Au cours de ce travail, des revêtements intermétalliques TiAlx (x=1,2,3) ont été élaborés sur des substrats à base titane : le titane pur et l’alliage commercial, TA6V. L’objectif était de réaliser des revêtements d’aluminiure en surface et d’étudier le comportement des matériaux revêtus vis-à-vis de l’oxydation à haute température sous air, sous air enrichi en vapeur d’eau et en présence de soufre. Les matériaux revêtus ont été testés à trois températures : 700°C, 800°C et 900°C. Les revêtements ont été réalisés à 1000°C par la méthode de cémentation en caisse. Les revêtements réalisés par ce procédé sont toujours adhérents au substrat. Pendant la réaction d’oxydation, l’existence d’un processus de rétrodiffusion de l’aluminium modifie la nature des phases et l’organisation du revêtement. Les phases TiAl et TiAl2 ne sont pas suffisamment riches en aluminium pour promouvoir la formation d’une couche d’alumine protectrice quelle que soit la température d’oxydation. Lorsque ce sont ces phases qui sont à la surface du revêtement, on assiste toujours à la formation d’une couche superficielle de rutile TiO2. Quand elle constitue la sous-couche externe du revêtement, la phase TiAl3 est assez riche en aluminium pour former une couche d’alumine -Al2O3 couvrante, compacte et protectrice. / During this study, intermetallic coatings TiAlx (x=1,2,3) were performed on titanium substrates: pure titanium and the commercial alloy, TA6V. The aim of this study was to elaborate aluminiure coatings on the surface and characterize the behaviour of these coated materials in oxidation at high temperature under air laboratory, under air enriched with water vapour and with sulfur. The coated materials were tested at three temperatures: 700°C, 800°C and 900°C. The coatings were realized at 1000°C by the pack-cementation process. The coatings realized are always adherent to the substrate. During oxidation the retrodiffusion of aluminium changes the nature of the phases and the organisation of the coating. TiAl and TiAl2 phases are not enough rich in aluminium to promote the formation of a protective alumina layer, whatever the temperature. When these phases are present on the surface of the coating, we always observe the formation of a TiO2 rutile top layer. When TiAl3 is the external sub-layer of the coating, this phase is rich enough in aluminium to form an -Al2O3 alumina layer, which is covering, compact and protective.

Les superalliages à base nickel des turbines aéronautiques sont susceptibles de subir des phénomènes de corrosion et/ou d’oxydation à haute température par les environnements agressifs rencontrés en service. Aussi, des revêtements d’aluminure sont appliqués par dépôt chimique afin d’assurer la protection des pièces contre ces phénomènes. La dégradation progressive de ces revêtements mène à la nécessité de les enlever afin d’en appliquer des nouveaux. Les bains chimiques industriels pour enlever les revêtements et les oxydes sont très toxiques, polluants et plutôt empiriques. Ainsi, ce travail de thèse se proposait d’étudier une méthode alternative et originale, par voie électrochimique permettant de contrer les limitations des approches chimiques. La voie électrochimique par application d’un potentiel (mode potentiostatique) a été étudiée afin de procurer la sélectivité entre le substrat et le revêtement lors de la dissolution, ainsi que le contrôle in-situ du procédé à l’aide d’une cellule à 3 électrodes. La faisabilité de la méthode a d’abord été démontrée, puis différentes procédures (par cycles cathodique/anodique, en continu et, parfois, avec modification du potentiel imposé) ont été développées. Nous avons pu mettre en relation les états métallurgiques des systèmes revêtement/substrat avec leur comportement électrochimique et avons mis également en lumière que le taux de dissolution est principalement gouverné par la concentration d’aluminium dans le revêtement alors que lorsque le platine est incorporé à ce même revêtement, le taux de dissolution est homogène. De même, nous avons démontré par XPS et par MET que la teneur en chrome modifie de manière significative l’homogénéité du décapage lors des phases de polarisation cathodique par un mécanisme de passivation de la surface, qui bloque l’activité électrochimique. Cependant, la tenue en oxydation cyclique des revêtements décapés par voies chimique et électrochimique n’a pas pu véritablement être démontrée car les revêtements avaient une microstructure différente. Enfin, des essais sur pièces