Technical Field
[0001] The present disclosure relates to a porous copper body formed from copper or a copper
alloy, a porous copper composite member in which the porous copper body is bonded
to a main member body, a method of manufacturing the porous copper body, and a method
of manufacturing the porous copper composite member.
Background Art
[0003] The porous copper body and the porous copper composite member are used, for example,
as electrodes and current collectors in various batteries, heat exchanger components,
heat pipes, and the like.
[0004] For example, PTL 1 discloses a method in which a pressure-sensitive adhesive is applied
to a skeleton of a three-dimensional network structure (for example, synthetic resin
foam having open cells such as urethane foam, polyethylene foam, natural fiber cloth,
man-made fiber cloth, and the like) made of a material burned off by heating and a
formed body on which a metal powdery material is adhered is used, or a method of using
a sheet-like formed body which is made of a material burned off by heating and in
which a metal powder material has been mixed to a material (for example, pulp or wool
fiber) capable of forming a three-dimensional network structure, as a method of manufacturing
a metal sintered body (porous copper sintered body) forming the three-dimensional
network structure.
[0005] In addition, PTL 2 discloses a method of obtaining a porous material by electrically
heating a copper fiber under pressure.
Citation List
Patent Literature
[0006]
[PTL 1] Japanese Unexamined Patent Application, First Publication No. H08-145592
[PTL 2] Japanese Patent No. 3735712
SUMMARY OF DISCLOSURE
Technical Problem
[0007] In the above-described porous copper body, in addition to having a high porosity
and an open cell structure, in a case of being used as a conductive member such as
an electrode and a current collector, excellent conductivity is required, and in a
case of being used as a heat conduction member such as a heat exchanger component
and heat pipe, excellent heat conductivity is required.
[0008] In the porous copper body described in PTL 1 and PTL 2, conductivity and heat conductivity
are not considered, and in particular, in a case where the porosity is high, bonding
between metal powders or the copper fibers is insufficient, resulting in a concern
that conductivity and heat conductivity may be insufficient.
[0009] The disclosure has been made in consideration of the above-described circumstances,
and an object thereof is to provide a porous copper body which has sufficient conductivity
and heat conductivity, even in a case where a porosity is high, and is particularly
suitable for a conductive member and a heat-transfer member, a porous copper composite
member in which the porous copper body is bonded to a main member body, a method of
manufacturing the porous copper body, and method of manufacturing the porous copper
composite member.
Solution to Problem
[0010] To solve the above-described problem and to accomplish the above-described object,
according to an aspect of the disclosure, a porous copper body is provided. The porous
copper body is a porous copper body, including: a skeleton having a three-dimensional
network structure, in which a porosity is in a range of 50% to 90%, and a porosity-normalized
electrical conductivity σ
N which is defined by dividing a electrical conductivity of the porous copper body,
measured by a 4-terminal sensing, by an apparent density ratio of the porous copper
body is 20% IACS or higher.
[0011] According to the porous copper body having the above-described configuration, even
in a case where a porosity is in a range of 50% to 90%, a porosity-normalized electrical
conductivity σ
N which is defined by dividing a electrical conductivity of the porous copper body,
measured by a 4-terminal sensing, by an apparent density ratio of the porous copper
body is 20% IACS or higher. Accordingly, the porous copper body is excellent in conductivity
and particularly suitable for a conductive member. In addition, free electrons are
responsible for thermal conduction as well as electrical conduction. Accordingly,
when conductivity is ensured, heat conductivity is also ensured. Therefore, the porous
copper body of the disclosure is also excellent in heat conductivity and particularly
suitable for a heat-transfer member.
[0012] Here, in the porous copper body according to an aspect of the disclosure, it is preferable
that an oxidation-reduction layer be formed on a surface of the skeleton.
[0013] In this case, since the oxidation-reduction layer is formed on the surface of the
skeleton, unevenness is formed on the surface to increase a specific surface area.
For example, it is possible to greatly improve various characteristics such as heat-exchange
efficiency through a porous skeleton surface and the like. In addition, by performing
an oxidation-reduction treatment, it is possible to further improve the porosity-normalized
electrical conductivity σ
N.
[0014] In addition, in the porous copper body according to an aspect of the disclosure,
the skeleton may be a sintered body of: at least one of copper powders and copper
fibers; or both of copper powders and copper fibers, both of copper powders and copper
fibers being made of copper or a copper alloy.
[0015] In this case, it is possible to obtain the porous copper body in which the porosity
is in the range of 50% to 90% by adjusting a filling rate of copper powders and copper
fibers which are formed from copper or a copper alloy.
[0016] Further, in the porous copper body according to an aspect of the disclosure, it is
preferable that, in each of the copper fibers, a diameter R be in a range of 0.02
mm to 1.0 mm and a ratio L/R between a length L and the diameter R be in a range of
4 to 2500.
[0017] In this case, since in each of the copper fibers, the diameter R is set in a range
of 0.02 mm to 1.0 mm, and the ratio L/R between the length L and the diameter R is
set in a range of 4 to 2500, a sufficient void is secured between the copper fibers,
and a shrinkage rate in the sintering can be suppressed. Accordingly, it is possible
to raise the porosity, and it is possible to attain excellent dimensional accuracy.
[0018] In addition, in the porous copper body according to an aspect of the disclosure,
in a bonding portion of: at least one of copper powders and copper fibers; or both
of copper powders and copper fibers, it is preferable that the oxidation-reduction
layers formed on surfaces of: at least one of copper powders and copper fibers; or
both of copper powders and copper fibers, be integrally bonded to each other.
[0019] In this case, the oxidation-reduction layers are integrally bonded to each other
in the bonding portion of: at least one of copper powders and copper fibers; or both
of copper powders and copper fibers, accordingly, the porous copper body is excellent
in bonding strength. In addition, since the copper fibers and the copper powders are
strongly bonded to each other, it is also possible to improve conductivity and heat
conductivity.
[0020] According to another aspect of the disclosure, a porous copper composite member is
provided, including a bonded body of a main member body and the above-described porous
copper body.
[0021] According to the porous copper composite member having the configuration, the porous
copper composite member is formed from a bonded body of the porous copper body which
is excellent in conductivity and heat conductivity and the main member body, accordingly,
it is possible to exhibit excellent conductivity and heat conductivity as the porous
copper composite member.
