SLIDING MEMBER AND PRODUCTION THEREOF

Abstract: A ceramic sliding member provided with a sliding face having a surface roughness of 1.0 µm or less in terms of arithmetical mean deviation (Ra). The ceramic includes silicon nitride sinter which contains crystal grains in a linear density of 35 or above per unit length of 30 µm, has a volumetric grain boundary ratio of 15 vol.% or less, and contains pores with a maximum diameter of 20 µm or less in a content of 3 % or less. The production process comprises machining a sliding face and then heating the ceramic in an atmosphere of either an inert gas or air to secure the smoothness of the sliding face. The obtained member has an excellent wear resistance and can be used under severe sliding conditions including high-speed sliding. It can inhibit the occurrence of seizure or abnormal wear on the sliding face even when applied to a sliding part of a compressor using chlorine-free fluorocarbon as the refrigerant.

Description: Technical Field of the Invention The present invention generally relates to a slide member which is required to be wear-resistant and a method of manufacturing the same, and more specifically, it relates to a slide member which can withstand strict sliding conditions of high-speed sliding or the like, a slide member which is used in an atmosphere of a cooling medium, and a method of manufacturing the same. Background of the Invention Bearing members making sliding motions can be classified into those making a rolling motion and a sliding motion. A rolling bearing making the former motion is applied to a ball bearing, for example. This ball bearing is generally in a complicated structure. Bearings making the latter sliding motion include contact type bearings (metal bush bearing and oil retaining bearing) and non-contact bearings (oil bearing, air bearing and magnetic bearing). These bearings have extremely simple structures as compared with the former bearing. A slide bearing is widely used as a mechanical component, since its structure is simple. With increase in machine speed, problems of seizure and durability are caused in a conventional slide bearing which is made of bearing steel. To this end, ceramics has been watched with interest as a material for a slide member which is required to be wear-resistant under high-speed sliding. In an office automation product or the like, further, requirement for an oil-free bearing is increased with increase in requirement for cleaning. Also in this field, ceramics has been watched with interest as a material for a slide member. As to such ceramics, Aℓ 2 O 3 , ZrO 2 , SiC, Si 3 N 4 and the like are now being developed. In oil-free high-speed sliding exceeding 1 m/sec., however, an. impactive knock wear phenomenon is caused by contact between bearing members. In a conventional bearing body which is made of ceramics, therefore, it has been difficult to withstand such sliding. On the other hand, a slide bearing body is also incorporated in a sliding part of a compressor of a refrigerator, a freezer or a car cooler. In this case, the sliding part of the bearing body is placed in a cooling medium. A chlorofluorocarbon (CFC), which is one of fluorocarbons (hereinafter referred to as flons), has been employed as the cooling medium. In particular, a typical cooling medium of such a chlorofluorocarbon is CFC12. Chlorine (Cℓ) is contained in molecules of this CFC12. This chlorine prevents adhesion and reaction of the slide member on a sliding surface. Namely, the chlorine prevents seizure between sliding surfaces or the like as an extreme pressure additive. Therefore, the CFC12 containing this chlorine itself serves as an extremely effective lubricant. Under a flon atmosphere of CFC12 or the like containing chlorine, therefore, the sliding part of the slide member hardly seizes or causes abnormal wear. In general, therefore, a metal member of cast iron or the like has been applied to a sliding part of a compressor of a refrigerator or the like, which is used in an atmosphere of a cooling medium. Under a flon atmosphere containing chlorine, as hereinabove described, neither seizure nor abnormal wear of the sliding part has been caused even if a metal member of cast iron or the like is applied to the sliding part. In recent years, however, employment of chlorofluorocarbons, which are represented by CFC12, has been regulated in relation to the problem of destruction of the ozonosphere in the stratosphere. This is because chlorine contained in the chlorofluorocarbons is one of the factors destroying the ozonosphere. HFC134a containing no chlorine in its molecules, for example, is now expected as a substitute for these chlorofluorocarbons. Thus, a study is now being made in order to apply a flon containing no chlorine to a cooling medium. In such a flon containing no chlorine, however, no lubricating effect by chlorine can be expected. Thus, there is caused such a problem that a metal such as cast iron which is applied to a sliding part of a compressor or the like seizes to another metal or causes abnormal wear. GB 2 170 279 A discloses a slide member having a sliding surface having a surface roughness which is not greater than 0.05 micron. Further prior art slide members are disclosed in EP-A-454618, JP-A-2150504 and EP-A-272066. It is an object of the invention to provide a slide member having an improved wear resistance, and a method of manufacturing such slide member. This problem is solved by providing a slide member comprising the features defined in appended independent claims 1 and 9, by providing a sliding part structure according to independent claim 3 and by providing a method of manufacturing a slide member according to independent claim 5. Advantageous embodiments of the invention are defined in the dependent claims. Namely, the slide member according to the present invention comprises a sliding surface which is made of a silicon nitride sintered body in accordance with claim 1, and has surface roughness of not more than 1.0 µm in center line average roughness Ra. Preferably, the sliding surface has surface roughness of not more than 0.1 µm in center line average roughness Ra. The center line average roughness Ra is defined under JISB0601 (ISO468). The silicon nitride sintered body contains crystal grains being in linear density of at least 35 per 30 µm in length with a boundary phase volume rate of not more than 15 volume % while containing pores of not more than 20 µm in maximum diameter in a content of not more than 3 %. The sliding part structure according to the present invention comprises a first slide member and a second slide member. The first slide member has one sliding surface. The second slide member has another sliding surface which is in contact with the one sliding surface. At least said one sliding surface is made of a silicon nitride sintered body in accordance with claim 1, and has surface roughness of not more than 1.0 µm in center line average roughness Ra. The method of manufacturing a slide member according to the present invention is a method of manufacturing a slide member, comprising a sliding surface which is made of a silicon nitride sintered body in accordance with claim 1, and comprises the following steps: (a) A step of grinding the