<p> This thesis is concerned with the cooperative growth problem of the discontinuous precipitation reaction. Previous theories are examined, and the kinetic details of a model, which assumes the existence of a metastable monotectoid reaction and the adherence & local equilibrium, are derived. As with other attempt to describe the parameters of duplex growth situations we cannot find a unique relation between the rate of growth and the lamellar spacing. The various optimal or variational procedures used to remove this degree of freedom are considered. The Cu-In system is subject to quantitative experimental study, and the extent of interference of the concurrent general precipitation reaction is determined. Finally the kinetic data and auxiliary information are used to test the various theories. </p> / Thesis / Doctor of Philosophy (PhD)

[pt] Este trabalho é uma investigação da microestrutura e cinética dos fenômenos de precipitação que ocorrem na Liga 33 (Fe-Ni-Cr-Mo-Cu-N), sistema metálico desenvolvido pela Krupp VDM com o intuito de suportar altas temperaturas e ambiente corrosivo. A Liga 33 incorre precipitação contínua e descontínua simultaneamente, como resultado do tratamento de envelhecimento realizado numa faixa de temperatura correspondente àquela que o material atinge quando submetido a um processo de soldagem. A caracterização microestrutural foi realizada por microscopia ótica, microscopia eletrônica de varredura, e microscopia eletrônica de transmissão, incluindo microanálise, devido à ordem de grandeza nanométrica das fases precipitadas. A precipitação descontínua ocasiona uma estrutura lamelar no contorno dos grãos, resultado do crescimento cooperativo entre as lamelas, envolvendo átomos substitucionais (Cr, por exemplo) e intersticiais (N). A precipitação contínua ocorre no interior dos grãos gerando precipitados com diferentes morfologias. A microanálise revela que os produtos gerados em ambas as reações crescem competindo pelo Cr. Uma análise cinética- morfológica aponta para a natureza não estacionária da reação descontínua, que sofre gradativa diminuição de sua taxa de transformação, até ser totalmente paralisada. / [en] This work is an investigation of the microstructure and kinetics of the phenomena occurring inside Alloy 33 (Fe-Ni- Cr-Mo-Cu-N), a metallic system developed by Krupp VDM to endure high temperatures and corrosive environment. Alloy 33 incurs continuous and discontinuous precipitation simultaneously, as a result of the aging treatment induced in a temperature range correspondent to the one of a welding process in the referred material. The microstructural characterization was performed by optical microscopy, scanning electron microscopy and transmission electron microscopy, including microanalysis, due to the nanometric nature of the precipitated phases. Discontinuous precipitation produces a lamellar structure along grain boundaries as a result of a cooperative growth between the lamellae, involving substitucional and interstitial atoms, Cr and N respectively. Continuous precipitation occurs inside grains, generating precipitates with different morphologies. Microanalysis reveals that products of both precipitation reactions grow competing for Cr. A kinetic-morphological analysis points to the non-stationary characteristic of the discontinuous precipitation, where the transformation rate diminishes until it stops completely, as aging occurs.

The primary intention with this Doctoral thesis is to fillin the knowledge gaps and raise the level of understandingregarding the different metal dusting mechanisms in general andexplain the process in detail for high alloyed materials.Considerable effort is put into identifying the driving forcesand elucidating the diffusional processes in metal dusting. The results are based on a series of long-term laboratory exposures of stainless steels and high-performance commercial alumina-forming Fe- and Ni-base alloys in synthesis gasmixtures, plus a separate shorter study on ultra pure iron. ANi-base alloy was also investigated after a two years field exposure in a methanol plant. Post exposure metallographic examinations and analysis aswell as thermodynamic calculations were made in order toidentify and describe the operating metal dusting mechanisms.Two main mechanisms were previously used to explain metaldusting, one on the basis of decomposition of metastable carbides (Type I) the other on graphite formation (TypeII). A new metal dusting mechanism has been identified in this Thesis which appears on high alloyed steels and Ni-base alloys,an active corrosion induced by carbon and oxygen, denoted TypeIII. Both the mechanisms and the type of corrosion products were consistent with the thermodynamic conditions of the material under the influence of a carbon and oxygen gradient.It was shown that this mechanism not only accelerates the metaldusting process, in fact, it determines the overall metaldusting kinetics on stainless steels and Ni-base alloys. Another feature, which may occur at temperatures where metalbulk and even static grain boundary diffusion is too slow forexplaining the metal dusting corrosion process, was identifiedon a Ni-base alloy. It involves a fast growing cellular structure with discontinuous precipitated carbides whichprovides fast metal dusting kinetics by the Type IIImechanism. A Type IV metal dusting mechanism, continued fragmentationby graphitization until nano-sized particles are formed andcatalyse carbon nanotube formation is also described. Thesteady state process and the driving force for metal dusting onpure iron was identified and described. With these additional processes it is now possible to extendour understanding of the metal dusting processes to a widerange of engineering alloys. / QC 20100825

