WO2005092541A1

WO2005092541A1 - Powders of nano crystalline copper metal and nano crystalline copper alloy having high hardness and high electric conductivity, bulk material of nano crystalline copper or copper alloy having high hardness, high strength, high conductivity and high rigidity, and method for production thereof

Info

Publication number: WO2005092541A1
Application number: PCT/JP2005/006554
Authority: WO
Inventors: Harumatsu Miura; Nobuaki Miyao; Kazuo Oda; Masaru Mizutani; Hidenori Ogawa; Munehide Katsumura; Takao Araki; Masayuki Hirota; Keiichi Murakami; Akihiro Murakami; Tsukasa Hirahara; Tadayuki Yano; Toshio Ito; Toru Kishi
Original assignee: Nano Technology Institute, Inc
Priority date: 2004-03-29
Filing date: 2005-03-29
Publication date: 2005-10-06

Abstract

A nano crystalline copper metal powder, which comprises aggregates of nano crystal grains of copper metal or a copper alloy, wherein the nano crystal grain has a size of 2 to 1000 nm; a bulk material of a nano crystal copper or copper alloy exhibiting high hardness, high strength, high electric conductivity and high toughness, which comprises a great number of above nano crystal grains being firmly bound with one another; and a method for producing the above bulk material of a nano crystal copper or copper alloy exhibiting high hardness, high strength, high electric conductivity and high toughness, which comprises subjecting the above copper powder or copper alloy powder to a solidification forming such as a vacuum hot solidification forming or an explosive forming, for example, a spark plasma sintering at a temperature of 250 to 700°C, hot pressing, sheath rolling, hot forging, extruding or hot isotropic pressure forming (HIP).

Description

Description Powder of nanocrystalline copper metal and nanocrystalline copper alloy having high hardness and high conductivity, high hardness, high strength and high strength, bulk material of nanocrystalline copper or copper alloy having high conductivity, and methods for producing them

Technical field

The present invention relates to a powder of a nanocrystalline copper metal and a nanocrystalline copper alloy having high hardness and high conductivity, a high hardness and a strong nanocrystalline copper having high strength and high conductivity ^ are copper alloy bulk materials and The present invention relates to a method for producing powders and bulk materials such as a nano-sized copper alloy having a high strength conductive copper or a copper alloy composition and a nano-sized intermetallic compound having a high strength conductive copper or copper alloy composition, and a method for producing the same.

Background art

The strength and hardness of the metal material increase as the crystal grain size d decreases, as shown by the Hallbeck relation, and this relationship holds true until d is around several tens of nm. Therefore, ultra-fine crystal grain size down to the nanometer level is one of the most important ways to strengthen metallic materials. This is extremely important as a method of strengthening copper alloy materials. In a copper alloy, if hard substances such as intermetallic compounds are precipitated or dispersed in the microcrystalline structure thus obtained, the strength characteristics can be further improved.

However, research on nano-crystallization of high-strength conductive copper alloy materials, which are extremely important as practical materials, has not yet been made. In particular, in the case of beryllium copper, which is widely used as a conductive high-strength spring material in telecommunications equipment, if the strength is significantly increased by refining the crystal grains to the nanometer level, the electric This makes it possible to reduce the weight and size of equipment, and its practical significance is extremely large.

Disclosure of the invention

Problems to be solved by the invention

However, the crystal grain size d of many metal materials, including copper alloys manufactured by the melting method, is usually several micron to several hundred micron, and d is in the nano order even by post-processing. For example, even in the case of controlled rolling, which is important as a process for reducing the grain size of steel, the lower limit of the grain size that can be reached is about 4 to 5 / xm. Therefore, such a conventional method does not provide a material having a fine particle size down to a nanosize. Means for solving the problem

The present invention solves the above problems, and is the following month.

