JPS60208402A - Production of dispersion-strengthened copper alloy powder - Google Patents

Abstract

PURPOSE:To obtain copper alloy powder which is uniformly dispersed with hard particles in copper and has high heat-resisting strength by coating the surface of copper with an org. metallic compd. and subjecting the compd. to a heat treatment to form hard particles then grinding and alloying the powder by a mechanical alloying method. CONSTITUTION:The surface of copper (alloy) powder is coated with an org. metallic compd. such as Al-propoxide or the like. Such powder is heat-treated to form hard particles (e.g.; Al2O3) consisting of the oxide, carbide, nitride, carbonitride, etc. of the metal in the compd. on the surface of the copper (alloy) powder. The powder is ground and alloyed by a mechanical alloying method to disperse uniformly the hard particles as dispersion particles into the copper alloy powder. The powder is further subjected, if necessary, to an annealing treatment at the temp. from >=60% the m.p. of the copper (alloy) to the m.p. or below. The dispersion-strengthened copper alloy combined with solid soln. hardening and precipitatioi hardening is obtd. if such dispersion-strengthened copper alloy powder is used.

Description

[Detailed description of the invention]

The present invention relates to a method for producing dispersion-strengthened copper alloy powder.
The present invention relates to a method for manufacturing a dispersion-strengthened steel alloy powder in which the hard particles are uniformly dispersed and contained in the copper alloy powder as dispersed particles by applying a mechanical alloying method. The purpose of the 1134 strengthened copper alloy is to improve its heat resistance strength by dispersing fine hard particles such as oxides, carbides, nitrides, or carbonitrides of appropriate metals inside as dispersed particles. copper or copper alloy. Usually, this dispersion-strengthened copper alloy is often obtained by preparing dispersion-strengthening 1114 alloy powder in advance and using the powder metallurgy method. Methods for manufacturing dispersion-strengthened copper alloys using this conventionally known powder metallurgy method include, for example, the mixing method, coprecipitation method, molten salt method, internal oxidation method, etc. With the exception of the oxidation method, the dispersibility of the grains was poor and sufficient properties as a dispersion-strengthened copper alloy could not be obtained.In the case of the internal oxidation method, sufficient properties as a dispersion-strengthened steel alloy were not obtained. Although it is possible to obtain properties, practical use is limited to some copper alloys (Cu-Al□03) because there are restrictions on the combination of the copper alloy as the base metal and hard particles. In addition, with the internal oxidation method, it is not possible to add other alloying elements to the S-1 alloy as the base metal, so the dispersion-strengthened copper alloy obtained by this method has difficulty in medium and low temperature ranges. There was also the problem of insufficient strength.Recently, a dispersion-strengthened alloy powder was produced by mixing base metal powder and hard particles and pulverizing this into a pulverized alloy using a mechanical alloying method. This method is used to obtain alloys, and has already been put into practical use in some cases (such as Sokel alloys).However, this method requires long grinding to uniformly disperse hard particles in the base metal. In addition, when using this method, the hard particles themselves are rarely crushed during the crushing process, so it is necessary to use fine hard particles from the beginning, but such fine hard particles are difficult to mass produce. Therefore, this method has not been used as a method for manufacturing dispersion-strengthened copper alloys that can be applied to the internal oxidation method. As an innovative method for producing reinforced alloys, a mixture of metal complexes or alkoxides capable of forming oxides, carbides, nitrides, or carbonitrides and metal powders or alloy powders is shaped, fired, or melted. By solidifying the metal oxide, carbide, etc. in the metal complex compound or alkoxide by using the heat during the treatment,
A method for uniformly dispersing and containing nitrides or carbonitrides in a dispersion-strengthened copper alloy has been invented (Japanese Patent Publication No. 58-366).
(See Publication No. 60). In view of the problems of the above-mentioned conventional method, the present inventors have conducted various studies and found that if the invention described in the above-mentioned Japanese Patent Publication No. 58-36660 is combined with the mechanical alloying method, problems like those of the above-mentioned internal oxidation method can be solved. We came up with the idea that it is possible to obtain a dispersion-strengthened copper alloy that has the same properties as the dispersion-strengthened steel alloy obtained by the oriented region oxidation method.
