Solidification of Al2O3–YAG eutectic composites with off-metastable eutectic composition from undercooled melt produced by melting Al2O3–YAP eutectics

It has been reported that solidification of the Al₂O₃–YAG equilibrium eutectic structure follows melting of the Al₂O₃–YAP metastable eutectic structure. Since the exothermic heat due to solidification was consumed by the endothermic heat due to melting, a fine and uniform eutectic structure was obtained. However, the composition of the Al₂O₃–YAG eutectic structure is restricted to the metastable eutectic composition. In this paper, Al₂O₃–YAG eutectic compacts with an off-metastable eutectic composition were prepared by the addition of Al₂O₃ particles to Al₂O₃–YAP eutectic particles with diameters less than 20 μm. In compositions ranging from 18.5 mol%Y₂O₃ to 13.5 mol%Y₂O₃, dense Al₂O₃–YAG eutectic compacts were formed without any Al₂O₃ segregation. The flexural strength and the fracture toughness remained almost unchanged with the increase in the Al₂O₃ phase. The addition of Al₂O₃ particles to the Al₂O₃–YAP eutectic particles enabled the matrix phase to change from the YAG phase to the Al₂O₃ phase.     

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.     

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.     

Phase diagram of the Al2O3–ZrO2–La2O3 system

The phase diagram of the Al₂O₃–ZrO₂–La₂O₃ system was constructed in the temperature range 1250–2800 °C. The liquidus surface of the phase diagram reflects the preferentially eutectic interaction in the system. Three new ternary and two new binary eutectics were found. The minimum melting temperature is 1665 °C and it corresponds to the ternary eutectic LaAlO₃ + T-ZrO₂ +  La₂O₃·11Al₂O₃. The solidus surface projection and the schematic of the alloy crystallization path confirm the preferentially congruent character of phase interaction in the ternary system. The polythermal sections present the complete phase diagram of the Al₂O₃–ZrO₂–La₂O₃ system. No ternary compounds or regions of remarkable solid solution were found in the components or binaries in this ternary system. The latter fact is the theoretical basis for creating new composite ceramics with favorable properties in the Al₂O₃–ZrO₂–La₂O₃ system.     

Effect of Si additions on the Al2O3 grain refinement upon oxidation of Cr2AlC MAX phase

The effect of Si additions on the oxidation behavior of Cr₂AlC based coatings is investigated. Oxidation experiment was performed at 1120 °C in air for 4 h for Cr₂AlC and Cr₂Al_1−xSi_xC (0 < x ≤ 0.06) coatings. The crystal structure, microstructure and chemical composition of the as-deposited as well as oxidized coatings have been investigated. Alloying Cr₂AlC with up to 0.7 at.% Si causes an increase in Al₂O₃ scale thickness by up to 40 ± 17%. Electron microscopy and atom probe tomography data support the notion that the here reported Si concentration induced 40% increase in Al₂O₃ layer thickness (during oxidation at 1120 °C for 4 h) is enabled by the Si concentration induced, and hence concomitant, increase in nucleation density of Al₂O₃.     

Sintering,microstructure and mechanical properties of Al2O3–Y2O3–ZrO2 (AYZ) eutectic composition ceramic microcomposites

We report on how the mechanical properties of sintered ceramics (i.e., a random mixture of equiaxed grains) with the Al₂O₃–Y₂O₃–ZrO₂ eutectic composition compare with those of rapidly or directionally solidified Al₂O₃–Y₂O₃–ZrO₂ eutectic melts. Ceramic microcomposites with the Al₂O₃–Y₂O₃–ZrO₂ eutectic composition were fabricated by sintering in air at 1400–1500 °C, or hot pressing at 1300–1400 °C. Fully dense, three phase composites of Al₂O₃, Y₂O₃-stabilized ZrO₂ and YAG with grain sizes ranging from 0.4 to 0.8 μm were obtained. The grain size of the three phases was controlled by the size of the initial powders. Annealing at 1500 °C for 96 h resulted in grain sizes of 0.5–1.8 μm. The finest scale microcomposite had a maximum hardness of 19 GPa and a four-point bend strength of 282 MPa. The fracture toughness, as determined by Vickers indentation and indented four-point bending methods, ranged from 2.3 to 4.7 MPa m^1/2. Although strengths and fracture toughnesses are lower than some directionally or rapidly solidified eutectic composites, the intergranular fracture patterns in the sintered ceramic suggest that ceramic microcomposites have the potential to be tailored to yield stronger, tougher composites that may be comparable with melt solidified eutectic composites.     

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.     

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.     

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.     