The present invention basically relates to (1) a mixed material of each of the components of the copper alloy, (2) a wrought copper alloy material, or (3) a material of (1) and (2). A mixture of materials containing elements or their alloys is processed by mechanical milling (MA) or mechanical milling (MM) using a ball mill or the like to make the crystal grain size ultra-fine to the nano-size level. Nanocrystalline powder of copper alloy with strength (high strength) close to its limit, which can be achieved by precipitation and dispersion of ultra-hard nanosized intermetallic compounds, etc. Next, the object of the present invention is to provide a bulk material of the nanocrystalline copper alloy which retains the properties of the powder by hot solidifying and molding the powder of the nanocrystalline copper alloy. That is, the present invention is a powder material and a bulk material of a nanocrystalline copper alloy having high hardness, high strength and toughness having the following constitution, and a method for producing both materials.

[1] Nanocrystalline copper having high hardness and high conductivity, characterized in that copper metal powder composed of an aggregate of copper metal nanocrystal particles is composed of nanocrystals having a size of 2 to 100 nm. Metal powder.

[2] A copper alloy powder comprising an aggregate of copper alloy nanocrystal particles, the alloy element of which is beryllium, chromium, zirconium, titanium, silver, cobalt, nickel, zinc, iron, cadmium, manganese, aluminum, It is composed of at least one selected from molybdenum, vanadium, tungsten, niobium, tantalum, phosphorus, silicon, and boron. 40% by mass, and when there are two or more alloying elements, the total concentration is 0.05 to 45% by mass, and the nanocrystalline copper alloy powder is made of these alloying elements. A nanocrystalline copper alloy powder having high hardness and high conductivity characterized by solid solution strengthening and crystal grain strengthening to a size of 2 to 100 nm.

[3] A copper alloy powder comprising an aggregate of copper alloy nanocrystal particles, as a precipitation / dispersion strengthening substance and a Z or crystal grain growth inhibiting substance, (1) any one selected from the alloy elements according to claim 2. Or more, or (2) a nanocrystalline copper alloy having high hardness and high conductivity, characterized by being present in the presence of at least one kind of a metal tube compound composed of each of the above elements and copper. Powder.

[4] Copper or copper alloy powder composed of aggregates of copper or copper alloy nanocrystals is a substance that suppresses the decrease in conductivity due to solid-solution impurities in copper or copper alloy; zinc, cadmium, silicon, phosphorus, or oxygen. The nanocrystalline copper or copper alloy powder having high hardness and high electrical conductivity according to any one of the above items [1] to [3], characterized in that at least one of the above is present.

[5] A copper or copper alloy powder composed of an aggregate of copper or copper alloy nanocrystals contains oxygen in the form of a metal or metalloid oxide in an amount of 0.05 to 1.0% by mass. The nanocrystalline copper or copper alloy having high hardness and high conductivity according to any one of the preceding items [1] to [4], characterized in that: Powder o

[6] The copper metal nanocrystal particles are characterized by being obtained by subjecting a lump, flake, granular, or powdered copper metal material to mechanical milling (MM) using a pole mill or the like. The nanocrystalline copper gold) h powder having high hardness and high conductivity according to any one of [1], [4] and [5] above.

[7] The copper alloy nanocrystal particles are formed into a block, flake, granule, or powdered copper alloy.

The nanocrystalline copper alloy powder having high hardness and high electrical conductivity according to any one of the above items [2] to [5], which is obtained by performing (MM).

[8] The copper alloy nanocrystal particles are in a lump, flake, granular, powdery copper, beryllium copper, chromium copper, zirconium copper, silver copper, titanium copper, silicon bronze, kelmet alloy, brass, aluminum bronze, Nickel copper, nickel bronze, Corson alloy, copper manganese alloy, phosphor bronze, nickel silver, cupronickel, other alloying elements or alloys One or more copper alloy components selected from two or more , Obtained by mechanical milling (MM) or mechanical grooving (MA) using a ball mill or the like, characterized in that the height is as described in any one of the above items [2] to [5]. Nanocrystalline copper alloy powder with high hardness and high conductivity.

[9] In the mechanical arranging (MA) or mechanical milling (MM) process, input by selecting the mass ratio of the crushing medium and raw material powder used for the pole mill and / or the operating energy of the ball mill etc. By adjusting the mechanical energy, (1) the crystal grain size of other substances such as nanocrystalline copper or copper alloy or the second phase composed of copper and other elements in the aggregate of nanocrystalline particles, (2) (1) the generation of other substances such as the second phase, or (3) the amount of the generation is controlled by at least one selected from (1) to (3). A nanocrystalline copper alloy powder having high hardness and high electrical conductivity according to any one of the above items [8] to [8].

