Tailoring thermal and mechanical properties of rare earth niobates by coupling entropy and composite engineering

In this paper, a series of high-entropy rare earth niobates, including fluorite RE₃NbO₇ (HE317), monoclinic RENbO₄ (HE114) and RENbO₄/RE₃NbO₇ composite (HE-composite), are prepared via solid state reaction, following by a study about their thermal and mechanical properties. The high-entropy rare earth niobates exhibit excellent phase stability after thermally exposed to 1300 °C for 100 h, indicating entropy can stabilized high-entropy rare earth niobates. Compared with the single element rare earth niobates, high-entropy rare earth niobates have higher fracture toughness and hardness. The high-entropy RENbO₄/RE₃NbO₇ composite has the best mechanical properties, with a fracture toughness of 2.71 ± 0.17 MPa·m^1/2 and hardness of 9.46 ± 0.24 GPa, respectively. The high-entropy niobates exhibit high coefficients of thermal expansion which is close to 7 wt% Y₂O₃ stabilized ZrO₂. It is also proved that the configurational entropy has little effect on the critical temperature from monoclinic to tetragonal phase transition. The thermal conductivity of HE-composite is lower than HE114, indicating the combination of HE114 and H317 is a more efficient strategy to decrease the thermal conductivity of HE114 than entropy engineering.     

CMAS corrosion resistance in high temperature and rainwater environment of double-layer thermal barrier coatings odified by rare earth

In order to explore the difference of CMAS corrosion resistance in high temperature and rainwater environment of single-layer and double-layer thermal barrier coatings (TBCs), and further reveal the mechanism of CMAS corrosion resistance in above environment of double-layer TBCs modified by rare earth, two TBCs were prepared by air plasma spraying, whose ceramic coating were single-layer ZrO₂–Y₂O₃ (YSZ) and double-layer La₂Zr₂O₇(LZ)/YSZ, respectively. Subsequently, CMAS corrosion resistance tests at 1200 °C and rainwater environment of two TBCs were carried out. Results demonstrate that after high temperature CMAS corrosion for the same time, due to phase transformation, the volume of YSZ ceramic coating in single-layer TBCs shrank and surface cracks formed, which would lead to coating failure. When LZ ceramic coating of double-layer TBCs reacted with CMAS, compact apatite phases and fluorite phases formed, the penetration of CMAS into ceramic coating was inhibited effectively. Raman analysis and calculation results show that both of the surface residual stress of ceramic coating in two TBCs were compressive stress, and the residual stress of ceramic coating in double-layer TBCs were smaller than that of single-layer TBCs. Atomic force microscopy of TBCs after CMAS corrosion show that surface of double-layer TBCs was more uniform and compact than that of single-layer TBCs. The electrochemical properties in simulated rainwater of two TBCs after high temperature CMAS corrosion showed that double-layer TBCs possessed higher free corrosion potential, lower corrosion current and higher polarization resistance than those of single-layer TBCs. Consequently, the presence of LZ ceramic coating effectively improved CMAS corrosion resistance in high temperature and rainwater environment of double-layer TBCs.     

稀土氧化物在SiAlON陶瓷材料中的应用研究进展

简要论述了稀土氧化物在SiAlON陶瓷材料中的应用研究概况;介绍了Y_2O_3、Sm_2O-3、Dy_2O_3和Nd_2O_3等单一稀土氧化物以及复合掺杂稀土氧化物在SiAlON陶瓷材料中的应用进展,并比较了它们对SiAlON陶瓷材料性能的影响;最后对稀土氧化物在SiAlON陶瓷材料中的应用前景作了扼要的分析和展望。     

Preparation and characterization of branched polyesteramide/mix rare earth oxides composites

Branched polyester amide containing various amount of mix rare earth oxides (RE₂O₃) were synthesized by in-situ solution condensation of AB₂ monomer synthesized based on the reaction between maleic anhydride and diethanolamine (DEA). The effect of AB₂ monomer self-polycondensation on the RE₂O₃ surface and the properties of synthesized composites were investigated by using Fourier-transform infrared spectra (FT-IR), ultraviolet–visible absorption spectra (UV–vis), X-ray photoelectron spectroscopy, scanning electron microscopy, thermogravimetric analysis and viscosity determination. AB₂ monomer can envelop RE₂O₃ particles as an organic matrix (HBPEA′) by self-polycondensation under the proposed condition. Ionization of surface of RE₂O₃ aggregates can result in the rare earth ionic (RE³⁺) and the resulting RE³⁺ might coordinate with the organic matrix. Thermal stability of branched polyesteramide can be significantly improved in presence of 5 wt% RE₂O₃, possibly due to the coordination reaction between RE₂O₃ and the active group of the organic matrix.     

