Effect of the HfO2/SiO2 pre-mixing ratio and heating temperature on the formation of HfSiO4 as a bond coat of environmental barrier coatings

As the operating temperature of advanced gas turbines typically exceeds 1400 °C, it has been required to replace conventional Si bond coat in environmental barrier coatings (EBCs) with materials possessing higher thermal stability. Since HfSiO₄ has excellent thermal properties such as a high melting point, phase stability over 1400 °C, and CTE matches with that of the SiC-based ceramic matrix composites, it has attracted much attention as a next-generation bond coat material. In this study, HfSiO₄ bond coat was successfully formed by atmospheric plasma spray with pre-mixed HfO₂-SiO₂ powders (molar ratios: 7:3 and 5:5) followed by heat treatment. Effect of molar ratios of the HfO₂-SiO₂ and post-heat treatment temperature (1375 and 1475 °C) on the formation of HfSiO₄ were studied. An oxidation test of the HfSiO₄ coating was carried out at 1475 °C with the conventional Si bond coat to verify whether the new bond coat was suitable for use in a thermal environment of 1400 °C or higher. From the results, the HfO₂/SiO₂ ratio of 5:5 was suitable for the formation of HfSiO₄ than that of 7:3. After heat treatment at 1475 °C, the ratio of HfSiO₄ phase was 84.35%. The higher content of HfSiO₄ formed under 1475 °C, meaning the higher heat treatment temperature accelerated the HfSiO₄ formation. In the oxidation test at 1475 °C, the new HfSiO₄ bond coat showed no cracks and maintained its integrity, but the Si bond coat was oxidized and cracked severely. Therefore, it can be concluded that the new HfSiO₄ bond coat formed from 5HfO₂–5SiO₂ coating is a potential candidate as a next-generation bond coat material in EBCs.     

High-temperature performances of Si-HfO2-based environmental barrier coatings via atmospheric plasma spraying

To improve high-temperature bearing capability of coatings, novel agglomerated Si-HfO₂ powders were prepared by adding HfO₂ powders into original Si powders by spray drying method. Three-layer environmental barrier coatings (EBCs) with Si-HfO₂ bond layer, Yb₂Si₂O₇ intermediate layer and Yb₂SiO₅ surface layer were prepared on SiC ceramic substrates by atmospheric plasma spraying (APS). The high temperature properties of coatings were systematically investigated. The results indicated that the coatings had good high temperature oxidation resistance, and remained intact after being oxidized or steam corrosion at 1400 °C for 500 h, so the addition of HfO₂ improved the thermal cycling performances of the coating. The HfO₂ in Si bond coating could effectively inhibit the growth of thermal grown oxide at high temperatures. This work indicates that the high temperature properties of the coatings are improved by this novel EBCs using the novel agglomerated Si-HfO₂ powders.     

Phase transformation and thermal conductivity of the APS Y2O3 doped HfO2 coating with hybrid structure

Hafnia-based materials are very promising to serve as thermal protecting coatings at temperature above 1200 °C. In this work, two kinds of 8 mol% Y₂O₃ stabilized HfO₂ ceramic coatings (YSH-SN and YSH-MX) with conventional and hybrid structures were prepared by air plasma spray (APS) method. The microstructure, thermal conductivity and the mechanical properties of the coatings before and after thermal exposure at 1300 °C were compared in detail. Results show that the as-sprayed YSH-MX has a hybrid laminated structure of monoclinic HfO₂ and cubicY₂O₃ splats, and transforms to monoclinic HfO₂ and cubic YSH after thermal exposure, while the YSH-SN is composed of major tetragonal YSH phase and transforms to monoclinic HfO₂ and cubic YSH afterward. Thermal conductivities at ultra-high temperature (1600 °C) before and after thermal exposure for those two coatings are close, and the fracture toughness in the direction parallel to the interface exceeds 2.1 MPa m^0.5. The YSH-MX coating with a hybrid structure provides insights to conveniently prepare gradient coating or other coatings with complex structures.     

