JP2799857B2 - Aluminum clad steel plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum clad steel sheet having excellent workability.

[0002]

2. Description of the Related Art Various methods have been used to develop a clad material of aluminum and a steel plate. For example, there are a cold rolling joining method (JP-A-53-85759, etc.) and an organic adhesive method (JP-A-60-223683, etc.). However, there is a disadvantage that the processing adhesion is poor due to the presence of the oxide film present on the surface of aluminum.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aluminum clad steel sheet which is excellent in workability by using a low pressure without using an adhesive.

[0004]

The clad steel sheet of the present invention is coated on one side of an electrolytic iron foil, a rolled steel foil or a steel sheet with copper of 0.1 to 50 g / m ² in terms of copper amount. A foil or plate of aluminum or an aluminum alloy having a thickness of 5 to 300 μm is coated thereon, and the other surface of the electrolytic iron foil, rolled steel foil or steel plate is copper, nickel, chromium, tin, zinc, lead or Is coated. Further, the clad steel sheet according to claim 2 is an electrolytic iron foil,
One or both surfaces of a rolled steel foil or a steel plate are coated with copper, nickel, chromium, tin, zinc, lead or an alloy containing these as a main component, and 0.1 to 50 g / m in terms of copper amount thereon. ²
And a foil or plate of aluminum or an aluminum alloy having a thickness of 5 to 300 μm.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The steel foil or steel sheet used for the aluminum clad steel sheet of the present invention means a steel sheet manufactured by an electrolytic method or a rolling method. The steel sheets include low-carbon steel sheets, chromium-added steel sheets, steel sheets subjected to nickel diffusion treatment, and copper, nickel, chromium, tin, zinc,
Steel plates coated with lead or alloys containing these as main components are included. Of course, the aluminum foil of the steel plate or the surface not coated with the plate can be subjected to chromate treatment and phosphate treatment. On the other hand, a rolled foil or a rolled plate made of aluminum or an aluminum alloy is an aluminum or aluminum alloy plate having a thickness of 5 to 300 microns produced by a rolling method. Aluminum alloy plates include magnesium, manganese, silicon,
Alloy plates containing copper, iron, zinc, chromium, titanium or zirconium are included. If the thickness is less than 5 microns, the workability is reduced, the production cost is increased, and it is uneconomical.

On the other hand, if it exceeds 300 microns, it is uneconomical in terms of materials. Next, in order to obtain good bonding strength and processing adhesion, on the surface of a steel foil or a steel plate, or an aluminum or aluminum alloy plate, copper or an alloy containing copper as a main component is converted into a copper amount. , 0.1-50
g / m ² . Preferably, it is coated with 1 to 30 g / m ² .

[0007] If the oxide on the surface of the aluminum is removed, it is easier to achieve uniform bonding. The surfaces of both metal plates may be coated with copper or an alloy containing copper as a main component.
In that case, the total copper amount at the joint surface may be 0.1 to 50 g / m ² . If it is less than 0.1 g / m ² , sufficient bonding strength cannot be obtained, and if it is more than 50 g / m ² , it is uneconomical in terms of production cost.

Before coating the copper plate with copper or an alloy containing copper as a main component, nickel, chromium, tin, zinc,
Lead or an alloy containing these as a main component, 0.01 to
50 g / m ² may be coated.

In addition, copper, nickel, chromium,
A steel sheet coated with tin, zinc, lead, or an alloy containing these as a main component may be used. However, in the case of chromium or an alloy containing chromium as a main component, 0.01 to 2 g / m
² may be coated.

When the metal or alloy is coated in advance, copper or an alloy containing copper as a main component may be coated in an amount of 0.1 to 50 g / m ² in terms of copper amount. Preferably, 0.5 to 20 g / m ² may be applied. Thus, nickel, chromium,
Coating with tin, zinc, lead, or an alloy containing these as a main component makes the bonding layer more uniform and improves the adhesion.

The amount of nickel is 50 g / m ² and the amount of chromium is 2
If g / m ² is rubbed, workability is poor. As a method of coating copper, nickel, chromium, tin, zinc, lead, or an alloy containing these as a main component, there are an electroplating method, a chemical plating method, a vacuum deposition plating method, and the like.

[0012] Copper-based alloys include cobalt, bismuth, iron, germanium, indium, manganese, molybdenum, nickel, tin, antimony, tellurium, thallium, zinc, tungsten and the like.

[0013] Alloys containing nickel as a main component include niobium, chromium, aluminum, rhodium, titanium, cobalt, copper, iron, germanium, indium, manganese, molybdenum, tin, antimony, tellurium, thallium, zinc,
Including tungsten and the like.

The alloys containing chromium as a main component include vanadium, cobalt, iron, manganese, molybdenum, tin, tungsten, nickel and the like.

The alloy containing zinc as a main component includes zirconium, vanadium, thallium, antimony, lead, copper, indium, cobalt, iron, manganese, molybdenum, tin, tungsten, nickel and the like.

The alloy containing tin as a main component includes zinc, germanium, chromium, bismuth, antimony, lead, copper, indium, cobalt, iron, manganese, molybdenum, tungsten, nickel and the like.

At the time of heating, a pressing force is not particularly required, and it is sufficient to simply overlap the plates.
Preferably, pressure is applied in the range of 0.01 to 200 kgf / cm ² .

The heating is carried out in a vacuum, inert, non-oxidizing atmosphere at a temperature of about 300 ° C. to a temperature lower than the melting point of aluminum or aluminum alloy (about 650 ° C.). 300
If the temperature is lower than 0 ° C., the adhesion is inferior.

The heating time varies depending on the type and thickness of the metal to be coated, but may be about 0.1 second to 15 minutes. 0.1
If it is less than seconds, it is difficult to adhere uniformly, and if it exceeds 15 minutes, it is uneconomical.

The aluminum cladding can be applied to one or both sides of a steel foil or a steel plate. The atmosphere is preferably a non-oxidizing atmosphere, for example, hydrogen, nitrogen, helium, neon, argon, or a mixed gas thereof.

On the other hand, aluminum is an aluminum foil having a thickness of 5 to 100 μm manufactured by a rolling method. 5
When the thickness is less than μm, the workability is reduced, and when the thickness exceeds 100 μm, the material cost is uneconomical. Further, the non-bonded surface can be subjected to a chemical conversion treatment such as a chromate treatment and a phosphoric acid treatment.

When a steel sheet and aluminum are joined by cold rolling, first, the steel sheet is plated with nickel or an alloy plating containing nickel as a main component in an amount of 0.5 to 5 g / m ² . The method of coating nickel or an alloy containing nickel as a main component is not particularly limited, and examples thereof include an electroplating method and a chemical plating method. Alloys based on nickel include phosphorus, cobalt, copper, chromium,
Can contain zinc, tin or iron.

[0023]

EXAMPLES (Example 1) Aluminum foil having a thickness of 100 μm (JIS1100 material)
Was immersed in a solution containing 30 g / l of p-3 anther (manufactured by Henkel Hakusui) at a temperature of 60 ° C. for 5 seconds. Using a solution containing 90 g / l of copper pyrophosphate and 330 g / l of potassium pyrophosphate in a steel plate having a thickness of 200 μm,
Under conditions of 0 ° C. and a current density of 5 A / dm ² , copper was added at 50 g / m 2.
^{2 was} plated. Then, the aluminum foil and the copper-plated steel sheet are stacked, a pressure of 0.04 kgf / cm ² is applied, and the plate is heated at a temperature of 610 ° C. for 10 minutes in an atmosphere containing 95% of nitrogen gas and 5% of hydrogen gas. An aluminum clad steel sheet was obtained.

Example 2 An aluminum foil (JIS 1070 material) having a thickness of 5 μm was
In a solution containing 50 g / l of sodium hydroxide, at a temperature of 6
It was immersed for 5 seconds at 0 ° C. 250μm thick steel plate,
A 50 g solution containing 250 g / l of copper sulfate and 50 g / l of sulfuric acid was immersed, and copper was plated on both sides at 20 g / m ² . Then, an aluminum foil is placed on both sides of the copper-plated steel sheet, a pressure of 1.0 kgf / cm ² is applied, and the temperature of the sheet is set to 6 in an atmosphere containing 95% of nitrogen gas and 5% of hydrogen gas.
It was heated at 10 ° C. for 1 second to obtain an aluminum-clad steel sheet.

Example 3 An aluminum alloy foil having a thickness of 30 μm (JIS 3003)
10 g / m ^{2 of} copper and copper sulfate at a temperature of 40 ° C. and a current density of 5 A / dm ² in a solution containing 250 g / l of copper sulfate and 50 g / l of sulfuric acid. Then, the copper-plated aluminum alloy foil is overlaid on a steel plate having a thickness of 200 μm, a pressure of 0.5 kgf / cm ² is applied, and the plate is heated at a plate temperature of 600 ° C. for 30 seconds in an atmosphere of hydrogen gas to obtain an aluminum-clad steel plate. Was.

Example 4 Aluminum foil having a thickness of 50 μm (JIS 1070 material)
In a solution containing 100 g / l of sodium hydroxide,
At a temperature of 60 ° C. and a current density of 10 A / dm ² , the aluminum foil was used as a cathode for 5 seconds. Thickness 100μ
Using a Watt bath (nickel sulfate 240 g / l, nickel chloride 45 g / l, boric acid 30 g / l) at a temperature of 50 ° C. and a current density of 5 A / dm ² , 0.01 g / m ² was plated. Next, a solution containing copper sulfate 250 g / l and sulfuric acid 50 g / l was applied to the nickel-plated steel foil at a temperature of 50 ° C. and a current density of 5 A / dm ^2.
Under the conditions described above, copper was plated at 3 g / m ² . Then, the aluminum foil and the steel foil plated with nickel and then plated with copper were overlaid, a pressure of 0.04 kgf / cm ² was applied, and the film was heated at 630 ° C. for 1 minute in an argon gas atmosphere to obtain an aluminum-clad steel sheet. .

Example 5 An aluminum alloy plate having a thickness of 200 μm (JIS5052)
2 g / m ^{2 of} copper was plated in a solution containing 250 g / l of copper sulfate and 50 g / l of sulfuric acid at a temperature of 40 ° C. and a current density of 5 A / dm ² . Then, 70μm thick
Was plated on a steel foil of 3 g / m ^{2 at} 50 ° C. and a current density of 5 A / dm ² using a solution containing 90 g / l of copper pyrophosphate and 330 g / l of potassium pyrophosphate.
Next, a copper-plated aluminum alloy plate and a copper-plated steel foil are stacked, and a pressure of 0.01 kgf / cm ² is applied.
The sheet was heated at 650 ° C. for 1 second in an atmosphere containing 95% of nitrogen gas and 5% of hydrogen gas to obtain an aluminum-clad steel sheet.

Embodiment 6 An aluminum alloy plate having a thickness of 300 μm (JIS 5082)
Using a solution containing 90 g / l of copper pyrophosphate and 330 g / l of potassium pyrophosphate, copper was plated at 10 g / m ^{2 at} 50 ° C. and a current density of 5 A / dm ² .
Next, a steel foil having a thickness of 30 μm was placed on a watt bath (240 g / l nickel sulfate, 45 g / l nickel chloride, 30 g boric acid).
g / l) at a temperature of 50 ° C. and a current density of 10 A / dm ^2.
Under the conditions described above, nickel was plated at 0.5 g / m ² . A solution containing 30 g / l of copper sulfate, 300 g / l of ferrous sulfate, and 30 g / l of ammonium sulfate was applied to the nickel-plated steel foil at a temperature of 50 ° C. and a current density of 10 A / dm ^2.
Under the conditions described above, the copper-iron alloy plating was converted to copper at 5 g / m
^{2 was} plated. Next, a copper-plated aluminum alloy plate and a nickel-plated copper-iron alloy-plated steel foil are overlaid, a pressure of 10 kgf / cm ² is applied, and the plate is placed in an atmosphere containing 95% of nitrogen gas and 5% of hydrogen gas. Heating was performed at a temperature of 590 ° C. for 1 minute to obtain an aluminum-clad steel sheet.

Example 7 An aluminum alloy plate having a thickness of 200 μm (JIS 3004)
Material), copper sulfate 5 g / l, nickel sulfate 5 g / l, ammonium tartrate 13 g / l, ammonium hydroxide 0.0
Using a solution containing 25 g / l, a copper-nickel alloy was plated at 0.05 g / m ² in terms of copper at a temperature of 30 ° C. and a current density of 5 A / dm ² . Then, thickness 15
μm electrolytic iron foil, watt bath (nickel sulfate 240g /
1, nickel chloride 45 g / l, boric acid 30 g / l), and nickel was plated at 50 g / m ² at a temperature of 50 ° C. and a current density of 10 A / dm ² . Using a solution containing 90 g / l of copper pyrophosphate and 330 g / l of potassium pyrophosphate on the nickel-plated iron foil, copper was plated at 10 g / m ^{2 at} 50 ° C. and a current density of 5 A / dm ² . . Then, copper-nickel alloy-plated aluminum alloy plate and nickel-plated and then copper-plated iron foil,
Applying a pressure of 50 kgf / cm ² and a plate temperature of 580 ° C. in an atmosphere containing 95% of nitrogen gas and 5% of hydrogen gas.
For a minute to obtain an aluminum clad steel sheet.

Example 8 Aluminum foil having a thickness of 70 μm (JIS 1070 material)
Was immersed in a solution containing 30 g / l of p-3 anther (manufactured by Henkel Hakusui) at a temperature of 60 ° C. for 10 seconds.
A steel plate having a thickness of 210 μm is treated with a sargent bath (chromic anhydride 250 g / l, sulfuric acid 2.5 g / l) to form a 50
Chromium at a current density of 20 A / dm ²
1 g / m ^{2 was} plated. Then, on a chromium-plated steel sheet, copper pyrophosphate 90 g / l, potassium pyrophosphate 33
Using a solution containing 0 g / l, 50 ° C., current density 5 A
Under the condition of / dm ² , copper was plated at 3 g / m ² . Next, the aluminum foil and the steel plate plated with chromium and then plated with copper were overlapped, a pressure of 2 kgf / cm ² was applied, and the plate was heated at 600 ° C. for 15 minutes in a nitrogen gas atmosphere to obtain an aluminum-clad steel plate.

Example 9 An aluminum alloy plate having a thickness of 150 μm (JIS 5082)
The material was immersed in a solution containing 90 g / l of copper pyrophosphate and 330 g / l of potassium pyrophosphate and adjusted to pH 11.5 by adding sodium hydroxide at 60.degree. 05 g / m ^{2 was} plated. Then, 90 g / l of copper pyrophosphate and potassium pyrophosphate 33 were coated on a 200 μm-thick tin-plated steel sheet coated with 2.8 g / m ² of tin.
Using a solution containing 0 g / l, a current density of 5 A at 50 ° C.
/ Dm ² , copper was plated at 0.05 g / m ² .
The copper-plated aluminum alloy sheet and the copper-plated tin-plated steel sheet were stacked, and a pressure of 200 kgf / cm ² was applied thereto, and the sheet was heated at 301 ° C. for 5 minutes in a nitrogen gas atmosphere to obtain an aluminum-clad steel sheet.

Example 10 Aluminum plate having a thickness of 250 μm (JIS1100 material)
Was immersed in a solution containing 30 g / l of p-3 anther (manufactured by Henkel Hakusui) at a temperature of 60 ° C. for 10 seconds.
50 ° C., using a Sargent bath (chromic anhydride 250 g / l, sulfuric acid 2.5 g / l) on a 50 μm thick steel foil.
Under the condition of a current density of 20 A / dm ² , chromium was 2 g / m ²
Plated. Then, using a solution containing 90 g / l of copper pyrophosphate and 330 g / l of potassium pyrophosphate on a chromium-plated steel foil, plating copper at 10 g / m ^{2 at} 50 ° C. and a current density of 5 A / dm ^2. did. Then, the aluminum plate and chromium plating and then copper-plated steel foil are stacked,
A pressure of 5 kgf / cm ² was applied and the plate was heated at a plate temperature of 600 ° C. for 3 minutes in a nitrogen gas atmosphere to obtain an aluminum-clad steel plate.

The aluminum clad steel sheet thus obtained was subjected to the following work adhesion test. 6 m with an Erichsen tester (manufactured by Tokyo Koki Co., Ltd.) so that the aluminum or aluminum alloy plate side protrudes
m overhanging. The overhanging part on the surface of the aluminum or aluminum alloy plate was scratched with a cutter until it reached the base iron part, and a peeling test was forcibly performed with tweezers. As a result, no peeling was observed in the clad steel sheets of Examples 1 to 10.

[0034]

By interposing copper or the like between the steel sheet and the aluminum or aluminum sheet, an aluminum clad steel sheet having a strong bonding strength in a non-oxidizing atmosphere can be obtained. Also, nickel, chromium, tin, zinc,
When coated with lead or an alloy containing these as main components,
At the time of heat treatment, diffusion between iron and aluminum is suppressed, so that a more uniform bonding layer is formed and processing adhesion is also improved.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) B23K 20/00 B23K 20/02 B23K 20/16 C23C 28/02

Claims (2)

(57) [Claims] 1. One side of an electrolytic iron foil, a rolled steel foil or a steel sheet is coated with copper of 0.1 to 50 g / m ² in terms of copper amount, and aluminum or aluminum alloy having a thickness of 5 to 300 μm is coated thereon. Foil or plate is coated, the electrolytic iron foil,
On the other side of rolled steel foil or steel sheet, copper, nickel, chromium,
Aluminum clad steel sheet coated with tin, zinc, lead or an alloy containing these as main components. 2. One or both sides of an electrolytic iron foil, a rolled steel foil or a steel sheet is coated with copper, nickel, chromium, tin, zinc, lead or an alloy containing these as a main component, and the copper content is converted onto the alloy. An aluminum clad steel sheet coated with 0.1 to 50 g / m ² of copper and further coated with a foil or plate of aluminum or an aluminum alloy having a thickness of 5 to 300 μm.