Hot corrosion behavior of NdYbZr2O7 exposed to V2O5 and Na2SO4 + V2O5 molten salts

In order to evaluate the application prospects of NdYbZr₂O₇ as a novel TBC material, NdYbZr₂O₇ ceramic was synthesized via a solid-state reaction sintering method, and its hot corrosion behavior exposed to V₂O₅ and Na₂SO₄ + V₂O₅ molten salts at 900 °C, 1000 °C, and 1100 °C was comparatively investigated. For the V₂O₅ salt, the primary corrosion products were granular (Nd,Yb)VO₄ as well as cube-like m-ZrO₂. The corrosion layer consisted of two distinct layers, one of which was Zr-rich layer and another was V-rich layer. In the case of Na₂SO₄ + V₂O₅, NaVO₃, as an intermediate product, played an important role in dissolving the NdYbZr₂O₇ ceramic. Herein, the (Nd,Yb)VO₄ exhibited a rod/plate-like morphology, which could be attributed to the synergistic effect of low driving force and low nucleation rate. Since the molten salt infiltration rate was superior to the pore filling rate throughout the hot corrosion, the thickness of corrosion layer increased with the rise of temperature. The hot corrosion mechanisms of NdYbZr₂O₇ ceramic in various molten salts were discussed based on the phase diagram, Lewis acid-base rule and chemical thermodynamics. On this basis, the NdYbZr₂O₇ coating was prepared by atmospheric plasma spray (APS) and it exhibits a higher corrosion resistance compared to YSZ coating.     

Corrosion products evolution and hot corrosion mechanisms of REPO4 (RE= Gd,Nd, La) in the presence of V2O5 + Na2SO4 molten salt

REPO₄ (RE = Gd, Nd, La) ceramics with a monazite structure were fabricated by a chemical co-precipitation and calcination method. Hot corrosion tests were carried out in V₂O₅+Na₂SO₄ molten salt at 800 °C, 900 °C and 1000 °C for 2 h and 10 h. The temperature and heat duration had little effect on the type of corrosion products in this study. However, GdPO₄ and REPO₄ (RE = Nd, La) revealed different hot corrosion behavior. Exposed to the molten salt, GdVO₄ and Gd₄(P₂O₇)₃ formed as the corrosion products for the GdPO₄ case, while an RE(P,V)O₄ (RE = Nd, La) solid solution was generated for NdPO₄ and LaPO₄ cases. The formation of the solid solution had less damage to the original microstructure, which benefited the hot corrosion resistance of the ceramics. From the crystallographic characteristics of rare earth phosphates/vanadates and a thermodynamics perspective, the hot corrosion mechanisms of REPO₄ (RE = Gd, Nd, La) are discussed.     

Effects of laser surface remelting on the molten salt corrosion resistance of yttria-stabilized zirconia coatings

In the present study, atmospheric plasma-sprayed yttria-stabilized zirconia coatings were post-remelted by a continuous diode laser to improve the hot corrosion resistance for as-sprayed coatings. The coating surfaces were covered with a salt mixture (V₂O₅ and Na₂SO₄) and then subjected to a hot corrosion test at 1100?°C in air. The influence of laser parameters including power and scanning rate on the coating microstructure and corrosion resistance was investigated. Results showed that the hot corrosion resistance can be improved by producing a dense and smooth surface and reducing the coating permeability to the molten salt. The transformation of the hot corrosion mechanisms was clarified on the basis of the observed corrosion behaviors. A laser power of 1500?W and scanning rate of 9?mm/s can produce minimal surface roughness with few segmented cracks, which can provide improved performance of the hot corrosion resistance.     

Hot corrosion behaviors of SrZrO3 ceramic co-doped with Y2O3 and Yb2O3 in molten Na2SO4, V2O5, and Na2SO4 + V2O5 salts mixture

The hot corrosion behaviors of Sr(Y_0.05Yb_0.05Zr_0.9)O_2.95 (SYYZ) ceramic were investigated in Na₂SO₄, V₂O₅, and Na₂SO₄ + V₂O₅ salts mixture, respectively. Na₂SO₄ did not react with SYYZ ceramic at 900, 950 and 1000 °C. m-ZrO₂, YVO₄ and YbVO₄ were the main corrosion products on the SYYZ ceramic surface in V₂O₅ at 800 and 900 °C, whereas Sr₃V₂O₈ and t-ZrO₂ appeared at 1000 °C. In Na₂SO₄ + V₂O₅ salts mixture, the corrosion products were Sr₃V₂O₈ and t-ZrO₂ at 800 and 900 °C on the SYYZ ceramic surface, however, a new phase of SrZrO₃ developed at 1000 °C. The phase transformation and chemical interaction are the primary corrosion mechanisms for degradation of SYYZ ceramic.     

