US20180297118A1 - Porous copper body and porous copper composite part - Google Patents

Porous copper body and porous copper composite part Download PDF

Info

Publication number
US20180297118A1
US20180297118A1 US15/580,055 US201615580055A US2018297118A1 US 20180297118 A1 US20180297118 A1 US 20180297118A1 US 201615580055 A US201615580055 A US 201615580055A US 2018297118 A1 US2018297118 A1 US 2018297118A1
Authority
US
United States
Prior art keywords
copper
porous
fibers
composite part
porous copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US15/580,055
Other languages
English (en)
Inventor
Koichi Kita
Jun Kato
Toshihiko Saiwai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Assigned to MITSUBISHI MATERIALS CORPORATION reassignment MITSUBISHI MATERIALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KITA, KOICHI, KATO, JUN, SAIWAI, Toshihiko
Publication of US20180297118A1 publication Critical patent/US20180297118A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1103—Making porous workpieces or articles with particular physical characteristics
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • 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
    • C22C1/08—Alloys with open or closed pores
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent

Definitions

  • the present invention relates to a porous copper body made of copper or a copper alloy, and a porous copper composite part in which the porous copper body is bonded to a main body of the composite part.
  • porous copper body and the porous copper composite part are used, for example, as electrodes and current collectors in various batteries, heat exchanger components, silencing components, filters, impact-absorbing components, and the like.
  • PTL 1 discloses a heat exchange member in which a porous copper layer is formed on the surface of a copper tube.
  • PTL 2 discloses that the surface of a porous metal body with a three-dimensional network structure is reformed into a porous metal film.
  • a powder made of copper or a copper alloy is used as a raw material, and the raw material powder is temporarily bonded to the surface of the copper tube using a binder, followed by an oxidation treatment and a reduction treatment to form the porous copper layer.
  • an uneven metal body with the three-dimensional network structure is subjected to an oxidation treatment to form the oxidation film, and then subjected to a reduction treatment. Thereby, the porous metal body in which the surface of the uneven metal body is reformed into the porous metal film, is formed.
  • a porous metal body disclosed in PTL 2 an oxidation treatment and a reduction treatment are performed after forming an uneven metal body with a three-dimensional network structure. Since the porosity and specific surface area of the porous metal body itself are highly dependent on the properties of the uneven metal body before being subjected to the oxidation treatment and the reduction treatment, it is difficult to obtain a porous metal body with sufficient porosity and a specific surface area. Further, in an uneven metal body manufactured using electrolytic plating or a metal powder, it is difficult to retain sufficient strength.
  • PTL 2 discloses an example using an uneven metal body made of stainless steel, PTL 2 does not disclose conditions of the oxidation treatment and the reduction treatment which can refine the surface of an uneven metal body made of copper or a copper alloy.
  • the present invention has been made in consideration of the above-described circumstances, and an objective thereof is to provide a porous copper body which has a sufficient porosity and specific surface area, and a porous copper composite part in which the porous copper body is bonded to a main body of the composite part.
  • porous copper body of the present invention includes a skeleton having a three-dimensional network structure, in which a porous layer having unevenness is formed on a surface of the skeleton, a specific surface area is set to be 0.01 m 2 /g or greater, and the porosity is set to be in a range of 50% to 90%.
  • the porous layer having unevenness is formed on the surface of the skeleton having the three-dimensional network structure, the specific surface area is set to be 0.01 m 2 /g or greater, and the porosity is set to be in a range of 50% to 90%. Therefore, it is possible to greatly improve heat exchange efficiency via, for example, the surface of the porous skeleton and the like.
  • the skeleton be constituted by a sintered body made of a plurality of copper fibers, and in each of the copper fibers, a diameter R be set to be in a range of 0.02 mm to 1.0 mm and a ratio L/R of a length L to the diameter R be set to be in a range of 4 to 2500.
  • the copper fibers in which the diameter R is set to be in a range of 0.02 mm to 1.0 mm, and the ratio L/R of the length L to the diameter R is set to be in a range of 4 to 2500 are sintered. Therefore, voids are sufficiently retained between the copper fibers, and the shrinkage ratio in the sintering can be limited. Accordingly, it is possible to raise the porosity relatively high to 50% to 90%, and the dimensional accuracy is excellent.
  • porous copper composite part of the present invention includes: a main body of the composite part; and the above-described porous copper body bonded to the main body of the composite part.
