Method of fabricating a copper plated aluminium wire

Abstract: A copper plated aluminum wire improved in the adhesion is fabricated by a method which comprises a zinc displacement step of forming a zinc thin layer by zinc displacement on the surface of an aluminum or aluminum alloy conductor, an electroplating step of coating the surface of the zinc thin layer continuously with copper layers by electroplating to have a copper coated aluminum conductor, and a thermal diffusion step of heat treating the copper coated aluminum conductor at a temperature of 120 °C to 600 °C under an inert gas atmosphere for thermal diffusion to ease the electrodeposition stress. Accordingly, the resultant copper plated aluminum wire can easily be shaped by cold plastic working process, decreased in the diameter at higher efficiency, and improved in the power of adhesion. A plated aluminum wire is provided comprising an anchor metal layer by displacement plating, a low thermally conductive metal layer by electroplating, and a high electrically conductive metal layer by electroplating which all are deposited in a sequence on the outer surface an aluminum or aluminum alloy conductor. Accordingly, the resultant plated aluminum wire or insulating plated aluminum wire can be minimized in the overall weight and prevented from disconnection caused by thermal diffusion. A plated aluminum wire is provided comprising an anchor metal layer by displacement plating and a high electrically conductive metal layer by electroplating which both are deposited in a sequence on the outer surface an aluminum or aluminum alloy conductor. Accordingly, the resultant plated aluminum wire or insulating plated aluminum wire can be minimized in the overall weight. A composite light-weighted plated wire is provided having an electrically conductive metal layer, which has a potential equal to or higher than that of zinc, deposited by electroplating on the outer surface of a zinc anchor metal layer provided on an aluminum conductor, said electroplating carried out under a condition that the concentration of hydrogen ion in an electrolyte solution is higher than 4 (pH) as an electrolysis parameter and the thickness of plating x (micrometer) is 0.2<x≦5. Accordingly, the resultant composite light-weighted plated wire can be improved in the adhesion between the aluminum conductor and the electrically conductive metal layer, easily shaped by plastic forming process, decreased in the diameter at higher efficiency, and improved in the reliability of soldering work.

Description: The present invention relates to a method of fabricating copper plated aluminum wire. As electronic devices and electronic components have been reduced in the weight and the size, their conductors such as coils are decreased in the diameter. Also, to satisfy the demand for decreasing their weight, the conductors are selected from aluminum conductors or aluminum alloys (referred to as aluminum conductors hereinafter) of which specific gravity is substantially one-third that of copper or less. However, such aluminum conductors have electric potentials electrochemically unfavorable. When a metal surface of the conductor newly produced e.g. by wire drawing is exposed to air, an oxide layer is developed instantly on the surface hence making the soldering difficult. The aluminum conductor itself is low in the mechanical strength and requires a particular joining technique for providing a desired degree of reliability on each joint. Considering that the soldering of the aluminum conductors for joining is troublesome, copper-clad aluminum wires are now marketed as easily solderable, light-weighted wires which are fabricated by providing a copper pipe cladding over the surface of an aluminum conductor by welding a tape of copper and drawing them to a length. However, the copper-clad aluminum wire when being drawn to have a desired small diameter may often produce disconnections due to a poor adhesion at the interface between the aluminum conductor and the copper cladding. It is also known that a plating process is favorably used for providing a higher adhesion between the aluminum conductor and the copper coat. In that case, the process of developing a closely plate coating over the surface of the aluminum conductor may be a conventional zincating technique by which a coat of zinc or zinc alloy (referred to as a zinc coat hereinafter) is tightly produced on the surface of the conductor. When the zinc coat is plated directly with a copper, a resultant copper plated aluminum wire has an improved copper plated layer. However, during the cold plastic working process with dies, the wire is drawn several times. The adhesion at the interface between the aluminum conductor and the copper layer produced by plating is not so high. In case that its diameter is less than 0.15 mm, the copper plated aluminum wire may frequently produce disconnections. As electronic devices have been reduced in