Point defects control many properties of technological importance in intermetallic compounds such as atomic diffusion, creep, hardness, mechanical properties and sintering. Farther, since intermetallic compounds are characterized by long range atomic order, the point defects in these compounds can be qualitatively different from those in pure metals and disordered alloys. In the present study, we have chosen β-NiAl for our point defect studies since it is a potential candidate for high temperature applications and a model system for the study of basic phenomena in ordered alloys. We have used a mean field formulation for studying point defect concentrations. The outline of the formulation is as follows: We divide the rigid, body centred cubic lattice into two interpenetrating cubic sublattices called α and j3 which are made up of the cube corners and body centres respectively. We write a generic free energy function (G) that involves the temperature T and the six sublattice occupancies viz., the A (Ni), B (Al) and vacancies (V) on the two sublattices α andβ. We use the constraints on the number of α and β sublattice sites viz., the number of α sublattice sites is equal to the number of β sublattice sites, to write G as a function of four of the six sublattice occupancies and T. We define three auxiliary parameters η1, η2 and η3 which correspond to the vacancy concentration, the differential B species population on the two sublatices (the chemical or atomic order), and the differential vacancy population on the two sublattices, respectively. We then rewrite G as a function of T, xB and ηi. The G can now be minimized with respect to the three auxiliary variables so that we recover the free energy (G) as a function of XB and T only. The formulation requires as inputs the Ni-Ni, Al-Al, Ni-Al, Ni-V and Al-V interaction energies in the nn and nnn shells. We have obtained the Ni-Ni, Al-Al and Ni-Al interaction energies from the effective pair potentials reported in the literature. For the Ni-V and Al-V interaction energies we have used a bond breaking model in which we have assumed that the Ni-V and Al-V interaction energies in the nnn shell to be zero. Using the above interaction parameters in our mean field formulation we have determined the concentrations of various types of point defects in β-NiAL We have specifically chosen the temperature range of 800 - 2000 K and the composition range of 45 - 55 atomic% Al. Our results can be summarised as follows: 1.The predominant defect in the stoichiometric alloy is a combination of an Ni-antisite defect and two vacancies on the Ni sublattice. 2.The Al-rich alloys of composition (50 + ∆) atomic% contain 2∆% vacancies;since the alloys are almost perfectly ordered, these vacancies predominantly occupy the Ni sublattice. Similarly, the Ni-rich alloys of composition (50 — ∆)atomic% contain ∆% Ni antisites. 3.Both the vacancies on the Ni sublattice (in Al-rich alloys) and Ni-antisites (in Ni-rich alloys) show negligible temperature dependence, and hence owe their origin to the off-stoichiometry. 4.In all the alloys, the Al-antisites have the lowest concentration (of the order 10-6 even at 2000 K) and the concentration of the vacancies on the β sublattice is the next lowest. Thus, our results support the view that β-NiAl is a triple defect B2 and, if we consider constitutional vacancies as those which have a little or no temperature dependence, there exist constitutional vacancies in Al-rich β-NiAl. This conclusion is in agreement with some of the experimental results. However, it must be pointed out that there is considerable disagreement among experimental results from different groups.