Preparation,properties and high-temperature oxidation resistance of MoSi2-HfO2 composite coating to protect niobium using spent MoSi2-based materials

Industrial spent MoSi₂-based materials and HfO₂ were recycled as raw materials to fabricate MoSi₂-HfO₂ composite coating by spark plasma sintering (SPS). The microstructural evolution of the coatings was characterized and the 1500 °C oxidation behavior was explored. Cracks penetrated through the MoSi₂ coating while no cracks can be found in the HfO₂-containing composite coating owing to the reduction of the mismatch of thermal expansion coefficient (CTE). Good metallurgical bonding was exhibited since (Mo,Nb)₅Si₃ diffusion layer was found in the HfO₂-containing coating by the diffusion of Nb and Si across the interface without gaps. After 1500 °C oxidation of 20 h, cracks appeared in the surface of SiO₂ layer on MoSi₂ coating while the HfO₂-containing composite coating possessed crack-free oxide scale. HfSiO₄ with high temperature (>2900 °C) is formed during oxidation and it inlays in the silica oxide scale to improve the stability. Compared to MoSi₂ coating, Nb coated MoSi₂-HfO₂ has thinner oxide scale with lower mass gain during oxidation, thus presenting better high-temperature anti-oxidation properties.     

Thermochemical degradation of HfSiO4 by molten CMAS

The thermochemical degradation of hafnium silicate (HfSiO₄) was investigated with a molten calcium-magnesium-aluminosilicate (CMAS) glass relevant to gas turbine engine applications. Sintered HfSiO₄ coupons were fabricated, within which wells were drilled and filled with CMAS glass powder at a loading of ～35 mg/cm². Samples were heat treated at 1200°C, 1300°C, 1400°C, and 1500°C for 1 h, 10 h, and 50 h. At 1200°C and 1300°C, slow formation of a Ca₂HfSi₄O₁₂ cyclosilicate phase was observed at the HfSiO₄-CMAS interface. At 1300°C and higher, rapid infiltration of CMAS into the material along the grain boundaries was observed. Initial conjecture into CMAS degradation mechanisms of HfSiO₄ are presented herein.     

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.     

Hafnium silicate formation during the reaction of β-cristobalite SiO2 and monoclinic HfO2 particles

Hafnium silicate (HfSiO₄; hafnon) is under consideration as an environmental barrier coating material for high-temperature applications. However, its rate of formation from mixtures of monoclinic HfO₂ and crystalline (β-cristobalite) SiO₂ powders is unknown. Here it has been synthesized and its formation rate measured during their solid-state reaction at temperatures from 1250°C to 1400°C. Rietveld refinement of X-ray diffraction patterns indicates that at 1250°C the hafnon phase fraction increases linearly with time, while at the highest reaction temperature, the hafnon phase fraction exhibited a parabolic dependence upon time. Between these two limiting temperatures, a region of linear behavior preceded a transition to parabolic kinetics, with the transition occurring at an earlier time as the reaction temperature increased. Arrhenius relations fitted the kinetics of hafnium silicate formation in both the linear and parabolic regimes. Scanning electron microscopy indicated that the reaction proceeded by diffusion of SiO₂ into HfO₂, similar to the mechanism by which zirconium silicate has been formed from vitreous SiO₂ and tetragonal ZrO₂. The initial linear rate of reaction is consistent with the growth of the contact area between the SiO₂ and HfO₂ particles combined with rapid permeation of the Si⁴⁺ and O²⁻ through the initial, incompletely formed hafnon. After a thin hafnon layer had formed between the reactants, the rate of hafnium silicate growth slowed and further growth was governed by the rate of diffusion of Si⁴⁺ and O²⁻ through the reaction product consistent with the observed parabolic dependence of the phase fraction upon time.     

Failure mechanisms of (Gd0.9Yb0.1)2Zr2O7/Yb2SiO5/Si thermal/environmental barrier coatings during thermal exposure at 1300 °C/1400 °C

A novel tri-layer (Gd_0.9Yb_0.1)₂Zr₂O₇/Yb₂SiO₅/Si (GYbZ/YbMS/Si) thermal and environmental barrier coatings (TEBCs) was first proposed for protecting SiC-based ceramic matrix composites (CMCs). Wherein, the GYbZ layer by plasma spray physical vapor deposition (PS-PVD) was quasi-columnar structured while the YbMS and the Si layers by atmospheric plasma spray (APS) were lamellar structured. The oxidation behavior and the failure mechanisms of the GYbZ/YbMS/Si TEBCs at 1300 °C/1400 °C are revealed. At 1300 °C, the mud-cracks penetrated through the GYbZ/YbMS layer and transversely deflected in the Si layer are responsible for the oxidation at YbMS/Si interface. When the temperature increased to 1400 °C, the propagation of mud-cracks, cavities, and TGO channel cracks occurred due to the sintering of GYbZ and the fast growth of cristobalite. Eventually, these defects caused delaminating failure at interface. Moreover, another de-bonding failure of the coating was observed resulting from the significant thickening of oxide scale at the edge region.     