the size and the weight, the demand for decreasing the weight of wiring materials such as coils installed in the electronic devices is increased. For satisfying the demand, simple drawn wires fabricated by copper conductors are replaced with specific copper-clad aluminum wires (referred to as copper-clad aluminum wires hereinafter) in which a coat of copper is provided on the surface of a mother material or an aluminum core (referred to as an aluminum core hereinafter) of a small density. However, such copper-clad aluminum wires produced by the known manner are fabricated by welding a copper tape which is thus required to have a considerable thickness. This accordingly limits to increase the area of cross section of the aluminum core in relation to entire cross section of the copper-clad aluminum wire for minimizing the overall weight and its maximum rate for fabrication may be about 85 %. Therefore, further decrease of the weight will be difficult. In the soldering, the copper-clad aluminum wire of a minimal diameter (for example, 0.10 mm or less) undergoes a high degree of heat (e.g. 380 °C) and may be disconnected by thermal diffusion. When aluminum conductors are employed as wire materials in an electronic device and intended to join to corresponding terminals of the device, they have to be treated through dissolving and removing oxide layers from their surface with a heated alkali solution, neutralized using an acid, rinsed with hot water, and subjected to ultrasonic cleaning before aluminum soldering and their joining process to the terminals will not be easy. Also, the aluminum conductors are low in the mechanical strength and thus, require a specific technique for ensuring the reliability of joining strength at each joint. To overcome the difficulty of joining the aluminum conductors to the terminals, copper-clad aluminum wires are fabricated by welding a copper tape over the surface of an aluminum conductor to form a copper pipe cladding, which is slightly greater in the specific gravity than the aluminum conductor, and drawing them and marketed as solderable, light-weighted wires. The disadvantage is that when the copper-clad aluminum wires having the copper pipe cladding provided over the surface of the aluminum conductor are decreased to a desired small diameter by drawing, they may often be disconnected due to a poor joining strength at the interface between the aluminum conductor and the copper cladding. It is known that a plating method is preferably used for improving the adhesion at the interface between an aluminum conductor and a copper cladding. In that case, a known zincating technique may be employed for forming a plating layer directly over the surface of the aluminum conductor. A resultant layer of zinc or zinc alloy is tightly bonded to the surface. However, during the electric plating conducted directly on the zinc layer produced by the zincating technique, when the plated one is electrically connected and immersed in a solution, the zinc layer may be susceptible to significant dissolution on the acidic side of the solution. This causes portions of the aluminum conductor to be exposed and also, a resultant plating copper layer to be declined in the quality by chemical displacement, thus resulting in breakage in the drawing process. For compensation, electroless nickel plating is conducted before the zinc plating. However, a resultant nickel plating layer has unfavorable physical properties, 2 % of the elongation and equal to or more than 500 Hv of Vickers hardness, thus being low in the extensibility. Accordingly, in the drawing process, the plating layer may produce lateral flaws. Also, in case that the electroless plating produces a plating layer which is high in the extensibility and easily drawn, its speed of deposition is on the order of 3 micrometers/hour thus declining the working efficiency. US-A-2891309 discloses a method of fabricating a coated aluminum wire in which a zinc layer is formed on an aluminum conductor, and the surface of the zinc layer is coated with copper by electroplating. Moreover, US-A-2891309 discloses that the coated wire may be annealed at temperatures from 316°c to 400°c (600°f to 750°f). In accordance with the present invention there is provided a method of fabricating a copper coated aluminum wire comprising: a zinc displacement step of forming a zinc thin layer by zinc displacement on the surface of an aluminum or aluminum alloy conductor; an electroplating step of coating the surface of the zinc thin layer continuously with copper layers by electroplating to have a copper coated aluminum conductor; wherein; a thermal diffusion step of heat treating the copper coated aluminum conductor at a temperature of 120°C to 200°C under an inert gas atmosphere for thermal diffusion to ease the electrodeposition stress is executed, whereby the resultant copper coated aluminum wire will be improved in the adhesion. A copper plated aluminum