Doping effect of divalent cations on sintering of polycrystalline yttria

The sintering behavior of Y₂O₃ doped with 1 mol% of Ca²⁺, Mg²⁺, Mn²⁺, Ni²⁺, Sr²⁺ or Zn²⁺ was investigated by pressureless sintering in air at a sintering temperature in the range 900–1600 °C. The sintering temperature required for full densification in Y₂O₃ was reduced by 100–400 °C by the cation doping, while undoped Y₂O₃ was densified at 1600 °C. The most effective dopant among the examined cations was Zn²⁺. The grain growth kinetics of undoped and cation-doped Y₂O₃ was described by the parabolic law. The grain boundary mobility of Y₂O₃ was accelerated by doping of the divalent cations. High-resolution transmission electron microscopy (HRTEM) observations and nano-probe X-ray energy dispersive spectroscopy (EDS) analyses confirmed that the dopant cations tended to segregate along the grain boundaries without forming amorphous layers. The improved sinterability of Y₂O₃ is probably related to the accelerated grain boundary diffusion owing to the grain boundary segregation of the dopant cations.     

Effect of Fe2O3 doping on sintering of yttria-stabilized zirconia

This paper reports the effect of Fe₂O₃ doping on the densification and grain growth in yttria-stabilized zirconia (YSZ) during sintering at 1150 °C for 2 h. Fe₂O₃ doped 3 mol% YSZ (3YSZ) and 8 mol% YSZ (8YSZ) coatings were produced using electrophoretic deposition (EPD). For 0.5 mol% Fe₂O₃ doping, both 3YSZ and 8YSZ coatings during sintering at 1150 °C has similar densification. However, a significant grain growth occurred in 8YSZ during sintering, whereas grain size remains almost constant in 3YSZ. XRD results suggest that Fe₂O₃ addition substitutionally and interstitially dissolved into the lattice of 3YSZ and 8YSZ. In addition, colour of 3YSZ and 8YSZ changes differently with doping of Fe₂O₃. A Fe³⁺ ion interstitial diffusion mechanism is proposed to explain the densification and grain growth behaviour in the Fe₂O₃ doped 3YSZ and 8YSZ. A retard grain growth observed in the Fe₂O₃ doped 3YSZ is attributed to Fe³⁺ segregation at grain boundary.     

Effect of cation doping on lattice and grain boundary diffusion in superplastic yttria-stabilized tetragonal zirconia

Lattice diffusion coefficients D_l and grain boundary diffusion D_gb coefficients of hafnium were studied for 0.5 and 1 mol% cation-doped yttria-stabilized tetragonal zirconia at the temperature range from 1283 to 1510 °C. The diffusion profiles were determined by two experimental techniques: secondary ion mass spectroscopy and electron microprobe analysis. Additionally the first principle calculations of the electronic states of Zr⁴⁺, dopant cations and O^2? anions and elastic properties in 3Y-TZP were performed. Superplastic strain rate versus stress and inverse temperature was also measured. For 1 mol% doped samples the significant increase of the grain boundary diffusion and superplastic strain rate was observed. Correlations between the calculated ionic net charges and D_gb indicate that enhancement of D_gb was caused by the reduction of ionic bonding strength between metal cation and oxygen anion in zirconia. The new constitutive equation for superplastic flow of yttria-stabilized tetragonal zirconia ceramics was obtained.     

Diffusion of niobium in yttria-stabilized zirconia and in titania-doped yttria-stabilized zirconia polycrystalline materials

Bulk and grain boundary diffusion of Nb⁵⁺ cations in yttria-stabilized zirconia (YSZ, 8 mol% Y₂O₃–92 mol% ZrO₂) and in titania-doped yttria-stabilized zirconia (Ti–YSZ, 5 mol% TiO₂–8 mol% Y₂O₃–87 mol% ZrO₂) was studied in air in the temperature range from 900 to 1300 °C. Experiments were performed in the B-type kinetic region. Diffusion profiles were determined using the secondary ion mass spectrometry (SIMS). The temperature dependencies of the bulk diffusion coefficient D and the grain boundary diffusion parameter D′δs for both the materials were calculated. The activation energies of these transport processes in YSZ amounts to 258 and 226 kJ mol⁻¹, respectively, and 232 and 114 kJ mol⁻¹ in Ti–YSZ. The results were compared to the diffusion data of other cations previously obtained for the same material.     

