The performance of polymeric diphenylmethane diisocyanate (PMDI) resin is known to be highly dependent on the wood species. This species dependence may be due to differences in: cure chemistry, interphase morphology, or both of these factors. This study addresses aspects of the cure chemistry and interphase morphology of wood/PMDI bondlines; specifically these effects are compared using two woods: yellow-poplar and southern pine. In this study, the cure chemistry of wood-PMDI system was analyzed with solid state NMR (SSNMR) using wood samples cured with doubly labeled (15N,13C) PMDI resin. The kinetics of PMDI cure in the presence of wood was analyzed with differential scanning calorimetry. Thermogravimetric analysis was used to analyze the effect of resin impregnation on the degradation patterns of wood. The wood-PMDI bond morphology was probed with dynamic and static (creep) mechanical analyses in both dry and plasticized conditions. The effect of resin on wood polymer relaxations was quantitatively analyzed by both the time-temperature superposition principle and the Kohlrausch-Williams-Watts equation. The presence of a small but statistically significant species effect was observed on both the cure chemistry and bond morphology of wood-PMDI system at low cure temperatures. The cure of PMDI resin was found to be significantly faster in pine relative to corresponding poplar samples. Resin impregnation showed a significant species dependent effect on the wood mechanical properties; the resinated pine samples showed increase in compliance while the corresponding poplar samples became stiffer. The in situ lignin relaxation was studied with both dynamic and static modes, using plasticized wood samples. Results showed that the lignin relaxation was slightly affected by resin impregnation in both woods, but the effect was relatively larger in pine. Static experiments of dry wood samples showed a significant reduction in the interchain interactions of wood polymers in pine samples, exclusively. Investigation of plasticized pine samples, which focuses on the in situ lignin relaxations, showed only minor changes with resin impregnation. This led us to hypothesize that the large changes observed in dry samples, were due to the in situ amorphous polysaccharides. The wood-PMDI interactions were significantly reduced upon acetylation of wood. This study also discusses three new and highly sensitive methods for the analysis of wood-resin interactions. / Ph. D.

The viscoelastic behavior of concrete, nearly completely attributable to changes in properties in the cement paste, is an ongoing area of research with the objective of avoiding unpredictable response and potentially failure of concrete structures. This research explores the elastic and viscoelastic response in cement paste beams using relaxation testing, with and without strain reversals in the load history. It was seen that strain reversal imparts significant changes in mechanical response, retarding load relaxation. Companion beams were tested for chemical composition at varying depths in the beam section and the results were compared to those of control specimens not subject to stress. Results indicate significant variations in composition implying that stress accelerates the hydration process. The reasons behind the acceleration are discussed and incorporated into a preliminary solidification-dissolution model for beam relaxation. The model, though in need of improvement through further research, shows promise in potentially predicting relaxation in cement paste and by extension, in concrete structures. / Ph. D.

As renewable energy production becomes more prevalent, the challenge of producing renewable dispatchable fuel for the transportation sector remains unresolved. One promising approach is to produce hydrogen from solar energy with a two step thermochemical cycle which utilizes an oxygen storage material (OSM) to split water through two reversible reactions. Due to the strong coupling between reactor design, operational parameters, and OSM properties, the direct comparison of two OSMs is not straightforward. In order to guide the designs of OSMs for two-step thermochemical hydrogen production, a methodology is developed to model the max performance possible for a two-step thermochemical cycle. The novel contribution of this model considers the strong coupling between reactor operation, OSM properties, and reactor performance. Next, a method for screening and evaluating new OSMs which utilizes thermogravimetric analysis (TGA) is proposed. With this data, the modeling method previously developed is applied to determine maximum reactor efficiency possible with new materials. This allows many materials to be evaluated quickly, and facilitates further characterization new OSMs. Additionally, by comparing the predicted maximum efficiency of a new material with the efficiency of current ones, this method facilitates the comparison of two different OSMs on equal footing.

