Molten silicate interactions with plasma sprayed thermal barrier coatings: Role of materials and microstructure

Ingestion of siliceous particulate debris into both propulsion and energy turbines has introduced significant challenges in harnessing the benefits of enhanced operation efficiencies through the use of higher temperatures and thermal barrier coatings (TBCs). The so-called CMAS (for calcium-magnesium alumino-silicate) particles can melt in the gas path at temperatures greater than 1200C, where they will subsequently impact the coating surface and infiltrate through the carefully engineered porosity or cracks in a TBC. Ultimately, this CMAS attack causes premature spallation through its solidification and stiffening the ceramic during cooling. It has been noted in recent years, that TBCs based on yttria stabilized zirconia (YSZ) are completely non-resistant to CMAS attack due to their lack of reactivity with infiltrant liquid. New TBC ceramics such as Gadolinium Zirconate (GZO) show promise of CMAS resistance through rapid reaction-induced crystallization and solidification of the infiltrant, leading to its arrested infiltration. In both situations, the microstructure (porosity, micro and macro cracks) can be important differentiators in terms of the infiltration and subsequent failure mechanisms. This paper seeks to examine the interplay among microstructure, material, and CMAS attack in different scenarios. To do so, different types of YSZ & GZO single and multilayer coatings were fabricated using Air Plasma Spray (APS) and exposed to CMAS through isothermal and gradient mechanisms. In each of the cases, beyond their unique interactions with CMAS, it was observed the inherent microstructure and character of the porosity of the coating will have an additional role on the movement of the melt. For instance, vertical cracks can provide pathways for accelerated capillaric flow of the melt into both YSZ and GZO coatings. Based on these observations multilayer coatings have been proposed and realized toward potentially reducing complete coating failure and supporting multiple CMAS attack scenarios.     

Solution combustion synthesis of calcia-magnesia-aluminosilicate powder and its interaction with yttria-stabilized zirconia and co-doped yttria-stabilized zirconia

Thermal Barrier Coatings (TBCs) play a significant role in improving the efficiency of gas turbines by increasing their operating temperatures. The TBCs in advanced turbine engines are prone to silicate particles attack while operating at high temperatures. The silicate particles impinge on the hot TBC surfaces and melt to form calcia-magnesia-aluminosilicate (CMAS) glass deposits leading to coating premature failure. Fine powder of CMAS with the composition matching the desert sand has been synthesized by solution combustion technique. The present study also demonstrates the preparation of flowable yttria-stabilized zirconia (YSZ) and cluster paired YSZ (YSZ-Ln₂O₃, Ln = Dy and Gd) powders by single-step solution combustion technique. The as-synthesized powders have been plasma sprayed and the interaction of the free standing TBCs with CMAS at high-temperatures (1200 °C, 1270 °C and 1340 °C for 24 h) has been investigated. X-ray diffraction analysis of CMAS attacked TBCs revealed a reduction in phase transformation of tetragonal to monoclinic zirconia for YSZ-Ln₂O₃ (m-ZrO₂: 44%) coatings than YSZ (m-ZrO₂: 67%). The field emission scanning electron microscopic images show improved CMAS resistance for YSZ-Ln₂O₃ coatings than YSZ coatings.     

Microstructure and thermo-physical properties of yttria stabilized zirconia coatings with CMAS deposits

Yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs) are used to protect hot-components in aero-engines from hot gases. In this paper, the microstructure and thermo-physical and mechanical properties of plasma sprayed YSZ coatings under the condition of calcium-magnesium-alumina-silicate (CMAS) deposits were investigated. Si and Ca in the CMAS rapidly penetrated the coating at 1250 °C and accelerated sintering of the coating. At the interface between the CMAS and YSZ coating, the YSZ coating was partially dissolved in the CMAS, inducing the phase transformation from tetragonal phase to monoclinic phase. Also, the porosity of the coating was reduced from ∼25% to 5%. As a result, the thermal diffusivity at 1200 °C increased from 0.3 mm²/s to 0.7 mm²/s, suggesting a significant degradation in the thermal barrier effect. Also, the coating showed a ∼40% increase in the microhardness. The degradation mechanism of TBC induced by CMAS was discussed.     