The morphology,thermal property,and failure mechanism of GdNdZrO thermal barrier coatings by EB-PVD

Nowadays, the Gd₂Zr₂O₇ thermal barrier coatings (TBCs) have been evaluated as a promising alternative to yttria-stabilized zirconia (YSZ). Thus, this investigation focuses on the thermal property, morphology, and failure mechanism of double ceramic layers (DCLs) GdNdZrO/YSZ advanced TBCs. The GdNdZrO coatings with columnar morphology have been deposited on NiCoCrAlYHf bond coating using an electron beam physical vapor deposition method. Material characterizations mainly include X-ray diffraction, scanning electron microscope, and transmission electron microscopy. The thermal conductivity of GdNdZrO ceramic material is 0.494 W/mK at 1200°C. The thermal shock life of GdNdZrO/YSZ TBCs shows an average shock life of 5235 cycles. The TBC degradation occurs on the crack area within thermally grown oxide layer leading to the interface instability. The interface broken might play an important role in the failure mechanism of TBCs.     

Enhanced properties of Al-modified EB-PVD 7YSZ thermal barrier coatings

7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coating (TBC) prepared by electron beam-physical vapor deposition (EB-PVD) has been used in gas turbine engines for many years, where the TBC must successfully withstands the damage caused by a variety of environmental and mechanical aspects. The primary failure modes for TBC are oxidation of bond coating, particle erosion and CMAS (calcium-magnesium-alumina-silicates) corrosion. The lifetime of TBC associated with above three failure factors will be reduced significantly. In order to prolong the operation time, an alternative approach depositing Al film on 7YSZ TBC surface by magnetron sputtering is proposed. An α-Al₂O₃ overlay was in-situ synthesized on each 7YSZ column through reaction of Al and ZrO₂ during vacuum heat treatment. And the results indicate that the Al-modified EB-PVD 7YSZ TBC shows better oxidation resistance, as well as lower particulate erosion and CMAS corrosion.     

Phase structure and thermal conductivities of Er2O3 stabilized ZrO2 toughened Gd2Zr2O7 ceramics for thermal barrier coatings

3.5 mol% Er₂O₃ stabilized ZrO₂ (ErSZ) and Gd₂Zr₂O₇ powders were produced by a chemical co-precipitation and calcination method, and ErSZ was used to toughen Gd₂Zr₂O₇. The phase structure, toughness and thermal conductivities of ErSZ toughened Gd₂Zr₂O₇ ceramics were investigated. When the ErSZ content was below 15 mol%, the compound consisted of pyrochlore phase, the ordering degree of which decreased with the increase of the ErSZ content. High ErSZ doping led to the formation of metastable tetragonal (t′) phase in the compound. The addition of ErSZ in Gd₂Zr₂O₇ benefited its toughness, mainly attributable to the presence of t′ phase in the compound. With the increase of the ErSZ content in the compound, the thermal conductivity first decreased and then showed an upward tendency, and 10 mol% ErSZ toughened Gd₂Zr₂O₇ exhibited the lowest thermal conductivity.     

Effects of rare earth oxides additions on microstructure and properties of alumina-magnesia refractory castables

To accommodate the glaring requirements of castables with high performances for the iron and steel making industry, effects of rare earth oxides additions on microstructure and properties of alumina-magnesia refractory castables were investigated. The properties of castables including phase compositions, apparent porosity, permanent linear change and strength were compared. It was demonstrated that yttria and ceria presented varying degrees of influence on in-situ reactions and volumetric stability of castables. The solid-soluted content of spinel and calcium hexaluminate (CA₆) was both dependent on the additions.     

