CN111032892A - Copper alloy wire rod and method for producing copper alloy wire rod - Google Patents
Copper alloy wire rod and method for producing copper alloy wire rod Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/02—Making non-ferrous alloys by melting
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
The invention provides a copper alloy wire rod and a manufacturing method of the copper alloy wire rod, wherein the copper alloy wire rod does not damage excellent electric conductivity and has excellent tensile strength even when the diameter of the wire rod is reduced. The copper alloy wire has the following alloy composition: the copper alloy wire rod contains 1.5-6.0 mass% of Ag, 0-1.0 mass% of Mg, 0-1.0 mass% of Cr and 0-1.0 mass% of Zr, and the balance of Cu and inevitable impurities, wherein when a cross section parallel to the longitudinal direction of the copper alloy wire rod is observed, the area ratio (A) of precipitates precipitated in a matrix Cu in a rectangular observation region of 240nm x 360nm is within the range of the following formula (I): (0.393 xx-0.589)% < A ≦ (3.88 xx-5.81)% (I) wherein x represents the mass% of Ag.
Description
Technical Field
The present invention relates to a copper alloy wire rod having high tensile strength, which can be used for, for example, a tinsel wire or the like, and a method for producing the copper alloy wire rod.
Background
For example, a speaker is provided with a coil and a diaphragm, and generates sound by causing current to flow into the coil to vibrate the coil and causing the diaphragm to vibrate in conjunction with the vibration of the coil. A nylon wire was used as a wire for connecting the coil and the substrate terminal. Therefore, the silk thread is required to have high vibration durability capable of withstanding vibration generated by sound. The dimensional effect is utilized to improve vibration durability by generally processing the wire rod to be thin. On the other hand, if the wire rod is made smaller in diameter, the tensile durability is reduced, and therefore handling at the time of manufacturing the wire rod becomes difficult, and there is a problem that breakage, winding, and the like occur, and the yield is deteriorated.
Therefore, for example, as an alloy material for improving tensile strength, the following copper alloy is proposed, which has a composition of: contains Ag: 8.0 to 20.0 wt%, Cr: 0.1 to 1.0 wt%, the balance being Cu and unavoidable impurities; and has a structure in which fine precipitates of Cr are dispersed in a matrix in which primary crystals and eutectic crystals are oriented in a fibrous form (patent document 1).
However, in patent document 1, fine precipitates of Cr are merely dispersed in a matrix in which primary crystals and eutectic crystals are oriented in a fibrous state, and the structure in which the state of precipitation of fine precipitates made of Cr is controlled is not.
Therefore, in the copper alloy of patent document 1, when the wire rod is made smaller in diameter, there is room for improvement in tensile strength, and further, there is room for improvement in terms of improvement in yield by improving handling properties at the time of manufacturing the wire rod, preventing breakage, twisting, and the like.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 5-90832
Disclosure of Invention
Problems to be solved by the invention
In view of the above circumstances, an object of the present invention is to provide a copper alloy wire rod excellent in tensile strength even when the wire rod is made smaller in diameter without impairing excellent electrical conductivity, and a method for producing the same.
Means for solving the problems
[1] A copper alloy wire rod having an alloy composition of: the copper alloy wire rod contains 1.5-6.0 mass% of Ag, 0-1.0 mass% of Mg, 0-1.0 mass% of Cr and 0-1.0 mass% of Zr, and the balance of Cu and inevitable impurities, wherein when a cross section parallel to the longitudinal direction of the copper alloy wire rod is observed, the area ratio (A) of precipitates precipitated in a matrix Cu in a rectangular observation region of 240nm x 360nm is within the range of the following formula (I):
(0.393×x-0.589)％≤A≤(3.88×x-5.81)％ (I)
in the formula (I), x represents the mass% of Ag.
[2] The copper alloy wire according to [1], wherein the total content of at least one component selected from the group consisting of Mg, Cr, and Zr is 0.01 to 3.0 mass%.
[3] The copper alloy wire according to [1] or [2], wherein the precipitates coherently precipitated in the matrix Cu are present in a fiber shape along a longitudinal direction of the copper alloy wire.
[4] The copper alloy wire according to [3], wherein, when a cross section parallel to a longitudinal direction of the copper alloy wire is observed, an average width (W) of the precipitates coherently precipitated in the matrix Cu is in a range of the following formula (II) in a rectangular observation region of 240nm × 360 nm:
(8.3×d)nm≤W≤(24.9×d)nm (II)
in the formula (II), d represents the wire diameter (mm) of the copper alloy wire.
[5] The copper alloy wire according to [3] or [4], wherein, when a cross section parallel to a longitudinal direction of the copper alloy wire is observed, an average length (L) of the precipitates precipitated in the matrix Cu is in a range of the following formula (III) in a rectangular observation region of 240nm × 360 nm:
(11.3/d)nm≤L≤(33.8/d)nm (III)
in the formula (III), d represents the wire diameter (mm) of the copper alloy wire.
[6] The copper alloy wire rod according to any one of [3] to [5], wherein, when a cross section parallel to a longitudinal direction of the copper alloy wire rod is observed, an average interval (S) of the precipitates precipitated in the matrix Cu is in a range of the following formula (IV) in a rectangular observation region of 240nm × 360 nm:
(760×x＾-2.25)×dnm≤S≤(2300×x＾-2.25)×dnm (IV)
in the formula (IV), d represents the wire diameter (mm) of the copper alloy wire rod, and x represents the mass% of Ag.
