JP2670504B2 - Aluminum clad steel sheet and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aluminum clad steel sheet having excellent corrosion resistance, workability, work adhesion, and adhesion to an organic coating, and a method for producing the same.

[Prior Art] At present, an aluminum or aluminum alloy plate has an oxide on the surface thereof, so that it has excellent corrosion resistance and, since work hardening is small, it has excellent workability, but it is expensive. On the other hand, steel sheets are inexpensive, but have the drawback that red rust easily occurs. Therefore, as a method of compensating for the drawbacks of the aluminum plate and the steel plate, the development of a clad material composed of the aluminum plate and the steel plate is underway. As a method of joining an aluminum plate and a steel sheet, a joining method by cold rolling (Japanese Patent Laid-Open No. 53857857) is used.
JP-A-55-68195, JP-A-56-109183, JP-A-5
8-141882, JP-A-61-67581), a bonding method using an organic adhesive (JP-A-60-223683) or a bonding method using a resin adhesive film (JP-A-63-40689) However, since the oxide existing on the surface of aluminum is strong, it is inferior in terms of work adhesion or bonding strength. In order to solve these drawbacks, there is a method of removing the oxide in advance by sputtering with argon in a high vacuum, but the workability is poor. Further, when cold rolling is performed, softening annealing after rolling is required.

[Problems to be Solved by the Invention] In the method for producing an aluminum clad steel sheet, the conventional method requires an organic adhesive, and has problems in heat resistance and adhesive strength. In the method using cold rolling, the amount of plastic deformation differs between the aluminum plate and the steel plate, so the curling of the clad material occurs, softening annealing is required, and the process becomes complicated. Further, the method of removing the aluminum oxide in a high vacuum has a problem in cost.

[Means for Solving the Problems] Therefore, the present invention provides a clad material excellent in bonding strength and work adhesion by an inexpensive and low pressing force without using an organic adhesive in the method for producing an aluminum clad steel sheet. The purpose is to do.

The gist is electrolytic iron foil, rolled steel foil (hereinafter abbreviated as steel foil) or steel plate or copper, nickel, chromium, zinc,
Copper or copper is the main component between the surface of a steel foil or steel plate coated with tin, lead or an alloy containing these as the main component and the surface of a rolled foil or plate made of aluminum or an aluminum alloy with a thickness of 5 to 300 μm. The joining layer is formed by heat-treating the foil or plate at a temperature of 300 ° C to 650 ° C, which is lower than the melting point of aluminum or aluminum alloy, in an inert or non-oxidizing atmosphere with the alloy layer 0.01% copper or copper alloy layer
Another object is to provide an aluminum clad steel sheet having a thickness of 10 μm and coated with aluminum on one side or both sides.

 Hereinafter, the present invention will be described in detail.

The steel foil or steel plate used for the aluminum clad steel plate of the present invention is a steel plate manufactured by an electrolytic method or a rolling method. Examples of the steel sheet include a low carbon steel sheet, a chromium-added steel sheet, a nickel diffusion-treated steel sheet, and a steel sheet coated with copper, nickel, chromium, tin, zinc, lead, or an alloy containing these as the main components. Of course, the surface of the steel sheet that does not cover the aluminum foil or the sheet can be subjected to chromate treatment or phosphate treatment.

On the other hand, the rolled foil or rolled plate made of aluminum or aluminum alloy is an aluminum or aluminum alloy plate having a thickness of 5 to 300 μm manufactured by a rolling method. The aluminum alloy plate includes an alloy plate containing magnesium, manganese, silicon, copper, iron, zinc, chromium, titanium or zirconium. 5
If the thickness is less than μm, the workability is lowered, the manufacturing cost is increased, and it is uneconomical. Further, if it exceeds 300 μm, it is uneconomical in terms of material cost.

