JP2010165528A - Aluminum alloy wire - Google Patents

Abstract

An aluminum alloy wire excellent in corrosion resistance, an aluminum alloy stranded wire, an insulated wire using the alloy stranded wire as a conductor, and an electric wire with a terminal including the insulated wire are provided.
An aluminum alloy wire used for a conductor of an automobile electric wire, and a coating layer is provided on an outer surface of an end portion of an alloy wire to which a terminal member made of copper or copper alloy is attached. The outermost layer of the coating layer is made of nickel or a nickel alloy. A battery is formed between the aluminum alloy and copper or copper alloy, and the aluminum alloy is corroded. On the other hand, since the potential difference between copper and nickel is small, it becomes difficult to make a battery between copper and nickel. Therefore, the presence of nickel or a nickel alloy on the surface of the aluminum alloy wire can reduce electrolytic corrosion between the aluminum alloy and the terminal member.
[Selection] Figure 2

Description

  The present invention relates to an aluminum alloy wire and an aluminum alloy stranded wire used for a conductor of an electric wire, an insulated wire using the alloy wire as a conductor, and an electric wire with a terminal including the insulated wire and a terminal member. In particular, the present invention relates to an aluminum alloy wire and a terminal-attached electric wire having excellent corrosion resistance.

  Conventionally, electric wires of transport equipment such as automobiles and airplanes and industrial equipment such as robots are used by removing an insulating layer and exposing a conductor at an end thereof, and attaching a terminal to the conductor. Copper-based materials such as copper and copper alloys, which are excellent in conductivity, are the mainstream as constituent materials for conductors and terminals of electric wires.

  In recent years, the performance and functionality of automobiles have been rapidly increased, and with the increase of various electric devices and control devices mounted on the vehicle, the number of electric wires used for these devices is also increasing. On the other hand, in recent years, improvement of fuel consumption of automobiles, airplanes and the like is desired for environmental protection. When the weight is reduced, fuel consumption can be improved. Therefore, in order to reduce the weight of the electric wire, use of aluminum having a specific gravity of about 1/3 of copper or an alloy thereof as a conductor has been studied (Patent Document 1).

Japanese Patent Laid-Open No. 2005-108608

  It is desired to improve the corrosion resistance of an electric wire using an aluminum alloy wire as a conductor.

  As described above, the terminal is often made of copper or a copper alloy. Therefore, when the constituent material of the conductor is an aluminum alloy, a battery is formed between the conductor made of an aluminum alloy and the terminal made of copper or the like because the constituent material of the conductor and the constituent material of the terminal are different metals. And the aluminum alloy corrodes.

  In Patent Document 1, in order to reduce the electrolytic corrosion, it is proposed that tin plating is performed on a portion of the terminal excluding the portion where the conductor is welded. However, Patent Document 1 does not discuss a configuration for improving the corrosion resistance of a conductor. Further, as a result of investigation by the present inventors, it was found that corrosion of an aluminum alloy is likely to proceed when tin applied to a terminal is alloyed with copper as a base material due to aging. Therefore, it is desired that the conductor itself is excellent in corrosion resistance.

  Then, the objective of this invention is suitable for the conductor of the electric wire for motor vehicles, and is providing the aluminum alloy wire and aluminum alloy strand wire which are excellent in corrosion resistance. Another object of the present invention is to provide an insulated wire excellent in corrosion resistance using the alloy wire or stranded wire as a conductor, and a wire with terminal.

  In order to improve the corrosion resistance of the aluminum alloy wire, it is effective to prevent a battery from being formed by the aluminum alloy and copper or a copper alloy which is a constituent material of the terminal member. Therefore, in order to suppress the formation of a battery between an aluminum alloy and copper or copper alloy, the present invention provides a layer made of a material having a small potential difference from copper or copper alloy on the surface of the aluminum alloy wire. Suggest to prepare.

  The aluminum alloy wire (hereinafter referred to as “Al alloy wire”) of the present invention is used as a conductor of an automobile electric wire, and includes a coating layer on at least a part of the outer surface of the Al alloy wire. The outermost layer of the coating layer is made of nickel or a nickel alloy.

  The Al alloy wire of the present invention is nickel which is provided on at least a part of the outer surface (surface) of the Al alloy wire even when a terminal member made of a metal such as copper or copper alloy, which is more precious than aluminum, is connected. It is difficult to form a battery between the layer or the nickel alloy layer and the terminal member. Therefore, the Al alloy wire of the present invention can reduce electrolytic corrosion with the terminal member due to the presence of the nickel layer or nickel alloy layer, and is excellent in corrosion resistance. Therefore, the Al alloy wire of the present invention can be suitably used for a conductor of an automotive electric wire that is desired to have excellent corrosion resistance. Hereinafter, the present invention will be described in more detail.