[7] The copper alloy wire rod according to any one of [1] to [6], wherein the precipitates are coherent in the same crystal axis direction with respect to the parent phase Cu.
[8] A method for producing a copper alloy wire according to any one of [1] to [7], comprising:
a step of melting a raw material, a step of casting the melted raw material to obtain an ingot, a step of subjecting a copper alloy material obtained from the ingot to a first heat treatment, a step of further subjecting the copper alloy material to a second heat treatment, and a step of subjecting the copper alloy material subjected to the second heat treatment to a final wire drawing process to obtain a copper alloy wire rod,
the first heat treatment step is carried out at a temperature of 700 ℃ or higher,
the second heat treatment step is performed at a temperature of 350 to 600 ℃,
the final drawing step is performed with a degree of working loge (A0/A1)' 2 of 2.5 or more, wherein A0 is a cross-sectional area of the copper alloy material to be subjected to the final drawing in a direction perpendicular to the longitudinal direction, and A1 is a cross-sectional area of the copper alloy material immediately after the final drawing in a direction perpendicular to the longitudinal direction.
[9] The method for producing a copper alloy wire according to item [8], wherein wire drawing is performed between the step of obtaining an ingot and the first heat treatment step, and/or between the first heat treatment step and the second heat treatment step.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the aspect of the present invention, a copper alloy wire rod having an alloy composition containing 1.5 to 6.0 mass% of Ag, 0 to 1.0 mass% of Mg, 0 to 1.0 mass% of Cr, 0 to 1.0 mass% of Zr, and the balance being Cu and unavoidable impurities, can be obtained which has excellent tensile strength without impairing excellent electrical conductivity by setting the area ratio (a) of precipitates precipitated in Cu within an observation region of 240nm × 360nm in a cross section parallel to the longitudinal direction to the above range.
Thus, a copper alloy wire rod excellent in tensile strength even when the wire rod is reduced in diameter can be obtained, and therefore, high vibration durability is obtained, and the workability at the time of manufacturing the wire rod is improved, and the yield is improved by preventing breakage, twisting, and the like of the wire rod.
According to the aspect of the present invention, the total content of at least one component selected from the group consisting of Mg, Cr, and Zr is 0.01 to 3.0 mass%, which contributes to further improvement of vibration durability and further improvement of tensile strength even when the wire rod is made smaller in diameter.
According to the aspect of the present invention, the precipitates precipitated in the matrix Cu are present in a fiber shape along the longitudinal direction of the copper alloy wire rod, and the average width (W) of the precipitates present in the fiber shape, the average length (L) of the precipitates, and/or the average interval (S) of the precipitates are in the above-described range, thereby contributing to further improvement of the vibration durability and further improving the tensile strength even when the wire rod is made finer in diameter.
Drawings
FIG. 1 is an electron micrograph of a diffraction spot generated when an electron beam is incident on a Cu crystal in the [010] direction.
Fig. 2 is an electron micrograph showing a dark field image of the copper alloy wire rod.
Fig. 3 is a graph showing the result of calculating the number of pixels of the white contrast portion for each line after binarizing the contrast of the dark field image.
Detailed Description
The copper alloy wire rod of the present invention will be described in detail below. The copper alloy wire of the present invention is a copper alloy wire having the following alloy composition: the copper alloy wire rod contains 1.5-6.0 mass% of Ag, 0-1.0 mass% of Mg, 0-1.0 mass% of Cr and 0-1.0 mass% of Zr, and the balance of Cu and inevitable impurities, wherein when a cross section parallel to the longitudinal direction of the copper alloy wire rod is observed, the area ratio (A) of precipitates precipitated in the matrix Cu in a rectangular observation region of 240nm x 360nm is within the range of the following formula (I).
(0.393×x-0.589)％≤A≤(3.88×x-5.81)％ (I)
(in the formula (I), x represents% by mass of Ag.)
[ alloy composition of copper alloy wire ]
The copper alloy wire of the present invention contains 1.5 to 6.0 mass% of Ag (silver). Therefore, Ag is an essential additive component. The Ag element exists in a state of being dissolved in Cu (copper) as a matrix phase, or in a state of being crystallized as second phase particles at the time of casting the copper alloy material or being precipitated as second phase particles in a heat treatment after casting the copper alloy material (hereinafter, these may be collectively referred to as "precipitates" in the present specification), and exhibits an effect of strengthening solid solution or strengthening dispersion. The second phase means a crystal having a different crystal structure from the Cu matrix phase (first phase).
If the content of Ag is less than 1.5% by mass, the effect of strengthening solid solution or strengthening dispersion is insufficient, and sufficient tensile strength and vibration durability cannot be obtained. On the other hand, if the content of Ag exceeds 6.0 mass%, sufficient conductivity cannot be obtained, and the raw material cost also increases. As is clear from the above, the content of Ag is 1.5 to 6.0 mass% in order to obtain excellent tensile strength even when the wire rod is made smaller without impairing the electrical conductivity. Although the requirements for tensile strength and electrical conductivity vary depending on the application of the copper alloy wire, the balance between tensile strength and electrical conductivity can be set in a desired manner by adjusting the Ag content within a range of 1.5 to 6.0 mass%. The Ag content is preferably 1.5 to 4.5 mass% in view of the balance between tensile strength and electrical conductivity in a wide range of applications.
