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.

Effect of rare earth doping on thermo-physical properties of lanthanum zirconate ceramic for thermal barrier coatings

The effect of rare earth doping on thermo-physical properties of lanthanum zirconate was investigated. Oxide powders of various compositions La2Zr2O7 were synthesized by coprecipitation-calcination method. High-temperature dilatometer, DSC, and laser thermal diffusivity methods were used to analyze thermal expansion coefficient （TEC）, specific heat, and thermal diffusivity. The results showed that CeO2 doped pyrochlores La2（Zr1.8Ce0.2）2O7 and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had higher TEC than La2Zr2O7 and La1.7Dy0.3Zr2O7. La2（Zr1.8Ce0.2）2O7, La1.7Dy0.3Zr2O7, and La1.7（DyNd）0.15（Zr0.8Ce0.2）2O7 had lower thermal conductivity than undoped La2Zr2O7. The Dy2O3, Nd2O3, and CeO2 codoped composition showed the lowest thermal conductivity and the highest TEC. Thermo-physical results also indicated that TEC of rare earth oxide doped La2Zr2O7 ceramic was slightly higher than that of conventional ZrO2-8Wt.% Y2O3 （8YSZ）, and its thermal conductivity was lower than that of 8YSZ.

Study of High-Temperature Stability of Pyrochlore Zirconates

Based on defect chemistry theory and molecular dynamics,the defect formation energy and its relationship with the mechanism of pyrochlore-fluorite phase change were investigated,so as to reveal the underlying mechanism of high-temperature stability of pyrochlore zirconates.Results showed that with the rise of the atom mass of A,the defect formation energies decreased that meant the crystal structure tended to become more disordered.Noticeably,the first nearest cation antisite dominated the pyrochlore disorder transformation process.In addition,it was found that the diffusion of oxygen atoms was far higher than that of cations,and was increased with the temperature,thus also promoting the pyrochlore-fluorite transformation process.

Fabrication and Growing Kinetics of Highly Dispersed Gadolinium Zirconate Nanoparticles

Highly dispersed gadolinium zirconate(GZ)nanoparticles with fluorite structure were successfully synthesized by co-precipitation method,and their phase composition and microstructure,formation mechanism,and grain growth kinetics were investigated.The results suggest that the nanoparticles were obtained through hydroxide dehydration and solid phase reaction.High dispersion was accomplished by ethanol solvent to reduce the hydrogen bond and sodium dodecyl benzene sulfonate(SDBS)surfactant to increase the electrostatic repulsion between the nanoparticles.The grain growth activation energy of GZ powders calcined at lower temperature(<1200°C)is 86.5 kJ/mol(Ql),and the grain growth activation energy of GZ powders calcined at higher temperature(>1200°C)is 148.4 kJ/mol(Qh).The current study shows that the optimal process to synthesize dispersed GZ nanoparticles includes ethanol solvent,3 wt.%SDBS surfactant,and 1100°C as calcining temperature.

Improving the fatigue endurance of lead zirconate titanate thin films through PbO interfacial modification

The effects of the modification of electrode/ceramic interfaces through a chemical solution deposition-derived PbO buffer layer on the fatigue endurance of lead zirconate titanate（PZT） thin films were investigated.The grain size and the surface roughness of the PZT films increased through PbO interfacial modification.Moreover,the PZT films with PbO interfacial modification had a better crystallographic structure and no evident secondary phases were observed.While the remanent polarization and dielectric constant were reduced,the fatigue endurance was improved.Based on the results,the mechanism for the fatigue endurance improvement was discussed.

Lead zirconate titanate behaviors in an LDMOS

The behaviors of lead zirconate titanate （PZT） deposited as the dielectric for high-voltage devices are investigated experimentally and theoretically. The devices demonstrate not only high breakdown voltages above 350 V, but also excellent memory behaviors. A drain current–gate voltage （ID-VG） memory window of about 2.2 V is obtained at the sweep voltages of ±10 V for the 350-V laterally diffused metal oxide semiconductor （LDMOS）. The retention time of about 270 s is recorded for the LDMOS through a controlled ID-VG measurement. The LDMOS with memory behaviors has potential to be applied in future power conversion circuits to boost the performance of the energy conversion system.

