METHOD OF MANUFACTURING SINTERED CERAMIC BODY

Abstract: A method of sintering a ceramic body, has the steps of preparing a composition containing a binder and a ceramic powder having a particle size distribution given such that 0 to 1 weight % of ceramic particles with an average particle size of less than 0.2 µm, 0 to 2 weight % of ceramic particles with an average particle size of 0.2 µm to less than 0.5 µm, 5 to 15 weight % of ceramic particles with an average particle size of 0.5 µm to less than 1.0 µm. 5 to 15 weight % of ceramic parti­ cles with an average particle size of 1.0 µm to less than 1.5 µm, 5 to 15 weight % of ceramic particles with an average particle size of 1.5 µm to less than 2.0 um, and 50 to 80 weight % of ce­ ramic particles of not less than 2.0 µm, the binder being con­ tained in the amount of 15 to 25 weight % of the total weight of the composition, injection-molding the composition into a pre­ determined shape to obtain a molded body, removing the binder from the molded body by heating, and sintering the molded body which is free from the binder. Since packing pro­ perties of the ceramic powder can be improved, the amount of binder to be used can be decreased. The density of the resul­ tant sintered body can be improved, and the contraction per­ centage of the sintered body can be decreased. A complicated sintered body can be fabricatetd with high precision.

Description: The present invention relates to a method of manufacturing a sintered ceramic body by forming a ceramic powder into a predetermined shape by injection molding and sintering the molded body. In a conventional method of manufacturing a sintered body made of a ceramic material such as silicon nitride, a sintering accelerator is added to a ceramic powder, and a resultant mixture is sintered in a mold having a cavity of a predetermined shape at a pressure of 15 to 50 MPa (150 to 500 kg/cm²) at a temperature of 1,700 to 1,800°C. This method is called hot pressing. According to this method, a sintered body having a high density and high mechanical strength can be obtained. However, it is difficult to prepare a sintered body of complicated shape. In addition to this disadvantage, hot pressing is not suitable for mass production. Since it allows mass production, a sintering method has received a great deal of attention, wherein an organic binder is added to a ceramic powder and a sintering accelerator, the resultant composition is injection-molded, the binder is removed from the molded body, and the molded body which is free from the binder is sintered. A conventional ceramic material for injection molding is milled by wet milling in a solvent such as n-butanol to obtain a ceramic powder. Ceramic powder of this type is low in packing density, thus requiring a great amount of binder and a long period of time for removing the binder. In addition, contraction of the material at the time of sintering is great. As a result, a sintered ceramic body having precise dimensions cannot be prepared, resulting in inconvenience. The present inventors have made extensive studies in order to solve the conventional drawbacks and found that the binding property of the ceramic powder was related to a particle size distribution, and that the packing property could be improved by widening the particle size distribution within a predetermined range. Prior art document AU-A-67 299 / 65 discloses a method of sintering a ceramic body comprising the steps of preparing a composition containing a binder and a ceramic powder, injection molding said composition, removing said binder from the molded body by heating and sintering said mold. The ceramic powder used in this process has a widened particle size distribution within a range of 0.1 µm - 100 µm. This powder additionally contains a small amount of particles below 0.1 µm. It is an object of the present invention to provide a method of manufacturing a sintered ceramic body, wherein a particle size distribution range of a ceramic powder is widened to improve a packing property thereof, and only a small amount of binder is required. In order to achieve the above object the present invention provides a method of sintering a ceramic body as defined in claim 1. A preferable method of preparing a ceramic powder having the above-mentioned particle size distribution comprises the steps of adding, as needed, a milling accelerator of oleic acid, stearic acid or the like to a silicon nitride powder having a particle size of 1.0 to 10 µm and a sintering accelerator such as yttrium oxide, alumina, titanium dioxide, and aluminum nitride, and dry-milling a resultant composition in a ball mill for 24 to 100 hours. Another preferable