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The excellent high temperature microstructure stability, high strength, and oxidation resistance of intermetallics has for long driven the development of intermetallic based alloys. More recent studies demonstrated attractive properties of eutectic intermetallic in the Ni-Al-Zr systems. This thesis deals with study of binary Ni3Al+Ni7Zr2, NiAl+Ni7Zr2 and Ni3Al+NiAl+Ni7Zr2 ternary intermetallic eutectic alloys in this system and includes the identification of compositions that would yield each eutectic structure and their microstructural characterization, mechanical and oxidation behavior. The thesis is divided into six chapters. Chapter 1 reviews the study on high temperature materials development and presents the objectives of work in the current thesis. Various experimental techniques used for alloy preparation (vacuum arc melting and vacuum suction casting), microstructural characterization (optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray Diffraction (XRD), electron probe micro analyzer (EPMA), differential scanning calorimetry (DSC)), compression tests, microhardness tests and thermo gravimetric analysis (TGA) are described in Chapter 2. The specific background of work related to each chapter together with experimental results and discussion are given in next three chapters. Chapter 3 reports the method of identification of the composition for each of the eutectic alloys referred to above. The identification of alloy compositions of binary eutectics Ni3Al+Ni7Zr2 (Ni-13.5Al-11Zr), NiAl+Ni7Zr2 (Ni-19Al-12Zr) and Ni3Al+NiAl+Ni7Zr2 ternary eutectic (Ni-18.4Al-11.6Zr) is carried out with the help of available liquidus projection of Ni-Al-Zr system, and the iterative melting of numerous compositions that were refined to define the critical compositions for each eutectic. The microstructural features of these alloys have been characterized using optical and electron microscopy. Phase identification is confirmed by X ray diffraction, EPMA and TEM. The microstructure of Ni3Al+Ni7Zr2 and Ni3Al+NiAl+Ni7Zr2 ternary eutectic alloy shows similar eutectic morphologies. The eutectic colony consists of lamellar plates at center and intermixed lamellar-rod irregular morphologies towards the boundaries of the colonies. However, the NiAl+Ni7Zr2 eutectic alloy shows a fine, lamellar plate morphology throughout the microstructure. The orientation relationship between eutectic phases is determined using TEM technique for each alloy composition. Onsets of melting and liquidus temperatures have been identified by Differential Scanning Calorimetry. Modified liquidus projections of Ni-Al-Zr system near the Ni3Al+NiAl+Ni7Zr2 ternary eutectic region have been derived from present experimental work. Chapter 4 focuses on understanding the mechanical behaviour of these individual eutectics at room temperature and high temperature. An attempt has been made to correlate the microstructure and mechanical properties of eutectics by measuring room temperature hardness, compressive yield strength at various temperatures, and examination of slip bands, crack initiation and fractography. It is observed that NiAl+Ni7Zr2 eutectic possesses the highest yield strength and hardness followed by ternary eutectic and then the Ni3Al+Ni7Zr2 eutectic. The yield strength of these eutectics decreases rapidly beyond 700oC and this decrease is accompanied by substantial increase in compressive ductility and steady state flow, with little work hardening. Chapter 5 explores the isothermal oxidation behavior at high temperatures of these eutectic alloys. Oxidation kinetics have been measured at various temperatures (900oC, 1000oC, 1050oC and 1100oC) are carried out using the thermo gravimetric analysis technique (TGA). The oxidation behavior has been characterized using TGA, X ray diffraction and EPMA. The Top surface of oxide layer shows compact, NiO layer with a fine grain size. The cross section of oxide samples shows five distinct microstructural and compositional layers at steady state. Attempt has been made to understand the oxidation mechanism, sequence of layer formation in correlation with microstructure and weight gains, rate constants and activation energy analysis. Finally Chapter 6 presents a summary of the current work and suggests for further work.

