Rapid fabrication of bulk graded Al2O3/YAG/YSZ eutectics by combustion synthesis under ultra-high-gravity field

A rapid and simple way of producing bulk graded Al₂O₃/YAG/YSZ ternary eutectics was investigated. The combustion reaction between Al/Fe₂O₃/Y₂O₃/ZrO₂ led to the formation of molten mixtures consisting of Al₂O₃/YAG/YSZ, and the subsequent separation of the ceramic melt from the iron melt was realized under ultra-high-gravity field, followed by the solidification of the ceramic melt. The as-solidified ceramic ingot sank into the iron melt, where an instantaneous isostatic pressure about 2 MPa was exerted on the around of the ceramic ingot resulting in an enhanced degree of densification. Microstructure analysis demonstrated that densified ceramic was composed of Al₂O₃/YAG/YSZ ternary eutectics. The phase composition, morphologies, hardness and fracture toughness of the eutectic product changed gradually along the direction of high gravity field. The maximum density of the eutectic ceramic was 97.32%, correspondingly, the maximum value of the Vickers hardness and fracture toughness reached 17.82 GPa and 5.51 MPa m^1/2, respectively.     

Investigation of the solidification behavior of Al2O3/YAG/YSZ ceramic in situ composite with off-eutectic composition

Directionally solidified Al₂O₃/YAG/YSZ ceramic in situ composite is an interesting candidate for the manufacture of turbine blade because of its excellent mechanical property. In the present study, two directionally solidified hypoeutectic and hypereutectic Al₂O₃/YAG/YSZ ceramic in situ composites are prepared by laser zone remelting, aiming to investigate the solidification behavior of the ternary composite with off-eutectic composition under high-temperature gradient. The results show that the composition and laser scanning rate significantly influence the solidification microstructure. The ternary in situ composite presents ultra-fine microstructure, and the eutectic interspacing is refined with the increase of the scanning rate. The Al₂O₃/YAG/YSZ hypoeutectic ceramic displays an irregular hypoeutectic network structure consisting of a primary Al₂O₃/YAG binary eutectic and fine Al₂O₃/YAG/YSZ ternary eutectic. Only at low scanning rate, homogeneous ternary eutectic-like microstructures are obtained in the hypoeutectic composition. Meanwhile, the Al₂O₃/YAG/YSZ hypereutectic ceramic shows homogeneous eutectic-like microstructure in most cases and the eutectic interspacing is finer than the ternary eutectic. Furthermore, the formation and evolution mechanism of the off-eutectic microstructure of the ternary composite are discussed.     

Microstructure, growth mechanism and mechanical property of Al2O3-based eutectic ceramic in situ composites

Directionally solidified Al₂O₃-based eutectic ceramic in situ composites with inherently high melting point, low density, excellent microstructure stability, outstanding resistance to creep, corrosion and oxidation at elevated temperature, have attracted significant interest as promising candidate for high-temperature application. This paper reviews the recent research progress on Al₂O₃-based eutectic ceramic in situ composites in State Key Laboratory of Solidification Processing. Al₂O₃/YAG binary eutectic and Al₂O₃/YAG/ZrO₂ ternary eutectic ceramics are prepared by laser zone melting, electron beam floating zone melting and laser direct forming, respectively. The processing control, solidification characteristic, microstructure evolution, eutectic growth mechanism, phase interface structure, mechanical property and toughening mechanism are investigated. The high thermal gradient and cooling rate during solidification lead to the refined microstructure with minimum eutectic spacing of 100 nm. Besides the typical faceted/faceted eutectic growth manner, the faceted to non-faceted growth transition is found. The room-temperature hardness H_V and fracture toughness K_IC are measured with micro-indentation method. For Al₂O₃/YAG/ZrO₂, K_IC = 8.0 ± 2.0 MPa m^1/2 while for Al₂O₃/YAG, K_IC = 3.6 ± 0.4 MPa m^1/2. It is expectable that directionally solidified Al₂O₃-based eutectic ceramics are approaching practical application with the advancement of processing theory, technique and apparatus.     

