Oxygen interstitial and vacancy conduction in symmetric Ln2 ± x Zr2 ± x O7 ± x/2 (Ln = Nd,Sm) solid solutions

We have compared (Ln_{2 ? x} Zr _x )Zr₂O_{7 + x/2} (Ln = Nd, Sm) pyrochlore-like solid solutions with interstitial oxide ion conduction and Ln₂(Zr_{2 ? x} Ln _x )O_{7 ? δ} (Ln = Nd, Sm) pyrochlore-like solid solutions with vacancy-mediated oxide ion conduction in the symmetric systems Nd₂O₃-ZrO₂ (NdZrO) and Sm₂O₃-ZrO₂ (SmZrO). We have studied their structure, microstructure, and transport properties and determined the excess oxygen content of the (Sm_{2 ? x} Zr _x )Zr₂O_{7 + x/2} (x = 0.2) material using thermal analysis and mass spectrometry in a reducing atmosphere (H₂/Ar-He). The Ln_{2 ± x} Zr_{2 ± x} O_{7 ± x/2} (Ln = Nd, Sm) solid solutions have almost identical maximum oxygen vacancy and interstitial conductivities: (3–4) × 10^?3 S/cm at 750°C. The lower oxygen vacancy conductivity of the Ln₂(Zr_{2 ? x} Ln _x )O_{7 ? δ} (Ln = Nd, Sm; 0 < x ≤ 0.3) solid solutions is due to the sharp decrease in it as a result of defect association processes, whereas the interstitial oxide ion conductivity of the (Ln_{2 ? x} Zr _x )Zr₂O_{7 + x/2} (Ln = Nd, Sm; 0.2 ≤ x < 0.48) pyrochlore-like solid solutions is essentially constant in a broad range of Ln₂O₃ concentrations.     

Phase structure evolution and thermal expansion variation of Sc2O3 doped Nd2Zr2O7 ceramics

(Nd_1−xSc_x)₂Zr₂O₇ (x = 0, 0.1, 0.3, 0.5, 0.7) compounds were synthesized by solid state reaction at 1700 °C for 10 h, and characterized by XRD, Raman spectroscopy, SEM and high-temperature dilatometer. Nd₂Zr₂O₇ exhibited pyrochlore phase, and its lattice parameter increased after Sc₂O₃ doping, which could be attributed to the presence of Sc³⁺ interstitial ions in pyrochlore lattice. Fluorite phase formed in the doped Nd₂Zr₂O₇, and (Nd_0.3Sc_0.7)₂Zr₂O₇ exhibited pure fluorite phase. The thermal expansion coefficient (TEC) of Nd₂Zr₂O₇ was significantly enhanced by 10 mol% Sc₂O₃ doping, but higher Sc₂O₃ doping decreased the TEC. The reduced crystal energy due to the presence of Sc³⁺ interstitial ions could cause the initial increase in the TEC, and the formation of fluorite phase might contribute to the reduced TEC. Considering the alleviation of the thermal expansion mismatch stress for the high-temperature applications of Nd₂Zr₂O₇, Sc₂O₃ was an excellent dopant and there existed an optimal Sc₂O₃ content for the optimization design of compound compositions.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Effect of Zr doping on the microstructure and electric properties of BaHf0.1Ti0.9O3 ceramics

Pure and Zr-doped barium titanate hafnate (BaHf_0.1Ti_0.9O₃, short for BHT) ceramics were prepared by conventional solid state reaction method. The microstructures, dielectric and ferroelectric properties of BaHf_0.1Ti_0.9-x Zr _x O₃ (x = 0, 0.02, 0.04, 0.10) ceramics have been investigated. From the X-ray diffraction patterns it is indicated that Zr⁴⁺ ions have entered the unit cell maintaining the tetragonal perovskite structure of solid solution and the lattice constant of Zr-doped BHT ceramics increases with the increase of Zr content. There is an obvious difference between the grain shape of pure BHT ceramics and that of Zr-doped BHT ceramics. The temperature dependences of dielectric constant indicated that all of the three phase transition temperatures increase after doped zirconium. It is found that well-behaved hysteresis loops can be observed in pure and Zr-doped BHT ceramics. The remanent polarization (2P _r) and the coercive electric field (2E _C) of BaHf_0.1Ti_0.9-x Zr _x O₃ ceramics gradually decrease as the Zr content increases from 2 to 10 mol %.     

