Structural-phase state and lasing of 5–15 at% Yb3+:Y3Al5O12 optical ceramics

Yttrium aluminum garnet (Yb³⁺:Y₃Al₅O₁₂) laser ceramics doped by 5, 10 and 15 at% of ytterbium ions were obtained by reactive sintering. Optimal sintering temperature range for the formation of highly-dense transparent Yb³⁺:Y₃Al₅O₁₂ ceramics under normal recrystallization conditions was found to be T = 1750–1800 °C. The influence of Yb³⁺ ions on structural-phase state, phase composition, microstructure, optical and luminescent properties of sintered samples was experimentally investigated. It was shown that lattice parameter a of Yb³⁺:Y₃Al₅O₁₂ ceramics decreases linearly with increasing of Yb³⁺ concentration in a good agreement with L. Vegard’s rule, that indicates to the formation of (Y_1−xYb_x)₃Al₅O₁₂ (х = 0.05–0.15) substitutional solid solutions. No concentration quenching of Yb³⁺ luminescence was observed in Yb³⁺:Y₃Al₅O₁₂ within the 5–15 at% doping range. Quasi-CW lasing of Yb³⁺:Y₃Al₅O₁₂ ceramics was studied under diode-pumping at 970 nm. A highest slope efficiency of about 50% was obtained for 15 at%-doped Yb³⁺:Y₃Al₅O₁₂ ceramics sintered at T = 1800 °C for 10 h.     

The influence of Gd doping on thermophysical properties,elasticity modulus and phase stability of garnet-type (Y1-xGdx)3Al5O12 ceramics

In this work, Gd³⁺ was selected to partially substitute the Y³⁺ in yttrium aluminum garnet (YAG) in order to improve the thermophysical properties of YAG. A series of (Y_1-xGd_x)₃Al₅O₁₂ (x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were synthesized through chemical co-precipitation route. The microstructure, thermophysical properties and elasticity modulus of (Y_1-xGd_x)₃Al₅O₁₂ were investigated. The (Y_1-xGd_x)₃Al₅O₁₂ ceramics was comprised of single garnet-type Y₃Al₅O₁₂ phase. The thermal conductivities of (Y_1-xGd_x)₃Al₅O₁₂ bulk samples decreased with increasing doping concentration to 0.2, but increased with furthering increasing the concentration to 0.4. The thermal conductivity of (Y_0.8Gd_0.2)₃Al₅O₁₂ was 1.51 W m⁻¹ K⁻¹ at 1200 °C. The average thermal expansion coefficient of (Y_0.8Gd_0.2)₃Al₅O₁₂ was slightly larger than that of Y₃Al₅O₁₂. (Y_0.8Gd_0.2)₃Al₅O₁₂ bulk sample exhibited the lowest elasticity modulus among the investigated (Y_1-xGd_x)₃Al₅O₁₂. In addition, (Y_0.8Gd_0.2)₃Al₅O₁₂ ceramic remained good phase stability from room temperature to 1600 °C.     