Processing,microstructure and performance of Al2O3/Er3Al5O12/ZrO2 ternary eutectic ceramics prepared by laser floating zone melting with ultra-high temperature gradient

Directionally solidified Al₂O₃/Er₃Al₅O₁₂(EAG)/ZrO₂ ternary eutectic/off-eutectic composite ceramics with high density, homogeneous microstructures, well-oriented growth have been prepared by laser floating zone melting at different solidification rates from 4 to 400 µm/s. Uniform and stable melting zone is obtained by optimizing temperature field distribution to keep continuous and stable eutectic growth and prevent from cracks and defects. The as-solidified composite ceramic exhibits complexly irregular eutectic structure, in which the eutectic spacing is rapidly refined but dotted ZrO₂ number inside Al₂O₃ phase is decreased as increasing the solidification rate. The formation mechanism of ZrO₂ distributed inside Al₂O₃ matrix is revealed by examining the depression of solid/liquid interface. Furthermore, after heat exposure 1500 °C for 200 h, the eutectic microstructure only shows tiny coarsening, which indicates it has excellent microstructural stability. As increasing the ZrO₂ content, the fracture toughness can be improved up to 3.5 MPa m^1/2 at 20.6 mol% ZrO₂.     

Microstructural refinement and mechanical response of Al2O3–ZrO2 eutectics fabricated by a novel pulse discharge plasma assisted melting method

In the present work, microstructural refinement and mechanical response of Al₂O₃–ZrO₂ eutectics fabricated by a pulse discharge plasma assisted melting (PDPAM) method were investigated. The solidified microstructure evolves from polygonal eutectic colonies into irregular cellular colonies with increasing the superheating temperature of the melt from 1820 °C to 1900 °C. The average eutectic spacing inside the colonies decreases from 1.80 ± 0.10 μm to 0.25 ± 0.06 μm, and the coarse inter-colonial structure is refined, which is attributed to the increase in undercooling temperature. High-temperature microstructural stability of Al₂O₃–ZrO₂ eutectics is improved significantly as contrasted with the as-sintered ceramics. Besides, the load dependence of Vickers hardness for Al₂O₃–ZrO₂ eutectics is investigated.     

Eutectic structure evolution of Al2O3-ZrO2-Y2O3 system for potential hybrid solar cell application

Abstract

Ternary Al₂O₃-ZrO₂-Y₂O₃ samples with a eutectic composition were prepared by slow cooling. The microstructural evolution was observed with X-ray diffraction (XRD), scanning electron microscopy (SEM).

The SEM observation of the ternary samples agreed with the XRD with a completion of crystallisation by slow cooling. The target materials commonly have ‘cantaloupe skin’ microstructures as shown in the previous studies by Han et al. The nanocomposite may have experienced different cooling rates with two different microstructures, near the surface having experienced optimal conditions for the eutectic reaction during their cooling and thus formed the eutectic microstructure, near the centre having experienced a slower cooling rate. The crystallised eutectic ternary Al₂O₃-ZrO₂-Y₂O₃ system had three different phases with a 3Y₂O₃-5Al₂O₃ (yttrium-aluminium garnet phase), an alumina phase formed by the eutectic reaction, and a solid solution of ZrO₂ and Y₂O₃.     

Microstructural evolution of supra-nanostructure Al2O3/ZrO2 eutectic powders by combustion synthesis-spray cooling

Eutectic powders with fine microstructure are difficult to synthesize by crushing eutectic bulk because of the damage of crystal structure and the introduction of milling media during preparation process. In this work, a novel combustion synthesis-spray cooling (CSSC) method is developed to fabricate supra-nanostructure Al₂O₃/ZrO₂ eutectic powders. CSSC is a kind of self-heating technique, which simplifies operations, reduces costs and supplies ultra-high cooling rate. The phase composition and the microstructural evolution are investigated using experiment studies and ANSYS simulation. During the process, the t-ZrO₂ are stabilized at room temperature because of the solubility of Al₂O₃ in ZrO₂. The ultra-high cooling rate greatly refined eutectic structure. Although the eutectic structure coarsens with increases in particle size, the interphase spacing of all particles reaches supra nanoscale. The work provides a route for preparing supra-nanostructure Al₂O₃/ZrO₂ eutectic powders and for better understanding the microstructural evolution.     