Next, in order to obtain good joining force and working adhesion, on the surface of a steel foil or steel plate or aluminum or aluminum alloy plate, copper or an alloy containing copper as a main component is converted into a copper amount of 0.1 to Cover with 50 g / m ² . It is preferably 1 to 30 g / m ² . When the aluminum or aluminum alloy plate is not coated with copper or an alloy containing copper as a main component, and when a strong oxide layer is formed on the surface of aluminum or an aluminum alloy, use an alkaline solution to soak, Alternatively, if the aluminum oxide is removed by performing anodization, it is easier to join more uniformly. Further, 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 amount of copper at the joint surface should be 0.1 to 50 g / m ² . If it is less than 0.1 g / m ² , sufficient bonding strength cannot be obtained. If it exceeds 50 g / m ² , it is uneconomical in terms of manufacturing cost. In addition, before coating the steel sheet with copper or an alloy containing copper as a main component, nickel, chromium,
0.01% tin, zinc, lead or alloys containing these as the main components
It may be coated up to 50 g / m ² . Further, a steel plate coated beforehand with copper, nickel, chromium, tin, zinc, lead or an alloy containing these as main components may be used. However, in the case of chromium or alloys containing chromium as the main component, 0.01-
It may be coated with ² g / m ² . Further, in the case of coating the above metal or alloy in advance, when coating copper or an alloy containing copper as a main component, it may be coated in an amount of 0.1 to 50 g / m ² in terms of the amount of copper. It is preferably 0.5 to 20 g / m ² . As described above, when nickel, chromium, zinc, tin, lead or an alloy containing these as a main component is coated in advance, the bonding layer becomes more uniform and the adhesion is further improved. The amount of nickel is 50
If the g / m ² and chromium content exceeds ² g / m ² , the process adhesion is poor.

The method for coating copper, nickel, chromium, tin, zinc, lead, or an alloy containing these as the main components is not particularly limited, but as these methods, electroplating,
There is a chemical plating method or a vacuum deposition plating method. Copper-based alloys include cobalt, bismuth, iron, germanium, indium, manganese, molybdenum, nickel,
It may contain tin, antimony, tellurium, thallium, zinc or tungsten. Nickel-based alloys can include molybdenum, manganese, niobium, chromium, indium, cobalt, copper, iron, aluminum, germanium, rhodium, tin, tellurium, titanium, thallium, tungsten, antimony, or zinc.
The chromium-based alloy can include cobalt, iron, manganese, molybdenum, tin, vanadium, nickel or Langsten. The zinc-based alloy may include zirconium, tungsten, vanadium, thallium, antimony, lead, nickel, iron, molybdenum, manganese, copper, cobalt, tin or indium. The tin-based alloy can include zinc, tungsten, antimony, indium, germanium, lead, nickel, molybdenum, manganese, iron, cobalt, copper, chromium or bismuth.

At the time of heating, the pressing force is not particularly limited, and it is possible to simply stack the plates, but in order to bond them uniformly, it is preferably 0.01
The range of ~ 200kgf / cm ² is good. The heating conditions are vacuum, inert or non-oxidizing atmosphere and foil or plate temperature of 300.
C. to 650.degree. C., which is lower than the melting point of aluminum or aluminum alloy. If it is less than 300 ° C, the adhesion between the aluminum or aluminum alloy plate and the steel plate is poor. If the melting point is higher than the melting point of aluminum or aluminum alloy, the aluminum melts, which deteriorates workability. The heating time may be in the range of 0.1 seconds to 15 minutes, but it depends on the type and thickness of the aluminum plate or the metal to be coated. If it is less than 0.1 seconds, it is difficult to uniformly bond the aluminum or aluminum alloy plate and the steel plate. It will join even if it exceeds 15 minutes, but it is uneconomical because of high manufacturing cost.
Aluminum clad can be applied to one or both sides of steel foil or steel sheet.

The atmosphere may be an atmosphere containing no oxygen. For example, an atmosphere composed of hydrogen, nitrogen, helium, neon or argon gas is preferable. Further, an atmosphere containing a mixed gas composed of these gases may be used.

[Operation] When copper is interposed between the steel plate and aluminum or aluminum alloy plate, the heating temperature is 300 ° C in a non-oxidizing atmosphere.
To 650 degrees below the melting point of aluminum or aluminum alloy, a strong alloy layer is formed, and this alloy layer joins the steel plate and aluminum or aluminum alloy plate to form an aluminum clad steel plate with excellent bonding strength and work adhesion. It is thought to be obtained. The interposition of nickel, chromium, zinc, tin, lead, or an alloy layer containing these as the main components suppresses the diffusion amount of iron and aluminum due to heat treatment, thus forming a more uniform bonding layer and improving the work adhesion. It is supposed to do.

[Examples] The present invention will be specifically described with reference to Examples.

Example 1 Using an aluminum foil (JIS 1100 material) having a thickness of 100 μm,
-3 Anther (manufactured by Henkel Hakusui Co., Ltd.) was immersed in a solution containing 30 g / at a temperature of 60 ° C. for 5 seconds. Thickness 200 μm
90g / copper pyrophosphate, 33 potassium pyrophosphate
Using a solution containing 0 g /, temperature 50 ℃, current density 5 A / dm
^Under the conditions of ² , copper was plated at 50 g / m ² . Then, stack the aluminum foil and the copper-plated steel sheet, apply a pressure of 0.04 kg / cm ² , and in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas,
The aluminum clad steel plate was obtained by performing heat treatment for 10 minutes at a plate temperature of 610 ° C.

Example 2 An aluminum foil having a thickness of 5 μm (JIS 1070 material) was immersed in a solution containing 50 g / sodium hydroxide at a temperature of 60 ° C. for 5 seconds. 250 μm thick steel plate, copper sulfate 250 g /
, In a solution containing sulfuric acid 50 g / at a temperature of 50 ° C.,
It was dipped and copper was plated at 20 g / m ² on each side. Next, place aluminum foil on both sides of the steel plate to be copper-plated, apply a pressure of 1.0 kgf / cm ² , apply nitrogen gas 95% and hydrogen gas 5
%, An aluminum clad steel plate was obtained by heat treatment for 1 second at a plate temperature of 610 ° C.

Example 3 An aluminum foil having a thickness of 30 μm (JIS 3003 material) was placed in a solution containing 250 g / of copper sulfate and 50 g / of sulfuric acid at a temperature of 40 ° C.
Copper was plated at 10 g / m ^{2 under} the condition of current density of 5 A / dm ² . A copper-plated aluminum alloy foil is stacked on a steel plate with a thickness of 200 μm, a pressure of 0.5 kgf / cm ² is applied, and in an atmosphere of hydrogen gas,
The aluminum clad steel plate was obtained by heat treatment for 30 seconds under the condition that the plate temperature was 600 ° C.

Example 4 An aluminum foil having a thickness of 50 μm (JIS 1070 material) was treated in a solution containing 100 g / sodium hydroxide at a temperature of 60 ° C. and a current density of 10 A / dm ² for 5 seconds using the aluminum foil as a cathode. . Watt bath (240g / of nickel sulfate, 45g / of nickel chloride, 30g / of boric acid) on 100μm thick steel foil
0.01 g / m ² of nickel was plated under the conditions of a temperature of 50 ° C. and a current density of 5 A / dm ² . Then, on a nickel-plated steel foil, using a solution containing 250 g / of copper sulfate and 50 g / of sulfuric acid, at a temperature of 50 ° C. and a current density of 5 A / dm ² , copper was 3 g / m ²
Plated. Next, the aluminum foil and the nickel-plated and copper-plated steel foil are overlaid, a pressure of 0.04 kgf / cm ² is applied, and the foil is heat-treated in the atmosphere of argon gas at a temperature of 630 ° C. for 1 minute to form aluminum. A clad steel plate was obtained.

Example 5 200 μm thick aluminum alloy plate (JIS 5052 material)
2 g / m ^{2 of} copper was plated in a solution containing 250 g / of copper sulfate and 50 g / of sulfuric acid at a temperature of 40 ° C. and a current density of 5 A / dm ² . Next, 90 g / copper pyrophosphate on a 70 μm thick steel foil
Using a solution containing 330 g / potassium pyrophosphate, 3 g / m ^{2 of} copper was plated at a temperature of 50 ° C. and a current density of 5 A / dm ² . Next, the copper-plated aluminum alloy plate and the copper-plated steel foil are overlaid, a pressure of 0.01 kgf / cm ² is applied, and the plate temperature is 650 ° C in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas. Heat treatment was performed for 1 second to obtain an aluminum clad steel plate.

Example 6 Aluminum alloy plate having a thickness of 300 μm (JIS 5082 material)
, Copper pyrophosphate 90g /, potassium pyrophosphate 330g /
10 g / m ^{2 of} copper was plated at a temperature of 50 ° C. and a current density of 5 A / dm ² in a solution containing Then, on a steel foil with a thickness of 30 μm, a Watt bath (240 g of nickel sulfate /, 45 g of nickel chloride)
/, Boric acid 30g /), temperature 50 ℃, current density 10A / d
Nickel was plated at 0.5 g / m ^{2 under} the condition of m ² . On this nickel-plated steel foil, copper sulfate 30g /, ferrous sulfate 300g /
A solution containing 30 g / ammonium sulfate was used to convert the copper-iron alloy plating to 5 g / m ^{2 under} the conditions of a temperature of 50 ° C. and a current density of 10 A / dm ² . Then, after copper-plated aluminum alloy plate and nickel-plated, copper-iron alloy-plated steel foil is overlaid, a pressure of 10 kgf / cm ² is applied, and the plate is placed in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas. Temperature 59
A heat treatment was performed for 1 minute at 0 ° C. to obtain an aluminum clad steel plate.

Example 7 Aluminum alloy plate having a thickness of 200 μm (JIS 3004 material)
A solution containing 5 g / copper sulfate, 5 g / nickel sulfate, 13 g / ammonium tartrate, and 0.025 g / ammonium hydroxide at a temperature of 30 ° C. and a current density of 5 A / dm ² , copper-
The nickel alloy plating was converted to copper and plated at 0.05 g / m ² . Then, on an electrolytic iron foil with a thickness of 15 μm, a Watts bath (nickel sulfate 240 g /, nickel chloride 45 g /, boric acid 30 g /
) Was used to perform nickel plating at 50 g / m ² under conditions of a temperature of 50 ° C. and a current density of 10 A / dm ² . On this nickel-plated iron foil, copper pyrophosphate 90 g /, potassium pyrophosphate 330 g /
Copper was plated at 10 g / m ² under conditions of a temperature of 50 ° C. and a current density of 5 A / dm ² using a solution containing Next, the copper-nickel alloy plated aluminum alloy plate and the nickel-plated and then copper-plated iron foil are overlaid, a pressure of 50 kgf / cm ² is applied, and the temperature of the plate is kept in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas. 58
A heat treatment was performed for 1 minute at 0 ° C. to obtain an aluminum clad steel plate.

Example 8 A 70 μm thick aluminum foil (JIS 1070 material) was
It was immersed for 10 seconds in a solution containing 3 g of Anther (manufactured by Henkel Hakusui Co., Ltd.) at a temperature of 60 ° C. for 10 seconds. On a 210 μm thick steel plate, a Sargent bath (chromic anhydride 250 g /, sulfuric acid
Chromium was plated at 0.01 g / m ^{2 under} the conditions of a temperature of 50 ° C. and a current density of 20 A / dm ² . Next, on a chrome-plated steel plate, copper pyrophosphate 90g /, potassium pyrophosphate 33
Using a solution containing 0 g /, temperature 50 ℃, current density 5 A / dm
Copper was plated at 3 g / m ^{2 under} the condition of ² . Then, stack the aluminum foil and the steel plate plated with chromium and then copper, and press
Apply ² kgf / cm ² and in a nitrogen gas atmosphere, the plate temperature 600
The aluminum clad steel plate was obtained by performing heat treatment for 15 minutes under the condition of temperature.

Example 9 150 μm thick aluminum alloy plate (JIS 5082 material)
Copper pyrophosphate 90g /, potassium pyrophosphate 330g /
Sodium hydroxide was added to the solution containing to adjust the pH to 11.5.
Dipped in the solution prepared as above at a temperature of 60 ° C.
g / m ² plated. Using a solution containing 90 g / copper pyrophosphate and 330 g / potassium pyrophosphate on a tin-plated steel sheet with a thickness of 200 μm coated with tin at 2.8 g / m ² at a temperature of 50 ° C. and a current density of 5
In the conditions of A / dm ^2, copper was 0.05 g / m ² Plating. Then, the copper-plated aluminum alloy plate and the copper-plated tin-plated steel plate are stacked, a pressure of 200 kgf / cm ² is applied, and the plate is heat-treated for 5 minutes in a nitrogen gas atmosphere at a temperature of 301 ° C. A clad steel plate was obtained.