de turbine ont montré le haut degré de sélectivité de l’approche ici étudiée. / Nickel based superalloys of aeronautical turbines are subjected to high temperature oxidation and/or corrosion in service conditions. Thus, protective aluminide coatings are applied onto the parts by chemical vapor deposition. The degradation of the coatings with time requires them to be removed prior to recoating the parts. The chemical baths industrially employed are toxic, polluting and quite empirical. Therefore, this thesis aimed at studying an alternative and original electrochemical method to circumvent the drawbacks of the chemical approach. Fixed potentials (potentiostatic mode) were thus applied to provide selectivity between the coating and the substrate upon the dissolution process, as well as to ensure in-situ control through a 3-electrode cell. The feasibility of the method was first demonstrated, then different procedures (cathodic/anodic cycles; continuous anodic and sometimes with modification of the potential) were investigated. The correlations between the metallurgical phases of the coating/substrate systems were elucidated. It also appeared that dissolution is mainly governed by the concentration of aluminium in the coating whereas the incorporation of platinum to the coating brought about the homogeneous dissolution. In addition, XPS and MET confirmed the hypothesis by which the chromium content drastically change the stripping homogeneity upon the cathodic polarization step by passivation of the surface and the subsequent electrochemical blocking. However, the results on the cyclic oxidation behaviour of the coatings priorly stripped chemically or electrochemically were not conclusive enough as the microstructure of the original coatings was different. Finally, quite a few stripping trials were carried out onto real turbine parts that confirmed the high selectivity of the electrochemical approach studied.

Pt-aluminide (PtAl) coatings form an integral part of thermal barrier coating (TBC) systems that are applied on Ni-based superalloy components operating in the hot sections of gas turbine engines. These coatings serve as a bond coat between the superalloy substrate and the ceramic yttrium stabilized zirconia (YSZ) coating in the TBC system and provide oxidation resistance to the superalloy component during service at high temperatures. The PtAl coatings are formed by the diffusion aluminizing process and form an integral part of the superalloy substrate. The microstructure of the PtAl coatings is heavily graded in composition as well as phase constitution. The matrix phase of the coating is constituted of the B2-NiAl phase. Pt, in the coating, is present as a separate PtAl2 phase as well as in solid solution in B2-NiAl. The oxidation resistance of the PtAl bond coat is derived from the B2-NiAl phase. At high temperatures, Al from the B2-NiAl phase forms a regenerative layer of alumina on the coating surface which, thereby, lowers the overall oxidation rate of the superalloy substrate. The presence of Pt is beneficial in improving the adherence of the alumina scale to the surface and thereby enhancing the oxidation resistance of the coating. However, despite its excellent oxidation resistance, the B2-NiAl being an intermetallic phase, renders the PtAl coating brittle and imparts it with a high brittle-to-ductile-transition-temperature (BDTT). The PtAl coating, therefore, remains prone to cracking during service. The penetration of these cracks into the substrate is known to degrade the strain tolerance of the components. Evaluation of the mechanical behavior of these coatings, therefore, becomes important from the point of views of scientific understanding as well as application of these coatings in gas turbine engine components. Studies on the mechanical behavior of coatings have been mostly carried on coated bulk superalloy specimens. However, since the coating is brittle and the superalloy substrate more ductile when compared to the coating, the results obtained from these studies may not be representative of the coating. Therefore, it is imperative that the mechanical behavior of the coating in stand-alone condition, i.e. the free-standing coating specimen without any substrate attached to it, be evaluated for ascertaining the true mechanical response of the coating. Study of stand-alone bond coats involves complex specimen preparation techniques and challenging testing procedures. Therefore, reports on the evaluation of mechanical