  • the porous copper composite part having such configuration the above-described porous copper body having a high porosity, a large specific surface area, excellent dimensional accuracy, and excellent strength is strongly bonded to the main body of the composite part. Therefore, as the porous copper composite part, various excellent properties such as the heat transfer properties and the electrical conductivity are exhibited in addition to the properties of the porous copper body itself which has a large surface area and is excellent in heat exchange efficiency and the like.
  • a bonding surface of the main body of the composite part, to which the porous copper body is bonded be made of copper or a copper alloy, and the porous copper body and the main body of the composite part be bonded to each other through sintering.
  • the porous copper body and the main body of the composite part are integrally bonded to each other through the sintering, and thus the porous copper body and the main body of the composite part are strongly bonded to each other. Therefore, as the porous copper composite part, various excellent properties such as the strength, the heat transfer properties, and the electrical conductivity are exhibited.
  • a porous copper body which has sufficient porosity and specific surface area, and a porous copper composite part in which the porous copper body is bonded to a main body of the composite part.
  • FIG. 1 is an enlarged schematic view of a porous copper body according to a first embodiment of the present invention.
  • FIG. 2 is a partially enlarged observation image of the porous copper body shown in FIG. 1 .
  • FIG. 3 is a flowchart showing an example of a method for manufacturing the porous copper body shown in FIG. 1 .
  • FIG. 4 is a view showing a manufacturing process of manufacturing the porous copper body shown in FIG. 1 .
  • FIG. 5 is a view showing an external appearance of a porous copper composite part according to a second embodiment of the present invention.
  • FIG. 6 is a flowchart showing an example of a method for manufacturing the porous copper composite part shown in FIG. 5 .
  • FIG. 7 is an external view of a porous copper composite part according to still another embodiment of the present invention.
  • FIG. 8 is an external view of a porous copper composite part according to still another embodiment of the present invention.
  • FIG. 9 is an external view of a porous copper composite part according to still another embodiment of the present invention.
  • FIG. 10 is an external view of a porous copper composite part according to still another embodiment of the present invention.
  • FIG. 11 is an external view of a porous copper composite part according to still another embodiment of the present invention.
  • FIG. 12 is an external view of a porous copper composite part according to still another embodiment of the present invention.
  • FIG. 13 is an enlarged observation image of a bonding portion of a porous copper body according to Inventive Example 1.
  • porous copper body 10 according to a first embodiment of the present invention will be described with reference to FIG. 1 to FIG. 4 .
  • the porous copper body 10 includes a skeleton 13 formed by sintering a plurality of copper fibers 11 .
  • Each of the copper fibers 11 is made of copper or a copper alloy, and has a diameter R set to be in a range of 0.02 mm to 1.0 mm and a ratio L/R of a length L to the diameter R set to be in a range of 4 to 2500.
  • each of the copper fibers 11 is made of C1100 (tough pitch copper).
  • the copper fibers 11 are subjected to shape imparting such as twisting and bending.
  • an apparent density D A is set to be 51% or less of a true density D T of the copper fibers 11 .
  • the shape of each copper fiber 11 is an arbitrary shape, such as a linear shape and a curved shape, as long as the apparent density D A is 51% or less of the true density D T of the copper fibers 11 .
  • a processing for imparting a predetermined shape such as twisting and bending
  • it is possible to improve the isotropy of various properties such as the heat transfer properties and the electrical conductivity of the porous copper body 10 .
  • a porous layer 12 having scale-like unevenness is formed on the surface of the skeleton 13 (copper fibers 11 ).
  • the porous layers 12 formed on surfaces thereof are integrally bonded to each other.
  • This porous layer 12 has a scale-like unevenness as described above, and a specific surface area of the entirety of the porous copper body 10 is set to be 0.01 m 2 /g or greater, and the porosity thereof is set to be in a range of 50% to 90%.
  • the upper limit of the specific surface area of the entirety of the porous copper body 10 is 0.50 m 2 /g.
  • a range of the specific surface area of the entirety of the porous copper body 10 is preferably 0.03 m 2 /g to 0.4 m 2 /g, and more preferably 0.05 m 2 /g to 0.30 m 2 /g.
  • the range of the porosity is 60% to 90%, and more preferably 70% to 90%.
  • the copper fibers 11 as a raw material of the porous copper body 10 according to this embodiment are distributed from a distributor 31 toward the inside of a stainless-steel container 32 to bulk-fill the stainless-steel container 32 . Thereby, the copper fibers 11 are laminated (copper fibers lamination step S 01 ).
  • the copper fibers lamination step S 01 a plurality of the copper fibers 11 are laminated so that a bulk density D P after the filling becomes 50% or less of the true density D T of the copper fibers 11 .
  • the copper fibers 11 are subjected to a processing for imparting a shape such as twisting and bending, and thus it is possible to retain three-dimensional and isotropic voids between the copper fibers 11 during lamination.
