Thesis (M.Sc.(Chemistry))--University of Pretoria, 2001. / Summaries in Afrikaans and English.

Thesis (Ph.D.)--Auburn University, 2005. / Abstract. Vita. Includes bibliographic references (ℓ. 156-170)

Current body armor technologies need further improvements in their design to help reduce combat injuries of military and law enforcement personnel. Kevlar-based body armor systems have good ballistic resistance up to a certain ballistic threat level due to limitations such as decreased mobility and increased weight [1,2]. Kevlar fibers have been modified in this work using a nano-scale boron carbide coating and a marked increase in the puncture resistance has been experimentally observed. It is hypothesized that this improvement is due to the enhancement of the mechanical properties of the individual Kevlar fibers due to the nano-scale coatings. This study presents a comprehensive experimental investigation of individual Kevlar fibers based on nanoindentation to quantify the cause of the enhanced puncture resistance. The experimental setup was validated using copper wires with a diameter size in the same order of magnitude as Kevlar fibers. Results from nanoindentation did not show significant changes in the modulus or hardness of the Kevlar fibers. Scanning Electron Microscopy revealed that the coated fibers had a marked change in their surface morphology. The main finding of this work is that the boron carbide coating did not affect the properties of the individual fibers due to poor adhesion and non-uniformity. This implies that the observed enhancement in puncture resistance originates from the interaction between fibers due to the increase in roughness. The results are important in identifying further ways to enhance Kevlar puncture resistance by modifying the surface properties of fibers.

This study focused on molten salt purification processes to effectively reduce or eliminate the corrosive contaminants without altering the salt's chemistry and properties. The impurity-driven corrosion behavior of HAYNES® 230® alloy in the molten KCl-MgCl2-NaCl salt was studied at 800 ºC for 100 hours with different salt purity conditions. The H230 alloy exhibited better corrosion resistance in the salt with lower concentration of impurities. Furthermore, it was also found that the contaminants along with salt's own vaporization at high temperatures severely corroded even the non-wetted surface of the alloy. The presence of Mg in its metal form in the salt resulted in an even higher mass-loss possibly due to Mg-Ni interaction. The study also investigated the corrosion characteristics of several nickel and ferrous-based alloys in the molten KCl-MgCl2-NaCl salt. The average mass-loss was in the increasing order of C276 < SS316L < 709-RBB* < IN718 < H230 < 709-RBB < 709-4B2. The corrosion process was driven by the outward diffusion of chromium. However, other factors such as the microstructure of the alloy i.e. its manufacturing, refining, and heat-treatment processes have also shown to influence the corrosion process. Lowering the Cr content and introducing W and Mo in the alloy increased its resistance to corrosion but their non-uniform distribution in the alloy restricted its usefulness. To slow-down the corrosion process, and enhance the material properties, selected alloys were boronized and tested for their compatibility in the molten KCl-MgCl2-NaCl salt. The borided alloys exhibited better resistance to molten salt attack, where the boride layer in the exposed alloy was still intact, non-porous, and strongly adhered to the substrate. The alloys also did not show any compensation in their properties (hardness). It was also found that the boride layer always composed of an outermost silicide composite layer, which is also the weakest and undesired layer as it easily cracks, breaks, or depletes under mechanical and thermal stresses. Various different grades of "virgin" nuclear graphites were also tested in the molten KF-UF4-NaF salt to assist in the selection of tolerable or impermeable graphites for the MSR operational purposes. It was found that molten salt wettability with graphite was poor but it still infiltrated at higher pressure. Additionally, the infiltration also depended on the pore-size and porosity of the graphite. The graphite also showed severe degradation or disintegration of its structure because of induced stresses. / Doctor of Philosophy / Molten salts are considered as potential fuel and coolant candidates in MSRs because of their desirable thermophysical properties and heat-transfer capabilities. However, they pose grave challenges in material selection due to their corrosive nature, which is attributed to the impurities and their concentration (mostly moisture and oxygen-based) in the salt. This study focused on purifying the salt to reduce these contaminants without compromising its composition and properties. The influence of purification processes on the corrosion behavior of HAYNES® 230® alloy was studied in the molten chloride salt with different purity conditions. Various nickel and ferrous-based alloys were also studied for their compatibility in the molten chloride salt. This will assist in expediting the material selection process for various molten salt applications. It was observed that several factors such as alloy composition, its microstructure, impurities in the salt attribute to molten salt corrosion. It was also quite evident that corrosion in molten salts is inevitable and hence, the focus was shifted on slowing down this process by providing protective barriers in the form of coatings (i.e. boronization). The borided (coated) alloys not only improved the corrosion resistance but also enhanced and retained their properties like hardness after exposure to molten salts. Since these studies were conducted under static conditions, a more detailed investigation is needed for the selected alloys by subjecting them to extreme flow-conditions and for longer a duration of time. To achieve this objective, a forced circulation molten salt loop was designed and fabricated to conduct flow corrosion studies for alloys in molten chloride salt. Graphite is another critical component of the MSR where it is used as a moderator or reflector. Generally, molten salts exhibit poor wettability with graphite, but they can still infiltrate (graphites) at higher applied pressures, and result in the degradation or disintegration of graphite's structure, and eventually its failure in the reactor. This study provides infiltration data, and understanding of the degradation of various 'virgin' nuclear graphite grades by the molten fluoride salt. This should assist in the selection of tolerable or impermeable graphite grades for MSR operational purposes.