A computational modeling framework for reaction and failure of environmental barrier coatings under silicate deposits

Environmental barrier coatings (EBCs) for use with SiC-based composites in gas turbine engines may fail following reaction with molten silicate deposits. The processes involved may include dissolution of the EBC material into the deposit, reactions that produce new phases, and cracking or spallation upon cooling, the latter driven by thermal expansion mismatch between the reaction products and the underlying EBC and substrate. Here, we describe an integrated computational framework to simulate the processes and to predict the conditions leading to coating loss through reactive consumption and/or spallation. The framework integrates distinct models to determine: (a) the nature and quantity of phases resulting from dissolution and chemical reactions; (b) thermo-physical properties of those phases; and (c) energy release rates for penetration cracking and spallation upon cooling. We demonstrate the use of the framework by computing critical deposit thicknesses for one specific EBC material (Y₂Si₂O₇) as a function of deposit composition. In this system, the critical deposit thickness for typical coating thicknesses is dictated mainly by spallation, not by consumption, and may vary by orders of magnitude, depending on deposit composition and coating thickness and toughness. With respect to deposit composition, the key parameter governing coating failure is the Ca:Si ratio.     

High-temperature interactions of desert sand CMAS glass with yttrium disilicate environmental barrier coating material

A calcium-magnesium aluminosilicate (CMAS) glass was prepared by melting a sample of desert sand to evaluate the high-temperature interactions between molten CMAS and yttrium disilicate (Y₂Si₂O₇), an environmental barrier coating (EBC) candidate material. Cold-pressed pellets of 80?wt% Y₂Si₂O₇ powder and 20?wt% CMAS glass powder were heat treated at 1200?°C, 1300?°C, 1400?°C and 1500?°C for 20?h in air. The resulting phases were evaluated using powder X-ray diffraction. In the second set of experiments, free standing hot-pressed Y₂Si₂O₇ substrates with cylindrical wells were filled with CMAS powder to a loading of ~35?mg/cm² and heat treated in air at 1200?°C, 1300?°C, 1400?°C and 1500?°C for 20?h. Scanning electron microscopy, energy-dispersive spectroscopy and electron microprobe analysis were used to evaluate the microstructure and phase compositions of specimens after heat treatment. An oxyapatite silicate (Ca₂Y₈(SiO₄)₆O₂) phase was identified in all specimens after CMAS exposure regardless of heat treatment temperature. Apatite appeared to form by dissolution of Y₂Si₂O₇ into molten CMAS, reacting with CaO in the melt according to the reaction 4Y₂Si₂O₇ +?2CaO → Ca₂Y₈(SiO₄)₆O₂ +?2SiO₂, and followed by precipitation of the apatite phase.     

High-temperature interface stability of tri-layer thermal environmental barrier coatings

Thermal environmental barrier coatings (TEBCs) are capable of protecting ceramic matrix composites (CMCs) from hot gas and steam. In this paper, a tri-layer TEBC consisting of 16 mol% YO_1.5 stabilized HfO₂ (YSH16) as thermal barrier coating, ytterbium monosilicate (YbMS) as environmental barrier coating, and silicon as the bond coating was designed. Microstructure evolution, interface stability, and oxidation behavior of the tri-layer TEBC at 1300 °C were studied. The as-sprayed YSH16 coating was mainly comprised of cubic phase and ～3.4 vol% of monoclinic (M) phase. After 100 h of heat exposure, the volume fraction of the M phase increased to ～27%. The YSH16/YbMS interface was proved to be very stable because only slight diffusion of Yb to YSH16 was observed even after thermal exposure at 1300 °C for 100 h. At the YbMS/Si interface, a reaction zone including a Yb₂Si₂O₇ layer and a SiO₂ layer was generated. The SiO₂ grew at a rate of ～0.039 μm²/h in the first 10 h and a reduced rate of 0.014 μm²/h in the subsequent exposure.     