Π 0] The solidification molding process between nanocrystalline particle aggregates (powder) obtained by mechanical alloying (MA) or mechanical milling (MM) when copper alloy powder consisting of aggregates of copper or copper alloy nanocrystalline particles is obtained Wherein titanium, zirconium or vanadium is contained in an amount of 0.01 to 5.0% by mass as an atomic bond promoting substance in the method described in any one of the above items [1] to [9]. Nanocrystalline copper or copper alloy powder with high conductivity and hardness.

Π 1) High hardness characterized by a large number of nanocrystalline copper or copper alloy powders according to any one of the above items [〗] to [〗 0] being consolidated · High strength and high conductivity A tough nanocrystalline copper or copper alloy bulk material with

[12] Spark plasma sintering of the powder of the copper or copper alloy nanocrystal particles according to any one of [1] to U0] at a temperature of 250 to 700 ° C (Spark Plasma S intering), hot pressing, sheath rolling (S heath Ro IIing), hot forging, extrusion, hot isostatic pressing (HIP), etc., or vacuum hot solidification or solidification such as explosion molding. A method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness, high strength and high conductivity, which is formed into a nanocrystalline copper or copper alloy bulk material by molding.

(13) The powder of the copper alloy nanocrystal particles according to any one of the above (2) to (10), spark plasma sintering at a temperature of 250 to 700 ° C, hot pressing, Extrusion molding, hot forging, hot isostatic pressing, rolling and other vacuum hot solidification molding, or solidification molding by explosion molding to form a nanocrystalline copper alloy bulk material. Annealing at a temperature of 0 to 600 ° C

(Hard heat input) to precipitate and disperse copper and other intermetallic compounds consisting of the elements described in [2] above. High hardness · High strength and high toughness with high conductivity Of bulk nanocrystalline copper alloy bulk material.

[4] The atmosphere in which the mechanical milling or mechanical alloying is performed is any one selected from (1) an inert gas such as an argon gas, (2) an N ₂ gas, or (3) an NH ₃ gas, or ( 4) The tough nano-structure having high hardness and high conductivity according to the above item [2] or [13], characterized in that the atmosphere is a mixed gas atmosphere of two or more types selected from (1) to (3). Manufacturing method of crystalline copper or copper alloy bulk material.

[15] The above item [12] or [13], wherein the atmosphere in which the mechanical milling or mechanical alloying is performed is a gas atmosphere to which a reducing substance such as a slight amount of H ₂ gas is added. A method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness and high conductivity as described above. [16] The atmosphere in which the mechanical milling or mechanical alloying is performed is a vacuum or a reduced atmosphere in which a reducing substance such as a slight amount of H ₂ gas is added in a vacuum or vacuum. Or the method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness, high strength and high conductivity according to [13].

[17] Use of a microwave heating method or a low-frequency induction heating method for rapid heating of nanocrystalline copper or copper alloy powder to the hot solidification molding temperature and for maintaining Z or the same hot solidification molding temperature. Features High hardness · A method for manufacturing tough nanocrystalline copper or copper alloy bulk materials with high strength and high conductivity.

[18] In order to perform rapid hot-solidification molding of nanocrystalline copper or copper alloy powder, the powder is subjected to microwave heating and pressure sintering or low frequency induction heating and pressure sintering. A method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness, high strength, and high conductivity, characterized in that the material is a nanocrystalline copper or copper alloy bulk material.

BEST MODE FOR CARRYING OUT THE INVENTION

Normally, in copper alloy-based materials, the alloying elements that are constituents of the material are present as micron-sized intermetallic compounds, but the mechanical alloying method is used for such high-strength conductive copper alloy materials. And a substance such as an intermetallic compound close to nano-sized granular or spherical ¾ ^ (Nanocrystalline phase) A very tough powder that is precipitated and dispersed in the (nanocrystalline phase) is obtained. Due to the synergistic effect of the precipitation and dispersion of such substances in the same parent phase, it is possible to produce materials with extremely excellent strength properties that cannot be produced by conventional dissolution methods.

