Through the development of physical chemistry and chemical physics over the late-nineteenth and early-twentieth centuries, the relationship between physics and chemistry changed to create a broad interdisciplinary framework in which chemists and physicists could make contributions to problems of common value. It is here argued that evolving disciplinary factors such as physical and chemical responses to the atomic hypothesis, the nature of disciplinary formation in Germany and the United States, the reception of quantum mechanics within physics and chemistry, and the application of quantum mechanics to the problem of chemical bonding by physicists and chemists, formed the chemical bond into a physico-chemical theory. In the late nineteenth-century context of early physical chemistry, the chemical bond was known as a physical link between atoms, which could not be studied by chemical means because of the lack of an adequate atomistic framework. Both chemists and physicists broadly accepted the atomistic hypothesis following the discovery of the electron at the turn of the twentieth century, which afforded theoretical study of chemical bonding. Between 1916 and 1919, Gilbert N. Lewis and Irving Langmuir proposed the valence bond to be a pair of electrons shared between two atoms, within the context of a cubic model of the atom. However, the lack of a physical mechanism for the shared electron pair prevented the formation of a fully physico-chemical view of bonding. In 1927, physicists Walter Heitler and Fritz London showed the stability of the valence bond was caused by the wave mechanical phenomenon of resonance. Chemist Linus Pauling extended their treatment of the valence bond to a theory of structural chemistry in The Nature of the Chemical Bond. His synthesis of the physical and chemical views, his value as a physico-chemical researcher during the 1930s, and the research of his contemporaries John Slater and Robert Mulliken show that a true physico-chemical blend was only realized within the amorphous discipline of chemical physics. Finally, it is seen that this interdisciplinarity of chemical bonding and its supporting framework force a reevaluation of the reductionist criteria, and a re-definition of the chemical bond as a physico-chemical work.

Through the development of physical chemistry and chemical physics over the late-nineteenth and early-twentieth centuries, the relationship between physics and chemistry changed to create a broad interdisciplinary framework in which chemists and physicists could make contributions to problems of common value. It is here argued that evolving disciplinary factors such as physical and chemical responses to the atomic hypothesis, the nature of disciplinary formation in Germany and the United States, the reception of quantum mechanics within physics and chemistry, and the application of quantum mechanics to the problem of chemical bonding by physicists and chemists, formed the chemical bond into a physico-chemical theory. In the late nineteenth-century context of early physical chemistry, the chemical bond was known as a physical link between atoms, which could not be studied by chemical means because of the lack of an adequate atomistic framework. Both chemists and physicists broadly accepted the atomistic hypothesis following the discovery of the electron at the turn of the twentieth century, which afforded theoretical study of chemical bonding. Between 1916 and 1919, Gilbert N. Lewis and Irving Langmuir proposed the valence bond to be a pair of electrons shared between two atoms, within the context of a cubic model of the atom. However, the lack of a physical mechanism for the shared electron pair prevented the formation of a fully physico-chemical view of bonding. In 1927, physicists Walter Heitler and Fritz London showed the stability of the valence bond was caused by the wave mechanical phenomenon of resonance. Chemist Linus Pauling extended their treatment of the valence bond to a theory of structural chemistry in The Nature of the Chemical Bond. His synthesis of the physical and chemical views, his value as a physico-chemical researcher during the 1930s, and the research of his contemporaries John Slater and Robert Mulliken show that a true physico-chemical blend was only realized within the amorphous discipline of chemical physics. Finally, it is seen that this interdisciplinarity of chemical bonding and its supporting framework force a reevaluation of the reductionist criteria, and a re-definition of the chemical bond as a physico-chemical work.

