Papers by Author: Junichi Tatami

Abstract: Liquid-phase sintering of aluminum nitride (AlN) with additives was reviewed. The most important innovation was the discovery of critical sintering aids for AlN densification, specifically rare-earth compounds and alkali-earth compounds. These additives are extremely valuable for increasing thermal conductivity by trapping and removing oxygen in the AlN lattice during firing. Consequently, thermal conductivities in AlN ceramics of 100 to 260W/mK were developed. We also studied the effects of parameters such as raw powder, additives, composition, and firing condition in liquid-phase sintering with AlN-sintering aids, focusing on oxygen impurities in the system. The sintering behavior of powder compacts was investigated by evaluating the densification, the lattice constant c for AlN, and the dihedral angle of the interface between the AlN grains and the grain boundary liquid-phase. In our results, the change in densification was closely related to changes in the lattice constant c and the dihedral angle. That is, the sintered density increased with an increase in the oxygen dissolved in the AlN grains and with the improvement in wettability between the solid and liquid phase.

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: Silicon nitride (Si3N4) is one of the most attractive materials for wear applications because it has excellent wear resistance and offers advantages such as light weight, higher strength and toughness, and good corrosion resistance. In 1984, Materials Div., Toshiba Corp. (today, Toshiba Materials Co., Ltd.) and Koyo Seiko Co. Ltd. (today JTEKT Corp.) successfully utilized high-strength silicon nitride for anti-friction bearings for the first time in the world.1-3 This ceramic bearing was a most successful product and has expanded in area and volume through key innovations such as pioneered compositions, further improvement of durability against a steel ball and the development of a conventional fabrication process. Since 1989, Yokohama National University group has investigated new materials development in silicon nitride ceramics, densification/strengthening mechanisms in an optimized sintering aids system, powder processing for reliable components and tribological evaluation for bearing applications. Subsequently it was confirmed that the addition of TiO2 and AlN to an Si3N4-Y2O3-Al2O3 system promoted densification at low temperatures.4 During firing, the TiO2 changed into TiN at the grain boundary, causing grain boundary strengthening.5,6 Most recently, it has developed a carbon nanotube (CNT) dispersed silicon nitride with high strength and high electrical conductivity that is expected to open up new applications as a new functional silicon nitride.7 However, there are many items to be overcome toward the future, which are the development of cost reduction processes with higher material reliability, and the opening up of new applications supported by validated evaluation techniques including tribology, flaw detection and life prediction, raw powder problems related to cost and production volume, and the classification of silicon nitride bearings for various graded applications.

Abstract: Dense and homogenous Si3N4-TiN composites (5 vol% TiN) were prepared by using in situ synthesis method from Si3N4, AlN and TiO2 mixtures, containing Y2O3 and Al2O3 as sintering aids. In the prepared Si3N4-TiN composites, TiN grains were formed from TiO2 and AlN powders during the sintering process, in which ammonium citrate was used as a dispersant for raw TiO2 powders. The microstructures of the Si3N4-TiN composites with the increase of ammonium citrate were investigated by scanning electron microscopy (SEM). Citrate ions modified on the surface of TiO2 particles and protected the TiO2 particles in the mixed slurry to reduce the aggregations of TiO2 powders, and homogenous Si3N4-TiO2-AlN composite powder was prepared for sintering. The microstuctures of Si3N4-TiN were developed after sintering with the uniform distribution of TiN grains in the Si3N4 ceramics. It was found that the microstructure of Si3N4-TiN composite was improved significantly with 0.20 g ammonium citrate in the system, TiN grains with 0.2-0.3 μm in diameter distributed throughout Si3N4 matrix. It was a practical and useful way to improve the microstructure of Si3N4-TiN composite without the alteration of the preparation procedure.

Abstract: AlN-SiC ceramics with 0 to 75 mol% of AlN were fabricated through pressureless sintering of very fine AlN and SiC. Powder compacts with different amounts of AlN were fired at 2000°C for 1 h in Argon gas flow using an induction-heating furnace. The microstructure and phases present in the products were evaluated using SEM and XRD. The AlN-SiC ceramics had a porous structure with 30% porosity, and the grain size was increased with the addition of AlN. XRD analysis showed that 2H was a main phase in all samples, though 3C and 6H phases were found in 25 mol%AlN-75 mol%SiC ceramic. The electrical properties of the AlN-SiC ceramics were evaluated at various temperatures ranging from room temperature to 300°C. The electrical conductivity of the AlN-SiC ceramics depended on the amount of AlN and on the temperature. The 75 mol%AlN-SiC ceramic had higher electrical resistance, though the other samples were electrical conductors. The highest electrical conductivity was obtained with the 25 mol% AlN composition, which was 7 S/m at room temperature and 30 S/m at 300°C. The Seebeck coefficient for the AlN-SiC ceramics increased with rising temperatures. The AlN-SiC ceramics with 50 mol%AlN had the highest Seebeck coefficient of 220 2V/K at 300°C.

