JPH02117783A - Aluminum clad steel plate and its manufacture - Google Patents

Abstract

PURPOSE:To improve joining force and working adhesion by interposing a Cu or Cu alloy layer having specific thickness between a steel plate and Al or an Al alloy. CONSTITUTION:The Cu or Cu alloy layer having 0.01-10mum thickness is joined to rolled foil or a rolled plate made of the Al or Al alloy on one surface or both surfaces of electrolytic Fe foil, rolled steel foil or the steel plate surface. Namely, when Cu is interposed between the steel plate and the Al plate, the firm alloy layer is formed in the temperature range below the Al melting point in a nonoxidizing atmosphere and this alloy layer joins the steel plate to the Al plate and the Al clad steel plate excellent in joining force and working adhesion can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an aluminum clad steel sheet with excellent corrosion resistance, workability, work adhesion, and adhesion to an organic coating, and a method for producing the same.

[Prior Art] At present, aluminum or aluminum alloy plates have oxides on their surfaces, so they have excellent corrosion resistance, and have low work hardening, so they have excellent workability, but they are expensive. On the other hand, although steel plates are inexpensive, they have the disadvantage of being susceptible to red rust. Therefore, as a way to compensate for the drawbacks of aluminum plates and steel plates, cladding materials of aluminum plates and steel plates are being developed. As a method of joining aluminum plates and steel plates, there is a method of joining by cold rolling (Japanese Patent Application Laid-Open No. 5345759).
No., JP-A-55-68195, JP-A-56-1091
No. 83, JP-A-58-14N182, JP-A-61-6
No. 7581), bonding method using organic adhesive (Japanese Patent Application Laid-open No. 1983
-223683) or a bonding method using a resin adhesive film (Japanese Patent Laid-open No. 63-40689), but since the oxides present on the surface of aluminum are strong, the processing adhesion and Inferior in 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 is required after rolling.

[Problems to be Solved by the Invention] Conventional methods for producing aluminum clad steel sheets require an organic adhesive, which poses problems in terms of heat resistance and adhesive strength. In the cold rolling method, since the amount of plastic deformation is different between the aluminum plate and the steel plate, the clad material curls, requiring softening annealing, which complicates the process.

Furthermore, the method of removing aluminum oxide in a high vacuum has problems in terms of cost.

[Means for Solving the Problems] Accordingly, the present invention provides a method for producing aluminum clad steel sheets that uses a clad material that is inexpensive and has excellent bonding strength and process adhesion, without using an organic adhesive, and with low pressure. The purpose is to provide

The gist is electrolytic iron foil, rolled steel foil (hereinafter abbreviated as steel foil).
Or steel plate or copper, nickel, chromium, zinc, tin,
Between the surface of a steel foil or steel plate coated with lead or an alloy containing lead as a main component and the surface of a rolled foil or plate made of aluminum or aluminum alloy with a thickness of 5 to 300 μm, a copper or copper-based alloy Copper is added to the bonding layer by interposing an alloy layer and heat-treating the foil or plate in an inert or non-oxidizing atmosphere at a temperature ranging from 300°C to 650'C, below the melting point of aluminum or aluminum alloy. Or the copper alloy layer is 0
．． An object of the present invention is to provide an aluminum clad steel plate coated with aluminum on one or both sides and having a thickness of 01 to 10 μm.

The present invention will be explained in detail below.

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. In addition, steel plates include low carbon steel plates, chromium-added steel plates, nickel diffusion treated steel plates, and copper, nickel, chromium, and tin steel plates.

Includes steel sheets coated with zinc, lead, or alloys containing these as main ingredients. Of course, the surface of the steel plate that is not coated with the aluminum foil or plate can be subjected to chromate treatment or phosphate treatment.

On the other hand, a rolled foil or plate made of aluminum or an aluminum alloy is an aluminum or aluminum alloy plate manufactured by a rolling method and has a thickness of 5 to 300 μm. Examples of the aluminum alloy plate include alloy plates containing magnesium, manganese, silicon, copper, iron, zinc, chromium, titanium, or zirconium. 5
If the thickness is less than μm, workability decreases, manufacturing cost increases, and it is uneconomical. Moreover, if it exceeds 300 μm, it is uneconomical in terms of material cost.

Next, in order to obtain good bonding force and processing adhesion,
Copper or an alloy containing copper as a main component is coated on the surface of an IR foil, a steel plate, or an aluminum or aluminum alloy plate in an amount of 0.1 to 50 g/m 2 in terms of copper.