Microstructural characterization of GZ/CYSZ thermal barrier coatings after thermal shock and CMAS+hot corrosion test

In this study, first, Gd₂Zr₂O₇/ceria–yttria stabilized zirconia (GZ/CYSZ) TBCs having multilayered and functionally graded designs were subjected to thermal shock (TS) test. The GZ/CYSZ functionally graded coatings displayed better thermal shock resistance than multilayered and single layered Gd₂Zr₂O₇ coatings. Second, single layered YSZ and functionally graded eight layered GZ/CYSZ coating (FG8) having superior TS life time were selected for CMAS + hot corrosion test. CMAS + hot corrosion tests were carried out in the same experiment at once. Furthermore, to generate a thermal gradient, specimens were cooled from the back surface of the substrate while heating from the top surface of the TBC by a CO₂ laser beam. Microstructural characterizations showed that the reaction products were penetrated locally inside of the YSZ. On the other hand, a reaction layer having ∼6 μm thickness between CMAS and Gd₂Zr₂O₇ was seen. This reaction layer inhibited to further penetration of the reaction products inside of the FG8.     

CMAS corrosion resistance,thermal shock resistance and numerical simulation of novel surface micromesh thermal barrier coatings

Thermal barrier coatings (TBCs) are widely used as insulating layers to protect the underlying metallic structure of gas turbine blades. However, the thermal cycling performance of TBCs is affected by their complex working environments, which may shorten their service life. Previous studies have shown that preparing a mesh structure in the bonding layer can relieve thermal stress and improve the bonding strength, thereby prolonging the service life of TBCs. In this paper, a micromesh structure was prepared on the surface of the bonding layer via wet etching. The microstructure and failure mechanism of the micromesh TBCs after CMAS (CaO-MgO-Al₂O₃-SiO₂) thermal erosion were investigated. Numerical simulation was combined with thermal shock experiments to study the stress distribution of the micromesh-structured TBCs. The results showed that the circular convex structure can effectively improve the CMAS corrosion resistance and thermal shock resistance of TBCs.     

Failure mechanisms of calcium magnesium aluminum silicate affected thermal barrier coatings

Depth profiles of the phase composition of two examples of calcium magnesium aluminum silicate (CMAS) affected thermal barrier coatings (TBCs) from an aero gas turbine engine were obtained using a monochromatic and collimated beam of synchrotron radiation. One TBC was deposited by plasma spray and the other by electron beam physical vapor deposition. These examples were complemented with an X‐ray diffraction (XRD) study of mixtures of TBC zirconia powder and sand heated in a furnace. The XRD results were compared with electron backscatter images and energy dispersive spectroscopy studies of the cross sections and mixtures. It was found that when liquid, the CMAS enhances mass transport leading to the densification of the zirconia, which then leads to spalling because of the increased residual stresses generated on cooling. Even without spalling densification will reduce a TBC's ability to thermally insulate. The enhanced mass transport can also lead to destabilization of the zirconia if yttrium ions preferentially transfer to the liquid or greater stabilization if calcium or magnesium ions transfer from the liquid to the zirconia. Zircon also precipitates when the zirconium from the TBC reacts with the silicon in the liquid CMAS.     

