Sintering behavior,microstructural evolution,and mechanical properties of ultra-fine grained alumina synthesized via in-situ spark plasma sintering

Ultra-fine grained Al₂O₃ was fabricated by in-situ spark plasma sintering (SPS) process directly from amorphous powders. During in-situ sintering, phase transformation from amorphous to stable α-phase was completed by 1100 °C. High relative density over 99% of in-situ sintered Al₂O₃ was obtained in the sintering condition of 1400 °C under 65 MPa pressure without holding time. The grain size of in-situ sintered Al₂O₃ body was much finer (~400 nm) than that of Al₂O₃ sintered from the crystalline α-Al₂O₃ powders. For in-situ sintered Al₂O₃ from amorphous powders, we observed a characteristic microstructural feature of highly elongated grains in the ultra-fine grained matrix due to abnormal grain growth. Moreover, the properties of abnormally grown grains were controllable. Fracture toughness of in-situ sintered Al₂O₃ with the elongated grains was significantly enhanced due to the self-reinforcing effect via the crack deflection and bridging phenomena.     

Thermal ageing of nanostructured tetragonal zirconia ceramics: Characterization of interfaces

This paper reports the preparation of nanometric powders of 3.5 mol% Y₂O₃-doped ZrO₂, with controlled microstructure, by the spray pyrolysis process, assisted by ultrasonic atomizer, at relatively low temperature. As-prepared powders were found crystalline and consisted of dense and chemically homogeneous spherical particles. Conventional sintering at 1500 °C for 2 h in air yields dense ceramics of 83 nm of average grain size. The electrical properties of electrode/electrolyte interface were determined by impedance spectroscopy measurements before, during and after thermal ageing for 2000 h at 700 °C in dry air. The effect of thermal ageing on the electrical responses of the ceramic and interfaces with platinum electrodes was investigated.     

Synthesis of La0.9Sr0.1Al0.85Mg0.1Co0.05O2.875 using a polymeric method

Nanocrystalline La_0.9Sr_0.1Al_0.85Mg_0.1Co_0.05O_2.875 (LSAMC) powders were synthesized via a polymeric method using poly(vinyl alcohol) (PVA). The effect of PVA content on the synthesized powders was studied. When the ratio of positively charged valences (Mⁿ⁺) to hydroxyl groups (OH) is 1.5:1, crystalline LaAlO₃ could be obtained at such a low calcination temperature as 700 °C. While at 900 °C the ratio is of less importance, since pure LaAlO₃ perovskite could be formed for all powders after calcination at 900 °C. Thermal analysis (TG/DTA) was utilized to characterize the thermal decomposition behaviour of precursor powders. The chemical structure of the calcined powder was studied by Fourier transform infrared (FTIR) spectroscopy. The powder morphology and microstructure were examined by SEM. Dense pellets with well-developed submicron microstructures could be formed after sintering at 1450 °C for 5 h. Compared with the solid-state reaction method, the sintering temperature is substantially lower for powder prepared by the PVA method. This is due to the ultrafine and highly reactive powder produced.     

Sintering process optimization for multi-layer CGO membranes by in situ techniques

The sintering of asymmetric CGO bi-layers (thin dense membrane on a porous support; Ce_0.9Gd_0.1O_1.95?δ = CGO) with Co₃O₄ as sintering additive has been optimized by combination of two in situ techniques. Optical dilatometry revealed that bi-layer shape and microstructure are dramatically changing in a narrow temperature range of less than 100 °C. Below 1030 °C, a higher densification rate in the dense membrane layer than in the porous support leads to concave shape, whereas the densification rate of the support is dominant above 1030 °C, leading to convex shape. A flat bi-layer could be prepared at 1030 °C, when shrinkage rates were similar. In situ van der Pauw measurements on tape cast layers during sintering allowed following the conductivity during sintering. A strong increase in conductivity and in activation energy E_a for conduction was observed between 900 and 1030 °C indicating an activation of the reactive sintering process and phase transformation of cobalt oxide.     