There has been an urge for increasing the efficiency in advanced gas turbine engines. To fulfill these needs the inlet gas temperatures should be increased in the gas turbine engines, thermal barrier coatings (TBCs) have gained significant applications in increasing the gas inlet temperatures. Insulating characteristics of ceramic TBCs allow the operation at up to 150~250 ˚C higher gas temperatures. Because of the severe turbine engine operating conditions that include high temperature, steep temperature gradient, thermal cycling, oxidation and hot-corrosion, TBCs can fail by spallation at the interface between the metal and ceramic. The lack of understanding in failure mechanisms and their prediction warrant a development of non-destructive evaluation technique that can monitor the quality and degradation of TBCs. In addition, the development of NDE technique must be based on a robust correlation to the characteristics of TBC failure. The objective of this study is to develop electrochemical impedance spectroscopy (EIS) as a Non-destructive evaluation (NDE) technology for application to TBCs. To have a better understanding of the multilayer TBCs using EIS they were divided into individual layers and EIS were performed on them. The individual layers included polycrystalline ZrO2-7~8 wt.%Y2O3 (YSZ) (topcoat) of two different densities were subjected to sintering by varying the sintering temperature and holding time for three different thickness and hot extruded NiAl alloy buttons which were subjected to isothermal oxidation with varying temperature and time. NiAl is as similar to the available commercial bondcoats used in TBCs. Then degradation monitoring with electrolyte penetration was carried out on electron beam physical vapor deposited (EB PVD) TBCs as a function of isothermal exposure. Quality control for air plasma sprayed TBCs were carried out as a function of density, thickness and microstructure. Dense vertically cracked TBCs were tested as a function of vertical crack density and thickness. Electrochemical impedance response was acquired from all specimens at room temperature and analyzed with an AC equivalent circuit based on the impedance response as well as multi-layered structure and micro-constituents of specimens. Physical and microstructural features of these specimens were also examined by optical and electron microscopy. The EIS measurement was carried out in a three-electrode system using a standard Flat Cell (K0235) from Princeton Applied Research™ and IM6e BAS ZAHNER™ frequency response analyzer. The electrolyte employed in this investigation was 0.01M (molar) potassium Ferri/Ferro Cyanide {(K3Fe(CN)6/K4Fe(CN)6·3H2O)}. The thickness and density were directly related to the resistance and capacitance of the polycrystalline YSZ with varying thickness and open pores. As the effective thickness of the YSZ increased with sintering time and temperature, the resistance of the YSZ (RYSZ) increased proportionally. The variation in capacitance of YSZ (CYSZ) with respect to the change in porosity/density and thickness was clearly detected by EIS. The samples with high porosity (less dense) exhibited large capacitance, CYSZ, compared to those with less porosity (high density), given similar thickness. Cracking in the YSZ monoliths resulted in decrease of resistance and increase in capacitance and this was related to the electrolyte penetration. Growth and spallation of TGO scale on NiAl alloys during isothermal oxidation at various temperatures and holding time was also correlated with resistance and capacitance of the TGO scale. With an increase in the TGO thickness, the resistance of the TGO (RTGO) increased and capacitance of the TGO (CTGO) decreased. This trend in the resistance and capacitance of the TGO changed after prolonged heat treatment. This is because of the spallation of the TGO scale from the metal surface. The parabolic growth of TGO during high temperature oxidation was inversely proportional to the capacitance of TGO, excluding the abrupt changes associated with the failure. As a function of isothermal exposure for EB-PVD TBCs, initial increase in the resistance of YSZ with thermal exposure was observed perhaps due to the high temperature sintering of YSZ. The parabolic growth of TGO during high temperature oxidation was inversely proportional to the capacitance of TGO. An explanation based on electrolyte penetration into sub-critical damage is proposed for the gradual decrease in the resistances of YSZ and TGO with prolonged thermal exposure. Observation of exposed metallic bond coat surface on the fracture surface, which readily provides conduction, was related to the abrupt and large increase in the capacitance of YSZ and TGO. A direct relation between the resistance of the YSZ (RYSZ) and density of the YSZ was observed for APS TBCs with varying topcoat density. APS TBCs with varying topcoat chemistry and thickness were tested and directly related to resistance of topcoat. With the increase in the topcoat thickness, the capacitance decreased and the resistance increased. The higher values of CCAT and RCAT compared to that of CYSZ and RYSZ were related to the higher dielectric constant and resistivity of CaTiO3. Dense vertically cracked TBCs were tested with varying crack density were tested and the variation in the resistance was related indirectly to the cracks and directly to the difference in the thickness of the topcoat. EB-PVD TBCs with varying density (dense and columnar) were tested and the variation in resistance was attributed to the dense structure and columnar structure of the topcoat with columnar structure having lower resistance because of more electrolyte penetration through the columnar structure. From this study, EIS showed a potential as a NDE technique for quality assurance and lifetime remain assessment of TBCs. Future work should continue on developing a mathematical model to study the impedance curves and come up with a model for individual layers of TBC and then sum them up to get the multilayered TBC response. The flexible instrument probe of EIS needs to be designed and tested for field evaluation of TBCs.