aforementioned sliding surface. (b) A step of heating the silicon nitride sintered body in an atmosphere of either an inert gas or the atmospheric air after grinding the aforementioned sliding surface. According to a preferred embodiment of the method of manufacturing a slide member according to the present invention, the step of heating the silicon nitride sintered body is carried out at a temperature of at least 800°C and not more than 1500°C. A method of manufacturing a slide member according to a further aspect of the present invention comprises the following step, in addition to the aforementioned steps (a) and (b): (c) A step of polishing the aforementioned sliding surface after heating the aforementioned silicon nitride sintered body. A slide bearing body can be listed as an example of the inventive slide member. The slide member may comprise a sliding surface which is placed in an atmosphere of a cooling medium containing fluorine, and the sliding surface is made of a silicon nitride sintered body in accordance with claim 1. Preferably, the sliding surface is provided with a film which is mainly composed of carbon. The film which is mainly composed of carbon may be previously formed before the same is applied to the slide member, while the same may alternatively be formed during sliding. In the slide member according to the present invention, the center line average roughness Ra of the sliding surface is not more than 1.0 µm. Thus, it is possible to reduce the wear rate and the driving torque at the same rotational frequency as compared with the conventional slide member. More preferably, the center line average roughness Ra is so reduced at 0.1 µm or less as to attain a further effect. The reason for this can be considered as follows: On a surface of ceramics which is subjected to machining such as grinding, surface imperfection such as surface roughening is formed. Such surface roughening may act as a critical factor which exerts an influence on performance of a sliding material. When fine irregularity of the surface is properly controlled and smoothed, worn powder hardly results even if abrupt contact of the sliding part or the like is caused by disturbance or the like. Namely, the wear rate is reduced. Thus, vibration which is caused by intervention of worn powder in the sliding surface is suppressed. Therefore, it is possible to reduce torque for driving the slide member at least by such suppression of the vibration. Consequently, the slide member according to the present invention is capable of withstanding high-speed sliding. Depending on the structure of the sliding part or sliding conditions, it is also possible to prepare only one of a pair of members forming a pair of sliding surfaces which are in contact with each other from the aforementioned ceramics. If the ceramics is silicon ceramics, a fine and dense surface layer of silica or the like is easily formed in sliding. Thus, an effect of improvement in a sliding property such as reduction of a coefficient of friction, for example, can be expected. Particularly when the ceramics includes an Si 3 N 4 phase, it is possible to obtain a sliding surface which is excellent in chipping resistance with no chipping resulting from fall of crystal grains or the like in at least the surface of ceramics forming the sliding surface. A slide member, in which at least a sliding surface is made of ceramics including an Si 3 N 4 phase, has excellent wear resistance also against high-speed sliding accompanied by a knock wear phenomenon. Therefore, it is possible to suppress increase of the driving torque with respect to increase of the sliding speed. When the sliding surface is formed of a sintered body including an Si 3 N 4 phase, the silicon nitride sintered body contains crystal grains which are in linear density of at least 35 per 30 µm in length with a boundary phase volume ratio of not more than 15 volume %, preferably not more than 10 volume %. Further, the silicon nitride sintered body contains pores of not more than 20 µm, preferably not more than 10 µm in maximum diameter, while the content of the pores is controlled at 3 % or less. Therefore, the surface of the silicon nitride sintered body forming the sliding surface is not chipped by fall of crystal grains or the like, but is also excellent in chipping resistance. Thus, the slide member of a silicon nitride sintered body according to the present invention has excellent wear resistance also against high-speed sliding accompanied by a knock wear phenomenon. In the method of manufacturing the slide member according to the present invention, heat treatment is performed on the silicon nitride sintered ceramics in an inert atmosphere or the atmospheric air after grinding the sliding surface. The reason for this is now described. In addition to surface roughening, fine microcracks of micron or submicron order and residual stress are introduced into the ground ceramics. These can also serve as critical factors exerting influences on the performance of the slide member. When the ceramics is heated under an inert atmosphere or in the atmospheric air, reaction products are formed in the ceramics. The reaction products are SiO x (x: arbitrary positive integer) in Si ceramics, for example. Due to this heat treatment, further, atomic migration takes place in the ceramics through diffusion. Therefore, the microcracks are recombined and the defect is remedied by such formation of the reaction products or atomic migration, or a synergistic effect of these. In addition, this heat treatment also has an effect of removing residual stress. Thus, it is possible to remove microcracks and residual stress from the ceramics by performing the heat treatment. Therefore, worn powder is hardly caused by abrupt contact of a sliding part resulting from disturbance or the like. Thus, it is possible to suppress increase of driving torque following increase of the sliding speed. The ceramics is preferably heated at a temperature of at least 800°C and not more than 1500°C. It is possible to further facilitate formation of reaction products and atomic migration in the ceramics by heating the same at a temperature of at least 800°C. If the heating temperature exceeds 1500°C, on the other hand, the ceramics is unpreferably resintered to cause regrowth of the crystal grains. When the sliding surface is polished after the ceramics is subjected to heat treatment, fragile ones of reaction products formed on the surface are removed with an effect of smoothing of the products, whereby a slide member comprising a more stable sliding surface having disturbance resistance can be obtained. When the inventive slide member is applied to a slide bearing body, the driving torque is so reduced that a high-speed sliding motion is enabled with small driving torque. Further, the inventors have made deep studies to find that it is extremely effective to introduce ceramics into a slide member which is used in an atmosphere of a cooling medium containing fluorine, in order to prevent seizure and abnormal wear. The reason why seizure and abnormal wear can be prevented may be considered as follows: Ceramics is superior in Young's modulus and inferior in chemical reactivity as compared with a metal material such as cast