Annealing induced discoloration of transparent YAG ceramics using divalent additives in solid-state reaction sintering

Tetraethyl orthosilicate (TEOS) was commonly served as a sintering additive to promote the densification of transparent Y₃Al₅O₁₂ (YAG) ceramics. However, Si⁴⁺ that decomposed from TEOS would restrain the conversion of dopants into a higher valence state (e.g., Cr³⁺ → Cr⁴⁺). In this study, by using divalent sintering additives (CaO and MgO), the colorless and highly transparent YAG ceramics (T = 84.6%, at 1064 nm) were obtained after vacuum sintering at 1840 °C for 8 h and without subsequent annealing in air. An absorption peak centered at ∼320 nm was observed before annealing, and it extended to ∼550 nm after annealing at 1450 °C for 10 h in air. A discoloration phenomenon occurred and more scattering centers were observed with the formation of new [Mg/Ca²⁺F⁺] color centers. Air annealing did not improve the optical quality of the as-fabricated YAG ceramics with divalent dopants as sintering additives, owing to the formation of scattering centers.     

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.     

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.     

Structural,thermal and mechanical properties of aluminum nitride ceramics with CeO2 as a sintering aid

AlN ceramics have been prepared with CeO₂ as a sintering aid at a sintering temperature of 1900 °C. The effect of CeO₂ contents on the microstructure, density, thermal conductivity and hardness was investigated. Addition of CeO₂ exerted a significant effect on the densification of AlN ceramics and hence on the microstructure. Thermal conductivity of AlN ceramics increased with CeO₂ content and was greater than that of Y₂O₃-doped AlN ceramics at a similar sintering temperature. The resulting AlN ceramics with 1.50 wt% of CeO₂ had the highest relative density of 99.94%, thermal conductivity of 156 W m⁻¹ K⁻¹ and hardness of 72.46 kg/mm².     

High quality microwave dielectric ceramic sintered at extreme-low temperature below 200° and co-firing with base metal

Ultra-low temperature co-fired ceramics technology (ULTCC) requires the microwave dielectric ceramics with lower intrinsic sintering temperature than the melting point of inner electrodes. In the present work, a novel HBO₂ ceramic was found to be densified at extreme-low temperature below 200 °C, with pores, residual H₃BO₃, amorphous B₂O₃ inside, with a relative permittivity ∼2.12 ± 0.02, a Qf value ∼32,700 ± 300 GHz and a temperature coefficient of resonant frequency value ∼ − 43 ± 3 ppm/°C. This material can be easily obtained by dehydration from H₃BO₃ by sintering at low temperature below 200 °C. Its extreme-low sintering temperature and water solubility also provides the possibility to achieve some novel multi-functional inorganic-organic composite in the future.     

Additive-free superhard B4C with ultrafine-grained dense microstructures

A unique combination of high-energy ball-milling, annealing, and spark-plasma sintering has been used to process superhard B₄C ceramics with ultrafine-grained, dense microstructures from commercially available powders, without sintering additives. It was found that the ultrafine powder prepared by high-energy ball-milling is hardly at all sinterable, but that B₂O₃ removal by gentle annealing in Ar provides the desired sinterability. A parametric study was also conducted to elucidate the role of the temperature (1600–1800 °C), time (1–9 min), and heating ramp (100 or 200 °C/min) in the densification and grain growth, and thus to identify optimal spark-plasma sintering conditions (i.e., 1700 °C for 3 min with 100 °C/min) to densify completely (>98.5%) the B₄C ceramics with retention of ultrafine grains (∼370 nm). Super-high hardness of ∼38 GPa without relevant loss of toughness (∼3 MPa m^1/2) was thus achieved, attributable to the smaller grain size and to the transgranular fracture mode of the B₄C ceramics.     

Low temperature consolidation for fine-grained zirconium carbide from nanoparticles with ZrH2 as sintering additive

Zirconium carbide (ZrC_0.84O_0.13) nanopowders were consolidated using plasma activated sintering with 0–8 wt% ZrH₂ as the sintering additive to improve the sinterability. Compared with pure ZrC sintering, ZrH₂ additive led to the higher sintering kinetics and lower sintering temperature. This improvement was attributed to the increased carbon-vacancy concentration in the non-stoichiometric ZrC in the presence of ZrH₂ additive during the sintering process. Fully dense and fine-grained ZrC ceramics (1.3 ± 0.2 μm) were achieved at 1650 °C with 6 wt.% ZrH₂. The final product exhibited the Vicker’s hardness of 21.2 ± 1.0 GPa and fracture toughness of 2.2 ± 0.3 MPa m^1/2.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.     

