Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.     

Thermal cycling behavior of nanostructured 8YSZ，SZ/8YSZ and 8CSZ/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The nanostructured single-ceramic-layer (SCL) 8YSZ thermal barrier coatings (TBCs), double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZ)/8YSZ and SZ doped with 8 wt% CeO₂ nanoscale particles (8CSZ)/8YSZ TBCs were fabricated by atmospheric plasma spraying (APS) on nickel-based superalloy substrates with NiCoCrAlY as the bond coating. The thermal cycling behavior of the three as-sprayed TBCs was investigated systematically at 1000 ℃ and 1200 ℃. The results reveal that the thermal cycling lifetime of the nanostructured DCL 8CSZ/8YSZ TBCs is the longest among them, which is largely due to the fact that the intermediate layer buffer effect of the DCL structure, more porosity and improvement of thermal expansion coefficient from doping CeO₂ nanoparticles can relieve thermal stress to a great extent at elevated temperature. The failure mechanism of the nanostructured TBCs has been discussed in detail.     

Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.     

Characterisation of the microstructure and thermal properties of Nd2Zr2O7 and Nd2Zr2O7/YSZ thermal barrier coatings

The microstructure of following thermal barrier coatings (TBC) was characterised in this paper: monolayer coatings Nd₂Zr₂O₇ and 8YSZ; a double ceramic layered (DCL) coating. Coatings were characterised by thicknesses that did not exceed 300 μm and porosities of approx. 5%. The chemical and phase composition analysis of the DCL layers revealed an external Nd₂Zr₂O₇ ceramic layer approx. 80 μm thick, a transitional zone approx. 120 μm thick and an internal 8YSZ layer 100 μm thick. For the case of the monolayer coating, the Nd₂Zr₂O₇ pyrochlore phase was the only one-phase component. The surface topography of both TBC systems was typical for plasma sprayed coatings, and compressive stress state had a value of approx. 5–10 MPa. Measurements of the thermal parameters, i.e., thermal diffusivity, point to considerably better insulative properties for both new types of layers when compared to the standard 8YSZ layers.     

Preparation and photoluminescence properties of Eu3+-doped ZrO2 nanotube arrays

Zr–Eu alloy containing 3 at% Eu was prepared by a powder metallurgical method and Eu³⁺-doped ZrO₂ nanotube arrays were prepared by anodising the Zr–Eu alloy. The properties of Eu³⁺-doped ZrO₂ nanotube arrays were studied in contrast to undoped ZrO₂ nanotube arrays under different annealing temperatures. Results showed that the Eu³⁺ ions could not only stabilise the tetragonal phase of zirconium oxide, but also make the crystallite sizes smaller. Annealing temperature exerted a significant influence on the absorbance value, as well as the intensity and position of the photoluminescence peaks. When the excitation wavelength was either 248 nm or 270 nm, the sample annealed at 600 °C displayed the strongest emission peak; while under excitation at 232 nm, the sample annealed at 400 °C exhibited the strongest emission peak.     

Molten salt synthesis and optical properties of Eu3+, Dy3+or Nd3+ doped NiNb2O6 columbite-type phosphors

Pure, Eu³⁺, Dy³⁺ or Nd³⁺-doped NiNb₂O₆ powders have been prepared by a molten salt synthesis method by using Li₂SO₄–Na₂SO₄ salt mixture as a flux at relatively low temperatures as compared to the solid state reaction method. X-ray diffraction patterns of pure NiNb₂O₆ samples indicated an orthorhombic single phase. For Eu³⁺-doped NiNb₂O₆ samples, the luminescence of Eu³⁺ was observed at 615 nm as red emission while Dy³⁺-doped NiNb₂O₆ showed yellow emission at 577 nm and Nd³⁺ doped sample exhibited a typical emission at 1064 nm varying with the Eu³⁺ or Nd³⁺ doping concentrations. These luminescence characteristics of the doped samples may be attributed to the energy transfer between rare earth ions and NiO₆ octahedral groups in the columbite structure.     

Effect of Fe2O3 doping on sintering of yttria-stabilized zirconia

This paper reports the effect of Fe₂O₃ doping on the densification and grain growth in yttria-stabilized zirconia (YSZ) during sintering at 1150 °C for 2 h. Fe₂O₃ doped 3 mol% YSZ (3YSZ) and 8 mol% YSZ (8YSZ) coatings were produced using electrophoretic deposition (EPD). For 0.5 mol% Fe₂O₃ doping, both 3YSZ and 8YSZ coatings during sintering at 1150 °C has similar densification. However, a significant grain growth occurred in 8YSZ during sintering, whereas grain size remains almost constant in 3YSZ. XRD results suggest that Fe₂O₃ addition substitutionally and interstitially dissolved into the lattice of 3YSZ and 8YSZ. In addition, colour of 3YSZ and 8YSZ changes differently with doping of Fe₂O₃. A Fe³⁺ ion interstitial diffusion mechanism is proposed to explain the densification and grain growth behaviour in the Fe₂O₃ doped 3YSZ and 8YSZ. A retard grain growth observed in the Fe₂O₃ doped 3YSZ is attributed to Fe³⁺ segregation at grain boundary.     