It is preferably 1 to 30 g/m2, when the aluminum or aluminum alloy plate is not coated with copper or an alloy mainly composed of copper, and when a strong oxide layer is formed on the surface of the aluminum or aluminum alloy.

It is easier to bond more uniformly by using an alkaline solution to remove aluminum oxides by immersion, cathodic treatment, or anodic treatment. In that case, the amount of gold/copper on the bonding surface may be 0.1 to 50 g/m2: f is good; if it is less than 0.1 g//, sufficient bonding force cannot be obtained; Exceeding this amount is uneconomical in terms of manufacturing costs. Further, before coating the steel plate with copper or an alloy mainly composed of copper, 0.01 to 50 g/m2 of nickel, chromium, tin, zinc, lead, or an alloy mainly composed of these may be coated. In addition, a steel plate coated with copper, nickel, chromium, tin, zinc, lead, or an alloy containing these as the main ingredients may be used.In the case of chromium or an alloy containing chromium as the main ingredient, 0.01~2g/
I/May be coated, or pre-coated with the metal or alloy mentioned above.

When coating copper or an alloy containing copper as the main component, it is sufficient to coat 0.1 to 50 g/m2 in terms of copper amount, preferably 0.5 to 20 g/yj.In this way, nickel is coated in advance. When coated with chromium, zinc, tin, lead, or an alloy containing these as main ingredients, the bonding layer becomes more uniform and the adhesion is further improved. Nickel amount is 50g/
m2, the amount of chromium is 2 g/w? If it exceeds , processing adhesion will be poor.

The method of coating copper, nickel, chromium, tin, zinc, lead, or alloys containing these as main components is not particularly limited, but these methods include electroplating, chemical plating, or vacuum evaporation plating. There is a law. Copper-based alloys can include cobalt, bismuth, iron, germanium, indium, manganese, molybdenum, nickel, tin, antimony, tellurium, thallium, zinc or tungsten. Nickel-based alloys can include molybdenum, manganese, niobium, chromium, indium, cobalt, steel, iron, aluminum, germanium, rhodium, ladle, tellurium, titanium, thallium, tungsten, antimony, or zinc. Alloys with chromium as the main component include cobalt, iron, manganese,
It can include molybdenum, tin, vanadium, nickel or tungsten. Alloys based on zinc include zirconium, tungsten, vanadium, thallium,
It can contain antimony, lead, nickel, iron, molybdenum, manganese, copper, cobalt, pot or indium. Alloys based on tin include zinc, tungsten,
It can include antimony, indium, germanium, lead, nickel, molybdenum, manganese, iron, cobalt, copper, chromium or bismuth.

During heating, the pressing force is not particularly limited, and it is sufficient to simply overlap the plates, but in order to bond uniformly, it is preferably 0.0
A range of 1 to 200 kgf/- is preferable.

The heating conditions are preferably such that the temperature of the foil or plate is in the range of 300°C to 650°C, below the melting point of aluminum or aluminum alloy, in a vacuum, inert or non-oxidizing atmosphere; below 300°C, aluminum or aluminum alloy is heated. Adhesion between the plate and the steel plate is poor. If the temperature is above the melting point of aluminum or aluminum alloy, aluminum will melt into a layer, impairing workability. The heating time may be in the range of 0.1 seconds to 15 minutes, but it varies depending on the type and thickness of the aluminum plate or the metal to be coated. 0.1
If the time is less than 1 second, it is difficult to uniformly bond the aluminum or aluminum alloy plate and the steel plate, and if it takes more than 15 minutes, the bonding will still be possible, but the manufacturing cost will be high and this is uneconomical. Aluminum cladding can be applied to one or both sides of the steel foil or sheet.

The atmosphere may be any atmosphere that does not contain oxygen.

For example, an atmosphere containing hydrogen, nitrogen, helium, neon, or argon gas is preferable, or an atmosphere containing a mixed gas of these gases may be used.

[Effect 1: When copper is present between the steel plate and the aluminum or aluminum alloy plate, the heating temperature is 300°C in a non-oxidizing atmosphere.
In the range of 650°C 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, resulting in an aluminum-clad steel plate with excellent bonding strength and work adhesion. This is considered to be what can be obtained. When nickel, chromium, zinc, tin, lead, or an alloy layer containing these as main components is present, the amount of diffusion of iron and aluminum during heat treatment is controlled by D, forming a more uniform bonding layer and improving processing adhesion. This is expected to improve.