properties of stand-alone coatings are limited in open literature. Further, no systematic effort has so far been made to examine important aspects such as the effect of temperature and strain rate on the tensile behavior of these coatings. The deformation mechanisms associated with these bond coats have also not been reported in the literature. In light of the above, the present research study aims at evaluating the tensile behavior of free-standing PtAl coatings by the micro-tensile testing technique. The micro-tensile testing method was chosen for property evaluation because of its inherent ability to generate uniform strain in the specimen while testing, which makes the results easy to interpret. Further, since the technique offers the feasibility to test the entire graded PtAl coating in-situ, the results remain representative of the coating. Using the above testing technique, the tensile behavior of the PtAl coating has been evaluated at various temperatures and strain rates. The effect of strain rate on the BDTT of the coating has been ascertained. Further, the effect of Pt content on the tensile behavior of these coatings has also been evaluated. Attempts have been made to identify the mechanisms associated with tensile deformation and fracture in these coatings. The thesis is divided into nine chapters. Chapter 1 presents a brief introduction on the operating environment in gas turbine engines and the materials that are used in the hot sections of gas turbine engines. The degradation mechanisms taking place in the superalloy in gas turbine environments and the need for application of coatings has also been highlighted. The basic architecture of a typical thermal barrier coating (TBC) system applied on gas turbine engine components has been presented. The constituents of the TBC system, i.e. the ceramic YSZ coating, MCrAlY overlay as well as diffusion aluminide bond coats and, the various techniques adopted for the deposition of these coatings have been described in brief. Chapter 2 presents an overview of the literature relevant to this study. This chapter is divided into four sub-chapters. The formation of diffusion aluminide coatings on Ni-based superalloys has been described in the first sub-chapter. Emphasis has been laid on pack cementation process for the formation of the coatings. The fundamentals of pack aluminizing process, including the thermodynamic and kinetic aspects, have been mentioned in brief. The microstructural aspects of high activity and low activity plain aluminide and Pt-aluminide coatings have also been illustrated. The techniques applied for the mechanical testing of bond coats have been discussed in the second sub-chapter. The macro-scale testing techniques have been mentioned in brief. The small scale testing methods such as indentation, bend tests and micro-tensile testing have also been discussed in the context of evaluation of mechanical properties of bond coats. Since the matrix in the aluminide bond coats is constituted of the B2-NiAl phase, a description of the crystal structure and deformation characteristics of this phase including the flow behavior, ductility and fracture behavior has been mentioned in the third sub-chapter. In the fourth sub-chapter, reported literature on the tensile behavior and brittle-to-ductile-transition-temperature (BDTT) of diffusion aluminide bond coats has been discussed. In Chapter 3, details on experiments carried out for the formation of various coatings used in the present study and, their microstructural characterization, are provided. The method for extraction of stand-alone coating specimens and their testing is discussed. The microstructure and composition of the various coatings used in the present study are discussed in detail in Chapter 4. Unlike in case of bulk tensile testing, for which standards on the design of specimens exist, there are no standards available for the design of micro-tensile specimens. Therefore, as part of the present research work, a finite element method (FEM)-based study was carried out for ascertaining the dimensions of the specimens. The simulation studies predicted that failure of the specimens within the gage length can be ensured only when certain correlations between the dimensional parameters are satisfied. Further, the predictions from the simulation study were validated experimentally by carrying out actual testing of specimens of various dimensions. Details on the above mentioned aspects of specimen design are provided in