  • the copper fibers 11 bulk-filling the stainless-steel container 32 are subjected to an oxidation-reduction treatment (oxidation-reduction treatment step S 02 ).
  • the oxidation-reduction treatment step S 02 includes: an oxidation treatment step S 21 of performing an oxidation treatment on the copper fibers 11 , and a reduction treatment step S 22 of reducing and sintering the copper fibers 11 subjected to the oxidation treatment.
  • the stainless-steel container 32 filled with the copper fibers 11 is put in a heating furnace 33 and heated in an air atmosphere to perform an oxidation treatment on the copper fibers 11 (oxidation treatment step S 21 ).
  • an oxide layer for example, with a thickness of 1 ⁇ m to 100 ⁇ m is formed on a surface of each of the copper fibers 11 .
  • Conditions of the oxidation treatment step S 21 in this embodiment are set such that the holding temperature is in a range of 520° C. to 1050° C. and the holding time is in a range of 5 minutes to 300 minutes.
  • the holding temperature in the oxidation treatment step S 21 is lower than 520° C., there is a concern that the oxide layers are not sufficiently formed on the surfaces of the copper fibers 11 .
  • the holding temperature in the oxidation treatment step S 21 is higher than 1050° C., there is a concern that the copper oxide (II) formed through the oxidation may be decomposed.
  • the holding temperature in the oxidation treatment step S 21 is set to be 520° C. to 1050° C.
  • the lower limit of the holding temperature be set to be 600° C. or higher, and the upper limit of the holding temperature be set to be 1000° C. or lower in order to surely form the oxide layers on the surfaces of the copper fibers 11 .
  • the holding time in the oxidation treatment step S 21 is shorter than 5 minutes, there is a concern that the oxide layers may not be sufficiently formed on the surfaces of the copper fibers 11 .
  • the holding time in the oxidation treatment step S 21 is longer than 300 minutes, there is a concern that oxidation may progress to the inside of the copper fibers 11 , the copper fibers 11 may become brittle, and the strength thereof may decrease.
  • the holding time in the oxidation treatment step S 21 is set to be in a range of 5 minutes to 300 minutes. It is preferable that the lower limit of the holding time in the oxidation treatment step S 21 be set to be 10 minutes or longer in order to surely form the oxide layers on the surfaces of the copper fibers 11 . It is preferable that the upper limit of the holding time in the oxidation treatment step S 21 be set to be 100 minutes or shorter in order to surely limit embrittlement of the copper fibers 11 due to the oxidation thereof.
  • the stainless steel container 32 filled with the copper fibers 11 is put in the heating furnace 34 and is heated in a reduction atmosphere. According to this, the oxidized copper fibers 11 are subjected to a reduction treatment, and the copper fibers 11 are bonded to each other (reduction treatment step S 22 ). Thereby, the above-described porous layer 12 is formed.
  • Conditions of the reduction treatment step S 22 in this embodiment are set such that the atmosphere is a mixed gas atmosphere of nitrogen and hydrogen, the holding temperature is in a range of 600° C. to 1080° C., and the holding time is in a range of 5 minutes to 300 minutes.
  • the holding temperature in the reduction treatment step S 22 is lower than 600° C.
  • the oxide layers formed on the surfaces of the copper fibers 11 may not be sufficiently reduced.
  • the holding temperature in the reduction treatment step S 22 is higher than 1080° C.
  • the copper fibers are heated to near the melting point of copper, and thus there is a concern that the unevenness of the porous layer 12 may become small and thus the specific surface area may decrease, and that the strength and the porosity may decrease.
  • the holding temperature in the reduction treatment step S 22 is set to be 600° C. to 1080° C. It is preferable that the lower limit of the holding temperature in the reduction treatment step S 22 be set to be 650° C. or higher in order to surely reduce the oxide layers formed on the surfaces of the copper fibers 11 . It is preferable that the upper limit of the holding temperature in the reduction treatment step S 22 be set to be 1050° C. or lower in order to surely limit a decrease in the specific surface area, the strength and the porosity.
  • the holding time in the reduction treatment step S 22 is shorter than 5 minutes, there is a concern that the oxide layers formed on the surfaces of the copper fibers 11 may not be sufficiently reduced.
  • the holding time in the reduction treatment step S 22 is longer than 300 minutes, there is a concern that the unevenness of the porous layer 12 may become small and thus the specific surface area may decrease.
  • the holding time in the reduction treatment step S 22 is set to be in a range of 5 minutes to 300 minutes. It is preferable that the lower limit of the holding temperature in the reduction treatment step S 22 be set to be 10 minutes or longer in order to surely reduce the oxide layers formed on the surfaces of the copper fibers 11 . It is preferable that the upper limit of the holding time in the reduction treatment step S 22 be set to be 100 minutes or shorter in order to surely maintain the unevenness of the porous layer 12 .
