Microstructure and mechanical properties of ceramics obtained from chemically co-precipitated Al2O3-GdAlO3 nano-powders with eutectic composition

An efficient and flexible chemical co-precipitation method has been used to synthesize nanoscale Al₂O₃-GdAlO₃ powders with eutectic composition. The as-synthesized powders exhibit a highly dispersive and homogeneous distribution with an average particle size of 50 nm. The phase transition in the resulting powders strongly depends upon the calcination temperature. GdAlO₃ undergoes complete crystallization after calcination at 1050 °C, however, the diffraction peaks of α-Al₂O₃ are found at a relatively high calcination temperature of at least 1300 °C. The fully-densified Al₂O₃-GdAlO₃ ceramic with eutectic composition obtained by hot pressing the nanoscale powders at 1500 °C exhibits a room temperature flexural strength of 556 MPa, a Vickers hardness of 17.3 GPa and a fracture toughness of 7.5 MPa m^1/2. The high temperature flexural strength of the as-sintered Al₂O₃-GdAlO₃ ceramic is measured to be 515 MPa after bending tests at 1000 °C.     

Electrical properties of La2Mo2O9/Al2O3 nanocomposites fabricated by microwave sintering method

High density La₂Mo₂O₉/Al₂O₃ nanocomposite electrolytes were successfully fabricated by microwave sintering method from the nano-scaled La₂Mo₂O₉/Al₂O₃ powders. Phase formation, microstructure, grain size and electrical properties of the specimens were examined using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and AC impedance spectroscopy. It was confirmed that the composite electrolytes consist of nanocrystalline La₂Mo₂O₉ phase with an average grain size of 70–150 nm and a small amount of crystalline α-Al₂O₃ phase at grain boundary. With increasing alumina content, the total conductivity at 600 °C of the composite specimens increases at first and then decreases with a maximum value of about 0.024 S/cm appearing at 2.25 mol% alumina. It was suggested that the enhancement of total conductivity of the composites may be ascribed to the improvement of both grain and grain-boundary conduction introduced by the addition of appropriate amount of alumina.     

Fabrication of transparent ceramics through melt solidification of near eutectic compositions in HfO2–Al2O3–GdAlO3 system

Solidification of eutectic melts in multiple oxide systems can produce directionally solidified eutectic composites by slow cooling, while rapid cooling would give the formation of amorphous phases as super cooled liquids. We have successfully fabricated an amorphous bulk ceramics in the ternary system HfO₂–Al₂O₃–GdAlO₃ for the first time. It has the near eutectic composition of HfO₂ (14 mol%), Al₂O₃ (63 mol%) and Gd₂O₃ (23 mol%) and highly transparent, >85%, in the visible region after the cooling of around 200–500 K/s for 2–5 mm Ø globules. The sample had kept amorphous up to 1073 K but crystallized above 1273 K then lost the transparency. The formation of an amorphous phase could be discussed by the equilibrated temperature (T₀) lines in meta-stable phase diagram. The present study suggests possible formation of transparent bulk ceramics by the melt-solidification of eutectic melts in various ternary or multiple phase systems.     

Carbon nanotube/boehmite-derived alumina ceramics obtained by hydrothermal synthesis and spark plasma sintering (SPS)

Preparation, structure and properties of hydrothermally treated carbon nanotube/boehmite (CNT/γ-AlOOH) and densification with spark plasma sintering of Al₂O₃ and CNT/Al₂O₃ nanocomposites were investigated. Hydrothermal synthesis was employed to produce CNT/boehmite from an aluminum acetate (Al(OH)(C₂H₃O₂)₂) and multiwall-CNTs mixture (200 °C/2 h.). TEM observations revealed that the size of the cubic shape boehmite particles lies around 40 nm and the presence of the interaction between surface functionalized CNTs and boehmite particles acts to form ‘nanocomposite particles’. Al₂O₃ and CNT/Al₂O₃ compact bodies were formed by means of spark plasma sintering (SPS) at 1600 °C for 5 min using an applied pressure of 50MPa resulting in the formation of stable α-Al₂O₃ phase and CNT–alumina compacts with nearly full density. It was also found that CNTs tend to locate along the alumina grain boundaries and therefore inhibit the grain coarsening and cause inter-granular fracture mode. The DC conductivity measurements reveal that the DC conductivity of CNT/Al₂O₃ is 10^?4 S/m which indicate that there is a 4 orders of magnitude increase in conductivity compared to monolithic Al₂O₃. The results of the microhardness tests indicate a slight increase in hardness for CNT/Al₂O₃ (28.35 GPa for Al₂O₃ and 28.57 GPa for CNT/Al₂O₃).     