[Example] The present invention will be specifically explained with examples.

Example 1 Aluminum foil (JIS 1100 material) with a thickness of 100 μm was mixed with P-3 Anzer (manufactured by Henkel Hakusuisha) at 30 g/l.
It was immersed in a solution containing I for 5 seconds at a temperature of 60°C. Copper pyrophosphate 90g/i on a 200μm thick steel plate
t, 50g/m2 of copper was plated using a solution containing 330g/l of potassium birophosphate at a temperature of 50°C and a current density of 5A/d♂.Next, an aluminum foil and a copper-plated steel plate were layered, A pressure of 0.04 kgf/cd was applied and heat treatment was performed for 10 minutes at a plate temperature of 610°C in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas to obtain an aluminum clad steel plate.

Example 2 Aluminum i (JIS 1070 material) with a thickness of 5 μm was immersed for 5 seconds at a temperature of 60° C. in a solution containing 50 g/II of sodium hydroxide. Thickness 250μ
m steel plate, copper sulfate 250 g/lI, il! In a solution containing 50g/41 of acid at a temperature of 50°C,
9 which was immersed and plated with 20g/m2 of copper on both sides.
Next, aluminum foil was placed on both sides of the copper-plated steel plate, and a pressure of 0 kgf/- was applied, and heat treatment was performed for 1 second at a plate temperature of 610°C in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas. An aluminum clad steel plate was obtained.

Example 3 A 30 μm thick aluminum alloy foil (lI33003 material) was heated with copper in a solution containing 250 g/f of copper sulfate and 50 g/l of sulfur at a temperature of 40° C. and a current density of 5 A/d m. Copper-plated aluminum alloy foil was layered on a 200 μm thick steel plate, and a pressure of 0.5 kgf/ad was applied in a hydrogen gas atmosphere.
Heat-treat the plate for 30 seconds at a temperature of 600°C to obtain an aluminum-clad aluminum plate.

Example 4 Aluminum foil with a thickness of 50 μm (JIS 1070 material)
in a solution containing 100 g/l of sodium hydroxide,
The treatment was carried out for 5 seconds at a temperature of 60° C. and a current density of 10 A/d♂ using an aluminum foil as a cathode. Thickness 100μ
Using a Watts bath (nickel sulfate 240 g/j, nickel chloride 45 g/i, real acid 30 g/J), nickel was added to a steel foil of m at a temperature of 50°C and a current density of 5 A/d m2. The Ni-plated steel foil was then coated with 250 g/m of copper acid and 50 g/m of sulfuric acid.
Using a solution containing g/f, aluminum foil was plated with 3 g/m2 of copper at a temperature of 50°C and a current density of 5 A/ds/. Next, aluminum foil and steel foil that was nickel-plated and then copper-plated were layered. , applying a pressure of 0.04 kgf/d,
A heat treatment was performed for 1 minute at a foil temperature of 630° C. in an argon gas atmosphere to obtain an aluminum clad steel plate.

Example 5 Aluminum alloy plate with a thickness of 200 μm (JIS 505
2), copper sulfate 250 g/It, iEa 50 g/
In a solution containing jl, the temperature was 40°C and the current density was 5A/d.
Lol? Next, a solution containing 90 g/l of pyrophosphate steel and 330 g/J2 of potassium pyrophosphate was applied to a 70 μm thick steel foil plated with 2 g/m2 of copper at a temperature of 50°C and a current density of 5 A/da. ” under the condition of 3g/copper
Next, a copper-plated aluminum alloy plate and a copper-plated steel foil were stacked and a pressure of 0.01 kgf/
ad, and heat treatment was performed for 1 second at a plate temperature of 650° C. in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas to obtain an aluminum clad steel plate.

