JPH03170693A - Production of alloy coated conductor and multilayer plating apparatus used therefor - Google Patents

Abstract

PURPOSE:To efficiently produce an alloy-coated conductor having high performance by separately and alternately plating a conductor with alloying elements and alloying the resulting plating layers by counter diffusion by heating. CONSTITUTION:A metal wire 1 is pretreated and wound around two rotating rolls 2, 3 arranged at a prescribed interval in the longitudinal direction of the wire 1. In plating vessels 4, 5, the wire 1 is alternately plated with an alloying element and other alloying element or quasi-alloy in layers and the plated wire 1 is coiled after passing through a washing vessel and a drier. The coiled wire 1 is then heated to a prescribed temp. to alloy the resulting plating layers by counter diffusion. The alloying elements are uniformly distributed and an alloy coated conductor having superior corrosion resistance is obtd.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for manufacturing an alloy-coated conductor used for lead wires, contact materials or corrosion-resistant materials for electronic and electrical equipment, electrode wires for electric discharge machining, etc., and the method thereof. Regarding the multilayer plating equipment used. [Conventional technology and its problems] Leads for electronic and electrical devices are made of composite conductors in which Ag or Ag alloy is coated on a filament such as Cu or Cu alloy. It is widely used due to its solderability and corrosion resistance. By the way, as a method of coating Ag etc. on the above-mentioned filament bodies such as Cu, plating is generally applied, but when plating alloys, especially Ag-In, Ag-Sn, Cu-Zn etc. Alloys require strict adjustment of the metal ion concentration and pH of the plating bath in order to maintain a stable plating film composition, resulting in poor productivity. Furthermore, when the coating alloy becomes a ternary or higher alloy, although it can be manufactured on an experimental scale, it is completely impossible to mass-produce it on an industrial scale. For this reason, as shown in Figure 6, there is a method in which, for example, each of alloying elements A and B is plated as a single layer on a metal wire body, and this plated layer is then heated and diffused to form an alloy. was suggested. However, such a method of alloying by heating and diffusing after plating requires a long heat treatment to form a homogeneous composition over the entire plated film, which again poses the problem of lack of productivity.

In addition, as shown in the plan view of FIG. 5, the plating equipment also includes, for example, a plating bath for alloy element A, a washing bath, a plating bath for alloy element B, and a washing bath after each of the degreasing, washing, pickling, and washing tanks. Because the tanks were arranged in series and the dryer was placed after them, the entire device became long, which was disadvantageous in terms of space.

Conventionally, brass wires have been used as electrode wires for electrical discharge machining, but for the purpose of high-speed machining and cleaning of cut surfaces, CuvA uses Z-wire wires.
An electrode wire plated with n and heated to diffuse it has been developed. However, this electrode wire had a problem in that the Znf degree decreased from the surface toward the inside, making it impossible to obtain stable performance.

[Means to solve problems]

The present invention was achieved as a result of intensive research in view of the above situation, and its purpose is to provide a method for efficiently manufacturing a high-performance alloy coated conductor.

In other words, the claimed invention involves dividing the coating alloy element into quasi-alloys containing each element and/or at least two of the above elements when coating the surface of the metal wire to be a conductor with an alloy layer. , after plating in at least two layers alternately with other alloy element layers or quasi-alloy layers, the metal wire is heated to a predetermined salinity to mutually diffuse the plated layers to form an alloy. This is a characteristic feature. To specifically explain the invention of claim 1, as shown in FIG. 1, three layers of Ag and In are alternately laminated on a Cu wire, and then the Cu wire is heated at 450° C.
This is a method of forming an AgIn alloy on the CU line by mutually diffusing the n-layers. When the coating alloy is divided into parts and plated, it is not necessary to separate the alloying elements individually, and the alloy may be plated as a quasi-alloy containing at least two types of elements that are easy to perform alloy plating. The number of plating layers for each element or quasi-alloy in the coating alloy may be divided into two or more layers, and the greater the number of layers and the thinner the thickness, the shorter the heat treatment time for alloying. , the concentration of the alloy coating layer becomes more uniform, improving properties such as corrosion resistance.

The invention of claim 2 is a method for efficiently carrying out the claimed invention without increasing the size of the plating apparatus, the metal wire serving as a conductor being passed between at least two rotating rolls at least twice. The metal wire is made to travel back and forth and sequentially passed through at least two plating baths disposed between the rotating rolls to coat the surface of the metal wire with an alloying element containing each element or/and at least two of the above elements. The method is characterized in that it is divided into semi-alloys and plated in at least two layers alternately with other alloying element layers or semi-alloy layers.

