Microstructure and mechanical properties of Al2O3/Y3Al5O12/ZrO2 ternary eutectic materials

Directionally solidified fibers and rods have been grown from the ternary Al₂O₃/Y₃Al₅O₁₂/ZrO₂ system using micro-pulling-down method. Fiber diameter could be varied 0.3 mm–2 mm at pull-rates ranging 6–900 mm/h and 500 mm in length. The ternary eutectic fibers had homogeneous colony patterned eutectic microstructures. The interlamellar spacing λ exhibited an inverse-square-root dependence on the growth speed v according to λ = 8 × v^−1/2, where λ has the dimension of μm and v is in μm/s. The tensile strength was recorded 1730 MPa at 25 °C and 1100 MPa at 1200 °C for a fiber crystals grown at a growth speed of 900 mm/h. Eutectic rods having 5 mm of diameter and up to 80 mm in length were also successfully grown by the micro-pulling-down method. The eutectic rods showed 1400 MPa of mechanical strength by compressive mode at 1500 °C with homogeneous colony microstructures.     

Ruby micro-piezospectroscopy in GdAlO3/Al2O3(/ZrO2), Er3Al5O12/Al2O3(/ZrO2) and Y3Al5O12/Al2O3(/ZrO2) binary and ternary directionally solidified eutectics

The fluorescence from (naturally present) Cr³⁺ impurities was used to measure the residual stress in the alumina phase of six melt-grown ceramic eutectic composites associating gadolinum aluminum perovskite (GAP), erbium aluminum garnet (EAG) or yttrium aluminum garnet (YAG) with α-alumina and cubic zirconia. Such measurements are reported for the first time in the GAP containing eutectics.In the usual hydrostatic assumption, we conclude to a residual compression in the range of ～70–400 MPa depending on the sample composition. The validity of the hydrostatic assumption is questioned when a microscope is used for the measurements.     

Separation of Phases by Spinodal Decomposition in the Systems Al2O3−Cr2O3 and Al2O3−Cr2O3−Fe2O3

Separation of phases was investigated in the hexagonal (rhombohedral) systems Al₂O₃−Cr₂O₃ and Al₂O₃−Cr₂O₃−Fe₂O₃. The binary system shows a miscibility gap with a T_c of 950°C; the miscibility gap for the ternary system was determined for a constant Cr₂O₃ content of 16.6 mol%. Dark field transmission electron microscopy of solid solutions annealed within the miscibility gap showed dark and light lamellas ∼50 to 200 Å thick. X-ray diffraction results for the solid solutions in the ternary system indicated that, in the early stages of annealing, broadening occurred only on (hkl) reflections where l≠0. There was no major change in the X-ray diffraction patterns of the annealed solid solutions in the binary system. Electron diffraction results indicated, however, that phase separation in both systems proceeded in the [001] direction. Solid solutions in the binary system separated very slowly; the separation could be enhanced hydrothermally. The mechanism of the separation of phases in both systems is spinodal and proceeds as follows: solid solution→intermediate modulated phase→equilibrium phases.     

Strain measurement of the directionally solidified eutectic Al2O3/Y3Al5O12 (YAG) ceramic by neutron diffraction

The eutectic Al₂O₃/Y₃Al₅O₁₂ (YAG) ceramic has been reported to be composed by single-crystalline Al₂O₃ and YAG, the microstructure of which is characterized by the three dimensionally entangled two single-crystalline composites. Therefore, Laue diffraction and high-resolved energy-dispersive neutron diffraction (time-of-flight method) techniques were employed to measure residual strain precisely. It was found that the YAG phase was in tension and the Al₂O₃ phase was in compression with strains in the range of ∼10⁻⁴ at room temperature through comparing the lattice spacings of the sintered YAG and sintered Al₂O₃ as the references of strain-free materials.     

Mechanical properties of directionally solidified Al2O3/Y3Al5O12 eutectic ceramic prepared by optical floating zone technique

Al₂O₃/Y₃Al₅O₁₂(YAG) directionally solidified eutectic (DSE) crystal was prepared by optical floating zone technique. Al₂O₃/YAG DSE consists of continuous entangled Al₂O₃ and the YAG forming a three-dimensional networks structure. The volume fraction of porosity is ultra-low (0.013%) and the average equivalent diameters of most pores (>84%) are smaller than 4?μm. The Al₂O₃/YAG DSE shows excellent high-temperature elastic stiffness. The Young’s modulus at 1500?°C maintains more than 85% of the value at room temperature. Bending strength exhibits excellent retention up to high temperature as well. High-temperature ball indentation testing shows plastic deformation involving dislocations and twinning, which predominantly occur in Al₂O₃ phase, while the YAG phase is stable. Evaluation on H_v/E index predicts Al₂O₃/YAG DSE with moderate capability to accommodate damages. Our results highlight Al₂O₃/YAG DSE as excellent high-temperature structural materials.     