Les barres de commande du futur démonstrateur de réacteur à neutrons rapides refroidi au sodium (RNR – Na) nommé ASTRID sont constituées de pastilles de B4C enfermées dans une gaine en acier inoxydable AIM1 (15Cr-15Ni-0,4Ti). En service, les pastilles de B4C sont plongées dans le sodium liquide à une température allant de 500 à 600 °C. Les retours d’expérience des RNR - Na ont mis en évidence que la durée de vie des barres de commande était limitée par leur cinétique de carburation. Cependant, un phénomène de boruration des gaines a été observé lors d’essais réalisés « hors réacteur / hors irradiation ». Afin de maîtriser la durabilité des barres de commandes, il est donc nécessaire d’évaluer précisément la nature de l’interaction entre les gaines en acier et le B4C dans le sodium liquide. Ainsi, deux campagnes d’essai ont été menées : 1. Trois aciers inoxydables (AIM1, 316L et EM10) ont été exposés dans du sodium liquide fortement carburant (ac > 1) à 500, 600 et 650 °C. 2. Les mêmes nuances d’aciers ont été exposées dans du sodium liquide contenant de la poudre de B4C en excès à 500 et 600 °C. La première campagne a été réalisée pour avoir une meilleure compréhension des mécanismes et des cinétiques de carburation des barres de commande. Tout d’abord, l’état de carburation a été caractérisé finement au moyen de différentes techniques d’analyse (microsonde de Castaing, diffraction des rayons X du rayonnement synchrotron, microscopie électronique en transmission). Ensuite, la cinétique de carburation a été simulée à l’aide d’un modèle analytique simplifié de la carburation puis grâce à un outil commercial plus complet de simulation numérique de la diffusion à l’équilibre thermodynamique (DICTRA). Des écarts ont été observés entre les simulations des états de carburation réalisées avec DICTRA et les mesures expérimentales (profil de concentration en carbone et population de carbures). Afin de prédire au mieux l’état de carburation des aciers rencontré à 500 et 600 °C, il a notamment été démontré qu’il est probablement nécessaire de prendre en compte la diffusion du carbone dans les joints de grains et un écart à l’équilibre thermodynamique entre le carbone piégé dans les carbures et le carbone dissout dans la matrice. La deuxième campagne expérimentale a concerné l’étude du système : acier – B4C – Na. Des caractérisations couplées à des études thermodynamique et cinétique ont permis de proposer un mécanisme de carburation et de boruration des aciers. Après la dissolution du B4C dans le sodium, deux phénomènes ont été observés. Le bore réagit avec les aciers pour former une couche duplexe de borures à la surface (MB, M2B) et des borures dans les joints de grains du substrat. La cinétique de formation de la couche de borures dans les aciers suit une loi parabolique. Le carbone entraine une légère carburation des aciers plus en profondeur et le degré de carburation des aciers s’est avéré constant entre 250 et 3000 h d’exposition, ce qui suggère que le phénomène de carburation s’opère probablement avant la formation d’une couche continue de borures. / Pellets of boron carbide, B4C, enclosed in AIM1 (15Cr-15Ni-0.4Ti) stainless steel tubes are constitutive materials of the control rods in the future French Advanced Sodium Technological Reactor for Industrial Demonstration (ASTRID). During reactor operation, the B4C pellets are immersed in liquid sodium in the temperature range 773-873 K. Based on the feedback from operation of former Sodium Fast Reactors (SFR), the lifetime of the control rods has been shown to be limited by their carburization kinetics. Although, boriding of the steels was observed in out-ofpile studies. In order to increase the lifetime prediction of the aforementioned components in service, detailed information on the chemical interaction between the steel and B4C in liquid sodium is required. As a result, two sets of out-of-pile experiments were conducted: 1. Three stainless steels (AIM1, 316L, EM10) were exposed to highly carburizing sodium (ac > 1) at 773, 873 and 923 K. 2. The same grades were exposed to high purity