This thesis investigates the structure and thermal behaviour of LiBH4, NaBH4, KBH4, LiK(BH4)2, Ca(BH4)2 and Sr(BH4)2. LiK(BH4)2 is the first mixed alkali metal borohydride and was synthesised and characterised during this work. The crystal structures of these borohydrides were studied using variable temperature neutron and synchrotron X-ray diffraction. The synthesis of isotopically enriched samples of 7Li11BD4, Li11BD4, Na11BD4 and K11BD4 allowed high quality neutron diffraction data to be collected. Particular attention was paid to the exact geometry of the borohydride ions which were generally found to be perfect tetrahedra but with orientational disorder. New structures of Ca(BH4)2 were identified and the first crystal structure of Sr(BH4)2 was determined from synchrotron X-ray diffraction data. Solid state 11B NMR and Raman spectroscopy provided further information about the structure of these borohydrides. The thermal behaviour of the borohydrides was investigated using thermogravimetric analysis with mass spectrometry of the decomposition gas products. Hydrogen is the main decomposition gas product from all of these compounds but small amounts of B2H6 and BH3 were also detected during decomposition. Thermogravimetic analyses of Na11BD4 and K11BD4 were completed whilst collecting in-situ neutron diffraction data allowing information about structural changes and mass losses to be combined in order to better understand the decomposition process.

Les émissions anthropiques de dioxyde de carbone, gaz à effet de serre, sont considérées comme les principales causes du réchauffement climatique. Le captage du dioxyde de carbone par l’oxyde de calcium, qui s’avère être une masse de captage appropriée, au cours de plusieurs cycles de carbonatation/décarbonatation est une solution à la diminution des émissions industrielles. Néanmoins, la capacité de captage du dioxyde de carbone par l’oxyde de calcium diminue au cours des cycles, soulevant ainsi des problèmes économiques majeurs. Actuellement, cette perte d’efficacité de captage est largement étudiée contrairement à la réaction même de carbonatation de CaO d’un point de vue fondamental.Dans l’optique de mieux comprendre la réaction de carbonatation de CaO, une étude cinétique a été menée par le biais d’expériences de thermogravimétrie sur poudre. L’approche cinétique a été basée sur des tests de cinétiques hétérogènes fondés sur les hypothèses de l’état pseudo-stationnaire et de l’étape limitante. Les courbes cinétiques expérimentales obtenues en conditions isothermes (450-650°C) et isobares (2-30 kPa) ont montré un temps de latence lié au processus de germination de la nouvelle phase, ainsi qu’un fort ralentissement de la réaction à partir d’un certain degré d’avancement. Ce temps de latence et le degré d’avancement correspondant au frein cinétique dépendent de la température et de la pression partielle de CO2. Afin d’en expliquer l’origine, des caractérisations texturales et morphologiques ont été effectuées à différents degrés d’avancement. Les modifications observées à l’échelle des agrégats ont suggéré une limitation de la vitesse de réaction par des phénomènes de transport de matière, susceptibles de bloquer l’accès du gaz au cœur des agrégats. Les décrochements en température réalisées en thermogravimétrie ont mis en évidence un comportement cinétique complexe. Trois domaines ont pu être distingués au cours de la réaction, quelles que soient la température et la pression partielle de CO2. L’interprétation de ces résultats a souligné le rôle de la porosité et de son évolution sur la cinétique, ainsi qu’un effet anti-Arrhenius dans le deuxième domaine.La modélisation cinétique a dû faire intervenir à la fois un modèle proche de la réalité physique à l’échelle des grains denses, mais également les processus de transport de matière et de chaleurs au sein de l’agrégat, afin de rendre compte des courbes expérimentales et de quantifier l’impact des différents paramètres expérimentaux sur la vitesse de réaction. Ce couplage échelle de la population des grains-échelle de l’agrégat a été réalisé à l’aide d’un logiciel de cinétique hétérogène, CIN4, développé au département PRESSIC, en collaboration avec la société ASTEK. Les simulations obtenues ont permis de décrire la réaction jusqu’au freinage cinétique. / Anthropogenic carbon dioxide (CO2) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO2 is captured by sorbents like calcium oxide (CaO) in multi-cycle process of carbonation/decarbonation. However, it was shown