Highly transparent yttrium titanate (Y2Ti2O7) ceramics from co-precipitated powders

Highly transparent yttrium titanate (Y₂Ti₂O₇) ceramics were fabricated by vacuum sintering using co-precipitated powders for the first time. The effects of the powder calcination temperature on the phase composition, morphology of the calcined powders, and on the microstructure and transmittance of the Y₂Ti₂O₇ ceramics were investigated. When the calcination temperature was above 850 °C, pure phase Y₂Ti₂O₇ nanopowders with high sintering activity were obtained. Transparent Y₂Ti₂O₇ ceramics were obtained after vacuum sintered at 1600 °C for 6 h and annealed at 1100 °C for 5 h in air. The highest transmittance reached 73% at 1000 nm when the calcination temperature was 1150 °C. The measured refractive index of Y₂Ti₂O₇ ceramics was higher than 2.24 at the wavelength range of 350–1000 nm, making it a promising candidate for optical devices.     

Synthesis of nanostructured Nd:Y2O3 powders by carbonate-precipitation process for Nd:YAG ceramics

Neodymium doped yttria (Nd:Y₂O₃) nanopowders were synthesized by a co-precipitation method, and the effect of thermal decomposition behavior of the precursors were studied. Nonlinear and linear heating schedules (NHS and LHS) were adopted during the calcination processes. The results show that as compared to the LHS the NHS can not only lower the crystallization temperature substantially, but also decrease the mean particle size and lighten the particle agglomeration in the obtained Nd:Y₂O₃ nanopowders. Using the obtained well-dispersed Nd:Y₂O₃ and commercial Al₂O₃ powders, transparent Nd:YAG ceramics were fabricated at 1750 °C in vacuum. Better transparency can be obtained by using the Nd:Y₂O₃ powders calcined in the NHS instead of the LHS.     

Carbonate-precipitation synthesis of Yb:Y2O3 nanopowders and its characteristics

Ytterbium-doped yttria (Yb³⁺:Y₂O₃) nanopowders for transparent ceramics were synthesized by using a carbonate-precipitation method. The characteristics of precursor and powders calcined at different temperatures were investigated. The pure yttria phase can form through calcining at 700 °C. The Yb³⁺:Y₂O₃ nanopowders calcined at 1100 °C were well dispersed with a spherical morphology, and had a narrow particle size distribution with a mean particle size of about 70 nm. By using 1100 °C-calcined powders, nearly full dense Yb³⁺:Y₂O₃ ceramics were fabricated at 1750 °C for 8 h without any additives under vacuum conditions. The fluorescence spectrum of the sintered ceramics illustrates that there are two emission peaks locating at 1028 and 1071 nm respectively, all corresponding to the ²F_5/2 → ²F_7/2 transitions of Yb³⁺ ion. Homogeneous Yb³⁺:Y₂O₃ nanopowders synthesized by carbonate-precipitation method are suitable for the fabrication of IR-transparent ceramics.     

Densification of zirconia doped yttria transparent ceramics using co-precipitated powders

Ho:Y₂O₃ ceramics were prepared using co-precipitated powders, with ammonium sulfate as dispersant. Y³⁺ was co-precipitated together with Ho³⁺ and Zr⁴⁺ to produce precursors, which were calcined at 1100–1400 °C to produce yttria-based powders. At calcination temperatures of ≤1300 °C, agglomeration of powders was not observed. When the temperature was increased to 1400 °C, severe agglomeration was detected. Densification was closely related to the calcination temperature: a lower calcination temperature resulted in a faster densification of ceramics to the relative density of 99.7%. The ultimate densification to ~100% was also closely related to powders' impurity level and agglomeration. Grain growth was mainly determined by sintering temperature, but not by the initial crystallite size of powders. The optimal calcination temperature was 1300 °C, at which the obtained Ho:Y₂O₃ powder was free from agglomeration. Using this powder, the resultant Ho:Y₂O₃ ceramics showed pore-free microstructure and good optical transparency.     