iron. Since the ceramics is inferior in chemical reactivity, reaction such as chemical adhesion is hardly caused on a sliding surface of a slide member containing ceramics. Thus, it is possible to prevent seizure and abnormal wear resulting from chemical adhesion or the like in a slide member containing ceramics. Therefore, the slide member containing ceramics normally operates also when the same is used in an atmosphere of a cooling medium containing fluorine, such as a flon containing no chlorine. The atmosphere of a cooling medium containing fluorine in the present invention may be at least either a gas or a liquid of a flon. Further, the cooling medium in the present invention may be at least either a hydrofluorocarbon (HFC) or a hydrochlorofluorocarbon (HCFC). Molecular formulas of typical hydrofluorocarbons are shown in Table 1. Code Molecular Formula HFC 32 CH 2 F 2 HFC 125 CHF 2 - CF 3 HFC 134 CHF 2 - CHF 2 HFC 134a CH 2 F - CF 3 HFC 143a CH 3 - CF 3 HFC 152a CH 3 - CHF 2 HFC 227 CF 3 - CHF - CF 3 The slide member according to the present invention is also effective under an atmosphere of a hydrofluorocarbon other than those shown in Table 1. Further, molecular formulas of typical hydrochlorofluorocarbons are shown in Table 2. Code Molecular Formula HCFC 22 CHCℓF 2 HCFC 123 CHCℓ 2 - CF 3 HCFC 124 CHCℓF - CF 3 HCFC 141b CH 3 - CCℓ 2 F HCFC 142b CH 3 - CCℓF 2 HCFC 225ca CF 3 - CF 2 - CHCℓ 2 HCFC 225cb CF 2 Cℓ - CF 2 - CHCℓF The ceramics forming the sliding surface according to the present invention is sintered silicon nitride. Tables 3 and 4 show typical monolithic ceramics and composite materials employing those ceramics. Monolithic Ceramics Oxide Alumina, Mullite, Spinel, Zirconia Carbide Silicon Carbide, Titanium Carbide Nitride Silicon Nitride, Aluminum Nitride, Titanium Nitride Boride Boron Nitride, Boron Carbide Silicide Titanium Silicide Composite Material Long Fiber Reinforced Composite Material Carbon Fiber Reinforced Silicon Nitride, Silicon Carbide Fiber Reinforced Silicon Nitride, Alumina Fiber Reinforced Glass Whisker Reinforced Composite Material Silicon Carbide Whisker Reinforced Alumina, Silicon Carbide Whisker Reinforced Silicon Nitride Particle Dispersion-Strengthened Composite Material Titanium Nitride Particle Dispersion-Strengthened Silicon Nitride, Silicon Carbide Nanoparticle Dispersion-Strengthened Alumina, Silicon Carbide Nanoparticle Dispersion-Strengthened Silicon Nitride It is preferable that the slide member consists of a pair of members forming a pair of sliding surfaces which are in contact with each other, and at least one of the members is made of ceramics. In this case, one of the members forming the sliding surfaces must be made of ceramics, while the other member may be made of a metal, or may be prepared from a material such as the same of different types of ceramics, a carbon material, resin such as Teflon. The inventors have found that there is a relation between surface roughness, seizure resistance and wear of a sliding surface of a slide member which is used in an atmosphere of a cooling medium containing fluorine. According to this, surface roughness of the sliding surface of the inventive slide member is not more than 1.0 µm Ra. If the surface roughness of the sliding surface exceeds 1.0 µm Ra, one ceramics member may damage another metal member, or one and another ceramics members may cause abnormal wear, depending on the surface pressure of the sliding surface. When the surface roughness of the sliding surface is not more than 1.0 µm Ra, on the other hand, one ceramics member hardly damages another member or hardly causes abnormal wear with another member. The reason for this may be considered as follows: When the surface roughness of the sliding surface of the slide member is made not more than 1.0 µm Ra, irregularity on the sliding surface is reduced. Namely, the surface is smoothed. Thus, wear is hardly caused by abrupt contact of the sliding part resulting from disturbance or the like. Consequently, it is possible to suppress a mechanical frictional phenomenon by making the sliding surface not more than 1.0 µm Ra. The inventors have also found that it is possible to attain a further effect by further smoothing the surface roughness of the sliding surface of the inventive slide member to be not more than 0.1 µm Ra. It has been recognized that an excellent low coefficient of friction is obtained particularly in an atmosphere of a cooling medium containing fluorine, to attain excellent wear resistance. This is conceivably because irregularity of the sliding surface can be further reduced by making the surface roughness not more than 0.1 µm Ra. Thus, it is possible to further suppress a mechanical frictional phenomenon also in an atmosphere of a cooling medium containing fluorine. Further, the inventors have found that the sliding surface exhibits a low coefficient of friction and high wear resistance when a film which is mainly composed of carbon is formed on the sliding surface of the slide member. This is because friction and wear are reduced by a solid lubricating action of the carbon. Thus, it is possible to further reduce a mechanical frictional phenomenon also in an atmosphere of a cooling medium containing fluorine by forming a film which is mainly composed of carbon on the sliding surface. The inventors have found that there is a relation between surface roughness and wear resistance of a slide member which is provided with a film mainly composed of carbon on its sliding surface. According to this, the surface roughness of the inventive slide member which is provided with the film mainly composed of carbon is preferably not more than 1.0 µm Ra. This is because one member may damage a film, mainly composed of carbon, which is formed on a surface of another member or cause abnormal wear thereon depending on the surface pressure of the sliding surface if the surface roughness of the sliding surface exceeds 1.0 µm Ra, and a solid lubricating action of the film which is mainly composed of carbon may not be sufficiently attained as the result. Further, the inventors have found that it is possible to attain a low coefficient of friction and excellent wear resistance in an atmosphere of a cooling medium containing fluorine by making the surface roughness of the inventive slide member provided with a film, which is mainly composed of carbon, not more than 0.1 µm Ra. This is conceivably because it is possible to further reduce irregularity of the sliding surface by making the surface roughness not more than 0.1 µm Ra, whereby it is possible to further reduce a mechanical frictional phenomenon also in an atmosphere of a cooling medium containing fluorine as the result. The inventors have found a method of forming a film which is mainly composed of carbon on the sliding surface during sliding, by employing a material such as cast iron containing free carbon for one of the inventive sliding members. According to this, the free carbon falls in an initial stage of sliding, to form a carbon film on the sliding surface of the other slide member. When the surface roughness of the sliding surface exceeds 1.0 µm Ra, a wear speed exceeds the speed of formation of the film which is mainly composed of carbon, leading to formation of no