Papers by Author: Kiyoshi Hirao

Abstract: The widely used Si3N4-SiC sidewall refractories for aluminum smelting cells, and β SiAlON-SiC composites that can be potentially used for this purpose, have been produced by reaction bonding and their corrosion performance assessed in simulated aluminum electrochemical cell conditions. The formation of the Si3N4 and SiAlON phases were studied by reaction bonding of silicon powders in a nitrogen atmosphere at low temperatures to promote the formation of silicon nitride, followed by a higher heating step to produce β SiAlON composites of different composition. The corrosion performance was studied in a laboratory scale aluminum electrolysis cell where samples were exposed to both liquid attack from molten salt bath and corrosive gas attack. The corrosion resistance of the samples was shown to be dependent on the composition but more importantly on the environment during corrosion, with samples in the gas phase showing higher corrosion.

Abstract: Six kinds of silicon nitrides with different microstructures were fabricated by changing the amount of sintering additives, Al2O3 and Y2O3. The hardness decreased with an increase in the amount of additives, whereas the indentation fracture resistance increased in the samples with large amount of additives due to the formation of coarse and elongated grains. The wear property of various Si3N4 ceramics was investigated in the sliding contact test without lubricant and was compared with the mechanical properties. The specific wear rate varied notably from 4x10-4 to 6x10-6 mm-3N-1m-1 depending on the compositions, which was difficult to explain directly from the hardness and fracture resistance. An indentation fracture model for material removal could correlate the wear properties with a function of hardness and fracture resistance of the materials, suggesting that the indentation model was likely to be valid for analyzing the wear behavior in this study.

Abstract: Post-reaction sintering is one of the fabrication processes of Si3N4 ceramics, which has received considerable attention as a cost-effective process due to the use inexpensive Si powder as a raw material. So far, many researches on the development of this method have been performed in order to improve their properties; however, the sintering shrinkage behavior, which is valuable for the optimization of the firing conditions, has not been well clarified. In this study, we focus on the post-reaction sintering of the Si-Y2O3-Al2O3 system, and investigate its sintering shrinkage behavior by dilatometery. It was found that there is no shrinkage from 1400 to 1600 °C due to grain rearrangements in the green body of the reaction-bonded Si3N4. Furthermore, the shrinkage of the reaction-bonded Si3N4 commenced at approximately 1750 °C, which is higher than the shrinkage temperature of the green body of conventional Si3N4 powder. The restriction of the shrinkage appears to result from the neck growth and strong aggregation among the reacted Si3N4 particles.

Abstract: Post-reaction sintering as a technique for the fabrication of Si3N4 ceramics has received much attention as a cost-effective process due to the use of cheap Si powder as a raw material. In this method, the rapid exothermic nitridation of Si results in local melting of Si to cause its agglomeration, which is expected to be a flaw after densification. Therefore, control of the exothermic reaction is needed to improve the reliability of post-reaction sintered Si3N4 ceramics. In this study, Si3N4 ceramics were fabricated by post-reaction sintering with Si3N4 or SiO2 powders in order to control the exothermic reaction. As a result, the microstructure and bending strength of Si3N4 ceramics was changed by adding these additives. In particular, the addition of SiO2 resulted in the high strength of Si3N4 ceramics. Consequently, it was found that Si3N4 and SiO2 particles played the role of diluents, and SiO2 was effective in post-reaction sintering as an oxygen donor.

Abstract: Mesoporous silicon carbide with and without SiC filler was prepared from the pyrolysis of polycarbosilane (PCS), and the relationship between pyrolysis and properties of micro/meso pores was investigated. The surface area of pyrolyzed PCS without filler significantly decreased from 268 to 0.5m2/g with increasing pyrolysis temperature, and disappearance of the micropores was observed. In contrast, the pyrolyzed PCS with filler showed the retention of micro/mesopores, regardless of pyrolysis temperature. In addition, high surface area ranging from 120 to 180m2/g and a bimodal pore distribution were observed in pyrolyzed PCS with filler. FT-IR showed the decomposition of Si-H, Si-CH3 and Si-CH2-Si in the PCS network during pyrolysis, which led to the evolution of hydrogen and methane gas. However, the obtained pores might be larger than the size of evolved gases. Thus, though micro/meso pores and large surface area were retained by the addition of filler, coalescence between pores could occur during pyrolysis.

