CN100467102C - Method for manufacturing filter for hydrogen production - Google Patents

Abstract

In the through hole plugging process, a metal plate is attached to one surface of the conductive base material having a plurality of through holes by using a magnet, and in the copper plating process, from the side of the conductive base material surface where the metal plate is not attached, A copper plating layer is formed on the conductive base material and the metal plate exposed in the through hole to fill the through hole. In the film formation process, a Pd alloy film is formed on the conductive base material after the metal plate is removed by electroplating. In the removal step, the copper plating layer is removed by selective etching. Therefore, it is possible to manufacture a filter for hydrogen production that can stably produce high-purity hydrogen gas, which is used in a reformer of a fuel cell.

Description

Method for manufacturing filter for hydrogen production

technical field

The present invention relates to a method for manufacturing a filter for hydrogen production, in particular to a method for producing a filter for hydrogen production by steam reforming various hydrocarbon fuels to generate hydrogen-rich gas for fuel cells.

In addition, it relates to a filter for hydrogen production, and in particular to a thin film support substrate for a hydrogen production filter that converts various hydrocarbon fuels into a hydrogen-rich gas to generate hydrogen-rich gas for fuel cells, and This supporting thin film supporting substrate is used in a method of manufacturing a filter for hydrogen production.

Background technique

In recent years, from the viewpoint of global environmental protection, there has been concern about the generation of global warming gases such as carbon dioxide, and the use of hydrogen as a fuel has attracted attention due to its high energy efficiency. In particular, fuel cells are also attracting attention because of their high energy conversion efficiency, which can directly convert hydrogen gas into electricity, or use the generated heat to generate electricity and waste heat heating systems. So far, although fuel cells have been used in special conditions such as space development and ocean development, recently, they have entered the development of distributed power sources for automobiles and households. In addition, fuel cells for portable devices are also being developed.

A fuel cell is a hydrogen-rich gas obtained by modifying hydrocarbons such as natural gas, gasoline, butane gas, and methanol, and a power generation device that directly extracts electricity through an electrochemical reaction with oxygen in the air. Generally, a fuel cell is composed of a reformer that reforms carbohydrate-based fuels with water vapor to generate hydrogen-rich gas, a fuel cell body that generates electricity, and an inverter that converts the generated direct current into alternating current.

Such fuel cells are classified into phosphoric acid fuel cells (PAFC), molten carbonate fuel cells (MCFC), solid oxide fuel cells (SOFC), strong Alkaline fuel cell (AFC) and solid polymer fuel cell (PEFC). Among them, compared with other fuel cells such as phosphoric acid fuel cell (PAFC) and strong alkali fuel cell (AFC), solid polymer fuel cell (PEFC) has the advantage that the electrolyte is solid.

However, the solid polymer fuel cell (PEFC) uses platinum as a catalyst, and, due to the low operating temperature, the electrode catalyst is poisoned by a small amount of CO, especially, there is a disadvantage of performance degradation in the high current density region. Therefore, it is necessary to reduce the CO concentration contained in the reformed gas (hydrogen-rich gas) generated by the reformer to about 10 ppm in order to produce high-purity hydrogen.

As one of methods for removing CO from reformed gas, a membrane separation method using a Pd alloy membrane as a filter is utilized. The Pd alloy film is based on the assumption that small holes or cracks on the film allow only hydrogen to permeate in principle. By making the modified gas side into a high temperature and high pressure (for example, 300 ° C, 3 ~ 100kg/cm ² ), at a low hydrogen partial pressure side to let the hydrogen pass through.

Using the above-mentioned membrane separation method, although the passing speed of hydrogen gas is inversely proportional to the film thickness, it is required to be thinner. However, in terms of mechanical strength, the Pd alloy film is limited to a thin film of about 30 μm alone. In the case of using a Pd alloy film having a film thickness of about ten tens of μm, a porous structure support is disposed on the low hydrogen partial pressure side of the Pd alloy film. However, since the Pd alloy film and the support body are installed on the reformer in a separate manner, the workability will be reduced in order to obtain good welding. In addition, scratches will be generated between the Pd alloy film and the support body, and there is a Pd alloy film. The problem of insufficient durability.

In order to solve the above-mentioned problems, a filter in which a Pd alloy film is integrated with a support having a porous structure using an adhesive has been developed. However, it is necessary to remove the adhesive from the Pd alloy film located in the pores of the support, which brings about a problem that the manufacturing process is complicated. In addition, since the reformer is used under high temperature and high pressure, it is difficult to avoid deterioration of the adhesive, and the durability of the filter cannot be fully exhibited.

Further, in order to maintain the desired strength of the support body, the size of the opening diameter of the hole that the support body has is limited, and furthermore, the expansion of the area of the effective Pd alloy film for hydrogen penetration is also limited, which brings about the improvement of hydrogen gas. Through efficiency barriers.

Contents of the invention

Accordingly, an object of the present invention is to provide a method for producing a hydrogen production filter which can be used in a reformer of a fuel cell and which can stably produce high-purity hydrogen gas.

In order to achieve the above object, the present invention includes: on one surface of the conductive base material having a plurality of through holes, a through-hole plugging process of attaching a metal plate by a magnet; On one side, the above-mentioned copper plating process of forming a copper plating layer on the conductive base material and the above-mentioned metal plate exposed in the through-hole, and filling the above-mentioned through-hole; on the surface of the above-mentioned conductive base material after removing the above-mentioned metal plate Above, a film formation process of forming a Pd alloy film by electroplating; and a removal process of removing the above-mentioned copper plating layer by selective etching.

In addition, the present invention includes: on one surface of the conductive base material having a plurality of through holes, a sticking step of sticking an insulating film; layer to fill the above-mentioned through-hole copper plating process; on the surface of the conductive base material after the above-mentioned insulating film is removed, a film forming process of forming a Pd alloy film by electroplating; and removing the above-mentioned copper-plated layer by selective etching process.

In addition, the present invention includes: a step of filling the through-holes of a conductive base material having a plurality of through-holes with a resin member; Any of the following, a base forming process of forming a Pd alloy film to form a conductive base layer; a film forming process of forming a Pd alloy film on the conductive base layer by electroplating; and a process of removing only the above resin member by dissolving it Remove process.

Furthermore, the present invention includes: forming a given resist pattern on both sides of the conductive base material, using the resist pattern as a mask, etching the above-mentioned conductive base material from both sides to form a plurality of through holes an etching step; a film forming step of forming a Pd alloy film by electrolytic plating to block the through-hole of the conductive base material; and a removing step of removing the resist pattern.

According to the present invention as described above, even if the Pd alloy film is thin, since it is adhered to the conductive base material with high strength to integrate it, the durability of the film can be greatly improved. Therefore, according to the present invention, the Pd alloy film formed by electroplating is adhered to the conductive base material having a plurality of through holes with high strength to make it integrated, and since no adhesive is used, the heat resistance can be excellent, It can be used under high temperature and high pressure, and at the same time, even if the hydrogen permeation efficiency is improved by making the Pd alloy film thinner, it can still manufacture a hydrogen production filter with excellent durability and optimized workability such as installation to the reformer. .

Another object of the present invention is to provide a thin film support substrate that enables a hydrogen production filter used in a reformer of a fuel cell to stably produce high-purity hydrogen gas, and a device using the thin film support substrate. A method of manufacturing a filter for hydrogen production.

In order to accomplish the above object, the thin film support substrate of the present invention is a thin film support substrate used in a filter for hydrogen production, which includes: a metal substrate; a plurality of columnar protrusions formed on one surface of the metal substrate; and The non-formed portion of the columnar protrusion is a plurality of through holes formed through the metal substrate, and the area of the non-formed portion of the columnar protrusion occupies a range of 20% to 90% of the area of the side surface on which the columnar protrusion is formed.

In addition, the manufacturing method of the filter for hydrogen production using the above-mentioned film support substrate of the present invention includes: disposing an insulating film on the surface of the above-mentioned film support substrate on which the columnar protrusions are formed, and adhering the insulating film to the above-mentioned Step of disposing the upper end surface of the columnar protrusion; forming a conductive base layer by electroless plating on the film support substrate except the upper end surface of the columnar protrusion, and on the side of the adhesive surface of the insulating film A base layer forming step; a copper plating step of forming a copper plating layer on the conductive base layer, and filling the space formed between the metal substrate of the thin film supporting substrate and the insulating thin film and the inside of the through hole of the thin film supporting substrate; A film forming step of forming a Pd alloy film by electroplating on the upper end surface of the columnar protrusion after removing the insulating thin film and the surface formed with the copper plating layer; and a removing step of removing the copper plating layer by selective etching.

