Hard sintered compact for tools

Abstract: A hard sintered compact for tools is a sintered compact obtained by super-high pressure sintering of 45 - 75% by vol. of cubic boron nitride powder and the remaining proportion of binder powder. The binder includes 5 - 25% by wt. of Aℓ and the remaining proportion of at least one species of compounds represented by (Hf 1-z M z ) C (where M denotes elements of IVa, Va and VIa groups in a periodic table except for Hf, and 0 < z < 0.3 is satisfied). Because of this composition, improvements are made in strength, wear resistance and heat resisting property of the binder, and a hard sintered compact for tools having excellent strength and excellent wear resistance can be obtained.

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to hard sintered compacts for tools employing cubic boron nitrides (hereinafter referred to as "cBN") and, more particularly, to a hard sintered compact for tools having enhanced strength and wear resistance with improvements of a binder. Description of the Background Art cBN is the hardest material next to diamond, and a sintered compact of cBN is employed for various cutting tools. As one example of cBN sintered compacts suitable for cutting tools, Japanese Patent Publication No. 57-3631 (the corresponding USP: No. 4,334,928) discloses a hard sintered compact for tools, containing 80-40% by vol. of cBN and the remaining proportion of carbide, nitride, boride and silicide of elements of IVa, Va and VIa groups in a periodic table, mixtures thereof or counter solid solution compounds as principal components. These compounds constitute a continuous bound phase in the texture of the sintered compact. This sintered compact exhibits high performance in general as a material for cutting tools; however, it has a disadvantage that the cutting edge of the cutting tool is liable to be damaged due to insufficient strength and abrasion of the cutting edge when subjected to a considerably strong impact, for example, in the application for a continuous cutting of a highly hardened steel. An improved hard sintered compact for tools, in which the strength and wear resistance of a cutting edge made of the sintered compact is improved in order to eliminate the damage of the cutting edge, is disclosed in Japanese Patent Laying-Open No. 62-228450. In this sintered compact, a binder includes 25-50% by wt. of Aℓ, a compound containing Ti such as carbide of Ti, and 4-40% by wt. of W contained in the compound containing Ti or contained as WC. These components react with cBN in sintering, to produce aluminum boride, titanium boride and the like, which serve to firmly couple the binder and cBN or another binder. USP 4,911,756 discloses a hard sintered compact for tools, including 50-75% by vol. of cBN and 25-50% by vol. of a binder containing 20-50% by wt. of aluminum, carbon nitride titanium and the like and 4-40% by wt. of tungsten. Even the sintered compacts disclosed in the above-described Japanese Patent Publication No. 57-3631, Japanese Patent Laying-Open No. 62-228450 and USP 4,911,756 have, however, the following disadvantages when used for tools for cutting a cast iron. In cutting of a graphite cast iron and fast cutting of a gray cast iron, for example, abrasion of the cutting edge abruptly proceeds, so that the life of the cutting edge is shortened. Further, crater abrasion occurs in the cutting edge, so that the cutting edge is damaged. These problems still remain unsolved. Patent Abstracts of Japan, vol. 5, no. 168, and JP-A-56 096 050 disclose a sintered body for a tool with enhanced toughness obtained by adding a specified amount of Aℓ, Cu and a Fe group metal to cubic boron nitride of a prescribed grain size. SUMMARY OF THE INVENTION An object of the present invention is to provide a hard sintered compact for tools having excellent strength and wear resistance and exhibiting an excellent cutting performance even for a cast iron. In order to accomplish the above object, a hard sintered compact for tools according to the present invention is a sintered compact obtained by super-high pressure sintering of 45-75% by vol. of cBN powder and the remaining proportion of binder powder. The binder contains 5-25% by wt. of Aℓ and the