Die Cu – Ag - Mikroverbund – Werkstoffe besitzen das Potenzial die gegensätzlichen Anforderungen an das Leitermaterial für den Einsatz in einem Hochfeldmagneten, wie hohe Festigkeit bei gleichzeitig hoher elektrischen Leitfähigkeit und ausreichender Verformbarkeit, zu erfüllen. Außerdem bieten diese Werkstoffe gegenüber den anderen, die dafür in Frage kommen können, den großen technologischen Vorteil einer konventionellen schmelzmetallurgischen Herstellung. Jedoch wurde bisher dafür eine sehr aufwändige Technologie verwendet, die die Herstellung des Leitermaterials nur im Labormaßstab ermöglicht. Die vorliegende Arbeit befasst sich mit einer Technologie der Herstellung von Leitern, die den Anforderungen für den Einsatz in einem Hochfeldmagneten genügen können und in einem großtechnischen Maßstab verfügbar sind. Der Schwerpunkt der Leiterherstellung aus Cu – Ag - Legierung lag in der Einstellung der geeigneten Mikrostruktur über metallkundliche Mechanismen vor der Drahterzeugung. Hierfür wurden während der einzelnen Prozessschritten die Gefügeentwicklung und für die Anwendung relevante Eigenschaften der Legierungen in binären Cu – Ag – Legierungen und in ternären Cu – Ag -X –Legierungen untersucht. Darüber hinaus wurde der Einfluss der Mikrostruktur und der Zusammensetzung auf die mechanischen und elektrischen Eigenschaften der Drähte ermittelt sowie eine Korrelation zwischen Mikrostruktur und elektrischen Eigenschaften aufgestellt.

Die Cu – Ag - Mikroverbund – Werkstoffe besitzen das Potenzial die gegensätzlichen Anforderungen an das Leitermaterial für den Einsatz in einem Hochfeldmagneten, wie hohe Festigkeit bei gleichzeitig hoher elektrischen Leitfähigkeit und ausreichender Verformbarkeit, zu erfüllen. Außerdem bieten diese Werkstoffe gegenüber den anderen, die dafür in Frage kommen können, den großen technologischen Vorteil einer konventionellen schmelzmetallurgischen Herstellung. Jedoch wurde bisher dafür eine sehr aufwändige Technologie verwendet, die die Herstellung des Leitermaterials nur im Labormaßstab ermöglicht. Die vorliegende Arbeit befasst sich mit einer Technologie der Herstellung von Leitern, die den Anforderungen für den Einsatz in einem Hochfeldmagneten genügen können und in einem großtechnischen Maßstab verfügbar sind. Der Schwerpunkt der Leiterherstellung aus Cu – Ag - Legierung lag in der Einstellung der geeigneten Mikrostruktur über metallkundliche Mechanismen vor der Drahterzeugung. Hierfür wurden während der einzelnen Prozessschritten die Gefügeentwicklung und für die Anwendung relevante Eigenschaften der Legierungen in binären Cu – Ag – Legierungen und in ternären Cu – Ag -X –Legierungen untersucht. Darüber hinaus wurde der Einfluss der Mikrostruktur und der Zusammensetzung auf die mechanischen und elektrischen Eigenschaften der Drähte ermittelt sowie eine Korrelation zwischen Mikrostruktur und elektrischen Eigenschaften aufgestellt.

