JP2000026992A - Ni-PLATED STEEL SHEET - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an Ni-plated steel sheet for a battery can. SOLUTION: Both surface and back faces of a steel stock 10 are provided with Fe-Ni diffusion layers 11A and 11B, furthermore, the thicknesses of the Fe-Ni diffusion layers on both surface and back faces are made different, moreover, the whole body of the surface of the Fe-Ni diffusion layer on both sides is provided with a nonlustrous Ni plating layer 12A, the whole body of at least either surface of the nonlustrous Ni plating layer is provided with a lustrous Ni plating layer 13A, in the sheet thickness direction, the steel stock and the Fe-Ni diffusion layer, the Fe-Ni diffusion layer and the nonlustrous Ni plating layer and the nonlustrous Ni plating layer and lustrous Ni plating layer are laminated respectively via almost rectilineal boundaries.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Ni-plated steel sheet, and more particularly, to an Ni-plated steel sheet provided with an Fe--Ni diffusion layer for strengthening the bonding between the steel base and the Ni plating layer to enhance the adhesion of plating. , Corrosion resistance, workability, and specularity.

[0002]

2. Description of the Related Art Conventionally, products in which a normal cold-rolled steel sheet is plated with Ni have been manufactured. However, in the case where the Ni plating layer is provided directly on the surface of the steel substrate, the adhesion between the plating layer and the steel substrate is not good. Therefore, depending on its shape, the Ni plating layer follows the deformation of the steel plate depending on its shape. And peeling may occur. In addition, since the Ni plating layer is hard and brittle, cracks are likely to occur even in areas where exfoliation has been avoided, and even if the amount of plating is increased, the generation of pinholes cannot be avoided. For the various reasons described above, the Ni-plated steel sheet having the Ni-plated layer directly provided on the surface of the steel sheet has problems in workability, corrosion resistance and the like.

In order to solve the above problem, for example, as disclosed in Japanese Patent Application Laid-Open No. 61-235594, a steel substrate is coated with Ni at a deposition amount of 9 to 62 g / m ² , 600-8 in neutral or reducing gas atmosphere
Perform an annealing treatment by heating and holding at 00 ° C. for 1 minute to 15 hours.
There is provided a method of forming a Fe—Ni diffusion layer between a steel substrate and a Ni plating layer by diffusing the steel substrate and the Ni plating layer. As described above, when the metallurgically bonded Fe—Ni diffusion layer is provided at the interface between the steel base and the Ni plating layer, the adhesion of the plating layer to the steel base is increased, and the corrosion resistance, workability, and the like are improved. be able to.

[0004]

However, in the above-mentioned conventional method, it is extremely difficult to make the thicknesses of the Fe—Ni diffusion layer, the Ni plating layer, and the steel base material substantially uniform and constant. It is difficult, and as shown in FIG. 27, the thicknesses of the three layers of the steel substrate 1, the Fe—Ni diffusion layer 2 and the Ni plating layer 3 are not constant. The above-mentioned problem that the thickness of each layer is not constant is that, after performing Ni plating on the steel substrate with all the necessary adhesion amounts, the plating is performed in a state where the Ni plating layer is left on the surface layer of the plating layer. This is caused by an attempt to form an Fe—Ni diffusion layer by annealing treatment only at the interface between the layer and the steel substrate.

[0005] That is, there are a batch annealing method and a continuous annealing method as the above-mentioned annealing method. In the case of batch annealing, for example, a coil-shaped Ni-plated steel sheet is usually stacked in an annealing vessel. Annealed and gradually heated from the outside to the inside of the coil, from the upper stage to the lower stage of the stacking stage. For example, when the temperature is set to 600 ° C., a portion having a low temperature of 550 ° C. appear. Because of the different temperature distributions, the diffusion of Fe-Ni starts early on the outside and on the upper side of the coil where the temperature is high, while the diffusion starts on the inside and on the lower side with a delay, and thus the thickness of the generated Fe-Ni diffusion layer. Inevitably causes non-uniformity. Therefore, as shown in comparison with FIG. 28, the portion where the temperature is low has a small thickness of the Fe—Ni diffusion layer 2, and therefore the thickness of the Ni plating layer is large, and the portion where the temperature is high is a Fe—Ni diffusion layer. The thickness of the diffusion layer 2 is large, and thus the thickness of the Ni plating layer is small. In particular, in the part where the temperature is extremely high, the entire Ni plating layer becomes the Fe—Ni diffusion layer 2 and
The i-plated layer does not remain on the surface layer side, and the Fe-Ni diffusion layer penetrates into the steel base, and the thickness of the steel base itself becomes uneven. Further, in the case where the plated steel sheet is formed in a coil shape, if the temperature is set to a high temperature of 700 ° C. or more, the Ni plating layers on the wound surface may adhere to each other.

Normally, when the Fe-Ni diffusion layer is formed between the steel substrate and the Ni plating layer by batch annealing using the above-mentioned conventional method, in practice, the purpose is to provide an Fe-Ni diffusion layer of about 3 μm. After annealing at 500 to 700 ° C. for 10 to 36 hours for a long time, the thickness of the formed Fe—Ni diffusion layer varies from 1 to 7 μm. On the other hand, in the case of continuous annealing, the temperature is set to a high temperature for heating in a short time, for example, annealing is performed at 800 ° C. for about 0.5 to 4 minutes. Since the diffusion speed is high and the diffusion is performed in a short time, the thickness of the Fe—Ni diffusion layer 2 cannot be controlled. Therefore, as in the case of the batch annealing, a uniform diffusion layer having a constant thickness cannot be formed.