[0022] Here, in the porous copper composite member according to another aspect of the disclosure,
it is preferable that a bonding surface in the main member body with the porous copper
body be formed from copper or a copper alloy and a bonding portion of the porous copper
body and the main member body be a sintered layer.
[0023] In this case, since the bonding portion of the porous copper body and the main member
body is the sintered layer, the porous copper body and the main member body are strongly
bonded to each other, and thus it is possible to obtain excellent strength, conductivity,
and heat conductivity, as the porous copper composite member.
[0024] In addition, according to still another aspect of the disclosure, a method of manufacturing
the above-described porous copper body is provided, the method including performing
an oxidation treatment on a skeleton having a three-dimensional network structure
under conditions of a holding temperature of 500°C to 1050°C in an oxidizing atmosphere;
performing a reduction treatment on the skeleton having a three-dimensional network
structure under conditions of a holding temperature of 500°C to 1050°C in a reducing
atmosphere; and setting the porosity-normalized electrical conductivity σ
N to 20% IACS or higher by the oxidation treatment and the reduction treatment.
[0025] According to the method of manufacturing the porous copper body as described above,
by performing the oxidation treatment and the reduction treatment on the skeleton
having a three-dimensional network structure under the conditions, the conductivity
is improved. Accordingly, it is possible to set the porosity-normalized electrical
conductivity σ
N to 20% IACS or higher.
[0026] In addition, according to still another aspect of the disclosure, a method of manufacturing
the above-described porous copper body is provided, the method including: performing
an oxidation treatment on at least one of copper powders and copper fibers, or both
of copper powders and copper fibers, under conditions of a holding temperature of
500°C to 1050°C in an oxidizing atmosphere; and performing a reduction treatment on
at least one of copper powders and copper fibers, or both of copper powders and copper
fibers, under conditions of a holding temperature of 500°C to 1050°C in a reducing
atmosphere, in which the skeleton including a sintered body of: at least one of copper
powders and copper fibers; or both of copper powders and copper fibers, are formed
and the porosity-normalized electrical conductivity σ
N is set to 20% IACS or higher by the oxidation treatment and the reduction treatment.
[0027] According to the method of manufacturing the porous copper body as described above,
by performing the oxidation treatment and the reduction treatment on at least one
of copper powders and copper fibers, or both of copper powders and copper fibers,
under above-described conditions, it is possible to form the skeleton including a
sintered body of: at least one of copper powders and copper fibers; or both of copper
powders and copper fibers, and it is possible to obtain a porous copper body formed
from the sintered body. In addition, the conductivity is improved. Accordingly, it
is possible to set the porosity-normalized electrical conductivity σ
N to 20% IACS or higher.
[0028] According to still another aspect of the disclosure, a method of manufacturing a
porous copper composite member including a bonded body of a main member body and a
porous copper body is provided, the method including a bonding process of bonding
the porous copper body that is manufactured by the above-described method of manufacturing
the porous copper body, and the main member body.
[0029] According to the method of manufacturing a porous copper composite member as described
above, the porous copper body, which is manufactured by the above-described method
of manufacturing the porous copper body, is provided, and thus it is possible to manufacture
a porous copper composite member excellent in heat conductivity and conductivity.
Examples of a shape of the main member body include a plate, a rod, a pipe, and the
like.
[0030] Here, in the method of manufacturing a porous copper composite member of an aspect
of the disclosure, in the main member body, a bonding surface to which the porous
copper body is bonded may be constituted by copper or a copper alloy, and the porous
copper body and the main member body may be bonded to each other through sintering.
[0031] In this case, the main member body and the porous copper body can be integrated with
each other through sintering, and thus it is possible to manufacture a porous copper
composite member excellent in stability of characteristics.
Advantageous Effects of Disclosure
[0032] According to the disclosure, it is possible to provide a porous copper body which
has sufficient conductivity and heat conductivity, even in a case where a porosity
is high, and is particularly suitable for a conductive member and a heat-transfer
member, a porous copper composite member in which the porous copper body is bonded
to a main member body, a method of manufacturing the porous copper body, and method
of manufacturing the porous copper composite member.
Brief Description of Drawings
[0033]
FIG. 1 is an enlarged schematic view of a porous copper body according to a first
embodiment of the disclosure.
FIG. 2 is a flowchart illustrating an example of a method of manufacturing the porous
copper body illustrated in FIG. 1.
FIG. 3 is a view illustrating a manufacturing process of manufacturing the porous
copper body illustrated in FIG. 1.
FIG. 4 is a view illustrating an external appearance of a porous copper composite
member according to a second embodiment of the disclosure.
FIG. 5 is a flowchart illustrating an example of a method of manufacturing the porous
copper composite member illustrated in FIG. 4.
FIG. 6 is an external view of a porous copper composite member according to another
embodiment of the disclosure.
FIG. 7 is an external view of a porous copper composite member according to still
another embodiment of the disclosure.
FIG. 8 is an external view of a porous copper composite member according to still
another embodiment of the disclosure.
FIG. 9 is an external view of a porous copper composite member according to still
another embodiment of the disclosure.
FIG. 10 is an external view of a porous copper composite member according to still
another embodiment of the disclosure.
FIG. 11 is an external view of a porous copper composite member according to still
another embodiment of the disclosure.
Description of Embodiments
[0034] Hereinafter, description will be given of a porous copper body, a porous copper composite
member, a method of manufacturing the porous copper body, and a method of manufacturing
the porous copper composite member according to embodiments of the disclosure with
reference to the accompanying drawings.
(First Embodiment)
[0035] First, description will be given of a porous copper body 10 according to a first
embodiment of the disclosure with reference to FIG. 1 to FIG. 3.
[0036] As illustrated in FIG. 1, the porous copper body 10 according to this embodiment
includes a skeleton 12 in which a plurality of copper fibers 11 are sintered.
[0037] Here, the copper fibers 11 are formed from copper or a copper alloy, a diameter R
is set in a range of 0.02 mm to 1.0 mm, and a ratio L/R between a length L and the
diameter R is set in a range of 4 to 2500. In this embodiment, the copper fibers 11
are formed from, for example, C1020 (oxygen-free copper).