Preparation and microstructure of large-sized directionally solidified Al2O3/Y3Al5O12 eutectics with the seeding technique

A large-sized Al₂O₃/Y₃Al₅O₁₂ (YAG) eutectic single crystal is successfully prepared with the external seed by a modified Bridgman furnace. The microstructure, crystallography and interface structure of the large-sized Al₂O₃/YAG eutectic are well investigated. It is found that the longitudinal eutectic microstructure shows large length-to-width phase ratios. The crystallographic orientation relationship of the as-obtained large-sized Al₂O₃/YAG eutectic is consistent with that of the seed. The epitaxial solidification of the binary eutectic occurs, and the dominating of the seed is not lost in the long-range growth. The observed Al₂O₃/YAG interface structure is studied by near-coincidence site lattice (NCSL) theory. The volume strain for the NCSL is very low (0.02), which suggests that the interfaces have locally low interfacial energies. This small volume strain might be the reason for stable induced-growth along the seed.     

Microstructure and mechanical properties of Al2O3/Y3Al5O12/ZrO2 hypereutectic directionally solidified ceramic prepared by laser floating zone

Al₂O₃/Y₃Al₅O₁₂/ZrO₂ directionally solidified ceramic has been considered as a promising candidate for ultrahigh temperature structural materials due to its excellent performance even close to its melting point. In this work, laser floating zone (LFZ) solidification experiments were performed on Al₂O₃/Y₃Al₅O₁₂/ZrO₂ hypereutectic with the solidification rates between 2 μm/s and 30 μm/s. The full eutectic lamellar microstructure is obtained with hypereutectic composition. The solid/liquid interface morphology is investigated. The microstructure characteristic is discussed based on the solid/liquid interface. The variation of lamellar spacing with different compositions and solidification rates was reported and discussed by considering an irregular eutectic growth model. The maximum hardness and fracture toughness are 19.06 GPa and 3.8 MPa m^1/2, respectively. The toughening mechanism of ZrO₂ is discussed based on the scenario of the crack propagation pattern.     

甲烷在Cr改性Pd/Al2O3催化剂上的催化燃烧性能

研究了Cr改性Pd/Al2O3催化剂上低浓度甲烷的催化燃烧反应,考察了载体Cr Al的制备方法和活性组分Pd的负载方法对催化剂催化活性的影响以及添加Ce对催化剂高温稳定性的影响。采用X射线衍射、程序升温还原等表征手段分析了催化剂结构和氧化还原性。结果表明,与采用沉淀法制备的载体P-Cr Al相比,采用浸渍法制备的载体I-Cr Al具有较高的比表面积和反应活性;用Na BH3对Pd负载过程进行还原处理能明显提高催化剂活性,其原因是还原过程加强了催化剂上Pd与载体Cr Al之间的作用,通过H2-TPR证明了其还原能力得到了增加;添加Ce缓解了Al2O3高温条件下的烧结,增强了催化剂的高温稳定性。     

On the growth and structure of Al2O3-Y3Al5O12-ZrO2:Y solidified eutectic

Structural features of Al₂O₃-YAG-ZrO₂:Y eutectic plates grown by the EFG process have been studied. X-ray tomography shows that all three phases are continuous along the whole sample, suggesting a fully coupled ternary eutectic growth. However the growth of alumina and YAG is well described by a classical binary coupled growth, in spite of the facetted structure of their growth interface. Colonies are observed at high growth rate and have been related to the chemical rejection of zirconium ions at the solid-liquid interface, possibly due to a slight off-stoechiometry of the raw material.     

Luminescent properties of doped amorphous and polycrystalline Y3Al5O12-Al2O3

Transparent polycrystalline ceramics (TPCs) are crystalline materials with single-crystal-like transparency, which, however, have to rely on fabrication processes with a relatively high cost. Here, we produced lab-scale TPCs based on the typical refractory Y₂O₃-Al₂O₃ system, through full congruent crystallization of the parent glass prepared by aerodynamic levitation melting method. Doping of the glass and TPCs by rare-earth (RE) ions (Ce³⁺, Tb³⁺, Nd³⁺, and Yb³⁺) and transition-metal (TM) ions (Cr³⁺) results in strong visible and near-infrared (NIR) photoluminescence with high quantum yield. The dominance of Stark splitting of the emission band for RE and TM ions in the TPCs as compared with that of the glass confirms crystallization of the parent glasses.     

