Thermal shock resistance and mechanical properties of La2Ce2O7 thermal barrier coatings with segmented structure

La₂Ce₂O₇ (LCO) is a promising candidate material for thermal barrier coatings (TBCs) application because of its higher temperature capability and better thermal insulation property relative to yttria stabilized zirconia (YSZ). In this work, La₂Ce₂O₇ TBC with segmentation crack structure was produced by atmospheric plasma spray (APS). The mechanical properties of the sprayed coatings at room temperature including microhardness, Young's modulus, fracture toughness and tensile strength were evaluated. The Young's modulus and microhardness of the segmented coating were measured to be about 25 and 5 GPa, relatively higher than those of the non-segmented coating, respectively. The fracture toughness of the LCO coating is in a range of 1.3–1.5 MPa m^1/2, about 40% lower than that of the YSZ coating. The segmented TBC had a lifetime of more than 700 cycles, improving the lifetime by nearly two times as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Characterization of Ce0.9Gd0.1O1.95 powders synthesized by spray drying

Ce_0.9Gd_0.1O_1.95 powders were synthesized by spray drying and successive calcinations. The phase purity, BET surface area, and particle morphology of as-sprayed and calcined powders were characterized. After calcination above 300 °C, the powders were single phase and showed a BET surface area of 68 m²/g when calcined at 300 °C. The conductivity, in air, of sintered pellets was measured by electrochemical impedance spectroscopy (EIS) and it was found to be comparable with literature values. The activation energy for the total conductivity was around 0.83 eV. The powder calcined at lower temperature showed better sinterability and higher total conductivity due to an increased bulk conductivity.     

Thermophysical properties and cyclic lifetime of plasma sprayed SrAl12O19 for thermal barrier coating applications

About 6-8 wt% yttria-stabilized zirconia (YSZ) is the industry standard material for thermal barrier coatings (TBC). However, it cannot meet the long-term requirements for advanced engines due to the phase transformation and sintering issues above 1200°C. In this study, we have developed a magnetoplumbite-type SrAl₁₂O₁₉ coating fabricated by atmospheric plasma spray, which shows potential capability to be operated above 1200°C. SrAl₁₂O₁₉ coating exhibits large concentrations of cracks and pores (~26% porosity) after 1000 hours heat treatment at 1300°C, while the total porosity of YSZ coatings progressively decreases from the initial value of ~18% to ~5%. Due to the contribution of porous microstructure, an ultralow thermal conductivity (~1.36 W m⁻¹ K⁻¹) can be maintained for SrAl₁₂O₁₉ coating even after 1000 hours aging at 1300°C, which is far lower than that of the YSZ coating (~1.98 W m⁻¹ K⁻¹). In thermal cyclic fatigue test, the SrAl₁₂O₁₉/YSZ double-ceramic-layer coating undertakes a thermal cycling lifetime of ~512 cycles, which is not only much longer than its single-layer counterpart (~163 cycles), but also superior to that of YSZ coating (~392 cycles). These preliminary results suggest that SrAl₁₂O₁₉ might be a promising alternative TBC material to YSZ for applications above 1200°C.     

A new approach to protect and extend longevity of the thermal barrier coating by an impermeable layer of silicon nitride

A sample representation of a gas turbine engine blade, consisting of a nickel superalloy substrate with a deposited thermal barrier coating (TBC), was covered with silicon nitride, Si₃N₄, as an impermeable layer using plasma enhanced chemical vapor deposition (PECVD). The silicon nitride layer was used to seal the topcoat of yttria-stabilized zirconia (YSZ) surface of the TBC to mitigate calcium–magnesium–aluminum–silicon oxide (CMAS) attack. CMAS testing was carried out on the covered and uncovered surfaces by melting a ratio of 25 mg/cm² of CMAS powder onto the surface of each sample in a furnace at 1100°C for 1 h. The conformal surface reaction of the sealed layer confirmed no cracking or delamination at high temperatures. Scanning electron microscopy (SEM) micrographs confirmed that the surface of YSZ was successfully sealed. The new coating of silicon nitride was shown to be a viable solution and technique to significantly block CMAS infiltration in porous thermal barrier coatings.     

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.     