[0038] Furthermore, in this embodiment, the copper fiber 11 is subjected to shape imparting
such as twisting and bending. In addition, in the porous copper body 10 according
to this embodiment, an apparent density ratio D
A is set to 51% or less of a true density D
T of the copper fiber 11. A shape of the copper fiber 11 is an arbitrary shape such
as a linear shape and a curved shape as long as the apparent density ratio D
A is 51% or less of the true density D
T of the copper fiber 11. However, when using the copper fiber 11 in which at least
a part thereof is subjected to predetermined shape-imparting processing such as twisting
processing and bending processing, it is possible to form a void between fibers in
a three-dimensional and isotropic shape. As a result, it is possible to improve isotropy
in various characteristics such as heat-transfer characteristics and conductivity
of the porous copper body 10.
[0039] Furthermore, the copper fiber 11 is manufactured through adjustment into a predetermined
circle-converted diameter R by a drawing method, a coil cutting method, a wire cutting
method, a melting spraying method, and the like, length adjustment for satisfying
predetermined L/R, and cutting.
[0040] Here, the circle-converted diameter R is a value that is calculated on the basis
of a cross-sectional area A of each fiber, and is defined by the following expression
on the assumption of a perfect circle regardless of a cross-sectional shape.

[0041] In addition, in the porous copper body 10 according to this embodiment, an oxidation-reduction
layer is formed on a surface of the skeleton 12 (copper fiber 11). In addition, in
a bonding portion between the plurality of copper fibers 11, oxidation-reduction layers
formed on surfaces of the plurality of copper fibers 11 are integrally bonded to each
other.
[0042] Furthermore, each of the oxidation-reduction layers has a porous structure, which
causes minute unevenness on the surface of skeleton 12 (copper fiber 11). According
to this, a specific surface area of the entirety of the porous copper body 10 is set
to 0.01 m
2/g or greater. The specific surface area of the entirety of the porous copper body
10 is preferably 0.03 m
2/g or greater. However, there is no limitation thereto.
[0043] In addition, in the porous copper body 10 according to the embodiment, a porosity
P is in a range of 50% to 90% and a porosity-normalized electrical conductivity σ
N (% IACS) which is defined by dividing a electrical conductivity σ
P of the porous copper body 10, measured by a 4-terminal sensing, by an apparent density
ratio D
A of the porous copper body 10 is 20% IACS or higher. The porosity-normalized electrical
conductivity σ
N, the apparent density ratio D
A, and the porosity P are respectively calculated by the following expressions.

[0044] Here, m is the mass (g) of the porous copper body 10. V is the volume (cm
3) of the porous copper body 10. D
T is the true density (g/cm
3) of the copper fibers 11 constituting the porous copper body 10.
[0045] The porosity P is preferably in a range of 70% to 90%. However, there is no limitation
thereto.
[0046] Next, description will be given of a method of manufacturing the porous copper body
10 according to this embodiment with reference to a flowchart in FIG. 2, a process
diagram of FIG. 3, and the like.
[0047] First, as illustrated in FIG. 3, the copper fiber 11 is distributed from a distributor
31 toward the inside of a stainless steel container 32 to volumetrically fill the
stainless steel container 32. According to this, lamination of the copper fibers 11
is performed (copper fiber lamination process S01).
[0048] Here, in the copper fiber lamination process S01, a plurality of the copper fibers
11 are laminated so that a volume density Dp after the filling becomes 50% or less
of the true density D
T of the copper fibers 11. Furthermore, in this embodiment, shape-imparting processing
such as twisting processing and bending processing is carried out with respect to
the copper fibers 11, and thus it is possible to secure a three-dimensional and isotropic
void between the copper fibers 11 during lamination.
[0049] Next, the copper fibers 11, which volumetrically fill the stainless steel container
32, are subjected to an oxidation-reduction treatment (oxidation-reduction treatment
process S02).
[0050] As illustrated in FIG. 2 and FIG. 3, the oxidation-reduction treatment process S02
includes an oxidation treatment process S21 of performing an oxidation treatment of
the copper fibers 11, and a reduction treatment process S22 of reducing and sintering
the copper fibers 11 which are subjected to the oxidation treatment.
[0051] In this embodiment, as illustrated in FIG. 3, the stainless steel container 32, which
is filled with the copper fibers 11, is put in a heating furnace 33 and is heated
in an oxidizing atmosphere to perform an oxidation treatment of the copper fiber 11
(oxidation treatment process S21). For example, an oxide layer having a thickness
of 1 µm to 100 µm is formed on a surface of each of the copper fibers 11 through the
oxidation treatment process S21.
[0052] Conditions of the oxidation treatment process S21 in this embodiment are as follows.
Specifically, an atmosphere is set to an atmospheric atmosphere (atmospheric atmosphere
(a)), a holding temperature is set to 500°C to 1050°C, and a holding time is set in
a range of 5 minutes to 300 minutes.
[0053] Here, in a case where the holding temperature in the oxidation treatment process
S21 is lower than 500°C, there is a concern that the oxide layer is not sufficiently
formed on the surface of the copper fiber 11. On the other hand, in a case where the
holding temperature in the oxidation treatment process S21 is higher than 1050°C,
there is a concern that oxidation may progress to the inside of the copper fiber 11.
[0054] In this regard, in this embodiment, the holding temperature in the oxidation treatment
process S21 is set to 500°C to 1050°C. Furthermore, in the oxidation treatment process
S21, it is preferable that the lower limit of the holding temperature be set to 600°C
or higher, and the upper limit of the holding temperature be set to 1000°C or lower
so as to reliably form the oxide layer on the surface of the copper fiber 11.
[0055] In addition, in a case where the holding time in the oxidation treatment process
S21 is shorter than 5 minutes, there is a concern that the oxide layer may not be
sufficiently formed on the surface of the copper fiber 11. On the other hand, in a
case where the holding time in the oxidation treatment process S21 is longer than
300 minutes, there is a concern that oxidation may progress to the inside of the copper
fiber 11.
[0056] In this regard, in this embodiment, the holding time in the oxidation treatment process
S21 is set in a range of 5 minutes to 300 minutes. Furthermore, it is preferable that
the lower limit of the holding time in the oxidation treatment process S21 be set
to 10 minutes or longer so as to reliably form the oxide layer on the surface of the
copper fiber 11. In addition, it is preferable that the upper limit of the holding
time in the oxidation treatment process S21 be set to 100 minutes or shorter so as
to reliably suppress oxidation to the inside of the copper fiber 11.
