Improvement strategy on thermophysical properties of A_(2)B_(2)O_(7)-type rare earth zirconates for thermal barrier coatings applications:A review

The A_(2)B_(2)O_(7)-type rare earth zirconate compounds have been considered as promising candidates for thermal barrier coating(TBC) materials because of their low sintering rate,improved phase stability,and reduced thermal conductivity in contrast with the currently used yttria-partially stabilized zirconia (YSZ) in high operating temperature environments.This review summarizes the recent progress on rare earth zirconates for TBCs that insulate high-temperature gas from hot-section components in gas turbines.Based on the first principles,molecular dynamics,and new data-driven calculation approaches,doping and high-entropy strategies have now been adopted in advanced TBC materials design.In this paper,the solid-state heat transfer mechanism of TBCs is explained from two aspects,including heat conduction over the full operating temperature range and thermal radiation at medium and high temperature.This paper also provides new insights into design considerations of adaptive TBC materials,and the challenges and potential breakthroughs are further highlighted for extreme environmental applications.Strategies for improving thermophysical performance are proposed in two approaches:defect engineering and material compositing.

Zircon deposit and rare earth element enriched metasomatic alkaline rocks at Kyemyeongsan Formation, Chungju, Korea: Paleozoic magmatism and Zr-REE-Nb mineralization

The zircon ore deposit in metasediments and peralkaline granite of the Kyemyeongsan Formation is located in southwest of Chungju city, Korea. The deposit, closely associated with REE and Nb,is composed of metasomatic alkaline rocks and rare metal alkali granite, and was formed in late Carboniferous (340～343Ma). Zircon occurs in different paragenetic sequence: (1) earlier rare metal alkali granite, (2) later metasomatic zircon ore. The metasomatic zone contains abundant microcline, albite and quartz with minor biotite, magnetite, hornblende, allanite and zircon. The alkali granites have high silica (72.13～74.52wt.% as SiO 2), and total iron content (5.95～6.89%), and are characterized by low Al 2O 3 content (7.12～9.74%). They also show variable K 2O content (3.60～6.98%), and high ratios of K 2O/Na 2O. The REE patterns of rare metal alkali granite are similar to those of felsic volcanics from rifts, or back arc basins in, or near continental crust. Zircon ores are characterized by high iron content and low Al 2O 3, SiO 2, and K 2O content and have unusually high total REE content (0.18～2.33%). REE patterns show relatively flat to somewhat heavy REE (HREE) depleted characteristics (Ce/Yb=0.39～5.17) with large Eu negative anomaly (Eu/Eu *=0.16～0.29). Laser ablation microprobe inductively coupled plasma mass spectrometer (LAM ICP MS) analyses has been carried on zircon. The REE patterns of mineral zircons are almost the same to those of zircon ores and rare metal alkali granites, which may reflect the inability of zircons to effectively fractionated REE at formation of origin. The Sm Nd isochron age of the zircon ore and rare metal alkali granite are 330Ma, and 331Ma, respectively with ε Nd(t) being range from -2.00 to -1.84. This data suggest that the ore forming material came from the mantle. Alkali granite has suffered extensive post magmatic metasomatism of a high temperature to produce zircon ores. Geochemical characteristics show that metasomatism of alkaline fluid was probably the dominant ore forming process in Chungju district.

Recent progress in thermal/environmental barrier coatings and their corrosion resistance

Thermal/environmental barrier coatings(T/EBCs)play important roles in jet and/or gas turbine engines to protect the Ni-based superalloys and/or ceramic matrix composite substrates from the high-temperature airflow damage.Great efforts have been contributed to searching for enhanced T/EBC materials to improve the efficiency of the engines,which is the key of improving thrust-to-weight ratio and energy saving.The practical candidates,rare earth-contained materials,are widely used for T/EBCs in gas turbines due to their excellent properties such as low thermal conductivity,high melting point,hightemperature strength and durability as exhibited in yttriastabilized zirconia,pyrochlore oxides and rare earth silicates.In addition to the intrinsic properties,the microstructures obtained by different synthesis processes and the service performances,as well as the underlying failure mechanism,are also significant to this specific application.However,the main challenges for T/EBCs developments are T/EBC materials selection with balanced properties and their anti-corrosion performances at higher operating temperature.In this review,we summarized the progress in their fabrication techniques and mechanical/thermal properties of typically rare earth-contained T/EBCs,together with their anti-corrosion performance under the condition of molten salts or oxides(such as Na2SO4,V2O5and NaVO3),calcium–magnesium–alumina–silicate(CMAS)and high-temperature water vapor.

Chemical stability of Ce-doped zircon ceramics:Influence of p H,temperature and their coupling effects

Zircon was employed to immobilize simulated tetravalentactinide nuclide（Ce^4＋）. Zr_（1–x）Ce_xSiO_4（0≤x≤0.10） ceramics were synthesized and their chemical durabilities were investigated systematically. The effects of p H and temperature on the chemical durability of the as-prepared compounds were investigated using the MCC-1 static leaching test, and their coupling effects were also explored. It was found that the normalized release rates of Ce in deionized water and alkaline solutions（pH=10） were smaller than those in acid solutions（p H=4）. At a certain p H value, the normalized release rate of Ce（LR Ce） increased with the temperature in the initial period. However, the leaching progress almost reached a balance after 14 days, and both of the p H and the temperature had slight impact on the leaching of Ce element. Moreover, the LR_（Ce） were below 10^（–5）g/m^2/d after 42 days, which was lower than those of other nuclear waste forms in all discussed leachates.

Chemical stability of simulated waste forms Zr1–xNdxSiO4–x/2： Influence of temperature, pH and their combined effects

The chemical stability of simulated waste forms Zr_（1–x）Nd_xSiO_（4–x/2） was investigated using the static leach test（MCC-1） with lixiviants of three pH values（pH=4, 6.7 and 10） at three temperature points（40, 90 and 150 oC） for periods ranging from 1 to 42 d, and the influence of temperature, pH, as well as their combined effects were explored in detail. The results showed that all the normalized release rate of Nd firstly decreased with leaching time and closed to equilibrium after 14 d. As the temperature increased, the normalized release rate of Nd also increased, but it was no more than 3×10^（–5） g/（m^2·d）. And, the normalized release rate of Nd reached the highest values（~5×10^（–5） g/（m^2·d）） when pH=4, whilst the normalized release rate of Nd remained the lowest value（~1×10^（–5） g/（m^2·d）） near neutral environment（pH=6.7）.