film. When the surface roughness of the sliding surface is not more than 1.0 µm Ra, on the other hand, a film which is mainly composed of carbon is formed since wear is hardly caused. According to this, it is possible to suppress a mechanical frictional phenomenon without coating the sliding surface with a material having solid lubricity such as carbon or molybdenum disulfide in advance of employment of the slide member. Further, they have found that it is possible to form a film which is mainly composed of carbon on the sliding surface during sliding in a cooling medium containing fluorine by making the surface roughness of the sliding surface not more than 0.5 µm Ra, thereby obtaining a sliding surface having a lower coefficient of friction, which is particularly excellent in wear resistance. This is based on the fact that it is possible to further reduce irregularity of the sliding surface by making the surface roughness not more than 0.5 µm Ra for enabling stable formation of a film which is mainly composed of carbon on the surface, whereby a solid lubricating action of the carbon is properly attained as the result. Thus, it is possible to further suppress a mechanical frictional phenomenon also in an atmosphere of a cooling medium containing fluorine. More preferably, the aforementioned effect can be further remarkably implemented by making the surface roughness of the sliding surface not more than 0.1 µm Ra. According to the present invention, as hereinabove described, a slide member having excellent wear resistance, which is applicable to a use under strict sliding conditions of high-speed sliding or the like, is applied. Particularly in the slide member according to the present invention, it is possible to reduce surface roughening on the sliding surface by controlling center line average roughness Ra to not more than 1.0 µm as surface roughness of the sliding surface. Thus, worn powder is hardly caused also by abrupt contact of a sliding part resulting from disturbance or the like. Therefore, it is possible to suppress increase of driving torque with respect to increase of a vibration frequency which is caused by worn powder. Consequently, the inventive slide member can withstand high-speed sliding. Further, it is possible to prevent seizure and abnormal wear also when the inventive slide member is used in an atmosphere of a cooling medium containing fluorine. Brief Description of the Drawings Fig. 1 is a diagram showing results of an experiment of an Amsler abrasion test made on respective samples shown in Table 5. Fig. 2 is a schematic diagram showing a structure of a composite bearing body for testing sliding properties in a case of applying respective samples shown in Table 6 to bearing members. Fig. 3 is a schematic diagram showing a structure of a performance evaluation tester employing the composite bearing body shown in Fig. 2. Fig. 4 is a diagram showing results of an experiment for performance evaluation of composite bearing bodies formed by the respective samples of Table 6. Fig. 5 illustrates graphs (A) and (B) showing relations between wear rates and P·V values of sintered bodies forming the inventive slide members with those of conventional and comparative examples. Fig. 6 is a graph showing relations between wear rates and P·V values of sintered bodies forming the inventive slide members in a substitutional flon with those of comparative examples. Best Modes for Carrying Out the Invention Example 1 The inventors have made the following experiment on Si 3 N 4 ceramics, which is excellent in toughness among ceramics materials. First, raw material powder of Si 3 N 4 having a mean particle diameter of 0.3 µm, particle size distribution 3σ = 0.2 µm, an α crystallization rate of 96.5 % and an oxygen content of 1.4 weight % was prepared. 92 weight % of this raw material powder of Si 3 N 4 was mixed with 4 weight % of Y 2 O 3 powder having a mean particle diameter of 0.8 µm, 3 weight % of Aℓ 2 O 3 powder having a mean particle diameter of 0.5 µm, and 1 weight % of AℓN powder having a mean particle diameter of 1.0 µm. Utilizing a ball mill, these powder materials were wet-blended in ethanol for 100 hours. Thereafter the mixed powder after drying was subjected to CIP (cold isostatic pressing) treatment under a pressure of 5000 kg/cm 2 . The as-obtained compact was heated/held in a gaseous nitrogen atmosphere of 1 atm. at 1600°C for 4 hours. Further, sintering treatment was performed on this compact at a temperature of 1750°C for 6 hours, thereby obtaining a sintered body. Thereafter this sintered body was subjected to HIP (hot isostatic pressing) treatment at a temperature of 1700°C under a pressure of 1000 atm. in a gaseous nitrogen atmosphere for 2 hours. The as-obtained Si 3 N 4 sintered body contained crystal grains which were in linear density of at least 35 per 30 µm in length while containing pores of not more than 20 µm in maximum diameter in a boundary phase volume ratio of not more than 15 volume %, with porosity of not more than 3 %. Further, this Si 3 N 4 sintered body had a mean major axis particle diameter of not more than 5 µm, an aspect ratio of at least 4, and a maximum major axis particle diameter of not more than 15 µm. In addition, this sintered body had JIS three-point bending strength of at least 80 kg/mm 2 , and a fracture toughness value of at least 5 MPa•m 1/2 . Sintered bodies having such characteristics were subjected to cylindrical grinding by a cylindrical grinder. Conditions employed at this time were a peripheral speed of 1400 m/min. and a feed rate of 260 m/min. Further, the grindstones of the cylindrical grinder were successively exchanged from that of 200 meshes/in. to that of 800 meshes/in., thereby finishing surfaces of the sintered bodies in desired surface roughness level. Thus obtained are samples Nos. 1 to 4 shown in the following Table 5. After this cylindrical grinding was performed, the sintered bodies were subjected to heat treatment in a heating furnace at a temperature of 1000°C for 1 hour. Thereafter the sintered bodies were polished by a buffing machine under conditions of a peripheral speed of 1400 m/min. and a feed rate of 260 m/min., using a diamond lapping solution of 1500 meshes/in. in grain size as a polishing solution. Thus obtained are samples Nos. 5 to 8 shown in the following Table 5. No. Curve Finished Surface Roughness Ra(µm) Heat Treatment 1000°C × lhr. Mark 1 a 2.0µm No Δ 2 b 1.0 No □ 3 c 0.5 No ○ 4 d 0.1 No ⋄ 5 e 2.0 Yes ▴ 6 f 1.0 Yes ▪ 7 g 0.5 Yes • 8 h 0.1 Yes ◆ The samples Nos. 1, to 8 (1 to 5 are comparative samples) shown in Table 5 obtained in the aforementioned manner were subjected to wear resistance evaluation by an Amsler abrasion test. The Amsler abrasion test is a test of employing two ring-type test samples (outer diameter of 16 mm by inner diameter of 30 mm by thickness of 8 mm) and making a sliding test with a prescribed load P and a rotational speed V for thereafter measuring weight reduction values of the samples, thereby evaluating wear resistance. Fig. 1 is a diagram showing the results of the experiment for making an Amsler abrasion test on the respective samples shown in Table 5. Referring to Fig. 1, the axis of abscissas shows products (P·V values) of loads P and rotational