Thermal Barrier Coating System for Gas Turbine Application ~ A Review B. Goswami, A.K. Ray, and S.K. Sahay*, National Metallurgical Laboratory (CSIR), Jamshedpur, India “Department of Metallurgy and Materials Science, National Institute of Technology, Jamshedpur, India (Received December 4, 2003) ABSTRACT. Ceramic coatings are refractory metal compounds deposited on substrates to reduce thermal loss and to protect components from high temperature. Thermal barrier coatings (TBC) are composite overlay of bond coat and ceramic coat on a superalloy substrate. Atomised deposition or splat deposition of fine semi- ‘molten particle technique deposits thin coatings of brittle ceramic ‘Thermal and mechanical strains arising from service exposure require structural compliance tolerances. This is facilitated by brittle constituent deposition over a ductile substrate. Electron beam physical vapour deposition and plasma spray technique lead to a tortuous intergranular network of coating. Porous deposition technique is applied in all cases instead of cementation ‘or continuous section thicknéss. ‘Thermal barrier coating is inevitable in aerospace engine sections operating at limiting conditions of strains. Thermal barrier coatings help in protection of high temperature components for maximum utilisation of component lives, and maximum utilisation of energy by operating at optimum allowable temperature limits ‘Thermo mechanical behaviour of TBC is optimised by in-situ formation and transformation mechanisms of alumina fom aluminium of substrate/bond coat and ‘metastable tetragonal. zirconia to stable tetragonal Zirconia respectively at temperature of service. While the former produces a volumetric contraction, the latter produces volumetric expansion. In service the composite system provides auto-toughening effects in due course. An intergranular tortuous network of ‘coating forms cracks on exposure of strain and the crack tip blunting forms cubic allotropy from metastable tetragonal phase, resulting in an increase in toughness due to elimination of e/a ratio. However, a prolonged exposure forms localised spallation zones, which are initiated by volumetric expansion stresses associated with nickel enrichment of thermally grown oxides (TGO) at bond coat/ceramic coat interface, and auto-sintering, Bond coat is applied to produce mechanical adherence and stress relaxation effects. Generally M-CrAlY families of bond coating alloys are used for this purpose. Exposure to operatingitest temperature produces thermally grown oxides (TGO) at interface. This occupies an intermediate zone in response to property interactions. TGO m ists of alumina being catalyzed by chromia and adhered by yttria, Active research is going on to study the mechanisms of auto sintering and auto-toughening of TBC. Work is in progress to explore how to decrease thermal expansion mismatch stresses by application of composite coatings made from functionally graded materials, microlaminated, and multilayered ceramic! ceramic or metalliciceramic or —metallie/metallic coatings. The application of laser scaling or remelting to inly cons BVol. 23, No. 2, 2004 reduce porosity of free surface and to increase glaze are other avenues to reduce diffusion of reactive gases and to increase internal heat transfer respectively. ‘The former increases life of bond coat/substrate, whereas the latter "increases energy efficiency -by maximum utilisation of heat ‘The main unsolved problem is spallation of ceramic coating, which is cohesively induced in either side of interface and spread out to interfaces of adhesion. TBC increases life more than two-fold for cases of aerospace engines, However localised spallation may rise by high temperature corrosion of bond coat/substrate, TGO stresses, gaseous/liquid contaminant diffusion’ impregnation through tolerance networking of voids, and erosion, Key words: Theimal barrier coating, Ceramic coating, Spallation, Bond coating, Life evaluation, and Functionally graded materials. INTRODUCTION Interest in the thermal barrier coating has increased dramatically in the past few decades as more and more successful applications are being reported. A remarkable combination of high temperature properties can be obtained by a suitable choice of the thermal barrier coatings. Thermal barrier coatings have been meticulously studied for a number of years and are currently being used to develop remarkable combinations of high temperature properties in a number of high temperature super-alloys. Under- standing of the complex interplay ‘of phenomena such as Uitfusion, oxidation, phase transformation, elas deformation, plastic deformation, creep deformation, thermal expansion, thermal conduction, radiation, fracture, fatigue and sintering, becomes a challenging task in design and development of TBCs. ‘Thermo-mechanical: and thermo-chemical_pheno- mena ate complex and diverse in nature. Hence it becomes a challenging task to analyse them in terms of fundamental principles to achieve their full potential. It is recognised that basic understanding of TBCs must be gained so that they can be developed to last the 74 Thermal Barrier Coating System for Gas Turbine Application- 4 Review lifetime of the components. Thermal barrier coatings suffer from problems of spalling and reduced adherence to substrate due to a number of reasons. It is believed thatthe thermal expansion mismatch across the interface is: responsible for such damaging behaviour. ‘Thermal barrier coatings are of considerable importance in applications such as aerospace engine sections operating at limiting conditions of strains, Thermal barrier coatings on high temperature alloys provide protection from environmental degradation, The choice of coating depends upon several variables such as the operating temperature, the nature of the environment, the nature of substrate, and the process of coating. The review covers in depth the current understanding of thermal barrier coatings and the future outlook. Ceramic coatings are high melting metallic oxides resistant to degradation tendencies within aggressive environments at high temperatures. Ceramic coatings that protect substrates from both high temperature corrosion and thermal fatigue are called Thermal Barrier Coatings (TBCs). Ceramics are oxides immune to oxidation, but are prone to spallation and lower adherence to substrate. Bond Coats (BCs) are applied between ceramic coat and substrate to reduce spallation and to increase adherence of life of the components by decreasing corrosion and thermal diffusion. Efficiency of the TBC components increases by maximum utilisation of energy and usage of high temperature of operation /1,2/. It is thought that TBC's are indispensable for the gas turbines along with cooling technologies to enharice its performance. It is now desired to give higher durability to TBC's so as to endure higher combustion temperature /3/. Thermo- mechanical characterisations of ceramic coatings have been tentatively based on relations of variation in thermal barrier coating properties with thermal and mechanical strain. The study of phase transformations is of prime importance to characterise ceramic coating