Effect of amount of doping agent on sintering,microstructure and optical properties of Zr- and La-doped alumina sintered by SPS

SPS-produced α-alumina samples are prepared from powders doped with different amounts of Zr⁴⁺ and La³⁺ cations. Zr⁴⁺ cations segregate at grain boundaries. m-ZrO₂ particles are formed at 570 but not at 280 cat ppm. A β-alumina LaAl₁₁O₁₈ structure is found at 310 cat ppm when the lanthanum grain boundary solubility limit is exceeded (∼200 cat ppm). 100 cat ppm La is sufficient to block the diffusion path across grain boundaries and inhibit grain growth. Both doping cations disturb the grain boundary diffusion whatever their amount. They delay the densification at higher temperatures while limiting grain growth. The real in-line transmittance (RIT) of α-alumina is improved due to the reduced grain size. Nevertheless, increasing the cation amount leads to an increase in porosity or even the formation of secondary phase particles, both detrimental for optical properties. Finally, optimised amounts of cation of 200 and 150 cat ppm are found for La- and Zr-doped alumina, respectively.     

Phase structure and piezoelectric properties of Ca- and Ba-doped K1/2Na1/2NbO3 lead-free ceramics

Piezoelectric lead-free ceramics, K_1/2Na_1/2NbO₃ (KNN) modified with alkaline-earth (AE) Ca²⁺ and Ba²⁺, have been prepared by the conventional solid-state reaction method. The effect of doping level on sinterability and functional response of KNN was studied. In this way, discs doped with 0 to 2 mol% of Ba²⁺ and Ca²⁺ were sintered at 1125 °C for 2 h. It was observed that AE changed drastically the microstructure and grain size of KNN when it was added in concentrations higher than 0.5 mol%. Addition of 0.5 mol% of Ba²⁺ and Ca²⁺ produced a softening effect in the ferroelectric properties of the material, while samples prepared with higher contents than 0.5 mol% showed poor properties.     

Effects of TiO2 doping on the defect chemistry and thermo-physical properties of Yb2O3 stabilized ZrO2

Yb₂O₃ stabilized ZrO₂ (YbSZ) doped with different TiO₂ contents were produced, and their phase structure, thermal conductivities and thermal expansion coefficients were investigated. A new solid-solution model is proposed, i.e. Ti⁴⁺ would take the interstitial sites when its content is below a critical value (≤2.5 mol%) and then substitute for Zr⁴⁺. The abnormal lattice volume and thermo-physical properties of 2.5 mol% TiO₂ doped YbSZ, and the positive effects of TiO₂ doping on the thermal conductivity at moderate doping level are consistent with the new defect model. However, monoclinic phase is formed when the TiO₂ content reaches to 10 mol% and its content increases with doping content, which have negative influence on the thermo-physical properties. Considering the comprehensive properties, 10 mol% TiO₂ doped YbSZ is considered as a promising thermal barrier coating ceramic.     

Nonisothermal sintering of Mn doped ZnO

The sintering of pure ZnO and ZnO doped with Mn, obtained by addition of Mn(NO₃)₂. 4H₂O in the concentration from 0·1 to 1·2 mol%, was investigated by dilatometry at constant heating rates, from 1 to 15 °C min⁻¹. Mn shifts the onset of the sintering towards higher temperatures, but no significant effect of the Mn doping level on the shrinkage was observed. Accordingly, the calculated activation energy for the first stage, changed from ∼320 kJ mol⁻¹ for pure ZnO to ∼440 kJ mol⁻¹ for Mn doped ZnO. Using classical sintering models to analyse the initial stage sintering of all the compositions, two sintering mechanisms were found to control the initial stage sintering. The first region is identified with a grain boundary sliding mechanism, while volume diffusion is the controlling mechanism in the second region. With the increase of the Mn content, the grain boundary sliding rate remains constant, but the volume diffusion rate is reduced.     