Molecular Dynamics Simulation of Binary Fluorozirconate Glass ZrF_(4)·BaF_(2)

Binary fluorozirconate glassZrF_(4)·BaF_(2) has been studied by molecular dynamical simulation using parameter-free Gordon-Kim potentials.In these simulations a novel technique is employed to monitor the motion of ions,thus the structure pictures of glass and the microscopic motion mechanism of ionic conduction are clearly and directly obtained.The glass networks commonly are formed by ZrF8,ZrF7 or ZrF6 polyhedra,cross linked by Ba-F ionic bonds.The mean distance of the ionic nearest neighboring at 300K is about 3.90Å(Zr-Zr),3.87Å(Zr-Ba),and 1.96Å(Zr-F).The two stronger peaks of five main peaks of vibrational spectra are at about 540-600 and 460-510cm^(-1) and three weaker peaks at about 386-416,322-348,and 183-196cm^(-1).The other properties of glass:density,thermal expansion coefficient,polarization,and glass transition temperature are also examined.

Lead zirconate(PbZrO_(3))embedded in natural rubber as electroactive elastomer composites

Perovskite lead zirconate(PbZrOz)was synthesized in an orthorhombic form at a temperature below the Curie temperature,Tc.The orthorhombic form is a noncentrosymmetric structure which is capable of spontaneous polarization.Fourier transform infrared(FTIR)spectra and X-ray diffraction(XRD)patterns confirm the siuccessful synthesis of the lead zirconate;and scanning electron microscopy(SEM)micrographs indicate that PbZrO_(3) particles are moderately dispersed in the natural rubber(NR)matrix.Without an electrical field,the particles merely act as a ferroelectric fller,which can absorb and store additional stress.Under an electrical field,particle induced dipole motents are generated,leading to interparticle interaction and a sub-stantial increase in the storage modulus.At a small amount of lead ziroonate part iculates present in the natural rubber matrix,at a volume fraction of 0.007306,the electrical conductivity increases dramatically by nearly two orders of magnitude at the electrical frequency of 500 kHz.

An Improved Cymbal Hydrophone Made of Lanthanum-Modified Lead Zirconate Titanite

Lanthanum-modified lead zirconate titanite （PLZT） piezoelectric ceramics has higher piezoelectric and dielectric properties compared with the common lead zirconate titanite （PZT） ceramics. These properties endue the cymbal hydrophones made of PLZT usually with stable performance but lower receiving sensitivity. In order to improve the sensitivity, through a static analysis on hydrophone we did some changes for the PLZT hydrophone by reducing the radius of the piezoelectric ceramics and sealing its boundary. Furthermore, ANSYS simulations were made, and the experiments for the improved PLZT hydrophone and the original one were carried out in water pool. The results show that the receiving sensitivity of the improved cymbal hydrophone made of PLZT is 3 -4 dB higher than that of the original, and that the frequency response still keeps flat within 18 kHz band.

FABRICATION OF PIEZOELECTRIC BIMORPH USING LEAD ZIRCONATE TITANATE THIN FILM DEPOSITED BY HYDROTHERMAL METHOD

In order to describe the characteristics of piezoelectric bimorph, properties of lead zirconate titanate （LZT） film are studied by X-ray diffraction （XRD） and scanning eletron microscope （SEM）. The ratio of PbTiOJPbZrO3 in LZT is 53/47, which is around morphotropic phase boundary （MPB）. LZT film is composed of cubic particles with the average size of 5 ~ma. Density of thin film is figured out through the datum measured in experiments. The displacement model used to analyze the driving ability of bimorph is set up, and the effect of elastic intermediate layer is taken into account. Piezoelectric coefficient of LZT film is worked out by using the displacement model. Experiments of driving ability show that deformation of bimorph free end does not increase with times of crystal growth processes and the maximum deformation is obtained after two times crystal growth processes. Finally, the ferroelectric property of the bimorph is investigated and coercive voltage of the bimorph is obtained.

Nickel-based cerium zirconate inorganic complex structures for CO_(2)valorisation via dry reforming of methane

The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a worthwhile chemical intermediate.Among the different active phases for DRM,the use of nickel as catalyst is economically favourable,but typically deactivates due to sintering and carbon deposition.The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts.XRD and TPR-H2analyses confirmed the existence of different phases according to the Ni loading in these materials.Besides,superficial Ni is observed as well as the existence of a CeNiO_(3)perovskite structure.The catalytic activity was tested,proving that 10 wt.%Ni loading is the optimum which maximises conversion.This catalyst was also tested in long-term stability experiments at 600and 800℃in order to study the potential deactivation issues at two different temperatures.At 600℃,carbon formation is the main cause of catalytic deactivation,whereas a robust stability is shown at 800℃,observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO_(2)and biogas mixtures upgrading catalysts.