The present invention was completed based on this idea. That is, the method for producing a dispersion-strengthened copper alloy powder according to the first invention of the present application uses an oxide. By coating the surface of copper or copper alloy powder with an organometallic compound containing a metal that can form carbides, nitrides, or carbonitrides, and heat-treating this, metal oxides, carbides, and nitrides in the organometallic compound can be formed. Hard particles made of one or more of carbonitrides or carbonitrides are generated on the surface of the copper or copper alloy powder, and then pulverized and alloyed by a mechanical alloying method so that the hard particles are dispersed inside the copper alloy powder. Average minute nIl! It is characterized by every step. Further, the method for producing a dispersion-strengthened copper alloy powder according to the second invention of the present application further includes the method of manufacturing a dispersion-strengthened copper alloy powder obtained by the first invention. It is characterized by performing the annealing treatment at a temperature below the melting point. The finer the particle size of the copper or copper alloy powder used in the present invention, the better, and it is preferable to use 15] powder with a maximum particle size of 50 μm or less. When using powder larger than 50 IJm,
This is because, as will be described later, the grinding process requires a long time and the hard particles make the 11k worse. The organometallic compound coated on the copper or copper alloy powder is a metal complex compound such as acetylacetonatochelate, trimethylenediamine chelate, propylenediamine chelate-1
, etc., or alkoxides such as methoxide, ethoxide, propoxide, butoxide, and phtoxylate, metal salts of naphthenate, metal salts of octylate, metal salts of caprylate, metal salts of carboxylate, organometallic fatty acids, and the like. The metals contained in this organometallic compound include titanium,
zirconium. Aluminum, cadmium, silicon, vanadium. #H
Alternatively, it may be selected and applied in combination with copper alloy powder. When coating copper or copper alloy powder with the organometallic compound, if the organometallic compound is liquid at room temperature, apply it as is, or if it is solid or powder, melt it by heating or dissolve it in an appropriate solvent. After applying common and uniform IW, the solvent may be removed by drying or burning. The amount of an organometallic compound added is determined by the amount of metal contained in the compound,
Although it is determined by the intended alloy composition, it is not preferable to add more than 50-1% of the organic metal compound (copper or 1M alloy powder). If it is added in an amount of 50-1% or more, when hard particles are formed by heat treatment, they will become coarse, reducing their contribution to dispersion strengthening, and deteriorating mechanical and physical properties. be. The reason for this is not clear, but it is thought that the 1 m thick layer causes hard particles to bond with each other during decomposition. In the present invention, the IW metal compound
By processing the 1-4 or 1-1 alloy powder, the hard particles of metal oxides, carbides, nitrides, and carbonitrides contained in the metal compound are removed from copper or copper alloy. However, the atmosphere at this time should be one that will generate the desired hard particles.For example, when generating oxides, use air or hydrogen containing some moisture. In the case of expanded products, heat treatment can be performed in hydrogen using the carbon contained in the organometallic compound, and in the case of nitrides, heat treatment can be performed in nitrogen after the organometallic compound has been decomposed. is carried out at a temperature from about 300°C to around the melting point of the copper or copper alloy, because about 300°C is required for the organometallic compound to start decomposing; This is because if the temperature exceeds the temperature, the hard particles will agglomerate and uniform dispersion will not be possible. Therefore, this heat treatment temperature is usually applied at 500 to 700°C. They only adhere to the surface, and even if a copper alloy was manufactured using this, the dispersion of hard particles would be insufficient for a dispersion-strengthened copper alloy, and it would also impede sinterability. Therefore, in the present invention, this is further pulverized and alloyed by a mechanical alloying method.9 For this pulverized alloying, a pulverizer with high crushing energy, such as a vibration mill or a one-car type ball mill, is used. Copper or copper alloy powder coated with hard particles is passed through a pulverizer to repeatedly join and crush each other, and in this process, the hard particles are crushed into pieces. It will be dispersed uniformly inside the ζ copper or copper alloy powder by ladle. The time for which the copper or copper alloy powder coated with hard particles is subjected to the grinding machine is as follows:
