WO2006046313A1 - Méthode de synthèse d’un composite de type carbure cémenté wc-cuivre - Google Patents

Méthode de synthèse d’un composite de type carbure cémenté wc-cuivre Download PDF

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Publication number
WO2006046313A1
WO2006046313A1 PCT/JP2004/016378 JP2004016378W WO2006046313A1 WO 2006046313 A1 WO2006046313 A1 WO 2006046313A1 JP 2004016378 W JP2004016378 W JP 2004016378W WO 2006046313 A1 WO2006046313 A1 WO 2006046313A1
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WIPO (PCT)
Prior art keywords
copper
powder
composite
cemented carbide
hardness
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PCT/JP2004/016378
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English (en)
Japanese (ja)
Inventor
Kousei Sumizaki
Toyoaki Ishibachi
Original Assignee
York Corporation Co, Ltd
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Publication date
Application filed by York Corporation Co, Ltd filed Critical York Corporation Co, Ltd
Priority to PCT/JP2004/016378 priority Critical patent/WO2006046313A1/fr
Publication of WO2006046313A1 publication Critical patent/WO2006046313A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to the provision of a method for producing a cemented carbide WC—Cu composite.
  • Non-patent document 1 Kunita Matsubara, Industrial rare metal, N0.77, 1982,
  • Copper is a good electrical conductor, but its ⁇ may be too soft for some applications.
  • One way to achieve both hardness and electrical conductivity is to combine copper and hard powder. The concept of compounding by powder metallurgy is known.
  • the assumed application of the composite material of the present invention is an electrical contact material.
  • Non-patent document 1 is probably the first to disclose a composite material as a contact material in which the conductivity is silver and the hardness is tungsten carbide powder. Japan is thought to have received this disclosure, but this system has been standardized. (Non-patent document 2).
  • Non-Patent Document 1 H. Holzmann: Metall 12, Juli 1958, Heft 7, S630
  • the characteristic cost of the composite relates to the combination of the constituent materials and the composite method. Therefore, the composite is a production-limited product because of its properties. Therefore, the composite will be described as a manufacturing invention.
  • the composite is porous. This is an outline of the manufacturing method, in which a cemented carbide of this type is used as a skeleton and copper or a copper alloy (hereinafter referred to as copper) is infiltrated or impregnated therein. This will be described in detail below.
  • WC hard tungsten monocarbide powder
  • a soft torso it is essential that the WC powder forms a skeleton that is resistant to compression. It is the skeleton, not the bone, that can be distinguished from the WC powder, which can be compacted by pressing and compacting the WC powder, but since it lacks the bonding between the particles, it is difficult to make a sufficiently hard composite.
  • a typical example of a composite that has a strong skeleton structure as a composite is a cemented carbide made of cemented WC powder with cobalt (hereinafter referred to as a cemented cemented carbide). Therefore, the skeleton is modeled on cemented carbide, and copper is infiltrated into it to obtain a composite.
  • the simplest framework is a sintered pair. It is not a matter of course, because ordinary cemented carbide is a liquid-phase sintered pair, it will be a dense pair that does not allow penetration, a porous pair is required, and sintering of a porous pair is a solid phase Only possible with sintering.
  • cemented cemented carbide powder that has been made into a sintered pair and then returned to powder with a cemented slag, called cemented carbide powder (Non-Patent Document 1, 1 0 8 to 1 1 2)
  • the powder can be solid-phase sintered, or can be liquid-phase sintered by increasing the sintering temperature. At this time, the sintered body returns to the starting cemented carbide. It is not unreasonable to call cemented carbide as a sintered pair with a framework.
  • cemented carbide used as the starting material of the cemented carbide powder does not bother to be made, it is sufficient to finish the function as a tool. At this time, the cemented carbide powder is compared with the virgin powder used as the starting material.
  • the text is also called “recycled powder”, but its utilization follows the spirit of resource reuse and energy saving.
  • Recycled powder is supplied after being classified, but the deviation from the nominal composition is unavoidable due to the nature of the starting material, and whether the deviation is acceptable depends on the purpose of use. It is insensitive to.
  • the degreasing process before entering sintering is premised on the darkness.
  • the sintering temperature for the determined holding time and the molding pressure during pressure molding are controlled.