[0007] As described above, the steel substrate is subjected to an annealing process after all the necessary amount of Ni plating is applied to the steel substrate, and Ni surface is applied to the surface portion of the Ni plating layer.
In the method of forming a Fe—Ni diffusion layer at the interface between the steel substrate and the Ni plating layer while leaving the plating layer, Fe—N
The i-diffusion layer cannot be made uniform and constant in thickness. However, it is indispensable for the Ni-plated steel sheet to have a uniform and uniform thickness of the Fe-Ni diffusion layer. If the thickness is not uniform, a product manufactured by post-processing such as pressing. A problem arises. That is, Fe-Ni
In a portion where the diffusion layer is thinner than the required thickness, the corrosion resistance is inferior. In a portion where the Fe-Ni diffusion layer is thicker than the required thickness, cracks occur during processing, and the corrosion resistance is significantly impaired.

Further, different thicknesses of F on both the front and back surfaces of the steel sheet.
In the case where an e-Ni diffusion layer and / or a Ni plating layer are provided, in the conventional method, as in the case of the single side, FIG.
As shown in FIG. 1, after forming different Ni plating layers 4A and 4B by applying different total plating amounts to both surfaces of the steel base 1, annealing treatment is performed, and the Fe-N
Thus, i diffusion layers 2A and 2B are formed. However, it is difficult to accurately and arbitrarily control the thickness of the Fe—Ni diffusion layer even on only one side, so that the Fe—Ni
The thickness of each of the diffusion layers and the N on the surface of these Fe-Ni layers
It is also very difficult to control the thickness of the i-plated layer.
For example, since the temperature of the front and back of the steel sheet is the same during the annealing process, the thickness of the Ni plating layer 4A required for the thick Ni plating layer 4A is reduced.
When an attempt is made to form a -Ni diffusion layer, in the portion where the annealing temperature is high, the entire Ni plating layer in the thin Ni plating layer 4B becomes an Fe-Ni diffusion layer, and the Ni plating layer is eliminated. .

In a molded product made of this type of Ni-plated steel sheet, the required thickness of the same or different thickness on both front and back surfaces is obtained.
An e-Ni diffusion layer and / or a Ni plating layer may be required. For example, when corrosion resistance is particularly required on one of the front side and the back side, it is necessary to meet the requirement by making the Fe—Ni diffusion layer on one side thicker than the other side. However, as described above, it is difficult to control the thickness of the Fe—Ni diffusion layer by the conventional method, so that it is natural to form the Fe—Ni diffusion layer and / or the Ni plating layer having a different thickness. It was difficult.

Furthermore, the Ni-plated steel sheet manufactured by the above-mentioned conventional method usually forms an Fe-Ni diffusion layer after applying a matte plating and performing a full plating, so that the manufactured Ni-plated steel sheet is manufactured. The surface layer portion of the plated steel sheet has a drawback that the mirror finish is not sufficient. In particular, when the Ni-plated steel sheet manufactured by the above method is deep drawn, for example, as shown in FIG.
As shown in FIG. 6, the positive side portion 6 of the battery casing 5
When manufactured by deep drawing, there was a defect that gloss was completely lost due to a large degree of processing of the deep drawn portion, and that the plus side of the battery, which was seen as an external appearance, was not glossy, resulting in reduced product value.

The present invention has been made in view of the problems of the above-described conventional Ni-plated steel sheet, a molded product made of the Ni-plated steel sheet, and a method of manufacturing the same, and has as its main objects the following points. The thickness of the Fe-Ni diffusion layer provided on at least one of the front and back surfaces of the steel substrate is made uniform. The thickness of the Fe—Ni diffusion layer provided on at least one of the front and back surfaces of the steel base can be arbitrarily controlled. Since the thickness of the Fe—Ni diffusion layer can be arbitrarily controlled, the same or different thickness of F
An e-Ni diffusion layer can be formed. When manufacturing a molded product from a Ni-plated steel sheet provided with an Fe-Ni diffusion layer, a molding process such as press working is performed using Fe
-It can be appropriately selected before or after the Ni plating step after the formation of the Ni diffusion layer.

[0012]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a steel base material having Fe-Ni diffusion layers on both front and back surfaces thereof, different thicknesses of the Fe-Ni diffusion layers on both front and back surfaces, and A matte Ni plating layer is provided on the entire surface of the Fe-Ni diffusion layers on both sides, and a gloss Ni plating layer is provided on at least one entire surface of the matte Ni plating layer. Diffusion layer, Fe-Ni diffusion layer and matte Ni plating layer, matte Ni plating layer and gloss N
It provides a Ni-plated steel sheet in which each of the i-plated layers is laminated via a substantially linear interface.

The thickness of the matte Ni plating layers on both sides laminated on the Fe—Ni diffusion layer is the same or different.

Further, the present invention provides a steel base material having F
While having an e-Ni diffusion layer, the thickness of the Fe-Ni diffusion layers on both the front and back surfaces is made different, and a matte Ni plating layer is provided on the whole surface of the one Fe-Ni diffusion layer, while the other Fe -A bright Ni plating layer is provided on the entire surface of the Ni diffusion layer, and the steel base and the Fe-Ni diffusion layer
The present invention provides a Ni-plated steel sheet in which a Ni diffusion layer and a matte Ni plating layer, and an Fe-Ni diffusion layer and a bright Ni plating layer are each laminated via a substantially linear interface.

The thickness of the matte Ni plating layer laminated on one side of the Fe—Ni diffusion layer and the thickness of the glossy Ni plating layer laminated on the other side are the same or different.

Further, according to the present invention, the steel base is provided with a Fe-Ni diffusion layer having a constant thickness in the range of 1.0 μm to 8.0 μm on both sides thereof, and the thickness of the Fe—Ni diffusion layer on both sides is different. And at least one of the Fe—Ni diffusion layers has a matte Ni plating layer of 1.0 to 6.0 μm,
3.5μ bright Ni plating layer, or 1.0-6.
The present invention provides a Ni-plated steel sheet provided with a 0.2-1.5 µm bright Ni-plated layer on the surface of a 0 µm matte Ni-plated layer.

