JPH0919985A - Clad material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a clad material which can be made simply with the use of seam welding and has high joining strength. SOLUTION: A Ni-type metal layer 2 is laminated on an Fe-type base metal layer, and a metal net 3 is laminated on the Ni-type metal layer 2 from the opposite side of the Fe-type base metal layer 1. On the opposite side of the Ni-type metal layer 2, a corrosion resistant metal coat layer 4 is placed on the metal net 3, and the Fe-type base metal layer 1, the Ni-type metal layer 2, the metal net 3, and the corrosion resistant metal coat layer 4 are bonded by a seam welding part which is formed in a shape of line or surface by a roller electrode 6. The corrosion resistant metal coat layer 4 is made from a metal containing Ti, Zr, Nb, Ta, or Ni as a main component or stainless steel.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to Fe-based or C-based
The present invention relates to a clad material in which a corrosion-resistant metal coating layer is joined to a u-based base metal by seam welding.

[0002]

2. Description of the Related Art Conventionally, as a method for joining a corrosion-resistant metal coating layer such as Ti or Zr to a Fe-based or Cu-based base metal, a corrosion-resistant metal plate is superposed on the surface of the base metal plate and arranged on it. Explosive pressure welding method that uses the explosive force of the explosives to press them together, rolling method that rolls the base metal plate and the corrosion resistant metal plate that are laminated on each other by rolling rolls, and joins them, and also spot welding is used How to do
Various things have been implemented or proposed.

[0003]

The above-mentioned conventional method has the following problems. (1) In the explosive pressure welding method, noise is generated due to the explosion of explosives, so that there are many cases where the place of implementation is restricted. Further, there are many restrictions on the size and shape of the clad material that can be manufactured, and the manufacturing cost is relatively high. Further, it is not suitable for manufacturing a thin plate-shaped clad material, and in order to obtain such a thin plate-shaped clad material, it is necessary to further subject the thick plate to explosive pressure welding and then further rolling. . (2) In the rolling method, the clad material that can be produced is limited to the plate-shaped one, and a large-scale rolling facility is required. Further, there is a problem that the base metal having a curved surface cannot be coated, and the flexibility of the shape of the base metal is lacking. Further, only by rolling, the joining force tends to be insufficient as compared with the explosive pressure welding method and the like, and diffusion heat treatment after rolling is often required, and there is a drawback that the man-hour and cost are likely to increase. (3) In the method using spot welding, it is necessary to form a large number of spot-like spot welded portions, and therefore joining takes time. Further, since it is a point-joint, the joining force is likely to be insufficient, and furthermore, it is difficult to obtain a sealing property between the base metal and the corrosion-resistant metal coating.

An object of the present invention is to provide a clad material which is easily manufactured by using seam welding and has excellent bonding strength.

[0005]

Means for Solving the Problem, Action and Effect The clad material according to claim 1 of the present invention is characterized by the following constitution in order to solve the above problems. That is, a Ni-based metal layer is laminated on a Fe-based base metal layer composed of Fe or an Fe alloy, and a metal net is further laminated on the Ni-based metal layer from the side opposite to the Fe-based base metal layer. To be done. Then, on the side opposite to the Ni-based metal layer, a corrosion-resistant metal coating layer is arranged in contact with the metal net, and the Fe-based base metal layer, the Ni-based metal layer, the metal net and the corrosion-resistant metal coating layer are linearly formed by the roller electrode. Alternatively, they are joined by a seam weld formed in a plane shape. The corrosion resistant metal coating layer is made of a metal containing any one of Ti, Zr, Nb, Ta and Ni as a main component, or stainless steel. This realizes a clad material in which the corrosion-resistant metal coating layer and the base metal layer are firmly bonded. Note that F
The e-based base metal layer can be made of, for example, carbon steel, stainless steel, or other alloy steel.

In the clad material having the above-mentioned structure, a Ni-based metal layer, a metal net, and a corrosion-resistant metal coating layer are laminated in this order on the base metal layer, and a roller electrode is applied in the laminating direction to apply electricity. By doing so, the laminated body is heated by resistance, and in that state, the roller electrode is relatively rotated with respect to the laminated body to form a seam welded portion. In this case, the laminated body can be sandwiched between a plurality of roller electrodes to conduct electricity. On the other hand, a method of performing seam welding without sandwiching the laminate by roller electrodes,
For example, a roller electrode is arranged on the corrosion-resistant metal coating layer side, and another roller electrode is arranged correspondingly on the same side, and at least the corrosion-resistant metal coating layer, the metal net and the Ni-based metal layer are arranged from one roller electrode side. After penetrating and bending in the lateral direction along the laminated surface, the so-called series seam welding method is used, in which each layer is penetrated again in the reverse order of the above to form an energization path leading to the other roller electrode side and welding is performed. You can also The energizing current may be either an alternating current or a direct current.

Since the metal mesh has a mesh, it has a small current-carrying cross-sectional area and a small contact area with the adjacent Ni-based metal layer and corrosion-resistant metal coating layer, so that resistance heat generation is particularly large in the vicinity thereof. The metal mesh that has reached a high temperature bites into at least one of the corrosion-resistant metal coating layer and the base metal layer softened by the heat generated by the pressure applied by the roller electrode, and the biting effect or the increase in the joint area due to the unevenness of the metal mesh increases. Based on the above, it is speculated that the bond strength between the corrosion resistant metal coating layer and the base metal layer is enhanced.

The Ni-based metal layer is presumed to have at least one of the following functions. (1) A liquid phase is generated by melting at least a part of itself due to resistance heat generation or by melting together with a part of the base metal layer or the metal net, and the liquid phase forms a metal net and the base metal layer Supplied to the contact part. Since Ni and its alloy have good wettability with the Fe-based material forming the base metal layer, the resulting liquid phase acts as a kind of brazing filler metal, and the Ni and the alloy between the metal network and the base metal layer. It works to increase the bond strength. Also, the generated liquid phase is also supplied to the mesh of the metal mesh, and in the case of the mesh, the liquid phase also serves as a brazing material for joining the corrosion-resistant metal coating layer and the base metal layer or the corrosion-resistant metal coating layer and the metal mesh. It is possible. (2) Even if the liquid phase does not occur, at least a part of the components diffuses and alloys into the metal mesh and the base metal layer due to resistance heating, and further into the corrosion-resistant metal coating layer through the mesh. This serves to increase the bond strength between them.

As the Ni-based metal layer, a liquid phase excellent in fluidity and wettability is generated by resistance heating, so that Cr,
Ni alloy containing at least one of B, Si, C, P, Mo, W and Fe, particularly Ni as a main component, 5 to 16
Alloys containing wt% Cr, 2-4 wt% B, 3.5-5.5 wt% Si and 2-5 wt% Fe can be preferably used.

Thus, the functions of the metal net and the Ni-based metal layer realize a clad material in which the corrosion-resistant metal coating layer and the base metal layer are firmly bonded. In particular, due to the brazing effect or diffusion bonding effect of the Ni-based metal layer,
The welding pressure and welding current during seam welding can be kept low compared to the case of producing a clad material without using a system-based metal layer, so the thickness of the base metal layer or corrosion-resistant metal coating layer is Even if it is large, a good joining state can be obtained by a relatively small pressing force or welding current.

If the metal net is made of a material harder than the corrosion-resistant metal coating layer in the vicinity of the welding temperature, the effect of biting of the metal mesh into the corrosion-resistant metal coating layer side is increased, so that the joining strength is increased. It can be further enhanced. Further, by adjusting the amount of heat generated by the heat generated in the metal mesh and its contact portion so that the corrosion-resistant metal coating layer is appropriately softened, penetration of the metal mesh into the corrosion-resistant metal coating layer is promoted and the metal mesh and the corrosion-resistant metal The binding force with the coating layer can be made stronger. Further, by forming the metal net and the corrosion-resistant metal coating layer with materials having a good affinity for each other, the joint strength between the two can be increased. In this case, "excellent in affinity" means, for example, that the mutual diffusivity in the vicinity of the bonding temperature is excellent, or that the wettability with a liquid phase generated by melting a part of them is excellent. Means

As a specific example, a combination in which the metal network is composed mainly of Fe-based material and the corrosion-resistant metal coating layer is composed of a metal whose main component is either Ti or Zr can be exemplified. In this case, excellent results are obtained in both the bonding effect due to the mutual diffusion of both layers and the biting effect of the metal net. As the Fe-based material forming the metal net, various stainless steels (for example, SUS304 alloy) are unlikely to cause rust on the net surface, and have a relatively high electrical resistivity and excellent heat generation when energized. Are preferably used.