Reduced grain boundary energies in rare-earth doped MgAl2O4 spinel and consequent grain growth inhibition

Grain growth inhibition in MgAl₂O₄ spinel nanostructure was achieved by grain boundary (GB) segregation of rare-earth dopants. Microcalorimetric measurements showed that dense spinel compacts doped with 3 mol% of R₂O₃ (R = Y, Gd, and La) had decreased GB energies as compared to the undoped spinel, representing reduction in the driving force for grain growth. Segregation energies of the three dopants to the Σ3 (111) GB were calculated by atomistic simulation. The dopants with higher ionic radius tend to segregate more strongly to GBs. The GB energies were calculated from atomistic simulation and, consistent with experiments, a systematic reduction in GB energy with dopant ionic size was found. High temperature grain growth experiments revealed a significant reduction of grain growth in the doped nanostructures as compared to the undoped one, which was attributed to increased metastability or possibly also a GB dragging originated from the dopant segregation.     

Improvements in microstructural and mechanical properties of ZrO2 ceramics after addition of BaO

The effects of the addition of BaO on the sinterability, phase balance, microstructure, and mechanical properties of 8 mol% yttria-stabilized cubic zirconia (8YSZ) were investigated using scanning electron microscopy, X-ray diffraction (XRD) analyses, and micro-hardness testing. The 8YSZ powder was doped with 0–15 wt% BaO using a colloidal process. The undoped and BaO-doped 8YSZ specimens were sintered at 1550 °C for 1 h. The XRD analyses results showed that the specimens doped with up to 1 wt% BaO did not exhibit BaO-related peaks, indicating that BaO was completely solubilized in the 8YSZ matrix. However, when more than 1 wt% BaO was added, BaZrO₃-related peaks appeared, suggesting that the overdoped BaO did not dissolve in the 8YSZ matrix but formed a secondary phase of BaZrO₃ at high temperatures. Grain size measurements showed that the grain size of 8YSZ decreased with an increase in the amount of BaO added. The decrease in the grain size was owing to the fact that the grains of BaZrO₃, which precipitated at the grain boundaries and grain junctions of 8YSZ, increased the grain boundary cohesive resistance because of the pinning effect. This resulted in a decrease in the grain boundary mobility, and an increase in the grain boundary energy. Furthermore, while the addition of BaO to 8YSZ caused a slight decrease in the hardness of 8YSZ, the fracture toughness of 8YSZ increased from 1.64 MPa m^1/2 to 2.08 MPa m^1/2, owing to the resulting decrease in the grain size.     

Densification of nanocrystalline Y2O3 ceramic powder by spark plasma sintering

Nanocrystalline Y₂O₃ powders with 18 nm crystallite size were sintered using spark plasma sintering (SPS) at different conditions between 1100 and 1600 °C. Dense specimens were fabricated at 100 MPa and 1400 °C for 5 min duration. A maximum in density was observed at 1400 °C. The grain size continuously increased with the SPS temperature into the micrometer size range. The maximum in density arises from competition between densification and grain growth. Retarded densification above 1400 °C is associated with enhanced grain growth that resulted in residual pores within the grains. Analysis of the grain growth kinetics resulted in activation energy of 150 kJ mol^?1 and associated diffusion coefficients higher by 10³ than expected for Y³⁺ grain boundary diffusion. The enhanced diffusion may be explained by combined surface diffusion and particle coarsening during the heating up with grain boundary diffusion at the SPS temperature.     

Doping behaviors of NiO and Nb2O5 in BaTiO3 and dielectric properties of BaTiO3-based X7R ceramics

Doping behaviors of NiO and Nb₂O₅ in BaTiO₃ in two doping ways and dielectric properties of BaTiO₃-based X7R ceramics were investigated. When doped in composite form, the additions rendered higher solubility than that doped separately due to the identical valence between the complex (Ni_1/3²⁺Nb_2/3⁵⁺)⁴⁺ and Ti⁴⁺. NiO–Nb₂O₅ composite oxide was more effective in broadening dielectric constant peaks which was responsible for the temperature-stability of BaTiO₃ ceramics. A reduction in grain size was observed in the specimens with 0.5–0.8 mol% NiO–Nb₂O₅ composite oxide, whereas the abnormal growth of individual grains took place in the 1.0 mol% NiO–Nb₂O₅ composite oxide-doped specimen. When the specimen of BaTiO₃ doped with 0.8 mol% NiO–Nb₂O₅ composite oxide was sintered at 1300 °C for 1.5 h in air, good dielectric properties were obtained and the requirement of (EIA) X7R specification with a dielectric constant of 4706 and dielectric loss lower than 1.5% were satisfied.     

