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.     

Crucible-free fabrication of ZrB2–SiC composite ceramics with ultra-fine eutectic microstructure by laser surface zone-melting: The selection of lasers

Here we report the crucible-free fabrication of ZrB₂–SiC composite ceramics by laser surface zone-melting (LSZM, a rapid solidification method) using Nd: YAG laser, ytterbium-doped fiber laser, and CO₂ laser, respectively. Based on the comparative investigation of the thickness and the microstructure of the laser processed zone, this work highlights that the CO₂ laser is the most suitable laser resource for the fabrication of highly dense and large-scale ZrB₂–SiC composite ceramics with the eutectic colonies consisting of maze-shaped eutectic microstructure by LSZM. The high temperature gradient up to ～4 × 10⁵ K/m using CO₂ laser extremely reduces the phase size down to submicron-scale, which contributes to the high relative density (～99%), Vickers hardness (24.18 GPa) and fracture toughness (7.4 MPa m^1/2) of the ZrB₂–SiC composite ceramics. This work demonstrates for the first time that LSZM is a promising method for the rapid fabrication of dense ZrB₂ based ultra-high temperature bulk ceramics.     

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.     

Effect of scanning speed on the solidification process of Al2O3/GdAlO3/ZrO2 eutectic ceramics in a single track by selective laser melting

Al₂O₃/GdAlO₃/ZrO₂ ternary eutectic ceramics with fine microstructure were directly fabricated from mixed pure ceramic powders by selective laser melting. The specimen forming quality, molten pool morphology and microstructure characteristic were investigated as functions of scanning speed. Solidification defects such as cracks and pores were effectively suppressed when the scanning speed was 12 mm/min. The relative density of the as-solidified eutectic specimens decreased from 98.7% to 95.7% with increasing the scanning speed up to 48 mm/min. The melting in this study was governed by conduction mode, leading to a decrease tendency of both melting width and depth with the increase of the scanning speed. Different from ordinary cognition, the eutectic spacing in top zone of the molten pool first decreased and then increased with increasing the scanning speed from 6 mm/min to 48 mm/min. The transition point appeared at 12 mm/min, where the dominant factor affecting the solidification rate changed from the scanning speed to the value of the angle between microstructure growth direction and laser scanning direction.     

Microstructure and mechanical properties of directionally solidified Al2O3/GdAlO3 eutectic ceramic prepared with horizontal high-frequency zone melting

Directionally solidified eutectic oxide ceramics are very promising as a next-generation structural material for ultrahigh-temperature applications, above 1600?°C, owing to their outstanding properties of high corrosion resistance, oxidation resistance, high fracture strength and toughness, and high hardness. Herein, Al₂O₃/GdAlO₃ eutectic ceramic was prepared with horizontal high-frequency induction zone melting (HIZM), and the effects of the processing parameters on the eutectic microstructure and mechanical properties were investigated. The results indicated that the directionally solidified Al₂O₃/GdAlO₃ eutectic ceramic was composed only of the Al₂O₃ phase and GdAlO₃ phase penetrating mutually, and the Al₂O₃ phase was the substrate in which the GdAlO₃ phase was embedded. As the solidification rate increased from 1 to 5?mm/h, the eutectic microstructure underwent a transformation from an irregular pattern to a relatively regular “rod” or “lamellar” pattern, and the eutectic spacing constantly decreased, reaching a minimum value of 0.5?μm. The eutectic ceramic hardness and fracture toughness at room temperature increased continuously, reaching 23.36?GPa and 3.12?MPa?m^1/2, which were 2.3 times and 2.5 times those of the sintered ceramic with the same composition, respectively. Compared with the samples obtained from vertical high-frequency induction zone melting, the orientation of eutectic phases along the growth direction decreased significantly, and the size uniformity of the GdAlO₃ phase became poorer in the samples prepared with HIZM at the same solidification rate; nevertheless, the hardness and fracture toughness of the samples increased by 11% and 63%, respectively.     

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.     