remaining proportion of at least one species of compounds represented by (Hf 1 - z M z ) C, where M denotes elements of IVa, Va and VIa groups other than Hf in the periodic table, and 0 ≦ z ≦ 0.3 is satisfied, and, optionally, of at least one species of the iron group elements. In accordance with the present invention, since the binder includes 5-25% by wt. of Aℓ and the remaining proportion of (Hf 1 - z M z ) C compound as shown in the foregoing composition, these components react with cBN in sintering under high-temperature high-pressure, to produce aluminum boride (AℓB₂), aluminum nitride (AℓN), hafnium boride (HfB₂) or titanium boride (TiB₂). Alternatively, Aℓ and the (Hf 1 - z M z ) C compound react with each other. These reaction products firmly couple cBN having an excellent resisting property to abrasion and the binder, or the binder and another binder. This results in a sintered compact having excellent strength and excellent wear resistance. It is confirmed by X-ray diffraction that a slight amount of Aℓ exist also as aluminum oxide in the sintered compact; however, the existing Aℓ does not affect the action and effects of the present invention. The (Hf 1 - z M z ) C compound such as HfC and a reaction product such as HfB₂ can provide sufficient resisting properties to heat and oxidation when the temperature of the cutting edge becomes higher by cutting of a cast iron or the like. These compound and reaction product have excellent wear resistance and excellent strength under high temperature and can enhance the strength, wear resistance, heat resisting properties, etc. of the binder per se. When the content of Aℓ in the binder is less than 5% by wt., the retention of cBN by the binder decreases due to an insufficient reaction between Aℓ and cBN. When the Aℓ content exceeds 25% by wt., AℓB₂ or the like increases, and the bonding strength between cBN and the binder increases. The relative content of the (Hf 1 - z M z ) C compound such as HfC having superior wear resistance to that of AℓB₂ or the like, however, decreases. Accordingly, the hardness of the binder per se decreases, and hence the sintered compact fails to obtain sufficient wear resistance for the cast iron cutting and the like. As compounds represented by the formula (Hf 1 - z M z ) C in the binder, there are many kinds of carbides containing Ti, Mo, W, etc. together with Hf in the case of 0 < z as well as HfC in the case of z = 0. Carbide containing Ti or W is especially preferable because it serves to reduce the wear resistance and the strength of the binder and to exhibit good characteristics. When z exceeds 0.3 in the foregoing formula, however, the content of HfC having relatively excellent wear resistance decreases. Thus, z is set to 0.3 or less. Further, adding at least one species of iron group elements in the binder causes the strength and hardness of the binder to further increase, resulting in further improvements of the characteristics of the sintered compact. This is because enhanced wetness between the iron group elements and borides such as HfB₂ and AℓB₂ causes the binder to firmly couple the borides. When the amount of cBN in the sintered compact is less than 45% by vol., the strength and hardness of the sintered compact decreases. In addition, as the number of binders relatively increases, mechanical abrasion advances rapidly by, for example, a hard graphite contained in a cast iron and hard portions of a pearlite base in matrix, a base subjected to austempering and the like. Also, a crack is liable to occur due to an applied impact. When the amount of cBN in the sintered compact exceeds 75% by vol., cBN makes contact with another cBN. Thus, in the case of a strong member to be cut or an interrupted cutting in which high pressure is applied to a cutting edge, a crack is produced in contact portion between grains, and the number of binders relatively decreases. This results in a reduction in bonding strength between the binders and cBN and thus a reduction in strength of the sintered compact. In abrasion of a general cBN sintered compact, it is considered that since cBN has excellent wear resistance, a binder is abraded with priority and cBN drops off. Therefore, the grain size of cBN is preferably