The invention of claim 4 provides a multilayer plating apparatus used in the invention of claim 2, that is, a semi-alloy containing each of the alloy elements individually or/and at least two of the above elements on the surface of the metal wire serving as the conductor. A multilayer plating device that divides and plating each of the alloying elements individually and/or between at least two rotating rolls for winding and reciprocating the filament and the rotating roll. The present invention is characterized in that at least two plating baths are arranged for dividing and plating semi-alloys containing at least two types.

Next, the inventions of claims 2 and 4 will be specifically explained with reference to the drawings.

FIG. 2 shows an apparatus for carrying out the invention of claim 2, that is, claim 4.
1 is an explanatory plan view showing an example of a multilayer plating apparatus. In the figure, 1 is a metal filament, 2 and 3 are rotating rolls, and 4 and 5 are plating baths. After the running metal filament 1 is pretreated by passing it through degreasing, water washing, pickling, and water washing tanks in sequence, two metal filaments 1 are arranged at a predetermined interval in the longitudinal direction. The alloy elements A and B are plated in layers in the order of ABABA by winding them around rotating rolls 2 and 3 and making four turns.
That is, alloying element A is first applied onto the metal filament 1 in a plating bath 4.
is plated, and then washed with water in a washing tank 6. The metal filament 1 is then wound around a rotating roll 3 and turned, plated with alloy element B in a plating bath 5, and then washed with water in a washing tank 7. Thereafter, it is wound around the rotary roll 2, turned, and passed through the plating bath 4 again to coat the alloy element A.

Thereafter, the same procedure is repeated to alternately stack and plate layers of alloy elements A and B, and then the film is passed through a washing tank and a dryer and wound into a winder (not shown).

The device shown in FIG. 3 is a partial explanatory diagram of a device for plating ternary alloys. Three rotating rolls 2, 3, and 8 are arranged at the apexes of a triangle, and between each roll, alloy elements A, B,
Plating baths 4, 5, and 9 for plating C are arranged, and washing tanks 6, 7, and 10 are arranged behind each plating bath.
is located. In addition, in the case of an alloy of four or more elements, the number of rotating rolls may be increased accordingly.

The device shown in FIG. 4 is one in which rotating rolls 2 and 3 for winding the metal filament 1 are arranged so that their axes are horizontal. can be placed vertically, which is effective in saving space. In the above, if the rotating roll is provided with a groove and the metal filament is inserted into the groove and guided, not only will tangling of the metal filament be prevented, but the running position of the metal filament in the vertical or horizontal direction will be controlled. It can be set accurately. Power may be supplied to the above-mentioned metal filament from a rotating roll or by providing a separate power supply brush. Furthermore, the thickness of the plating layer can be set arbitrarily by changing the plating conditions such as current density and by changing the length of the bath. By feeding power with a feeding brush and feeding every 1 wire turn,
The plating thickness of each layer can be changed arbitrarily, and by heating and diffusing it, it is possible to coat an alloy with an arbitrary concentration gradient. It is also possible to arrange a heat treatment furnace after drying the plated metal filament to continuously heat and diffuse the plated layer to form an alloy. The invention of claim 3 is a method for producing an electrode wire for electric discharge machining, in which a multi-layered Cu and Zn layer is plated on a Cu filament, and this is heated to a predetermined temperature to form a Cu-Zn alloy layer. be. According to the method of this invention, a Cu-Zn alloy layer having a constant concentration can be formed by plating Cu and Zn in multiple thin layers.

[Function] In the present invention, each alloy element is used alone or/and divided into quasi-alloys containing at least two of the above elements,
Since at least two layers are plated alternately with other alloying element layers or quasi-alloy layers, each alloying element layer or quasi-alloy layer is formed thinly, and the heat treatment time required for alloying can be shortened. The coating alloy layer becomes uniform in composition, and mass production on an industrial scale becomes possible even when the coating alloy is a ternary or higher alloy. In addition, when plating each alloy element in multiple layers alternately,
The metal filament to be plated is wound around rotating rolls, moved back and forth, and repeatedly plated in a plating bath placed between the rotating rolls, so the length occupied by the plating equipment is shortened. [Example] The present invention will be explained in detail below with reference to Examples.

Example I Using the apparatus shown in FIG. 6 n+mφ Cu
7 layers of Ag and In are alternately laminated on the wire, 3 and 2 layers each, and heat treated at 450"CXIH to make 13% Ag.
A Cu wire coated with an In alloy to a thickness of 11 μI was manufactured.

Example 2 Using the apparatus shown in FIG. 3, 2, and 2 layers of Ag, Sn, and Pd were alternately plated on a 6 mmφ Cu wire, and then this was plated with a 900"C
Ag-14%Sn 24%Pd after 2H heat treatment
A Cu wire coated with an alloy to a thickness of IO μm was manufactured.

Comparative Example 1 A CU alloy coated with Ag-1r+ alloy was produced in the same manner as in Example 1, except that one layer each of Ag and In was coated on the Cu wire using the apparatus shown in FIG.