Yb2O3 and Gd2O3 doped strontium zirconate for thermal barrier coatings

Yb₂O₃ (10 mol%) and Gd₂O₃ (20 mol%) doped SrZrO₃ was investigated as a material for thermal barrier coating (TBC) applications. The thermal expansion coefficients (TECs) of sintered bulk Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 were recorded by a high-temperature dilatometer and revealed a positive influence on phase transformations of SrZrO₃ by doping Yb₂O₃ or Gd₂O₃. The results for the thermal conductivities of Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 indicated that both dopants can reduce the thermal conductivity of SrZrO₃. Mechanical properties (Young's modulus, hardness, and fracture toughness) of dense Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 showed lower Young's modulus, hardness and comparable fracture toughness with respect to YSZ. The cycling lifetimes of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ and Sr(Zr_0.8Gd_0.2)O_2.9/YSZ double layer coatings (DLC), which were prepared by plasma spraying, were comparable to that of YSZ at operating temperatures <1300 °C. However, the cycling lifetime of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ DLC was 25% longer, whereas Sr(Zr_0.8Gd_0.2)O_2.9/YSZ DLC had a shorter lifetime compared to the optimized YSZ coating at operating temperatures >1300 °C.     

Solution combustion synthesis of calcia-magnesia-aluminosilicate powder and its interaction with yttria-stabilized zirconia and co-doped yttria-stabilized zirconia

Thermal Barrier Coatings (TBCs) play a significant role in improving the efficiency of gas turbines by increasing their operating temperatures. The TBCs in advanced turbine engines are prone to silicate particles attack while operating at high temperatures. The silicate particles impinge on the hot TBC surfaces and melt to form calcia-magnesia-aluminosilicate (CMAS) glass deposits leading to coating premature failure. Fine powder of CMAS with the composition matching the desert sand has been synthesized by solution combustion technique. The present study also demonstrates the preparation of flowable yttria-stabilized zirconia (YSZ) and cluster paired YSZ (YSZ-Ln₂O₃, Ln = Dy and Gd) powders by single-step solution combustion technique. The as-synthesized powders have been plasma sprayed and the interaction of the free standing TBCs with CMAS at high-temperatures (1200 °C, 1270 °C and 1340 °C for 24 h) has been investigated. X-ray diffraction analysis of CMAS attacked TBCs revealed a reduction in phase transformation of tetragonal to monoclinic zirconia for YSZ-Ln₂O₃ (m-ZrO₂: 44%) coatings than YSZ (m-ZrO₂: 67%). The field emission scanning electron microscopic images show improved CMAS resistance for YSZ-Ln₂O₃ coatings than YSZ coatings.     

Synthesis of nano-crystalline Ce0.9Gd0.1O1.95 electrolyte by novel sol–gel thermolysis process for IT-SOFCs

In the present work, nano-crystalline Ce_0.9Gd_0.1O_1.95 (GDC) powder has been successfully prepared by a novel sol–gel thermolysis method using a unique combination of urea and PVA. The gel precursor obtained during the process was calcined at 400 and 600 °C for 2 h. A range of analyzing techniques including XRD, TGA, BET, SEM, EDS and TEM were employed to characterize the physical and chemical properties of obtained powders. GDC gel precursors calcined at 400 and 600 °C were found to have an average crystallite size of 10 and 19 nm, respectively. From the result of XRD patterns, we found that well-crystalline cubic fluorite structure GDC was obtained by calcining the precursor gel at 400 and 600 °C. It has been also found that the sintered samples with lower temperature calcined powder showed better sinterability as well as higher ionic conductivity of 2.21 × 10⁻² S cm⁻¹ at 700 °C in air.     

Crystal defects and phase transitions of nanocrystalline yttria-stabilised zirconia induced by high-energy ball milling

Yttria-stabilised zirconia (YSZ) is a promising electrolyte for SOFCs and gas sensors. In this study, the particle size of a co-precipitated 5 mol% yttria-stabilised zirconia (5 YSZ) powder was refined from 10.47 μm to 130 nm via high-energy ball milling to improve its sinterability and ionic conductivity. The ball milling process increased the specific surface area of the 5 YSZ powder from approximately 11 to 22 m² g^?1. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) results indicated that the 5 YSZ crystallites decomposed into irregular shapes with the evolution of point, linear, and planar defects. An increase in the milling duration increased the number of oxygen defects in the 5 YSZ powder, as revealed by the X-ray photoelectron spectroscopy results. The tetragonal-to-monoclinic phase transformation occurring in the powder was investigated by X-ray diffraction, Raman spectroscopy, HRTEM, and selected-area electron diffraction pattern analyses. The ball-milled powders could be easily densified, but the presence of too many crystal defects and the large fraction of the m-ZrO₂ phase were detrimental to the further densification of the 5 YSZ powders. In spite of the high sintering temperature (1500 °C) used in this study, the maximum relative density of 99.67% could be achieved for the powder ball-milled for 60 min at the rotor speed of 1500 rpm. Moreover, the ionic conductivity of 5 YSZ was improved significantly from 20.6 to 36.2 mS cm^?1 (850 °C) after the high-energy ball milling process.     