As the material of the metal net, in addition to Fe, N
A material containing i or Cu as a main component can also be used. In such a metal net, the corrosion-resistant metal coating layer is N
It can be suitably used when it is made of a metal containing any one of b, Ta, and Ni as a main component, or stainless steel. The metal nets of these materials have a liquid phase generated by melting a part of them at the time of seam welding, and have excellent wettability with the corrosion-resistant metal coating layer of the above-mentioned materials. It becomes possible to achieve good bondability.

The Ni-based metal layer may include a metal foil containing Ni as a main component (claim 2). The metal foil has good thermal conductivity, functions as a kind of heat sink that dissipates heat generated from the seam weld, and prevents oxidation of the part where seam welding is not completed on the joint surface of the corrosion-resistant metal coating layer. The effect is obtained. On the other hand, the Ni-based metal layer is
It may be a plating layer formed on the base metal layer. The plating layer can be formed by electrolytic plating, electroless plating, various vapor phase film forming methods such as vapor deposition and sputtering. The Ni-based metal layer can also be a powder layer of a metal containing Ni as a main component. As a method for forming the powder layer, there can be exemplified a method in which a metal powder is kneaded in a paste form with a flux or the like and applied to the base metal layer. Alternatively, the Ni-based metal layer can be formed by spraying a metal powder on the base metal layer.

Next, when the metal net is made of a single material, a metal plate having a plurality of cuts penetrating in the plate thickness direction formed in a zigzag pattern is intersected with the cut forming direction. It can be used as a metal mesh (hereinafter, such a metal mesh is referred to as "metal lath mesh" in the present specification) by deforming in a direction and opening a cut in the deformation direction. (Claim 3). Metal lath network is Fe, N
It can be made of a metal whose main component is either i or Cu. Such a metal lath net is easy to manufacture and is effective in reducing the manufacturing cost of the clad material. More specifically, the metal lath net is such that the cuts are opened by deforming portions on both sides of the metal plate in the direction of forming the cuts in directions opposite to each other in the plate thickness direction of the metal plate. can do. Alternatively, a metal lath net obtained by forming and opening cuts may be rolled and used.

As the metal net, a plurality of metal nets of the same type or different types may be laminated and used.

In the above clad material, metal net and Ni
Although the corrosion-resistant metal coating layer and the base metal layer were joined by using the metal-based metal layer together, the Ni-based metal layer is not included when sufficient bonding force can be secured only by interposing the metal mesh. It can also be configured. As an example, the corrosion-resistant metal coating layer is Ti, Zr, Nb, Ta, N.
i is composed of a metal containing any one of i as a main component or stainless steel, and the metal net is partly composed of a metal containing Fe as a main component, or all or part of the metal net is Ni or Cu. There can be mentioned an aspect composed of a metal containing any of the above as a main component (claim 4). When the metal network is formed of a metal containing Cu as a main component, it can be composed of a Cu alloy containing at least one of Zn, Sn, Ni, and P (claim 5).
Specifically, it can be composed of an alloy containing Sn in the range of 1 to 20% by weight, more specifically an alloy further containing 0.5% by weight or less of P.

On the other hand, when a part of the metal network is composed of a metal containing Fe as a main component, a specific mode is as follows.
It is possible to exemplify a mode in which a multi-layer structure net in which a plurality of metal nets made of a material containing as a main component and metal nets made of a material containing a metal other than Fe as a main component are laminated is used. For example, a net having a two-layer structure in which a metal net made of a material containing Fe as a main component is arranged on the corrosion-resistant metal coating layer side, and a metal net made of a material containing Ni or Cu as a main component is arranged on the Fe-based base metal layer side. Alternatively, a three-layer structure net in which a metal net made of a material containing Ni or Cu as a main component is disposed between two metal nets made of a material containing Fe as a main component can be used.

As another example of the structure not including the Ni-based metal layer, the corrosion-resistant metal coating layer is formed of Ti, Zr, Nb, or T.
a, a metal mainly composed of any one of Ni or stainless steel, and the entire metal net is Fe, Ni,
It is possible to exemplify a mode in which a metal lath network composed of a metal containing any of Cu as a main component is used (claim 6). By using the metal lath net, the manufacturing cost of the clad material can be saved.

Next, the clad material according to a seventh aspect is characterized as follows. That is, a metal net formed by weaving two or more kinds of metal wire rods different in material from each other is laminated on a base metal layer made of Fe or Fe alloy or Cu or Cu alloy. Further, on the side opposite to the metal net, a corrosion-resistant metal coating layer is arranged so as to be in contact with the metal net, and the base metal layer, the metal net and the corrosion-resistant metal coating layer are formed in a linear or planar shape by the roller electrode. Are joined by seam welds.

By using a metal net having two or more kinds of metal wires, for example, the following effects can be obtained. (1) By combining metal wire rods made of materials having different electric specific resistances, the electric resistance value of the entire metal net can be adjusted according to the combination of the material. For example,
With a single material, the electrical resistivity is too high and the amount of heat generated increases, causing the metal net to melt or scatter, or the corrosion-resistant metal coating layer or the base metal layer to become too soft and the metal net to either of them. In some cases, the metal may be buried and the bonding force between the corrosion-resistant metal coating layer and the base metal layer due to the biting of the metal net may be reduced. Therefore, by configuring the metal net using a plurality of materials, the phenomenon as described above can be avoided by adjusting the electrical specific resistance, and a good coupling state can be achieved. (2) For example, when a metal net is composed of two kinds of metal wires, one is made of a material having a high affinity or erosion property with respect to the corrosion-resistant metal coating layer, and the other is made of a material having an affinity or erosion property with respect to the base metal layer. By using a high material, the bonding strength between the two can be increased.

Here, it is also possible to dispose an intermediate metal layer between the base metal layer and the metal net (claim 8). In this case, the material of the intermediate metal layer can be appropriately selected according to the materials of the base metal layer and the metal net, and for example, Fe
Alternatively, a base metal layer composed of Fe alloy (hereinafter referred to as F
Ni-based base metal layer) is used, Ni
A Cu-based or Cu-based metal layer can be used. In this case, Ni
The form and function of the Cu-based or Cu-based metal layer are almost the same as those of the Ni-based metal layer in the clad material according to the first aspect of the present invention, and the description thereof is omitted. The material and function of the intermediate metal layer suitable for the Cu-based base metal layer will be described later.

The corrosion-resistant metal coating layer is specifically Ti, Z
a metal containing any one of r, Nb, Ta, and Ni as a main component,
Alternatively, it can be made of stainless steel (claim 10). The metal net is a set of a first wire rod made up of a large number of metal wire rods arranged substantially parallel to each other along a predetermined direction, and is arranged substantially parallel to each other along a direction intersecting with the first wire rod. It can be configured as including one set of wire rods and a second set of wire rods composed of a large number of metal wire rods of different materials (claim 9).

When a Fe-based base metal layer is used, specifically, at least one of the above-mentioned first and second wire rods is made of a metal whose main component is Fe, Ni, or Cu. It can be configured (claim 11). Also,
More specifically, the first set of wire rods can be made of stainless steel, and the second set of wire rods can be made of a material having a smaller electrical resistivity. In this case, the second set of wire rods can be made of a metal whose main component is Fe, Ni, or Cu. As an example, the second wire rod set can be made of carbon steel wire. In addition,
The surface of the carbon steel wire may be coated with anticorrosion such as zinc.

On the other hand, when a base metal layer made of Cu or a Cu alloy (hereinafter referred to as a Cu-based base metal layer) is used, it can be specifically configured as follows. That is, an intermediate metal layer made of a metal having a melting point lower than that of the Cu-based base metal layer is laminated. Further, a metal net is laminated on the intermediate metal layer from the side opposite to the Cu-based base metal layer. The metal mesh is composed of a first set of wire rods composed of a large number of metal wire rods arranged substantially parallel to each other along a predetermined direction, and is arranged substantially parallel to each other along a direction intersecting with the first wire rod. A second wire rod set consisting of a large number of metal wire rods made of a material different from that of the above wire rod, and at least one of the first and second wire rods mainly contains Fe, Ni, or Cu. It is composed of metal as a component. Then, a corrosion-resistant metal coating layer is laminated from the side opposite to the intermediate metal layer with respect to the metal mesh, and the base metal layer, the intermediate metal layer, the metal mesh and the corrosion-resistant metal coating layer are linear or planar by the roller electrode. They are connected to each other by a seam weld formed on the surface (claim 1).
2).

