Mémoire de DEA : Chimie : Lille 1 : 2002. / Sur la p. de titre : DEA-Structure et dynamique des systèmes réactifs, PERF-Procédés d'élaboration de revêtements fonctionnels. Bibliogr. f. : 21-22. Annexes.

Thèse de doctorat : Spectrochimie, molécules, solides, réactivité : Lille 1 : 2001. / Résumé en français et en anglais. Bibliogr. en fin de chapitres.

Thèse de doctorat : Chimie organique : Lille 1 : 2002. / N° d'ordre (Lille) : 3249. Résumé en français et en anglais. Bibliogr. en fin de chapitres. Glossaire.

Fire presents a great risk to humans and their possessions. Polymeric compounds are highly flammable and compounds are added to increase their fire resistance. These additives are referred to as flame retardants. Intumescent flame retardants are systems that form a carbon rich foam on the surface of the polymer during thermal degradation. A new field of metal catalysed intumescence is discussed in this document. The influence of both the metal ion and organic backbone of polyhydroxylcarboxylic acid metal salts was studied. The intumescence and foaming properties of selected salts were studied in more detail. Gluconic acid proved to be the best intumescent and showed the best combination of carbon char yield, foam structure and volume, stability and open flame characteristics. As a general rule of thumb, the char volume and structure improved with an increased number of hydroxyl groups in the compound. Carbon char yield increased with an increase in the number of hydroxyl groups for a constant number of carbons in the complex. The number of acid groups in the compound played a lesser role in intumescence. Most metal complexes catalyse intumescent decomposition of polyhydric compounds such as polyhydroxylcarboxylic acids and pentaerythritol. The reduction in the volatilisation losses implies that the metal cations catalyse carbonisation reactions in the polyhydroxyl compound. Unfortunately, the resultant carbon-foams are unstable: the metal residues also catalyse the further oxidative degradation of the char. The low thermal stability of the compositions tested, as well as the afterglow effect makes them unsuitable for use as flame retardant additives in plastics. From the studies of the different metal complexes with acetylacetone and gluconic acid, it was concluded that the calcium ion exhibited the most promise. When pyrolysed in air with an open gas flame or in a furnace, calcium gluconate monohydrate produces voluminous foam. The foam is of a closed cell structure, densely packed and has no mechanical strength. The cell walls are very thin (5 to 50 nm) and the cells are between 50 µm and 200 µm in size. If the sample is compressed before heating, the resultant foam produced during pyrolysis is less voluminous than that of the loose powder. The BET surface area of the calcium gluconate monohydrate foamed at 300°C for 5 min. is 16.0 m2/g. The foam produced after 5 min heating at 300°C has a thermal conductivity similar to standard polystyrene foam. Adding leached silica to the calcium gluconate monohydrate increases mechanical strength of the foam, but influences the foam volume negatively. The optimum silica level was calculated to be 1:1 gluconate to silica on a mole ratio (11.8% SiO2 by mass). The mechanical strength of the foam can also be increased with the addition of expandable graphite. The graphite has a lesser influence on the foam volume than the silica, but also reduces the foam volume. However, the addition of the expandable graphite gives the sample more .opening. force, as the foam volume of a compressed sample pyrolysed, is similar to that of the heated loose powder. Calcium gluconate monohydrate starts to degrade at 120°C, losing its crystal water and shows a mass loss of 4% at 180°C. The exothermic peak (shown in the DSC/TGA data) associated with the metal catalysed carbon oxidation (afterglow) is observed at 570°C in air. For the calcium gluconate monohydrate the transition from CaCO3 to CaO occurs above 650°C in air. It has been shown that the foaming of polyhydroxylcarboxylic acids is due to the formation of water vapour during degradation. For calcium gluconate monohydrate, foaming starts due to the loss of crystal water and is continued by the loss of hydroxyl groups as water. The bulk of the foaming is due to the second reaction. It has been shown that compounds with crystal waters produce a more voluminous and lower density foam. The foam is an amorphous carbon rich residue. The molecular mass of the carbon residue increases up to a heating temperature of 300°C. This implies that the carbon residue crosslinks during formation, forming a stretchable cell wall for the foam. Compounds with a .free. hydroxyl group at the end of the carbon chain produce a foam of larger volume and lower density. This supports the crosslinking theory. The foam produced when calcium gluconate monohydrate is heated for 5 min at 300°C in air is of very low density . 2.5 kg/m3 based on residual mass. The density of the calcium gluconate monohydrate pyrolysed at 1000°C for 5 min in air yields a CaO with a density of 20 kg/m3 . This implies that the high temperature pyrolysis of calcium gluconate can produce an inorganic oxide of low bulk density and possible high specific surface area. The BET surface area of CaCO3 from the gluconate pyrolysed at 600°C is ~ 12 m2 /g. An intumescent coating containing calcium gluconate monohydrate, leached silica and expandable graphite as a system was prepared and compared to commercial formulations. This gluconate based system was at least as efficient as the commercial formulations when painted on balsa wood planks or aluminium plates. On cardboard sheets it did not perform as well as the commercial systems. More work should be done to overcome the afterglow effect observed with metal- based intumescent systems. The crystal structure of calcium gluconate monohydrate should be determined as to understand the decomposition better. It is unclear whether the decomposition is catalysed inter- or intramolecularly. / Thesis (PhD(Chemical Engineering))--University of Pretoria, 2005. / Chemical Engineering / unrestricted