Example 10 A 250 μm thick aluminum plate (JIS 1100 material) was
-3 Anther (manufactured by Henkel Hakusui Co., Ltd.) was immersed in a solution containing 30 g / at a temperature of 60 ° C. for 10 seconds. On a steel foil with a thickness of 50 μm, a Sargent bath (chromic anhydride 250 g /, sulfuric acid
Chromium was plated at ² g / m ² at a temperature of 50 ° C. and a current density of 20 A / dm ² . Then, on the chromium-plated steel foil, copper pyrophosphate 90g /, potassium pyrophosphate 330g
Using a solution containing /, temperature 50 ℃, current density 5A / dm ²
Under the above conditions, copper was plated at 10 g / m ² . Next, stack the aluminum plate and steel foil plated with chromium and then copper, and press
Apply 5 kgf / cm ² and in a nitrogen gas atmosphere, plate temperature 600
The aluminum clad steel plate was obtained by performing heat treatment for 3 minutes under the condition of temperature.

Using the aluminum clad steel plate thus obtained, the following working adhesion test was conducted.

An Erichsen tester (manufactured by Tokyo Koki Co., Ltd.) was used to project 6 mm so that the aluminum or aluminum alloy plate side would project. The overhanging portion of the surface of the aluminum or aluminum alloy plate was cross-shaped with a cutter until it reached the base metal portion, and a peeling test was performed with force using tweezers.

As a result, in the aluminum clad steel sheets according to the present invention of Examples 1 to 10, no peeling of the rolled foil or rolled sheet made of aluminum or aluminum alloy was observed.

[Advantages of the Invention] In the aluminum clad steel plate and the manufacturing method thereof according to the present invention, copper or an alloy layer containing copper as a main component is interposed between a rolled foil or a rolled plate made of aluminum or an aluminum alloy and a steel foil or a steel plate. It is suitable for providing an economical aluminum clad steel sheet, which is characterized by being excellent in joining force and work adhesion.

Claims (4)

(57) [Claims] 1. An electrolytic iron foil, a rolled steel foil or a steel sheet is coated on one or both sides with 0.1 to 50 g / m ² of copper in terms of the amount of copper, and an aluminum foil or aluminum having a thickness of 5 to 300 μm is coated thereon. Alloy foil, aluminum plate or aluminum clad steel plate coated with aluminum alloy plate. 2. A surface of an electrolytic iron foil, a rolled steel foil or a steel sheet, or one or both sides of a rolled foil or a rolled plate made of aluminum or an aluminum alloy having a thickness of 5 to 300 μm.
Copper or an alloy containing copper as the main component is converted into the amount of copper and is 0.
After coating 1 ~ 50g / m ² electrolytic iron foil, rolled steel foil or steel plate, and rolled foil or rolled plate made of aluminum or aluminum alloy, 300 ℃ ~ 650 in an inert or non-oxidizing atmosphere A method for producing an aluminum clad steel sheet, which comprises performing heat treatment in the range of ° C. 3. A surface of an electrolytic iron foil, a rolled steel foil or a steel sheet is coated with nickel, chromium, tin, zinc, lead or an alloy containing them as a main component, and copper or an alloy containing copper as a main component,
After coating 0.1 to 50 g / m ² in terms of the amount of copper, a rolled foil or rolled plate made of aluminum or an aluminum alloy having a thickness of 5 to 300 μm is laid on the coated foil, and 300 The manufacturing method of the aluminum clad steel plate characterized by heat-processing in the range of 650-650 degreeC. 4. A surface of an electrolytic iron foil, a rolled steel foil or a steel sheet coated with nickel, chromium, tin, zinc, lead or an alloy containing these as a main component in an amount of 0.01 to 50 g / m ² or a thickness of 5.
~ 300μm aluminum or aluminum alloy rolled foil or rolled plate on one or both sides, copper or an alloy containing copper as a main component, converted to copper amount of 0.1 ~ 50g / m ² after coating, electrolytic iron foil , Rolled steel foil or steel plate, and rolled foil or rolled plate made of aluminum or aluminum alloy,
A method for producing an aluminum clad steel sheet, which comprises heat-treating in an inert or non-oxidizing atmosphere in the range of 300 ° C to 650 ° C.