Preparation of Al2O3 nanowires on 7YSZ thermal barrier coatings against CMAS corrosion

The commonly-employed material for thermal barrier coatings(TBCs)is 7 wt.%Y2O3 ZrO2(7YSZ),generally deposited by electron beam-physical vapor deposition(EB-PVD).Due to the increasing demand for higher operating temperature in aero-derivative gas turbines,a lot of effort has been made to prevent the premature failure of columnar 7YSZ TBCs,which is induced by the microstructure degradation,sintering and spallation after the deposition of infiltrated siliceous mineral(consisting of calcium magnesium aluminum silicate(CaO MgO Al2O3 SiO2,i.e.,CMAS)).A new method called Al-modification for columnar 7YSZ TBCs against CMAS corrosion was present.The Al film was magnetron-sputtered on the surface of the columnar 7YSZ TBCs,followed by performing vacuum heat treatment of the Al-deposited TBCs.During the heat treatment,the molten Al reacted with ZrO2 to formα-Al2O3 overlay that effectively hindered CMAS infiltration.Moreover,the Al film could evaporate and re-nucleate,leading to the generation of Al2O3 nanowires,which further restrained the moving of molten CMAS.

CMAS corrosion resistance characteristics of RE_(50)Ta_(x)Zr_(50-x)O_(175+0.5x)thermal barrier oxides in RE_(2)Zr_(2)O_(7)-RETaO_(4)systems

The corrosion resistance characteristics of RE-rich RE_(50)Ta_(x)Zr_(50-x)O_(175+0.5x)oxides in RE_(2)Zr_(2)O_(7)-RETaO_(4)systems to calcium-magnesium-alumino-silicate(CMAS)at 1300°C,and the influence of RE^(3+)and Ta^(5+)on chemical reactions and reactive crystallization of CMAS melts were investigated.The results show that following the thermochemical reactions,apatite,pyrochlore,reprecipitated fluorite and residual Yb(Y)TaO4phases were the predominant reaction products.Formation abilities of apatite and pyrochlore were found to be proportional to the ionic radius of RE^(3+).The increase of Ta^(5+)amount can decrease the number of available RE^(3+)to form apatite.Moreover,the resistance characteristic to CMAS corrosion in RE_(50)Ta_(x)Zr_(50-x)O_(175+0.5x)systems was decided by the combined action of apatite and pyrochlore phases.The cohesive mixture of apatite and pyrochlore phases can generate a dense layer near the reaction front,which had a positive effect on suppressing CMAS infiltration.The ability of the fluorite+RETaO4two-phase field was determined to be sufficient to mitigate CMAS corrosion.

(Lu_(1/7)Yb_(1/7)Sc_(1/7)Er_(1/7)Y_(1/7)Ho_(1/7)Dy_(1/7))_(2)Si_(2)O_(7)high entropy rare-earth disilicate with low thermal conductivity and excellent resistance to CMAS corrosion

Low thermal conductivity,compatible thermal expansion coefficient,and good calcium–magnesium–aluminosilicate(CMAS)corrosion resistance are critical requirements for environmental barrier coatings used on silicon-based ceramics.RE2Si2O7(RE=rare earth)has been widely recognized as one of the most promising candidates for environmental barrier coatings due to its good water vapor corrosion resistance.However,the relatively high thermal conductivity and poor resistance to CMAS corrosion have limited its practical application.Inspired by the high entropy effect,in this work,a novel rare earth disilicate(Lu_(_(1/7))Yb_(_(1/7))Sc_(_(1/7))Er_(_(1/7))Y_(_(1/7))Ho_(_(1/7))Dy_(_(1/7)))2Si2O7((7RE_(_(1/7)))2Si2O7)has been designed and synthesized by a solid reaction process.(7RE_(_(1/7)))2Si2O7 showed a low thermal conductivity of 1.81 W·m^(−1)·K^(−1)at 1273 K.Furthermore,the thermal expansion coefficient of(7RE_(_(1/7)))_(2)Si_(2)O_(7)(4.07×10^(−6)℃^(−1)from room temperature(RT)to 1400℃)is close to that of the SiC-based ceramic matrix composites(SiC-CMCs)((4.5–5.5)×10^(−6)℃^(−1)).Additionally,(7RE_(_(1/7)))2Si2O7 exhibited excellent resistance to CMAS corrosion.When exposed to CMAS at 1300℃for 48 h,the reaction layer thickness was 22μm.The improved performance of(7RE_(_(1/7)))2Si2O7 highlights its potential as a promising candidate for thermal/environmental barrier coatings.