Fabrication and properties of Y2O3 transparent ceramic by sintering aid combinations

Transparent Y₂O₃ ceramics were fabricated by the solid-state reaction and vacuum sintering method using La₂O₃, ZrO₂ and Al₂O₃ as sintering aids. The microstructure of the Y₂O₃ ceramics sintered from 1550 °C to 1800 °C for 8 h were analyzed by SEM. The sintering process of the Y₂O₃ transparent ceramics was optimized. The results showed that when the samples were sintered at 1800 °C for 8 h under vacuum, the average grain sizes of the ceramics were about 3.5 µm. Furthermore, the transmittance of Y₂O₃ ceramic sintered at 1800 °C for 8 h was 82.1% at the wavelength around the 1100 nm (1 mm thickness), which was close to its theoretical value. Moreover, the refractive index of the Y₂O₃ transparent ceramic in the temperature range from 30 °C to 400 °C were measured by the spectroscopic ellipsometry method.     

Effect of glassy bonding materials on the properties of LAS/SiC porous ceramics with near zero thermal expansion

Near zero thermal expansion porous ceramics were fabricated by using SiC and LiAlSiO₄ as positive and negative thermal expansion materials, respectively, bonded by glassy material. The coefficient of thermal expansion value of a desired porous composite can be easily controlled by choosing the appropriate ratios of the different phases. It was shown that some of LiAlSiO₄ was decomposed to LiAlSi₂O₆ and LiAlO₂, some of LiAlSiO₄ reacted with SiO₂ to form LiAlSi₂O₆ during sintering. With increasing the content of glassy materials, the reaction between LiAlSiO₄ and SiO₂ was accelerated. The Young's modulus increased due to the neck growth between the SiC grains. The 52.5 vol% LiAlSiO₄ (LAS)/SiC ceramics with ∼36% porosity had a combination of near zero coefficient of thermal expansion ∼0.39 × 10⁻⁶ K⁻¹ at room temperature and relatively high Young's modulus ∼59 GPa.     

The influence of nano-silica and zircon additions on the sintering and mechanical properties of in situ formed forsterite

The influence of nano-silica and zircon additions on the sintering and mechanical properties of in situ formed forsterite fired at 1550 °C for 2 h was investigated. The results indicated that, nano-silica improved in situ formed forsterite at the firing temperature, while zircon additions enhanced the sintering of the investigated samples. XRD analysis and SEM examination observed a good crystallinity of in situ formed forsterite with nano-silica and/or zircon additions. Densification parameter (BD ∼3.22 g/cm³ and AP ∼5.82%), cold crushing strength (CCS ∼285 MPa) and micro-hardness (Hv ∼660) were enhanced with zircon additions.     

Microwave dielectric properties of Pb2MoO5 ceramic with ultra-low sintering temperature

Ultra-low firing microwave dielectric ceramic Pb₂MoO₅ with monoclinic structure was prepared via a conventional solid state reaction method. The sintering temperature ranged from 530 °C to 650 °C. The relative densities of the ceramic samples were about 97% when the sintering temperature was greater than 570 °C. The best microwave dielectric properties were obtained in the ceramic sintered at 610 °C for 2 h with a permittivity ∼19.1, a Q × f value about 21,960 GHz (at 7.461 GHz) and a temperature coefficient value of −60 ppm/°C. From the X-ray diffraction, backscattered electron image results of the co-fired samples with 30 wt% silver and aluminum additive, the Pb₂MoO₅ ceramics were found not to react with Ag and Al at 610 °C for 4 h. The microwave dielectric properties and ultra-low sintering temperature of Pb₂MoO₅ ceramic make it a promising candidate for low temperature co-fired ceramic applications.     

Fine grained Nd3+:Lu2O3 transparent ceramic with enhanced photoluminescence

Fine-grained Nd³⁺:Lu₂O₃ transparent ceramic was developed by a two-step sintering method in flowing H₂ atmosphere at T₁ = 1720 °C for 15 min and T₂ = 1620 °C for 10 h. The initial nanopowders were synthesized by a wet chemical processing with a uniform particle size of about 40 nm. The average grain size of the obtained 3 at.% Nd³⁺:Lu₂O₃ ceramic was 406 nm, which is ∼150 times smaller than the coarse-grained ceramic by normal H₂ sintering. The emission intensity of the fine-grained transparent ceramic is 3 times of its coarse-grained counterpart, indicating higher Nd concentration without serious quenching in fine-grained transparent ceramic is possible, which agreed well with the prediction of an atomistic modeling work with YAG. EXAFS research demonstrated that with decreasing grain size, higher degree of disorder factor of the local environment of doped Nd atoms was discovered.     