Comparative Example 2 Ag, Sn, and P were deposited on the Cu wire using the apparatus shown in Figure 5.
A Cu wire coated with an Ag-SnPd alloy was manufactured by the same method as in Example 2, except that one layer of d was plated on each layer.

C coated each Ag alloy thus obtained.
The distribution of alloying elements in the plating layer was measured by AES for U-ray, and the corrosion resistance was investigated by a salt spray test (spraying 5% NaCl! aqueous solution at 40°C for 24 hours).The results are also shown along with the structure of the plating layer. The results are shown in Table 1.

As is clear from Table 1, the method products of the present invention (Examples I and 2)
) has a homogeneous distribution of alloying elements and therefore has excellent corrosion resistance.

On the other hand, the comparative method products (Comparative Examples 1 and 2) had a non-uniform distribution of alloying elements, and as a result, had poor corrosion resistance. Further, in order to homogenize the plating layer of the product manufactured using the comparative method, the plated layer was further heated at 900°C for 2 hours, but it could not be homogenized.

Example 3 Using the apparatus shown in FIG.
After plating 1μ of Zn and 10 layers of Zn alternately,
Heat treated at 600°C x 20 sec to form Cu-4
A CU wire coated with 4% Zn alloy to a thickness of 20 μm was manufactured. Comparative Example 3 A Cu wire with a diameter of 0.6 mm was plated with 1OtlI of Zn, and then heat treated at 600°C for 20 seconds to produce a Cu wire coated with a Cu-Zn alloy. Each Cu-Zn alloy coated mCu obtained in this way
The Zn:a degree distribution near the surface of the wire was measured by AES, and the SUS material was cut to compare the processing speed.

As a result, the product manufactured by the method of the present invention (Example 3)
Zn is uniformly distributed in the n-alloy layer, so the processing speed is also improved to 1.7 times that of conventional brass wire.

On the other hand, in the comparative method product (Comparative Example 3), Zn was unevenly distributed and the processing speed was only 1.3 times that of the conventional brass wire. Although the case where an alloy based on Ag or Cu is used as the coating material has been described above, it goes without saying that the method of the present invention can be applied to any other alloy. In the method of the present invention, by lightly reducing the surface area after plating, the density of the alloy layer after heat treatment increases, resulting in even higher properties such as corrosion resistance. [Effects] As described above, according to the present invention, the elements of the coating alloy are distributed homogeneously, and therefore an alloy coated conductor with excellent corrosion resistance etc. can be efficiently manufactured, and a remarkable effect is achieved industrially. .

[Brief explanation of the drawing]

Fig. I is a cross-sectional view showing an example of the structure of the multilayer film used in the method of the present invention, Figs. 2 and 3 are plan views showing an example of an apparatus for carrying out the method of the present invention, and Fig. 4 is A side view showing another example of the apparatus for carrying out the method of the present invention, FIG. 5 is a plan view of the apparatus used in the conventional method, and FIG. 6 is a cross-sectional view showing the structure of the plating layer used in the conventional method. It is. 1-・Lingen striatum, 2, 3, 8 one rotation roll, 4, 5,
9-・Menki bathtub, 6, 7, 10- Washing tank.

Claims (4)

[Claims] (1) When coating the surface of a metal wire to be a conductor with an alloy layer, the coating alloy element is divided into quasi-alloys containing each element and/or at least two of the above elements, and the other alloy elements are An alloy coated conductor characterized in that the metal filament is plated in at least two layers alternately with layers or quasi-alloy layers, and then the metal filament is heated to a predetermined temperature to cause the plated layers to mutually diffuse and alloy. manufacturing method. (2) A metal filament serving as a conductor is made to travel between at least two rotating rolls at least twice, and the metal filament is sequentially passed through at least two plating baths arranged between the rotating rolls. Dividing the alloy element coated on the surface into semi-alloys containing each element or/and at least two of the above elements, and plating the alloy elements in at least two layers alternately with other alloy element layers or semi-alloy layers. The method for manufacturing an alloy coated conductor according to claim 1, characterized in that: (3) The method for producing an alloy coated conductor according to claim 1 or 2, wherein the metal wire forming the conductor is copper, and each element of the coated alloy is copper and zinc. A method for producing a featured alloy-coated electrode wire for electrical discharge machining. (4) A multilayer plating device for plating each of the alloying elements individually or/and divided into quasi-alloys containing at least two of the above elements on the surface of a metal wire serving as a conductor, the wire Plating for plating each of the alloying elements individually or/and divided into semi-alloys containing at least two of the above elements between at least two rotating rolls for winding and reciprocating the above-mentioned rotating rolls. at least 2 bathtubs
A multilayer plating device characterized by the arrangement of individual pieces.