The mechanical pulping industry has been developing throughout the years, due to competitive prices in the electricity market and good accessibility of wood. This has made it possible for such and “expensive” process to further develop. Today, with increasing electricity prizes, it is of great interest to reduce electrical consumption in mechanical pulping industry, since the process consumes large amounts of electricity. Braviken paper mill is starting up a new thermomechanical pulping line, scheduled for start-up in August 2008, which aims to reduce electrical consumption. The new line will include chip pre-treatment equipment such as an impregnator, an Andrtiz Impressafiner (Screw press), a high intensity primary stage refines double disc (DD), and a new low consistency refiner (LC), significantly bigger than those earlier available on the market. This master´s thesis is one out of three Master´s thesis made at Braviken paper mill during spring 2008. They all are connected, and are investigating the possibility to reduce electric energy consumption within TMP production. Master´s thesis concerning high consistency refining was done by Dino Muhic, “High consistency refining of mechanical pulps during varying refining conditions”, and low consistency refining written by Fredrik Johansson “Increased energy efficiency in low consistency refining”. Chip pre-treatment is to be used to reduce electrical consumption. Mechanical pre-treatment, such as using an Andrtiz Impressafiner demolishes the chips while also making it possible to impregnate the chips with chemicals, the later giving additional possibilities to reduce electricity consumption. Chemical chip pre-treatment decreases the lignin softening temperature, which benefits the refining process, yielding longer and less damaged fibers that will create a fibrous pulp with reduced electrical energy input.The goal for this study was to investigate the effect of alkaline-peroxide on chip pre-treatment by using a design of experiment method, in terms of electric energy consumption for the process, strength properties, opacity and ISO-brightness within the pulp/sheets. The trials were built up as a factorial experiment, with two factors, alkaline and peroxide, with two levels each (high and low). The high level for alkaline was 15 kg/t and 10 kg/t for the low level, and the high level for peroxide was 10 kg/t and 5 kg/t for the low level. This resulted in four trials with two zero-points, and two reference pulps, one normal TMP, thermomechanical pulp, and the other TMP with pressafiner and water. The trials showed that adding alkaline-peroxide clearly had an impact on pulp properties, such as increased strength properties, fiber length improvements and less shives could be found in the alkaline-peroxide treated pulps. The yield was highest for the normal TMP, about 99% and it decreased with increasing alkaline addition, the lowest value was achieved for the pulps containing the highest dose of alkaline, about 95%. The optical properties were more or less as expected. Opacity had the highest value for the pulps that had been made from chips with the highest total alkaline level. The ISO brightness was highest for pulps containing low level of alkaline. It could not be decided if the electricity demand had been reduced for the chemically treated pulps; it actually had the opposite effect as expected. The chemically treated pulps demanded a higher SEC, specific energy consumption, compared to the reference pulps. This result could have depended on the small pilot plant high consistency refiners at CTP, Centre technique du papier, Grenoble, France, due to the plate size and what kind of plats that were used. To do trials like this and to be able to draw correct conclusions relevant for a full scale plant, bigger refiners might give a more comparable result. It was clear that the fiber properties had improved, which could be the key to reduce electricity when LE- (low-energy) plates are used in the HC-refiner. A higher intensity could be used and electricity energy could be saved.

