TECHNICAL FIELD
[0001] The present disclosure relates to a copper alloy wire rod.
BACKGROUND ART
[0002] Electrical wire diameters are in a trend of being further thinned in diameter compared
to conventional due to a size reduction of products, space savings of electrical wires,
an increase in signal lines, etc. in equipment connection cables. For example, in
place of pure copper wire which is lacking in strength, wires of copper alloy such
as Cu-Sn, Cu-Cr, Cu-Ag have come to be used. Among copper alloys, a Cu-Ag alloy is
superior in the balance of high strength and high electric conductivity.
[0003] For example, Patent Document 1 discloses a manufacturing method of a copper alloy
which cold works an ingot of a copper alloy composition containing 1 to 10% by weight
of Ag, with a remainder consisting of Cu and inevitable impurities, then heat treats
for 0.5 to 5 hours at a temperature of 570 to 680°C in a vacuum atmosphere or an inert
gas atmosphere in the middle of this cold working, further performs cold working,
and conducts heat treatment over 0.5 to 40 hours at a temperature of 400 to 550°C
in a vacuum atmosphere or an inert gas atmosphere in the middle of this cold working.
[0004] In addition, Patent Document 2 discloses a Cu-Ag alloy wire having an Ag content
of 1 to 10 wt%, and a remainder which is Cu and inevitable impurities, in which the
entirety of the structure consisting of a solid solution of Cu consists of a recrystallized
texture.
[0005] In the above Patent Documents 1 to 2, the eutectic phase of Cu and Ag is extended
into filament shape, and achieves an improvement in strength and electric conductivity.
In addition, in the manufacturing method of Cu-Ag alloy wire in Patent Document 2,
an improvement in strength is achieved by heat treatment to develop a recrystallized
texture, and high processing after the heat treatment.
[0006] However, in Patent Document 1, the strength characteristic is insufficient due to
the control of the precipitation distribution of the eutectic phase contributing to
the strength after wire drawing being improper. In addition, in Patent Document 2,
since the appropriate wire drawing conditions are not being set prior to heat treatment,
material embrittlement during heat treatment progresses, and it is difficult to perform
wire thinning. For this reason, it is not a finished product having cost competitiveness
due to the inferiority in productivity. In this way, in addition to improvements in
strength and electric conductivity, it is difficult to simultaneously achieve an improvement
in drawability, which is manufacturability, in Patent Documents 1 to 2.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0008] An object of the present disclosure is to provide a copper alloy wire rod superior
in the balance of strength, electric conductivity and drawability.
Means for Solving the Problems
[0009] A copper alloy wire rod according to a first aspect of the present disclosure includes
an alloy composition including 1.0% by mass or more and 6.0% by mass or less of Ag,
a remainder being Cu and inevitable impurities, in which, for a peak intensity I(111)
of 111 diffraction, a peak intensity I(200) of 200 diffraction, a peak intensity I(220)
of 220 diffraction and a peak intensity I(311) of 311 diffraction obtained by X-ray
diffraction analysis of a surface, a peak intensity ratio of a total intensity of
the peak intensity I(111), the peak intensity I(200) and the peak intensity I(311)
relative to the peak intensity I(220) ((the peak intensity I(111) + the peak intensity
I(220) + the peak intensity I(311)) / the peak intensity I(220)) is 1.20 or more and
3.00 or less.
[0010] According to a second aspect of the present disclosure, in the copper alloy wire
rod as described in the first aspect, the alloy composition further includes a total
of 0.05% by mass or more and 0.30% by mass or less of at least one element selected
from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr.
[0012] According to a fourth aspect of the present disclosure, in the copper alloy wire
rod as described in any one of the first to third aspects, a cross section is circular
shape having a diameter of 0.02 mm or more and 0.08 mm or less.
[0013] According to a fifth aspect of the present disclosure, in the copper alloy wire rod
as described in any one of the first to third aspects, a cross section is a ribbon
shape having a long side of 0.060 mm or more and 0.500 mm or less and a short side
of 0.005 mm or more and 0.040 mm or less.
Effects of the Invention
[0014] According to the present disclosure, it is possible to provide a copper alloy wire
rod superior in the balance of strength, electric conductivity and drawability.
PREFERRED MODE FOR CARRYING OUT THE INVENTION
[0015] Hereinafter, the present invention will be explained in detail based on embodiments.
[0016] The present inventors, as a result of thorough research, found by focusing on the
peak intensity of a predetermined plane obtained by X-ray diffraction analysis of
the surface of a copper alloy wire rod, and controlling the ratio of peak intensities
of the predetermined plane to within a predetermined range, that it was superior in
the balance of strength, electric conductivity and drawability, and based on this
knowledge, arrived at completion of the present disclosure.
[0017] A copper alloy wire rod of the embodiment has an alloy composition containing 1.0%
by mass or more and 6.0% by mass or less of Ag, a remainder being Cu and inevitable
impurities, in which, for a peak intensity I(111) of 111 diffraction, a peak intensity
I(200) of 200 diffraction, a peak intensity I(220) of 220 diffraction and a peak intensity
I(311) of 311 diffraction obtained by X-ray diffraction analysis of a surface, a peak
intensity ratio of a total intensity of the peak intensity I(111), the peak intensity
I(200) and the peak intensity I(311) relative to the peak intensity I(220) ((the peak
intensity I(111) + the peak intensity I(220) + the peak intensity I(311)) / the peak
intensity I(220)) is 1.20 or more and 3.00 or less.
[0018] First, the alloy composition of the copper alloy wire rod will be explained.