by thermo-mechanical facts, Ceramic coatings undergo complex phase transformations. with variations in emperature and strain, Usually stabilised zirconias are used for these purposes. Stabilisations have been ied by incorporation of molecules into crystal ‘nia to resist phase transformation within required thermal and mechanical stress variations. ForB, Goswami et al, example, yttria stabilised zitconia produces a similar system, This at high temperature exists in cubie form, while rapid solidification transforms cubic to tetragonal ‘or metastable tetragonal form and retained cubic phases. Cooling at a rate lower than critical rate produces mixed phase compositions of metastable tetragonal, tetragonal, monoclinic, and cubic, Metastable tetragonal phases are more stable during thermal cycling /4/. A longer period or higher temperature of exposure transforms metastable tetragonal zirconia to monoclinic, or tetragonal zirconia, or retained cubic phases. Retained cubic phases transform to monoclinic with associated volume increment of 3-5% /5,6/. Similarly, strain associated at the crack tip of a propagating microcrack or pore and tortuous structural compliance tolerance, changes its phase from tetragonal to cubic at the second stage of crack tip blunting /7/. These are responsive to fracture toughness properties in ceramics. Ceramic coatings are lower in strength properties, so always depend on substrate properties. Ceramic coating resists heat conduction (up to 200°C) and protects substrate from overheating. The performance of TBC depends upon underneath bond coat, substrate and on interlayer properties. Nevertheless in most cases failure of ceramic coatings in service exposure is from initiation of crack at the interface of substrate, Generally ceramic coatings ‘are prepared by plasma spray deposition /1/. Rapid solidification of splats from spray produces highly columnar microstructure by inhomogeneous solidifica- tion’ process. Grain boundaries of interlameller ot columnar grains are often of an amorphous glassy composition /S/. This spalls later on by thermal cycling, and thus provides structural compliance. Aerodynamically smooth surfaces of TBC can be achieved by dense coating using homogeneous solidification to form fine grains consisting of boundaries without amorphous phases. Microcracks or tortuous as solidified intersplat voids increase thermal insulation and thermal shock resistance. However they enhance diffusion of gaseous oxygen from environment in addition to ionic diffusion to substrate. In-situ oxide Al03) layer formation at interface aluminised bond coat) reduce gaseous diffusion to substrate /2/ Increasing operating period increases interfacial out grown oxide (TGO) layer. /8/.. Volume expansion High Temperature Materials and Processes stresses, in addition to cyclic thermal stresses, produces, compressive loads on the ceramic coating and leads to spalling. Application of thermal barrier coatings in diesel engines reduces heat loss and overheating of ‘components. This raises fuel efficiency in addition 10 thermal efficiency by weight reduction and elimination of cooling devices like radiator respectively /9/. Application of ceramic microlaminated coating of alumina and yttria stabilised zirconia produces increasing phase -stability of composite coating than monolithic coating. Application of metallic micro laminations with gradually decreasing thermal conductivity towards outer layer produces, greater thermal compatibility in thermal barrier coating interfaces /10/. Implementation of laser sealing, improves surface properties to resist surface penetration and diffusion. The penetrations are responsive for accidental flaw formation through enhanced degradation rate due to heat permeability, and diffusion is, responsive to slow rate of degradation from corrosive contaminant /11/. Increase in strain tolerance and thermal fatigue, as well as corrosion resistance ‘of bonding layer are possible by shielding effects produced by laser remelting of plasma sprayed ceramic coat, Smooth surfacing of ceramics backed by porous ceramic coating in contact to bond coat provides a desirable combination of properties /12,13. PHASE TRANSFORMATION OF CERAMIC COATINGS AND CERAMIC STABILITY Zirconia forms a cubic phase above transformation temperature and monoclinic below transformation temperature at slower cooling rate. Any cation of similar ranges and cubic crystallinity stabilises zirconia polymorphism. Magnesia, ceria, yttria, lanthana etc. are used as stabilisers /14/. Phonon mode of conduction at, temperature of interest is interrupted by crystal lattice irregularity. ‘Thus stabiliser intérruption increases, insulation capacity. However associated . thermal gradient also raises thermal distress in the coating. For example, magnesium zirconate destabilises at above 950°C to form magnesia precipitate. The system on cooling zirconia transforms to monoclinic phases /2/. 15Vol. 23, No. 2, 2004 Fully stabilised 8-wi% yttria stabilised zirconia transforms cubic phase to tetragonal by diffusionless shear transformation on rapid solidification. This phase decomposes at 1400°C and yttria is diffused out of crystal lattice. However, this polymorph is stable at gas turbine aero-engine operating temperature, Limitations are imposed to this system by acid attack from combustion environment contamination. The reaction products formed in most cases are either volatile compounds or low eutectic compounds. Zirconia exists in three types of crystal phases, a low temperature monoclinic, an intermediate temperature tetragonal, and a high temperature cubic phase. Phase transition from tetragonal 10 monoclinic increase volume by 3-5% and causes failure. Proper selection of zirconia stabilisers Fepresses occurrences of monoclinic phase. Yttria partially stabilised zirconia on rapid solidification forms ‘on-transformable tetragonal phase without any change in composition. However, isothermal ageing transforms non-transformable tetragonal to a transformable tetra- gonal phase (low stabiliser) and a cubic phase (high stabiliser). During subsequent cooling stages transformable tetragonal phase transforms to ‘monoclinic: Comparative heat treatments of yttria stabilised Zirconia and ceria-yttria stabilised zirconia within 1300- 100°C for 100 hours show the absence of monoclinic phase in both ceramics, whereas at 150°C for 100 hours they show the presence of monoclinic phase in yttria stabilised zirconia only. The comparatively smaller ionic radii increase the diffusion tendency. As sprayed tetragonal phase content is more in yttria stabilised zirconia /14/, Partial stabilisation reduces vacancies at treatment temperatures. Consequently anion diffusion takes place at a lower rate than fully stabilised ceramics /15/. Degradation in yttria stabilised Zirconia system is mainly due to transformation from tetragonal to monoclinic phase at low ageing ‘temperatures, yttria concentration and distribution, Zirconia grain size, and stress affected in humid atmosphere. It is observed that tetragonality of zirconia increases after annealing, and subsequent hydrothermal ageing reduces monoclinic phase fraction, Stress relief annealing