[Al alloy wire and Al alloy stranded wire]
"composition"
As the Al alloy constituting the Al alloy wire of the present invention, those having various compositions containing an additive element and the balance of Al and inevitable impurities can be used. Examples of the additive element include one or more selected from Fe, Mg, Si, Cu, Zn, Ni, Mn, Ag, Cr, and Zr. A preferable total content of additive elements is 0.005% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less. The preferred content of each element is mass%, Fe: 0.005% to 2.2%, Mg: 0.05% to 1.0%, Mn, Ni, Zr, Zn, Cr, and Ag: 0.005% to 0.2% in total Cu: 0.05% to 0.5%, Si: 0.04% to 1.0%. These additive elements may be contained alone or in combination of two or more. Examples of such alloys include Al-Fe alloys, Al-Fe-Mg alloys, Al-Fe-Si alloys, Al-Fe-Mg- (Mn, Ni, Zr, Ag) alloys, and Al-Fe-Cu alloys. Al-Fe-Cu- (Mg, Si) alloy, Al-Mg-Si-Cu alloy, and the like.

Specific examples of the Al alloy include the following (1) to (6).
(1) By mass%, Fe is 0.90% or more and 1.20% or less, Mg is 0.10% or more and 0.25% or less, and the balance is Al and inevitable impurities.
(2) By mass%, Fe is 1.01% or more and 2.2% or less, Mg is 0.05% or more and 0.5% or less, and one or more elements selected from Mn, Ni, Zr, and Ag are combined in a total of 0.005% or more and 0.2%. Contains below, the balance being Al and inevitable impurities.
(3) By mass%, Fe contains 1.01% or more and 2.2% or less, Cu contains 0.05% or more and 0.5% or less, and the balance is Al and inevitable impurities.
(4) Containing at least one of Fe by 1.0% to 2.2%, Cu by 0.05% to 0.5%, Mg by 0.1% to 0.5%, and Si by 0.04% to 0.3% by mass. Contains, the balance being Al and inevitable impurities.
(5) By mass%, Mg is 0.2% to 1.0%, Si is 0.1% to 1.0%, Cu is 0.1% to 0.5%, the balance being Al and inevitable impurities.
(6) By mass%, Mg is 0.2% to 1.0%, Si is 0.1% to 1.0%, Cu is 0.1% to 0.5%, the balance being Al and inevitable impurities. However, the mass ratio Mg / Si of Mg and Si satisfies 0.8 ≦ Mg / Si ≦ 2.7.

  Fe has an Al alloy wire with excellent strength.The higher the content, the higher the strength of the Al alloy, but the electrical conductivity and toughness tend to decrease, and wire breakage tends to occur during wire drawing, so Fe: 2.2 mass% or less is preferable. Mn, Ni, Zr, and Cr are elements that have a high effect of improving the strength, although the decrease in conductivity is large. Ag and Zn have a small effect of reducing the conductivity and have a certain effect on improving the strength. Cu has little decrease in conductivity and can improve strength. Although Mg has a large decrease in electrical conductivity, the effect of improving the strength is high, and in particular, the strength can be further improved by containing it together with Si. In addition, when aging is performed when Mg and Si are contained, an improvement in strength due to age hardening can be expected.

  Furthermore, when the Al alloy contains at least one of Ti and B, there is an effect of making the crystal structure of the Al alloy at the time of casting fine, and an improvement in strength due to the fine crystal structure can be expected. In order to sufficiently obtain this fine effect, it is preferable that Ti is contained in a mass ratio of 100 ppm to 500 ppm and B is contained in an amount of 10 ppm to 50 ppm.

"Characteristic"
It is composed of an Al alloy having the above composition and, as will be described later, by appropriately performing a softening treatment after drawing, an Al alloy wire having excellent conductivity and toughness such as conductivity: 58% IACS or more and elongation: 10% or more is obtained. be able to. Although depending on the kind and amount of additive elements and softening conditions, the Al alloy wire of the present invention can also satisfy electrical conductivity: 59% IACS or more and elongation: 25% or more. By being excellent in toughness, the conductor hardly breaks in the vicinity of the boundary between the conductor and the terminal member, and the Al alloy wire of the present invention can be suitably used for the conductor of the electric wire with terminal. The Al alloy wire of the present invention preferably has a tensile strength of 110 MPa or more and 200 MPa or less because both high toughness and high strength can be achieved. By appropriately adjusting additive elements (type and content), manufacturing conditions (working degree during wire drawing (cross-sectional reduction rate), softening conditions, etc.), conductivity, elongation, and tensile strength are within the above specified ranges. A satisfying Al alloy wire is obtained.