that the most important limitations of such process are related to the reversibility of reaction. CaO rapidly loses activity towards CO2, so the maximum extent of carbonation decreases as long as the number of cycles increases. In order to well understand the processes and parameters influencing the capture capacity of CaO-based sorbents, it appears important to get details on the kinetic law governing the reaction, which have not been really studied up to now. To investigate this reaction, CaO carbonation kinetics was followed by means of thermogravimetric analysis (TGA) on divided materials. Special care was given to the validation of the usual kinetic assumptions such as steady state and rate-determining step assumptions. The aim was to obtain a model describing the reaction in order to explain the influence of intensive variables such as carbonation temperature and CO2 partial pressure. TGA curves obtained under isothermal and isobaric conditions showed an induction period linked to the nucleation process and a strong slowing down of the reaction rate once a given fractional conversion was reached. Both phenomena were observed to depend on carbonation temperature and CO2 partial pressure. To explain these results, the evolution of texture and microstructure of the solid during the reaction was regarded as essential. Reaction at the grain scale induces a volume increase from CaO to CaCO3 which causes a change in the porosity characteristics at the aggregates scale, which could block the access of the gas to the core of aggregates. Temperature jumps during TGA experiments have put in evidence a complex kinetic behavior since three distinct domains must be distinguished, over all the conversion range, whatever the temperature and CO2 pressure could be. The discussion of the results emphasizes the role of the porosity on the kinetic anti-Arrhenius behavior observed in the second domain. So carbonation reaction can be described by a two scales model: at a nonporous grain scale for the chemical reaction and at the aggregate scale, for the CO2 intergranular diffusion. The kinetic modeling, thanks to the software CIN4 (developed in collaboration with Astek), is able to couple both modeling scales in order to explain the kinetic slowing down and the influence of temperature and CO2 partial pressure on the reaction rate.

Une étude de l’oxydation d’une poudre de nanoparticules de cuivre a été menée à 120 - 145°C sous des pressions partielles d’oxygène allant de 1 à 40 kPa. La réaction a été suivie par thermogravimétrie afin d’obtenir les données cinétiques. Des caractérisations chimiques, texturales et morphologiques de la poudre ont été réalisées à différents moments de la transformation. La cuprite (Cu2O) (produit unique) de la réaction croît d’une manière anisotrope et par développement externe autour de la particule initiale qui devient creuse. Une diminution de la surface spécifique et de la porosité de la poudre au cours de la transformation a été mise en évidence.Des tests cinétiques ont montré l’existence d’une étape limitante de croissance jusqu’à un taux de conversion de 0,7 à 140°C. Il a également été montré que pour P(O2) ≤ 4 kPa, les processus de germination et de croissance de l’oxyde interviennent simultanément pendant la réaction et que l’adsorption de l’oxygène est l’étape limitante. Pour P(O2) ≥ 20 kPa, la germination se fait instantanément au début de la transformation dont la vitesse est contrôlée par le processus de croissance, la diffusion du cuivre étant alors l’étape limitante. Deux modèles ont été construits et testés avec succès pour décrire la cinétique dans les deux gammes de P(O2) jusqu’à un taux de conversion donné. Pour expliquer le ralentissement observé au-delà de ce taux de conversion et pour P(O2) ≤ 4 kPa, le modèle a été couplé aux phénomènes de transfert de chaleur et de matière au sein des agglomérats. Ce couplage permet d’évaluer l’hypothèse d’un ralentissement de la réaction par la diffusion des molécules d’oxygène dans les pores de l’agglomérat. / The oxidation of copper nanoparticles at 120 – 145°C was investigated using TGA, DSC, XRD, SEM, TEM and nitrogen adsorption techniques (BET, BJH,..). Isothermal and isobaric studies of the oxidation reaction were carried out under various oxygen partial pressures 1 kPa – 40 kPa. The cuprous oxide (Cu2O) (the unique product of the reaction) grows in an anisotropic manner by outward diffusion of the copper. A considerable decrease of the specific surface area and the porosity of the