Fabrication of Lu2O3:Eu transparent ceramics using powder consisting of mono-dispersed spheres

Mono-dispersed spherical Lu₂O₃:Eu (5 mol%) powders for transparent ceramics fabrication were synthesized by urea-based homogeneous precipitation technique. The effects of the doped-Eu³⁺ on the synthesis of Lu₂O₃:Eu particles were investigated in detail. The results show that the doping of Eu³⁺ ions into Lu system can significantly decrease the particle size of the resultant precursor spheres. Owing to the sequential precipitation in Lu/Eu system, there are compositional gradients within each of the resultant precursor spheres. Well dispersed, homogeneous and spherical/near spherical Lu₂O₃:Eu powders were obtained after calcination at 600–1000 °C for 4 h. The powder calcined at 600 °C shows better sintering behavior and can be densified into transparent ceramic after vacuum sintering at 1700 °C for 5 h. The luminescence properties of the obtained Lu₂O₃:Eu powder and transparent ceramic were also studied.     

Effects of Sintering Temperature on Open‐Volume Defects and Thermoluminescence of Yttria and Lutetia Ceramics

The effects of different processing steps and processing conditions for the fabrication of Y₂O₃ and Lu₂O₃ ceramics were investigated, particularly the effects of calcination, and sintering temperature on the content of open‐volume and electronic defects. Ceramic bodies were prepared from calcined powders by sintering from 1400°C to 1700°C for 20 h. Density was determined by the Archimedes method and showed pellets reached about 99% of Y₂O₃ density for temperatures ≥1450°C, and reached 98% for sintering at 1700°C for Lu₂O₃. The content of open‐volume defects was followed by positron annihilation lifetime (PAL) measurements. For both materials, two lifetimes were obtained. The faster lifetime, 211 ps for Y₂O₃ and 204 ps for Lu₂O₃, was assigned to bulk annihilation with possible contribution of grain boundaries. The longer lifetime was assigned to positronium annihilation in open‐volume defects with radii of 2–4 Å. Doppler broadening analysis revealed the same type of defect in Lu₂O₃ ceramics for all sintering temperatures. PAL analysis results showed that densification was achieved through the elimination and agglomeration of open‐volume defects. Thermoluminescence (TL) measurements of Y₂O₃ showed that sintering is beneficial in eliminating traps and/or recombination centers, and that higher sintering temperatures increase TL signal.     

Effect of powder milling routes on the sinterability and optical properties of transparent Y2O3 ceramics

In ceramic processing, the size distribution of the starting powder to a certain degree is inevitable. It is prerequisite to control the size distribution, which influences the fabrication of a sound green body featuring both smaller pores and a narrower pore structure for full-density sintering facilitated by the easier elimination of pores. The milling process was systematically investigated here to elucidate the effect of powder characteristics on the sinterability and transmittance of Y₂O₃ ceramics. Three types of powder sets having different width of particle size distribution (W_PSD) while keeping the same median size (D₅₀) were prepared by changing the milling condition. By means of narrowing the W_PSD in this research, pore free transparent polycrystalline Y₂O₃ with average grain size of 730 nm was successfully fabricated by hot-pressing at 1500℃, which is 100℃ lower than the previously lowest known sintering temperature.     

Influence of Yb and Si on the fabrication of Yb:YAG transparent ceramics using spherical Y2O3 powders

Yb:YAG (yttrium aluminum garnet) transparent ceramics were fabricated by the solid-state method using monodispersed spherical Y₂O₃ powders as well as commercial Al₂O₃ and Yb₂O₃ powders. Pure YAG phase was obtained at low temperature due to homogeneous mixing of powders. Under the same sintering conditions, the Yb:YAG ceramics with different doping contents of Yb³⁺ had similar morphologies and densification rates. After being sintered at 1700 °C in vacuum, the ceramic samples had high transparencies. The Yb:YAG ceramics doped with 0.5 wt% SiO₂ formed Y–Si–O liquid phase and nonstoichiometric point defects that enhanced sintering. Compared with Nd doping, Yb doping hardly affected the YAG grain growth, sintering densification or optical transmittance, probably because Yb³⁺ easily entered the YAG lattice and had a high segregation coefficient.     