  • penetration is a capillary action
  • placing copper on the skeleton is one of the ways of penetration
  • copper permeated at this time oozes from the side of the skeleton due to gravity action
  • the infiltration of the black pencil with a small gap is one way to suppress the seepage, there are other measures, a thin skeleton There is no need for consideration.
  • the formation of the skeleton can be done by vacuum overheating, but the penetration should be carried out even in a hydrogen atmosphere, because the hydrogen atmosphere has a great advantage for copper permeability. There is also the benefit that it can be covered by conventional equipment for producing copper-tonsten composites.
  • the desired hardness for the electrode material is approximately 30 HRC or more, and more desirably 35 HRC or more.
  • the old copper-tungsten composite is at most 100HRB (equivalent to 22HRC).
  • the WC-Ag composite is 60% by weight 0 and is not as hard as 220HB (equivalent to 18.1HRC).
  • the object of the present invention is to achieve the above goal with a WC-Cu composite.
  • the core image of a WC-Cu composite that resists compression is a state in which copper fills the gaps between WC particles oriented strongly against compression. Such an orientation is obtained by pressing the WC powder particles. To fill the gap, copper can be penetrated later.
  • composites made by mixing, pressing, and sintering copper powder and WC powder do not become hard is because the procedure is reversed, and the effect is naturally reversed. Specifically, one reason is that the presence of copper powder hinders the WC powder from taking a strong orientation against compression when pressed, and the second is the presence of WC that itself does not shrink. However, when the amount is particularly large, the sintering shrinkage of the compact is hindered.
  • voids may become the third component of the composite and prevent curing. This is the reason why the present invention dislikes the sintering method and inclines into the infiltration method.
  • Penetration may mean the effect of penetration of copper into the molded body and the mode of penetration. The immersion in the formed body in the molten copper is one mode of penetration.
  • the problem with the infiltration method is the permeability of the osmotic material to the molded body, or the wettability with the molded body that looks like a material that does not necessarily overlap. If the permeability is poor, a portion (nest) that does not penetrate into the molded body tends to be formed. The penetration of molten copper is definitely better than molten silver.
  • the quality of wettability is related to the penetration temperature as well as the compatibility between the penetration material and the molded body. When the infiltration temperature is 1 1600 ° C, nests can be formed at a considerable frequency in a compact with only WC powder.
  • Example 1 In order to avoid such a situation or to increase the reliability of the composite obtained, it is common knowledge of those skilled in the art to use the same or similar priming as the permeable material for the WC powder before molding. Whether the permeability is good or not, the amount of priming water, the size of the molded body, and the method for determining the penetration temperature are not uniquely determined. In Example 1, it was disliked that the temperature was high, and it was judged that 1 2 0 0 ° C corresponding to the lower limit of the permeation temperature of W—Cu or W—Ag was sufficient, and this temperature was adopted uniformly.
  • the permeation temperature is 120 ° C
  • only a small amount of copper powder as priming water eg 0.2%
  • the priming volume remains indefinite.
  • the present invention stems from the question of what determines the amount.
  • the presence of priming powder affects the orientation of the hard powder by molding. As shown in Comparative Example 1, the molded product shrinks upon penetration. That is, the orientation due to molding is not final but changes upon penetration. Since shrinkage is due to the presence of priming water, the hardness of the composite is related not only to molding pressure but also to the amount of priming water. Both quantities are entangled from the above reasoning and facts. The same is true for the conductivity of the composite.
  • Table 1 summarizes the experience from the above viewpoints, and summarizes the relationship between the effects when considering the amount of priming water in the molded body and molding compression as control factors, and the hardness and conductivity of the composite as effective.
  • Figure 1 is an illustration of it. Molding pressure is 392MPa (4t / ciu) and 192MPa, nominal water volume is 0.05%
  • the hardness-conductivity range for the resulting composite is approximately linear. It can be divided into two areas by the boundary line that can be considered. There is no point on the other side of the origin from this straight line. It is a forbidden area that is inaccessible for the layman. It is always possible to have a point on the origin side, but it is best to have a point on the line because of the wishes of both conductivity and hardness. This is characteristic optimization. Where to choose on the line is a matter of taste. In order to make things, it was natural to optimize.
