Mechanical activation-assisted autoclave processing and sintering of HfB2-HfO2 ceramic powders

This study reports on the synthesis and consolidation of HfB₂-HfO₂ ceramic powders via mechanical activation-assisted autoclave processing followed by pressureless sintering (PS) or spark plasma sintering (SPS). HfCl₄, B₂O₃ and Mg starting powders were mechanically activated for 5 min to obtain homogeneously blended precursors with active particle surfaces. Autoclave synthesis was carried out at a relatively low temperature at 500 °C for 6 or 12 h. As-synthesized powders were purified from reaction by-products such as MgO and MgCl₂ by washing and acid leaching treatments. The characterization investigations of the as-synthesized and purified powders were performed by using an X-ray diffractometer (XRD), stereomicroscope (SM), scanning electron microscope (SEM) and particle size analyzer (PSA). The purified powders with an average particle size of about 190 nm comprised the HfB₂ phase with an amount of 79.6 wt% in addition to the HfO₂ phase and a very small amount of Mg₂Hf₅O₁₂ phase after mechanical activation for 5 min and autoclave processing for 12 h. They were consolidated at 1700 °C both by PS for 6 h and SPS for 15 min. The Mg₂Hf₅O₁₂ phase decomposed during sintering and bulk samples only had the HfB₂ and HfO₂ phases. The bulk properties of the sintered samples were characterized in terms of microstructure, density, microhardness and wear characteristics. The HfB₂-HfO₂ ceramics consolidated by PS exhibited poor densification rates. A considerable improvement was obtained in the relative density (~91%), microhardness (~16 GPa) and relative wear resistance (2.5) values of the HfB₂-HfO₂ ceramics consolidated by SPS.     

Influence of the ratio of sintering aids on the properties of porous Si3N4 ceramics fabricated by digital light processing

The sintering aids play an important role in affecting the properties of porous Si₃N₄ ceramics. However, there are few researches on the properties of porous Si₃N₄ ceramics fabricated by digital light processing (DLP) with different ratios of sintering aids. In this paper, porous Si₃N₄ ceramics with different ratios of sintering aids (Y₂O₃-Al₂O₃) were formed by DLP technology. The influence of Y₂O₃-Al₂O₃ ratios on the properties of Si₃N₄ slurry and porous ceramic was studied systematically. The ratio of Y₂O₃-Al₂O₃ had little effect on the rheology and cure depth of Si₃N₄ slurry due to the low addition of sintering aids. The increase of Y₂O₃-Al₂O₃ ratio promoted the anisotropic growth of β-Si₃N₄. When the ratio of Y₂O₃-Al₂O₃ was 9:1, the aspect ratio of β grains reached the maximum. As the ratio of Y₂O₃-Al₂O₃ powders increased, the linear shrinkage of porous Si₃N₄ ceramics showed an increasing and then decreasing trend in three directions. When the Y₂O₃-Al₂O₃ ratio was 3:7, the shrinkage rate in the length, width and height direction reached the maximum (27.03%, 30.27% and 40.02%, respectively). The bulk density and flexural strength exhibited an initial increase followed by a subsequent decrease, while the porosity showed the opposite trend. When the Y₂O₃-Al₂O₃ ratio was 9:1, the porosity reached a maximum of 28.1%. And the bulk density and flexural strength were 2.42 g/cm³ and 421.58 MPa, respectively. This study is of great significance as it lays the experimental foundation in the performance control of porous Si₃N₄ ceramics fabricated by DLP.     