speeds V. Further, the axis of ordinates shows wear rates. Marks such as ○ and • appearing in the figure correspond to the respective samples shown in Table 5. For the purpose of comparison, Fig. 1 also shows the results of 5Y5A and 5Y5L materials, which are Si 3 N 4 sintered bodies indicated in Yogyo Kyokai-Shi, Vol. 93, 1985, p. 73, in solid and two-dot chain lines respectively. As obvious from this figure, wear resistance is improved as surface roughness Ra is reduced. Further, it is understood that wear resistance of the sintered body is further improved when heat treatment is performed at a temperature of 1000°C for 1 hour. In addition, it is understood that an effect of improving wear resistance is remarkable when surface roughness is not more than 1.0 µm in Ra. As hereinabove described, it has been proved that an Si 3 N 4 sintered body having finished surface roughness Ra of not more than 1.0 µm is extremely excellent in wear resistance. Further, it has also been proved that the wear resistance is further improved by performing heat treatment on this Si 3 N 4 sintered body. It has also been confirmed that an effect of improving wear resistance can be similarly attained also when the aforementioned treatment is performed on Aℓ or Zr ceramics, under conditions of not changing original mechanical properties (bending strength, for example) of the material. Therefore, the aforementioned treatment for controlling surface roughness is applicable to all ceramics. Then, performance attained in a case of applying the inventive slide member to a bearing body was examined. First, Si 3 N 4 sintered bodies obtained in the aforementioned method were employed as the materials for bearing bodies. As hereinabove described, the sintered bodies which were subjected to HIP treatment were surface-ground by a surface grinder. Conditions employed at this time were a peripheral speed of 1800 m/min. and a feed rate of 260 m/min. Further, grindstones of the surface grinder were successively exchanged from that of 200 meshes/in. to that of 800 meshes/in., thereby finishing surfaces of the sintered bodies in desired surface roughness levels. Thus, respective samples were prepared. Parts of the samples were subjected to heat treatment in a heating furnace at a temperature of 1000°C for 1 hour after the surface grinding. Further, other parts of the samples were subjected to buffing as polishing. A diamond lapping solution of 1500 meshes/in. in grain size was employed as a polishing solution under conditions of a peripheral speed of 1800 r.p.m. and a feed rate of 260 m/min., to polish the samples by a buffing machine. Thus, the samples shown in the following Table 6 were obtained. Surface Roughness (Ra) Heat Treatment Condition Treatment after Grinding Mark Remarks A0 2.0µm --- --- ▪ Conventional Material A1 2.0µm 1000°C for 1 Hour in Atmospheric Air Polish □ Comparative Material B0' 1.0µm --- --- ▾ Developed Material B1' 1.0µm 1000°C for 1 Hour in Atmospheric Air --- ▿ Developed Material B0 1.0µm --- Polish Δ Developed Material B1 1.0µm 1000°C for 1 Hour in Atmospheric Air Polish Δ Developed Material C0 0.5µm --- --- • Developed Material C1 0.5µm 1000°C for 1 Hour in Atmospheric Air Polish ○ Developed Material D0 0.08µm --- --- ◆ Developed Material D1 0.08µm 1000°C for 1 Hour in Nitrogen --- ⋄ Developed Material The aforementioned samples shown in Table 6 were employed to form bearing bodies. Fig. 2 is a schematic diagram showing a structure of a composite bearing body for testing performance of a bearing body. Referring to Fig. 2, the composite bearing body 10 is formed by an inner ring 1, an outer ring 2 and thrust plates 3 and 4. The inner ring 1 has a cylindrical shape, to enclose an outer peripheral surface of a prescribed shaft. The thrust plates 3 and 4 are set to be in contact with both end surfaces of the inner ring 1. The outer ring 2 is adjusted to maintain prescribed clearances with respect to the inner ring 1 and the thrust plates 3 and 4. Further, the clearances are adjusted to fine values, in order to maintain radial rotation accuracy during high-speed rotation. Fig. 3 is a schematic diagram showing a structure of an evaluation tester for evaluating performance of the aforementioned composite bearing body. The composite bearing body is formed by an inner ring 11, an outer ring 12 and thrust plates 13 and 14. This composite bearing body is formed from each sample of the Si 3 N 4 ceramics sintered body shown in Table 6. The outer ring 12 is so provided as to maintain a prescribed clearance with respect to the inner ring 11. Further, this outer ring 12 also maintains prescribed clearances with respect to the thrust plates 13 and 14. The inner ring 11 to which the thrust plates 13 and 14 are bonded is provided with a hole having an inner diameter of 10 mm from its cylindrical upper surface to its cylindrical lower surface. A rotator 15 is fitted in this hole. The inner ring 11 is rotatable with this rotator 15. The rotator 15 is set to be rotatable by a motor 16. Driving torque of this motor 16 is measured by a torque meter 17. The bearing performance evaluation tester is formed in the aforementioned manner. This bearing performance evaluation tester was employed for making the rotational frequency of the rotator 15 reach a set value, thereafter holding the same for 10 minutes, and measuring driving torque at that point of time by the torque meter 17. Fig. 4 is a diagram showing the results of driving torque of rotators measured using composite bearing bodies which were formed by the respective samples of Table 6. Referring to Fig. 4, marks such as ○ and • appearing in the figure correspond to the respective samples of Table 6. The axis of abscissas shows rotational frequencies (r.p.m.) of the rotators supported by the respective composite bearing bodies (or, peripheral speeds (m/sec.) in inner peripheral surfaces of the inner rings). The axis of ordinates shows driving torque values (g•cm). As obvious from this figure, it is understood that the ratio of an increase rate of the driving torque to that of the rotational frequency (peripheral speed) is reduced as surface roughness Ra after grinding is reduced. It is also understood that the ratio of the increase rate of the driving torque to that of the rotational frequency is reduced by performing heat treatment, while such ratios were further reduced in the samples subjected to buffing as polishing. In the samples A0 and A1, seizure occurred in sliding parts when the rotational frequencies exceeded 15000 r.p.m. From the aforementioned results, it is understood that increase of driving torque with respect to increase of the rotational speed can be extremely suppressed in each sample having surface roughness Ra of not more than 1.0 µm. As to Example of the inventive slide member, the slide member according to the present invention is applied to a bearing for an office automation product which is required to rotate at a high speed, a turbine bearing for a supercharger which rotates at a high speed of 80000 to 150000 r.p.m., a bearing for a turbine or a compressor which rotates at a high speed of 20000 to 30000 r.p.m., a bearing for high-speed rotation which is employed for a rocket engine turbo-pump, a bearing which is employed for a machine tool such as a CNC ultraprecise lathe, an ultraprecise lathe for cylindrical working or an ultraprecise surface grinder, and the like. Example 2 A method of manufacturing a silicon nitride sintered body as a material for a slide member according to Example of the present invention is now described. Raw material powder of Si 3 N 4 having a mean particle diameter of 0.3 µm, grain size distribution of 3σ = 0.20 µm, an α crystallization rate of 96.5 % and an oxygen content of 1.4 weight % was prepared. 