[pt] A presente tese tem como objetivo estudar as reações descontínuas que ocorreram nos contornos de grão (CG) sob condições de envelhecimento a altas temperaturas e identificar as fases que precipitam em função do tempo em uma liga de alto teor de Cr e Ni – Liga 33, tendo em vista o efeito destas transformações nas potenciais aplicações em indústrias de alto desempenho. Amostras na condição como recebida foram submetidas a tratamentos isotérmicos de envelhecimento a 700 graus C, 800 graus C e 900 graus C. Ênfase foi dada ao estudo do envelhecimento a 800 graus C em intervalos de tempo entre 10 minutos e 100 horas com o objetivo de promover fenômenos de precipitação nos modos convencional e descontínua. A caracterização microestrutural foi realizada por microscopia óptica (MO), microscopia eletrônica de varredura (MEV) analítica por espectroscopia por dispersão de energia de raios-X (XEDS), difração de elétrons retroespalhados (EBSD) e microscopia eletrônica de transmissão (MET) no modo convencional, utilizando contraste de difração, e no modo analítico (STEM/XEDS). Resultados obtidos por STEM/XEDS e difração de elétrons mostraram que a transformação descontínua, pela partição de solutos, gera colônias de precipitação descontínua (PD) concomitante à migração do CG e resulta na precipitação de cinco diferentes fases dentro de uma mesma colônia de PD: (1) carbeto-M(23)C(6) rico em Cr com estrutura CFC; (2) fase-eta enriquecida em Si com estrutura cúbica-diamante; (3) fase alfa rica em Cr com estrutura CCC; (4) fase intermetálica sigma com estrutura tetragonal e (5) nitreto-M(2)N rico em Cr com estrutura hexagonal. Em geral, as colônias de PD na Liga 33 evoluem no envelhecimento seguindo a sequência, a saber: nos estágios iniciais do processo ocorre precipitação intergranular (carbeto-M(23)C(6) e fase-eta) no CG original; com o aumento no tempo de envelhecimento, os contornos migraram alimentados pela difusão de soluto num processo conhecido como DIGM (diffusion-induced grain boundary migration), enquanto precipitados da fase alfa-Cr nuclearam adjacente ao CG e cresceram com morfologia lamelar acompanhando a migração do contorno, desenvolvendo, assim, as colônias de PD. Eventualmente, a fase-eta também precipita no interior da colônia e na frente de reação. Nos estágios finais do processo de crescimento das colônias de PD ocorre a formação da fase-sigma na frente de reação da PD e, posteriormente, a formação do nitreto-M(2)N na frente de reação e dentro da colônia. Foi verificado que a reação de PD é controlada, primeiramente, pela difusão de CG do Cr e, com o tempo de reação pela difusão de volume do Cr, o que resultou em um crescimento no estado não-estacionário da reação. Além da ocorrência de cinco fases precipitadas dentro da mesma colônia, outra característica marcante da reação de PD na Liga 33 refere-se à consistente evidência que a fase inicialmente precipitada nos CG (carbeto-M(23)C(6) é diferente da fase precipitado com morfologia lamelar (fase alfa-Cr) dentro da colônia. Tal observação constitui a primeira evidência para o fenômeno de PD envolvendo colônias multi-fases em materiais multicomponentes estruturais. / [en] This thesis aims at study the discontinuous reactions taking place at grain boundaries (GB) under high-temperature aging conditions and to identify the precipitated phases as a function of the time in a Cr-Fe-Ni alloy - Alloy 33, in view of the deleterious effect of these transformations on potential applications of this alloy in high-performance industries. Samples in the as-received condition were submitted to isothermal aging treatments at 700 C degrees, 800 C degrees and 900 C degrees. Emphasis was given to the study of aging at 800 C degrees in time intervals between 10 minutes and 100 hours in order to promote precipitation phenomena in the conventional and discontinuous modes. The microstructural characterization was carried out by light optical microscopy (LOM), analytical scanning electron microscopy (SEM) by X-ray energy dispersive spectroscopy (XEDS), electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) under conventional mode using diffraction contrast and analytical mode (STEM/XEDS). Results obtained by STEM/XEDS and electron diffraction revealed that the discontinuous transformation, by solutes partitioning, generates discontinuous precipitation (DP) colonies concomitant with GB migration and results in the precipitation of five different phases within a single DP colony: (1) Cr-rich M(23)C(6)-carbide with FCC structure, (2) Si-enriched eta-phase with diamond-cubic structure, (3) Cr-rich alpha-phase with BCC structure, (4) intermetallic sigma-phase with tetragonal structure, and (5) Cr-rich M(2)N-nitride with hexagonal structure. In summary, DP colonies in Alloy 33 upon aging at 800 C degrees evolve according the following the sequence: in the initial stages of the process intergranular precipitation (M(23)C(6)-carbide and n-phase) occurs at original GB; with the increase in aging time, the boundaries migrated fed by solute atoms in a process known as diffusion-induced grain boundary migration (DIGM), whereas alpha-Cr phase precipitates have nucleated adjacent to the GB and grew with lamellar morphology accompanying the migration of the boundary thereby developing the DP colonies. Eventually, the n-phase also precipitates both within the colony and at the DP reaction-front. Over the final stages of the DP colonies growth process occurs the nucleation and growth of the sigma-phase at the GB reaction-front and, later, M(2)N-nitride precipitates also at the reaction-front and within the DP colony. It was verified that the DP reaction growth is controlled, initially by GB diffusion of Cr and, with the progress of reaction time by the volume diffusion of the Cr, which resulted in a non-steady state growth process. In addition to the occurrence of five precipitated phases within the same colony, another striking feature of the DP reaction in Alloy 33 refers to the consistent evidence that the phase initially precipitated at original GB position (M(23)C(6)-carbide) is different from the precipitated phase with lamellar morphology (alpha-Cr phase) within the colony. This observation constitutes the first evidence for the DP phenomenon resulting in multi-phase DP colonies in multicomponent structural materials.