des composites ...comme substituants des fibres de verre, de carbone ou d'aramide. Cependant, les fibres naturelles doivent être modifiées pour surmonter certains inconvénients tels que l'inflammabilité, l'hydrophilie et l'oléophilie. Dans ce travail, les retardateurs de flamme (RF) phosphorés et fluoro-phosphorés sont greffés par bombardement électronique et par modification chimique sur des tissus de lin afin d’améliorer leur comportement au feu, l’hydrophobicité et l’oléophobie. L'effet de la composition chimique sur le greffage a été également évalué en utilisant des fibres de miscanthus comparativement aux tissus de lin. La réactivité de la double liaison C = C des monomères phosphorés est étudiée pour contrôler l’efficacité de greffage de différents RF. Les étapes du radiogreffage sont étudiées et contrôlées. L'efficacité de greffage a été évaluée par fluorescence X et analyse par rayons X à dispersion d'énergie (EDS) / microscopie électronique à balayage (SEM). La résonance magnétique nucléaire du proton est utilisée pour analyser l'effet de l'irradiation sur les différents monomères. Le comportement au feu des tissus modifiés est étudié en utilisant l’analyse thermogravimétrique, la microcalorimétrie de combustion, cône calorimètre et un test au feu préliminaire. Des tissus ignifuges et oléophobes ont été développés avec succès.
Many natural fibers have been used for a long time in textile industry as cotton and flax. Moreover, natural fibers are getting more importance in composites industry as a substitute for glass, carbon, or aramid fibers. However, they must be modified to overcome some disadvantages such as flammability, hydrophilicity and oleophilicity. In this work, phosphorus and fluoro-phosphorus flame retardants were grafted by e-beam radiation and chemical modification on flax fabrics to improve their flame retardancy, hydrophobicity and oleophobicity. The effect of chemical composition on grafting were also evaluated using miscanthus fibers in comparison to flax fabrics. The reactivity of the double bond C=C of the P-monomers was studied to control the grafting yield of various FRs. Radiation grafting steps were studied and controlled carefully. Grafting efficiency was assessed by X-ray fluorescence and Energy Dispersive X-Ray Analysis (EDX) / Scanning Electron Microscopy (SEM). Proton nuclear magnetic resonance was used to analyze the effect of irradiation on different monomers. Fire behavior of the modified fabrics was studied using thermogravimetric analysis, pyrolysis combustion flow calorimetry, cone calorimetry and a preliminary fire test. Flame retardant and oleophobic fabrics were successfully developed.
En milieu marin le carbone organique particulaire (POC) représente 25 % du carbone organique total. Sa dégradation est réalisée par des microorganismes hétérotrophes ayant mis en place diverses ...stratégies pour parvenir à le dissoudre et l’assimiler. Peu d’études se sont intéressées à la dégradation des composés polymériques et/ou hydrophobes, quasiment insolubles dans l’eau constituant le POC. Parmi ces composés, on retrouve les lipides et les hydrocarbures regroupés sous le terme de COH (composés organiques hydrophobes). La dégradation des COH est réalisée par des bactéries dîtes oléolytiques ayant entre autre pour stratégie la formation de biofilms également qualifiés d’oléolytique. Nos connaissances sur la diversité et la fonctionnalité des biofilms oléolytiques se limitent actuellement aux bactéries spécifiquement étudiées pour leur capacité à dégrader les HC. Ainsi la dégradation des lipides est souvent négligée alors que cette famille de molécules représente une part significative du POC.La diversité taxonomique des bactéries formant des biofilms oléolytiques a été déterminée par un criblage de 199 souches marines sur 4 substrats : un alcane (paraffine), un triglycéride (tristéarine), un acide gras (acide palmitique) et une cire (l’hexadécyl palmitate). Cette étude a révélé que les bactéries oléolytiques (formant un biofilm sur au moins 1 des substrats) sont relativement répandues parmi les bactéries marines puisque qu’elles représentent 18.7 % des souches testée. Cette étude montre également que les bactéries capables d’assimiler les alcanes sont également capables d’assimiler au moins un lipide. Les bactéries hydrocarbonoclastes, jusqu’alors décrites comme spécialisées, voir restreintes à l’assimilation des hydrocarbures, présentent donc une gamme de substrats s’étendant aux lipides. La corrélation positive entre la capacité d’assimilation des alcanes et l’assimilation des lipides suggère un lien physiologique entre l’assimilation de ces deux familles de COH. L’activité lipase qui est essentielle à