Room-temperature densification of MgO bulk ceramics with dispersed nitride phosphor particles

Wave conversion materials with high thermal conductivity are necessary for high-power semiconductor lighting. Ceramics have higher thermal conductivity than existing matrices such as resin or glass in which phosphor particles are dispersed. However, the high densification of ceramics generally requires high-temperature sintering, which degrades and alters the phosphor particles. In this study, we aimed to achieve the high densification of MgO ceramics at room temperature. Applying high hydrostatic pressure with water addition improved the sample packing ratio and promoted the formation of Mg(OH)₂. As a result, the relative density was ≥95%. Additionally, various nitride phosphor particles (CaAlSiN₃:Eu²⁺, β-SiAlON:Eu²⁺, and α-SiAlON:Eu²⁺) were dispersed in the MgO matrix at room temperature without degrading the luminescence property. The thermal conductivity of the obtained sample was about 8 W m^?1K^?1, 40 times higher than that of the epoxy matrix.     

Oxygen-ion conductivity and mechanical properties of Lu2O3-doped ZrO2 as a solid electrolyte

The characteristics of Lu₂O₃-doped ZrO₂ as a solid electrolyte material were investigated in terms of its oxygen ion conductivity and flexural strength to realize its electrolytic function at intermediate and high temperatures. The effect of doping Lu³⁺, which has a high nuclear charge electric field strength, was examined through impedance spectroscopy, open-circuit potential measurements, and bending tests. The results with Lu₂O₃ dopant were compared with those obtained with a widely used dopant, Y³⁺, having a similar ionic radius with Lu³⁺, as well as a dopant that provides high ionic conduction, Sc³⁺, having a smaller ionic radius with Zr⁴⁺. The results revealed that, at the same dopant concentration, both the ionic conductivity and the flexural strength of Lu₂O₃-doped ZrO₂ are higher than those of the widely used Y₂O₃-doped ZrO₂. The conductivity of 8 mol% Lu₂O₃-doped ZrO₂ surpassed that of 8 mol% Sc₂O₃-doped ZrO₂ in the range of 800–950 °C (0.153 S/cm vs. 0.121 S/cm at 900 °C). These results indicate the potential of Lu³⁺ as a dopant for enhancing the performance of ZrO₂ solid electrolytes.     

Fabrication of Al2O3/AlN composite ceramics with enhanced performance via a heterogeneous precipitation coating process

To improve the thermal and mechanical properties of Al₂O₃/AlN composite ceramics, a novel heterogeneous precipitation coating (HPC) approach was introduced into the fabrication of Al₂O₃/AlN ceramics. For this approach, Al₂O₃ and AlN powders were coated with a layer of amorphous Y₂O₃, with the coated Al₂O₃ and AlN powders found to favor the formation of an interconnected YAG second phase along the grain boundaries. The interconnected YAG phase was designed to act as a diffusion barrier layer to minimize the detrimental interdiffusion between Al₂O₃ and AlN particles. Compared with samples prepared by a conventional ball-milling method, the HPC Al₂O₃/AlN composites exhibited less AlON formation, a higher relative density, a smaller grain size and a more homogeneous microstructure. The thermal conductivity, bending strength, fracture toughness and Weibull modulus of the HPC Al₂O₃/AlN composite ceramics were found to reach 34.21 ± 0.34 W m⁻¹ K⁻¹, 475.61 ± 21.56 MPa, 5.53 ± 0.29 MPa m^1/2 and 25.61, respectively, which are much higher than those for the Al₂O₃ and Al₂O₃/AlN samples prepared by the conventional ball-milling method. These results suggest that HPC is a more effective technique for preparing Al₂O₃/AlN composites with enhanced thermal and mechanical properties, and is probably applicable to other composite material systems as well.     