Laser additive manufacturing of melt-grown Al2O3/GdAlO3 eutectic ceramic composite: Powder designs and crack analysis with thermo-mechanical simulation

Directed energy deposition method is an efficient one-step laser additive manufacturing technology to achieve eutectic ceramic composite with high property and ultra-fine microstructures. In this paper, melt grown dense Al₂O₃/GdAlO₃(GAP) eutectic ceramic composites have been directly fabricated from the spherical powder reconstructed by an optimized spray granulation method. Effects of the powder size distribution, feeding rate, and heat treatment on the morphology and microstructure of the as-solidified eutectic ceramic composites have been investigated. Results show that the powder fluidity plays an important role in the heat conduction of the laser process. Finer powder (imperfect spherical powder with diameter less than 10 µm) gives rise to the disturbance of molten pool. Moreover, this powder greatly aggravates the phenomenon of powder’ sticking on surface of the specimen, which subsequently induces the leading growth of coarse dendrite-like GAP primary phases (higher interface temperature of dendrite tip for GAP phase) and sintered eutectic phases at the specimen edge. The finite element modeling (FEM) method is used to analysis the coupled thermal dynamic during the process after verification with infrared thermal image. It shows that longitudinal maximum principal stress exhibits a steep gradient at the edges of the as-solidified ceramic, making the specimen susceptible to cracking along the deposited direction at the first few layers. By optimizing the feedstock powder characteristics and the directed energy deposition process, completely solidified cylindrical and thin-walled Al₂O₃/GAP eutectic ceramic composites with the maximum dimensions of ? 4 × 95 mm³ and 10 × 4 × 44 mm³ have been successfully fabricated. The solidified specimens present smooth glossy surface and fine microstructures with the average eutectic spacing of 0.31 µm. The average micro-hardness and fracture toughness of 15.16 ± 0.29 GPa and 4.3 ± 0.09 MPa·m^1/2 have been obtained, respectively.     

Microstructures and mechanical properties of directionally solidified Al2O3/GdAlO3 eutectic ceramic by laser floating zone melting with high temperature gradient

Directionally solidified Al₂O₃/GdAlO₃ eutectic ceramic rods with high densities and low solidification defects are prepared by laser floating zone melting at solidification rate from 2 to 200 μm/s. The microstructure evolution, eutectic growth behavior and mechanical properties are investigated. At low solidification rates (<30 μm/s), the eutectic rods present a homogeneous irregular eutectic microstructure, whereas cellular microstructure containing regular lamella/rod structure is developed at higher solidification rates. The relationship is established between the eutectic interphase spacing and solidification rate, which follows the Magnin-Kurz eutectic model. The Vickers hardness (15.9–17.3 GPa) increases slightly with decreasing interphase spacing, but the fracture toughness (4.08 MPa m^1/2) shows little dependence with the solidification rate. Different crack propagation mechanisms are revealed among the indentation cracks. The flexural strength at ambient temperature reaches up to 1.14 GPa for the eutectic grown at 100 μm/s. The fracture surface analysis indicates that the surface defects are the main crack source.     

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.     

Comparative investigation of microstructure,mechanical properties and strengthening mechanisms of Al-12Si/TiB2 fabricated by selective laser melting and hot pressing

Near-fully dense Al-12Si matrix composites reinforced with TiB₂ ceramic particles (2?wt%) were successfully fabricated by selective laser melting (SLM) and hot pressing (HP) of powder mixtures. TiB₂ ceramic particles are homogeneously distributed in the Al-12Si matrix at the micrometer-scale owing to a very good wetting between molten Al-12Si alloy and TiB₂ ceramic. The microstructural analysis of the as-fabricated SLM samples show the formation of a supersaturated α-Al phase and the decrease of free residual Si with respect to the hot-pressed ones. Both composites exhibit a fine microstructure with a grain size of ~?5.1?µm and ~?5.8?µm for SLM- and HP-fabricated samples with addition of TiB₂ ceramic particles. The SLM Al-12Si/TiB₂ composite exhibits significantly improved microhardness (~?142?±?6.0 HV_0.05) and yield strength (~247?±?4.0?MPa) compared to the corresponding HP one. Fine cell morphology and nanostructured dispersion strengthening are responsible for the improved mechanical strength of the Al-12Si/TiB₂ composite processed by SLM.     