The present invention is basically based on a method of mechanically milling (MA) or mechanical milling (MM) a material such as a mixed material of a nanocrystalline copper alloy forming component or a melted copper alloy powder material by using a ball mining or the like. ) To provide a nanocrystalline copper alloy powder material with ultra-hardness and high conductivity, and to limit the limits that can be achieved when the crystal grain size is reduced to the nanometer level by solidification molding of the powder. It is an object of the present invention to provide a precipitation-dispersion-strengthened high-conductivity copper alloy bulk material having near strength (high strength) or hardness (ultra-hardness) and corrosion resistance, such as a nano-sized intermetallic compound. According to the present invention, a mechanical luer ring at room temperature in an atmosphere such as argon gas using a ball mill or the like for a mixed material of a copper alloy forming component obtained by adding another element to copper or a smelted copper alloy material. (MA) or mechanical milling (MM) treatment, the MM or MA-treated powder can be easily refined to a crystal grain size of about 5 to 50 nm by the mechanical energy added by the pole mill. For example, the hardness of beryllium copper refined to a particle size of about 15 nm is about 500 to 600.

Next, such MM and MA treated powder was vacuum-sealed in a stainless steel tube (sheet) with an inner diameter of about 1 Omm, and this was rolled using a rolling mill at a temperature around 700 to 75 ° C. When solidified by sheath rolling, for example, in the case of beryllium copper containing about 2% by mass of beryllium, sheets with a thickness of about 1.5 mm exhibiting a tensile strength of about 1.9 GPa or more can be easily formed. It can be manufactured in In addition, usually up to about 0.5 mass% of oxygen, which is necessarily mixed in the process of MA or MM processing, into the powder of the mechanical alloying (MA) or mechanical milling (MM) process described in the preceding paragraph is a metal or semi-metal. It exists in the form of a metal oxide and suppresses coarsening of grains during the solidification forming process due to the pinning effect of the grain boundaries caused by the oxide. In the present invention, a nanocrystalline copper alloy is obtained by subjecting a material such as an elemental powder material of a copper alloy forming component or a melted copper alloy to a mechanical milling (MA) or a mechanical milling (MM) using a ball mill or the like. An extremely hard and tough powder material in which nano-sized intermetallic compounds are precipitated and dispersed in the phase can be easily manufactured, and when this material is subjected to solidification molding such as sheath rolling or extrusion, high hardness, high strength and high conductivity are obtained. A nanocrystalline copper alloy bulk material having properties such as toughness and excellent corrosion resistance can be easily produced. As a result, powdered nanocrystalline copper alloys such as CU _97.7 Be ₂ CO 03 (mass%), CU 99.85 Z Γ _0,5 (mass%) and CU _S935 C Γθ.65 (mass%) A bulk material is obtained.

Example 1:

A mechanical mill using a pole mill from an elemental powder of copper (Cu), beryllium (Be), chromium (Cr), zirconium (Zr), titanium (Ti), silver (Ag) or phosphorus (P). Row (MA) (atmosphere: Argon gas ZM A time: 200 h) By processing, Cu _S7 A ₃ (mass%) (A = Be, Cr, Zr, Ti, Ag, or P) composition Copper alloy and copper powder were made. Table 1 shows the average crystal grain size d of these MA-treated powders obtained by using the Sierra equation.

As can be seen from Table 1, according to the present invention, the addition of about 3% by mass of any element greatly promotes the refinement of crystal grains of copper, and particularly the element having a very low solid solubility in copper and a high melting point. (Zirconium, Chromium, etc.) are more effective.

table 1

* No other elements added

* [Mechanical alloying (MA) C U97A3 (% by mass) (A = Be, Cr, Zr, Tί, Ag, or P) Average crystal grain size d of alloy powder]

Example 2:

Mechanical alloying (MA) using a ball mill from an elemental mixed powder of copper (Cu), beryllium (Be), cobalt (Co), zirconium (Zr), or chromium (Cr) (atmosphere: argon gas A time:. by 200 h) _{_{_{processing, C u 97 7 B e 2}}} C o »3 ( wt%), C u _99.