Oxygen ionic transport in SrFe1−yAlyO3−δ and Sr1−xCaxFe0.5Al0.5O3−δ ceramics

The oxygen permeability of mixed-conducting Sr_1−xCa_xFe_1−yAl_yO_3−δ (x=0–1.0; y=0.3–0.5) ceramics at 850–1000 °C, with an apparent activation energy of 120–206 kJ/mol, is mainly limited by the bulk ionic conduction. When the membrane thickness is 1.0 mm, the oxygen permeation fluxes under pO₂ gradient of 0.21/0.021 atm vary from 3.7×10⁻¹⁰ mol s⁻¹ cm⁻² to 1.5×10⁻⁷ mol s⁻¹ cm⁻² at 950 °C. The maximum solubility of Al³⁺ cations in the perovskite lattice of SrFe_1−yAl_yO_3−δ is approximately 40%, whilst the brownmillerite-type solid solution formation range in Sr_1−xCa_xFe_0.5Al_0.5O_3−δ system corresponds to x>0.75. The oxygen ionic conductivity of SrFeO₃-based perovskites decreases moderately on Al doping, but is 100–300 times higher than that of brownmillerites derived from CaFe_0.5Al_0.5O_2.5+δ. Temperature-activated character and relatively low values of hole mobility in SrFe_0.7Al_0.3O_3−δ, estimated from the total conductivity and Seebeck coefficient data, suggest a small-polaron mechanism of p-type electronic conduction under oxidising conditions. Reducing oxygen partial pressure results in increasing ionic conductivity and in the transition from dominant p- to n-type electronic transport, followed by decomposition. The low-pO₂ stability limits of Sr_1−xCa_xFe_1−yAl_yO_3−δ seem essentially independent of composition, varying between that of LaFeO_3−δ and the Fe/Fe_1−γO boundary. Thermal expansion coefficients of Sr_1−xCa_xFe_1−yAl_yO_3−δ ceramics in air are 9×10⁻⁶ K⁻¹ to 16×10⁻⁶ K⁻¹ at 100–650 °C and 12×10⁻⁶ K⁻¹ to 24×10⁻⁶ K⁻¹ at 650–950 °C. Doping of SrFe_1−yAl_yO_3−δ with aluminum decreases thermal expansion due to decreasing oxygen nonstoichiometry variations.     

Improved dielectric properties and grain boundary response of SrTiO3 doped Y2/3Cu3Ti4O12 ceramics fabricated by Sol-gel process for high-energy-density storage applications

A chemical solution processing method based on sol-gel chemistry (SG) was used to synthesize (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.25) ceramics successfully. The 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics sintered at 1050 °C for 20 h showed fine-grained microstructure and high dielectric constant (ε′ ≈ 1.7 × 10⁵) at 1 kHz. Furthermore, the 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics appeared distinct pseudo-relaxor behavior. Two electrical responses were observed in the combined modulus and impedance plots, indicating the presence of Maxwell-Wagner relaxation. Sr vacancies and additional oxygen vacancies had substantial contribution to the sintering behavior, an increase in grain growth, and relaxation behaviors in grain boundaries. The contributions of semiconducting grains with the nanodomain and insulating grain boundaries (corresponding to high-frequency and low-frequency electrical response, respectively) played important roles in the dielectric properties of (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ ceramics. The occurrence of the polarization mechanism transition from the grain boundary response to the electrode one with temperature change was clearly evidenced in the low frequency range.     

Sintering of Yb3+:Y2O3 transparent ceramics in hydrogen atmosphere

Highly transparent Yb³⁺:Y₂O₃ ceramics with doping concentration up to 40.0 at.% had been fabricated successfully via hydrogen atmosphere sintering, where the raw powders were synthesized by co-precipitation method. The sintering temperature is about 600 °C lower than its melting temperature. SEM investigation revealed the average grain size of Yb³⁺:Y₂O₃ ceramics sintered at 1850 °C for 9 h was about 7 μm. The highest transmittance of as-prepared 1 mm thickness samples around wavelength of 1050 nm reached 80%, which is close to the theoretical value of Y₂O₃. The optical spectroscopic properties of Yb³⁺:Y₂O₃ transparent ceramics have also been investigated, which shows that it is a very good laser material for diode laser pumping and short pulse mode-locked laser.     

Electronic conductivity,oxygen permeability and thermal expansion of Sr0.7Ce0.3Mn1−xAlxO3−δ

The maximum solubility of aluminum cations in the perovskite lattice of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ is approximately 15%. The incorporation of Al³⁺ increases oxygen ionic transport due to increasing oxygen nonstoichiometry, and decreases the tetragonal unit cell volume and thermal expansion at temperatures above 600 °C. The total conductivity of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ (x = 0–0.2), predominantly electronic, decreases with aluminum additions and has an activation energy of 10.2–10.9 kJ/mol at 350–850 °C. Analysis of the electronic conduction and Seebeck coefficient of Sr_0.7Ce_0.3Mn_0.9Al_0.1O_3−δ, measured in the oxygen partial pressure range from 10⁻¹⁸ to 0.5 atm at 700–950 °C, revealed trends characteristic of broad-band semiconductors, such as temperature-independent mobility. The temperature dependence of the charge carrier concentration is weak, but exhibits a tendency to thermal excitation, whilst oxygen losses from the lattice have an opposite effect. The role of the latter factor becomes significant at temperatures above 800 °C and on reducing p(O₂) below 10⁻⁴ to 10⁻² atm. The oxygen permeability of dense Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ (x = 0–0.2) membranes, limited by both bulk ionic conduction and surface exchange, is substantially higher than that of (La, Sr)MnO₃-based materials used for solid oxide fuel cell cathodes. The average thermal expansion coefficients of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ ceramics in air are (10.8–11.8) × 10⁻⁶ K⁻¹.     