Example 6 Aluminum alloy plate with a thickness of 300 μm (JIS 508
2) was plated with copper at 10 g/s+'' in a solution containing 90 g/J of copper pyrophosphate and 330 g/It of potassium pyrophosphate at a temperature of 50°C and a current density of 5 A/d♂. , a Watts bath (nickel sulfate 240 g/iI, nickel chloride 45 g/iI) was applied to a 30 μm thick steel foil.
jl, boric acid 30 g/j)) at a temperature of 5
Nickel plating was performed at 0.5 g/m2 at a current density of 10 A/d g/ at 0°C. This nickel-plated steel foil was coated with 30 g/tI of copper sulfate and 300 g/tI of ferrous sulfate.
Using a solution containing 30 g/l of ammonium sulfate, the copper-iron alloy plating is 5 g/l in terms of copper under the conditions of a temperature of 50°C and a current density of 10 A/dwi.
W? Next, a copper-plated aluminum alloy sheet and a nickel-plated, copper-iron alloy-plated steel foil were stacked together, a pressure of 10 tgf/- was applied, and the plate was heated in an atmosphere containing 95% nitrogen gas and 5% hydrogen gas. A heat treatment was performed for 1 minute at a plate temperature of 590°C to obtain an aluminum clad steel plate.

Example 7 Aluminum alloy plate with a thickness of 200 μm (JIS 300
4), copper sulfate 5g/l, nickel sulfate 5g/J,
Using a solution containing 13 g/jl of ammonium tartrate and 0.025 g/N of ammonium hydroxide, the copper-nickel alloy plating was converted into copper under the conditions of a temperature of 30°C and a current density of 5 A/d m. 0.05g/
Then, on the electrolytic iron foil with a thickness of 15 μm,
Watt bath (nickel sulfate 240g/4, nickel chloride 4
5g/II, boric acid 30g/), temperature 50°C,
Nickel plating was carried out at 50 g/m2 at a current density of 10 A/drm.The nickel-plated iron foil was coated with a solution containing 90 g/jl of pyrophosphate steel and 330 g/jl of potassium pyrophosphate. At a temperature of 50℃ and a current density of 5A/d♂, 10g/d of copper was
Next, a copper-nickel alloy plated aluminum alloy plate and a nickel-plated and body-plated iron foil were stacked, a pressure of 50 kgf/- was applied, and a nitrogen gas of 95% was applied.
In an atmosphere containing 5% hydrogen gas, the temperature of the plate was 580℃.
An aluminum clad steel plate was obtained by heat treatment for 15 minutes under the following conditions.

Example 8 Aluminum foil with a thickness of 70 μm (JIS 1070 material)
was immersed for 10 seconds at a temperature of 60° C. in a solution containing 30 g/l of P-3 Amplifier (manufactured by Henkel Hakusuisha). Chromium was removed from a 210 μm thick steel plate using a Sargent bath (chromic anhydride 250 g/f, sulfuric acid 2.5 g/l) at a temperature of 50°C and a current density of J*20 A/d♂.
．． 01 g/■2 plated 0 Next, a solution containing 90 g/A' of pyrophosphate steel and 330 g/II of potassium pyrophosphate was applied to the chromium-plated steel plate at a temperature of 5.
0℃, current density 5A/dWI? 3 g of copper under the conditions of
/ Wi-plated first, then aluminum foil and chrome-plated, then body-plated steel plate, stacked together under a pressure of 2 kgf/-
Then, heat treatment was performed for 15 minutes at a plate temperature of 600° C. in a nitrogen gas atmosphere to obtain an aluminum clad steel plate.

Example 9 Aluminum alloy plate with a thickness of 150 μm (JIS 508
Material 2) was added to a solution containing 90 g/l of pyrroline-coated copper and 330 g/II potassium pyrophosphate to adjust the pH to 1.5 at a temperature of 60°C. Copper was plated at 0.05g/wl by dipping. A 200 μm thick damaged steel plate coated with 2.8 g/m2 of tin was heated at a temperature of 50°C and a current density of 5 A/d♂ using a solution containing 90 g/41 of birophosphate steel and 330 g/41 of potassium pyrophosphate. Under the conditions, 0.05g of copper
/m2f> 0 Next, the copper-plated aluminum alloy plate and the copper-plated tin-plated steel plate were stacked and the pressure was 2
00 kgf/-, heat treatment was performed for 5 minutes at a plate temperature of 301° C. in a nitrogen gas atmosphere to obtain an aluminum clad steel plate.