A copper alloy powder having a composition of 85 Z ro. ₁₅ (% by mass) and Cu ₃₉₃₅ C ro. 65 (% by mass) was prepared.

Next, these alloy powders were vacuum-sealed in a stainless steel tube (sheath) having an inner diameter of about 1 Omm, subjected to hot rolling at 600 ° C, and then cooled with water to obtain a solidified molded sample. This The average crystal grain size d and the Vickers hardness Hv of these solidified copper alloy compacts and the above-mentioned copper alloy MA powder samples are as shown in Table 2. In this table, the value of d was determined using the Sierra equation. The Vickers hardness of the MA-treated powder is a micro-Vickers hardness measured under a load of 100 g.

As can be seen from Table 2, according to the present invention, the growth of considerably large crystal grains was observed during the solidification molding process, but the nanocrystalline structure was maintained after the molding. The Vickers hardness Hv of the MA-treated powder was about 3 to 5 times larger than the hardness of each annealed material produced by the melting method, and these values were further increased by the solidification molding treatment. It can be seen that such an effect of increasing the Hv value is more remarkable in the case of beryllium copper. Table 2

* Hardness Hv of MA powder is micro-Vickers hardness measured under a load of 100g

* [Mechanical alloying (MA) treated, (a) C U97.TB e ₂ COO 3 (% by mass),

(b) C U 99.85 Z ス 0.15 (% by mass) and (C) C U 99.35 C Γ 0.65 (% by mass) alloy powder and average crystal grain size d and Vickers hardness H V of their hot-solidified compacts

Example 3:

Mechanical alloying (MA) using a pole mill from an elemental mixed powder of copper (Cu), beryllium (Be), cobalt (C0), zirconium (to Z), or chromium (Cr) ( Atmosphere: Argon gas ZM A time: 200 h) Treatment, Cu ₉₇₇ Be _{2 Co.} ₃ (% by mass), Cu ₉₉ .

85 Z gamma 0.15 (wt%) and CU _93. ₃₅ C Γ 0.65 (wt%) were made of copper alloy powder composition.

Next, the three types of alloy powders were subjected to hot rolling at 600 ° C. in the same manner as in Example 2 above, and were cooled with water to obtain a ^ F uniform crystal grain diameter d, The Vickers hardness H v, tensile strength σ _Β and elongation δ are as shown in Table 3.

As can be seen from Table 3, according to the present invention, each of the solidified molded articles has extremely excellent strength characteristics that surpass ultrahigh-strength steel having both strength and elongation without significantly impairing the high conductivity of copper. Can be: Table 3

* [(A) CU 97.7B e 2 C oo ( _{wt%), (b) Cu 39} . 85 Z r 015 ( % by weight) and (c) Cu C ro (wt%) Mechanical § b keying (MA) sample Hot solidified compact

Average grain size d, conductivity% l ACS *, tensile rust and elongation]

❖ I n t e r n a t i o n a l An n e a l e d Co p p e r S t a n d a r d

Industrial applicability

The bulk material of the tough nanocrystalline copper or copper alloy having high hardness, high strength and high conductivity of the present invention can be used as a conductive high-strength spring material for telecommunications equipment, and is lightweight for electric and electronic equipment. And miniaturization.

According to the present invention, by subjecting a material such as an elemental mixture of components forming a copper alloy material or a melted copper alloy to mechanical alloying (MA) or mechanical milling (MM), Copper crystal grains are ultra-fine to nano size, and finer nano-sized intermetallic compounds etc. are precipitated and dispersed as granular or nearly spherical particles in the same crystal phase. It is possible to produce more excellent nanocrystalline copper alloy materials by strengthening crystal grain refinement at the nano-size level that cannot be achieved and precipitation-dispersion of intermetallic compounds.