Corrosion behavior of air plasma spraying zirconia-based thermal barrier coatings subject to Calcium–Magnesium–Aluminum-Silicate (CMAS) via burner rig test

Three different kinds of thermal barrier coatings (TBCs) — 8YSZ, 38YSZ and a dual-layered (DL) TBCs with pure Y₂O₃ on the top of 8YSZ were produced on nickel-based superalloy substrate by air plasma spraying (APS). The Calcium–Magnesium–Aluminum-Silicate (CMAS) corrosion resistance of these three kinds of coatings were researched via burner rig test at 1350 °C for different durations. The microstructures and phase compositions of the coatings were characterized by SEM, EDS and XRD. With the increase of Y content, TBCs exhibit better performance against CMAS corrosion. The corrosion resistance against CMAS of different TBCs in descending was 8YSZ + Y₂O₃, 38YSZ and 8YSZ, respectively. YSZ diffused from TBCs into the CMAS, and formed Y-lean ZrO₂ in TBCs because of the higher diffusion rate and solubility of Y³⁺ in CMAS than Zr⁴⁺. At the same time, 38YSZ/8YSZ + Y₂O₃ reacts with CAMS to form Ca₄Y₆(SiO₄)₆O/Y_4·67(SiO₄)₃O with dense structure, which can prevent further infiltration of CMAS. The failure of 8YSZ coatings occurred at the interface between the ceramic coating and the thermally grown oxide scale (TGO)/bond coating. During the burner rig test, the Y₂O₃ layer of the DL TBCs peeled off progressively and the 8YSZ layer exposed gradually. DL coatings keep roughly intact and did not meet the failure criteria after 3 h test. 38YSZ coating was partially ablated, the overall thickness of the coating is thinned simultaneously after 2 h. Therefore, 8YSZ + Y₂O₃ dual-layered coating is expected to be a CMAS corrosion-resistant TBC with practical properties.     

Spark plasma sintering of self-propagating high-temperature synthesized TiC0.7/TiB2 powders and detailed characterization of dense product

In this work, the fabrication of bulk TiC_0.7/TiB₂ nanostructured composites through metastable transformation processing is investigated by taking advantages of two non-conventional powder metallurgy methods. First, the highly metastable TiC_0.7/TiB₂ agglomerated powders are synthesized by the so-called self-propagating high-temperature synthesis (SHS), followed by rapid quenching. Then, the spark plasma sintering (SPS) method is adopted to consolidate the SHSed powders.A bulk ceramic composite with nanocrystalline microstructure characterized by a high-relative density is then obtained. Dwell temperature of 1400 °C, heating time of 3 min, and total processing time equal to 5 min, while applying a mechanical pressure of 20 MPa, are found to be the optimal SPS experimental conditions in order to obtain near-fully densified samples.The obtained TiC_0.7/TiB₂ samples exhibit hardness HV5 as high as 24 GPa, modulus of elasticity of about 400 GPa, fracture toughness of about 5.6 MPa m^1/2, and a compressive strength of about 2.9 GPa. A very low-wear rate (W_v = 3.8 × 10⁻⁶ mm³/(N m)) and a good thermal shock resistance (ΔT_c = 250 °C) are also displayed. In addition, a high-abrasive wear factor (AWF) equal to 1.84 is evaluated on the basis of the achieved mechanical properties. These results make the obtained TiC_0.7/TiB₂ composite suitable for wear resistant parts as well as cutting tool materials.     

Molten salt attack on t′ yttria-stabilised zirconia by dissolution and precipitation

Degradation due to molten salt attack is one of the failure mechanisms of thermal barrier coatings. Thermochemical attack of the salt mixture Na₂SO₄–30 mol% NaVO₃ on ZrO₂–8 mol% YO_1.5 (8YSZ) at 950 °C was studied by two types of experiments. Sintered compacts were exposed to 25 mg cm^?2 salt dosage for up to 96 h. In the other set of experiments, 10–35 wt.% 8YSZ powder was mixed with the salts to study the dissolution of 8YSZ in the molten salt. The role of volatile losses was also examined. The results show that more than 25 wt.% 8YSZ dissolves in the sulphate-vanadate melt at 950 °C, followed by slow reactions to form YVO₄ and NaYV₂O₇ at 950 °C. The unreacted Y₂O₃ and monoclinic ZrO₂ precipitate out separately during rapid cooling (～300 °C/min). Slow cooling at ～3 °C/min leads to the formation of ZrOS apart from ZrO₂ and Y₂O₃.     

