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A detailed overview of oxygen insertion in titanium nitrides is presented. Our atomic-scale approach is based on DFT point defect energetics and thermodynamics based on the Independent-Point-Defect Approximation (IPDA). In the first part, the study of intrinsic defects (vacancies, anti-sites, interstitials, and dumbbells) is carried out in the δ-TiN, ϵ-Ti2N, and δ′-Ti2N binary compounds. It is shown that nitrogen vacancies are the main point defects in all of the Ti-rich nitrides. The N-rich phases show a more complicated behavior, with either interstitial N or Ti vacancies as the predominant defects. Noticeably, while the stability of δ′ is pointed out as controversial, the thermodynamic modeling of ϵ- and δ′-Ti2N shows that a proper identification of the relevant interstitial sites is crucial for understanding the physico-chemistry of these two nitrides. The thorough investigation of the Ti–N phase equilibria resulting from point defect thermodynamics confirms the validity of the chosen IPDA approach, which provides a solid basis for further studies, forming the second part of this work, on oxygen effects in Ti nitrides. The effect of O on the point defect structures of Ti nitrides is studied, and it is shown that this element has a strong tendency to substitute nitrogen, explaining the diffusion barrier effect of the nitrides. Finally, to emphasize the far-reaching practical implications of these atomic-scale results, we consider the oxygen behavior and related oxidation trends of Ti-based alloys under air conditions. We show how ab initioIPDA helps to rationalize the identification of the relevant Ti–N–O system at stake for oxidation, the roles of the phases, and the external conditions to which it is subjected as it relaxes toward equilibrium. We also show how the thermodynamic criteria derived from IPDA can help unravel the ambiguous experimental links between nitride formation and lower amounts of O dissolved in the metal of preoxidized Ti-based alloys.

The protection of the titanium based Ti6242S alloy against oxidation at moderate temperature is investigated, through the application on its surface of a 300 nm thick, amorphous alumina film. The latter is processed by metalorganic chemical vapor deposition at 500 °C from dimethyl aluminum isopropoxide. Upon oxidation at 600 °C for 5000 h, an interfacial zone is created between the alloy and the external protective layer, composed of unaffected alumina. In these conditions, the mass gain per unit area is eight times lower than that of the bare alloy, while the hardness of the alloy remains unaffected, revealing negligible oxygen ingress attributed to the efficiency of the protective coating. Finally, alumina coated samples show negligible mass change after 80 one-hour thermal cycles between 50 °C and 600 °C, showing excellent coating adherence on the Ti alloy.

Exhaust manifolds for diesel engines are made of high-Si ferritic nodular cast irons. It is experimentally well established that their oxidation kinetics are highly sensitive to the presence of water vapor, though the mechanism for such an effect is still controversial. In the present work, isothermal oxidation tests were performed on a SiMo nodular cast iron at 700°C and 800°C in dry and humid air for 25 and 50 hours. Other samples were oxidized for 50 h with in-situ change in H2O content after 25 h, switching from dry air to humid air or the other way round. Samples were then analyzed using XRD, SEM-EDS and Raman spectroscopy. Thermogravimetric records clearly showed the effect of temperature and environment on oxidation and decarburization. The kinetics of these phenomena depends on silica formation at the metal-oxide interface. At both temperatures, water vapor was seen to promote internal oxidation of Si instead of its external oxidation. This leads to higher oxidation kinetics at 700°C and higher decarburization kinetics at 800°C.

In the field of advanced ceramics, Spark Plasma Sintering (SPS) is known to be very efficient for superfast and full densification of ceramic nanopowders. This property is attributed to the simultaneous application of high density dc pulsed current and load, even though the sintering mechanisms involved remain unclear. In the first part of the paper, the mechanisms involved during SPS of two insulating oxide nanopowders (Al2O3 and Y2O3) are discussed while in the second part illustrations of the potential of SPS will be given for (i) Consolidation of mesoporous or unstable nanomaterials like SBA-15 or biomimetic apatite, respectively; (ii) Densification of core (BT or BST)/shell (SiO2 or Al2O3) nanoparticles with limited or controlled reaction at the interface. (iii) In-situ preparation of surface-tailored Fe–FeAl2O4–Al2O3 nanocomposites, and finally (iv) One-step preparation of multilayer materials like a complete thermal barrier system on single crystal Ni-based superalloy.

Aeronautic gas turbine blades, vanes and combustion chambers are protected against high temperature oxidation and corrosion by single or multilayered coatings. These include environmental coatings, generally based on Pt-modified Ni aluminides or MCrAlY overlays (where M = Ni and/or Co), thermal barrier coating (TBC) systems including a ceramic thermally insulating layer, and abradable seals. The present work shows the ability of the Spark Plasma Sintering technique to rapidly develop new coatings compositions and microstructures. This technique allows combining powders and metallic foils on a superalloy substrate in order to obtain multilayered coatings in a single short production step. Fabrication of MCrAlY overlays with local Pt and/or Al enrichments is shown, as well as fabrication of coatings made of -PtAl2, -PtAl, α-AlNiPt2, martensitic and (Ni,Pt)Al or Pt-rich ’ phases, including their doping with reactive elements. The fabrication of a complete TBC system with a porous and adherent Yttria Stabilized Zirconia (YSZ) layer on a bond-coating is also demonstrated, as well as the fabrication of a CoNiCrAlY-based cermet coating for abradable seal application. Difficulties of fabrication are reviewed, such as Y segregation, risks of carburization, local over-heating, or difficulty to coat complex shaped parts. Solutions are given to overcome these difficulties.