Influence of doping with various cations on electrical conductivity of apatite-type neodymium silicates

Apatite-type neodymium silicates doped with various cations at the Si site, Nd₁₀Si₅BO_27?δ (B=Mg, Al, Fe, Si), were synthesized via the high-temperature solid state reaction process. X-ray diffraction and complex impedance analysis were used to investigate the microstructure and electrical properties of Nd₁₀Si₅BO_27?δ ceramics. All Nd₁₀Si₅BO_27?δ ceramics consist of a hexagonal apatite structure with a space group P63/m and a small amount of second phase Nd₂SiO₅. Neodymium silicates doped with Mg²⁺ or Al³⁺ cations at the Si site have an enhanced total conductivity as contrasted with undoped Nd₁₀Si₆O₂₇ ceramic at all temperature levels. However, doping with Fe³⁺ cations at the Si site has a little effect on improving the total conductivity above 873 K. The enhanced oxide-ion conductivity in a hexagonal apatite-type structure depends upon the diffusion of interstitial oxide-ion through oxygen vacancies induced by the Mg²⁺ or Al³⁺ substitution to the Si⁴⁺ site and through the channels between the SiO₄ tetrahedron and Nd³⁺ cations. At 773 K, the highest total conductivity is 4.19×10^?5 S cm^?1 for Nd₁₀Si₅MgO₂₆ ceramic. At 1073 K, Nd₁₀Si₅AlO_26.5 silicate has a total conductivity of 1.55×10^?3 S cm^?1, which is two orders of magnitude higher than that of undoped Nd₁₀Si₆O₂₇.     

Constrained sintering of 8 mol% Y2O3 stabilised zirconia films

Constrained sintering kinetics of 8 mol% Y₂O₃/92 mol% ZrO₂ (8YSZ) films approximately 10–15 μm thick screen-printed on dense YSZ substrates, and the resulting stress induced in the films, were measured in the temperature range 1100–1350 °C. The results are compared with those reported earlier for 3YSZ films.Both materials behave similarly, although there are differences in detail. The constrained densification rate was greatly retarded compared with the unconstrained densification rate due to the effect of the constraint on the developing anisotropic microstructure (3YSZ) and, in the case of 8YSZ, considerable grain growth. The stress generated during constrained sintering was typically a few MPa. The apparent activation energies for free sintering, constrained sintering, creep and grain growth are found to cover a wide range (135–670 kJ mol^?1) despite all probably being mainly controlled by grain boundary cation diffusion.     

Synthesis,characterization, and electrical conduction of 10 mol% Dy2O3-doped CeO2 ceramics

Well-densified 10 mol% Dy₂O₃-doped CeO₂ (20DDC) ceramics with average grain sizes of ∼0.12–1.5 μm were fabricated by pressureless sintering at 950–1550 °C using a reactive powder thermally decomposed from a carbonate precursor, which was synthesized via a carbonate coprecipitation method employing nitrates as the starting salts and ammonium carbonate as the precipitant. Electrical conductivity of the ceramics, measured by the dc three-point impedance method, shows a V-shape curve against the average grain size. The sample with the smallest grain size of 0.12 μm exhibits a high conductivity of ∼10^−1.74 S/cm at the measurement temperature of 700 °C, which is about the same conduction level of the micro-grained 10 mol% Sm₂O₃- or Gd₂O₃-doped CeO₂, two leading electrolyte materials.     

Electron trapping of laser-induced carriers in Er-doped SnO2 thin films

In order to investigate optically excited electronic transport in Er-doped SnO₂, thin films are excited with the fourth harmonic of an Nd:YAG laser (266 nm) at low temperature, yielding conductivity decay when the illumination is removed. Inspection of these electrical characteristics aims knowledge for electroluminescent devices operation. Based on a proposed model where trapping defects present thermally activated cross section, the capture barrier is evaluated as 140, 108, 100 and 148 meV for doped SnO₂ thin films with 0.0, 0.05, 0.10 and 4.0 at% of Er, respectively. The undoped film has vacancy levels as dominating, whereas for doped films, there are two distinct trapping centers: Er³⁺ substitutional at Sn⁴⁺ lattice sites and Er³⁺ located at grain boundary.     