Reproduction de : Thèse de doctorat : Structure et dynamique des systèmes réactifs : Lille 1 : 2005. / N° d'ordre (Lille 1) : 3721. Résumé en français et en anglais. Titre provenant de la page de titre du document numérisé. Bibliogr. à la suite de chaque chapitre.

Reproduction de : Thèse de doctorat : Spectrochimie, molécules, solides, réactivité : Lille 1 : 2001. / Label européen. Résumé en français et en anglais. Titre provenant de la page de titre du document numérisé. Bibliogr. en fin de chapitres.

Master of Science / Department of Horticulture, Forestry, and Recreation Resources / Kimberly A. Williams / Ivy geranium (Pelargonium peltatum L’Herr ex. Ait.) and tomato (Solanum lycopersicum L.) are two economically important greenhouse crops known to be affected by non-pathogenic lesions on leaf tissues. These physiological disorders are often termed edema (oedema) or intumescences, but several other names have been used including enations, non-pathogenic galls or tumors, and neoplasms. These lesions, characterized by small protrusions on leaf tissues that become necrotic over time, are considered to be the result of environmental factors. Our research focused on determining what environmental factors affect these disorders on ivy geranium and tomato. The physiological disorder of ivy geranium is thought to be the result of water uptake exceeding transpiration, resulting in a build-up of water and solutes in leaf tissue that results in the blister-like protrusions in the epidermal layer. Current convention suggests that susceptible plants be grown in an environment that promotes transpiration with low humidity and infrequent watering. Over four experiments, we evaluated the effects of four root medium water contents, five rates of supplemental calcium application and two vapor pressure deficit (VPD) environments on three cultivars of ivy geranium. Our results indicate that high root medium water contents do not increase the incidence of edema on ivy geranium, but increase overall plant growth. Supplemental calcium had no affect on edema or growth, while our VPD results were inconclusive. These results suggest that current convention regarding cultural practices that abate the disorder be revisited. In tomato var. hirsutum ‘Maxifort’, the physiological disorder is characterized by individual epidermal cells swelling, which is unlike the disorder in ivy geranium where solutes build up across a group of epidermal cells. The environmental factors we focused on were two root medium water contents and supplemental UVB light. Our results suggest that root medium water content may play a role in development of tomato intumescences based on visual observation, and UVB light supplementation helps prevent the lesions from forming.