Abstract: β-SiAlON nanoceramics were fabricated from β-SiAlON nano powder using the spark-plasma sintering (SPS) technique. The β-SiAlON nanopowder (Si4Al2O2N6) was synthesized from a mixture of SiO2 (QS-102, Tokuyama Co., Japan), AlOOH (Tomita, Japan) and C (Mitsubishi Chemical, Japan) using the carbothermal reduction nitridation (CRN) method. The heating rate for SPS was 50
/min. The β-SiAlON nanoceramics had high strength (500 MPa). TEM observation showed that the intergranular glassy phase was scarcely present at the grain boundary of the β-SiAlON nanoceramics. Aqueous corrosion resistance was evaluated by measuring the weight loss after soaking in 5 and 35 wt.% H2SO4aq. and 5 wt.% HNO3aq. at 80
for 100 h. It was found that β-SiAlON nanoceramics have much higher corrosion resistance than commercialized silicon nitride ceramics in acid solutions. Commercialized Si3N4 ceramics have an intergranular glassy phase created as a result of the sintering aids in them. Thus, they are easily corroded by acid solutions because the intergranular glassy phase is easily corroded under such conditions. The excellent corrosion resistance of the β-SiAlON nanoceramics stems from their glass-free grain boundaries, since the β-SiAlON nanoceramics were produced without using a sintering aid.

Abstract: AlN powders were synthesized by gas-reduction- nitridation of γ-Al2O3 powders using NH3 and C3H8 as reactant gases. AlN was identified from the products that synthesized at 1100-1400 oC for 120 min in the NH3-C3H8 gas flow, and it was confirmed that AlN can be easily fabricated by the gas-reduction-nitridation of γ-Al2O3. The products synthesized at 1100oC for 120min contained unreacted γ-Al2O3. By the 27A1 MAS NMR spectra, Al-N bonding in the product increased with an increase in the nitridation ratio of the tetrahedral AlO4 shoulder which decreased prior to that of the octahedral AlO6 shoulder. It seems that γ-Al2O3 was preferentially nitrided from AlO4 rather than AlO6. AlN nano particles were easily converted directly from γ -Al2O3 at a low temperature because the AlO4 within γ-Al2O3was preferentially nitrided.

Abstract: The Master Sintering Curve (MSC) is quite useful for analyzing the shrinkage behavior of ceramics. It is possible to compare shrinkage behavior using MSCs that are obtained from different firing profiles. In this study, shrinkage behavior during sintering of green bodies of several kinds of Al2O3 based ceramics were evaluated, using an electric furnace equipped with a dilatometer to be controlled based on the MSC theory. Although all of the samples shrank monotonically, shrinkage behavior depended on the additive and heating rate. The MSC theory was applied to analyze shrinkage behavior. As a result, a different MSC could be obtained in Al2O3 with and without the addition of MgO. In the pure Al2O3, a single MSC could be obtained from shrinkage curves by firing at a heating rate of 7.5-20oC/min, though the shrinkage curve at a heating rate of 3-5oC/min did not correspond with the MSC. In contrast, shrinkage curves at heating rate of 5-20oC/min were converged in the case of the MgO doped Al2O3 to obtain a unique MSC independent of firing profile. Apparent activation energy for sintering was estimated as 555 kJ/mol in the pure Al2O3 and 880 kJ/mol in the MgO doped Al2O3. The firing profile to obtain a requested sintering shrinkage curve was predicted from the resultant MSC. A comparison between the predicted and the experimental shrinkage curves, showed good consistency, thus confirming that it is possible to control shrinkage behavior using the MSC.

Abstract: Observation of fracture surfaces in ceramics is useful for improving their mechanical properties. In this study, fracture surfaces of polycrystalline alumina were observed using scanning-probe microscopy (SPM) on a nanoscale, also called “nano-fractography.” The average grain size of polycrystalline alumina specimen used in this study was 4.5µm, and the fracture toughness was 3.0MPa･m-1/2. The fracture mode was found to be a mixture of intergranular and transgranular fractures. The fracture surface of intergranular fractures consisted of smooth and rough areas composed of very small steps, whose detection was impossible using scanning electron microscopy. Cleavage and non-cleavage fractures were observed in transgranular fracture grains. The fracture surface of single-crystalline alumina, which is the typical model of the transgranular fracture, was also observed by SPM. The cleavage plane of alumina macroscopically exhibited a very smooth, glass-like surface. However, sub-nano meter steps can be observed on the cleavage fracture surface and appear to be formed by plastic deformation during crack propagation because the size of the step nears that of the Burgers vector.