Ultra‐High‐Temperature Ceramic HfB2‐SiC Coating for Oxidation Protection of SiC‐Coated Carbon/Carbon Composites

To protect the carbon/carbon (C/C) composites from oxidation, an outer ultra‐high‐temperature ceramics (UHTCs) HfB₂‐SiC coating was prepared on SiC‐coated C/C composites by in situ reaction method. The outer HfB₂‐SiC coating consists of HfB₂ and SiC, which are synchronously obtained. During the heat treatment process, the formed fluid silicon melt is responsible for the preparation of the outer HfB₂‐SiC coating. The HfB₂‐SiC/SiC coating could protect the C/C from oxidation for 265 h with only 0.41 × 10^?2 g/cm² weight loss at 1773 K in air. During the oxidation process, SiO₂ glass and HfO₂ are generated. SiO₂ glass has a self‐sealing ability, which can cover the defects in the coating, thus blocking the penetration of oxygen and providing an effective protection for the C/C substrate. In addition, SiO₂ glass can react with the formed HfO₂, thus forming the HfSiO₄ phase. Owing to the “pinning effect” of HfSiO₄ phase, crack deflecting and crack termination are occurred, which will prevent the spread of cracks and effectively improve the oxidation resistance of the coating.     

Experimental and first-principles simulation study on oxidation behavior at 1700 °C of Lu2O3–SiC-HfB2 ternary coating for SiC coated carbon/carbon composites

The oxidation behavior and microstructure evolution of Lu₂O₃–SiC-HfB₂ ceramic coating specimen at 1700 °C were investigated systematically by experimental study and first-principles simulation. The prepared ternary coating possesses a compact morphology, which effectively defends C/C substrate against oxidation at 1700 °C for 130 h, showing a good antioxidant property. The formed HfSiO₄, Lu₂Si₂O₇, and HfO₂ with high melting points play an active role in developing the thermal stability of the oxidized scale. Besides, Lu and Hf atoms incline to diffuse into SiO₂, which enhances its structural stability. The improved thermal property of the oxidized scale for the Lu₂O₃–SiC-HfB₂/SiC ceramic coating can delay the effective delivery of oxygen inwardly and thus prolong its oxidation protection time. The quick volatilization of SiO₂ at 1700 °C induces that some glass phase evaporates with being not completely stabilized, which causes the formation of holes and the consumption of the inner coating.     

Steam oxidation of ytterbium disilicate environmental barrier coatings with and without a silicon bond coat

The current generation of multilayer Si/Yb₂Si₂O₇ environmental barrier coatings (EBCs) are temperature limited by the melting point of Si, 1414°C. To investigate higher temperature EBCs, the cyclic steam oxidation of EBCs comprised of a single layer of ytterbium disilicate (YbDS) was compared to multilayered Si/YbDS EBCs, both deposited on SiC substrates using atmospheric plasma spray. After 500 1-h cycles at 1300°C in 90 vol%H₂O-10 vol%air with a gas velocity of 1.5 cm/s, both multilayer Si/YbDS and single layer YbDS grew thinner silica scales than bare SiC, with the single layer YbDS forming the thinnest scale. Both coatings remained fully adherent and showed no signs of delamination. Silica scales formed on the single layer coating were significantly more homogeneous and possessed a markedly lower degree of cracking compared to the multilayered EBC. The single layer EBC also was exposed at 1425°C in steam with a gas velocity of 14 cm/s in an alumina reaction tube. The EBC reduced specimen mass loss compared to bare SiC but formed an extensive 2nd phase aluminosilicate reaction product. A similar reaction product was observed to form on some regions of the bare SiC specimen and appeared to partially inhibit silica volatilization. The 1425°C steam exposures were repeated with a SiC reaction tube and no 2nd phase reaction product was observed to form on the single layer EBC or bare SiC.     

Fabrication and investigation of Ca/Tb co-doped HfO2 infrared coatings

In this study, Ca/Tb co-doped HfO₂ coatings were prepared by atmosphere plasma spraying. The chemical composition, morphology and infrared property of the coatings were characterized. The coatings possessed a layer-stacked morphology. When the Ca/Tb doping atomic ratio was 1:1, the phase of the coatings gradually changed from monoclinic to cubic with increasing the doping mass. The CTH2 coating had the highest emissivity which was 0.820 in 0.75–6.5 µm and 0.902 in 6.5–15 µm respectively. The enhancement in short band was mainly due to the introduction of Ca²⁺ and Tb³⁺ ions that generated oxygen vacancies in the lattice forming impurity levels within the forbidden band, moreover, the transfer of Tb³⁺ to Tb⁴⁺ increased the concentration of free electrons, which promoted the absorption of free carriers. The increase in long band attributed to the lattice distortion that reduced the lattice symmetry and strengthened the absorption of lattice polar vibration.     