As described above, in the present invention, at least one of the front and back surfaces of the steel substrate is Ni-plated with an appropriate thickness, and the Ni plating is entirely changed to Fe by a subsequent annealing process. -By using a Ni diffusion layer,
The main feature is that the thickness of the Fe-Ni diffusion layer can be arbitrarily controlled, and the thickness of the Fe-Ni diffusion layer is made uniform and uniform over the entire surface. This makes it possible to provide Fe—Ni diffusion layers and / or Ni plating layers having the same or different thicknesses on the front and back surfaces of the substrate.

As described above, the Fe—Ni diffusion layer may be formed only on one of the front and back surfaces of the steel substrate.
Alternatively, it may be formed on both front and back surfaces, and when formed on both front and back surfaces, the thickness of the Fe—Ni diffusion layers on both front and back surfaces can be the same or different. In addition, the Ni plating layer may be any one of a matte Ni plating layer alone, a glossy Ni plating layer only, and a glossy Ni plating layer laminated on the surface of the matte Ni plating layer.

The Ni-plated steel sheet is subjected to Ni plating at a thin thickness on at least one of the front and back surfaces of the steel base, and then annealed by heating in a neutral or reducing gas atmosphere. All the plating was formed as a Fe-Ni diffusion layer, a Fe-Ni diffusion layer having a constant thickness was formed on the surface of the steel substrate, and after temper rolling, the surface of the Fe-Ni diffusion layer was subjected to Ni plating (that is, Ni plating). , Matte Ni plating only, shiny Ni plating only, or matte Ni plating on the surface of the Ni plating by any one of three methods of applying shiny Ni plating) to obtain a steel base material and an Fe-Ni diffusion layer. And Ni-plated steel sheets in which Ni-plated layers are laminated with a substantially linear interface therebetween.

[0020] The first N
The i-plating is performed by forming the same thickness Ni plating on the front and back surfaces of the steel substrate simultaneously or separately on one surface to form an Fe-Ni diffusion layer of the same thickness. In the case where a different thickness of Ni-plating is applied to the back side after the application, and a different thickness Fe-Ni diffusion layer is formed, and a different thickness of Ni plating is applied simultaneously to the front and back surfaces of the steel substrate, This includes the case where a -Ni diffusion layer is formed.

Further, at least one of the front and back surfaces of the steel substrate is plated with Ni with a small thickness, and then heated and annealed in a neutral or reducing gas atmosphere. -Forming a Fe-Ni diffusion layer of a certain thickness on the surface of the steel substrate as a Ni diffusion layer, and then performing temper rolling, and then cutting the steel sheet provided with the Fe-Ni diffusion layer into required dimensions. Then, the cut steel sheet is press-formed to form a molded product composed of a container or the like. Then, at least one surface of the Fe-Ni diffusion layer on one side of the molded product is formed with Ni.
Plating may be applied to produce a molded product made of Ni-plated steel sheet.

The above-described method of manufacturing a molded product also includes a case where the thickness of the Fe—Ni diffusion layer formed on the front and back surfaces of the steel base is the same and a case where the thickness is different.

As described above, the Ni-plated steel sheet of the present invention is obtained by subjecting a thin Ni plating applied to a steel substrate to an annealing treatment in a neutral or reducing gas atmosphere so that all of the Ni plating is made of an Fe—Ni diffusion layer. After that, Ni plating is performed, so that an Fe—Ni diffusion layer having a uniform thickness can be formed, and the thickness of the Fe—Ni diffusion layer can be arbitrarily controlled.

In addition, the Ni-plated steel sheet manufactured by the above method has a diffusion layer having an arbitrary thickness on the surface of the steel base and a uniform thickness over the entire surface, so that the thickness of the diffusion layer becomes more than necessary. There is no portion that is too thin or too thick, and no variation occurs in workability and corrosion resistance. In addition, after forming the Fe-Ni diffusion layer, Ni
In order to form the plating layer, it is possible to reliably form an Ni plating layer of an arbitrary thickness (including the difference thickness and the same thickness) on both the front and back surfaces of the steel base, and to apply a bright Ni plating on the surface. The specularity can also be improved.

Further, when using a method of forming a steel sheet provided with an Fe—Ni diffusion layer with a press or the like and then plating with a barrel plating device or the like, when cracks occur during press bending, Ni plating is performed later. This can compensate for the problem of crack generation. In addition, it is possible to solve the case where the glossiness during press bending is reduced.

[0026]

Next, the present invention will be described in detail with reference to the embodiments shown in the drawings. FIG. 1 shows a Ni-plated steel sheet according to a first embodiment of the present invention, and one side (front side) of a steel substrate.
Is provided with a Fe-Ni diffusion layer and a Ni plating layer, and a method for manufacturing the Ni-plated steel sheet is shown in FIGS.

In FIG. 1, reference numeral 10 denotes a steel base made of a normal cold-rolled steel sheet, and the steel base 10 in the embodiment is an unannealed material, but may be an annealed material. Reference numeral 11 denotes an Fe—Ni diffusion layer having a substantially constant thickness laminated on one surface (surface) of the steel substrate 10, reference numeral 12 denotes a matte Ni plating layer laminated on the surface of the Fe—Ni diffusion layer 11, and 13.
Is a glossy plating layer laminated on the surface of the matte Ni plating layer 12.