Synthesis of yttrium aluminum garnet (YAG) powder by homogeneous precipitation combined with supercritical carbon dioxide or ethanol fluid drying

YAG precursors were synthesized by the urea method in aqueous solution using supercritical carbon dioxide and ethanol fluid drying technique, respectively. The composition of the precursors, the phase formation process and the properties of the calcined powders were investigated by means of XRD, IR, TG/DSC, BET, TEM and SEM. Compared with the classically prepared powders at room temperature in air, the amorphous precursor dried by supercritical CO₂ fluid was loosely agglomerated and directly converted to pure YAG at about 900 °C. The resultant YAG powders showed good dispersity with an average crystallite size about 20 nm and specific surface area of 52 m² g⁻¹. However, the precursor dried by supercritical ethanol fluid was crystalline. Extensive phase segregation occurred during the drying process and resulted in the formation of separate phases such as monoclinic Y(OH)₃ and pseudoboehmite. YAM and YAP phases appeared in the calcination process and phase pure were not detected until 1200 °C.     

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.     

Rapid synthesis of Ti3AlC2/TiB2 composites by the spark plasma sintering (SPS) technique

Dense Ti₃AlC₂/TiB₂ composites were successfully fabricated from B₄C/TiC/Ti/Al powders by spark plasma sintering (SPS). The microstructure, flexural strength and fracture toughness of the composites were investigated. The experimental results indicate that the Vickers hardness increased with the increase in TiB₂ content. The maximum flexural strength (700 ± 10 MPa) and fracture toughness (7.0 ± 0.2 MPa m^1/2) were achieved through addition of 10 vol.% TiB₂, however, a slight decrease in the other mechanical properties was observed with TiB₂ addition higher than 10 vol.%, which is believed to be due to TiB₂ agglomeration.     

Effect of sintering temperature on varistor properties and aging characteristics of ZnO–V2O5–MnO2 ceramics

The microstructure, electrical properties, dielectric characteristics, and DC accelerated aging behavior of the ZVM-based varistors were investigated for different sintering temperatures of 800–950 °C. The microstructure of the ZVM-based ceramics consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂, which acts as liquid-phase sintering aid. The Zn₃(VO₄)₂ has a significant effect on the sintered density, in the light of an experimental fact, which the decreases of the Zn₃(VO₄)₂ distribution with increasing sintering temperature resulted in the low sintered density. The breakdown field exhibited the highest value (17,640 V/cm) at 800 °C in the sintering temperature and the lowest value (992 V/cm) at 900 °C in the sintering temperature. The nonlinear coefficient exhibited the highest value, reaching 38 at 800 °C and the lowest value, reaching 17 at 850 °C. The varistor sintered at 900 °C exhibited not only high nonlinearity with 27.2 in nonlinear coefficient, but also the highest stability, in which %ΔE_1 mA = −0.6%, %Δα = −26.1%, and %Δ tan δ = +21.8% for DC accelerated aging stress of 0.85 E_1 mA/85 °C/24 h.     

One-step synthesis of fine SrTiO3 particles using SrSO4 ore under alkaline hydrothermal conditions

The employment of mineral SrSO₄ crystals and powders for preparing SrTiO₃ compound was investigated, with coexistence of Ti(OH)₄·4.5H₂O gel under hydrothermal conditions, at various temperatures (150–250 °C) for different reaction intervals (0.08–96 h) in KOH solutions with different concentrations. The complete dissolution of the SrSO₄ crystal occurred at 250 °C for 96 h in a 5 M KOH solution, resulting in the synthesis of SrTiO₃ particles with two different shapes (peanut-like and cubic). In contrast, very fine SrTiO₃ pseudospherical particles were crystallized when SrSO₄ powders were employed as precursor. Variations on the SrTiO₃ particle shape and size were found to be caused by the differences in the dissolution rate of the SrSO₄ phase in the alkaline KOH solution. The crystallization of SrTiO₃ particles was achieved by a bulk dissolution–precipitation mechanism of the raw precursors, and this mechanism was further accelerated by increasing the reaction temperature and concentration of the alkaline media. Kinetic data depicted that the activation energy required for the formation of SrTiO₃ powders from the complete consumption of a SrSO₄ single crystal plate under hydrothermal conditions, is 27.9 kJ mol⁻¹. In contrast, when SrSO₄ powders were employed (28–38 μm), the formation of SrTiO₃ powder proceeded very fast even for a short reaction interval of 3 h at 250 °C in a 5 M KOH solution.     