Facile synthesis of high-entropy zirconate nanopowders and their sintering behaviors

The challenge in synthesizing high-entropy ceramic(HEC)nanopowders is to suppress severe grain coarsening and particle agglomeration,which occur at elevated temperatures.This challenge could be addressed by the polyacrylamide gel method.In this work,single-phase high-entropy(Lao.2Ndo.2Smo.2Gdo.2 Ybo.2)2Zr2O7 and(Lao.2Ndo.2Yo.2Euo.2Gdo.2)2Zr2O7 nanopowders without agglomeration were successfully synthesized using the polyacrylamide gel method for the first time.The results showed that phase composition,particle size,and agglomeration degree of the nanopowders were greatly influenced by the molar ratio of acrylamide(AM)/Zr and calcination temperature.These as-synthesized high-entropy zirconate(HEZ)nanopowders could be sintered into fully dense ceramics at 1500 C for 2 h.These HEZ nanopowders showed a phase transformation from a defect-fluorite phase to a pyrochlore phase with the increase of sintering temperature.Additionally,two-step sintering of these nanopowders was conducted,and the HEZ ceramics with fine grains were prepared.The polyacrylamide gel method is simple and easily operated,which is a facile approach of producing the HEC nanopowders with excellent sinterability.

Ultrafine-grained high-entropy zirconates with superior mechanical and thermal properties

Ultrafine-grained(Sm_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Zr_(2)O_(7)high-entropy zirconates with single fluorite structure have been fabricated by high-pressure sintering of the self-synthesized nanopowders for the first time.The as-sintered samples exhibit a good microstructure with a grain size of 220 nm and a relative density of 96.8%,which yield excellent comprehensive mechanical properties with a high Vickers hardness of 12.5 GPa and a high fracture toughness of 3.4 MPa·m1/2.In addition,the as-sintered samples possess a good thermostability with the grain growth rate of 30 nm/h,and a low thermal conductivity of 1.57 W·m^(-1)·℃^(-1)at room temperature.The superior mechanical and thermal properties are primarily attributed to the“high-entropy”and grain-refinement effects and good interface bonding.

Corrosion resistance of non-stoichiometric gadolinium zirconate fabricated by laser-enhanced chemical vapor deposition

Gadolinium zirconate (GZ) is a promising candidate for next-generation thermal barrier coating (TBC) materials.Its corrosion resistance against calcium-magnesium-alumino-silicate(CMAS) needs to be further increased for enhancing its in-service life.As the Gd element plays an important role in the CMAS resistance,three GZ coatings (GZ-0.75,GZ-1.0,and GZ-1.2) with different Gd/Zr atomic ratios are designed and deposited by laser enhanced chemical vapor deposition(LCVD) in this work.It is found that the generated Gd-apatite in GZ-1.2 would block micro-cracks inside the column structure and the inter-columnar gap more efficiently.Thus,the CMAS penetration rate (5.2 μm/h) of GZ-1.2 decreases over 27% comparing with GZ-1.0 and GZ-0.75,which is even lower than the Gd_(2)Zr_(2)O_(7) coatings fabricated by electron-beam physical vapor depositions (EB-PVDs).This work provides a feasible way to adjust the coating's corrosion resistance and may guide the development of future coating for long in-service life.

High-entropy rare-earth zirconate ceramics with low thermal conductivity for advanced thermal-barrier coatings