Synthesis, microstructure and thermal expansion studies on Ca0·5+x/2Sr0·5+x/2Zr4P6−2x Si2x O24 system prepared by co-precipitation method

We report on the synthesis, microstructure and thermal expansion studies on Ca_0·5?+?x/2Sr_0·5?+?x/2Zr₄P_6???2x Si_2x O₂₄ (x = 0·00 to 1·00) system which belongs to NZP family of low thermal expansion ceramics. The ceramics synthesized by co-precipitation method at lower calcination and the sintering temperatures were in pure NZP phase up to x = 0·37. For x ≥ 0·5, in addition to NZP phase, ZrSiO₄ and Ca₂P₂O₇ form as secondary phases after sintering. The bulk thermal expansion behaviour of the members of this system was studied from 30 to 850 °C. The thermal expansion coefficient increases from a negative value to a positive value with the silicon substitution in place of phosphorous and a near zero thermal expansion was observed at x = 0·75. The amount of hysteresis between heating and cooling curves increases progressively from x = 0·00 to 0·37 and then decreases for x > 0·37. The results were analysed on the basis of formation of the silicon based glassy phase and increase in thermal expansion anisotropy with silicon substitution.     

Nanostructured Ce1−xZrxO2 solid solutions produced by mechanochemical processing

The nanostructured Ce_1−xZr_xO₂ solid solutions (x ≤ 0.2) have been successfully synthesized from CeCl₃–ZrCl₄–NaOH mixtures by mechanochemical processing as a gradual transformation, involving in-situ CeO₂ and amorphous ZrO₂ formation as intermediates. Solid solutions type-Ce_1−xZr_xO₂ along with NaCl as diluent were obtained at different milling times, with a final composition of Ce_0.8Zr_0.2O₂ after 5 h and 15 h under high and low energetic milling conditions, respectively. The NaCl formed during the mechanochemical reaction, which is eliminated by washing after calcination of the as-milled sample, allows to obtain a Ce_0.8Zr_0.2O₂ solid solution with high surface area and nanometric grains. The nanostructured Ce_0.8Zr_0.2O₂ solid solution shows good thermal stability after prolonged heating at 600 °C. However, the addition of an extra amount of diluent during mechanochemical reaction evidences a detrimental effect, avoiding the formation of solid solution or deteriorating the textural/microstructuctural characteristics of the obtained Ce_1−xZr_xO₂ solid solution. Removal of NaCl previous to calcination improves notably the textural/microstructural characteristics of the Ce_0.8Zr_0.2O₂ solid solution.     

Sol–Gel Synthesis and Distinctive Structural Features of Ce<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> Solid Solutions

We have synthesized Ce_xZr_1–xO₂ solid solutions via the thermal decomposition of xerogels of different compositions prepared by drying appropriate hydrosols. The synthesized materials have been characterized by thermal analysis, X-ray diffraction, and Raman spectroscopy. The results demonstrate that the solid solutions are formed at relatively low temperatures (450–600°C). The Ce_xZr_1–xO₂ samples with x = 0.5–0.9 consist of a cubic solid solution. At a lower CeO₂ content (x = 0.2), the material consists of a mixture of cubic and tetragonal phases.     

