The complex oxides with octahedral structures:Existence areas and phase transitions

The experimental and calculated data on the existence of complex oxides in solid state with the octahedral structures of four families,namely perovskites,Bi-containing layered perovskite-like ones,tetragonal tungsten bronzes and pyrochlores,and about their phase transitions are systematized and summarized on the basis of the quasi-elastic or geometric models of these structures.It has been established that similar existence areas and similar correlations between the interatomic bond strains in their structures,on the one hand,and the temperatures of their ferroelectric or antiferroelectric phase transitions,on the other hand,are observed for all of them,despite the differences in the compositions and structures of these oxides,but taking into account their similar parameters.

Ultralow oxygen ion diffusivity in pyrochlore-type La_(2)(Zr_(0.7)Ce_(0.3))_(2)O_(7)

Thermally grown oxides(TGOs)at the ceramic top-coat/metallic bond-coat interface are a pressing chal-lenge in advanced thermal barrier coating(TBC)systems as they can affect the performance and ser-vice lifetime of TBCs.Thus,developing novel TBC materials with ultralow oxygen ion diffusivity is very urgent.In this study,we reported the diffusive properties of oxygen ions in a novel pyrochlore-type La_(2)(Zr_(0.7)Ce_(0.3))_(2)O_(7)(LZ7C3)material.The measured ionic conductivity and atomistic simulation revealed that the oxygen ion diffusivity in LZ7C3 grains is two orders of magnitude lower than that in conventional 8 wt.%yttria-stabilized zirconia(8YSZ)grains.This is due to the relatively high energy barrier for oxygen hopping in LZ7C3.In addition,it was found that enhancing the order distribution of cations is a strategy to reduce the intrinsic oxygen diffusion of pyrochlore-type oxides.On the other hand,we observed that La^(3+) cations segregate at the grain boundaries(GBs)of LZ7C3,which results in the electrostatic poten-tial at GBs being comparable to that in the bulk.Furthermore,we found that the oxygen ion diffusion is facilitated at the GBs of LZ7C3 due to the stretched O-Zr/Ce bond and the low coordination at GBs.How-ever,the segregations of Y^(3+)cations and the increase in the number of oxygen vacancies resulted in the formation of an electrostatic layer at the GBs of 8YSZ,which shielded the oxygen ion diffusion.Despite this,the oxygen ion diffusivity in LZ7C3 was still considerably less than that in conventional 8YSZ.This study offers a stepping stone toward utilizing pyrochlore-type LZ7C3 materials as advanced TBCs at high temperatures.

Effects of Er^(3+)doping on structure and thermal properties of(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)ceramics for thermal barrier coating

Rare earth Er^(3+)doped(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)(x=0.1,0.2,and 0.3)ceramic samples were synthesized using a solid state reaction method.The microstructure and thermal properties of these ceramics were investigated to evaluate their potential as thermal barrier coating materials.The results show that ceramics are compact with regular-shaped grains of 1-5μm size.(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)has a pyrochlore structure mainly determined by ionic radius ratio,but the ordering degree decreases with increase of the Er_(2)O_(3)content.There is no phase transformation from 1000 to 1200℃,and the(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)ceramics exhibit excellent phase stability during thermal treatment at 1200℃for 100 h and 1400℃for 50 h.The thermal conductivities of dense(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)ceramics range from 1.52 to 1.59 W/(m·K),which is lower than that of Sm_(2)Zr_(2)O_(7),and decrease as the Er2O3content increases.Besides,the thermal expansion coefficient of(Sm_(1-x)Er_(x))_(2)Zr_(2)O_(7)is higher than that of Sm_(2)Zr_(2)O_(7).

Effect of Nb^(5+)and Cu^(2+)codoping on thermal properties of Gd_(2)Zr_(2)O_(7)ceramic

In this work,Nb^(5+)and Cu^(2+)were selected to partially substitute Zr4+in Gd_(2)Zr_(2)O_(7)for studying the phase structure,microscopic morphology and thermal properties.Gd_(2)(Zr_(1-3 x/2)Nb_(x)CU_(x/2))_(2)O_(7)(x=0,0.05,0.1,0.15,0.2,0.25)ceramic materials were synthesized by high-temperature solid-state reaction method.The results show that the Gd_(2)(Zr_(1-3 x/2)Nb_(x)Cu_(x)/2)_(2)O_(7)ceramics present cubic pyrochlore structure with clear grain boundaries and dense cell structure.And the thermal expansion coefficient of Gd_(2)(Zr_(1-3 x/2)Nb_(x)Cu_(x/2))_(2)O_(7)ceramics gradually decreases because of the incorporation of Nb^(5+)and Cu^(2+)into Zr-site in Gd_(2)Zr_(2)O_(7).Meanwhile,its thermal conductivity decreases firstly and then increases with the doping of Nb^(5+)and Cu^(2+),which reaches the lowest value for the composition of Gd_(2)(Zr_(0.85)Nb_(0.1)Cu_(0.05))_(2)O_(7).

Calcium-magnesium-alumina-silicate(CMAS)resistant high entropy ceramic(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7) for thermal barrier coatings

A novel high-entropy material,(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)was successfully synthesized by the solid state reaction method and spark plasma sintering,and investigated as a promising thermal barrier coating material.Rare-earth elements were distributed homogeneously in the pyrochlore structure.It was found that the prepared high-entropy ceramic maintains pyrochlore structure at the temperature up to 1600℃,and it possesses a similar thermal expansion coefficient(10.2×10^(−6)K^(−1) at 25-900℃)to that of YSZ,low thermal conductivity(<0.9 W m^(-1)K^(−1) at 100-1000℃)and good CMAS resistance(infiltration depth is 22μm after annealed at 1300℃for 24 h).The corrosion process was investigated,and RE elements distributing homogeneously in(Y_(0.2)Gd_(0.2)Er_(0.2)Yb_(0.2)Lu_(0.2))_(2)Zr_(2)O_(7)show different diffusion rates in CMAS.RE^(3+) with a larger radius(closer to Ca^(2+))is easier to react with CMAS to form an apatite phase.

Effects of rare earth oxides on dielectric properties of Y_2Ti_2O_7 series ceramics

A series of Y2Ti2O7 microwave dielectric ceramics were synthesized by conventional solid-state method. The effects of rare earth oxide (La2O3, CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3 and Dy2O3) and Nd2O3 doping content on the microstructure and dielectric properties of Y2Ti2O7 ceramics were investigated. The experimental results showed that the rare earth ions were considered to dissolve in Y-sites of the pyrochlore structure, different rare earth oxides and concentration had different influences on Y2Ti2O7 cerami...