  • the mixing method of WC powder and priming water powder by the ball mill and the setting of the conditions will be a pitfall. This is because the WC powder functions as an abrasive for the balls used, and when the abrasive debris is metallic, it moves to the infiltrant and lowers the conductivity of the composite. This does not necessarily mean that the ball mill method is not possible. If the ball material, dimensions, and amount used, pot capacity, time and number of revolutions, and amount of powder filling are appropriate, damage can be kept within an acceptable range. The use of ceramic balls or the V-pender blending method may be good. In Example 1, parts that were not familiar with the description of the ball mill conditions were omitted. Just say it was a common sense treatment.
  • the amount of copper in the composite was approximated by the sum of the nominal amount of water in the compact and the amount of copper commensurate with the voids. Regarding the points where the boundary line is placed, 2, 7 and 11, the volume ratio is 58, 54 and 50%, and the weight ratio is 44, 40 and 36%.
  • the conductivity of the composite does not follow the mixing rule in the sense that it is not equal to the volume ratio.
  • the proportionality factor or conduction efficiency is about 0.7. Note that the composition can only be changed as an effect.
  • the heating atmosphere also needs attention. With vacuum heating, there is no risk of gas being trapped in the compact, but at the cost of concern for the higher vapor pressure of copper. A non-oxidizing gas atmosphere is sufficient, but experience has shown that a hydrogen atmosphere is desirable. It seems to affect wettability. In this case, avoid using tough pitch copper containing oxygen. Since there are times when we want to use copper containing oxygen, the atmosphere is also selective.
  • the copper used in the present invention does not exclude solid solution hardening or precipitation hardening type conductive copper other than blunt copper. This is because, in addition to contributing to hardness, there is a benefit in preventing welding.
  • Figure 1 is a graph of Table 1.
  • FIG. 2 is a half sectional view showing one side of a float tender seal for a tank wheeler wheel of the present invention.
  • Fig. 3 is a half sectional view of the material of the present invention welded to a welding tip.
  • Fig. 4 is a half cross-sectional view of the WC-Cu bearing using the recycled powder of the present invention.
  • FIG. 5 is a plan cross-sectional view of a welding tip containing a WC-Cu rod using the new powder of the present invention.
  • Fig. 6 is a front view of a rotating electrode roll for can manufacturing.
  • the process of claim 1 was conditioned as follows to make a cemented carbide-copper-based composite.
  • the characteristics of the commercial recycled powder used were: manufacturing method, high heat method, average particle size 1.05, composition 5.90T, C-6, 02Co ⁇ 0.25Tic 1 0, 17TaC-o, 25TaC-0, 08Fe— 0, 230— 0, 18Cr3C2-0, 09VC—remaining WC, weight 0 /. , C / WC ratio 0.0621, calculated apparent density 14.8g / CM 3.
  • Molding pressure was 196MPa.
  • the molded body was vacuum heated at 1300 ° C for lh to infiltrate copper, and the infiltrated temperature. 1 2 0 0 ° C, holding time 30 minutes, hardness of the resulting composite was 63.8HRC, and it was confirmed by precision cutting that there was no nest inside.
  • Fig. 2 shows an inner wheel of a rocker such as a bull tozer, dirt, mud, flow tender seal peristaltic material as an intrusion prevention mechanism, material (A) for the recycled cemented carbide powder of the present invention, and other items Composite with copper (HRC 6 3 hardness, wrapping the mating surfaces to finish with a high precision flatness roughness of 0.1 / and holding with a seal to hold this, B) is a rubber Z and R casing that is sealed in a sealed container. Epoxy-based, heat resistant, durable, and baked adhesives are used to join them. Clutch type unevenness method is also possible A is hardness HRC 63, the sliding torque value is 150% to 70% compared to the steel seal currently in use. According to the results of the material, and the improvement in durability was measured without the occurrence of ironing. Katatate rubber seal with retainer.
  • HRC 6 3 Composite with copper
  • B is a rubber Z and R casing that is sealed in a sealed container.
  • Figure 3 shows spot welding tips used for joining plates such as automobile bodies and refrigerator cases.
  • the tip member (A) is provided with a new powdered carbide composite. (Hardness: approx. HRC 50) Electric conductivity 50% IACS center 1.5 1.5 and taper fixing part (B) with chrome copper Welded Z body welded parts (conductivity 80% IACS)
  • Fig. 4 is a hard and highly accurate bearing diagram using the magnetic properties of WC. Similar to balls and needle bearings, the reclaimed powder sintered material of the present invention has a self-lubricating property on the periphery of the hardened copper shaft, and a small amount of copper penetrates, hardness, HRC48. Magnetic paste (fluorine oil + silicon oil is impregnated with 50% WT Fe04 ultrafine powder in the air in the middle of the axis of hardened copper HRC40, and the product is mixed with 10% WT morrigate oil.