In the structure in which the Cu-based base metal layer is used, as a combination of two kinds of wire rods constituting the metal net, specifically, one of the first and second wire rods is coated with a corrosion resistant metal coating. By forming the layer with a material having a high affinity or biting property and the other with a material having a high affinity for the Cu-based base metal layer, the bonding strength between the two can be increased. Here, among the materials having a high affinity for the base metal layer, it is desirable to select a material having good wettability with the liquid phase generated by melting of the intermediate metal layer. Then, as the material of the intermediate metal layer, it is desirable to select a material having good wettability for both the Cu-based base metal layer and the metal net.

By selecting the material of each layer and the metal net in this way, the following effects are achieved. That is,
Since the metal mesh has a mesh and thus has a small current-carrying cross-sectional area, resistance heating is large in the vicinity of the metal mesh. Then, the metal net digs into at least the corrosion-resistant metal coating layer side by the pressure applied by the roller electrode, and at least a part of the intermediate metal layer melts due to the heat generation to generate a liquid phase, which functions as a brazing filler metal. By fusing the metal net and the base metal layer, the clad material in which the corrosion-resistant metal coating layer is firmly bonded to the base metal layer is formed.
This liquid phase may pass through the mesh of the metal network and reach the contact side with the corrosion-resistant metal coating layer, and contribute to the improvement of the bonding strength.

Further, in the structure in which the Cu-based base metal layer is used, the melting point of the intermediate metal layer is 1000 ° C. or less, preferably 950 ° C. so that a sufficient amount of liquid phase is generated due to heat generation during seam welding. The following materials should be used. On the other hand, when an alloy having a melting point of 70 ° C. or lower is used, the intermediate metal layer is softened and the bonding strength between the base metal layer and the metal net is rapidly reduced even if the temperature of the environment in which the clad material is used is slightly increased. Therefore, it is preferable to use one having a melting point higher than that, and more desirably a melting point of 100 ° C.
You should use the above.

The intermediate metal layer is specifically a metal or alloy having excellent wettability with Cu or a Cu alloy, for example,
50 at least one of Pb, Sn, and Zn in total
It can be constituted by one containing at least wt% (claim 13). Of these, alloys based on Pb-Sn (for example, various solders) can be particularly preferably used. By forming the intermediate metal layer with the alloy as described above, the brazing property between the metal net and the Cu-based base metal layer is enhanced, and a clad material having a better bonding strength can be obtained. As a method of forming the above-mentioned intermediate metal layer on the base metal layer, in addition to the method of using the foil of the constituent metal or alloy, the hot-dip plating method or the one in which the alloy powder is kneaded in a paste form with the flux or the like is used. A method of coating on the surface of the base metal layer can also be adopted. It should be noted that one or more of In, Ga, Zn, Ag, and Cu can be added to the above alloy in order to adjust the melting point of the intermediate metal layer and increase the strength.

On the other hand, in alloys other than the above, the following materials can be used as the constituent material of the intermediate metal layer. -A material containing Ag and Cu in a total amount of 50% by weight or more. -A material containing 70% by weight or more of Cu and 3% by weight or more of P.

When the corrosion-resistant metal coating layer is composed of a metal containing either Ti or Zr as a main component in the structure in which the Cu-based base metal layer is used, one of the wire rods constituting the metal net is used. Can be made of stainless steel, and the other can be made of a metal containing Cu as a main component. With the above-described structure, the corrosion-resistant metal coating layer is appropriately softened by the heat generated by the metal net, the biting effect of the stainless steel wire rod portion is promoted, and the joining strength is enhanced.

On the other hand, the corrosion-resistant metal coating layer is Nb, Ta, N
When composed of a metal containing any one of i as a main component or stainless steel, one of the wire rods constituting the metal net is composed of a metal containing Ni as a main component and the other is composed of Cu as a main component. It is effective to use a metal. In this case, in the set of wire rods containing Ni as a main component, a part of the wire rod melts during seam welding to generate a liquid phase, and the brazing effect of the liquid phase causes a bonding force between the corrosion-resistant metal coating layer and the metal net. Will increase.

Next, the clad material according to the fourteenth aspect is a clad material having a structure not including a metal net. That is, depending on the material of the corrosion-resistant metal coating layer, a seam weld having good bonding strength may be formed only by the Ni-based or Cu-based metal layer without using a metal net.
The clad material according to claim 14, wherein the Fe-based base metal layer, the Ni-based or Cu-based metal layer laminated on the Fe-based base metal layer, and the Ni-based or Cu-based metal from the side opposite to the Fe-based base metal layer. A corrosion-resistant metal coating layer formed of a metal containing any one of Nb, Ta, Ni, and Zr as a main component, or stainless steel, and a seam weld portion connecting the layers to each other. To do. In this case, similarly to the Ni-based metal layer in the clad material according to claim 1, the Ni-based metal layer and the Cu-based metal layer in the clad material according to the present invention are metal foils containing Ni or Cu as a main component, Alternatively, it may be a plated layer formed on the base metal layer, and may be a powder layer or a sprayed layer.

In the above structure, particularly good bonding strength is achieved when the corrosion-resistant metal coating layer is made of a metal containing Ni as a main component or stainless steel. For example, the corrosion-resistant metal coating layer contains Ni as a main component, and 1
3 to 35% by weight of Cr, 3 to 25% by weight of Fe, and 3
Ni alloy containing ~ 35 wt% Mo (eg trade name Hastelloy, claim 15) or Ni containing Ni as the main component and 13 to 30 wt% Cr and 3 to 35 wt% Fe. A clad material having particularly excellent chemical resistance and high temperature corrosion resistance can be obtained by using an alloy (for example, Inconel brand name) or the like.

If a Ni-based metal layer is used, this is C
At least 1 of r, B, Si, C, P, Mo, W, Fe
Ni alloy containing seed, especially Ni as main component, 5-1
It may be composed of an alloy containing 6 wt% Cr, 2 to 4 wt% B, 3.5 to 5.5 wt% Si and 2 to 5 wt% Fe (claim 16). The Ni-based metal layer composed of such an alloy melts at the time of resistance heat generation to generate a liquid phase having excellent fluidity and wettability, so that a clad material having excellent bonding strength can be obtained.

On the other hand, when a Cu-based metal layer is used, it is possible to obtain a clad material having excellent bonding strength by constructing the Cu-based metal layer with a Cu alloy containing at least one of Zn, Sn, Ni and P. Yes (claim 17). in this case,
The Cu-based metal layer can be specifically composed of the following Cu alloy. An alloy containing Zn in the range of 20 to 50% by weight (eg brass). -Zn 3 to 30% by weight, Ni 5 to 40% by weight (however, the total content of Zn and Ni does not exceed 50% by weight)
Alloys contained within the range (for example, nickel silver).

Among the clad materials of the present invention described above, those having an Fe-based base metal layer can be suitably used for the following equipment or structure, for example.・ Inner surface lining of various tower tanks such as distillation tower, reactor, reaction tower, reaction tank, chemical storage tank, stirring tank, high pressure gas tower, head tank, and separator. -Inner surface coating of heat exchanger. Especially the coating of the tube sheet.・ Inner coating for tank truck.・ Inner surface coating of vacuum evaporator.

Further, the clad material having the Cu-based base metal layer can be suitably used, for example, as an electrode or bus bar used in electroplating or various electrolytic treatments.

In all of the above-mentioned clad material structures, the corrosion-resistant metal coating layer can be bonded to not only one side of the base metal layer but also the other side in the same manner. Further, it is possible to make the material or the joining mode of the corrosion resistant metal coating layer different on both sides of the base metal layer.