Microstructure evolution of CMAS glass below melting temperature and its potential influence on thermal barrier coatings

CaO–MgO–Al₂O₃–SiO₂ (CMAS) deposition significantly degrades the performance of thermal barrier coatings (TBCs). In this study, the microstructure evolution of CMAS glass at temperatures below its melting point was investigated in order to study the potential influence of temperature on the applicability of CMAS glass in TBCs. The CMAS glass fabricated in this study had a melting point of 1240 °C, became opaque, and underwent self-crystallization when the temperature reached 1000 °C. After heat treatment at 1050 °C, diopside and anorthite phases precipitated from the glass; at a higher temperature (1150 °C), diopside, anorthite, and wollastonite were formed as the self-crystallization products. An increase in the dwelling time resulted in the transformation of diopside to wollastonite and anorthite. At 1250 °C, all products formed a eutectic microstructure and melted. The results indicate that even at low temperatures, CMAS glass underwent microstructure evolution, which could influence the coating surface and stress distribution when deposited on TBCs.     

CMAS corrosion of YSZ thermal barrier coatings obtained by different thermal spray processes

Degradation of yttria-stabilized zirconia (YSZ) layers by molten CaO-MgO-Al₂O₃-SiO₂ (CMAS)-based deposits is an important failure mode of thermal barrier coating (TBC) systems in modern gas turbines. The present work aimed to understand how the chemical purity and microstructure of plasma-sprayed YSZ layers affect their response to CMAS corrosion. To this end, isothermal corrosion tests (1 h at 1250 °C) were performed on four different kinds of YSZ coatings: atmospheric plasma-sprayed (APS) layers obtained from standard- and high-purity feedstock powders, a dense – vertically cracked (DVC) layer, and a suspension plasma sprayed (SPS) one. Characterization of corroded and non-corroded samples by FEG-SEM, EBSD and micro-Raman spectroscopy techniques reveals that, whilst all YSZ samples suffered grain-boundary corrosion by molten CMAS, its extent could vary considerably. High chemical purity limits the extent of grain-boundary dissolution by molten CMAS, whereas high porosity and/or fine crystalline grain structure lead to more severe degradation.     

Reaction between environmental barrier coatings material Er2Si2O7 and a calcia-magnesia-alumina-silica melt

The suitability of sintered erbium disilicate (Er₂Si₂O₇) as an environmental barrier coatings (EBCs) for gas turbine applications was assessed by characterizing its high-temperature corrosion behavior in contact with a synthetic calcia-magnesia-alumina-silica (CMAS) melt. Er₂Si₂O₇ was fabricated using spark plasma sintering at 1400 °C for 20 min. Corrosion tests were performed by coating sintered Er₂Si₂O₇ pellets with CMAS and heating them to 1400 °C for 2, 12, and 48 h. High-temperature X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analysis were used to identify and analyze the reaction products. The two materials were found to react chemically to form an apatite phase, Ca₂Er₈(SiO₄)₆O₂, at their interface. The Ca₂Er₈(SiO₄)₆O₂ grains were observed to have shard-like morphologies oriented perpendicular to the Er₂Si₂O₇ surface; the reaction layer thickened with increasing heat-treatment time, with the thickness after exposure for 48 h approximately three times the thickness after 2 h.     

Thermal insulation of CMAS (Calcium-Magnesium-Alumino-Silicates)- attacked plasma-sprayed thermal barrier coatings

The impact of the penetration of small quantities of calcium-magnesium-alumino- silicates (CMAS) glassy melt in the porous plasma-sprayed (PS) thermal barrier coatings (TBCs) is often neglected even though it might play a non-negligible role on the sintering and hence on the thermal insulation potential of TBCs. In this study, the sintering potential of small CMAS deposits (from 0.25–3 mg.cm⁻²) on freestanding yttria-stabilized zirconia (YSZ) PS TBCs annealed at 1250 °C for 1 h was investigated. The results showed a gradual in-depth sintering with increasing CMAS deposits. This sintering was concomitant with local transformations of the tetragonal YSZ and resulted in an increase in the thermal diffusivity of the coatings that reached a maximum of ∼110 % for the fully penetrated coating.     