Kinetic effects of substitution Er3+ for Y3+ in (Y1-xErx)3Al5O12 garnet

The crystallization kinetics of erbium-substituted yttrium aluminum garnet (Er:YAG) from the amorphous phase was studied depending on the degree of substitution of yttrium by erbium: (Y_1-xEr_x)₃Al₅O₁₂, x = 0 – 0.9. The corresponding series of nanopowders were synthesized using the sol-gel method with binary sols as the starting materials. Crystallized single-phase Er:YAG powders were obtained at temperatures as low as 1370 K through the formation of intermediate phases. The crystallization kinetics of the Er:YAG precursors was analyzed using non-isothermal differential scanning calorimetry and X-ray diffraction analysis. The proposed unified crystallization model, based on which the kinetic parameters of the crystallization process of the Er:YAG from the amorphous phase were determined, depending on the content of erbium oxide. Time-temperature-transformation curves were developed from the obtained data to determine the optimal modes in the heat treatment and sintering of optical ceramics. Er:YAG transparent ceramics were obtained by vacuum sintering of sol-gel powders.     

Density measurements of molten Y3Al5O12 and Y2O3-Al2O3 compounds using an electrostatic levitation technique

The densities of molten Y₂O₃-Al₂O₃ compounds, including yttrium aluminum garnet (Y₃Al₅O₁₂), were determined over a wide temperature range that included an undercooled region, using an electrostatic levitation furnace. The density of the molten Y₃Al₅O₁₂ varied with temperature according to the relationship 3750 − 0.25(T − T_m) (kg/m³) with T_m = 2240 K and for the range of 1300 K ≤ T ≤ T_m, yielding the thermal expansion coefficient ɑ = 6.7×10⁻⁵ K⁻¹. The molar volumes of molten (100-x)Y₂O₃-xAl₂O₃ (x = 0, 33.3, 50, 55, 62.5, 76.5, 81.5, or 100 mol%) were found to vary with the value of x in a linear manner within the superheated temperature range. However, the molar volumes in the undercooled region deviated from those calculated using an ideal solution model owing to attractive interactions between Y₂O₃ and Al₂O₃.     

Longitudinal cross-section microstructure of growth striation in Al2O3/Y3Al5O12/ZrO2 directionally solidified eutectic ceramic prepared by laser floating zone

Periodic growth striations with a width of 380 μm are observed in Al₂O₃/Y₃Al₅O₁₂/ZrO₂ ternary directionally solidified eutectic ceramic prepared by laser floating zone. It is found that the microstructure of the growth striations exhibits disparate growth characteristics. The direct experimental evidence of the formation of the microstructure of the growth striations is obtained through examining the solid–liquid interface. The lamellar coarsening of the growth striations is related to the nucleation of Al₂O₃ particles and their engulfment by the extended Y₃Al₅O₁₂ phase. The mechanism accounting for this phenomenon is explained by considering eutectic growth behavior under mutative condition induced by oscillatory convection.     

Thermal emission properties of Al2O3/Er3Al5O12 eutectic ceramics

The mechanical properties and thermal stability of the Al₂O₃/Er₃Al₅O₁₂ (EAG) eutectic ceramics have been investigated at very high temperature. The emissive properties of this eutectic ceramics have also been measured and its possibilities of application to an emitter have been discussed. The present eutectic ceramic has excellent high-temperature strength characteristics, showing that tensile yielding stress is approximately 300 MPa at 1650 °C and superior thermal stability at 1700 °C in an air atmosphere. The present material shows strong selective emission bands at wavelength 1.5 μm due to Er³⁺ ion. The emission bands of this material are nearly coincident with the sensitive region of GaSb PV cell, therefore, the Al₂O₃/EAG eutectic ceramic can be regarded as one of the promising emitter materials in TPV systems.     

Modeling and Monte Carlo simulation on photothermal effect in Gd3Al3Ga2O12:Ce3+/Y3Al5O12:Cr3+ layered composite ceramic

Layered composite ceramics have wide application in solid-state lasers. However, the photothermal effect in the layered ceramics has not been clarified, due to the interface effect between layers. In this work, the model of photon propagation and thermal distribution in the Gd₃Al₃Ga₂O₁₂:Ce³⁺/Y₃Al₅O₁₂:Cr³⁺ layered ceramics are established. The property of photon absorption, reflection, transmission, and thermal distribution are studied by combining the Monte Carlo method and the convolution method. It is found that the photon absorption distribution and thermal distribution of this layered ceramics show the gradient change. Furthermore, this change is strongly dependent on the type, beam width, and power of laser. The temperature of layered ceramics induced by Gaussian beam is higher than that induced by flat circular beam. This work provides a useful research method for the design of layered ceramic materials with excellent scintillation performance.     