shrinks ‘a’ axis and extends ‘c’ axis to increase tetragonality. Limits of tetragonality increase 16 ‘Thermal Barrier Coating System for Gas Turbine Application A Review with temperature, The change in tetragonality is due to residual stress relief in crystal lattice. Low temperature hydrothermal ageing treatments show more monoclinic phases in low temperature annealed sample than high temperature one. This implies that the higher the tetragonality the higher is the reduction of tetragonal to monoclinic phase transformation, Cyclic ageing and annealing increases marginal tetragonal phase content as compared to stress relief annealing. However a high temperature annealing and low temperature ageing show marginal increase in monoclinic phase content, On eycling at low anneal temperatures the marginal monoclinic phase is reduced due to comparatively higher residual stress and lower volumetric stress, whereas on cycling at high annealing temperatures the reverse consequence of stress existence raises marginal monoclinic phase content. ‘The durability of zirconia thermal barrier coating is related to volume fraction of initial phases present in the system. It is observed that 5-10% ytiria improve toughness and prolong life by crack branching and release of intemal stresses by controlled tetragonal to monoclinic transformation. Below 6% yttria a fully metastable tetragonal structure is formed and results in volume variation by transformation to monoclinic Phase. At 10-12% yttria, autocatalytic transformation results in intergranular convoluted cracks. These appear due to volume expansion and contraction by 5-6% during tetragonal to monoclinic transformation. At 12% ytria the respective result is toughening by cubic ireonia at elevated temperature and monoclinic Zirconia at lower temperature, whereas at 14-16% yttria forms fully cubic yitria stabilised zirconia. BOND COATING Bond coating is a thermal sprayed coating applied to provide a ‘key’ for subsequent build-up coats of a different material. It gives adhesion between coating and substrate, the thermal barrier bond strength depends fon the process, and materials used /16,17/. Some sprayed materials adhere strongly to clean smooth surface, They are adherent over a wide range of conditions and a thin layer can serve as an‘anchor’ forB. Goswami et al. materials sprayed on top. Interface of superalloy (Substrate) and ceramic coating (TBC) plays a most important role in resisting failure. This interface is usually produced from different types of bond coating (BC). Based on variation of temperature of service exposure/experiment, every metallic constituent plays different roles to transform to lower state of energy. As a result, the respective effects are reflected to substrate ‘and bond coat, with increasing periods of exposure. The depletion of valuable constitutions results in loss of thermo mechanical properties. Role of individual elements Role of aluminium: The function of Al as an MCrALY alloy constituent is to provide a reservoir or reserve of metal to constantly replenish the oxide /18/, Scale growth, however, is governed by the inward diffusion of oxygen along its grain boundaries. The diffusivity of oxygen is relatively low, due to the alumina-corundum structure, The behaviour or activity of alumina is also proportional to the Cr content. Role of chromium: ‘The oxidation of a MCrAIY coating is directly proportional to the formation rate of the continuous alumina scales present on its external surface. The rate of formation of the scale is related to aluminium activity and its diffusivity in to the alloy. Chromium substantially increases aluminium activity and enhances its diffusivity rate /18/. The addition of chromium thus effectively lowers the aluminium content required to form and maintain the oxide film, Role of yttrium: The addition of yttrium to the alloy promotes scale adhesions. Yttrium has limited solubility in MCrAIY, therefore the excess quantities precipitate within grain boundaries as yttria, The yttria forms pegs, which protrude into the coating alloy and its surface scale /18. ‘The coating alloy and the alumina film are thus ‘mechanically pinned together and hence scale adhesion is improved /19/, High Temperature Materials and Processes Analytical models are presented for pre bond coat properties of thermal barrier coatings (TBC’s) during crack propagation studies induced by bending. Studies on crack propagation behaviour in TBC’s are performed with plasma spray coated zirconia, bonded by a MCrAIY layer to Ni-base superalloys (Inconel 617 and CMSX-4). Such thermal barrier composites are currently considered as candidate materials for advanced gas turbine stationary components. Coating as 4 protective layer improves the surface properties of the substrate, At a temperature of 800°C, the crack propagation is found to be confined to the TBC (Ceramic layer), as the ductile bond coat offers an attractive sink for stress relaxation. The stress-strain behaviour is a function of the elastic modulus of TBC and that of substrate, the elastic modulus of the bond coat is a basic parameter for characterising coating Performance. The elastic modulus of the bond coat has been determined by modifying the existing model for a two-layered composite beam to a_ three-layered composite beam /20.21/. FAILURE MECHANISM Mechanisms of bond coat deformation at high temperature are described on the basis of (a) bond coat deformation, (b) compressive stress formation during ‘cooling, (c) marginal increment of compressive stress from lesser plastic one and (4) partially oxidised bond coat from thermal cycling. Sustaining high bond coat temperature and cooling rate affects thermal cycle life of coating, Ceramic coating develops stress concentration at a flaw or defect in the interface and fails with explosive force during the heating cycle, due to interruption of heat transfer. Surface roughness on the bond coat improves adhesion through mechanical keying and diffusion. The initiation of delamination is always in the cohesive zone and in the ceramic layer as well as adjacent to the interface, therefore geometry of stress transmission across the interface is more important in affecting durability than adhesion-zone alterations. ‘The coating fails near the interface on cooling from high temperature isothermal exposure in air at slow nVol. 23, No. 2, 2004 cooling rate. The coating failure originates from the ‘metal ceramic thermal expansion mismatches across the interface. The coating life generally increases as thermal expansion mismatch between different coatings and substrate decreases. In the case of dense coatings stress developed on cooling leads to spalling /22/. Spalling has been observed on cooling of plasma sprayed coating onto an excessively hot substrate. It is reported that the coating spalls or at least cracks within the ceramic near the interface. An expression for the thermal expansion mismatch stress using a balanced biaxial stress state approximation and assuming a thin coating is given as gr = AT. Aa. E/(I-p), where, 4 = Poisson’s ratio, E Young’s modulus of ceramic, AT = Difference in temperature between the temperature after