Fabrication of in situ elongated β-Sialon grains bonded to tungsten carbide via two-step spark plasma sintering

In order to reduce the difficulty of preparing binder-less cemented carbide and further broaden its application prospects, tungsten carbide toughened by in situ elongated β-Sialon grains was developed via sintering ball-milled WC and α-Si₃N₄ powders using Al₂O₃–ZrO₂ as a sintering aid and transformation additive. The two-step spark plasma sintering of the mixture at 1650 °C with dwelling at 1500 °C for 10 min was conducted under 30 MPa uniaxial pressure, and the densification behaviors, phase transformations, mechanical properties, and microstructures of the produced composites were investigated. The addition of Al₂O₃–ZrO₂ reduced the initial temperature of the densification process by approximately 100 °C and its final temperature by 200 °C (compared with the densification temperatures of pure WC and Si₃N₄ materials) and fully transformed α-Si₃N₄ to Sialon (Si–Al–O–N) phases. Microstructural characterization data showed that the WC matrix contained homogeneously distributed equiaxed and elongated β-Si₅AlON₇ grains. The WC composites containing in situ elongated β-Sialon grains exhibited an optimal hardness of 18.93 ± 0.03 GPa and enhanced fracture toughness of 10.43 ± 0.27 MPa m^1/2. The toughening mechanism of the β-Sialon phase involved the pull-out of elongated grains and crack bridging.     

Ultra-high-temperature tantalum-hafnium carbonitride ceramics fabricated by combustion synthesis and spark plasma sintering

We report the fabrication of dense single-phase (Ta,Hf)CN carbonitride ceramics using a combination of combustion synthesis (CS) and spark plasma sintering (SPS). The ceramic powder was produced by high-energy ball milling of the reactants (Ta, Hf, C) in different atomic ratios followed by CS of the obtained nanostructured composites in a nitrogen atmosphere. X-ray diffraction analysis of the combustion products revealed the formation of (Ta,Hf)CN with cubic B1 structures as the dominant phases for all investigated compositions. The SPS of the as-synthesized powders allowed both homogenization of the composition and consolidation of the bulk single-phase carbonitride ceramics with a relative density of 98 ± 1 %. Ta₂₅Hf₇₅CN showed the highest hardness (19.4 ± 0.2 GPa) and fracture toughness (5.4 ± 0.4 MPa m^1/2) among the investigated composites and excellent oxidation resistance in air.     

Sintering characteristics and microwave dielectric properties of ultralow-loss SrY2O4 ceramics

A SrY₂O₄ microwave dielectric ceramic suitable for 5G systems is synthesised via a solid-state reaction in a sintering temperature range of 1425–1525 °C. X-ray diffraction patterns and Rietveld refinement analysis show that the ceramic has an antispinel orthorhombic crystal structure belonging to the Pnma space group. Scanning electron microscopy images show that the ceramic particles are closely connected, the grain boundaries are clear, and the particles are uniform at the optimal sintering temperature of 1475 °C. The optimal microwave dielectric performances are ε_r = 14.78, Q × f = 84090 GHz, τ_? = ?14.98 ppm/°C. The relatively low dielectric constant, high Q × f value, low τ_? value, and easily available raw materials indicate that it is a good choice for 5G equipment.     

Pressureless-sintered boron nitride nanosheets/glass composite ceramics for excellent mechanical,dielectric and thermo-conductive performances

Because they have a high application potential in the thermal management of insulation environments, high-quality hexagonal boron nitride (h-BN)-based multiphase ceramics have been highly desired. However, so far, their synthesis is still full of challenges. Here, a kind of boron nitride nanosheets (BNNSs)/glass (GS) composite ceramics was prepared by a pressureless sintering method at a lower temperature of 900 °C. Due to a tightly bonded interaction between BNNSs and GS, the formed BNNSs/GS ceramics exhibit excellent multifunction performance. They have an outstanding compressive strength in the range of 19 ∼ 64 MPa and Vickers hardness ranging from 50 to 179 HV. For the BNNSs/GS ceramics with BNNS’s filling fraction of 90 wt%, their maximum side-surface TC values are 12.01 ± 0.18 W m⁻¹ K⁻¹ at 25 °C and 13.64 ± 0.37 W m⁻¹ K⁻¹ at 300 °C, respectively. In the ultra-high frequency range of 26.5 ∼ 40 GHz, the dielectric constant values of the BNNSs/GS ceramics are primarily between 2 and 3, and the corresponding loss tangent values are < 0.3. In addition, based on the remarkable integrity of their structure, these BNNSs/GS ceramics exhibit outstanding thermal-shock stability and prominent thermal management capacity during lots of heating/cooling-testing cycles. Therefore, we believe this kind of BNNSs/GS ceramic system will have great application potential in the new-generation thermal management and/or insulation packaging fields.     