Production of nanopowder and bulk aluminate ceramic scintillators

The developed nanotechnology makes it possible to prepare lots of standard powders of Aluminates such as lutetium and yttrium orthorombic LuAlO₃, YAlO₃ (LuAP, YAP – perovskite), aluminum garnets Lu₃Al₅O₁₂, Y₃Al₅O₁₂ (LuAG, YAG) with cubic structure and aluminates with monoclinic structure Lu₄Al₂O₉, Y₄Al₂O_9, (LuAM, YAM). Powders of scintillation materials are prepared by sol-gel method, co-precipitation method and a combination of sol-gel method with combustion reactions. Crystallization process of LuAG phase starts at 900 °C. At lower temperatures, during the pyrolysis of the gel, amorphous powders have been produced. After pyrolysis of the gels without additives of aminoacetic acid a mixture of LuAG+Lu₂O₃ has been formed instead of LuAP. New phase of LuAP in a cubic form is detected. Diffraction peak profile analyzes and scanning electron microscope (SEM) investigations are performed to approximately establish grain size of the obtained powder. Thermogravimetry analysis (TGA) was carried out for detection of thermal effects in the range up to sintering temperature. Perovskite phases of aluminates have been synthesized via pyrolysis (at <900 °C) of the gel. Prepared nanopowders of aluminates are sintered using spark plasma processing. The best density of YAG has been detected at the following conditions of SPS process: 1650 °C/3 min/40 MPa.     

Alon-based materials prepared by SHS technique

The aim of the presented paper was preparation of the highly reactive in the sintering powders in the Al–O–N system by SHS method. Combustion reactions of metallic aluminium and corundum powder mixtures (from 15% Al–85% Al₂O₃ to 50% Al–50% Al₂O₃) were performed in nitrogen atmosphere. The obtained powders were ground and hot-pressed at 1750, 1850 and 1950 °C for 1 h under 25 MPa in nitrogen flow. In contrast to conventional methods, which require 24 h of the precursor heat treatment at 1200 °C our studies, showed that it is possible to prepare almost pure γ-alon materials using SHS reaction. Sintering of the powders led to obtained dense materials composed of pure γ-alon or γ-alon–AlN composites. The phase composition of the sintered bodies was controlled by the chemical composition of the starting mixture and the sintering temperature.     

Effects of oxidation curing and Al atoms on the formation of near-stoichiometric freestanding SiC(Al) films derived from polyaluminocarbosilane (PACS)

The effects of oxygen pick-up and Al atoms on the formation and microstructure of freestanding SiC(Al) films by melt spinning of polyaluminocarbosilane (PACS) precursor were studied. PACS green films were cross-linked for 1 h, 2 h, 3 h and 4 h, pre-pyrolyzed at 900 °C, respectively. They were continuously pyrolyzed at 1800 °C to convert initial PACS into SiC(Al) ceramic films. Results reveal that the strict control of oxygen content during the oxidation curing is essential to produce near-stoichiometric SiC(Al) films. The microstructure of the dense films is a mixture of β-SiC crystals, α-SiC nano-crystals, C clusters and a small amount of Al₄O₄C and Al₄SiC₄. Al atoms which play important roles as both sintering aids and grain growth inhibitor are well distributed in the films due to the presence of stable composition and structure. SiC(Al) films with excellent mechanical properties would be attractive candidate materials for MEMS in harsh environments.     

Synthesis of lutetium aluminum garnet powders by nitrate–citrate sol–gel combustion process

Polycrystalline lutetium aluminum garnet (Lu₃Al₅O₁₂) powders were prepared by a simple sol–gel combustion method using aluminum nitrate, lutetium oxide and citric acid as the starting materials. The XRD results showed that the amorphous precursor converted directly to pure LuAG at 900 °C. The TEM investigations revealed that the synthesized LuAG powders are nano-sized with an average particle size 20–30 nm.     