In the copper alloy wire rod of the present invention, in addition to Ag as an essential additive component, at least 1 element selected from the group consisting of Mg (magnesium), Cr (chromium), and Zr (zirconium) may be contained as an optional additive component.
Mg, Cr, and Zr are all present mainly in a state of solid solution in Cu as a matrix phase or as a second phase, and are elements that exert an effect of strengthening solid solution or strengthening dispersion, as in the case of Ag. Further, the presence of Ag as a ternary or higher secondary phase such as Cu — Ag — Zr can contribute to further strengthening of solid solution and strengthening of dispersion.
From the above, it is understood that the total content of at least one component selected from the group consisting of Mg, Cr and Zr is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and particularly preferably 0.10 mass% or more, from the viewpoint of sufficiently exhibiting the effect of strengthening solid solution or strengthening dispersion. On the other hand, if the contents of Mg, Cr and Zr respectively exceed 1.0 mass%, there may be cases where excellent electrical conductivity cannot be obtained depending on the application, and therefore the contents of Mg, Cr and Zr are respectively preferably 1.0 mass% or less, more preferably 0.7 mass% or less, and particularly preferably 0.5 mass% or less. Therefore, the total content of at least one component selected from the group consisting of Mg, Cr, and Zr is preferably 0.01 to 3.0 mass%, more preferably 0.05 to 2.1 mass%, and particularly preferably 0.10 to 1.5 mass% in view of not impairing the electric conductivity and obtaining excellent tensile strength even when the wire rod is made smaller in diameter.
The balance other than the above components is Cu and unavoidable impurities. Cu is a parent phase of the copper alloy wire of the present invention. In Cu as a matrix phase, Ag as an essential additive component exists in a solid solution state or a state of precipitation as precipitates. In addition, if necessary, at least one component selected from the group consisting of Mg, Cr, and Zr as an optional additive component is present in a solid solution state or a state of being precipitated as precipitates in Cu as a matrix phase.
The inevitable impurities are those inevitably contained in the copper alloy wire rod of the present invention in a content level. Unavoidable impurities may also become a major factor in lowering the conductivity depending on the content. Therefore, if the decrease in conductivity is taken into consideration, it is preferable to suppress the content of inevitable impurities. Examples of the inevitable impurities include Ni, Sn, and Zn.
[ area ratio (A) of precipitates coherently precipitated in the matrix Cu ]
In the copper alloy wire rod of the present invention, when a cross section parallel to the longitudinal direction thereof is observed, the area ratio (a) of precipitates (hereinafter, sometimes referred to as "coherent precipitates") coherently precipitated in the matrix Cu in a rectangular observation region of 240nm × 360nm is within the range of the following formula (I).
(0.393×x-0.589)％≤A≤(3.88×x-5.81)％ (I)
(in the formula (I), x represents% by mass of Ag.)
Therefore, in the copper alloy wire rod of the present invention, the range of the area ratio (a) of coherent precipitates also changes according to the change in the Ag content. When the area ratio (a) of the coherent precipitates is in the above range, a copper alloy wire rod excellent in tensile strength and vibration durability can be obtained without impairing excellent electrical conductivity even when the wire rod is made smaller in diameter. The formula (I) is derived from experimental results of various selections of Ag content in the copper alloy wire.
When the area ratio (a) of the coherent precipitates is less than (0.393 × x-0.589)%, the amount of the coherent precipitates precipitated is small, and therefore the coherent precipitates do not inhibit deformation of the copper alloy wire rod, and as a result, excellent tensile strength and vibration durability cannot be obtained. On the other hand, when the area ratio (A) of the coherent precipitates exceeds (3.88 Xx-5.81)%, the sizes such as the length and the width of the coherent precipitates become large, and therefore the coherent precipitates do not inhibit the deformation of the copper alloy wire rod, and as a result, excellent tensile strength and vibration durability are not obtained.
Since the coherent precipitates are mainly composed of Ag, the area ratio (a) of the coherent precipitates varies depending on the content of Ag. That is, it is considered that the area ratio (a) increases if the content of Ag increases, and the area ratio (a) decreases if the content of Ag decreases. If the area ratio (A) of the coherent precipitates is increased, the coherent precipitates become an obstacle to deformation of the copper alloy wire rod, and as a result, the tensile strength and vibration durability are improved. On the other hand, it was found that even if the area ratio (a) of coherent precipitates is excessive, the coherent precipitates do not inhibit the deformation of the copper alloy wire rod, and as a result, excellent tensile strength and vibration durability are not obtained. Therefore, in the copper alloy wire rod of the present invention, by adjusting not only the range of the content of Ag but also the range of the area ratio (a) of coherent precipitates, excellent tensile strength and vibration durability are achieved without impairing electric conductivity.
[ coherent precipitation in parent phase Cu ]
In the present specification, the phrase "precipitates in the matrix phase Cu" refers to precipitates having a specific crystal orientation with respect to the crystal of Cu as the matrix phase. As a method for determining whether or not the precipitates are precipitated with a specific crystal orientation with respect to the crystal of Cu as the matrix phase, that is, whether or not the precipitates are coherent precipitates, a method of reading from a diffraction pattern is included.
When a specimen is irradiated with an electron beam in a transmission electron microscope, diffraction of the electron beam occurs. The diffraction wave generated by the diffraction of the electron beam is strong or weak depending on the crystal form, the atomic spacing constituting the crystal, and the like, and a specific diffraction pattern is formed depending on the crystal. For example, if an electron beam is incident in the [010] direction for the crystallization of Cu, diffraction spots are generated at the apexes of squares and the midpoints thereof as shown in FIG. 1.
