U.S. patent application number 16/434632 was filed with the patent office on 2020-12-10 for copper-iron alloy electroplating solution and electroplating method using the same.
This patent application is currently assigned to JCU INTERNATIONAL, INC.. The applicant listed for this patent is JCU INTERNATIONAL, INC.. Invention is credited to Masao HORI.
Application Number | 20200385882 16/434632 |
Document ID | / |
Family ID | 1000004259049 |
Filed Date | 2020-12-10 |
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United States Patent
Application |
20200385882 |
Kind Code |
A1 |
HORI; Masao |
December 10, 2020 |
COPPER-IRON ALLOY ELECTROPLATING SOLUTION AND ELECTROPLATING METHOD
USING THE SAME
Abstract
Provided are a copper-iron alloy electroplating solution
containing divalent copper ions, trivalent iron ions, and an
organic compound having a carboxy group, and a technique for
producing a copper-iron alloy through a method other than a melting
method by an electroplating method using the copper-iron alloy
electroplating solution.
Inventors: |
HORI; Masao; (Wixom,
MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JCU INTERNATIONAL, INC. |
Wixom |
MI |
US |
|
|
Assignee: |
JCU INTERNATIONAL, INC.
Wixom
MI
|
Family ID: |
1000004259049 |
Appl. No.: |
16/434632 |
Filed: |
June 7, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 3/58 20130101; C25D
3/562 20130101 |
International
Class: |
C25D 3/56 20060101
C25D003/56; C25D 3/58 20060101 C25D003/58 |
Claims
1. A copper-iron alloy electroplating solution, comprising divalent
copper ions, trivalent iron ions, and an organic compound having a
carboxy group.
2. The copper-iron alloy electroplating solution according to claim
1, wherein a source of the divalent copper ions is cupric sulfate
or cupric chloride.
3. The copper-iron alloy electroplating solution according to claim
1, wherein a source of the trivalent iron ions is ferric sulfate or
ferric chloride.
4. The copper-iron alloy electroplating solution according to claim
1, wherein the organic compound having a carboxy group is
ethylenediaminetetraacetic acid, sodium gluconate, or citric
acid.
5. The copper-iron alloy electroplating solution according to claim
1, wherein the solution has a pH in a range of from 4 to 11.
6. The copper-iron alloy electroplating solution according to claim
1, wherein a molar ratio of copper ions/iron ions is in a range of
from 0.1 to 0.8.
7. A copper-iron alloy electroplating method, comprising
electroplating a material to be plated in the copper-iron alloy
electroplating solution according to claim 1, thereby forming a
copper-iron alloy film on the material to be plated.
8. A copper-iron alloy film obtained by the copper-iron alloy
electroplating method according to claim 7.
Description
BACKGROUND OF THE INVENTION
Field of the Invention
[0001] The present invention relates to a copper-iron alloy
electroplating solution and an electroplating method using the
same.
Background Art
[0002] A copper-iron alloy has properties of both copper and iron,
and therefore is expected to be used for a structural material, a
thermally conductive material, a magnetic material, an electrically
conductive spring raw material, an electrically conductive
material, etc.
[0003] However, copper and iron have different specific gravities,
and therefore, it is difficult to uniformly alloy these together,
and a melting method is known as a technique for producing a
copper-iron alloy for the time being (for example,
JP-A-2016-216758). However, a copper-iron alloy produced by a
melting method has difficulty in processing, and use thereof is
limited.
SUMMARY OF THE INVENTION
[0004] In view of this, an object of the present invention is to
provide a technique for producing a copper-iron alloy by a method
other than the melting method.
[0005] The present inventors made intensive studies for achieving
the above object, and as a result, they found that a copper-iron
alloy can be electroplated using an electroplating solution
prepared by combining copper ions and iron ions both having a
specific valence, and thus completed the invention.
[0006] That is, the present invention is directed to a copper-iron
alloy electroplating solution containing divalent copper ions,
trivalent iron ions, and an organic compound having a carboxy
group.
[0007] Further, the present invention is directed to a copper-iron
alloy electroplating method including electroplating a material to
be plated in the above-mentioned copper-iron alloy electroplating
solution, thereby forming a copper-iron alloy film on the material
to be plated.
[0008] In addition, the present invention is directed to a
copper-iron alloy film obtained by the above-mentioned
electroplating method.
[0009] By using the copper-iron alloy electroplating solution of
the present invention, a copper-iron alloy film can be formed by
plating, and therefore can be used for materials or applications to
which it could not be applied so far.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The patent or application file contains at least one drawing
executed in color. Copies of this patent or patent application
publication with color drawing(s) will be provided by the Office
upon request and payment of the necessary fee.