<p> </p><p><p>The mechanical pulping industry has been developing throughout the years, due to competitive prices in the electricity market and good accessibility of wood. This has made it possible for such and “expensive” process to further develop. Today, with increasing electricity prizes, it is of great interest to reduce electrical consumption in mechanical pulping industry, since the process consumes large amounts of electricity. Braviken paper mill is starting up a new thermomechanical pulping line, scheduled for start-up in August 2008, which aims to reduce electrical consumption. The new line will include chip pre-treatment equipment such as an impregnator, an Andrtiz Impressafiner (Screw press), a high intensity primary stage refines double disc (DD), and a new low consistency refiner (LC), significantly bigger than those earlier available on the market. This master´s thesis is one out of three Master´s thesis made at Braviken paper mill during spring 2008. They all are connected, and are investigating the possibility to reduce electric energy consumption within TMP production. Master´s thesis concerning high consistency refining was done by Dino Muhic, “<em>High consistency refining of mechanical pulps during varying refining conditions</em>”, and low consistency refining written by Fredrik Johansson “I<em>ncreased energy efficiency in low consistency refining</em>”.</p><p><p>Chip pre-treatment is to be used to reduce electrical consumption. Mechanical pre-treatment, such as using an Andrtiz Impressafiner demolishes the chips while also making it possible to impregnate the chips with chemicals, the later giving additional possibilities to reduce electricity consumption. Chemical chip pre-treatment decreases the lignin softening temperature, which benefits the refining process, yielding longer and less damaged fibers that will create a fibrous pulp with reduced electrical energy input.The goal for this study was to investigate the effect of alkaline-peroxide on chip pre-treatment by using a design of experiment method, in terms of electric energy consumption for the process, strength properties, opacity and ISO-brightness within the pulp/sheets. The trials were built up as a factorial experiment, with two factors, alkaline and peroxide, with two levels each (high and low). The high level for alkaline was 15 kg/t and 10 kg/t for the low level, and the high level for peroxide was 10 kg/t and 5 kg/t for the low level. This resulted in four trials with two zero-points, and two reference pulps, one normal TMP, thermomechanical pulp, and the other TMP with pressafiner and water.</p><p>The trials showed that adding alkaline-peroxide clearly had an impact on pulp properties, such as increased strength properties, fiber length improvements and less shives could be found in the alkaline-peroxide treated pulps. The yield was highest for the normal TMP, about 99% and it decreased with increasing alkaline addition, the lowest value was achieved for the pulps containing the highest dose of alkaline, about 95%. The optical properties were more or less as expected. Opacity had the highest value for the pulps that had been made from chips with the highest total alkaline level. The ISO brightness was highest for pulps containing low level of alkaline. It could not be decided if the electricity demand had been reduced for the chemically treated pulps; it actually had the opposite effect as expected. The chemically treated pulps demanded a higher SEC, specific energy consumption, compared to the reference pulps. This result could have depended on the small pilot plant high consistency refiners at CTP, Centre technique du papier, Grenoble, France, due to the plate size and what kind of plats that were used. To do trials like this and to be able to draw correct conclusions relevant for a full scale plant, bigger refiners might give a more comparable result. It was clear that the fiber properties had improved, which could be the key to reduce electricity when LE- (low-energy) plates are used in the HC-refiner. A higher intensity could be used and electricity energy could be saved.</p></p></p>

L'étude comparée des réactions de formation de paires d'ions et de simple photoionisation de la molécule NO2 induites par rayonnement synchrotron (RS) d'une part et par impulsions laser femtosecondes (fs) d'autre part, démontre le rôle remarquable de l'excitation résonante d'états de Rydberg dans la dynamique électronique et nucléaire induite. Trois réactions principales, la photoionisation non dissociative (NO2+ (X 1Σ+g) + e), la photoionisation dissociative (NO+ (X 1Σ+) + O(3P) + e) et la formation de paires d'ions, (NO+ (X 1Σ+) + O- (2P)), ont été caractérisées en utilisant la méthode des corrélations vectorielles ou spectroscopie en coïncidence des impulsions du photoélectron et des photoions, auprès des sources RS (SOLEIL, DESIRS) et lasers fs (CEA, Saclay), respectivement. Le diagramme de corrélation des énergies cinétiques électron-ion, première observable issue de ces mesures, met en évidence un partage de l'énergie en excès entre noyaux et électrons qui dépend fortement du mode d'excitation photonique. Les déviations significatives observées par rapport aux profils d'ionisation de type Franck Condon sont attribuées à des couplages vibroniques entre états excités NO2*, tels que ceux induits par une intersection conique. Les chemins réactionnels identifiés confirment le rôle de l'excitation des séries de Rydberg [R*(6a1)-1] et [R*(4b2)-1] intervenant comme états intermédiaires dans l'excitation multiphotonique ou dans le continuum d'ionisation exploré. Une étude complémentaire par spectroscopie à haute résolution des états [R*(6a1)-1] a été mise en œuvre (UBC, Vancouver).Pour une réaction de photoionisation dissociative (PID), l'observable la plus complète est la distribution angulaire des photoélectrons dans le référentiel lié à la vitesse de recul de l'ion fragment (RFPAD) déduite de la mesure de la corrélation vectorielle (Vi, Ve, P). Afin d'accéder aux éléments de matrice dipolaire décrivant la photoionisation de l'état électronique considéré, le formalisme développé en collaboration avec R. R. Lucchese (Texas A&M) décrivant la photoémission dans le référentiel moléculaire pour la simple PID d'une molécule linéaire par excitation à un photon, a été étendu à l'étude des réactions de PID par excitation multiphotonique d'une molécule polyatomique, telle que la molécule NO2 de symétrie C2v. L'analyse multivariée de la RFPAD multiphotonique proposée constitue une stratégie fructueuse en vue d'extraire l'information optimale sur la dynamique complexe de photoionisation et de réaliser une comparaison détaillée entre les résultats expérimentaux et les calculs de photoionisation des états excités de la molécule.