Phase formation in Al2O3-C refractories with Al addition

Depending on the recipe and the firing conditions, several non-oxides can be formed in Al₂O₃-C refractories. In this paper, the effect of the purity of the recipe components on the phase formation in Al₂O₃-C refractories with Al addition was investigated. Two test series were sintered from 800 °C to 1600 °C under air embedded in coke breeze. One test series was with brown fused alumina, and the other was with tabular alumina. At temperatures of up to 1200 °C the phase formation was the same for both recipes. For temperatures greater than 1400 °C, the impurities of brown fused alumina enhanced the formation of a polytype, while Al₄O₄C and Al₂₈O₂₁C₆N₆ were formed in the other series. The findings explain the occurrence of several non-oxides in disequilibrium at the chosen temperatures. The occurrence of Al₄C₃ was of particular interest due to its low hydration resistance. It was formed at 1200 °C.     

Fabrication and electromagnetic interference shielding effectiveness of Ti3Si(Al)C2 modified Al2O3/SiC composites

A dense alumina fiber reinforced silicon carbide matrix composites (Al₂O₃/SiC) modified with Ti₃Si(Al)C₂ were prepared by a joint process of chemical vapor infiltration, slurry infiltration and reactive melt infiltration. The conductive Ti₃Si(Al)C₂ phase introduced into the matrix modified the microstructure of Al₂O₃/SiC. The refined microstructure was composed of conductive phase, semiconductive phase and insulating phase, which led to admirable electromagnetic shielding properties. Electromagnetic interference shielding effectiveness (EMI SE) of Al₂O₃/SiC and Ti₃Si(Al)C₂ modified Al₂O₃/SiC were investigated over the frequency range of 8.2–12.4 GHz. The EMI SE of Al₂O₃/SiC-Ti₃Si(Al)C₂ exhibited a significant increase from 27.6 to 42.1 dB compared with that of Al₂O₃/SiC. The reflection and absorption shielding effectiveness increased simultaneously with the increase of the electrical conductivity.     

High resolution optical microprobe investigation of surface grinding stresses in Al2O3 and Al2O3/SiC nanocomposites

It has previously been suggested that Al₂O₃/SiC nanocomposites develop higher surface residual stresses than Al₂O₃ on grinding and polishing. In this work, high spatial resolution measurements of residual stresses in ground surfaces of alumina and nanocomposites were made by Cr³⁺ fluorescence microspectroscopy. The residual stresses from grinding were highly inhomogeneous in alumina and 2 vol.% SiC nanocomposites, with stresses ranging from ～ ?2 GPa within the plastically deformed surface layers to ～ +0.8 GPa in the material beneath them. Out of plane tensile stresses were also present. The stresses were much more uniform in 5 and 10 vol% SiC nanocomposites; no significant tensile stresses were present and the compressive stresses in the surface were ～ ?2.7 GPa. The depth and extent of plastic deformation were similar in all the materials (depth ～ 0.7–0.85 μm); the greater uniformity and compressive stress in the nanocomposites with 5 and 10 vol% SiC was primarily a consequence of the lack of surface fracture and pullout during grinding. The results help to explain the improved strength and resistance to severe wear of the nanocomposites.     

Investigation on a postmortem resin-bonded Al-Si-Al2O3 sliding gate with functional gradient feature

A resin-bonded Al-Si-Al₂O₃ sliding gate was designed on the basis of sintered alumina containing both Al and Si fine powders, and the sliding gate achieved good application results in the practical process of steel pouring. Moreover, the postmortem sliding gate was characterized and analysed by X-ray diffraction, scanning electron microscope, and energy dispersive X-ray spectroscopy. The results show that the postmortem sliding gate presents a functional gradient feature with a reinforcement zone–transition zone–plastic zone phase distribution, in which the phases in the reinforcement zone from 0 mm to 5 mm are Al₂O₃, Al₄O₄C, SiC, and Al₄C₃; i.e., the Al, Si, and carbon in the composite totally converted into non-oxide phases. Further, phases in the transition zone from 5 mm to 10 mm are Al₂O₃, SiC, and Al₄C₃, whereas phases in the plastic zone from 10 mm to 15 mm are Al₂O₃, SiC, Al₄C₃, Al and Si. The formation mechanism of the grade distribution of phases in the postmortem sliding gate is described as follows. During operation, Al and Si reacted with C so that Al₄C₃ and SiC formed in situ; then, Al₄C₃ further reacted with Al₂O₃, whereby Al₄O₄C was formed as the reinforcement phase at the 0–5-mm zone with a high temperature. As the temperature decreased from the hot face to interior, a part of the free Al and Si remained in the form of plastic phases.     