[0040]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Some embodiments of the present invention will be described below with reference to the drawings. FIG. 1 schematically shows a method for producing a clad material of the present invention having a Fe-based base metal layer, and as shown in (a), Fe-based material composed of carbon steel, stainless steel, or the like. A Ni foil 2 as a Ni-based metal layer is laid on the base metal layer 1, and a metal net 3 made of stainless steel or the like and Ti,
Corrosion resistant metal plate materials 4 as a corrosion resistant metal coating layer made of Zr or the like are laminated in this order. Then, as shown in FIG. 3B, the laminated body 5 is formed in the laminating direction.
The laminated body 5 is sandwiched between two roller electrodes 6 and an electric current is applied to the laminated body 5 through the roller electrodes 6 by the AC power source 7 while applying a pressure by a load applying means such as a pneumatic mechanism (not shown). As a result, the laminated body 5 generates resistance heat at the energized portion, and in that state, the roller electrode 6 is relatively rotated with respect to the laminated body 5 in the direction along the plate surface thereof, so that the base metal is A linear seam weld 8 for connecting the layer 1, the Ni foil 2, the metal net 3, and the corrosion-resistant metal plate 4 to each other is formed to form the clad material 10 of the present invention. Here, a plurality of seam welds 8 are formed at a predetermined interval along the plate surface direction of the laminated body 5. The roller electrode 6 may be energized continuously or intermittently. In the following drawings, the thickness of the Ni foil 2, the metal net 3, and the corrosion-resistant metal plate 4 may be exaggerated and may not necessarily correspond to the actual size of the clad material.

On the other hand, as shown in FIG. 24, the roller electrode 6
Therefore, a method of performing seam welding without sandwiching the laminated body 5, for example, a series seam welding method can be used. That is, the roller electrode 6 is arranged on the corrosion-resistant metal plate 4 side, and another roller electrode 6 is arranged on the same side corresponding to this. Then, when the roller electrodes 6 are energized, they penetrate at least the corrosion-resistant metal plate 4, the metal net 3 and the Ni foil 2 from one roller electrode 6 side, and after being bent in the lateral direction along the laminated surface thereof, each layer is again formed as described above. A current-carrying path I is formed which penetrates in the reverse order to and goes out to the other roller electrode 6 side, and a seam weld is formed.

3 and 4 show the clad material 1 shown in FIG.
The schematic diagram of the estimated cross-sectional structure of 0 is shown (FIG. 3 is a BB cross section, FIG. 4 is an AA cross section). Since the metal mesh 3 has a mesh, the contact area between the adjacent Ni foil 2 and the corrosion-resistant metal plate material 4 (that is, the cross-sectional area of current flow) is small, so that resistance heat generation is particularly large in the vicinity thereof. Due to this heat generation, the corrosion-resistant metal plate material 4 made of Ti or Zr, which is more easily softened than the Fe-based base metal layer 1, is moderately softened, and the metal net 3 is formed by the pressure applied by the roller electrode 6.
It is considered that the two are firmly bonded to each other by biting into the softened corrosion-resistant metal sheet 4 relatively large.

On the other hand, the Ni foil 2 generates a liquid phase by melting at least part of itself due to its resistance heat generation, or by melting together with part of the base metal layer 1 or the metal mesh 3, and the liquid phase is generated. Is mainly supplied to the contact portion between the metal net 3 and the base metal layer 1.
Since the Ni forming the Ni foil 2 has good wettability or mutual diffusibility with the Fe-based material forming the base metal layer 1, the bonding force between the metal net 3 and the base metal layer 1 is increased. It is presumed to act to enhance it.

In this way, as shown in FIG. 3, the corrosion-resistant metal plate material 4 is firmly bonded to the base metal layer 1 by the synergistic effect of the biting effect of the metal net 3 and the brazing or component diffusion effect of the Ni foil 2. It is thought to be combined with. A diffusion layer 3a may be formed at the biting portion between the metal net 3 and the corrosion-resistant metal plate material 4 due to component diffusion between the two.

Further, as shown in FIG. 4, the layers 1 to 4 are formed in a portion of the laminated body 5 where the seam welded portion 8 is not formed.
No binding occurs between. Here, the bonding force between the corrosion-resistant metal plate material 4 and the base metal layer 1 in the entire clad material 10 can be appropriately adjusted by changing the number of seam welded portions 8 formed, the formation interval, and the formation width. Further, the width of the seam welded portion 8 is adjusted by changing the width of the roller electrode 6. Also, especially when a wide seam weld 8 (or a planar seam weld) is required,
The adjacent seam welds 8 may be formed so as to be in contact with each other or partially overlap each other.

Next, the material and thickness of the corrosion-resistant metal plate material 4 are set according to the environment in which the clad material is used.
The thickness of the metal net 3 (or the wire diameter of the wire forming the metal net), the opening of the net, and the material and thickness of the Ni-based metal layer depend on the material and thickness of the corrosion-resistant metal plate material 4. It is appropriately selected so as to obtain an optimum bonding force with the base metal layer 1. In this way, when the materials and dimensions of the layers 1 to 4 are determined, the conditions for seam welding are correspondingly corresponding, that is, the welding current value, the pressure applied by the roller electrode 6, and the welding speed (for example, the rotation speed of the roller electrode 6). The energization time, rest time, etc. will be set appropriately. For example, the value of the welding current is adjusted within a range in which the resistance heat generation becomes extremely large and the metal net 3 is melted, or conversely, the heat generation becomes too small and the bonding state of each layer becomes insufficient. Further, the pressure applied by the roller electrode 6 causes the metal net 3 to be pressed into the corrosion-resistant metal plate 4 (or the base metal layer 1) just enough, and the electrode roller 6 is extremely bited into the surface of the laminate 5. Adjusted to the extent that it does not exist.

For example, when the Ti or Zr-based corrosion-resistant metal sheet 4 and the carbon steel base metal layer 1 are joined using the stainless steel net 3 and the Ni foil 2, the thickness of the corrosion-resistant metal sheet 4 is Is T and the wire diameter of the metal mesh 3 is M, M /
It is preferable to set the value of T in the range of 0.1 to 0.4. M / T
If it is less than 0.1, the corrosion of the metal net 3 into the corrosion-resistant metal plate material 4 is insufficient and the joint strength is reduced. On the other hand, when it exceeds 0.4, the biting becomes excessively large, and the mesh of the metal net 3 floats up on the surface of the corrosion-resistant metal plate 4 to cause a defective appearance, or a part of the metal net 3 is on the surface side of the corrosion-resistant metal plate 4. This may lead to cracks and the like, resulting in a loss of the anticorrosion effect on the base metal layer 1. M
The value of / T is preferably 0.15 to 0.30.

On the other hand, when the distance between meshes (the distance between the insides of adjacent wire rods, that is, the distance between voids) is D, D /
It is preferable to set M in the range of 1-10. If D / M is less than 1, the mesh spacing becomes too small, the penetration depth of the metal mesh 3 becomes insufficient, the joint strength decreases, and the liquid phase generated by melting of the Ni foil 2 penetrates into the mesh. It becomes difficult, and the brazing effect between the corrosion resistant metal plate material 4 and the base metal layer 1 through the mesh of the metal mesh 3 cannot be sufficiently achieved. On the other hand, D / M
When it exceeds 10, the wire rods of the metal net 3 that bite into the corrosion-resistant metal plate member 4 become sparsely spaced, which leads to a decrease in the joining effect. The value of D / M is preferably 1.5 to 7.

Next, even when the metal mesh 3 alone or only the Ni-based metal layer or the Cu-based metal layer is laminated between the corrosion-resistant metal plate 4 and the base metal layer 1 to form the clad material 10, seam welding is performed. The formation of the portion 8 is performed based on the same principle as that shown in FIG. And the seam weld 8
It is presumed that, for example, in the configuration using the metal net 3 made of stainless steel and the corrosion-resistant metal plate material 4 made of Zr, the result is as shown in FIG. That is, the metal net 3 largely digs into and is fixed to the corrosion-resistant metal plate 4 side, and at the contact portion with the base metal layer 1, a component diffusion layer 13 is formed by resistance heat generation due to energization to form the metal net 3 and the base metal. It is considered that the metal layer 1 is bonded. In addition, in the mesh of the metal mesh 3, some component diffusion layers 11 may be formed in a portion where the corrosion-resistant metal plate material 4 and the base metal layer 1 are in direct contact with each other. Further, the component diffusion layer 12 may be formed around the portion of the metal net 3 into which the corrosion-resistant metal plate 4 is eroded.

On the other hand, in the case where the metal net 3 is not used, for example, when the Ni foil 2 is used as the metal layer and the Nb thin plate is used as the corrosion-resistant metal plate material 4, the seam weld 8 is shown in FIG. It is assumed that the structure will be as shown. That is, resistance heating occurs at the contact portion between the Ni foil 2 and the corrosion-resistant metal sheet 4 and the base metal layer 1, and the Ni foil 2 is melted, and the generated liquid phase and the corrosion-resistant metal sheet 4 and the base metal layer 1 Diffusion layers 14 and 15 are formed due to component diffusion between the layers, and the corrosion-resistant metal plate 4 and the base metal layer 1 are formed.
It is considered that and are joined.

