SiAlONs and Non-oxides

Volume 403

doi: 10.4028/

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Authors: Derek P. Thompson, Yue Zhang
Abstract: The preparation of high temperature ceramics simultaneously containing silicon, nitrogen and carbon has only relatively recently become an area of interest for inorganic crystal chemists, and the recent discovery of a new series of carbonitrides with the general formula MM’Si4N6C is of interest because of the good high temperature properties they appear to display. On the one hand, M and M’ can be the same trivalent metal - either rare earth or yttrium; in this case, the resulting compounds display orthorhombic (pseudo-hexagonal) structures. Alternatively the metals may be a mix of di- (Ca,Sr, Ba) and tri-valent (Y,Ln) cations, in which case the carbon is replaced by nitrogen, and the overall symmetry is hexagonal. Other quaternary nitrides of a similar type can be produced if the two metal cations remain trivalent and one of the silicon atoms is replaced by aluminium. The present study describes the preparation of powder samples of Y2Si4N6C and LaYSi4N6C starting from YH2, La, Si3N4 and carbon precursors, and summarises attempts to achieve a dense product by hot-pressing at 1700-1800oC. Some preliminary mechanical property measurements are included.
Authors: Malgorzata Sopicka-Lizer, Tomasz Pawlik, Tomasz Włodek, Marta Tańcula
Abstract: The high-energy milling uses the mechanical energy to activate chemical reactions by developing structural changes in the powder particles. High-energy milling with an acceleration of 28g was applied for the mechanical activation of the aluminium and silicon nitrides mixture with yttria additive. The activated powders showed the significant damage of the crystal structure and limited formation of a solid solution. Sintering of the activated precursor demonstrated higher ability for densification and started at 300 °C lower temperature in comparison to the standard mixture. The phase evolution during sintering was dependent on the starting composition and degree of powder activation.
Authors: Masayoshi Mikami, Satoshi Shimooka, Kyota Uheda, Hiroyuki Imura, Naoto Kijima
Abstract: A new oxynitride, Ba3Si6O12N2, has been synthesized. The crystal structure has been successfully determined by close collaboration between experiment and first-principles calculation. This compound doped with Eu exhibits intense green photoluminescence with high color purity under near-ultraviolet to blue light excitation; in particular, it has much less thermal quenching than (Ba,Sr,Eu)2SiO4. Thus (Ba,Eu)3Si6O12N2 appears promising green phosphor for white LED backlight for display. The atomic/electronic structure is discussed in comparison with Ba3Si6O9N4, which could not become efficient phosphor by doping Eu due to strong thermal quenching at room temperature.
Authors: Kyota Uheda
Abstract: Multiternary nitride and oxynitride compounds doped with rare earth ions, such as Eu2+ and Ce3+ have been enthusiastically applied as various phosphors to white LED. New red and green phosphors, CaAlSiN3:Eu and Ba3Si6O12N2:Eu, have been successfully synthesized, recently. The red phosphor has intense emission around 650 nm under two different irradiations at 405 and 455 nm from blue- and near UV-LED chips, respectively; while strong emission is observed around 520 nm from the green phosphor. Both phosphors also show small thermal quenching over the temperatures up to 150 °C. In addition, both LaSi3N5:Ce and La3Si8O4N11:Ce in lanthanum silicon nitride and oxynitride were examined as candidates for a blue phosphor in white LED with near UV-LED chip.
Authors: Sara Yoshio, Junichi Tatami, Toru Wakihara, Katsutoshi Komeya, Takeshi Meguro
Abstract: Electrically conductive Si3N4 ceramics were fabricated by dispersion of different characteristics of carbon nanotubes (CNTs). When the sintering aid of Y2O3-Al2O3-TiO2-AlN was used for lower temperature densification, it was confirmed that CNTs existed in Si3N4 ceramics from SEM observation and SiC was not identified in XRD analysis, which means that CNTs did not react with Si3N4. Relative density and electrical conductivity of the CNT dispersed Si3N4 ceramics depended on the characteristics of CNTs. Aggregation of CNTs, which is outstanding in much thinner CNTs, should limit densification of Si3N4. CNTs were well-dispersed by beads milling in ethanol. As a result, beads milling process was confirmed to be effective in unraveling and dispersing CNTs. It was shown that better dispersion of CNTs with higher aspect ratio resulted in higher density and electrical conductivity.