[0019] The copper alloy wire rod of the above embodiment has an alloy composition containing
1.0% by mass or more and 6.0% by mass or less of Ag, in which the remainder is Cu
and inevitable impurities.
<Ag: 1.0% by mass to 6.0% by mass>
[0020] Ag (silver) is a necessary element for raising the strength of the copper alloy wire
rod, and Ag is contained in 1.0% by mass or more and 6.0% by mass or less. If the
content of Ag is 1.0% by mass or more, it is possible to increase the strength of
the copper alloy wire rod by the solid solution and the precipitation of Ag. In addition,
if the content of Ag is 6.0% by mass or less, it is possible to suppress a decline
in electric conductivity of the copper alloy wire rod, and maintain high electric
conductivity of the copper alloy wire rod. Furthermore, if the content of Ag exceeds
6.0% by mass, since enhanced strength cannot be expected to counterbalance the increase
in material cost due to the increase in the amount used of Ag, it is difficult to
contribute to the product added value for the customer. To achieve a balance in strength
improvement and electric conductivity improvement of the copper alloy wire rod, the
content of Ag is 1.0% by mass or more, and preferably 1.5% by mass or more, while
being 6.0% by mass or less, and preferably 4.0% by mass or less.
<Sub Component of Copper Alloy Wire Rod: 0.05% by mass to 0.30% by mass>
[0021] The alloy composition of the copper alloy wire rod can further contain a total of
0.05% by mass or more and 0.30% by mass or less of at least one element selected from
the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr. In other words, the copper
alloy wire rod, in addition to the Ag which is an essential basic component, can further
contain as a sub component which is an optional component, a total of 0.05% by mass
or more and 0.30% by mass or less of at least one component selected from the group
consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr. If the content of the sub components
is 0.05% by mass or more, the strength characteristic of the copper alloy wire rod
improves, and some elements bring about an effect of alleviating brittleness of the
copper alloy wire rod. In addition, if the content of the sub components is 0.30%
by mass or less, it will not greatly harm the electric conductivity of the copper
alloy wire rod. For this reason, the content of the sub components is preferably 0.05%
by mass or more, more preferably 0.08% by mass or more, and even more preferably 0.10%
by mass or more, while preferably 0.30% by mass or less, more preferably 0.25% by
mass or less, and even more preferably 0.20% by mass or less.
<Sn: 0.05% by mass to 0.20% by mass>
[0022] If the content of Sn (tin) is 0.05% by mass or more, it will contribute to enhanced
strength of the copper alloy wire rod, and if the content of Sn is 0.20% by mass or
less, it will not greatly harm the electric conductivity of the copper alloy wire
rod. For this reason, the content of Sn is preferably 0.05% by mass or more, more
preferably 0.07% by mass or more, even more preferably 0.08% by mass or more, and
particularly preferably 0.10% by mass or more, while preferably 0.20% by mass or less,
more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less,
and particularly preferably 0.12% by mass or less.
<Mg: 0.05% by mass to 0.20% by mass>
[0023] If the content of Mg (magnesium) is 0.05% by mass or more, there are effects contributing
to enhanced strength of the copper alloy wire rod, and alleviating brittleness of
the copper alloy wire rod. If the content of Mg is 0.20% by mass or less, it will
not greatly harm the electric conductivity of the copper alloy wire rod or the manufacturability
during casting. For this reason, the content of Mg is preferably 0.05% by mass or
more, more preferably 0.07% by mass or more, even more preferably 0.08% by mass or
more, and particularly preferably 0.10% by mass or more, while preferably 0.20% by
mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by
mass or less, and particularly preferably 0.12% by mass or less.
<Zn: 0.05% by mass to 0.30% by mass>
[0024] If the content of Zn (zinc) is 0.05% by mass or more, there are effects contributing
to enhanced strength of the copper alloy wire rod, and alleviating brittleness of
the copper alloy wire rod. If the content of Zn is 0.30% by mass or less, it will
not greatly harm the electric conductivity of the copper alloy wire rod. For this
reason, the content of Zn is preferably 0.05% by mass or more, more preferably 0.07%
by mass or more, even more preferably 0.08% by mass or more, and particularly preferably
0.10% by mass or more, while preferably 0.30% by mass or less, more preferably 0.25%
by mass or less, even more preferably 0.20% by mass or less, and particularly preferably
0.15% by mass or less.
<In: 0.05% by mass to 0.20% by mass>
[0025] If the content of In (indium) is 0.05% by mass or more, it will contribute to enhanced
strength of the copper alloy wire rod, and if the content of In is 0.20% by mass or
less, it will not greatly harm the electric conductivity of the copper alloy wire
rod. For this reason, the content of In is preferably 0.05% by mass or more, more
preferably 0.07% by mass or more, even more preferably 0.08% by mass or more, and
particularly preferably 0.10% by mass or more, while preferably 0.20% by mass or less,
more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less,
and particularly preferably 0.12% by mass or less.
<Ni: 0.05% by mass to 0.30% by mass>
[0026] If the content of Ni (nickel) is 0.05% by mass or more, there is an effect contributing
to enhanced strength of the copper alloy wire rod. If the content of Ni is 0.30% by
mass or less, it will not greatly harm the electric conductivity of the copper alloy
wire rod. For this reason, the content of Ni is preferably 0.05% by mass or more,
more preferably 0.07% by mass or more, even more preferably 0.08% by mass or more,
and particularly preferably 0.10% by mass or more, while preferably 0.30% by mass
or less, more preferably 0.25% by mass or less, even more preferably 0.20% by mass
or less, and particularly preferably 0.15% by mass or less.