Further, the method of manufacturing a filter for hydrogen production using the above-mentioned thin-film support substrate of the present invention includes: disposing an insulating thin film on the surface of the above-mentioned thin-film support substrate opposite to the surface on which the columnar protrusions are formed. Step: forming a copper plating layer on the surface of the above-mentioned film supporting substrate on which the columnar protrusions are formed, filling the inside of the above-mentioned through holes and covering the copper plating process of the columnar protrusions; removing the above-mentioned copper plating layer flatly to make the above-mentioned columnar protrusions The upper end surface of the part is exposed and forms the same planar surface as the upper end surface; the film forming process of forming a Pd alloy film by electroplating on the flat surface formed by the upper end surface of the columnar protrusion and the copper plating layer; and After removing the insulating thin film, the copper plating layer is removed by selective etching.

Furthermore, the manufacturing method of the filter for hydrogen production using the above-mentioned film support substrate of the present invention includes: forming a resin layer on the surface of the above-mentioned film support substrate on which the columnar protrusions are formed, filling the inside of the above-mentioned through hole and covering the above-mentioned The resin layer forming process of the columnar convex part; the planarization process of removing the above-mentioned resin layer flatly, exposing the upper end surface of the above-mentioned columnar convex part, and constituting the same plane as the upper end surface; and a flat surface composed of a resin layer, by any one of electroless plating and vacuum film-forming methods, forming a base layer forming process of a conductive base layer; on the above-mentioned conductive base layer, forming a Pd alloy film by electroplating a film forming step; and a removing step of dissolving and removing only the above-mentioned resin layer.

Also, the manufacturing method of the filter for hydrogen production using the above-mentioned thin-film support substrate of the present invention includes: forming a Pd alloy film by electroplating on one surface of the metal base material that can be selectively etched with respect to the above-mentioned thin-film support substrate The film forming process; on the surface of the above-mentioned thin film supporting substrate on which the columnar protrusions are formed, the diffusion bonding process of disposing the above-mentioned metal base material by diffusion bonding the above-mentioned Pd alloy film and the upper end surface of the columnar protrusions; and by selectively A removal process of etching and removing the above-mentioned metal base material.

According to the present invention, since the film supporting substrate is equipped with a metal substrate, even if the ratio of the area of the non-formation portion of the columnar protrusion to the area of the columnar protrusion forming surface is increased, the film supporting substrate can be provided with very high strength, and as a result , can expand the area of the effective Pd alloy film in hydrogen permeation, and improve the hydrogen permeation efficiency. In addition, the manufacturing method of the present invention using the thin film support substrate of the present invention described above, since the Pd alloy film formed by electroplating is adhered with high strength to the upper end surface of the columnar convex portion of the thin film support substrate having a plurality of through-holes. The integration, so it can have a large effective hydrogen permeation area. Furthermore, since no adhesive is used, heat resistance can be excellent, and it can be used under high temperature and high pressure. At the same time, even if the hydrogen permeation efficiency is improved by making the Pd alloy film thinner, it is still possible to manufacture extremely durable, A filter for hydrogen production with optimized operability such as installation to the reformer.

Description of drawings

1A to 1D are process diagrams showing an embodiment of a method for manufacturing a filter for hydrogen production according to the present invention.

2A to 2D are process diagrams showing another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

3A to 3D are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

4A to 4D are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

Fig. 5 is a plan view showing an embodiment of the thin film supporting substrate of the present invention.

Fig. 6 is a longitudinal sectional view taken along line I-I of the thin film supporting substrate shown in Fig. 5 .

Fig. 7 is a vertical cross-sectional view taken along line II-II of the film support substrate shown in Fig. 5 .

Fig. 8 is a longitudinal sectional view taken along line III-III of the thin film support substrate shown in Fig. 5 .

9A to 9E are process diagrams showing an embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

10A to 10E are process diagrams showing another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

11A to 11E are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

12A to 12C are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

Detailed ways

Next, embodiments of the present invention will be described.

1A to 1D are process diagrams showing an embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

In the production method of the present invention, first, in the through-hole plugging step, a metal plate 14 is attached to one surface 12a of the conductive base material 12 having a plurality of through-holes 13 by using a magnet 15, whereby the through-holes 13 are blocked ( Figure 1A). As the material of the conductive base material 12, there are conductive materials such as ferritic stainless steel Fe-Cr-based materials such as SUS430 that can be adhered to the magnet, and its thickness can be appropriately set at 20 to 500 μm. The range is preferably in the range of 50 to 300 μm. Furthermore, the through hole 13 can be formed by means of etching through a given resist pattern, punching, laser processing, or the like. The opening size of each through-hole 13 is 10-500 μm, preferably in the range of 50-300 μm, and the opening area of a plurality of through-holes 13 can be made to account for 5-75% of the entire area of the conductive base material 12, preferably In the range of 10 to 50%, and the above-mentioned opening size refers to the diameter when the opening shape of the through hole 13 is a circle, and refers to the maximum opening when the opening shape is a polygon or the like. The average value of the position and the minimum opening position. Hereinafter, the present invention has the same meaning.

As the above-mentioned metal plate 14, a conductive and strong magnetic or soft magnetic material can be used, such as Fe-Cr-based materials and Fe-C-based materials of ferritic stainless steel that can be adhered to magnets such as SUS430. , or Fe-Cr-Ni materials such as SUS304 that do not stick to the magnet. The thickness of such a metal plate 14 can be appropriately set in consideration of the material, the magnetic charge of the magnet 15 to be used, and the like, and can be, for example, about 20 to 500 μm.

The magnet 15 used to attach the metal plate 14 to the conductive base material 12 can be a film or plate-shaped permanent magnet, an electromagnet, or the like.

Next, in the copper plating step, copper plating is performed on the conductive base material surface 12b not provided with the metal plate 14, and the copper plated layer 16 is formed on the conductive base material surface 12b and the metal plate 14 exposed in the through hole 13. , fill the through hole 13 (FIG. 1B). The purpose of this copper plating step is to fill the through hole 13 with copper plating, and the thickness and shape of the copper plating layer 16 formed on the conductive base material surface 12b are not particularly limited.

Next, in the film forming step, the above-mentioned metal plate 14 and magnet 15 are removed, and electroplating is performed on the removed conductive base material surface 12b to form a Pd alloy film 17 (FIG. 1C). The formation of Pd alloy film 17 can adopt following method to carry out, promptly the method for directly forming Pd alloy film by electrolytic plating; After that, heat treatment is applied, the method of forming a Pd alloy film by component diffusion, etc. For example, Pd with a thickness of 10 μm is formed by electroplating, and Ag with a thickness of 1 μm is formed on it by electroplating, and then heat treated at 250° C. for 10 minutes to achieve Pd alloying. In addition, heat treatment may be performed after performing multilayer plating such as three layers consisting of Pd/Ag/Pd and four layers consisting of Pd/Ag/Pd/Ag. The thickness of the Pd alloy film 17 may be 0.5 to 30 μm, preferably about 1 to 15 μm.

In addition, before forming the Pd alloy film 17, Ni strike plating or the like is applied to the conductive base material 12a to improve the adhesion to the formed Pd alloy film 17. The thickness of such Ni strike plating can be set, for example, in the range of 0.01 to 0.5 μm.

Next, in the removal step, the copper plating layer 16 is removed by selective etching to obtain a filter for hydrogen production ( FIG. 1D ). Selective etching is performed using an ammonia-based etchant by means of a jet method, dipping method, air blowing, or the like.

In the hydrogen production filter 11 manufactured as described above, the Pd alloy film 17 adheres to the conductive base material 12 with high strength. Although the Pd alloy film is thinned in order to improve the hydrogen permeation efficiency, even in this way, A filter with extremely high durability can be obtained. In addition, since no adhesive is used, heat resistance can be excellent, and it can be used under high temperature and high pressure, and further, workability such as installation to a reformer can be optimized.