Authors: Toyohiko Yano, Junichi Yamane, Katsumi Yoshida
Abstract: For the transmutation of the very long half-lived isotopes which are separated from the spent nuclear fuels, it is necessary to find proper inert matrices these are stable under heavy neutron irradiation at high temperature. Silicon nitride ceramics is a candidate since it is very tolerant for heavy neutron irradiation and keeps relatively high thermal conductivity. For these reasons, we try to sinter Si3N4 ceramics containing large amounts of CeO2 as a simulant for Am2O3, a typical transuranium element. The low-temperature pressureless-sintering behavior of the ceramics and chemical and thermal properties of the obtained sintered bodies are reported.
Authors: S. Chockalingam, J.P. Kelly, V.R.W. Amarakoon, James R. Varner
Abstract: Microwave sintered Si3N4-MgO system that contains 2, 4 and 10 wt% of ZrO2 as secondary particulates were investigated with respect to phase transformation and microstructure development. The experimental results of microwave sintered samples were compared with conventional methods. Complete α to β phase transformation was observed in the case of microwave sintered samples due to the volumetric nature of microwave heating. High temperature X-ray diffraction (HTXRD) analysis was performed to study in-situ the oxidation behavior of Si3N4 specimens. Si3N4 specimens with 10 wt % ZrO2 were exposed to air at temperature between 25°C and 900°C for up to 24 hours. Microwave sintered sample were structurally stable in air 25°C and 900°C for up to 24 hours of testing.
Authors: Hiromasa Yabuki, Toru Wakihara, Junichi Tatami, Katsutoshi Komeya, Takeshi Meguro, Hideki Kita, Naoki Kondo, Kiyoshi Hirao
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.
Authors: Daisuke Horikawa, Junichi Tatami, Toru Wakihara, Katsutoshi Komeya, Takeshi Meguro
Abstract: HfO2-added Si3N4 ceramics are known to exhibit excellent high-temperature strength and excellent damage characteristics because HfO2 assists the crystallization of the grain boundary phase. However, the sintering shrinkage behavior and mechanical properties of HfO2-added Si3N4 have not been well clarified so far, although it has been reported that TiO2, in which Ti is from the same group as Hf in the periodic table, enhances the densification of the Si3N4-Y2O3-Al2O3-AlN system and wear resistance due to TiN formed from TiO2 and AlN in the grain boundary. In the present study, we focus on HfO2 as the sintering aid to investigate the sintering shrinkage behavior and mechanical properties of HfO2-added Si3N4. The powder mixtures are prepared by the addition of HfO2 to the Si3N4-Y2O3-Al2O3 or Si3N4-Y2O3-Al2O3-AlN system. The sintering shrinkage curves of HfO2-added Si3N4 ceramics show rapid shrinkage at 1600°C as compared with those of the Si3N4 ceramics without HfO2.The shrinkage can be explained by the formation of SiO2-Y2O3-HfO2 derived liquid phases. Furthermore, the mechanical properties of HfO2-added Si3N4 were as excellent as those of the Si3N4 ceramics without HfO2.
Authors: Ryota Kobayashi, Junichi Tatami, Toru Wakihara, Katsutoshi Komeya, Takeshi Meguro, Rong Tu, Takashi Goto
Abstract: AlN–SiC solid solutions with p-type electrical conduction were fabricated with the addition of small amounts of Al and C. Powder mixtures of AlN and SiC with small amounts of Al and C (below 10 mol%) were consolidated by spark plasma sintering (SPS) at 2000°C for 10 min under 1 atm Ar, and then heat-treated at 2200°C for 3 h in an Ar flow to afford 2H AlN–SiC solid solutions. The relative densities of the 50AlN-50SiC-Al4C3 (A50-1AC) and 50AlN-50SiC-3Al4C3 (A50-3AC) samples were about 95%, whereas that of the 75AlN-25SiC-Al4C3 (A75-1AC) sample was about 86%. X-ray diffractometry (XRD) analysis showed that the samples comprised only the 2H phase, and except in the case of the A50-3AC sample, no diffraction peaks of Al and C were observed. Although the samples without the additives (Al and C) were electrical insulators, addition of Al and C introduced p-type semiconduction. The electrical conductivities at 300°C of the A50-1AC and A50-3AC samples were about 30 and 100 S/m, respectively, whereas that of the A75-1AC sample was about 10–1 S/m. It was found that addition of Al and C brought about electrical conduction in AlN–SiC solid solutions.

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