<Co: 0.05% by mass to 0.20% by mass>
[0027] If the content of Co (cobalt) is 0.05% by mass or more, it will contribute to enhanced
strength of the copper alloy wire rod, and if the content of Co is 0.20% by mass or
less, it will not greatly harm the electric conductivity of the copper alloy wire
rod. For this reason, the content of Co is preferably 0.05% by mass or more, more
preferably 0.07% by mass or more, even more preferably 0.08% by mass or more, and
particularly preferably 0.10% by mass or more, while preferably 0.20% by mass or less,
more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less,
and particularly preferably 0.12% by mass or less.
<Zr: 0.05% by mass to 0.20% by mass>
[0028] If the content of Zr (zirconium) is 0.05% by mass or more, there are effects contributing
to enhanced strength of the copper alloy wire rod, and alleviating brittleness of
the copper alloy wire rod. If the content of Zr is 0.20% by mass or less, it will
not greatly harm the electric conductivity of the copper alloy wire rod or the manufacturability
during casting. For this reason, the content of Zr is preferably 0.05% by mass or
more, more preferably 0.07% by mass or more, even more preferably 0.08% by mass or
more, and particularly preferably 0.10% by mass or more, while preferably 0.20% by
mass or less, more preferably 0.18% by mass or less, even more preferably 0.15% by
mass or less, and particularly preferably 0.12% by mass or less.
<Cr: 0.05% by mass to 0.20% by mass>
[0029] If the content of Cr (chromium) is 0.05% by mass or more, it will contribute to enhanced
strength of the copper alloy wire rod, and if the content of Cr is 0.20% by mass or
less, it will not greatly harm the electric conductivity of the copper alloy wire
rod. For this reason, the content of Cr is preferably 0.05% by mass or more, more
preferably 0.07% by mass or more, even more preferably 0.08% by mass or more, and
particularly preferably 0.10% by mass or more, while preferably 0.20% by mass or less,
more preferably 0.18% by mass or less, even more preferably 0.15% by mass or less,
and particularly preferably 0.12% by mass or less.
<Remainder: Cu and inevitable impurities>
[0030] The remainder other than the aforementioned components is Cu (copper) and inevitable
impurities. The inevitable impurities inevitably mix in the manufacturing process,
and are also a factor decreasing at least any one of the strength, electric conductivity
and drawability of the copper alloy wire rod according to the content, they impact
the environment, and are a cause for material embrittlement. For this reason, a smaller
content of inevitable impurities is more preferable. As the inevitable impurities,
for example, elements such as S, Pb, Sb and Bi can be exemplified. The upper limit
for the content of the above-mentioned inevitable impurities is preferably less than
0.0001% by mass for each of the above-mentioned elements, and the total of the above-mentioned
elements is preferably less than 0.0005% by mass.
[0031] Next, the peak intensity ratio obtained by X-ray diffraction analysis of the surface
of the copper alloy wire rod will be explained.
[0032] When setting each peak intensity of 111, 200, 220, 311 diffraction obtained by X-ray
diffraction analysis of the surface of the copper alloy wire rod as I(111), I(200),
I(220), I(311), the peak intensity ratio ((peak intensity I(111) + peak intensity
I(200) + peak intensity I(311)) / peak intensity I(220)) (hereinafter also referred
to as peak intensity ratio) of the total intensity of the peak intensity I(111), the
peak intensity I(200) and the peak intensity I(311) relative to the peak intensity
I(220) is 1.20 or more and 3.00 or less.
[0033] If the peak intensity ratio is 1.20 or more, it is possible to improve the drawability
of the copper alloy wire rod. In addition, if the peak intensity ratio is 3.00 or
less, it will be possible to increase the strength of the copper alloy wire rod. To
establish both the strength improvement and the drawability improvement of the copper
alloy wire rod, as well as achieve a balance with the electric conductivity, the peak
intensity ratio is 1.20 or more, preferably 1.30 or more and more preferably 1.50
or more, while being 3.00 or less, preferably 2.80 or less and more preferably 2.50
or less.
[0034] The peak intensity I(111) of 111 diffraction obtained by X-ray diffraction analysis
of the surface of the copper alloy wire rod is a maximum value (highest intensity)
of the peak height within the range of 2θ=43±1°. For the correlated {111} plane, there
is a tendency of contributing to enhanced strength of the copper alloy wire rod, while
decreasing drawability of the copper alloy wire rod. However, in the case of not conducting
heat treatment in the manufacturing process of the copper alloy wire rod described
later, even in a state in which the peak intensity I(111) is high, the copper alloy
wire rod shows a drawability decline without strength enhancement.
[0035] The peak intensity I(200) of 200 diffraction obtained by X-ray diffraction analysis
of the surface of the copper alloy wire rod is a maximum value (highest intensity)
of the peak height within the range of 2θ=50±1°. For the correlated {100} plane, there
is a tendency of contributing to a drawability improvement of the copper alloy wire
rod, while the contribution of enhanced strength is relatively low.
[0036] The peak intensity I(220) of 220 diffraction obtained by X-ray diffraction analysis
of the surface of the copper alloy wire rod is a maximum value (highest intensity)
of the peak height within the range of 2θ=74±1°. For the correlated {110} plane, if
the total amount thereof is large, it is necessary to be a suitable value or less
due to the proportion of the {111} plane, as well as the {100} plane relatively decreasing,
and thus the effect reducing relatively, and although the contribution is relatively
low, it contributes to enhanced strength and a drawability improvement of the copper
alloy wire rod.