  • the oxide layers are formed on the surfaces of the copper fibers 11 by the oxidation treatment step S 21 , and a plurality of the copper fibers 11 are cross-linked through the oxide layers. Then, by performing the reduction treatment S 22 , the oxide layers formed on the surfaces of the copper fibers 11 are reduced so as to form the above-described porous layers 12 .
  • the stainless steel container 32 filled with the copper fibers 11 is put in the heating furnace 35 to sinter the copper fibers 11 (sintering step S 03 ).
  • Conditions of the sintering step S 03 in this embodiment are set such that the atmosphere is an inert gas atmosphere such as Ar and N 2 (Ar atmosphere in this embodiment), the holding temperature is in a range of 600° C. to 1080° C., and the holding time is in a range of 5 minutes to 300 minutes.
  • the atmosphere is an inert gas atmosphere such as Ar and N 2 (Ar atmosphere in this embodiment)
  • the holding temperature is in a range of 600° C. to 1080° C.
  • the holding time is in a range of 5 minutes to 300 minutes.
  • the sintering step S 03 the sintering of the copper fiber 11 is progressed.
  • the closed pore is formed in the reduction treatment step S 22 , the closed pore is removed by volume diffusion.
  • the holding temperature in the sintering step S 03 is lower than 600° C.
  • the volume diffusion may not sufficiently progress and thus the sintering may become insufficient.
  • the holding temperature in the sintering step S 03 is higher than 1080° C.
  • the copper fibers are heated to near the melting point of copper, and thus there is a concern that the shape cannot be maintained and strength and porosity may decrease.
  • the holding temperature in the sintering step S 03 is set to be 600° C. to 1080° C. It is preferable to set the lower limit of the holding temperature in the sintering step S 03 to be 700° C. or higher in order to surely sinter the copper fibers 11 . It is preferable to set the upper limit of the holding temperature in the sintering step S 03 to be 1000° C. or lower in order to surely limit a decrease in strength and the porosity.
  • the sintering step S 03 is consecutively performed after the reduction treatment step S 22 , it is preferable in terms of energy saving to set the holding temperatures in the sintering step S 03 and the reduction treatment step S 22 to be the same temperature.
  • the holding time in the sintering step S 03 is shorter than 5 minutes, there is a concern that the volume diffusion may not sufficiently progress and thus the sintering may become insufficient.
  • the holding time in the sintering step S 03 is longer than 300 minutes, there is a concern that thermal shrinkage due to the sintering may increase, the shape cannot be maintain, and thus the specific surface area and the porosity may decrease.
  • the holding time in the sintering step S 03 is set to be 5 minutes to 300 minutes. It is preferable to set the lower limit of the holding time in the sintering step S 03 to be 10 minutes or longer in order to surely sinter the copper fibers 11 . It is preferable to set the upper limit of the holding time in the sintering step S 03 to be 100 minutes or shorter in order to surely limit the thermal shrinkage due to the sintering.
  • the copper fibers 11 are sintered so as to form the skeleton 13 , and the porous layer 12 is formed on the surface of the skeleton 13 .
  • the porous copper body 10 according to this embodiment is manufactured.
  • the porous layer having the unevenness is formed on the surface of the skeleton 13 (copper fibers 11 ), the specific surface area is set to be 0.01 m 2 /g or greater. Therefore, it is possible to greatly improve heat exchange efficiency via, for example, the surface of the porous skeleton and the like.
  • the skeleton 13 is formed by sintering the copper fibers 11 in which the diameter R is set to be in a range of 0.02 mm to 1.0 mm, and the ratio L/R of the length L to the diameter R is set to be in a range of 4 to 2500. Therefore, voids are sufficiently retained between the copper fibers 11 , and it is possible to limit the shrinkage ratio in the sintering. As a result, the porosity is high and the dimensional accuracy is excellent.
  • the copper fibers 11 are bonded to each other by integrally bonding the porous layers 12 formed on the surface thereof to each other. Therefore, the sintering strength can be greatly improved.
  • This embodiment includes the copper fibers lamination step S 0 I in which the copper fibers 11 having the diameter R in a range of 0.02 mm to 1.0 mm and the ratio L/R of the length L to the diameter R in a range of 4 to 2500 are laminated so that the bulk density D P is 50% or less of the true density D T of the copper fibers 11 . Therefore, it is possible to retain voids between the copper fibers 11 even in the sintering step S 02 and to limit shrinkage. According to this, it is possible to manufacture the porous copper body 10 with high porosity and excellent dimensional accuracy.
  • the apparent density D A of the porous copper body 10 which is manufactured by sintering the copper fibers 11 laminated so that the bulk density D P is 50% or less of the true density D T of the copper fibers 11 , is set to be 51% or less of the true density D T of the copper fibers 11 . Therefore, shrinkage during the sintering is limited, and thus a high porosity can be retained.
  • the diameter R of the copper fibers 11 is less than 0.02 mm, there is a concern that a bonding area between the copper fibers 11 may be small and thus the sintering strength may be deficient.