powder during the transformation was highlighted.It was found that working under P(O2) ≤ 4 kPa leads to reaction where nucleation of Cu2O is in competition with its growth. The study of the dependency of the growth rate on the oxygen partial pressure has shown the adsorption of oxygen to be the rate-determining step. However, when the reaction is conducted under P(O2) ≥ 20 kPa, the nucleation occurs instantaneously in the early beginning of the reaction which will be governed by the growth process. Under these latter conditions of oxygen partial pressure the diffusion of copper ionized vacancies becomes the rate determining step. Hence, two kinetic models have been established to interpret the experimental curves in the two different oxygen partial pressure ranges. The expression of the extent of conversion was successfully confronted to the kinetic data up to an extent of conversion corresponding to the slowdown of the reaction. The kinetic model for P(O2) ≤ 4 kPa was coupled with mass and heat transfer within the porous agglomerate to verify if the diffusion of oxygen molecules in pores is in the origin of the reaction slowdown, this latter hypothesis was found not satisfactory.

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Science), Vaal University of Technology / Cadmium and cobalt complexes of urea and thiourea were synthesized using ethanol as a solvent. All complexes were refluxed at 70 - 80 °C, left to cool at room temperature, washed with methanol and acetone to remove impurities and dried at an open environment. The characterization of complexes was done using FTIR spectroscopy, elemental analysis and TGA. The complexes were found to coordination with the ligands through sulphur and oxygen atoms to the metal, instead of nitrogen. These were as results of wavelength shifting from high to low frequency from spectra of the complexes as compare to their free ligands. These observations make these complexes good candidates for the possible use in synthesis of metal sulphides or oxides nanoparticles. Thermogravimetric analyses of all the complexes were conducted to check the stability of use as precursors for nanoparticles at low and high temperature. A number of thiourea and urea complexes with cadmium and cobalt have been prepared and used in the preparation of metal sulphides/oxides nanoparticles. Complexes start to decompose at low temperature about 100°C and the last decomposition step was at about 800-900°C, which is convenient to thermal decomposition of precursors in the high boiling solvents or capping agent to prepare surface capped metal sulphides/oxides nanoparticles. The complexes were easy to synthesize, low cost and stable in air and were obtained in reasonable yields. All the complexes reported in this study have been used as single source molecular precursor in the preparation of cadmium oxide, cadmium sulphide, cobalt oxide, cobalt sulphide nanoparticles (normal) and as mixture of any two complexes to form core-shells nanoparticles. Quality nanoparticles synthesis requires three components: precursors, organic surfactants and solvents. The synthesis of the nanoparticles can be thought of as a nucleation event, followed by a subsequent growth period. Both the nucleation and growth rates were found to be dependent upon factors such as temperature, growth time, and precursor concentration. For a continuous flow system the residence time (at nucleation and growth conditions) was also found to be important. In order to separate the nucleation and growth events, injection techniques were employed to achieve rapid nucleation of nanoparticles with final size dictated by the growth temperature and/or residence time through the growth zone of the reaction system. Good crystalline normal nanoparticles were obtained from thermolysis of the precursors in hexadecylamine (HDA) as the capping agent at fixed concentrations, temperature and time. All nanoparticles showed a blue-shift in band edges with good photoluminescence behaviour which is red-shifted from their respective band edges and XRD patterns, the crystal structure are in hexagonal phase. The particles showed rods, spheres and hexagonal shapes. Nucleation and growth mechanism brings new avenue in nanostructures called core-shells, which have been reported to have improved luminescence, quantum yields, decreased fluorescence lifetimes, and benefits related to the tailoring of the relative band-gap positions between the two materials. In this study cadmium and cobalt complexes of urea and