Two step hot pressing sintering of dense fine grained WC–Al2O3 composites

WC–40 vol% Al₂O₃ composites were prepared by high energy ball milling and the following two step hot pressing sintering (TSS). The tungsten carbide (WC) and commercial alumina (Al₂O₃) powders composed of amorphous Al₂O₃, boehmite (AlOOH) and χ-Al₂O₃ were used as the starting materials. The feasibility of two step sintering (TSS) method to WC–40 vol% Al₂O₃ composites was demonstrated, optimum TSS regime was discussed and phase transformation during TSS process was investigated. The results showed that both the pre-sintering at a proper first step temperature (T₁) to obtain a critical initial density and isothermal hot pressing at an appropriate second step temperature (T₂) to inhibit grain boundary migration (GBM) were of significant importance. When the as milled WC–40 vol% Al₂O₃ powders were hot pressed under TSS₄ regime, a relative density of 99% and a grain size of 2.38 μm were obtained, an excellent Vickers hardness of 19.71 GPa was achieved, combining a fracture toughness of 12 MPa m^1/2 with a flexural strength of 1285 MPa. Compared with the near full dense samples consolidated under CS₁ regime (1540 °C for 90 min), the grain size decreased, the Vickers hardness, fracture toughness and flexural strength were all improved due to the refined microstructure and the transgranular fracture mode. The amorphous Al₂O₃, AlOOH and χ-Al₂O₃ were transformed to α-Al₂O₃ completely during the sintering process.     

Transparent mullite ceramic from single-phase gel by Spark Plasma Sintering

Monophasic mullite precursors with composition of 3Al₂O₃·2SiO₂ (3:2) were synthesized and then were sintered by Spark Plasma Sintering (SPS) to form transparent mullite ceramics. The precursor powders were calcined at 1100 °C for 2 h. The sintering was carried out by heating the sample to 1450 °C, holding for 10 min. The sintered body obtained a relative bulk density of above 97.5% and an infrared transmittance of 75–82% in wavelength of 2.5–4.3 μm without any additive. When the precursor powders were calcined at below 1100 °C, it was unfavorable for completely eliminating the residual OH, H₂O and organic compound. However, when calcined temperature was too high, it was unfavorable either for full densification due to the absence of viscous flow of amorphous phase. At the same calcined temperature, the transmittance of sintered body was decreased with the increase of the sintering temperature above 1450 °C owing to the elongated grain growth.     

Characteristics of BaNd2Ti5O14 powders directly prepared by high-temperature spray pyrolysis

BaNd₂Ti₅O₁₄ powders were directly prepared by high-temperature spray pyrolysis. The powders prepared at temperatures of 1300 and 1500 °C exhibited a pure BaNd₂Ti₅O₁₄ phase. The powders prepared at 1300 °C were spherical in shape. However, the powders prepared at 1500 °C showed non-spherical shapes. The BaNd₂Ti₅O₁₄ powders had a composition similar to that of the spray solution. The mean sizes of the BaNd₂Ti₅O₁₄ powders increased from 0.23 to 0.60 μm when the concentration of the spray solution was increased from 0.01 to 0.2 M. At a sintering temperature of 1100 °C, bridge-like structures were formed between the powders. Pellets sintered at 1300 °C exhibited a dense structure comprising rod-like crystals.     

Dielectric properties of nano-sized Ba0.7Sr0.3TiO3 powders prepared by spray pyrolysis

Nano-sized Ba_0.7Sr_0.3TiO₃ powders are prepared by post-treatment of the precursor powders with hollow and thin wall structure at temperatures between 900 and 1100 °C. Ethylenediaminetetraacetic acid and citric acid improve the hollowness of the precursor powders prepared by spray pyrolysis. The mean sizes of the powders post-treated at temperatures of 900, 1000 and 1100 °C are 42, 51 and 66 nm, respectively. The densities of the Ba_0.7Sr_0.3TiO₃ pellets obtained from the powders post-treated at 900, 1000 and 1100 °C are each 5.36, 5.55 and 5.38 g cm^?3 at a sintering temperature of 1300 °C. The pellet obtained from the powders post-treated at 1000 °C has higher maximum dielectric constant than those obtained from the powders post-treated at 900 and 1100 °C.     