Influence of the deposition energy on the composition and thermal cycling behavior of La2(Zr0.7Ce0.3)2O7 coatings

Lanthanum–zirconium–cerium composite oxide (La₂(Zr_0.7Ce_0.3)₂O₇, LZ7C3) coatings were prepared under different conditions by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphologies, cyclic oxidation behavior of these coatings were studied. Elemental analysis indicates that the coating composition has partially deviated from the stoichiometry of the ingot, and the existence of excess La₂O₃ is also observed. The optimized composition of LZ7C3 coatings could be effectively achieved by the addition of excess CeO₂ into the ingot or by properly controlling the deposition energy. Meanwhile, when the deposition energy is 1.15 × 10⁴–1.30 × 10⁴ J/cm², the coating has a similar X-ray diffraction (XRD) pattern to the ingot, and the thermal cycling life of the coating is also superior to other coatings. The spallation of the coatings occurs either within the ceramic layer approximately 6–10.5 μm above its thermally grown oxide (TGO) layer or at the interface between ceramic layer and bond coat.     

Preparation of YSZ/Al2O3 micro-laminated coatings and their influence on the oxidation and spallation resistance of MCrAlY alloys

YSZ/Al₂O₃ micro-laminated coatings were successfully prepared on the surface of MCrAlY substrates by means of electrolytic deposition and microwave sintering. The as-prepared YSZ/Al₂O₃ coatings were characterized by high-resolution field emission SEM and XRD. Laminated structures of alternate YSZ and Al₂O₃ layers were observed in the coating with the phase composition of Y₂O₃ stabilized t-ZrO₂, α-Al₂O₃ and θ-Al₂O₃. High-temperature cyclic oxidation test at 1000 °C in air was also performed to investigate the oxidation and spallation resistance of such coatings on MCrAlY substrates. The results indicate that such coatings exhibit not only excellent oxidation resistance but also good spallation resistance under thermal cycling due to the structure of multi-sealed Al₂O₃ layers and the preferable high-temperature mechanical properties induced by the designed laminated composite structures, respectively.     

Synthesis and characterization of the crystalline powders on the basis of Lu2O3:Eu3+spherical submicron-sized particles

This study is devoted to the preparation of the crystalline powders on the basis of non-agglomerated monodisperse Lu₂O₃:Eu³⁺ spherical particles with the diameters in the range of 50–250 nm by the soft chemistry co-precipitation route. The influence of the synthesis parameters on control morphology, particles size and agglomeration in the final Lu₂O₃:Eu³⁺ powder was considered. Lu₂O₃:Eu³⁺ crystalline powders were characterized by means of electron microscopy methods (TEM, SEM), FT-IR spectroscopy, thermal analysis (TG-DTA) and X-ray diffractometry. The mechanisms of the precursor decomposition and crystallization at the temperatures ranging from 60 to 900 °C were discussed. It was shown that the powders obtained were characterized by the effective luminescence under X-ray excitation in λ = 575–725 nm spectral region corresponding to ⁵D₀ → ⁷F_J transitions (J = 0–4) of Eu³⁺ ions with a maximum at 612 nm and the luminescence intensity strongly depends on annealing temperature. The relative densities of the green-bodies on the basis of Lu₂O₃:Eu³⁺ powders were estimated and the sintering of compacts at the temperatures up to 1500 °C was studied.     

Preparation,characterization and photoluminescence properties of SiO2 and SiO2:Eu3+ submicron rods

SiO₂ and Eu³⁺-doped SiO₂ submicron rods were conveniently fabricated via a sol–gel process at room temperature. In this process, citric acid served as a unique structural modifier through hydrolysis of TEOS at alkaline condition to obtain the silica submicron rods. The morphology of the products was sensitive to the conditions, such as stirring, gelation time and the dropping speed of NH₄OH. By sampling the products at different reaction times, we discussed the formation and growing mechanism of SiO₂:Eu³⁺ submicron rods in detail. The weak interactions between ammonium citrate crystals and silica species may be the reasons of the rods formation. The obtained silica submicron rods were 5–6 μm in length and 650–750 nm in width and there was no obvious change after doping. Under UV light excitation, the undoped silica submicron rods exhibited blue emission, which may be associated with defect centers in the structures of the products. The Eu³⁺-doped silica submicron rods exhibited red emission, which was due to the 4f→4f transition of Eu³⁺. The effect of different doping concentrations of Eu³⁺ ions on the luminescence was investigated. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR), Thermo-gravimetry Analysis (TGA), Scanning electron microscope (SEM), Transmission electron microscope (TEM), Energy-dispersive spectroscopy (EDS) and Photoluminescence spectrum.     