[0057] Next, in this embodiment, as illustrated in FIG. 3, after performing the oxidation
treatment process S21, the stainless steel container 32, which is filled with the
copper fiber 11, is put in the heating furnace 34 and is heated in a reduction atmosphere.
According to this, the oxidized copper fiber 11 is subjected to a reduction treatment
to form an oxidation-reduction layer, and the copper fibers 11 are bonded to each
other to form the skeleton 12 (reduction treatment process S22).
[0058] Conditions of the reduction treatment process S22 in this embodiment are as follows.
Specifically, an atmosphere is set to a mixed gas atmosphere of argon and hydrogen
(Ar+H2 atmosphere (b)), a holding temperature is set to 500°C to 1050°C, and a holding
time is set in a range of 5 minutes to 300 minutes.
[0059] Here, in a case where the holding temperature in the reduction treatment process
S22 is lower than 500°C, there is a concern that the oxide layer formed on the surface
of the copper fiber 11 may not be sufficiently reduced. On the other hand, in a case
where the holding temperature in the reduction treatment process S22 is higher than
1050°C, there is a concern that heating may be performed to near the melting point
of copper, and thus a decrease in strength and porosity may occur.
[0060] In this regard, in this embodiment, the holding temperature in the reduction treatment
process S22 is set to 500°C to 1050°C. Furthermore, it is preferable that the lower
limit of the holding temperature in the reduction treatment process S22 be set to
600°C or higher so as to reliably reduce the oxide layer formed on the surface of
the copper fiber 11. In addition, it is preferable that the upper limit of the holding
temperature in the reduction treatment process S22 be set to 1000°C or lower so as
to reliably suppress the decrease in strength and the porosity.
[0061] In addition, in a case where the holding time in the reduction treatment process
S22 is shorter than 5 minutes, there is a concern that the oxide layer formed on the
surface of the copper fiber 11 may not be sufficiently reduced, and sintering may
become insufficient. On the other hand, in a case where the holding time in the reduction
treatment process S22 is longer than 300 minutes, there is a concern that thermal
shrinkage may increase and strength may decrease due to the sintering.
[0062] In this regard, in this embodiment, the holding time in the reduction treatment process
S22 is set in a range of 5 minutes to 300 minutes. Furthermore, it is preferable that
the lower limit of the holding time in the reduction treatment process S22 be set
to 10 minutes or longer so as to reliably reduce the oxide layer formed on the surface
of the copper fiber 11 and to allow sintering to sufficiently progress. In addition,
it is preferable that the upper limit of the holding time in the reduction treatment
process S22 be set to 100 minutes or shorter so as to reliably suppress the thermal
shrinkage or the decrease in strength due to the sintering.
[0063] An oxidation-reduction layer is formed on the surface of the copper fiber 11 (skeleton
12) by the oxidation treatment process S21 and the reduction treatment process S22,
and thus minute unevenness having a unique microporous structure occurs. That is,
the oxidation-reduction layers has a porous structure, which causes minute unevenness
on the surface of the copper fiber 11. According to this, a specific surface area
of the entirety of the porous copper body 20 is set to 0.01 m
2/g or greater.
[0064] In addition, the oxide layer is formed on the surface of the copper fiber 11 by the
oxidation treatment process S21, and a plurality of the copper fibers 11 are cross-linked
by the oxide layer. Then, when the reduction treatment process S22 is performed, the
oxide layer formed on the surface of the copper fiber 11 is reduced, and thus the
above-described oxidation-reduction layer is formed. In addition, a plurality of the
oxidation-reduction layers are bonded to each other, and the copper fibers 11 are
sintered, and thus the skeleton 12 is formed.
[0065] According to the manufacturing method as described above, the copper fibers 11 are
sintered, and thus the skeleton 12 is formed, and the oxidation-reduction layer is
formed on the surface of the skeleton 12 (copper fiber 11). Further, the above-described
porosity-normalized electrical conductivity σ
N is set to 20% IACS or higher. Accordingly, the porous copper body 10 according to
this embodiment is manufactured.
[0066] According to the porous copper body 10 according to this embodiment having the above-described
configuration, the porosity P is as high as in a range of 50% to 90% and the porosity-normalized
electrical conductivity σ
N is 20% IACS or higher. Accordingly, the porous copper body is excellent in conductivity
and heat conductivity, and has excellent characteristics as a conductive member and
a heat-transfer member.
[0067] In addition, according to the porous copper body 10 according to this embodiment,
since the oxidation-reduction layer is formed on the surface of the skeleton 12, unevenness
having a unique microporous structure is formed on the surface to increase a specific
surface area. For example, it is possible to greatly improve various characteristics
such as heat-exchange efficiency through a porous skeleton surface and the like. In
addition, by performing an oxidation-reduction treatment, it is possible to further
improve the porosity-normalized electrical conductivity σ
N.
[0068] Further, in this embodiment, in the bonding portion between the copper fibers 11,
oxidation-reduction layers formed on surfaces of the copper fibers 11 are integrally
bonded to each other. Accordingly, the porous copper body 10 is excellent in bonding
strength.
[0069] In addition, according to the porous copper body 10 according to this embodiment,
since the copper fibers 11, in which the diameter R is set in a range of 0.02 mm to
1.0 mm and the ratio L/R between the length L and the diameter R is set in a range
of 4 to 2500, are sintered to form the skeleton 12, a sufficient void is secured between
the copper fibers 11, and a shrinkage rate in the sintering can be suppressed. Accordingly,
it is possible to raise the porosity, and it is possible to attain excellent dimensional
accuracy.
[0070] In addition, this embodiment includes the copper fiber lamination process S01 in
which the copper fibers 11 of which the diameter R is set in a range of 0.02 mm to
1.0 mm and the ratio L/R between the length L and the diameter R is set in a range
of 4 to 2500 are laminated so that the volume density D
P becomes 50% or less of the true density D
T of the copper fibers 11. Accordingly, it is possible to secure a void between the
copper fibers 11, and thus it is possible to suppress shrinkage. According to this,
it is possible to manufacture the porous copper body 10 in which the porosity is high
and the dimensional accuracy is excellent.