Microstructure and properties of Al2O3–TiC nanocomposites fabricated by spark plasma sintering from high-energy ball milled reactants

In situ synthesis of Al₂O₃–TiC nanocomposite powders from a mixture of titanium, graphite, and Al₂O₃ powders by high-energy ball milling (HEBM) and its consolidation through spark plasma sintering (SPS) were investigated. After being milled for 25 h at ambient temperature, the powder mixtures were mainly composed of homogeneous nanosized Al₂O₃ particle and amorphous TiC solid solution. The relative density of the samples consolidated by SPS technique in vacuum at 1480 °C for 4 min reached 99.2%. The final products exhibited very fine microstructure, and the grain sizes of Al₂O₃ and TiC were about 400 nm and 200 nm, respectively, with a flexure strength of 944 ± 21 MPa, Vickers hardness 21.0 ± 0.3 GPa, fracture toughness 3.87 ± 0.2 MPa m^1/2, and electrical conductivity 1.2787 × 10⁵ S m⁻¹.     

Sinter forging of rapidly quenched eutectic Al2O3–ZrO2(Y2O3)-glass powders

Spray dried agglomerates of Al₂O₃–ZrO₂ (1% Y₂O₃) with 4 wt.% borosilicate glass were arc plasma sprayed and rapidly quenched into water. Because of the rapid quenching the particles <25 μm were mostly amorphous. After annealing 1 h at 1200 °C the scale of the microstructure of the particles was on the order 30 nm. Hot forging of this powder yielded dense specimens with the width of the ZrO₂ phase still less than 100 nm. Since the particle size ranged from 5 to 25 μm and the scale of the particle microstructure was <100 nm, densification was controlled by creep of the particles rather than by the typical hot pressing mechanism of diffusion along the neck between particles to fill the pores. Thus, the scale of the microstructure controls densification rather than the particle size. These powders offer an alternate source for manufacturing nanostructured parts and should be more suitable for hot pressing or forging than nanoparticulate powders.     

Fabrication of porous Al2O3-based ceramics using ball-shaped powders by preceramic polymer process in N2 atmosphere

Porous Al₂O₃-based ceramics were successfully fabricated using ball-shaped powders by preceramic polymer process in N₂ atmosphere. These results showed that the amorphous Si-O-C ceramics were formed on the surface of ball-shaped Al₂O₃ particles by the pyrolysis of the silicone resin during sintering in N₂ atmosphere, which played a role in connecting the Al₂O₃ particles by forming the sintering necks. When the sintering temperatures increased from 1100 °C to 1600 °C, the formed Si-O-C ceramics still existed in the amorphous state and had no crystallization. Interestingly, the amorphous β-SiC formed at 1300 °C and its amount gradually increased with further increasing temperatures. The linear shrinkage rate of the samples varied from 0.49% to 0.73% and the weight loss rate increased from 2.01% to 10.77%. The apparent porosity remarkably varied with the range of 24.9% and 34.5%, as the bulk-density varied from 2.66 to 2.47 g/cm³. The bending strength gradually increased from 9.36 to 22.51 MPa with increasing temperatures from 1100 °C to 1500 °C, however, the bending strength remarkably decreased at 1600 °C, which was attributed to the comprehensive function of the high porosity, broken Al₂O₃ particles and weak connection between Al₂O₃ particles in the samples.     

Highly transparent AlON ceramics sintered from powder synthesized by carbothermal reduction nitridation

Aluminum oxynitride (AlON) powders were synthesized by the carbothermal reduction and nitridation process using commercial γ-Al₂O₃ and carbon black powders as starting materials. And AlON transparent ceramics were fabricated by pressureless sintering under nitrogen atmosphere. The effects of ball milling time on morphology and particle size distribution of the AlON powders, as well as the microstructure and optical property of AlON transparent ceramics were investigated. It is found that single-phase AlON powder was obtained by calcining the γ-Al₂O₃/C mixture at 1550 °C for 1 h and a following heat treatment at 1750 °C for 2 h. The AlON powder ball milled for 24 h showed smaller particles and narrower particle size distribution compared with the 12 h one, which was benefit for the improvement of optical property of AlON transparent ceramics. With the sintering aids of 0.25 wt% MgO and 0.04 wt% Y₂O₃, highly transparent AlON ceramics with in-line transmittance above 80% from visible to infrared range were obtained through pressureless sintering at 1850 °C for 6 h.     