wire produced by the method of the invention may be easily treated by cold plastic working process thus to have a smaller diameter and is high in the adhesion. Moreover, the plated aluminum wire may have reduced in weight and be unlikely to disconnect due to thermal diffusion. In the method of the present invention, the thermal diffusion step provides heat treatment of the copper plated aluminum conductor at the temperature of 120°C to 200°C under the inert gas atmosphere to cause thermal diffusion and thus ease the electrodeposition stress. As a result, a thermal diffusion layer is developed at the interface between the aluminum conductor and the copper plating layer and a combination of the adhesion provided by the electroplating and the adhesion provided by the thermal diffusion will work effectively. The copper plated aluminum wire is thus improved in the adhesion. The electroplating for continuously forming the copper layers may comprise strike copper plating of depositing a strike copper plating layer and then copper sulfate plating of depositing a thick copper plating layer. The temperature for heat treatment is set to a range with a lower limit of 120°C because the thermal diffusion layer at the interface between the aluminum conductor and the copper plating layer is hardly developed at less than 120 °C of the temperature Preferably the thermal diffusion step allows the temperature T (°C) and the time S (minute) for thermal treatment to be defined by the following Statement (1): 50exp{-0.012T}≦S≦1400exp{-0.012T} where 120≦T≦200 In the method of said second feature of the present invention, the temperature T (°C) and the time T (minute) for thermal diffusion are defined by Statement (1) thus allowing the thermal diffusion layer to be favorably developed at the interface between the aluminum conductor and the copper plating layer. Therefore, as the adhesion in combination provided by said first feature is further enhanced, the copper plated aluminum wire will be improved in the adhesion. This minimizes the probability of disconnection on particularly the wire of a smaller diameter (for example, less than 0.10 mm) during the cold plastic working such as wire drawing. The above Statement (1) was obtained through a series of experiments over the relation between the temperature and the time for the thermal treatment. Preferably the aluminum conductor has a diameter of less than 1.0 mm and is selected from 99.0 % or higher pure drawing aluminum, an alloy of 90.0 % or higher pure drawing aluminum-magnesium (Al-Mg), and an alloy of 90.0 % or higher pure drawing aluminum-magnesium-silicon (Al-Mg-Si). The method may include a cold plastic working step of cold plastic working the copper plated aluminum wire used as a mother material to have a desired size. Embodiments of the present invention will now be described in detail, by way of example, with reference to the accompanying drawings, in which; Fig. 1 is a flowchart showing a method of fabricating copper plated aluminum wire useful in understanding the invention; Fig. 2 is a cross sectional view of copper plated aluminum wire useful in understanding the invention; Fig. 3 illustrates cross sectional views of composite light-weighted plated wires having a single layer of conductive metal; Fig. 4 illustrates cross sectional views of composite light-weighted plated wires having two layers of conductive metal; Fig. 5 illustrates SEM photographic pictures of the surface of plating of a composite light-weighted plated wire useful in understanding the invention; Fig. 6 illustrates SEM photographic pictures of the surface of plating of an example of an embodiment of the composite light-weighted plated wire according to the present invention; and Fig. 7 illustrates SEM photographic pictures of the surface of plating of on an Comparison 2. The present invention will be described in more detail referring to the embodiments shown in the accompanying drawings. It would be understood that the present invention is not limited to the illustrated embodiments. Fig. 1 is a flowchart showing a method of fabricating copper plated aluminum wire. Fig. 2 is a cross sectional view of the copper plated aluminum wire thus fabricated. Shown in the drawings are an aluminum conductor 1, a zinc thin layer 2, a copper coating 3, a strike copper plating layer 3a, a thick copper plating layer 3b, and a copper plated aluminum wire 9. Background Example 1 The method, which is useful in understanding the invention started with a zinc displacement step S1 of forming a zinc thin layer 2 by zinc displacement over the surface of an aluminum conductor 1 which was made of a 0.90 mm diameter wire of 99.0 % pure aluminum and had been degreased and etched. An electroplating step S2 followed in which the aluminum conductor 1 coated with the zinc thin layer 2 was immersed in a strike copper plating bath at a temperature of 40 °C and energized for one minute under a plating condition of 2 A/square-dm current density to develop a copper plating layer 3a of 2 micrometers in thickness on its surface. In succession, the same was immersed in a copper sulfate plating bath at a temperature of 40 °C and energized for forty minutes under a plating condition of 5 A/square-dm current density to develop a thick copper plating layer 3b of 40 micrometers in thickness on its surface. Hence, a resultant copper coated aluminum conductor had a copper coating 3 composed of the two plating layers 3a and 3b. Then, a thermal diffusion step S3 was applied in which the copper coated aluminum conductor was rinsed with water, dried out, and heat treated in an inert gas atmosphere of mainly nitrogen gas at 500 °C for one minute, thus yielding a copper plated aluminum wire 9 which has an outer diameter of 0.98 mm. Also, the 0.98 mm diameter copper plated aluminum wire was subjected to a cold plastic working step S4 where it was passed through dies in a wire drawing machine and drawn to have 0.10 mm in outer diameter of the copper plated aluminum wire 9. Example 1 A copper plated aluminum wire 9 of 0.10 mm in outer diameter was fabricated from an aluminum conductor 1, which was identical to that of Background Method 1, by the same manner as of Background Example 1 except that the thermal diffusion step S3 comprised water rinsing, drying, and thermal treatment under an inert gas atmosphere of mainly nitrogen gas at 200 °C for sixty minutes. Thus this example is in accordance with the present invention Comparison 1 A 0.90 mm diameter wire of 99.0 % pure aluminum which was identical to that of Background Example 1 was employed as the aluminum conductor and subjected to the zinc displacement step S1 and the electroplating step S2 to provide a copper coating on its surface. Similar to Background Example 1, a resultant copper coated aluminum conductor having an outer diameter of 0.98 mm was drawn in the cold plastic working step S4, thus producing a copper plated aluminum wire of 0.10 mm in outer diameter. Examination for a number of disconnection in drawing process Example 1, Background Example 1 and Comparison 1 were examined for how many times disconnection occurred in the drawing process. The result of the examination is listed in Table 1 shown below. It is noted that the number of disconnections was counted from 10 kg of the copper plated aluminum wires having an outer diameter of 0.10 mm at each assignment. The wire drawing was carried out uniformly using a reduction of 15 % and a velocity of 400 m/min. As apparent from the above Table 1, the method of the present invention allows a less number of disconnections encountered during the wire drawing process and thus provides a greater value of the average weight which represents an average quantity of drawn wire per disconnection. According to the method of fabricating copper plated aluminum wire (Fig. 1) according to the present invention, the thermal diffusion step S3 is specified in that the copper plated aluminum conductor is heat treated under an inert gas atmosphere at a temperature ranging from 120°c to 200°c so that thermal diffusion eases the stress of electrical deposition. Hence, a thermal diffusion layer is developed at the interface between the aluminum conductor 1 and the copper coating 3. Since the adhesion created by the electroplating and the adhesion produced by the thermal diffusion act in a combination, the copper plated aluminum wire 9 can be minimized in the diameter and the weight. Also, when the temperature T (°C) and the time T (minute) for the heat treatment are defined by Statement (1), the thermal diffusion layer at the interface between the aluminum conductor 1 and the copper coating 3 is formed in optimum conditions. Accordingly, the adhesion in a combination will be enhanced and undesired disconnection of the small diameter wire (e.g. of less than 0.10 mm) during the cold plastic working step S4 will be reduced remarkably. It is thus clear that the contribution of the present invention to relevant industries is significant. Fig. 3 and Fig. 4 are cross sectional views of composite light-weighted plated wire. Fig. 3 illustrates a composite light-weighted plated wire having a single layer of conductive metal and Fig. 4 shows the composite light-weighted plated wire having two layers of conductive metal. As shown in Fig. 3 and Fig. 4, there are an aluminum or aluminum alloy conductor 1 (an aluminum conductor), a zinc or zinc alloy anchor metal layer 12 (a zinc anchor metal layer), a conductive metal layer 23 (a first conductive metal layer) having a potential higher than that of zinc, another conductive metal layer 33 (a second conductive metal layer) having a potential higher than that of zinc, and composite light-weighted plated wires 50 and 60. Background Example 2 A 0.10 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to a zincating process, which comprises degreasing, etching, neutralizing, first zinc replacing, zinc removing, and second zinc replacing, to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. The same was immersed in a copper pyrophosphate plating bath, which contained 100 g/l of copper pyrophosphate, 300 g/l of potassium pyrophosphate, and 2 ml/l of liquid ammonia and was maintained at 55 °C, and energized under a condition of 2 A/square-dm at cathode current density and 8.5 at pH level for four minutes to deposit a copper conductive metal layer 23 of 2 micrometers in thickness. A resultant was a composite light-weighted plated wire 50 having an outer diameter of 0.104 mm. This composite light-weighted plated wire 50 may be used as the composite light-weighted plated wire mother material. Example 2 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Background Example 2 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in the same copper pyrophosphate plating bath as of Background Example 2 at 55°c and energized under a condition of 1 A/square-dm at cathode current density and 8.5 at pH level for two minutes to deposit a first copper conductive metal layer 23 of 0.4 micrometer in thickness. The same was further immersed in a copper sulfate plating bath, which contained 200 g/l of copper sulfate and 50 g/l of sulfuric acid, and was maintained at 30°c, and energized under a condition of 5 A/square-dm at cathode current density and 0.5 at pH level for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first copper conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.922 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 3 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Background Example 2 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in a copper cyanide plating bath, which contained 40 g/l of copper cyanide, 60 g/l of sodium cyanide, 20 g/l of potassium sodium tartrate, and 10 g/l of sodium carbonate and was maintained at 50 °C, and energized under a condition of 2 A/square-dm at cathode current density and 12 at pH level for two minutes to deposit a first copper conductive metal layer 23 of 0.8 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 4-2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first copper conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.923 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200°c for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 4 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Background Example 2 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in a nickel sulfate plating bath, which contained 80 g/l of nickel sulfate, 30 g/l of ammonia chloride, and 80 g/l of sodium sulfuric anhydride and was maintained at 30 °C, and energized under a condition of 2 A/square-dm at cathode current density and 5.5 at pH level for two minutes to deposit a first nickel conductive metal layer 23 of 0.4 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first nickel conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.922 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 5 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Example 4-1 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in a zinc cyanide plating bath, which contained 60 g/l of zinc cyanide, 40 g/l of sodium cyanide, and 80 g/l of sodium hydroxide and was maintained at 30 °C, and energized under a condition of 2 A/square-dm at cathode current density and 12 at pH level for two minutes to deposit a first zinc conductive metal layer 23 of 1.0 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first zinc conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.926 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 6 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Background Example 2 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in a silver cyanide plating bath, which contained 2 g/l of silver cyanide and 100 g/l of potassium cyanide and was maintained at 25 °C, and energized under a condition of 1 A/square-dm at cathode current density and 12 at pH level for one minute to deposit a first silver conductive metal layer 23 of 0.6 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first silver conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.922 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 7 A 0.90 mm diameter wire of 93 % pure aluminum-magnesium alloy was used as the aluminum conductor 1 and subjected to the same zincating process as of Background Example 2 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in a gold cyanide plating bath, which contained 8 g/l of gold cyanide, and 30 g/l of potassium hydrogen phosphate and was maintained at 60 °C , and energized under a condition of 0.5 A/square-dm at cathode current density and 12 at pH level for one minute to deposit a first gold conductive metal layer 23 of 0.2 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first copper conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.921 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200°c