[0011] FIG. 1 shows an EDS spectrum of a copper-iron alloy film
obtained in Example 1.
[0012] FIG. 2 shows EDS elemental mapping of the copper-iron alloy
film obtained in Example 1.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The copper-iron alloy electroplating solution of the present
invention (hereinafter referred to as "the plating solution of the
present invention") contains divalent copper ions, trivalent iron
ions, and an organic compound having a carboxy group.
[0014] The content of the divalent copper ions in the plating
solution of the present invention is not particularly limited, but
is, for example, from 0.05 to 5 mass % (hereinafter simply referred
to as "%"), preferably from 0.1 to 2.5%.
[0015] A source of the divalent copper ions is not particularly
limited, but examples thereof include sulfates such as cupric
sulfate and chlorides such as cupric chloride.
[0016] The content of the trivalent iron ions in the plating
solution of the present invention is not particularly limited, but
is, for example, from 0.1 to 20%, preferably from 0.25 to 10%.
[0017] A source of the trivalent iron ions is not particularly
limited, but examples thereof include sulfates such as ferric
sulfate and chlorides such as ferric chloride.
[0018] In the plating solution of the present invention, the ratio
of copper ions/iron ions is not particularly limited, but is
preferably from 0.05 to 0.95, more preferably from 0.1 to 0.8.
[0019] The organic compound having a carboxy group contained in the
plating solution of the present invention is not particularly
limited, but examples thereof include ethylenediaminetetraacetic
acid, carboxylic acids such as gluconic acid and citric acid, and
alkali metal salts of carboxylic acids such as sodium gluconate and
sodium citrate. Among these, ethylenediaminetetraacetic acid,
sodium gluconate, and citric acid are preferred. Among these
organic compounds having a carboxy group, one type or two or more
types, preferably two or more types may be used. The content of the
organic compound having a carboxy group in the plating solution of
the present invention is not particularly limited, but is, for
example, from 2 to 25%, preferably from 5 to 10%.
[0020] The plating solution of the present invention is preferably
a solution composed only of the above-mentioned essential
components, and more preferably a chloride bath containing
chlorides as the source of copper ions and the source of iron ions,
a sulfate bath containing sulfates as the source of copper ions and
the source of iron ions, or the like, however, an electrically
conductive salt such as potassium chloride, sodium chloride,
potassium sulfate, or sodium sulfate, a surfactant such as
polyethylene glycol or polypropylene glycol, a pH buffer agent such
as boric acid or sodium borate, or the like may be further
incorporated therein.
[0021] The pH of the plating solution of the present invention is
not particularly limited, but is, for example, from 4 to 11. In the
adjustment of this pH, an alkaline substance such as sodium
hydroxide or an acidic substance such as hydrochloric acid may be
used.
[0022] As preferred embodiments of the plating solution of the
present invention, the following solutions are exemplified.
<Chloride Bath 1>
[0023] Ferric chloride: 2.5 to 10 g/L as iron
[0024] Cupric chloride: 1.25 to 5 g/L as copper
[0025] Sodium gluconate: 40 to 100 g/L
[0026] Disodium ethylenediaminetetraacetate: 15 to 60 g/L
[0027] pH: 7 to 11
<Chloride Bath 2>
[0028] Ferric chloride: 2.5 to 10 g/L as iron
[0029] Cupric chloride: 1.25 to 5 g/L as copper
[0030] Sodium gluconate: 40 to 100 g/L
[0031] Citric acid: 1 to 50 g/L
[0032] pH: 4 to 7
<Sulfate Bath>
[0033] Ferric sulfate: 2.5 to 10 g/L as iron
[0034] Copper sulfate: 1.25 to 5 g/L as copper
[0035] Sodium gluconate: 40 to 100 g/L
[0036] Disodium ethylenediaminetetraacetate: 15 to 60 g/L
[0037] pH: 7 to 11
[0038] A method for preparing the plating solution of the present
invention is not particularly limited, and for example, the
above-mentioned components may be added and mixed in water, and if
necessary, the pH may be adjusted.
[0039] A method for electroplating a material to be plated using
the plating solution of the present invention is not particularly
limited, and for example, a material to be plated may be
electroplated in the plating solution of the present invention
under conditions at a bath temperature of 10 to 70.degree. C. using
an anode of copper, iron, carbon, stainless steel, iridium oxide,
or the like, and at a current density of 0.25 to 4 A/dm.sup.2,
preferably at a bath temperature of 30 to 60.degree. C. using an
anode of carbon, iridium oxide, or the like, and at a current
density of 0.5 to 3 A/dm.sup.2. By doing this, a copper-iron alloy
film is formed on the material to be plated. Whether or not this
copper-iron alloy film is formed can be confirmed by analysis such
as EDS or X-ray fluorescence.