The above-described steel substrate 1 laminated in the thickness direction
0, each of the Fe—Ni diffusion layer 11, the matte plating layer 12, and the glossy plating layer 13 has a substantially constant thickness in the length direction of the steel sheet as shown in the figure, and the interfaces Ll, L
2, L3 is substantially linear. Therefore, in any cross section in the thickness direction of the steel sheet, the steel substrate 10, Fe-N
The proportions of the i-diffusion layer 11, the matte plating layer 12, and the glossy plating layer 13 are substantially constant.

A method of manufacturing the Ni-plated steel sheet shown in FIG. 1 will be described with reference to FIGS. First, as shown in FIG. 2, as a first plating treatment, the surface of a steel base 10 of an unannealed ordinary cold-rolled steel sheet wound into a coil is unwound by electroplating to 1.5 to 1.5 mm. 9.0 g / m
^The Ni plating 15 is applied to a thickness of ² and then wound into a coil.

Next, in order to diffuse the Ni-plated layer and the steel sheet base into the coiled steel sheet after the first plating, the coiled steel sheet is put into a container or the like using a batch annealing apparatus. An annealing process is performed. Processing conditions include N
₂ Heated to 500-900 ° C in a gas atmosphere, 0.5
Hold for minutes to 36 hours. By this heat treatment, the Ni plating layer is diffused with the steel base to form the Fe—Ni diffusion layer 11. At this time, as shown in FIG.
Are all diffused and the Ni plating layer is lost,
-Annealing treatment is performed until the Ni diffusion layer 11 is obtained. The Fe
The thickness of -Ni diffusion layer 11 is determined in correspondence with the coating weight of the first round (1.5~9.0g / ^{m 2),} 1.0
It is preferable to set the range to 8.0 μm.

The Fe—Ni diffusion layer 11 formed by the above annealing treatment has a constant thickness without being affected even if the annealing temperature varies in the coil. This is because the Ni adhered in the first plating is diffused all the way to the surface layer and the Fe-Ni
The reason for this is that the first Ni
Since the amount of adhesion is extremely small as compared with the conventional case, the Fe—Ni diffusion layer does not bite into the steel base even in a high temperature portion, and the thickness of the Fe—Ni diffusion layer 11 and the steel base 10 is small. Can be kept constant, and
The interface Ll between the steel substrate 10 and the Fe-Ni diffusion layer 11 has a substantially linear shape.

The thickness of the Fe—Ni diffusion layer 11 is
As described above, it is determined by the amount of the first Ni plating adhesion.
Therefore, the thickness of the Fe—Ni diffusion layer 11 to be formed can be simplified.
You can simply control it. For example, the first N
2.0 g / m i-plated coating weight ²In the case of
The thickness of the spray layer is approximately 1.5 to 2.0 μ, 5.0 g / m²Place
In this case, it is approximately 2.5 to 3.0 μ.

It is preferable that the thickness of the Fe--Ni diffusion layer 11 formed be between 1.0 and 8.0 .mu.m, and if the thickness of the diffusion layer is 1.0 .mu. Adhesion deteriorates, causing a problem in corrosion resistance when the product is used. On the other hand, if the thickness is 8.0 μ or more, since the Fe—Ni diffusion layer is hard, cracks occur during deep drawing and the like. This is because it is significantly impaired. The thickness of the Fe—Ni plating layer 11 is more preferably 2 to 5 μm, and most preferably 3 μm.

The gas atmosphere for the above annealing treatment is not limited to N ₂ gas, but may be other reducing gas or H ₂ and N ₂ gas.
A neutral gas such as a mixed gas of No. ₂ may be used. When the above annealing treatment is completed, temper rolling of about 1.5 to 2.0% is performed. By this temper rolling, the entire steel sheet, in particular, the steel substrate 10
The thickness of the steel sheet and the shape of the steel sheet are adjusted, and hip breakage is prevented.

Next, as a second plating process, Ni plating is performed by electrolytic plating, and as shown in FIG.
Matte Ni plating is performed at an adhesion amount of 9.0 to 54 g / m ² to form a 1 to 6 μ Ni plating layer 12. By forming the matte Ni plating layer 12 on the Fe—Ni diffusion layer 11, a Ni plating layer having a set constant thickness can be formed.

After the matte plating layer 12 is formed by the second plating, Ni plating is performed by electrolytic plating as a third plating treatment. In the third plating process, a small amount of an organic substance is added to the Ni solution to obtain a bright Ni solution.
The plating is performed so that the formed Ni plating layer has a mirror surface. This bright Ni plating layer 13 is 1.8
The thickness is 0.2 to 1.5 μm with an adhesion amount of １３13.5 g / m ² , and the manufacturing process is completed by forming the third bright plating layer 13, and the Ni plating shown in FIG. The steel plate is formed in a state of being wound in a coil shape.

In the case where the surface layer of the Ni-plated steel sheet does not need to have a mirror surface, the third bright plating is not required.

Although the above embodiment uses the electroplating method as the plating method, other suitable plating methods, for example,
It goes without saying that an electroless plating method, a vapor deposition plating method, or the like may be used.

FIG. 5 shows a second reference embodiment in which the same thickness of Fe—Ni diffusion layer and the same thickness of Ni plating are applied to both the front and back surfaces of the steel base. Ni of the same thickness on both sides of this embodiment
The method of manufacturing the plated steel sheet is the same as that of the above-described reference embodiment. First, Ni plating with the same adhesion amount is simultaneously applied to both the front and back surfaces of the steel substrate 10 by the electrolytic method. Next, an annealing treatment is performed under the same conditions as those for the one side of the first embodiment,
The Ni plating layers on both front and back sides and the steel substrate 10 are diffused to form Fe—Ni diffusion layers 11A and 11B having a constant thickness. Next, matte Ni plating is applied to the outer surfaces of the Fe-Ni diffusion layers on both the front and back surfaces with the same adhesion amount by an electrolytic method,
The matte plating layers 12A and 12B are formed. Finally, bright plating is performed to form bright plating layers 13A and 13B on the surface layer portions on both the front and back surfaces of the steel plate.