Cu and Ag have the same face-centered cubic lattice structure (fcc structure), and therefore have the same diffraction pattern, but have different lattice constants, and therefore have different intervals between diffraction spots. The larger the lattice constant, the narrower the interval between diffraction spots, and therefore the diffraction spots of Ag appear in a narrower range than those of Cu. If Ag precipitates are present in the Cu alloy and crystals of the Ag precipitates are aligned in a specific direction, diffraction spots of the Ag precipitates appear slightly inside the diffraction spots of Cu as a parent phase. In the case where the crystal orientation of Cu completely coincides with that of Ag, that is, in the case where both the crystal of Cu and the crystal of Ag face in the [100] direction, the diffraction pattern is the same, and the diffraction pattern of Ag appears slightly inside the diffraction pattern of Cu.
On the other hand, when Cu and Ag are aligned in a specific direction but the crystal orientation of Cu does not completely match that of Ag, for example, when the crystal orientation of Cu is oriented in the [100] direction but the crystal orientation of Ag is oriented in the [110] direction with respect to the [100] direction of the observation axis, a diffraction pattern of Cu corresponding to the [100] direction and a diffraction pattern of Ag corresponding to the [110] direction appear.
As is clear from the above, when the diffraction pattern of Cu is the same as that of Ag and the diffraction pattern of Ag appears slightly inside the diffraction pattern of Cu, or when a diffraction pattern of Cu indicating that the crystals of Cu correspond to a predetermined direction and a diffraction pattern of Ag indicating that the crystals of Ag correspond to Ag in a predetermined direction appear, it is determined that Ag "coherently precipitates in the parent phase Cu", that is, Ag precipitates are coherent with Cu as the parent phase.
However, when Cu and Ag are not completely aligned, that is, the crystal orientation of Cu and the crystal orientation of Ag do not completely match, Ag is arranged in various crystal directions with respect to Cu, and therefore, the diffraction pattern of Ag is randomly formed with respect to the diffraction pattern of Cu. In this case, it was judged that the Ag precipitates were not coherent with Cu as the matrix phase.
[ average width (W) of precipitates coherently precipitated in the matrix Cu ]
The precipitates precipitated in the matrix Cu are more effective if they are present in a fiber shape along the longitudinal direction of the copper alloy wire rod, that is, if they are fibrous substances extending in a direction substantially parallel to the longitudinal direction of the copper alloy wire rod. In the copper alloy wire rod of the present invention, when a cross section parallel to the longitudinal direction thereof is observed, the average width (W) of fibrous coherent precipitates extending in the longitudinal direction of the copper alloy wire rod, which are coherently precipitated in the matrix Cu in a rectangular observation region of 240nm × 360nm, is not particularly limited, but is preferably within the range of the following formula (II) in terms of further improving the effect of inhibiting the deformation of the copper alloy wire rod by the coherent precipitates:
(8.3×d)nm≤W≤(24.9×d)nm (II)
in the formula (II), d represents the wire diameter (mm) of the copper alloy wire rod, and is particularly preferably in the range of (9.0 xd) nm. ltoreq.W.ltoreq.24.0 xd nm. Therefore, in a preferred embodiment of the copper alloy wire rod according to the present invention, the range of the preferred average width (W) of coherent precipitates also varies depending on the change in wire diameter. The formula (II) is determined based on the wire diameter and the average width of coherent precipitates in examples of the present application described later.
When the average width (W) of the coherent precipitates is less than (8.3 × d) nm, the coherent precipitates become thinner than the wire diameter, and there is a possibility that the effect of inhibiting the deformation of the copper alloy wire rod by the coherent precipitates is limited. On the other hand, in the case of more than (24.9 × d) nm, the size of the average width (W) becomes large with respect to the wire diameter, and therefore it is still possible to limit the effect of inhibiting the deformation of the copper alloy wire rod by coherent precipitates.
[ average width (W) of precipitates coherently precipitated in the matrix Cu ]
In the copper alloy wire rod of the present invention, the average length (L) of the fibrous coherent precipitates extending in the longitudinal direction of the copper alloy wire rod coherently precipitated in the matrix Cu in the rectangular observation region of 240nm × 360nm when a cross section parallel to the longitudinal direction thereof is observed is not particularly limited, but is preferably within the range of the following formula (III) in terms of further improving the effect of inhibiting the deformation of the copper alloy wire rod by the coherent precipitates:
(11.3/d)nm≤L≤(33.8/d)nm (III)
in the formula (III), d represents the wire diameter (mm) of the copper alloy wire rod, and is particularly preferably in the range of (14.0/d) nm. ltoreq.L.ltoreq.30.0/d) nm. Therefore, in a preferred embodiment of the copper alloy wire rod according to the present invention, the range of the preferred average length (L) of coherent precipitates also varies depending on the wire diameter. The formula (III) is determined based on the wire diameter and the average length of coherent precipitates in examples of the present application described later.
When the average length (L) of the coherent precipitates is less than (11.3/d) nm, the coherent precipitates become shorter than the wire diameter, and there is a possibility that the effect of inhibiting the deformation of the copper alloy wire rod by the coherent precipitates is limited. On the other hand, in the case of exceeding (33.8/d) nm, the size of the average length (L) becomes large with respect to the wire diameter, and therefore there is still a possibility of defining the effect of inhibiting the deformation of the copper alloy wire rod by coherent precipitates.