<Cross-sectional area>
The Al alloy wire of the present invention can change the cross-sectional area by appropriately adjusting the degree of processing at the time of wire drawing. As described later, when the cross-sectional area is small, the effect of improving the corrosion resistance is large. Among the conductors for automobile wires, the power cable conductor has the largest cross-sectional area, which is about 100 mm ² (100 sq). On the other hand, many signal line conductors have a cross-sectional area of 50 mm ² or less. Therefore, the cross-sectional area of the conductor using the Al alloy wire, stranded wire, and compressed wire of the present invention is 8 mm ² (8 sq) or less (for example, when the cross-sectional shape of the Al alloy wire is circular, the wire diameter (diameter) is 3.2. mm or less), and further, when the cross-sectional area is 3 mm ² (3 sq) or less, and especially when the cross-sectional area is 1 mm ² (1 sq) or less, the effect of improving the corrosion resistance due to the presence of the coating layer is remarkable.

"Cross-sectional shape"
The Al alloy wire of the present invention can have various cross-sectional shapes depending on the die shape at the time of wire drawing. A cross-sectional circular shape is typical, and other cross-sectional shapes such as an elliptical shape, a polygonal shape such as a rectangle or a hexagon are listed. The shape is not particularly limited.

《Wire form》
<Single wire>
The Al alloy wire of the present invention can be used as it is.
<Stranded wire>
A plurality of the above-described Al alloy wires of the present invention can be prepared and twisted together. Even a thin Al alloy wire (single wire) can be made into a high strength wire by twisting together. The number of twists is not particularly limited. For example, 7,11,19,37 are mentioned. In addition, when the Al alloy stranded wire of the present invention is a compression wire that is compression-molded after being twisted, the wire diameter can be made smaller than that of a simply twisted state.

[Coating layer]
"composition"
In the coating layer provided on the outer surface of the Al alloy wire of the present invention, at least the outermost layer is made of nickel (Ni) or a nickel alloy. Ni has a small potential difference from copper or copper alloy, and it is difficult to make a battery with copper or copper alloy, so that electrolytic corrosion between Al alloy and copper or copper alloy can be reduced. Examples of the nickel alloy include Ni-P alloy, Ni-B alloy, Ni-Zn alloy and the like.

  The coating layer may be a single layer made only of nickel or nickel alloy, or a multilayer structure including an intermediate layer made of another material between the outermost layer made of nickel or nickel alloy and the Al alloy wire, that is, an Al alloy. A configuration including an intermediate layer provided immediately above the line and the outermost layer provided on the intermediate layer may be employed. Examples of the constituent material of the intermediate layer include at least one metal selected from copper (Cu), copper alloy, zinc (Zn), and zinc alloy. These metals are familiar to both Al alloys and nickel and nickel alloys, and are present between Al alloys and nickel or nickel alloys, making it easy to adhere between the outermost layer and Al alloy wires. . The intermediate layer may be one layer or two or more layers. Examples of the copper alloy include a Cu—Sn alloy and a Cu—Zn alloy, and examples of the zinc alloy include a Zn—Sn alloy.

  Note that by providing a resin layer on the outer surface of the Al alloy wire in addition to the coating layer made of the metal, the exposed portion of the Al alloy can be eliminated, so that electrolytic corrosion can be reduced. For example, it can be set as the structure which provides the said coating layer in the surrounding surface of Al alloy wire, and provides the resin layer in an end surface. Alternatively, even if it is an Al alloy wire that does not have the coating layer, at least a part of the surface of the terminal member that is not in direct contact with the Al alloy wire, preferably nickel, nickel alloy, tin, tin over the entire region At least one metal selected from an alloy, zinc, and a zinc alloy, preferably a corrosion-resistant layer made of nickel or a nickel alloy, or a thin plate made of the above metal between the end of an Al alloy wire and a terminal member You may make it exist or you may cover the edge part of Al alloy wire with the bottomed cylindrical body which consists of the said metal. When a terminal member having the corrosion-resistant layer on the surface is further used for the Al alloy wire having the coating layer, the electrolytic corrosion of the Al alloy wire can be more effectively reduced. In particular, when the corrosion-resistant layer is made of nickel or a nickel alloy, the electrolytic corrosion of the Al alloy wire can be further effectively reduced by substantially not forming a battery between the wire and the terminal member. Further, when the corrosion-resistant layer is made of tin, even if the corrosion-resistant layer deteriorates with time, the Al alloy wire is hardly corroded by providing the Al alloy wire itself with a nickel layer or a nickel alloy layer.