92 weight % of this Si 3 N 4 raw material powder, 4 weight % of Y 2 O 3 powder having a mean particle diameter of 0.8 µm, 3 weight % of Aℓ 2 O 3 powder having a mean particle diameter of 0.5 µm and 1 weight % of MgO powder having a mean particle diameter of 1.0 µm were wet-blended in ethanol for 100 hours through a ball mill. Thereafter mixed powder which was obtained by drying was subjected to CIP (cold isostatic press) molding under a pressure of 5000 kg/cm 2 . The as-obtained compact was heated/held under a gaseous nitrogen atmosphere of 1 atm. at a temperature of 1600°C for 4 hours. Further, sintering treatment was performed at a temperature of 1750°C for 6 hours, to obtain a sintered body. Thereafter HIP (hot isostatic press) treatment of 2 hours was performed on this sintered body at a temperature of 1700°C in a gaseous nitrogen atmosphere of 1000 atm. In the silicon nitride sintered body obtained in the aforementioned manner, the mean major axis particle diameter was not more than 5 µm, the aspect ratio of crystal grains thereof was at least 4, and the maximum major axis particle diameter was not more than 15 µm. This sintered body had mechanical properties of JIS three-point bending strength of at least 80 kg/mm 2 and a fracture toughness value of at least 5 MPa•m 1/2 . Test pieces were cut from the as-obtained sintered body, to evaluate wear resistance levels in accordance with an Amsler abrasion test. (A) in Fig. 5 is a graph showing relations between products (P•V) of loads applied to the samples and rotational speeds, and wear rates. Referring to Fig. 5, respective curves a to e show results of measurement obtained by the following samples: a: Inventive Sample A silicon nitride sintered body obtained by the aforementioned manufacturing method, having crystal grain linear density of 40 per 30 µm in length, a boundary phase volume ratio of 8 volume %, porosity of 0.05 %, and a maximum pore diameter of 8 µm. b: Comparative Sample A silicon nitride sintered body obtained by the aforementioned manufacturing method, having crystal grain linear density of 30 per 30 µm in length, a boundary phase volume ratio of 16 volume %, porosity of 3.2 %, and a maximum pore diameter of 22 µm. c, d and e: Conventional Samples Samples of silicon nitride sintered bodies shown in Yogyo Kyokai-shi, Vol. 93, 1985, pp. 73 to 80 (Fig. 3, in particular). The Amsler abrasion test was made by fixing two ringshaped samples (inner diameter of 16 mm by outer diameter of 30 mm by thickness of 8 mm) to a rotary shaft of a tester in such a state that respective circumferential surfaces were correctly in contact with each other, applying a prescribed load and driving the rotary shaft at a prescribed rotational frequency thereby making a sliding test of about 100,000 revolutions, and thereafter measuring degrees of weight reduction of the two samples. As clearly understood from (A) in Fig. 5, the sintered body according to the present invention is extremely excellent in wear resistance. (B) in Fig. 5 shows the value of P·V (kg·m/s) in Fig. 5 converted per unit area of a sliding surface. Example 3 An Amsler abrasion test was carried out in a liquid of HFC134a, using sintered bodies of the inventive sample a and the comparative sample b obtained in Example 2. At this time, the abrasion test was carried out under the same load and rotational frequency conditions as Example 2, in such a state that contact portions of two ringshaped samples (outer diameter of 16 mm by inner diameter of 30 mm by thickness of 8 mm) were dipped in the liquid of HFC134a. Fig. 6 is a graph showing relations between products (P·V) of the loads. (surface pressures) applied to the samples and the rotational speeds, and wear rates. As obvious from Fig. 6, it is understood that the sintered body according to the present invention is extremely excellent in wear resistance also in a substitutional flon. Example 4 Rings were prepared from sintered bodies of the inventive sample a and the comparative sample b obtained in Example 2, bearing steel and high-speed steel respectively. Rings having sliding surfaces whose surface roughness levels were adjusted to 0.01, 0.1, 0.5 and 3 µm Ra respectively were prepared every material. Rings of spheroidal graphite cast iron were prepared as counter materials for sliding with respect to these rings. The respective rings having various surface roughness levels of the sliding surfaces and the rings of spheroidal graphite cast iron were made to slide in a three-type mixture substitutional flon solution of HCFC22/HFC152a/HCFC124. At this time, seizure loads were measured using a ring-on-ring friction tester while varying the loads under a condition of a peripheral speed of 2 m/sec. Each seizure load was determined at a point of time when an echo was generated during the test and vibration of the tester took place. The results are shown in Table 7. Seizure Load (kg/cm 2 ) Sliding Surface Roughness 3µmRa 0.5µmRa 0.1µmRa 0.01µmRa Sample Sintered Body of Inventive Sample a 49 103 152 185 Sintered Body of Comparative Sample b 23 47 72 86 Bearing Steel 2 5 8 12 High-Speed Steel 2 6 9 14 As obvious from Table 7, it has been proved that a high seizure load can be attained by using a slide member which is formed by the sintered body of the inventive sample a , and a higher seizure load can be attained when surface roughness is reduced to not more than 1.0 µm Ra, and further reduced to not more than 0.1 µm Ra. Example 5 Shoes to be in contact with swash plates of an Aℓ-Si alloy in swash plate compressors for car coolers were formed by sintered bodies of the inventive sample a and the comparative sample b obtained in Example 2. These shoes were employed for evaluating peripheral speeds causing seizure caused between the same and the swash plates while using HFC134a as a cooling medium and polyalkylene glycol as a lubricant. Surface roughness levels of sliding surfaces of the shoes were set at 0.1 µm RA. Occurrence of seizure was determined by generation of an abnormal noise and abnormal increase of a driving current value. The results are shown in Table 8. Sample Seizure Peripheral Speed (m/sec.) Sintered Body of Inventive Sample a 18 Sintered Body of Comparative Sample b 8 As obvious from Table 8, it has been proved that seizure occurs at a high peripheral speed when a shoe of the sintered body according to the inventive sample is employed. Although a sliding component for a compressor has been shown as Example of the inventive slide member, the present invention is not restricted to this. The slide member according to the present invention is also applicable to a turbine bearing for a supercharger which rotates at a high speed of 80000 to 150000 r.p.m., a bearing employed for a turbine which rotates at a high