Thermal conductivity of plasma sprayed Sm2Zr2O7 coatings

Rare-earth zirconates with a pyrochlore structure have been developed for potential application in thermal barrier coating systems to further improve the performance and durability of gas turbines. The Sm₂Zr₂O₇ (abbreviated as SZ) powder was synthesized by solid state reaction and then deposited by air plasma spraying. The phase stability, microstructure and thermal conductivity of SZ and 8 wt% Y₂O₃ stabilized zirconia (8YSZ) coatings were investigated. The X-ray diffraction results indicated that the crystal structure of the as-sprayed SZ coatings was defect-fluorite, and after heat treating at 1200 °C for 50 h, it started to transform to pyrochlore, and the content of pyrochlore increased with increase in temperature of the heat treatment. The thermal conductivities of SZ coatings were significantly lower than those of 8YSZ coatings before and after heat treatments, which increased considerably after heat treatments compared to the as-sprayed states for both coatings due to sintering effects.     

Phase stability and thermal conductivity of RE2O3 (RE=La,Nd, Gd,Yb) and Yb2O3 co-doped Y2O3 stabilized ZrO2 ceramics

Y₂O₃ stabilized ZrO₂ (YSZ) has been considered as the material of choice for thermal barrier coatings (TBCs), but it becomes unstable at high temperatures and its thermal conductivity needs to be further reduced. In this study, 1 mol% RE₂O₃ (RE=La, Nd, Gd, Yb) and 1 mol% Yb₂O₃ co-doped YSZ (1RE1Yb–YSZ) were fabricated to obtain improved phase stability and reduced thermal conductivity. For 1RE1Yb–YSZ ceramics, the phase stability of metastable tetragonal (t′) phase increased with decreasing RE³⁺ size, mainly attributable to the reduced driving force for t′ phase partitioning. The thermal conductivity of 1RE1Yb–YSZ was lower than that of YSZ, with the value decreasing with the increase of the RE³⁺ size mainly due to the increased elastic field in the lattice, but 1La1Yb–YSZ exhibited undesirably high thermal conductivity. By considering the comprehensive properties, 1Gd1Yb–YSZ ceramic could be a good potential material for TBC applications.     

Low thermal conductivity of atomic layer deposition yttria-stabilized zirconia (YSZ) thin films for thermal insulation applications

Thermal insulation applications have long required materials with low thermal conductivity, and one example is yttria (Y₂O₃)-stabilized zirconia (ZrO₂) (YSZ) as thermal barrier coatings used in gas turbine engines. Although porosity has been a route to the low thermal conductivity of YSZ coatings, nonporous and conformal coating of YSZ thin films with low thermal conductivity may find a great impact on various thermal insulation applications in nanostructured materials and nanoscale devices. Here, we report on measurements of the thermal conductivity of atomic layer deposition-grown, nonporous YSZ thin films of thickness down to 35 nm using time-domain thermoreflectance. We find that the measured thermal conductivities are 1.35–1.5 W m⁻¹ K⁻¹ and do not strongly vary with film thickness. Without any reduction in thermal conductivity associated with porosity, the conductivities we report approach the minimum, amorphous limit, 1.25 W m⁻¹ K⁻¹, predicted by the minimum thermal conductivity model.     

Fabrication of Lu2O3:Eu transparent ceramics using powder consisting of mono-dispersed spheres

Mono-dispersed spherical Lu₂O₃:Eu (5 mol%) powders for transparent ceramics fabrication were synthesized by urea-based homogeneous precipitation technique. The effects of the doped-Eu³⁺ on the synthesis of Lu₂O₃:Eu particles were investigated in detail. The results show that the doping of Eu³⁺ ions into Lu system can significantly decrease the particle size of the resultant precursor spheres. Owing to the sequential precipitation in Lu/Eu system, there are compositional gradients within each of the resultant precursor spheres. Well dispersed, homogeneous and spherical/near spherical Lu₂O₃:Eu powders were obtained after calcination at 600–1000 °C for 4 h. The powder calcined at 600 °C shows better sintering behavior and can be densified into transparent ceramic after vacuum sintering at 1700 °C for 5 h. The luminescence properties of the obtained Lu₂O₃:Eu powder and transparent ceramic were also studied.     