thiourea were separately dispersed in TOP and injected separately (allowing nucleation/core to occur, followed by the shell) in hot HDA at 180ºC for 1hour to yield core-shell nanoparticles. Parameters, such as concentration, temperature and capping molecule as factor affecting nucleation and growth of the core-shells were monitored. The core-shell nanoparticles were characterized by UV/Vis spectroscopy, XRD and TEM. We observed spherical, tripod, bipods, hexagonal and irregular shaped nanoparticle as the concentration of the precursors was increasing, however we were able to form core-shells nanoparticles in one set of experiment 1:3 CdS-CdO, which are assumed to be a reverse type I coreshells nanoparticles. Exciton absorption peaks at higher energy than the fundamental absorption edge of bulk indicate quantum confinement effect in nanoparticles as a consequence of their small size. XRD patterns, crystals range from hexagonal, cubic and mixture of hexagonal and orthorhombic. A low temperature studies were also conducted a mixture of hexagonal and sphererical shapes with sheets like onion morphology were observed. / NRF HUB & SPOKES (VUT)

Les cermets, nommés M(p)-CMC(s), « Ceramic Matrix Composite dispersed with Metallic Particles », sont prometteurs dans les applications à haute température. Un cermet modèle (304L-YSZ) constitué de 40 % vol. de particules d'acier inoxydable 304L dispersées dans une matrice de zircone partiellement stabilisée à l’yttrium a été préparé par métallurgie des poudres. Les cermets sont homogènes et possèdent une densité voisine de 97 % par rapport à la densité théorique. Une étude cinétique basée sur l’hypothèse de l’étape limitante, a été réalisée afin de proposer un mécanisme et un modèle d’oxydation du cermet. Dans un premier temps, l’oxydation de la poudre d’acier inoxydable a été étudiée sous oxygène à 800 °C. Les expériences d'oxydation sous He (80 %)-O2 (20 %) ont été conduites par thermogravimétrie. Conformément à la littérature, la cinétique d’oxydation de la poudre suit un régime de diffusion. Une couche d’oxyde à base de chrome à croissance externe est observée.En revanche, la cinétique d’oxydation du cermet modèle est différente de celle de la poudre de 304L. Un fort gain de masse est observé dès l’introduction de l’oxygène au début du palier isotherme. Pendant le palier isobare, la prise de masse est lente et n’est pas régie par la diffusion. La caractérisation des cermets oxydés montre que des nodules riches en chrome apparaissent tout d’abord à l’intérieur du métal. Puis une couche d’oxyde à base de chrome et de fer se forme par croissance externe. La matrice de zircone ne limite pas la diffusion de l’oxygène vers le métal. Elle se fissure sous l’action des contraintes mécaniques induites par le changement de volume des particules de 304L pendant l’oxydation. / Ceramic matrix composite dispersed with metallic particles, called M(p)-CMC(s), are being developed for optimizing several functions of industrial components in severe atmospheres at high temperature.The corrosion of a model M(p)-CMC(s), based on 304L stainless steel and yttrium doped zirconia (304L(p)-ZrO2(s); 40%/60% in volume) is studied and compared with the oxidation behaviour of the stainless steel powders. The oxidation behaviour of the model 304L(p)-ZrO2(s) composite produced by powder metallurgy, studied by means of the thermogravimetry under 20 % O2 in helium at 800 °C, is presented. Oxidation curves show a fast increase in mass gain followed by slow one for the composite material. SEM observations and Auger spectroscopy measurements of the oxidized composite indicate an outward complex Cr and Fe rich oxide layer whereas Cr2O3 nodules are observed to nucleate and develop inward. For 304L stainless steel powder, the shape of the mass gain curve is parabolic, in agreement with a diffusion controlled oxidation. SEM observations of oxidised powder and in situ XRD measurements at 800 °C under oxygen show an external growth of Cr2O3 oxide layer.The low resistance to oxidation of the composite (compared to the powder) in the initial period seems to be due to the properties of the zirconia/metallic particles interface obtained after the sintering process. Under reducing conditions, the initial Cr2O3 layer reacts with zirconia matrix. TEM observation of the “as sintered” interface between the metallic particles and the ceramic shows no chromia layer. Sudden changes in oxygen partial pressure during experiments reveal an accelerating effect of the oxygen pressure.