[ average spacing (S) of precipitates precipitated in the matrix Cu
In the copper alloy wire rod of the present invention, the average interval (S) of coherent precipitates coherently precipitated in the matrix Cu in a rectangular observation region of 240nm × 360nm is not particularly limited when a cross section parallel to the longitudinal direction thereof is observed, and is preferably within the range of the following formula (IV):
(760×x＾-2.25)×dnm≤S≤(2300×x＾-2.25)×dnm (IV)
in the formula (IV), d represents the wire diameter (mm) of the copper alloy wire rod, and x represents the mass% of Ag. Therefore, in a preferred embodiment of the copper alloy wire rod according to the present invention, the range of the preferred average spacing (S) of coherent precipitates also varies depending on the wire diameter and the Ag content. The above formula (IV) is derived from experimental results of various selections of Ag content in the copper alloy wire rod.
In the case where the average spacing (S) of the coherent precipitates is smaller than (760 xx-2.25). times.dnm, the spacing of the coherent precipitates becomes narrow with respect to the wire diameter and the Ag content, and there is a possibility that the effect of inhibiting the deformation of the copper alloy wire material by the coherent precipitates is limited. On the other hand, in the case of exceeding (2300 × x ^ -2.25) × dnm, the intervals of coherent precipitates become wide with respect to the wire diameter and the Ag content, and there is still a possibility of defining the hindering effect of the coherent precipitates on the deformation of the copper alloy wire rod.
[ coherent precipitates coherent in the same crystal axis direction ]
In the copper alloy wire rod of the present invention, it is preferable that the coherent precipitates are coherent in the same crystal axis direction with respect to the matrix phase Cu. "coherent in the same crystal axis direction" means that the crystal of Cu as the matrix phase and the crystal of coherent precipitates mainly composed of Ag are aligned in the same crystal axis direction. By having such a crystal arrangement, strain is generated between the crystal of Cu as a matrix phase and the crystal of coherent precipitates. This strain acts as an obstacle when the copper alloy wire rod is deformed, and therefore, higher tensile strength is imparted to the copper alloy wire rod.
Whether or not coherent precipitates are coherent in the same crystal axis direction with respect to Cu as a parent phase can be determined by the following method. First, a copper alloy wire material to be a sample is made into a thin film by a Focused Ion Beam (FIB) method, and a predetermined observation region (for example, an observation region formed of a rectangular shape of 240nm × 360 nm) is observed with a Transmission Electron Microscope (TEM). The sample was cut parallel to the longitudinal direction, and observed with the longitudinal direction arranged laterally in TEM observation.
Next, in order to confirm coherent precipitation of the precipitates, a diffraction pattern was obtained as described above. In this case, the diffraction pattern can be imaged by using any zone axis incidence, for example, a [110] zone axis incidence, which is easy to know the pattern, is generally used. The diffraction pattern generated by the crystal of Cu as the matrix phase was observed to have the highest brightness, but in addition to this, the diffraction pattern was observed, and by confirming the diffraction pattern having the same type as Cu and a slightly narrower spot interval, the precipitates were confirmed to be coherently precipitated.
Then, the angle of the sample was changed, and a diffraction pattern was obtained by using [100] or [111] zone axis incidence with respect to Cu as a parent phase, and whether or not a diffraction pattern having the same type as Cu and a slightly narrower spot interval was present was similarly confirmed. When the diffraction pattern identical to that of Cu was confirmed in both of the band axis shots of the 2-axis, it was evaluated that coherent precipitates were coherent in the same crystal axis direction with respect to Cu as a parent phase.
[ method for producing copper alloy wire rod of the present invention ]
Next, a method for manufacturing the copper alloy wire rod of the present invention will be explained. The method for manufacturing a copper alloy wire rod of the present invention includes: (a) a step of melting a raw material, (b) a step of casting the melted raw material to obtain an ingot, (c) a step of performing a first heat treatment on a copper alloy material obtained from the ingot, (d) a step of further performing a second heat treatment after the step of performing the first heat treatment, and (e) a step of performing a final wire drawing process on the copper alloy material subjected to the second heat treatment to obtain a copper alloy wire rod, wherein the final wire drawing process is performed so that a degree of working loge (a0/a1) · 2 (in the formula, a0 is a cross-sectional area of the copper alloy material to be subjected to the final wire drawing process, which is orthogonal to a longitudinal direction, and a1 is a cross-sectional area of the copper alloy material immediately after the final wire drawing process, which is orthogonal to the longitudinal direction) is 2.5 or more.
(a) The step of melting the raw material and the step of (b) casting the melted raw material to obtain an ingot can be carried out by a known general method. The raw materials used in the step (a) are mixed in a predetermined ratio such that Ag is 1.5 to 6.0 mass%, Mg is 0 to 1.0 mass%, Cr is 0 to 1.0 mass%, Zr is 0 to 1.0 mass%, and the balance is Cu.
(c) The heat treatment temperature in the step of performing the first heat treatment on the copper alloy material is 700 ℃ or higher. When the temperature in the first heat treatment step is less than 700 ℃, it is difficult to fibrillate precipitates mainly composed of Ag in the final drawing process, and excellent tensile strength and vibration durability may not be obtained. The lower limit of the temperature in the first heat treatment step is preferably 750 ℃ and more preferably 800 ℃ from the viewpoint of obtaining more excellent tensile strength. On the other hand, the upper limit of the temperature in the first heat treatment step is not particularly limited, but is preferably 900 ℃.