Superalloys used in aeroengines are designed to offer superior strength at increasingly higher operating temperatures. In order to optimise the working efficiency and provide additional protection to the components such as turbine blades; a thermal barrier coating (TBC) system is applied. The TBC is a multilayer system consisting of mainly two layers i.e. bond coat (BC) and topcoat (TC). In addition, a third layer grows between the TC and BC during oxidation known as a reaction layer or thermally grown oxide (TGO). The function of the TC (usually, yttria stabilised zirconia (YSZ)) is to provide thermal insulation to aeroengine parts or reduce their surface temperatures; whereas, the BC provides binding between the TC and the substrate, and oxidation resistance to the underlying alloy by forming an adherent and continuous oxide i.e. α-Al2O3. During service, in the absence of mechanical damage to the TBC, most failures are attributed to the BC performance. The most frequently adopted BCs are; β-(Pt, Ni)Al, Pt-γ-Ni/γ’-Ni3Al and MCrAlY. In addition, reactive elements (REs) are incorporated in the BCs due to their ability to enhance oxidation resistance significantly. In the present study βNiAl based coatings/BCs and alloys with and without REs (Zr and Hf) and Pt were prepared. For the coatings CMSX-4 single crystal superalloy was used as a substrate material and pack aluminising/cementation or in-situ chemical vapour deposition (CVD) as a coating process. The isothermal oxidation testing was carried out at 1150oC for 50 and 100 hours in air. The preparation and oxidation performance of a δNi2Al3 coating was carried out, as, this is a starting material for βNiAl matrix based coatings/or BCs. The oxidation of δNi2Al3 coating showed large volumetric changes (thickness variations), multiphase TGO, TGO/coating interface melting and spallation during oxidation. In contrast, the ‘simple βNiAl’ coating (or βNiAl matrix) was found to exhibit comparably enhanced thermal stability than that of the δNi2Al3 coating. Moreover, a detailed study of the simple βNiAl coating was also carried out in order to understand the oxidation performance. The coating before oxidation in the as-deposited condition was found to contain residual compressive stresses of 140 – 200 MPa. In contrast, after oxidation analysis exhibited substantial interdiffusion between the coating and the substrate resulting in a large reduction of the Al content and influx of substrate elements into the coating. This in turn caused coating transformation from βNiAl to the γ’-Ni3Al phase and formation of a multiphase TGO (TiO2, NiAl2O4, and ϴ-Al2O3 intrusion in α-Al2O3). Moreover, the degree of the TGO spallation and residual stresses increased with the oxidation time. In order to enhance the oxidation performance of the βNiAl coatings, the substrate pre-treatment was carried out i.e. CMSX-4 superalloy was electrolytically etched to remove the γ-Ni phase and fabricate βNiAl coatings on the remaining γ’-Ni3Al. This coating is termed as E-βNiAl. In comparison to simple βNiAl, the E-βNiAl coating showed improved spallation resistance. However, E-βNiAl revealed increased surface area due to etching of the substrate and triggered fast TGO growth rates when tested in an un-polished condition. Furthermore, simple βNiAl coatings were doped with Zr and Hf separately using a two-step aluminising method. The appropriate addition of either Zr or Hf was found to reduce the substrate elements (W, Ta, Cr and Ti etc.) in the coating before and after oxidation. After oxidation, examination of the presence of Zr or Hf in the coating was found to confirm the commonly reported beneficial effects. The TGOs grown on these coatings were almost pure α-Al2O3 which subsequently reduced growth and stresses. In addition to Zr/& Hf doped coatings, a study on Hf and Zr doped βNiAl bulk alloys was also carried out in order to understand the dopant effects on the oxidation resistance of βNiAl alloys in the absence of interdiffusion (as in case of coatings). In general, the commonly reported oxidation benefits were confirmed by the addition of these elements such as reduced TGO growth, oxide pegging, a columnar morphology of the TGO and segregation of REs at alumina grain boundaries etc. In addition, two more beneficial effects are suggested to be the ‘TGO crack filling up (or crack-healing)’ and formation of the ‘dense-TGO’. Within this study, the investigation of commercially available Pt-βNiAl BC was also carried out in air and vacuum atmospheres. The results demonstrated that the initial chemistry and elemental distribution (particularly Al/& Pt) was found to affect the TGO growth and phases significantly. In addition to its well established beneficial effects, the main effect of a Pt addition is suggested to be the stabilisation of the βNiAl structure even at a lower Al content.