Effects of CMAS penetration on the delamination cracks in EB-PVD thermal barrier coatings with curved interface

During the high-temperature operation of electron beam physical vapor deposited (EB-PVD) thermal barrier coating (TBC), the penetration of environmental calcium-magnesium-alumina-silicate (CMAS) compositions into the ceramic top-coat would affect the growth of delamination cracks. In this work, the effects of CMAS penetration on the delamination cracks in EB-PVD TBC with curved interface are investigated by finite element analysis. In the numerical model, the curved interface evolves as the cyclic displacement instability of the thermally grown oxide (TGO) layer. The penetration of CMAS into the columnar gaps of EB-PVD TBC mainly increases the in-plane modulus of TC layer. It is demonstrated that, with the increase of in-plane modulus in an intact TC, the level of tensile stress, which mainly occurs in the region above the curved interface and responsible for initiating the delamination cracks, presents a decrease; meanwhile, the level of shear stress, which mainly occurs in the region at the periphery of the curved zone to drive the delamination crack when it propagates into this region, presents a increase. Furthermore, the calculation of the strain energy release rate shows that, for the crack located above the curved interface, the increase of in-plane modulus in TC layer can prevent the accumulation of strain energy release rate, and therefore make it more difficult for delamination initiation. However, once the crack propagates into the flat periphery, CMAS penetration would begin to enhance its growth.     

Crystallization behavior of CMAS and NaVO3+CMAS mixture and its potential effect to thermal barrier coatings corrosion

Calcium-magnesium-alumina-silicate (CMAS) and molten salt corrosion pose great threats to thermal barrier coatings (TBCs), and recently, a coupling effect of CMAS and molten salt has been found to cause even severer corrosion to TBCs. In this study, the crystallization behavior of CMAS and CMAS+NaVO₃ is investigated for potentially clarifying their corrosion mechanisms to TBCs. Results indicated that at 1000 °C and 1100 °C, CMAS was crystallized to form CaMgSi₂O₆, while at 1200 °C, the crystallization products were CaMgSi₂O₆, CaSiO₃ and CaAl₂Si₂O₈. The introduction of NaVO₃ in CMAS reduced the crystallization ability, and as the NaVO₃ content increased, glass crystallization occurred at a lower temperature, with crystallization products mainly consisting of CaAl₂Si₂O₈ and CaMgSi₂O₆. At 1200 °C, CMAS+10 wt% NaVO₃ was in a molten state without any crystallization, which suggested that NaVO₃ addition in CMAS could reduce its melting point, indicating enhanced penetration ability in TBCs and thus increased corrosiveness.     

Protocol for selecting exemplary silicate deposit compositions for evaluating thermal and environmental barrier coatings

A protocol for selecting representative silicate compositions for comparative testing of gas turbine coating materials is presented. It begins with a curated dataset of compositions of engine deposits and naturally occurring siliceous debris including volcanic ashes, sands, and dusts. The compositions are first reduced to the five major oxides—those of Ca, Mg, Fe, Al, and Si—and then distilled further using principal component analysis and k-means clustering. The process ultimately yields four classes of possible deposits with common chemical characteristics. Each class is represented by a composition centroid and a range in Ca:Si ratios. Key thermophysical properties of the possible deposits are calculated and related to the glass network connectivity, characterized by the Si:O ratio. Finally, deposits from each of these classes are compared in terms of their reactions with prototypical thermal and environmental barrier oxides, with due consideration of the effects of composition variations within each deposit class. The protocol is, in principle, adaptable to datasets compiled by OEMs and researchers in gas turbine coatings.     