The heat treatment time in the first heat treatment step is not particularly limited, but is preferably 0.1 to 10 hours, particularly preferably 0.5 to 5 hours, from the viewpoint of dispersing a large amount of precipitates and fibrillating the precipitates in the subsequent steps.
Cooling the copper alloy material after the first heat treatment step, and (d) further performing a second heat treatment. The heat treatment temperature of the second heat treatment step is 350 to 600 ℃. When the heat treatment temperature in the second heat treatment step is less than 350 ℃ or exceeds 600 ℃, precipitates mainly composed of Ag are not sufficiently precipitated, and excellent tensile strength and vibration durability may not be obtained. The heat treatment time in the second heat treatment step is not particularly limited, but is preferably 0.5 to 20 hours, and particularly preferably 1.0 to 15 hours.
Cooling the copper alloy material after the second heat treatment step, and (e) performing final drawing. In the final drawing, the degree of working loge (A0/A1)' 2 (in the formula, A0 is the cross-sectional area of the copper alloy material to be subjected to the final drawing and perpendicular to the longitudinal direction, and A1 is the cross-sectional area of the copper alloy material immediately after the final drawing and perpendicular to the longitudinal direction) is 2.5 or more. When the degree of finish of the final drawing is less than 2.5, coherent precipitates may not be sufficiently elongated or fiberized, and excellent tensile strength and vibration durability may not be obtained.
The above-mentioned degree of working in the final drawing may be 2.5 or more in view of sufficiently elongating and fibrillating coherent precipitates, and the higher the degree of working, the more excellent the tensile strength. Therefore, the upper limit of the above-mentioned degree of finish in the final drawing is not particularly limited.
If necessary, intermediate wire drawing may be performed between (b) the step of obtaining an ingot and (c) the first heat treatment step and/or between (c) the first heat treatment step and (d) the second heat treatment step. The degree of intermediate drawing is not particularly limited, but from the viewpoint of increasing the degree of final drawing, it is preferable that the degree of intermediate drawing is low in loge (B0/B1) ^ 2 (where B0 is the cross-sectional area of the copper alloy material immediately before intermediate drawing and B1 is the cross-sectional area of the copper alloy material immediately after intermediate drawing, the cross-sectional area being perpendicular to the longitudinal direction), and in order to sufficiently precipitate coherent precipitates, the coherent precipitates are sufficiently elongated and fiberized in the final drawing, and the degree of intermediate drawing is high. From the above, the degree of processing is preferably 0 to 1.0 in terms of balance between the two.
In the copper alloy wire rod of the present invention, particularly by performing the above-described (c) first heat treatment step and (d) second heat treatment step, a copper alloy wire rod having excellent tensile strength even when the wire rod is reduced in diameter can be produced without impairing excellent electrical conductivity.
Examples
Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
Examples 1 to 40
Raw materials (oxygen-free copper, silver, magnesium, chromium, and zirconium) were charged into a graphite crucible so as to have an alloy composition shown in table 1 below, and the raw materials were melted by heating the inside of the crucible to 1250 ℃. A resistance heating furnace was used for melting. The atmosphere in the crucible is made to be a nitrogen atmosphere so as to prevent oxygen from being mixed into the molten copper. Further, after keeping the casting mold at 1250 ℃ or higher for 3 hours or longer, the cooling rate is set to 500 to 1000 ℃/s, and the casting diameter is made by graphite mold
An ingot of a size of about 10 mm. After the start of casting, the above-described raw materials are appropriately charged to perform continuous casting. When chromium is contained in the raw material (examples 23, 27, 28, 31, 33 and 34), the raw material is melted by maintaining the temperature in the crucible at 1600 ℃ or higher.
Next, with respect to the ingot obtained as described above, the first heat treatment was performed at the temperature and time shown in table 1 below. After the first heat treatment step, the test material was subjected to intermediate wire drawing until the test material was subjected to intermediate wire drawing
To then, furtherThe second heat treatment was performed at the temperature and time shown in table 1 below. After the second heat treatment step, final drawing was performed to wire diameters shown in table 1 below with a predetermined degree of working, to obtain copper alloy wire rods. The first heat treatment and the second heat treatment are performed in a box furnace in a nitrogen atmosphere.
Comparative examples 1 to 7
Comparative examples 1, 4 to 7 were all cast
An ingot having a size of about 8mm, and subjected to a drawing process in a final drawing process without performing an intermediate drawing process until the final drawing process is completed
Except for this, a copper alloy wire rod was obtained by the same steps as in the above example and under the production conditions shown in table 1 below. Comparative example 2 a copper alloy wire rod was obtained by the same steps as in comparative examples 1 and 4 to 7, except that the first heat treatment and the second heat treatment were not performed. Comparative example 3 a copper alloy wire rod was obtained by the same steps as in comparative examples 1 and 4 to 7, except that the second heat treatment was not performed. Therefore, in comparative example 3
A first heat treatment is performed.