l’assimilation des triglycérides mais pas à l’assimilation des alcanes, a été mesurée dans des cultures de souches oléolytiques poussant sur acétate, triglycéride ou hexadécane. Comme attendu, les cultures sur triglycérides montrent toutes une surexpression de l’activité lipases par rapport aux cultures sur acétate. Les cultures sur hexadécane montraient aussi une surexpression de l’activité lipase renforçant l’idée d’un lien physiologique entre dégradation des alcanes et dégradation des lipides. De plus les souches oléolytiques n’ont pas montré de capacité à former un biofilm sur une surface inerte hydrophobe telle que le polystyrène ou sur une surface hydrophile telle que le verre à la hauteur de celles constaté sur COH. Une étude quantitative de l’adhésion sur COH et substrats inertes réalisée par microscopie montre que l’adhésion (dans les conditions testées) n’est pas un facteur déterminant de la formation de biofilm sur ces mêmes substrats. Cela suggère que la spécificité de formation de biofilm sur les substrats COH, ne réside pas dans l’adhésion mais vraisemblablement dans les étapes de développement du biofilm plus tardives.Enfin, les biofilms oléolytiques mettant en jeux des produits extracellulaires (enzymes et facteurs de solubilisation) qui constituent des biens communs, sont propices à l’établissement de comportements sociaux. Nous avons mis en évidence des comportements synergiques (5/8 des comportements observés) ou compétitifs au sein de biofilm oléolytiques (3/8 des comportements observés).
Particulate organic carbon (POC), in marine environment, accounts for 25% of total organic carbon. POC degradation is carried out by heterotrophic microorganisms which have developed strategies to dissolve and assimilate it. Few studies have investigated the degradation of the polymeric and / or hydrophobic components of POC, which are almost insoluble in the water. Among these compounds, there are lipids and hydrocarbons (HC) grouped under the term of HOCs (hydrophobic organic compounds). The degradation of the HOCs is carried out by oleolytic bacteria which form biofilms at the HOC– water interface. Our knowledge of the diversity and functionality of oleolytic biofilms is mostly limited to HC degrading bacteria, while the degradation of lipids is often neglected although this family of molecules represents a significant part of the POC. A screening of 199 marine strains on 4 substrates: an alkane (paraffin), a triglyceride (tristearin), a fatty acid (palmitic acid) and a wax ester (hexadecyl palmitate) was performed to determine the taxonomic diversity of bacteria able to form oleolytic biofilms. This study revealed that oleolytic bacteria (forming a biofilm on at least 1 substrate) were relatively widespread among marine bacteria since they represented 18.7% of tested strains. This study also showed that bacteria able to assimilate alkanes were also able to assimilate at least one lipid. Hydrocarbonoclastic bacteria, previously described as specialized, or restricted to the assimilation of hydrocarbons, have actually a substrate range spanning from HC to lipids. The positive correlation between the ability to form a biofilm on alkanes and on lipids suggested a physiological link between the assimilation of these two HOC families. The lipase activity, which is essential for triglycerdides assimilation but not for the alkanes assimilation, was measured in oleolytic strains cultures growing on acetate, triglyceride or hexadecane. As expected, overexpression of lipase activity was observed in cultures on triglycerides compared to cultures on acetate. Moreover, overexpression of lipase activity was also observed in cultures on hexadecane reinforcing the idea of a physiological link between alkanes and lipids degradation.Oleolytic strains exhibited a very weak ability to form a biofilm on the inert surfaces (non-nutritive) polystyrene or glass compared to the HOC nutritive surface indicating that oleolytic strains have a specificity for HOC to form a biofilm. A quantitative study of adhesion on HOC and inert substratums carried out by microscopy shows that adhesion (in the tested conditions) is not a determining factor of the biofilm formation on these same substrates. This suggests that the specificity of biofilm formation on HOC substrates does not reside in adhesion but presumably in later biofilm development stages.Lastly, oleolytic biofilms, involving extracellular products (enzymes and solubilization factors) that constitute public goods, are favorable to the establishment of social behaviors. We have demonstrated synergistic behaviors (5/8 of observed behaviors) or competitive behaviors (3/8 of observed behaviors) in oleolytic biofilms.