2A to 2D are process diagrams showing another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

In the manufacturing method of the present invention, first, in the bonding step, an insulating film 24 is bonded to one surface 22a of a conductive base material 22 having a plurality of through holes 23 (FIG. 2A). The material of the conductive base material 22 may be austenitic or ferritic stainless steel such as SUS304 or SUS430, and its thickness may be appropriately set within the range of 20 to 500 μm, preferably 50 to 300 μm. within range. Furthermore, the through-holes 13 can be formed by means of etching, punching, laser processing, etc. through a given resist pattern, and the opening size of each through-hole 13 is 10-500 μm, preferably in the range of 50-300 μm. The total opening area of the plurality of through-holes 13 can occupy 5 to 75% of the entire area of the conductive base material 22, preferably in the range of 10 to 50%. The above-mentioned opening size refers to the diameter when the opening shape of the through-hole 13 is circular, and refers to the average value of the largest opening portion and the smallest opening portion when the opening shape is polygonal or the like. Hereinafter, the present invention has the same meaning.

As the insulating film 24 described above, resin films such as polyethylene terephthalate, polypropylene, and polycarbonate can be used. The thickness of such an insulating film 24 can be appropriately set in consideration of its material, electrical insulating performance, film strength, and the like. It may be, for example, about 30 to 300 μm. Attaching the insulating film 24 to the conductive base material 12 can be performed by a method using a polyamide-based adhesive or a method utilizing the heat-welding properties of the insulating film.

Next, in the copper plating step, copper plating is performed on the conductive base material surface 22b on which the insulating film 24 is not attached, and a copper plating layer 25 is formed to fill the through hole 23 ( FIG. 2B ). The purpose of this copper plating step is to fill the through hole 23 with copper plating, and the thickness and shape of the copper plating layer 25 formed on the conductive base material surface 22b are not particularly limited.

Next, in the film forming step, the above-mentioned insulating thin film 24 is removed, and a Pd alloy film 26 is formed by electroplating on the removed conductive base material surface 22a (FIG. 2C). The insulating film 24 can be removed by peeling or melting. In addition, the formation of the Pd alloy film 26 is formed by the method of directly forming the Pd alloy film by electrolytic plating; On the base material surface 22a, after that, heat treatment is applied to form a Pd alloy film by component diffusion, etc. For example, 10 μm thick Pd is formed by electroplating, 1 μm thick Ag is formed on it by electroplating, and then heat treatment is performed at 900° C. for 10 hours to achieve Pd alloying. In addition, heat treatment may be performed after performing multilayer plating such as three layers consisting of Pd/Ag/Pd and four layers consisting of Pd/Ag/Pd/Ag. The thickness of the formed Pd alloy film 26 may be 0.5 to 30 μm, preferably about 1 to 15 μm.

Further, on the conductive base material surface 22a, for example, by applying Ni strike plating or the like, the adhesion to the Pd alloy film 26 formed is improved. The thickness of such Ni strike plating can be set, for example, in the range of 0.01 to 0.1 m.

Next, in the removal step, the copper plating layer 25 is removed by selective etching to obtain a filter 21 for hydrogen production ( FIG. 2D ). The selective etching can be carried out by using an ammonia-based etchant by means of jet flow, dipping, blowing, and the like.

In the hydrogen production filter 21 manufactured above, the Pd alloy film 26 adheres to the conductive base material 22 with high strength, and although the Pd alloy film is thinned in order to improve the hydrogen gas permeation efficiency, even in this way, it is possible to obtain Very durable filter. In addition, since no adhesive is used, it can be used under high temperature and high pressure with excellent heat resistance, and the workability such as installation to the reformer can be further optimized.

3A to 3D are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

First, in the filling step, a resin material 34 is filled in the plurality of through-holes 33 provided in the conductive base material 32 ( FIG. 3A ). The material and thickness of the conductive base material 32 may be the same as those of the above-mentioned conductive base material 22 , and the formation method, size, and formation density of the through-holes 33 are also the same as those of the above-mentioned through-holes 22 . In addition, the conductive base material 32 may be subjected to, for example, Ni strike plating after the through-hole 33 is formed, so that the adhesion of the Pd alloy film formed in a subsequent process can be improved. The thickness of such Ni strike plating can be set, for example, in the range of 0.01 to 0.5 μm.

The above-mentioned resin member exhibits stable resistance in the base formation step and film formation step described later, and can be reliably dissolved and removed in the removal step. For example, a phenolic resist resin can be used. When filling the through-hole 33 with such a resin material, a method such as grouting can be used.

Next, in the base forming step, a Pd alloy film is formed on one surface of the conductive base material 32 filled with the resin material 34 in the through hole 33, and a conductive base layer 35 is formed (FIG. 3B). In this base forming step, the purpose is to impart conductivity to the exposed surface of the resin material 34 filled in the through hole 33, and the thickness of the formed conductive base layer 35 can be set in the range of 0.01 to 0.2 μm. . The Pd alloy film to be the conductive base layer 35 can be formed by electroless plating, or can be formed by a vacuum film-forming method such as sputtering or vacuum deposition.

Next, in the film forming step, electroplating is performed on the conductive base layer 35 to form a Pd alloy film 36 ( FIG. 3C ). The formation of this Pd alloy film 36 is formed by the method of directly forming the Pd alloy film by electrolytic plating; On the upper base layer 35, thereafter, a heat treatment is applied, a method of forming a Pd alloy film by component diffusion, and the like. The thickness of the Pd alloy film 36 may be 0.5 to 30 μm, preferably about 1 to 15 μm.

Next, in the removal step, only the resin material 34 is dissolved and removed to obtain a filter 31 for hydrogen production ( FIG. 3D ). The dissolution and removal of the resin material 34 is performed by using solvents such as acetone, methyl ethyl ketone, methyl isobutyl (methyl) ketone, or Desmear solution (manufactured by Shipley Co., Ltd.) depending on the resin material used. It is carried out in the jet method, dipping method, etc.

In the filter 31 for producing hydrogen produced as described above, the Pd alloy film 36 is adhered to the conductive base material 32 with high strength relative to the conductive base layer 35. Although the Pd alloy film is thinned in order to improve the hydrogen permeation efficiency, However, even in this way, a highly durable filter can be obtained. In addition, since no adhesive is used, it can be used under high temperature and high pressure with excellent heat resistance, and the workability such as installation to the reformer can be further optimized.

4A to 4D are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

In the manufacturing method of the present invention, in the etching step, first, resist patterns 44a and 44b having a plurality of small openings are formed on both surfaces of the conductive base material 42 (FIG. 4A). The respective openings of the resist pattern 44a are opposed to the respective openings of the resist pattern 44b through the conductive base material 42, and the opening areas of the small openings facing each other are preferably the same, or on the other hand, for example, a resist pattern may be used. The opening area of the small opening of the etching pattern 44b is larger. The shape and size of the small openings of these resist patterns 44 a and 44 b can be appropriately set in consideration of etching conditions, the material and thickness of the conductive base material 42 , and the like. The material and thickness of the conductive base material 42 are the same as those of the conductive base material 22 . The resist patterns 44a and 44b can be formed, for example, by applying a material selected from conventionally known positive and negative photosensitive resist materials, exposing and developing with a predetermined mask.

Next, by using the above-mentioned resist patterns 44a and 44b as masks, the conductive base material 42 is etched to form a plurality of fine through-holes 43 in the conductive base material 42 ( FIG. 4B ). Etching of the conductive base material 42 is carried out by means of a jet method, dipping method, air blowing, etc., using an etching solution such as ferric chloride or copper chloride. The through hole 43 formed on the conductive base material 42 by etching in this way has an opening area on the side of the conductive base material surface 42a or an opening size on the side of the conductive base material surface 42b of 10 to 500 μm. The range is preferably in the range of 50-300 μm, and the total opening area of the plurality of through-holes 43 accounts for 5-75% of the entire area of the conductive base material 42, preferably in the range of 10-50%. In addition, when the above-mentioned resist patterns 44a and 44b are used as masks to etch the conductive base material 42 from both sides, generally, a protrusion is formed at a substantially central position of the inner wall surface of the formed through-hole 43 . Site 43a. Therefore, when there is such a protruding portion 43a, the opening area of the above-mentioned through hole 43 becomes the opening area of the protruding portion 43a.

