JP2017002379A - Copper porous body, copper porous composite member, manufacturing method of copper porous body and manufacturing method of copper porous composite member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper porous body having stable properties without largely changing surface quality of a skeleton section under use environment, a copper porous composite member where the copper porous body is jointed to a member body, a manufacturing method of copper porous body and a manufacturing method of a copper porous composite member.SOLUTION: There is provided a copper porous body having a skeleton section with a three-dimensional network, an oxidation reduction layer formed by an oxidation reduction treatment on a surface of the skeleton section and oxygen concentration of whole skeleton section in a range of 0.03 mass% to 1.0 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a copper porous body made of copper or a copper alloy, a copper porous composite member obtained by bonding the copper porous body to a member body, a method for producing a copper porous body, and a copper porous composite. The present invention relates to a method for manufacturing a member.

The above-mentioned copper porous body and copper porous composite member are used as, for example, electrodes and current collectors, heat exchanger members, silencers, filters, impact absorbing members and the like in various batteries.
For example, Patent Document 1 proposes a heat transfer member having a three-dimensional network structure by using powder made of copper or a copper alloy as a raw material and sintering in a reducing atmosphere.
Patent Document 2 proposes a heat sink in which a porous body formed using a fiber made of copper or a copper alloy is joined to a pipe by energization joining.
Further, Patent Document 3 proposes a metal porous body obtained by modifying the surface of a metal porous body having a three-dimensional network structure into a porous metal film.

Japanese Patent Laid-Open No. 08-145592 JP 2006-253346 A Japanese Patent No. 5166615

  By the way, in patent document 1 and patent document 2, sintering is performed in an inert gas atmosphere or a reducing atmosphere, and in patent document 3, surface modification is performed by oxidation-reduction treatment. Here, Patent Document 2 reports that when a copper porous body is heated with a hot plate, the color changes to black. That is, in the copper porous body as described in Patent Documents 1 to 3, when used for a long time in an environment where it is actually used, particularly under a weak corrosive environment such as high temperature of 100 ° C. or higher and water, for example, Different oxidation phenomena occur between the high temperature portion and the low temperature portion, and local characteristic changes may occur.

  The present invention has been made against the background as described above, and a copper porous body having stable characteristics in which the surface properties of the skeleton do not change greatly even under the use environment, and the copper porous body. It aims at providing the manufacturing method of the copper porous composite member, the copper porous body, and the copper porous composite member joined to the member main body.

  In order to solve such problems and achieve the above object, the copper porous body of the present invention is a copper porous body having a three-dimensional network structure skeleton part, on the surface of the skeleton part, It has a redox layer formed by a redox treatment, and the oxygen concentration of the entire skeleton is in the range of 0.03 mass% or more and 1.0 mass% or less.

According to the copper porous body having this configuration, since the redox layer formed by the redox treatment is provided on the surface of the skeleton portion, the specific surface area is increased, for example, the heat passing through the porous skeleton surface. Various characteristics such as exchange efficiency can be greatly improved.
And since the oxygen concentration of the whole skeleton part is in the range of 0.03 mass% or more and 1.0 mass% or less, a thin oxide film is formed on the skeleton part surface, It can suppress that a property changes.

Here, in the copper porous body of the present invention, the skeleton is preferably a sintered body of a plurality of copper fibers.
In this case, a sufficient gap is secured between the copper fibers, the shrinkage rate during sintering can be suppressed, and the porosity can be made relatively high.
And since the oxygen concentration of the whole skeleton part made of a sintered body is 0.03 mass% or more and 1.0 mass% or less, the deterioration of the copper fiber and the deterioration of the joint part between the copper fibers due to excessive oxidation. It is possible to stabilize the surface properties while maintaining the skeletal strength, thermal conductivity, and electrical conductivity without causing them.

In the copper porous body of the present invention, the copper fiber has a diameter R in the range of 0.02 mm to 1.0 mm, and a ratio L / R of the length L to the diameter R of 4 to 2500. It is preferable to be within the following range.
In this case, copper fibers having a diameter R in the range of 0.02 mm to 1.0 mm and a ratio L / R of the length L to the diameter R in the range of 4 to 2500 are baked. Since it is configured by being bonded, a sufficient gap is secured between the copper fibers, the shrinkage rate during sintering can be suppressed, the porosity can be increased, and the dimensions are further increased. Excellent accuracy.

The copper porous composite member of the present invention is characterized in that a member main body and the above-mentioned copper porous body are joined.
According to the copper porous composite member having this configuration, since the copper porous body having excellent surface texture stability is firmly joined to the member main body, the characteristics do not change greatly in the use environment, and the copper porous body As a quality composite member, excellent heat transfer characteristics and electrical conductivity can be exhibited.

Here, in the copper porous composite member of the present invention, the joint surface of the member main body with the copper porous body is composed of copper or a copper alloy, and the copper porous body and the member main body are sintered. It is preferable that it is joined by.
In this case, since the copper porous body and the member main body are integrally bonded by sintering, the copper porous body and the member main body are firmly bonded, and the copper porous composite Various properties such as excellent strength, heat transfer characteristics and conductivity are exhibited as members.

  The method for producing a copper porous body according to the present invention is a method for producing a copper porous body for producing the above-described copper porous body, wherein the redox layer is formed by oxidation-reduction treatment of the skeleton portion. It is characterized by comprising a treatment step and a stabilization treatment step for oxidizing the surface of the skeleton part.

  According to the method for producing a copper porous body having this configuration, an oxidation-reduction treatment step for forming the oxidation-reduction layer by oxidation-reduction treatment of the skeleton portion, a stabilization treatment step for oxidizing the surface of the skeleton portion, Therefore, in the stabilization process, an oxide film can be formed on the surface of the skeleton part, and the change in surface properties under the use environment can be suppressed. In this stabilization treatment step, heat treatment under an oxidizing atmosphere, surface treatment with an acidic liquid, or the like can be applied.

Here, in the method for producing a copper porous body of the present invention, the skeleton may be formed by sintering a copper raw material.
In this case, by sintering the copper raw material, a skeleton having a three-dimensional network structure can be formed, and a copper porous body made of a sintered body can be obtained. Moreover, the oxygen concentration of the whole frame | skeleton part which consists of a sintered compact can be 0.03 mass% or more and 1.0 mass% or less by the stabilization process, and frame | skeleton intensity | strength, thermal conductivity, and electrical conductivity were maintained. It is possible to stabilize the surface texture as it is.

  The method for producing a copper porous composite member according to the present invention is a method for producing a copper porous composite member for producing a copper porous composite member in which a member main body and a copper porous body are joined. It has the joining process which joins the copper porous body manufactured by the manufacturing method of a body, and the said member main body, It is characterized by the above-mentioned.

  According to the method for producing a copper porous composite member having this configuration, the copper porous body produced by the above-described method for producing a copper porous body is provided, and the change in surface properties under the use environment is suppressed. Thus, it becomes possible to produce a copper porous composite member having excellent characteristic stability.

Here, in the method for producing a copper porous composite member of the present invention, a joining surface to which the copper porous body is joined in the member body is made of copper or a copper alloy, and the copper porous body It is preferable to join the member main body by sintering.
In this case, the member main body and the copper porous body can be integrated by sintering, and a copper porous composite member having excellent characteristic stability can be manufactured.

  According to the present invention, the surface property of the skeleton does not change greatly even under the use environment, and a copper porous body having stable characteristics, a copper porous composite member in which this copper porous body is joined to a member body, The manufacturing method of a copper porous body and the manufacturing method of a copper porous composite member can be provided.

It is an expansion schematic diagram of the copper porous body which is 1st embodiment of this invention. It is a flowchart which shows an example of the manufacturing method of the copper porous body shown in FIG. It is explanatory drawing which shows the manufacturing process which manufactures the copper porous body shown in FIG. It is external appearance explanatory drawing of the copper porous composite member which is 2nd embodiment of this invention. It is a flowchart which shows an example of the manufacturing method of the copper porous composite member shown in FIG. It is an external view of the copper porous composite member which is other embodiment of this invention. It is an external view of the copper porous composite member which is other embodiment of this invention. It is an external view of the copper porous composite member which is other embodiment of this invention. It is an external view of the copper porous composite member which is other embodiment of this invention. It is an external view of the copper porous composite member which is other embodiment of this invention. It is an external view of the copper porous composite member which is other embodiment of this invention.

  Hereinafter, a copper porous body, a copper porous composite member, a copper porous body manufacturing method, and a copper porous composite member manufacturing method according to embodiments of the present invention will be described with reference to the accompanying drawings. .

(First embodiment)
First, the copper porous body 10 which is 1st embodiment of this invention is demonstrated with reference to FIGS. 1-3.
The copper porous body 10 which is this embodiment has the frame | skeleton part 12 in which the some copper fiber 11 was sintered as shown in FIG.

Here, the copper fiber 11 is made of copper or a copper alloy, the diameter R is in the range of 0.02 mm or more and 1.0 mm or less, and the ratio L / R of the length L to the diameter R is 4 or more and 2500. Within the following range. In this embodiment, the copper fiber 11 is comprised by C1100 (tough pitch copper), for example.
In the present embodiment, the copper fiber 11 is given a shape such as twisting or bending. Further, in the copper porous body 10 is this embodiment, the apparent density D _A is less 51% of the true density D _T of the copper fibers 11. The shape of the copper fiber 11 is arbitrary as long as the apparent density D _A is 51% or less of the true density _DT of the copper fiber 11. When using a material that has been subjected to a predetermined shape-forming process by twisting, bending, or the like, the void shape between the fibers can be formed three-dimensionally and isotropically. As a result, the copper porous body 10 This leads to an improvement in isotropy of various characteristics such as heat transfer characteristics and conductivity.

The copper fiber 11 is adjusted to a predetermined converted fiber diameter by a drawing method, a coil cutting method, a wire cutting method, a melt spinning method, etc., and the length is further adjusted to satisfy a predetermined L / R. It is manufactured by cutting.
Here, the converted fiber diameter R is a value calculated based on the cross-sectional area A of each fiber, and is defined by the following equation assuming that it is a perfect circle regardless of the cross-sectional shape.
R = (A / π) ^1/2 × 2

Moreover, in the copper porous body 10 which is this embodiment, the oxidation reduction layer is formed in the surface of the frame | skeleton part 12 (copper fiber 11), and in the coupling | bond part of copper fibers 11 and 11, mutual surface The redox layers formed on each other are bonded together.
The redox layer has a porous structure, and has fine irregularities on the surface of the skeleton 12 (copper fibers 11). Thereby, the specific surface area of the whole copper porous body 10 shall be 0.01 m < ² > / g or more, and the porosity shall be in the range of 50% or more and 90% or less.

And in the copper porous body 10 which is this embodiment, the oxygen concentration of the whole frame | skeleton part 12 is made into the range of 0.03 mass% or more and 1.0 mass% or less.
In the present embodiment, an oxide film is formed on the surface of the skeleton part 12.

Next, the manufacturing method of the copper porous body 10 which is this embodiment is demonstrated with reference to the flowchart of FIG. 2, the process drawing of FIG.
First, as shown in FIG. 3, the homogenized copper fiber 11 is sprinkled from the spreader 31 toward the stainless steel container 32 to be bulk-filled, and the copper fiber 11 is laminated (copper fiber laminating step). S01).
Here, in the copper fibers laminating step S01, a bulk density D _P after filling is stacked a plurality of copper fibers 11 to be equal to or less than 50% of the true density D _T of the copper fibers 11. In addition, in this embodiment, since shape provision processing, such as a twist process and a bending process, is given to the copper fiber 11, a three-dimensional and isotropic space | gap is ensured between the copper fibers 11 at the time of lamination | stacking. become.

Next, the copper fiber 11 bulk-filled in the stainless steel container 32 is subjected to oxidation reduction treatment (oxidation reduction treatment step S02).
In this oxidation-reduction treatment step S02, as shown in FIGS. 2 and 3, an oxidation treatment step S21 for carrying out the oxidation treatment of the copper fibers 11, and a reduction treatment step for reducing and sintering the oxidized copper fibers 11 S22.

In this embodiment, as shown in FIG. 3, the stainless steel container 32 filled with the copper fibers 11 is charged into a heating furnace 33 and heated in an air atmosphere to oxidize the copper fibers 11 (oxidation treatment step). S21). By this oxidation treatment step S21, an oxide layer having a thickness of 1 μm or more and 100 μm or less, for example, is formed on the surface of the copper fiber 11.
The conditions of the oxidation treatment step S21 in the present embodiment are set such that the holding temperature is 520 ° C. or higher and 1050 ° C. or lower, and the holding time is 5 minutes or longer and 300 minutes or shorter.

Here, when the holding temperature in the oxidation treatment step S <b> 21 is less than 520 ° C., the oxide layer may not be sufficiently formed on the surface of the copper fiber 11. On the other hand, when the holding temperature in the oxidation treatment step S <b> 21 exceeds 1050 ° C., the oxidation may progress to the inside of the copper fiber 11.
From the above, in the present embodiment, the holding temperature in the oxidation treatment step S21 is set to 520 ° C. or higher and 1050 ° C. or lower. In order to reliably form the oxide layer on the surface of the copper fiber 11, it is preferable that the lower limit of the holding temperature in the oxidation treatment step S21 is 600 ° C. or higher and the upper limit of the holding temperature is 1000 ° C. or lower.

Moreover, when the retention time in the oxidation treatment step S <b> 21 is less than 5 minutes, the oxide layer may not be sufficiently formed on the surface of the copper fiber 11. On the other hand, when the holding time in the oxidation treatment step S <b> 21 exceeds 300 minutes, the oxidation may progress to the inside of the copper fiber 11.
From the above, in this embodiment, the holding time in the oxidation treatment step S21 is set within a range of 5 minutes or more and 300 minutes or less. In addition, in order to form an oxide layer reliably on the surface of the copper fiber 11, it is preferable that the minimum of the retention time in oxidation treatment process S21 shall be 10 minutes or more. Moreover, in order to suppress reliably oxidizing to the inside of the copper fiber 11, it is preferable to make the upper limit of the retention time in oxidation treatment process S21 into 100 minutes or less.

Next, in this embodiment, as shown in FIG. 3, after performing the oxidation treatment step S21, the stainless steel container 32 filled with the copper fibers 11 is charged into the heating furnace 34 and heated in a reducing atmosphere. Then, the oxidized copper fibers 11 are reduced to form a redox layer, and the copper fibers 11 are joined together to form the skeleton part 12 (reduction treatment step S22).
The conditions of the reduction treatment step S22 in the present embodiment are such that the atmosphere is a mixed gas atmosphere of argon and hydrogen, the holding temperature is 600 ° C. or higher and 1080 ° C. or lower, and the holding time is 5 minutes or longer and 300 minutes or shorter. .

Here, when the holding temperature in the reduction treatment step S <b> 22 is less than 600 ° C., the oxide layer formed on the surface of the copper fiber 11 may not be sufficiently reduced. On the other hand, when the holding temperature in the reduction treatment step S22 exceeds 1080 ° C., it is heated to the vicinity of the melting point of copper, and the strength and the porosity may be reduced.
From the above, in this embodiment, the holding temperature in the reduction treatment step S22 is set to 600 ° C. or higher and 1080 ° C. or lower. In order to reliably reduce the oxide layer formed on the surface of the copper fiber 11, the lower limit of the holding temperature in the reduction treatment step S22 is preferably set to 650 ° C. or higher. Moreover, in order to suppress reliably the fall of intensity | strength and a porosity, it is preferable to make the upper limit of the retention temperature in reduction process process S22 into 1050 degrees C or less.

Further, when the holding time in the reduction treatment step S22 is less than 5 minutes, the oxide layer formed on the surface of the copper fiber 11 may not be sufficiently reduced, and the sintering may be insufficient. . On the other hand, when the holding time in the reduction treatment step S22 exceeds 300 minutes, the thermal shrinkage due to sintering increases and the strength may decrease.
From the above, in this embodiment, the holding time in the reduction treatment step S22 is set within a range of 5 minutes or more and 300 minutes or less. In order to surely reduce the oxide layer formed on the surface of the copper fiber 11 and sufficiently advance the sintering, the lower limit of the holding time in the reduction treatment step S22 is preferably set to 10 minutes or more. Moreover, in order to suppress reliably the heat shrinkage and strength reduction by sintering, it is preferable that the upper limit of the holding time in the reduction treatment step S22 is 100 minutes or less.

By the oxidation treatment step S21 and the reduction treatment step S22, an oxidation reduction layer is formed on the surface of the copper fiber 11 (frame portion 12), and fine irregularities are generated.
Moreover, an oxide layer is formed on the surface of the copper fiber 11 by the oxidation treatment step S21, and the plurality of copper fibers 11 are cross-linked by the oxide layer. Thereafter, by performing the reduction treatment step S22, the oxide layer formed on the surface of the copper fiber 11 is reduced to form the above-described oxidation-reduction layer, and the oxidation-reduction layers are bonded to each other. The fibers 11 are sintered to form the skeleton part 12.

Next, after forming the skeleton part 12 and the redox layer by the oxidation-reduction treatment step S02, the stainless steel container 32 filled with the copper fibers 11 is charged into the heat treatment furnace 35 in an oxidizing atmosphere to stabilize the skeleton part 12. The stabilization process is performed (stabilization process step S03).
The conditions of the stabilization treatment step S03 in the present embodiment are an air atmosphere, a holding temperature of 250 ° C. or higher and 450 ° C. or lower, and a holding time of 5 minutes or longer and 120 minutes or shorter.
By this stabilization processing step S03, the oxygen concentration of the entire skeleton part 12 is set in the range of 0.03 mass% or more and 1.0 mass% or less.

Here, when the holding temperature in the stabilization treatment step S03 is less than 250 ° C., the oxidation is insufficient and the oxygen concentration may not be 0.03 mass% or more. On the other hand, when the holding temperature in the stabilization treatment step S03 exceeds 450 ° C., the oxidation proceeds and the oxygen concentration may exceed 1.0 mass%.
From the above, in this embodiment, the holding temperature in the stabilization processing step S03 is set to 250 ° C. or higher and 450 ° C. or lower.

Further, when the holding time in the stabilization treatment step S03 is less than 5 minutes, there is a possibility that a sufficient oxide film cannot be formed on the surface of the skeleton part 12. On the other hand, when the retention time in the stabilization treatment step S03 exceeds 120 minutes, the oxidation proceeds and the oxygen concentration may exceed 1.0 mass%.
From the above, in this embodiment, the holding time in the stabilization processing step S03 is set within a range of 5 minutes or more and 120 minutes or less. In order to surely control the oxygen concentration of the entire skeleton part 12 within a range of 0.03 mass% or more and 1.0 mass% or less, the lower limit of the holding time in the stabilization treatment step S03 is 15 minutes or more, and the upper limit is It is preferable to set it as 100 minutes or less.

  According to the manufacturing method as described above, the copper fibers 11 and 11 are sintered to form the skeleton portion 12, and a redox layer is formed on the surface of the skeleton portion 12 (copper fiber 11). And the oxygen concentration of the whole frame | skeleton part 12 shall be in the range of 0.03 mass% or more and 1.0 mass% or less by stabilization process S03, and the copper porous body 10 which is this embodiment is manufactured.

  According to the copper porous body 10 of the present embodiment configured as described above, the oxygen concentration of the entire skeleton 12 is in the range of 0.03 mass% or more and 1.0 mass% or less. When a thin oxide film is formed on the surface of the skeletal part, and it is used for a long time in a weak corrosive environment such as high temperature of 100 ° C or higher or water while maintaining excellent skeletal strength, thermal conductivity and electrical conductivity. Even so, it is possible to suppress the surface property from changing greatly.

Here, when the oxygen concentration of the whole skeleton part 12 is less than 0.03 mass%, a sufficient oxide film is not formed on the surface of the skeleton part 12, and there is a possibility that the surface properties may change in the use environment. On the other hand, when the oxygen concentration of the entire skeleton part 12 exceeds 1.0 mass%, oxidation proceeds to the inside of the copper fiber 11 forming the skeleton part 12, and as a result, the strength of the skeleton part 12 itself may be reduced. There is.
From the above, in this embodiment, the oxygen concentration of the entire skeleton part 12 is set within a range of 0.03 mass% or more and 1.0 mass% or less. In order to reliably stabilize the surface properties of the skeleton part 12, it is preferable to set the lower limit of the oxygen concentration of the entire skeleton part 12 to 0.05 mass% or more and the upper limit to 0.8 mass% or less.

  Further, according to the copper porous body 10 of the present embodiment, the diameter R is in the range of 0.02 mm or more and 1.0 mm or less, and the ratio L / R of the length L to the diameter R is 4 or more, Since the skeleton part 12 is formed by sintering the copper fiber 11 within the range of 2500 or less, a sufficient gap is secured between the copper fibers 11 and the shrinkage rate during sintering The porosity is high and the dimensional accuracy is excellent.

In the present embodiment, the diameter R is in the range of 0.02 mm to 1.0 mm, and the ratio L / R of the length L to the diameter R is in the range of 4 to 2500. copper fibers 11, since the bulk density D _P is provided with a copper fiber lamination step S01 of stacked so that more than 50% of the true density D _T of the copper fibers 11, ensuring a gap between the copper fibers 11 to each other It is possible to suppress shrinkage. Thereby, the copper porous body 10 with high porosity and excellent dimensional accuracy can be manufactured.
Specifically, the bulk density D _P is the true density D apparent density D _A copper porous body 10 produced by sintering and stacked so that more than 50% of _T copper fibers 11 Copper Since it is 51% or less of the true density _DT of the fiber 11, the shrinkage | contraction at the time of sintering is suppressed and it becomes possible to ensure a high porosity.

Here, when the diameter R of the copper fibers 11 is less than 0.02 mm, the bonding area between the copper fibers 11 is small, and the sintered strength may be insufficient. On the other hand, when the diameter R of the copper fibers 11 exceeds 1.0 mm, the number of contacts with which the copper fibers 11 are in contact with each other is insufficient, and the sintering strength may be insufficient.
From the above, in this embodiment, the diameter R of the copper fiber 11 is set in the range of 0.02 mm or more and 1.0 mm or less. In order to further improve the strength, the lower limit of the diameter R of the copper fiber 11 is preferably 0.05 mm or more, and the upper limit of the diameter R of the copper fiber 11 is preferably 0.5 mm or less.

Further, when the ratio L / R of the length L and the diameter R of the copper fibers 11 is less than 4, bulk density D _P is 50% or less of the true density D _T copper fibers 11 when stacked It is difficult to obtain a copper porous body 10 having a high porosity. On the other hand, when the ratio L / R between the length L and the diameter R of the copper fiber 11 exceeds 2500, the copper fiber 11 cannot be uniformly dispersed, and the copper porous body 10 having a uniform porosity. May be difficult to obtain.
From the above, in this embodiment, the ratio L / R between the length L and the diameter R of the copper fiber 11 is set in the range of 4 or more and 2500 or less. In order to further improve the porosity, the lower limit of the ratio L / R between the length L and the diameter R of the copper fiber 11 is preferably 10 or more. Moreover, in order to obtain the copper porous body 10 with a uniform porosity, it is preferable to set the ratio L / R upper limit of the length L and the diameter R of the copper fiber 11 to 500 or less.

Moreover, according to the manufacturing method of the copper porous body which is this embodiment, since the oxidation treatment process S21 which oxidizes the copper fiber 11 and the reduction treatment process S22 which reduces the oxidized copper fiber 11 are provided. A redox layer can be formed on the surface of the copper fiber 11 (skeleton part 12).
And according to the manufacturing method of the copper porous body which is this embodiment, since the stabilization process process S03 which oxidizes the frame part 12 is provided, the oxygen concentration of the whole frame part 12 is 0.03 mass% or more, 1 It can be within the range of 0.0 mass% or less.

(Second embodiment)
Next, the copper porous composite member 100 which is 2nd embodiment of this invention is demonstrated with reference to attached drawing.
In FIG. 4, the copper porous composite member 100 which is this embodiment is shown. The copper porous composite member 100 includes a copper plate 120 (member main body) made of copper or a copper alloy, and a copper porous body 110 bonded to the surface of the copper plate 120.

Here, the copper porous body 110 according to the present embodiment is obtained by sintering a plurality of copper fibers to form a skeleton portion, as in the first embodiment. Here, the copper fiber is made of copper or a copper alloy, the diameter R is in the range of 0.02 mm to 1.0 mm, and the ratio L / R of the length L to the diameter R is 4 or more and 2500 or less. It is within the range. In the present embodiment, the copper fiber is made of, for example, C1100 (tough pitch copper).
In the present embodiment, the copper fiber is given a shape such as twisting or bending. Further, in the copper porous body 110 is a present embodiment, the apparent density D _A is less 51% of the true density D _T of copper fibers.

Furthermore, in this embodiment, a redox layer is formed by performing redox treatment (oxidation treatment and reduction treatment) on the surfaces of the copper fibers (skeleton part) and the copper plate 120 constituting the copper porous body 110 as described later. As a result, fine irregularities are formed on the surfaces of the copper fibers (skeleton part) and the copper plate 120. In the present embodiment, the specific surface area of the entire copper porous body 110 is 0.01 m ² / g or more, and the porosity is in the range of 50% to 90%.
Moreover, in the joint part of the copper fiber which comprises the copper porous body 110, and the surface of the copper plate 120, the oxidation reduction layer formed in the surface of the copper fiber and the oxidation reduction layer formed in the surface of the copper plate are united. Are connected.
And in this embodiment, the oxygen concentration of the whole frame | skeleton part of the copper porous body 110 is made into the range of 0.03 mass% or more and 1.0 mass% or less.

Next, a method for manufacturing the copper porous composite member 100 according to the present embodiment will be described with reference to the flowchart of FIG.
First, the copper plate 120 which is a member main body is prepared (copper plate arrangement | positioning process S100). Next, copper fibers are dispersed and arranged on the surface of the copper plate 120 (copper fiber lamination step S101). Here, in the copper fibers lamination step S101, bulk density D _P is stacked a plurality of copper fibers to be equal to or less than 50% of the true density D _T of copper fibers.

  Next, the copper fibers stacked and arranged on the surface of the copper plate 120 are sintered to form the copper porous body 110, and the copper porous body 110 and the copper plate 120 are bonded (sintering step S102 and joining step S103). ). In the sintering step S102 and the joining step S103, as shown in FIG. 5, the oxidation treatment step S121 for performing the oxidation treatment of the copper fiber and the copper plate 120 and the oxidized copper fiber and the copper plate 120 are reduced and sintered. Reduction processing step S122.

In the present embodiment, the copper plate 120 on which the copper fibers are laminated is placed in a heating furnace and heated in an air atmosphere to oxidize the copper fibers (oxidation treatment step S121). By this oxidation treatment step S121, an oxide layer having a thickness of 1 μm or more and 100 μm or less is formed on the surfaces of the copper fiber and the copper plate 120, for example.
Here, the conditions of the oxidation treatment step S121 in this embodiment are that the holding temperature is 520 ° C. or higher and 1050 ° C. or lower, desirably 600 ° C. or higher and 1000 ° C. or lower, and the holding time is 5 minutes or longer and 300 minutes or shorter, preferably 10 It is within the range of not less than 100 minutes and not more than 100 minutes.

Next, in the present embodiment, after performing the oxidation treatment step S121, the copper plate 120 on which the copper fibers are laminated is placed in a firing furnace, heated in a reducing atmosphere, and oxidized copper fibers and the copper plate 120. The copper fiber and the copper plate 120 are combined with each other (reduction process step S122).
Here, the conditions of the reduction treatment step S122 in the present embodiment are that the atmosphere is a mixed gas atmosphere of nitrogen and hydrogen, the holding temperature is 600 ° C. or higher and 1080 ° C. or lower, desirably 650 ° C. or higher and 1050 ° C. or lower, and the holding time is 5 Min. To 300 min., Preferably 10 min. To 100 min.

By the oxidation treatment step S121 and the reduction treatment step S122, a redox layer is formed on the surfaces of the copper fibers (skeleton part) and the copper plate 120, and fine irregularities are generated.
In addition, an oxide layer is formed on the surfaces of the copper fibers (skeleton) and the copper plate 120 by the oxidation treatment step S121, and the plurality of copper fibers and the copper plate 120 are cross-linked by the oxide layer. Thereafter, by performing the reduction treatment step S122, the copper fiber (skeleton part) and the oxide layer formed on the surface of the copper plate 120 are reduced, and the copper fibers are sintered through the oxidation-reduction layer, so that the skeleton part is formed. As formed, the copper porous body 110 and the copper plate 120 are bonded.

Next, the stabilization process process which oxidizes the surface of a skeleton part is performed (stabilization process process S104).
In the stabilization treatment step S104 in the present embodiment, the copper porous body 110 and the copper plate 120 are immersed in a commercially available oxidizing aqueous solution (etching agent), and an oxide film is formed until a predetermined oxygen concentration is reached.
The copper porous composite member 100 according to the present embodiment is manufactured by the manufacturing method as described above.

  According to the copper porous composite member 100 of the present embodiment configured as described above, the oxygen concentration of the entire skeleton of the copper porous body 110 is in the range of 0.03 mass% or more and 1.0 mass% or less. Therefore, a thin oxide film is formed on the surface of the skeletal part, and the surface properties change even when used for a long time in a weak corrosive environment such as high temperature of 100 ° C or higher and water. Can be suppressed.

  Further, in the copper porous composite member 100 according to the present embodiment, the diameter R is within the range of 0.02 mm to 1.0 mm on the surface of the copper plate 120, and the ratio L between the length L and the diameter R is L. / R is 4 or more and 2500 or less, and the copper porous body 110 having high porosity and excellent strength and dimensional accuracy is joined by sintering copper fibers, and has heat conduction characteristics and electrical properties. Excellent conduction characteristics.

Furthermore, in this embodiment, an oxidation-reduction layer is formed on the surfaces of the copper fibers and the copper plate 120 constituting the copper porous body 110, and the specific surface area of the entire copper porous body 110 is 0.01 m ² / g or more. The porosity is in the range of 50% to 90%, and various properties such as heat exchange efficiency through the porous skeleton surface can be greatly improved.
Moreover, in this embodiment, in the coupling | bond part of the copper fiber which comprises the copper porous body 110, and the surface of the copper plate 120, it formed in the surface of the copper plate 120 and the oxidation reduction layer formed in the surface of the copper fiber. Since the oxidation-reduction layer is integrally bonded, the copper porous body 110 and the copper plate 120 are firmly bonded, and the bonding interface strength, heat conduction characteristics, and electric conduction characteristics are excellent.

According to the manufacturing method of the copper porous composite member 100 according to the present embodiment, since the stabilization processing step S104 for oxidizing the surface of the skeleton part is provided, the oxygen concentration of the entire skeleton part of the copper porous body 110 is 0. It can be in the range of 0.03 mass% or more and 1.0 mass% or less.
Moreover, according to the manufacturing method of the copper porous composite member 100 which is this embodiment, a copper fiber is laminated | stacked on the surface of the copper plate 120 which consists of copper and a copper alloy, and sintering process S102 and joining process S103 are implemented simultaneously. Therefore, the manufacturing process can be simplified.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.
For example, although demonstrated as what manufactures a copper porous body using the manufacturing equipment shown in FIG. 3, it is not limited to this, Even if it manufactures a copper porous body using another manufacturing equipment Good.

  The atmosphere of the oxidation treatment steps S21 and S121 may be any oxidizing atmosphere in which copper or a copper alloy is oxidized at a predetermined temperature. Specifically, the atmosphere is not limited to the atmosphere, and 10 vol. In inert gas (for example, nitrogen). Any atmosphere containing at least% oxygen may be used. Also, the atmosphere of the reduction treatment steps S22 and S122 may be any reducing atmosphere in which copper oxide is reduced to metallic copper or copper oxide is decomposed at a predetermined temperature. Specifically, hydrogen of several vol% or more is used. A nitrogen-hydrogen mixed gas, an argon-hydrogen mixed gas, a pure hydrogen gas, or an ammonia decomposition gas or a propane decomposition gas that is often used industrially can also be suitably used.

  Furthermore, in this embodiment, although demonstrated as what forms the frame | skeleton part of a copper porous body by sintering copper fiber, it is not limited to this, Copper porous materials, such as a fiber nonwoven fabric and a metal filter, A material may be prepared, and the copper porous body may be subjected to a redox treatment step and a stabilization treatment step.

  Moreover, in this embodiment, although demonstrated as what uses the copper fiber which consists of tough pitch copper (JIS C1100) or oxygen-free copper (JIS C1020), it is not limited to this, As a material of the copper fiber 11, , Phosphorus deoxidized copper (JIS C1201, C1220), copper containing silver (for example, Cu-0.02-0.5 mass% Ag), chromium copper (for example, Cu-0.02-1.0 mass% Cr), zircon copper ( For example, Cu-0.02 to 1.0 mass% Zr), copper containing tin (for example, Cu-0.1 to 1.0 mass% Sn), or the like can be suitably used. In particular, when used in a high temperature environment of 200 ° C. or higher, it is preferable to use silver-containing copper, chromium copper, tin-containing copper, zircon copper, or the like excellent in high-temperature strength.

  In the second embodiment, the copper porous composite member having the structure shown in FIG. 4 has been described as an example. However, the present invention is not limited to this, and the copper having the structure as shown in FIGS. It may be a porous composite member.

For example, as shown in FIG. 6, a copper porous composite member 200 having a structure in which a plurality of copper tubes 220 are inserted into a copper porous body 210 as a member main body may be used.
Alternatively, as shown in FIG. 7, a copper porous composite member 300 having a structure in which a copper tube 320 curved in a U shape as a member main body is inserted into a copper porous body 310 may be used.

Furthermore, as shown in FIG. 8, the copper porous composite member 400 of the structure which joined the copper porous body 410 to the internal peripheral surface of the copper pipe 420 which is a member main body may be sufficient.
Moreover, as shown in FIG. 9, the copper porous composite member 500 of the structure which joined the copper porous body 510 to the outer peripheral surface of the copper tube 520 which is a member main body may be sufficient.

Furthermore, as shown in FIG. 10, a copper porous composite member 600 having a structure in which a copper porous body 610 is bonded to the inner peripheral surface and the outer peripheral surface of a copper tube 620 that is a member main body may be used.
Moreover, as shown in FIG. 11, the copper porous composite member 700 of the structure which joined the copper porous body 710 to both surfaces of the copper plate 720 which is a member main body may be sufficient.

Below, the result of the confirmation experiment performed in order to confirm the effect of this invention is demonstrated.
Using the raw materials shown in Table 1, a copper porous body having a three-dimensional network structure skeleton was produced.
And the oxidation reduction process and the stabilization process were performed on the conditions shown in Table 2, and the copper porous body of width 30mm * length 200mm * thickness 5mm was manufactured. In Comparative Examples 1 to 4, the stabilization process was omitted.
Furthermore, about the obtained copper porous body, oxygen concentration, porosity, relative tensile strength, and surface discoloration were evaluated. The evaluation results are shown in Table 3. The evaluation method is shown below.

(Fiber diameter R)
The fiber diameter R is a converted fiber diameter (Heywood diameter) R = (A / π) ^{1 /} calculated by image analysis based on JIS Z 8827-1 using a particle analyzer “Morphology G3” manufactured by Malvern. An average value of ² × 2 was used.

(Fiber length L)
As the fiber length L of the copper fiber, a simple average value calculated by image analysis using a particle analyzer “Morphology G3” manufactured by Malvern, Inc. was used.

(Oxygen concentration C _O )
About 1 g of the sample cut out from the obtained copper porous body was put into a gas analyzer (model number: TCEN-600) manufactured by LECO, and the oxygen concentration C _{O was} obtained by an inert gas melting method using helium gas as a carrier gas. (Mass%) was measured.

(Apparent density ratio _{D A} and porosity P)
The mass M (g), the volume V (cm ³ ), and the true density _DT (g / cm ³ ) of the copper fiber constituting the copper porous body were measured and apparent from the following formula: It was calculated density ratio _{D a} and porosity P (%). The true density _DT was measured by an underwater method using a precision balance.
D _A = M / (V × D _T )
P = (1− (M ÷ (V × D _T ))) × 100

(Relative tensile strength S _R )
After processing the obtained copper porous body into a test piece having a width of 10 mm, a length of 100 mm, and a thickness of 5 mm, a tensile test is performed using an Instron type tensile tester, and the maximum tensile load S _max (N) is apparent. was measured maximum tensile strength S (N / mm ²⁾ is divided by the sample cross-sectional area 50 mm ² above. To change the maximum tensile strength S is the apparent density obtained by the measurement, in this embodiment, the maximum tensile strength S of the (N / mm ²⁾ were normalized by the apparent density D _A value S / D _A The relative tensile strength S _R (N / mm ² ) was defined and compared.

(Surface discoloration)
The obtained copper porous body was left in a constant temperature and humidity chamber at a humidity of 80% and a temperature of 80 ° C. for 100 hours, and the color change before and after was visually confirmed.

In Comparative Examples 1 to 3 in which the stabilization treatment was not performed, significant surface discoloration was observed. On the other hand, in Comparative Example 4, although the surface discoloration was not observed, a significant decrease in tensile strength due to excessive oxidation was observed.
On the other hand, in the inventive examples 1 to 12 in which the stabilization treatment was performed, the relative tensile strength was sufficiently high and no surface discoloration was observed.
From the above, according to the present invention example, it was confirmed that the surface property of the skeleton did not change greatly even under the use environment, and it was possible to provide a copper porous body having stable characteristics.

10, 110 Copper porous body 11 Copper fiber 12 Skeletal part 100 Copper porous composite member 120 Copper plate (member main body)

Claims (9)

A porous copper body having a three-dimensional network structure skeleton,
It has a redox layer formed by redox treatment on the surface of the skeleton part,
The copper porous body, wherein the oxygen concentration of the entire skeleton is in the range of 0.03 mass% or more and 1.0 mass% or less.   The copper skeleton according to claim 1, wherein the skeleton is a sintered body of a plurality of copper fibers.   The copper fiber has a diameter R in the range of 0.02 mm to 1.0 mm, and a ratio L / R of the length L to the diameter R in the range of 4 to 2500. The copper porous body according to claim 2.   A copper porous composite member comprising a member main body and the copper porous body according to any one of claims 1 to 3 joined together.   The joining surface with the said copper porous body among the said member main bodies is comprised with copper or a copper alloy, and the said copper porous body and the said member main body are joined by sintering. The copper porous composite member described. It is a manufacturing method of the copper porous body which manufactures the copper porous body according to any one of claims 1 to 3,
A copper porous body comprising: a redox treatment step of oxidizing and reducing the skeleton portion to form the redox layer; and a stabilization treatment step of oxidizing the surface of the skeleton portion. Production method.   The method for producing a copper porous body according to claim 6, wherein the skeleton is formed by sintering a copper raw material. A method for producing a copper porous composite member for producing a copper porous composite member in which a member main body and a copper porous body are joined,
A copper porous composite member comprising a joining step of joining the copper porous body produced by the method for producing a copper porous body according to claim 6 or 7 and the member main body. Manufacturing method.   The joining surface to which the copper porous body is joined of the member main body is made of copper or a copper alloy, and the copper porous body and the member main body are joined by sintering. Item 9. A method for producing a copper porous composite member according to Item 8.

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