B4C powder in liquid sodium at 773 and 873 K. The first campaign was performed in order to have a better understanding of the carburization phenomenology and kinetics of the control rods. The extent of carburization was evaluated. A good description of the carburization kinetics was obtained by means of two models and a simulation tool (DICTRA). The limits of the simulation tools were exposed. It was shown that the grain boundary diffusion of carbon had to be taken into account. The second set of experiments was carried out in order to study the system: steel – B4C – Na. A thorough examination of the nature of the chemical interaction was performed. The characterizations were combined with a thermodynamic and kinetic study to propose a carburization and boriding mechanism. The B4C powder dissolved in liquid sodium and reacted with the steels to form a boride layer (MB and M2B) at the surface, borides in the grain boundaries and a carburized zone underneath. The growth kinetics of the boron affected zone was shown to be parabolic. The carburization depth did not evolve between 250 and 3000 h and suggested that this phenomenon occurred during a transient stage.

As ligas do sistema Fe-Mn-Al-C constituem-se numa das famílias mais promissoras para o atendimento dos requisitos crescentes de disponibilidade de aços com altas relações resistência/peso, principalmente nas indústrias de transporte aeronáutica e automotiva, visando a redução no consumo de combustível e a consequente emissão de CO2. Suas densidades, cerca de 10% a 13% inferiores aos dos aços convencionais e a possibilidade de aumento de resistência mecânica por tratamentos de endurecimento pela precipitação de carboneto k (Fe,Mn)Al3C possibilitam a obtenção de elevadas resistências específicas. O uso de técnicas da Engenharia de Superfícies, associadas aos tratamentos térmicos adequados, podem ampliar a faixa de desempenho dessas ligas. Neste trabalho foram realizados tratamentos termoquímicos de boretação em sais fundidos, nitrocementação a plasma e cromização por pó em amostras de um aço com a composição Fe-31,2Mn-7,5Al-1,3Si-0,9C (% em peso), visando à obtenção de camadas de elevados desempenhos mecânicos e físicos. As camadas produzidas foram caracterizadas por meio de ensaios micrográficos, de dureza, desgaste e corrosão. Todos os tipos de tratamentos produziram camadas com resistências ao desgaste muito superiores às do substrato, com destaque para os tratamentos de boretação e de cromização, que produziram camadas com resistências ao desgaste cerca de nove e seis vezes superiores às do substrato, respectivamente. O tratamento de cromização produziu camada com resistência à corrosão por pites muito superior à do substrato. / The alloys of the Fe-Mn-Al-C system belong to one of the most promising families to meet the increasing requirements of availability of steels with high resistance/weight ratio, particularly in the aeronautics and automotive industries, aimed at reducing the consumption of fuel and consequent CO2 emissions. Their densities, between 10% to 13% lower than those of conventional steels, and the possibility of increased strength by hardening treatment by the precipitation of k carbides (Fe, Mn)Al3C, allow to obtain high specific resistance. The use of techniques of surface engineering, attached to suitable heat treatment, can extend the performance range of these alloys. In this work were carried out thermochemical boriding treatment in molten salts, plasma nitrocarburizing and pack chromizing in a Fe-31,2Mn 7,5Al-1,3Si-0,9C(wt%) steel, in order to obtain coatings with high mechanical and physical performances. The layers produced were characterized using micrographic, hardness, wear and corrosion tests. All treatments produced layers with wear resistance superior to that the substrate, especially the boriding and chromizing treatments, which produced layers with wear resistance around nine and six times higher than that of substrate, respectively. The chromizing treatment produced layer with pitting corrosion resistance superior to that of the substrate.