"thickness"
Even if the thickness of the outermost layer is very thin, such as more than 0 and 15 μm or less, it is sufficiently effective for improving the corrosion resistance. If it is thicker than 15 μm, the coating layer is easily peeled off when the terminal member is attached. When the coating layer has a multilayer structure, the total thickness is preferably 15 μm or less. When the coating layer has a multilayer structure, if the total thickness is thicker than 15 μm, the coating layer is easily peeled off when the terminal member is attached. On the other hand, if the coating layer is too thin, pinholes are easily formed. When pinholes exist, electrolytic corrosion proceeds at the pinholes at an accelerated rate. Therefore, when the coating layer is a single layer made of nickel or a nickel alloy, the thickness is preferably 1 μm or more and 15 μm or less. When the coating layer has a multilayer structure, even if pinholes are present in the lower layer, the pinholes are filled with the upper layer, so each layer may be thin, and the total thickness is more preferably 1 μm or more and 15 μm or less, The thickness of each layer is preferably more than 0 μm and 10 μm or less.

<Coating area>
The coating layer is preferably provided on at least a part of the outer surface of the Al alloy wire, in particular, at least a part of the circumferential region at the end of the Al alloy wire to which the terminal member is attached. When an Al alloy wire is used as a conductor of an insulated wire, the insulating layer is removed from the end of the insulated wire, and a terminal member is attached to the exposed Al alloy wire (conductor). Of these exposed locations, the locations covered with the terminal members (locations that are in direct contact with the terminal members) are difficult for Al alloy wires to contact the atmosphere (especially dissolved oxygen in the atmosphere). Is difficult to corrode. On the other hand, among the exposed portions, a portion in the vicinity of the terminal member that is not covered by the terminal member and not covered by the insulating layer (hereinafter referred to as a conductor exposed portion) is a battery between the constituent metals of the terminal member. The Al alloy wire is easily corroded. Therefore, it is preferable that at least a region that can be exposed to the conductor in the end portion of the Al alloy wire includes the coating layer, and the end layer may include the coating layer in the entire circumferential direction. On the other hand, since the terminal member is not attached to the Al alloy wire and the portion sufficiently separated from the terminal member is usually covered with an insulating layer, the coating layer may not be provided. In addition, in the end portion of the Al alloy wire to which the terminal member is attached, not only the circumferential direction but also the end surface is provided with the coating layer, the exposed portion of the Al alloy can be eliminated. It can reduce effectively that a battery is formed between constituent metals.

<Formation method>
For the coating layer, various forming methods such as a plating method, a vapor deposition method such as a CVD method and a PVD method can be used. Plating methods such as electroplating, electroless plating, and hot dipping can easily form a coating layer. In addition, zincate treatment, double zincate treatment, or the like can be suitably used for forming the intermediate Zn layer. A formation method may be appropriately selected according to the constituent material of the coating layer. The formation time of the coating layer will be described later.

[Insulated wire]
The Al alloy wire (single wire), the Al alloy twisted wire, and the compressed wire can be suitably used as a conductor for electric wires. Depending on the application, it can be used as a conductor as it is, or can be used as an insulated wire having an insulating layer formed of an insulating material on the outer periphery of the conductor. The insulating material can be selected as appropriate. For example, polyvinyl chloride (PVC), a non-halogen resin, a material excellent in flame retardancy, and the like can be given. The thickness of the insulating layer can be appropriately selected in consideration of desired insulating strength, and is not particularly limited.

[Wire with terminal]
An insulated wire having a conductor made of an Al alloy wire, an Al alloy stranded wire, or a compressed wire, for example, when the covering layer is provided over the entire circumference of the conductor (which may include an end face), the end of the insulated wire The insulating layer is peeled off at the portion to expose the conductor portion, and a terminal member is attached to the exposed conductor portion so as to be connected to a connection target such as an external device, whereby the electric wire with terminal of the present invention is obtained. Alternatively, in the case of an insulated wire using an Al alloy wire, an Al alloy stranded wire, or a compressed wire material that does not have a coating layer such as nickel on the outer periphery thereof, an insulating layer is provided at the end of the insulated wire. The conductor part is exposed by peeling off, and the terminal layer is attached after the covering layer is provided on the exposed conductor part, or after the terminal member is attached to the exposed conductor part, the terminal member is not covered. An electric wire with a terminal of the present invention is obtained by providing the covering layer so as to cover the exposed conductor portion exposed to the wire.

  The said electric wire with a terminal may contain the electric wire group which shares one terminal member with respect to a some insulated wire. A plurality of insulated wires are excellent in handling property by being bundled together by a binding tool or the like. Such a terminal-attached electric wire can be suitably used in various fields in which weight reduction is desired, particularly in automobiles in which further weight reduction is desired in order to improve fuel consumption. As the terminal member, a crimp terminal attached by crimping (crimping) on the end of the electric wire can be preferably used.

[Production method]
The Al alloy wire of the present invention comprising the coating layer is, for example, casting → hot rolling → (in the case of billet cast material: homogenization treatment) → cold wire drawing → (appropriate softening treatment) → coating layer formation It can be formed by a process.