Dielectric and thermal properties of AlN ceramics

The effects of slow-cooling and annealing conditions on dielectric loss, thermal conductivity and microstructure of AlN ceramics were investigated. Y₂O₃ from 0.5 to 1.25 mol% at 0.25% increments was added as a sintering additive to AlN powder and pressureless sintering was carried out at 1900 °C for 2 h in a nitrogen flowing atmosphere. To improve the properties, AlN samples were slow-cooled at a rate of 1 °C min⁻¹ from 1900 to 1750 °C, subsequently cooled to 970 °C at a rate of 10 °C min⁻¹ and then annealed at the same temperature for 4 h. AlN and YAG (5Al₂O₃/3Y₂O₃) were the only identified phases from XRD. AlN doped with 0.5 and 0.75 mol% Y₂O₃ had a low loss of <2.0 × 10⁻³ and a high thermal conductivity of >160 W m⁻¹ °C⁻¹.     

Annealing effect on dielectric property of AlN ceramics

Effects of slow-cooling at high temperatures and annealing at intermediate temperatures on dielectric loss tangent of AlN ceramics were explored. Y₂O₃ was added as a sintering additive to AlN powders, and the powders were pressureless-sintered at 1900 °C for 2 h in a nitrogen flow atmosphere. In succession to the sintering, AlN samples were slow-cooled at a rate of 1 °C/min from 1900 to 1750 °C and/or annealed at 970 °C for 4 h. Al₅Y₃O₁₂ was detected in the AlN ceramics obtained by the slow-cooling and AlYO₃ was found in the ceramics cooled at a rate of 30 °C/min. AlN ceramics with a relative density of 0.986 were obtained by the slow-cooling method. On the other hand, very low tan δ values between 2.6 and 4.6 × 10⁻⁴ were obtained when the AlN ceramics were annealed at 970 °C for 4 h.     

Synthesis of BaCeO3 and BaCe0.9Y0.1O3−δ from mixed oxalate precursors

An oxalate precipitation route is proposed for the synthesis of BaCe_1−xY_xO₃ (x = 0 and 0.1) after calcination at 1100 °C. The precipitation temperature (70 °C) was a determinant parameter for producing a pure perovskite phase after calcination at 1100 °C for 1 h. TG/DTA measurements showed that the co-precipitated (Ba, Ce and Y) oxalate had a different thermal behaviour from single oxalates. Despite a simple grinding procedure, sintered BaCe_0.9Y_0.1O_3−δ pellets (1400 °C, 48 h) presented 90.7% of relative density and preliminary impedance measurements showed an overall conductivity of around 2 × 10⁻⁴ S cm⁻¹ at 320 °C.     

Correlations among sintering temperature,shrinkage, and open porosity of 3.5 YSZ/Al2O3 composites

Slip-cast ceramic samples of the system (100−x) (ZrO₂–3.5 mol% Y₂O₃)–xAl₂O₃ (abridged as (100−x) 3.5 YSZ/xAl₂O₃ composite, where x is expressed in wt%) were examined using dilatometry, isothermal sintering and electron microscopy methods. The shrinkage in the range 1100–1300 °C was found to be higher for the (100−x) 3.5 YSZ/xAl₂O₃ samples with prevailing fraction of PSZ than for the composites with a corundum matrix. When the weight fraction of corundum was increased, the relative shrinkage of the (100−x) 3.5 YSZ/xAl₂O₃ samples decreased and the open porosity of the ceramic materials grew. The effect of <gamma>-Al₂O₃ impurity on the sintering process and linear dimensions of ceramics is shown. Heat treatment of (50–40) 3.5 YSZ/(50–60) Al₂O₃ composites at 1300 °C are proposed as the optimum conditions for porous diaphragm formation.     