As tintas intumescentes vêm se tornando uma ótima alternativa para a proteção do aço contra o fogo. No entanto, o aço estrutural é aplicado em diversos setores da indústria, incluindo plataformas offshore de petróleo e gás e refinarias petroquímicas. Estas estruturas de alto desempenho ficam expostas a ambientes agressivos, o que torna necessário o desenvolvimento de tintas capazes de proteger o aço. Neste trabalho, foram preparadas tintas intumescentes epóxi formuladas com pó de gengibre e com casca de café como fonte de carbono e com trifenil fosfato (TPP) e fosfato de zinco (FZn) como fonte de fósforo. O objetivo principal deste trabalho foi desenvolver um sistema intumescente contendo compostos vegetais eficiente na proteção contra o fogo e capaz de proteger o substrato metálico contra a corrosão em ambiente salino. A avaliação foi realizada através de ensaio de resistência ao fogo (antes e após imersão em NaCl 3,5%), análise termogravimétrica (TGA), espectroscopia no infravermelho (FTIR), viscosidade Brookfield, aderência, ensaio estático de imersão, microscopia óptica (MO), microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), pirólise acoplada à cromatografia gasosa e à espectrometria de massas (Py-GC/MS), espectroscopia de impedância eletroquímica (EIE), metalografia e microdureza Vickers. Os compostos vegetais apresentaram potencial de aplicação como fonte de carbono em sistemas intumescentes, enquanto que o FZn foi eficiente substituindo o TPP como fonte de fósforo. O sistema contendo gengibre e TPP apresentou os melhores resultados gerais, mantendo o fenômeno de intumescência após imersão em solução salina e apresentando a melhor proteção contra a corrosão dentre as amostras de tinta intumescente. Por fim, o revestimento contendo TPP apresentou propriedades anticorrosivas superiores ao FZn na aplicação em sistemas intumescentes. / The intumescent coating have become a great alternative for the protection of steel against fire. However, structural steel is applied in several industry sectors, including offshore oil and gas platforms and petrochemical refineries. These high performance structures are exposed to aggressive environments, which makes it necessary to develop coatings capable of protecting steel. In this work, epoxy intumescent coatings formulated with ginger powder and coffee husk as carbon source and with triphenyl phosphate (TPP) and zinc phosphate (ZnP) as phosphorus source were prepared. The main objective of this work was to develop an intumescent system containing vegetable compounds efficient in fire protection and able to protect the metal substrate against corrosion in saline environment. The evaluation was performed by fire resistance test (before and after immersion in NaCl 3.5%), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR), Brookfield viscosity, adhesion tests, static immersion test, optical microscopy (OM), Scanning electron microscopy (SEM), X-ray diffraction (XRD), pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC / MS), electrochemical impedance spectroscopy (EIS), metallography and Vickers microhardness. Vegetable compounds presented potential as a carbon source in intumescent systems, while ZnP was efficient replacing TPP as a source of phosphorus. The system containing ginger and TPP presented the best overall results, maintaining the intumescence phenomenon after immersion in saline solution and presenting the best protection against corrosion among the intumescent coating samples. Finally, the coating containing TPP presented anticorrosive properties superior to FZn in the application in intumescent systems.

As tintas intumescentes vêm se tornando uma ótima alternativa para a proteção do aço contra o fogo. No entanto, o aço estrutural é aplicado em diversos setores da indústria, incluindo plataformas offshore de petróleo e gás e refinarias petroquímicas. Estas estruturas de alto desempenho ficam expostas a ambientes agressivos, o que torna necessário o desenvolvimento de tintas capazes de proteger o aço. Neste trabalho, foram preparadas tintas intumescentes epóxi formuladas com pó de gengibre e com casca de café como fonte de carbono e com trifenil fosfato (TPP) e fosfato de zinco (FZn) como fonte de fósforo. O objetivo principal deste trabalho foi desenvolver um sistema intumescente contendo compostos vegetais eficiente na proteção contra o fogo e capaz de proteger o substrato metálico contra a corrosão em ambiente salino. A avaliação foi realizada através de ensaio de resistência ao fogo (antes e após imersão em NaCl 3,5%), análise termogravimétrica (TGA), espectroscopia no infravermelho (FTIR), viscosidade Brookfield, aderência, ensaio estático de imersão, microscopia óptica (MO), microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), pirólise acoplada à cromatografia gasosa e à espectrometria de massas (Py-GC/MS), espectroscopia de impedância eletroquímica (EIE), metalografia e microdureza Vickers. Os compostos vegetais apresentaram potencial de aplicação como fonte de carbono em sistemas intumescentes, enquanto que o FZn foi eficiente substituindo o TPP como fonte de fósforo. O sistema contendo gengibre e TPP apresentou os melhores resultados gerais, mantendo o fenômeno de intumescência após imersão em solução salina e apresentando a melhor proteção contra a corrosão dentre as amostras de tinta intumescente. Por fim, o revestimento contendo TPP apresentou propriedades anticorrosivas superiores ao FZn na aplicação em sistemas intumescentes. / The intumescent coating have become a great alternative for the protection of steel against fire. However, structural steel is applied in several industry sectors, including offshore oil and gas platforms and petrochemical refineries. These high performance structures are exposed to aggressive environments, which makes it necessary to develop coatings capable of protecting steel. In this work, epoxy intumescent coatings formulated with ginger powder and coffee husk as carbon source and with triphenyl phosphate (TPP) and zinc phosphate (ZnP) as phosphorus source were prepared. The main objective of this work was to develop an intumescent system containing vegetable compounds efficient in fire protection and able to protect the metal substrate against corrosion in saline environment. The evaluation was performed by fire resistance test (before and after immersion in NaCl 3.5%), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR), Brookfield viscosity, adhesion tests, static immersion test, optical microscopy (OM), Scanning electron microscopy (SEM), X-ray diffraction (XRD), pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC / MS), electrochemical impedance spectroscopy (EIS), metallography and Vickers microhardness. Vegetable compounds presented potential as a carbon source in intumescent systems, while ZnP was efficient replacing TPP as a source of phosphorus. The system containing ginger and TPP presented the best overall results, maintaining the intumescence phenomenon after immersion in saline solution and presenting the best protection against corrosion among the intumescent coating samples. Finally, the coating containing TPP presented anticorrosive properties superior to FZn in the application in intumescent systems.