→Depending on the type and particle size of the alloy powder, it is generally said that if the time exceeds about 20 hours, the effect of uniformly dispersing hard particles cannot be expected to improve.If the crushing energy of the crusher is small, Only bonding between copper or 1H alloy powders coated with ?f particles may occur, forming extremely coarse particles.Such III large particles are essentially due to poor dispersion of hard T1 particles. It is homogeneous and cannot be used as a powder for dispersion-strengthened copper alloys.In such cases, the hard particles can be coated by adding a lubricant such as stearic acid in a range of about 0.1-1 wt%. Excessive bonding of copper or copper alloy powders can be prevented. However, since the lubricant may inhibit sintering, it is necessary to thoroughly remove it after grinding and alloying is completed. The dispersion-strengthened copper alloy powder obtained by the invention may have reduced formability due to significant work hardening during the pulverized alloying process.If formability is required, the formability may be improved by annealing. When this annealing is performed, the dispersion-strengthened copper alloy powder obtained by the present invention has high softening resistance to annealing because the dispersed particles are extremely uniformly and finely dispersed in the copper or copper alloy powder. So,
The annealing temperature is significantly higher than the recrystallization temperature of copper or copper alloys;
It needs to be 60% or more of the melting point ('C) of copper or copper alloy. However, temperatures above the melting point are not preferred because the matrix phase melts and the hard particles aggregate. With the above configuration, the amount obtained by the method of the present invention is 1
1. The reinforced copper alloy powder can have the following effects. That is, since the hard particles can be uniformly and finely dispersed inside the copper alloy powder as dispersed particles, if this dispersion-strengthened copper alloy powder is used, a dispersion-strengthened copper alloy having the same characteristics as the internal oxidation method can be produced. can be obtained. Furthermore, since there are no restrictions on the combination of copper alloy i as a base metal and a hard ladle as in the internal oxidation method, if the dispersion-strengthened copper alloy powder according to the present invention is used, dispersion-strengthened 1M Gold alloy can be obtained. moreover,
Since alloying elements that cannot be added using the internal oxidation method can be contained in the dispersion-strengthened copper alloy powder, if this dispersion-strengthened copper alloy powder is used, dispersion-strengthened copper alloy powder that combines solid solution strengthening and precipitation strengthening can be achieved. A copper alloy can be obtained, and as a result, it is possible to improve the lack of strength and other drawbacks of conventional dispersion-strengthened copper alloys in medium and low temperature ranges. Therefore, the dispersion-strengthened steel alloy obtained by the method of the present invention has not yet been used for the production of parts that require high hardness, good conductivity, heat resistance, etc., especially Subono H8 contact tips, IC leads, etc. It is useful as a raw material powder. Examples of the present invention are shown below. Example 1 3 wt % of ^l-propoxide was dissolved in petroleum ether and mixed with electrolytic copper powder having an average particle size of 3 μm, After coating the surface of the electrolytic copper powder with AI-propoxide by drying, it was heat-treated at 600°C for 30 minutes in an H2 stream to obtain AI, 0.
was generated on the surface of electrolytic copper powder. The obtained powder was pulverized into an alloy by a mechanical alloying method in a vibration mill for 12 hours. When this powder was analyzed, the dispersed particles were found to be 0.
75wt%^120. was included. The powder thus obtained was put into a mold with a diameter of 11.3φ
Molded to a gloss of 11.5 mm and a density of approximately 7.85 g/cm',