Additive manufacturing of Al2O3 ceramic core with applicable microstructure and mechanical properties via digital light processing of high solid loading slurry

Ceramic cores are essential intermediate mediums in casting superalloy hollow turbine blades. The developing of additive manufacturing (AM) technology provides a new approach for the preparation of ceramic cores with complex structure. In this study, alumina oxide (Al₂O₃) ceramic cores with fine complex geometric shapes were fabricated by digital light processing (DLP) in high resolution. The maximum solid content of 70 vol% of ceramic slurry was adopted in the printing process, which is important for the regulation of deformations and mechanical properties. The effects of the printing parameters, including exposure intensity, printing layer thickness and sintering temperature on the microstructures and mechanical properties of printed samples were investigated. The decrease of residual stress and similar shrinkage in X, Y, and Z directions could be obtained by adjusting the printing parameters, which are crucial to prepare complex ceramic cores with high quality. Besides, the flexure strength and open porosity of ceramic cores reached 34.84 MPa and 26.94%, respectively, which were supposed to meet the requirement of ceramic cores for the fabrication of superalloy blades.     

Mechanical and dielectric properties of Si3N4-SiO2 ceramics prepared by digital light processing based 3D printing and oxidation sintering

Si₃N₄-SiO₂ ceramics are considered as the preferred high-performance wave-transmitting material in the aerospace field. However, traditional fabrication methods for Si₃N₄-SiO₂ ceramics have the disadvantages of high cost and complicated fabrication process. In this paper, Si₃N₄-SiO₂ ceramics with excellent mechanical and dielectric properties were fabricated by digital light processing-based 3D printing combined with oxidation sintering. Firstly, the curing thickness and viscosity of slurries with different solid loadings for vat photopolymerization-based 3D printing were studied. Then, the effects of the sintering temperature on the linear shrinkage, phase composition, microstructure, flexural strength, and dielectric properties of Si₃N₄-SiO₂ ceramics, and the influences of solid loading on them were explored. The curing thickness and viscosity of the slurry with a solid loading of 55 vol% were 30 μm and ∼1.5 Pa‧s, respectively. The open porosity and the flexural strength of Si₃N₄-SiO₂ ceramic with a solid loading of 55 vol% were 4.3 ± 0.61% and 76 ± 5.6 MPa, respectively. In the electromagnetic wave band of 8–18 GHz, the dielectric constant of Si₃N₄-SiO₂ ceramics was within the range of less than 4, and the dielectric loss remained below 0.09. The method of digital light processing-based 3D printing combined with oxidation sintering can be further extended in the preparation of Si₃N₄-based structure-function integrated ceramics.     

纳米Al_2O_3和Cr_2O_3对镁铬材料烧结与力学性能的影响

利用纳米粉的粒径小及活性高等特性,在镁铬材料中加入不同质量分数(分别为2%、4%、6%)的纳米A l2O3或纳米Cr2O3粉体,研究了这两种纳米粉取代相应的微粉后对不同温度烧成的镁铬耐火材料烧结与力学性能的影响。结果表明:适量地用纳米粉体取代相应微粉可有效改善镁铬材料的烧结,提高其常温与高温力学性能,且烧成温度越低,纳米粉对镁铬材料性能的提高作用越明显;在本试验的镁铬材料的颗粒级配条件下,两种纳米粉的加入质量分数均以4%为最佳;纳米A l2O3的加入能降低镁铬质耐火材料的烧结温度,加入4%质量分数的纳米A l2O3可降低约100℃。     

Sintering behavior and mechanical properties of spark plasma sintering SiO2-MgO ceramics

SiO₂-MgO ceramics containing different weight fractions (0, 0.5, 1, 2, and 4 wt%) of SiO₂ powder were prepared by mixing nano MgO powder, and the powder mixtures were densified by spark plasma sintering (SPS). The effect of SiO₂ addition and SPS method on the sintering behavior, microstructure and mechanical properties were investigated. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The highest relative density, flexural strength and hardness of 2 wt% SiO₂-MgO ceramics reached 99.98%, 253.99 ± 7.47 MPa and 7.56 ± 0.21 GPa when sintered at 1400 °C by SPS, respectively. The observed improvement in the sintering behavior and mechanical properties are mainly attributed to grain boundary "strengthening" and intragranular "weakening" of the MgO matrix. Furthermore, the spark plasma sintering temperature could be decreased by more than 100 °C as compared with the HP method, SPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Mechanical properties and biocompatibility of MgO / Ca3(PO4)2 composite ceramic scaffold with high MgO content based on digital light processing