The insertion and diffusion energies of oxygen in presence of vacancies in nickel are studied by using the first-principle projector augmented waves (PAW). When the oxygen atom is located in a substitution site, the formation of a vacancy-oxygen pair is observed. Furthermore, we show that the formation of divacancies allows the oxygen atom to migrate more easily in the metal. A model for the migration process of the three-defect system is proposed. Finally, thermal expansion effects are included in our study; it is shown that temperature effects emphasize the diffusion.

Thermal cycling has been observed to cause a transition from superficial alumina formation to internal oxidation and nitridation, an effect that was shown to depend on the specimen thickness and geometry, which can be described by a spalling-probability model. Once protection by a dense and adherent alumina scale got lost, the internal-corrosion rate is determined by the diffusivity and solubility of nitrogen and oxygen in the alloy. These parameters seem to depend not only on the temperature and the alloy composition but also on the applied mechanical stress. Internal nitridation under a superimposed creep loading was found to follow a higher rate constant than under just isothermal exposure. This effect can probably be attributed to dislocation-pipe diffusion, a mechanism which has been claimed also to be relevant for outward solvent diffusion during internal corrosion, a phenomenon, which was observed as a stress-relief mechanism during various internal-reaction processes

To get a better understanding of oxidation behavior of Ni-base alloys in PWR primary water, a numerical model for oxide scale growth has been developed. The final aim of the model is to estimate the effects of possible changes of experimental conditions. Hence, our model has not been restricted by the classical hypothesis of quasi-steady state and can consider transient stages. The model calculates the chemical species concentration profiles, but also the vacancy concentration profiles evolution in the oxide and in the metal as a function of time. It treats the elimination of the possible supersaturated vacancies formed at the metal/oxide interface by introducing a dislocation density at the interface and in the metal bulk. This latter density can be related to the cold-working state. Its effect on the vacancy profile evolution is studied in the case of a pure metal. Eventually an extension of the present model to the oxidation of Ni-base alloys is discussed regarding a recent vacancy diffusion model adjusted on Ni-base alloys.

During service, TBC can suffer degradation by CMAS, FOD, erosion or spallation. Whereas the first three are due to foreign particles, the last one is related to thermal cycling. When subjected to high temperature exposures followed by rapid coolings under oxidizing conditions, a TBC system undergoes morphological changes and stress development. This will initiate cracks which propagate and finally lead to failure by spallation. Consequently, the aim of the present study is to understand better the mechanisms responsible for such spallation events. Two kinds of TBC systems with different bond coatings (NiCoCrAlYTa or Pt-modified nickel aluminide bond coatings) are thermally cycled. Subsequently, SEM investigations on TBC systems after spallation concentrate on failure path, defect, morphological and microstructural changes to propose way for improving TBC system lifetime.

A model using a finite elements code is developed to simulate degradation due to combined cyclic oxidation and interdiffusion in materials used in high temperature components of gas turbines. Coating recession due to cyclic oxidation (oxide growth and spalling) is also modelled using a statistical approach. Interdiffusion between coating and superallloy is modelled to predict total Al depletion in the coating. The phase transformations in the alumina-forming coating and the effects of the precipitates at the coating / superalloy interface are investigated. The results of simulations are compared with experimental data. Effects of diffusion parameters and of cyclic oxidation kinetics are discussed.

MCrAlY coatings (where M = Co, Ni or Co/Ni) are widely used on turbine blades and vanes as oxidation and corrosion resistant overlays or as a bond-coating in thermal barrier coatings systems. MCrAlY are usually fabricated by Plasma Spraying, Physical Vapour Deposition, High Velocity Oxy-Fuel spraying or electrolytic techniques. The use of emergent Spark Plasma Sintering technique as a preparation method for NiCoCrAlYTa coatings has been presented previously [1]. SPS technique allows fast development of new coatings with a one-step fabrication of multilayered coatings. This work presents first results of the long term isothermal oxidation behaviour of Pt-Ni aluminide/NiCoCrAlYTa multi layered coatings. The obtained coating is dense and homogeneous. Isothermal oxidation up to 500 h at 1100°C leads to the formation of an adherent alumina scale with Y-rich precipitates and deep intergranular oxidation.

A diffusion barrier based on a NiW electrolytic coating has been developed to limit interdiffusion between a Ni-base superalloy (MCNG) and a β-NiAl bondcoating. Isothermal oxidation tests of 50h at 1100°C confirmed that W-rich layer formed with NiW coating modifies the oxidation behaviour of the bondcoat and limits interdiffusion. The diffusion barrier reduced β-NiAl  γ’-Ni3Al transformation in the bondcoating and prevented SRZ formation.

This paper examines the erosion and cyclic oxidation performance of novel thermal barrier coatings produced via the sol-gel route. The ceramic top coat, with a thickness of 5-80 m, was deposited via a sol-gel route onto standard MCrAlY and PtAl bond coats. In both the erosion and the cyclic oxidation tests it was found that the bond coat had a profound affect on the results. The erosion of the sol-gel coatings were compared to standard EB PVD and PS TBCs and were found to be significantly higher. The effect of aging (100 h at 1100°C) on the erosion rates was also evaluated and was found to increase the erosion rates. The information obtained from the erosion and cyclic oxidation tests have highlighted the need to develop and optimise the parameters for producing thicker coatings

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