Neste trabalho estudou-se o efeito do tratamento de boretação na resistência ao desgaste, corrosão e oxidação dos aços AISI 1060 e AISI H13. As amostras dos aços foram boretadas com pó a 900 e 1000°C por 2 e 4 horas. Foram realizados ensaios de microdesgaste em máquina do tipo esfera fixa, sem uso de abrasivos, nas amostras boretadas e não boretadas. A resistência à corrosão, das amostras boretadas e não boretadas, em HCl 0.1M foi avaliada por ensaios de polarização potenciodinâmica. Ensaios de oxidação do tipo quase-isotérmica foram realizados nas amostras, utilizando temperatura de 550°C ao ar. Para todas as condições de tratamento empregadas foram formadas camadas de boretos com elevadas durezas sobre os substratos. As propriedades das camadas como dureza, espessura, morfologia da interface camada/substrato e as fases presentes, foram influenciadas pelas composições dos aços. No caso do aço AISI H13, que possui maior quantidade de elementos de liga, as camadas formadas foram mais duras, menos espessas, com interface lisa, e para todas as condições de tratamento foram formadas os compostos de boro Fe2B, FeB e CrB. Já no aço AISI 1060 as interfaces camada/substrato foram do tipo dentada e para a temperatura de boretação de 900°C apenas a fase Fe2B foi formada, aparecendo o FeB a partir da temperatura de boretação de 1000°C. A resistência ao desgaste, corrosão e oxidação dos aços boretados aumentou significativamente, sendo que em relação ao desgaste, os melhores resultados foram obtidos com as amostras boretadas a 1000°C. Quanto à oxidação, os dois aços boretados a 900°C por 2h apresentaram os melhores desempenhos, e quanto à corrosão, os parâmetros do tratamento de boretação não influenciaram significativamente os desempenhos. / In this work the effect of pack boriding on wear, corrosion and oxidation resistance of AISI 1060 and AISI H13 steels were studied. Samples of the steels were pack borided at 900 and 1000°C for periods of 2 and 4h. Fixed-ball microwear tests were performed on borided and non-borided samples, without use of abrasives. The samples corrosion resistances, in HCl 0.1M, were evaluated by potentiodynamic polarization tests. Quasiisothermal oxidation tests were performed at 550°C on air. High hard layers were formed on steels for all treatment conditions employed. The layers properties, such as hardness, thickness, layer/substrate interface morphology and phases formed, were influenced by steels compositions. For AISI H13 steel, which has a larger amount of lloying elements, the formed layers were arder, thinner, with smooth interface and for all treatments conditions the compounds Fe2B, FeB and CrB were formed. For borided AISI 1060 steel, the layer/substrate interfaces showed a saw-tooth morphology and for boriding temperature of 900°C only the Fe2B phase were formed, appearing FeB for boriding temperature of 1000°C. The wear, corrosion and oxidation resistances of borided steels significantly increased and in relation to wear, the best results were btained with the samples borided at 1000°C. In oxidation case, both steels borided at 900°C for 2h showed the best performances, and with respect to corrosion, boriding treatments parameters did not significantly affect the performances.