Fabrication,microstructure and spectroscopic properties of Yb:Lu2O3 transparent ceramics from co-precipitated nanopowders

Ytterbium doped lutetium oxide (Yb:Lu₂O₃) transparent ceramics were fabricated by vacuum sintering combined with hot isostatic pressing (HIP) of the powders synthesized by the co-precipitation method. The effects of calcination temperature on the composition and morphology of the powders were investigated. Fine and well dispersed 5?at% Yb:Lu₂O₃ powders with the mean particle size of 67?nm were obtained when calcined at 1100?°C for 4?h. Using the synthesized powders as starting material, we fabricated 5?at% Yb:Lu₂O₃ ceramics by pre-sintering at different temperatures combined with HIP post-treatment. The influence of pre-sintering temperature on the densities, microstructures and optical quality of the 5?at% Yb:Lu₂O₃ ceramics was studied. The ceramic sample pre-sintered at 1500?°C for 2?h with HIP post-treating at 1700?°C for 8?h has the highest in-line transmittance of 78.2% at 1100?nm and the average grain size of 2.6?µm. In addition, the absorption and emission cross sections of the 5?at% Yb:Lu₂O₃ ceramics were also calculated.     

Coating Y2O3 nano-particles with ZrO2-additive via precipitation method for colloidal processing of highly transparent Y2O3 ceramics

In the present work, transparent Y₂O₃ ceramics were prepared via colloidal processing method using ZrO₂-coated nano-sized Y₂O₃ powders. The chemical precipitation method was adopted for the coating of Y₂O₃ raw powder. The evolution of the coated-ZrO₂ layer upon calcination was studied. The rheological behaviors of the slurries of Y₂O₃ powders coated with different content of ZrO₂-additive were investigated. The pH_IEP of ZrO₂-coated Y₂O₃ powders shows intermediate values between that of raw Y₂O₃ and ZrO₂ powders. As the ZrO₂-coating concentration increased from 0 to 5.0 at%, the magnitude of the negative zeta potential at pH > pH_IEP shows a general trend of increment, whereas it decreased at pH < pH_IEP. The viscosity decreases pronouncedly with the increase of ZrO₂ content from 0.5 at% to 3.0 at%. The suspensions with low viscosity and high stability was achieved for a solid loading of 35.0 vol% using Y₂O₃ powders coated with 5.0 at% ZrO₂. The dispersed suspensions were consolidated by centrifugal casting method and the green bodies shown improved homogeneity. Transparent Y₂O₃ ceramics were fabricated by vacuum sintering at 1800 ℃ for 5 h. Transmittance at wavelength 800 nm (1.0 mm thick) reached 80.8%, close to the theoretical value of Y₂O₃.     

Fabrication of Er:Y2O3 transparent ceramics for 2.7 μm mid-infrared solid-state lasers

Laser grade 7 at.% Er:Y₂O₃ transparent ceramics with submicron grain size were fabricated by using one-step vacuum sintering followed by hot isostatic pressing (HIPing) technique. Through studying the sintering trajectory of Er:Y₂O₃ ceramics, the sintering temperature zone where sufficient relative density (>96%), no pore-boundary separation, and sub-micron grain size (<1 μm) ceramic samples could be identified. The samples pre-sintered in this zone were readily densified by HIPing. To maximum the densification and achieve high transparency, it is critical to suppress the final-stage grain growth. After HIPing at 1520 °C, the Er:Y₂O₃ ceramics were fully densified without further grain growth, and exhibited in-line transmission of about 81.6% at 2000 nm. Continuous wave (CW) room temperature laser operation of the Er:Y₂O₃ transparent ceramic at 2.7 μm was demonstrated.     