The high-entropy rare-earth zirconate((La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Yb_(0.2))_(2)Zr_(2)O_(7),5RE_(2)Zr_(2)O_(7)HEREZs)ceramics were successfully prepared by a new high-speed positive grinding strategy combined with solid-state reaction method.The microstructure,crystal structure,phase composition,and thermophysical and mechanical properties of the samples were systematically investigated through various methods.Results indicate that the samples have a single-phase defect fluorite-type crystal structure with excellent high-temperature thermal stability.The as-prepared samples also demonstrate low thermal conductivity(0.9–1.72 W·m^(−1)·K^(−1)at 273–1273 K)and high coefficient of thermal expansion(CTE,10.9×10^(−6)K^(−1)at 1273 K),as well as outstanding mechanical properties including large Young’s modulus(E=186–257 GPa)and high fracture toughness(KIC).Furthermore,the formation possibility of the as-prepared samples was verified through the first-principles calculations,which suggested the feasibility to form the 5RE_(2)Zr_(2)O_(7)HE-REZs in the thermodynamic direction.Therefore,in view of the excellent multifunctional properties exhibited by the as-prepared 5RE_(2)Zr_(2)O_(7)HE-REZs,they have great potential applications in next-generation thermal-barrier coatings(TBCs).

Synthesis of the superfine high-entropy zirconate nanopowders by polymerized complex method

The high-purity and superfine high-entropy zirconate nanopowders,namely(Y_(0.25)La_(0.25)Sm_(0.25)Eu_(0.25))_(2)Zr_(2)O_(7)nanopowders,without agglomeration,were successfully synthesized via polymerized complex method at low temperatures for the first time.The results showed that the crystallinity degree,lattice strain,and particle size of the as-synthesized powders were gradually enhanced with the increase of the synthesis temperature from 800 to 1300℃.The as-synthesized powders involved fluorite phase in the range of 800-1200℃while they underwent the phase evolution from fluorite to pyrochlore at 1300℃.It is worth mentioning that the as-synthesized powders at 900℃are of the highest quality among all the as-synthesized powders,which is due to the fact that they not only possess the particle size of 11 nm without agglomeration,but also show high purity and good compositional uniformity.

Effects of loading contact on electric-power generation of lead zirconate titanate piezoelectric ceramic plate

To better understand the generation of electric power for piezoelectric Pb Zr Ti O3(PZT)ceramic plate(?25 mm),an attempt was made to investigate experimentally and numerically electricpower generation characteristics during cyclic bending under various loading fixtures(?0–?20 mm),i.e.,different contact areas.Increasing the load-contact area on the PZT ceramic leads to a nonlinear decrease in the generated voltage.Decreasing contact area basically enhances the generated voltage,although the voltage saturates during loading when the contact area is less than?5 mm.A similar voltage is generated for?0 and?5 mm,which is attributed to strain status(ratio of compressive and tensile strain)and material failure due to different stress distribution in the PZT ceramic.On the basis of the obtained electric generation voltage,suitable loading conditions are clarified by loading with the?5 mm fixture,which generates a higher voltage and a longer lifetime of the PZT ceramic.From this approach,it is appeared that the area contact with the area ratio of 0.04(?5 mm/?20 mm)is suitable to obtain the high efficiency of the electric voltage.

Petrogenesis, oxidation state and volatile content of Dongga tonalite in the Gangdese belt, Xizang: Implication for porphyry Cu mineralization

The Gangdese belt in Xizang has experienced both Jurassic subduction and Cenozoic continental collision processes, making it a globally renowned region for magmatic rocks and porphyry copper deposits. Numerous Jurassic intrusions have been identified in the belt. Apart from the quartz diorite porphyry in the large Xietongmen deposit, the Cu mineralization potential of other Jurassic intrusions in this belt remains unclear. This study presents zircon U–Pb dating and trace elements, apatite major and trace elements as well as published whole-rock geochemical and isotopic data of the Dongga tonalite in the central part of the Gangdese belt, aiming to reveal the petrogenesis, oxidation state, volatile content, and Cu mineralization potential of this intrusion. The Dongga tonalite has a zircon U–Pb age of 179.4 ± 0.9 Ma. It exhibits high whole-rock V/Sc values(8.76–14.6), relatively low apatite CeN/CeN*ratios(1.04–1.28), elevated zircon(Eu/Eu*)Nvalues(an average of 0.44), high Ce4+/Ce3+values(205–1896), and high ?FMQ values(1.3–3.7), collectively suggesting a high magmatic oxygen fugacity. The Dongga tonalite features amphibole phenocrysts, relatively high whole-rock Sr/Y ratios(20.3–58.9), and lower zircon Ti temperatures (502–740 ℃), reflecting a high magmatic water content. Estimation of magmatic sulfur content(0.002–0.024 wt%) based on apatite SO3contents indicates an enriched magma sulfur content. Combined with previous studies and the collected Sr–Nd–Hf isotopes, the Dongga tonalite is derived from juvenile lower crust related with subduction of the Neo-Tethys oceanic slab. When compared with Xietongmen orebearing porphyries, the Dongga tonalite exhibits remarkable similarities with the Xietongmen ore-bearing porphyries in terms of magma source, tectonic background, magmatic redox state, and volatile components, which indicates that the Dongga tonalite has a high porphyry Cu mineralization potential, and therefore, provides important guidance for the future mineralization exploration.