Thermo-physical and mechanical properties of Yb2O3 and Sc2O3 co-doped Gd2Zr2O7 ceramics

Ceramic materials for the thermal barrier coating (TBC) application of Gd₂Zr₂O₇ (GZO), (Gd_0.94Yb_0.06)₂Zr₂O₇ (GYb_0.06Z), (Gd_0.925Sc_0.075)₂Zr₂O₇ (GSc_0.075Z), (Gd_0.865Sc_0.075Yb_0.06)₂Zr₂O₇ (GSc_0.075Yb_0.06Z), and (Gd_0.8Sc_0.1Yb_0.1)₂Zr₂O₇ (GSc_0.1Yb_0.1Z) were successfully synthesized by chemical co-precipitation. The effects of the doping of Sc₂O₃ and Yb₂O₃ on the phases, thermo-physical and mechanical properties of the ceramics were investigated. The results show that both Yb₂O₃ and Sc₂O₃ doping promoted the phase transition of GZO from pyrochlore to fluorite. All the Sc₂O₃-doped samples exhibited enhanced fracture toughness, as compared to the undoped sample. Furthermore, the GSc_0.075Yb_0.06Z sample revealed a thermal conductivity of ~0.8 W/mK at 1200 °C, which was nearly 30% lower than that of the undoped sample. The associated mechanisms related to the effects of the doping on the thermophysical and mechanical properties are discussed.     

Molten salt synthesis of La2Zr2O7 ultrafine powders

Ultrafine powders of pyrochlore-type La₂Zr₂O₇ were synthesized via a simple molten salt mediated process using zirconium oxide and lanthanum oxide as raw materials, and sodium chloride, potassium chloride and sodium fluoride to form a reaction medium. The effects of reaction temperature, salt/reactant ratio and salt type on the La₂Zr₂O₇ formation were investigated. Among the three attempted salt assemblies (KCl–LiCl, Na₂CO₃–K₂CO₃, and NaCl–KCl–NaF), NaCl–KCl–NaF showed the best accelerating effect on the La₂Zr₂O₇ formation. At a given temperature, the La₂Zr₂O₇ content in the final products increased with the increase in the salt amount. Phase pure submicron sized La₂Zr₂O₇ ultrafine powders were obtained after 3 h firing at 1100 °C with the salt/reactant weight ratio of 5:1 or at 1200 °C with salt/reactant weight ratio of 3:1. The synthesis temperature (1100 °C) was much lower than that required by the conventional solid-state mixing method or a wet chemical method. The “dissolution–precipitation” mechanism had dominated the synthesis process.     

Marked reduction in the thermal conductivity of (La0.2Gd0.2Y0.2Yb0.2Er0.2)2Zr2O7 high-entropy ceramics by substituting Zr4+ with Ti4+

The (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ (x = 0–0.5) high-entropy ceramics were successfully prepared by a solid state reaction method and their structures and thermo-physical properties were investigated. It was found that the high-entropy ceramics demonstrate pure pyrochlore phase with the composition of x = 0.1–0.5, while (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂Zr₂O₇ shows the defective fluorite structure. The sintered high-entropy ceramics are dense and the grain boundaries are clean. The grain size of high-entropy ceramics increases with the Ti⁴⁺ content. The average thermal expansion coefficients of the (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics range from 10.65 × 10^?6 K^?1 to 10.84 × 10^?6 K^?1. Importantly, the substitution of Zr⁴⁺ with Ti⁴⁺ resulted in a remarkable decrease in thermal conductivity of (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics. It reduced from 1.66 W m^?1 K^?1 to 1.20 W m^?1 K^?1, which should be ascribed to the synergistic effects of mass disorder, size disorder, mixed configuration entropy value and rattlers.     