Migration,transformation and solidification/stabilization mechanisms of heavy metals in glass-ceramics made from MSWI fly ash and pickling sludge

In consideration of recycling solid waste to achieve high value-added products, glass-ceramics have been fabricated from municipal solid waste incineration (MSWI) fly ash, pickling sludge (PS), and waste glass (WG) by melting at 1450 °C firstly to achieve parent glass and then crystallizing at 850 °C. Results demonstrated that heavy metals have been well solidified in the prepared glass-ceramics, and relatively/extremely low leaching concentrations of heavy metals have been detected. The synthetic toxicity index of heavy metals has been greatly reduced from 7-18 to <3.2 after crystallization treatment, and the leaching concentrations of Cr, Ni, Zn, Cu, and Pb are 0.15, 0.05, 0.26, 0.12, 0.19 mg L^-1 respectively. Chemical morphology analysis, principal component analysis, TEM and EPMA were utilized to clarify the migration, transformation, and solidification mechanism of heavy metals from the as-received solid wastes. The major heavy metals, Cr and Ni which is responsible for the most toxicity, mainly exist in form of the oxidation state and residual state in parent glass, while the residual state in the glass-ceramics. The solidification performance was mostly positively correlated with the form of residue state, which the stability of heavy metals in glass-ceramics is improved. The solidification mechanism of heavy metals in glass-ceramics could be explained by the combination of chemical solidification/stabilization and physical coating. The TEM and EPMA confirmed that Cr and Ni mainly exist in the spinel crystalline (NiCr₂O₄, Fe_0.99Ni_0.01Fe_1.97Cr_0.03O₄) by solid solution or chemical substitution, and a small amount of Cr in the diopside phase. Pb, Cu, and Zn are homogenously dispersed in the glass-ceramics, which is considered as physical coating solidification.     

Preparation of spherical and porous strontium titanate particles by hot water and hydrothermal conversion of hydrous titania

Uniform, micron-sized SrTiO₃ particles do not tend to aggregate, and the low surface area of larger particles can be improved by incorporating porous structures, thus offering superior performance for a range of applications. In this study, submicron-to micron-sized SrTiO₃ particles were prepared using hot water or hydrothermal conversion of spherical hydrous titania (TiO₂·nH₂O) and porous hydrous titania. When spherical hydrous titania particles were employed as the starting material, spherical SrTiO₃ particles of hydrous titania were obtained via treatment at 120 °C for 24 h. Similarly, the use of porous hydrous titania particles treated at 90 °C for 48 h resulted in spherical porous SrTiO₃ particles with macropores of porous hydrous titania. These porous SrTiO₃ particles have a specific surface area of ~115 m²/g, which is one of the largest among micron-sized SrTiO₃ particles, thereby making them suitable for use as catalysts or photocatalysts.     

Fabrication of sustainable magnesium phosphate cement micromortar using design of experiments statistical modelling: Valorization of ceramic-stone-porcelain containing waste as filler

Magnesium phosphate cement (MPC) is a potential sustainable alternative to Portland cement. It is possible to lower the total CO₂ emissions related to MPC manufacturing by using by-products and wastes as raw materials. When by-products are used to develop MPC, the resultant binder can be referred to as sustainable magnesium phosphate cement (sust-MPC). This research incorporates ceramic, stone, and porcelain waste (CSP) as a filler in sust-MPC to obtain a micromortar. Sust-MPC is formulated with KH₂PO₄ and low-grade MgO (LG-MgO), a by-product composed of 40–60 wt% MgO. CSP is the non-recyclable glass fraction generated by the glass recycling industry. The effect of water and CSP addition on the mechanical properties of sust-MPC was analyzed using design of experiments (DoE). A statistical model was obtained and validated by testing ideally formulated samples achieved through optimization of the DoE. The optimal formulation (15 wt% of CSP and a water to cement ratio of 0.34) was realized by maximizing the compressive strength at 7 and 28 days of curing, resulting in values of 18 and 25 MPa respectively. After one year of curing, the micromortar was physico-chemically characterized in-depth using backscattered scanning electron microscopy (BSEM-EDS) and Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR). The optimal formulation showed good integration of CSP particles in the ceramic matrix. Thus, a potential reaction between silica and the K-struvite matrix may have occurred after one year of curing.     