[12 Sintering was carried out at 1000° C. for 90 minutes in an air flow. This is 1
After cold forging into the shape of 6φ x approx. 511III+, H2 again.
Sintered at 1000℃ for 90 minutes in an air stream, and then 20φ x approx.
A final test piece was obtained by cold forging into a shape of IIl1m. Table 1 shows the annealing softening properties of the above test pieces. For comparison, dispersion-strengthened alloy powder with the same composition as in Example 1 was prepared using the conventional internal oxidation method and the conventional mechanical alloying method (A1□03 with an average particle size of 0.05 μm and A1 A final test piece was prepared under the same conditions as in Example 1, and the annealing softening characteristics of this final test piece are also shown in Table 1. The annealing softening characteristics were measured by heating to a predetermined temperature in H7 air flow, holding it for 60 minutes, cooling to room temperature, and measuring the hardness. Table 1 Hardness after annealing and softening HV5) > * Conventional corporation - Internal oxidation method * Conventional method B: Mechanical alloying method Example 2 ゛C^ Dissolve 1'3% of 1-propoxy in petroleum ether, mix and process in the same manner as in Example 1 to obtain Cu-
A 0,7Cr-0,75AI 203 dispersion strengthened alloy powder was manufactured. Next, this minute tls! 11. Reinforced alloy powder. It was annealed at 700°C for 60 minutes. The powder that has been iQed in this way is put into a mold for 11.3
It was molded to a size of φXI 2.5 mm and about 7.20 g/cm1, and sintered at 1000°C for 90 minutes in an H, air flow. After cold forging this into a shape of 16φ x approximately 5+III+, H
, sintered at 1000° C. for 90 minutes in an air stream7, and then water quenched. 20φ x approx. 311II11 after water quenching
After cold forging into the shape of It is the same as 1.For comparison,
The measurement results of Example 1 are reproduced, and the measurement results of Cu-0, ICr alloy, and pure copper are also shown in Table 2 along with the °C. Table 2 Hardness after annealing and softening HV5)>Example 3 5% Y-acetyl-17% was mixed with electrolytic copper powder having an average particle size of 3 μm while heating to approximately 200°C. This was then heat treated at 600°C for 30 minutes in an 11□ air stream. The obtained 151 powder was pulverized into an alloy by a mechanical alloying method in a vibration mill for 12 hours, and then heated at 700°C in H2.
Annealed for 60 minutes. As a result of analyzing the powder thus obtained, it was confirmed that the dispersed particles contained t, 2tvt% of Y, O, and so on. This powder was molded and sintered in the same manner as in Example 2. The hardness of the obtained final test piece at room temperature is Hv (5):
150, and the hardness after annealing at 800° C. for 60 minutes in H2 was Hv(5):141. Example 4 Electrolytic copper powder with an average particle size of 3 μm was mixed with 3% offnaric acid A1 while heating to about 250°C.
The sample was incubated for 30 minutes at 1 itlt)°C in an air flow. The obtained powder was crushed into 151 alloy by mechanical alloying method in a vibrating mill for 12 hours, and then heated at 700°C in 1□.
Annealed for 0 minutes. As a result of analyzing the powder obtained as described above, it was confirmed that 0.75 wt % of 81□03 was contained as dispersed particles. This powder was molded and sintered in the same manner as in Example 2 with a 7-way υ. The final test piece obtained had a hardness of 11ν (5) at room temperature.
: 148, and the hardness after annealing at 800°C for 60 minutes in [12] was 1lv(5):140. Example 5 Swt% f:r for electrolytic copper powder with an average particle size of 3μ
-7 cetyl acetonate was mixed while heating to about 190°C, and this was heat-treated at 600°C for 60 minutes in 2 air streams. The obtained powder was pulverized and alloyed using a mechanical alloying method in a vibration mill for 12 hours, and then annealed in H2 at 700°C for 60 minutes. As a result of analysis of the powder obtained in this way, it was found that the fraction of li&particles was approximately 1. It was confirmed that OWL% of Cry C3 or f:r3 C:z was contained. This powder was molded and sintered in the same manner as in Example 2. The hardness of the obtained final test piece at room temperature is t(v(5):
150, and the hardness after annealing at 800° C. for 60 minutes at +12 was Hv(5)=137. Patent Applicant: Fukuda Metal Foil & Powder Industry Co., Ltd. Kobe M Co., Ltd. Agent (6420) Patent Attorney Il■1 Kanji Continued from page 1 @ Inventor Masataka Noguchi @ Inventor Gonichi Omukai @ Inventor Assue Yoshio 8-21-305 Koshien Abiki-cho, Nishinomiya-shi 131-1-122 Arise, Ikawadani-cho, Nishi-ku, Kobe City 131-1-603 Arise, Ikawadani-cho, Nishi-ku, Kobe City J'': f, 1.L weight +l knee,' ! (1 fan) Opening June 26, 1951 lh'! fll, 'i 'l ζL'H'+:'I
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Claims (2)

[Claims] (1) The surface of copper or copper alloy powder is coated with an organometallic compound containing a metal that can form oxides, carbides, nitrides, or carbonitrides, and the metal in the organometallic compound is heat-treated. oxides, carbides. Hard particles consisting of one or more types of nitrides or carbonitrides are generated on the surface of the steel or copper alloy powder, and then they are crushed and alloyed by a mechanical alloying method to make the hard particles into fine particles. A method for producing dispersion-strengthened copper alloy powder, which is characterized by uniformly dispersing the powder inside. (2) Coating the surface of copper or copper alloy powder with an organometallic compound containing a metal that can form oxides, carbides, nitrides, or carbonitrides, and heat-treating the powder to remove the metal in the organometallic compound. oxides, carbides. Hard particles consisting of one or more types of nitrides or carbonitrides are generated on the surface of the steel or copper alloy powder, and then mechanical alloying is performed (pulverization is performed to form the hard particles into dispersed particles of the copper alloy powder). A method for producing a dispersion-strengthened copper alloy powder, characterized by dispersing it uniformly inside the powder, and further annealing it at a temperature of 60% or more of the melting point (°C) of the copper or copper alloy to less than the melting point.