Example 10 Thickness 250. um aluminum plate (JIS 1100
material), P-3 Anther (manufactured by Henkel Hakusuisha) 30g/
The sample was immersed for 10 seconds at a temperature of 60° C. in a solution containing L. Sargent bath (m water) was applied to a 50 μm thick steel foil.
Omj12250 g/11, hat! 122.5 g
/f) at a temperature of 50°C and a current density of 20A/d.
Then, 90 g of copper birophosphate was applied to the chromium-plated steel foil.
/ 1. Using a solution containing 330 g 71 J of potassium pyrophosphate, copper was plated at 10 g/m2 at a temperature of 50°C and a current density of 5 A/d/. Next, an aluminum plate was plated with 10 g/m2 of copper, followed by chromium plating and subsequent plating of steel. The foils were stacked, a pressure of 5 kgf/- was applied, and heat treatment was performed for 3 minutes at a plate temperature of 600°C in a nitrogen gas atmosphere to obtain an aluminum clad steel plate.

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

Using an Erichsen tester (manufactured by Tokyo Hoshiki), the aluminum or aluminum alloy plate side is bulged out.
It overhangs by 6mm. A cutter was used to scratch the overhanging part of the surface of the aluminum or aluminum alloy plate in a cross pattern until it reached the base metal part, and a forced peeling test was conducted using tweezers.

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

[Effects of the Invention] The aluminum clad steel sheet and the method for manufacturing the same according to the present invention include the interposition of a copper or copper-based alloy layer between a rolled foil or rolled sheet made of aluminum or an aluminum alloy and a steel foil or steel sheet. It is characterized by excellent bonding strength and processing adhesion, and is suitable for providing economical aluminum clad steel sheets.

Claims (6)

[Claims] (1) A method of joining rolled foil or rolled plate made of aluminum or aluminum alloy to one or both surfaces of electrolytic iron foil, rolled steel foil, or steel plate, in which a copper or copper alloy layer is added to the joining layer. 0.01~1
An aluminum clad steel plate characterized by having a thickness of 0 μm. (2) In a method of joining a rolled foil or plate made of aluminum or aluminum alloy to one side of an electrolytic iron foil, rolled steel foil, or steel plate surface, a copper or copper alloy layer of 0.01 to 100% is added to the joining layer. Aluminum cladding with a thickness of 10 μm and copper, nickel, chromium,
An aluminum clad steel sheet characterized by being coated with tin, zinc, lead, or an alloy containing these as main ingredients. (3) Aluminum or aluminum alloy on one or both surfaces of electrolytic iron foil, rolled steel foil, or steel sheet surface coated with copper, nickel, chromium, zinc, tin, lead, or alloys containing these as main components. An aluminum clad steel sheet, characterized in that the joining layer has a copper or copper alloy layer of 0.01 to 10 μm in thickness. (4) Copper or copper as a main component is applied to the surface of electrolytic iron foil, rolled steel foil, or steel plate, or to one or both surfaces of rolled foil or plate made of aluminum or aluminum alloy with a thickness of 5 to 300 μm. After coating the alloy with a copper content of 0.1 to 50 g/m^2,
Layer electrolytic iron foil, rolled steel foil, or steel plate and rolled foil or plate made of aluminum or aluminum alloy, and heat-treat the foil or plate at a temperature in the range of 300 to 650°C in an inert or non-oxidizing atmosphere. A method for producing an aluminum clad steel sheet. (5) After coating the surface of electrolytic iron foil, rolled steel foil, or steel plate with nickel, chromium, zinc, tin, lead, or alloys containing these as main components, convert copper or alloys containing copper as main components into copper. A rolled foil or rolled plate made of aluminum or aluminum alloy with a thickness of 5 to 300 μm is layered on the surface of the foil or plate in an inert or non-oxidizing atmosphere. A method for producing an aluminum clad steel sheet, which comprises performing heat treatment at a temperature in the range of 300 to 650°C. (6) The surface of electrolytic iron foil, rolled steel foil, or steel plate coated with copper, nickel, chromium, zinc, tin, lead, or an alloy containing these as main components at 0.01 to 50 g/m^2, or a thickness of 5 to 50 g/m^2 Copper or an alloy mainly composed of copper is applied to one or both surfaces of a rolled foil or plate made of aluminum or aluminum alloy with a thickness of 300 μm in an amount of 0.1 to 50 g/m^ in terms of copper content. 2 After coating, layer the electrolytic iron foil, steel foil or steel plate with a rolled foil or plate made of aluminum or aluminum alloy, and heat the foil or plate to a temperature of 300 to 650°C in an inert or non-oxidizing atmosphere. A method for producing aluminum clad steel sheets, which is characterized by subjecting them to heat treatment within a range.