Microstructure of the directionally solidified ternary eutectic ceramic Al2O3/MgAl2O4/ZrO2

The directionally solidified Al₂O₃/MgAl₂O₄/ZrO₂ ternary eutectic ceramic was prepared via induction heating zone melting. Smooth Al₂O₃/MgAl₂O₄/ZrO₂ eutectic ceramic rods with diameters of 10 mm were successfully obtained. The results demonstrate that the eutectic rods consist of Al₂O₃, MgAl₂O₄ and ZrO₂ phases. In the eutectic microstructure, the MgAl₂O₄ and Al₂O₃ phases form the matrix, the ZrO₂ phase with a fibre or shuttle shape is embedded in the matrix, and a quasi-regular eutectic microstructure formed, presenting a typical in situ composite pattern. During the eutectic growth, the ZrO₂ phase grew on non-faceted phases ahead of the matrix growing on the faceted phase. The hardness and fracture toughness of the eutectic ceramics reached 12 GPa and 6.1 MPa·m ^1/2, respectively, i.e., two times and 1.7 times the values of the pre-sintered ceramic, respectively. In addition, the ZrO₂ phase in the matrix reinforced the matrix, acting as crystal whiskers to reinforce the sintered ceramic.     

Superplastic deformation of directionally solidified nanofibrillar Al2O3–Y3Al5O12–ZrO2 eutectics

Nanofibrillar Al₂O₃–Y₃Al₅O₁₂–ZrO₂ eutectic rods were manufactured by directional solidification from the melt at high growth rates in an inert atmosphere using the laser-heated floating zone method. Under conditions of cooperative growth, the ternary eutectic presented a homogeneous microstructure, formed by bundles of single-crystal c-oriented Al₂O₃ and Y₃Al₅O₁₂ (YAG) whiskers of ≈100 nm in width with smaller Y₂O₃-doped ZrO₂ (YSZ) whiskers between them. Owing to the anisotropic fibrillar microstructure, Al₂O₃–YAG–YSZ ternary eutectics present high strength and toughness at ambient temperature while they exhibit superplastic behavior at 1600 K and above. Careful examination of the deformed samples by transmission electron microscopy did not show any evidence of dislocation activity and superplastic deformation was attributed to mass-transport by diffusion within the nanometric domains. This combination of high strength and toughness at ambient temperature together with the ability to support large deformations without failure above 1600 K is unique and shows a large potential to develop new structural materials for very high temperature structural applications.     

Synthesis,microstructure and mechanical properties of Cr2AlC/Al2O3 in situ composites by reactive hot pressing

Al₂O₃ particle-reinforced Cr₂AlC in situ composites were successfully fabricated from powder mixtures of Cr₃C₂, Cr, Al, and Cr₂O₃ by a reactive hot-pressing method at 1400 °C. A possible synthesis mechanism was proposed to explain the formation of the composites in which Al₂O₃ was formed by the aluminothermic reaction between Al and Cr₂O₃, meanwhile, Cr₃C₂, Al, together with Cr reacted to form Cr₂AlC in a shortened reaction route. The effect of Al₂O₃ addition on the microstructure and mechanical properties of Cr₂AlC/Al₂O₃ composites was investigated. The results indicated that the as-sintered products consisted of Cr₂AlC matrix and Al₂O₃ reinforcement, and the in situ formed fine Al₂O₃ particles dispersed at the matrix grain boundaries. The flexural strength and Vickers hardness of the composites increased gradually with increasing Al₂O₃ content. But the fracture toughness peaked at 6.0 MPa m^1/2 when the Al₂O₃ content reached 11 vol.%. The strengthening and toughening mechanism was also discussed.     

Mechanical properties up to 1900 K of Al2O3/Er3Al5O12/ZrO2 eutectic ceramics grown by the laser floating zone method

Directionally solidified Al₂O₃–Er₃Al₅O₁₂–ZrO₂ eutectic rods were processed using the laser floating zone method at growth rates of 25, 350 and 750 mm/h to obtain microstructures with different domain size. The mechanical properties were investigated as a function of the processing rate. The hardness, ∼15.6 GPa, and the fracture toughness, ∼4 MPa m^1/2, obtained from Vickers indentation at room temperature were practically independent of the size of the eutectic phases. However, the flexural strength increased as the domain size decreased, reaching outstanding strength values close to 3 GPa in the samples grown at 750 mm/h. A high retention of the flexural strength was observed up to 1500 K in the materials processed at 25 and 350 mm/h, while superplastic behaviour was observed at 1700 K in the eutectic rods solidified at the highest rate of 750 mm/h.     

Microstructure and mechanical properties of Al2O3–YSZ and Al2O3–YAG directionally solidified eutectic plates

Plates of Al₂O₃–YSZ and Al₂O₃–YAG eutectic composition with a thickness from 0.1 to 1 mm were prepared by directional solidification using a diode laser stack. The melt processed regions of plates exhibited colony microstructure consisting of finely dispersed phases. Due to the curved shape of the melted pool, the growth rate depends on the distance to the surface plate, decreasing from top to bottom. In this way, the microstructure characteristic length changes as a function of the distance to the plate surface. Vickers indentations and piezo-spectroscopy measurements were done on longitudinal and transverse cross-sections of the samples at different depths. From these measurements, we concluded that the Vickers hardness (H_V), indentation fracture toughness (K_IC) and residual stresses (σ_h) of the plates were mainly independent from the distance to the surface. The mean values that we obtained in the Al₂O₃–YSZ plates were H_V = 16 GPa, K_IC = 4.2 MPa m^1/2 and σ_h = −0.33 GPa, and in the Al₂O₃–YAG plates were H_V = 16 GPa, K_IC = 2.0 MPa m^1/2, and σ_h = −0.1 GPa. These values are similar to those found in directionally solidified eutectic rods.     