Microstructural formation and evolution of near-eutectic Al2O3–ZrO2 powders prepared by a rapid cooling technique: An exploration on coupled eutectic growth range

Regulation of eutectic compositions is a difficult challenge due to the limited formation range of this microstructure. Al₂O₃–ZrO₂ powders were successfully prepared through a modified high-temperature melt-assisted air atomization technique. Micron-sized raw powders of α-Al₂O₃ and m-ZrO₂ were used to regulate the temperature of system and the composition of final products. The high-temperature melt of 3500 K (3227 °C) was obtained based on the exothermic reaction between Al and O₂, which was subsequently atomized and quenched to form composite powders. The phase composition and microstructure of the as-prepared powders were characterized by X-Ray diffraction and scanning electron microscopy. Eutectic colonies with nanolamellae (62–79 nm) were observed in the as-prepared Al₂O₃-(28–58 mol%) ZrO₂ powders, with growth rates ranging from 1.9 to 2.8 mm s⁻¹. Importantly, the powders with ZrO₂ contents of 38 mol% and 42 mol% showed complete eutectic microstructures without primary dendrites, which indicated an extended coupled growth range deviating by ∼4.9 mol% from the eutectic composition (C_E). The microstructural formation mechanism was discussed based on solidification behavior analysis. Furthermore, the evolution of the microstructure and phase in Al₂O₃-42 mol% ZrO₂ powders was investigated. This work aims to develop a novel strategy for preparing oxide powders with eutectic structures and provide a reference for the composition regulation of eutectics.     

High temperature deformation of non-directionally solidified Al2O3/YAG/ZrO2 eutectic bulk ceramic

Excellent high temperature mechanical properties of melt-grown Al₂O₃-based eutectics have previously been demonstrated in samples prepared by directional solidification methods. In this study, the deformation behaviour of melt-grown Al₂O₃/YAG/ZrO₂ eutectic bulk prepared by a non-directional solidification method was investigated by means of compressive tests in a temperature range of 1200–1700 °C. The non-directionally solidified eutectic bulk ceramic has a colony structure and is polycrystalline. It begins to show ductility and has a compressive strength of 320 MPa at 1500 °C, which is much higher than that of the sintered ceramic with the same composition. However, its plastic deformability is insufficient, even at 1700 °C (just below the melting point of 1715 °C), and cracking occurs during compressive deformation.     

Orientations and seed type effect on Al2O3-YAG-ZrO2 eutectic microstructure solidified from the melt by the micro-pulling down technique

Al₂O₃-YAG-ZrO₂ eutectic ceramic rods of 5 mm in diameter were grown by micro-pulling down technique. The seeding and the solidification rate affect microstructure, morphology, crystallography, and thermal stress of the solidified ceramics. The ternary eutectic grown through zirconia (111) seed had inhomogeneous and irregular cellular microstructures. At the stationary stable regime, the microstructure spacing (λ) depends on the pulling rate (v). Under solidification rate of 0.5 mm.min^?1, the rods grown by using eutectic poly-crystal, (100), (111) YAG, and c(0001), A(1?210), M(10?10) sapphire seeds, the YAG and ZrO₂ phases are oriented along the <100> direction parallel to the growth direction. The zirconia (111) seeding X-ray diagram eutectic presents additional peaks and the monoclinic ZrO₂ phase appears at the solidification rate of 1 mm.min-1. The rods grown through ZrO₂ seeding are more stressed than those solidified by using eutectic, YAG and sapphire seeds, respectively.     

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.     