cooling and the stress free reference temperature, Aa = Difference in Coefficient of thermal expansion between the metal and ceramic /23/. By using this formula, one can calculate the stress value oyr at a particular temperature, where failure of coating occurs. Heating stresses tend to counteract compressive residual cooling stresses near the interface. Cooling stresses are most compressive at the interface and diminish towards the surface. On heating, stresses are ‘most compressive at the surface and are tensile at the interface. Stresses on cooling will increase if stress relief occurs at high temperature /24/. A probable mechanism for stress relief is believed to operate in the bond coat, after a suitable period of time at high temperature, at their common interface. Stress relaxation is also expected for single-layer MCrAlY coatings. Bond coat oxidation may affect the coating durability in several ways, The oxide that forms on the bond coat may spall. Specks of bond coat oxide ‘generally remain attached to the underside of the spalled ceramic pieces. However, since failure occurs mainly in the ceramic, this probably has only a secondary effect. Oxidation decreases bond coat durability through the formation of additional oxides at the splat boundaries or causes it to increase through aluminium depletion /23/. Oxidation plays a dominant role in the failure of graded thermal barrier coatings. In graded coatings, there is an intermediate layer consisting of a bond coat alloy and ceramic /25/. This layer is intended to mitigate 8 Thermal Barrier Coating System for Gas Turbine Application- A Review the effect of the thermal expansion mismatch stress However, at high temperatures the metal particles in the graded zone oxidise significantly. As the particles oxidise they expand, and thereby create buckling stresses in the coating, These residual stresses resulting from growth add to thermal stresses imposed by cyeling, and result in the formation of cracks parallel to the surface in the graded zone and cause subsequent spalling. ‘The surface of the bond coat is very rough and irregular. This morphology is required for coating attachment. However, the presence of such irregularities may also lead to coating failure, Even in the absence of oxidation, they could act as stress concentrators. When the bond coat oxidises, each asperity expands, thereby partially filling in the “basins” between them, The additional strain in the ceramic resulting from an additional micron of growth is considerable. Such strain may cause failure, provided the remaining metallic portion of each asperity doesn’t flow enough to relieve all the additional stresses. Other properties of ceramic such as fracture toughness, phase stability, structure and density influence the propensity for cracking in ceramic. In the Y20;- stabilised ZrO; controlling the coefficient of thermal expansion across the interface (Funkenbusch ‘et al) increases composition-coating life /26/. On cooling to ambient temperature, the thermal expansion ‘mismatch causes appreciable tension to develop normal to interface between the TGO and bond coat and the interface separates. A model has been developed for the stresses induced in the TBC, around interface imperfections, due to the growth of the TGO. These stresses arise because the growth strain cannot be accompanied by a rigid body displacement of the TBC. ‘These stresses induce a stress intensity factor Ke at crack located in the TBC. When this stress intensity factor is greater than fracture toughness, a crack starts growing and the coating fails /27/. The cracks ‘emanating from the individual imperfections are too small to satisfy large scale buckling; so many such ‘cracks coalesce, In brittle solids, containing dispersion of particles having a thermal expansion coefficient larger than the host, the residual stresses around the particle interact with the flaws in the matrix to cause ‘macroscopic cracking when the particles exceed aB. Goswami et al. critical size. The spontaneous failure of the TBC on cooling occurs after the thermally grown oxides have converted from an initially continuous alumina scale to a mixed chromia, spinel scale /28,29/. The delamination failure is presumably driven in by the increasing strai energy. It is suggested that the interfacial fracture resistance of the TBC/a- Cr:Os and the TBC/spinel ierface are also responsible for the delamination failure (27/. Under equilibrium conditions an initially continuous, and presumably protective, alumina scale is replaced by the formation of o- chromia and spinel although alumina is thermodynamically more stable oxide /30/. a-Chromia and spinel can form below the alumina scale once the activity of aluminium in the bond coat has fallen below that necessary to form more alumina at the interface /31/. However, they do not disrupt the alumina scale. The alumina coating on the highly convoluted bond coat surface cracks on cooling as a result of the high local curvature and thermal expansion mismatch, Such a crack, on heating back to the oxidation temperature, provides a direct transport path through the alumina for oxygen to react with the bond coat and maintain a high partial pressure of oxygen at the interface. If the bond coat contains sufficient aluminium, more alumina will form and re- stabilise the protective film. However, if the ‘alloy is locally depleted of aluminium, the other oxides can form. The large volumetric change associated with the formation of these oxides can lead to further cracking of the alumina by enhancing the formation of chromia and spinel /30/. Without a protective scale, oxygen can diffuse well into the bond coat alloy and form alumina by internal oxidation /32/. The formation of Cr,Os provides an explanation for the unusual dependence of the apparent residual stress in the thermally grown alumina on oxidation time. As oxidation proceeds, the compressive stress in the alumina under the TBC increases’ over short times and then remains essentially unchanged. The apparent compressive stress decreases the continued oxidation. ‘The decrease in the formation of CrO, results in an increase in the formation of a AhOs. When the thickness of a- Al,Os exceeds a particular value, failure occurs High Temperature Materials and Processes For high temperature application, MCrAlY is normally used (where M = Co, Ni or their combinations) as a bond coat. This group of materials belongs to nickel base (NiCrAlY), cobalt base CoCrAlY or combinations of these (NiCoCrAIY) /33/ (CoNiCrAIY) etc. /34/. Typical applications include environmental protection for airfoils, solid shrouds, abrasive blade tips and as a bonding layer for thermal barrier coatings (TBC). MCrAIY are widely used because they perform satisfactorily engine environment /33/, This is attributed to the ability of alloy metals to formulate and propose materials that are thermally and chemically compatible with their substrates and which have a minimal effect on the surface mechanical properties /35/. Performance depends on the materials’ ability to generate tenacious protective scales that produce chemical interaction between the substrate and the corrosive environment. The