  • the diameter R of the copper fibers 11 is greater than 1.0 mm, there is a concern that the number of contact points at which the copper fibers 11 come into contact with each other may be deficient and thus the sintering strength may be deficient.
  • the diameter R of the copper fibers 11 is set to be in a range of 0.02 mm to 1.0 mm. It is preferable that the lower limit of the diameter R of the copper fibers 11 be set to be 0.05 mm or greater, and the upper limit of the diameter R of the copper fibers 11 be set to be 0.5 mm or less in order to further improve strength.
  • the ratio L/R of the length L to the diameter R of the copper fibers 11 is less than 4, it is difficult for the bulk density D P to be 50% or less of the true density D T of the copper fibers 11 when laminating the copper fibers 11 , and thus there is a concern that it is difficult to obtain the porous copper body 10 with a high porosity.
  • the ratio L/R of the length L to the diameter R of the copper fibers 11 is greater than 2500, there is a concern that the copper fibers 11 cannot be uniformly dispersed and thus it is difficult to obtain the porous copper body 10 with a uniform porosity.
  • the ratio L/R of the length L to the diameter R of the copper fibers 11 is set to be in a range of 4 to 2500. It is preferable that the lower limit of the ratio L/R of the length L to the diameter R of the copper fibers 11 be set to be 10 or greater in order to further improve porosity. It is preferable that the upper limit of the ratio L/R of the length L to the diameter R of the copper fibers 11 be set to be 500 or less in order to surely obtain the porous copper body 10 with a uniform porosity.
  • the oxidation-reduction treatment step S 02 includes: the oxidation treatment step S 21 of oxidizing the copper fibers 11 ; and the reduction treatment step S 22 of reducing the oxidized copper fibers 11 . Therefore, as shown in FIG. 2 , it is possible to form the porous layers 12 on the surface of the copper fibers 11 . Thereby, it is possible to manufacture the porous copper body 10 with the specific surface area of 0.01 m 2 /g or greater and the porous of 50% to 90%.
  • the sintering step S 03 is performed after the oxidation-reduction treatment step S 02 . Therefore, the sintering can be surely conducted. Additionally, even in a case where the closed pore is formed in the reduction treatment step S 22 , it is possible to remove the closed pore and thus surely retain the strength.
  • a porous copper composite part 100 according to a second embodiment of the present invention will be described with reference to the accompanying drawings.
  • FIG. 5 shows the porous copper composite part 100 according to this embodiment.
  • the porous copper composite part 100 includes: a copper plate 120 (main body of the composite part) made of copper or a copper alloy; and a porous copper body 110 bonded to the surface of the copper plate 120 .
  • a plurality of copper fibers are sintered to form a skeleton with a three-dimensional network structure in the same manner as in the first embodiment.
  • the copper fibers are made of copper or a copper alloy, and have a diameter R set to be in a range of 0.02 mm to 1.0 mm, and a ratio L/R of a length L to the diameter R set to be in a range of 4 to 2500.
  • the copper fibers are made of, for example, C1100 (tough pitch copper).
  • the copper fibers are subjected to shape imparting such as twisting and bending.
  • an apparent density D A thereof is set to be 51% or less of a true density D T of the copper fibers.
  • the porous layers are formed on the surfaces of the skeleton (copper fibers) of the porous copper body 110 and the copper plate 120 . Thereby, minute unevenness is formed on the surfaces of the skeleton (copper fibers) and the copper plate 120 .
  • a porous layer formed on the surface of the skeleton (copper fibers) and a porous layer formed on the surface of the copper plate are integrally bonded to each other at bonding portions between the surfaces of the skeleton (copper fibers) constituting the porous copper body 110 and the copper plate 120 .
  • the above-described porous layer has a scale-like unevenness, a specific surface area of the entirety of the porous copper body 110 is set to be 0.01 m 2 /g or greater, and the porosity thereof is set to be in a range of 50% to 90%.
  • the copper plate 120 as a main body of the composite part is prepared (copper plate-disposing step S 100 ). Copper fibers are dispersed and laminated on the surface of the copper plate 120 (copper fibers lamination step S 101 ). In the copper fibers lamination step S 101 , a plurality of the copper fibers are laminated so that a bulk density D P is 50% or less of a true density D T of the copper fibers.
  • the surfaces of the copper fibers laminated on the surface of the copper plate 120 and the surface of the copper plate 120 are subjected to an oxidation-reduction treatment (oxidation-reduction treatment step S 102 ).
  • the oxidation-reduction treatment step S 102 includes: an oxidation treatment step S 121 of performing an oxidation treatment of the copper fibers and the copper plate 120 ; and a reduction treatment step S 122 of reducing and sintering the copper fibers and the copper plate 120 subjected to the oxidization treatment.
  • the copper plate 120 on which the copper fibers are laminated is put in a heating furnace, and is heated in an air atmosphere to perform an oxidization treatment on the copper fibers (oxidation treatment step S 121 ).