Experimental and numerical investigation on the thermal and mechanical behaviours of thermal barrier coatings exposed to CMAS corrosion

Calcium-magnesium-alumino-silicate(CMAS)corrosion is a critical factor which causes the failure of thermal barrier coating(TBC).CMAS attack significantly alters the temperature and stress fields in TBC,resulting in their delamination or spallation.In this work,the evolution process of TBC prepared by suspension plasma spraying(SPS)under CMAS attack is investigated.The CMAS corrosion leads to the formation of the reaction layer and subsequent bending of TBC.Based on the observations,a corrosion model is proposed to describe the generation and evolution of the reaction layer and bending of TBC.Then,numerical simulations are performed to investigate the corrosion process of free-standing TBC and the complete TBC system under CMAS attack.The corrosion model constructs a bridge for connecting two numerical models.The results show that the CMAS corrosion has a significant influence on the stress field,such as the peak stress,whereas it has little influence on the steady-state temperature field.The peak of stress increases with holding time,which increases the risk of the rupture of TBC.The Mises stress increases nonlinearly along the thick direction of the reaction layer.Furthermore,in the traditional failure zone,such as the interface of the top coat and bond coat,the stress obviously changes during CMAS corrosion.

Effects of pellet surface roughness and pre-oxidation temperature on CMAS corrosion behavior of Ti_(2)AlC

Calcium–magnesium–alumina–silicate(CMAS)corrosion is a serious threat to thermal barrier coatings(TBCs).Ti_(2)AlC has been proven to be a potential protection layer material for TBCs to resist CMAS corrosion.In this study,the effects of the pellet surface roughness and temperature on the microstructure of the pre-oxidation layer and CMAS corrosion behavior of Ti_(2)AlC were investigated.The results revealed that pre-oxidation produced inner Al_(2)O_(3)layer and outer TiO_(2)clusters on the pellet surfaces.The content of TiO_(2)decreased with decreasing pellet surface roughness and increased along with the pre-oxidation temperature.The thickness of Al_(2)O_(3)layer is also positively related to the pre-oxidation temperature.The Ti_(2)AlC pellets pre-oxidized at 1050℃could effectively resist CMAS corrosion by promoting the crystallization of anorthite(CaAl_(2)Si_(2)O_(8))from the CMAS melt rapidly,and the resistance effectiveness increased with the pellet surface roughness.Additionally,the CMAS layer mainly spalled off at the interface of CaAl_(2)Si_(2)O_(8)/Al_(2)O_(3)layer after thermal cycling tests coupled with CMAS corrosion.The Al_(2)O_(3)layer grown on the rough interface could combine with the pellets tightly during thermal cycling tests,which was attributed to obstruction of the rough interface to crack propagation.

Ti4+-incorporated fluorite-structured high-entropy oxide (Ce,Hf,Y,Pr,Gd)O_(2−δ): Optimizing preparation and CMAS corrosion behavior

Environmental barrier coatings(EBCs)with excellent chemical resistance and good high-temperature stability are of great significance for their applications in next-generation turbine engines.In this work,a new type of high-entropy fluorite-structured oxide(Ce_(0.2)Hf_(0.2)Y_(0.2)Pr_(0.2)Gd_(0.2))O_(2−δ)(HEFO-1)with different Ti^(4+)contents were successfully synthesized.Minor addition of Ti4+could be dissolved into a high-entropy lattice to maintain the structure stable,effectively reducing the phase formation temperature and promoting the shrinkage of bulk samples.Heat treatment experiments showed that all the samples remained a single phase after annealing at 1200–1600℃for 6 h.In addition,high-entropy(Ce_(0.2)Hf_(0.2)Y_(0.2)Pr_(0.2)Gd_(0.2)Ti_(0.2x)O_(2−δ)demonstrated great resistance to calcium–magnesium–alumina–silicate(CMAS)thermochemical corrosion.When the content of Ti was increased to x=0.5,the average thickness of the reaction layer was about 10.5µm after being corroded at 1300℃for 10 h.This study reveals that high-entropy(Ce_(0.2)Hf_(0.2)Y_(0.2)Pr_(0.2)Gd_(0.2)Ti_(0.2x)O_(2−δ)is expected to be a candidate for the next-generation EBC materials with graceful resistance to CMAS corrosion.