Chapter 5. The PtAl coatings undergo brittle fracture at lower temperatures while ductile fracture occurs at higher temperatures. Further, the coatings exhibit a scatter in the yielding behavior at temperatures in the vicinity of BDTT. Therefore, the BDTT, determined as the temperature at which yielding is first observed in the stress-strain curves, may not be representative of the PtAl coatings. In Chapter 6, a method for the precise determination of BDTT of aluminide bond coats, based on the variation in the plastic strain to fracture with temperature, has been demonstrated. The BDTT determined by the above method correlated well with the variation in fracture surface features of the coating and was found representative of these coatings. In Chapter 7, the effect of temperature and strain rate on the tensile properties of a PtAl bond coat has been evaluated. The temperature and strain rate was varied between room temperature (RT)-1100°C and 10-5 s-1-10-1 s-1, respectively. The effect of strain rate on the BDTT of the PtAl bond coat has been examined. Further, the variation in fracture surface features and mechanism of fracture with temperature and strain rate are illustrated. The micro-mechanisms of deformation and fracture in the coating at different temperature regimes have also been discussed. The coating exhibited brittle-to-ductile transition with increase in temperature at all strain rates. The BDTT was strain rate sensitive and increased significantly at higher strain rates. Above BDTT, YS and UTS of the coating decreased and its ductility increased with increase in the test temperature at all strain rates. Brittle behavior occurring in the coating at temperatures below the BDTT has been attributed to the lack of operative slip systems in the B2-NiAl phase of the coating. The onset of ductility in the coating in the vicinity of BDTT has been ascribed to generation of additional slip systems caused by climb of dislocations onto high index planes. The coating exhibited two distinct mechanisms for plastic deformation as the temperature was increased from BDTT to 1100°C. For temperatures in the range BDTT to about 100°C above it, deformation was controlled by dislocations overcoming the Peierls-Nabarro barrier. Above this temperature range, non-conservative motion of jogs by jog dragging mechanism controlled the deformation. The transition temperature for change of deformation mechanism also increased with increase in strain rate. For all strain rates, fracture in the coating at test temperatures below the BDTT, occurred by initiation of cracks in the intermediate single phase B2-NiAl layer of the coating and subsequent inside-out propagation of the cracks across the coating thickness. Ductile fracture in the coating above the BDTT was associated with micro-void formation throughout the coating. The effect of Pt content on the tensile behavior of PtAl coating, evaluated at various temperatures ranging from room temperature (RT) to 1100°C and at a nominal strain rate of 10-3 s-1, is presented in Chapter 8. Irrespective of Pt content in the coating, the variation in tensile behavior of the coating with temperature remained similar. At temperatures below BDTT, the coatings exhibited linear stress-strain response (brittle behavior) while yielding (ductile behavior) was observed at temperatures above BDTT. At any given temperature, the elastic modulus decreased while the strength increased with increase in Pt content in the coating. On the other hand, the ductility of the coating remained unaffected with Pt content. The BDTT of the coating also increased with increase in Pt content in the coating. Addition of Pt did not affect the fracture mechanism in the coating. Fracture at temperatures below BDTT was caused by nucleation of cracks at the intermediate layer and their subsequent inside-out propagation. At high temperatures, fracture occurred in a ductile manner comprising void formation, void linkage and subsequent joining with cracks. The deformation sub-structure of the coating did not get affected with Pt incorporation. Short straight dislocations were observed at temperatures below BDTT, while, curved dislocations marked by jog formation were observed at temperatures above BDTT. The factors controlling fracture stress and strength in the PtAl coatings at various temperatures have also been assessed. The overall summary of the present research study and recommendations for future studies are presented in the last chapter, i.e. Chapter 9.