Stirring speed assisted homogenization of precipitation reaction for enhanced optical performance of Y2O3 transparent ceramics

Y₂O₃ transparent ceramics were fabricated from precipitated powders prepared at different stirring speeds during the precipitation process. The influence of the stirring speed on the phase component of precursors, morphology of Y₂O₃ powders and properties of fabricated ceramics were systematically investigated. Crystalline phase precursors of (NH₄)_aY(OH)_b(CO₃)_c·H₂O were prepared from 110 rpm, 220 rpm and 550 rpm respectively. But amorphous precursors of Y(CO₃)(OH)·nH₂O (n = 1–1.5) were observed when stirring speeds were 330 rpm and 440 rpm. Y₂O₃ powders prepared from 440 rpm exhibited the lowest agglomeration and the smallest grain size, and the ceramics with the optimal transmittance was accordingly obtained. The results of computational fluid dynamics software CFX showed that a more homogeneous flow field distribution without local circulations could be produced at 440 rpm, which would be benefit for the optical quality of transparent ceramics. The study would provide a considerable reference for the controllable fabrication of well-dispersibility Y₂O₃ powders and Y₂O₃ transparent ceramics.     

Synthesis of nanocrystalline ytterbium-doped yttria by citrate-gel combustion method and fabrication of ceramic materials

Nanosized ytterbium doped yttria powders were prepared by citrate-gel combustion techniques. As-synthesized precursor and calcined powders were characterized for their crystalline structure, particle size and morphologies. Nanocrystalline Yb³⁺:Y₂O₃ powders with pure cubic yttria crystal structure were obtained by calcination of as-prepared precursors at 1100 °C for 3 h. Powders obtained were well dispersed with an average particle size of 60 nm. By using the obtained powders, nearly full dense Yb³⁺:Y₂O₃ ceramics were produced by vacuum sintering at 1800 °C for 12 h. The emission spectrum of the sintered ceramics under the excitation wavelength of 905 nm illustrates that there are three fluorescence peaks locating at 976 nm, 1030 nm and 1075 nm respectively, all corresponding to the ²F_5/2 → ²F_7/2 transitions of ytterbium ion.     

Rapidly fabricating Y2O3 transparent ceramics at low temperature by SPS with mesoporous powder

Fine-grained and dense highly transparent Y₂O₃ ceramics have been successfully prepared using high sintering activity mesoporous Y₂O₃ powders without any additive by spark plasma sintering (SPS). The influences of the sintering temperature on microstructure, density, optical, and mechanical properties of SPS-sintered Y₂O₃ ceramics were studied in detail. As results, the optimal Y₂O₃ ceramics with high relative density of 99.90% and fine average grain size of 140 nm were obtained at a low sintering temperature of 1140°C and a moderate load pressure of 60 MPa for 5 min. Meanwhile, the dense Y₂O₃ ceramics with 1 mm thickness after annealing show a high linear transmittance of 78% (close to 94% of the theoretical value) at 2.4–3 µm wavelength. In additions, the Vickers hardness and fracture toughness of samples can reach 8.48 GPa and 1.45 MPa m^1/2, respectively. This result proves that the high activity of mesoporous Y₂O₃ is considered to be an important means for preparing high-performance fine Y₂O₃ ceramics at low sintering temperature.     

Co-precipitation synthesis and two-step sintering of YAG powders for transparent ceramics

Yttrium aluminum garnet (Y₃Al₅O₁₂, YAG) precursor was synthesized by the co-precipitation method with ammonium hydrogen carbonate as the precipitant. The influence of aging and calcination temperature on the precursor composition and transformation temperature of the YAG phase was investigated. On that basis, a two-step sintering (TSS) method (heating the sample up to 1800 °C followed by holding it at 1600 °C for 8 h) was used to fabricate bulk transparent YAG ceramics in vacuum (10⁻³ Pa) in this communication. A variety of techniques, such as X-ray powder diffraction, infrared spectra, scanning electron microscopy and UV–vis–NIR spectrophotometry were adopted to characterize the resulting YAG powders and ceramics. The results showed that aging had a dramatic effect on the precursor composition, which in turn influenced the transformation temperature of the YAG phase. Loosely agglomerated YAG powders with a mean particle size of 50 nm were obtained by calcinating the precursor without aging at 1000 °C. Finally, a transparent YAG ceramic specimen, achieving the in-line transmittance of 41% in the visible wavelength region and a nearly pore-free microstructure with uniform grains of about 4 μm, was produced via the TSS technique.     