Next, in order to secure the current density required for seam welding when the corrosion-resistant metal sheet 4 having a particularly large thickness is joined to the base metal layer 1 using the metal net 3,
It becomes necessary to increase the welding current or lengthen the energization time according to the thickness of the corrosion-resistant metal plate material 4. However, since the metal net 3 has a small contact area with the corrosion-resistant metal plate material 4 and a high electric resistivity, the metal net 3 is increased as the welding current is increased.
Excessive heat generation is likely to occur in the vicinity. as a result,
As shown in FIG. 7 (a), the corrosion-resistant metal plate material 4 may be excessively softened and the metal net 3 may be completely embedded in the corrosion-resistant metal plate material 4, and the bonding effect due to the bite of the metal mesh 3 may be impaired. . In such a case, as shown in FIG.
If two or more metal nets 3 are stacked and used, even if the above-mentioned burial occurs, a part of the plurality of metal nets 3 will be formed between the base metal layer 1 and the corrosion-resistant metal plate material 4. By existing over the gap, it becomes possible to secure a predetermined binding force.

On the other hand, as shown in FIG. 7C, two metal nets 3a and 3b made of different materials may be laminated and used. As an example, when the corrosion-resistant metal plate material 4 is made of a Ti or Zr-based material, a net made of a material having a good bite into the corrosion-resistant metal plate material 4, for example, an Fe-based net 3
a (for example, stainless steel net) is arranged on the side of the corrosion-resistant metal plate 4, and a net made of a material having a high affinity with both the Fe-based net 3a and the Fe-based base metal layer 1, for example, the Ni-based net 3b.
When a seam weld is formed by arranging (for example, Ni metal net) on the base metal layer 1 side, the Fe-based net 3a becomes the Ni-based net 3b.
As a medium, it is firmly bonded to the Fe-based base metal layer 1 and a clad material having a large bonding force can be obtained. In this case, for example, the Ni-based net 3b is provided between two Fe-based nets 3a.
You may use the metal net of 3 layer structure which pinched | interposed.

On the other hand, as another method, a metal net 3
The vertical and horizontal wires constituting the above may be made of materials having different electric specific resistances, and the electric resistance value of the entire metal net may be adjusted according to the combination of the materials. FIG. 8 (a)
(B) shows a specific example thereof, in which one set 16 of the intersecting metal wire rods is made of stainless steel, and the other set 17 is made of carbon steel having a smaller electrical resistivity.
The carbon steel wire rod 17 may have a surface coated with zinc for corrosion protection. Instead of carbon steel, the wire rod set 17 may be formed of an alloy containing Ni or Cu as a main component and having a smaller electric resistivity than stainless steel. In addition, as shown in FIG. 8C, in each set of vertical and horizontal wire rods, wire rods 18 and 19 made of different materials are used.
May be arranged alternately.

Next, in addition to the metal net 3 manufactured by braiding a wire rod, as shown in FIG. 9, a metal plate on which a plurality of cuts penetrating in the plate thickness direction are formed in a zigzag pattern on the entire surface is formed. A mesh is formed by deforming in a direction intersecting the cut forming direction and opening the cut in the deformation direction.
A metal lath net 33 can be used. Such a metal lath net 33 can be manufactured by using a device 34 as shown in FIG. 10, for example.

The device 34 is provided with a table 36 for supporting the metal plate 35 on the upper surface thereof, and an elevating blade 37 provided corresponding to the end surface of the table 36 and elevating and lowering along the end surface. Although not shown, the device 34 also includes the following components. -A lifting mechanism for lifting the lifting blade 37. A lateral movement mechanism that moves the elevating blade 37 laterally relative to the metal plate 35 on the table 36. A plate feeding mechanism that intermittently feeds the metal plate 35 on the table 36 at a predetermined pitch to the end portion side to which the elevating blade 37 corresponds. A plurality of blade portions 39 are formed in a wavy shape on the lower portion of the elevating blade 37. A blade portion 38 corresponding to the blade portion 39 is formed along the upper edge of the table 36. Reference numeral 40 is a pressing member for preventing the metal plate 35 from rising.

Regarding the operation, as shown in FIG. 11A, when the metal plate 35 is projected from the end surface of the table 36 by one pitch, and the elevating blade 37 is lowered in that state,
The metal plate 35 includes a blade portion 38 on the table 36 side and a lifting blade 37.
The blade 41 is sheared in the thickness direction with the corresponding inner edge portion of the side blade portion 39 to form a broken line-shaped cut 41, and the cut portion 41 divides the protruding portion 42 from the main body of the metal plate 35 into blades. It is pushed down by the part 39. The pushed down protrusion 42 is deformed downward from the cut 41.
It will be opened.

Next, as shown in FIG.
7 is moved up and moved laterally by a distance corresponding to about half the length of the cut 41, and the metal plate 35 is further projected from the end of the table 36 by one pitch. Then, by lowering the elevating blade 37, the cut 41 which has already been formed is formed based on the same mechanism as in (a).
The new cuts 43 are formed substantially parallel to and at positions displaced by half the length of each cut 41 (that is, in a zigzag pattern), and the protrusions 44 thereof are pushed downward. As a result, as shown in (c), the table 36 is formed by the protrusion 44 and the protrusion 42 previously formed.
The diamond-shaped meshes 45 are formed in a row in the width direction. Then, if the elevating blade 37 is raised again and the elevating blade 37 is moved laterally in the opposite direction to the above and returned to the original position, the device 34 returns to the state shown in (a). Hereinafter, by repeating the same steps, the metal lath net 33 shown in FIG. 9 can be formed. Note that FIG.
As shown in (d), the metal lath net 33 thus obtained is obtained.
On the other hand, you may use what was rolled using the rolling roll 33a.

For example, the corrosion-resistant metal plate 4 made of Ti or Zr and the base metal layer 1 made of carbon steel are connected to the metal lath mesh 33.
When joining with (for example, Fe-based metal lath net), assuming that the thickness of the corrosion-resistant metal plate material 4 is T and the thickness of the metal plate for forming the metal lath net 33 is M, the value of M / T is 0.1 to It is recommended to set it in the range of 0.6. When M / T is less than 0.1, the corrosion of the metal lath net 3 into the corrosion-resistant metal plate material 4 is insufficient and the joint strength is reduced. On the other hand, when it exceeds 0.6, the biting becomes too large, and the mesh of the metal lath net 33 floats up on the surface of the corrosion-resistant metal plate 4 to cause a poor appearance, or a part of the metal lath net 33 has a mesh of the corrosion-resistant metal plate. It may penetrate to the surface side of 4 to cause cracks or the like, which may lead to deterioration of the anticorrosion effect on the base metal layer 1. The value of M / T is preferably 0.2 to 0.5.

On the other hand, as shown in FIG. 9, a diamond-shaped mesh 4
When the interval D of 5 is defined by the average value of the dimension R of the long diagonal line and the dimension S of the short diagonal line (that is, (R + S) / 2), D / M should be set in the range of 1.1 to 40. . D /
If M is less than 1.1, the mesh spacing becomes too small, the depth of penetration of the metal lath net 33 becomes insufficient, and the joint strength decreases. On the other hand, if D / M exceeds 40, the density of the meshes that bite into the corrosion-resistant metal plate material 4 becomes too sparse, leading to a reduction in the bonding effect. The value of D / M is preferably 2 to 3
It is better to set to 0.

An example of using the above clad material having the Fe-based base metal layer will be described below. FIG. 12 shows an example of the clad material 10 in which the base metal layer 1 is formed in a cylindrical shape. In this case, the corrosion-resistant metal plate member 4 has a cylindrical inner surface (or outer surface: in this case, in FIG.
And the corrosion-resistant metal plate material 4 are reversed), and the seam welded portions 8 are arranged along the circumferential direction of the cylinder as shown in FIG. Along the axis, at a predetermined interval, in a spiral shape as shown in (b), and as shown in (c), a plurality of linear shapes along the axial direction of the cylinder, It can be formed at a predetermined interval along the circumferential direction. Such shapes include, for example, tower tanks and the body of heat exchangers,
Alternatively, it can be applied when a corrosion resistant metal coating is applied to the inner surface or the outer surface of the pipe.