  The casting may be billet casting, but continuous casting is preferred in which a cast material having a microstructure is obtained by refining crystal grains and crystal precipitates by rapid solidification. By continuous casting, it is possible to improve strength by refining crystals and toughness by dispersing fine crystal precipitates. For rapid cooling, a water-cooled copper mold or a forced water cooling mechanism may be used. The cooling rate is preferably 20 ° C./sec or more at 600 to 700 ° C.

  When adding Ti or B, adding just before pouring the molten metal into the mold is preferable because it suppresses local sedimentation of Ti and the like and can produce a cast material in which Ti and the like are evenly mixed. .

  When the above casting process and rolling process are carried out continuously, it is possible to easily perform hot rolling using the heat accumulated in the cast material, and it is energy efficient and compared with a batch casting method. In addition, it is excellent in productivity of cast rolled material.

  In the wire drawing step, the degree of processing can be appropriately selected according to the desired wire diameter. As for the obtained wire drawing material, a desired number can be prepared and twisted together to form a stranded wire.

  The softening treatment is performed in order to increase the toughness of the wire by softening without extremely reducing the strength of the wire that has been increased by refinement of the crystal structure and work hardening. The conditions for the softening treatment may be appropriately selected. For example, the softening treatment is performed under such a condition that the elongation of the treated wire (single wire or stranded wire) is 10% or more. For the softening treatment, either continuous treatment or batch treatment can be used.

  The stranded wire is obtained by twisting together a plurality of wire drawing materials or soft materials, and the compression wire material is obtained by compression molding the stranded wire. In the case of a stranded wire or a compressed wire, the softening treatment may be performed only on the wire before twisting, or may be performed both before and after twisting, or not on the wire drawing material before twisting. Or may be applied only to the compressed wire.

  The Al alloy wire of the present invention and the Al alloy stranded wire can be obtained by forming a coating layer on a wire drawing material, a soft material, a stranded wire obtained by twisting these together, or a compression wire. The covering layer may be formed over the entire length of the wire drawing material or the like, or may be formed only at the end portion to which the terminal member is attached as described above. In the case of a stranded wire or a compressed wire, the coating layer may be formed in a twisted state, but if a coating layer is formed on the wire (drawn wire, soft material) before being twisted, the space between the twisted wires The presence of the coating layer increases the effect of improving corrosion resistance. Also, when creating long-length Al alloy wires or Al alloy stranded wires by cutting long drawn or soft wires, stranded wires that are twisted together, or compressed wires, What has no coating layer on the end face is obtained. In this case, you may provide a coating layer in an end surface separately. When a softening process is performed and a covering layer made of a material having a melting point lower than the heating temperature during the softening process is provided, the covering layer is formed after the softening process. When a coating layer made of a material having a melting point higher than the heating temperature during the softening treatment is provided, the coating layer can be formed either before or after the softening treatment.

  The Al alloy wire of the present invention, the twisted Al alloy wire of the present invention, the insulated wire of the present invention, and the electric wire with terminal of the present invention are excellent in corrosion resistance.

It is a partial block diagram which shows the outline of an electric wire with a terminal. It is a micrograph (25 times) explaining the corrosion situation of the electric wire with terminal, (A) is a partial enlarged photograph in the BB section of sample No. 1-3, (B) is a BB of sample No. 1-100 (C) shows a cross-sectional photograph of an insulated wire. It is a graph which shows the relationship between the area ratio of the aluminum alloy with respect to brass, and a corrosion current density.

(Test Example 1)
A terminal-attached electric wire with a crimp terminal attached to the end of an insulated electric wire using an Al alloy wire as a conductor was prepared and subjected to a corrosion test to evaluate the corrosion resistance.

  Among the samples, the electric wire was produced by the procedure of casting → rolling → drawing → formation of coating layer → twisted wire → softening → formation of insulating layer. Specifically, pure aluminum (99.7% by mass or more Al) is prepared and melted as a base, and the obtained molten metal (molten aluminum) is charged with the additive elements shown in Table 1 to the contents shown in Table 1. Then, an Al alloy molten metal is produced. It is desirable that the Al alloy molten metal whose components have been adjusted is appropriately subjected to a hydrogen gas removal treatment or a foreign matter removal treatment.

  Using a belt-wheel type continuous casting and rolling machine, the prepared molten Al alloy is continuously cast and hot-rolled to produce a φ9.5 mm wire rod (continuously cast rolled material).

  The wire rod was subjected to cold wire drawing to produce a wire drawing material having a wire diameter of φ0.3 mm.