Variation in structures and photoluminescence spectra of BaxEu1−xAl2O4 powders

Barium europium(II) aluminate (Ba_xEu_1?xAl₂O₄) powders were prepared by a solid-state reaction among barium carbonate (BaCO₃), europium oxide (Eu₂O₃), and alumina (Al₂O₃) powders at 1400 °C for 3 h under a mixed gas flow of H₂ and N₂. The powders were characterized by powder X-ray diffraction (XRD), infrared and Raman spectroscopy, and photoluminescence (PL). With increasing Ba²⁺ content in Ba_xEu_1?xAl₂O₄, the structure of Ba_xEu_1?xAl₂O₄ changed from a monoclinic (P2₁) to hexagonal (P6₃) phase. The hexagonal (P6₃22) phase was also observed between the two phases. The XRD pattern of a single Ba_0.6Eu_0.4Al₂O₄ phase, which has not been reported in the literature, was refined by the Rietveld method and its structure was confirmed by selected-area electron diffraction. With increasing x value, the emission peak in the PL spectra of Ba_xEu_1?xAl₂O₄ became weaker (x = 0–0.4) and then more intense (x = 0.6–0.98), and its position showed a blue shift from 520 to 498 nm.     

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.     

Wetting,densification and phase transformation of La2O3/A2O3/B2O3-based glass–ceramics

A lead-free, non-alkali La₂O₃–Al₂O₃–B₂O₃ (LAB) glass with Al₂O₃ filler had been investigated for low temperature co-firing ceramic (LTCC) application. The glass forming window and several physical properties of the LAB systems were investigated by ICP, TMA, XRD, DSC, and SEM/EDS. The results show that the densification and crystallization temperatures of LAB/Al₂O₃ were between 700 °C and 950 °C and depended greatly on the formulation. Crystalline phase LaBO₃ (LB) and LaAl₂B₃O₉ (L2A3B) crystallized starting at 825 °C and 925 °C, respectively. High degree of densification and crystallization of one glass–Al₂O₃ composition (L30A) was observed with the microstructure composed of tabular L2A3B grains interlocking with submicron Al₂O₃ and LB grains.     

Enhancing copper infiltration into alumina using spark plasma sintering to achieve high performance Al2O3/Cu composites

Al₂O₃/Cu (with 30 wt% of Cu) composites were prepared using a combined liquid infiltration and spark plasma sintering (SPS) method using pre-processed composite powders. Crystalline structures, morphology and physical/mechanical properties of the sintered composites were studied and compared with those obtained from similar composites prepared using a standard liquid infiltration process without any external pressure. Results showed that densities of the Al₂O₃/Cu composites prepared without applying pressure were quite low. Whereas the composites sintered using the SPS (with a high pressure during sintering in 10 min) showed dense structures, and Cu phases were homogenously infiltrated and dispersed with a network from inside the Al₂O₃ skeleton structures. Fracture toughness of Al₂O₃/Cu composites prepared without using external pressure (with a sintering time of 1.5 h) was 4.2 MPa m^1/2, whereas that using the SPS process was 6.5 MPa m^1/2. These toughness readings were increased by 18% and 82%, respectively, compared with that of pure alumina. Hardness, density and electrical resistivity of the samples prepared without pressure were 693 HV, 82.5% and 0.01 Ω m, whereas those using the SPS process were 842 HV, 99.1%, 0.002 Ω m, respectively. The enhancement in these properties using the SPS process are mainly due to the efficient pressurized infiltration of Cu phases into the network of Al₂O₃ skeleton structures, and also due to high intensity discharge plasma which produces fully densified composites in a short time.     

Creep mechanisms of laminated alumina/zirconia-toughened alumina composites

High-temperature plastic deformation of laminar composites containing alternate layers of Al₂O₃ and a mixture of 60 vol.% Al₂O₃ + 40 vol.% 3 mol% Y₂O₃-stabilized tetragonal ZrO₂ (ZTA) produced by tape casting is investigated in isostrain compression testing at temperatures between 1400 and 1500 °C. The stress exponent n and the creep activation energy Q are close to 1 and 700 kJ/mol, respectively. Microstructual observations reveal the lack of differential features in the ZTA layers and a general creep damage of the Al₂O₃ layers, with little microcracking by cavity coalescence even up to strains of 30%. The layer interfaces maintain their initial structural integrity after testing. An isostrain composite creep model predicts correctly the overall mechanical behavior of the laminates, which is dictated by the alumina phase via diffusional creep controlled by oxygen grain boundary diffusion.     