Preparation and ionic conduction of CaZr1−xScxO3−α ceramics

A series of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) perovskite oxide ceramics were successfully fabricated at 1400 °C for 10 h and then further sintered at 1650 °C for 10 h via a solid-state reaction sintering process. Conductivities of the ceramics were measured under the atmosphere that contains 1% H₂/Ar and 5.63 kPa H₂O/Ar by the electrochemical impedance spectra technique. It was found that the conductivities of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) ceramics increased with the increase of the measuring temperature, and the conductivity achieved its maximum value of 2.03×10⁻⁵–6.5×10⁻³ S cm⁻¹ when the doping amount of Sc (x) was 0.10. Additionally, element doping can increase the conductivities and decrease the conductivity activation energies of CaZr_1−xSc_xO_3−α ceramics. The results of transport number measurement indicated that the CaZr_0.9Sc_0.1O_3−α is almost a pure protonic conductor at 500–750 °C, while it is a mixed protonic-oxygen ionic-electronic conductor at 750–1300 °C.     

Effect of Al2O3 on the structure and microwave dielectric properties of Ca0.7Ti0.7La0.3Al0.3O3

The effect of excess Al₂O₃ on the densification, structure and microwave dielectric properties of Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) was investigated. CTLA ceramics were prepared using the conventional mixed oxide route. Excess Al₂O₃ in the range of 0.1–0.5 wt% was added. It was found that Al₂O₃ improved the densification. A phase rich in Ca and Al was found in the microstructure of Al₂O₃ doped samples. Additions of Al₂O₃ coupled with the slow cooling after sintering improved the microwave dielectric properties. CTLA ceramics with 0.25 wt% Al₂O₃ cooled at 5 °C/h showed high density and a uniform grain structure with ɛ_r = 46, Q × f = 38,289 and τ_f = +12 ppm/°C at 4 GHz. XRD and TEM examinations showed the presence of (1 1 2) and (1 1 0) type twins arising from a⁻a⁻c⁺ tilt system with the presence of anti-phase domain boundaries from the displacement of A-site cations of the orthorhombic perovskite structure.     

Influence of ytterbium- and samarium-oxides codoping on structure and thermal conductivity of zirconate ceramics

To increase operating temperature and improve performance of gas-turbine engines, it is urgently needed to develop new thermal barrier oxides with a lower thermal conductivity than 6–8 wt.% yttria-stabilized zirconia. (Yb_xSm_1?x)₂Zr₂O₇ (0 ≤ x ≤ 1.0) ceramics were synthesized by pressureless-sintered at 1700 °C for 10 h in air. The relative density, phase structure, morphology and thermal diffusivity coefficients of (Yb_xSm_1?x)₂Zr₂O₇ ceramics were investigated by the Archimedes method, X-ray diffraction, scanning electron microscopy and laser-flash method. Sm₂Zr₂O₇ and (Yb_0.1Sm_0.9)₂Zr₂O₇ ceramics exhibit a pyrochlore structure, while (Yb_xSm_1?x)₂Zr₂O₇ (0.3 ≤ x ≤1.0) ceramics have a defect fluorite-type structure. The thermal conductivities of (Yb_xSm_1?x)₂Zr₂O₇ ceramics first gradually decrease with increasing temperature, and then increase slightly above 800 °C due to the increased radiation contribution. YbSmZr₂O₇ ceramics have the lowest thermal conductivity over the entire temperature range, which is caused by the reduction of cation mean free path in ytterbium–samarium zirconate system.     