speed of 20000 to 30000 r.p.m., a machine tool such as a CNC ultraprecise lathe, an ultraprecise lathe for cylindrical working or an ultraprecise surface grinder, or the like. Example 6 Rings of spheroidal graphite cast iron were prepared as first members forming sliding surfaces. Further, rings were prepared from spheroidal graphite cast iron, bearing steel, alumina, silicon carbide, silicon nitride, boron nitride, carbon fiber reinforced silicon nitride, silicon carbide whisker reinforced alumina, and silicon carbide nanoparticle dispersion-strengthened alumina as second members forming the sliding surfaces. The first and second rings were made to slide for measuring seizure loads while varying loads in a liquid of HFC134a under a condition of a peripheral speed of 2 m/sec., through a ring-on-ring tester. Table 9 shows the results of this experiment. Nos. 1-3 and 1-5 indicate inventive samples, the others indicate comparative samples. No. Sliding Material Seizure Load (kg/cm 2 ) Samples 1-1 Alumina 56 1-2 Silicon Carbide 72 1-3 Silicon Nitride 87 1-4 Boron Nitride 103 1-5 Carbon Fiber Reinforced Silicon Nitride 92 1-6 Silicon Carbide Whisker Reinforced Alumina 75 1-7 Silicon Carbide Nanoparticle Dispersion-Strengthened Alumina 79 1-8 Spheroidal Graphite Cast Iron 2 1-9 Bearing Steel 5 As obvious from the results shown in Table 9, it has been proved that the seizure loads were extremely high in the inventive samples, in which the first members forming the sliding surfaces were made of sintered silicon nitride ceramics (monolithic ceramics, composite materials), as compared with the comparative samples. Thus, it has been recognized that seizure is hardly caused in the inventive samples also in an atmosphere of a cooling medium containing fluorine. Further, the sliding surfaces were examined in detail, whereby it was found that films mainly composed of carbon were formed on the surfaces. Each of the films mainly composed of carbon contained about 70 weight % of carbon (C), about 20 weight % of oxygen (O) and a rest which was made of elements forming the slide member. Example 7 Rings were prepared from mullite, silicon carbide, silicon nitride, aluminum nitride, boron carbide, alumina fiber reinforced crystallized glass, silicon carbide whisker reinforced silicon nitride, silicon carbide nanoparticle dispersion-strengthened silicon nitride, flake graphite cast iron and aluminum. Each pair of rings of the same material were made to slide with each other, for measuring a seizure load in a three-type mixture substitutional flon solution of HCFC22/HFC152a/HCFC124 through a ring-on-ring tester under a condition of a peripheral speed of 3 m/sec. while varying the load. In such measurement, surface roughness levels of the sliding surfaces were varied in a range of 0.01 to 3 µm Ra, to evaluate seizure loads at respective surface roughness levels. In a case of making a pair of rings of ceramics slide with each other, a seizure load was determined at a point of time when an echo was generated during the test and vibration took place in the tester. The results of this experiment are shown in Table 10. Referring to the Table, Nos. 2-3, 2-7 and 2-8 indicate inventive samples, and the others indicate comparative samples. As obvious from the results of the experiment shown in Table 10, the seizure loads were extremely high in the inventive samples, in which members forming the sliding surfaces were made of ceramics (monolithic ceramics, composite materials), as compared with the comparative samples. Thus, it has been proved that seizure of the sliding surfaces is hardly caused in the inventive samples also in an atmosphere of a cooling medium containing fluorine. Further, it has been proved that a load to reach seizure is increased as the surface roughness is reduced. Particularly, it has been proved that the seizure load is extremely increased when the surface roughness is not more than 0.1 µm Ra. Example 8 In swash plate compressors for car coolers, shoes to be in contact with swash plates of carbon fiber reinforced carbon composite materials were prepared from respective ones of silicon nitride, boron nitride, titanium nitride particle dispersion-strengthened silicon nitride and bearing steel. These shoes were employed for evaluating peripheral speeds causing seizure between the same and the swash plates while using HFC134a as a cooling medium and polyalkylene glycol as a lubricant. At this time, surface roughness levels of sliding surfaces of the shoes were set at 0.1 µm Ra. Determinations as to whether or not the shoes seized were made by occurrence of abnormal sounds and abnormal increase of driving current values. The results of this experiment are shown in Table 11. Referring to the Table, Nos. 3-1 and 3-3 indicate inventive samples, and Nos 3-2 and 3-4 indicate comparative samples. No. Material of Shoe Seizure Peripheral Speed (m/sec.) Samples 3-1 Silicon Nitride 20 3-2 Boron Nitride 18 3-3 Titanium Nitride Particle Dispersion-Strengthened Silicon Nitride 21 3-4 Bearing Steel 4 As obvious from Table 11, it has been proved that seizure is caused at extremely high peripheral speeds in the inventive samples in which the materials for the shoes were made of sintered silicon nitride ceramics (monolithic ceramics, composite materials), as compared with the comparative samples. Thus, it has been proved that the sliding surfaces hardly seize in the inventive samples also during cooling by a cooling medium containing fluorine. Example 9 A disk of silicon nitride, a disk which was prepared by depositing a carbon film of 1.0 µm in thickness on a surface of a disk of silicon nitride for forming a sliding surface, and a disk of bearing steel were prepared respectively. Further, rings to be in contact with sliding surfaces of the aforementioned respective disks were prepared from bearing steel. The respective disks and rings were made to slide in an atmosphere of HFC134a. At this time, seizure loads were measured using a ring-ondisk friction tester while varying loads under a condition of a peripheral speed of 1 m/sec. The results of this experiment are shown in Table 12. Surface roughness values in Table 12 indicate those of base materials for the disks. Surface roughness values of the sliding surfaces of the disks which were provided with carbon films were maintained below the values in the Table. No. Sliding Material Surface Roughness Seizure Load (kgf/cm 2 ) Inventive Sample 4-1 Silicon Nitride covered with Carbon Film 0.5µmRa 44 4-2 Silicon Nitride covered with Carbon Film 0.05µmRa 71 Comparative Sample 4-3 Silicon Nitride covered with Carbon Film 3µmRa 12 inv. sample 4-4 Silicon Nitride 0.5µmRa 32 comp. sample 4-5 Bearing Steel 0.5µmRa 2 As obvious from Table 12, it has been proved that seizure loads were higher in the inventive samples, in which first members forming the sliding surfaces were prepared from carbon films, as compared with the comparative samples. Thus, it has been proved that seizure is hardly caused in the sliding surfaces of the inventive samples also in an atmosphere of a cooling medium containing fluorine. Example 10 Disks were prepared by forming diamond-like carbon films of 3 µm in thickness on sliding surfaces of respective disks of silicon nitride and high-speed