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 and cytotoxicity of Al2O3-ZrO2 eutectic bioceramics with high mechanical properties prepared by laser floating zone melting

Developing new generation of strong, tough and stable bioceramics used in dental filed has been highly desired for attaining the clinical requirement of secure and reliable therapy. In this paper, a novel Al₂O₃-ZrO₂ eutectic bioceramics with nearly fully density and extremely aesthetic luster was in-situ prepared by innovative laser floating zone melting (LFZM) method. The influence of solidification rates on microstructure evolution, mechanical properties and cytotoxicity was investigated. The eutectic bioceramics displayed a special three dimensional interpenetrating microstructure evolving with increasing the solidification rate. The eutectic colony structure occurred when solidification rate overpassed 8?µm/s, and lamellar spacing was below 1?µm when solidification rate exceeded 30?µm/s. The eutectic bioceramics solidified at 100?µm/s exhibited optimal mechanical properties with an average hardness of 16.53?GPa, fracture toughness of 6.5?MPa?m^1/2 and flexural strength of 1.37?GPa. The cytotoxicity of Al₂O₃-ZrO₂ eutectic bioceramics was evaluated by MTT methods according to ISO 10993-5 standard. Non-cytotoxic behavior was detected for the eutectic bioceramics, indicating this eutectic bioceramic could be used as promising dental restoration material.     

Evolutions of rod diameter,molten zone and temperature gradient of oxide eutectic ceramics during laser floating zone melting

Laser floating zone melting (LFZM) is an important directional solidification (DS) technique in oxide ceramic fabrication owing to its very high temperature gradient and rapid cooling rate. In this work, variations and evolutions of rod diameter, molten zone, and temperature gradient are explored in fabrication of Al₂O₃-based eutectic ceramics. At low solidification rate of 4 μm/s, periodical oscillations with almost the same period (~275 s) are produced in melting zone shape/size, as-grown rod diameter, temperature distribution, and temperature gradient. The temperature gradient fluctuates between 3.6 × 10³ K/cm and 6.9 × 10³ K/cm with an average value of about 5.3 × 10³ K/cm. As increasing the solidification rate, the temperature gradient decreases and the periodical oscillation weakens. Based on the evolutions of the temperature field, interface location and molten zone shape, the formation mechanism of periodical oscillation during LFZM processing is evaluated.     

Compositionally graded YSZ–NiO composites by surface laser melting

Laser surface melting has been applied to near eutectic NiO–YSZ sintered ceramics. The objective is to generate a functional gradient composite material with graded microstructure and composition. At low solidification rates the resultant material has a graded composition, with a severe NiO segregation towards the surface. A thick NiO layer whose thickness depends on the travelling speed is formed. Below this layer the microstructure is eutectic like with composition varying with depth. In contact with the ceramic, excess YSZ coming from the hypereutectic composition forms an almost continuous YSZ layer. The thickness of both segregated layers, NiO and YSZ can be controlled by traverse speed. Thickness decreases as travelling speed increases until a limiting travelling rate of 110 mm/h, at which no more segregation is found. Possible causes to explain the relevant NiO segregation towards the surface are discussed.     

Laser-assisted, crack-free surface melting of large eutectic ceramic bodies

The modification of ceramic surfaces by directional laser melting is interesting because it can eliminate surface defects and thus improve the ceramics mechanical performance, as long as one prevents the formation of cracks. The feasibility of surface modification by laser-assisted melting on large t-ZrO₂-Al₂O₃ eutectic ceramic pieces was evaluated in this work. 0.4 mm thick, defect-free, resolidified layers were obtained on plates of 40 mm width by preheating at 1200 °C and processing at 1000 mm/h with a line-shaped CO₂ laser beam and 580 W/cm² irradiance. The surface finish was smooth, free from overlapping-track roughness. The resolidified layer had eutectic microstructure with lamellae-type Al₂O₃ and tetragonal ZrO₂(t-ZrO₂) colonies. The fracture tests of the samples confirmed the absence of crack-type resolidification defects and the removal of surface defects. Although no increase in average flexural strength was observed for surface resolidified samples, they showed significantly lower standard deviation.     

Microstructure and properties of directionally solidified LaB6 (100)-ZrB2 eutectic composite prepared by the optical zone melting method

Directionally solidified (DS) LaB₆ (001)-ZrB₂ eutectic composite is successfully prepared by optical zone melting technique. The effect of the solidification rate on the microstructure and properties is systemically investigated.With the increase in the solidification rate from 20 to 100 mm/h, the eutectic rods present a homogeneous eutectic microstructure. The relationship between the average eutectic spacing and the solidification rate is established. The fracture toughness shows an obvious anisotropy. Crack deflection and crack bridging play important roles in improving the fracture toughness of the material. As the solidification rate is increased from 20 to 300 mm/h, the fracture toughness, bending strength and current density firstly increase and then decrease. The highest fracture toughness of 5.16 MPa.m^1/2, bending strength of 809.04 MPa and current density of 36.24 A/cm² at 1873 K belong to the DS LaB₆ (001) - ZrB₂ eutectic composite obtained at V = 100 mm/h.