PtNiAl bond coats are diffusion aluminide coatings deposited on superalloy based turbine blades for oxidation resistance and improved adhesion between the substrate and the YSZ thermal barrier coating on top. They are deposited by pack aluminisation, which makes their microstructure inherently graded and heterogeneous as well as replete with a variety of precipitates and second phase particles. The microstructure also continuously evolves during thermal cycling, because of interdiffusion with the substrate and the continuous loss of Al to the thermally grown oxide scale on top. During service, the bond coats are exposed to impact, thermal expansion mismatch, thermo-mechanical fatigue and inter-diffusion accompanied by phase transformation, which become leading causes of their failure. The bond coats being B2 crystal structures are known to be brittle at room temperature, due to which they are expected to fail during cooling, although they undergo plastic relaxation by creep above the BDTT. Little attention has been paid to the mechanical response of the bond coats, while a number of studies focus on optimizing their composition for oxidation resistance. The fracture properties of these coatings, in particular, are not very well understood due to the several different length scales of their complex microstructure playing a part. In this context, there is an interest in determination of the fracture toughness of bond coats under different loading and temperature conditions. In the present work, the fracture properties of bond coats is measured with micron-scale resolution using edge notched doubly clamped microbeam structures positioned at individual zones of the graded bond coat, subjected to bending. In order to extract the stress intensity factor for this new configuration and to determine the stress distribution and stability of this geometry under different loading conditions, extended finite element analysis (XFEM) is carried out. After establishing the microbeam geometry as a viable fracture toughness testing configuration, the contribution of different microstructural variables to toughening at room temperature is studied using SEM based in-situ testing. Since the exact composition and structure of the coating depends principally on the elements constituting the matrix-Pt, Ni and Al content, which themselves depend on the deposition parameters, we have examined in detail, coatings aluminised at different temperatures (increasing coating thickness), varying Al content in the pack mixture and starting Pt thicknesses during electro-deposition. These parameters are by no means exhaustive and there is wide scope to investigate the effect of other processing variables as well as their synergistic effects on the mechanical behavior of these coatings. Following this, the high temperature fracture behavior of the stand-alone coatings in tension is also studied to determine their brittle to ductile transition mechanism in the presence of a notch. While this covers the average behavior of the entire coating cross-section, such a study is important to establish the BDTT unambiguously since there are chances of under-estimation of these temperatures in the absence of a notch. Also free¬standing coatings without the underlying substrate offer respite from residual stresses influencing the results of such tests. The present study essentially consists of two distinct parts, one focused on the development of the testing technique to cover multiple length scales of any graded thin film or coating and the other on the determination of fracture properties of the bond coat using these methods. The thesis reads in the following way: Chapter 1 gives an introduction to the diffusion aluminised bond coats, with a focus on the failure mechanisms associated with them while underlying the need for small scale testing in these systems. The conditions driving failure in bond coats can be vast and varied and it is extremely difficult to pin-point a single important cause and also to develop predictive capabilities regarding their failure. This is described as the motivation for the present work, with an objective of finding the variation in fracture toughness values for PtNiAl bond coats of different coating thicknesses and Pt content across the temperature range spanning the BDTT of the sample. Chapter 2 describes in detail all the available literature on thermal barrier coatings in general, and diffusion aluminide bond coats in particular, while specifically highlighting its mechanical response to loads during service. The deposition parameters during pack aluminizing and the graded microstructure which develops as a consequence of the diffusion process are described. The material’s microstructure dictates its properties, but there has been limited work on the mechanical behavior of the coatings themselves due to the difficulty in preparation and testing of free-standing films of the same. Since the base matrix is that of β¬NiAl, and there has been extensive work reported on bulk NiAl in the literature, which is discussed next. This would serve as a benchmark for comparison with the properties of the bond coats themselves, which are expected to respond differently due to their continuously evolving and complex microstructure. A summary of the known mechanical properties of the coatings themselves is given next along with the failure mechanisms that have been proposed. Since the study deals with fracture properties, a short introduction of linear elastic fracture mechanics follows before elaborating on the various small scale fracture testing geometries that have been developed. There are specific differences