Ce travail de thèse s'inscrit dans le cadre de l'étude et du développement de matériaux céramiques de type carbure pouvant être utilisés dans l'assemblage combustible des réacteurs nucléaires du futur. Depuis l'accident de Fukushima, ces céramiques réfractaires sont envisagées afin d'améliorer la sûreté dans les centrales à eau pressurisée actuelles. Sous forme de revêtements ou de gaines, ces matériaux pourraient en effet permettre de garantir une meilleure résistance de l'assemblage combustible notamment en conditions accidentelles à haute température. Le principal frein à l'utilisation en réacteur de céramiques carbures sous forme frittée est leur faible ténacité qui a conduit à envisager l'utilisation de matériaux composites à matrice céramique. Ces matériaux sont constitués de fibres ou de tubes insérés dans une matrice céramique. Depuis quelques années, des techniques complexes permettant d'envisager la fabrication de gaines étanches aux produits de fission gazeux ont été perfectionnées (Procédés CVI et NITE®, utilisation d'un liner...). Quel que soit le procédé ou la forme finale du matériau envisagé, la mise en oeuvre d'une matrice céramique à nanograins peut présenter un gain en termes de résistance à l'irradiation notamment. Certains matériaux sont à l'étude comme le carbure de titane qui présente l'avantage de présenter une très haute température de fusion et également une conductivité thermique relativement conservée sous irradiation et à haute température. Dans cette étude, nous avons choisi de nous intéresser à l'impact de la taille de grains sur certaines propriétés du matériau TiC. Notre démarche a été de synthétiser trois microstructures différentes par la technique SPS avec trois tailles de grains moyennes. Dans un premier temps, nous avons déterminé les meilleures conditions de dispersion d'une poudre commerciale nanométrique (≈40 nm). Nous avons ensuite défini les conditions optimales de frittage afin d'obtenir les trois microstructures souhaitées.

Ce travail s'inscrit dans le cadre des études sur la gestion des déchets graphités issus du démantèlement des centrales UNGG (Uranium Naturel Graphite Gaz). Les déchets graphités contiennent, entre autres, du 36Cl, radionucléide de longue période dimensionnant pour le stockage, car très mobile dans les ouvrages cimentaires et formations argileuses. Or, à ce jour, peu de données sont disponibles sur la localisation du 36Cl et sa spéciation dans le graphite nucléaire irradié. Ces informations sont nécessaires pour le dimensionnement d'un site de stockage adapté aux déchets graphités et leur obtention constitue l'objectif de ma thèse, réalisée en partenariat avec EDF, CEA et Andra. Dans ce contexte, nous avons mis en œuvre des études expérimentales permettant de simuler et d'évaluer l'impact de la température, de l'irradiation et de la radiolyse à l'interface gaz/graphite sur le comportement en réacteur du 36Cl. La présence de 36Cl dans le graphite est simulée par l'implantation ionique de 37Cl dans des échantillons de graphite nucléaire vierge ce qui permet de nous affranchir des contraintes liées à l'utilisation de graphite irradié. En extrapolant nos résultats aux déchets graphités, nos études sur les effets comparatifs de la température et de l'irradiation montrent que la température tend à appauvrir l'inventaire en chlore 36 des graphites irradiés et que l'irradiation en régime mixte, tel qu'elle a lieu dans les réacteurs UNGG, renforce cet effet d'appauvrissement