Nano–Nano Composite Powders of Lanthanum Zirconate and Yttria‐Stabilized Zirconia by Spray Pyrolysis

Powders composing of La₂Zr₂O₇ (LZ) and (Zr_0.8Y_0.2)O_1.9 (10YSZ) phases (volume ratio = 1:1) were synthesized by using a sol‐spray pyrolysis method. The effects of annealing temperature on the grain size and lattice parameter of the LZ–10YSZ powders were investigated. XRD results showed that the grain size of LZ and 10YSZ phases gradually grew from 10 to 95 nm and from 5 to 65 nm as the annealing temperature elevated from 900°C to 1200°C. The relative decreasing percentage of grain size comparing to that of the single‐phase LZ and 10YSZ powders were in the range 9%–36% and 37%–86%. The activation energy for grain growth of LZ and 10YSZ phases in the composite powders were 225 ± 12 and 382 ± 17 kJ/mol, which were 20% and 183% higher than that of the single‐phase counterparts. Obvious lattice contraction and lattice expansion for LZ and 10YSZ phases were observed at temperatures below 1100°C, respectively. SEM results revealed that LZ and 10YSZ phases were homogeneously distributed in the sintered bulk. The TEM results suggested that the grain growth was affected by the interaction on nanometer length scales of grain boundaries between LZ and 10YSZ phases in the composite.     

Effect of GDC addition method on the properties of LSM–YSZ composite cathode support for solid oxide fuel cells

Equal amounts of Gd_0.1Ce_0.9O_2−δ (GDC) were added to La_0.65Sr_0.3MnO_3−δ/(Y₂O₃)_0.08(ZrO₂)_0.92 (LSM/YSZ) powder either by physical mixing or by sol–gel process, to produce a porous cathode support for solid oxide fuel cells (SOFCs). The effect of the GDC mixing method was analyzed in view of sinterability, thermal expansion coefficient, microstructure, porosity, and electrical conductivity of the LSM/YSZ composite. GDC infiltrated LSM/YSZ (G-LY) composite showed a highly porous microstructure when compared with mechanically mixed LSM/YSZ (LY) and LSM/YSZ/GDC (LYG) composites. The cathode support composites were used to fabricate the button SOFCs by slurry coating of YSZ electrolyte and a nickel/YSZ anode functional layer, followed by co-firing at 1250 °C. The G-LY composite cathode-supported SOFC showed maximum power densities of 215, 316, and 396 mW cm⁻² at 750, 800, and 850 °C, respectively, using dry hydrogen as fuel. Results showed that the GDC deposition by sol–gel process on LSM/YSZ powder before sintering is a promising technique for producing porous cathode support for the SOFCs.     

Equimolar YO1.5 and TaO2.5 co-doped ZrO2 as a potential CMAS-resistant material for thermal barrier coatings

Calcium-magnesium-alumino-silicates (CMAS) corrosion in thermal barrier coatings (TBCs) is becoming more serious with increasing operation temperature of turbine engines. Here, we report an equimolar YO_1.5 and TaO_2.5 co-doped ZrO₂ (Zr_0.66Y_0.17Ta_0.17O₂, ZYTO) as a potential CMAS-resistant material for TBCs, which shows a significantly enhanced CMAS resistance than the conventional 17 mol% YO_1.5-stabilized ZrO₂ (17YSZ). After exposure at 1300°C for 100 hours, the CMAS infiltration depth in ZYTO bulk is ~80 μm (for a 20 mg/cm² CMAS deposition), in contrast to ~700 μm in 17YSZ bulk (50 hours). Compositional and morphological analyses on the CMAS reaction zone reveal that the excellent CMAS resistance of ZYTO originates from the uniform corrosion through grain and grain boundary, along with densification of the reaction layer. The high CMAS infiltration rate of 17YSZ is attributed to the severe dissolution and infiltration through grain boundary. The reaction mechanisms of CMAS with ZYTO and 17YSZ bulks are discussed and a strategy of enhancing the CMAS resistance is proposed for ZrO₂-based TBC materials.