between testing geometries, stress states as well as in the instrumentation between small scale and bulk fracture toughness tests, which are highlighted. Since these configurations are material and device specific, each group has worked out its own instrument capabilities and mechanics required to extract the mechanical properties of interest from these testing techniques. Due to these differences in addition to the differences in the size scales of the samples tested, the reported properties show a wide variation. Lack of standards add to the difficulty in interpretation of the data; moreover add to the controversy on whether a size effect exists for fracture, as it does for strength. All the non-standard small scale testing configurations require modeling and simulation to extract the desired properties from them, and the present study applies the XFEM to determine the stress distribution and calculate the stress intensity factors corresponding to the fracture loads recorded from experiments. An introduction to the XFEM method is given in the last part. Chapter 3 gives all the experimental and simulation procedures that were carried out in the present work. Since the bond coat properties need to be compared with their bulk counterparts, both the samples are characterized. The exact material compositions chosen for the study were plain NiAl, 2PtAl and 5PtAl among the pack aluminized coatings and bulk arc-melted PtNiAl samples with varying concentrations of Ni and Pt which matched the bond coat matrix compositions. The choice of the three coatings was made depending on the previously known information regarding their microstructure. The deposition conditions, temperature and times of annealing are listed, followed by a brief summary of the general characterization techniques used to study the microstructure of the bond coats before and after fracture testing. Since the micro-beams under bending were fabricated using a focused ion beam, and the micro-tensile specimen were machined by electro-discharge machining, both the micro-machining procedures are described. At such small length scales, conventional testing methods cannot be used and several modifications were incorporated to the testing geometries which are described in the next section which covers two principal fracture testing methods-microbeam bending and mini-tensile testing, along with the advantages and limitations of each. Modeling is an indispensable tool for determining stress distributions in such new geometric configurations involving material property variations, and details of the exact XFEM procedure that was implemented in ABAQUS is given in the last part of this chapter. Chapter 4 summarises the microstructure and indentation properties of the bond coat and bulk NiAl samples characterised using X-ray diffraction, electron microscopy and nanoindentation. XRD was used for phase identification, texture and determination of lattice parameters of the specimen, which confirmed β-NiAl (with no texture) as the matrix with the lattice parameter varying as a function of composition. The SEM-EPMA combination was used for probing the compositional and microstructural gradients, grain size and precipitate distribution across the coating cross-sections. The bond coat was found to have 4 distinct zones with the Ni:Al ratio gradually rising across its thickness. In addition to this, the four zones had very different grain sizes, precipitate type and distributions. Hardness and modulus values were reported from nanoindentation measurements across the coating thickness over a temperature range from 25 to 400˚C and were seen to follow the composition gradients in different ways based on the effect of the off-stoichiometric defects on these properties. The hardness was found to be a minimum for the zone with stoichiometric composition, as was the case in the bulk sample, while the modulus dropped continuously with increasing Ni content in the matrix. These are important to develop a one-to-one correlation with the fracture properties and to understand the micro-mechanisms of the same. Chapter 5 gets on with the specifics of the testing geometry. Since most of the variables of the testing technique were studied using simulation procedures, a large part of this chapter deals with the results from the modeling technique using XFEM. The XFEM is introduced in detail and its applicability in modeling of cracks and discontinuities and advantages over conventional FEM are explained. The material properties are taken from the nanoindentation data and the modeling assumes linear elastic fracture mechanics. As a validation measurement, a conventional three point beam is modeled in bending and the results compared with analytical solutions of the same. The three point beam bending geometry is also used as a benchmark to study the stability of the new geometry, now with fixed boundaries in place of a free ends. This is followed by the results from the modeling for different variables like mesh density, notch root radius, loading offsets, beam dimensions and crack length (a)/specimen width (W) ratios where both the stress distribution as well as KI are captured in 3-D for stationary cracks while crack trajectories are obtained for propagating cracks. The notch root radius is seen to not affect KI below ~300 nm and such notch radii are easily machinable in the FIB at lower currents. The crack trajectory from the experiments is seen to follow the direction of maximum tangential stress, which is also modeled very well in the XFEM. The contribution of KII to the measured stress intensity factor with increasing offsets is also calculated from the