A single-source molten salt synthesis of rod-shaped Na2Ti6O13 crystals

As one of the most potential negative electrode materials, Na₂Ti₆O₁₃ is expected to play an important role in the area of high-performance battery. In this work, we have developed an easy, efficient and controllable method to prepare rod-shaped Na₂Ti₆O₁₃ crystals. This approach utilized a single-source molten salt strategy and only needed to sinter a special precursor synthesized from an aqueous solution containing H₃BO₃ and (NH₄)₂TiF₆ in presence of sodium salts. The component and shape of precursor crystals can be tuned by adjusting the reagent concentration and reaction temperature. By sintering precursor crystals in air at 900 °C for 30 min, Na₂Ti₆O₁₃ with high crystallinity and purity can be obtained. X-ray diffraction and scanning electron micrographs results of different sintering times show that the sintering process can be divided into two steps. Firstly, the precursor crystals are converted to TiO₂ (anatase) nano-particles and amorphous sodium salts. Subsequently, molten salt reaction occurs between amorphous sodium salts and TiO₂ and forms rod-shaped Na₂Ti₆O₁₃ crystals.     

Effect of molten V2O5 salt on the corrosion behavior of micro- and nano-structured thermal sprayed SYSZ and YSZ coatings

The corrosion resistance of micro-and nano-structured scandia and yttria codoped zirconia (nano-4 mol%SYSZ and micro-8.6SYSZ) and yttria doped zirconia (4YSZ) in the presence of molten vanadium oxide were investigated. To this end, duplex TBCs (thermal barrier coatings), composed of a bond coat (NiCrAlY) and a top coat (4SYSZ or 4YSZ), were deposited on the IN738LC Ni-based supper-alloy by atmospheric plasma spraying (APS). The corrosion studies of plasma sprayed TBCs were conducted in 25 mg V₂O₅ molten salt at 910 °C for different times. The nanostructured coating, as compared to its micro-structured counterpart, in spite of a further reaction with the V₂O₅ salt, showed a higher degradation resistance during the corrosion test due to increased compliance capabilities resulting from the presence of an extra source of porosity associated with the nano-zones. Finally, the corrosion resistance and degradation mechanism of SYSZ and YSZ coatings were compared with the presence of molten NaVO₃ and V₂O₅ salt, respectively.     

Hot corrosion behavior of Yb2Si2O7 ceramic under NaVO3 salt attack

Hot corrosion behavior of Yb₂Si₂O₇ bulk exposed to NaVO₃ molten salt was investigated at 1000–1500 °C for 2 h. Results showed that YbVO₄ was produced on the bulk surface at 1000–1200 °C because of the acidity of the corrosion medium. The corrosion product of Yb₂SiO₅ was yielded at 1300–1500 °C due to the transformation of the corrosion medium from acidity to alkalinity. The content of YbVO₄ in the products decreased as the temperature increased, while that of Yb₂SiO₅ increased with an increase in temperature. In this paper, various hot corrosion mechanisms of Yb₂Si₂O₇ bulk exposed to NaVO₃ molten salt are discussed based on the formation of YbVO₄ and Yb₂SiO₅.     

Evaluation of hot corrosion behavior of plasma sprayed ceria and yttria stabilized zirconia thermal barrier coatings in the presence of Na2SO4+V2O5 molten salt

In this study, substrates of Inconel 738 LC superalloy coupons were first sprayed with a NiCoCrAlY bondcoat and then with a ceria and yttria stabilized zirconia (CYSZ; ZrO₂−25 wt%CeO₂−2.5 wt%Y₂O₃) topcoat by air plasma spraying (APS). Hot corrosion studies of plasma sprayed thermal barrier coatings (TBCs) were conducted in 45 wt%Na₂SO₄+55 wt%V₂O₅ molten salt at 1000 °C for 30 h. The results showed that the coating defects, such as pores and microcracks play important roles as effective paths for the salt penetration in hot corrosion. Based on the results, the reaction between molten salt and stabilizers of zirconia (Y₂O₃ and CeO₂), the formation of YVO₄, CeVO₄ and CeO₂ crystals, the detrimental phase transformation of zirconia from tetragonal to monoclinic due to the depletion of stabilizers and finally, the creation of stresses were recognized to be in the degradation mechanism of CYSZ ceramic coatings in the presence of molten sulfate–vanadate salt.     

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.     