Made available in DSpace on 2016-12-08T17:19:17Z (GMT). No. of bitstreams: 1 Anael Krelling.pdf: 4334549 bytes, checksum: 5f6d37933553590fff7bc05b902644dc (MD5) Previous issue date: 2012-06-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work, solid boriding thermochemical treatment was carried out using Ekabor® 1-V2 and one blend as boriding agents and heat treatment of quenching and tempering of AISI H13 tool steel in order to compare and evaluate the tribological behavior and the properties acquired for four studied conditions, that were: Ekabor® powder boriding, Ekabor® powder boriding followed by quenching and tempering, boriding with a blend as boriding agent and quenched and tempered condition. Sliding wear tests were performed in pin-on-disc apparatus in order to evaluate the friction coefficient and the volume of material removed (measured with the aid of a profiling equipment). After the wear tests the samples were transversally cut for metallographic evaluation by optical and scanning electron microscopy. X-ray diffraction was used to confirm the formation of borided layer. The results showed that the boriding treatments, regardless the boriding agent used, are effective in increasing wear resistance. The thickness of borided layer was greater for boriding with Ekabor® powder than the blend agent, this one, nevertheless, showed significant improvement in wear resistance compared to the quenched and tempered condition. There are several wear mechanisms that take place in the sliding wear test but the adhesive wear mechanism was reduced by boriding treatment. / Neste trabalho foram realizados tratamentos termoquímicos de boretação por via sólida com pó comercial Ekabor® 1-V2 e mistura boretante, além de tratamentos térmicos de têmpera e revenimento em aço ferramenta AISI H13 com o intuito de comparar e avaliar o comportamento tribológico e as propriedades adquiridas para quatro condições estudadas, sendo elas: boretação com pó Ekabor®, boretação com pó Ekabor® seguida de têmpera e revenimento, boretação com uma mistura como agente boretante e condição apenas temperada e revenida. Testes de desgaste por deslizamento foram realizados em tribômetro de pino-sobre-disco para avaliação do coeficiente de atrito e volume de material removido (avaliado com o auxílio de perfilômetro). Após os ensaios de desgaste as amostras foram cortadas transversalmente para avaliação metalográfica através de microscopia óptica, microscopia eletrônica de varredura e microdureza. Os mecanismos de desgaste foram analisados por microscopia eletrônica de varredura. Difratometria de raios-X foi utilizada para a comprovação da formação da camada de boretos. Os resultados mostraram que o tratamento de boretação, independentemente do agente boretante utilizado, é eficaz no aumento da resistência ao desgaste. A espessura das camadas de boretos foi maior para boretação realizada com pó Ekabor® em comparação com a mistura boretante, esta última, apesar disto, apresentou melhoria significativa em comparação com a condição de têmpera e revenimento. Vários são os mecanismos de desgaste que ocorrem no ensaio por deslizamento sendo que o mecanismo de desgaste por adesão foi reduzido com a realização dos tratamentos de boretação.

Made available in DSpace on 2016-12-08T17:19:21Z (GMT). No. of bitstreams: 1 Mario Augusto Morozo.pdf: 3275631 bytes, checksum: 146bb363d630204d1f0a795658dce502 (MD5) Previous issue date: 2013-08-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work, solid boriding thermochemical treatment was carried out using Ekabor® 1-V2 and heat treatment for hardening and tempering hot work tool steel AISI H13 in order to compare and evaluate the tribological behavior and properties acquired for four conditions studied, namely: boriding with Ekabor used powder ® 1-V2, boriding with Ekabor new powder ® 1-V2, quenched and tempered, and as supplied (annealed). Fixed-ball Microabrasive wear tests were performed to evaluate the steady-state wear, wear coefficient, wear volume and friction coefficient. After wear tests, the samples were transversally cut for metallographic evaluations by optical microscopy and microhardness. The wear mechanisms were analyzed by scanning electron microscopy. X-ray diffraction was used to confirm the formation of a borided layer. The results showed that the layer formed after the boriding with Ekabor ® 1-V2 used powder had become quite uneven, which may directly influence in reducing the wear resistance. The same irregularity was detected after boriding with Ekabor® 1-V2 new powder. However, for this second condition, in all áreas, thicker layer was noted. The quenched and tempered condition had the highest average wear coefficient, followed by the annealed condition and boride powder Ekabor ® 1-V2 used, whose coefficients were virtually identical. The boride with Ekabor new powder ® 1-V2 had the lowest average wear coefficient. / Neste trabalho foi realizado tratamento termoquímico de boretação por via sólida com pó comercial Ekabor® 1-V2 e tratamento térmico de têmpera e revenimento em aço ferramenta para trabalho a quente AISI H13 com o intuito de comparar e avaliar o comportamento tribológico e as propriedades adquiridas para quatro condições estudadas, sendo elas: boretação com pó Ekabor® 1-V2 usado, boretação com pó Ekabor® 1-V2 novo, condição temperada e revenida e condição como fornecida (recozida). Ensaios de desgaste microabrasivo foram realizados em equipamento de microabrasão do tipo esfera fixa para avaliação da obtenção do regime permanente de desgaste, coeficiente de desgaste, volume de desgaste e coeficiente de atrito. Após os ensaios de desgaste as amostras foram cortadas transversalmente para avaliação metalográfica através de microscopia óptica e microdureza. Os mecanismos de desgaste foram analisados por microscopia eletrônica de varredura. Difratometria de raios-X foi utilizada para a comprovação da formação da camada de boretos. Os resultados mostraram que a camada formada após a boretação com pó Ekabor® 1-V2 usado apresentou-se bastante irregular, o que pode ter influenciado diretamente na redução da resistência ao desgaste. A mesma irregularidade foi verificada após a boretação com pó Ekabor® 1-V2 novo. Entretanto, para esta segunda condição, em todas as regiões se observou uma espessura de camada maior. A condição temperada e revenida apresentou o maior coeficiente de desgaste médio, sendo seguida pelas condições recozida e boretada com pó Ekabor® 1-V2 usado, cujos coeficientes foram praticamente idênticos. A condição boretada com pó Ekabor® 1-V2 novo apresentou o menor coeficiente de desgaste médio.