  • oxide layers with a thickness of 1 ⁇ m to 100 ⁇ m are formed on the surfaces of the copper fibers and the copper plate 120 .
  • Conditions of the oxidation treatment step S 121 in this embodiment are set such that the holding temperature is in a range of 520° C. to 1050° C. and preferably 600° C. to 1000° C., and the holding time is in a range of 5 minutes to 300 minutes and preferably 10 minutes to 100 minutes.
  • the copper plate 120 on which the copper fibers are laminated is put in a sintering furnace, and is heated in a reduction atmosphere to perform a reduction treatment on the oxidized copper fibers and the oxidized copper plate 120 (reduction treatment step S 122 ).
  • Conditions of the reduction treatment step S 121 in this embodiment are set such that the atmosphere is a mixed gas atmosphere of nitrogen and hydrogen, the holding temperature is in a range of 600° C. to 1080° C. and preferably 650° C. to 1050° C., and the holding time is in a range of 5 minutes to 300 minutes and preferably 10 minutes to 100 minutes.
  • a porous layer is formed on the surfaces of the copper fibers and the copper plate 120 and minute unevenness is formed.
  • the copper fibers are sintered to form the porous copper body 110 and bond the porous copper body 110 (copper fibers) and the copper plate 120 to each other (sintering and bonding step S 103 ).
  • the copper fibers are sintered and the copper fibers and the copper plate 120 are bonded to each other through the porous layer.
  • Conditions of the sintering and bonding step S 103 in this embodiment are set such that the atmosphere is an Ar gas atmosphere, the holding temperature is 600° C. to 1080° C. and preferably 700° C. to 1000° C., and the holding time is 5 minutes to 300 minutes and preferably 10 minutes to 100 minutes.
  • the porous copper composite part 100 according to this embodiment is manufactured.
  • the porous copper body 110 is obtained through sintering of the copper fibers having the diameter R set to be in a range of 0.02 mm to 1.0 mm and the ratio L/R of the length L to the diameter R set to be in a range of 4 to 2500, and thus has a high porosity and excellent strength and dimensional accuracy.
  • This porous copper body 110 is bonded to the surface of the copper plate 120 . Therefore, various properties thereof, such as the heat transfer properties and the electrical conductivity, are excellent.
  • the porous layers are formed on the surfaces of the skeleton (copper fibers) of the porous copper body 110 and the copper plate 120 . Therefore, the specific surface area of the entirety of the porous copper body 110 is set to be 0.01 m 2 /g or greater, the porosity thereof is set to be in a range of 50% to 90%, and thus it is possible to greatly improve the heat exchange efficiency via the surface of the porous skeleton and the like.
  • a porous layer formed on the surface of the skeleton (copper fibers) and a porous layer formed on the surface of the copper plate 120 are integrally bonded to each other at bonding portions between the surfaces of the skeleton (copper fibers) of the porous copper body 110 and the copper plate 120 . Therefore, the porous copper body 110 and the copper plate 120 are strongly bonded to each other, and thus various properties thereof, such as the strength of a bonding interface, the heat transfer properties, and the electrical conductivity, are excellent.
  • This embodiment includes the copper fibers lamination step S 01 in which the copper fibers 11 having the diameter R in a range of 0.02 mm to 1.0 mm and the ratio L/R of the length L to the diameter R in a range of 4 to 2500 are laminated on the surface of the copper plate 120 so that the bulk density D P is 50% or less of the true density D T of the copper fibers 11 . Therefore, it is possible to retain voids between the copper fibers 11 even in the sintering and bonding step S 103 and limit shrinkage. Thereby, it is possible to form the porous copper body 110 having high porosity and excellent dimensional accuracy. Accordingly, it is possible to manufacture a porous copper composite part 100 having various excellent properties such as the thermal conductivity and the electrical conductivity.
  • the copper fibers are laminated on the surface of the copper plate 120 made of copper or a copper alloy and the sintering and bonding step S 103 is performed. Therefore, it is possible to simplify the manufacturing process.
  • the surfaces of the copper fibers and the copper plate 120 are oxidized and then the oxidized surfaces of the copper fibers and the copper plate 120 are reduced. Therefore, the porous layers are formed on the surfaces of the copper fibers and the copper plate 120 and the minute unevenness is formed. Thereby, the bonding area is retained, and thus it is possible to strongly bond the copper fibers to each other and to the copper plate 120 .
  • porous copper body is manufactured using a manufacturing facility shown in FIG. 4
  • the porous copper body can be manufactured using another manufacturing facility.
  • the atmosphere of the oxidation treatment steps S 21 and S 121 has only to be an oxidation atmosphere in which copper or a copper alloy is oxidized at a predetermined temperature.
  • the atmosphere is not limited to the air atmosphere, and has only to be an atmosphere in which 10 vol % or greater of oxygen is contained in an inert gas (for example, nitrogen).
  • the atmosphere of the reduction treatment steps S 22 and S 122 has only to be a reduction atmosphere in which a copper oxide is reduced into metal copper or the copper oxide is decomposed at a predetermined temperature.