protective scale is principally AhOs. All AMDRY and MCrALY alloys promote Al,O; formation. It has been determined that, besides Al, other elements present in the alloy can oxidise. If these mixed oxides are allowed to form then they are not as protective as AO, and failure of coating may be accelerated. Knowledge of the mechanics of the selective oxidation and the ‘Al:0s formation is necessary for alloy development. Crack propagation studies under bending are performed with plasma sprayed zirconia bonded by a MCTALY layer to Ni-base superalloy. Such thermal barrier composites are currently considered as candidate materials for advanced stationary gas _ turbine ‘components, The crack propagation behaviour of the ceramic thermal barrier coatings (TBC’s) at room temperature, in as received and’ oxidised conditions reveals that cracks grow linearly in the TBC with increase in bending load until about the yield point of the superalloy is reached. Approaching the interface between the ceramic layer and the bond coat, a high threshold load is required to propagate the crack further into the bond coat. Once the threshold is surpassed, the crack grows rapidly into the brittle bond coat without an appreciable increase in the load. At a temperature of 800°C, the crack is found to propagate only in the TBC (ceramic layer), as the ductile bond coat offers an attractive sink for stress relaxation. Effects of bond coat 9Vol. 23, No. 2, 2004 oxidation on crack propagation in the interface regime have been examined and are discussed /36-38. EXPERIMENTAL DEGRADATIONS OF DIFFERENT TYPES OF COATING (1) In platinum aluminised coatings degradations have been observed due to (i) Oxidation induced cracks within inhomogeneous microstructures, chemical segregation at surface inhomogenity, micropores, and deep scratches, (i) Limitations of strain ranges, i) Phase transformation cracks from formation of close packed tetragonal of round shaped 1 phase and acicular © phase, and (iv) Rough surfaces of repeated build up and break down of oxides without deep cracks and oxide spikes after prolonged exposure /39,40,41/ (2) In CoNiCrAIY overlay coatings degradations have bbeen observed due to (i) Crack initiation and propagation, (ii) Occurrences of rumpling on coating, where rumpling is a stress relaxation process for sintered layers, (iii) Initiation of cracks in troughs of rumple when in tension or compression, (iv) Super plasticity above 900°C and rnon-load bearing property, and (v) Tensile hardening, and compressive softening owing to creep of substrate /40,42/ (3) In thermal barrier coating degradations occur because of (i) Failure of bond coat by cfacks and top. coat penetration, (ii) Thermally grown oxide formation in voids and porosity, (ji) Open interfaces and thermally grown oxides, (iv) No significant Tumpling of ceramic coating after thermo mechanical fatigue, (v) Crack penetration in bond coat and sometimes through ceramie coat, and (vi) The coat does not respond to comparative creep phenomenon and produces thermal shielding to inhibit rumpling by reducing plastic deformation and bending elastic strain /40/. Thermal cycling experiments within 250-1177°C for different cycles have shown the presence of interfacial cracks under lower number of thermal cycles, and thermally grown oxides, for higher number of thermal 80 ‘Thermal Barrier Coating System for Gas Turbine Application- A Review cycles. The latter results in separation at the middle of substrate rather than at the edges. Higher temperatures increase oxidation and initiate damage in bond coat while at lower temperatures of thermal cycle produce delaminating stresses to spall coatings. Thermal barrier coating performance is less at high rates of thermal cycling than at isothermal exposure, higher substrate temperature, and compressive stresses. Interfacial crack length and thermally grown oxides increase proportionally with the number of cycles. Further increase in the number of cycles increases thermally grown oxide thickness more at the central zone than at the edges. This, in addition to elongated crack, forms a buckled coating, which leads to spallation. A higher resolution of microstructure of buckled surface shows the existence of voids. The phenomenon of spallation has been confirmed in laser spall resistance of coating 141,43-501. EFFECTS OF CORROSION AND EROSION Protective coating produces thermal shielding and chemical reaction protection to substrate. In-service interfacial oxides resist oxidation of substrate from diffusing species of environment. The corrosion-erosion phenomenon in this case plays either exogenously from the environment or endogenously from the substrate. Environmental degradation of petrochemical com- ponents is due to reactive contamination of gases consisting of low oxygen, sulphur. carbon, sodium sulphate, sodium chloride, and vanadium compounds. At low temperatures environmental variation arising from liquid compound deposition of sodium sulphates and nitrates on coated surface, the variations of interfacial pH of respective metal/coating and corroding deposition to gaseous media increase the corrosion rate. The corrosion rate is high in the presence of liquid deposition than gas-metal/coating surface reaction Concentrations of desirable elements perform the following functions. Aluminium forms alumina layer, yttrium improves adherence property of alumina, platinum and precious elements like rhodium and palladium reduce other elemental depletion, The Undesirable elements like sulphur /51/ and boron reduce illB, Goswami et al. alumina adhesion and increase oxide pit formation. In the presence of boron, incomplete transformation of silicon to silica forms low melting silicate compounds within interfacial oxide layer. This disrupts the strength of interface even at lower temperatures. Similarly the presence of sulphides increases oxygen diffusion rate and oxidation after carbide formation, The subsequent reaction products further raise chromium oxidation rate, At lower oxygen partial pressure, chlorides, sulphides, carbides ete. present in interfacial oxide layer either increase corrosion by oxidation due to enhancement of diffusion or form volatile oxides. Coating degradation takes place by thermally induced stresses arising from differences in coefficient of thermal expansion, in-situ scale thickness variation, thermal fatigue, and loads in service. Fluxing reaction at interface is exemplified by alumina and sodium sulphate reactions. Erosion at the surface leads to depletion of reaction products Occurrence of both erosion and corrosion limits the rate of reaction by either corrosion enhanced erosion or erosion enhanced corrosion phenomenon /S2-S61. INTERFACIAL PHENOMENON Adhesion is the state in which interfacial forces, which may consist of valence or interlocking forces or both, hold two surfaces together /57/, Effective forces across coating-substrate interface are either Vandarwall’s electrostatic and/or chemical reaction forces /58-60/. Ceramic films on metallic substrate are applied to resist high temperature insulation/corrosion. Reactive metal additions improve adhesion properties. Elements like yttrium and