Neste trabalho estudou-se o efeito do tratamento de boretação na resistência ao desgaste, corrosão e oxidação dos aços AISI 1060 e AISI H13. As amostras dos aços foram boretadas com pó a 900 e 1000°C por 2 e 4 horas. Foram realizados ensaios de microdesgaste em máquina do tipo esfera fixa, sem uso de abrasivos, nas amostras boretadas e não boretadas. A resistência à corrosão, das amostras boretadas e não boretadas, em HCl 0.1M foi avaliada por ensaios de polarização potenciodinâmica. Ensaios de oxidação do tipo quase-isotérmica foram realizados nas amostras, utilizando temperatura de 550°C ao ar. Para todas as condições de tratamento empregadas foram formadas camadas de boretos com elevadas durezas sobre os substratos. As propriedades das camadas como dureza, espessura, morfologia da interface camada/substrato e as fases presentes, foram influenciadas pelas composições dos aços. No caso do aço AISI H13, que possui maior quantidade de elementos de liga, as camadas formadas foram mais duras, menos espessas, com interface lisa, e para todas as condições de tratamento foram formadas os compostos de boro Fe2B, FeB e CrB. Já no aço AISI 1060 as interfaces camada/substrato foram do tipo dentada e para a temperatura de boretação de 900°C apenas a fase Fe2B foi formada, aparecendo o FeB a partir da temperatura de boretação de 1000°C. A resistência ao desgaste, corrosão e oxidação dos aços boretados aumentou significativamente, sendo que em relação ao desgaste, os melhores resultados foram obtidos com as amostras boretadas a 1000°C. Quanto à oxidação, os dois aços boretados a 900°C por 2h apresentaram os melhores desempenhos, e quanto à corrosão, os parâmetros do tratamento de boretação não influenciaram significativamente os desempenhos. / In this work the effect of pack boriding on wear, corrosion and oxidation resistance of AISI 1060 and AISI H13 steels were studied. Samples of the steels were pack borided at 900 and 1000°C for periods of 2 and 4h. Fixed-ball microwear tests were performed on borided and non-borided samples, without use of abrasives. The samples corrosion resistances, in HCl 0.1M, were evaluated by potentiodynamic polarization tests. Quasiisothermal oxidation tests were performed at 550°C on air. High hard layers were formed on steels for all treatment conditions employed. The layers properties, such as hardness, thickness, layer/substrate interface morphology and phases formed, were influenced by steels compositions. For AISI H13 steel, which has a larger amount of lloying elements, the formed layers were arder, thinner, with smooth interface and for all treatments conditions the compounds Fe2B, FeB and CrB were formed. For borided AISI 1060 steel, the layer/substrate interfaces showed a saw-tooth morphology and for boriding temperature of 900°C only the Fe2B phase were formed, appearing FeB for boriding temperature of 1000°C. The wear, corrosion and oxidation resistances of borided steels significantly increased and in relation to wear, the best results were btained with the samples borided at 1000°C. In oxidation case, both steels borided at 900°C for 2h showed the best performances, and with respect to corrosion, boriding treatments parameters did not significantly affect the performances.