FIG. 13 shows an example in which the base metal layer 1 is formed in the shape of a hollow cone or a truncated cone, and the corrosion-resistant metal plate 4 is arranged on the inner surface side thereof. The seam welded portion 8 can be formed along the circumferential direction thereof as shown in (a), or can be formed in the direction along its generatrix as shown in (b). Such a shape can be applied to, for example, the reduced diameter portion of the upper or lower part of the tower tank.

The base metal layer 1 shown in FIG. 14 has a circular planar shape, and is formed in a lid shape in which the central portion bulges in a convex curved shape, and the inner surface side (concave side) thereof is a corrosion-resistant metal plate material. Four
Covered with. Those having such a shape can be applied to, for example, end plates such as tower tanks and heat exchangers. FIG. 15 shows an example of the formation pattern of the seam welded portion 8, where (a) and (b) are examples of concentric circles.
(C) and (d) are examples of radial formation, and (e)
Shows an example in which a concentric shape and a radial shape are combined, and (f) shows an example in which linear shapes extending in the diameter direction are formed at predetermined intervals.

Here, the corrosion-resistant metal plate member 4 may be formed into a shape that covers the entire inner surface by joining a plurality of divided parts in advance by welding (for example, TIG welding) or the like. FIG. 15G shows an example in which the corrosion-resistant metal plate material 4 is formed by being radially divided. The radial butting portions are joined and integrated by the seam welding portion 9, and the base metal is formed by the seam welding portion 8. Joined with layer 1. In addition,
The seam weld 8 is formed concentrically while avoiding the seam weld 9. On the other hand, in the examples shown in (e) and (h), the corrosion-resistant metal plate member 4 is divided into a circular inner portion 4a and a donut-shaped outer portion 4b by a circular dividing surface, and the outer portion 4b is further divided. It is radially divided, and the respective abutting portions are joined by the seam welding portion 9. The base metal layer 1 can be divided into an inner portion corresponding to the inner portion 4a of the corrosion-resistant metal plate member 4 and a portion (outer portion) other than the inner portion. In this case, the corrosion-resistant metal plate materials 4 are separately joined to the divided inner and outer parts in advance by the seam welds 8, and then the base metal layers 1 of the inner and outer parts and the corrosion-resistant metal plate material are joined together. The four members may be joined together by welding or the like.

FIG. 16 shows an example of a clad material in which the base metal layer 1 is formed in a rectangular plate shape. (A) shows a plurality of seam welded portions 8 extending in the direction along one side of the clad material 10. In the example (b), the seam welds 8 extending in the direction intersecting with the seam welds 8 are arranged side by side at predetermined intervals in the direction intersecting with the seam welds 8. For example, (c) shows an example in which a seam weld 8 extending radially from the center of the plate is formed. Further, as shown in FIG. 17, when the protrusion 10b is formed on the plate surface of the base metal layer 1, the seam weld 8 can be formed while avoiding the protrusion 10b.

In FIG. 18, a shallow recess 1a is formed on the plate surface of the base metal layer 1 formed in the shape of a thick plate, and a corrosion-resistant metal plate 4 having a corresponding shape is fitted therein and the corrosion-resistant metal plate 4 is formed. An example in which the seam welded portion 8 is formed only on the edge portion of is shown. Further, FIG. 19 shows an example in which the clad material 10 is applied to the tube sheet 71 of the heat exchanger. In the manufacturing method, first, a large number of through holes 40a are formed in the base metal layer 1 and the corrosion-resistant metal plate material 4 in advance, the corrosion-resistant metal plate material 4 is superposed on the upper surface of the base metal layer 1, and seam welding is performed at the overlapping portion. The part 8 is formed. Next, the base metal layer 1 is integrated with the cylindrical body portion 50 by welding. Then, the pipe material 4 is provided in each through hole 40a of the base metal layer 1.
0 is inserted, and the peripheral edge of the pipe 40 and the corrosion-resistant metal plate 4 are fixed and welded with their end faces aligned.

The embodiments of the clad material having the Fe-based base metal layer have been described above.
An embodiment of a clad material having a Cu-based base metal layer will be described. Here, as a method of manufacturing the clad material, since a method based on a principle substantially similar to that described with reference to FIGS. 1 and 2 can be applied to the clad material having the Fe-based base metal layer, I will mainly explain the differences.

First, in the embodiment shown in FIG. 20, Cu
An intermediate metal layer such as Sn- is formed on the system base metal layer 51.
A 37 wt% Pb alloy layer (hereinafter referred to as a solder layer) 52 is formed, and a metal net 53 and a corrosion-resistant metal plate material 54 made of Ti, Zr or the like as a corrosion-resistant metal coating layer are laminated on the laminated body 55. Is formed. Sn-Pb alloy layer 5
2 can be formed by applying a mixture of an alloy powder and a flux in a paste form (solder paste or the like) to the surface of the base metal layer 51, but using an alloy foil or as a hot-dip plating layer. It can also be formed.

Next, in the metal net 53, as shown with reference to FIG. 8, one set 56 of intersecting metal wires is made of stainless steel, and the other set 57 is made of Cu. When electricity is applied to the laminated body 55 including such a metal net 53, resistance heat generation becomes large in the vicinity of the metal net 53 having a small cross-sectional area of electricity, as in the case of the clad material having the Fe-based base metal layer. Here, since the Cu wire rod portion 57 of the metal net 53 has a low electric resistivity, the resistance heat is mainly generated in the stainless steel wire rod portion 5.
6 and the contact portion between it and the corrosion-resistant metal plate 54 or the solder layer 52. And seam weld 5
The structure of No. 8 is supposed to be as shown in FIG. That is, in the metal net 53, the stainless steel wire rod portion 56 bites into the corrosion-resistant metal plate material 54 side softened by resistance heat generation comparatively largely by the pressure applied by the roller electrode 6 (FIG. 1 etc.), and the Cu-based wire rod portion 57 is The solder layer 52 melted by resistance heating is joined to the Cu-based base metal layer 51 in a so-called soldered form. In this way, it is presumed that the corrosion-resistant metal plate material 54 and the Cu-based base metal layer 51 are bonded to each other through the metal net 53 and the solder layer 52 to form the clad material 20.

For example, when a Ti or Zr-based corrosion-resistant metal plate material is joined to a Cu-based base metal layer, the thickness of the corrosion-resistant metal plate material is T, the wire diameter of the metal mesh is M, and the mesh spacing (inside of adjacent wire materials). When the distance between each other, that is, the space between the voids) is D, there is a preferable range of M / T and D / M as in the case of the clad material using the Fe-based base metal layer. In this case, the value of M / T is 0.1 to 0.4, preferably 0.
The value of D / M is preferably 1 to 10, and more preferably 1.5 to 7.

An example of using the above clad material having a Cu-based base metal layer will be described below. First, FIG.
In the example shown in (a), the base metal layer 51 includes a main body 51a formed in a horizontally long plate shape, projections 51b formed by projecting upward from both ends of the main body 51a, and each projection. And a plate-shaped projecting portion 51c projecting laterally outward from the upper end of 51b. The entire surface including both plate surfaces is covered with a corrosion-resistant metal plate material 54 such as Ti or Zr, and the main body part 51a. A seam welded portion 58 is formed on the protruding portion 51c.

FIG. 22B shows a cross-sectional view of the main body 51a, in which the solder layer 5 is formed on both sides of the base metal layer 51.
2 is formed on the metal mesh 53 as shown in FIG.
Are laminated, and the whole is covered with a corrosion-resistant metal plate material 54. The corrosion-resistant metal plate material 54 encloses the base metal layer 51 by joining the both side edge portions on one edge side of the base metal layer 51 by the welded portions 59. And
By performing seam welding with the roller electrode 6 in this state, the seam welded portions 58 are simultaneously formed on both surfaces of the base metal layer 51. Where the seam weld 58
A plurality of those extending along the longitudinal direction of the body 51a and a plurality of extending along the direction of the extension 51c are formed at predetermined intervals. The clad material 20 having such a shape can be applied to an electrode used for electroplating or various electrolytic treatments, a bus bar for power feeding, or the like, and particularly, the overhanging portion 51c is arranged outside the electrolytic solution to feed power. Main body 51a
Can be suitably used as a liquid-immersion type bus bar, which is a suspension part for suspending a member to be plated, a basket for holding a plating material, etc., while being immersed in the electrolytic solution. .