  • a high magnetic force bearing In order to improve the sealing performance for low pressure, gas, and liquid, use a high magnetic force bearing. If the magnetic N and S are arranged alternately at both ends of the groove, the magnetic bearing becomes a high holding force bearing.
  • Figure 5 shows seven WC wires (approximately W) (approximately 1.5 ⁇ ), aiming to improve durability by improving the electrical conductivity and hardness retention, which are other steel plate spot welding tips.
  • Ag—15% was added to CR—Cu.
  • F Further, the WC—Cu composite of the present invention was joined to the outer periphery only at the tip.
  • the center conductivity (85% IACS) is high, and it is possible to achieve high hardness around.
  • Fig. 6 is used for welding for coffee cans, canned foods, and iron cans for paint cans.
  • the electrical conductivity of 50% IACS and hardness HRC 3 2 of the WC-cu composite of the present invention was joined to the CU wire contact part of the inner one-turn electrode roll (A), and the durability was improved 2 to 3 times. Conventionally, it uses lithium copper or chromium copper. Make a separate WC-cu ring and fit it like a tire. Cost reduction and high electrical conductivity could be secured by molding on one side at the same time.
  • welding was performed with a copper wire passing through the groove, but the roll surface heat generation reached about 1000 ° C, so wear was fast and the number of groove repairs was reduced.
  • the composite hardness is not the strength of the skeleton itself, but the skeleton is strong. There is no reason to compete with a dense cemented carbide, but it is the strength in the balance with the opposite porosity. Fortunately, the skeleton functions as if it has increased the hardness of the penetrant to produce the hardness of the composite, but it can also increase the strength of the skeleton corresponding to the amplification factor. It is better to expect the effect. Pure copper is more advantageous than pure silver for the penetrant, and copper alloy is more advantageous for producing hardness than pure copper. It is easy to reach 64HRC even if it penetrates pure copper.
  • the copper that has entered the skeleton is not the infiltrated copper, but even if pure copper in which the regenerated powder of cobalt is in solid solution is infiltrated, the infiltrated copper is not pure copper in terms of conductivity. Therefore, its use as a contact material is sealed and can be achieved with the new powder described below. This is because of the identity of the phase of what is preserved in composite materials.
  • the atmosphere of penetration can affect the hardness of the composite. This is probably because the skeleton is related to the wettability of copper. This may be the same reason why hydrogen atmosphere is preferred due to the penetration of copper-tungsten.
  • the hardness of the composite material obtained in Comparative Example 1 is the standard value (Non-Patent Document 2) or the maximum hardness at 80% WC—Ag listed in Non-Patent Document 1 270HR B ( 27.6HRC equivalent) is too different. Only the differences are described.
  • Silver powder as priming water has a particle size of 5 to 15 / im, and a mixing ratio with WC of 2.4%. Molding pressure of mixed powder 196MPa. The penetrant is 106% IACS.
  • the resulting composite has a conductivity of 39% and a hardness of 11 HRC. At least 0.7% shrinkage of the original molded product due to penetration
  • Bearing housing Magnetic shaft sleeve Industrial applicability
  • this composite Since this composite has not yet obtained practical trials, its useful applications are not expected.In general, this composite is used as a model, and cemented carbide is not wear resistant except for cutting tools. Because it has a variety of uses as a part, it seems that it will be a substitute for cemented carbide instead of a substitute here. When it is a wear-resistant part, there is always a counterpart material, a mechanical attack in the future To endure WC material is superior. In the case of cemented carbide, the attack may extend physically and chemically to the cement material cobalt. It is attack sensitive by infiltrating copper.
  • Electrode materials such as welding of spot, seam and can-making rotating electrodes are more conventional than many low-hardness copper such as chromium copper, oxidized alumina-dispersed copper, copper tungsten, copper iron HZ alloy and beryllium copper. It can be changed to the WC-Cu composite of the present invention as a much higher performance and higher durability copper. Maintaining the same conductivity as that of conventional electrode materials and increasing the hardness for durability improvement to HRC 50 can improve the productivity of the welding line by 2 to 3 times. Welding electrode contacts and electrodes that conduct electricity efficiently are all made of new WC powder. (Same for item 6)
  • a shaft bearing shield (including the use of sleeves, etc.) is made of a hard shield such as iron or ceramic. It is done. Suitable for wind power bearings.