Structure evolution,thermal properties and sintering resistance of promising thermal barrier coating material La2(Zr0.75Ce0.25)2O7

Rare-earth doped zirconates are promising candidate materials for high-performance thermal barrier coatings (TBCs). The phase and microstructure stability is an important issue for the materials that must be clarified, which is related to the long-term stable work of TBCs at high temperatures. In this work, La₂(Zr_0.75Ce_0.25)₂O₇ (LCZ) ceramic coatings prepared by atmospheric plasma spraying present a metastable fluorite phase, which can transform into stable pyrochlore under high-temperature annealing. The detailed structure evolution of the ceramic coatings is characterized systematically by SEM, XRD and Raman. The associated thermal properties of LCZ ceramics were also reported. Results show that LCZ ceramic has an ultralow thermal conductivity (0.65 W/m·K, 1200 °C), which is only 1/3 of that of yttria-stabilized zirconia (YSZ). The thermal expansion coefficients of LCZ ceramic increase from 9.68 × 10^-6 K^-1 to 10.7 × 10^-6 K^-1 (300 - 1500 °C), which are relatively larger than those of La₂Zr₂O₇. Besides, Long-term sintering demonstrates that LCZ ceramic coating has preferable sintering resistance at 1500 °C, which is desirable for TBC applications.     

Structure,electrical properties and reaction mechanism of (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 ceramics synthesized by the molten salt method

Lead-free (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ (BCZT) ceramics with excellent electrical properties were successfully synthesized by a molten salt method (MSS). The submicron BCZT powders with pure perovskite phase were obtained by adjusting the KCl-NaCl content that was used as the eutectic salt. The effects of salt content and reaction temperature on the structure and properties of the BCZT materials were systematically investigated. Comparing with BCZT ceramics prepared by solid state method (SS), the reaction temperature of BCZT ceramics synthesized by MSS decreased approximately 200 °C. Moreover, BCZT ceramics sintered at 1360 °C with 50% eutectic salt showed the most outstanding electrical properties, which are as follows: d₃₃ = 604 pC/N, k_p = 57%, P_s = 17.11 µC/cm², P_r = 9.98 µC/cm², ε_m = 15872, ε_r = 2654 and tan δ = 0.013. In addition, this work revealed a possible reaction course processes and mechanism about MSS. The results provide a new design to optimize the performance of BCZT lead-free piezoelectric ceramics.     

La2Zr2O7 based high entropy ceramic with a low thermal conductivity and enhanced CMAS corrosion resistance

Herein, five new La₂Zr₂O₇ based high-entropy ceramic materials, such as (La_0.2Ce_0.2Gd_0.2Y_0.2Er_0.2)₂Zr₂O₇, (La_0.2Ce_0.2Gd_0.2Er_0.2Sm_0.2)₂Zr₂O₇, (La_0.2Gd_0.2Y_0.2Er_0.2Sm_0.2)₂Zr₂O₇, (La_0.2Ce_0.2Y_0.2Er_0.2Sm_0.2)₂Zr₂O₇, (La_0.2Ce_0.2Gd_0.2Y_0.2Sm_0.2)₂Zr₂O₇), were synthesized using a sol-gel and high-temperature sintering (1000 °C) method. The spark plasma sintered (SPS) (La_0.2Ce_0.2Gd_0.2Er_0.2Sm_0.2)₂Zr₂O₇ pellet shows a low thermal conductivity of 1.33 W m^-1 K^-1 at 773 K, and it also exhibits better CaO–MgO–Al₂O₃–SiO₂ corrosion resistance than that of Y₂O₃ stabilized ZrO₂. It shows that (La_0.2Ce_0.2Gd_0.2Er_0.2Sm_0.2)₂Zr₂O₇ has a promising application potential as a thermal barrier coating.     

High-entropy thermal barrier coating of rare-earth zirconate: A case study on (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 prepared by atmospheric plasma spraying

We report a double-ceramic-layer (DCL) thermal barrier coating (TBC) with high-entropy rare-earth zirconate (HE-REZ) as the top layer and yttria stabilized zirconia (YSZ) as the inner layer sprayed on Ni-based superalloy by atmospheric plasma spraying. La₂Zr₂O₇ (LZ) was selected as a reference for the HE-REZ. Thermal cycling test results demonstrate that the HE-REZ/YSZ DCL coating exhibited obviously improved thermal stability when compared to the LZ/YSZ DCL coating. The reasons for the improvement of the thermal shock resistance are considered to be the anti-sinterability of the HE-REZ ceramics during the thermal cycling test attributed to the sluggish diffusion effect and as well as the better match in the coefficient of thermal expansion of HE-REZ coating with the YSZ inner layer. In addition, the HE-REZ coating maintains fluorite structure after thermal cycling test. This study makes one step forward in the development and application of high-entropy rare-earth zirconate ceramic thermal barrier coatings.     