Abstract: The influence of two measuring conditions, the elapsed time after indentation and the condition of edge of an indenter, on the indentation fracture toughness of silicon nitrides was assessed. No slow crack-growth after unloading was confirmed by optical microscopic observation of a crack tip induced by the indentation, which led to the negligible difference in fracture toughness measured at 1 and 30 min after the indentation. Measurements with relatively new and used indenters gave almost the same fracture toughness data, indicating that the crack lengths were hardly affected by the slight damage of the corner of the indenter. It was suggested that the large scattering of the indentation fracture toughness reported by the round-robin tests such as VAMAS was not originated from these factors.

Abstract: Effect of microstructure of silicon nitride on the fracture toughness, KIc evaluated by the IF method was studied with various indentation loads ranging from 49 N to 490 N, since practical assessment of fracture toughness of small Si3N4 parts is needed in the ceramic ball bearing market. The plot of KIc against the as-indented crack length revealed the rising R-curve behavior for the coarse Si3N4 and slight R-curve for the fine Si3N4. By comparing KIc estimated from the SEPB and IF methods using 4 different equations, it was revealed that the IF equation which gave the nearest value to KIc from SEPB was different depending on the microstructures. These results were discussed in conjunction with their R-curve behavior and the effective crack length in the SEPB specimens.

Abstract: Silicon nitride ceramics with and without β-Si3N4 seed addition were prepared via tape casting nonaqueous ceramic slurries, laminating the green ceramic tapes, and gas pressure sintering the green bodies in nitrogen atmosphere. Lu2O3 and SiO2 were used as sintering additives. The results showed that the rod-like β-Si3N4 seed was helpful to enhance β-Si3N4 grain growth unidirectionally. The elongated grains grown from seeds were preferentially oriented parallel to the casting direction, resulting in anisotropic microstructure. When a stress was applied with along the grain alignment, the bending strength of the tape-cast Si3N4 with 3 wt% β-Si3N4 seed addition measured at 1500oC was 738 MPa, which was almost the same as the room temperature bending strength 739 MPa, and the fracture energy can be improved from 301 J/m2 at room temperature to 781 J/m2 at 1500oC. The large fracture energy and bending strength at 1500oC were attributable primarily to the unidirectional alignment fibrous grains and a high melting point grain boundary phase.

Abstract: Reaction bonded MgSiN2 (RBMSN) was prepared by direct nitridation of a Si/Mg2Si/Mg/Si3N4 powder compact in a temperature range of 1350-1550°C. The oxygen content of MgSiN2 was in the range of 0.4 – 0.6 wt%. A thermal stability examination showed that MgSiN2 is stable up to 1400°C at 0.1 MPa N2 pressure. The activation energy of decomposition calculated from the temperature dependence of weight loss is H = 383 kJ⋅mol-1. The time dependence and nitrogen pressure dependence of MgSiN2 decomposition was also investigated at constant temperature. MgSiN2 is stable at 1560°C in 0.6 MPa nitrogen atmosphere. Using these experimental data together with the heat capacity published in a literature the Gibbs free energy of formation of MgSiN2 was calculated in a temperature range 300-2500 K. Dense MgSiN2 ceramics or MgSiN2/Si3N4 composites with fluorine-based additives were prepared by hot pressing. The composite materials had a 4-point bending strength of 427 MPa and Vickers hardness (HV1) of 20.8 GPa, respectively. The indentation fracture toughness was 5.3 MPa.m1/2, due to the presence of elongated β-Si3N4 grains. The dielectric constant of dense reaction bonded MgSiN2 at 100 kHz was 9.5-10, while that of MgSiN2/Si3N4 composite in a wide range 50 – 6000, depending on composition and heat treatment.

Abstract: A bundle of feedrod composed of ordinary arranged alumina and zirconia green rods was co-extruded through a 6:1 reduction die. The volume fraction of zirconia phase was varied from 10 to 88 vol%. After the first co-extrusion, the individual pieces were bundled and co-extruded again, reducing the lateral size of each phase and multiplying the number of continuous monofilaments. After a 3rd extrusion step and sintering at 1600oC, crack-free composites with a fiber diameter of ~50 μm were obtained for all compositions. The fracture toughness of the composites was improved by introducing fine second phase filaments into the matrix. The maximum fracture toughness of 6.2 MPa
m1/2 was attained in the 3rd co-extruded composite which consisted of 53 vol% alumina and 47 vol% zirconia. Bending strength of the composites was almost the same as that of the monolithic alumina regardless of the composition.