  • Submersible pumps, construction machinery, military tanks, and agricultural machinery that require a muddy water seal have traditionally been made of materials such as alumina ceramics, tungsten copper, and chrome steel.
  • alumina ceramics such as tungsten copper, and chrome steel.
  • High-conductivity hardness and durability are required for switches for recharging electrical components, general circuit breakers, electrical contacts, electrodes, and rotary slipping contacts.
  • copper tungsten, chrome copper, alumina oxide dispersed copper, etc. have been used in the past. Can be used.
  • a highly conductive fluorine oil impregnated paste of Fe0 4 or a liquid conductive material of gallium, indium, tin, or zinc When the mixture of Fe04 was made transparent, the conductivity could be effectively improved without scattering by magnetic force.
  • the injection needles for animals are thin, small in outer diameter, sharp at the tip and hard enough not to be broken, and are required to have a smooth surface.
  • WC recycled powder Cu alloy with a hardness of about HRC 30 can be processed to approximate the tip dimension of a mosquito mouthpiece, so the conventional Crim steel SUS needle is used as the material of the present invention. By changing it, the wear of the needle is reduced, and if the degreasing and disinfection placement is devised, it can be changed to a needle with improved durability.
  • Iron and other hard (HRC 30 or higher) materials that require good electrical heat transfer have traditionally used copper tungsten, copper iron, high speed steel, etc., but they have high conductivity and heat conductivity. It can be changed to the hard WC-Cu material of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention a pour objet une méthode de synthèse d'un composite de type carbure cémenté-Cu, qui comprend les étapes suivantes : 1) mélanger de façon homogène une poudre régénérée de carbure cémenté ou une poudre de carbure de tungstène avec une poudre de cuivre dans les proportions appropriées indiquées, et façonner la poudre mélangée résultante de manière à lui donner la forme désirée, présentant les dimensions désirées, 2) chauffer le produit formé précédent sous vide ou sous atmosphère non-oxydante, afin de le convertir en un article fritté présentant le taux d’interstices attendu, et 3) imprégner l’article fritté avec du cuivre ou un article de cuivre adéquats. Ladite imprégnation peut être préférentiellement menée A) dans un creuset de graphite où toute fuite du cuivre ou de l’alliage de cuivre imprégné est impossible, et B) sous atmosphère d’hydrogène.
PCT/JP2004/016378 2004-10-28 2004-10-28 Méthode de synthèse d’un composite de type carbure cémenté wc-cuivre WO2006046313A1 (fr)

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PCT/JP2004/016378 WO2006046313A1 (fr) 2004-10-28 2004-10-28 Méthode de synthèse d’un composite de type carbure cémenté wc-cuivre

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112059175A (zh) * 2020-08-12 2020-12-11 西安理工大学 一种WC增强WCu双梯度结构复合材料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS509794A (fr) * 1973-06-04 1975-01-31
JPS5482308A (en) * 1977-12-15 1979-06-30 Toshiba Corp Current flowing jig for plastic working
JPS5482309A (en) * 1977-12-15 1979-06-30 Toshiba Corp Current flowing jig for plastic working
JPS56126535A (en) * 1980-02-06 1981-10-03 Minnesota Mining & Mfg Electron discharge electrode and its manufacture
JPS61183439A (ja) * 1985-02-06 1986-08-16 Hitachi Metals Ltd 耐酸化性の優れた耐摩用超硬合金

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS509794A (fr) * 1973-06-04 1975-01-31
JPS5482308A (en) * 1977-12-15 1979-06-30 Toshiba Corp Current flowing jig for plastic working
JPS5482309A (en) * 1977-12-15 1979-06-30 Toshiba Corp Current flowing jig for plastic working
JPS56126535A (en) * 1980-02-06 1981-10-03 Minnesota Mining & Mfg Electron discharge electrode and its manufacture
JPS61183439A (ja) * 1985-02-06 1986-08-16 Hitachi Metals Ltd 耐酸化性の優れた耐摩用超硬合金

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112059175A (zh) * 2020-08-12 2020-12-11 西安理工大学 一种WC增强WCu双梯度结构复合材料的制备方法

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