Lanthanum magnesium hexaluminate thermal barrier coatings with pre-implanted vertical microcracks: Thermal cycling lifetime and CMAS corrosion behaviour

Atmospheric plasma-sprayed (APS) coatings have a layered structure as well as lower strain tolerance and a shorter lifetime than EB-PVD coatings. In this study, TBCs composed of a LaMgAl₁₁O₁₉ (LMA) top coat and a NiCrAlY bond coat were prepared by APS coupled with dry-ice blasting to implant vertical microcracks in the top coat. The thermal cycling lifetime and CMAS corrosion behaviour of LMA-TBCs with pre-implanted vertical microcracks were investigated in detail. The results show that the LMA top coat possesses an improved proportion of vertical microcracks and that the corresponding TBC has an improved thermal cycling lifetime. The vertical microcracks in the top coats, which not only reduce the thermal stress but also improve the strain tolerance of TBCs, dramatically contribute to the improvement in the thermal cycling lifetime. Surprisingly, the CMAS corrosion resistance of LMA-type TBCs with implanted vertical microcracks is better than that of conventional TBCs with a typical layered structure.     

Recycling in ceramic glazes of zirconia overspray from thermal barrier coatings manufacturing

Glazed ceramic tiles are the most common building material for floor and wall covering. Glazes are produced from frits. The aim of this work is to make a total or partial replacement of a raw material, zircon, widely used in ceramic tiles manufacturing, with a waste material, in order to prepare ceramic frits. The waste material used in this work, is the overspray zirconia, which is produced during the deposition process by atmospheric plasma spraying (APS) of thermal barrier coatings (TBC) on turbine blades. In particular, a replacement of 100 wt%, 1 wt% and 0.2 wt% of zirconium silicate with zirconia has been studied. Ceramic glazes prepared mixing frits and other raw materials are applied on a single-fired tile. The glazes obtained were characterized with different analytical techniques. This study has revealed that the substitution of zircon with waste zirconia is possible in small percentages due to the presence of small amount of chromophore ions in the overspray zirconia, which tend to colour the glaze.     

Evolution of porosity,crack density,and CMAS penetration in thermal barrier coatings subjected to burner rig testing

Degradation of thermal barrier coatings (TBCs) in gas-turbine engines due to calcium–magnesium–aluminosilicate (CMAS) glassy deposits from various sources has been a persistent issue since many years. In this study, state of the art electron microscopy was correlated with X-ray refraction techniques to elucidate the intrusion of CMAS into the porous structure of atmospheric plasma sprayed (APS) TBCs and the formation and growth of cracks under thermal cycling in a burner rig. Results indicate that the sparse nature of the infiltration as well as kinetics in the burner rig are majorly influenced by the wetting behavior of the CMAS. Despite the obvious attack of CMAS on grain boundaries, the interaction of yttria-stabilized zirconia (YSZ) with intruded CMAS has no immediate impact on structure and density of internal surfaces. At a later stage the formation of horizontal cracks is observed in a wider zone of the TBC layer.     

Interaction of CMAS on thermal sprayed ytterbium disilicate environmental barrier coatings: A story of porosity

Molten calcium magnesium alumina-silicates (CMAS) represent a challenge for the current generation of rare earth silicates environmental barrier coatings (EBCs). Their interaction with ytterbium disilicate (Yb₂Si₂O₇) free-standing coatings deposited using thermal spraying technique has been studied to further understand the reaction mechanisms. Three coatings, deposited with different porosity levels and thickness, representing traditional EBCs (<3% porosity and ～350 μm thickness) and abradable coatings (～20% porosity and 500–1000 μm thickness) were exposed to CMAS at 1350 °C. The results show that higher porosity levels facilitates CMAS infiltration in the first hour of exposure, in combination with infiltration through the inter-splat boundaries. Preferential dissolution of ytterbium monosilicate (Yb₂SiO₅) takes place, forming a 10–15 μm Ca₂Yb₈(SiO₄)₆O₂ apatite layer as the reaction product, producing a network of fine porosity (<10 μm) as the inter-splat boundary material is consumed. After exposure for 48 h, CMAS has completely infiltrated all three coatings, with apatite crystals present across the coatings, up to a depth of ～550 μm. Despite the extensive CMAS infiltration and apatite formation, no damage could be observed in any of the coatings, providing a promising first step for environmental barrier abradable coatings.