Microstructural and main mechanical properties of novalac based carbon–carbon composites as the pyrolysis heating rate

In this study, the effects of pyrolysis heating rate on microstructural and main mechanical properties of Novalac-based carbon/carbon composites were investigated by CHNS, optical microscope, FE-SEM, BET N₂ adsorption, XRD, Raman, FT-IR, wear analyzing, three-point bending test, tensile and Vickers micro-hardness tests. Firstly, PAN-derived carbon nanofibers (reinforcing agent) was synthesized using electrospinning followed by the functionalizing via the wet chemical oxidation to improve the strength of nanofiber bonding to the matrix of composites. Firstly, novalac resin (acting as a matrix), hexamethylenetetramine (hardener agent) and carbon nanofibers (reinforcing agent) were mixed and hot-pressed at 180 °C under the compression load of 40 kN to produce compressed CNFs-Novolac composites. Carbon/Carbon composites were obtained from the pyrolysis of CNFs-Novolac composites up to 1000 °C by the various heating rates under the compression press of 400 bar, finally. Structural and mechanical studies confirmed that the heating rates below or equal to 10 °C.min⁻¹ resulted in the production of low porosity (≤17%) carbon composite with high carbon content (>90 wt%), high fracture strength (≥270 MPa), high toughness (≥9 MPa m^1/2), high hardness (≥156 Hv), and low friction coefficient (<0.6).     

High-performance zirconia ceramic additively manufactured via NanoParticle Jetting

Additive manufacturing has received tremendous attention in the manufacturing and materials industry in the past three decades. Zirconia-based advanced ceramics have been the subject of substantial interest related to structural and functional ceramics. NanoParticle Jetting (NPJ), a novel material jetting process for selectively depositing nanoparticles, is capable of fabricating dense zirconia components with a highlydetailed surface, precisely controllable shrinkage, and remarkable mechanical properties. The use of NPJ greatly improves the 3D printing process and increases the printing accuracy. An investigation into the performance of NPJ-printed ceramic components evaluated the physical and mechanical properties and microstructure. The experimental results suggested that the NPJ-fabricated ZrO₂ cuboids exhibited a high relative density of 99.5%, a glossy surface with minimum roughness of 0.33 μm, a general linear shrinkage factor of 17.47%, acceptable hardness of 12.43 ± 0.09 GPa, outstanding fracture toughness of 7.52 ± 0.34 MPa m^1/2, comparable flexural strength of 699 ± 104 MPa, dense grain distribution of the microstructure, and representative features of the fracture. Subsequently, the exclusive printing scheme that achieved these favorable properties was analyzed. The innovative NanoParticle Jetting? system was shown to have significant potential for additive manufacturing.     

Tuning the electronic and thermal transport behaviors of metal-dispersed Ti2O3 composites derived by metal–insulator transition

Thermal management requires an understanding of the relations among the thermal energy transfer, electronic properties, and structures of thermoconductive materials. Here, we enhanced the metal–insulator transition (MIT)-induced effect on the thermal conductivities of microstructure-controlled Ti₂O₃ composites containing W as a thermal conductive filler at approximately 450 K. To change the electronic and thermal transport properties, we varied the particle radii of the conductive phases in the raw material. The change in the calculated electronic thermal conductivity relative to the electrical conductivity of the W_x(Ti₂O₃)_1?x composite was enhanced by compounding the material. When x was reduced from 50 vol% to 20 vol% and the W particle diameter was reduced from 150 μm to 5 μm, the variation in the estimated electronic thermal conductivity of the W_x(Ti₂O₃)_1?x composite was increased by a factor of 2.01. The total thermal conductivity was also changed by the MIT. At x = 50 vol% and a W particle diameter of 5 μm, the maximum thermal conductivity change was 6.34 times larger than that of pure Ti₂O₃. The detailed relation between the MIT-induced changes in thermal transport and the microstructure were elucidated in classical effective medium approximations.     