As tintas intumescentes vêm se tornando uma ótima alternativa para a proteção do aço contra o fogo. No entanto, o aço estrutural é aplicado em diversos setores da indústria, incluindo plataformas offshore de petróleo e gás e refinarias petroquímicas. Estas estruturas de alto desempenho ficam expostas a ambientes agressivos, o que torna necessário o desenvolvimento de tintas capazes de proteger o aço. Neste trabalho, foram preparadas tintas intumescentes epóxi formuladas com pó de gengibre e com casca de café como fonte de carbono e com trifenil fosfato (TPP) e fosfato de zinco (FZn) como fonte de fósforo. O objetivo principal deste trabalho foi desenvolver um sistema intumescente contendo compostos vegetais eficiente na proteção contra o fogo e capaz de proteger o substrato metálico contra a corrosão em ambiente salino. A avaliação foi realizada através de ensaio de resistência ao fogo (antes e após imersão em NaCl 3,5%), análise termogravimétrica (TGA), espectroscopia no infravermelho (FTIR), viscosidade Brookfield, aderência, ensaio estático de imersão, microscopia óptica (MO), microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), pirólise acoplada à cromatografia gasosa e à espectrometria de massas (Py-GC/MS), espectroscopia de impedância eletroquímica (EIE), metalografia e microdureza Vickers. Os compostos vegetais apresentaram potencial de aplicação como fonte de carbono em sistemas intumescentes, enquanto que o FZn foi eficiente substituindo o TPP como fonte de fósforo. O sistema contendo gengibre e TPP apresentou os melhores resultados gerais, mantendo o fenômeno de intumescência após imersão em solução salina e apresentando a melhor proteção contra a corrosão dentre as amostras de tinta intumescente. Por fim, o revestimento contendo TPP apresentou propriedades anticorrosivas superiores ao FZn na aplicação em sistemas intumescentes. / The intumescent coating have become a great alternative for the protection of steel against fire. However, structural steel is applied in several industry sectors, including offshore oil and gas platforms and petrochemical refineries. These high performance structures are exposed to aggressive environments, which makes it necessary to develop coatings capable of protecting steel. In this work, epoxy intumescent coatings formulated with ginger powder and coffee husk as carbon source and with triphenyl phosphate (TPP) and zinc phosphate (ZnP) as phosphorus source were prepared. The main objective of this work was to develop an intumescent system containing vegetable compounds efficient in fire protection and able to protect the metal substrate against corrosion in saline environment. The evaluation was performed by fire resistance test (before and after immersion in NaCl 3.5%), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR), Brookfield viscosity, adhesion tests, static immersion test, optical microscopy (OM), Scanning electron microscopy (SEM), X-ray diffraction (XRD), pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC / MS), electrochemical impedance spectroscopy (EIS), metallography and Vickers microhardness. Vegetable compounds presented potential as a carbon source in intumescent systems, while ZnP was efficient replacing TPP as a source of phosphorus. The system containing ginger and TPP presented the best overall results, maintaining the intumescence phenomenon after immersion in saline solution and presenting the best protection against corrosion among the intumescent coating samples. Finally, the coating containing TPP presented anticorrosive properties superior to FZn in the application in intumescent systems.