  A coated wire having the composition shown in Table 1 is applied to the wire drawing material by a known electroplating method, electroless plating method, zincate treatment, and double zincate treatment, and a coated wire material having a coating layer on the entire peripheral surface and end surface of the wire drawing material. Make it. In the coating layer shown in Table 1, the left side of the column is the Al alloy wire side, the right side of the column is the outermost side, () indicates the thickness measured using an observation image of an optical microscope, ``-'' , Indicating that it does not have a coating layer. Note that the zinc layer by the zincate treatment and the double zincate treatment has a thickness of several tens of nanometers at most, and this thickness can be measured using an observation image by a TEM (transmission electron microscope), for example. .

  A plurality of the above-mentioned covered wire materials are twisted together to produce a stranded wire. Here, a total of 11 covered wires, 3 inside and 8 outside, were twisted together.

The obtained stranded wire (cross-sectional area: about 0.77 mm ² ) is subjected to softening treatment (batch treatment, reducing gas atmosphere) at 350 ° C. for 3 hours to produce a soft material. Regarding the obtained soft material, the electrical conductivity, elongation, and tensile strength of each coated wire constituting the soft material were examined. As for all the coated wires, conductivity: 58% IACS or more, elongation: 10% or more Tensile strength: 110 to 200 MPa. An insulating layer (thickness 0.2 mm) is formed on the outer periphery of the obtained soft material with an insulating material (here, a halogen-free insulating material) to produce an insulated wire. A crimp terminal is attached to the end portion of the insulated wire to produce a terminal-attached wire shown in FIG.

  The terminal-attached electric wire 10 includes a conductor 11 formed by twisting a plurality of Al alloy wires, and an insulating layer 12 covering the outer periphery of the conductor 11, and the insulating layer 12 on one end side is peeled off to expose the conductor 11. A terminal member (crimp terminal) 20 is attached. The terminal member 20 is formed by bending a piece formed by appropriately making cuts on both edge sides of the copper alloy plate, and is flattened so that the edges of both pieces 22a and 22b on one end side are in contact with each other. A male terminal portion 22 is provided. Further, both pieces 21a and 21b on the other end side of the terminal member 20 are bent so as to sandwich the insulating layer 12 portion of the electric wire 10. In the terminal member 20, a conductor 11 exposed from the insulating layer 12 is vertically attached to an intermediate portion between the sandwiched portion of the insulating layer portion and the male terminal portion 22, and both pieces 23a are sandwiched so as to sandwich the conductor 11. 23b is bent. Therefore, most of the exposed conductor 11 is covered with the segments 23a and 23b, and the end surface and the vicinity thereof are exposed from the segments 23a and 23b. Samples Nos. 1-1 to 1-7 have a coating layer on the exposed portion, and the exposure of the Al alloy is substantially zero.

  Corrosion resistance was evaluated as follows. The salt spray test is known as a corrosion resistance test. However, if the salt spray test is applied to a sample that is composed of dissimilar metals and can undergo electrolytic corrosion, such as the sample in this test, the sample may be damaged by electrolytic corrosion. It is too large to evaluate the corrosion resistance substantially. Therefore, in order to appropriately evaluate the corrosion resistance of a sample in which such electrolytic corrosion can occur, the following test method simulating an environment where the progress of corrosion is performed relatively slowly was adopted.

First, NaCl (electrolyte) is dissolved in ultrapure water (solvent) to prepare a neutral aqueous solution (200 g) having a concentration of 26% by mass. Further, 100 g of silica (SiO ₂ ) powder having an average particle diameter of about 100 μm is prepared. The electrolyte, solvent, and silica powder used are all commercially available products.

The prepared silica powder is placed on a filter paper, and the prepared aqueous solution (26% NaCl) is dropped from above the silica powder, then placed in a thermostatic chamber heated to 150 ° C., dried, and the NaCl adheres. the obtained (Cl ^- deposition amount: 35,000 ppm). Sprinkle the obtained powder evenly over the sample (especially the joint between the wire and the terminal member) to the extent that a part of the sample can be visually confirmed (thickness 1 mm or less), and set to 60 ° C and 95% RH. Put in a thermo-hygrostat and hold for 6 days (144 hours). Six days later, the sample was taken out from the thermo-hygrostat and the corrosion state was examined. Specifically, in FIG. 1, the portion where the insulating layer 12 is removed and the conductor 11 is exposed, and the vicinity of the portion sandwiched between the sections 23a and 23b is cut (BB cutting), and this cross section is observed. Then, the residual rate (%) = {(the area of the remaining Al alloy wire) / (the area of the produced Al alloy wire)} × 100 is obtained, and the corrosion resistance is evaluated based on the residual rate. The area can be easily obtained by performing image processing or the like on the cross-sectional photograph. It can be said that the higher the residual ratio, the higher the corrosion resistance. The results are shown in Table 2. In addition, when the salt spray test was conducted, the sample was so severely damaged that it was difficult to measure the area of the remaining Al alloy wire.

  As shown in Table 2, it can be seen that a sample using a conductor made of an Al alloy wire having a coating layer made of nickel or a nickel alloy as the outermost layer has a high residual rate and is excellent in corrosion resistance. Fig. 2 (A) is a micrograph of the BB cross section of sample No. 1-3, Fig. 2 (B) is a micro photo of the BB cross section of sample No. 1-100, and Fig. 2 (C) is the coated wire. It is a microscope picture of a section. 2A to 2C, the whitish region is a portion made of an Al alloy, and FIGS. 2A and 2B show a part of the conductor. Note that the photograph in FIG. 2 (C) shows a covered electric wire using a compressed wire obtained by compressing a stranded wire as a conductor so that the cross-sectional outer shape is circular. As shown in FIG. 2 (B), it can be seen that Sample No. 1-100, which does not have the coating layer described above, is inferior in corrosion resistance because the Al alloy wire is corroded and lost, and the outer shape is broken. On the other hand, it can be seen that Sample No. 1-3 provided with the coating layer has a sufficient Al alloy wire remaining and is excellent in corrosion resistance.

  Further, as shown in Table 2, when the coating layer was provided with an intermediate layer made of Zn or the like, it was superior in corrosion resistance. The reason for this is considered to be that the outermost layer made of nickel or a nickel alloy is easily formed by providing the intermediate layer, and this outermost layer is sufficiently present.

  Further, a coated wire material having a coating layer only on the entire peripheral surface and not having a coating layer on the end surface is produced. Using this coated wire material, an electric wire with a terminal is produced as described above, and the above-mentioned NaCl is adhered. A corrosion test was conducted to evaluate the corrosion resistance. As a result, it was confirmed that the sample having the coating layer on the end face of the wire rod was superior in corrosion resistance.

(Test Example 2)
Prepare multiple insulated wires with conductors consisting of Al alloy wires with the same composition and different conductor cross-sectional areas, and use these insulated wires to make a terminal-attached wire in the same way as in Test Example 1, and as in Test Example 1. Thus, the corrosion resistance was evaluated. The results are shown in Table 3.

  In this test, sample Nos. 2-1, 2-2, 2- of insulated wires using conductors having the wire sizes shown in Table 3 and having a coating layer as an Al alloy wire constituting the conductors. 3 and sample Nos. 2-110, 2-120, 2-130, and 2-200 of insulated wires using those that did not have a coating layer were produced and their corrosion resistance was compared. As the conductor, wire rods with various wire diameters were prepared in the same manner as in Test Example 1, and after twisting an appropriate number of wires, the wire rods were compressed and then subjected to a softening treatment, and then used. For example, the conductor of sample No. 2-1 was twisted a total of 11 conductors with a wire diameter of φ0.3 mm formed in the same manner as in Test Example 1, and then the sample No. 2-200 As the conductor, a wire drawing material having a wire diameter of φ0.32 mm was prepared in the same manner as in Test Example 1, and after a total of 128 wires were twisted, a compression wire produced by compressing was used. The coating layer was formed in the same manner as in Test Example 1.

The test results, and the conductor of Al alloy wire, the end wire with terminals to the terminal members attached to the conductor, the larger the cross-sectional area of the conductor, in particular if the 8 mm ^2, greater than the outermost layer Even if it does not have a coating layer made of nickel or a nickel alloy, it can be seen that the corrosion resistance is somewhat high. On the other hand, when the cross-sectional area of the conductor is 8 mm ² or less, it can be seen that the corrosion resistance can be improved by providing the outermost layer with a coating layer made of nickel or a nickel alloy. The result is that, in a thick Al alloy wire, the ratio of the exposed area of the Al alloy to the exposed area of the copper or copper alloy (hereinafter referred to as Al) at the end where the terminal member made of copper or copper alloy is attached. Electrolytic corrosion is less likely to occur because the exposure ratio is relatively large), and the Al exposure ratio is small for thin Al alloy wires (the exposed area of copper and the like is increased). This is thought to be because it became easier to proceed.

Prepare multiple brass plates and aluminum alloy plates (1.05 mass% Fe-0.15 mass% Mg-Al) with different areas, connect one end of both plates with a conductor, and impregnate both plates with 0.5 mass% NaCl aqueous solution To do. In this state, an ammeter is attached to the conducting wire and the corrosion current is measured. The current density was determined by dividing the measured current value by the area of the aluminum alloy plate. FIG. 3 shows the relationship between the area ratio of aluminum alloy to brass (Al exposure ratio) and the current density. FIG. 3 shows that the current density decreases as the area ratio (Al exposure ratio) increases, that is, as the exposed area of the aluminum alloy relative to the copper alloy increases. In addition, FIG. 3 shows that the relationship between the area ratio and the current density is not a proportional relationship, and that the current density increases rapidly as the area ratio decreases. From this result, it can be said that the electrolytic corrosion of the Al alloy wire can be more effectively reduced by providing the coating layer made of nickel or the like on the outer surface of the thin Al alloy wire of 8 mm ² or less.