This thesis is interested in new materials for lithium – ion batteries. Two different samples were investigated, one intercalation and one conversion cathode material. The theoretical part is focused to the structure of cells, their advantages and disadvantages compared to other secondary batteries. Also other materials used in batteries are described. The practical part describes the preparation of cathode materials for subsequent testing by scanning elektron microscopy and thermogravimetric analysis. In conclusions two different materials were evaluated and compared with each other.

La corrosion à haute température d'alliages métalliques représente un processus d’endommagement critique dans de nombreux domaines industriels. Le suivi en service de la dégradation des équipements opérant sous une atmosphère agressive à haute température devient un objectif majeur pour les industriels. Grâce à sa sensibilité et à son caractère non destructif, l'émission acoustique constitue une méthode intéressante pour suivre l’évolution de la détérioration des matériaux soumis à des formes sévères de corrosion comme le metal dusting pour les alliages de fer ou de nickel en pétrochimie. Notre étude a montré que les transformations irréversibles des matériaux telles que la fissuration peuvent être détectées grâce aux signaux acoustiques émis pendant la corrosion. Un couplage innovant a été développé associant l'émission acoustique in situ avec la thermogravimétrie. Dans un premier temps, ce couplage nous a permis d’étudier et d’approfondir nos connaissances de la corrosion à 900 °C sous atmosphère oxydante d’un alliage de zirconium. Les phénomènes comme la diffusion de l’oxygène dans la zircone ne sont pas émissifs ; par contre les mécanismes de dégradation irréversibles, comme l'initiation et la propagation des fissures dans la couche de zircone, sont décelables dès leur apparition. Dans un second temps, lors de l’étude de la carburation du fer pur ou du fer pré-Oxydé, nous avons démontré que la corrosion par metal dusting qui comporte une étape d’insertion des atomes de carbone dans la matrice de fer est détectable grâce à l’émission acoustique. Il est donc envisageable de suivre ce type de dégradation au moyen de l’émission acoustique lorsqu’il affecte les équipements industriels. / High temperature corrosion of metallic alloys can cause damage to chemical and petrochemical industrial equipment. On line monitoring of the behaviour of components, which operate under corrosive atmosphere at high temperature, has become an important challenge. In order to quantify the level of damage of materials affected by corrosion, acoustic emission seems to be an interesting method due to its sensitivity and its non-Destructive aspect. Based on bibliographic supports, we have developed an experimental device combining thermogravimetric analysis with acoustic emission in order to simultaneously record the sample mass variations and the acoustic signals mainly due to the degradation of materials such as cracks formation during oxidation of metal at high temperature for example.First of all, we have studied Zircaloy-4 corrosion behavior at 900 °C under oxidant gas by means of this innovative equipment. We have demonstrated the feasibility of such a coupling method; mass measurements are not disrupted by acoustic emission chain connected to the thermobalance. Irreversible mechanisms, as cracks initiation and propagation, generate acoustic emission bursts. Analysis of the burst waveforms and of the oxidized sample cross sections allows us to attribute the acoustic events to corrosion or cooling processes. Secondary, metal dusting of pure iron at 650 °C under highly carburising gases (i-C4H10 + H2) was studied. Iron bulk degradation caused by graphite deposition and insertion has been detected using acoustic emission. This result lets us think that this technique can be adapted to monitoring of industrial equipment.