Annealing effect on dielectric property of AlN ceramics

Effects of slow-cooling at high temperatures and annealing at intermediate temperatures on dielectric loss tangent of AlN ceramics were explored. Y₂O₃ was added as a sintering additive to AlN powders, and the powders were pressureless-sintered at 1900 °C for 2 h in a nitrogen flow atmosphere. In succession to the sintering, AlN samples were slow-cooled at a rate of 1 °C/min from 1900 to 1750 °C and/or annealed at 970 °C for 4 h. Al₅Y₃O₁₂ was detected in the AlN ceramics obtained by the slow-cooling and AlYO₃ was found in the ceramics cooled at a rate of 30 °C/min. AlN ceramics with a relative density of 0.986 were obtained by the slow-cooling method. On the other hand, very low tan δ values between 2.6 and 4.6 × 10⁻⁴ were obtained when the AlN ceramics were annealed at 970 °C for 4 h.     

Metallization of Al2O3 ceramic by magnetron sputtering Ti/Mo bilayer thin films for robust brazing to Kovar alloy

Ti/Mo bilayer thin films were deposited onto Al₂O₃ ceramic by magnetron sputtering with a subsequent high temperature sintering to ensure the robust brazing of Al₂O₃ ceramic to Kovar (Fe–Ni–Co) alloy. The interface reaction process between Ti film and Al₂O₃ ceramic as well as the joining strength between metallized Al₂O₃ ceramic and Kovar alloy were investigated systematically using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy, and electronic universal testing machine. The results show that the active Ti film can react with Al₂O₃ ceramic to form Ti₃Al and TiO during high-temperature sintering process, in which the amount, size and morphology of TiO crucially depend on the sintering temperature. As the sintering temperature reaches 1200 °C, a plenty of spherical TiO nanoparticles with ~ 150 nm in diameter and metallic nature can be created across the Ti/Al₂O₃ interfaces, which can effectively act as ‘bridges’ to join Ti film to Al₂O₃ substrate firmly. Hence, the optimal joining strength of 69.6±3.1 MPa between metallized Al₂O₃ ceramic and Kovar alloy can be obtained, much better than those counterparts metallized at 900 °C and 1050 °C almost without the existence of observable TiO.     

Fabrication of tough SiCf/SiC composites by electrophoretic deposition using a fabric coated with FeO-catalyzed phenolic resin

A hybrid processing route based on vacuum infiltration, electrophoretic deposition, and hot-pressing was adopted to fabricate dense and tough SiC_f/SiC composites. The as-received Tyranno SiC fabric preform was infiltrated with phenolic resin containing 5 wt.% FeO and SiC powders followed by pyrolysis at 1700 °C for 4 h to form an interphase. Electrophoretic deposition was performed to infiltrate the SiC-based matrix into the SiC preforms. Finally, SiC green tapes were sandwiched between the SiC fabrics to control the volume fraction of the matrix. Densification close to 95% ρ_theo was achieved by incorporating 10 wt.% Al₂O₃-Sc₂O₃ sintering additive to facilitate liquid phase sintering at 1750 °C and 20 MPa for 2 h. X-ray diffraction and Raman analyses confirmed the catalytic utility of FeO by the formation of a pyrolytic carbon phase. The flexural response was explained in terms of the extensive fractography results and observed energy dissipating modes.     

High Li-ion conductivity of Al-doped Li7La3Zr2O12 synthesized by solid-state reaction

Li₇La₃Zr₂O₁₂ (LLZO) has cubic garnet type structure and is a promising solid electrolyte for next-generation Li-ion batteries. In this work, Al-doped LLZO was prepared via conventional solid-state reaction. The effects of sintering temperature and Al doping content on the structure and Li-ion conductivity of LLZO were investigated. The phase composition of the products was confirmed to be cubic LLZO via XRD. The morphology and chemical composition of calcined powders were investigated with SEM, EDS, and TEM. The Li-ion conductivity was measured by AC impedance. The results indicated the optimum sintering temperature range is 800–950 °C, the appropriate molar ratio of LiOH·H₂O, La(OH)₃, ZrO₂ and Al₂O₃ is 7.7:3:2:(0.2–0.4), and the Li-ion conductivity of LLZO sintered at 900 °C with 0.3 mol of Al-doped was 2.11×10⁻⁴ S cm⁻¹ at 25 °C.