Structure and thermal conductivity of Gd2(TixZr1 − x)2O7 ceramics

The Gd₂(Ti_xZr_1 − x)₂O₇ (x = 0, 0.25, 0.50, 0.75, 1.00) ceramics were synthesized by solid state reaction at 1650 °C for 10 h in air. The relative density and structure of Gd₂(Ti_xZr_1 − x)₂O₇ were analyzed by the Archimedes method and X-ray diffraction. The thermal diffusivity of Gd₂(Ti_xZr_1 − x)₂O₇ from room temperature to 1400 °C was measured by a laser-flash method. The Gd₂Zr₂O₇ has a defect fluorite-type structure; however, Gd₂(Ti_xZr_1 − x)₂O₇ (0.25 ≤ x ≤ 1.00) compositions exhibit an ordered pyrochlore-type structure. Gd₂Zr₂O₇ and Gd₂Ti₂O₇ are infinitely soluable. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ increases with increasing Ti content under identical temperature conditions. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ first decreases gradually with the increase of temperature below 1000 °C and then increases slightly above 1000 °C. The thermal conductivity of Gd₂(Ti_xZr_1 − x)₂O₇ is within the range of 1.33 to 2.86 W m^− 1 K^− 1 from room temperature to 1400 °C.     

Synthesis,sintering and thermal expansion of Ca1-x Sr x Zr4P6O24 — an ultra-low thermal expansion ceramic system

Ca_1-x Sr _x Zr₄P₆O₂₄ (O × 1.0) system which belongs to a new large family of low thermal expansion materials known as NZP or CTP, was synthesized by the solid state and the sol-gel methods. The conventional sol-gel method was modified by introducing a seeding step which resulted in significant improvement in the sintering characteristics and the microstructure of the sintered material. Sintering data were compared with those obtained by the powder mixing technique. Thermal expansion of the sintered samples was measured by classical dilatometry and by high-temperature X-ray diffractometry. It was found that CaZr₄P₆O₂₄ (x= 0) and SrZr₄P₆O₂₄ (x= 1) phases had opposite anisotropies in their respective axial thermal expansions. This behaviour led to the development of a crystalline solution composition of nearly zero expansion characteristic. Microstructures of the sintered specimens were examined by scanning electron microscopy.     

Ultralow thermal conductivity of cerium-doped Nd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> over a wide doping range

In this paper, we report an ultralow thermal conductivity and a high-temperature phase stability of the (Nd_1?x Ce _x )₂Zr₂O_7+x system over the temperature range from room temperature to 1600 °C and over a wide composition range (0.2 ≤ x ≤ 0.8), and the (Nd_1?x Ce _x )₂Zr₂O_7+x system is therefore considered a strong candidate material for the fabrication of next-generation high-temperature thermal barrier coatings. The observed thermal conductivities (0.65–1.0 W/mK) are about 60–40% lower than those of undoped Nd₂Zr₂O₇ over the same temperature range (100–700 °C) and indicate a glass-like behavior. For comparison, the variation in the thermal conductivity with the temperature of the (Gd_1?x Ce _x )₂Zr₂O_7+x system with similar point defects was also measured, and the observed behavior was almost the same as that of undoped Gd₂Zr₂O₇ and was mostly determined by phonon–phonon scattering (λ ∝ 1/T). The effect of point defect scattering and strong phonon scattering sources (rattlers) on the thermal conductivity is also discussed in this paper. The results of this study suggest that the ultralow thermal conductivity of (Nd_1?x Ce _x )₂Zr₂O_7+x can be attributed to the presence of rattlers because of the large difference between the ionic radii of the Nd³⁺ and Ce⁴⁺ ions.     

Synthesis, structure and oxygen-storage capacity of Pr1−xZrxO2−δ and Pr1−x−yPdyZrxO2−δ

Nanocrystalline Pr_1−xZr_xO_2−δ (0 ≤ x ≤ 1) and Pr_1−x−yPd_yZr_xO_2−δ (x = 0.50, y = 0.02) solid solutions have been synthesized by a single step solution combustion method. The whole range of solid solution compositions crystallize in cubic fluorite structure. The lattice parameter ‘a’ linearly varied up to x = 1.0. Oxygen-storage capacity (OSC) and redox properties of Pr_1−xZr_xO_2−δ (0.0 ≤ x ≤ 0.8) solid solutions have been investigated by temperature-programmed reduction (TPR) and are compared with those of Ce_1−xZr_xO₂. Pr_1−xZr_xO_2−δ exhibited H₂ uptake and CO oxidation at a lower temperature than Ce_1−xZr_xO₂. Small amount of Pd ion (y = 0.02) substitution was found to bring down the temperature of oxygen release-storage significantly.     