Effect of solidification path on the microstructure of Al2O3–Y2O3–ZrO2 ternary oxide eutectic ceramic system

The solidification path of the Al₂O₃–Y₂O₃–ZrO₂ ternary oxide eutectic composite ceramic is determined by a high temperature DTA and laser floating zone (LFZ) directional solidification method to investigate the effect of solidification path on the microstructure of the ternary oxide. The DTA and microstructure analyses show that the YAG or Al₂O₃ tends to form as primary phase under the unconstrained solidification conditions, and then the system enters ternary eutectic solidification during cooling from 1950 °C at rate of 20 °C/min. The as-solidified composite ceramic shows a divorced irregular eutectic structure consisting of Al₂O₃, YAG and ZrO₂ phases with a random distribution. The primary phases are however completely restrained at the directional solidification conditions with high temperature gradient, and the ternary composite by LFZ presents well coupled eutectic growth with ultra-fine microstructure and directional array. Furthermore, the eutectic transformation and growth mechanism of the composite ceramic under different solidification conditions are discussed.     

Formation mechanism and process optimization of nano Al2O3-ZrO2 eutectic ceramic via laser engineered net shaping (LENS)

Periodic banded structure has great influence on the microstructure and fracture toughness of eutectic ceramic produced by LENS system. Formation Mechanism of periodic banded structure and influence regularity from laser power, scanning speed, feeding rate and feeding proportion were studied. X-ray diffractometer analysis and scanning electron microscopy observation were carried out for sample phase composition and microstructure respectively. Microhardness was measured by vivtorinox hardness tester, and surface fracture toughness was calculated by indentation crack length. The results show that periodic banded structure is divided into organizational coarsening zone and divorced eutectic zone. Due to the influence of upper cladding layer heat, the eutectic structure in the interlayer bonding zone is obviously coarsening in organization coarsening zone. When laser power is lower, Al₂O₃ phase takes the lead in nucleation and grows up quickly, forming a discrete block structure of Al₂O₃ particles in divorced eutectic area. When laser power is higher, ZrO₂ phase takes the lead in nucleation and forms a discrete block structure of ZrO₂ particles. Al₂O₃-ZrO₂ ceramics with the shape of thin-walled and cylinder were manufactured under the optimized process conditions, whose independent nucleation disappears and the thickness of periodic banded structure reduces to 10 µm. The eutectic spacing of prototype structure reaches 120–130 nm, has uniform microstructure and good surface morphology. The average micro-hardness is 18.59 GPa. Surface fracture toughness increases to 6.52 MPa m^1/2.     

Effects of Cr content and morphology on the luminescence properties of the Cr-doped alpha-Al2O3 powders

Al₂O₃:Cr³⁺ samples were synthesized via hydrothermal and microwave solvothermal methods and thermal decomposition of Cr³⁺ doped precursors. The sample characterizations were carried out by means of X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectra and decay curves. XRD results indicated that Cr³⁺ doped samples were pure α-Al₂O₃ phase after being calcined at 1573 K. SEM results showed that the length and diameter of these Cr³⁺ doped alumina microfibers by hydrothermal route were about 2–5 μm and 100–300 nm, respectively; the obtained α-Al₂O₃ based powders via the microwave solvothermal method were microspheres with an average diameter about 1–2 μm. PL spectra showed that the Al₂O₃:Cr³⁺ samples presented a broad R band at 696 nm. It is shown that the 0.3 mol% of doping concentration of Cr³⁺ ions in α-Al₂O₃:Cr³⁺ is optimum. According to Dexter's theory, the critical distance between Cr³⁺ ions for energy transfer was determined to be 24 Å. It is found that the curve followed the single-exponential decay. Furthermore, the luminescence properties of the samples are also dependent on the morphology.     

Liquid phase sintering of Al2O3/SiC nanocomposites

Al₂O₃/SiC nanocomposites are usually prepared by hot pressing or using high sintering temperatures, viz. 1700°C. This is due to the strong inhibiting effect of the nano-sized SiC particles on the densification of the material. Liquid phase sintering (LPS) can be used to improve densification. This work explored two eutectic additive systems, namely MnO₂.SiO₂ (MS) and CaO.ZnO.SiO₂ (CZS). The additive content in Al₂O₃/5 wt% SiC nanocomposite material varied from 2 to 10 wt%. Densities of up to 99% of the theoretical value were achieved at temperatures as low as 1300°C. Characterisation of the materials by XRD, indicated the formation of secondary crystalline phases in addition to Al₂O₃ and SiC. SEM and TEM analysis showed the presence of a residual glassy phase in the grain boundaries, and an increase in the average grain size when compared to nanocomposites processed without LPS additives.