method of preparing the above-mentioned ceramic powder comprises the steps of adding, as needed, a milling accelerator to a silicon nitride powder or a mixture of a silicon nitride powder and a sintering accelerator, and performing a heat treatment of a resultant composition in an atmosphere of an inert gas such as nitrogen at a temperature of 1,500 to 1,750°C for 30 minutes to 2 hours; and dry-milling the composition. The resultant ceramic powder has a wide particle size distribution range and good packing properties. A ceramic powder having an initial particle size of 1 to less than 20 µm has good packing properties. In particular, when a ceramic powder having an initial particle size of 1 to 10 µm is used, its binding properties can be greatly improved. According to the present invention, 15 to 25 weight %, preferably, 18 to 22 weight % of a binder such as paraffin, a styrene resin or an ethylene resin is added to and mixed with the resultant ceramic powder. The resultant component is injection-molded into a predetermined shape. A molding temperature is preferably 70 to 80°C for the paraffin binder and 180 to 220°C for the resin binder. The molded body is heated in a vacuum, inert gas or reducing atmosphere at a temperature of 600 to 900°C, preferably 700 to 800°C to remove the binder. Abrupt heating must be avoided since the molded body is blistered. When the paraffin binder is used, the molded body is gradually heated at a heating rate of 1 to 2°C/hour to a temperature of 300°C. When the resin binder is used, the molded body is gradually heated at a heating rate of 1 to 2°C/hour to a temperature of 500°C. When gradual heating is performed and about half of the binder is removed, the heating rate may be increased. The molded body is sintered at atmopheric pressure in an inert gas or reducing atmosphere at a temperature of 1,600 to 1,900°C, preferably 1,700 to 1,800°C, thereby obtaining a sintered ceramic body. The present invention will be best understood by way of examples and a comparative example described below. Example 1 10 g of oleic acid were added to 1,000 g of a silicon nitride powder having a particle size of 1.0 to 10 µm and 100 g of a sintering accelerator (yttrium oxide, alumina and aluminum nitride mixed at a weight ratio of 2 : 1 : 1). The resultant mixture was dry-milled by an alumina ball mill for about 70 hours. The powder was filtered to prepare about 1 weight % of ceramic particles with a particle size of less than 0.2 µm, 2 weight % of ceramic particles with a particle size of 0.2 µm to less than 0.5 µm, 10 weight % of ceramic particles with a particle size of 0.5 µm to less than 1.0 µm, 15 weight % of ceramic particles with a particle size of 1.0 µm to less than 1.5 µm, 15 weight % of ceramic particles with a particle size of 1.5 µm to less than 2.0 µm, and 57 weight % of ceramic particles with a particle size of not less than 2.0 µm. A packing property (tap density) of the resultant ceramic powder was 45 to 47%. Paraffin was added to the ceramic powder in the amount of 18 to 20 weight % with respect to the total weight of the ceramic powder. A turbo charger rotor was injection-molded using this composition. A molded body was heated in nitrogen gas at a temperature of 700 to 800°C to remove the binder. The binder was completely removed in 100 to 125 hours, a period half that in the conventional method. The molded body which was free from the binder was sintered in a nitrogen gas atmosphere at a temperature of 1,750°C for two hours. The contraction percentage of the sintered body was 12 to 14%. Example 2 A mixture of 1,000 g of a silicon nitride powder having a particle size of 1.0 to 10 µm and 100 g of a sintering accelerator (yttrium oxide, alumina and aluminium nitride mixed at a weight ratio of 1 : 1 : 1) was heated in a nitrogen atmosphere at a temperature of 1,600°C for one hour. Subsequently, 10 g of oleic acid were added to the mixture, and the resultant composition was dry-milled by a ceramic ball mill for about 70 hours, thereby preparing a ceramic powder having a particle size distribution given by 0.1 weight % of ceramic particles with a particle size of less than 0.2 µm, 0.9 weight % of ceramic particles with a particle size of 0.2 µm to less than 0.5 µm, 10 weight % of ceramic particles with a particle size of 0.5 µm to less than 1.0 µm, 14 weight % of ceramic particles with a particle size of 1.0 µm to less than 1.5 µm, 10 weight % of ceramic particles of 1.5 µm to less than 2.0 µm, and about 65 weight % of ceramic particles of not less than 2.0 µm. A packing property (tap density) of the resultant ceramic powder was 48 to 50%. Paraffin was added to the ceramic powder in the