scandium in the bond coat react early and act as vacancy scavengers. Otherwise accumulation of these vacancies forms voids at interface and reduces adhesion. The formation of oxides anchors scale to the substrate, prevents vacancy coalescence at the interface of scale-metal after providing alternating coalescence sites, enhances scale plasticity by altering its structures, alters scale growth process, and forms graded oxide layer. Sulphur segregation to outer surface Promotes scale exfoliation. Reactive elements reduce sulphur segregation to interface by reacting with sulphur during fiquid phase processing and thereby High Temperature Materials and Processes removing/reducing sulphur activity. They react with sulphur in solid state to transform to refractory sulphur and reduce the concentration of sulphur in solution, which is available for segregation /SV/. Massive spallation at oxide-metal interface is believed to be due to sulphur segregation /61/. Sulphur even reduces inter- oxide adhesion by phenomenon similar to inter-granulat embrittlement, Dopants like yttrium, hafnium, and zirconium prevent sulphur activity and so segregate to the surface. These dopants strengthen oxide-metal bond. Change from non-adherent to adherent alumina (a- alumina) scale formation by simple repeated oxidation and sulphur removal, is a new approach to improve adherence, From the energy balance approach the cause of spallation at interface may be explained as follows. Scale attachments occur when total elastic energy stored in scale exceeds fracture energy of interface. A change in critical temperature of thermal mismatch initiates scale spallation. Thermally grown oxide scales suffer from a wide variety of mechanical loading configurations, such as (i) growth in oxide volume produces compressive stresses as per Pilling-Bedworth ratio in plane of scale, (ii) compressive stresses as induced by thermal mismatch on cooling from growth temperature, tensile stresses induced by loading of alloy. SURFACE AND GRAIN BOUNDARY SEGREGATION includes —metallui The following table phenomena affected by physico-chemical parameter that is influenced by surface and grain-boundary equilibrium segregation /55/. ‘The schematic illustrates interfacial segregation influences of metallurgical phenomena through their impingement on several basic physicochemical properties, involving the energetics, kinetics or the cohesion of the interfaces. Grain-boundary segregation will in general retard the boundary diffusivity and this in tum affects the rate of diffusion creep or the rate of boundary cavity growth involved in creep embrittlement. Again, because it retards grain-boundary 8Vol, 23, No, 2, 2004 ionic mobility in polycrystalline oxides, this should also inhibit the rate of surface oxide growth. In some instances, the particular metallurgical property may be affected through changes in more than one of the basic Physicochemical properties considered. For example, the rate of oxidation of nickel alloys containing aluminum may be affected through the kinetics of ion transport across or through the boundaries. In addition smicrochemistry, in Thermal Barrier Coating System for Gas Turbine Application. ‘A Review the integrity of the oxide layer is enhanced by improved ierfacial adhesion resulting from the presence of segregated species at the metal/oxide interface. Numerous metallurgical and micro. structural Phenomena in alloys are influenced by interfacial some cases this may be a determining factor while in others it may be simply one ‘of a number of contributing factors /55) Interfacial Interfacial Interfacial Grain boundary Interfacial energetics | icy cohesion electrochemistry mobility Stress relief cracking Temper brittleness | Intergranular Sintering corrosion Creep embritlement Secondary Reactions Liquid metal | Intergranular stress recrystalisation | inhibited by | embritlement | corrosion texture barrier layers Oxidation Diffusion creep | Hydrogen (Coble) embrittlement Fatigue The multicomponent solid mass is held at and unloading/eloading change metal’ dimensions quilt in an isothermal enclosure and at a temperature which permits rapid thermal transport. The ‘chemical potentials of all species, assumed here to be in Solid solution, are constant. throughout the system. Instead of a random distribution of solute species, as in an ideal single crystal, it is found that at equilibrium there is @ heterogeneous partitioning, which results in the enrichment are defined only by the system Parameters at equilibrium and not by the history of material. The chemical enrichment at any interface can be reported simply by re-establishing the identical Physicochemical conditions. It is in this sense that the segregation is truly reversible /55/ State of stresses across ceramic protective coating interfaces under thermo mechanical exposure The — following combinations schematic shows different ‘of thermal and mechanical load variations. Heating and cooling of composites change the temperature of metals faster than ceramics; the related property is thermal expansion, Similarly, loading 82 faster; the related property is ductility, Considering periods of every event separately, only the loading stage shows that the stress variation at interface works in reverse order, ie., compression at bond coat and tension at the ceramic coat, The effect of such variations at the interface appears to be closely linked to the symptoms Of failure as tabulated in the model. Void growth and ‘oxide scale formation rate increase, during (i) heating- ‘cooling cases, when the additive stresses play a part in tension in the metallic coat and compression in the ceramic coat, (ii) heating-loading cases, when mutually reverse consequences of stresses play at the interface, and (iii) heating-unloading/reloading cases when the additive stresses cause tension in the metallic coat and Compression in the ceramic coat. However, buckling and delamination rate increase during (i) cooling-load- ing cases, when mutually reverse consequences of stresses play al the interface. (i) cooling-unloading/ reloading cases when the additive stresses play tension in ‘metallic coat and compression in ceramic coat, (i loading-unloading/reloading cases, when mutually reverse consequences of stresses are at work at the interface,B. Goswami et al. High Temperature Materials and Processes ‘Thermal cycling period Mechanical cyeling period Hai Period] Coan POE | ey chan toate pari] nian i “ ed cycling period © Ps Compression | Compression Compression | Compression (Uc) (He) (ce) (ie) Tension (Ht) | Tension (C) Tension (Lt) ___| Tension (U) Stress distribution Stages Heated Cooled Loaded Unloaded ‘Types of stress He [ms [Ht [ce [ms [cr [te [ms [ur [uc [Ms [ur nit No es | no es no | no es Boe deut y yes | y y Inter metace SESS | eto He CrtoCe LetoLt Utto Ue | gradient Stress in TBC Yes no_| yes no | no es_|yes no MS = Mismatched stresses from bond coat to TBC, TBC = Thermal; Barrier Coatings Fatigue stress distribution from bond coat to ceramic coat atthe interface: pv Heated [Heated and | Heated and | Cooled and | Cooled and | Loaded and and cooled | loaded unloaded | toaded unloaded | unloaded HttoHe | Htto He HttoHe — | Cttoce CttoCe | LetoLt Stress distribution at | CttoCe | Leto Lt Uttoue | LetoLe UttoUe | UttoUe the interface Additive | Subtractive | Additive | Subtractive | Additive | subtractive Symptoms of fale | Void growth and oxide scale formation Buckling and delamination Elemental incorporation into metallic coating Introduction of platinum. aluminide and chromium into cementation coatings shows following characteristic phases from outer surface to matrix of substrate /62,63/. The features are tabulated below. 