Investigation of improving the thermophysical properties and corrosion resistance of RE_(2)SiO_(5)/RE_(2)Si_(2)O_(7)multiphase silicates by component design with RE doping

In this research,a novel method for regulating components in RE_(2)SiO_(5)/RE_(2)Si_(2)O_(7)multiphase silicates was developed,combining the benefits of a suitable thermal expansion coefficient(CTE)and outstanding corrosion resistance against calcium–magnesium–alumino–silicate(CMAS).This approach enhanced the overall thermophysical properties.Additionally,the results from the CMAS corrosion resistance test indicated that(Lu_(1/3)Yb_(1/3)Tm_(1/3))_(2)SiO_(5)/(Lu_(1/3)Yb_(1/3)Tm_(1/3))_(2)Si_(2)O_(7)and(Lu_(1/4)Yb_(1/4)Tm_(1/4)Er_(1/4))_(2)SiO_(5)/(Lu_(1/4)Yb_(1/4)Tm_(1/4)Er_(1/4))_(2)Si_(2)O_(7)exhibited exceptional resistance to CMAS penetration,even at temperatures up to 1500℃.To comprehend the corrosion mechanism of CMAS on these silicates,we introduced a reaction–diffusion model,which involved observing the changes in the interface between the corrosion product layer and the silicate block.This was achieved using electron backscatter diffraction(EBSD).These findings lay a theoretical basis for selecting rare earth elements in RE_(2)SiO_(5)/RE_(2)Si_(2)O_(7)multiphase silicates based on the radii of different rare earth cations.

High toughness and CMAS resistance of REAlO_(3)/RE_(2)Zr_(2)O_(7)(RE=La,Nd,Sm,Eu,Gd,and Dy)composites with eutectic composition for thermal barrier coatings

Although rare earth zirconates(RE_(2)Zr_(2)O_(7))have garnered attention as viable candidates for thermal barrier coatings(TBCs),they suffer from low fracture toughness and accelerated calcium–magnesium–alumina–silicate(CMAS)melt corrosion at high service temperatures,which impedes their practical application.In this work,we developed a series of REAlO_(3)/RE_(2)Zr_(2)O_(7)(RE=La,Nd,Sm,Eu,Gd,and Dy)composites with a eutectic composition that not only significantly enhanced the fracture toughness by more than 40%relative to that of RE_(2)Zr_(2)O_(7)but also exhibited improved resistance to CMAS corrosion.The increase in toughness arises from multiple mechanisms,such as ferroelastic toughening,fine-grain strengthening,and residual stress toughening,all of which trigger more crack defects and energy consumption.Additionally,the CMAS penetration depth of the REAlO_(3)/RE_(2)Zr_(2)O_(7)composites is approximately 36%lower than that of RE_(2)Zr_(2)O_(7).Al–O constituents in composites can capture CaO,SiO_(2),and MgO in CMAS melts and increase their viscosity,resulting in enhanced CMAS corrosion resistance.The thermophysical properties of the REAlO_(3)/RE_(2)Zr_(2)O_(7)composites were also investigated,and their coefficient of thermal expansion and thermal conductivity are comparable to those of 7–8 wt%Y_(2)O_(3)partially stabilized ZrO2(YSZ),indicating their potential as TBC materials.

In-situ observation and mechanism of calcium–magnesium–alumina–silicate(CMAS)melts-induced degradation of RE_(2)SiO_(5)(RE=Tb,Dy,Ho,Y,Er,Tm,and Yb)ceramics at 1500℃

Rare earth(RE)silicate is one of the most promising environmental barrier coatings for silicon-based ceramics in gas turbine engines.However,calcium-magnesium-alumina-silicate(CMAS)corrosion becomes much more serious and is the critical challenge for RE silicate with the increasing operating temperature.Therefore,it is quite urgent to clarify the mechanism of high-temperature CMAS-induced degradation of RE silicate at relatively high temperatures.Herein,the interaction between RE_(2)SiO_(5) and CMAS up to 1500℃was investigated by a novel high temperature in-situ observation method.High temperature promotes the growth of the main reaction product(Ca_(2)RE_(8)(SiO_(4))6O_(2))fast along the[001]direction,and the precipitation of short and horizontally distributed Ca_(2)RE_(8)(SiO_(4))6O_(2) grains was accelerated during the cooling process.The increased temperature increases the solubility of RE elements,decreases the viscosity of CMAS,and thus elevates the corrosion reaction rate,making RE_(2)SiO_(5) fast interaction with CMAS and less affected by RE element species.