Next, in the film forming step, an alloy film 46 is formed by electrolytic plating ( FIG. 4C ) so as to close the through-hole 43 of the conductive base material 42 . The formation of the Pd alloy film 46 is carried out by the method of directly forming the Pd alloy film with the resist patterns 44a, 44b as masks by electrolytic plating; and forming the various components constituting the Pd alloy by electrolytic plating. After that, heat treatment is applied to form a Pd alloy film by component diffusion, etc. In the formation of such a Pd alloy film 46, if there is a protruding part 43a in the approximate center of the inner wall surface of the through-hole 43 formed by the above-mentioned etching process, the current density can be increased by the protruding part 43a, and the Pd alloy film can be formed. 46, to block at the protruding part 43a. The thickness of the formed Pd alloy film 46 may be 0.5 to 30 μm, preferably about 1 to 15 μm. In addition, before the above-mentioned Pd alloy film 46 is formed, Ni strike plating is applied to the inside of the through hole 43 of the conductive base material 42 to improve the adhesion to the Pd alloy film. The thickness of such Ni strike plating can be set, for example, in the range of 0.01 to 0.1 μm.

Next, in the removal step, the resist patterns 44a and 44b are removed to obtain a filter 41 for hydrogen production (FIG. 4D). Removal of the resist patterns 44a and 44b can be performed using a sodium hydroxide solution or the like.

In the hydrogen production filter 41 manufactured above, the Pd alloy film 46 is strongly adhered to the conductive base material 42 so as to close the through-hole 43. Although the Pd alloy film is thinned in order to improve the hydrogen gas permeation efficiency, Even so, a highly durable filter can be obtained. In addition, since no adhesive is used, it can be used under high temperature and high pressure with excellent heat resistance, and the workability such as installation to the reformer can be further optimized.

Fig. 5 is a plan view showing an embodiment of the thin film supporting substrate of the present invention, Fig. 6 is a longitudinal sectional view of the I-I line of the thin film supporting substrate shown in Fig. 5 , and Fig. 7 is a II-I line of the thin film supporting substrate shown in Fig. 5 A vertical cross-sectional view on line II, FIG. 8 is a vertical cross-sectional view on line III-III of the thin film support substrate shown in FIG. 5 . In FIGS. 5 to 8, the thin film support substrate 51 of the present invention is provided with: a metal substrate 52; a plurality of columnar protrusions 53 formed at a given position on one surface of the metal substrate 52; A plurality of through-holes 54 are formed so as to penetrate the metal substrate 52 at a given portion of the non-formation portion 52a of the metal substrate 52 . Furthermore, the area of the columnar convex portion non-formation portion 52a occupies a range of 20 to 90%, preferably 30 to 85%, of the area of the surface on which the columnar convex portion 53 is formed. If the area of the non-columnar convex part 52a is less than 20%, the effect of effectively expanding the area of the Pd alloy film in the hydrogen gas permeation is not sufficient. On the other hand, if it exceeds 90%, it will cause obstacles to the support of the hydrogen gas permeation film. , because the durability of the filter for hydrogen production is reduced, so it is not very good.

The material of the metal substrate 52 constituting the thin film support substrate 51 may be, for example, austenitic or ferritic stainless steel such as SUS304 or SUS430. The thickness of the metal substrate 52 (the thickness of the columnar protrusion non-formed portion 52 a ) can be appropriately set within a range of 20 to 300 μm. When the thickness of the metal substrate 52 is less than 20 μm, the strength of the thin film supporting substrate 51 is insufficient. On the other hand, when the thickness exceeds 300 μm, there is a problem of increased weight, and the formation of the through hole 54 is also disadvantageous.

The columnar protrusions 53 constituting the film support substrate 51 have a diameter of 20 to 500 μm, preferably 30 to 300 μm, and a formation pitch of 40 to 700 μm, preferably 60 to 520 μm. The area of 52a is set to account for 20 to 90% of the above. In addition, the height of the columnar convex portion 53 may be in the range of 10 to 200 μm, preferably in the range of 20 to 150 μm. In the illustrated example, although the columnar protrusion is cylindrical, it is not limited thereto. The columnar protrusions 53 can be formed, for example, by half-etching a metal substrate from one surface of a resist pattern with a plurality of desired openings.

The through hole 54 constituting the thin film support substrate 51 has an opening diameter of 20 to 200 μm, preferably 50 to 150 μm. However, when the inner diameter of the through hole 54 is not uniform, the smallest inner diameter is used as the opening diameter. The thin film support substrate 51 of the present invention is formed by forming a Pd alloy film on the upper end surface 53a of the columnar convex portion 53 to form a filter for hydrogen production, and the side of the through hole 54 is the low hydrogen partial pressure side. Therefore, the formation density of the through holes 54 is sufficient as long as it is within a range that does not affect the strength of the metal substrate 52. For example, the number A of the columnar protrusions 53 and the number B of the through holes 54 per unit area are sufficient. The ratio A/B may be about 1-10. Such a through-hole 54 can be formed by etching the metal substrate 52 from both sides, for example, with a resist pattern having a plurality of desired openings.

In the illustrated example, the triangle formed with the centers of the three closest columnar protrusions 53 as vertices is an equilateral triangle, and the triangle formed with the centers of the three closest through holes 54 as vertices is an equilateral triangle. , although the columnar convex portion 53 and the through hole 54 are formed so that the apex of one equilateral triangle becomes the position of the center of gravity of the other equilateral triangle, the present invention is not limited thereto.

The above-mentioned thin film support substrate 51 of the present invention, since the metal substrate 52 is provided, can maintain desired strength even if the area ratio of the area where the columnar protrusions are not formed 52a to the side where the columnar protrusions 53 are formed is increased. , can expand the effective area of Pd alloy film in hydrogen permeation.

Next, a method for producing the filter for hydrogen production of the present invention using the thin film support substrate of the present invention will be described.

9A to 9E are process diagrams showing an embodiment of a method for manufacturing a filter for hydrogen production of the present invention using the thin film support substrate 51 described above.

In the manufacturing method of the present invention, at first, in the arrangement step, on the surface of the film supporting substrate 51 where the columnar projections 53 are formed, the insulating film 62 is adhered to the upper end surface 53a of the columnar projections 53 and arranged (FIG. 9A ). As the insulating film 62, resin films such as polyethylene terephthalate, polypropylene, and polycarbonate can be used, for example. The thickness of such an insulating film 62 can be appropriately set in consideration of its material, electrical insulating performance, film strength, and the like. For example, it is about 30 to 300 μm. Adhesion of the insulating film 62 to the upper end surface 53a of the columnar protrusion 53 can be performed by, for example, a method using a polyamide-based adhesive or a method utilizing the heat-welding property of the insulating film. In addition, as an insulating film, a dry film resist may also be provided. By using a dry film, the insulating film 62 described later can be removed using a stripper such as a strong alkali aqueous solution. Compared with the case of using the above-mentioned resin film, Advantageously, there is no physical damage to the thin film support substrate 51 . When a photosensitive dry film resist is used as the insulating film, the adhesion to the upper end surface 53a of the columnar convex portion 53 is carried out by means of roll lamination or vacuum lamination, complete exposure, And according to the need to carry out the corresponding heat hardening treatment method and so on.

Next, in the base layer forming step, on the film support substrate 51 (including the inside of the through hole 54 ) except the upper end surface 53 a of the columnar convex portion 53 , and on the side of the adhesive surface of the insulating film 62 , a layer is formed by electroless plating. Conductive base layer 63 (FIG. 9B). The formation of the conductive base layer 63 can be performed by electroless nickel plating, electroless copper plating, etc., and the thickness of the conductive base layer 63 is set in the range of about 0.01 to 0.2 μm. In addition, these electroless plating conditions can be appropriately set according to the material of the insulating thin film 62 to be used.

Next, in the copper plating process, a copper plate is formed on the conductive base layer 63 so as to fill the space formed between the metal substrate 52 and the insulating film 62 of the film supporting substrate 51 and the inside of the through hole 54 of the film supporting substrate 51. Copper plated layer 64 (FIG. 9C).