L’objectif de cette thèse était de concevoir denouveaux matériaux polymères hydrophobes pour la protectionde composants semi-conducteurs, résistants à hautetempérature, aux forts champs électriques ...et aux atmosphèresagressives. Dans ce contexte, les polyimides d’addition sontapparus comme la famille de polymères la mieux adaptée pourl’application envisagée. La synthèse de l’encapsulant étantréalisée directement dans les boîtiers des modules, elle ne peutdonc pas contenir de solvant organique exogène. Ainsi, nousavons développé de nouvelles voies de synthèse sans solvantde poly(aminobismaléimide)s et de poly(bismaléimide)s.Dans un premier temps, différentes diamines aliphatiques ontété utilisées comme solvant réactif lors de la synthèse depoly(aminobismaléimide)s à une température bien inférieure à latempérature de fusion du bismaléimide utilisé (Tf > 300 °C). Unepremière série de 3 nouveaux poly(aminobismaléimide)sréticulés de 70 à 95 % a ainsi été réalisée. A partir de cespremières synthèses, 10 nouveaux poly(aminobismaléimide)sont été élaborés. Pour 9 d’entre eux, des diamines aromatiquesont été utilisées et, pour le dernier, une diamine siloxane. Cesrésultats démontrent la possibilité de généraliser ce procédé desynthèse.Dans un second temps, des poly(bismaléimide)s ont étésynthétisés, toujours sans solvant. Pour cela, les synthèses dequatre nouveaux bismaléimides liquides à température ambianteont été mises au point. Ces composés ont une structurealiphatique ou siloxane dans laquelle un motif pyroméllitique aété, ou pas, introduit. Leur polymérisation amorcée avecl’amorceur radicalaire ad hoc, conduit à la formation desmatériaux sans l’usage de solvant.Selon le choix des réactifs, des matériaux thermodurcissablesou élastomères sont obtenus. Ces derniers semblent mieuxadaptés à l’application souhaitée car, d’une part, la faibleviscosité des mélanges réactionnels permet leur applicationsans difficulté dans un module de puissance et, d’autre part, leurcaractère hydrophobe est plus marqué. L’un d’eux présente unestabilité thermique à 250 °C particulièrement intéressante et unetempérature de relaxation mécanique quasi hors gamme detempérature de fonctionnement. Ce matériau peut doncvraisemblablement être utilisé comme encapsulant.
The aim of this work is to develop new hydrophobicpolymeric materials for the protection of semi-conductorcomponents. These materials must withstand high temperature,strong electric fields and aggressive atmospheres such asmoisture. In this context, addition polyimides emerged as themost suitable polymers for the intended application. Thesynthesis of the encapsulant being made directly in the powermodules, it must be solvent free. Thus, we have developed newsolvent free synthesis routes of poly(aminobismaleimide)s andpoly(bismaleimide)s.First of all, different aliphatic diamines were used as a reactivesolvent in the synthesis of poly(aminobismaleimide)s to atemperature well below the melting point of the usedbismaleimide (m.p. > 300 °C). A first series of 3 newpoly(aminobismaleimide)s, crosslinked from 70 to 95 %, hasthus been made. From these first syntheses, 10 newpoly(aminobismaleimide)s have been developed. For 9 of them,aromatic diamines were used and, for the latter, a siloxanediamine. These results demonstrate that this process can begeneralized.Secondly, poly(bismaleimide)s were synthesized, still withoutany solvent. In order to do so, the syntheses of four newbismaleimides, liquid at room temperature, have beendeveloped. These compounds have an aliphatic or siloxanestructure in which a pyromellitic pattern has been or notintroduced. Their polymerization initiated with the suitable radicalinitiator leads to the formation of materials without the use of anysolvent.Depending on the choice of reagents, thermosetting materials orelastomers are obtained. These latter seem more suitable for thedesired application because, on one hand, the low viscosity ofthe reaction mixtures enables their application in a powermodule without any difficulty and, on the other hand, theirhydrophobic behaviour is stronger. One of them has aparticularly attractive thermal stability at 250 ° C and amechanical relaxation temperature almost out of the workingtemperature range. Therefore, this material may be used asencapsulant.