  • a nitrogen-hydrogen mixed gas or an argon-hydrogen mixed gas which contains several vol % or greater of hydrogen, a pure hydrogen gas, or an ammonia decomposed gas or a propane decomposed gas which is industrially used in many cases, and the like.
  • the embodiments are described such that copper fibers made of tough pitch copper (JIS C1100) or oxygen-free copper (JIS C1020) are used, there is no limitation thereto and as a material of the copper fibers 11 , it is possible to suitably use phosphorus deoxidized copper (JIS C1201, C1220), silver-containing copper (for example, Cu-0.02 to 0.5 mass % of Ag), chromium copper (for example, Cu-0.02 to 1.0 mass % of Cr), zirconium copper (for example, Cu-0.02 to 1.0 mass % of Zr), tin-containing copper (for example, Cu-0.1 to 1.0 mass % of Sn), and the like.
  • phosphorus deoxidized copper JIS C1201, C1220
  • silver-containing copper for example, Cu-0.02 to 0.5 mass % of Ag
  • chromium copper for example, Cu-0.02 to 1.0 mass % of Cr
  • zirconium copper for example, Cu-0.02 to 1.0 mass % of
  • the silver-containing copper, the chromium copper, the tin-containing copper, the zirconium copper and the like which are excellent in high-temperature strength.
  • the embodiments are described such that the skeleton of the porous copper body is formed by sintering the copper fibers, there is no limitation thereto and the same effect is expected by using a porous copper body such as fiber non-woven fabric and a metal filter as a raw material.
  • porous copper composite part having a structure shown in FIG. 5 is described as an example, there is no limitation thereto and a porous copper composite part having a structure as shown in FIG. 7 to FIG. 12 may be employed.
  • a porous copper composite part 200 in which a plurality of copper tubes 220 as a main body of the composite part are inserted into a porous copper body 210 , may be employed.
  • a porous copper composite part 300 in which a copper tube 320 as a main body of the composite part curved in a U-shape is inserted into a porous copper body 310 , may be employed.
  • a porous copper composite part 400 in which a porous copper body 410 is bonded to an inner peripheral surface of a copper tube 420 as a main body of the composite part, may be employed.
  • a porous copper composite part 500 in which a porous copper body 510 is bonded to an outer peripheral surface of a copper tube 520 as a main body of the composite part, may be employed.
  • porous copper composite part 600 in which porous copper bodies 610 are bonded to an inner peripheral surface and an outer peripheral surface of a copper tube 620 as a main body of the composite part, may be employed.
  • porous copper composite part 700 in which porous copper body 710 are bonded to both surfaces of a copper plate 720 as a main body of the composite part, may be employed.
  • porous copper bodies having 30 mm of width ⁇ 200 mm of length ⁇ 5 mm of thickness were manufactured using raw materials for sintering shown in Table 1.
  • the raw material filled a forming die without imparting a pressure.
  • a mass M (g) and a volume V (cm 3 ) of the obtained porous copper body, and a true density D T (g/cm 3 ) of the copper fibers constituting the porous copper body were measured, and the apparent density Ratio D A /D T , and the porosity P (%) were calculated using the following expressions.
  • the true density D T was measured by an under-water method using a precision balance.
  • the obtained porous copper body was processed into a sample having 10 mm of width ⁇ 100 mm of length ⁇ 5 mm of thickness. Then, a tensile test was conducted using a universal tensile testing machine, and a maximum tensile load S max (N) was divided by an apparent sample sectional area of 50 mm 2 , thereby measuring a maximum tensile strength S (N/mm 2 ). The maximum tensile strength S obtained by the above measurement varies depending on the apparent density.
  • the value S/(D A /D T ) obtained by normalizing the maximum tensile strength S (N/mm 2 ) using the apparent density ratio D A /D T was defined as the relative tensile strength S R (N/mm 2 ) and compared.
  • Air 730 30 Ar—3% H 2 840 30 Ar 960 90 Examples 2 Air 600 120 N 2 —3% H 2 650 60 Ar 910 30 3 Air 950 60 N 2 —20% H 2 600 20 Ar 740 150 4 Air 700 60 N 2 —3% H 2 750 180 N 2 890 15 5 Air 800 60 Ar—3% H 2 1070 120 N 2 630 280 6 Air 1040 5 Ar—3% H 2 660 10 N 2 1070 5 7 Air 530 290 100% H 2 780 90 Ar 780 100 8 Air 650 30 N 2 —3% H 2 700 60 Ar 830 120 9 Air 1000 15 Ar—3% H 2 950 300 N 2 730 60 10 Air 750 60 Ar—3% H 2 900 60 Ar 770 30 11 Air 675 90 N 2 —3%
  • Comparative Example 1 where the electrolyte copper powder with an average particle size of 0.06 mm was used as a raw material, high porosity and specific surface area could not be retained.
  • the specific surface area was large and the porosity was high. Additionally, it was confirmed that the relative tensile strength was excellent.
  • the present invention is applicable to electrodes and current collectors in various batteries, heat exchanger components, silencing members, filters, impact-absorbing members, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
US15/580,055 2015-06-12 2016-05-24 Porous copper body and porous copper composite part Abandoned US20180297118A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015119522A JP6065058B2 (ja) 2015-06-12 2015-06-12 銅多孔質体、及び、銅多孔質複合部材
JP2015-119522 2015-06-12
PCT/JP2016/065283 WO2016199571A1 (ja) 2015-06-12 2016-05-24 銅多孔質体、及び、銅多孔質複合部材