[0037] The peak intensity I(311) of 311 diffraction obtained by X-ray diffraction analysis
of the surface of the copper alloy wire rod is a maximum value (highest intensity)
of the peak height within the range of 2θ=90±1°. For the correlated {311} plane, if
the total amount thereof is large, it is necessary to be a suitable value or less
due to the proportion of the {111} plane, as well as the {100} plane relatively decreasing,
and thus the effect reducing relatively, and although the contribution is relatively
low, it contributes to enhanced strength and a drawability improvement of the copper
alloy wire rod.
[0038] X-ray diffraction analysis of the surface of the copper alloy wire rod measures in
the following way. Using an X-ray diffractometer, and establishing a lateral face
which is a surface of the copper alloy wire rod as the measurement target in the θ-2θ
method, the X-ray diffraction intensity between 40° to 100° is measured, and the background
value that is noise was subtracted from the confirmed peak intensity to obtain the
peak intensity of each plane. In the X-ray diffraction analysis, a plurality of copper
alloy wire rods were brought into contact, and placed in parallel in the same direction
on a sample holder.
[0040] The tensile strength of the copper alloy wire rod is measured by performing a tensile
test based on JIS Z2241:2011.
[0041] The electric conductivity of the copper alloy wire rod is measured based on JIS H0505:1975.
[0042] In addition, the cross section of the copper alloy wire rod is preferably a circular
shape having a diameter of 0.02 mm or more and 0.08 mm or less. Even if the copper
alloy wire rod having a cross section which is circular having a diameter within the
above-mentioned range, i.e. the copper alloy wire rod is a cylindrical extra fine
wire, it is superior in the balance of the high strength and the high electric conductivity.
[0043] In addition, the cross section of the copper alloy wire rod may be a ribbon shape
having a long side of 0.060 mm or more and 0.500 mm or less, and a short side of 0.005
mm or more and 0.040 mm or less. Even if an extra fine wire having a cross section
which is a ribbon shape having a long side and a short side within the above-mentioned
ranges, the copper alloy wire rod will be superior in the balance of the high strength
and the high electric conductivity.
[0044] The strength and the electric conductivity of the ribbon-shaped copper alloy wire
rod do not greatly change from the strength and the electric conductivity of the cylindrical
copper alloy wire rod prior to molding into a ribbon shape, e.g., cylindrical extra
fine wire. In other words, so long as the strength and the electric conductivity of
the cylindrical copper alloy wire rod prior to molding into a ribbon shape are the
desired values or more, the strength and the electric conductivity of the ribbon-shaped
copper alloy wire rod will be the desired values or more.
[0045] In this way, due to the copper alloy wire rod having high drawability, even if thinning
the copper alloy wire rod to extra fine wire, it can obtain an extra fine wire superior
in the balance of the high strength and the high electric conductivity which had not
existed conventionally. A size reduction in electronic appliances, space savings of
circuits, an increase in circuit number, etc. to a level which had not been realizable
thus far thereby become possible, and thus can contribute to adding to the value of
the finished product.
[0046] Next, a manufacturing method of the copper alloy wire rod of the present embodiment
will be explained.
[0047] The manufacturing method of the copper alloy wire rod of the embodiment performs
heat treatment at least one time while drawing an ingot having the above-mentioned
alloy composition until the final wire diameter of the copper alloy wire rod. This
heat treatment is an aging heat treatment with the purpose of recrystallization and
precipitation of Ag. The heat treatment temperature is preferably 400°C or more and
500°C or less. In addition, the heat treatment time is preferably 10 hours or more
and 100 hours or less in order to obtain a sufficient precipitated amount of Ag.
[0048] In addition, cold wire drawing was performed on the sample before and after the above-mentioned
heat treatment. Herein, cold wire drawing prior to the heat treatment is referred
to as first wire drawing, and cold wire drawing after the heat treatment is referred
to as second wire drawing. By performing the second wire drawing on the cooled sample
after the heat treatment, it is possible to manufacture the copper alloy wire rod.
[0049] The ratio of the processing degree of the first wire drawing relative to the processing
degree of the second wire drawing (the processing degree of the first wire drawing/the
processing degree of the second wire drawing) (hereinafter referred to simply as processing
degree ratio) is 5.0 or more and 12.0 or less. If the above-mentioned processing degree
ratio is less than 5.0, since the final drawing ratio greatly declines for the copper
alloy wire rod obtained after the second wire drawing, it is not possible to obtain
the desired strength. If the above-mentioned processing degree ratio is 5.0 or more,
it is possible to eliminate the accumulated strain by recrystallizing at an early
stage from the temperature rise during the above-mentioned heat treatment to the heated
and retained temperature region, and possible to suppress embrittlement which is a
cause for poor wire drawing in the second wire drawing, which is a post process. If
the above-mentioned processing degree ratio exceeds 12.0, since it comes to lower
the wire drawing ratio of the first wire drawing prior to the heat treatment, it comes
to heat treat the sample with a low processing degree. As a result thereof, the strain
release during the heat treatment is slowed to progress the embrittlement, and thus
wire thinning of the post process becomes difficult.
[0050] In addition, the 1-pass area reduction ratio in each wire drawing is 15% or more
and 35% or less for wire diameter of more than 0.9 mm, and 10% or more and 25% or
less for wire diameter of 0.9 mm or less. Other wire drawing conditions adopt the
wire drawing speed, die dimensions, and capstan diameter, which are each very common
conditions used in operation.
[0051] Herein, the processing degree of each wire drawing can be calculated by the following
formula.
[0052] Processing degree: η=2×ln (wire diameter before wire drawing/wire diameter after
wire drawing)
ln: natural logarithm
[0053] In addition, the processing degree of the wire drawing and the recrystallization
orientation during heat treatment greatly contribute to the above-mentioned peak intensities
of the copper alloy wire rod.