[0071] Here, in a case where the diameter R of the copper fibers 11 is less than 0.02 mm,
a bonding area between the copper fibers 11 is small, and thus there is a concern
that sintering strength may be deficient. On the other hand, in a case where the diameter
R of the copper fibers 11 is greater than 1.0 mm, the number of contact points at
which the copper fibers 11 come into contact with each other is deficient, and thus
there is a concern that the sintering strength also becomes deficient.
[0072] In this regard, in this embodiment, the diameter R of the copper fibers 11 is set
in a range of 0.02 mm to 1.0 mm. Furthermore, it is preferable that the lower limit
of the diameter R of the copper fibers 11 be set to 0.05 mm or greater, and the upper
limit of the diameter R of the copper fibers 11 be set to 0.5 mm or less so as to
attain an additional improvement in strength.
[0073] In addition, in a case where the ratio L/R between the length L and the diameter
R of the copper fibers 11 is less than 4, when laminating the copper fibers 11, it
is difficult for the volume density D
P to be 50% or less of the true density D
T of the copper fibers 11, and thus there is a concern that it is difficult to obtain
the porous copper body 10 having a high porosity P. On the other hand, in a case where
the ratio L/R between the length L and the diameter R of the copper fibers 11 is greater
than 2500, it is difficult to uniformly disperse the copper fibers 11, and thus there
is a concern that it is difficult to obtain the porous copper body 10 having a uniform
porosity P.
[0074] In this regard, in this embodiment, the ratio L/R between the length L and the diameter
R of the copper fibers 11 is set in a range of 4 to 2500. Furthermore, it is preferable
that the lower limit of the ratio L/R between the length L and the diameter R of the
copper fibers 11 be set to 10 or greater so as to attain an additional improvement
in porosity. In addition, it is preferable that the upper limit of the ratio L/R between
the length L and the diameter R of the copper fibers 11 be set to 500 or less so as
to reliably obtain the porous copper body 10 having a uniform porosity P.
[0075] In addition, according to the method of manufacturing the porous copper body according
to this embodiment, the oxidation treatment process S21 of oxidizing the copper fibers
11 and the reduction treatment process S22 of reducing the oxidized copper fibers
11 are provided, and thus it is possible to form the oxidation-reduction layer on
the surface of the copper fibers 11 (skeleton 12). In addition, it is possible to
set the porosity-normalized electrical conductivity σ
N to 20% IACS or higher by the oxidation treatment process S21 and the reduction treatment
process S22.
(Second Embodiment)
[0076] Next, description will be given of a porous copper composite member 100 according
to a second embodiment of the disclosure with reference to the accompanying drawings.
[0077] FIG. 4 illustrates the porous copper composite member 100 according to this embodiment.
The porous copper composite member 100 includes a copper plate 120 (main member body)
formed from copper or a copper alloy, and a porous copper body 110 that is bonded
to a surface of the copper plate 120.
[0078] Here, in the porous copper body 110 according to this embodiment, a plurality of
copper fibers are sintered and a skeleton is formed in the same manner as in the first
embodiment. Here, the copper fibers are formed from copper or a copper alloy, and
a diameter R is set in a range of 0.02 mm to 1.0 mm, and a ratio L/R between a length
L and the diameter R is set in a range of 4 to 2500. In this embodiment, the copper
fibers are formed from, for example, C1020 (oxygen-free copper).
[0079] Furthermore, in this embodiment, the copper fibers are subjected to shape imparting
such as twisting and bending. In addition, in the porous copper body 110 according
to this embodiment, an apparent density ratio D
A is set to 51% or less of a true density D
T of the copper fiber.
[0080] In addition, in this embodiment, an oxidation-reduction treatment (an oxidation treatment
and a reduction treatment) is performed as described later. According to this, an
oxidation-reduction layer is formed on the surface of the copper fibers (skeleton)
which constitute the porous copper body 110 and the copper plate 120, and minute unevenness
occurs on the surface of copper fibers (skeleton) and the copper plate 120. According
to this, a specific surface area of the entirety of the porous copper body 110 is
set to 0.01 m
2/g or greater. The specific surface area of the entirety of the porous copper body
110 is preferably 0.03 m
2/g or greater. However, there is no limitation thereto.
[0081] In addition, an oxidation-reduction layer formed on the surface of the copper fibers
and an oxidation-reduction layer formed on the surface of the copper plate are integrally
bonded to each other at a bonding portion between the copper fibers which constitute
the porous copper body 110 and the surface of the copper plate 120.
[0082] In addition, in the porous copper body 110 according to the embodiment, a porosity
P is in a range of 50% to 90% and a porosity-normalized electrical conductivity σ
N which is defined by dividing a electrical conductivity σ
P of the porous copper body 110, measured by a 4-terminal sensing, by an apparent density
ratio D
A of the porous copper body 110 is 20% IACS or higher.
[0083] The porosity P is preferably in a range of 70% to 90%. However, there is no limitation
thereto.
[0084] Next, description will be given of a method of manufacturing the porous copper composite
member 100 according to this embodiment with reference to a flowchart in FIG. 5.
[0085] First, the copper plate 120 that is a main member body is prepared (copper plate-disposing
process S100). Next, copper fibers are dispersed and laminated on a surface of the
copper plate 120 (copper fiber lamination process S101). Here, in the copper fiber
lamination process S101, a plurality of the copper fibers are laminated so that a
volume density D
P becomes 50% or less of the true density D
T of the copper fibers.
[0086] Next, the copper fibers laminated on the surface of the copper plate 120 are sintered
to shape the porous copper body 110, and the porous copper body 110 and the copper
plate 120 are bonded to each other (a sintering process S102 and a bonding process
S103). As illustrated in FIG. 5, the sintering process S102 and the bonding process
S103 include an oxidation treatment process S121 of performing an oxidation treatment
of the copper fibers and the copper plate 120, and a reduction treatment process S122
of reducing and sintering the copper fibers and the copper plate 120 which are subjected
to the oxidation treatment.
[0087] In this embodiment, the copper plate 120 on which the copper fibers are laminated
is put in a heating furnace, and is heated in an oxidizing atmosphere to perform an
oxidation treatment of the copper fibers (oxidation treatment process S121). According
to the oxidation treatment process S121, for example, an oxide layer having a thickness
of 1 µm to 100 µm is formed on the surface of the copper fibers and the copper plate
120.
[0088] Here, conditions of the oxidation treatment process S121 in this embodiment are as
follows. Specifically, a holding temperature is set to 500°C to 1050°C and preferably
600°C to 1000°C, and a holding time is set in a range of 5 minutes to 300 minutes
and preferably in a range of 10 minutes to 100 minutes.
[0089] Next, in this embodiment, after performing the oxidation treatment process S121,
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
of the copper fibers and the copper plate 120 which are oxidized. According to this,
the copper fibers are bonded to each other, and the copper fibers and the copper plate
120 are bonded to each other (reduction treatment process S122).
[0090] Here, conditions of the reduction treatment process S122 in this embodiment are as
follows. An atmosphere is set to a mixed gas atmosphere of nitrogen and hydrogen,
a holding temperature is set to 500°C to 1050°C and preferably 600°C to 1000°C, and
a holding time is set in a range of 5 minutes to 300 minutes and preferably in a range
of 10 minutes to 100 minutes.
[0091] An oxidation-reduction layer is formed on the surface of the copper fibers (skeleton)
and the copper plate 120 by the oxidation treatment process S121 and the reduction
treatment process S122, and minute unevenness occurs.
[0092] In addition, the oxide layer is formed on the copper fibers (skeleton) and the surface
of the copper plate 120 by the oxidation treatment process S121. Due to the oxide
layer, a plurality of the copper fibers are cross-linked to each other, and the copper
fibers and the copper plate 120 are cross-linked to each other. Then, when the reduction
treatment process S122 is performed, the oxide layer formed on the surface of the
copper fibers (skeleton) and the copper plate 120 is reduced, and the copper fibers
are sintered through the oxidation-reduction layer. According to this, the skeleton
is formed, and the porous copper body 110 and the copper plate 120 are bonded to each
other. Further, the above-described porosity-normalized electrical conductivity σ
N of the porous copper body 110 is set to 20% IACS or higher.
[0093] According to the manufacturing method as described above, the porous copper composite
member 100 according to this embodiment is manufactured.
[0094] According to the porous copper composite member 100 according to this embodiment
having the above-described configuration, the porosity-normalized electrical conductivity
σ
N of the porous copper body 110 is set to 20% IACS or higher. Accordingly, the porous
copper composite member 100 is excellent in conductivity and heat conductivity, and
it is possible to improve conductivity and heat conductivity of the entirety of the
porous copper composite member 100.
[0095] In addition, in this embodiment, the oxidation-reduction layer is formed on the surface
of the copper fibers which constitute the porous copper body 110 and the copper plate
120, the specific surface area of the entirety of the porous copper body 110 is set
to 0.01 m
2/g or greater, and the porosity P is set in a range of 50% to 90%. Accordingly, it
is possible to greatly improve heat-exchange efficiency, water retention and the like.
[0096] In addition, in this embodiment, an oxidation-reduction layer formed on the surface
of the copper fibers and an oxidation-reduction layer formed on the surface of the
copper plate 120 are integrally bonded to each other at a bonding portion between
the copper fibers which constitute the porous copper body 110 and the surface of the
copper plate 120. Accordingly, the porous copper body 110 and the copper plate 120
are strongly bonded to each other, and thus strength of a bonding interface, conductivity,
and heat conductivity are excellent.
[0097] According to the method of manufacturing the porous copper composite member 100 according
to this embodiment, the copper fibers are laminated on the surface of the copper plate
120 formed from copper or a copper alloy, and the sintering process S102 and the bonding
process S103 are simultaneously performed, and thus it is possible to simplify a manufacturing
process.
[0098] In addition, it is possible to set the porosity-normalized electrical conductivity
σ
N to 20% IACS or higher by carrying out the oxidation treatment process S121 and the
reduction treatment process S122.
[0099] Hereinbefore, description has been given of the embodiments of the disclosure, but
approximate modifications can be made in a range not departing from the scope of the
disclosure without limitation thereto.
[0100] For example, description has been given of manufacturing of the porous copper body
by using a manufacturing facility illustrated in FIG. 3. However, there is no limitation
thereto, and the porous copper body can be manufactured by using another manufacturing
facility.
[0101] With regard to the atmosphere of the oxidation treatment processes S21 and S121,
an oxidation atmosphere in which copper or a copper alloy is oxidized at a predetermined
temperature may be used. Specifically, the atmosphere is not limited to the atmospheric
atmosphere, and may be an atmosphere in which 0.5 vol% or greater of oxygen is contained
in an inert gas (for example, nitrogen). In addition, with regard to the atmosphere
of the reduction treatment processes S22 and S122, it is possible to use a reduction
atmosphere in which a copper oxide is reduced into metal copper or the copper oxide
is decomposed at a predetermined temperature. Specifically, it is possible to appropriately
use a nitrogen-hydrogen mixed gas containing several vol% or greater of hydrogen,
an argon-hydrogen mixed gas, a pure hydrogen gas, an ammonia decomposed gas which
is industrially used in many cases, and the like and a propane decomposed gas which
is industrially used in many cases, and the like.
[0102] In addition, in this embodiment, description has been given of an example in which
the skeleton of the porous copper body is formed by sintering the copper fibers. However,
there is no limitation thereto. For example, a porous copper body such as a fiber
nonwoven fabric or a metal filter is prepared, and by performing the oxidation treatment
on the porous copper body under conditions of a holding temperature of 500°C to 1050°C
in an oxidizing atmosphere and performing the reduction treatment on the porous copper
body under conditions of a holding temperature of 500°C to 1050°C in a reducing atmosphere,
the porosity-normalized electrical conductivity σ
N may be set to 20% IACS or higher.
[0103] Further, in this embodiment, description has been given of an example in which the
oxidation-reduction layer is formed on the surface of the skeleton. However, there
is no limitation thereto. The oxidation-reduction layer may not be sufficiently formed
as long as the porosity-normalized electrical conductivity σ
N is 20% IACS or higher.
[0104] In addition, in this embodiment, description has been given of an example in which
copper fibers formed from oxygen-free copper (JIS C1020), phosphorous-deoxidized copper
(JIS C1201 and C1220), or tough pitch copper (JIS C1100) are used. However, there
is no limitation thereto, and as a material of the copper fibers 11, other high conductivity
copper alloys such as Cr-copper (C18200) or Cr-Zr copper (C18150) may be used. In
this embodiment, the copper fibers are used, however, copper powders may be used and
both the copper powders and the copper fibers may also be used. An average particle
diameter of the copper powders is preferably 0.005 mm to 0.3 mm and more preferably
0.01 mm to 0.1 mm. However, there is no limitation thereto. In addition, in a case
where both the copper fibers and the copper powders are used, the copper powder content
is preferably 5% to 20% based on the copper fiber content. However, there is no limitation
thereto.