In the case of Ni plating with the same thickness on the front and back sides, the thickness of each layer can be easily controlled to a constant width and an arbitrary thickness. The Ni plating layer can be easily formed. still,
When plating with the same thickness on the front and back surfaces, the plating is performed simultaneously on the front and back surfaces in the above-described embodiment. However, plating may be performed separately on each surface to have the same thickness on the front and back surfaces.

FIG. 6 shows a third embodiment in which the same thickness of Fe—Ni diffusion layers is formed on both the front and back surfaces of a steel sheet, and the outer surfaces of these Fe—Ni diffusion layers are plated with Ni having different thicknesses. It was done. In this embodiment, the matte Ni plating layer formed on the outer surface of each of the Fe—Ni diffusion layers 11A and 11B having the same thickness is such that the surface layer 12A is thicker than the rear surface layer 12B. Also, a glossy plating layer 13A is formed only on the front side of the matte plating layer 12A on the front side, and no glossy plating layer is provided on the back side. If necessary, a glossy plating layer may be provided on the outer surface of the matte plating layer on the back side, and the thickness of the glossy plating layer may be different from the thickness of the glossy plating layer on the front side.

FIG. 7 shows Ni according to the first embodiment of the present invention.
This shows a steel plate having a difference in thickness between Fe-Ni diffusion layers 11A and 11B on both front and back surfaces of a steel substrate 10.
The Ni-plated steel sheet is provided with a thick Fe-Ni diffusion layer 11B on the back side of the steel base 10 as shown in the figure, while a thin Fe-Ni diffusion layer 11A is provided on the front side of the steel base 10.
And a matte Ni plating layer 12A and a matte Ni plating layer 12A on the surface side of the Fe—Ni diffusion layer 11A on the front side.
A surface is provided with a bright Ni plating layer 13A.

In the first embodiment, the thickness of the Fe—Ni diffusion layer 11B on the back surface is 6 μm, the thickness of the steel substrate 10 is 250 μm, and the thickness of the Fe—Ni diffusion layer 11A on the front surface is 3 μm. The thickness of the matte Ni plating layer 12A is 3 μm, and the thickness of the glossy Ni plating layer 13A is 0.5 μm.

The Ni-plated steel sheet according to the first embodiment is manufactured by the steps shown in FIGS.

That is, first, a Ni plating 11A 'having a required thickness is applied to the surface side of the steel substrate 10 (unannealed ordinary cold steel plate). Next, Ni plating 11B 'having a required thickness is applied to the back surface of the steel substrate 10. In this embodiment, 0.5
μ and 0.8 μ on the back side. Steel base 1 described above
The plating for each of the front side and the back side with respect to 0 is performed by the plating apparatus shown in FIGS. 10 to 14, and the plating apparatus and operation will be described later.

After Ni plating of a different thickness is applied to both the front and back surfaces of the steel base 10, in order to diffuse the Ni plating layer and the steel base, annealing is performed in a batch or continuous manner as in the first embodiment. Has been treated. By the annealing treatment,
Ni plating 11A ', 11 on both sides of the steel base 10
B ′ is diffused with the steel substrate 10 and the Fe—Ni diffusion layer 11 is diffused.
A and 11B are formed. Each Fe—Ni diffusion layer 11
The thickness of A, 11B is determined according to the amount of plating applied,
On the surface side plated with 0.5 μm, a 3 μm thick Fe
One Ni diffusion layer 11A is formed, and a Fe-Ni diffusion layer 11B having a thickness of 6 µ is formed on the back surface side on which plating of 0.8 µ is applied. As described above, the thickness of the Fe—Ni diffusion layer to be formed can be arbitrarily and accurately controlled according to the amount of plating attached to both surfaces of the steel base.

When the above annealing treatment is completed, about 1.5 to
Perform 2.0% temper rolling. By this temper rolling, the entire steel plate, in particular, the thickness of the steel substrate 10 and the shape of the steel plate are adjusted, and the buckling is prevented.

After the temper rolling is completed, the Fe-N
The surface side of the i-diffusion layer 11A is provided with a matte Ni plating at an arbitrary thickness to provide a matte Ni plating layer 12A, and the surface side of the matte Ni plating layer 12A is further provided with a glossy Ni plating. A plating layer 13A is provided.

In the first embodiment, the surface side Fe-Ni
Matte Ni plating and bright Ni only for diffusion layer
Although a plating layer is provided by lamination, the back side Fe-Ni
The diffusion layer may also be formed by laminating a matte Ni plating layer and a glossy Ni plating layer, and only one or both sides of the Fe-Ni diffusion layer having the different thickness may have only the same thickness or the same thickness of the matte Ni plating or Only bright Ni plating may be adhered.

Next, a Ni plating apparatus and a plating method for each of the front and back surfaces of the steel substrate 10 will be described with reference to FIGS.

The Ni plating method for one side of the steel substrate 10 is generally performed by unwinding a sheet-shaped steel substrate 10 wound in a coil shape as shown in FIG. The first tank 40 conveys N
After the i-plating 11A 'is applied, the steel substrate is continuously conveyed to the second tank 41, the Ni base 11B' is applied to the back side of the steel base 10, and the Ni base 11A 'and 11B' are applied to the front and back surfaces. 10 is wound in a coil shape.

Specifically, above the inlet side of the first tank 40,
A conductor roll 42 is provided in contact with the sheet-shaped steel base 10 and using the steel base 10 as a cathode. The conductor roll 42 also serves as a guide roll for guiding the steel base 10 into the first tank 40. First tank 40 and second tank
The tank 41 has a similar structure.
And the description of the second tank 41 will be omitted.