[0054] For example, in the case of not performing the heat treatment, since the final processing
degree becomes high or the recrystallized structure is not formed, the peak intensity
I(200) will be too low, the peak intensity I(111) will be too high, and the drawability
of the copper alloy wire rod declines. Furthermore, normally, if the peak intensity
I(111) increases, although enhanced strength of the copper alloy wire rod tends to
be brought about, if not performing the heat treatment, the degree of rise in strength
of the copper alloy wire rod may lower.
[0055] In addition, in the case of the above-mentioned processing degree ratio being less
than 5.0, the peak intensity I(200) will be too high, the peak intensity I(111) will
be too low, and thus affect the above-mentioned peak intensity ratio. In the case
of the above-mentioned processing degree ratio exceeding 12.0, the peak intensity
I(200) will be too low, the peak intensity I(111) will be too high, and thus affect
the above-mentioned peak intensity ratio.
[0056] In addition, although not meant to actively control the peak intensity I(220) and
the peak intensity I(311), if these ratios increase, there is an adverse effect in
that the effect brought about by the peak intensity I(200) and the peak intensity
I(111) relatively declines. By satisfying the above-mentioned manufacturing conditions,
it becomes possible to converge to the desired range.
[0057] In this way, by performing the heat treatment, the first wire drawing and the second
wire drawing, and setting the processing degree ratio to within the above-mentioned
range, it is possible to control the peak intensity obtained in X-ray diffraction
analysis.
[0058] In addition, for the above-mentioned heat treatment, if setting the temperature rising
rate to 1°C/min or more, it is possible to efficiently suppress progression of embrittlement
in the course of temperature rise. In addition, with higher temperature rising rate
during the heat treatment, it is more effective in suppression of the embrittlement
progression; however, the upper limit value of the temperature rising rate is preferably
15° C/min or less, for simplification of the device performing the heat treatment.
[0059] In addition, if the processing degree in the first wire drawing prior to the heat
treatment is 0.69 or more and 2.31 or less, it is possible to suppress the progression
of the embrittlement, and thus wire thinning in the second wire drawing which is the
post process becomes easy.
[0060] In addition, prior to the above-mentioned heat treatment, solution heat treatment
for promoting the precipitation of Ag in the above-mentioned heat treatment may be
performed. For the solution heat treatment, the heat treatment temperature is preferably
700°C or more and 900°C or less, and the heat treatment time is preferably 10 minutes
or more and 5 hours or less. The solution heat treatment is for making Ag into a solid
solution, and is effective in abundantly precipitating more homogeneous Ag phase.
[0061] In addition, as described above, the strength and the electric conductivity of the
cylindrical copper alloy wire rod prior to molding into a ribbon shape will not greatly
change from the strength and the electric conductivity of the ribbon-shaped copper
alloy wire rod. For this reason, by rolling the copper alloy wire rod obtained by
the second wire drawing, it is possible to manufacture a ribbon-shaped copper alloy
wire rod.
[0062] The above-mentioned copper alloy wire rod is suitably used in an equipment connection
cable such as a micro speaker lead for which excellent balance in strength, electric
conductivity and drawability is sought.
[0063] According to the above explained embodiment, by focusing on the peak intensity of
predetermined planes obtained by the X-ray diffraction analysis of a surface, and
controlling the ratio of the peak intensities of predetermined planes to within a
predetermined range, it is possible to obtain a copper alloy wire rod superior in
the balance of the strength, the electric conductivity and the drawability.
[0064] Although an embodiment has been explained above, the present invention is not to
be limited to the above-mentioned embodiment, and it is possible to modify in various
ways within the scope of the present disclosure, including every mode encompassed
by the gist of the present disclosure and scope of the claims.
EXAMPLES
[0065] Next, examples and comparative examples will be explained; however, the present disclosure
is not to be limited to these examples.
(Examples 1 to 34 and Comparative Examples 1 to 12 and 14)
[0066] For an ingot having the alloy composition shown in Table 1 and cast with an outside
diameter of 6 mm or more and 39 mm or less, at the conditions shown in Table 2, the
first wire drawing which is a cold wire drawing was performed until the wire diameter
of 4 mm or more and 9 mm or less, the heat treatment with a temperature rising rate
of 10°C/min was performed, and the second wire drawing which is a cold wire drawing
was performed after cooling until the final wire diameter to manufacture a cylindrical
copper alloy wire rod. The processing degree in each wire drawing was calculated from
the processing degree η=2×ln (wire diameter before wire drawing/wire diameter after
wire drawing) (ln is natural logarithm). In addition, the processing degree ratio
was calculated by dividing the processing degree of the first wire drawing by the
processing degree of the second wire drawing.
(Example 35)
[0067] A cylindrical copper alloy wire rod was obtained similarly to Example 1. Next, a
ribbon-shaped copper alloy wire rod having a cross section with a long side of 0.080
mm and a short side of 0.007 mm was manufactured by rolling the cylindrical copper
alloy wire rod.
(Examples 36 to 37)
[0068] A copper alloy wire rod was manufactured similarly to Example 1, other than performing
solution heat treatment for 2 hours at 800°C for the ingot, prior to performing the
first wire drawing.
(Comparative Example 13)
[0069] The cylindrical copper alloy wire rod having the alloy composition shown in Table
1, and having a final wire diameter shown in Table 2 was manufactured by casting.
In other words, the heat treatment, the first wire drawing and the second wire drawing
of Example 1 were not performed in Comparative Example 13.