Further, according to the present invention, in the hot solidification molding of the nanocrystalline copper alloy powder, a rapid heating method using microwaves is used for heating the powder to the solidification molding temperature (even if it is not a dielectric substance, it can be used in the case of metal). If the powder is also a powder, microwave heating (microwave heating) can be applied) and / or if a low-frequency induction heating method is applied, the growth of crystal grains during the heating process is suppressed and the nanocrystalline copper alloy bulk The material can be manufactured more effectively.

Claims

1. A copper metal powder comprising an aggregate of copper metal nanocrystal particles, wherein the nanocrystal particles are nanocrystal particles having a size of 2 to 100 nm, and have high hardness and high conductivity. Having nanocrystalline copper metal powder.

2. Copper alloy powder consisting of aggregates of copper alloy nanocrystal particles, the alloying elements of which are beryllium, chromium, zirconium, titanium, silver, cobalt, nickel, zinc, iron, cadmium, manganese, aluminum, It is composed of at least one selected from molybdenum, vanadium, tungsten, niobium, tantalum, phosphorus, silicon, and boron.

In the case of two, the concentration contains 0.05 to 40% by mass of the copper alloy powder, and when there are two or more alloying elements, the total concentration is 0.05 to 45% by mass. Containing, said nanocrystalline copper alloy powder is solid solution strengthened by these alloy elements and crystal grain refinement strengthened to a size level of 2 to 100 nm to 100 nm, and is characterized by high hardness and high hardness. Nanocrystalline copper alloy powder with conductivity.

3-Copper alloy powder consisting of aggregates of copper alloy nanocrystal particles is used as precipitation / dispersion strengthening material and Z or crystal grain growth inhibiting material. (1) Beryllium, chromium, zirconium, titanium, silver, cobalt, At least one selected from one or more alloying elements selected from nickel, zinc, iron, cadmium, manganese, aluminum, molybdenum, vanadium, tungsten, niobium, tantalum, phosphorus, silicon and boron; Or (2) a nanocrystalline copper alloy powder having high hardness and high electrical conductivity, characterized in that at least one of the above-mentioned intermetallic compounds composed of each element and copper is present. .

4. Copper or copper alloy powder consisting of aggregates of copper or copper alloy nanocrystal particles is used as a substance that suppresses the decrease in conductivity due to solid solution impurities in copper or copper alloy, as zinc, cadmium, silicon, phosphorus, or phosphorus. The nanocrystalline copper having high hardness and high electrical conductivity according to any one of claims 1 to 3, wherein at least one of oxygen is present. Or copper alloy powder.

5. Copper or copper alloy powder consisting of an aggregate of copper or copper alloy nanocrystal particles containing oxygen in the form of a metal or metalloid oxide in an amount of 0.05 to 1.0% by mass. 5. The nanocrystalline copper or copper alloy powder having high hardness and high electrical conductivity according to any one of claims 1 to 4, wherein the powder is characterized in that the powder comprises:

6. The copper metal nanocrystal particles are obtained by mechanically milling (MM) a lump, flake, granular, or powdered copper metal material using a ball mill or the like. Item 6. The nanocrystalline copper metal powder having high hardness and high conductivity according to any one of Items 1, 4 and 5.

7. The copper alloy nanocrystal particles are in a lump, flake, or granular form. A mixture of the constituent materials of the copper alloy is mechanically milled (MA) or mechanically milled (MM) using a pole mill or the like. 6. The nanocrystalline copper alloy powder having high hardness and high conductivity according to any one of claims 2 to 5, characterized in that the powder is obtained by the method described above.

8. The copper alloy nanocrystal particles are aggregated, flake, granular, powdered copper, beryllium copper, chromium copper, zirconia copper, silver copper, titanium copper, silicon bronze, kelmet alloy, brass, aluminum bronze , Nickel copper, nickel bronze, Corson alloy, copper, manganese alloy, phosphor bronze, nickel silver, cupper nickel, other alloying elements or alloys. The method according to any one of claims 2 to 5, wherein the constituent material is obtained by mechanical milling (MM) or mechanical alloying (MA) using a ball mill or the like. A nanocrystalline copper alloy powder having high hardness and high conductivity according to the description.