Next, as shown in FIGS. 23 (a) to 23 (d), the outer peripheral surface of the base metal layer 51 formed in the shape of a rod or bar having a circular or rectangular cross-section is corroded. The seam weld 58 can be formed by covering with 54. A plurality of seam welds 58 are formed along the longitudinal direction of the rod-shaped or bar-shaped base metal layer 51, and are formed at predetermined intervals along the circumferential direction of the cross section.
In addition, in (b) and (d), the base metal layer 51
Is formed in a hollow shape. These shapes are also
It can be preferably used as an electrode substrate or a bus bar.

[0073]

【Example】

(Example 1) On a base metal layer formed in a plate shape having a length of 50 cm, a width of 50 cm and a thickness of 12 mm, various metal foils having the same area (thickness)
10 to 100 μm), various metal nets (wire diameter: 0.1 to 0.5 mm, mesh spacing: 16 to 100 mesh), corrosion-resistant metal plate material (thickness 0.5 to 1.5 m)
m) are appropriately laminated and seam welds along the longitudinal direction of the base metal layer are formed at intervals of 25 mm by the method shown in FIG. 1 to form a clad material (Table 1: Sample Nos. 1 to 20, Table 2: Sample No. 21-28). On the other hand, for comparison, a sample (Table 3: Sample Nos. 31 to 38) in which a corrosion-resistant metal plate and a base metal layer were directly overlapped and seam welded without using a metal net and a metal foil was also prepared. did.

The materials used for each part are as follows.・ Base metal layer: Carbon steel (SS400), stainless steel (SUS
304). -Corrosion resistant metal plate material: Ti, Zr, Nb, Ta, Ni, T
i-Pd alloy (Pd: 0.15 wt%, balance Ti, wt% is wt%
, Stainless steel (SUS316), Ni alloy (Hastelloy C-276, Fe: 5 wt%, Cr: 16 wt%, Mo: 16 wt%,
The balance Ni).・ Metal mesh: Stainless steel mesh (SUS304), composite mesh of stainless steel and carbon steel (vertical wire is stainless steel (SUS304)
The horizontal wire is carbon steel (SS400, zinc coated)
, Wire diameter: 0.1 ~ 0.5 mm, mesh spacing: 16 ~ 100 mes
h), composite mesh of stainless steel and Ni or Cu (vertical wire is stainless steel (SUS304), horizontal wire is Ni or C)
Consists of u, wire diameter: 0.1 to 0.5 mm, mesh spacing: 16 to 100 mes
h), Cu-Sn-P alloy mesh (JIS-C5111, Sn: 3.5-
4.5 wt%, P: 0.03 to 0.35 wt%, balance Cu) and Ni mesh (wire diameter: 0.1 to 0.5 mm, mesh interval: 16 to 100 mesh). Sample Nos. 7 and 18 in Table 1 are stainless steel (SUS30
4) Made of metal lath net. The thickness of the stainless steel plate material used for producing the metal lath net was 0.6 mm, the mesh formed was a diamond shape as shown in FIG. 9, and the dimension R on the long diagonal side was 6.0 mm and the dimension on the short diagonal side. S was 3.2 mm.・ Metal foil: Ni, Cu, brass (Zn: 30 wt%, balance C)
u), nickel silver, (JIS-C7521, Cu: 61.0-67.0wt%, Ni: 1
6.5 to 19.5 wt%, balance Zn), Ni brazing material (made by Allied,
MBF-20, Cr: 7.0wt%, Fe: 3.0wt%, Si4.5w
t%, boron 3.2 wt%, balance Ni).

The conditions for seam welding were adjusted within the following ranges: -Welding current: 5000 to 25000 A-Electrification time: 5 to 50 cycles-Pause time: 5 to 50 cycles-Pressure force: 500 to 1500 kg-Electrode width : 5 ~ 20mm ・ Welding speed: 500 ~ 1500mm / min. Then, a bending test is performed on the obtained clad material (inner bending radius: twice the thickness of the clad material, bending angle: 180 °).
Then, the quality of the joined state was judged based on the presence or absence of peeling between the corrosion-resistant metal plate and the base metal layer.
The results are shown in Tables 1 to 3.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

It can be seen that the clad materials of the present invention shown in Tables 1 and 2 all showed good bonding conditions, whereas the clad materials of the comparative examples shown in Table 3 all had peeling. .

Example 2 An intermediate metal layer (thickness: 10 to 100 μm) was arranged on a Cu-based base metal layer formed in a plate shape having a length of 5 cm, a width of 100 cm, and a thickness of 6 mm, and a metal mesh was formed thereon. And, corrosion-resistant metal plate materials (thickness 0.5 to 1.5 mm) were laminated. A linear seam weld along the longitudinal direction of the base metal layer was formed in close contact with the laminated body by the method shown in FIG. 1 to obtain a clad material (Table 4, sample numbers 41 to 51). . Here, a sample using only the intermediate metal layer (Table 4, Sample No. 5
2), and the samples (Sample Nos. 53 to 56) in which the corrosion resistant metal plate and the base metal layer were directly overlapped and seam welded without using the metal net and the intermediate metal layer were also prepared.

The materials used for each part are as follows. -Base metal layer: oxygen-free copper. -Corrosion resistant metal plate material: Ti, Zr, Nb, Ta, stainless steel (SUS304), Ni.・ Metal mesh: Composite mesh of stainless steel (SUS304) and Cu (vertical wire made of stainless steel, horizontal wire made of Cu, wire diameter: 0.1 to 0.5 mm, mesh spacing: 16 to 100 mesh), Ni and C
u composite mesh (vertical wire made of Ni, horizontal wire made of Cu, wire diameter: 0.1-0.5 mm, mesh spacing: 16-100 mesh). -Intermediate metal layer: solder (composition: Sn-37wt% Pb, Sn
-47 wt% Pb-3 wt% Cu, and Sn-50 wt% Pb, melt coated on the base metal layer).

The conditions for seam welding were adjusted within the following ranges: -Welding current: 5000-25000A-Electrification time: 5-50 cycles-Pause time: 5-50 cycles-Pressure force: 500-1500kg-Electrode width : 5 ~ 20mm ・ Welding speed: 500 ~ 1500mm / min. Then, a bending test is performed on the obtained clad material (inner bending radius: twice the thickness of the clad material, bending angle: 180 °).
Then, the quality of the joined state was judged based on the presence or absence of peeling between the corrosion-resistant metal plate and the base metal layer.
The results are shown in Table 4.

[0083]

[Table 4]

It can be seen that the clad materials of the examples all showed a good joint state, while the clad materials of the comparative examples all had peeling.

[Brief description of the drawings]

FIG. 1 is a diagram conceptually showing a method for manufacturing a clad material according to the present invention.

FIG. 2 is a perspective view showing a step of forming a seam welded portion of the clad material of the present invention.

3 is a sectional view taken along line BB of FIG.

FIG. 4 is a sectional view taken along line AA of FIG.

FIG. 5 is a schematic cross-sectional view of a seam welded portion when a corrosion-resistant metal plate material is joined to the Fe-based base metal layer using only a metal net.

FIG. 6 is a schematic sectional view of a seam welded portion when a corrosion-resistant metal plate material is joined using only a Ni-based or Cu-based metal layer.

FIG. 7 is a schematic diagram illustrating a difference in effect between the case where only one metal net is used and the case where two metal nets are used.

FIG. 8 is an explanatory view showing an example of a composite metal net formed by using wires made of different materials.

FIG. 9 is a plan view showing an example of a metal lath net.

FIG. 10 is a conceptual diagram of a metal lath net manufacturing apparatus.

FIG. 11 is an explanatory view of the manufacturing process of the metal lath net.

FIG. 12 is a perspective view showing an example in which a base metal layer is formed in a cylindrical shape.

FIG. 13 is a perspective view showing an example of the same conical shape.

FIG. 14 is a perspective view showing an example similarly formed in a flat lid shape.

FIG. 15 is a schematic view showing a formation pattern of the seam welded portion.

FIG. 16 is a schematic view showing an example in which a base metal layer is formed in a rectangular plate shape.

FIG. 17 is a plan view and a side view showing an example in which a seam weld is formed while avoiding a protrusion formed on a plate surface.

FIG. 18 is a plan view and a side view showing an example in which a seam weld is formed only on an edge of a corrosion-resistant metal plate.