controlled as follows in order to uniform the texture of the compact and to inhibit the priority of abrasion of the binder. The average grain size of cBN is preferably smaller. When the grain size exceeds 4 µm in particular, a binder portion becomes larger and abraded with priority. Accordingly, the average grain size of cBN is preferably 4 µm or less. More preferably, if the grain size of cBN is controlled so that cBN of 1 µm or less in grain size may be 35-80% by wt. and that cBN of 3-6 µm in grain size may be 20-65% by wt., smaller cBN grains fill among larger cBN grains, so that the microstructure becomes homogeneous. It is preferable in view of enhancement of wear resistance to employ micro binder powder having an average grain size smaller than 1/3 that of cBN because such micro binder powder advances uniform distribution of the binders. According to another aspect, a hard sintered compact for tools in accordance with the present invention is a sintered compact obtained by super-high pressure sintering of 45-75% by vol. of cubic boron nitride powder and contains the remaining proportion of binder powder. The binder contains 4-20% by wt. of Aℓ and 5-20% by wt. of Hf and contains the remaining proportion of HfC and a compound represented by (Ti 1 - x M x ) C z , where M denotes elements of IVa, Va and VIa groups except for Hf in the periodic table; and 0 ≦ x ≦ 0.15, 0.55 ≦ z ≦ 0.9 are satisfied, in the range of volume ratio 9:1 - 1:2, and, optionally, of at least one species of the iron group elements. With this composition, since the binder contains 4-20% by wt. of Aℓ and 5-20% by wt. of Hf, and HfC and the above (Ti 1 - x M x ) C z compound, these components react with cBN in sintering under high-temperature high-pressure, to produce aluminum boride (AℓB₂), aluminum nitride (AℓN), and hafnium boride (HfB₂) or titanium boride (TiB₂). Further, Aℓ reacts with HfC or the (Ti 1 - x M x ) C z compound. These reaction products firmly couple cBN having excellent wear resistance and the binder, or alternatively the binders. Therefore, a sintered compact superior in its strength and wear resistance can be obtained. The HfC and the (Ti 1 - x M x ) C z compound along with those reaction products can provide sufficient resisting properties to heat and oxidation when the temperature of the cutting edge becomes higher in cast iron cutting or the like, as has been already described. Since those reaction products and compound have excellent wear resistance and excellent strength under high temperature, the strength, wear resistance, heat resistivity, etc. of the binder per se can be enhanced. When the content of Aℓ in the binder is less than 4% by wt., the reaction between Aℓ and cBN becomes insufficient. When the content of Hf is less than 5% by wt., the reaction between Hf and Aℓ or (Ti 1 - x M x ) C z becomes insufficient. In both cases, the retention of cBN by the binder decreases. Conversely, when the content of Aℓ or Hf exceeds 20% by wt., a larger amount of AℓB₂, HfB₂ or the like is produced, resulting in increased bonding strength of cBN and the binder. Since the relative content of HfC and the (Ti 1 - x M x ) C z compound having superior wear resistance to that of AℓB₂ and HfB₂ decreases, however, the hardness of the binder per se and the wear resistance of the sintered compact decrease. The reason why the volume ratio of HfC to the (Ti 1 - x M x ) C z compound in the binder is limited in the range of 9:1 - 1:2 is given below. First, when the amount of HfC relatively increases exceeding 9:1, Aℓ in the binder still exceeds in amount even if reacting with HfC or the (Ti 1 - x M x ) C z compound. Thus, the excess Aℓ remains unreacting, to degrade the wear resistance. Conversely, when the (Ti 1 - x M x ) C z compound relatively increases in amount exceeding 1:2, the reaction between HfC and the (Ti 1 - x M x ) C z compound becomes supersaturation, and thus Hf remains as a metal component, to degrade the wear resistance. In the formula (Ti 1 - x M x ) C z , x = 0, i.e. the state where M is not included may be satisfied. When x exceeds 0.15, the amount of TiC having excellent resisting properties to heat and abrasion relatively decreases, and the wear resistance and the strength under high