As shown in the figure, a pair of front and rear partition walls 44 are installed inside a horizontally long rectangular outer tank 43 over the entire length thereof, and the left and right outer walls 43a of the partition wall 44 and the outer tank 43 are provided.
To form a plating tank 45 surrounded by. Guide rolls 46 and 47 are provided on both left and right sides of the plating tank 45 at a slight distance from the upper surface of the partition wall 44, and
A conductor roll 48 is provided above the guide roll 47 on the outlet side (right side in the figure). Therefore, the sheet-shaped steel base material 10 unwound from the coil is connected to the conductor roll 4.
2, guide rolls 46 and 47 and conductor roll 4
8, is inserted into the first tank 40, is horizontally conveyed along the upper surface of the partition wall 44 of the plating tank 45, is led out of the first tank 40 at the outlet side, and is guided to the second tank 41. I will At that time, in the first tank 40, the lower surface of the steel substrate 10 facing the upper surface of the partition wall 44 is the front surface side, and in the second tank 41, the lower surface of the steel substrate 10 facing the upper surface of the partition wall 44 is the back surface side. Is set to

An anode ball 49 (cathode ball) is arranged inside the plating tank 45, and a nozzle pipe 50 for ejecting a plating solution is installed at one end in the length direction (steel base material conveying direction) of the plating tank 45. The plating solution is discharged into the plating tank 45. The plating solution fills the inside of the plating tank 45 and is discharged to such an extent that it overflows from the gap between the upper surface of the partition wall 44 and the lower surface of the steel substrate 10. Therefore, only the lower surface of the steel substrate 10 located on the upper surface of the plating tank 45 is plated by the plating solution. The overflowing plating solution is supplied to the outer tank 43.
Drain holes 5 which are collected in the plating solution reservoirs 51 on both front and rear sides between the plating tank 45 and the bottom of the other end of the plating tank 45.
It is discharged from 2. The drain hole 52 is connected to a drain tube 53, and the plating solution is collected in a plating solution reservoir 54 through the drain tube 53. A plating solution is supplied from the plating solution reservoir 54 by a pump 55 through a supply pipe 56 to the nozzle pipe 5.
0 to circulate the plating solution.

In the above-described apparatus, since only the lower surface of the sheet-like steel substrate 10 supported by the guide roll is positioned on the upper surface of the plating tank, plating is applied only to the lower surface. In this way, the sheet-like steel substrate unwound from the coil body can be plated on both sides one by one, so that both sides can be plated with the same thickness. And plating can be performed.

The method of plating one side of the steel substrate on each of the front and back surfaces is not limited to the above method. For example, it can be immersed in a plating bath with one surface sealed. It is also possible to simultaneously apply a plating of a different thickness to both the front and back surfaces of the steel base.

FIGS. 15 and 16 show that Fe-
1 shows a container 100 molded from a Ni-plated steel sheet in which a Ni diffusion layer and a Ni plating layer are laminated. As will be described later, the container 100 has a first method in which an Fe—Ni diffusion layer is formed on the surface of a steel substrate, and then subjected to Ni plating and then press-molded, and a Fe—Ni diffusion layer is formed. After cutting the steel plate to the required dimensions, press molding to form a container,
It can be manufactured by the second method of manufacturing by applying Ni plating to the container.

First, a method of manufacturing the container 100 by forming a Fe—Ni diffusion layer, performing Ni plating, and press-forming the Ni-plated steel sheet, which is the first method, will be described.

FIG. 17 and FIG.
As shown in FIG. 8, the difference in thickness of Fe-
The Ni diffusion layers 11A and 11B are formed. In this embodiment, the backside Fe—Ni diffusion layer 11B is thicker than the frontside Fe—Ni diffusion layer 11A. The steel sheet provided with the Fe—Ni diffusion layer on both front and back surfaces is temper rolled. Next, N is applied only to the surface of the Fe-Ni diffusion layer 11A on the front side.
i-plating (in this embodiment, Ni plating is only glossy Nl plating) and wound around a coil. Next, after the coil body is cut into required dimensions, a cylindrical molded product 100 having one end opening shown in FIGS. 15 and 16 is manufactured by press molding.

As described above, before press forming, N
In the case of performing i-plating and press-molding after completing the plating process, automation is easy depending on the line,
High productivity and cost reduction.

FIGS. 19 and 20 show a container manufacturing process according to the second method, in which both sides of the steel base 10 are simultaneously plated with Ni of the same thickness, and both sides of the steel base 10 have the same thickness. Fe-Ni diffusion layers 11A and 11B are formed. The coiled body of the steel sheet provided with the above-mentioned Fe-Ni diffusion layers 11A and 11B is slitted (cut) in a coil shape to each dimension width, and then a continuous press machine (not shown).
To form a molded product 100 'composed of a cylindrical container having one end open as shown in FIGS.

After the above press molding, the molded container 10
0 ′ is plated with Ni. As the plating, a plating method (commonly called glass plating) using a barrel plating apparatus 30 shown in FIGS. 21 to 23, which is usually used when plating a molded product, is preferably used.

In the barrel plating apparatus 30, 31
Denotes an anode (+), 32 denotes a cathode (-), and the plating tank 33
An anode plate 34 connected to the anode 31 is hung in the plating bath, and a cathode contact 36 is provided on a barrel (cage) 35 filled with the molded article 100 ′, and the cathode contact is connected to the cathode 32. ing.