9. In the mechanical alloying (MA) or mechanical milling (MM) process, input by selecting the mass ratio of the grinding media to the raw material powder used in ball mills and the like, and selecting the operating energy such as Z or ball mills. By adjusting the mechanical energy to be applied, the crystal grain size of other substances such as (2) nanocrystalline copper or a copper alloy or the second phase composed of copper and other elements in the aggregate of nanocrystalline particles, And / or (3) controlling the production of other substances such as the second phase, or (3) the amount of the production, at least one of (1) to (3); Range The nanocrystalline copper alloy powder having high hardness and high conductivity according to any one of Items 1 to 8.

10. Solidification molding between nanocrystal particle aggregate (powder) obtained by mechanical alloying (MA) or mechanical milling (MM) when copper alloy powder consisting of aggregate of copper or copper alloy nanocrystal particles is obtained 10. The method according to any one of claims 1 to 9, wherein titanium, zirconium or vanadium is contained in the process in an amount of 0.01 to 5.0% by mass. 4. A nanocrystalline copper or copper alloy powder having high hardness and high electrical conductivity according to 1.

1 1 · High hardness characterized by a large number of nanocrystalline copper or copper alloy powders according to any one of claims 1 to 0 being claimed · High strength and high strength Strong conductive nanocrystalline copper or copper alloy bulk material.

1 2. Spark plasma sintering of the copper powder or the copper alloy powder according to any one of claims 1 to 10 at a temperature of 250 to 700 ° C (S park Plasma S intering), Hot pressing, Sheath rolling (S heath Ro IIing), Hot forging, Extrusion molding, Hot isostatic pressing (HIP), etc. A method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness, high strength and high conductivity, characterized in that the bulk material is a nanocrystalline copper or copper alloy bulk material.

1 3. Discharge plasma sintering of the copper alloy powder according to any one of claims 2 to 10 at a temperature of 250 to 700 ° C, hot pressing, extrusion molding, hot forging, After forming into a nanocrystalline copper alloy bulk material by solidifying by hot isostatic pressing, rolling or other vacuum hot solidification molding or explosion molding, the bulk material is heated to 100 to 600 ° C. A method for producing a tough nanocrystalline copper alloy bulk material with high hardness, high strength and high conductivity, characterized by annealing at a temperature (input of thermal energy).

1 4. The atmosphere in which mechanical milling or mechanical alloying is performed is selected from the group consisting of (1) an inert gas such as argon gas, (2) N ₂ gas, and (3) NH ₃ gas. (4) The tough nanoparticle having high hardness and high conductivity according to claim 12 or 13, wherein the atmosphere is a mixed gas atmosphere of two or more kinds selected from (1) to (3). Manufacturing method of bulk material of crystalline copper or copper alloy.

15. The mechanical milling or mechanical alloying atmosphere is a gas atmosphere to which a reducing substance such as a slight amount of H ₂ gas is added. 4. A method for producing a bulk material of tough nanocrystalline copper or copper alloy having high hardness and high electrical conductivity according to 1).

1 6. The scope of the request, characterized in that the atmosphere in which the mechanical milling or the mechanical alloying is performed is a vacuum or a reduced atmosphere in which a reducing substance such as H ₂ gas is added in a vacuum or a vacuum. 4. The method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness and high strength and high conductivity according to item 2 or 13.

1 7. Rapid heating of the powder of nanocrystalline copper or copper alloy according to any one of claims 1 to 10 to the hot solidification molding temperature and holding of Z or the same hot solidification molding temperature Therefore, a method for producing a tough nanocrystalline copper or copper alloy bulk material having high hardness, high strength and high conductivity, characterized by using a microwave heating method or a low-frequency induction heating method. Ί 8. In order to perform rapid hot solidification molding of the nanocrystalline copper or copper alloy powder described in any of paragraphs 1 to 10 of Claims 1 to 10; High hardness ■ High strength, high conductivity, tough nanocrystals characterized by being made into bulk material of nanocrystalline copper or copper alloy by pressure sintering or low frequency induction heating and pressure sintering A method for producing a copper or copper alloy bulk material.