Competitive growth of Al2O3/YAG/ZrO2 eutectic ceramics during directional solidification: Effect of interfacial energy

The microstructure evolution and growth behavior of the Al₂O₃/Y₃Al₅O₁₂(YAG)/ZrO₂ ternary eutectic ceramics during directional solidification were well investigated. During directional solidification of the Al₂O₃/YAG/ZrO₂ ternary eutectic ceramics, {} Al₂O₃ paralleled with {001}ZrO₂ while they did not parallel with {001}YAG at the same time in the competitive growth stage. All of the interfaces parallel to each other finally. The area percentage of the Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are 40.4 ± 0.2% and 30.8 ± 0.1%, respectively, higher than that of the Al₂O₃/YAG (28.8 ± 0.2%). The content of Al₂O₃ and YAG phases are 39.9% and 41.1%, respectively, almost double of that of ZrO₂. The interfaces of Al₂O₃/ZrO₂ and YAG/ZrO₂ are shorter and more dispersed than that of the Al₂O₃/YAG. It was found that the interfacial energy of Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are lower than that of Al₂O₃/YAG. It can be concluded that interfacial energy plays a decisive role in affecting the crystallographic orientation and interfaces distribution in the Al₂O₃/YAG/ZrO₂ eutectic since the interfaces of Al₂O₃/ZrO₂ and YAG/ZrO₂ with lower interfacial energy can be formed more easily during directional solidification. Therefore, the contents of Al₂O₃/ZrO₂ and YAG/ZrO₂ interfaces are higher. This study can provide theoretical guidance for interface design of multi-phase 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.     

Laser machining of Al2O3-ZrO2 (3%Y2O3) eutectic composite

In this work we present the study of the interaction between NIR pulsed laser and Al₂O₃-ZrO₂ (3%Y₂O₃) eutectic composite. The effect produced by modifying the reference position as well as the working conditions and laser beam features has been studied when the samples are processed by means of pulse bursts.The samples were obtained by the laser floating zone technique using a CO₂ laser system. The laser machining was carried out with a Q-switched Nd:YAG laser at its fundamental wavelength of 1064 nm with pulse-widths in the nanosecond range.Geometric dimensions, i.e. ablated depth, machined width and removed volume as well as ablation yield of the resulting holes have been studied. We have described and discussed the morphology, composition and microstructure of the processed samples.     

Phase separation in melts of the ZrO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The morphology of the quenched and slowly crystallized samples in the ZrO₂-Al₂O₃ system is investigated in the composition range 25–70 wt % ZrO₂. It is revealed that, irrespective of the cooling rate, the samples contain large baddeleyite (or corundum) crystals, eutectic mixtures, and characteristic regions of intergrown elongated baddeleyite and corundum grains with micron sizes. These regions have the same phase composition at any initial ratio between zirconium and aluminum oxides and at any cooling rates of the melt. A hypothesis is put forward that these regions are products of the decomposition of ZrO₂ · 2Al₂O₃ associates.     

One-step additive manufacturing and microstructure evolution of melt-grown Al2O3/GdAlO3/ZrO2 eutectic ceramics by laser directed energy deposition

Synchronized-powder-feeding-based laser directed energy deposition (LDED) has great application potential for the rapid fabrication of large-scale composite ceramics with complex shapes. In this study, near-full-density Al₂O₃/GdAlO₃/ZrO₂ ternary eutectic ceramics with different shapes and smooth surfaces were directly prepared by using an improved LDED device. Spherical ceramic powders with eutectic composition and good flowability were obtained by centrifugal spray drying. The microstructure characteristics and microstructure evolution of the rapidly solidified 3D-printed eutectic ceramic were systematically elucidated. In particular, the formation mechanism of the observed periodic banded structures was revealed through a unique laser partial remelting technique. The result indicated that the appearance of the banded structure is attributed to the drastic abnormal coarsening of the nanoscale microstructures adjacent to the molten pool. On the basis these results, a physical model was proposed to illustrate the microstructure evolution of the 3D-printed Al₂O₃/GdAlO₃/ZrO₂ eutectic ceramic.     