[0070] It should be noted that S, Pb, Sb and Bi were contained as inevitable impurities
in the copper alloy wire rods shown in Table 1, and the content of inevitable impurities
was less than 0.0001% by mass for every element, and less than 0.0005% by mass in
total of the elements.
[Table 1]
| |
Alloy components (% by mass) |
| Ag |
Sn |
Mg |
Zn |
In |
Ni |
Co |
Zr |
Cr |
Cu |
Sub components total |
| Example 1 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 2 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 3 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 4 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 5 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 6 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 7 |
1.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 8 |
1.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 9 |
1.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 10 |
1.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 11 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 12 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 13 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 14 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 15 |
3.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 16 |
3.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 17 |
3.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 18 |
3.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 19 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 20 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 21 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 22 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 23 |
5.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 24 |
5.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 25 |
5.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 26 |
5.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 27 |
2.0 |
0.10 |
- |
- |
- |
- |
- |
- |
- |
Bal. |
0.10 |
| Example 28 |
2.0 |
- |
0.10 |
- |
- |
- |
- |
- |
- |
Bal. |
0.10 |
| Example 29 |
2.0 |
- |
- |
0.30 |
- |
- |
- |
- |
- |
Bal. |
0.30 |
| Example 30 |
2.0 |
- |
- |
- |
0.10 |
- |
- |
- |
- |
Bal. |
0.10 |
| Example 31 |
2.0 |
- |
- |
- |
- |
0.20 |
- |
- |
- |
Bal. |
0.20 |
| Example 32 |
2.0 |
- |
- |
- |
- |
- |
0.10 |
- |
- |
Bal. |
0.10 |
| Example 33 |
2.0 |
- |
- |
- |
- |
- |
- |
0.05 |
- |
Bal. |
0.05 |
| Example 34 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
0.10 |
Bal. |
0.10 |
| Example 35 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 36 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Example 37 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 1 |
0.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 2 |
0.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 3 |
0.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 4 |
0.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 5 |
6.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 6 |
6.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 7 |
6.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 8 |
6.5 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 9 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 10 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 11 |
2.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 12 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 13 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
| Comparative Example 14 |
4.0 |
- |
- |
- |
- |
- |
- |
- |
- |
Bal. |
- |
[Table 2]
| |
Final wire diameter (mm) |
Heat treatment conditions |
Processing degree of first wire drawing |
Processing degree of second wire drawing |
Processing degree ratio (Processing degree of first wire drawing/Processing degree
of second wire drawing) |
| Temperature (°C) |
Time (h) |
| Example 1 |
0.03 |
400 |
24 |
2.0 |
10.4 |
5.2 |
| Example 2 |
0.03 |
450 |
24 |
1.6 |
10.6 |
6.6 |
| Example 3 |
0.03 |
425 |
24 |
1.4 |
10.1 |
7.2 |
| Example 4 |
0.02 |
425 |
16 |
1.8 |
10.0 |
5.6 |
| Example 5 |
0.03 |
450 |
24 |
1.5 |
10.2 |
6.8 |
| Example 6 |
0.06 |
425 |
24 |
1.4 |
9.4 |
6.7 |
| Example 7 |
0.05 |
450 |
24 |
1.4 |
10.4 |
7.4 |
| Example 8 |
0.05 |
450 |
24 |
1.2 |
10.4 |
8.7 |
| Example 9 |
0.05 |
425 |
24 |
1.0 |
11.7 |
10.2 |
| Example 10 |
0.05 |
400 |
48 |
1.0 |
10.6 |
10.6 |
| Example 11 |
0.03 |
400 |
24 |
1.8 |
10.4 |
5.8 |
| Example 12 |
0.03 |
450 |
24 |
1.6 |
10.4 |
6.5 |
| Example 13 |
0.03 |
400 |
24 |
1.2 |
10.2 |
8.5 |
| Example 14 |
0.03 |
400 |
24 |
1.0 |
10.6 |
10.6 |
| Example 15 |
0.02 |
400 |
48 |
1.5 |
11.5 |
7.7 |
| Example 16 |
0.03 |
450 |
24 |
1.0 |
10.4 |
10.4 |
| Example 17 |
0.06 |
425 |
24 |
1.0 |
10.4 |
10.4 |
| Example 18 |
0.08 |
400 |
24 |
1.2 |
9.0 |
7.5 |
| Example 19 |
0.02 |
400 |
24 |
1.8 |
10.6 |
5.9 |