Tb3+/Yb3+ co-doped Y2O3 upconversion transparent ceramics: Fabrication and characterization for IR excited green emission

Tb³⁺/Yb³⁺ co-doped Y₂O₃ transparent ceramics were fabricated by vacuum sintering of the pellets (prepared from nanopowders by uniaxial pressing) at 1750 °C for 5 h. Zr⁴⁺ and La³⁺ ions were incorporated in Tb³⁺/Yb³⁺ co-doped Y₂O₃ nanoparticle to reduce the formation of pores which limits the transparency of ceramic. An optical transmittance of ∼80% was achieved in ∼450 to 2000 nm range for 1 mm thick pellet which is very close to the theoretical value by taking account of Fresnel’s correction. High intensity luminescence peak at 543 nm (green) was observed in these transparent ceramics under 976 and 929 nm excitations due to Yb–Tb energy transfer upconversion.     

Ferroelectric,upconversion emission and optical thermometric properties of color-controllable Er3+-doped Pb(Mg1/3Nb2/3)O3-PbTiO3-Pb(Yb1/2Nb1/2)O3 ferroelectrics

The (0.98-x)(0.6Pb(Mg_1/3Nb_1/3)O₃-0.4PbTiO₃)-xPb(Yb_1/3Nb_1/3)O₃-0.02Pb(Er_1/2Nb_1/2)O₃ ((0.98-x)(PMN-PT)-xPYN:Er³⁺) ceramics were prepared through a solid-state reaction method. The phase structure, piezoelectric response, ferroelectric performance and upconversion emission of the ceramics were systematically investigated. The phase structure, the electrical and optical properties are strongly related to the content of PYN. The optimized piezoelectric response and upconversion emissions of the ceramics were achieved near x = 0.12, which locates in the morphotropic phase boundary (MPB) composition. Furthermore, the temperature sensing behaviors of the resultant compounds based on the thermally coupled levels of ²H_11/2 and ⁴S_3/2 of Er³⁺ ions in the temperature range of 133–573 K were studied by utilizing the fluorescence intensity ratio technique. Additionally, the thermal effect, which is induced by the laser pump power, of the studied ceramics is also investigated and the produced temperature is enhanced from 268 to 348 K with the pump power rising from 109 to 607 mW.     

Synthesis and characterization of yttrium and ytterbium silicates from their oxides and an oligosilazane by the PDC route for coating applications to protect Si3N4 in hot gas environments

Environmental barrier coatings are required to protect Si₃N₄ against hot gas corrosion and enable its application in gas turbines, among which yttrium and ytterbium silicate-coatings stand out. Thus, the polymer-derived ceramic route was used to synthesize these silicates for basic investigations regarding their intrinsic properties from a mixture of Y₂O₃ or Yb₂O₃ powders and the oligosilazane Durazane 1800. After pyrolysis above 1200 °C in air, the silicates are predominant phases. The corrosion behaviour of the resulting composites was tested at 1400 °C for 80 h in moist environments. The material containing x₂-Yb₂SiO₅ and Yb₂Si₂O₇ undergoes the lowest corrosion rate (−1.8 μg cm⁻² h⁻¹). Finally, the processing of Y₂O₃/Durazane 1800 as well-adherent, crack-free and thick (40 μm) coatings for Si₃N₄ was achieved after pyrolysis at 1400 °C in air. The coating consisted of an Y₂O₃/Y₂SiO₅ top-layer and an Y₂O₃/Y₂Si₂O₇ interlayer due to the interaction of the coating system with the substrate.     

Phase,microstructure and ferroelectric properties of new complex-structured ferroelectric ceramics in the PZT–SBN system

This study aimed to fabricate and characterize new complex-structured ceramics with formula (1-x)Pb(Zr_0.52Ti_0.48)O₃–xSrBi₂Nb₂O₉ or (1-x)PZT–xSBN (where x=0, 0.1, 0.3 and 0.5 weight fraction). The ceramics were prepared by a solid-state mixed-oxide method and sintered at temperatures between 1000 and 1250 °C. Optimum sintering temperature for this system was found to be 1050 °C for 3 h dwell time. X-ray diffraction patterns of (1-x)PZT–xSBN powders showed peak intensities of two-phase mixture corresponding to the relative amount of each phase as a result of SBN addition. Microstructure of (1-x)PZT–xSBN ceramics showed a variation in grain shape and grain size. The small addition of SBN (x=0.1) was also found to improve ferroelectric properties of pure PZT ceramic.     