Rare-earth-doped PbTiO<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions

(Pb_{1 ? x} Ln _x )(Zr_0.53Ti_0.47)O₃ and (Pb_{1 ? x} Ln _x )(Zr_0.65Ti_0.35)O₃ (x = 0.02, 0.06; Ln = La, Pr, Gd, Yb) solid solutions have been prepared by modified solid-state synthesis using organic-ligand precursors. The solid solutions have been characterized by thermal analysis, IR spectroscopy, x-ray powder diffraction, and atomic force microscopy. All of them have a rhombohedrally distorted perovskite structure (sp. gr. R3c).     

Preparation and thermophysical properties of (NdxGd1?x)2Zr2O7 ceramics

Ceramic powders of (Nd _x Gd_1−x )₂Zr₂O₇ (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0) were synthesized by chemical-coprecipitation followed by calcination method, and were then pressureless-sintered at 1,600 °C for 10 h in air. Phase constituents and morphologies of the synthesized powders and sintered ceramics were identified by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A high-temperature dilatometer and a laser-flash method were used to analyze the thermal expansion coefficient and thermal diffusion coefficient of different ceramics from room temperature up to 1,400 °C. Thermal conductivity was calculated from thermal diffusivity, density, and specific heat. (Nd _x Gd_1−x )₂Zr₂O₇ (0.1 ≤ x ≤ 1.0) ceramics are with a pyrochlore-type structure; however, pure Gd₂Zr₂O₇ exhibits a defective fluorite-type structure. The average linear thermal expansion coefficients of different (Nd _x Gd_1−x )₂Zr₂O₇ ceramics decrease with increasing the value of x from 0 to 1.0 in the temperature range of 25–1,400 °C. The thermal conductivities of (Nd _x Gd_1−x )₂Zr₂O₇ ceramics are located within the range of 1.33 to 2.04 W m⁻¹ K⁻¹ from room temperature to 1,400 °C.     

Preparation and Thermal Expansion of Calcium Iron Zirconium Phosphates with the NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> Structure

Ca_{0.5(1 + x)}Zr_2–xFe _x (PO₄)₃ phosphates have been synthesized by a sol–gel process. The individual compounds and solid solutions obtained crystallize in the NaZr₂(PO₄)₃ structure (trigonal symmetry, sp. gr. R\(\bar 3\)). Using high-temperature X-ray diffraction, we have determined their thermal expansion parameters in the temperature range from 25 to 800°C. With increasing x, the magnitudes of their linear thermal expansion coefficients and thermal expansion anisotropy decrease. Most of the synthesized phosphates can be rated as low-thermal-expansion compounds and can be regarded as materials capable of withstanding thermal “stress.”     

Synthesis and sintering of Ca0.5Zr2P3O12 -a low thermal expansion material

The single phase compound Ca_0.5Zr₂P₃O₁₂ (CZP) was prepared by solid state reaction technique. This material shows a negative thermal expansion in the temperature region of 30°–500°C. The effect of MgO and ZnO addition on the sintering behavior and thermal expansion characteristics of Ca_0.5Zr₂P₃O₁₂ was investigated. Mg₃(PO₄)₂ and Zn₃(PO₄)₂ were observed as minor phases responsible for improving the overall thermal expansion of CZP + MgO, ZnO systems. SEM studies and density data are also discussed. Observed sintering kinetics suggest that a liquid phase is promoting the sintering reaction. 98+% of theoretical density and near zero expansion behavior in certain compositions were observed.     