Synthesis of highly-infrared transparent Y2O3–MgO nanocomposites by colloidal technique and SPS

Infrared (IR) transparent Y₂O₃–MgO nanocomposites with a volume ratio of 50:50 were synthesized by combining colloidal and spark-plasma-sintering (SPS) techniques. In order to attain well-dispersed and homogeneous starting Y₂O₃–MgO nanopowder mixture, the effects of the pH value and the amount of polyetherimide (PEI) dispersant on the suspension stability were studied. Rheological measurement reveals that highly-dispersed and stable suspension was obtained at 7 wt% of PEI dispersant under pH = 10.6. The obtained nanopowders with particle size of 20–30 nm were densified using SPS at several sintering temperatures. The sintered composites show fine grains, narrow grain size distribution and uniform microstructure. The nanocomposite sintered at 1250 °C showed the maximum IR transmittance of 84% at a wavelength range of 2.5–6 μm. The Vickers hardness of the nanocomposite was about 11.9 ± 0.3 GPa, which is significantly higher than those of single phase MgO or Y₂O₃. Successful fabrication of the high-performance Y₂O₃–MgO nanocomposite indicates that i) the colloidal technique is an effect method to obtain highly dispersed and homogeneous nanopowders and ii) the SPS technique is a powerful tool to fabricate fine-grained dense transparent ceramics, which are suitable for fabricating IR transparent Y₂O₃–MgO composite ceramics from commercial starting powders.     

Fabrication and characterization of highly transparent ZrO2-doped Tm2O3 ceramics

Highly transparent polycrystalline Tm₂O₃ ceramics were successfully fabricated by vacuum sintering at temperatures from 1650 to 1850 °C for 8 h using commercial Tm₂O₃ and ZrO₂ (1 at%) powders as starting materials. It is the first time that ZrO₂ was reported as a sintering additive to prepare Tm₂O₃ transparent ceramics. The effects of sintering temperature on the optical transmittance and microstructure of Tm₂O₃ transparent ceramics were studied. The desired Tm₂O₃ ceramics with relative density of 99.8% and an average grain size of approximately 9.7 μm were obtained at 1800 °C and the in-line transmittance reached 75% at 880 nm and fluctuated around 80% from 2100 to 2400 nm, respectively. This study demonstrated that Tm₂O₃ transparent ceramics with higher in-line transmittance and smaller grain size could be prepared by using ZrO₂ as sintering additive at a relatively lower vacuum sintering temperature compared to those already reported in open literatures.     

Fabrication and characterization of highly transparent Y2O3 ceramics by hybrid sintering: A combination of hot pressing and a subsequent HIP treatment

We succeeded in the optimization of highly transparent Y₂O₃ ceramics with a submicrometer grain size approximately 0.6?μm by hot pressing (1300–1550?°C) and a subsequent HIP (1450?°C) treatment using commercial Y₂O₃ powders as starting powders and ZrO₂ as a sintering additive. The optimum microstructure for the HIP treatment was prepared by hot pressing at a temperature as low as 1400?°C for 3?h with a relative density of 99.3%. The thus HIP-treated specimen showed the best transmittance (2?mm thick) ever reported of 83.4% and 78.3% at 1100 and 400?nm, respectively. Specifically, the transmittance using this hybrid sintering method improved substantially in the visible range compared to that of the counterpart using hot pressing only. A simulation of the transmittance based on the Beer-Lambert law and Mie scattering theory has proved that this improvement is mainly due to the elimination of nanopores below 15?nm in size.     

Fabrication and properties of Y2Ti2O7 transparent ceramics with excess Y content

Transparent Y₂Ti₂O₇ ceramics with excess Y content were fabricated by solid state reactive sintering in vacuum using Y₂O₃ and TiO₂ powders as the starting materials. Phase composition, microstructure, density and in-line transmittance of the Y₂Ti₂O₇ ceramics were investigated. The detailed results indicated that as Y content increased, the density and in-line transmittance increased at first and then decreased. And the highest in-line transmittance of Y₂Ti₂O₇ ceramics is 49.9% at 1100?nm when the excess amount of Y to Ti is 2%. The effect of Y content on densification process of Y₂Ti₂O₇ ceramics was discussed based on an assumption that oxygen vacancy defects were the dominated defects.     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.