Hot corrosion studies of nanostructured gadolinium zirconate thermal barrier coatings

Improvement of hot corrosion resistance is one of the important parameters governing the lifetime and efficiency of the thermal barrier coatings (TBCs). In this study, the Gadolinium Zirconate (GZ) was synthesized by ball milling method and deposited by Electron Beam-Physical Vapour Deposition (EB-PVD) on Ni-based superalloy substrate with NiCrAlY as an intermediate bond coat. The effect of nanostructured GZ TBCs on hot corrosion resistance were studied under three different salt mixture environments viz; SM1, SM2 and SM3 in isothermal condition at 900 °C for 12 h. The results indicated that EB-PVD coated nanostructured GZ TBCs have improved the hot corrosion resistance and performed well under SM1 and SM3 conditions with minimal weight gain and without any spallation, whereas, the TBC suffered severe spallation under of SM2 salt condition with higher weight gain among the other two conditions. The formation of microcracks along the columnar gaps of the topcoat were found in the SM2 condition, have allowed the molten salts infiltration up to the coating interface. The formation of dense corrosive products GdVO₄ and m-ZrO₂ phases were identified after hot corrosion in SM1 and SM3 condition, which were absent in SM2 condition.     

A review on recent applications and future prospects of rare earth oxides in corrosion and thermal barrier coatings,catalysts, tribological,and environmental sectors

Rare earth oxides (REOs) and metals as an important class of materials have generated global interest in modern technology. Here, eight REOs (R₂O₃, R = Yb, Er, Sm, Eu, Y, Gd, Dy, and Ce) are identified those are mostly used in diverse chemical and industrial sectors. In this concise review the applications of these REOs in corrosion protection, thermal barrier coating, hydrophobic coating, catalytic reactions, refrigeration, photoactivity, environmental, and tribological sector are briefly summarized, which are sparsely documented in the existing literature review. In what follows, recently published relevant literature is systematically evaluated and key insights are addressed. The use of REOs as nonstoichiometric compounds or as doping agents to enhance the system performance of specific applications is commendable. Related lab-scale studies, therefore, will invoke the potential exploitation of individual or blended REOs for large-scale commercialization. However, phase transformation and high energy consumption in the thermal coating, multi-step fabrication of hydrophobic coating, the building of aromatic pollutants in catalysis, magnetic entropy shift in refrigeration, and photo corrosion are some of the inherent hindrances of these oxides. These issues warrant prompt actions from the scientific community to deliver cost-effective, efficient, and environmentally sustainable applications. Regardless, this review is expected to provide critical insights into REOs for contrasting industrial applications and encourage interested researchers to dig deeper in finding the best strategic solutions to counter prevalent challenges.     

Thermophysical properties of Yb2O3 doped Gd2Zr2O7 and thermal cycling durability of (Gd0.9Yb0.1)2Zr2O7/YSZ thermal barrier coatings

(Gd_1−xYb_x)₂Zr₂O₇ compounds were synthesized by solid reaction. Yb₂O₃ doped Gd₂Zr₂O₇ exhibited lower thermal conductivities and higher thermal expansion coefficients (TECs) than Gd₂Zr₂O₇. The TECs of (Gd_1−xYb_x)₂Zr₂O₇ ceramics increased with increasing Yb₂O₃ contents. (Gd_0.9Yb_0.1)₂Zr₂O₇ (GYbZ) ceramic exhibited the lowest thermal conductivity among all the ceramics studied, within the range of 0.8–1.1 W/mK (20–1600 °C). The Young's modulus of GYbZ bulk is 265.6 ± 11 GPa. GYbZ/YSZ double-ceramic-layer thermal barrier coatings (TBCs) were prepared by electron beam physical vapor deposition (EB-PVD). The coatings had an average life of more than 3700 cycles during flame shock test with a coating surface temperature of ∼1350 °C. Spallation failure of the TBC occurred by delamination cracking within GYbZ layer, which was a result of high temperature gradient in the GYbZ layer and low fracture toughness of GYbZ material.     

Effect of rare earth oxides addition on the mechanical properties and coloration of silicon nitride ceramics

The aim of this study was to evaluate the mechanical properties and coloration of silicon nitride ceramics in the presence of RE₂O₃ (RE = Nd, Eu or Dy). Dense Si₃N₄ ceramics were prepared by gas pressure sintering at 1800 °C for 2 h. XRD analysis confirmed the complete transformation of α-Si₃N4 to β-Si₃N₄. The fracture toughness and flexure strengths were 11.93 ± 0.56 MPa·m^1/2, 667 ± 40.98 MPa with the addition of Eu₂O₃ (SE). Base on the SEM image, the pull-out, bridging and deflection of large grains were observed and contributed to the increase in mechanical properties. The chromaticity of sintered bodies was measured using a spectrophotometer. The color difference of the ceramics is due to the formation of different color developing compounds according to the EDS. Results showed that high-toughness and colorful Si₃N₄ ceramics can be prepared using YAG:Ce³⁺ as sintering additive and RE₂O₃ as the colorant.     