Thermal expansion behaviour of barium and strontium zirconium phosphates

Ba_1.5-xSr_xZr₄P₅SiO₂₄ compounds withx = 0, 0.25, 0.5, 0.75, 1.0, 1.25 and 1.5, belonging to the low thermal expansion NZP family were synthesized by the solid state reaction method. The XRD pattern could be completely indexed with respect to space group indicating the ordering of vacancy at the divalent cation octahedral sites. The microstructure and bulk thermal expansion coefficient from room temperature to 800°C of the sintered samples have been studied. All the samples show very low coefficient of thermal expansion (CTE), withx = 0 samples showing negative expansion. A small substitution of strontium in the pure barium compound changes the sign of CTE. Similarly,x = 1.5 sample (pure strontium) shows a positive CTE and a small substitution of barium changes its sign.X = 1.0 and 1.25 samples have almost constant CTE over the entire temperature range. The low thermal expansion of these samples can be attributed to the ordering of the ions in the crystal structure of these materials     

Thermal stabilization of aluminium titanate and properties of aluminium titanate solid solutions

Aluminium titanate has a near zero thermal expansion coefficient (=0.8×10^–6 °C^–1) in the range 20 to 1000 °C, nevertheless it decomposes below 1200 °C.The thermal stabilization of Al₂TiO₅ without altering its thermal expansion has been considered by partial substitution in the structure compound of Al³⁺ ions by Fe³⁺ ions.The solid solutions prepared by solid state reaction are in agreement with the general formula Al(1–x)₂Fe_2x TiO₅(0<x<0.2)The iron ions present in the crystal structure of Al₂TiO₅ act on its lattice parameters and bring about a catalytic effect in the formation of materials.Solid solutions show a strong thermal stability and a thermal expansion coefficient specially for the solid solution (x=0.1) which is not far from the Al₂TiO₅ value even after annealing for 300 h at 1000 °C.The mechanical properties of such materials corresponding to that solid solution present strength values lower than Al₂TiO₅ ones. After annealing, however, these are improved later due to a microcrystallization.     

Thermal expansion and isothermal compressibility of TlGaSe<Subscript>2(1 −<Emphasis Type="Italic">x</Emphasis>)</Subscript>S<Subscript>2<Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">x</Emphasis> = 0.1, 0.2)

The temperature dependences of the thermal expansion coefficient and isothermal compressibility for TlGaSe_{2(1 ? x)}S_2x (x = 0.1, 0.2) solid solutions show an anomaly attributable to a second-order phase transition. The thermal expansion data have been used to evaluate the Debye characteristic temperature Θ, rms atomic displacement, and specific heat difference of the solid solutions.     

Combustion synthesis and properties of nanostructured ceria-zirconia solid solutions

Nanostructured ceria-zirconia solid solutions (Ce_{1 − x}Zr_xO₂, x = 0 to 0.9) have been synthesized by a single step solution combustion process using cerous nitrate, zirconyl nitrate and oxalyl dihydrazide (ODH) / carbohydrazide (CH). The as-synthesized powders show extensive XRD line broadening and the crystallite sizes calculated from the XRD line broadening are in the nanometer range (6–11 nm). The combustion derived ceria zirconia solid solutions have high surface area in the range of 36–120 m²/g. Calcination of Ce_{1 −x}Zr_xO₂ at 1350 °C showed three distinct solid solution regions: single phase cubic (x ≤ 0.2), biphasic cubic-tetragonal (0.2 < x 0&#x030C;.8) and tetragonal (x > 0.8). When x ≥ 0.9, the metastable tetragonal phase formed transforms to monoclinic phase on cooling after calcination above 1100 °C. The homogeneity of Ce_{1 − x}Zr_xO₂ has been confirmed by EDAX analysis. The Temperature Programmed Reduction (TPR) measurement of Ce_0.5Zr_0.5O₂ was carried out with H₂ and the TPR profile showed two water formation peaks corresponding to the utilization of surface and bulk oxygen.     

Black nanocrystalline cubic zirconia: Manganese-stabilized c-ZrO2 prepared via the sol–gel method

Nanostructured manganese-stabilized cubic zirconia (MnSZ) powders, solid solutions of Zr_1−xMn_xO_2−yx = 0, 0.03, 0.06 and 0.09, were obtained via the sol–gel method. The doped phases crystallized at 500 °C into black cubic nanocrystalline zirconia.