| Example 20 |
0.03 |
450 |
24 |
1.4 |
10.4 |
7.4 |
| Example 21 |
0.06 |
425 |
24 |
1.2 |
9.6 |
8.0 |
| Example 22 |
0.08 |
400 |
24 |
1.2 |
9.5 |
7.9 |
| Example 23 |
0.02 |
475 |
12 |
1.8 |
10.4 |
5.8 |
| Example 24 |
0.03 |
450 |
24 |
1.4 |
10.4 |
7.4 |
| Example 25 |
0.06 |
425 |
24 |
1.2 |
11.6 |
9.7 |
| Example 26 |
0.08 |
400 |
48 |
1.6 |
10.0 |
6.3 |
| Example 27 |
0.03 |
400 |
24 |
1.0 |
10.6 |
10.6 |
| Example 28 |
0.03 |
450 |
24 |
1.8 |
10.4 |
5.8 |
| Example 29 |
0.03 |
400 |
24 |
1.6 |
10.4 |
6.5 |
| Example 30 |
0.03 |
400 |
24 |
1.0 |
10.6 |
10.6 |
| Example 31 |
0.03 |
450 |
24 |
1.8 |
10.4 |
5.8 |
| Example 32 |
0.03 |
400 |
24 |
1.6 |
10.4 |
6.5 |
| Example 33 |
0.03 |
400 |
24 |
1.2 |
10.2 |
8.5 |
| Example 34 |
0.03 |
400 |
24 |
1.2 |
10.2 |
8.5 |
| Example 35 |
Long side 0.080mm, Short side 0.007mm |
400 |
24 |
1.2 |
10.2 |
8.5 |
| Example 36 |
0.03 |
400 |
24 |
1.2 |
10.2 |
8.5 |
| Example 37 |
0.03 |
400 |
24 |
1.2 |
10.2 |
8.5 |
| Comparative Example 1 |
0.02 |
450 |
24 |
1.0 |
10.4 |
10.4 |
| Comparative Example 2 |
0.03 |
450 |
24 |
1.0 |
10.4 |
10.4 |
| Comparative Example 3 |
0.06 |
425 |
24 |
1.4 |
102 |
7.3 |
| Comparative Example 4 |
0.08 |
400 |
48 |
1.8 |
10.6 |
5.9 |
| Comparative Example 5 |
0.02 |
400 |
24 |
1.4 |
10.6 |
7.6 |
| Comparative Example 6 |
0.03 |
450 |
24 |
1.2 |
10.2 |
8.5 |
| Comparative Example 7 |
0.06 |
425 |
24 |
1.4 |
102 |
7.3 |
| Comparative Example 8 |
0.08 |
400 |
24 |
1.0 |
10.2 |
10.2 |
| Comparative Example 9 |
0.03 |
350 |
8 |
1.0 |
10.4 |
10.4 |
| Comparative Example 10 |
0.06 |
350 |
24 |
1.4 |
102 |
7.3 |
| Comparative Example 11 |
0.08 |
450 |
3 |
1.8 |
10.6 |
5.9 |
| Comparative Example 12 |
0.02 |
475 |
12 |
2.5 |
8.0 |
32 |
| Comparative Example 13 |
0.03 |
- |
- |
- |
- |
- |
| Comparative Example 14 |
0.02 |
400 |
6 |
0.4 |
9.0 |
22.5 |
(Measurement and Evaluation)
[0071] The following measurements and evaluations were carried out on the copper alloy wire
rods obtained in the above examples and the comparative examples. The results are
shown in Table 3.
(1) X-ray Diffraction Analysis
[0072] Using an X-ray diffractometer (X' Pert PROMRD manufactured by Spectris Co., Ltd.),
the surface of the copper alloy wire rod was defined as the measurement target in
the θ-2θ method for the copper alloy wire rods obtained in the above examples and
the comparative examples, the X-ray diffraction intensity between 40° to 100° was
measured in a state lined up side by side so as to fill and secure the minimum area
of 20 mm × 40 mm due to the wire diameter being fine, and the background value that
is noise was subtracted from the confirmed peak intensity to obtain the peak intensity
of each plane. In the X-ray diffraction analysis, a plurality of copper alloy wire
rods were brought into contact and placed in parallel in the same direction on a sample
holder.
(2) Tensile Strength
[0073] Using two (n=2) copper alloy wire rods obtained in the above examples and the comparative
examples, the tensile test was performed based on JIS Z2241:2011, and the tensile
strength was calculated by averaging the two measured values.
(3) Electric Conductivity
[0074] Using two (n=2) copper alloy wire rods obtained in the above examples and the comparative
examples, measurement was performed based on JIS H0505:1975, and the electric conductivity
was calculated by averaging the two measured values.
[0075] (4)

[0076] Defining the content of Ag as X (% by mass) and the tensile strength of the copper
alloy wire rod as Y (MPa), Formula (1) was calculated, and the following rankings
were given.
[0077]
Satisfies Formula (1): yes
Does not satisfy Formula (1): no
[0078] (5)

[0079] Defining the content of Ag as X (% by mass) and the electric conductivity of the
copper alloy wire rod as Z (%IACS), Formula (2) was calculated, and the following
rankings were given.
[0080]
Satisfies Formula (2): yes
Does not satisfy Formula (2): no
[0081] (6)

[0082] Defining the tensile strength of the copper alloy wire rod as Y (MPa) and the electric
conductivity of the copper alloy wire rod as Z (%IACS), Formula (3) was calculated,
and the following rankings were given.
[0083]
Satisfies Formula (3): yes
Does not satisfy Formula (3): no
(7) Drawability
[0084] For the copper alloy wire rods obtained in the above examples and the comparative
examples, the total length after drawing to a wire diameter of 0.02 mm and the number
of disconnections occurred during overall wire drawing were measured, and the following
rankings were given. It should be noted that, in Example 35, the cylindrical copper
alloy wire rod (wire diameter of 0.02 mm) before rolling into ribbon shape was measured.
When the number of times of disconnection relative to the wire drawing length is 1
time/ 100 km or less, the drawability is favorable.