Ce travail de thèse a porté sur l’étude des propriétés d’adsorption et de séparation en milieu humide par des polymères de coordination poreux. Nous avons utilisé les techniques de volumétrie ...d’adsorption, de séparation par chromatographie en phase gaz, de spectroscopie de fluorescence ainsi que et de la modélisation Monte Carlo afin de comprendre les mécanismes qui gouvernent l’adsorption de ces matériaux. Les molécules adsorbables étudiées sont l’eau et des vapeurs d’hydrocarbures linéaires (pentane et n-hexane), cycliques (cyclohexane et cyclohexène) et polycycliques (anthracène). Les adsorbants étudiés sont les Analogues de Bleu de Prusse (ABP) ainsi que deux matériaux organométalliques poreux de référence, le ZIF8 et le CuBTC. Parmi les résultats principaux apportés par ce travail, nous avons montré que les Analogues de Bleu de Prusse ont une stabilité hydrothermale remarquable leur conférant des propriétés d’adsorption en milieu humide très prometteuses. Parmi les ABP étudiés, le CoCoIII(CN)60.66 ⊡0.33 .5.2H2O a montré des propriétés d’adsorption et de séparation très supérieures à celles d’autres ABPs. Par exemple, il a été possible de moduler sa balance hydrophobe/hydrophile par le contrôle de la coordination de l’eau sur le centre métallique insaturé, tout en préservant son caractère lipophile. Nous avons aussi montré que cet analogue de bleu de Prusse est capable de séparer des mélanges d’hydrocarbures secs ou très humides de façon répétée. Sur un aspect plus fondamental, nous avons montré que le confinement d’anthracène par le ZIF-8, qui est un composé organométallique poreux possédant des cavités de taille ajustée à celle du fluorophore, pouvait induire une extinction complète de certaines bandes d’absorption de celui-ci.
This PhD thesis is focused on the study of wet adsorption and separation properties by porous coordination polymers. We used adsorption volumetry, gas chromatography separation techniques, fluorescence spectroscopy techniques and Monte Carlo modeling to understand the mechanisms governing the adsorption of these materials. The adsorbable molecules studied are water and hydrocarbon vapors linear (pentane and n-hexane), cyclic (cyclohexane and cyclohexene) and polycyclic (anthracene). The adsorbents studied are the Prussian Blue Analogues (ABP) as well as two reference porous organometallic materials, ZIF8 and CuBTC. Among the main results provided by this work, we have shown that Prussian Blue Analogues have remarkable hydrothermal stability conferring them very promising wet adsorption properties. Among the ABPs studied, Co CoIII (CN)6 0.66 ⊡0.33 .5.2H2O showed adsorption and separation properties far superior to those of other ABPs. For example, it has been possible to modulate its hydrophobic / hydrophilic balance by controlling the coordination of water on the unsaturated metal center, while preserving its lipophilic character. We have also shown that this Prussian blue analogue is capable of separating mixtures of dry or very wet hydrocarbons repeatedly. On a more fundamental aspect, we have shown that the confinement of anthracene by ZIF-8, which is a porous organometallic compound with cavities of size adjusted to that of the fluorophore, could induce a complete extinction of certain absorption bands of this one.