Telechelic associating polymer networks consist of polymer chains terminated by endgroups that have a different chemical composition than the polymer backbone. When dissolved in a solution, the endgroups cluster together to form aggregates. At low temperature, a strongly connected reversible network is formed and the system behaves like a gel. Telechelic networks are of interest since they are representative for biopolymer networks (e.g. F-actin) and are widely used in medical applications (e.g. hydrogels for tissue engineering, wound dressings) and consumer products (e.g. contact lenses, paint thickeners). In this thesis such systems are studied by means of a molecular dynamics/Monte Carlo simulation. At first, the system in rest is studied by means of graph theory. The changes in network topology upon cooling to the gel state, are characterized. Hereto an extensive study of the eigenvalue spectrum of the gel network is performed. As a result, an in-depth investigation of the eigenvalue spectra for spatial ER, scale-free, and small-world networks is carried out. Next, the gel under the application of a constant shear is studied, with a focus on shear banding and the changes in topology under shear. Finally, the relation between the gel transition and percolation is discussed.

Les colloïdes sont utilisés dans de nombreuses applications médicales tels les agents de contraste en IRM ou l'immuno-agglutination magnétique dans le diagnostic. Pour en améliorer leurs performances, l'interaction entre les particules et les milieux biologiques - en particulier les protéines - a été étudiée depuis plus de 150 ans ; mais ce phénomène n'est toujours pas correctement décrit. La première partie de cette thèse est dédiée à une des applications des colloïdes : la détection de protéines cible. Basée sur l'orientation d'agrégats magnétiques anisotropes, une nouvelle méthode a été mise au point, permettant de mesurer un signal d'agrégation uniquement proportionnel à la quantité de protéines à doser, la limite de détection est donc abaissée. Cette technique a été validée sur un système réel : la protéine C-réactive. La seconde partie de cette thèse est consacrée à l'adsorption des protéines sur les colloïdes. Le premier objectif a été la mise au point d'un protocole de mesure capable de fournir des données fiables ; l'adsorption a ainsi pu être caractérisée sur un système modèle, l'albumine de sérum bovin sur la silice. Les mesures obtenues ont ainsi permis de lever certains paradoxes et de proposer un nouveau modèle d'adsorption. Enfin, ces connaissances ont permis de comprendre comment des protéines, en s'adsorbant sur deux particules, agrègent les colloïdes. En quantité suffisante, elles peuvent également les protéger de l'agrégation, ouvrant la voie à une nouvelle méthode de stabilisation des particules.

Le travail de cette thèse consiste à mettre au point des gels stimulables à partir d'un polymère hydrosoluble simple : la polyallylamine. Nous avons choisi d'utiliser la réaction réversible entre les acides boroniques et les diols pour former les points de réticulation (esters boroniques). La formation de ces esters boroniques a été étudiée pour deux systèmes modèles composés d'acide 4-carboxyphénylboronique et de cyclopentanediol ou de glucose. La fonctionnalisation de la polyallylamine est effectuée selon deux méthodes : les fonctions phénylboroniques par une réaction d'amidification via un agent de couplage carbodiimide. Les fonctions diol par une réaction d'ouverture du cycle de la gluconolactone. Cette deuxième réaction de greffage peut être réversible à pH élevé. Les mélanges de ces deux polymères permettent la formation de gels réversibles sur une large gamme de pH (pH>6). Cette efficacité de gélification, même à pH neutre, est attribuée à l'effet stabilisateur qu'exercent les fonctions amines du polymère sur les esters boroniques. Il a été également montré que les polymères greffés gluconamide peuvent facilement former des gels en présence de borax. La réaction entre une polyamine et la gluconolactone s'avère être une méthode simple et efficace pour conférer à ce type de polymère un pouvoir viscosifiant important lorsqu'il est combiné avec des dérivés portant des fonctionnalités acides boriques ou boroniques.