H.E. Evans

Smart overlay coatings — concept and practice

Smart overlay coatings are a functionally gradient coating system designed to provide high temperature corrosion protection over a wide range of operating conditions. The SMARTCOAT design consists of a MCrAlY base, enriched first in chromium, then aluminium to provide a chemically graded structure. At elevated temperatures, above 900°C (1650°F), the coating oxidises to form a protective alumina scale. However, at lower temperatures this alumina scale does not reform rapidly enough to confer protection under type II hot corrosion conditions. The coating is therefore designed with an intermediate chromium-rich interlayer, which permits the rapid formation of chromia healing areas of type II corrosion damage. Laboratory and burner rig tests have been carried out on a series of developmental smart overlay coatings. These have shown that the development of an intermediate chromium-rich phase provides protection under low temperature hot corrosion conditions, while the aluminium-rich surface layer provides resistance to high temperature oxidation and type I hot corrosion. Thus, the single application of SMARTCOAT permits operation over a broad range of industrial and marine turbine conditions.

Mechanisms of breakaway oxidation and application to a chromia-forming steel

Breakaway oxidation or chemical failure has beendescribed in this paper in terms of two possiblemechanisms and applied to the behavior of achromia-forming 20Cr-25Ni austenitic steel. Bothmechanisms relate to the depletion of chromium arisingfrom its selective oxidation and quantitative modelingof the depletion profile is used to identify thedominant chemical-failure mechanism as a function oftemperature. Intrinsic Chemical Failure (InCF) develops whenthe chromium concentration within the alloy at theoxide-metal interface is less than that in equilibriumwith chromia. This occurs at high temperatures, typically above 1390 K, but the temperature atwhich the alloy becomes susceptible to this form offailure increases as the alloy grain size decreases. Atlower temperatures, chemical failure is associated with the general depletion of chromium acrossthe specimen section to a level below which reformationof a healing chromia layer will not occur, should thesurface layer become damaged. In this regime, failure is termed Mechanically Induced ChemicalFailure (MICF).

The Failure of Protective Oxides on Plasma-Sprayed NiCrAlY Overlay Coatings

The oxidation behavior in air of air-plasma sprayed (APS) overlay coatingsof Ni–25Cr–6Al–Y have been studied at 1100°C. Aprotective alumina scale developed after 5- to 10-hr exposure with, initially,parabolic growth kinetics. With protracted exposures (>100 hr),subparabolic behavior developed, associated with aluminum depletion withinthe coating caused, principally, by internal oxidation of the low-densityAPS structure. This depletion caused intrinsic chemical failure, manifestedby the formation of a layer of Cr,Al,Ni-rich oxide beneath the residualalumina layer. Associated with this process of chemical failure was theformation of a layer of porous Ni,Cr-rich oxide above the aluminalayer. Oxide spallation occurred by delamination within this layer duringcooling; the spallation sites tended to lie above protuberances in theunderlying coating. Initial spallation occurred at a critical temperaturedrop, which decreased rapidly with increasing exposure time. A nonrigorousmodel of this spallation process has been developed which envisages thatdelamination occurs by the propagation of an oxide void under the action ofout-of-plane tensile stresses developed during cooling. Agreement with thespallation data is encouraging and shows that the deterioration ofspallation resistance with exposure time arises not only because oxidethickness increases but also because the maximum void size within the porousoxide layer increases.

A physics-based life prediction methodology for thermal barrier coating systems

A novel mechanistic approach is proposed for the prediction of the life of thermal barrier coating (TBC) systems. The life prediction methodology is based on a criterion linked directly to the dominant failure mechanism. It relies on a statistical treatment of the TBC’s morphological characteristics, non-destructive stress measurements and on a continuum mechanics framework to quantify the stresses that promote the nucleation and growth of microcracks within the TBC. The last of these accounts for the effects of TBC constituents’ elasto-visco-plastic properties, the stiffening of the ceramic due to sintering and the oxidation at the interface between the thermally insulating yttria stabilized zirconia (YSZ) layer and the metallic bond coat. The mechanistic approach is used to investigate the effects on TBC life of the properties and morphology of the top YSZ coating, metallic low-pressure plasma sprayed bond coat and the thermally grown oxide. Its calibration is based on TBC damage inferred from non-destructive fluorescence measurements using piezo-spectroscopy and on the numerically predicted local TBC stresses responsible for the initiation of such damage. The potential applicability of the methodology to other types of TBC coatings and thermal loading conditions is also discussed.