稀土氧化物在陶瓷涂层中的应用

综述了稀土氧化物在陶瓷涂层中的应用状况,论述了稀土氧化物对陶瓷涂层的力学性能、抗热震性能、耐磨性和耐蚀性的影响,认为稀土氧化物对陶瓷涂层的改性作用主要表现在细化晶粒、净化组织、产生固溶强化和弥散强化等方面。     

稀土氧化物对钛酸铝陶瓷显微结构和力学性能的影响

研究了添加稀土氧化物Y2O3和Y2O3+Nd2O3对钛酸铝陶瓷的烧结温度、力学性能和显微结构的影响.结果表明,添加1%的稀土氧化物可以降低钛酸铝陶瓷的烧结温度,改善其显微结构,提高其力学性能,尤其是添加1%的复合稀土氧化物(Y2O3+Nd2O3)后,钛酸铝陶瓷的抗折强度和断裂韧性是未添加的试样的1.96倍和1.82倍.其性能提高的主要原因是由于稀土元素的细晶强化、净化界面、固溶强化、自增韧补强等作用.     

Microstructure and luminescence properties of YSZ-based thermal barrier coatings modified by Eu2O3

In order to study the variation of rare earth oxides during thermal failure of thermal barrier coatings, Eu2O3-doped YSZ coatings with 0.5 mol%, 1.0 mol% and 1.5 mol% were prepared by explosive spraying. SEM, XRD, EDS and microhardness tester were used to analyze the effect of different rare earth oxide doping content on the morphology, composition and mechanical properties of the coatings. The results showed that with the increase of rare earth oxide doping content, the porosity of the coatings decreased, and the microhardness and fracture toughness increased. When the doping amount of rare earth oxide is 1.0 mol%, the bonding strength and thermal cycle times of the coating are the highest, 33.4 Mpa and 185 times respectively. With the increase of the doping amount of rare earth, the luminous intensity of the sprayed coating increases. After thermal shock test, the luminous intensity of Eu2O3-doped YSZ coatings at 592 and 608 nm decreased to a certain extent.     

Friction delamination mechanism of EB-PVD thermal barrier coatings in high-temperature and high-speed rotating service environment

High-speed rotation is an indispensable working state in the service process of aero-engines, therefore, the centrifugal load cannot be ignored in the failure analysis of thermal barrier coatings. However, due to the lack of service environment simulators that can realize high-temperature as well as high-speed rotation, the failure mechanism of high-speed rotation thermal barrier coatings is still unclear. Here, the effects of rotational speed variation on the service life and failure mode of thermal barrier coatings at high temperatures are studied by experiments and finite element method (FEM). The results show that the service life of high-speed rotating thermal barrier coatings decreases with the increase of rotational speed. The failure is mainly governed by the thinning and spalling of the columnar crystal region of the ceramic layer and the delamination and exfoliation of the equiaxed crystal region, rather than the abnormal growth of TGO. Further in-depth analysis shows that the failure of high-speed rotating thermal barrier coatings is mainly due to the joint driving of centrifugal force and wall shear stress, as well as the contribution of thermal fatigue at high temperatures. This work adds to the understanding of the failure mechanism of thermal barrier coatings under extreme working conditions, and also provides guidance for the safe and reliable service of thermal barrier coatings on working blades.     