Effect of cooling rate on the microstructure and mechanical properties of melt-grown Al2O3/YAG/ZrO2 eutectic ceramic

Melt-grown Al₂O₃/YAG/ZrO₂ ternary eutectic samples were solidified by quenching and with controlled cooling rates of 10, 50, and 250 °C/min, respectively. Effect of cooling rate on microstructure and mechanical properties were examined. With the increase of cooling rate, three classical characteristic microstructures are obtained and developed from colony structure to dendrite structure and to cell structure. In the quenching process, the sample consists of lamellar eutectic cells and its fracture toughness increases to 4.13 ± 0.8 MPa m^1/2. The microstructure transitions with the cooling rate are attributed to instability of the solid–liquid interface. In this work, the interface instability is analyzed to explain the microstructure evolutions in terms of undercooling and characteristic lengths of solute diffusion and capillarity effect.     

Melt differentiation and crystallization of clinker minerals in a CaO-SiO2-Al2O3-Fe2O3 pseudoquaternary system

In the CaO-SiO₂-Al₂O₃-Fe₂O₃ pseudoquaternary system, the solid solutions of Ca₃SiO₅ [C₃S(ss)], Ca₂SiO₄ [C₂S(ss)], Ca₂(Al_xFe_1 − x)₂O₅ with 0.40 ≤ x ≤ 0.57 (ferrite) and Ca₃Al₂O₆ [C₃A(ss)] were crystallized out of a complete melt with 52.9 mass% CaO and Al₂O₃/Fe₂O₃ = 0.70. When the melt was cooled from 1673 K at 80 K/h, the crystals of ferrite with x = 0.40, C₃S(ss) and C₂S(ss) would start to nucleate from the melt at 1630 K. During further cooling, the x value of the precipitating ferrite would progressively increase and eventually approach 0.57 at 1613 K. The resulting ferrite crystals showed a zonal structure, the x value of which successively increased from the cores toward the rims. Actually, the x values of 0.43 and 0.52 were confirmed for, respectively, the cores and rims by EPMA. As the simultaneous crystallization of zoned ferrite, C₃S(ss) and C₂S(ss) proceeded, the coexisting melt would become progressively enriched in the Al₂O₃ component. After the termination of the ferrite crystallization, the C₃A(ss), C₃S(ss) and C₂S(ss) crystallized out of the differentiated melt. The end result was the four phase mixture of ferrite, C₃A(ss), C₃S(ss) and C₂S(ss), being free from the nucleation of Ca₁₂Al₁₄O₃₃ solid solution.     

Effect and mechanism of ZrO2 doping on the cracking behavior of melt-grown Al2O3 ceramics prepared by directed laser deposition

Directed laser deposition (DLD) is a new method for rapidly preparing melt-grown ceramics, but cracking problem greatly limited its application. In this study, cracking behavior of Al₂O₃ ceramics was suppressed by doping ZrO₂. Crack suppression mechanism of ZrO₂ doping in melt-grown ceramics was also analyzed. Process parameters which are prone to generating cracks were adopted in the experiments, and they contribute to showing the crack clearly. Results show that ZrO₂ doping has remarkable crack suppression effects. It is most obvious when ZrO₂ content is 37 mol%. Compared with those of pure Al₂O₃ ceramics, crack density reduces by 43.2%, and the number of longitudinal main cracks reduces by 63.2%. Doping of ZrO₂ forms dense composite microstructure with primary α-Al₂O₃ grains discretely distributing in eutectic continuous matrix. Therefore, initial crack sources are effectively reduced. Morphology of primary Al₂O₃ grains transforms from cellular to dendritic, which changes crack propagation mode from inter-granular to trans-granular. Mismatch of thermo-physical properties of different phase promotes the arrest, deflection, and bridging phenomena in crack propagation, contributing to crack suppression. On the basis of ZrO₂ doping, we have realized the preparation of crack-free eutectic ceramic (37 mol%ZrO₂) samples through further process optimization. The maximum size of the sample reaches 230 mm.     

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.