[ method of observing precipitates precipitated in the matrix Cu
The copper alloy wires in examples and comparative examples were formed into thin films by FIB method, and an observation region consisting of a rectangle having a length of 240nm in the cross-sectional direction (width direction) × a length of 360nm in the longitudinal direction was observed by a Transmission Electron Microscope (TEM). The copper alloy wire rod was cut out parallel to the longitudinal direction, and the longitudinal direction was arranged laterally in TEM observation. Next, a diffraction pattern was obtained to confirm coherent precipitation of the precipitates. In this case, the diffraction pattern is generally imaged by using the [110] zone axis incidence, which makes it easy to know the pattern. The diffraction pattern produced by the Cu crystal as the matrix phase was observed to have the highest brightness, but in addition to this, the diffraction pattern was observed, and the precipitates in the diffraction pattern were identified as Ag by the shape of the diffraction pattern and the measurement of the spot interval.
Next, the objective lens diaphragm was attached to observe the diffraction pattern of the deposit so that only the diffraction wave of the diffraction pattern obtained above could be selected and observed, and in this case, only the portion where the diffraction wave for forming the diffraction pattern was generated (i.e., coherent deposit) was brightly observed. This was referred to as a dark field image, and the dark field image (shown in fig. 2) was captured for the copper alloy wires in examples and comparative examples. From the dark field image obtained above, the area ratio, average width, average length, and average interval of precipitates (coherent precipitates) coherently precipitated in Cu as a matrix were determined as follows.
First, the contrast obtained by the dark field image is binarized. The p-tile method is used for binarization. If the p-tile method is used, since the threshold value is determined without changing the order of the brightness, photographs of the same range taken in different observation environments can be binarized almost identically to each other. However, it is not a prerequisite that there is an environment in which the brightness changes as in a local portion on the image. Then, the total number of pixels of the obtained photograph was calculated as the number of pixels of the portion of the white contrast, that is, the number of pixels of the coherent precipitates (coherent precipitates), and the area ratio was calculated by dividing the number of pixels of the coherent precipitates by the total number of pixels.
The number of pixels of the coherent precipitates in the longitudinal direction was calculated using the cross-sectional direction of the dark field image as the row number, and the number of pixels per row was plotted as shown in fig. 3. The line numbers 0 to 275 observed in fig. 3 correspond to the length 240nm in the cross-sectional direction. The part with the number of pixels of 25 or more is obtained as one peak, the half-width of each peak is defined as the width of the coherent precipitates, the width of the coherent precipitates is obtained from each peak, and the average value is calculated as the average width. The maximum value of the peak is defined as the length of coherent precipitates, the length of coherent precipitates is obtained from the number of pixels of each peak with respect to the total number of pixels of the photograph, and the average value is calculated as the average length. The interval of the maximum value of the peak adjacent to the maximum value of the peak is measured, each interval is defined as the interval of coherent precipitates, each peak interval is obtained, and the average value is calculated as the average interval of precipitates.
In each of the above embodiments of coherent precipitates, the sample thickness of the thin film was calculated with a reference thickness of 0.15 μm. When the thickness of the copper alloy wire is different from the reference thickness, the dispersion density can be calculated by converting the thickness of the copper alloy wire into the reference thickness, that is, multiplying the (reference thickness/thickness of the copper alloy wire) by the dispersion density calculated based on the photographed photograph. In the examples and comparative examples, the thickness of the sample was set to about 0.15 μm in all the copper alloy wires by the FIB method.
[ evaluation method of coherent precipitates coherent in the same crystal axis direction with respect to Cu as a parent phase ]
As described above, whether coherent precipitates were coherent in the same crystal axis direction with respect to Cu as a matrix was evaluated in the order of a method of obtaining a diffraction pattern by using [110] zone axis incidence for Cu as a matrix in order to confirm precipitate coherent precipitation and a method of obtaining a diffraction pattern by using [110] or [111] zone axis incidence for Cu as a matrix in order to confirm that coherent precipitates were coherent in the same crystal axis direction with respect to Cu as a matrix, and in Table 1, ○ was marked if coherent precipitates were coherent in the same crystal axis direction with respect to Cu as a matrix and x was marked if coherent.
[ method for measuring tensile Strength ]
Tensile test was carried out in accordance with JIS Z2241 using a precision universal testing machine (manufactured by Shimadzu corporation) to determine the tensile strength (MPa). The tensile strength of each copper alloy wire was determined by performing 3 tests described above on each copper alloy wire and determining the average value (N — 3).
[ method for measuring conductivity ]
As for the conductivity, the resistivity of 3 test pieces having a length of 300mm was measured by a four-terminal method in a constant temperature bath maintained at 20 ℃ (± 0.5 ℃), and the average conductivity thereof was calculated. The inter-terminal distance was set to 200 mm.
[ Table 1]
As shown in Table 1 above, in examples 1 to 40 in which the first heat treatment step at 700 ℃ or more and the second heat treatment step at 350 to 600 ℃ were performed and the area ratio of coherent precipitates was (0.393 Xx-0.589)% A.ltoreq.3.88 Xx-5.81)% (in the formula, x represents mass% of Ag), a copper alloy wire rod excellent in tensile strength without impairing excellent electrical conductivity and even when the wire rod was reduced in diameter to 0.02mm to 2.6mm could be obtained.
On the other hand, in comparative example 1 in which 8.0 mass% of Ag was added, the conductivity was significantly reduced. In addition, in comparative example 2 in which the first heat treatment step and the second heat treatment step were not performed, and in example 4 in which the same production conditions as in comparative example 2 and the same composition as in comparative example 2 were used except that the first heat treatment step and the second heat treatment step were performed, coherent precipitates were not obtained, and a good tensile strength was not obtained. In comparative example 3 in which the second heat treatment step was not performed, comparative examples 4 and 6 in which the temperature of the second heat treatment step was as low as 300 ℃, and comparative examples 5 and 7 in which the temperature of the second heat treatment step was as high as 700 ℃, coherent precipitates were not obtained, and good tensile strength was not obtained.