temperature also decrease, resulting in an inadequate material for tools. The reason why the relation 0.55 ≦ z ≦ 0.9 is satisfied is that when z is less than 0.55, the amount of free Ti increases, and the strength and hardness of the binder per se decreases, whereas when z exceeds 0.9, the free Ti becomes insufficient in amount, and the bonding force of the binder decreases. If W is employed as M, the wear resistance and strength of the binder improves and exhibits good characteristics. The reason why at least one species of iron group elements is added in the binder and why the amount of cBN in the sintered compact is set to 45-75% by vol. are given in the foregoing description. DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 Carbide containing Hf and Aℓ powder are ground and mixed by employing a superhard alloy pot and bowl, to produce binder powder of 0.9 µm or less in average grain size having such composition as shown in Table 1 below. The produced binder powder and cBN powder of 2.5 - 4 µm in average grain size are mixed in the volume ratio of 42:58. The mixed powder are then put in a Mo container, heated in a vacuum furnace at 10⁻⁴ torr, 1000°C for 20 minutes and then deaired. Thereafter, the resultant powder is sintered under the pressure of 5,5·10⁹Pa (55Kb), at the temperature of 1400°C for 25 minutes. When each of the resulting sintered compacts is identified by X-ray diffraction, the peak of cBN, that of the carbide containing Hf and those of HfB₂, AℓB₂ and AℓN are confirmed with respect to all the sintered compacts. The peaks of carbides including Ti, Mo and W other than Hf are also confirmed from samples. In addition, when the texture of the sintered compacts is observed by a scanning electron microscope, it is confirmed that cBN grains are mutually bonded by binders. Furthermore, each sintered compact is processed to be an insert for cutting and undergoes a cutting test of a nodular cast iron FCD 45 member (hardness H B = 200). The test is carried out on conditions of 280 m/min in cutting speed, 0.25 mm in depth of cut, 0.22 mm/rev in feed rate and 20 minutes in cutting time by dry process. Table 1 shows the result of the test. Sample No. Binder Composition (% by wt.) Abrasion width of Relief Plane (mm) 1 HfC:95, Aℓ:5 0.059 2 HfC:90, Aℓ:10 0.042 3 (Hf 0·7 Ti 0·3 )C:80, Aℓ:20 0.055 4 HfC:75, Aℓ:25 0.072 5 (Hf 0·95 Mo 0·05 )C:88, Aℓ:12 0.047 6 (Hf 0·95 Mo 0·05 )C:92, Aℓ:8 0.055 7 (Hf 0·9 Ti 0·1 )C:85, Aℓ:15 0.037 8* HfC:97, Aℓ3 0.098 9* HfC:72, Aℓ:28 0.110 10* (Hf 0·65 Mo 0·35 )C:75, Aℓ:25 0.127 11* (Hf 0·9 Ti 0·1 )C:70, Aℓ:30 0.154 12* Hf 0·6 V 0·4 )C:90, Aℓ:10 0.108 Note: Marks * in the table show comparative examples. (The same is applied to Tables 2, 3, 4 and 5.) Embodiment 2 HfC powder of 89% by wt. and Aℓ powder of 11% by wt. are ground and mixed in the same manner as embodiment 1, to produce binder powder having average grain size shown in Table 2 below. The produced binder powder is mixed with cBN powder shown in table 2, deaired as in embodiment 1 and then sintered under the pressure of 4,5·10⁹Pa (45 Kb), at the temperature of 1300°C for 20 minutes, thereby to obtain sintered compacts. Each of the sintered compacts is processed to be an insert for cutting. Then, the end surface of a cylinder cylinder of a ductile cast iron FCD 70 member (hardness H B = 290) is cut by dry process at 180 m/min in cutting speed, 0.2 mm in depth of cut and 0.17 mm/rev in feed rate. The cutting time during which the abrasion width of a relief plane reaches 0.2 mm is measured. The result of the test is shown in Ttable 2. Sample Average Grain Size of Binder (µm) Amount of cBN (vol %) Distribution of cBN Grain Size (µm : %) Average Grain Size of cBN(µm) Cutting Time (min) 13 0.3 45 0 - 1 : 35 2 -4 : 45 4 - 8 : 20 3.6 34 14 0.4 55 0 - 1 : 40 1 -2 : 25 3 - 6 : 35 2.3 40 15 0.5 65 0 - 1 : 40 3 -6 : 60 3.8 38 16 0.2 75 0 - 1 : 75 3 -6 : 25 2.2 33 17 0.4 60 0 - 1 : 45 3 -6 : 55 3.1 45 18 0.4 58 0 - 2 : 80 3 -6 : 20 2.1 58 19 0.3 50 0 - 1 : 40 1 -2 : 30 3 - 6 : 30 1.9 51 20 0.3 70 0 - 2 : 65 2 -4 : 35 2.8 47 21 1.5 65 0 - 1 : 32 3 -6 : 68 4.0 27 22 1.4 70 3 - 6 : 100 4.1 24 23 2.2 65 4 - 8 : 100 6.0 21 24* 0.2 43 0 - 2 : 58 4 -8 : 42 2.7 Damaged in 6 min. 25* 0.4 78 0 - 1 : 50 4 -8 : 50 3.0 