[0105] In addition, in the second embodiment, description has been given of the porous copper
composite member having a structure illustrated in FIG. 4 as an example. However,
there is no limitation thereto, and a porous copper composite member having a structure
as illustrated in FIG. 6 to FIG. 11 is also possible.
[0106] Further, in the second embodiment, the bonding method in which the sintered layer
including oxidation-reduction layer is formed on the bonding portion of the porous
copper body and the main member body is exemplified as a desirable method, but there
is no limitation thereto. Various welding methods (laser welding method and resistance
welding process) or a bonding method by a brazing method using brazing material melting
at low temperature may also be used as long as the porosity-normalized electrical
conductivity σ
N of the porous copper body is 20% IACS or higher.
[0107] For example, as illustrated in FIG. 6, it may be a porous copper composite member
200 having a structure in which, as a main member body, a plurality of copper tubes
220 are inserted into a porous copper body 210.
[0108] Alternatively, as illustrated in FIG. 7, it may be a porous copper composite member
300 having a structure in which, as a main member body, a copper tube 320 curved in
a U-shape is inserted into a porous copper body 310.
[0109] In addition, as illustrated in FIG. 8, it may be a porous copper composite member
400 having a structure in which a porous copper body 410 is bonded to an inner peripheral
surface of a copper tube 420 that is a main member body.
[0110] In addition, as illustrated in FIG. 9, it may be a porous copper composite member
500 having a structure in which a porous copper body 510 is bonded to an outer peripheral
surface of a copper tube 520 that is a main member body.
[0111] In addition, as illustrated in FIG. 10, it may be a porous copper composite member
600 having a structure in which a porous copper body 610 is bonded to an inner peripheral
surface and an outer peripheral surface of a copper tube 620 that is a main member
body.
[0112] In addition, as illustrated in FIG. 11, it may be a porous copper composite member
700 having a structure in which a porous copper body 710 is bonded to both surfaces
of a copper plate 720 that is a main member body.
Examples
[0113] Hereinafter, description will be given of the results of a confirmation experiment
carried out to confirm the effect of the disclosure.
[Example 1]
[0114] Various porous bodies manufactured by the materials and manufacturing method shown
in Table 1 were prepared. First, the porosity and the porosity-normalized electrical
conductivity before the heat treatment were measured. Thereafter, an oxidation treatment
and reduction treatment were performed under the conditions described in Table 1,
and the porosity and the porosity-normalized electrical conductivity after the oxidation
treatment and reduction treatment were measured. The porosity and the porosity-normalized
electrical conductivity were measured in the following manner. Evaluation results
are illustrated in Table 1.
(Porosity)
[0115] The true density D
T (g/cm
3) was measured by a precision balance to calculate the porosity P by the following
expression. The mass of the porous copper body was represented as m(g), and a volume
of the porous copper body was V (cm
3).

(Porosity-normalized electrical conductivity)
[0116] Using a sample cut into a plate having dimensions of 30 mm (width)×200 mm (length)×5
mm (thickness), the electrical conductivity σ
P (% IACS) was measured by the 4-terminal sensing under conditions of a voltage terminal
interval of 150 mm and measuring current of 0.5 A with a microohm high tester 3227
manufactured by HIOKI E.E. CORPORATION, in accordance with JIS C 2525. In addition,
the porosity-normalized electrical conductivity σ
N was calculated by the following expression.

[0117] The apparent density ratio D
A (%) was calculated according to the following expression.

[0118] Here, m is the mass (g) of the porous copper body. V is the volume (cm
3) of the porous copper body. D
T is the true density (g/cm
3) of copper or copper alloy constituting the porous copper body.
[Table 1]
|
Porous copper body before treatment |
Oxidation treatment process |
Reduction treatment process |
Porous copper body after treatment |
Material |
Manufacturing method |
Porosity (%) |
Porosity -normalized electrical conductivity (% IACS) |
Atmosphere |
Temperature (°C) |
Time (min) |
Atmosphere |
Temperature (°C) |
Time (min) |
Porosity (%) |
Porosity -normalized electrical conductivity (%IACS) |
Example |
1 |
C1100 |
Nonwoven fabric |
55 |
17.5 |
Atmospheric |
500 |
60 |
N2-10%H2 |
1050 |
10 |
51 |
24.6 |
2 |
C1100 |
Foaming method |
85 |
16.3 |
N2-1%O2 |
700 |
120 |
N2-10%H2 |
500 |
90 |
77 |
26.3 |
3 |
C1100 |
Spacer method |
70 |
19.1 |
Atmospheric |
900 |
30 |
H2 |
700 |
30 |
63 |
30.0 |
4 |
C1100 |
Precision casting method |
85 |
18.8 |
Atmospheric |
1050 |
10 |
H2 |
900 |
60 |
81 |
29.1 |
Comparative Example |
1 |
C1100 |
Foaming method |
85 |
16.3 |
Atmospheric |
450 |
60 |
N2-10%H2 |
600 |
120 |
83 |
17.9 |
2 |
C1100 |
Spacer method |
70 |
19.1 |
N2-10%O2 |
700 |
30 |
H2 |
450 |
60 |
69 |
18.8 |
[0119] In Examples 1 to 4 in which the oxidation treatment and the reduction treatment were
performed under the conditions specified in the disclosure, the porosity P was in
a range of 50% to 90% and all the porosity-normalized electrical conductivity was
higher than 20% IACS.
[0120] In contrast, in Comparative Example 1 in which a temperature condition of the oxidation
treatment was low and Comparative Example 2 in which a temperature condition of the
reduction treatment was low, even after the oxidation treatment and the reduction
treatment, the electrical conductivity was not sufficiently improved, and the porosity-normalized
electrical conductivity σ
N was lower than 20% IACS.