Claims (9)
1. A copper alloy wire having an alloy composition of: the copper alloy wire rod contains 1.5-6.0 mass% of Ag, 0-1.0 mass% of Mg, 0-1.0 mass% of Cr and 0-1.0 mass% of Zr, and the balance of Cu and inevitable impurities, wherein when a cross section parallel to the longitudinal direction of the copper alloy wire rod is observed, the area ratio (A) of precipitates precipitated in a matrix Cu in a rectangular observation region of 240nm x 360nm is within the range of the following formula (I):
(0.393×x-0.589)％≤A≤(3.88×x-5.81)％ (I)
in the formula (I), x represents the mass% of Ag.
2. The copper alloy wire according to claim 1, wherein the total content of at least one component selected from the group consisting of Mg, Cr, and Zr is 0.01 to 3.0 mass%.
3. The copper alloy wire according to claim 1 or 2, wherein the precipitates coherently precipitated in the parent phase Cu are present in a fiber shape along a longitudinal direction of the copper alloy wire.
4. The copper alloy wire according to claim 3, wherein, when a cross section parallel to the longitudinal direction of the copper alloy wire is observed, in a rectangular observation region of 240nm x 360nm, an average width W of the precipitates coherently precipitated in the matrix Cu is within a range of the following formula (II):
(8.3×d)nm≤W≤(24.9×d)nm (II)
in the formula (II), d represents the wire diameter of the copper alloy wire rod, and the unit is mm.
5. The copper alloy wire according to claim 3 or 4, wherein, when a cross section parallel to a longitudinal direction of the copper alloy wire is observed, an average length L of the precipitates precipitated in the matrix Cu is in the range of the following formula (III) in a rectangular observation region of 240nm x 360 nm:
(11.3/d)nm≤L≤(33.8/d)nm (III)
in the formula (III), d represents the wire diameter of the copper alloy wire rod, and the unit is mm.
6. The copper alloy wire according to any one of claims 3 to 5, wherein, when a cross section parallel to a longitudinal direction of the copper alloy wire is observed, an average spacing S of the precipitates precipitated in the matrix Cu is in the range of the following formula (IV) in a rectangular observation region of 240nm x 360 nm:
(760×x＾-2.25)×dnm≤S≤(2300×x＾-2.25)×dnm (IV)
in the formula (IV), d represents the wire diameter of the copper alloy wire rod, and the unit is mm, and x represents the mass% of Ag.
7. The copper alloy wire according to any one of claims 1 to 6, wherein the precipitates are coherent in the same crystal axis direction with respect to the parent phase Cu.
8. A method for producing a copper alloy wire according to any one of claims 1 to 7, comprising:
a step of melting a raw material, a step of casting the melted raw material to obtain an ingot, a step of subjecting a copper alloy material obtained from the ingot to a first heat treatment, a step of further subjecting the copper alloy material to a second heat treatment, and a step of subjecting the copper alloy material subjected to the second heat treatment to a final wire drawing process to obtain a copper alloy wire rod,
the first heat treatment step is carried out at a temperature of 700 ℃ or higher,
the second heat treatment step is performed at a temperature of 350 to 600 ℃,
the final drawing step is performed with a degree of working loge (A0/A1)' 2 of 2.5 or more, wherein A0 is a cross-sectional area of the copper alloy material to be subjected to the final drawing in a direction perpendicular to the longitudinal direction, and A1 is a cross-sectional area of the copper alloy material immediately after the final drawing in a direction perpendicular to the longitudinal direction.
9. The method of manufacturing a copper alloy wire according to claim 8, wherein wire drawing is performed between the step of obtaining an ingot and the first heat treatment step, and/or between the first heat treatment step and the second heat treatment step.
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| PCT/JP2019/005812 WO2019181320A1 (en) | 2018-03-20 | 2019-02-18 | Copper alloy wire rod and method for producing copper alloy wire rod |
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| EP (1) | EP3770287A4 (en) |
| JP (1) | JPWO2019181320A1 (en) |
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| CN115398014A (en) * | 2021-03-23 | 2022-11-25 | 古河电气工业株式会社 | Copper alloy wire |
| CN115427595A (en) * | 2021-03-23 | 2022-12-02 | 古河电气工业株式会社 | Copper alloy wire |
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| CN113369473B (en) * | 2021-06-10 | 2023-05-12 | 盘星新型合金材料(常州)有限公司 | High-strength high-conductivity copper alloy powder and preparation method thereof |
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- 2019-02-18 JP JP2019529676A patent/JPWO2019181320A1/en active Pending
- 2019-02-18 EP EP19771832.3A patent/EP3770287A4/en active Pending
- 2019-02-18 KR KR1020197029803A patent/KR20200129027A/en not_active IP Right Cessation
- 2019-02-18 CN CN201980003858.4A patent/CN111032892B/en active Active
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| KR20200129027A (en) | 2020-11-17 |
| CN111032892B (en) | 2021-12-14 |
| EP3770287A4 (en) | 2021-11-24 |
| WO2019181320A1 (en) | 2019-09-26 |
| JPWO2019181320A1 (en) | 2021-02-04 |
| EP3770287A1 (en) | 2021-01-27 |
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