Publications (1)

Publication Number Publication Date
US20180297118A1 true US20180297118A1 (en) 2018-10-18

Family

ID=57503543

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/580,055 Abandoned US20180297118A1 (en) 2015-06-12 2016-05-24 Porous copper body and porous copper composite part

Country Status (6)

Country Link
US (1) US20180297118A1 (ja)
EP (1) EP3308884A4 (ja)
JP (1) JP6065058B2 (ja)
KR (1) KR20180018494A (ja)
CN (1) CN107530777A (ja)
WO (1) WO2016199571A1 (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6733286B2 (ja) * 2016-04-27 2020-07-29 三菱マテリアル株式会社 銅多孔質体の製造方法、及び、銅多孔質複合部材の製造方法
JP2019086259A (ja) * 2017-11-09 2019-06-06 三菱マテリアル株式会社 気化部材用銅多孔質体、沸騰冷却器、及び、ヒートパイプ
KR102387629B1 (ko) * 2018-06-29 2022-04-18 주식회사 엘지화학 금속폼의 제조 방법
PL441413A1 (pl) * 2022-06-07 2023-12-11 Sieć Badawcza Łukasiewicz - Instytut Metali Nieżelaznych Sposób wytwarzania materiału kompozytowego na bazie brązu cynowego
PL441415A1 (pl) * 2022-06-07 2023-12-11 Sieć Badawcza Łukasiewicz - Instytut Metali Nieżelaznych Sposób wytwarzania materiału kompozytowego na bazie brązu cynowego

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2825005B2 (ja) * 1993-03-19 1998-11-18 日本重化学工業株式会社 多孔金属の製造方法とその製造方法により得られた多孔金属
IL108860A (en) * 1994-03-04 1998-10-30 Elisra Gan Ltd Heat radiating element
JP2000192107A (ja) * 1998-12-25 2000-07-11 Kogi Corp 多孔質金属及びその製造方法
JP4812823B2 (ja) * 2008-10-27 2011-11-09 Ｎｔｎ株式会社 複層軸受の製造方法
CN102305564A (zh) * 2011-08-26 2012-01-04 华南理工大学 一种纤维烧结式微热管及其制造方法
JP5825598B2 (ja) * 2012-03-13 2015-12-02 国立研究開発法人産業技術総合研究所 金属多孔体及び金属多孔体の製造方法。
CN103465543B (zh) * 2013-09-29 2015-07-29 西北有色金属研究院 强化沸腾传热用双重孔结构多孔铜材料的制备方法
JP6011593B2 (ja) * 2014-10-22 2016-10-19 三菱マテリアル株式会社 銅多孔質焼結体の製造方法及び銅多孔質複合部材の製造方法

Also Published As

Publication number Publication date
EP3308884A1 (en) 2018-04-18
EP3308884A4 (en) 2018-11-14
KR20180018494A (ko) 2018-02-21
WO2016199571A1 (ja) 2016-12-15
JP6065058B2 (ja) 2017-01-25
JP2017002374A (ja) 2017-01-05
CN107530777A (zh) 2018-01-02

Similar Documents

Publication Publication Date Title
US10478896B2 (en) Porous copper body, porous copper composite part, method for manufacturing porous copper body, and method for manufacturing porous copper composite part
US20180297118A1 (en) Porous copper body and porous copper composite part
US10493528B2 (en) Porous copper body, porous copper composite part, method for manufacturing porous copper body, and method for manufacturing porous copper composite part
EP3210698B1 (en) Copper porous sintered body, copper porous composite member, method for manufacturing copper porous sintered body, and method for manufacturing copper porous composite member
KR20140037104A (ko) 알루미늄 전해 커패시터용 전극 재료 및 이의 제조 방법
JP6589402B2 (ja) 銅多孔質体、銅多孔質複合部材、銅多孔質体の製造方法、及び、銅多孔質複合部材の製造方法
WO2018135575A1 (ja) 銅多孔質体、銅多孔質複合部材、銅多孔質体の製造方法、及び、銅多孔質複合部材の製造方法
US20210062300A1 (en) Metal porous material, fuel cell, and method of producing metal porous material
US20190076927A1 (en) Porous copper body, porous copper composite member, method for producing porous copper body, and method for producing porous copper composite member
CN116133732A (zh) 镍铬多孔体及镍铬多孔体的制造方法
JP6249060B2 (ja) 銅多孔質複合部材
JP2018193584A (ja) 銅多孔質体、銅多孔質複合部材、銅多孔質体の製造方法、及び、銅多孔質複合部材の製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: MITSUBISHI MATERIALS CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KITA, KOICHI;KATO, JUN;SAIWAI, TOSHIHIKO;SIGNING DATES FROM 20170711 TO 20170714;REEL/FRAME:044314/0152

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION