JPH08225989A - Production of metallic perforated body and apparatus therefor - Google Patents

Abstract

PURPOSE: To evenly and rapidly electrodeposit metal ions on the three-dimensional meshlike structure of a base material. CONSTITUTION: This apparatus is a combination of a preliminary electrodeposition device 1 and a normal electrodeposition device 2. This preliminary electrodeposition device 1 is provided with >=2 power feed rolls 4 and electrode plates 5 in a plating bath tank 3. The base material M to which an electrical conductivity is imparted is supported on the power feed rolls 4 arranged in series in a plating bath tank 3 and while this material is moved linearly along a transporting line L in a horizontal direction, the metal ions supplied from the electrode plates 5 are uniformly deposited at least on the surfaces. The base material M is carried into the normal electrodeposition device 2 after the preliminary electrodeposition treatment. The normal electrodeposition device 2 is a combination of a transporting mechanism 12, electrodes 13 and an exciter 14. The base material is supported by the transporting mechanism 12 and is repetitively passed near the electrodes 13. In addition, the transporting mechanism 12 is excited by the exciter 14, by which water flow is generated in a plating liquid to forcibly press fit the plating liquid into the base material structure. The electrodeposition is executed into and out of the structure of the base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a porous metal body for use in electrodes of various batteries such as nickel-cadmium batteries, lithium batteries, nickel-hydrogen batteries, fuel cells, and filters, and an apparatus thereof.

[0002]

2. Description of the Related Art The metal porous body used for the above purpose is
Sliced urethane foam sheet, non-woven fabric, etc. are used as the base material. The urethane foam sheet has a three-dimensional network skeleton, and the metal porous body is obtained by subjecting the network of the urethane foam sheet to electrical conductivity treatment in advance, and plating the skeleton surface with a metal having a predetermined thickness. To be The procedure is the same when a nonwoven fabric is used as the substrate.

[0003]

By the way, the metal plating treatment is a treatment in which the network of the base material is used as a skeleton and a metal is electrodeposited over the entire surface leaving a gap in the texture.
Unlike a case where plating is simply performed on a flat surface, a plating solution is permeated into the inside to perform metal plating on a three-dimensional mesh structure, so that a high technique is required.

As one of the methods for solving this problem, Japanese Patent Laid-Open No. 1-290792 discloses that a plating solution is conveyed in a direction substantially perpendicular to the plane of the base material with respect to the base material which is conveyed transversely in the plating bath. There has been proposed a method of forcibly flowing with a flow velocity so as to hit the surface of the substrate to plate the entire surface of the holes on both side surface portions and the inner layer portion of the substrate with a uniform thickness. This method uses an already-plated porous body that has already been metal-plated as a support, supports an unplated substrate on this support, and continuously moves two substrates in a stacked state to plate the substrate surface. It is a method of hitting the liquid, and since the grain size of the electrodeposited metal becomes very fine, the grain boundary strength is strong, the adhesion is excellent, and the metal ion can be electrodeposited on the inner surface of the inner layer with a uniform thickness. Is emphasized, it seems that the effect depends on the supporting strength of the substrate. When the supporting strength is insufficient, the base material may be corrugated or curved to cause uneven plating thickness. Naturally, only the flexible and easily breakable base material should be transported for metal plating. I can't.

On the other hand, another problem with the electrodeposition treatment of the substrate is the problem of the electroconductivity treatment of the substrate which is carried out as a pretreatment for the electrodeposition treatment. If the conductive treatment is sufficiently performed prior to the original electrodeposition treatment, the electrodeposition treatment can be performed at a high current density. The electroconductivity treatment is a treatment for applying or impregnating a conductive material on a base material which is a dielectric, or performing electroless plating to deposit a metal on the surface of the base material. This conductivity treatment reduces the resistance value of the base material and enables metal plating on the base material.

When metal plating is applied to the base material subjected to the electroconductivity treatment, the net of the three-dimensional network of the base material serves as a skeleton, and the plated metal adheres to the periphery to form a metal porous body. When the substrate is incinerated as a post-treatment, a metal porous body having a three-dimensional network structure containing only plated metal is obtained.

[0007]

However, when the metal plating treatment of the base material is performed only by the above-mentioned conductive treatment,
It was pointed out that the current density varies between the surface layer and the inner layer of the substrate, which hinders uniform electrodeposition on the three-dimensional network structure. , Metal plating is performed in the first tank to electrodeposit the plated metal on the skeleton surface of the base material to a thickness of 0.1 to several μm, and then in the second tank to the planned thickness from both surfaces of the base material. Has been proposed (Japanese Patent Publication No. 57-
(See Japanese Patent No. 39317).

This method, in short, improves the plating conditions and makes it possible to use a current density almost equal to that of ordinary plating, and all parts of the base material soaked in the plating solution start electrodeposition at the same time. In addition, the electrodeposition rate of the plated metal is improved and a uniform metal porous body is obtained.

However, with respect to this method, the following problems have been pointed out in the above-mentioned prior art (Japanese Patent Laid-Open No. 1-290792). That is, in the above method, after the secondary conductivity treatment is performed in the first tank at a low current density (several A / dm ² ), the metal plating treatment is performed in the second tank at a high current density (10 A / dm ² ). Doing so causes a difference in the grain size of the metal plated at a low current density and causes distortion at the grain boundaries, weakening the grain boundary strength, weakening the strength of the porous body, and making the shape unstable,
As a result, uneven plating thickness and local unevenness on both surfaces in the second tank are promoted, and it is impossible to wind the sheet-shaped porous metal body into a coil.

Certainly, it seems to be the case that the obtained metal porous body has a nonuniform plating thickness locally. It has been confirmed by the inventors' experiments that the metal porous body obtained also has cracks across the substrate. However, the fact that the grain boundary strength decreases due to the difference in the grain size of the plated metal depending on the magnitude of the current density was not recognized.

The cause of non-uniformity in the plating thickness is not necessarily clear, but it is not the problem of the plating conditions pointed out in Japanese Patent Laid-Open No. 1-290792, but the cause seems to be the plating method. That is, Japanese Examined Japanese Patent Publication Sho 57-3
In the method for continuously producing a metal porous body described in Japanese Patent No. 9317, the conductive treatment is performed by a curved surface of the base material M that rotates in contact with the circumferential surface of the power feeding roll 20 in the first tank, as shown in FIG. 7. When the plated metal adheres to the network structure of the base material M, the structure is fixed and the strength is increased. But,
The adhesion amount of the plating metal is different between the inner surface side of the base material M contacting the power supply roll 40 and the outer surface side facing the electrode plate 41. Since the adhesion amount of the plating metal on the outer surface side is large, the outer surface side becomes hard and the base material. When M is shaped into a curved surface along the shape of the power feeding roll 40, and then separated from the power feeding roll 40 and returned to a flat surface, the inner surface having a small amount of plated metal adhered is forcibly stretched. As a result, as shown in FIG. 8, stripe cracks 42 are formed in parallel on the inner surface of the base material M across the base material at fine intervals.

When the base material M in which the cracks 42 have been generated is next sent into the second tank and electrodeposition is performed from both sides thereof with a high current density, the cracks 42 are broken. It seems that conductivity may be poor when used as an electrode.

An object of the present invention is to provide a method and an apparatus for uniformly plating metal on a flexible network of a base material in a short time without causing a crack in the base material.

[0014]

In order to achieve the above object, in the method for producing a metal porous body according to the present invention, a base material having electroconductivity is plated by electrodeposition treatment and vibration treatment. A method for producing a metal porous body in which a skeleton surface of a three-dimensional network of a substrate is metal-plated while being immersed in a liquid and continuously fed, wherein the electrodeposition treatment includes a preliminary electrodeposition treatment and a main electrodeposition treatment. The pre-electrodeposition treatment is performed by immersing the base material to which conductivity has been imparted in the plating solution and moving the metal in a linear direction to perform metal plating to deposit metal ions on at least the surface of the base material. In this electrodeposition treatment, the base material after pre-electrodeposition treatment is held between pairs of mesh belts, and metal is plated on the base material while passing through the vicinity of the anode and carrying it out onto the plating solution. The mesh belt has mesh holes, and the mesh holes are formed from the anode. The supplied metal ions are passed through, and the vibration treatment vibrates the pair of mesh belts that hold the base material in the plating solution to generate a water flow in the plating solution and to form a three-dimensional mesh of the base material. This is a process of forcibly permeating the plating solution into the tissue.

The vibration treatment is a treatment for rocking the pair of mesh belts in the opening direction of the mesh holes to forcibly press the plating solution into the mesh belts.

Further, in the apparatus for producing a porous metal body according to the present invention, there is provided an apparatus for producing a porous metal body having a preliminary electrodeposition apparatus and the present electrodeposition apparatus, wherein the preliminary electrodeposition apparatus feeds two or more power supplies. A roll and an electrode plate are provided in the plating bath, and each power supply roll is arranged in series in the plating bath by supplying power to the cathode, and the base material having conductivity is provided along a linear transport line. A negative charge is applied to the base material while it is continuously fed to convey it in the plating solution.The electrode plate is a feed line for the base material that supplies power to the anode and supplies metal ions to the base material. The electrodeposition apparatus has a transfer mechanism, a vibrating device, and an electrode, and the transfer mechanism is an endless conveyor that forms a set, and is installed in a plating bath. The eggplant endless conveyor supports the substrate carried out from the preliminary electrodeposition device, The base material is carried into the cleaning solution and is carried out onto the plating solution via the plating solution. It has a mesh belt, and the mesh belt forms a pair between one set of endless conveyors. It is a belt of an endless conveyor that sandwiches a material between them and supports at least one surface thereof to convey the plating solution, and has a mesh hole for passing the plating solution over the entire surface, and an electrode is provided for each endless conveyor of the set. The pair of mesh belts are installed so as to face each other and are fed to the anode as a metal ion supply source, and the vibrating device vibrates the transport mechanism.

Further, the electrode of the present electrodeposition apparatus, which is supplied with power to the anode, is installed in the space surrounded by the mesh belt of each set of endless conveyors.

Further, each endless conveyor forming a set of transfer mechanisms is pivotally supported in a plating bath at one of the reversing positions thereof, and the vibrating device reciprocates about the pulley shafts of the endless conveyors of each set. It is an angular exercise.

Further, each endless conveyor forming a set of the transport mechanism is supported by a frame and is hung in a plating bath, and the vibration device has a frame supporting each set of endless conveyors in the plating bath. The apparatus for producing a metal porous body according to claim 3, wherein the apparatus is reciprocating.

The opening area of the mesh holes of the mesh belt is different for each endless conveyor, and the opening area of the mesh holes of the preceding mesh belt is relatively smaller than that of the latter stage.

The vibrating device has a frame body that connects the endless conveyors of each set, and the preliminary electrodeposition device is integrally assembled with the frame body.

[0022]

Operation: The electroconductive base material is subjected to the preliminary electrodeposition treatment and the main electrodeposition treatment, and the three-dimensional network structure of the base material is electroplated with the plated metal to a predetermined thickness. In the pre-electrodeposition treatment, the base material is immersed in the plating solution, metal ions are supplied from the electrodes while linear movement feed is provided across a pair of power supply rolls arranged in series in the plating bath, The plated metal evenly adheres to the flat surface of the substrate. The base material after the pre-electrodeposition treatment is once pulled up to the plating bath and then immersed in the plating solution for the main electrodeposition treatment. Prior to this, a negative charge was applied while rolling on the guide roll. It becomes a cathode, is sandwiched between the pair of endless conveyors in the front stage of the transfer mechanism, is continuously introduced into the plating solution from above, and then is inverted and taken out upward through the set of endless conveyors in the subsequent stage.
Meanwhile, the transfer mechanism is vibrated by the vibrating device, a water flow is generated in the plating solution, and the metal ions supplied from the electrodes are
It is forcibly pressed into the mesh belt of the endless conveyor and electrodeposited on the substrate.

The set of endless conveyors means a combination of a pair of conveyors for dipping the base material into the tank and a pair of conveyors for pulling the base material onto the tank. The pair of conveyors share the central endless conveyor. The vibrating device is a device that reciprocates a set of endless conveyors in the plating solution toward the anode. When the set of endless conveyors is reciprocated in the plating solution, the plating solution is forced to flow in through the mesh belt of the endless conveyor from the movement direction, and the plating is applied inside the base material sandwiched between the mesh belt pairs. Liquid penetrates.

It is easy to vibrate a set of endless conveyors by making a reciprocating angular motion around the pulley shaft of the endless conveyors. The groups may be reciprocated in parallel. The front endless conveyor and the mesh belt of the next endless conveyor adjacent to the front endless conveyor form a pair.

When a multistage endless belt is provided in the transport mechanism and the electrodeposition process is repeated, the opening areas of the mesh belts of the front and rear endless conveyors are made different so that the opening area of the front stage is made smaller and the opening area of the latter stage becomes smaller. By increasing the opening area of the mesh belt, the degree of penetration of the plating solution into the base material is large in the former stage, and the electrodeposition on the internal tissue progresses exclusively, and the electrodeposition on the surface occurs in the latter stage. Thereby, uniform metal plating is applied to the inside and outside as a whole. In particular, by using an endless belt for the transport mechanism, even if the support strength of the base material itself is weak, the base material will not break or stretch and the thickness will not be uneven, and uniform metal plating will be performed inside and outside. Is applied.

[0026]

Embodiments of the present invention will be described below with reference to the drawings. In FIG. 1, the device of the present invention comprises a preliminary electrodeposition device 1 and
It is a combination with the present electrodeposition apparatus 2. As shown in FIG. 2, the preliminary electrodeposition apparatus 1 has a power supply roll 4 and an electrode plate 5 which are arranged in series along a transport line L of a base material M which is horizontally formed in a plating bath 3. is there. The plating bath 3 is installed on a frame 19 provided in the electrodeposition apparatus 2 as shown in FIG. Each of the power feeding rolls 4 and 4 is driven to rotate in one direction, and a guide roller 6 that applies the base material M and guides it in the feeding direction is arranged on the lower peripheral surface thereof.
The electrode plate 5 is a metal to be electrodeposited on the base material, for example, a nickel plate, and extends across both the power feed rolls 4 and 4 and the transport line L
It is located below. The plating bath 3 has a liquid supply pipe 7 for supplying the plating liquid in the plating bath 11 of the present electrodeposition apparatus 2 and a drain pipe 8 for discharging the plating liquid in the plating bath 3, A pump 9 is attached to the pipe 7. The electro-deposition apparatus 2 includes a transport mechanism 12 in a plating bath 11.
And the electrode 13 are installed, and the vibration device 14 installed outside the tank is directly connected to the transport mechanism 12.

The plating bath 11 is a horizontally long bath having an open upper surface, and has a depth capable of accommodating the transport mechanism 12. The transport mechanism 12 is a vertically long endless conveyor 15X (X =
1, 2, ..., N) are closely combined in parallel with each other, and in the embodiment, three endless conveyors 151, 15
The first and second endless conveyors 15 are a set of 2, 153.
1, 152 are used for loading the base material into the tank, and the second and third endless conveyors 152, 153 are used for loading the base material from the tank. In FIG. 1, the first set of endless conveyors 151, 152,
153 sets and a part of the final set of conveyors 15 (n-1),
Although only 15n is shown, in the meantime, the second set, the third
A set of conveyors is provided. The endless conveyors 15 (X-1) and 15X that are adjacent to each other are given continuous movement feeds in opposite directions, and in the case of the first set of conveyors, between the first endless conveyor 151 and the second endless conveyor 152. , A downward feed is given to the base material carried in during this, and a feed is given between the second endless conveyor 152 and the third endless conveyor 153 so as to give an upward feed to the base material that has passed through the second endless conveyor 152. The direction is set.

Each endless conveyor is an endless mesh belt 18 laid between an upper pulley 16 and a lower pulley 17. In this embodiment, the lower pulley 17 is used.
The pulley shaft of is arranged near the bottom of the plating bath 11 and is pivotally supported at a fixed position, and the pulley shaft of the upper pulley 16 is supported by a frame 19 arranged on the plating bath 11.

The mesh belt 18 is a belt having mesh holes, but the opening area of the mesh holes is different for each endless conveyor of each stage. As shown in FIG. , The mesh holes Hx (x = 1, 2, ...
The opening area of n) is small, and the opening area of the mesh holes Hx is relatively enlarged toward the latter stage. The mesh hole does not necessarily mean a mesh formed between the warp yarn and the weft yarn,
Small holes may be evenly opened on the entire surface of the mesh belt. The small opening area of the mesh holes on the mesh belt means that the area covering the base material surface is large, and the large opening area of the mesh holes means that the area covering the base material surface is reduced. But also. Specifically, the opening area of the mesh belt of the endless conveyor in each stage is changed within the range of 100 mesh to 5 mm □.

The electrode 13 is a metal to be electrodeposited on the base material, such as a nickel plate or a nickel block. The electrodes 13 are all endless conveyors 151, 152, 151 that constitute the transport mechanism 12.
15n is placed in the space surrounded by the endless mesh belt 18 that is wound around the upper and lower pulleys 16 and 17, and this is fed to the anode.

In the embodiment, the vibrating device 14 uses a reciprocating slider crank mechanism. A connecting rod 21 driven by a motor 20 is connected to the frame body 19 and reciprocates using the frame body 19 as a sliding element to move the endless conveyors of each set to the lower pulley 1
A gentle reciprocal angular motion is performed around the pulley shaft of 7.

Reference numeral 22 in FIG. 1 denotes a guide roller for loading and unloading the base material delivered from the preliminary electrodeposition apparatus 1. The guide rollers 22 are the endless conveyors 15 (2
X-1) and the last endless conveyor 15n of the final stage are attached to the stay 23 established on the frame 19 and connected to the cathode side. The guide roller 22 is exposed at least on the liquid surface of the plating liquid.

Next, a method for producing a porous metal body using the apparatus of the present invention will be described. The metal porous body is obtained by subjecting a base material to a conductive treatment, subjecting the conductive-treated base material to a metal plating treatment, drying the base material, and then burning the base material off.

The substrate is a filmless polyurethane foam sheet. Preferably, two polyurethane foam sheets are laminated and integrated by a frame laminating method to prevent hollowing of the metal porous structure due to voids formed inside the sheets. The base material M is not limited to this, and in addition to a fibrous non-woven fabric having a three-dimensional network structure, a paper non-woven fabric, a lath-shaped or punch-shaped and other metal nets having independent pores, similarly a lath-shaped or punch-shaped and other resin net Etc. can be used. In addition, it is not necessary to take special strength retention measures on the base material for carrying and electrodeposition processing.

The conductive treatment is a treatment of applying or impregnating a conductive material on the entire surface of the structure including the three-dimensional network structure of the base material by another method. Conductive materials include carbon such as graphite and carbon black, or conductive resins such as polyacetylene, polyaniline, polyvirol, polythiophene and polyparaphenylene,
Use metal powder or mixtures thereof. Conductivity treatment is
In addition to coating and impregnating the conductive material and the base material for coating, it may be coated by chemically reducing and depositing a metal on the surface of the base material such as electroless plating. However, when using carbon fiber or metal fiber non-woven fabric as the base material,
No conductivity treatment is required. The base material after the electroconductivity treatment is wound into a roll and prepared for metal plating treatment.

The electrodeposition treatment is a treatment of immersing the electroconductive base material M in a plating solution filled in a plating bath to perform metal plating on the base material. As the plating metal, for example, Cu, Ni, Cr, Cd, Zn, Si or the like can be used.

In FIG. 1, the conductive material M is
It is installed in the carry-in device 24, one end of which is immersed in the plating tank 3 of the preliminary electrodeposition device 1 filled with the plating solution, and it is stretched horizontally in a straight line across the power supply rolls 4 and 4 to prepare a spare. When introducing the base material M drawn from the electrodeposition apparatus 1 into the electrodeposition apparatus 2, first, one end thereof is inserted downward between the pair of the first and second endless conveyors 151 and 152 of the first set, Further, after passing through the lower peripheral surface of the second endless conveyor 152,
It is inserted upward between the second and third endless conveyors 152 and 153 of the set, and thereafter similarly inserted between the endless conveyors of the subsequent set to form the endless conveyor 15n of the final set and the endless conveyor 15 (n-1 immediately before it). ) Between the guide roller 22 and the carry-out device 25.

In the preliminary electrodeposition process, the power supply rolls 4 and 4 are rotationally driven to supply the electrode plate 5 to the anode and the power supply rolls 4 and 4 to the cathode to start the electrodeposition process. Base material M
Are negatively charged through the power supply rolls 4 and 4 to serve as a cathode, and the metal ions 10 eluted from the electrode plate 5 while linearly moving between the power supply rolls 4 and 4 have a base material structure as shown in FIG. Is evenly electrodeposited on the surface. The electrodeposition amount of the metal ions attached to the base material M in the preliminary electrodeposition treatment is as small as about 0.1 to several μm. The substrate M is pulled up onto the plating bath 3 through the space between the power feeding rolls 4 and 4 and then introduced into the electro-deposition apparatus 2. In this electrodeposition process, when the base material M is introduced into the plating solution from above, the guide roller 22
The base material M comes into contact with the guide roller 22 in each step and becomes a cathode by passing through on the circumference of.

The endless conveyors of each set are driven in a predetermined direction in synchronization with each power feeding roll 4 of the preliminary electrodeposition apparatus 1,
The base material M is continuously fed and immersed in the plating solution. In the plating solution, metal ions dissolved in the solution from the electrode 13, which is an anode, pass through the mesh holes of the mesh belt 18 and come into contact with the base material M passing in the vicinity thereof to be electrodeposited. When the vibrating device 14 is driven to reciprocate the frame body 19 while continuously feeding, as shown in FIG.
, 15n make a reciprocating angular motion around the pulley shaft of the lower pulley 17 to generate a water flow in the plating solution, and the mesh belt 18 can be tilted to either the left or right side. The action of forcibly introducing the plating solution through the mesh holes occurs, the plating solution penetrates deeply into the base material M, and metal ions are also electrodeposited on the skeleton surface inside the tissue. In the above embodiments, the example in which the endless conveyor of each stage is swung with the pulley shaft of the lower pulley as the pivot has been shown.

According to this embodiment, the endless conveyors 151, 152, ...
The stroke of the angular movement of each part of n is different, the size of the water flow generated in the plating solution changes subtly depending on the size of the runout of the endless conveyor, and the plating on the base material depends on the size of the water flow of the plating solution. The degree of liquid penetration changes.

However, the force applied to the base material becomes excessive due to the difference in moving speed between the mesh belts of the endless conveyors in the front and rear stages forming a pair. When these problems occur, the upper and lower pulleys can be simultaneously reciprocated to reciprocate the endless conveyors in each stage in parallel. FIG. 5 is an example of reciprocating the endless conveyor in parallel. 5, in this embodiment, the frame 27 is integrally attached to the frame body 19, the pulley shaft of the lower pulley 17 of the endless conveyor of each stage is pivotally supported by the lower frame 28 of the frame 27, and the endless conveyor of each stage is supported. The pulley shaft of the upper pulley 16 is pivotally supported on the frame body 19,
9 and the lower frame 28 of the frame 27, the endless conveyors 151, 152, ... , Are provided on the lower surface of the frame body 19, and the rollers 29, 29, ... Are mounted on the guide rail 30 laid along the opening of the plating bath 11.

In the vibrating device 14, the connecting rod 21 driven by the motor 20 is connected to the frame body 19 as in the previous embodiment. Also in this embodiment, the connecting rod 21 cranks by the drive of the motor 20 and the frame 19 reciprocates.
The frame 27 moves integrally with the frame body 19, and the endless conveyors 151, 152, ..., 15n at each stage reciprocate in parallel.

According to this embodiment, there is no deviation in the feed speed between the pair of mesh belts of the endless conveyor forming a set, the base material can be smoothly conveyed, and the stroke of reciprocation is the whole feeding step of the endless conveyor. Will be the same in.

In this embodiment, since the endless conveyors at each stage are suspended from the frame 19 and installed in the plating bath 11, the endless conveyors can be easily removed from the plating bath 11 during maintenance and management. can do.

In each of the embodiments described above, since the mesh holes of the mesh belt 18 of the endless conveyor have a small area in the former stage, the plating solution permeates deep into the inside of the base material under strong pressure, and in the former stage. The outer surface of the base material M is exposed to the plating solution mainly as the electrodeposition inside progresses and the opening area of the mesh holes of the mesh belt increases.
Electrodeposition is performed on both outer surfaces of the base material M, and the entire surface of the three-dimensional network structure of the base material M is uniformly plated with metal to a required thickness while being repeatedly fed into and taken out of the plating solution by continuous feeding. To be done.

In order to accurately perform electrodeposition on the base material M, it is necessary to set a distance between the front and rear endless conveyors so that the base material is not pressed between the mesh belt pairs. desirable.

When the electrodeposition treatment is carried out in a state where pressure is applied between the pair of mesh belts during the transportation of the base material, the surface of the base material may be electro-deposited like a mesh belt. However, if the distance between the mesh belts is too wide compared to the thickness of the base material, it will interfere with the transfer of the base material and cause an accident such as poor contact between the guide roll and the base material or breakage of the base material. However, in practice, even if the distance between the mesh belt pairs is quite wide, the friction resistance and the vibration motion between the mesh belts may cause the base material to stick to one mesh belt and convey it without problems. In order to prevent the mesh hole shape of the mesh belt from being transferred to the surface of the base material, it is preferable to make the distance between the pair of mesh belts as wide as possible.

The last set of endless conveyors 15 (n-1), 1
The base material M carried out on the plating bath 11 from 5n is wound up in a roll shape, and then the base material is burned off.

The incineration process is a process of heating in air to burn off the urethane foam sheet component as the base material M.
By heating, the urethane foam of the base material disappears, and a porous body made of only metal having a three-dimensional network structure is formed.

However, the burning-off of the base material is a treatment required when it is used as an electrode of a battery, and it is not necessary to dare to burn off the base material when the metal porous body is used for a filter or the like. As described above, in the embodiment, the preliminary electrodeposition apparatus is installed on the frame body that constitutes the vibration device of the present electrodeposition apparatus, but the installation position is not limited to the frame body. Further, in the preliminary electrodeposition apparatus, the example in which the electrode plate is provided on only one of the substrate transfer lines is shown, but the electrode plates may be placed above and below the transfer line so as to sandwich it.

Examples of the present invention will be shown below.

(Example) A polyurethane foam sheet having a thickness of 1.2 mm and a width of 1.1 m was sandwiched between a pair of 10 mesh belts 32, 32 as shown in FIG. The sensitizing liquid shown in (1) was sprayed to perform the pretreatment (a) for making the material conductive.

(1) Sensitizing solution (conducting pretreatment liquid) SnCl ₂ · 2 was added to concentrated hydrochloric acid prepared by adding a small amount of water to concentrated hydrochloric acid.
After adding H ₂ O powder and completely dissolving it, a necessary amount of pure water is added. At the same time, a small amount of surfactant may be added. <Compounding example> SnCl ₂ · 2H ₂ O 7g HCl (concentrated hydrochloric acid) 5cc Pure water 25l After treatment, the base material is washed with pure water (b), and then conductive using the silver mirror reaction solution of the following (2) Chemical treatment (c) was performed.

(2) Conductivity treatment liquid (silver mirror reaction liquid) <Formulation example> Liquid A pure water 100 cc AgNO ₃ 12 g concentrated ammonia water 15 cc liquid B pure water 1000 cc hydrazine sulphate 45 g NaOH 22 g A liquid is 2 l of pure water. Dilute the liquid B with 20 l of pure water, and use a double-headed gun 33 that discharges at a ratio of 1: 1.
The liquid A and the liquid B were sprayed on the substrate M. After the electroconductivity treatment, a washing treatment (d) was performed with pure water, and the base material was wound into a roll.

The substrate after the conductive treatment is introduced into the apparatus for producing a porous metal body shown in FIG. 1 to perform metal plating. The composition of the plating solution filled in the plating bath is shown in (3). The plating conditions are shown in (4). Pre-electrodeposition equipment has a diameter of 300 m
m pairs of power supply rolls were used at intervals of 10 cm, 10 endless conveyors were used as the transport mechanism of the present electrodeposition apparatus, and 100 mesh belts were used for the first and second endless conveyors. The endless conveyor has a 50 mesh belt,
Hereinafter, a 5-mesh belt was used up to the tenth endless conveyor. Further, each endless conveyor was oscillated about the lower pulley in the range of a central angle of about 8 degrees and at a cycle of 20 times / minute.

(3) Composition of plating solution <Compounding example> Nickel sulfamate 370 g / l Boric acid 35 g / l Potassium bromide 0.15 to 0.28 g / l Sodium lauryl sulfate 0.4 g / l

(4) Plating conditions Liquid temperature 45 ° C. pH 4.2 Substrate feeding speed 5.0 m / H (width of substrate 1.1 m) In the preliminary electrodeposition apparatus, the current density was maintained at 10 A / m ² . 1
The electrode plate is moved for 0 cm while facing the electrode plate, and in this electrodeposition apparatus, each step is immersed in the plating solution to make the length of the base material 10 m.
× 1.1 m, current density 400 A / m ² (front and back sides) After metal plating treatment, the obtained porous sheet was washed, sufficiently dried, and then heated to 800 ° C. in an oven to obtain a base material. Burned out.

1 piece of the porous sheet taken out from the oven
A heat treatment was performed for 1 hour in an ammonia decomposition gas at 100 ° C., and then the mixture was cooled in the ammonia decomposition gas to obtain a metal porous body. The thus-obtained metal porous body has an average nickel basis weight of 40.
It was 0 g / m ² , there was no crack, and the structure formed a uniform structure in the network structure of the base material.

For comparison, when the same base material was subjected to electrodeposition treatment under the same conditions without using a preliminary electrodeposition apparatus, the obtained porous metal had a nickel basis weight of 100 g / m ² or less, Only uniform electrodeposition was possible. Further, when the main electrodeposition treatment was carried out under the same conditions except for the substrate feeding speed without using the preliminary electrodeposition apparatus, the nickel basis weight was 400 on average.
The feed rate of the base material to obtain the porous metal body of g / m ² was 1.0 m / H.

[0060]

As described above, according to the present invention, the electrodeposition treatment is divided into a preliminary electrodeposition treatment and a main electrodeposition treatment, and in the preliminary electrodeposition treatment, at least the surface of the substrate is provided while linearly feeding the substrate. Since metal ions are deposited on the base material and the base material is kept in a horizontal position during the pre-electrodeposition treatment to prevent deformation, cracks occur on the base material surface after the pre-electrodeposition treatment due to the difference in the amount of metal ion deposition. Absent. Then, after the preliminary electrodeposition process,
In the subsequent main electrodeposition process, the metal ions attached to the surface of the pre-electrodeposition treated substrate trigger the electrodeposition to proceed rapidly, and in particular, electrodes are installed in the endless conveyor at each stage, A mesh belt is used to introduce the plating solution to the surface of the base material through the mesh holes of the belt and to oscillate the endless conveyor, so that a water flow is generated in the plating solution and effectively penetrates into the base material through the mesh holes, and metal ions Is sequentially electrodeposited on one surface and the other surface of the base material, and the electrodeposition progresses rapidly under the conditions of high voltage and high current in this electrodeposition process, and the plating solution penetrates deeply into the internal structure of the base material. A high basis weight metal can be electrodeposited on the skeleton surface of internal and external tissues in a short time. Moreover, since the base material is sandwiched between a pair of multi-stage endless conveyors and is routed back through the plating tank 1, the base material is thin and easily damaged like a polyurethane foam sheet, and also wavy, Even if the material is easily curved, it can be transferred to the inside of the plating bath by holding the mold in a fixed shape without expansion and contraction.

Further, regarding the endless conveyor of each stage, the opening area of the mesh belt is sequentially enlarged from the first stage side, so that the base material is continuously moved and the inside and outside of the base material is moved while passing through the endless conveyor of each stage. The metal can be electrodeposited evenly on the mesh fibers.

Further, by installing the preliminary electrodeposition apparatus on the frame constituting the vibration mechanism of the present electrodeposition apparatus, the substrate can be applied to the substrate when the preliminary electrodeposition apparatus is transferred to the present electrodeposition apparatus. No unreasonable force is applied.

Further, when vibrating the rows of the endless conveyors of each set by the vibrating device, if the reciprocating angular motion is performed around one pulley shaft, it is mechanically simple and the length of the endless conveyors at each stage is long. It is possible to change the degree of penetration of the plating solution into the base material by making a subtle change in the water flow of the plating solution that occurs in the vertical direction, but with a structure that supports the endless conveyor at each stage and reciprocates the frame in parallel. According to this, relative displacement does not occur between the endless conveyors of the respective stages adjacent to each other, and therefore, the frictional resistance applied to the base material during conveyance is small. Moreover, with the structure in which the frame that supports the endless conveyor reciprocates in parallel, the support of the endless conveyor is independent of the plating bath, so it is possible to remove the endless conveyor from the plating bath for each frame, and maintain the endless conveyor. Has the effect of being easy.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a porous metal body manufacturing apparatus showing an embodiment of the present invention.

FIG. 2 is a diagram showing an adhesion procedure of a plating metal deposited on a base material by a pre-electrodeposition treatment.

FIG. 3 is a diagram showing changes in the opening area of mesh holes of a mesh belt.

FIG. 4 is a diagram showing a first example of a metal plating process.

FIG. 5 is a diagram showing a second embodiment of the metal plating process.

FIG. 6 is a diagram showing a conductive treatment step.

FIG. 7 is a diagram showing a problem of the conventional technique.

FIG. 8 is a diagram showing a base material in which a crack has occurred.

[Explanation of symbols]

 1 Preliminary Electrodeposition Device 2 Main Electrodeposition Device 3 Plating Bath 4 Power Feed Roll 5 Electrode Plate 7 Liquid Supply Pipe 8 Drainage Pipe 9 Pump 10 Metal Ion 11 Plating Bath 12 Transfer Mechanism 13 Electrode 14 Vibrating Device 151, 152, ..., 15n Endless conveyor 16 Upper pulley 17 Lower pulley 18 Mesh belt 19 Frame 20 Motor 21 Connecting rod 22 Guide roller 23 Stay 24 Loading device 25 Unloading device 26 Belt 27 Frame 28 Lower frame 29 Roller 30 Guide rail

Claims (8)

[Claims] 1. A base material having an electro-deposition treatment and an oscillating treatment, which is provided with conductivity, is immersed in a plating solution to continuously feed the base material to the skeleton surface of the three-dimensional network structure of the base material. A method for producing a metal porous body to which metal plating is applied, wherein the electrodeposition treatment comprises a preliminary electrodeposition treatment and a main electrodeposition treatment. The preliminary electrodeposition treatment involves plating a base material to which conductivity has been imparted with a plating solution. This is a treatment to perform metal plating while immersing the substrate in a linear direction and to deposit metal ions on at least the surface of the base material. It is a process of holding the metal mold between pairs and metal-plating the base material while passing it near the anode and discharging it onto the plating solution. The mesh belt has mesh holes, and the mesh holes are supplied from the anode. The metal ion to be passed through. A porous metal body is characterized in that it is a process of vibrating a pair of plates in a plating solution to generate a water flow in the plating solution and forcibly infiltrating the plating solution into the three-dimensional network structure of the base material. Method. 2. The metal according to claim 1, wherein the vibration treatment is a treatment for rocking the pair of mesh belts in the opening direction of the mesh holes to forcibly press the plating solution into the mesh belts. Method for manufacturing porous body. 3. An apparatus for producing a metal porous body having a preliminary electrodeposition apparatus and the present electrodeposition apparatus, wherein the preliminary electrodeposition apparatus has two or more power supply rolls and an electrode plate in a plating bath. Then, each feeding roll feeds power to the cathode and is arranged in series in the plating bath to apply a negative charge to the substrate while continuously feeding the substrate to which conductivity has been given along a linear transport line. The electrode plate is arranged in parallel with the base material transfer line as a supply source of metal ions to be supplied to the base material. The deposition device has a transport mechanism, a vibrating device, and an electrode.The transport mechanism is a set of endless conveyors installed in the plating bath, and the set of endless conveyors is carried out from the preliminary electrodeposition device. Support the base material, bring the base material into the plating solution, and pass through the plating solution. It is carried onto the plating solution and has a mesh belt. The mesh belt forms a pair between one set of endless conveyors.
It is a belt of an endless conveyor that sandwiches a base material and supports at least one surface to convey the plating solution.It has a mesh hole for passing the plating solution over the entire surface, and the electrode is a pair of endless conveyors. The pair of mesh belts facing each other are installed facing each other, and are fed to the anode as a source of metal ions, and the vibrating device vibrates the transport mechanism. Body manufacturing equipment. 4. The electrode of the present electrodeposition apparatus, wherein the electrode is fed to the anode,
The apparatus for producing a porous metal body according to claim 3, wherein the apparatus is installed in a space surrounded by mesh belts of each set of endless conveyors. 5. Each of the endless conveyors forming a set of transport mechanisms comprises:
The oscillating device is pivotably supported in the plating bath at one of the reversing positions, and the vibrating device reciprocates angularly around the pulley shaft of each set of endless conveyors. Of porous metal manufacturing equipment. 6. Each of the endless conveyors forming a set of transport mechanisms comprises:
The apparatus is supported by a frame and is hung in a plating bath, and the vibration device reciprocates a frame that supports each set of endless conveyors in the plating bath. Of porous metal manufacturing equipment. 7. The opening area of the mesh holes of the mesh belt is different for each endless conveyor, and the opening area of the mesh holes of the preceding stage mesh belt is relatively smaller than that of the latter stage. Of porous metal manufacturing equipment. 8. The vibrating device has a frame body that connects each set of endless conveyors, and the preliminary electrodeposition device is integrally assembled with the frame body. Or the manufacturing apparatus of the metal porous body as described in 6 above.