The continuing quest for higher performance levels of modern gas turbine engines has been accompanied by the demand for higher engine operating temperatures. The use of Thermal Barrier Coatings (TBCs) enabled gas turbines to operate at higher temperatures by protecting the blade material (nickel superalloy) while operating in extreme environments. The TBC system typically consists of a bond coat for protection of the nickel–based superalloy against oxidation followed by a top coat consisting of a thermally insulating zirconia-yttria. In addition to the complex gradation in phases, the coatings are subjected to continuous oxidation with service exposure, mechanical loading on rotating parts, fatigue, thermal mis-match and temperature gradients. Hence, the study of failure mechanisms of TBCs become important in deciding operational reliability and service life of the coating. As there are many systems in which the operating temperatures are not high enough to warrant the use of the top coat (ceramic layer), the study of failure mechanisms in superalloys coated with only the bond coat continue to be of great interest. The present work concentrates on the fracture behavior of NiAl bond coats on nickel superalloy and seeks to evaluate the fracture toughness of the coating through the use of micro-machined samples. A review of the relevant literature indicated that while a considerable body of work exists on bulk tests of failure (spalling, splitting, etc.), not much has been reported in the open literature on the evaluation of basic quantities such as the toughness of the coating itself. The present thesis seeks to establish a protocol for the evaluation of toughness and crack propagation mechanisms in coatings through a combination of micro-sample testing that allows fracture to be correlated with location in the film and the use of an analytical model to quantitatively evaluate stress intensity factors in a bi-material system. A system of NiAl coating produced by pack aluminizing is studied for the fracture properties of the coating. Specimen geometries are optimized to enable micro-cracks to be machined and propagated in a low load testing system, such as a depth sensing indenter, so that crack lengths (and position relative to the interface) can be correlated with load. To enable linear elastic theory to be used, dimensions are determined that allow fracture before general yielding. A three point bending test using miniaturized micro-beam specimens of ~ 4 X 0.3 X 0.3 mm is found to be suitable for the above purpose. The technique is a challenging one that requires focused ion beam machining (FIB) along with careful handling and alignment of small samples. The coatings are characterized for their microstructure by electron microscopy to identify compositional variation across the thickness and to determine the thickness of the coating and inter diffusion zone (IDZ). The crack advancement is monitored with increments of loading and the stress intensity factor is evaluated using a program written in “MAPLE” for an edge crack subjected to bending in a bilayered material. Surprisingly, fracture in this system is found to be stable owing to a gradual increase in toughness from the coating surface to the interface. Such an increase from less than 2 to more than 9 MPa m0.5 may be due to the increasing Ni/Al ratio across the thickness of the bond coat. Crack branching is observed as the crack approaches the IDZ and the reasons for such behaviour are not fully understood. This work establishes the viability of this technique to determine fracture properties in highly graded coated systems and may be readily extended to more complex coating architectures and other forms of loading such as cyclic, mixed mode, etc.

This thesis is an attempt to understand ways to improve thermo-mechanical and structural properties of nano-structured materials. A detailed study on computational design and analysis of metallic nanowires is carried out. Molecular dynamic simulation method is applied. In particular, FCC metallic nanowires, NiAl, and CuZr nanowires are studied. Various bottom-up approaches are suggested with improved structural and thermo¬mechanical properties. In the first part of the thesis, Cu nanowires are considered. Existence of a novel and stable pentagonal multi-shell nanobridge structure of Cu under high strain rate tensile loading is reported. Such a structure shows enhanced mechanical properties. A three-fold pseudo-elastic-plastic shape recovery mechanism in such nanowires is established. This study also shows that the length of the pentagonal nanobridge structures can be characterized by its inelastic strain. It is also reported that an initial FCC structure is transformed into a new HCP structure. The evidence of HCP structure is confirmed with the help of experimental data published in the literature. Subsequent to the above study, a novel mechanism involving coupled temperature-stress dependent reorientation in FCC nanowires is investigated. A detailed map is generated for size dependent stress-temperature induced solid-solid reorientation in Cu nanowires. In the second part of the thesis, deformation mechanisms in NiAl based intermetallic nanowires are studied. A novel mechanism of temperature and cross-section dependent pseudo-elastic/pseudo-plastic shape and strain recovery by an initial B2 phase of NiAl nanowire is reported. Such a recoverable strain, which is as high as ~ 30%, can potentially be utilized to realize various types of shape memory and strain sensing phenomena in nano-scale devices. An asymmetry in tensile and compressive yield strength behavior is also observed, which is due to the softening and hardening of the nanowires under tensile and compressive loadings, respectively. Two different deformation mechanisms dominated by twinning under tension and slip under compression are found. Most interestingly, a superplastic behavior with a failure strain of up to 700% in the intermetallic NiAl nanowires is found to exist at a temperature of 0.36Tm. Such superplastic behavior is attributed to the transformation of the nanowire from a crystalline phase to an amorphous phase after yielding of the nanowire. In the last part the work, another type of nanowires having Cu-Zr system is considered. A novel stress induced martensitic phase transformation from an initial B2 phase to BCT phase in a CuZr nanowire under tensile loading is reported. It is further shown that such a stress induced martenistic phase transformation can be achieved under both tensile as well as compressive loadings. Tensile-compressive asymmetry in the stress-strain behavior is observed due to two different phase transformation mechanisms having maximum transformation strains of ~ 5% under compressive loading and ~ 20% under tensile loading. A size and temperature dependent tensile phase transformation in the nanowire is also observed. Small nanowires show a single step tensile phase transformation whereas the nanowires with larger size show a two step deformation mechanism via an intermediate R-phase hardening followed by R-phase yielding. A study of energetic behavior of these nanowires reveals uniform distribution of stress over the nanowire cross-section and such stress distribution can lead to a significant improvement in its thermo-mechanical properties. Similar improvement is demonstrated by designing the nanowires via manipulating the surface configuration of B2-CuZr system. It is found that the CuZr nanowires with Zr atoms at the surface sites are energetically more stable and also give a uniform distribution of stresses across the cross-section. This leads to the improvement in yield strength as well as failure strain. An approach to design energetically stable nano-structured materials via manipulating the surface configurations with improved thermo-mechanical properties is demonstrated which can help in fundamental understanding and development of similar structures with more stability and enhanced structural properties. Further ab-initio and experimental studies on the confirmation of the stability of the nanowires via manipulating the surface site is an open area of research and related future scopes are highlighted in the closure.