Effects of electric field on microstructure evolution and defect formation in flash-sintered TiO2

Various ceramic materials have been successfully flash sintered via mostly direct current (DC) and some by alternative current (AC). However, a direct comparison on the effects of different field types on the overall microstructure and atomistic defect distribution in flash-sintered ceramics is still very limited. In this work, rutile TiO₂ was chosen as a model system to directly compare the effects of DC and AC fields on microstructure and defect distribution. DC flash-sintered TiO₂ presents asymmetrical distributions of grain sizes and defects, while AC sintered TiO₂ have more homogeneous microstructures. More interestingly, we demonstrated a reverse-polarity flash sintering technique can achieve dense TiO₂ bulk samples with homogeneous microstructure and tunable defect gradient, which are previously not attainable from either DC or AC sintering alone. This study shows the importance of field on the microstructures of flash-sintered ceramics and the great potential in achieving dense and uniform microstructures via effective field control process.     

Enhanced grain boundary ionic conductivity of LiTa2PO8 solid electrolyte by 75Li2O-12.5B2O3-12.5SiO2 sintering additive

LiTa₂PO₈(LTPO) has low electrolyte density and many pores at grain boundaries, and it is easy to precipitate dielectric phase LiTa₃O₈ at grain boundaries. The performance can be improved by adding 75Li₂O-12.5B₂O₃-12.5SiO₂ (LBS) sintering additive with low melting point during sintering. The effects of LBS addition on the microstructure and grain boundary ionic conductivity of LTPO electrolytes were studied. The results showed that the addition of LBS sintering additives reduced the sintering temperature, improved the density and stability of LTPO electrolyte samples, effectively inhibited the precipitation of LiTa₃O₈ phase, reduced the grain boundary impedance of samples, and improved the total ionic conductivity of electrolytes. When LBS was added at 0.4 wt%, the relative density of LTPO reached 93.54%, the grain boundary impedance decreased from 1243 Ω to 248.2 Ω, the total ionic conductivity increased from 1.55 × 10⁻⁴ S cm⁻¹ to 6.51 × 10⁻⁴ S cm⁻¹, and the ionic activation energy was 0.137 eV.     

Non-isothermal nitridation kinetics of Ti6Al4V in Al2O3-based refractories

To establish a kinetic model of nitridation of Ti6Al4V in Al₂O₃-based refractories, the non-isothermal nitridation of Ti6Al4V–Al₂O₃ composite refractories at various heating rates was investigated using a thermogravimetric (TG) analyzer for large samples. The activation energy (E) and kinetic model (G(α)) for the nitridation of Ti6Al4V were determined using the isoconversional and master plots methods, respectively. The nucleation and growth of nitriding products of the TiN solid solution was the controlling step in the nitridation of Ti6Al4V in Al₂O₃-based refractories. The Avrami-Erofeev kinetic model, depicted by the G(α) = [-ln (1-α)]⁴ equation, is the most rational kinetic model. The values of E and A for the nitridation of Ti6Al4V were calculated to be 214.99 kJ/mol and 1.46 × 10⁷ (S^?1), respectively.     

Low-temperature solution processing route for potassium sodium niobate (KNN) thin films

A major challenge for integration of functional oxides, such as ferroelectrics, into microelectronics and flexible electronics is the reduction of their processing temperature, which needs to be lower than the degradation temperature of silicon and flexible plastic substrates. Aiming that, attention has been given to low-temperature processing of oxide films by chemical solution deposition (CSD). In the field of ferroelectrics, potassium sodium niobate ((K_1−xNa_x)NbO₃, KNN) has aroused a special interest due to its eco-friendliness, despite the high crystallization temperature. In this work, polycrystalline KNN thin films have been fabricated for the first time at a temperature as low as 400 °C using a modified CSD process, the Seeded Photosensitive Precursor Method (SPPM). Despite this low processing temperature, monophasic and stoichiometric films with appreciable values of remnant polarization, P_r ∼ 10.8 μC/cm², and hysteretic piezoresponse are obtained. These results open a window to the direct integration of KNN films into the high-performance electronic devices.     