Diffusion Cells and Chemical Failure of MCrAlY Bond Coats in Thermal-Barrier Coating Systems

It is proposed that bond coats in thermal-barrier coating (TBC) systems, particularly those deposited by plasma spraying, can contain regions which are diffusionally isolated from the bulk of the coating. This can arise through the internal formation of alumina layers as a consequence of the ingress of molecular oxygen into the relatively porous structure. Such isolated regions, termed diffusion cells, will experience enhanced depletion of aluminum as a result of the continued thickening of the alumina layer at their surface. This process has been demonstrated for a CoNiCrAlY bond coat after oxidation in air at 1100°C. A consequence of this enhanced depletion is that chemical failure will occur sooner in diffusion cells and voluminous breakaway oxides will form above them at the interface of the bond coat and the ceramic top coat. The associated spatial variation in oxidation and displacement rates across the surface of the bond coat are expected to aid delamination of the outer ceramic layer.

Mechanical failure of thin brittle coatings

Abstract Thin brittle layers are deposited or developed on component surfaces for a variety of reasons. In many practical applications the layers are stressed by internal residual stresses (due to growth, deposition processes or thermal transients) or by externally applied loads. Under such conditions, coating failure can occur, which may consist of through-thickness cracking and/or cracking along (or parallel to) the coating substrate interface. This paper reviews proposed mechanisms and models for cracking and spallation of thin brittle coatings, specifically due to differential strains between the coating and substrate. Failure of coatings on flat substrates, under tensile or compressive stress, is discussed and the effect of surface curvature is addressed.

Comparison of Oxidation-Growth Stresses in NiO Film Measured by Deflection and Calculated Using Creep Analysis or Finite-Element Modeling

An attempt was made to determine the strain and the stresses generated by the growth of an oxide film using several approaches: an experimental one by means of deflection tests and modeling using either a recently developed creep analysis or a finite-element simulation. A new deflection apparatus was developed and NiO growth studied during the early stages of oxidation of a Ni80Cr20 alloy at 900°C, since many microstructural, kinetics and mechanical data are available for this system. The comparison of experiments and modeling indicate that the oxide layers are mostly subjected to compressive stresses when NiO is growing and the stress level and evolution clearly show that viscoplastic strain occurs in both the substrate and the oxide during oxidation. The comparison between the two modeling approaches with experiment leads to good agreement and suggests that the compressive-growth stresses derive from the lateral expansion of the fraction of new oxide that is formed within the oxide layer.

Modelling oxide spallation

Temperature changes pose a significant threat to the integrity of protective oxide layers because of the differential strains developed between oxide and substrate. These may induce either tensile ...

The Oxidation of NdFeB Magnets

The oxidation kinetics in air of a commercial NdFeB magnet have been investigated over the temperature range 335–500°C. The oxide microstructure has been characterized by SEM, XRD and cross-sectional TEM. The results show that the external scale formed consists of an outer layer of Fe2O3 and an inner layer of Fe3O4 but that the principal degradation process is the formation of an extensive zone of internal oxidation. HREM has been used to show that this zone contains NdO particles embedded in an α-Fe matrix. These particles are discrete and very small, approximately 2 nm in diameter, and have an amorphous structure. The α-Fe matrix has a columnar grain structure with a grain width of approximately 100 nm. It is argued that the high rates of internal oxidation arise because the external-oxide layers are not protective at the oxidation temperature, and oxygen penetrates to the zone front by fast diffusion along the columnar α-Fe grain boundaries.

Creep relaxation and the spallation of oxide layers

Abstract The ability to predict the onset of spallation of protective oxide layers is an important requirement in evaluating the endurance of high temperature coatings or thin-sectioned components. Oxide spallation tends to occur during cooling, when the oxide layer is usually in compression. Considerable progress has been made in modelling spallation from flat substrates under such conditions, and much of this work is reviewed in this paper. In particular, the results of finite-element modelling of oxide/metal interfacial cracking are presented for both chromia-and alumina-forming substrates. It is shown that creep relaxation in the coating or alloy can retard the growth of the interfacial crack even during fast cooling but the extent of retardation increases with lower cooling rates. When such creep relaxation is extensive, i.e. at low cooling rates or with substrates weak in creep, improved spallation resistance results. For such cases, a simple critical strain-energy approach can be used to predict the onset of spallation.