Impact of ZrO2 alloying on thermo-mechanical properties of Gd3NbO7

The ZrO₂ alloying effect is widely used to optimize the thermo-mechanical properties of potential thermal barrier coatings. In this study, dense x mol% ZrO₂-Gd₃NbO₇ with C222₁ space group were manufactured via a solid-state reaction. The crystalline structure was determined through X-ray diffraction and Raman spectroscopy, when the surface morphology was observed by scanning electron microscopy. ZrO₂-Gd₃NbO₇ had identical orthorhombic crystal structures, and there was no second phase. The crystalline structure of ZrO₂-Gd₃NbO₇ shrunk with the increasing ZrO₂ content as indicated by XRD and Raman results. The heat capacity and thermal diffusivity of ZrO₂-Gd₃NbO₇ were 0.31–0.43 J g⁻¹ K⁻¹ (25–900 °C) and 0.25–0.70 mm²/s (25–900 °C), respectively. It was found that ZrO₂-Gd₃NbO₇ had much lower thermal conductivity (1.21–1.82 W m⁻¹ K⁻¹, 25–900 °C) than YSZ (2.50–3.00 W m⁻¹ K⁻¹) and La₂Zr₂O₇ (1.50–2.00 W m⁻¹ K⁻¹). The thermal expansion coefficients (TECs) were higher than 10.60 × 10⁻⁶ K⁻¹ (1200 °C), which were better than that of YSZ (10.00 × 10⁻⁶ K⁻¹) and La₂Zr₂O₇ (9.00 × 10⁻⁶ K⁻¹). The mechanical properties of Gd₃NbO₇ change little with the increasing ZrO₂ content, Vickers hardness was about 10 GPa, and Young's modulus was about 190 GPa, which was lower than YSZ (240 GPa). Compared with previous work about alloying effects, much lower thermal conductivity was obtained. Due to the high melting point, high hardness, low Young's modulus, ultralow thermal conductivity and high TECs, it is believed that ZrO₂-Gd₃NbO₇ is promising TBCs candidate.     

ZrO2-doped YTaO4 as potential CMAS-resistant materials for thermal barrier coatings application

In this contribution, the ZrO₂-doped YTaO₄ (Zr_xY_0.5−x/2Ta_0.5−x/2O₂ (x = 0, 0.1, 0.2, 0.28)) are proposed as potential CMAS-resistant materials for TBCs. The corrosion behavior of those materials under CMAS attack are investigated from thermodynamics and kinetics. The results show that all compositions have the much better CMAS resistance than the classical Gd₂Zr₂O₇. After 50 h corrosion at 1300℃, the corrosion depth in ZrO₂-doped YTaO₄ bulks is about 50–80 µm (for a 20 mg/cm² CMAS deposition) in contrast with ~140 µm in Gd₂Zr₂O₇ bulk. The CMAS corrosion mechanism of ZrO₂-doped YTaO₄ is elucidated, and the excellent CMAS resistance is attributed to the rapid formation and followed thickening of dense reaction product layer. Furthermore, the effects of ZrO₂ doping content on CMAS resistance of YTaO₄ is discussed. It is elucidated that ZrO₂ doping can inhibit the precipitation of apatite, decrease the consumption of CMAS melt, and change the morphology of dense reaction layer. In summary, minor doping of ZrO₂ can ensure the excellent short- and long-term CMAS resistance, but heavy doping of ZrO₂ will degrade the long-term CMAS resistance.     

Atmospheric plasma sprayed 7%-YSZ thick thermal barrier coatings with controlled segmentation crack densities and its thermal cycling behavior

Yttria-stabilized zirconia (YSZ)-coatings are deposited on Ni-based superalloy IN738 by atmospheric plasma spraying (APS). For the first time, controlled segmentation crack densities are manually developed in the coatings, even after the APS deposition. This method allows to user to control segmentation densities as well as cracks depth, which could be designed as per coating thickness and required application. Thermal cycling test shows promising strain tolerance behavior for the segmented coatings, whereas coating without segmentation could not sustain even for its first thermal cycle period. Further, microstructural studies reveal that a very thin layer of TGO was formed and obvious no coating failure or spallation was observed after thermal cycling test at 1150 °C for 500 cycles.     

Peridynamic-based investigation of the cracking behavior of multilayer thermal barrier coatings

Numerical simulations of the cracking behavior of the top layers of multilayer thermal barrier coatings (TBCs) can effectively reveal the failure mechanisms of the TBCs. Current finite element method (FEM)-based simulation means have been applied to solve certain simple cracking problems in TBCs; however, they cannot effectively describe complex cracking problems in TBCs such as coalescence, intersection, and interference among multiple cracks. Peridynamic (PD), a newly developed mechanical theory, has been widely studied to provide analysis for cracking problems in TBCs. In this paper, a numerical model of TBCs is built by the bond-based PD (BB-PD) theory. Complex cracking behaviors, such as spontaneous crack propagation at both interfacial and internal regions, coalescence, and interference among multiple cracks, are simulated under isothermal cooling and gradient cooling conditions. In addition, the effects of interfacial roughness and calcium–magnesium–alumina–silicate (CMAS) inclusions on the cracking behavior are discussed. The results show that the PD model accurately captures complex cracking behaviors observed via scanning electron microscopy (SEM). Given the ability of the model for analyzing discontinuities in TBCs, it can help to further clarify the fracture mechanisms of TBCs.