Magnesium oxide-calcium phosphate (MgO/Ca3(PO4)2) composite ceramic materials are considered a promising class of bioactive materials, expected to be used in artificial bone scaffolds. However, there are few pieces of research on the content of magnesium oxide in composite ceramic scaffolds. To study the effect of magnesium oxide content on the biocompatibility and mechanical properties of magnesium oxide-calcium phosphate composite ceramic scaffolds, six groups of scaffolds with magnesium oxide content of 10 wt%, 20 wt%, 30 wt%, 40 wt%, 100 wt%, and 0 wt% were produced by digital light processing (DLP) printing technology. And scaffolds’ pores size and porosity percentage were 0.6–1 mm and 50%, respectively. The compressive strength of the scaffold increased with the magnesium oxide proportion, and the 40 wt% group was almost twice that of the 0 wt% magnesium oxide group. The 40 wt% and 0 wt% magnesium oxide groups performed better for biocompatibility. Comprehensive analysis of the biocompatibility and mechanical properties of the scaffold confirmed that the 40 wt% magnesium oxide group was the best. The results show that high magnesium oxide content enhanced the mechanical properties and achieved well biocompatibility of the composite scaffolds, broadening the scope of future experimental research.     

Pressureless sintering and mechanical properties of 3Y-TZP-reinforced LZAS glass-ceramic composites

LZAS glass-ceramic composites toughened by 5, 10, 15 and 20 vol% 3-mol%-Y₂O₃-tetragonal-ZrO₂-polycrystal (3Y-TZP) were prepared via pressureless sintering. Sinterability of composites was investigated in the temperature range of 520–720 °C using soaking time of 30 min. The sintered specimens were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods. The results revealed that during sintering 3Y-TZP particles agglomerated between the glass powders and were not dissolved by glass-matrix. Mechanical properties of the sintered samples such as bending strength, Vickers micro-hardness and fracture toughness were also investigated. Measurements showed that the relative density of the samples decreased with increasing 3Y-TZP content. The composite containing 15 vol% 3Y-TZP has a best mechanical properties and it would be the optimum composition. It can be confirmed that crack deflection and transformation toughening are the dominant mechanisms for improving mechanical properties of the composites.     

Sintering of lunar regolith structures fabricated via digital light processing

Architectural and functional structures composed of lunar regolith-simulant CLRS-2 were fabricated via digital light processing and sintered at 1100 °C and 1150 °C under an air or argon atmosphere. This work is to investigate effects of atmosphere and temperature on mechanical properties, microstructure, and chemical composition of lunar regolith products. Samples sintered at 1150 °C in air underwent the highest sintering shrinkage and showed the best mechanical properties, likely due to the formation of glassy phase and dense structure following sintering. Conversely, argon-sintered samples exhibited lower density resulting from the lack of glassy phase. Phase analysis revealed varying chemical composition and therefore different underlying reaction mechanisms under two sintering atmospheres, indicating that sintering atmosphere significantly influences the microstructure and macroscopic properties of lunar regolith products.     

Influence of the content of polymethyl methacrylate on the properties of porous Si3N4 ceramics fabricated by digital light processing