Environmental barrier coatings on enhanced roughness SiC: Effect of plasma spraying conditions on properties and performance

Environmental barrier coatings for SiC/SiC composites are limited by the melting temperature of the Si bond coating near 1414 °C. Systems without a bond coating may be required for future turbine applications where material temperatures go beyond 1350 °C. Enhanced roughness SiC substrates were developed to assess coating adhesion without the bond coating. Two EBCs with different YbMS/YbDS ratios were produced via modified plasma spraying parameters. Coating microstructure, thermal expansion, and modulus were measured for comparison of coating properties. Cyclic steam exposures at 1350 °C were performed to assess oxidation resistance. The EBC with increased concentration of Yb₂SiO₅ secondary phase displayed a higher CTE, which is typically expected to decrease adhesion lifetimes due to an increase in stress upon thermal cycling. Yet, the EBC chemistry with increased Yb₂SiO₅ concentration was able to experience longer cycling times prior to coating delamination, likely due to interface interactions with the substrate and the thermally grown oxide.     

SiC fiber strength after low pO2 oxidation

Hi‐Nicalon?‐S SiC fiber was heat treated for 1 hour at 1300°C, 1400°C, and 1500°C in argon with pO₂ of 3.7, 10, 20, 50, 100, and 200 ppm. Fiber strengths were measured by 30 single‐filament tensile tests. Fiber microstructure and surface morphology were characterized by TEM. Active oxidation occurred in all cases except at 1500°C with 200 ppm pO₂, 1400°C with 100 ppm pO₂ or higher, and 1300°C with 50 ppm pO₂ or higher. When active oxidation did not occur, a glass SiO₂ scale formed at 1300°C and 1400°C, and a cristobalite scale formed at 1500°C. The thickness of these scales was much larger than that predicted by linear dependence of oxidation rate on pO₂. Fiber strengths were lowest after heat treatment at 1300°C and a pO₂ of 3.7 ppm, 1400°C and a pO₂ of 20 ppm, and 1500°C and a pO₂ of 200 ppm. Active oxidation caused fiber surface roughening, but no obvious changes to the internal fiber microstructure. Decreased fiber strength correlated with increased fiber surface roughness, but roughness magnitudes were not large enough to explain the amount by which strength was degraded. Fiber strengths, surface roughness, scale thicknesses, and the passive‐active oxidation transition for SiC are compared with previous observations. Possible strength degradation mechanisms are discussed.     

Deposition and ablation resistance of HfC-based coatings prepared on SiC-coated C/C composites by supersonic atmospheric plasma spraying

In order to improve the ablation properties of C/C composites, HfC-based coatings with different mass ratios of SiC were deposited on the surface of SiC-coated carbon/carbon composites by supersonic atmospheric plasma spraying. The morphologies and microstructures of the HfC-based coatings were characterised. The ablation resistance test was carried out by oxyacetylene torch. The results show that the as-prepared coatings are multiphase coatings consisting of HfC, HfO₂, SiC and SiO₂. The structure of different coatings is dense. After ablation for 60?s, the ablation centre region of coating is smooth without obvious microcrack and pinhole, and no interlaminar crack can be observed at the cross-section. An Hf–Si–O compound oxide layer is generated on the surface of coating, which is beneficial for protecting the C/C composites from being ablated. Meanwhile, the further generated HfSiO₄ can play a pinning effect, which can prevent crack extension.     

Fabrication and characterization of Pr6O11-HfO2 ultra-high temperature infrared radiation coating

In this study, pure HfO₂ and Pr₆O₁₁-HfO₂ coatings were prepared by atmospheric plasma spraying. The chemical compositions, morphologies, infrared radiation performances and thermal resistances of the coatings were characterized. The results showed that doping Pr₆O₁₁ could effectively improve the infrared emittance of the HfO₂ coating. The HfO₂ coating doping with 10 wt. % Pr₆O₁₁ exhibited the highest infrared emittance, which was 0.859 at room temperature and 0.883 at 1600 °C, correspondingly. This was mainly attributed to the oxygen vacancies, which created by the substitution of Hf⁴⁺ by Pr³⁺, could introduce localized energy states within the HfO₂ band gap and increase the lattice distortion, producing lower symmetry vibrations. In addition, the Pr₆O₁₁-HfO₂ infrared radiation coating possessed high tensile adhesive strength and good thermal resistance, which could withstand a high temperature treatment at 1700 °C for at least 50 h without exfoliation, and there was only a slight reduction in emittance.     