A large number of molded articles 1 are placed inside the barrel 35.
00 ′ are filled in contact with each other. For example,
In the case of AA batteries, several hundred to several thousand cases can be filled into the barrel at one time. The barrel 35 filled with the molded product 100 ′ is plated while rotating inside the plating tank 33. When plating a cylindrical container by this barrel plating method, it is impossible to make the plating thickness of each container uniform, and plating is almost completely adhered to the outer surface side of the container with a required thickness. However, the plating hardly adheres to the inner surface side because the containers overlap each other or the shape is cylindrical, and the plating adheres only thinly. Therefore, the cylindrical container 100
On the inner surface side, a Ni plating layer is formed on the surface of the Fe—Ni diffusion layer 11B unevenly and only very thinly.
On the outer surface side of the container 100, there is a disadvantage that a Ni plating layer having a substantially required thickness is laminated on the surface of the Fe—Ni diffusion layer 11A.

However, in general, when plating is performed by the above-described barrel plating method or spot plating (octopus hanging plating), the plating adheres thickly to the projections, so that the plating is thickly applied to the 90 ° bent portion of the cylindrical container 100 ′. It has the property of adhering, and since this portion is also a portion where cracks are likely to occur at the time of press bending in the previous step, Fe-
In the method of performing press molding after forming the Ni diffusion layer and then performing plating again, even if cracks are generated in the portion during press molding, the plating is thickly attached, so Ni plating is performed after forming the Fe-Ni diffusion layer. After application, there is an advantage that a container 100 having better corrosion resistance is manufactured than a press-molded molded product.

As a plating method for the molded article, spot plating (commonly called an octopus hanging plating method) in which each molded article is suspended from a plating bath by a hook or the like, as described above, is possible. Not so suitable for high.

In the above-described embodiment, the Ni plating to be barrel-plated is composed of matte Ni plating and glossy Ni plating.
Plating is performed to form a matte Ni plating layer on the surfaces of the Fe—Ni diffusion layers 11A and 11B, and then a matte Ni plating is performed by another barrel plating apparatus.
A bright Ni plating layer is formed on the surface of the plating layer.

FIGS. 24 and 25 show the difference in the thickness of Fe--Ni.
This shows a step of press-forming the steel sheet on which the diffusion layers 11A and 11B are formed, and then applying Ni plating by barrel plating or the like.

In the press-formed container 100 ′, the thin Fe—Ni diffusion layer 11 A on the front side is the cylindrical outer surface, and the thick Fe—Ni diffusion layer 11 B on the rear side is the inner surface. In the present embodiment, the case where particularly corrosion resistance is required on the inner surface side of the container is taken into consideration, due to the relationship between the members to be filled in the cylindrical container. Therefore, when corrosion resistance is required on the outer surface side from the inner surface side of the container, for example, especially in the case of a battery case or the like where the outer surface is required to have corrosion resistance, the back surface side with the thick Fe-Ni diffusion layer is referred to as the outer surface side of the container. It is preferable to perform press molding so that In this case, cracks are apt to occur on the outer surface side where the Fe-Ni diffusion layer is thick, when the drawing angle is set to 90 degrees, but the cracks can be protected by Ni plating after the molding.

[0070]

[Experimental example] The Ni-plated steel sheet according to the present invention and the conventional N
The corrosion resistance test of the i-plated steel sheet was performed.

As a test piece, as shown in the following table,
No. 1 according to the first embodiment of the present invention. 1, 2, 3
No. Ni-plated steel sheet and the conventional No. Four and five Ni-plated steel sheets were provided. As shown in the table, three types of Ni of the present invention were used.
For plated steel sheets, change only the amount of plating applied for the first time,
The other conditions are the same, and the thickness of the Fe—Ni diffusion layer is 1.6 μm, 2.6 μm, and 4.5 μm, respectively. Conventional Ni
The plated steel sheet is obtained by directly forming a Ni plating layer on a steel base.

The test method was based on the JIS before and after the deep drawing of each test piece in the shape of the top casing of the AA battery shown in FIG. 26, and before and after the processing.
A salt spray test according to Z2371 was carried out. The method of examining the corrosion resistance based on 8 was adopted.
After the deep drawing, the corrosion resistance of the corner portion of the portion A in FIG. 26 was examined. As a result, as shown in the table, in the Ni-plated steel sheets according to the present invention, almost no difference was observed in the corrosion resistance between before and after processing. on the other hand,
Prior to processing, the conventional Ni-plated steel sheet did not show a significant difference in corrosion resistance from the Ni-plated steel sheet of the present invention, but the corrosion resistance after processing was significantly inferior to the Ni-plated steel sheet according to the present invention. From the above experiments, it was confirmed that the Ni-plated steel sheet according to the present invention did not decrease in corrosion resistance even after processing.

[0073]

As is apparent from the above description, according to the present invention, the Ni plating applied to the steel substrate is annealed,
In order to make all of the Ni plating a Fe-Ni diffusion layer, an Fe-Ni diffusion layer having a uniform thickness can be provided, and the thickness of the Fe-Ni diffusion layer can be controlled to an arbitrary thickness. Can be done. In addition, such a uniform thickness of Fe-N
Since Ni plating is performed on the surface of the i-diffusion layer, the thickness of the Ni-plated layer can be made uniform, and thus a Ni-plated steel sheet having a uniform thickness of the Fe-Ni diffusion layer and the Ni-plated layer is manufactured. be able to.

Further, since the thickness of the Fe—Ni diffusion layer itself can be arbitrarily controlled, it is possible to form the same or different thickness Fe—Ni diffusion layer and Ni plating layer on both front and back surfaces of the steel base. Become.

Since the Ni-plated steel sheet manufactured by the above method has a uniform thickness of the Fe—Ni diffusion layer and the Ni plating layer, the thickness of the Fe—Ni diffusion layer is small as in the related art. Since it is not too thick or too thick, there is no variation in corrosion resistance after processing into a product.