Effect of grain boundary state and grain size on the microstructure and mechanical properties of alumina obtained by SPS: A case of the amorphous layer on particle surface

The work was aimed at the investigation of kinetics of Spark Plasma Sintering (SPS) of the α-Al₂O₃ particles with amorphous surface layers and investigation of the effect of the amorphous layers on the grain growth and on the mechanical properties of alumina. The objects of investigations comprised:(i) submicron α-Al₂O₃ powder, (ii) submicron α-Al₂O₃ powder with the amorphous layers on the particles' surfaces, and (iii) the fine-grained α-Al₂O₃ powder. The submicron powders (i) and (ii) were used to analyze the effect of the amorphous layers on the sintering kinetics. Powders (i) and (iii) were used to analyze the effect of the initial particle sizes on the shrinkage kinetics. The effect of the temperature regime and of the rate (V_h) on the shrinkage kinetics of the submicron and fine alumina powders has been studied. The shrinkage curves were analyzed using the Young–Cutler and Coble models. The sintering kinetics was shown to be determined by the intensity of grain boundary diffusion for the submicron powders and by simultaneous lattice diffusion and grain boundary one for the fine powders. The amorphous layers on the surfaces of the submicron α-Al₂O₃ particles were found to affect the grain boundary migration rate and the Coble equation parameters at the final stages of SPS. The abnormal characteristics of the alumina ceramics sintered from the submicron powder with the amorphous layers on the particles’ surfaces were suggested to originate from the increased concentration of the defects and of the excess free volume at the grain boundaries formed during crystallization of the amorphous layers.     

Highly compressible ceramic/polymer aerogel-based piezoelectric nanogenerators with enhanced mechanical energy harvesting property

Ceramic piezoelectric materials have orders of magnitude higher piezoelectric coefficients compared to polymers. However, their brittleness precludes imposition of large strains in mechanical energy harvesting applications. We report here that ice templating affords low bulk modulus lead-free aerogel piezoelectric nanogenerators (PENG) with unprecedented combination of flexibility and high piezoelectric response (voltage and power density). A modified ice templating protocol was used to fabricate piezoelectric nanocomposites of surface modified BaTiO₃ (BTO) nanoparticles in crosslinked polyethylene imine. This protocol allowed incorporating a significantly high fraction of BTO particles (up to 83 wt %) in the aerogel, while retaining remarkably high compressibility and elastic recovery up to 80% strain. The output voltage, at an applied compressive force of 20 N (100 kPa), increased with BTO loading and a maximum output voltage of 11.6 V and power density of 7.22 μW/cm² (49.79 μW/cm³) was obtained for PENG aerogels containing 83 wt% BTO, which is orders of magnitude higher than previously reported values for foam-based piezoelectric energy harvesters. The BTO/PEI PENGs also showed cyclic stability over 900 cycles of deformation. PENGs with higher porosity showed better elastic recovery and piezoelectric properties than lower porosity and higher BTO content aerogels. To the best of our knowledge, this is the first report to demonstrate the piezoelectric properties of high ceramic content aerogels having very high compressibility and elastic recovery.     

Evaluation of mechanical properties of YSZ TBCs doped by different ratios of Eu3+ ions after isothermal oxidation

Thermal barrier coatings (TBCs) are essential to improve the thermal insulation performance of high-temperature components. Rare earth element (Eu³⁺) doped yttrium stabilized zirconia (YSZ) TBCs have been proved to be an ideal solution for non-destructive testing of internal damages. Based on this theory, two types of coatings deposited by air plasma spray (APS) on Hastelloy-X were investigated: (1) Eu³⁺ doped YSZ (dopant ratios 1 mol%, 2 mol%, 4 mol%, respectively), (2) traditional undoped 8YSZ. Isothermal oxidation treatment at 1100 °C, in increments of 10h until the failure of the coatings are conducted to evaluate the mechanical properties of different coatings. The microscopic morphology and phase of the coatings were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) patterns, respectively. The indentation testing methods were used to study the apparent interfacial fracture toughness and the hardness of the ceramic top coat. Results show that the Vickers hardness of the top coat increases with the decrease of porosity in the early stage and then decreases with the heat treatment time increasing in the long-term stage. Simultaneously, compared with the undoped 8YSZ coating, the fracture toughness increased with the dopant of Eu³⁺ ions increasing, from 1 mol% to 2 mol%, nevertheless, that of 4 mol% Eu³⁺ doped YSZ decreased compared with in the undoped 8 YSZ. For all types of specimens, the interfacial fracture toughness decreases with the increase of isothermal oxidation time. Results also indicate that the content of Eu³⁺ doping does not affect the microstructure and interfacial morphology of the YSZ coating as well as the growth law of thermally grown oxides (TGO). Furthermore, EDS detection found that the Eu³⁺ ions almost do not diffuse inside the TBCs system after isothermal oxidation treatment.