Next, in the film forming process, the above-mentioned insulating thin film 62 is removed, and then, on the surface formed by the upper end surface 53a of the columnar protrusion 53 and the copper plating layer 64 (conductive base layer 63), Pd is formed by electroplating. Alloy film 65 (FIG. 9D). The insulating thin film 62 can be removed by methods such as peeling or melting. In addition, the formation of the Pd alloy film 65 is formed by the method of directly forming the Pd alloy film by electrolytic plating; , heat treatment, the method of forming a Pd alloy film by component diffusion, etc. For example, 10 μm thick Pd is formed by electroplating, 1 μm thick Ag is formed on it by electroplating, and then heat treatment is performed at 250° C. for 10 minutes to achieve Pd alloying. In addition, heat treatment may be performed after performing multilayer plating such as three layers consisting of Pd/Ag/Pd and four layers consisting of Pd/Ag/Pd/Ag. The thickness of the Pd alloy film 65 may be 0.5 to 30 μm, preferably about 1 to 15 μm.

Next, in the removal step, the copper plating layer 64 (conductive base layer 63 ) is removed by selective etching to obtain a filter 61 for hydrogen production ( FIG. 9E ). Selective etching is performed using an ammonia-based etchant by means of a jet method, dipping method, air blowing, or the like.

10A to 10E are process diagrams showing another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

First, in the disposing step, the insulating film 72 is disposed on the surface of the film support substrate 51 opposite to the surface on which the columnar protrusions 53 are formed ( FIG. 10A ). The insulating film 72 may be the same film as the insulating film 62 described above, and the method of disposing the insulating film 72 may be the same as the method of disposing the insulating film 62 described above.

Next, in the copper plating step, a copper plating layer 74 is formed on the surface of the thin film support substrate 51 on which the columnar protrusions 53 are formed to fill the inside of the through hole 54 and cover the columnar protrusions 53 ( FIG. 10B ).

Next, in the planarization step, the upper end surface 53a of the columnar protrusion 53 is exposed, and the copper plating layer 74 is removed flatly to form the same plane as the upper end surface 53a ( FIG. 10C ). The flat removal of the copper plating layer 74 can be performed, for example, by mechanical polishing or the like.

Next, in the film forming step, a Pd alloy film 75 is formed by electroplating on the flat surface formed by the upper end surface 53 a of the columnar protrusion 53 and the copper plating layer 74 ( FIG. 10D ). The formation of the Pd alloy film 75 can be performed in the same manner as the formation of the Pd alloy film 65 described above.

Finally, in the removal step, the insulating thin film 72 is removed, and then the copper plating layer 74 is removed by selective etching to obtain a filter 71 for hydrogen production ( FIG. 10E ). The removal of the insulating film 72 can be performed in the same manner as the removal of the insulating film 62 described above. In addition, the removal of the copper plating layer 74 can also be performed similarly to the removal of the above-mentioned copper plating layer 64 .

In addition, in the above example, although the insulating thin film 72 is removed in the removing step, the insulating thin film 72 may also be removed before the planarization step, or may be recoated after the planarization step and before the film formation step. The insulating thin film 72 is disposed on the surface opposite to the surface on which the columnar protrusions 53 of the film support substrate 51 are formed, and is removed in the removing step.

11A to 11E are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

First, in the resin layer forming step, a resin layer 82 is formed on the surface of the film support substrate 51 on which the columnar protrusions 53 are formed so as to fill the inside of the through hole 54 and cover the columnar protrusions 53 ( FIG. 11A ). The formation of the resin layer 82 is carried out by such a method as to allow thermosetting resin monomer solutions such as epoxy resin, viscose maleimide resin, phenol resin, etc. to flow in by grouting or the like to give a given hardening effect. temperature for heat hardening.

Next, in the flattening step, the upper end surface 53a of the columnar convex portion 53 is exposed, and the resin layer 82 is removed flatly to form the same plane as the upper end surface 53a ( FIG. 11B ). The flat removal of the resin layer 82 can be performed, for example, by mechanical grinding or the like.

Next, in the base layer forming step, a conductive base layer 83 is formed on the flat surface formed by the upper end surface 53a of the columnar protrusion 53 and the resin layer 82 by either electroless plating or vacuum film formation (Fig. 11C). When forming the conductive base layer 83 by electroless plating, it can be performed by electroless nickel plating, electroless copper plating, etc., and the thickness of the conductive base layer 83 can be set in the range of about 0.01 to 0.2 μm. In addition, these electroless plating conditions can be appropriately set according to the material of the resin layer 82 . In addition, when the conductive base layer 83 is formed by a vacuum film-forming method, a thin film of Ni, Cu, Ag, Pd, etc. can be formed, and the thickness of these thin films can be set in the range of about 0.01 to 0.2 μm.

Next, in the film forming process, a Pd alloy film 85 is formed on the conductive base layer 83 by electroplating (FIG. 11D). The formation of the Pd alloy film 85 can be performed in the same manner as the formation of the Pd alloy film 65 described above.

Finally, in the removal step, only the resin layer 82 is dissolved and removed to obtain a hydrogen production filter 81 ( FIG. 11E ). Removal of the resin layer 82 can be performed using an organic solvent capable of dissolving the resin layer 82 . In addition, in the removal of the resin layer 82 , the conductive base layer 83 is removed so that the surface of the Pd alloy film 85 on the thin film support substrate 51 side is exposed. The removal of the conductive base layer 83 can be implemented with hydrogen peroxide and sulfuric acid when nickel is used; when copper is used, it can be implemented with an amine-alkaline etching solution; when Ag is used, it can be realized by its own thermal diffusion Alloyed with Pd, so removal is not necessary.

12A to 12C are process diagrams showing still another embodiment of the method for manufacturing a filter for hydrogen production according to the present invention.

First, in the film forming step, one surface of the metal base material 92 which can be selectively etched with respect to the thin film support substrate 51 is plated to form a Pd alloy film 95 ( FIG. 12A ). Copper, a copper alloy, etc. can be used as said metal base material 92, and its thickness can be set suitably in the range of 0.05-0.3 mm. In addition, the formation of the Pd alloy film 95 is performed in the same manner as the formation of the Pd alloy film 65 described above. Also, on the metal base material 92, for example, by applying Ni strike plating, the adhesion to the formed Pd alloy film 95 can be improved. The thickness of such Ni strike plating can be set, for example, in the range of 0.01 to 0.1 μm.

Next, in the diffusion bonding step, the above-mentioned Pd alloy film 95 is diffusely bonded to the upper end surface 53a of the columnar projection 53 on the surface of the thin film support substrate 51 on which the columnar projection 53 is formed, thereby disposing the metal base material 92 ( Figure 12B). The bonding of the Pd alloy film 95 and the upper end surface 53a of the columnar protrusion 53 by diffusion bonding is achieved by heat treatment at 900 to 1400°C for 12 to 18 hours in vacuum.

Finally, in the removal step, the metal base material 92 is removed by selective etching to obtain a filter 91 for hydrogen production ( FIG. 12C ). Selective etching is performed, for example, when the metal base material 92 is a copper base material, using an ammonia-based etchant, by a jet method, dipping method, air blowing, or the like.

The filters 61, 71, 81, and 91 for producing hydrogen produced as described above can use any of the thin film support substrates 51 of the present invention, so the area of the effective Pd alloy film in hydrogen permeation can be enlarged, and the relative strength The columnar protrusions 53 of the tall thin film support substrate 51 can adhere the Pd alloy film with high strength, and even if the Pd alloy film is thinned to increase the hydrogen gas permeability, an extremely durable filter can be obtained. In addition, since no adhesive is used, the heat resistance can be optimized, and it can be used under high temperature and high pressure, and the workability of installation to the reformer can be further optimized.

In the following, the present invention will be further described by showing more specific embodiments.

[Example 1]

Fabrication of filters for hydrogen production

Prepare a SUS430 material with a thickness of 50 μm as a base material, and apply a photosensitive resist material (OFPR manufactured by Tokyo Ohka Industry Co., Ltd.) (film thickness 7 μm (when dry)) to both sides of the SUS430 material by dipping method, Next, a photomask in which a plurality of circular openings having an opening size (opening diameter) of 120 μm is arranged at a pitch of 200 μm is placed on the above-mentioned resist coating film, and the resist coating is applied through the photomask. The film was exposed and developed using sodium bicarbonate solution. In this way, a resist pattern having a circular opening with an opening size (opening diameter) of 120 μm was formed on both surfaces of the SUS430 material. In addition, the centers of the openings of the resist patterns formed on the respective surfaces were made uniform by the SUS430 material.

Then, using the above resist pattern as a mask, the SUS430 material was etched under the following conditions.

(etching conditions)

·Temperature: 50℃

·Concentration of ferric chloride: 45 Baume

·Pressure: 3kg/cm ²

After the above etching treatment, the resist pattern was removed using a sodium hydroxide solution, and finally washed with water. Thus, a conductive base material in which a plurality of circular through-holes were formed in the SUS430 material was obtained. The formed through hole has a protruding portion in the approximate center of the inner wall surface, and the opening size (opening diameter) of the protruding portion is 70 μm.

Next, a metal plate (SUS430 material) with a thickness of 200 μm was attached to one surface of the above-mentioned SUS430 material by using a plate-shaped permanent magnet to close the through hole. (The above is the through-hole plugging step).

Next, electrolytic plating is performed on the surface of the SUS430 material without the metal plate under the following conditions, a copper plating layer is formed on the surface of the SUS430 material and the metal plate exposed in the through hole, and the through hole is filled with the copper plating layer. The thickness of the copper plating layer on the surface of the SUS430 material is 80 μm. (The above is the copper plating process).

(conditions for copper plating)

·Copper sulfate electroplating solution

·Liquid temperature: 30℃

·Current density: 1A/dm ²

Next, the metal plate and the plate-shaped permanent magnet were removed from the SUS430 material, and electrolytic plating was performed on the surface of the removed SUS430 material under the following conditions to form a Pd alloy film (thickness: 8 μm). (The above is the film forming step).

(Film formation conditions of Pd alloy film produced by electrolytic plating)

·Pd Chloride Plating Solution

·Temperature 40℃

·Current density: 1A/dm ²

Finally, the copper plating layer is selectively etched and removed. (The above is the removal process).

After the copper plating layer was removed, it was cut into a size of 3 cm x 3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for hydrogen production manufactured above is installed on the reformer, and the mixture of butane gas and water vapor is continuously supplied to the Pd alloy membrane of the filter under high temperature and high pressure (300°C, 10kg/cm ² ) conditions , to measure the CO concentration of the hydrogen-rich gas penetrating into the porous base material side of the filter and the flow rate of the hydrogen-rich gas. As a result, the concentration of CO from the start of modification to 300 hours was extremely low at 8 to 10 ppm, and the flow rate of hydrogen-rich gas was 10 L/hour. Thus, it was confirmed that the filter for hydrogen production manufactured according to the present invention Has excellent durability and hydrogen permeation efficiency.

[Comparative example 1]

Fabrication of filters for hydrogen production

In the same manner as in Example 1, a plurality of through holes were formed in the SUS430 material to obtain a conductive base material. Next, a Pd alloy film having a thickness of 30 µm was adhered to the conductive base material through an adhesive to integrate it, and then the adhesive remaining in the through-holes of the conductive base material was removed with acetone. This integrated product was cut into a size of 3 cm×3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porosity to the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it was confirmed that the CO concentration was very low at 8 to 10 ppm after 300 hours from the start of modification, which was good, but after 300 hours, the adhesive deteriorated due to high temperature and high pressure The peeling of the Pd alloy film, and therefore, the occurrence of cracks in the Pd alloy film, etc., increase the CO concentration to about 3%, deteriorating the durability.

[Example 2]

Fabrication of filters for hydrogen production

A SUS304 material with a thickness of 50 μm was prepared as a base material, and a photosensitive resist material (OFPR manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied (film thickness 7 μm (when dry)) to both sides of the SUS304 material by a dipping method. Next, a photomask in which a plurality of circular openings having an opening size (opening diameter) of 120 μm is arranged at a pitch of 200 μm is placed on the above-mentioned resist coating film, and the resist coating is applied through the photomask. The film was exposed and developed using sodium bicarbonate solution. In this way, a resist pattern with circular openings having an opening size (opening diameter) of 120 μm was formed on both surfaces of the SUS304 material. In addition, the centers of the openings of the resist patterns formed on the respective surfaces were made uniform by the SUS304 material.

Next, using the above resist pattern as a mask, the SUS304 material was etched under the following conditions.

(etching conditions)

·Temperature: 50℃

·Concentration of ferric chloride: 45 Baume

·Pressure: 3kg/cm ²

After the above etching treatment, the resist pattern was removed using a sodium hydroxide solution, and finally washed with water. Thus, a conductive base material in which a plurality of circular through-holes were formed in the SUS304 material was obtained. The formed through hole has a protruding portion in the approximate center of the inner wall surface, and the opening size (opening diameter) of the protruding portion is 70 μm.

Next, an insulating film with a thickness of 200 μm was pasted on one surface of the above-mentioned SUS304 material. (The above is the pasting process)

Next, electrolytic copper plating was performed on the surface of the SUS304 material where the insulating film was not attached under the following conditions, and a copper plating layer (thickness about 80 μm) was formed on the surface of the SUS304 material while filling the through holes with copper plating. (The above is the copper plating process)

(conditions for copper plating)

·Using electroplating solution: copper sulfate electroplating solution

·Liquid temperature: 30℃

·Current density: 1A/dm ²

Next, the insulating thin film was peeled off from the SUS304 material and removed, and electrolytic plating was performed on the surface of the removed SUS304 material under the following conditions to form a Pd alloy film (thickness: 8 μm). (The above is the film formation process)

(Film formation conditions of Pd alloy film produced by electrolytic plating)

·Use electroplating solution: palladium chloride electroplating solution (Pd concentration: 12g/L)

·PH value: 7～8

·Current density: 1A/dm ²

·Liquid temperature: 40℃

Finally, the copper plating layer is selectively etched and removed. (The above is the removal process)

After the copper plating layer was removed, it was cut into a size of 3 cm x 3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porous structure of the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of modification to 300 hours has become an extremely low 8 to 10 ppm, and the flow rate of hydrogen-rich gas is 10 L/hour. With filter, it has excellent durability and hydrogen permeation efficiency.

[Example 3]

Fabrication of filters for hydrogen production

In the same manner as in Example 2, a plurality of through holes were formed in the SUS304 material to obtain a conductive base material.

Next, Ni strike plating (thickness: 0.01 μm) was performed on the above-mentioned SUS304 material under the following conditions, and then resin parts (AZ111 manufactured by Shipley Co., Ltd.) were filled in the through-holes of the above-mentioned SUS304 material. The filling of these resin parts is carried out by means of grouting. (The above is the filling process)

(Conditions for Ni strike plating)

·Electroplating solution composition: nickel chloride ...... 300g/L

Boric acid ...... 30 g/l

·PH:2

·Liquid temperature: 55～65℃

·Current density: 10A/dm ²

Next, the following pretreatment is performed on one surface of the SUS304 material filled with the resin component in the through hole, and then electroless plating is performed under the following conditions to form electroless plating on the surface of the resin material filling the through hole and the surface of the SUS304 material. Ni plating layer (thickness 0.4 μm) and as conductive base layer. (The above is the base formation process)

(preprocessing)

Strong alkali degreasing→water washing→chemical etching (in 200g/L ammonium persulfate aqueous solution (20℃±5℃))→water washing→acid treatment (10% dilute sulfuric acid (normal temperature))→water washing→acid treatment (30% dilute hydrochloric acid ( Normal temperature)) → immersion in the additional solution of sensitive agent (composition: palladium chloride 0.5g, stannous chloride 25g, hydrochloric acid 300ml, water 600ml) → water washing

(Electroless nickel plating conditions)

·Electroplating solution composition: nickel sulfate ... 20g/L

Sodium hypophosphite ... 10g/L

Lactic acid ... 3g/L

Sodium citrate ... 5g/L

Sodium acetate ... 5g/L

·PH:4.5～6.0

·Liquid temperature: 55～65℃

Next, a Pd metal mold (thickness: 8 μm) was formed on the conductive base layer by electrolytic plating under the following conditions. (The above is the film formation process)

(Film formation conditions of Pd alloy film produced by electrolytic plating)

·Use electroplating solution: palladium chloride electroplating solution (Pd concentration: 12g/L)

·PH value: 7～8

·Current density: 1A/dm ²

·Liquid temperature: 40℃

Next, the resin material filled in the through-holes was removed using the following treatment solution (Desmear solution manufactured by Shipley Co., Ltd.). (The above is the removal process)

(Desmear plating solution treatment conditions)

·The composition of the electroplating solution in the swelling process: MLB-211 ... 20% by volume

                                                                                                                                                                                    , 

The temperature of the electroplating solution in the swelling process: 80°C

·The composition of the electroplating solution in the roughening process: MLB-213A ... 10% by volume

MLB-213B ... 15% by volume

·The temperature of the electroplating solution in the roughening process: 80°C

After the removal of the above-mentioned resin member was completed, it was cut into a size of 3 cm×3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porous structure of the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of reforming to 300 hours has become an extremely low 8 to 10 ppm. In addition, the flow rate of hydrogen-rich gas is 10 L/hour, and the filter for hydrogen production manufactured according to the present invention devices with excellent durability and hydrogen permeation efficiency.

[Example 4]

Fabrication of filters for hydrogen production

In the base forming process, instead of the electroless plating method, a Pd metal mold (0.2 μm in thickness) was formed by sputtering under the following conditions as a conductive base layer, except that it was the same as in Example 3 Similarly, a filter for hydrogen production was produced.

(Cathode spraying conditions)

·RF power: 500W

Argon pressure: 5.4×10 ^-2 Pa

·DC current: 2.5A

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porous structure of the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of reforming to 300 hours has become an extremely low 8 to 10 ppm. In addition, the flow rate of hydrogen-rich gas is 10 L/hour, and the filter for hydrogen production manufactured according to the present invention devices with excellent durability and hydrogen permeation efficiency.

[Example 5]

Fabrication of filters for hydrogen production

Similar to Example 2, a plurality of through holes were formed in the SUS304 material by etching using the resist pattern as a mask. However, after the etching process was completed, the resist pattern was left on the surface of the SUS304 material without removing it (the above is an etching step).

Next, Ni strike plating (thickness: 0.2 μm) was performed in the through-holes of the aforementioned SUS304 material under the following conditions.

(Conditions for Ni strike plating)

·Electroplating solution composition: nickel chloride ... 300g/L

Boric acid ... 30 g/l

·PH:2

·Liquid temperature: 55～65℃

·Current density: 10A/dm ²

Then, using the resist pattern as a mask, a Pd alloy film (thickness: 15 µm) was formed by electrolytic plating under the following conditions to close the inside of the through hole. (The above is the film formation process)

(Film formation conditions of Pd alloy film produced by electrolytic plating)

·Use electroplating solution: palladium chloride electroplating solution (Pd concentration: 12g/L)

·PH value: 7～8

·Current density: 1A/dm ²

·Liquid temperature: 40℃

Next, the resist pattern on the SUS304 material was removed using a 5% sodium hydroxide aqueous solution. (The above is the removal process)

After the removal of the above-mentioned resist pattern was completed, it was cut into a size of 3 cm×3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porous structure of the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of reforming to 300 hours has become an extremely low 8 to 10 ppm. In addition, the flow rate of hydrogen-rich gas is 10 L/hour, and the filter for hydrogen production manufactured according to the present invention devices with excellent durability and hydrogen permeation efficiency.

[Comparative example 2]

Fabrication of filters for hydrogen production

In the same manner as in Example 2, a plurality of through holes were formed in the SUS304 material to obtain a conductive base material. Next, a Pd alloy film with a thickness of 30 μm was adhered to the conductive base material through an adhesive to be integrated, and thereafter, the adhesive remaining in the through-holes of the conductive base material was removed with acetone. This integrated product was cut into a size of 3 cm×3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porosity to the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it was confirmed that the CO concentration was very low at 8 to 10 ppm after 300 hours from the start of modification, which was good, but after 300 hours, the adhesive deteriorated due to high temperature and high pressure The peeling of the Pd alloy film, the occurrence of cracks in the Pd alloy film, and the like increase the CO concentration to about 3%, deteriorating the durability.

[Example 6]

Fabrication of Thin Film Support Substrates

A SUS304 material with a thickness of 150 μm was prepared as a base material, and a photosensitive resist material (OFPR manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied (film thickness 7 μm (when dry)) to both sides of the SUS304 material by a dipping method. Next, a photomask having a plurality of circular refraction portions with a diameter of 390 μm at a pitch of 430 μm was provided on the resist coating film of the SUS304 material on the side where the columnar protrusions were formed. A photomask having a plurality of circular openings with an opening size (opening diameter) of 100 μm at a pitch of 430 μm is provided on the resist coating film, and the resist is exposed through these photomasks, using sodium bicarbonate Solution imaging. Thus, on one surface of the SUS304 material, a circular resist pattern with a diameter of 390 μm was formed at a pitch of 430 μm, and on the opposite surface, a resist pattern having a circular opening with an opening size (opening diameter) of 100 μm was formed. Eclipse pattern. In addition, the vertices of the triangles with the centers of the three closest circular resists (diameter 390 μm) as vertices are defined as the centers of the three closest openings with the resist pattern on the opposite side across the SUS304 material. The position of the center of gravity of the triangle at the vertex, for position coincidence.

Next, using the above resist pattern as a mask, the SUS304 material was etched under the following conditions. In this etching, columnar protrusions were formed by half-etching from one surface of the SUS304 material, and at the same time, through-holes were formed by etching from both surfaces. The time required for etching was 6 minutes.

(etching conditions)

·Temperature: 50℃

·Concentration of ferric chloride: 45 Baume

·Pressure: 3kg/cm ²

After the above-mentioned etching treatment, the resist pattern was removed using a sodium hydroxide solution, and finally washed with water. Thus, at a pitch of 430 μm, cylindrical columnar protrusions with a diameter of 290 μm and a height of 60 μm are formed on one surface of the SUS304 material with a thickness of 90 μm, and on the SUS304 material at the non-formed portion of the columnar protrusions, the SUS304 material is formed at a pitch of 430 μm. Through-holes with an opening diameter of 70 to 100 μm were formed at a pitch to obtain a thin film support substrate as shown in FIG. 5 . In this thin film support substrate, the area of the portion where the columnar protrusions are not formed accounts for about 50% of the area of the side where the columnar protrusions are formed.

Fabrication of filters for hydrogen production

An insulating film (polyethylene terephthalate) having a thickness of 200 μm was pasted and attached to the surface of the columnar protrusions of the film supporting substrate prepared above (the above is an attaching step).

Next, the following pretreatment is performed on the film support substrate (including the inside of the through hole) and the side of the bonding surface of the insulating film from which the upper end surface of the columnar protrusion is removed, and then electroless plating is performed under the following conditions. , forming an electroless Ni plating layer (thickness 0.4 μm) and serving as a conductive base layer. (The above is the base layer formation process)

(preprocessing)

Strong alkali degreasing→water washing→chemical etching (in 200g/L ammonium persulfate aqueous solution (20℃±5℃))→water washing→acid treatment (10% dilute sulfuric acid (normal temperature))→water washing→acid treatment (30% dilute hydrochloric acid ( Normal temperature)) → immersion in the additional solution of sensitive agent (composition: palladium chloride 0.5g, stannous chloride 25g, hydrochloric acid 300ml, water 600ml) → water washing

(Electroless nickel plating conditions)

·Electroplating solution composition: nickel sulfate ... 20g/L

Sodium hypophosphite ... 10g/L

Lactic acid ... 3g/L

Sodium citrate ... 5g/L

Sodium acetate ... 5g/L

·PH:4.5～6.0

·Liquid temperature: 50～65℃

Next, electroplating is performed on the conductive base layer under the following conditions to form a copper plating layer so as to fill the space formed between the non-pillar-shaped protrusion-formed surface of the film support substrate and the insulating film and the inside of the through-hole of the film support substrate. . (The above is the copper plating process)

(conditions for copper plating)

·Using electroplating solution: copper sulfate electroplating solution

·Liquid temperature: 30℃

·Current density: 1A/dm ²

Next, the insulating film was peeled off from the film support substrate and removed, and electrolytic plating was performed on the removed film support substrate (the upper end surface of the columnar protrusion) and the copper plating layer under the following conditions to form a Pd alloy film (thickness 3 μm) . And, in this electrolytic plating, the copper plating layer on the rear side of the film supporting substrate is covered with an insulating film. (The above is the film formation process)

(Film formation conditions of Pd alloy film produced by electrolytic plating)

·Use electroplating solution: palladium chloride electroplating solution (Pd concentration: 12g/L)

·PH value: 7～8

·Current density: 1A/dm ²

·Liquid temperature: 40℃

Finally, the insulating film is peeled off and removed, and further, the copper plating layer is selectively etched to remove the copper plating layer. (The above is the removal process)

After the copper plating layer was removed, it was cut into a size of 3 cm x 3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porosity to the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of modification to 300 hours has become an extremely low 8-10ppm, and the flow rate of hydrogen-rich gas is 10L/hour, and the filter for hydrogen production manufactured according to the present invention Appliances with excellent durability and hydrogen permeation efficiency.

[Example 7]

Fabrication of Thin Film Support Substrates

In the same manner as in Example 6, a thin film support substrate of the present invention was produced.

Fabrication of filters for hydrogen production

An insulating film (polyethylene terephthalate) with a thickness of 200 μm is pasted and arranged on the surface of the above-prepared film support substrate opposite to the side on which the columnar protrusions are formed (the above is the arrangement step) .

Next, electrolytic copper plating is performed on the surface of the film support substrate on which the columnar protrusions are formed to fill the inside of the through hole, and a copper plating layer (about 80 μm in thickness) is formed on the film support substrate to cover the columnar protrusions. . In addition, the conditions of copper plating are the same as Example 6 (the above is a copper plating process).

Next, the copper plating layer is removed flatly by grinding, so that the upper end surface of the columnar protrusion is exposed, and the same plane as the upper end surface of the columnar protrusion is formed. At this time, make the grinding surface as smooth as possible (the above is the planarization process).

Next, a Pd alloy film (thickness: 3 μm) was formed on the flat surface. In addition, the electrolytic plating conditions of this Pd alloy film were the same as in Example 6. (The above is the film formation process)

Finally, the insulating film is peeled off and removed, and further, the copper plating layer is selectively etched to remove the copper plating layer. (The above is the removal process)

After the copper plating layer was removed, it was cut into a size of 3 cm x 3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porosity to the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of reforming to 300 hours has become an extremely low 8 to 10 ppm. In addition, the flow rate of hydrogen-rich gas is 10 L/hour, and the filter for hydrogen production manufactured according to the present invention devices with excellent durability and hydrogen permeation efficiency.

[Example 8]

Fabrication of Thin Film Support Substrates

In the same manner as in Example 6, a thin film support substrate of the present invention was produced.

Fabrication of filters for hydrogen production

A resin member (AZ111 manufactured by Shipley Co., Ltd.) was filled and coated with a resin member (AZ111 manufactured by Shipley Co., Ltd.) by grouting on the surface of the film support substrate formed in the above-mentioned manner to fill the inside of the through-hole, and , covering the cylindrical convex part. (The above is the resin formation process)

Next, the resin layer is removed flatly by grinding, so that the upper end surface of the columnar protrusion is exposed, and the same plane as the upper end surface of the columnar protrusion is formed. At this time, make the grinding surface as smooth as possible. (The above is the planarization process)

Then, electroless plating was performed on the flat surface to form an electroless nickel plating layer (thickness: 0.4 μm) as a conductive base layer. In addition, the electroless nickel plating conditions were the same as in Example 6 (the above is the base layer forming step).

Next, a Pd alloy film (thickness: 3 μm) was formed on the conductive base layer. In addition, the conditions of the electrolytic plating of the Pd alloy film were the same as in Example 6. In addition, during the electrolytic plating, the surface opposite to the formation of the Pd alloy film was covered with an insulating thin film. (The above is the film formation process)

Finally, the insulating film was peeled off and removed, and further, the resin layer was dissolved and removed using the following treatment solution (Desmear plating solution manufactured by Shipley Co., Ltd.). (The above is the removal process)

(Desmear plating solution treatment conditions)

·The composition of the electroplating solution in the swelling process: MLB-211 ... 20% by volume

                                                                                                                                                                                                     , 

The temperature of the electroplating solution in the swelling process: 80°C

·The composition of the electroplating solution in the roughening process: MLB-213A ... 10% by volume

MLB-213B ... 15% by volume

·The temperature of the electroplating solution in the roughening process: 80°C

After the removal of the above-mentioned resin layer was completed, it was cut into a size of 3 cm×3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porous structure of the filter was measured. The concentration of CO and the flow rate of hydrogen-rich gas permeating the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of modification to 300 hours has become an extremely low 8-10ppm, and the flow rate of hydrogen-rich gas is 10L/hour, and the filter for hydrogen production manufactured according to the present invention devices with excellent durability and hydrogen permeation efficiency.

[Example 9]

Fabrication of Thin Film Support Substrates

In the same manner as in Example 6, a thin film support substrate of the present invention was produced.

Fabrication of filters for hydrogen production

Ni strike plating (thickness: 0.01 μm) was performed on a copper base material having a thickness of 0.2 μm under the following conditions.

(Conditions for Ni strike plating)

·Electroplating solution composition: nickel chloride ... 300g/L

Boric acid ... 30 g/l

·PH:2

·Liquid temperature: 55～65℃

·Current density: 10A/dm ²

Next, a Pd alloy film (thickness: 3 μm) was formed on one surface of the copper base material subjected to the above-mentioned Ni strike plating. In addition, the electrolytic plating conditions of this Pd alloy film were the same as in Example 6. In addition, during electrolytic plating, the opposite surface formed by the Pd alloy film is covered with an insulating thin film. (The above is the film formation process)

Next, the insulating film is peeled off and removed from the copper base material, and the above-mentioned Pd alloy film is butted on the upper end surface of the columnar protrusion of the film support substrate, and is heated at 1000° C. for 12 hours in a vacuum. A copper base material is arranged so that the Pd alloy film is diffusion bonded to the upper end surface of the columnar protrusion. (The above is the diffusion bonding process)

Finally, the copper base material is selectively etched and removed. (The above is the removal process)

After the removal of the above-mentioned copper base material was completed, it was cut into a size of 3 cm×3 cm, and used as a filter for hydrogen production.

Evaluation of filters for hydrogen production

The filter for producing hydrogen produced above was mounted on a reformer, and under the same conditions as in Example 1, a mixture of butane gas and water vapor was supplied to the Pd alloy membrane of the filter, and the porosity to the filter was measured. The CO concentration and the flow rate of the hydrogen-rich gas permeated from the side of the matrix material. As a result, it can be confirmed that the concentration of CO from the start of modification to 300 hours has become an extremely low 8-10ppm, and the flow rate of hydrogen-rich gas is 10L/hour, and the filter for hydrogen production manufactured according to the present invention devices with excellent durability and hydrogen permeation efficiency.

Possibility of industrial application

As described above, the method for producing a hydrogen production filter according to the present invention is suitable for producing a hydrogen production filter capable of stably producing high-purity hydrogen gas used in a reformer of a fuel cell.

Claims (5)

1. A manufacturing method of a filter for hydrogen production, characterized in that it comprises: A through-hole plugging process in which a metal plate is attached to one surface of a conductive base material having a plurality of through-holes by a magnet; Forming a copper plating layer on the conductive base material and the metal plate exposed in the through hole from the side of the conductive base material surface where the metal plate is not attached, and filling the copper plating of the through hole process; A film forming step of forming a Pd alloy film by electroplating on the surface of the conductive base material after removal of the metal plate; and A removal step of removing the copper plating layer by selective etching. 2. The method of manufacturing a filter for hydrogen production according to claim 1, wherein in the film forming step, a Pd alloy film is formed by electrolytic plating. 3. The method of manufacturing a filter for hydrogen production according to claim 1, wherein in the film forming step, first, thin films of various components constituting the Pd alloy are laminated by electroplating, and then heat-treated , forming a Pd alloy film by component diffusion. 4. The method of manufacturing a filter for hydrogen production according to claim 1, wherein the conductive base material is a ferritic stainless steel substrate. 5. The method of manufacturing a filter for hydrogen production according to claim 1, wherein the metal plate is a ferritic stainless steel substrate.

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