Made available in DSpace on 2016-12-08T17:19:19Z (GMT). No. of bitstreams: 1 Cleber P Fenili.pdf: 5079728 bytes, checksum: e3ab5832297ac591534e15390527a095 (MD5) Previous issue date: 2013-02-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work is a study of the behavior of iron and nickel aluminides, since the high energy milling until the consolidation. Particle size and morphology of aluminides after milling and heat treatment were evaluated. A high energy milling with predetermined time and speed along with a defined stoichiometry of elemental powders were thus directed in order to obtain the intermetallic Fe3Al and Ni3Al. By obtaining the intermetallic was studied consolidation processes. The consolidation has great influence on the mechanical and microstructural properties of aluminides, motivating in recent years the study of consolidation as the density x porosity relationship. With the consolidation processes defined, which evaluates the influence of temperature, time, velocity, pressure and atmosphere. The sintering process, sintering and hot forming (S-HP) and hot pressing assisted field (FAHP) were used. The materials obtained after the consolidation processes were evaluated for density, hardness, formation of other phases and oxidation. These properties were evaluated by optical microscopy, scanning electron microscopy, vickers hardness, density, semiquantitative analysis (EDS) and X-ray diffraction. The results showed that the process FAHP is effective in consolidating the iron aluminides and nickel, for resulted in greater densification and therefore a good hardness confirming other studies using similar processes. The other cases in this study had less impressive results when compared to process FAHP, but compared to other references are considered suitable. / Neste trabalho foi realizado um estudo do comportamento dos aluminetos de ferro e níquel, desde a moagem de alta energia até a consolidação. Avaliou-se o tamanho das partículas e morfologia dos aluminetos após a moagem e tratamento térmico. A moagem de alta energia com tempo e velocidade pré determinados juntamente com uma estequiometria dos pós elementares definidos, foram assim direcionados com o intuito de obter os intermetálicos Fe3Al e Ni3Al. Com a obtenção dos intermetálicos estudou-se os processos de consolidação. A consolidação possui grande influência nas propriedades mecânicas e microestruturais dos aluminetos, motivando nos últimos anos o estudo dos processos de consolidação quanto a densidade x porosidade. Com os processos de consolidação definidos, avaliou-se a influência da temperatura, tempo, velocidade, atmosfera e pressão de compactação. Foram utilizados os processos de sinterização, sinterização e conformação a quente (S-HP) e prensagem a quente assistida por campo (FAHP). Os materiais obtidos após os processos de consolidação foram avaliados quanto a densidade, dureza, formação de outras fases e oxidação. Estas propriedades foram avaliadas através das metalografias mediante microscopia óptica, microscopia eletrônica de varredura, microdureza vickers, densidade, análise semiquantitativa (EDS) e difratometria de raios-X. Os resultados mostraram que o processo FAHP é eficaz na consolidação dos aluminetos de ferro e níquel, pois resultou em maior densificação e, por conseguinte uma boa dureza comparando com outros estudos utilizando processos parecidos. Os outros processos deste estudo obtiveram resultados menos expressivos quando comparados ao processo FAHP, porém comparados a outras referências são considerados adequados.

O presente trabalho objetiva o desenvolvimento in situ por plasma por arco transferido (PTA) de aluminetos de Níquel resistentes à oxidação, baseados em uma liga NiCrAlC referência. Para tanto, foram depositadas misturas preliminares de pós elementares e também utilizando o pó atomizado, variando somente a intensidade de corrente (130 e 160 A) para se obter diferentes misturas com o substrato. Após as deposições, a incorporação de elementos do substrato nos cordões não permitiu a formação de aluminetos para os revestimentos processados com a mistura de pós elementares. Estes apresentaram valores de diluição consideravelmente maiores do que os cordões obtidos com pó atomizado, que resultaram em aluminetos de Níquel. Com base nos resultados preliminares, quatro novas composições com mistura de pós elementares foram estimadas e os cordões finais, processados com 100 ou 130 A, resultaram em aluminetos como esperado. Duas composições foram submetidas a ensaios em balança termo gravimétrica (TGA) e a ciclos isotérmicos em forno mufla para diferentes temperaturas (máximo de 1000 graus Celsius) e tempos de exposição (até 72 horas no máximo). Os resultados mostraram que a incorporação de Ferro nos revestimentos durante a deposição retardou a formação das camadas de óxidos, sendo que maiores teores deste elemento aceleraram a formação da camada de alumina alfa, o que propiciou uma redução nos valores de constante de oxidação parabólica a 1000 graus Celsius nos estágios iniciais da oxidação. Os revestimentos apresentaram melhores desempenhos à oxidação do que a liga NiAlCrC fundida, traduzido pelo menor ganho de massa. A exposição nas temperaturas de ensaio provocou uma queda de dureza e na evolução ou nucleação de uma provável fase sigma. / This research aimed at the development in situ by plasma transferred arc (PTA) of nickel aluminides resistant to the oxidation, based on a reference NiCrAlC alloy. For this purpose, preliminary mixtures of elemental powders were deposited, and also using the atomized powder, varying the current intensity (130 and 160 A) only to obtain different mixtures with substrate. After the depositions, the incorporation of substrate elements into the welds did not allow the formation of aluminides in the coatings processed with the elemental powder mixture. These coatings presented dilution values considerably higher than those obtained with atomized powder, which result in nickel aluminides. Based on the preliminary results, additional four compositions with elemental powders were estimated and the final welds, processed with 100 or 130 A, were composed by aluminides as expected. Two compositions were submitted to the thermogravimetry tests and isothermal cycles in an oven for different temperatures (1000 Celsius max) and exposure times (for 72 hours at maximum). The results showed that the iron incorporation in the coatings during depositions delayed the oxides scales formation, since higher contents of this element accelerated the formation of -alumina, which promoted a reduction in the parabolic constant of oxidation for 1000 Celsius in the earlier stages of oxidation. The coatings presented better oxidation resistance than that observed for as-cast NiCrAlC, observed by their smaller mass losses. The exposure to the testing temperatures resulted in a decrease of hardness and in the evolution or nucleation of sigma phase.