Ultra-selective gas phase catalytic hydrogenation of aromatic nitro compounds over Au/Al2O3

We report, for the first time, the exclusive (and time invariant) gas phase hydrogenation of p-chloronitrobenzene to p-chloroaniline over Au/Al₂O₃ where 393 K ⩽ T ⩽ 523 K (ΔE_a = 49 kJ mol⁻¹). Under the same conditions, Pd/Al₂O₃ promoted the formation of nitrobenzene and aniline, i.e. composite hydrodechlorination and hydrogenation. Reaction over Au–Pd/Al₂O₃ delivered equivalent activity/selectivity to that obtained with Pd/Al₂O₃. Temperature programmed reduction analysis and hydrogen uptake measurements suggest there is negligible Au–Pd interaction in the bimetallic. Exclusive formation of the corresponding haloaniline is also demonstrated over Au/Al₂O₃ for a series of mono- and di-substituted halonitroarenes; the activity sequence is consistent with electron withdrawing substituent activation.     

Orientation relationships of unidirectionally aligned GdAlO3/Al2O3 eutectic fibers

Unidirectionally solidified rare-earth activated GdAlO₃(GAP)/Al₂O₃ eutectic crystal with well-aligned fibrous structure exhibits excellent light guiding property and can be used as a scintillator plate for high-resolution X-ray imaging. In this paper, the microstructures and orientation relationships of the GAP/Al₂O₃ eutectic fibers were investigated. The regular GAP single crystal fibers with a hexagonally close-packed arrangement grew straight in the same direction along the solidification direction, and were embedded in a c-axis oriented Al₂O₃ single crystal matrix. The majority of GAP fibers had the orientation relationships of [0 1 0]GAP//[0 0 0 1]Al₂O₃ to the growth direction and $(100)\text{GAP}//(11\overline{2}0){\text{Al}}_2{\text{O}}_3$ to the interface plane, while slight misorientation angle of both [0 1 0]GAP axis and (1 0 0)GAP plane were observed. In the GAP/Al₂O₃ interface boundary, the lattice misfit between the two phases was relieved by insertion of extra half-planes on the Al₂O₃ side.     

Microstructure and mechanical properties of hot pressed Al2O3/SiC nanocomposites

Al₂O₃/SiC micro/nano composites containing different volume fractions (5, 10, 15, and 20 vol.%) of SiC were prepared by mixing a sub-micron alumina powder with respective amounts of either micro- or nano-sized silicon carbide powders. The powder mixtures were hot pressed 1 h at 1740 °C and 30 MPa in the atmosphere of Ar. The effect of SiC addition on the microstructure and mechanical properties, i.e. hardness, fracture toughness, and room temperature flexural strength were investigated. The flexural strength increased with increasing volume fraction of silicon carbide particles. The maximum flexural strength (655 ± 90 MPa) was achieved for the composite containing 20 vol.% of coarse-grained SiC, which is more than twice as high as in the Al₂O₃ reference. Hardness and fracture toughness were also moderately improved. The observed improvement of mechanical properties is mainly attributed to alumina matrix grain refinement and grain boundary reinforcement.     

Constrained sintering of YSZ/Al2O3 composite coatings on metal substrates produced from eletrophoretic deposition

Yttria stabilized zirconia/alumina (YSZ/Al₂O₃) composite coatings were prepared from electrophoretic deposition (EPD), followed by sintering. The constrained sintering of the coatings on metal substrates was characterized with microstructure examination using electron microscopy, mechanical properties examination using nanoindentation, and residual stress measurement using Cr³⁺ fluorescence spectroscopy. The microstructure close to the coating/substrate interface is more porous than that near the surface of the EPD coatings due to the deposition process and the constrained sintering of the coatings. The sintering of the YSZ/Al₂O₃ composite coating took up to 200 h at 1250 °C to achieve the highest density due to the constraint of the substrate. When the coating was sintered at 1000 °C after sintering at 1250 °C for less than 100 h, the compressive stress was generated due to thermal mismatch between the coating and metal substrate, leading to further densification at 1000 °C because of the ‘hot pressing’ effect. The relative densities estimated based on the residual stress measurements are close to the densities measured by the Archimedes method, which excludes an open porosity effect. The densities estimated from the hardness and the modulus measurements are lower than those from the residual stress measurement and the Archimedes method, because it takes account of the open porosity.     

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.