Porous Si₃N₄ ceramics are highly regarded as ideal materials for radomes due to their unique characteristics. However, the slurry used for the preparation of porous Si₃N₄ ceramics suffers from a low cure depth, making it challenging to fabricate ceramic components using DLP technology. In this study, porous Si₃N₄ ceramics were prepared by combining DLP technology with pore-forming agent method. The addition of polymethyl methacrylate (PMMA) powders with lower refractive index than that of Si₃N₄ powders can improve the penetration depth of ultraviolet light in the Si₃N₄ slurry. A systematic study was conducted to investigate the influence of the addition of PMMA powders on the properties of Si₃N₄ slurries and porous Si₃N₄ ceramics. When PMMA powders were added at 10 wt%, the slurry with a lowest viscosity of 0.13 Pa s (the shear rate is 30 s⁻¹) and cure depth of 40.0 μm (the exposure energy is 600 mJ/cm²) was obtained. With the increase of PMMA content, porous Si₃N₄ ceramics experienced a gradual decrease in both the flexural strength and bulk density, while the porosity increased from 14.41% to 27.62%. Specifically, when 20 wt% PMMA was added, the resulting porous Si₃N₄ ceramics had a lowest bulk density (2.41 g/cm³), a maximum porosity (27.62%), and a flexural strength (435.87 MPa). The study is of great significance in establishing an experimental foundation for fabricating porous Si₃N₄ ceramics by using DLP technology.     

Effect of preparation conditions on mechanical,dielectric and microwave absorption properties of SiC fiber/mullite matrix composite

Silicon carbide fiber-reinforced mullite matrix (SiC_f/Mu) composites were fabricated via an infiltration and sintering method. Effects of sintering parameters on microstructure, mechanical, dielectric and microwave absorption properties of SiC_f/Mu composites have been investigated. The flexural strength is significantly improved with increasing sintering temperature, and the highest flexural strength of 213?MPa is obtained in vacuum at 1000?°C for 2?h. The performances of composites with different holding time are further studied at 1000?°C. The flexural strengths of composites sintered at 1000?°C for 2 and 4?h reach 213 and 219?MPa, respectively. The failure displacement of the composite sintered at 1000?°C for 4?h reaches 0.39?mm. The excellent microwave absorption properties are achieved for the composite sintered at 1000?°C for 2?h. The minimum reflection loss (RL) reaches ?38?dB with a thickness of 2.9?mm?at 12?GHz and the effective absorbing bandwidth (RL?≤??10?dB) with a thickness of 3.4?mm covers the whole X?band, which indicate that SiC_f/Mu composite is a good candidate for microwave absorbing materials. These results provide valuable solutions to obtaining structural-functional materials for microwave absorption applications in civil and military areas.     

Effect of YAG content on creep resistance and mechanical properties of Al2O3-YAG composite

Comprehensive study on effect of YAG amount on densification, creep resistance and room-temperature mechanical properties of Al₂O₃-YAG composite pressureless sintered at 1600 °C was conducted. The main goal was to optimize the amount of YAG in order to fabricate a composite with improved creep resistance and sufficiently good room-temperature mechanical properties. The composite was made by mixing a commercially available Al₂O₃ powder with fine YAG powder obtained by glycine-nitrate combustion synthesis starting from aluminum nitrate and yttrium nitrate. Increased driving force for sintering of fine YAG powder allowed fabrication of dense Al₂O₃-YAG composite with up to 30 vol% YAG. The presence of YAG was found to be very effective in improving creep resistance of Al₂O₃-YAG composite. Large Y³⁺ ions blocked diffusion along Al₂O₃ grain boundaries, reduced diffusivity and therefore enhanced creep resistance of Al₂O₃-YAG composite which continuously increased as the YAG amount increased. Тhe presence of YAG was also found to improve mechanical properties such as hardness and elastic modulus. The improvement of these properties was ascribed to increased density of Al₂O₃-YAG composites owing to high sintering activity of YAG powder. While fracture strength of the composite can be as high as that of monolithic Al₂O₃, fracture toughness of composite decreased continuously as the YAG content increased. The decrease was ascribed to transgranular fracture of both YAG and Al₂O₃ grains in samples containing larger amounts of YAG. The proper balance between fracture toughness and creep resistance was found in composite containing 18 vol% YAG which had considerably improved creep resistance accompanied by a relatively small decrease in fracture toughness.     