7 26* 1.3 40 2 - 4 : 100 3.1 Damaged in 3 min. Embodiment 3 HfC powder, carbide powder containing Ti, Hf powder and Aℓ powder are all ground and mixed together employing a superhard alloy pot and bowl, to produce binder powder of 0.8 µm or less in average grain size having a composition shown in Table 3 below. The produced binder powder and cBN powder of 2.5 - 4 µm in average grain size are mixed in the volume ratio of 50 : 50. The mixed powder is put in a Mo container, heated in a vacuum furnace at 10⁻⁴ torr, 100°C for 20 minutes and then deaired. The resultant powder is then sintered under the pressure of 5,5·10⁹Pa (55Kb) and at the temperature of 1400°C for 30 minutes. Sample No. Binder Composition (% by wt.) 27 HfC:87, TiC 0·6 :4, Aℓ:4, Hf:5 28 HfC:64, (Ti 0·9 W 0·1 )C 0·55 :6, Aℓ:10 Hf:20 29 HfC:72, TiC 0·9 :14, Aℓ:7, Hf:7 30 HfC:46, TiC 0·7 :36, Aℓ:12, Hf:6 31 HfC:41. 5, (Ti 0·95 Mo 0·05 ) C 0·8 :32.5 Aℓ:20, Hf:6 32 HfC:75, TiC 0·85 :6, Aℓ:9, Hf:10 33 HfC:63. 6, TiC 0·75 :12.4, Aℓ:15, Hf:9 34 HfC:75, (Ti 0·95 W 0·05 )C 0·6 :10, Aℓ:9 Hf:6 35* HfC:89. 6, TiC 0·7 :8.4, Aℓ:2 36* HfC:67.9, (Ti 0·95 W 0·05 )C 0·8 :3.1 Aℓ:22, Hf:7 37* HfC:32, TiC 0·89 :38, Aℓ:10, Hf:20 38* HfC:72. 2, TiC 0·55 :2.8, Aℓ:20, Hf:5 39* HfC:18.4, (Ti 0·95 Mo 0·05 )C 0·7 :71.6 Aℓ:5, Hf:5 40* HfC:45, TiC 0·4 :35, Aℓ:10, Hf:10 41* HfC:41. 5, TiC 0·95 :32.5, Aℓ:4, Hf:22 Each of the resultant sintered compacts is identified by X-ray diffraction. The peak of cBN, that of carbide including Hf, and those of HfB₂, AℓB₂, AℓN and TiB₂ are confirmed with respect to all the sintered compacts. The peaks of carbides of Mo, W other than Hf are also confirmed from samples. When the texture of the sintered compacts is observed by a scanning electron microscope, it is confirmed that cBN micro grains are mutually coupled by binders. In addition, each sintered compact is processed to be a insert for cutting and undergoes a cutting test of a nodular graphite cast iron FCD 45 member (hardness H B = 200). This test is carried out on such conditions as 300 m/min in cutting speed, 0.3 mm in depth of cut, 0.2 mm/rev in feed rate and 20 min. in cutting time by dry process. The result of the test is shown in Table 4 below. Sample Abrasion Width of Relief Plane(mm) Sample Abrasion Width of Relief Plane(mm) 27 0.073 35* Damaged in its course. 28 0.091 36* 0.110 29 0.058 37* 0.149 30 0.087 38* 0.102 31 0.099 39* 0.117 32 0.065 40* 0.126 33 0.086 41* 0.135 34 0.048 Embodiment 4 HfC powder of 73% by wt., TiC 0.75 powder of 12% by wt., Aℓ powder of 10% by wt. and Hf powder of 5% by wt. are all ground and mixed together in the same manner as embodiment 1, to produce binder powder having average grain size shown in Table 5 below. The produced binder powder is mixed with cBN powder shown in Table 5 and deaired as in embodiment 1. The resultant powder is then sintered under the pressure of 5,0·10⁹Pa (50Kb), at the temperature of 1300°C for 30 minutes, thereby to obtain sintered compacts. Each of the sintered compacts is processed to be a insert for cutting. The outer circumference of a cylinder of an austempered ductile cast iron FCD100 member (hardness H B = 300) is cut by dry process at the cutting speed of 150 m/min, depth of cut 0.15 mm and feed rate of 0.15 mm/rev. The cutting time during which the abrasion width of a relief plane reaches 0.3 mm is measured. The result of the test is shown in Table 5. Sample Average Grain Size of Binder (µm) Amount of cBN (vol %) Distribution of cBN Grain Size (µm : %) Average Grain Size of cBN(µm) Cutting Time (min) 42 0.3 55 0 - 1 : 35 2 -4 : 45 4 - 8 : 20 3.6 47 43 0.35 45 0 - 1 : 40 1 -2 : 25 3 - 6 : 35 2.3 49 44 0.5 68 0 - 1 : 40 3 -6 : 60 3.8 36 45 0.2 73 0 - 1 : 75 3 -6 : 25 2.2 28 46 0.42 62 0 - 1 : 45 3 -6 : 55 3.1 34 47 0.41 58 0 - 2 : 80 3 -6 : 20 2.1 31 48 0.29 52 0 - 1 : 40 1 -2 : 25 3 - 6 : 35 1.9 41 49 0.3 70 0 - 2 : 65 2 4 : 35 2.8 32 50 1.3 60 0 - 1 : 32 3 -6 : 68 4.0 26 51 1.4 50 3 - 6 : 100 4.1 25 52 2.0 70 4 - 8 : 100 6.0 20 53* 0.3 78 0 - 2 : 60 4 -8 : 40 2.9 8 54* 0.25 43 0 - 1 : 50 3 -6 : 50 3.3 Damaged in 6 min. 55* 1.5 78 2 - 4 : 30 3 -6 : 70 4.2 Damaged in 4 min. The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings. Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation.

