Made available in DSpace on 2016-08-18T18:19:27Z (GMT). No. of bitstreams: 1 LUCIENE ARAUJO NASCIMENTO.pdf: 1402629 bytes, checksum: b9ce204098b2c4fe0362b6792a692744 (MD5) Previous issue date: 2010-02-25 / FUNDAÇÃO DE AMPARO À PESQUISA E AO DESENVOLVIMENTO CIENTIFICO E TECNOLÓGICO DO MARANHÃO / Austenitic stainless steels have low economic value compared to titanium and its alloys, considered the most resistant to corrosion in biological environment, and for over fifty years are widely used in the manufacture of orthopedic implants, particularly in public health service. Currently the ISO 5832-1 steel (ASTM F 138) is the most used in the manufacture of orthopedic prosthesis, especially the temporary ones. However, because it is susceptible to localized corrosion when in contact with human tissue, it is being gradually replaced by austenitic stainless steel of low carbon and high nitrogen called ISO 5832-9. The same is already used extensively in Europe and the United States, while in Brazil it's use is more recent and smaller scale. This work investigates the behavior of dynamic recrystallization in an ISO 5832-9 steel through hot torsion tests and optical microscopy, for different conditions of temperature, strain and strain rate. It was found through the plastic flow curves of the studied material crystallizes dynamically and that the high value of its apparent activation energy for deformation can be attributed to the presence of a large amount of precipitated particles and nitrogen dissolved in the matrix. Micrographs confirmed that tests carried out at low temperatures reveal a strong retardation of dynamic recrystallization. Moreover, the presence of serrated grain boundaries and nucleation of new grains in the old deformed grain boundaries, are strong indications that the recrystallization occurred by a necklace mechanism. The behavior of the average recrystallized grain size, DDRX, with temperature resembles the behavior of the austenitic grain growth in microalloyed steels. The presence of a minimum in the behavior of DDRX with the strain rate can be attributed to a minimum strain rate required to cause the greatest amount of dynamics precipitation. / Os aços inoxidáveis austeníticos possuem um baixo valor econômico quando comparados ao titânio e suas ligas, considerados os mais resistentes à corrosão em meio biológico, e há mais de cinquenta anos são amplamente utilizados na confecção de implantes ortopédicos, em especial no serviço de saúde pública. Atualmente o aço ISO 5832-1 (ASTM F 138) é o mais utilizado na confecção de próteses ortopédicas, principalmente as temporárias. Entretanto, devido o mesmo ser suscetível à corrosão localizada quando em contato com tecido humano, ele está sendo gradativamente substituído pelo aço inoxidável austenítico de baixo teor de carbono e alto teor de nitrogênio denominado de ISO 5832-9. O mesmo já é utilizado em larga escala na Europa e nos Estados Unidos, enquanto no Brasil a sua utilização é mais recente e em menor escala. Este trabalho investiga o comportamento da recristalização dinâmica em um aço ISO 5832-9, através de ensaios de torção a quente e microscopia ótica, para diferentes condições de temperatura, deformação e taxa de deformação. Foi constatado através das curvas de escoamento plástico que o material estudado recristaliza dinamicamente e, que o alto valor da sua energia de ativação aparente para a deformação pode ser atribuído à presença de uma grande quantidade de partículas de precipitados e ao nitrogênio em solução na matriz. Micrografias confirmam que ensaios realizados a baixas temperaturas revelam um forte retardamento da recristalização dinâmica. Além disso, a presença de contornos de grão serrilhados e nucleação de novos grãos nos antigos contornos de grãos deformados, são fortes indícios de que a recristalização ocorreu por mecanismo colar. O comportamento do tamanho de grão médio recristalizado, DDRX, com a temperatura, se assemelha ao comportamento do crescimento de grão austeníticos de aços microligados. A presença de um mínimo no comportamento do DDRX com a taxa de deformação pode ser atribuído a uma taxa de deformação mínima necessária para que ocorra a maior quantidade de precipitação dinâmica.

The prediction of detonation properties of the new generation of high-nitrogen energetic materials (HNEM) is based on knowledge of their heats of formation, which are sum of values of particular nitrogen heterocyclic fragments. The diploma thesis describes theoretical calculations of heats of formation in gas phase ?f H°(298,g) for series of azines (number of N atoms 2-6) and azoles (number of N atoms 2-5) by means of quantum chemical methods. The semiempirical methods as PM3, DFT methods utilizing isodesmic approach and finally thermochemical G-recipes were used. All calculated values of heats of formation were scrutinized and for future application to HNEM materials the DFT B3LYP/cc-pVTZ method and thermochemical recipe T1 were recommended.

The main goal of the presented thesis is a theoretical study of heat of formation for high-nitrogen energetic materials. A modification of the classical approach to the isodesmic reactions is realized with the intent that molecules on both sides of the corresponding equation have not only the same number of atoms but also approximately the same size and skeletal similarity. This approach is designated as a method "Alternative Isodesmic Reaction (AIR method)". At its base, using the DFT B3LYP / cc-pVTZ and B3PW91 / cc-pVTZ, for the high nitrogen heterocycles, which are selected from the group of triazoles, triazines, tetrazines, the enthalpy of formation values the gaseous phase f H°(298,g), were obtained whose values are close to the published f H°(298,g). Their application in the calculation of the relevant characteristics of these heterocycles detonation gave real values.

η (eta) nitride, Cr3Ni2SiN, is a precipitate found in high temperature austenitic stainless steel and is not yet included in Thermo-Calc steel database TCFE7. The aim of this thesis is to collect thermodynamic data to enable the addition of η nitride in the databases. Three laboratory melts with varying levels of silicon, chromium and nickel have been aged at 700-1000 °C for 75 h, 300 h and 1200 h and examined by Light Optical Microscopy, Scanning Electron Microscopy, Energy Dispersive Spectroscopy, Wavelength Dispersive Spectroscopy, Electron Backscattered Diffraction and X-ray Powder Diffraction. η nitride is in the studied alloys an equilibrium phase stabilized with nitrogen. Presence of η nitride was confirmed by Energy Dispersive Spectroscopy and X-ray Powder Diffraction. It was found to precipitate in four different ways, at primary grain boundaries, intragranularly, as a "skeleton-like" precipitate and as a border around the occurring Cr2N precipitates. The area fraction of η nitrides increases with longer aging times and is favored by silicon and nickel. The composition of η nitride is not changing regardless of material composition, aging temperature and aging time. The composition of η nitride in all three materials are 8.7-9.7 wt.% silicon, 47-54 wt.% chromium, 1.4-4.1 wt.% iron and 33-36 wt.% nickel. The nitrogen content 2 determined by Wavelength Dispersive Spectroscopy is 2.8-3.2 wt.%. No complete equilibrium was achieved and together with incomplete mixing of the alloying elements during melting, the microstructure is difficult to evaluate. Other precipitates found are Cr2N, π nitride, σ phase and two unidentified phases, M and N. Of these phases at least Cr2N is not an equilibrium phase as it dissolves during aging. Further aging to achieve complete equilibrium is necessary.