for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 8 Similar to Example 2, a 0.10 mm diameter wire of 99.9 % pure aluminum was coated with a first copper conductive metal layer 23 of 0.4 micrometer in thickness on its surface. Then, the same was immersed in the same copper sulfate plating bath at 30°c as of Example 2 and energized under a condition of 5 A/square-dm at cathode current density and 0.5 at pH level for two minutes to deposit a second copper conductive metal layer 33 of 2 micrometers in thickness over the first copper conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.906 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200°c for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Example 9 Similar to Example 2, a 0.10 mm diameter wire of 99.9 % pure aluminum was coated with a first copper conductive metal layer 23 of 0.4 micrometer in thickness on its surface. Then, the same was immersed in the same copper sulfate plating bath at 30°c as of Example 2 and energized under a condition of 5 A/square-dm at cathode current density and 0.5 at pH level for forty minutes to deposit a second copper conductive metal layer 33 of 40 micrometers in thickness over the first copper conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.982 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Thus this example is in accordance with the present invention. Comparison 2 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Example 4-1 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in an acidic copper sulfate plating bath, which contained 100 g/l of copper sulfate and 50 g/l of sulfuric acid and was maintained at 30 °C, and energized under a condition of 2 A/square-dm at cathode current density and 0.5 at pH level for two minutes to deposit a first copper conductive metal layer 23 of 0.4 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first copper conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.922 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Comparison 3 A 0.90 mm diameter wire of 99.9 % pure aluminum was used as the aluminum conductor 1 and subjected to the same zincating process as of Background Example 2 to develop a zinc anchor metal layer 12 of 0.5 micrometer in thickness on its surface. Then, the same was immersed in a nickel chloride plating bath, which contained 100 g/l of nickel sulfate, 60 g/l of nickel chloride, 45 g/l of boric acid, and 10 g/l of ferrous sulfate and was maintained at 60 °C, and energized under a condition of 2 A/square-dm at cathode current density and 3.5 at pH level for two minutes to deposit a first nickel-iron alloy conductive metal layer 23 of 0.4 micrometer in thickness. The same was further immersed in the same copper sulfate plating bath as of Example 2 and energized under the same conditions as of Example 2 for ten minutes to deposit a second copper conductive metal layer 33 of 10 micrometers in thickness over the first conductive metal layer 23. A resultant was a composite light-weighted plated wire mother material having an outer diameter of 0.922 mm. Succeedingly, the composite light-weighted plated wire mother material was subjected to heat treatment at 200 °C for five minutes for easing its stress distortion and to cold drawing, yielding a composite light-weighted plated wire 60 having an outer diameter of 0.10 mm. Property Test The above composite light-weighted plated wires of Background Example 2, Examples 2 to 9 and of Comparisons 2 and 3 were tested for properties. Test results are illustrated below. (1) Wire drawing test The composite light-weighted plated wires of Examples 2 to 9 and of Comparisons 2 and 3 having an outer diameter of 0.10 mm were examined how many disconnections per unit of 5 kg appeared in the drawing process. The result is listed in Table 3 below. Number of disconnections in wire drawing (times/5 kg) Examples Comparisons 2 3 4 5 6 7 8 9 2 3 2 1 2 3 2 1 2 1 10 9 As apparent from Table 3, the plating bath used as an electrolyte solution for depositing a conductive metal layer 23 having a potential higher than that of zinc on the zinc anchor metal layer 12 and having a pH level of 4 or higher allows the composite light-weighted plated wires of Examples 2 to 9 to minimize the probability of disconnection during the wire drawing process. (2) Zinc dissolution test (for evaluating the holding of a zinc anchor metal layer) The composite light-weighted plated wires of Background Example 2, Examples 2 to 9 and of Comparisons 2 and 3 before subjected to the drawing process were tested for examining a rate of dissolution (%) of zinc by the zinc anchor metal layer holding evaluating test method wherein the anchor metal layer 12 and the electrically conductive metal layers 23 and 33 were exposed to nitric acid and a resultant dissolution of zinc per unit area from the layers was measured with an atomic absorption spectroscopy meter. A result of the test is shown in Table 4 below. The dissolution rate (%) of zinc = 100 - the remaining of zinc (%) in the zinc anchor metal layer. As apparent from Table 4, the composite light-weighted plated wires of the present invention exhibit less than 20 % of the dissolution of zinc thus holding 80 % and more of zinc in their zinc anchor metal layer 12. It is clear that the lower the pH level in the electrolyte solution for electroplating the zinc anchor metal layer 12, the higher the dissolution rate of zinc is increased or the more the remaining of zinc in the zinc anchor metal layer is declined. The dissolution of zinc is closely related to the cause of disconnection during the drawing process. Referring to Table 3, it may be understood that the electroplated wires with less than 20 % of the zinc dissolution rate produce a less number of disconnections. (3) Surface inspection test of composite light-weighted plated wires The composite light-weighted plated wires of Background Example 2, Example 3 and of Comparison 2 were inspected on the plating coatings on their surface using a scanning electron microscope (SEM). Resultant SEM pictures are shown in Fig. 5, Fig. 6 and Fig. 7. Fig. 5 illustrates the composite light-weighted plated wire of Background Example 2. Fig. 6 illustrates the composite light-weighted plated wire of Example 2. Fig. 7 illustrates the composite light-weighted plated wire of Comparison 2. As apparent from the SEM pictures of Fig. 5 to Fig. 7, the composite light-weighed plated wire of Comparison 2 (Fig.13) has a multiplicity of pits in its surface. Comparing between two Tables 3 and 4, it is proved that the pits in the plating layers produced by the dissolution and the chemical displacement of zinc defines its adhesion to the core thus causing disconnections during the plastic forming process such as wire drawing. It is also found through a solder wetting test, though not shown, that the reliability of soldered joints on the composite light-weighted plated wires of the present invention is higher. The composite light-weighted plated wires produced by the method of the present invention has an electrically conductive metal layer deposited on the surface of its zinc anchor metal layer over the aluminum conductor by the electroplating which is conditioned by the fact that the hydrogen ion concentration in the electrolyte solution (pH) is 4 or higher and the thickness x (micrometer) of plating is 0.2<x≦ 5. Accordingly, since the dissolution and the chemical displacement of zinc are attenuated, the resultant plating layers are improved in the adhesion thus minimizing the probability of disconnection during the wire drawing process and ensuring reduction of the diameter and the weight of the composite light-weighted plated wires. Also, the electrically conductive metal layer declines the effect of natural oxidation hence improving the reliability of soldering work. The composite light-weighted plated wires will thus contribute to the improvement of performance and the reduction of size and weight of electronic devices or components and will find major roles in the relevant industries.

Claims: A method of fabricating a copper coated aluminum wire (9) comprising: a zinc displacement step of forming a zinc thin layer (2) by zinc displacement on the surface of an aluminum or aluminum alloy conductor (1); an electroplating step of coating the surface of the zinc thin layer (2) continuously with copper layers (3) by electroplating to have a copper coated aluminum conductor; characterized in that ; a thermal diffusion step of heat treating the copper coated aluminum conductor at a temperature of 120 °C to 200 °C under an inert gas atmosphere for thermal diffusion to ease the electrodeposition stress is executed, whereby the resultant copper coated aluminum wire (9) will be improved in the adhesion. A method of fabricating a copper coated aluminum wire 9 according to claim 1, wherein the thermal diffusion step allows the temperature T (°C) and the time S (minute) for thermal treatment to be defined by the following Statement (1): 50exp{-0.012T}≦S≦1400exp{-0.012T} where 120≦T≦600 A method of fabricating a copper coated aluminum wire 9 according to claim 1 or 2, wherein the aluminum or aluminum alloy conductor 1 has a diameter of less than 1.0 mm and is selected from 99.0 % or higher pure drawing aluminum, an alloy of 90.0 % or higher pure drawing aluminum-magnesium (Al-Mg), and an alloy of 90.0 % or higher pure drawing aluminum-magnesium-silicon (Al-Mg-Si). A method of fabricating a copper coated aluminum wire (9) according to claim 1, 2, or 3, further comprising a cold plastic working step of cold plastic working the copper coated aluminum wire (9) used as a mother material to have a desired size.

Inventors: KITAZAWA HIROSHI, TSUKADA ETSURO, YAMAGUCHI TATSUO, KITAZAWA, HIROSHI, TSUKADA, ETSURO, YAMAGUCHI, TATSUO
Applicants: TOTOKU ELECTRIC, TOTOKU ELECTRIC CO., LTD.
Application year: 1998
Main classification: C25D5
IPC codes: C25D5, C25D7