Claims: A hard sintered compact for tools obtained by super-high pressure sintering of 45 - 75% by vol. of cubic boride nitride powder and a remaining proportion of binder powder, said binder including 5 - 25% by wt. of Aℓ and a remaining proportion of at least one species of compounds represented by (Hf 1 - z M z ) C, where M denotes elements of IVa, Va and VIa groups in a periodic table except for Hf, and 0 ≦ z ≦ 0.3 is satisfied, and, optionally, of at least one species of the iron group elements. The hard sintered compact for tools in accordance with claim 1, wherein said cubic boron nitride powder for said sintered compact has an average grain size of 4 µm or less, and includes 35 - 80% by wt. of cubic boron nitride powder of 1 µm or less and 20 - 65% by wt. of cubic boron nitride powder of 3 - 6 µm. The hard sintered compact for tools in accordance with claim 1, wherein the average grain size of said binder is smaller than 1/3 that of the cubic boron nitride powder. The hard sintered compact for tools in accordance with claim 1, wherein the element denoted with said M comprises one of Ti, W and Mo. The hard sintered compact for tools in accordance with claim 1, comprising compounds of one or more species selected from the group consisting of AℓB₂, AℓN, HfB₂ and TiB₂. The hard sintered compact for tools in accordance with claim 1, comprising a reaction product of Aℓ and the (Hf 1 - z M z ) C compound. A hard sintered compact for tools obtained by super-high pressure sintering of 45 - 75% by vol. of cubic boron nitride powder and a remaining proportion of binder powder, said binder including 4 - 20% by wt. of Aℓ and 5 - 20% by wt. of Hf and a remaining proportion of HfC and a compound represented by (Ti 1 - x M x ) C z , where M denotes elements of IVa, Va and VIa groups in a periodic table except for Hf, and 0 ≦ x ≦ 0.15, 0.55 ≦ z ≦ 0.9 are satisfied, in the range of 9:1 - 1:2 in volume ratio, and, optionally, of at least one species of the iron group elements. The hard sintered compact for tools in accordance with claim 7, wherein the cubic boron nitride powder for said sintered compact has an average grain size of 4 µm or less, and comprises 30 - 80% by wt. of cubic boron nitride powder of 1 µm or less in grain size and 20 - 65% by wt. of cubic boron nitride powder of 3 - 6 µm in grain size. The hard sintered compact for tools in accordance with claim 7, wherein the average grain size of said binder is less than 1/3 that of the cubic boron nitride powder. The hard sintered compact for tools in accordance with claim 7, wherein the element denoted with said M comprises either W or Mo. The hard sintered compact for tools in accordance with claim 7, comprising compounds of one or more species selected from the group consisting of AℓB₂, AℓN, HfB₂ and TiB₂.

Inventors: GOTO MITSUHIRO C O ITAMI WORKS, NAKAI TETSUO C O ITAMI WORKS O, GOTO, MITSUHIRO, C/O ITAMI WORKS OF SUMITOMO, NAKAI, TETSUO, C/O ITAMI WORKS OF SUMITOMO
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO ELECTRIC INDUSTRIES, LTD.
Application year: 1990
Main classification: C22C26
IPC codes: B01J3, C22C26