High-performance 0.9Al2O3-0.1TiO2 microwave dielectric ceramics prepared by digital light processing

In this work, the 0.9Al₂O₃-0.1TiO₂ ceramic sample with good microwave dielectric properties and complex structures can be well fabricated by digital light processing (DLP). A relationship between dispersant content and rheological behavior of 0.9Al₂O₃-0.1TiO₂ slurry was explored. When dispersant content was 3.0 wt%, 0.9Al₂O₃-0.1TiO₂ slurry with high solid loading (50 vol%) and low viscosity (2.9 Pa s) could be obtained. 0.9Al₂O₃-0.1TiO₂ ceramic parts with high accuracy were fabricated successfully by adding 3.0 wt% photoinitiator under 600 mJ/cm² exposure energy. With the increase of sintering temperature from 1400 °C to 1600 °C, relative density, dielectric constant (ε_r), and quality factor (Q × f) of 0.9Al₂O₃-0.1TiO₂ ceramic sample increased first and then decreased, and all reached the maximum value at 1550 °C due to the uniformity and densification of microstructures. The temperature coefficient of resonant frequency (τ_f) value showed an almost monotonous increase, changing from negative to positive, and near-zero τ_f value at 1550 °C. In addition, 0.9Al₂O₃-0.1TiO₂ ceramic samples sintered at 1550 °C fabricated by DLP method presented much better microwave dielectric properties: ε_r = 11.30 ± 0.02, Q × f = 35,345 ± 143 GHz (@～12 GHz), τ_f = 2.16 ± 0.21 ppm/°C than that of by dry pressing method: ε_r = 11.16 ± 0.11, Q × f = 30,195 ± 257 GHz (@～12 GHz), τ_f = 4.45 ± 0.13 ppm/°C, especially the Q × f value achieved a 17% increase. Accordingly, DLP technique, which has advantages of producing relatively high properties and complex geometry of microwave dielectric ceramics as well as without extra high-cost mold, greatly satisfies application requirements.     

Microstructure and mechanical properties of B4C matrix composites prepared via hot-pressing sintering with Pr6O11 as additive

High-performance B₄C-PrB₆ composites were prepared via hot-pressing sintering with matrix phase B₄C and with 2–5 wt% Pr₆O₁₁ as additive. The effects of different sintering processes and Pr₆O₁₁ content on the microstructure and mechanical properties of the composites were studied in detail. It is found that increasing sintering temperature and pressure will contribute to the densification of B₄C-PrB₆ composites. Coarse grains are formed in B₄C without additives at high temperature conditions, resulting in the decrease of the densification. Pr₆O₁₁ can effectively hinder the formation of coarse grains and finally promote the densification of the composites. The main toughening mechanisms of composites was crack deflection. The composites with 4 wt% Pr₆O₁₁ prepared at 2050 °C and 25 MPa had the best comprehensive mechanical properties. The relative density, hardness, flexural strength and fracture toughness reached to 98.9%, 37.6 GPa, 339 MPa and 4.4 MP am^1/2, respectively.     

Effects of sintering on the mechanical and ionic properties of ceria-doped scandia stabilized zirconia ceramic

The effect of conventional sintering from 1300 to 1550 °C on the properties of 1 mol% ceria-doped scandia stabilized zirconia was investigated. In addition, the influence of rapid sintering via microwave technique at low temperature regimes of 1300 °C and 1350 °C for 15 min on the properties of this zirconia was evaluated. It was found that both sintering methods yielded highly dense samples with minimum relative density of 97.5%. Phase analysis by X-ray diffraction revealed the presences of only cubic phase in all sintered samples. All sintered pellets possessed high Vickers hardness (13–14.6 GPa) and fracture toughness (~3 MPam^1/2). Microstructural examination by using the scanning electron microscope revealed that the grain size varied from 2.9 to 9.8 µm for the conventional-sintered samples. In comparison, the grain size of the microwave-sintered zirconia was maintained below 2 µm. Electrochemical Impedance Spectroscopy study showed that both the bulk and grain boundary resistivity of the zirconia decreases with increasing test temperature regardless of sintering methods. However, the grain boundary resistivity of the microwave-sintered samples was higher than the conventional-sintered ceramic at 600 °C and reduced significantly at 800 °C thus resulting in the enhancement of electrical conduction.     