O presente trabalho objetiva o desenvolvimento in situ por plasma por arco transferido (PTA) de aluminetos de Níquel resistentes à oxidação, baseados em uma liga NiCrAlC referência. Para tanto, foram depositadas misturas preliminares de pós elementares e também utilizando o pó atomizado, variando somente a intensidade de corrente (130 e 160 A) para se obter diferentes misturas com o substrato. Após as deposições, a incorporação de elementos do substrato nos cordões não permitiu a formação de aluminetos para os revestimentos processados com a mistura de pós elementares. Estes apresentaram valores de diluição consideravelmente maiores do que os cordões obtidos com pó atomizado, que resultaram em aluminetos de Níquel. Com base nos resultados preliminares, quatro novas composições com mistura de pós elementares foram estimadas e os cordões finais, processados com 100 ou 130 A, resultaram em aluminetos como esperado. Duas composições foram submetidas a ensaios em balança termo gravimétrica (TGA) e a ciclos isotérmicos em forno mufla para diferentes temperaturas (máximo de 1000 graus Celsius) e tempos de exposição (até 72 horas no máximo). Os resultados mostraram que a incorporação de Ferro nos revestimentos durante a deposição retardou a formação das camadas de óxidos, sendo que maiores teores deste elemento aceleraram a formação da camada de alumina alfa, o que propiciou uma redução nos valores de constante de oxidação parabólica a 1000 graus Celsius nos estágios iniciais da oxidação. Os revestimentos apresentaram melhores desempenhos à oxidação do que a liga NiAlCrC fundida, traduzido pelo menor ganho de massa. A exposição nas temperaturas de ensaio provocou uma queda de dureza e na evolução ou nucleação de uma provável fase sigma. / This research aimed at the development in situ by plasma transferred arc (PTA) of nickel aluminides resistant to the oxidation, based on a reference NiCrAlC alloy. For this purpose, preliminary mixtures of elemental powders were deposited, and also using the atomized powder, varying the current intensity (130 and 160 A) only to obtain different mixtures with substrate. After the depositions, the incorporation of substrate elements into the welds did not allow the formation of aluminides in the coatings processed with the elemental powder mixture. These coatings presented dilution values considerably higher than those obtained with atomized powder, which result in nickel aluminides. Based on the preliminary results, additional four compositions with elemental powders were estimated and the final welds, processed with 100 or 130 A, were composed by aluminides as expected. Two compositions were submitted to the thermogravimetry tests and isothermal cycles in an oven for different temperatures (1000 Celsius max) and exposure times (for 72 hours at maximum). The results showed that the iron incorporation in the coatings during depositions delayed the oxides scales formation, since higher contents of this element accelerated the formation of -alumina, which promoted a reduction in the parabolic constant of oxidation for 1000 Celsius in the earlier stages of oxidation. The coatings presented better oxidation resistance than that observed for as-cast NiCrAlC, observed by their smaller mass losses. The exposure to the testing temperatures resulted in a decrease of hardness and in the evolution or nucleation of sigma phase.

This work deals with issues of preparation of intermetallics based on iron, nickel and titanium aluminides. It works with an idea of preparation of bulk material by reaction synthe-sis from kinetic spraying deposits by cold spray. Theoretical part is concerned with phases and compounds of these aluminides for structural applications, their characteristics and present fabrication. In experimental part there are studied microstructures created by annealing of deposits.