83Vol. 23, No. 2, 2004 Thermal Barrier Coating System for Gas Turbine Application ‘A Review 7 Micro structural features | Intermediate layer surface Name of coatings = Outer surface Inner surface r Al rich NiAI matrix ae Pt aluminides of Ni ir anne Single phase PLA; layer | Pt_ and Substrate | note phase precipitates Ptalumindes of NI] Perch PYAL, and Al ich | ang tan precipitates (ITIA) B-NiAI matrix Craluminides of Ni] Cr rch NiAl mate, and | so phase (NLALCH) (LTHA) ‘o-Cr precipitates Cralumtinides OfNI | sich NiAL a-Cr precipitates (UTHA) _ Cr+ Pt ar precipitates, | a-Cr precipitates, Ni rich aluminides of Ni PtAl and Alrich NiAL | NiAI(PLCr) matrix, and | NiAL matrix, and MC (HTLA) recipitates precipitates PLecr PIAL, B-NIAI, Cr aluminides of Ni precipitates, and Al rich | Ni rich NiAL | (HTLA) NiAL matrix ‘Conventional ‘Al rich B-NiAT matrix, Ni Ni aluminides precipitates, and M | Al rich NiAI matrix, (HTLA) carbides i aluminidk [may “s Nirich B-NiAL Substrate IN738 y-¥ matrix N73 “ 7 Ni precipitates NB, - Interdiffusion zone contained Nirrich B-NiAl and substrate compositions in every case of structures stated inabove table. HTLA = high temperature low activity pack process, LTHA = low temperature high activity pack process, ITIA = intermediate temperature intermediate activity pack process, HTHC = high temperature hot corrosion process Plasma ion implantation improves scale adhesion, oxygen diffusion, cation diffusion to interface, scale exfoliation, and sulphidation, ‘The benefits of aluminised bond coats in thermal barrier coating applications are based on intermediate Phase formation, and reduction of aluminium depletion during plasma spray process /64/. These two factors increase life by about two times under thermal cycling tests than un-aluminised bond coats, However time dependent oxidation occurs and substrate metal oxidation product diffuses out through the alumina layer, Thermal barrier coating spallations are found to be limited by a combination of mechanisins such as (i) 84 Existence of bond coat alloying elemental oxides in ‘alumina layer, (ji) growth rate of substrate intermetallic oxides from outward cationic diffusion, (i) Pilling- Bedworth ratio of oxides and metal, (iv) Volume ratio ‘of other elemental oxides and alumina under conditions of anion diffusion through alumina layer at interface. ‘The thermal barrier coating life at high temperature depends on pure and continuous alumina scale formation at interface of bond coat and topcoat. Oxidation for prolonged periods shows depl aluminium and existence of bond coat alloying element oxides on exposed surfaces of spall areas. Relative oxidation tests on unimplanted bond coat alloy and n of LLB. Goswami et al. vanadium and cerium implanted bond coat alloy have shown improvements in cerium implanted bond coat alloys at lower time test than unimplanted ones. Vanadium implantation degrades performance more than unimplanted. Cerium promotes chromium oxidation. At longer periods porous and thick oxide layers form in implanted bond coat alloys /8/. Oxygen active efements like yttrium and hafnium improve oxidation resistance of bond coat alloy. Mechanical pinning of oxides to coat alloy enhances oxidation resistance. Other factors responsible for improvement in oxidation resistance are due to prevention of vacancy ‘Comparative airfoil degradations in marine service are tabulated below /68/: High Temperature Materials and Processes coalescence at scale-metal interface, increasing scale plasticity, modification of scale growth process, formation of graded oxides or sulphur segregation at interface after trapping by added element. Yttrium interface resists cation diffusion, Depletion of valuable elements is faster from grain boundary of bond coat alloy than grain interior. Kirkindal porosity formation is more effective at grain boundary. Both yttrium and hafnium resist this by relatively increasing anion (oxygen) transport from outer surface /17,19,31,32, 65-671. | Identity of process / AS prepared teristics Constitution prepared characteri TAs service exposed (1077 hours, in marine atmosphere) characteristics Salt penetration / sulphur attack Performances Penetration of low PVD CoCrAly alloy/ Non graded composition of CoAI and Worst and attacked cementation + Pt- electroplating Middle layer: (Co,P!)Al, CoCrPt rich phases Outer layer: PtAl phases scaling €0-22.5C¥-10.5AI-0.3Y | CoCr with discrete Cr-rich phases regions (esoinl 7 6. a VPS CoCrAlHalioy’ | Non graded composition of CoAT and | 5 iat igag | intermediate in C0-26Cr-10.5Al-2.5HE _| CoCrHf rich phases performance Multistep graded coatings PVD CoCrAlalloy+ [Inner layer: CoAl and CoCr and lean aluminising + hafnide | distribution of Cr-tich phases Discoloration and | 6. ned attack VPS CoCrAIHiPt alloy + chromising/ 26Cr-10.5A1-2.5HESPt Multistep graded coatings Inner layer: CoAl and CoCr and lean distribution of Cr-rich phases Middle layer: (Co,P)AL, CoCrPt rich phases, Cr layer | Outer layer: PtAl phases Best in performance and discolouration Confined attack, thick chromium oxide scale HighCr,PVD CoCraly/ Non graded single layer of B-CoAl Penetrations of low il) Ceramic top coat of Al & Cr and outer layer of Co Co-3Cr-12A1-0,5Y_ and CoCr phases ‘Attacked regions melting eutectic eet Selective coating gs 0 |pvocecra+ pvp | Gtaledcoaingsof double yer | performs. 700 | at by rain 20wi%YSZ () CoCrAlY bond coat “onsists of inner layer | and spallation, No bond coat attack, 85Vol. 23, No. 2, 2004 Increasing aluminium alloying to nickel base superalloys improves creep resistance and decreases corrosion resistance in salt contaminated environment of airfields. The service life has been found to be improved two-fold. Performance of Dart turbine and combustor section of aero engine in marine environment is as set out below /69/. I0SDART blades exposed for 4500 hours have shown better performances on alloyed samples than aluminised and not heat-treated for diffusion purposes. Increase of ductility by diffusion heat-treatment reduces corrosion resistance. SPEY250 engines involved in low level of flight over sea and consequent ingestion of salt and sulphidation attack of diffusion aluminide coat have recovered by thick diffusion aluminide and double aluminide diffusion coatings. ‘The thick layer has Service performances of modified turbine blade have shown the following morpholo; ‘Thermal Barrier Coating System for Gas Turbine Application A Review improved life about two times and a double layer has improved life by five times. Cr, Ti, & Mo rich layer formation at the midway of coating have improved life in double layer modification. MAR-M002 blades have resisted . corrosion penetration almost two-fold in S00 hours* exposure in an atmosphere of sand and salt contamination. ‘Application of 20% MSZ on Ni-Cr bond coat has performed 8000 hours in civil aeroengines with little degradation. The performance is twice the life of industrial RB211 engines. MCrAIY bond coat and YSZ's topcoat have improved the deficits of MSZ ‘TBC’s. The modification increases fracture toughness, slows the rate of crack propagation on thermal cycling, improves thermal fatigue resistance, and increases temperature capability of 200°C. I changes /70/: Type of surface modification applied Identification of phases Performances of service exposure in moist marine environment 500 hours, 1000 hours Outer layer: Ni, Al, and Cr ppt. Middle layer: Co, Cr, and B-NiAL Interdiffusion zone White zones and 50% Al depletion Sulphate penetration, total Al depletion ‘Outer layer: Pt, Ni, and ALO; pt Middle layer: B-NiA Interdiffusion zone. Pt modified aluminides Nie Lower Al depletion Little ‘marginal ‘Outer layer: Pt, Rh, Cr, Al, and ALO; ppt Middle layer: Ni, Al Interdiffusion zone Pt and Rh modified Ni- aluminides degradation, mottling of microstructure Stop Al depletion Pit and precipitate , ale Selectively pitted i and Cr modined ni | SBE ayer ALO Si, Cr Ni, | formation fom tow | Som code Al melting eutectic of | Sena ; Interdiffusion zone Al,O;- SiO,, and Al, Si on ee egieti senteon phase segregation Mn and Cr modified Penetration of corosion | viostiy degraded and ; product, Mn, Cr Ni-aluminides absence of coating depletion 86B. Goswami et al. Performance, ranked from best to worst, is: Pt-aluminides of Ni, Pt and Rh-aluminides of Ni, Ni- aluminides, Si-aluminides of Ni, Mn+Cr aluminides of Ni. Effects of micro laminated coatings Ceramic microlaminated coatings of alumina and yttria stabilised zirconia improve engine efficiency at higher operating temperatures, reduces cooling rates, and reduces mismatch coefficient of thermal expansion between metal substrate and ceramic coating. The respective changes are reduction of _ thermal, conductivity, increase in coefficient of thermal expansion, and decrease in marginal phase transformation from surface to underneath by declining diffusivity of alumina /10,71/. Functionally graded materials Spallation is reduced by application of functionally graded materials (FGM) /72/ which optimises the stress gradient profile. Control of elastic thermal stress distributions within a multilayered system of graded materials is of prime importance. The structure of ‘graded coating system is made up of a ceramic layer, a metallic layer, and an interlayer, which is a graded composite made of metal (Ni-Cr alloy), and a ceramic (210,-Y203). The variables like elastic modulus, graded interlayer thickness, ceramic porosity, and residual stress distribution affect spalling in functionally graded material /73,74/. Plasma deposition is one of the successful processes uused to produce functionally graded materials. The process has been designed to obtain steeper, linear and parabolic gradient profiles. The physical-thermal- mechanical characteristics of functionally graded materials have been studied by Sampath ef al. /75/. Graded thermal barrier coatings (GTBC) compared to two-layer TBC’s have achieved longer life times. GTBC’s are produced by co-deposition of mixtures of AL-ALO;-YSZ onto metallic bond coat. Stress. strain states on thermal rejection in GTBC show improvement as compared to two-layer TBC’s /76-78. High Temperature Materials and Processes Reduction in thermal conductivity of bond coat has been made possible by use of metallic micro laminations of Ni/NiCoCrAIY and Ti/CoCrAlY on metallic substrate, Microlaminated interfaces reduce mismatch of thermal conductivity. between metallic bond coat and ceramic topcoat. Variables such as structure of each component, thickness of individual layer, mutual solid solubility at exposure temperature, hours of exposure, and formation of intermetallic compound at the interface have dominating effects on the life of TBC /68/, Top coat surface modifications Topcoat surface modification is used to inhibit surface diffusion of reactive contaminant of combustion environment. The free surface of a coated implement is laser remelted and solidified to provide a smooth and shiny layer consisting of fine grain microstructure /79/, Laser remelted NiCrAIY overlay causes changes in the structure and elimination of porosity. This accounts for an increase in thermal conductivity of remelted coatings and at the same time a decrease in interaction efficiency and increase in exploitation stability /45,80/. Lifetime and aging processes Reduced thermal conductivity, sintering, and stresses within the ceramic coating affect the life of TBCs. Stresses are governed by the formation and growth of thermally grown oxide seale and therefore have been related to bond coat. TBCs have been developed for increasing high temperature capability and durability under thermal cyclic conditions as experienced in the hot section of gas turbine /81/. Post sintering mechanism by densification of service exposed TBCs has been studied with ceramics that undergo transformation at lower temperatures. Alumina based ceramic coating consisting of LaOs, AlLO;. and MgO possesses long term structural and thermo chemical stability upto 1400°C. Densification in this constitution is prevented by platelet formation before sintering /82/. Conditions have been established to obtain critical thermo mechanical and thermo physical properties of the coating systems under near realistic transient and 87Vol. 23, No. 2, 2004 steady state temperature and stress gradient encountered in advanced engine systems. It has been reported that the coating failure depends not only on the coating but also on the sintering, creep and bond coat oxidation under operating condition /83/. Durability of TBCs with increasing combustion ‘temperature has been studied. The 2/5"-power time law and Archenius type temperature dependence have been reported. Linear shrinkage of ZrO; by sintering forms shrinkage stress and residual stress, which produce cracking conditions of zirconia coating. The tensile stress at zirconia coating layer increases with inerease in the combustion temperature and heating time /3/. Evans et al. (84/ have developed theoretical life prediction ‘model based on interfacial variation of work of adhesion ‘on elemental segregation at interface. CONCLUSION ‘Thermal barrier coating leads to improved life of implements and increases marginal performance of hot section. Bond coat plays a most important role in Providing, thermal-physical-chemical-mechanical_com- patibility between the ductile substrate and ceramic topcoat. In most cases spallation is a dominant mode of failure. Interfaces are zones where elemental segregation takes place. Undesirable elements increase interfacial activity and reduce life of coating, Service and experimental performances of the thermal barrier coating system have shown improvement. Functionally graded materials, microlaminated coatings and laser surface scaling also have improved properties of coating. 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