Microstructure and mechanical properties of hot-pressed carbon nanotubes compacted by spark plasma sintering

Bulk carbon nanotube samples were prepared by spark plasma sintering. The as-prepared bulk carbon nanotube material exhibited brittle fracture similar to that of common ceramics. Its fracture toughness was around 4.2 MPa m^1/2 while flexural strength was 50 MPa due to the weak bonding between carbon nanotubes. Obvious carbon nanotube bridging was found during the development of the crack induced by an indenter, which provides a possibility of carbon nanotube tough material.     

Cure behaviour and mechanical properties of Si3N4 ceramics with bimodal particle size distribution prepared using digital light processing

Digital light processing is a vital additive manufacturing technology used for manufacturing ceramic parts. The particle size distribution of ceramic suspensions significantly affects the cure behaviour and mechanical properties of ceramics. In this study, the cure behaviour and mechanical properties of Si₃N₄ ceramics with a bimodal particle size distribution were studied. The results indicated that the suspension with coarse particles had a higher cure depth for a lower absorbance but poor mechanical properties. The bending strength of the samples with the optimal ratio (coarse:fine particles = 3:7) reached a maximum of 728.7 ± 10.33 MPa, which is 16.5% higher than that of the samples prepared using only fine particles.     

纳米Al2O3和SiO2对刚玉质耐火材料烧结与力学性能的影响

在普通的刚玉质耐火材料中分别加入少量纳米Al2 O3和SiO2 ,研究了这两种纳米材料对经不同温度烧成后刚玉质耐火材料烧结与力学性能的影响。结果发现 :这两种纳米材料均能使刚玉制品的烧成温度降低 1 0 0～ 2 0 0℃ ,并在相同烧成条件下能使试样的常温抗折强度和耐压强度提高1～ 2倍。     

Hydroxyapatite nanocomposites: Synthesis,sintering and mechanical properties

Two different hydroxyapatite based composites reinforced by oxide ceramic (20 wt%) nano crystals were synthesized by high-energy ball milling and sintered by pressure less technique. Alumina and titania nanoparticles as secondary phases improved densification and mechanical behavior of apatite and postponed its decomposition to the tricalcium phosphate (TCP) phases at elevated temperatures. Increasing the relative density of apatite using nano reinforcements leads to enhance the bending strength by more than 40% and 27% (as compared to the pure HA) and increase the hardness from 2.52 to 5.12 (Al₂O₃ composite) and 4.21 (TiO₂ addition) GPa, respectively. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction spectroscopy were employed to study morphologies, fracture surfaces and phase compositions, respectively. The morphological study and micro structural analysis confirm the X-ray diffraction and relative density diagrams.     

Effect of MgF2 addition on sinterability and mechanical properties of fluorapatite ceramic composites fabricated by wollastonite and phosphate glass

In this paper, we successfully report the design and synthesis of fluorapatite ceramic composites using phosphate glass and wollastonite as raw materials via a simple sintering method. The effects of MgF₂ additives in phase composition, microstructure, densification, and mechanical properties are investigated at various temperatures from 600 °C to 900 °C, and characterized by SEM/EDS, XRD, FTIR, linear shrinkage and water absorption, flexural strength analysis. It shows that the densification and mechanical behavior of composites increase with both the sintering temperature and MgF₂ content. Especially, the sample SCPF-7 exhibits the highest densification and optimal mechanical properties at 900 °C. At these conditions, the water absorption of fluorapatite ceramic composite is less than 0.20%, and the flexural strength is over 70 MPa. For the microstructure analysis, the formation of fluorapatite with a rod-like microstructure is enhanced with the increase of MgF₂ content. The amelioration of these properties is due to the formation of a new phase which helps to the formation of compact microstructure. The findings in this work provide a feasible strategy for the preparation of fluorapatite ceramic composites from available phosphate glass and wollastonite at a lower temperature.