Transparent cubic-ZrO2 ceramics for application as optical lenses

Optical transparent polycrystalline ZrO₂ ceramics were fabricated by solid-state sintering process using first vacuum sintering followed by hot isostatic pressing. In the visible wavelength range (400–800 nm), the in-line transmittance of 5.6-mm thick samples reaches 68% at exemplary wavelength 600 nm (corresponding to an in-line absorbance based on 10 of A₁₀ = 0.08 cm^?1), which is approximately 90% of theoretical limit. The refractive indices of the ZrO₂ optoceramics at 630 nm (n_d) are varying between 2.10 and 2.20, depending on TiO₂ contents, the latter being used as sintering aid. The appearance of birefringence is strongly correlated to the addition of TiO₂ as sintering additive in the ceramic samples, whereas addition of TiO₂ and simultaneous increase in Y₂O₃ content resulted in a decrease of birefringence.     

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.     

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.     

Enhanced sintering behavior of LSGM electrolyte and its performance for solid oxide fuel cells deposited by vacuum cold spray

How to obtain dense La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ (LSGM) electrolyte at low sintering temperature (<1300 °C) is a challenge to improve solid oxide fuel cell (SOFC) performance at intermediate operation temperature. In this study, a double-layer design method for vacuum cold spray (VCS) prepared-LSGM electrolyte assisted with two-step sintering at a low temperature was proposed. The sintering behavior of VCS deposited LSGM layers at 1200 °C was investigated. The LSGM layers became denser in most regions except the appearance of some cracks. Subsequently, the effect of a second LSGM layer on the sintered top layer was studied to block cracks. Results showed that the co-sintered layer with a thickness of approximately 5 μm presented a maximum open circuit voltage of ∼0.956 V at 650 °C and a maximum power density of 592 mW/cm² at 750 °C. Result indicates that the sintering assisted VCS is a promising method to prepare the LSGM electrolyte applied in intermediate temperature SOFCs.     

The effect of sintering temperature and time on microwave properties of Sm(Zn1/2Ti1/2)O3 ceramics for resonators

The microwave dielectric properties of Sm(Zn_1/2Ti_1/2)O₃ ceramics have been investigated. Sm(Zn_1/2Ti_1/2)O₃ ceramics were prepared by conventional solid-state route with various sintering temperatures and times. The prepared Sm(Zn_1/2Ti_1/2)O₃ exhibited a mixture of Zn and Ti showing 1:1 order in the B-site. Higher sintered density of 7.01 g/cm³ can be produced at 1310 °C for 2 h. The dielectric constant values (ɛ_r) of 22–31 and the Q × f values of 4700–37,000 (at 8 GHz) can be obtained when the sintering temperatures are in the range of 1250–1370 °C for 2 h. The temperature coefficient of resonant frequency τ_f was a function of sintering temperature. The ɛ_r value of 31, Q  ×  f value of 37,000 (at 8 GHz) and τ_f value of −19 ppm/°C were obtained for Sm(Zn_1/2Ti_1/2)O₃ ceramics sintered at 1310 °C for 2 h. For applications of high selective microwave ceramic resonator, filter and antenna, Sm(Zn_1/2Ti_1/2)O₃ is proposed as a suitable material candidate.     

Sintering behaviour and translucency of dense Eu2O3 ceramics

Eu₂O₃ ceramics have been obtained at sintering temperatures of between 1000 °C and 1550 °C. X-ray diffraction and scanning electron microscopy, in combination with dilatometry experiments, allowed understanding the sintering behaviour. Moderate grain growth followed an efficient densification process between 1400 °C and 1550 °C, which yielded high-density ceramics with an average grain size of 4 μm. The ceramics had Young modulus of 125 GPa, in agreement with the previously published data. The dense Eu₂O₃ ceramics were translucent (35.1% transmittance at 800 nm of 0.8 mm thick discs), showing in addition a slightly pink colour. We propose that the combination of high density and an average grain size of 4 μm is responsible for this novel functionality.     

Translucent and persistent luminescent SrAl2O4:Eu2+Dy3+ ceramics

Ceramics that exhibit persistent luminescence are usually opaque, which limits their utility. In this work, a laser-sintering technique is employed to produce persistent luminescent SrAl₂O₄:Eu²⁺Dy³⁺ ceramics that has enhanced translucency in the visible spectral range. In this technique, a CO₂ laser was used as the main heating source for sintering with no atmosphere control employed. The ceramics sintered at a power density of 3.1 W/mm² yielded homogeneous grain size distributions and transmittance up to 40% in the range of 600–800 nm. Upon sintering in air, the ceramics exhibited the characteristic green emission from the Eu²⁺ ion, corresponding to the 5d→4f transition (514 nm) and a weak emission from the Eu³⁺ ion at 614 nm, corresponding to the ⁵D₀→⁷F₂ transition. The valence of europium ions was further studied by the X-ray absorption spectroscopy in the XANES region and those details are reported herein.