FIG. 19 is a plan view and a side view showing an example in which a large number of pipe materials are joined to the plate surface of a corrosion-resistant metal plate material.

FIG. 20 is an explanatory diagram showing an example of a clad material using a Cu-based base metal layer.

FIG. 21 is an enlarged schematic sectional view of the seam welded portion.

FIG. 22 is a perspective view of an application example of a clad material using a Cu-based base metal layer and a cross-sectional view taken along the line CC.

FIG. 23 is a perspective view showing another application example of a clad material using a Cu-based base metal layer.

FIG. 24 is an explanatory view showing a method example of forming a seam welded portion by a series seam welding method.

[Explanation of symbols] 1 Fe-based base metal layer 2 Ni foil (Ni-based metal layer) 3 Metal mesh 4 Corrosion-resistant metal plate material (corrosion-resistant metal coating layer) 6 Roller electrode 8 Seam welded portion 10, 20 Clad material 16 Stainless steel wire rod 17 Carbon steel wire 33 Metal lath net 35 Metal plate 41, 43 Cut 45 Net 51 Cu-based base metal layer 52 Solder layer (intermediate metal layer) 53 Metal net 54 Corrosion resistant metal plate (corrosion resistant metal coating) 58 Seam weld

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location B23K 20/00 360 B23K 20/00 360D 360E 20/16 20/16

Claims (17)

[Claims] 1. An Fe-based base metal layer composed of Fe or an Fe alloy, a Ni-based metal layer laminated on the Fe-based base metal layer, and the Fe-based base metal layer with respect to the Ni-based metal layer. A metal net laminated from the opposite side, and a metal having one of Ti, Zr, Nb, Ta, and Ni as a main component, which is arranged in contact with the metal net on the side opposite to the Ni-based metal layer. Or seam welding, which is formed in a linear or plane shape by a roller electrode and a corrosion-resistant metal coating layer made of stainless steel, and connects the Fe-based base metal layer, Ni-based metal layer, metal net and corrosion-resistant metal coating layer to each other. A clad material comprising: 2. The Ni-based metal layer includes a metal foil containing Ni as a main component, and the metal network includes Fe, Ni, and C.
The clad material according to claim 1, which is composed of a metal containing any one of u as a main component. 3. The metal net deforms a metal plate, which has a plurality of cuts penetrating in the plate thickness direction in a zigzag pattern on the entire surface, in a direction intersecting the cut forming direction, and the cuts are deformed. The clad material according to claim 1 or 2, wherein a mesh is formed by opening in the direction. 4. An Fe-based base metal layer composed of Fe or an Fe alloy, a Fe-based base metal layer laminated on the Fe-based base metal layer, and a part of the Fe-based base metal layer.
A metal network composed of a metal containing e as a main component, or a metal network which is wholly or partially composed of a metal containing Ni or Cu as a main component, and a side opposite to the Fe-based base metal layer. Formed on the above-mentioned metal net by a roller electrode and a corrosion-resistant metal coating layer composed of a metal containing any of Ti, Zr, Nb, Ta, and Ni as a main component, or stainless steel, and formed into a linear or planar shape. And a seam weld for connecting the Fe-based base metal layer, the metal net and the corrosion-resistant metal coating layer to each other, and a clad material. 5. The clad material according to claim 4, wherein the metal net is made of a Cu alloy containing at least one of Zn, Sn, Ni and P. 6. An Fe-based base metal layer made of Fe or an Fe alloy, and a Fe-based base metal layer laminated on the whole Fe,
A metal net composed of a metal containing Ni or Cu as a main component, wherein a metal plate having a plurality of cuts penetrating in the plate thickness direction formed in a zigzag pattern is used as the cut forming direction. A metal net having a mesh formed by deforming in a direction intersecting with each other and opening the cut in the deformation direction, and a metal net laminated from the opposite side of the Fe-based base metal layer to Ti, Zr, Nb. , Ta, or Ni as a main component, or a corrosion-resistant metal coating layer made of stainless steel, and a roller electrode that is formed into a linear or planar shape. The Fe-based base metal layer, metal mesh, and corrosion resistance A clad material, comprising: a seam weld portion for joining metal coating layers to each other. 7. A base metal layer composed of Fe or Fe alloy or Cu or Cu alloy, and a metal mesh formed by laminating two or more kinds of metal wire rods which are laminated on the base metal layer and are made of different materials from each other. And on the side opposite to the metal mesh, the corrosion-resistant metal coating layer arranged in contact with the metal mesh and the roller electrode are formed into a linear or plane shape, and the base metal layer, the metal mesh and the corrosion-resistant metal coating layer are formed. A clad material comprising: a seam weld that is bonded to each other. 8. The clad material according to claim 7, wherein an intermediate metal layer is arranged between the base metal layer and the metal mesh. 9. The metal net comprises a first wire rod group consisting of a number of metal wire rods arranged substantially parallel to each other along a predetermined direction, and a metal wire rod arranged substantially parallel to each other along a direction intersecting with the first wire rod. 9. The clad material according to claim 7, further comprising: a second wire rod group consisting of a large number of metal wire rods made of a material different from that of the first wire rod group. 10. The corrosion-resistant metal coating layer comprises Ti, Z
a metal containing any one of r, Nb, Ta, and Ni as a main component,
Alternatively, the clad material according to any one of claims 7 to 9, which is made of stainless steel. 11. The base metal layer composed of Fe or an Fe alloy, and the metal net laminated on the base metal layer, wherein the plurality of metals are arranged substantially parallel to each other along a predetermined direction. A set of first wire rods made of wire rods, and second wire rods made of a large number of metal wire rods that are arranged substantially parallel to each other along a direction intersecting with the first wire rods and are made of a material different from that of the first wire rod set. And a metal net in which at least one of the first and second wire rods is composed of a metal containing Fe, Ni, or Cu as a main component, and The corrosion-resistant metal coating layer laminated from the side opposite to the base metal layer, and a seam weld portion formed in a linear or planar shape by the roller electrode and connecting the base metal layer, the metal mesh and the corrosion-resistant metal coating layer to each other. , Including Clad material according to claim 9 or 10. 12. The base metal layer made of Cu or a Cu alloy, an intermediate metal layer laminated on the base metal layer and made of a metal having a melting point lower than that of the Cu-based base metal layer, A metal net laminated from the side opposite to the base metal layer with respect to the intermediate metal layer, a first wire rod group consisting of a number of metal wire rods arranged substantially parallel to each other along a predetermined direction, And a second wire set composed of a large number of metal wires of a material different from that of the first wire set and arranged substantially parallel to each other along a direction intersecting with the first and second wire sets. At least one of the two wire sets is Fe,
The metal mesh composed of a metal containing Ni or Cu as a main component, the corrosion-resistant metal coating layer laminated from the side opposite to the intermediate metal layer with respect to the metal mesh, and a linear shape formed by a roller electrode. Alternatively, the clad material according to claim 9 or 10, further comprising a seam weld formed in a planar shape and connecting the base metal layer, the intermediate metal layer, the metal net, and the corrosion-resistant metal coating layer to each other. 13. The intermediate metal layer comprises Pb, Sn, Zn
The clad material according to claim 12, which contains at least one of the above in a total amount of 50% by weight or more. 14. An Fe-based base metal layer composed of Fe or an Fe alloy, a Ni-based or Cu-based metal layer laminated on the Fe-based base metal layer, and a side opposite to the Fe-based base metal layer. A corrosion-resistant metal coating layer laminated on the Ni-based or Cu-based metal layer and composed of a metal containing any of Nb, Ta, Ni, and Zr as a main component, or stainless steel, and a linear or planar shape with a roller electrode. And a seam weld for connecting the Fe-based base metal layer, the Ni-based or Cu-based metal layer, and the corrosion-resistant metal coating layer to each other, and a clad material. 15. The corrosion-resistant metal coating layer contains Ni as a main component and contains 13 to 35% by weight of Cr, 3 to 25% by weight of Fe, and 3 to 35% by weight of Mo. The clad material according to claim 14. 16. The Ni-based metal layer contains Ni as a main component, 5 to 16% by weight of Cr, 2 to 4% by weight of B, and 3.
The clad material according to claim 14 or 15, which contains 5 to 5.5% by weight of Si and 2 to 5% by weight of Fe. 17. The Cu-based metal layer comprises Zn, Sn, N
The clad material according to claim 14, which is made of a Cu alloy containing at least one of i and P.