Geochemistry, zircon U–Pb geochronology, and Hf isotopes of S-type granite in the Baoshan block, constraints on the age and evolution of the Proto-Tethys

Geochemistry, zircon U–Pb geochronology, and Hf isotope data for the Early Paleozoic granites in the Baoshan Block reveal the Early Paleozoic tectonic evolution of the Proto-Tethys. The samples are high-K, calcalkaline, strongly peraluminous rocks with A/CNK values of 1.37–1.46, are enriched in SiO2, K2O, and Rb, and are depleted in Nb, P, Ti, Eu, and heavy rare earth elements,which indicates the crystallization fractionation of the granitic magma. Zircon U–Pb dating indicates that they formed in ca. 480 Ma. The Nansa granites have εHf(t) values ranging from-16.04 to 4.36 with corresponding TC DMages of 2.10–0.81 Ga, which suggests the magmas derived from the partial melting of ancient metasedimentary with minor involvement of mantle-derived components. A synthesis of data for the Early Paleozoic igneous rocks in the Baoshan block and adjacent(Tengchong,Qiangtang, Sibumasu, Himalaya, etc.) blocks indicates that these blocks were all aligned along the proto-Tethyan margin of East Gondwana in the Early Paleozoic. The Early Paleozoic S-type granites from Nansa were generated in a high-temperature and low-pressure(HTLP) extensional tectonic setting, which resulted from Andean-type orogeny instead of the final assembly of Gondwana or crustal extension in a non-arc environment. In certain places, an expanding environment may exist in opposition to the tectonic backdrop of the lithosphere’s thickening and shortening, leading the crust to melt and decompress,mantle-derived materials to mix, and a small quantity of peraluminous granite to emerge.

The late Early-Paleozoic granitic magmatism in Northwestern Fujian, China: constraints on intraplate orogeny in the South China block

The Early Paleozoic tectono-thermal event was a significant orogenic activity during the Phanerozoic era,which had a profound impact on the early crust of the South China Block(SCB) and established the foundation for later tectonic activity.The Wuyi-Yunkai orogenic belt in Southeastern China was extensively exposed to Early Paleozoic magmatism,the genetic mechanism of which remains controversial.To shed light on this issue,detailed petrological,geochemical,and zircon U-Pb-Hf isotopic studies were carried out on two granitoids,namely the Yuntongshan pluton and the Gaoqiao pluton,identified in the central Wuyishan.Zircon U-Pb chronology of the Yuntongshan and Gaoqiao bodies yielded ages of437±4 Ma(MSWD=2.2) and 404±2 Ma(MSWD=12),respectively,indicating that they were emplaced during the Early Silurian and Early Devonian periods.These granitoids are primarily composed of biotite-granite and biotite-monzonitic-granites,with high concentrations of S_(i)O_(2)(73.59-75.91 wt%),K_(2)O+Na_(2)O(8.31-8.73wt%),and low contents of MgO,CaO,Cr,Ni.They are classified as high-K calc-alkaline and weakly metaluminous-strongly peraluminous S-type granites.These granitoids are enriched in light rare earth elements(LREEs) and large ion lithophile elements(LILEs) and depleted in heavy rare earth elements(HREEs) and high field strength elements(HFSEs) with arc affinity.The εHf(t) values of-3.3 to-15.4 with two-stage Hf model ages ranging from 2829 to 1644 Ma,combined with the presence of Neoproterozoic inherited zircons,suggest that the primary magma of these granitoids was derived from the partial melting of Neoproterozoic crust with a Paleoproterozoic crustal model age.These findings,combined with the spatio-temporal distribution of regional magmatism,reveal that the late Early-Paleozoic granitoids formed in the intraplate orogenic background originating from the subduction of the proto-Tethys Ocean and proto-Pacific Ocean around the margin of the east Gondwana supercontinent.