Size controllable synthesis and multicolor fluorescence of SiO2:Ln3+(Ln=Eu,Tb) spherical nanoparticles

A series of size controllable Tb³⁺ and/or Eu³⁺ activated nano-sized silica phosphors have been successfully synthesized through a facile sol-gel method. The structure, morphology, compositions, and luminescence properties of as-prepared samples were well investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) and photoluminescence spectroscopy (PL). The results showed that all as-prepared samples were spherical nanoparticles but the sizes reduced gradually with the temperature increased from 25 °C to 65 °C, which was contrary to the BET surfaces as well as the luminescence intensity. Under ultraviolet excitation, the SiO₂:Ln³⁺(Ln=Eu, Tb) spherical nanoparticles showed characteristic red and green emissions corresponding to f-f transition of Eu³⁺ and Tb³⁺, respectively. Moreover, the luminescence emissions of samples can be tuned from green to yellow, orange and red by co-doping the Tb³⁺ and Eu³⁺ ions in different concentration ratio into the SiO₂ host due to the efficient dipole–dipole energy transfer mechanism from Tb³⁺ to Eu³⁺ under 377 nm excitation. These results show that as-prepared phosphors may find potential applications in color display fields.     

Fabrication and evaluation of NiO/Y2O3-stabilized-ZrO2 hollow fibers for anode-supported micro-tubular solid oxide fuel cells

In this work NiO/3 mol% Y₂O₃–ZrO₂ (3YSZ) and NiO/8 mol% Y₂O₃–ZrO₂ (8YSZ) hollow fibers were prepared by phase-inversion. The effect of different kinds of YSZ (3YSZ and 8YSZ) on the porosity, electrical conductivity, shrinkage and flexural strength of the hollow fibers were systematically evaluated. When compared with Ni–8YSZ the porosity and shrinkage of Ni–3YSZ hollow fibers increases while the electrical conductivity decreases, while at the same time also exhibiting enhanced flexural strength. Single cells with Ni–3YSZ and Ni–8YSZ hollow fibers as the supported anode were successfully fabricated showing maximum power densities of 0.53 and 0.67 W cm⁻² at 800 °C, respectively. Furthermore, in order to improve the cell performance, a Ni–8YSZ anode functional layer was added between the electrolyte and Ni–YSZ hollow fiber. Here enhanced peak power densities of 0.79 and 0.73 W cm⁻² were achieved at 800 °C for single cells with Ni–3YSZ and Ni–8YSZ hollow fibers, respectively.     

First-principles calculation on the electronic structure and optical properties of Eu2+ doped γ-AlON phosphor

The crystal structure, electronic structure, and optical properties of Eu-doped γ-AlON at various Eu concentrations were obtained from density functional theory. Based on the calculated results, the luminescence properties and mechanism of Eu-doped γ-AlON are discussed. The calculated results demonstrate that AlON:Eu²⁺ phosphor exhibits a direct band gap, which is advantageous for luminescence. The absorption spectrum of AlON:Eu²⁺ phosphor has a single intense broad absorption band from 275 to 425 nm with a peak at 355 nm, which is consistent with corresponding experimental excitation spectra. The existence of Eu?N bonds enhanced the local covalence of Eu²⁺, hence the optical stability of AlON:Eu²⁺ phosphor.     

A single-phase white-emitting La10(SiO4)6O3：Eu2+/Eu3+ phosphor for near-UV LED-based application

A novel single-phase white-emitting phosphor La₁₀(SiO₄)₆O₃ (LSO): xEu has been synthesized by high-temperature solid-state reaction. Its crystal structure, luminescence properties, fluorescence decay time and oxygen vacancies have been characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. XRD result shows a typical oxyapatite structure with the space group of P6₃/m. Characteristic excitation and emission peaks of Eu²⁺ and Eu³⁺ were observed from PL studies. The optimum doping concentration of Eu was found to be 7.5 mol% (x = 0.075). In this work, the lifetimes of Eu³⁺ and Eu²⁺ were considerably longer than those from some references. Under the excitation of different near ultraviolet (n-UV) longer wavelengths (λex = 360, 370, and 380 nm), the white light emission can be realized with the CIE chromaticity coordinates (0.3907, 0.3595), (0.3472, 0.3282), and (0.3504, 0.3062) for the phosphor LSO: 0.075Eu. The chromaticity coordinates of the phosphor were all located in the white region. Therefore, it is suggested that the explored LSO: 0.075Eu phosphor can be a good candidate for white light-emitting diodes (W-LEDs) application.