(Test Example 3)
A terminal member (crimp terminal) having a corrosion-resistant layer on its surface was prepared, and a terminal-attached electric wire to which this crimp terminal was attached was prepared, and the corrosion resistance was evaluated in the same manner as in Test Example 1. The results are shown in Table 4.

  In this test, the same soft material as Sample No. 2-1 produced in Test Example 2 was used as the conductor of the insulated wire. As the crimp terminal, one having a corrosion-resistant layer made of at least tin (Sn) or nickel (Ni) at a portion other than the contact portion with the conductor was used. Sample No. 3-2 was prepared by heat-treating a crimp terminal having a corrosion-resistant layer of tin and then attaching it to an insulated wire, and simulated the aging of the crimp terminal by the heat treatment.

  As shown in Table 4, it can be seen that when a terminal member (crimp terminal) having a corrosion-resistant layer is provided, the corrosion resistance can be easily improved. In particular, when the corrosion-resistant layer is made of nickel, a battery is not substantially formed between the coating layer provided on the outer periphery of the conductor made of an aluminum alloy wire and the corrosion-resistant layer. The improvement effect is remarkable. Further, when the corrosion resistant layer is made of tin, it can be seen that the conductor made of the aluminum alloy wire is hardly corroded even if the terminal member (particularly the corrosion resistant layer) deteriorates with time.

  The above-described embodiment can be appropriately changed without departing from the gist of the present invention, and is not limited to the above-described configuration. For example, the composition of the Al alloy wire, the composition and thickness of the coating layer, and the composition of the terminal member may be appropriately changed. Moreover, you may change the magnitude | size and shape of a wire to twist together, and the number of twists.

  The electric wire with terminal of the present invention is excellent in corrosion resistance and lightweight, and therefore can be suitably used for, for example, wiring of automobiles, transportation equipment such as airplanes, and industrial equipment such as robots. The insulated wire of the present invention can be suitably used as a constituent material for the above-described wire with a terminal of the present invention. The aluminum alloy wire of the present invention and the aluminum strand wire of the present invention can be suitably used for the conductor of the above insulated wire of the present invention.

10 Electric wire with terminal 11 Conductor 12 Insulation layer 20 Terminal material
21a, 21b, 22a, 22b, 23a, 23b Section 22 Male terminal

Claims (9)

An aluminum alloy wire used for conductors of automobile wires,
A coating layer is provided on at least a part of the outer surface of the alloy wire;
An aluminum alloy wire, wherein the outermost layer of the coating layer is made of nickel or a nickel alloy. The coating layer comprises an intermediate layer provided immediately above the alloy wire, and the outermost layer provided on the intermediate layer,
2. The aluminum alloy wire according to claim 1, wherein the intermediate layer is made of at least one metal selected from copper, copper alloy, zinc, and zinc alloy.   3. The aluminum alloy wire according to claim 1, wherein the coating layer is provided on at least a part and an end surface of a peripheral surface of the alloy wire.   4. An aluminum alloy stranded wire comprising a plurality of aluminum alloy wires according to any one of claims 1 to 3 twisted together. An insulated wire having a conductor made of an aluminum alloy and an insulating layer on the outer periphery of the conductor,
The conductor is any one of the aluminum alloy wire according to any one of claims 1 to 4, a stranded wire obtained by twisting a plurality of the aluminum alloy wires, and a compressed wire material obtained by compression-molding a stranded wire. Characterized insulated wire. 6. The insulated wire according to claim 5, wherein a cross-sectional area of the conductor is 8 mm ² or less.   The end portion of the insulated wire has the conductor removed by removing the insulating layer, and the covering layer is provided on at least a part of the outer surface of the exposed conductor. The insulated wire as described in 1. The insulated wire according to claim 7, and a terminal member made of copper or a copper alloy attached to an end of the insulated wire,
An electric wire with a terminal, wherein the covering layer is provided on at least a part of an outer surface of a portion of the insulated wire where the insulating layer is removed and the conductor is exposed and is not covered with the terminal member.   On the surface of the terminal member, a corrosion-resistant layer made of at least one metal selected from nickel, nickel alloy, tin, tin alloy, zinc, and zinc alloy is provided at a location other than the location in contact with the exposed conductor. 9. The electric wire with a terminal according to claim 8, wherein the electric wire has a terminal.