[0085]
Number of times of disconnection relative to the wire drawing length is 1 time/ 100
km or less: O
Number of times of disconnection relative to the wire drawing length is more than
1 time/ 100 km: X
[Table 3]
| |
Peak intensity ratio (Peak intensity I(111)+Peak intensity I(200)+Peak intensity I(311))/Peak
intensity I(220) |
Tensile strength (MPa) |
Electric conductivity (%IACS) |
Formula (1) Y≧110X+880 |
Formula (2) Z≧-4.6X+82 |
Formula (3) Y≧-0.040Z+117 |
Drawability |
| Example 1 |
1.80 |
1120 |
79 |
Yes |
Yes |
Yes |
○ |
| Example 2 |
1.70 |
1140 |
80 |
Yes |
Yes |
Yes |
○ |
| Example 3 |
1.90 |
1130 |
80 |
Yes |
Yes |
Yes |
○ |
| Example 4 |
2.10 |
1355 |
70 |
Yes |
Yes |
Yes |
○ |
| Example 5 |
1.80 |
1340 |
71 |
Yes |
Yes |
Yes |
○ |
| Example 6 |
2.10 |
1330 |
72 |
Yes |
Yes |
Yes |
○ |
| Example 7 |
2.90 |
1005 |
83 |
Yes |
Yes |
Yes |
○ |
| Example 8 |
2.40 |
1025 |
83 |
Yes |
Yes |
Yes |
○ |
| Example 9 |
2.80 |
1003 |
83 |
Yes |
Yes |
Yes |
○ |
| Example 10 |
2.50 |
1015 |
83 |
Yes |
Yes |
Yes |
○ |
| Example 11 |
1.60 |
1120 |
80 |
Yes |
Yes |
Yes |
○ |
| Example 12 |
2.20 |
1130 |
80 |
Yes |
Yes |
Yes |
○ |
| Example 13 |
2.10 |
1115 |
80 |
Yes |
Yes |
Yes |
○ |
| Example 14 |
2.00 |
1100 |
80 |
No |
Yes |
Yes |
○ |
| Example 15 |
2.00 |
1220 |
75 |
Yes |
Yes |
Yes |
○ |
| Example 16 |
1.90 |
1230 |
74 |
Yes |
Yes |
Yes |
○ |
| Example 17 |
2.10 |
1180 |
76 |
No |
Yes |
Yes |
○ |
| Example 18 |
1.70 |
1210 |
75 |
No |
Yes |
Yes |
○ |
| Example 19 |
2.00 |
1350 |
71 |
Yes |
Yes |
Yes |
○ |
| Example 20 |
2.20 |
1340 |
72 |
Yes |
Yes |
Yes |
○ |
| Example 21 |
2.30 |
1350 |
70 |
Yes |
Yes |
Yes |
○ |
| Example 22 |
1.90 |
1330 |
71 |
Yes |
Yes |
Yes |
○ |
| Example 23 |
2.00 |
1550 |
65 |
Yes |
Yes |
Yes |
○ |
| Example 24 |
1.80 |
1510 |
66 |
Yes |
Yes |
Yes |
○ |
| Example 25 |
2.20 |
1490 |
66 |
Yes |
Yes |
Yes |
○ |
| Example 26 |
1.20 |
1500 |
67 |
Yes |
Yes |
Yes |
○ |
| Example 27 |
2.10 |
1180 |
73 |
Yes |
Yes |
Yes |
○ |
| Example 28 |
2.20 |
1160 |
73 |
Yes |
Yes |
Yes |
○ |
| Example 29 |
1.90 |
1170 |
74 |
Yes |
Yes |
Yes |
○ |
| Example 30 |
2.00 |
1180 |
74 |
Yes |
Yes |
Yes |
○ |
| Example 31 |
1.80 |
1155 |
75 |
Yes |
Yes |
Yes |
○ |
| Example 32 |
2.70 |
1140 |
74 |
Yes |
Yes |
Yes |
○ |
| Example 33 |
2.20 |
1180 |
75 |
Yes |
Yes |
Yes |
○ |
| Example 34 |
2.10 |
1175 |
74 |
Yes |
Yes |
Yes |
○ |
| Example 35 |
2.00 |
1120 |
77 |
Yes |
Yes |
Yes |
○ |
| Example 36 |
2.00 |
1146 |
78 |
Yes |
Yes |
Yes |
○ |
| Example 37 |
1.90 |
1122 |
78 |
Yes |
Yes |
Yes |
○ |
| Comparative Example 1 |
3.30 |
850 |
84 |
No |
Yes |
Yes |
○ |
| Comparative Example 2 |
3.10 |
830 |
84 |
No |
Yes |
Yes |
○ |
| Comparative Example 3 |
3.40 |
815 |
84 |
No |
Yes |
Yes |
○ |
| Comparative Example 4 |
3.30 |
790 |
84 |
No |
Yes |
No |
○ |
| Comparative Example 5 |
0.25 |
1400 |
58 |
No |
Yes |
No |
○ |
| Comparative Example 6 |
0.35 |
1395 |
58 |
No |
Yes |
No |
○ |
| Comparative Example 7 |
0.45 |
1391 |
59 |
No |
Yes |
No |
○ |
| Comparative Example 8 |
0.55 |
1399 |
59 |
No |
Yes |
No |
○ |
| Comparative Example 9 |
3.30 |
1010 |
72 |
No |
No |
No |
× |
| Comparative Example 10 |
3.40 |
980 |
71 |
No |
No |
No |
× |
| Comparative Example 11 |
3.20 |
1000 |
72 |
No |
No |
No |
○ |
| Comparative Example 12 |
0.15 |
850 |
72 |
No |
Yes |
No |
○ |
| Comparative Example 13 |
3.50 |
1050 |
65 |
No |
Yes |
No |
× |
| Comparative Example 14 |
3.30 |
900 |
71 |
No |
Yes |
No |
× |
[0086] As shown in Tables 1 to 3, in Examples 1 to 37, since the content of Ag and the
peak intensity ratio were respectively controlled to within predetermined ranges,
the tensile strength, the electric conductivity and the drawability were all favorable.
On the other hand, in Comparative Examples 1 to 14, since at least one of the content
of Ag and the peak intensity ratio were not controlled to within the predetermined
range, at least one of the tensile strength, the electric conductivity and the drawability
were inferior.