Accelerated oxidation during 1350°C cycling of ytterbium silicate environmental barrier coatings

Environmental barrier coatings (EBCs) will be needed to protect SiC-based ceramic matrix composite components for the next generation of high-efficiency industrial gas turbines (IGTs). The IGT application will require ≥25 kh lifetimes, and little data are available on EBC failure mechanisms, particularly at ≥1300°C. Initial 1-h furnace cycle testing at 1350°C in 90 vol% H₂O/10 vol% air was conducted ≥1000 cycles on thermally sprayed ytterbium disilicate (YbDS) coatings with and without an Si bond coating. By ≥1000 h, both EBCs formed thick, highly cracked, and fully crystalline cristobalite scales. Comparison of thermally grown oxide (TGO) microstructure and kinetics to isothermal rates of Si and SiC steam oxidation indicated a departure from slow-growing parabolic growth to more rapid rates of silica formation. Possible mechanisms and implications for this acceleration are discussed.     

Evolution mechanism of the microstructure and mechanical properties of plasma-sprayed yttria-stabilized hafnia thermal barrier coating at 1400 °C

Yttria stabilized hafnia (Hf_0.84Y_0.16O_1.92, YSH16) coatings were sprayed by atmospheric plasma spraying (APS). The effects of thermal aging at 1400 °C on the microstructures, mechanical properties and thermal conductivity of the coatings were studied. The results show that the as-sprayed coating was composed of the cubic phase, and the nano-sized monoclinic (M) phase was precipitated in the annealed coating. The presence of M phase effectively constrained the sintering of the coating due to its superior sintering-resistance. The Young's modulus kept at a nearly same level of ~78 GPa even after annealing, and the coating annealed for 6 h yielded a maximum value of hardness but revealed a declining tendency in the Vicker's hardness with prolonged sintering time. The thermal conductivity increased from 0.8-0.95 W m^-1 K^-1 at as-sprayed state to 1.6 W m^-1 K^-1 after annealing at 1400 °C for 96 h. The dual-phase coating is promising to serve at temperatures above 1400 °C due to its excellent thermal stability and mechanical properties.     

Structural characteristics and high-temperature oxidation behaviour of nano-HfO2-doped thermal barrier coatings

The uneven growth of thermally grown oxides (TGOs) in thermal barrier coating systems is an important cause of cracking failure at the coating interface in high-temperature environments. The doping of rare earth elements in the bonding layer can effectively inhibit the formation of spinel oxides in the TGO and improve the high-temperature oxidation resistance of the coating. However, a single rare earth element has a limited effect on inhibiting TGO failure. In this study, a NiCoCrAlYHf coating was prepared using a supersonic flame spraying (HVOF) technique. The effects of HfO₂ doping on the high-temperature oxidation behaviour of the coatings and diffusion behaviour of metallic elements in the coatings were investigated at 1100 °C. The results showed that the nano-sized HfO₂ filled the pores between the powder particles and improved the hardness of the coating. During the high-temperature oxidation process, the oxides formed by Hf and Y had a large size and low solubility, which effectively blocked the diffusion of Al. This slowed the generation of spinel oxides, effectively inhibited the growth of the TGO, it inhibits the initiation and propagation of cracks within the coating, reduces damage to the coating from tensile and compressive stresses at the interface, and improved the high-temperature oxidation resistance of the coating.     

Exploration of the oxidation behavior and doping ratio of the Si–HfO2 bond layer used in environmental barrier coatings

Hafnia doping is expected to improve the performance of the silicon-bond layer of environmental barrier coatings (EBCs) for SiC-based ceramic matrix composites. The optimal doping ratio, distribution of HfO₂, and oxidation mechanism of the bond layer have not yet been fully addressed. A prototype Si–HfO₂ bond layer with a designed HfO₂-rich area was used to examine its oxidation behavior. A random dispersion model was developed to calculate the optimal HfO₂ doping ratio and its appropriate distribution state. The simulation results recommended that 20–30 vol% is the optimal doping ratio, where HfO₂ is well dispersed inside Si without forming networks. This enables HfO₂ to react with and consume SiO₂ without accelerating oxygen diffusion inside the bond layer. This was confirmed by oxidation experiments on Si–xHfO₂ tablets, in which the thinnest thermally grown oxide was achieved for the 20 vol% HfO₂-doped Si tablet. Both the microstructure design and material composition selection are highly important to further boost the performance of the EBCs.