Optical absorption and selective thermal emission in directionally solidified Al2O3-Er3Al5O12 and Al2O3-Er3Al5O12-ZrO2 eutectics

Al₂O₃-Er₃Al₅O₁₂ and Al₂O₃-Er₃Al₅O₁₂-ZrO₂ eutectic ceramic rods were directionally solidified using the laser floating zone technique at several growth rates. Binary eutectic microstructure consisted in a three-dimensional interpenetrated network of the eutectic phases whereas the ternary eutectic showed a geometrical microstructure at low growth rates and a nanofibrillar pattern at high rates. The microstructure size was strongly dependent on the growth rate, decreasing when the processing rate increased. The optical absorption was measured in the samples at room temperature and Judd–Ofelt analysis was used to model the optical absorption of the Er³⁺ ions. Thermal emission of the eutectic rods was studied at temperatures up to 1600 °C. An intense narrow emission band at 1.55 μm matching with the sensitive region of the GaSb photoconverter was obtained. The intensity of the selective emission band is larger for the binary eutectic than for the ternary compound and increases as the microstructural size decreases.     

Layered Y3Al5O12:Pr/Gd3(Ga,Al)5O12:Ce optical ceramics: Synthesis and photo-physical properties

We report a study of composite scintillating ceramics based on coupled layers of two different garnets, namely Ce-doped gadolinium gallium aluminium (GGAG:Ce) and Pr-doped yttrium aluminium (YAG:Pr), fabricated by hot isostatic pressing. Two samples were prepared, with different GGAG:Ce layer thickness, 120 µm and 690 µm respectively, but with a comparable overall thickness of 1.4 mm. The key finding is that the material architecture strongly determines the scintillation response. The radioluminescence is that expected from the irradiated material when a thick layer of ceramic is exposed to X-rays. Conversely, exposing a thin layer allows a non-null probability —about 0.3% for 120 µm of GGAG— of finding an X-ray photon in the underlying layer, and thus radioluminescence from both materials is recorded. We believe these results can extend the potential of layered optical ceramics for advanced devices, such as energy- and direction-sensitive X-ray detectors.     

非均相Fe/Al_2O_3催化H_2O_2降解偶氮染料活性黑5

以活性氧化铝为载体,制备了Fe/Al2O3负载型催化剂,用于催化H2O2分解产生羟基自由基氧化降解偶氮染料活性黑5。探讨了pH、H2O2投加量、催化剂投加量等对染料脱色率的影响。结果表明,活性黑5的脱色率随催化剂投加量的增加而升高;随H2O2投加量的增加而降低;Fe/Al2O3/H2O2体系下,活性黑5在pH为2~9之间均有一定的脱色效果,活性黑5的脱色率随初始pH的增加而先增加后减少,其中在初始pH为3时,脱色效果最佳。     

Effect of Y2O3 on the corrosion resistance of two-step sintered Al5Y3O12-MgAl2O4 sidewalls in the aluminum electrolyte

Magnesium–aluminum spinel (MAS) precursor powder was synthesized through a microwave hydrothermal method. The synergistic effects of sintering process and sintering aids on the densification, hardness and corrosion resistance of MAS were revealed. X-ray diffraction analysis (XRD), Archimedes’ drainage method, fully automatic micro-Vickers hardness test and scanning electron microscopy (SEM) were performed to analyze the phase composition, bulk density, hardness microstructure and corrosion depth of the samples, respectively. Results revealed that the best two-step sintering condition is 1650 °C/3 min/1550 °C/20 h. The MAS products obtained under the best condition have clear grain boundaries, uniform particle size distribution, and few pores. When the amount of Y₂O₃ added is 4 wt.%, Y₂O₃ and Al₂O₃ form the second-phase solid solution Al₅Y₃O₁₂, which activates the crystal lattice and benefits the sintering densification of MAS. Under these conditions, the relative density of the MAS composite ceramics prepared is relatively large (95.94 %), the grain size is relatively uniform, the hardness is relatively large (1264 HV), and the corrosion depth is relatively small (94.58 μm).