(Example 2)
[0121] In addition, an oxidation-reduction treatment was performed using copper powders
illustrated in Table 2 under conditions illustrated in Table 2 to manufacture a porous
copper body. The porosity and the porosity-normalized electrical conductivity were
measured with respect to the porous copper body that was obtained. The porosity and
the porosity-normalized electrical conductivity were measured by the same method as
in Example 1, except that, in Example 2, D
T at the time of calculating the porosity-normalized electrical conductivity was set
to a true density (g/cm
3) of the copper powders constituting the porous copper body. Evaluation results are
illustrated in Table 2.
[Table 2]
|
Copper raw material (powder) |
Oxidation treatment process |
Reduction treatment process |
Porous copper body |
Material |
Average particle diameter (mm) |
Atmosphere |
Temperature (°C) |
Time (min) |
Atmosphere |
Temperature (°C) |
Time (min) |
Porosity (%) |
Porosity -normalized electrical conductivity (% IACS) |
Example |
11 |
C1020 |
0.07 |
Atmospheric |
1050 |
30 |
H2 |
600 |
90 |
70 |
24.5 |
12 |
C1100 |
0.06 |
N2-10%O2 |
500 |
60 |
H2 |
800 |
30 |
53 |
30.3 |
13 |
C1201 |
0.07 |
N2-1%O2 |
700 |
10 |
N2-10%H2 |
1050 |
10 |
61 |
28.2 |
14 |
C1220 |
0.06 |
Atmospheric |
900 |
90 |
N2-10%H2 |
500 |
60 |
51 |
29.2 |
Comparative Example |
11 |
C1201 |
0.07 |
Atmospheric |
450 |
60 |
N2-10%H2 |
600 |
120 |
74 |
19.7 |
12 |
C1100 |
0.06 |
Atmospheric |
700 |
30 |
H2 |
450 |
120 |
62 |
11.5 |
[0122] In Examples 11 to 14 in which the oxidation treatment and the reduction treatment
were performed under the conditions specified in the disclosure, the porosity P was
in a range of 50% to 90% and all the porosity-normalized electrical conductivity was
higher than 20% IACS.
[0123] In contrast, in Comparative Example 11 in which a temperature condition of the oxidation
treatment was low and Comparative Example 12 in which a temperature condition of the
reduction treatment was low, the porosity-normalized electrical conductivity σ
N was lower than 20% IACS.
(Example 3)
[0124] In addition, an oxidation-reduction treatment was performed using copper fibers illustrated
in Table 3 under conditions illustrated in Table 3 to manufacture a porous copper
body. The fiber diameter R and the fiber length L of the copper fiber were measured
by the following method.
(Fiber Diameter R)
[0125] As the fiber diameter R (mm), an average value of an equivalent circle diameter (Heywood
diameter) R=(A/π)
1/2×2, which was calculated through image analysis on the basis of JIS Z 8827-1 by using
a particle analyzer "Morphologi G3" manufactured by Malvern Instruments Ltd., was
used.
(Fiber Length L)
[0126] As the fiber length L (mm) of the copper fibers, a simple average value, which was
calculated through image analysis by using the particle analyzer "Morphologi G3" manufactured
by Malvern Instruments Ltd., was used.
[0127] First, with respect to the porous copper body that was obtained, the porosity and
the porosity-normalized electrical conductivity were measured. The porosity and the
porosity-normalized electrical conductivity were measured by the same method as in
Example 1, except that, in Example 3, D
T at the time of calculating the porosity-normalized electrical conductivity was set
to a true density (g/cm
3) of the copper fibers constituting the porous copper body. Evaluation results are
illustrated in Table 3.
[Table 3]
|
Copper raw material (fiber) |
Oxidation treatment process |
Reduction treatment process |
Porous copper body |
Material |
Diameter R (mm) |
Ratio L/R between length L and diameter R |
Atmosphere |
Temperature (°C) |
Time (min) |
Atmosphere |
Temperature (°C) |
Time (min) |
Porosity (%) |
Porosity-normalized electrical conductivity (% IACS) |
Example |
21 |
C1020 |
0.10 |
30 |
Atmospheric |
1000 |
30 |
N2-10%H2 |
550 |
120 |
77 |
28.1 |
22 |
C1020 |
0.10 |
30 |
N2-10%O2 |
550 |
150 |
AX gas |
900 |
60 |
71 |
24.3 |
23 |
C1100 |
0.03 |
1000 |
Atmospheric |
900 |
10 |
H2 |
1050 |
10 |
87 |
27.3 |
24 |
C1201 |
1.00 |
5 |
Atmospheric |
1050 |
60 |
H2 |
700 |
30 |
53 |
31.2 |
25 |
C1220 |
0.30 |
100 |
N2-1%O2 |
600 |
90 |
N2-10%H2 |
800 |
60 |
79 |
25.9 |
26 |
C1220 |
0.30 |
100 |
Atmospheric |
850 |
120 |
RX gas |
1000 |
90 |
83 |
26.5 |
Comparative Example |
21 |
C1220 |
0.30 |
100 |
Atmospheric |
450 |
60 |
N2-10%H2 |
600 |
120 |
85 |
18.1 |
22 |
C1020 |
0.10 |
30 |
N2-10%O2 |
700 |
30 |
H2 |
450 |
120 |
84 |
12.5 |
[0128] In Examples 21 to 26 in which the oxidation treatment and the reduction treatment
were performed under the conditions specified in the disclosure, the porosity P was
in a range of 50% to 90% and all the porosity-normalized electrical conductivity was
higher than 20% IACS.
[0129] In contrast, in Comparative Example 21 in which a temperature condition of the oxidation
treatment was low and Comparative Example 22 in which a temperature condition of the
reduction treatment was low, the porosity-normalized electrical conductivity σ
N was lower than 20% IACS.
[0130] As described above, it was confirmed that it is possible to provide a porous copper
body which has sufficient conductivity and heat conductivity, even in a case where
porosity is high, and is particularly suitable for a conductive member and a heat-transfer
member, according to examples.
Industrial Applicability
[0131] According to the porous copper body, a porous copper composite member in which the
porous copper body is bonded to a main member body, a method of manufacturing the
porous copper body, and method of manufacturing the porous copper composite member
of the disclosure, it is possible to obtain a porous copper body which has sufficient
conductivity and heat conductivity, even in a case where a porosity is high. The porous
copper body is suitable for a conductive member and a heat-transfer member.
Reference Signs List
[0132]
10, 110: Porous copper body
11: Copper fiber
12: Skeleton
100: Porous copper composite member
120: Copper plate (Main member body)