[0040] The material to be plated that can be plated in the plating
solution of the present invention is not particularly limited as
long as it can be plated, however, examples thereof include metals
such as brass, copper, nickel, stainless steel, and aluminum, and
resins such as ABS, nylon, polypropylene (PP), polybutylene
terephthalate (PBT), and polyphenylene sulfide (PPS).
[0041] The thus obtained copper-iron alloy film of the present
invention has properties of thermal conductivity, magnetism, and
electrical conductivity. The composition of this copper-iron alloy
film can be adjusted by changing the ratio of copper ions/iron ions
in the plating solution of the present invention, the pH of the
plating solution, and the temperature of the plating solution, and
therefore is not particularly limited, but is, for example, as
follows: copper: 5 to 97.9%, iron: 1.5 to 94.4%, O: 0.3 to 15%, and
C: 0.3 to 15%, preferably, copper: 10 to 96%, iron: 2 to 88%, O: 1
to 10%, and C: 1 to 10%. Incidentally, when the composition of the
copper-iron alloy film of the present invention is calculated only
in terms of metals, the composition is as follows: copper: 10 to
97.5% and iron: 2.5 to 90%, preferably copper: 20 to 95% and iron:
5 to 80%.
[0042] Since the copper-iron alloy film of the present invention
has properties of thermal conductivity, magnetism, and electrical
conductivity, the film can be utilized for a structural material, a
thermally conductive material, a magnetic material, an electrically
conductive spring raw material, an electrically conductive
material, etc. in the same manner as a copper-iron alloy film
produced by a method other than conventionally known plating.
EXAMPLE
[0043] Hereinafter, the present invention will be described in
detail with reference to Examples, however, the invention is by no
means limited to these Examples.
Examples 1 to 7 and Comparative Example 1
[0044] Copper-Iron Alloy Electroplating:
[0045] Copper-iron alloy electroplating solutions were prepared by
dissolving respective components shown in the following Table 1 in
water. In each of these copper-iron alloy electroplating solutions,
a test piece (one obtained by nickel plating a brass flat plate)
was placed, and electroplated for 5 minutes under conditions shown
in Table 1.
TABLE-US-00001 TABLE 1 Plating solution composition and Example
Example Example Example Example Example Example Comparative plating
conditions 1 2 3 4 5 6 7 Example 1 Ferric chloride 35 35 35 -- 35
35 25 -- hexahydrate g/L Ferric sulfate -- -- -- 25 -- -- -- --
n-hydrate g/L Ferrous sulfate g/L -- -- -- -- -- -- -- 25 Cupric
chloride g/L 7.5 7.5 7.5 -- 2.5 15.0 5 -- Copper sulfate g/L -- --
-- 5 -- -- -- 5 0.5 mol/L EDTA 200 -- -- 150 200 200 200 solution
ml/L Citric acid g/L -- 30 30 -- -- -- Sodium gluconate g/L 80 80
80 60 80 80 60 60 Plating solution pH* 10 4.5 8.5 8.4 10 10 6.8 4.5
Bath temperature .degree. C. 50 50 50 45 50 50 50 45 Current
density A/dm.sup.2 1 1 1 1 1 1 1 1 Cu content in film % 67.8 47.8
25.4 65.8 54.7 84.9 31.9 96.7 Fe content in film % 24.7 38.6 55.5
27.7 34.8 8.75 48.6 0 O content in film % 3.86 7.03 9.53 3.23 6.46
4.29 9.59 2.01 C content in film % 3.64 6.57 9.57 3.27 4.04 2.06
9.91 1.29 *adjusted with sodium hydroxide
[0046] The contents of copper and iron in each film after plating
were determined by EDS. These results are also shown in Table 1.
Further, the results of EDS of the test piece of Example 1 are
shown in FIG. 1 (spectrum) and FIG. 2 (elemental mapping).
[0047] From the above results, a copper-iron alloy film was
obtained only using a plating solution containing divalent copper
ions and trivalent iron ions. Further, from the result of EDS, it
could be confirmed that the alloy is uniform.
[0048] The present invention can be utilized for producing a
copper-iron alloy film, and a structural material, a thermally
conductive material, a magnetic material, an electrically
conductive spring raw material, an electrically conductive
material, etc. using the film.
* * * * *