amount of 16 to 18 weight % with respect to the total weight of the ceramic powder, thereby preparing a turbo charger rotor. The binder was removed from the molded rotor under the same conditions as in Example 1, and the molded rotor which was free from the binder was sintered. It took the binder 50 to 75 hours to be removed. The contraction percentage of the sintered body was 10 to 12%. Comparative Example 1,500 g of n-butyl alcohol were added to 1,000 g of a silicon nitride powder having a particle size of 1 to 10 µm and 100 g of a sintering accelerator (yttrium oxide, alumina and aluminum nitride were mixed at a weight ratio of 2 : 1 : 1). The resultant mixture was milled by a ceramic ball mill for 70 hours to prepare a ceramic powder. The particle size distribution of this ceramic powder was given by 3 weight % of ceramic particles with a particle size of less than 0.2 µm, 18 weight % of ceramic particles with a particle size of 0.2 µm to less than 0.5 µm, 47 weight % of ceramic particles with a particle size of 0.5 µm to less than 1.0 µm, 15 weight % of ceramic particles with a particle size of 1.0 µm to less than 1.5 µm, 10 weight % of ceramic particles with a particle size of 1.5 µm to less than 2.0 µm, and 7 weight % of ceramic particles with a particle size of not less than 2.0 µm. A packing property (tap density) of this ceramic powder was 30 to 32%. In order to injection-mold the ceramic powder to prepare the same turbo charger rotor as in Example 1, 30 to 35 weight % of binder had to be added to the ceramic powder. When the binder was removed from the molded body which was then sintered under the same conditions as in Example 1, the binder took 250 to 300 hours to be removed. Cracks occurred in the sintered body. In addition, the contraction percentage of the sintered body was 20 to 23%. As is apparent from the above examples, according the method of the present invention, the packing properties of the ceramic powder can be improved, only a small amount of binder is required, the density of the molded body is increased, and the time required for removing the binder can be shortened. In addition to these advantages, the contraction percentage of the sintered body is small, and complicated sintered bodies such as a turbo charger rotor and the like can be manufactured with high precision.

Claims: A method of sintering a ceramic body, comprising the steps of: dry milling a ceramic powder having a particle size of from 1 µm to less than 20 µm, preparing a composition containing a binder and the dry milled ceramic material having a particle size distribution of 0 to 1 weight % of ceramic particles with a particle size of less than 0.2 µm, 0 to 2 weight % of ceramic particles with a particle size of 0.2 µm to less than 0.5 µm, 5 to 15 weight % of ceramic particles with a particle size of 0.5 µm to less than 1.0 µm, 5 to 15 weight % of ceramic particles with a particle size of 1.0 µm to less than 1.5 µm, 5 to 15 weight % of ceramic particles with a particle size of 1.5 µm to less than 2.0 µm, and 50 to 80 weight % of ceramic particles of not less than 2.0 µm, said binder being contained in said composition in an amount of 15 to 25 weight % of the total weight of said composition; injection-molding said composition into a predetermined shape to obtain a molded body; removing said binder from said molded body by heating; and sintering said molded body which is free from said binder. A method according to claim 1, characterized in that said ceramic powder is prepared by milling in a dry atmosphere a powder mixture of a silicon nitride powder having a particle size of 1.0 to 10 µm and a sintering accelerator. A method according to claim 1, characterized in that said ceramic powder is prepared by heating in an inert gas atmosphere a powder mixture of a silicon nitride powder having a particle size of 1.0 to 10 µm and a sintering accelerator, and by milling the powder mixture. A method according to claim 3, characterized in that the powder mixture is heated at a temperature falling within a range between 1,400°C and 1,750°C. A method according to Claim 1, characterised in that the binder is removed by heating to a temperature between 600°C and 900°C. A method according to claim 1, characterized in that the molded body is sintered in an inert or reducing atmosphere at a temperature falling within a range between 1,600°C and 1,900°C.

Inventors: ANDO, AKIO C/O PATENT DIVISION, FUJIMOTO, YUUJI C/O PATENT DIVISION, KOMATSU, MICHIYASU C/O PATENT DIVISION, MIYANO, TADASHI C/O PATENT DIVISION, NAKANISHI, MASAE C/O PATENT DIVISION
Applicants: KABUSHIKI KAISHA TOSHIBA
Application year: 1984
Main classification: C04B35
IPC codes: C04B35