Effects of Yb and Sc co-doping on the thermal properties and CMAS corrosion of garnet-type (Y3-xYbx)(Al5-xScx)O12 ceramics

Thermal barrier coatings with excellent thermal performance and corrosion resistance are essential for improving the performance of aero-engines. In this paper, (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ (x = 0, 0.1, 0.2, 0.3) thermal barrier coating materials were synthesized by a combination of sol-gel method and ball milling refinement method. The thermal properties of the (Y_3-xYb_x)(Al_5-xSc_x)O₁₂ ceramics were significantly improved by increasing Yb and Sc doping content. Among designed ceramics, (Y_2.8Yb_0.2)(Al_4.8Sc_0.2)O₁₂ (YS-YAG) showed the lowest thermal conductivity (1.58 Wm^?1K^?1, at 800 °C) and the highest thermal expansion coefficient (10.7 × 10^?6 K^?1, at 1000 °C). In addition, calcium-magnesium- aluminum -silicate (CMAS) corrosion resistance of YS-YAG was further investigated. It was observed that YS-YAG ceramic effectively prevented CMAS corrosion due to its chemical inertness to CMAS as well as its unique and complex structure. Due to the excellent thermal properties and CMAS corrosion resistance, YS-YAG is considered to be prospective material for thermal barrier coatings.     

High-temperature conductivity,stability and redox properties of Fe3−xAlxO4 spinel-type materials

Iron-based oxides are considered as promising consumable anode materials for high temperature pyroelectrolysis. Phase relationships, redox stability and electrical conductivity of Fe_3?xAl_xO₄ spinels were studied at 300–1773 K and p(O₂) from 10^?5 to 0.21 atm. Thermogravimetry/XRD analysis revealed metastability of the sintered ceramics at 300–1300 K. Low tolerance against oxidation leads to dimensional changes of ceramics upon thermal cycling. Activation energies of the total conductivity corresponded to the range of 16–26 kJ/mol at 1450–1773 K in Ar atmosphere. At 1573–1773 K and p(O₂) ranging from 10^?5 to 0.03 atm, the total conductivity of Fe_3?xAl_xO₄ is nearly independent of the oxygen partial pressure. The conductivity values of Fe_3?xAl_xO₄ (0.1 ≤ x ≤ 0.4) at 1773 K and p(O₂) ～10^?5 to 10^?4 atm were found to be only 1.1–1.5 times lower than for Fe₃O₄, showing high potential of moderate aluminium additions as a strategy for improvement of refractoriness for magnetite without significant deterioration of electronic transport.     

Colossal dielectric permittivity and electrical properties of the grain boundary of Ca1−3x/2YbxCu3−yMgyTi4O12 (x=0.05, y=0.05 and 0.30)

Dielectric properties of Ca_1−3x/2Yb_xCu_3−yMg_yTi₄O₁₂ (x=0.05, y=0.05 and 0.30) prepared using a modified sol–gel method and sintered at 1070 °C for 4 h were investigated. The mean grain sizes of the CaCu₃Ti₄O₁₂ and co-doped Ca_0.925Yb_0.05Cu_3−yMg_yTi₄O₁₂ (y=0.05 and 0.30) ceramics were ≈15.86, ≈3.37, and ≈2.32 μm, respectively. Interestingly, the dielectric properties can be effectively improved by co-doping with Yb³⁺ and Mg²⁺ ions to simultaneously control the microstructure and properties of grain boundaries, respectively. These properties were improved over those of single-doped and un-doped CaCu₃Ti₄O₁₂ ceramics. A highly frequency−independent colossal dielectric permittivity (≈10⁴) in the range of 10²–10⁶ Hz with very low loss tangent values of 0.018–0.028 at 1 kHz were successfully achieved in the co-doped Ca_0.925Yb_0.05Cu_3−yMg_yTi₄O₁₂ ceramics. Furthermore, the temperature stability of the colossal dielectric response of Ca_1−3x/2Yb_xCu_3−yMg_yTi₄O₁₂ was also improved to values of less than ±15% in the temperature range from −70 to 100 °C.