model. Stable cracking is seen for the clamped beam geometry, with KI dropping off beyond a critical a/W ratio. This was true even for a model assuming homogeneous, elastic properties with a flat R-curve under load control. This makes the clamped beam structure require higher loads for continued propagation of cracks. This critical ratio is dimension dependent, making a shorter thicker beam stable in comparison to a longer, slender one. This is unusual, especially in comparison to the three point bend geometry which shows stable cracking only in displacement control, specifically for large a/W ratios alone. Also superimposition of the load-displacement curves from simulations with those of experiments gives a good-fit. The experimental results are shown next to back¬up the claims made on geometric stability of such clamped structures. Digital Image Correlation is introduced as a means for direct measurement of crack opening displacements (COD) and fracture toughness without the aid of KI formulations. This also served as a cross¬check on the assumptions of linear elastic fracture mechanics (LEFM) made in the simulation and a good correlation is seen between the CODs measured experimentally and that obtained from the FEM analysis. Fracture toughness measurements of brittle materials with known KIC values, like fused silica glass and single crystal Si film from this proposed geometry are reported as additional validation of this geometry. Further the capabilities of in-situ testing using this geometry to measure R-curve and fatigue properties along with the initiation KIC values are shown via results from monotonic and cyclic loading under different conditions. Chapter 6 returns to address bond coat fracture at room temperature, which is the main objective of the present study. Fracture toughness is evaluated both ex-situ and in-situ, using clamped microbeam bending experiments across individual zones of the 5PtAl bond coat and for different initial Pt contents in the zone 2. KIC is seen to rise sharply with increasing Ni content of the matrix in the former case, from 5 to 15 MPam1/2 which is attributed to the change in defect chemistry with changing stoichiometry. Al rich NiAl is found to be more brittle due to vacancy hardening while Ni rich NiAl is known to increase the metallic character of the NiAl bond. Both Ni rich and Pt rich (Pt,Ni)Al give higher toughnesses among the coatings studied while the crack trajectories and toughening mechanisms distinctly depend on the precipitate morphology in individual zones. Alloying additions are seen to add to the complexity of the fracture behavior of bond coats by strengthening the matrix or by improving its ductility. Micro-kinking, grain boundary and precipitate bridging are seen in the crack wake as contributing factors to partial closure of the crack on unload. The influence of each of the microstructural variable on the fracture mode is dissected in detail before coming to an overall conclusion. The microbeams show controlled, stable cracking, which enable following of the crack trajectories across micron-length scales and make R-curve measurements possible. Both 2PtAl and 5PtAl compositions show a rising R-curve within the length scale of an individual microbeam tested. Size and geometric effects on real vs apparent R-curve behavior are discussed at the end of the chapter. Chapter 7 addresses a different area of high temperature fracture of bond coats, which becomes relevant in terms of determination of brittle to ductile transition temperature (BDTT) in notched specimen and in evaluating topography after failure across this temperature range. This set of tests is designed to measure fracture toughness and study the fracture mode along the temperature scale to exactly identify the BDTT for a given bond coat composition and strain rate, below which the coating undergoes brittle catastrophic fracture and beyond which it creeps and relaxes plastically at very low stresses. Notched free¬standing bond coat specimens are pulled in uni-axial tension to fracture and the stress at failure is used to calculate the average fracture toughness of the bond coat. The stress-strain curve shows linear elastic behavior upto the BDTT of the bond coat as expected, beyond which it becomes increasingly plastic. The KIC is seen to rise marginally upto 750˚C beyond which it showed a significant increase, from which the BDTT was calculated to be ~775˚C for notched samples. The KIC is not reported beyond the BDTT due to irrelevance of LEFM after macroscopic plasticity sets in. Fracture mode is seen to change from transgranular cleavage below the BDTT to void coalescence and ductile rupture beyond it. The experimental challenges, differences in the through thickness KIC’s obtained from tensile tests vis a vi bend tests (due to changing stress states and size scales), as well as mechanisms of ductile to brittle transition in the context of previously available literature are discussed. Chapter 8 gives the closure and important conclusions from the present work. It summarises the key results from the testing technique and highlights the proposed mechanisms which bring about a rising fracture toughness with both increasing Ni:Al ratio across the bond coat cross-section and across individual micro-beams themselves. Some new techniques and geometries which can be adopted for fracture property determination, on which work was initiated but not complete, are also proposed. The last part of the chapter deals with the future implications of the results found and some open threads and challenges on bond coat optimisiation for different properties, which are yet to be dealt with.