steel by CVD. Further, disks of silicon nitride were prepared. Rings comprising sliding surfaces to be in contact with those of the respective disks were prepared from bearing steel. The respective disks and rings were made to slide in a liquid of HFC134a. At this time, seizure loads were measured through a ring-on-disk friction tester while varying loads under a condition of a peripheral speed of 1 m/sec. The results of this experiment are shown in Table 13. Surface roughness values appearing in Table 13 indicate those of base materials for the disks. Surface roughness values of the sliding surfaces of the disks provided with the carbon films were maintained below the values appearing in the Table. No. Sliding Material Surface Roughness Seizure Load (kgf/cm 2 ) Inventive Sample 5-1 Silicon Nitride covered with Diamond-Like Carbon 0.5µmRa 64 5-2 Silicon Nitride covered with Diamond-Like Carbon 0.05µmRa 96 Comparative Sample 5-3 Silicon Nitride covered with Diamond-Like Carbon 3µmRa 15 5-4 High-Speed Steel covered with Diamond-Like Carbon 0.5µmRa 2.3 inv. sample 5-5 Silicon Nitride 0.5µmRa 32 As obvious from Table 13, seizure loads were extremely high in the inventive samples, in which first members forming the sliding surfaces had the diamond-like carbon films, as compared with the comparative samples. Thus, it has been proved that the sliding surfaces hardly seize in the inventive samples also in an atmosphere of a cooling medium containing fluorine. Example 11 Disks were prepared from alumina, zirconia, silicon carbide, silicon nitride, aluminum nitride and high-speed steel, and surface roughness values of sliding surfaces were finished to be 0.05 µm Ra, 0.5 µm Ra and 3 µm Ra respectively. Rings having sliding surfaces to be in contact with those of the respective disks were prepared from flake graphite cast iron. The respective disks and rings were made to slide in a gas of HFC134a. At this time, a ring-on-disk friction test was made under conditions of a peripheral speed of 1 m/sec. and a load of 10 kgf, to measure amounts of wear of the disks. Occurrence of seizure was determined at a point of time when an echo was generated during the test and the tester vibrated. Results of this experiment are shown in Table 14. Referring to the Table, rings of bearing steel were employed as to comparative samples Nos. 6-7 to 6-11. As obvious from Table 14, it has been proved that the inventive sample, in which members forming the sliding surfaces were made of sintered silicon nitride ceramics and counter members were made of cast iron, were excellent in wear resistance. Then, the sliding surfaces were analyzed by ESCA (Electron Spectroscopy for Chemical Analysis), whereby it was proved that films formed on the sliding surfaces during sliding were mainly composed of carbon. From this, it has been proved that the sliding surfaces were excellent in wear resistance in the inventive samples having films mainly composed of carbon which were formed during sliding. Thus, it has been proved that sliding surfaces are excellent in wear resistance in the inventive sample also in an atmosphere of a cooling medium containing fluorine. Industrial Availability As hereinabove described, the slide member according to the present invention is a slide member having excellent wear resistance, which is applicable to a use under strict sliding conditions of high-speed sliding or the like. Thus, the inventive slide member is useful as a bearing member for a high-speed machine which is required to rotate at a high speed or an office automation product. Further, the inventive slide member is useful as a sliding component for a compressor of a refrigerator, a freezer or a car cooler employing a flon containing no chlorine as a cooling medium.

Claims: A slide member comprising a sliding surface being made of a silicon nitride sintered body having surface roughness of not more than 1.0 µm in center line average roughness Ra, said silicon nitride sintered body containing crystal grains being in linear density of at least 35 per 30 µm in length with a boundary phase volume ratio of not more than 15 volume %, and containing pores of not more than 20 µm in maximum diameter, the content of said pores being not more than 3 %. The slide member in accordance with claim 1, wherein said sliding surface has surface roughness of not more than 0.1 µm in center line average roughness Ra. A sliding part structure comprising: a first slide member having one sliding surface; and a second slide member having the other sliding surface to be in contact with said one sliding surface, at least said one sliding surface being made of a silicon nitride sintered body in accordance with claim 1. The sliding part structure in accordance with claim 3, wherein said one sliding surface has surface roughness of not more than 0.1 µm in center line average roughness Ra. A method of manufacturing a slide member comprising a sliding surface being made of a silicon nitride sintered body in accordance with claim 1 or 2, comprising the step of: grinding said sliding surface; and heating said silicon nitride sintered body in one atmosphere being selected from a group of an inert gas and an atmospheric air after grinding said sliding surface. The method of manufacturing a slide member in accordance with claim 5, wherein said step of heating said silicon nitride sintered body includes a step of heating said body at a temperature of at least 800°C and not more than 1500°C. The method of manufacturing a slide member in accordance with claims 5 or 6, further comprising the step of: polishing said sliding surface after heating said silicon nitride sintered body. The slide member according to one of claims 1 to 2, wherein said slide member includes a sliding bearing body. A slide member comprising a sliding surface being placed in an atmosphere of a cooling medium containing fluorine, said sliding surface being made of a silicon nitride sintered body in accordance with claim 1 or 2. The slide member in accordance with claim 9, wherein said slide member includes: a first slide member having one sliding surface, and a second slide member having the other sliding surface to be in contact with said one sliding surface, at least one member being made of said silicon nitride sintered body. The slide member in accordance with claim 10, wherein a film being mainly composed of carbon or diamond-like carbon is formed on said sliding surface.

Inventors: HIGUCHI MATSUO, KATAYAMA TETSUYA, KAWAI CHIHIRO, KOMURA OSAMU, MATSUNUMA KENJI, MIYAKE MASAYA, MURABE KAORU, YAMAKAWA AKIRA, YASUOKA NORIO, HIGUCHI, MATSUO, KATAYAMA, TETSUYA, KAWAI, CHIHIRO, KOMURA, OSAMU, MATSUNUMA, KENJI, MIYAKE, MASAYA, MURABE, KAORU, YAMAKAWA, AKIRA, YASUOKA, NORIO, HIGUCHI, MATSUO, ITAMI WORKS OF SUMITOMO, KATAYAMA, TETSUYA, ITAMI WORKS OF SUMITOMO, KAWAI, CHIHIRO, ITAMI WORKS OF SUMITOMO, KOMURA, OSAMU, ITAMI WORKS OF SUMITOMO, MATSUNUMA, KENJI, ITAMI WORKS OF SUMITOMO, MIYAKE, MASAYA, ITAMI WORKS OF SUMITO, MURABE, KAORU, ITAMI WORKS OF SUMITOMO, YAMAKAWA, AKIRA, ITAMI WORKS OF SUMITOMO, YASUOKA, NORIO, ITAMI WORKS OF SUMITOMO
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO ELECTRIC INDUSTRIES, LTD.
Application year: 1993
Main classification: C04B35
IPC codes: C04B35, C04B41, F16C33