Structure,thermal properties and hot corrosion behaviors of Gd2Hf2O7 as a potential thermal barrier coating material

In this work, Gd₂Hf₂O₇ ceramics were synthesized and investigated as a potential thermal barrier coating (TBC) material. The phase composition, microstructure and associated thermal properties of Gd₂Hf₂O₇ ceramics were characterized systematically. Results show that the thermal conductivity of Gd₂Hf₂O₇ ceramics is 1.40 Wm⁻¹K⁻¹ at 1200 °C, ~25% lower than that of 8 wt% yttria partially stabilized zirconia (8YSZ). Gd₂Hf₂O₇ ceramics also present large thermal expansion coefficients, which decrease from 12.0 × 10⁻⁶ K⁻¹ to 11.3 × 10⁻⁶ K⁻¹ (300–1200 °C). Besides, the hot corrosion behaviors of Gd₂Hf₂O₇ ceramics exposed to V₂O₅ and Na₂SO₄ + V₂O₅ salts at temperatures of 900–1200 °C were discussed in great detail. We pay much attention on the corrosion process, corrosion mechanism and corrosion damage of Gd₂Hf₂O₇ ceramics subjected to molten V₂O₅ and Na₂SO₄ + V₂O₅ salts at different temperatures.     

Effects of Yb and Sc co-doping on the thermal properties and CMAS corrosion of garnet-type (Y3-xYbx)(Al5-xScx)O12 ceramics

Thermal barrier coatings with excellent thermal performance and corrosion resistance are essential for improving the performance of aero-engines. In this paper, (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ (x = 0, 0.1, 0.2, 0.3) thermal barrier coating materials were synthesized by a combination of sol-gel method and ball milling refinement method. The thermal properties of the (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ ceramics were significantly improved by increasing Yb and Sc doping content. Among designed ceramics, (Y_2.8Yb_0.2)(Al_4.8Sc_0.2)O₁₂ (YS-YAG) showed the lowest thermal conductivity (1.58 Wm^?1K^?1, at 800 °C) and the highest thermal expansion coefficient (10.7 × 10^?6 K^?1, at 1000 °C). In addition, calcium-magnesium- aluminum -silicate (CMAS) corrosion resistance of YS-YAG was further investigated. It was observed that YS-YAG ceramic effectively prevented CMAS corrosion due to its chemical inertness to CMAS as well as its unique and complex structure. Due to the excellent thermal properties and CMAS corrosion resistance, YS-YAG is considered to be prospective material for thermal barrier coatings.     

Template formation of magnesium aluminate (MgAl2O4) spinel microplatelets in molten salt

Magnesium aluminate, MgAl₂O₄ (MA), microplatelets were synthesized using a molten salt technique. -Alumina platelets partially decomposed from aluminium sulphate were reacted with either commercial magnesium oxide or magnesium nitrate in the molar ratio 1:1 to synthesize spinel platelets. Molten salts such as chloride, MCl (M = Li, Na, and K) and potassium sulphate were used for MA synthesis and the salt to oxide ratio was kept at 3:1 for all compositions. Reactants and molten salt mixes were fired in an alumina crucible for 3 h at from 800 to 1150 °C. XRD revealed complete MA without formation of any secondary phase for powders fired for 3 h at 1100 °C. Electron microscopy revealed the MA platelet morphology and size was the same as the -alumina platelets indicating a ‘template process’ during molten salt synthesis.     

Preparation of plasma sprayed nanostructured GdPO4 thermal barrier coating and its hot corrosion behavior in molten salts

Nanostructured GdPO₄ coatings, designed as the outer layer of double-ceramic-layer thermal barrier coatings (DCL-TBCs), were produced by air plasma spraying (APS). The coatings have close chemical composition to that of the agglomerated particles used for thermal spray. Nanozones with porous structure are embedded in the coating microstructure, having a percentage of ~30%. Hot corrosion tests of the coatings were carried out in V₂O₅ and Na₂SO₄+V₂O₅ salts at 900 °C for 4 h. Results indicate that dense reaction layers, consisting of GdVO₄ and Gd₄(P₂O₇)₃, form on the coating surfaces, which could suppress further penetration of the molten salts. In the V₂O₅ molten salt, the reaction layer is thicker and less molten salt trace could be found beneath the layer.