The effect of Sm2O3 on the microstructure and electrical properties of SiO2-doped SnO2-Zn2SnO4 ceramic varistors

In this work, Sm₂O₃- and SiO₂-codoped SnO₂-Zn₂SnO₄ ceramic varistors were prepared through traditional ceramic processing, and the effect of Sm₂O₃ on the resulting microstructure and electrical properties was investigated. The results demonstrated that the ceramics were composed mainly of SnO₂ and Zn₂SnO₄, and Sm was distributed homogeneously in the grains and along the grain boundaries. With 0.2 mol% Sm₂O₃ doping, the grain growth was obviously promoted. Further increases in Sm₂O₃ to 0.4 mol% resulted in trace amount of SiO₂ and segregations containing elemental Sm via X-ray diffraction patterns and microstructure photos, respectively. In the sample doped with 0.3 mol% Sm₂O₃, optimal electrical characteristics of α=9.4, E_B=10 V/mm, J_L=46 μA/cm² and ε′=1.2×10⁴ were obtained. Simultaneously, the sample doped with 0.3 mol% Sm₂O₃ had the lowest conductance activation energy of 0.16 eV at temperatures lower than 110 °C. This good performance indicates that Sm₂O₃- and SiO₂-codoped SnO₂-Zn₂SnO₄ composite ceramics are viable candidate for the manufacture of capacitor-varistor functional devices.     

Structural and spectral properties of red light emitting Eu3+ activated TiO2 nanophosphor for white LED application

The structural and luminescent properties of Eu³⁺ doped TiO₂ nanophosphors synthesized by low cost combustion method were investigated. The X-ray diffraction analysis revealed that crystallite size decreases with doping concentration. Lattice volume expansion occurred due to the substitution of Ti⁴⁺ ions by larger ionic radii ions Eu³⁺. FESEM images showed prepared phosphors to be nano size spherical shaped particles. Energy band gap of 3 mol% Eu³⁺ doped samples decreased to 3.15 eV due to doping effect. The Eu³⁺ doped TiO₂ nanophosphors exhibited main red emission peak centered at 616 nm under 395 nm UV light excitation. Concentration quenching was observed at 3 mol% doping, that has been ascribed to dipole-dipole interaction. The covalent nature of Eu-O bond and environment around Eu³⁺ ions were discussed using Judd-Ofelt (J-O) intensity parameters. Internal quantum efficiency was calculated using excited state lifetime ⁵D₀ state of Eu³⁺ ion and J-O theory. The CIE colour coordinates and colour purity were calculated using the spectral energy distribution function. Low excited state life time indicated that Eu³⁺ doped TiO₂ can be used as red emitting phosphor for white light emitting diode applications.     

Improved ionic conductivity in NdGdZr2O7: Influence of Sc3+ substitution

Aliovalent Sc³⁺ doped pyrochlores NdGdZr_2?xSc_xO_7?δ (0.0 ≤ x ≤ 0.15) have been prepared by gel-combustion method followed by high temperature sintering. Detailed structural characterization of these compounds has been carried out using X-ray diffraction and Raman spectroscopy, which together have established the retention of pyrochlore structure of these compositions till x = 0.15 Sc³⁺ incorporation. Both X-ray diffraction and Raman results have also indicated the presence of local lattice distortion with net cell contraction upon Sc³⁺ incorporation in these solid solutions. Micro structural studies have revealed highly dense end products with uniform grain distribution and homogeneous compositions at grain size level. Ionic conductivity characterization of system been carried out from 473 to 573 K. A significant improvement in the total ionic conductivity of this series has been observed which has been explained in terms of additional oxygen vacancies created upon Sc³⁺ incorporation and enhanced lattice disorder.     

Intermediate-temperature conductivity of B-site doped Na0.5Bi0.5TiO3-based lead-free ferroelectric ceramics

Na_0.5Bi_0.5TiO₃ (NBT) based oxide-ion conductor ceramics have great potential applications in intermediate-temperature solid oxide fuel cells (SOFCs) and oxygen sensors. Na_0.5Bi_0.49Ti_1−xMg_xO_3−δ ceramics with x=0, 0.01, 0.02, 0.03, 0.05 and 0.08 were prepared by conventional solid-state reaction. XRD measurement and SEM analysis revealed the formation of pure perovskite structures without secondary phase. MgO doping greatly decreased the sintering temperature and inhibited grain growth. AC impedance spectroscopy measurement was adopted to measure the total conductivity, which was found to increase with MgO doping content ranging from 0 to 3 mol% and subsequently to decrease. High oxygen ionic conductivity σ_t=0.00629 S/cm was achieved for sample doped with 3 mol% MgO at 600 °C in air atmosphere.