In addition, since a Ni plating layer is formed on the surface of the Fe—Ni diffusion layer, when a bright Ni plating is performed, even when deep drawing is performed, a mirror surface of the Ni plated steel sheet surface can be ensured, and the quality can be improved. Can be improved.
In particular, when forming into a molded product by pressing or the like after forming the Fe-Ni diffusion layer, and then performing plating by barrel plating or the like, the cracks generated during the molding process should be protected by covering by post plating. In addition, there is an advantage that the mirror finish can be surely ensured due to the post plating. On the other hand, an Fe-Ni diffusion layer is formed,
When forming by press working etc. after applying Ni plating, the Ni plating thickness can be arbitrarily selected according to the way, such as applying the same thickness on both sides, difference thickness, or applying Ni plating only on the required surface, and Since a uniform plating thickness can be ensured on the entire surface, it is possible to stabilize and improve the quality, and it is easy to mount on an automation line, and thus N
This has the advantage that a container made of an i-plated steel sheet can be manufactured.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a Ni-plated steel sheet according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view illustrating a manufacturing method according to the first embodiment.

FIG. 3 is a cross-sectional view illustrating a manufacturing method according to the first embodiment.

FIG. 4 is a cross-sectional view showing a manufacturing method according to the first embodiment.

FIG. 5 is a sectional view of a Ni-plated steel sheet according to a second embodiment of the present invention.

FIG. 6 is a cross-sectional view of a Ni-plated steel sheet according to a third embodiment of the present invention.

FIG. 7 is a cross-sectional view of the Ni-plated steel sheet according to the first embodiment of the present invention.

FIG. 8 is a block diagram illustrating a manufacturing process of the first embodiment.

FIG. 9 is a cross-sectional view schematically showing the manufacturing process of the first embodiment.

FIG. 10 is a schematic view of a single-side plating apparatus for a steel substrate used in the above manufacturing process.

11 is a plan view of a first plating tank shown in FIG.

FIG. 12 is a sectional view taken along line XX of FIG. 11;

FIG. 13 is a sectional view taken along line YY of FIG. 11;

FIG. 14 is a sectional view taken along the line ZZ in FIG. 11;

FIG. 15 is a perspective view of a container molded from a Ni-plated steel sheet according to the present invention.

FIG. 16 is a sectional view of the container shown in FIG.

FIG. 17 is a block diagram showing a manufacturing process according to a first method of the container.

18 is a cross-sectional view schematically showing the manufacturing process shown in FIG.

FIG. 19 is a block diagram showing a manufacturing process according to a second method of the container.

FIG. 20 is a sectional view schematically showing the manufacturing process of FIG. 19;

FIG. 21 is a schematic plan view of a barrel plating apparatus used in a manufacturing process.

FIG. 22 is a schematic sectional view of FIG.

FIG. 23 is a view showing a state where a container is filled in the barrel.

FIG. 24 is a block diagram of a manufacturing process showing a modification of the second method.

FIG. 25 is a schematic sectional view of the manufacturing process shown in FIG. 24;

FIG. 26 is a sectional view of a top casing of a battery manufactured for an experimental example.

FIG. 27 is a cross-sectional view illustrating a defect of a conventional Ni-plated steel sheet having a Fe—Ni diffusion layer.

FIG. 28 is a cross-sectional view showing a conventional defect in comparison.

FIG. 29 is a cross-sectional view showing a conventional defect of a double-sided Ni-plated steel sheet having an Fe—Ni diffusion layer.

[Explanation of symbols]

 1, 10 ... steel plate base 2, 11 (11A, 11B) ... Fe-Ni diffusion layer 3, 12 (12A, 12B) ... Ni plating layer 13 ... gloss plating layer 100 ... container

Claims (5)

[Claims] 1. A steel base material comprising an Fe--Ni diffusion layer on both front and back surfaces, different thicknesses of the Fe--Ni diffusion layers on both front and back surfaces, and a matte Ni over the entire surface of the Fe--Ni diffusion layers on both sides. A plating layer, a glossy Ni plating layer on at least one entire surface of the dull Ni plating layer, a steel base and a Fe-Ni diffusion layer in a thickness direction, a Fe-Ni diffusion layer and a dull Ni plating layer, Matte Ni plating layer and glossy N
A Ni-plated steel sheet in which each of the i-plated layers is laminated via a substantially linear interface. 2. The Ni-plated steel sheet according to claim 1, wherein the thickness of the matte Ni plating layers on both sides laminated on the Fe—Ni diffusion layer is the same or different. 3. The steel base material is provided with an Fe—Ni diffusion layer on both front and back surfaces, the thicknesses of the Fe—Ni diffusion layers on both front and back surfaces are made different, and the entire surface of one side of the Fe—Ni diffusion layer is dull. While a Ni-plated layer is provided, a bright Ni-plated layer is provided on the entire surface of the Fe-Ni diffusion layer on the other side. , A Ni-plated steel sheet in which each of an Fe—Ni diffusion layer and a bright Ni plating layer is laminated via a substantially linear interface. 4. The method according to claim 3, wherein the thickness of the matte Ni plating layer laminated on one side of the Fe—Ni diffusion layer is the same as or different from the thickness of the glossy Ni plating layer laminated on the other side. Ni plated steel sheet. 5. A steel base having a surface of 1.0 μ to 8.0 μ on both sides.
And the thickness of the Fe-Ni diffusion layers on both the front and back surfaces is made different, and at least one of the Fe-Ni diffusion layers has a thickness of 1.0 to 6.0.
μ matte Ni plating layer, 0.2-3.5 μ gloss Ni
A Ni-plated steel sheet comprising a plating layer or a matte Ni plating layer of 1.0 to 6.0 µm and a bright Ni plating layer of 0.2 to 1.5 µm on the surface.